Review

pubs.acs.org/CR

Rechargeable LithiumSulfur Batteries

Arumugam Manthiram,* Yongzhu Fu, Sheng-Heng Chung, Chenxi Zu, and Yu-Sheng Su
Materials Science and Engineering Program and Texas Materials Institute, The University of Texas at Austin, Austin, Texas 78712,
United States

*
S Supporting Information

6.3. Chemical Synthesis of Li2S Cathode Materi-

als 11767
6.4. Solid-State Batteries with Li2S Cathodes 11768
7. Characterization Techniques and Mechanistic
Understanding 11768
7.1. In Situ Characterization 11768
7.2. Polysulde Dissolution 11769
7.3. Formation of the Passivation Layer 11770
7.4. Kinetics 11770
8. Electrolytes and Separators 11771
8.1. Liquid Electrolytes 11771
8.2. Carbonate-Based Electrolytes 11773
8.3. Polymer/Solid-State Electrolytes 11773
8.4. Separators 11774
CONTENTS 9. Anodes 11774
9.1. Lithium Metal Anode 11774
1. Introduction 11752 9.2. Silicon Anode 11775
2. Principles of LithiumSulfur Batteries 11752 9.3. Carbon Anode 11775
3. Historical Development 11753 10. Binders 11776
4. Technical Challenges 11754 11. Cell Congurations 11776
4.1. Shuttle Mechanism 11754 11.1. Interlayers 11777
4.2. Self-Discharge 11755 11.1.1. Polysulde-Interception Mechanism 11777
5. Sulfur Cathode 11755 11.1.2. Constructional Materials for Interlayers 11778
5.1. Conventional Sulfur Composite Electrodes 11755 11.2. Porous Current Collectors 11778
5.2. SulfurPorous Carbon Composite Materials 11756 11.2.1. Sulfur Impregnation Strategy 11779
5.2.1. Carbon Materials 11756 11.2.2. Constructional Materials for Porous
5.2.2. SulfurCarbon Composites 11756 Current Collectors 11780
5.2.3. Synthesis Methods 11759 11.3. Sandwiched Electrodes 11780
5.3. SulfurGraphene Composite Materials 11761 11.4. Dissolved Polysulde Catholytes 11780
5.3.1. Graphene and Graphene Oxide 11761 12. Voltage Window 11780
5.3.2. SulfurGraphene/Graphene Oxide 12.1. Upper Voltage Plateau 11781
Composites 11761 12.2. Lower Voltage Plateau 11781
5.4. Binder-Free SulfurCarbon Composite Elec- 13. Conclusions and Future Directions 11781
trodes 11762 13.1. Appropriate Dispersion of Active Sulfur 11781
5.5. SulfurPolymer Composite Materials 11763 13.2. Ecient Absorbing Materials 11781
5.5.1. SulfurPolyacrylonitrile Composites 11763 13.3. Flexible Conductive Matrix 11781
5.5.2. SulfurPolypyrrole Composites 11764 13.4. Stable Electrolyte Systems 11781
5.5.3. SulfurPolyaniline Composites 11764 13.5. Safe Anode Materials 11781
5.5.4. Other Sulfur-Conductive Polymer Com- 13.6. Li2S Cathode 11781
posites 11765 13.7. Novel Cell Congurations 11782
5.6. SulfurMetal Oxide/Chalcogenide Compo- 13.8. Smart Recharge Settings 11782
site Materials 11766 Associated Content 11782
5.6.1. Metal Oxide Additives/Composites 11766 Supporting Information 11782
5.6.2. Metal Oxide Coatings 11766 Author Information 11782
5.6.3. Intercalation Compounds/Chalcogenide
Composites 11766
6. Lithium Sulde Cathodes 11766 Special Issue: 2014 Batteries
6.1. Activation of Microsized Li2S Particles 11766 Received: February 3, 2014
6.2. Li2SCarbon Composites 11767 Published: July 15, 2014

2014 American Chemical Society 11751 dx.doi.org/10.1021/cr500062v | Chem. Rev. 2014, 114, 1175111787
Chemical Reviews
Corresponding Author 11782
Notes 11782
Biographies 11782
Acknowledgments 11783
References 11783
1. INTRODUCTION
The demand for energy increases steadily with time due to
population and economic growth and advances in lifestyle. As
energy usage increases, concerns about environmental pollution
associated with the use of fossil fuel are becoming serious. To
mitigate these issues and reduce our dependence on fossil fuel,
alternative energy technologies based on renewable sources
need to be developed and adopted, e.g., solar and wind
energies. However, solar and wind energies are intermittent;
therefore, it is critical for ecient and economical storage of
electricity produced by renewable sources to be competitive.1
Rechargeable batteries are one of the most viable options for
electrical energy storage (EES). Rechargeable battery systems,
such as leadacid, nickelcadmium, nickel metal hydride, and
lithium ion batteries, have serviced humankind for over a
century with their use in a variety of applications, e.g., portable
electronic devices and automobiles. As the functionalities of the
portable electronics become more sophisticated and the
demand for electric vehicles and storage of electricity from
renewable sources increases, advanced rechargeable batteries
need to be developed. Cost, energy, power, cycle life, safety,
and environmental compatibility are some of the most
important parameters to be considered.
Li ion batteries have become prominent over the past two
decades, particularly for portable electronics, as they oer much
higher energy density than other rechargeable systems. The
current Li ion technology is based on insertion-compound
anode and cathode materials, which limit their charge-storage
capacity and energy density. A further increase in energy
density needs to be achieved through an increase in the charge-
storage capacity of the anode and cathode materials or an
increase in the cell voltage or both. However, the limited
electrochemical-stability window of the currently available
liquid electrolytes makes it dicult to increase the cathode
operating voltage beyond 4.3 V.2 Also, the capacities of the
insertion-oxide cathodes have reached a limit of 250 mA h
g1. On the other hand, the capacity of the graphite anode is
also limited to 370 mA h g1. Therefore, alternative cathode
and anode materials that oer higher capacities need to be
developed. To overcome the charge-storage limitations of
insertion-compound electrodes, materials that undergo con-
version reactions while accommodating more ions and
electrons are becoming a promising option, but are highly
challenging. With this perspective, for example, LiO2 and Li
S batteries with high energy are being intensively pursued.3,4
However, the huge volume change accompanying the electro-
chemical reactions and maintenance of an electrochemically
favorable electrode structure during long-term cycling are some
of the challenges.
Sulfur, one of the most abundant elements in earths crust,
oers a high theoretical capacity of 1672 mA h g1, which is an
order of magnitude higher than those of the transition-metal
oxide cathodes. The high capacity is based on the conversion
reaction of sulfur to form lithium sulde (Li2S) by reversibly
incorporating two electrons per sulfur atom compared to one
or less than one electron per transition-metal ion in the
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insertion-oxide cathodes. However, the conversion reaction is
accompanied by a volume change of about 80%. In addition,
sulfur and lithium sulde are both insulators, which necessitates
the incorporation of conductive additives (e.g., carbon) into the
electrodes. Moreover, the intermediate lithium polysuldes
formed during the conversion reaction are soluble in the liquid
electrolytes currently used. All of these create tremendous
challenges in developing reversible, stable, and ecient sulfur
cathodes. However, signicant progress has been made with
rechargeable LiS batteries in recent years by developing novel
nanocomposites, ecient electrolytes, and novel cell cong-
urations. Also, an in-depth fundamental understanding of the
LiS cells has been gained by employing advanced character-
ization methodologies. Although the LiS batteries are believed
to be one of the most promising next-generation high-energy-
density rechargeable battery chemistries, the cycle life and
eciency need to be improved for them to be employed in
practical applications. In this review, we rst present the
principles, history, and technical challenges of LiS batteries
and then focus on sulfur and lithium sulde composite cathode
materials. Signicant attention is paid to the characterization
techniques used and the mechanistic understanding gained. We
then cover the electrolyte, separators, anodes, and binders used
in LiS batteries. Finally, we focus on novel cell congurations
including carbon interlayers between the sulfur cathode and the
separator. Overall, in this review we describe the advances in
LiS batteries and provide guidance for future development in
the eld.
2. PRINCIPLES OF LITHIUMSULFUR BATTERIES
A LiS cell is an electrochemical storage device through which
electrical energy can be stored in sulfur electrodes. A schematic
of the components in a single LiS cell and its operation
(charge and discharge) is shown in Figure 1. A conventional
Figure 1. Schematic diagram of a LiS cell with its charge/discharge
operations.
LiS cell consists of a lithium metal anode, an organic
electrolyte, and a sulfur composite cathode. Because sulfur is in
the charged state, the cell operation starts with discharge.
During the discharge reaction, lithium metal is oxidized at the
negative electrode to produce lithium ions and electrons. The
lithium ions produced move to the positive electrode through
the electrolyte internally while the electrons travel to the
positive electrode through the external electrical circuit, and
thereby an electrical current is generated. Sulfur is reduced to
produce lithium sulde by accepting the lithium ions and
electrons at the positive electrode. The reactions occurring
during discharge are given below, and the backward reactions
will occur during charge.
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Chemical Reviews
negative electrode: anodic reaction (oxidation, loss of
electrons)
2Li 2Li+ + 2e (1)
positive electrode: cathodic reaction (reduction, gaining
electrons)
S + 2Li+ + 2e Li 2S (2)
overall cell reaction (discharge)
2Li + S Li 2S (3)
The theoretical capacities of lithium and sulfur are 3.861 and
1.672 A h g1, respectively, which leads to a theoretical cell
capacity of 1.167 A h g1 for the LiS cell. The discharge
reaction has an average cell voltage of 2.15 V. Hence, the
theoretical gravimetric energy density for a LiS cell is 2.51 W
h g1.3
Sulfur atoms show a strong tendency to catenation, forming
long homoatomic chains or homocyclic rings of various sizes.4a
Octasulfur (cyclo-S8), crystallizing at 25 C as orthorhombic -
S8, is the most stable allotrope at room temperature. During an
ideal discharge process, cyclo-S8 is reduced and the ring opens,
resulting in the formation of high-order lithium polysuldes
Li2Sx (6 < x 8). As the discharge continues, lower order
lithium polysuldes Li2Sx (2 < x 6) are formed with the
incorporation of additional lithium. There are two discharge
plateaus at 2.3 and 2.1 V with ether-based liquid electrolytes,
which represent the conversions of S8 to Li2S4 and Li2S4 to Li2S,
respectively. At the end of discharge, Li2S is formed, as shown
in Figure 2.4b During the following charge, Li2S is converted to
Figure 2. Voltage proles of a LiS cell. Reprinted with permission
from ref 4b. Copyright 2012 Macmillan Publishers Ltd.
S8 via the formation of the intermediate lithium polysuldes,
resulting in a reversible cycle.5 However, the two charge voltage
plateaus are normally overlapped with each other.
3. HISTORICAL DEVELOPMENT
Sulfur was used as a positive electrode material in electric dry
cells and storage batteries by Herbet and Ulam in 1962.6 The
electrolyte was identied to be alkaline perchlorate, iodide,
bromide, or chlorate dissolved in a primary, secondary, or
tertiary saturated aliphatic amine, preferably selected from
among propylic, butylic, and amylic amines. Later on, Rao7
specically patented high-energy-density metalsulfur batteries
with organic electrolytes and presented the theoretical energy
densities of metalsulfur cells in 1966. The open-circuit voltage
of the cell was observed to be between 2.35 and 2.5 V, which
was slightly lower than the calculated 2.52 V. The electrolytes
contemplated in the patent consist of one or more of the
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solvents propylene carbonate, -butyrolactone, dimethylforma-
mide, and dimethyl sulfoxide. The subsequent developments
were focused mostly on primary LiS cells.8 An important
development during this period was the identication of the
electrolyte solvent for LiS cells from saturated aliphatic
amines,6 to propylene carbonate,7 to a mixture of tetrahy-
drofuran (THF)toluene,8c and nally to mixtures of
dioxolane-based electrolytes, which are being widely used
nowadays.8d,e The liquid electrolyte has a signicant impact on
the cell performance since the intermediate charged/discharged
products lithium polysuldes are soluble in it. For example,
more than 95% sulfur utilization was achieved at room
temperature with LiClO4 dissolved in a mixture of THF
toluene by Yamin et al.,8c but with a low discharge current
density (10 A cm2). In contrast, dioxolane-rich electrolytes
have an order of magnitude higher ionic conductivity than the
THFtoluene electrolyte.8d However, sulfur utilization in
dioxolane-rich electrolytes was only 50% even at a very low
discharge rate in primary LiS cells due to the partial discharge
product Li2S2. Further work by Peled et al.8e demonstrated
rechargeable LiS batteries with dioxolane-rich electrolytes. A
notable work by Rauh and Abraham et al.8b demonstrated a cell
with a conguration of Li/5 M S in Li2Sn, THF, 1 M LiAsF6/
C. Almost 100% of the theoretical capacity was achieved at 50
C and 1.0 mA cm2, and 75% cathode utilization was achieved
at 4 mA cm2. Cycling eciencies started at about 95% at 25
C but tended to deteriorate after 1020 cycles.
Starting in 2000, more eorts were focused on rechargeable
LiS batteries as evidenced by the exponentially growing
number of publications. Eorts have been focused on
developing more conductive sulfurcarbon composites and
solid electrolytes, fabricating ecient electrodes and cell
congurations, and understanding the degradation mechanism
and limiting factors for long cycle life LiS batteries.
Mikhaylik9 illustrated the status of the LiS battery technology
in his Electrochemical Society (ECS) meeting presentation in
2010, as shown in the spider chart in Figure 3. In comparison to
Figure 3. Year 2009 status of the LiS technology. Reprinted with
permission from ref 9. Copyright 2010 Y. V. Mikhaylik.
the specications of LiS batteries set by the U.S. Advanced
Battery Consortium (USABC), LiS batteries meet the
requirements of specic energy, specic power, power density,
and low-temperature performance. However, the energy
density, rate capability, and recharge time are barely met, and
the cycle life and high-temperature performance of current Li
S batteries are far below the minimum requirements, which
limit the LiS technology from wide commercial applications.
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Chemical Reviews
Signicant improvements have been made since then, including
a remarkable increase in the cycle life of LiS batteries in some
work presented in this review.
4. TECHNICAL CHALLENGES
There are many challenges facing the LiS technology, either
with the materials or with the system. First of all, the high
resistance of sulfur (1030 S cm1) and the intermediate
products (i.e., lithium polysuldes Li2Sx) formed during cycling
along with their structural and morphological changes are
formidable challenges, resulting in unstable electrochemical
contact within sulfur electrodes. In addition, the dissolved
polysuldes shuttle between the anode and cathode during
cycling, reacting with both the lithium metal anode and the
sulfur cathode.5a Moreover, the electrochemical conversion of
sulfur to lithium sulde involves structural and morphological
changes as well as repetitive dissolution and deposition of
reactive species, which tend to passivate both the electrodes,
leading to a signicant increase in impedance. These issues
result in a low utilization of the active material, poor cycle life,
and low system eciency. Thus, the conventional LiS battery
electrode shown in Figure 1 cannot meet all the requirements
of LiS batteries for practical applications.
As a result, the following issues need to be overcome to make
LiS batteries feasible: The shuttle mechanism resulting from
the dissolution of the active cathode material has to be
eliminated to avoid low Coulombic eciency and self-discharge
behavior. Also, the amount of carbon additives needs to be
reduced as much as possible since too much carbon could
reduce the volumetric energy density of LiS cells. Full
utilization of the sulfur cathode to achieve the full capacity of
sulfur (1.672 A h g1) is another challenge because the lower
plateau redox reaction is quite sluggish compared to the upper
plateau redox reaction due to slow solid-state diusion when
low-order polysuldes are reduced to Li2S.113c In addition,
some persistent issues such as dendrite formation and surface
passivation remain to be solved with the lithium metal anode.
Other alternative anode materials might be an option to replace
lithium metal due to safety concerns.
4.1. Shuttle Mechanism
The intermediate redox species formed, i.e., the high-order
lithium polysuldes Li2Sx (6 < x 8), are highly soluble in the
liquid electrolyte with glyme-based and dioxolane solvents.5a,10
These various polysulde anions can freely migrate between the
cathode and anode, leading to a so-called polysulde shuttle
phenomenon, as illustrated in Figure 4. Fundamentally, the
shuttle behavior is the main reason causing LiS batteries to
Figure 4. Illustration of the shuttle mechanism occurring in a LiS
cell.
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have low Coulombic eciency. The high-order polysuldes
migrate toward the anode, react with the lithium metal, reduce
to low-order polysuldes, migrate back to the cathode, form
high-order polysuldes again, and so on.11 Severe shuttle
behavior can lead to an innite recharge and poor charge
eciency.
The polysulde shuttle mechanism has been particularly
investigated in recent years. The shuttle equation below was
rst derived by Mikhaylik and Akridge5a to evaluate the degree
of shuttle behavior, which includes the impact from the charge
current and polysulde diusivity. The charge shuttle factor
( f C) is derived as
k Squp[Stotal ]
fC =
IC (4)
where IC, kS, qup, and [Stotal] represent, respectively, the charge
current, shuttle constant (heterogeneous reaction constant),
specic capacity of sulfur contributed by the upper plateau, and
total sulfur concentration. The value of qup is xed and equal to
419 mA h g1, which is a quarter of the full theoretical capacity
of LiS batteries (0.5 electron per sulfur atom).5a,12
The simulated charge proles can be seen in Figure 5. There
is no shuttle eect when f C approaches zero, which means the
Figure 5. Simulated charge plateaus with dierent charge shuttle
factors f C. Reprinted with permission from ref 5a. Copyright 2010 The
Electrochemical Society.
system has an innitely large current density, an innitely small
shuttle constant, or an innitely small sulfur concentration.
When f C > 1, the charge curves become horizontal without a
sharp voltage rise, oering overcharge protection. However,
prolonged shuttle reactions might cause severe corrosion of the
lithium anode and result in a short cycle life.5a,11,13 In addition,
the extension of the leveled upper plateau during charging is
not brought into play for the polysulde oxidation, but for the
extra energy consumed by the polysulde migration, leading to
poor charge eciency.
Equation 4 assumes that the reaction rate is proportional to
the active material concentration, so the high-order polysulde
concentration in the upper plateau can be presented by eq 5 in
consideration of the impact from the shuttle constant and
current density:
d[SH] I
= C k S[SH]
dt qup (5)
where [SH] represents the concentration of high-order
polysuldes. The equation can be simplied by assuming a
slow charge reaction (kStC 1) and considering that the upper
plateau capacity (Qup) depends on the concentration of high-
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Chemical Reviews
order polysuldes and the specic capacity. The reciprocal
shuttle constant can be given by the dierential equation as
dQ up 1
= This equation demonstrates that the self-discharge behavior still
dIC kS (6)
The shuttle constant kS can be obtained when small charge
currents are applied by measuring the charge capacity output
from the upper plateau. As a result, the lower the shuttle
constant the battery system possesses, the slighter the shuttle
eect.
4.2. Self-Discharge
Low self-discharge is another criterion to judge the practicality
of energy-storage devices. Unfortunately, LiS batteries have
strong self-discharge behavior, like nickelcadmium or tradi-
tional nickelmetal hydride batteries. Since the dissolution of
polysuldes is inevitable in the LiS cell while employing some
nonaqueous electrolytes, sulfur/high-order polysuldes after
charging continue to slowly dissolve in the electrolyte even in
the resting state. When batteries are resting, the self-discharge
occurs because the active material gradually dissolves and
migrates to the anode due to the concentration gradient and
then reacts with lithium metal followed by conversion into
high-order polysuldes, resulting in a decrease in the open-
circuit voltage and discharge capacity.5a,14
Figure 6 exhibits the initial discharge voltage plateaus of
pristine sulfur cathodes with dierent resting times. With a
Figure 6. Typical discharge plateaus of pristine sulfur cathodes with
dierent resting times.
short resting time (30 min), the cell displays a typical two-
plateau discharge prole. With a longer resting time of over a
week, the upper discharge plateau disappears and only the
lower discharge plateau can be observed. The open-circuit
voltage also decreases with increasing resting time. This
demonstrates that, with a conventional cell conguration,
sulfur dissolves in the electrolyte during cell resting, resulting in
a loss of the upper discharge plateau. Additionally, if the
dissolved polysulde species diuse out of the cathode region,
they will not be reutilizable, leading to permanent capacity
fading.
The level of self-discharge behavior can be determined by the
shuttle equation (eq 5) as well and vice versa.5a Thus,
Mikhaylik et al. devised a mathematical way of expressing the
relationship between the upper plateau capacity, resting time,
and shuttle constant as
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d ln Q up
= kS
dt R (7)
closely correlates with the shuttle constant, which means that
both the shuttle eect and the self-discharge eect originate
from the dissolution of the active material in the LiS battery
system. Consequently, design of electrode architectures and
novel cell congurations are needed to avoid these unwanted
side reactions.
A lot of eort has been devoted to reducing the shuttle eect
and improving the retention of active material within the sulfur
electrode. Some approaches are focused on developing sulfur
composites with favorable nanostructures and properties to
improve the discharge capacity, cyclability, and Coulombic
eciency.3,15 Other approaches being pursued include novel
cell congurations with trapping interlayers, Li/dissolved
polysulde cells, and ecient electrolytes.16 The following
sections give some representative examples of these approaches.
5. SULFUR CATHODE
5.1. Conventional Sulfur Composite Electrodes
After the prototype LiS cell was designed about 30 years ago,
the insulating active material and the polysulde shuttle eect
became major chronic technical problems impeding the LiS
technology.8b,c The solution to the problem of high cathode
resistance is straightforward: an appropriate electrical con-
ductor (conductive carbon/polymer additives) needs to be
added and well-dispersed in the active material to ensure
smooth electron transport between the electrical conductor and
the active material. About 10 years ago, conductive carbons and
conductive polymers were added to sulfur cathodes to form (i)
SC composites (see section 5.2) and (ii) sulfur-conductive
polymer composites (see section 5.5). The conductive carbon
was added to SC composites to enhance the conductivity and
active material utilization of the sulfur cathode. For example,
the carbon black that is very frequently used for preparing the
active material mixture paste has high electrical conductivity to
decrease the cathode resistance.17 The active carbon has a high
surface area and abundant micropores for absorbing the active
material, which is essential for limiting polysulde dissolution.18
On the other hand, the sulfur-conductive polymer composites
started with the application of polyacrylonitrile (PAN) and
showed a high initial discharge capacity of 850 mA h g1.19a As
a result, various types of conductive/porous carbon materials
and conductive polymers have been incorporated into sulfur
during the past decade.1719
Among these conductive additives, porous/conductive
carbon has received considerable attention due to its porous
structure and higher electrical conductivity compared to that of
polymers, which are essential criteria for simultaneously
accommodating the active material and enhancing the cathode
conductivity. The cathode conductivity is increased by two
morphological routes: (i) formation of a conductive carbon
network, e.g., carbon nanoparticle clusters, and (ii) intimate
connection between the conductive framework and the
insulating sulfur. Moreover, the engineered porous carbon,
mesoporous carbon, and macroporous network not only
promote retention of sulfur but also enhance the charge and
electrolyte transport in the composites. So far, various carbon
materials and synthesis routes that are dedicated to optimizing
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Figure 7. Schematic models, SEM observation (the SEM image of the carbon host is also shown), and cell performance of a representative S
microporous carbon composite. Reprinted with permission from ref 22. Copyright 2010 The Royal Society of Chemistry
the composite conguration have provided signicant improve-
ments in the cycling performance of LiS cells.
5.2. SulfurPorous Carbon Composite Materials
The rst sulfurporous carbon (PC) composites were the
sulfurcarbon nanocomposites presented by Wang et al.18 The
applied active carbon serves as an electrical conductor for
increasing the cathode conductivity and also as a storage
container for the active material in its micropores. This concept
made sulfur cathodes exhibit better cyclability compared to the
pure sulfur cathode. After several years of eorts on SPC
composites, a sulfurmesoporous carbon composite that
displayed a high discharge capacity and stable cyclability was
reported by Ji et al.20 in 2009. A high specic capacity of 1320
mA h g1, approaching 80% sulfur utilization, and stable
cyclability were accomplished by impregnating sulfur into a
highly ordered nanosized mesoporous carbon (MPC). The
hierarchical MPC not only satises the criteria listed in section
5.1 but also provides pathways for fast Li ion transport within
the mesoporous carbon substrates. The intimate contact among
the charges, active material, and liquid electrolyte with the
conductive substrate results in high sulfur utilization.
Furthermore, the ordered mesoporous space connes the
active material within the composites and suppresses the free
migration of polysulde species, leading to highly reversible
cyclability. Following this concept, numerous and various
porous carbon substrates have been developed within the past 4
years and dened as quick cures for the two chronic problems
described above.
However, quick cures usually cause side eects as they
address the major issues. Zhang et al.10 pointed out the side
eects associated with the SC composite cathode: several
excellent cycling performances published are due to a very low
S to C ratio in the cathode. The reasonable sulfur content
(65%) and sulfur loading (2 mg cm2) suggested for the sulfur
cathode should be the fundamental tenet for LiS cell
development.10,16b,21
On the other hand, several engineering-oriented studies
indicate that the initial morphology of sulfur may not enhance
the capacity.10,12,21 The reason is that, during cell discharge, the
originally solid sulfur is converted into soluble polysuldes and
then the polysulde species freely migrate to other preferred
locations during subsequent discharge processes. The morphol-
ogy of the rearranged sulfur may be inuenced by the
surrounding conductive carbon additive and not decided by
its original morphology. As a result, it is reasonable to expect
that the morphology of the active material in the SPC
composites is dominated by the carbon host and the
connection between them. Therefore, it is instructive to look
at how synthesis routes and manufacturing parameters of SPC
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composites inuence the cycling performance of the resultant
composite cathodes. Therefore, we present below several
carbon materials that are frequently used in SPC composites
and their electrochemical performances. We also summarize the
synthesis methods and manufacturing parameters as well as the
sulfur content in the cathode in Table S1 (Supporting
Information).
5.2.1. Carbon Materials. The categories of porous carbons
are classied by their pore size and major morphology.
According to the pore size (D), the porous structure of these
carbons has three major types, and each type of porous carbon
possesses unique morphological advantages: (i) the micropore
(D < 2 nm) has been demonstrated as the ideal container for
accommodating and immobilizing the active material;22 (ii) the
mesopore (2 nm < D < 50 nm) can enhance sulfur
encapsulation as the designed pore size is small or can improve
lithium ion and electrolyte transport as well as raise the
tolerance toward high sulfur loading as the pore size is
large;20,23 (iii) the macropore (D > 50 nm) is usually derived
from an interwoven network of carbon nanotubes (CNTs) or
carbon nanobers (CNFs) and is able to ensure excellent
electrolyte immersion or suppress polysulde migration due to
its high electrolyte absorbability.24 In addition, coalescing CNT
or CNF networks can further be decorated with various micro/
meso/macropores to from composited hierarchical porous
structures via delicate synthesis methods, which may lead to
improved cycling performance.25
According to the above categories, the frequently used
carbon materials in SPC composites include microporous
carbon,22,26 mesoporous carbon,23a,27 hierarchical porous
carbon,20,23b,28 carbon black,29 hollow carbon spheres,30
CNTs,24,25c,31 CNFs,25a,b,32 and graphene (see section 5.3 for
a detailed discussion).33 These porous carbons possess at least
one of the following specic functions for improving the cycling
performance: (i) containing/immobilizing the active material,
(ii) constraining/trapping the dissolved polysuldes, (iii)
accelerating the charge transport, and (iv) absorbing/
channeling the liquid electrolyte.
5.2.2. SulfurCarbon Composites. Microporous Car-
bon. Figure 7 shows the microporous carbon and the sulfur
microporous carbon composite. The eect of the micropores
on the electrochemical stability was evidenced by the
microporous carbon sphere encapsulating the melting sulfur
via a two-step heat treatment process.22 Zhang et al.22 designed
the microporous carbon spheres to constrain the electro-
chemical active material and reaction inside their narrow
micropores by their strong adsorption. As a result, sulfur
microporous carbon cathodes showed a long cycle life for 500
cycles with the remaining capacity around 650 mA h g1.
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Chemical Reviews
Figure 8. Schematic models, SEM observation (the SEM image of the carbon host is also shown), and cell performance of a representative S
mesoporous carbon composite. Reprinted with permission from ref 23a. Copyright 2011 The Royal Society of Chemistry.
Figure 9. Schematic models, SEM observation (the SEM image of the carbon host is also shown), and cell performance of a representative S
hierarchical porous carbon composite. Reprinted with permission from ref 20. Copyright 2009 Macmillan Publishers Ltd.
Recently, microporous carbon has facilitated the use of smaller
sulfur molecules as a new starting active material.26
The metastable S24 active material that is synthesized within
the conned narrow space of the microporous carbon avoids
the transition of the highly soluble polysuldes and, therefore,
shows only the lower discharge plateau at 1.9 V and a single
reduction peak in the cyclic voltammograms. This roundabout
discharge/charge process limits the loss of the active material
and thereby accomplishes a high reversible capacity of 1149 mA
h g1 after 200 cycles.26b Yin et al.26d have investigated the
eect of chainlike sulfur molecules on cycling performance. The
chainlike sulfur molecules have a strong interaction with the
conductive carbon substrate and are conned within the
micropores, avoiding the formation of unfavorable soluble
polysuldes. Thus, an eective cooperation of the metastable
S24 active material and the microporous carbon may overcome
the severe polysulde diusion problem in conventional
lithiumsulfur cells.
Mesoporous Carbon. The mesoporous carbon in Figure 8
has been identied as an ordered sulfur encapsulation
substrate.23a,27 After systematically analyzing a series of
mesoporous carbon materials with tunable pore sizes and
pore volumes, Li et al.23a indicated that mesoporous carbon
with a larger pore size can tolerate a higher maximum sulfur
loading and still display good cell performance under full sulfur-
lling conditions, which stimulates hopes of improving the
currently limited sulfur content/loading in SPC composite
cathodes. On the other hand, under partial sulfur-lling
conditions and surface modication, the encapsulated sulfur
has an optimized electrical contact with the mesoporous
substrate, which can limit the dissolution/diusion of
polysuldes and ensure a steady supply of lithium ions.23a
For example, an MPC that possesses a pore size of 22 nm and
has 50% sulfur lling in the mesoporous spaces (the theoretical
maximum sulfur loading in a composite is 84.7%) provides S
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MPC composites with an initial capacity as high as 1390 mA h
g1 and a capacity of 840 mA h g1 after 100 cycles.
Engineered Hierarchical Porous Carbon. Engineered
hierarchical porous carbon includes bimodal micro/mesopo-
rous carbon28a,c,d or a micro/mesopore-decorated porous
carbon framework.20,28b,e,f The rst signicant achievement
was contributed by the CMK-3 ordered MPC (Figure 9)
reported by Ji et al.20 The high sulfur utilization in this system
results from the complete redox reaction, which is stabilized
within the nanosized electrochemical reaction chamber of the
MPCs. Therefore, the MPC works not only as the electronic
conduit but also as the active material stockroom.
This success encourages the development of numerous
hierarchical porous carbon materials with micro/meso/macro-
pores for improving cycling performance by dierent physical/
chemical properties.20,23b,28 In the hierarchical porous carbon,
the micropore is designed for encapsulating/immobilizing the
active material, which improves the electrochemical activity and
also suppresses the loss of active material. The macroporous
network serves as the electrolyte pathway to ensure good
electrolyte immersion. The mesopore usually serves as an
essential supporter for reinforcing the physical properties of the
micropore or the macroporous network. Generally, a mesopore
with a smaller pore size can work with the micropore to
accommodate the active material and trap the dissolved
polysuldes, suppressing the severe capacity fade.20,23b,28ce
On the other hand, a mesopore with a larger pore size can
facilitate charge transport and cooperate with the macroporous
network to ensure electrolyte penetration, resulting in high
utilization of sulfur.28ac,f As a result, the major accomplish-
ment of the hierarchical porous carbon is the high cooperation
possibility among the functional micro/meso/macroporous
carbons.
Carbon Black. Conventionally, carbon black is only used as
an extra conductive additive in the cathode. However, the low
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Figure 10. Schematic models, SEM observation (the SEM image of the carbon host is also shown), and cell performance of a representative S
carbon black composite. Reprinted with permission from ref 29c. Copyright 2012 Elsevier.

Figure 11. Schematic models, SEM observation (the SEM image of the carbon host is also shown), and cell performance of a representative S
hollow carbon sphere composite. Reprinted with permission from ref 30a. Copyright 2011 Wiley-VCH Verlag GmbH & Co. KGaA.

Figure 12. Schematic models, SEM observation (the SEM image of the carbon host is also shown), and cell performance of a representative SCNT
composite. Reprinted with permission from ref 24b. Copyright 2012 The Royal Society of Chemistry.

cost and high electrical conductivity of carbon black oer
advantages for sulfur cathodes. After carbon black is coated on
the sulfur particle or sulfur is distributed in the carbon black
clusters, the sulfurcarbon black composites can improve the
sulfur utilization, as shown in Figure 10.18,29 Our group
reported a sulfurcarbon black composite cathode synthesized
by a facile in situ sulfur deposition route to exhibit a high rst
discharge capacity.29c The improved sulfur utilization was
attributed to the increased contact area between the conductive
carbon black clusters and the insulating sulfur as well as to the
good sulfur distribution in the carbon network structure. The
composite showed good cyclability with a reversible discharge
capacity of 777 mA h g1 after 50 cycles. The improved
cyclability is due to the carbon black matrix, which plays a
protective role as an adsorbent agent to keep the soluble
polysuldes within the electrode structure. This phenomenon
can be observed with many other materials as reported in the
literature, i.e., conductive carbon materials with intrinsic
nanopores18 and porous carbon black clusters.29ac
Hollow Carbon Spheres. Figure 11 shows the hollow carbon
spheres and their sulfur-based composites.30a The hollow
carbon spheres, which are synthesized by a hard template route,
possess a large interior void space with a diameter of 200500
nm and a mesoporous shell with a thickness of 3050
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nm.26e,30a,b Jayaprakash et al.30a reported porous hollow
carbonsulfur composites with excellent cycling performance:
high capacity retention of 91% after 100 cycles. In the
composite, the large interior void space of the porous hollow
carbon allows the starting active sulfur and polysuldes to be
stabilized within the conductive carbon sphere. Furthermore,
the mesoporous shell ensures a stable supply of lithium ions
and electrolyte.
Hollow carbon spheres recently synthesized by a hydro-
thermal method have a small diameter of 80 nm.30c The small
hollow carbon spheres may suppress the formation of inactive
sulfur cores as lling sulfur inside the carbon spheres and
enhance electron transport.
Carbon Nanotubes. The CNTs function as an interwoven
conductive network in the sulfur-based composites,24b,25c,31 as
shown in Figure 12. In Han et al.s work, a Smultiwall carbon
nanotube (MWCNT) composite cathode that has 20 wt %
MWCNTs, 20 wt % conductive carbon, 50 wt % sulfur, and 10
wt % poly(vinylidene diuoride) (PVdF) manifested a higher
discharge capacity and longer cycle life than the regular sulfur
cathode containing 0 wt % MWCNTs, 40 wt % conductive
carbon, 50 wt % sulfur, and 10 wt % PVdF. This is because the
MWCNTs have a high surface area for absorbing polysuldes
and can form a three-dimensional (3D) conductive network
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Figure 13. Schematic models, SEM observation (the SEM image of the carbon host is also shown), and cell performance of a representative SCNF
composite. Reprinted with permission from ref 25b. Copyright 2011 The Royal Society of Chemistry
Figure 14. Schematic models, SEM observation (the SEM image of the carbon host is also shown), and cell performance of a representative S
graphene composite. Reprinted from ref 33c. Copyright 2011 American Chemical Society.
structure to enhance electron transport.31a Although the rst
study reported limited improvement in cell performance (initial
discharge capacity 500 mA h g1), which may result from the
immature sulfur encapsulation technique, it showed that a
simple mechanical mixing of the long/thin MWCNTs with the
sulfur improves the capacity retention.
After combination of the advanced sulfur encapsulation
technique with CNTs, several cycle-stable sulfur cathodes have
demonstrated that the CNT network is a promising host
material. Guo et al.25c developed sulfur-impregnated disordered
carbon nanotubes in a vacuum environment. After sulfur vapor
is infused into the narrow pore channel in a carbon shell, the
carbon substrate can avoid severe polysulde dissolution. Our
group reported a self-weaving sulfurMWCNT composite
cathode24b,c having a coalescing MWCNT network as the
electrical and ionic pathway for facilitating a fast charge/
discharge process. Moreover, the sulfurMWCNT composite
has good electrolyte absorption ability, which connes the
soluble polysuldes within the electrode and avoids the
irreversible loss of the active materials during cycling.
Carbon Nanobers. The CNFs shown in Figure 13 have a
nanosized shape similar to that of the nanotubes and, therefore,
several morphological advantages similar to those of CNTs but
without a hollow space in the middle.25a,b,32 The CNFs are also
well-known for their good electrical conductivity and high
structural strength. The high conductivity ensures the CNFs to
be a suitable carbon conductor. Moreover, the CNF additives
can form a network-like structure for suppressing the S/Li2S
agglomeration that usually covers the sulfur cathode and
produces inactivation areas.32 Rao et al.32b reported a
nanocarbon/sulfur composite that has a CNF cluster as the
3D conductive network with nanoscale sulfur well dispersed in
the CNF substrate, which enhances cathode conductivity and
suppresses active material agglomeration.
The advanced sulfur encapsulation techniques allow
researchers to impregnate the porous CNFs or the hollow
anodic aluminum oxide (AAO) template CNFs with the active
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materials, achieving a uniform sulfur dispersion and localization
within the porous structures or facilitating sulfur coating onto
the inner surface of hollow CNFs for promoting rapid lithium
ion transport.25a,b Ji et al.25b developed porous CNFS
composites, which exhibit a high initial discharge capacity and
enhanced rate capability. The enhanced electrochemical
performance is due to the high electrical conductivity of the
porous CNFs that immobilize the active sulfur on their porous
structure during cell operation. Zheng et al.25a reported hollow
CNF-encapsulated sulfur cathodes based on the AAO template,
which showed a high initial discharge capacity of 1560 mA h
g1 and a capacity approaching 730 mA h g1 after 150 cycles.
However, an obvious capacity fade (400500 mA h g1)
appeared in the initial 50 cycles.
Graphene. Graphene is a novel 2D carbon monolayer that
can be extracted from graphite and is regarded as an ultralight,
thin, and hard material with high conductivity. With these
unique physical properties, graphene has risen abruptly in the
materials eld in recent years.34 The exible characteristics of
graphene render it suitable to be the sulfur carrier in LiS
batteries.33 The graphene in the composites coating or
wrapping the sulfur can suppress the loss of active sulfur
species due to dissolution during cycling, as shown in Figure
14. The detailed physical characteristics and cell performance of
sulfurgraphene composites are discussed in section 5.3.
5.2.3. Synthesis Methods. After the importance of various
carbon materials and their sulfur-based composites is under-
stood, it is instructive to look at how various synthesis routes
inuence the cell performance since a suitable sulfur
encapsulation will denitively improve the utilization of the
active material and limit the loss of the active material.35
Moreover, the feasibility and the cost associated with various
synthesis methods need to be sketched in detail for future
developments in the LiS battery area. According to the
incorporation of sulfur and carbon hosts, the synthesis methods
are classied into three major categories: (i) mechanical mixing,
(ii) heat treatment, and (iii) solution-based synthesis.
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Mechanical Mixing Method: Magnetic Stirring and Ball-
Milling. The mechanical mixing route that mixes materials by
magnetic stirring is widely applied in almost all kinds of pure
sulfur and sulfur-based cathode preparation.17,28b,29d,e,31a,36 The
conventional pure sulfur cathode17 is prepared by direct
mechanical mixing of elemental sulfur, conductive carbon,
and a binder and may have poor contact between the insulating
sulfur and the electrical conductor (the carbon black and the
current collector). The nonconductive sulfur agglomerations
may block the electron pathway, resulting in limited active
material utilization. As a result, the initial discharge capacity of
conventional cathodes may be as low as 300500 mA h
g1.17,31a,36a,b
Although the mechanical mixing process has several
disadvantages and has turned from a major synthesis route
into a minor process for preparing the active material mixture
slurry, it is still a necessary process for cathode preparation.
Most SPC composites still need to be well mixed with extra
conductive carbons to ensure their normal function and high
performance. The typical mixture in the whole cathode may
include SPC composites, conductive carbons (520 wt %),
and binders. On the other hand, some reports describe simply
using mechanical mixing to prepare a pure sulfur cathode
(without using SPC composites) but achieve excellent cycling
performance. In these cases, improvements may arise from the
application of an adsorbent carbon agent (6 wt % in the
cathode)28b or alternative porous current collectors.29d,e,36c
The ball-milling method is a branch of the mechanical mixing
route which uses attrition ball-milling. This process imparts
high energy to the mixtures and facilitates better connection
between sulfur and the conductive carbon host compared to
magnetic stirring.23b,31e,32a Chen et al.31e synthesized S
MWCNT composites by ball-milling for 6 h. The synthesized
composites form an interwoven/porous MWCNT structure
and approach a high initial discharge capacity of 1580 mA h g1.
Heat Treatment Method: Two-Step Heat Treatment,
Sulfur Melting Diusion, and Sulfur Vaporization. The heat
treatment method aims to melt or vaporize the solid sulfur and
then impregnate carbon matrixes with the low-viscosity melted
sulfur. The derived synthesis routes include the two-step heat
treatment (sulfur melting and then vaporizing),18,22,24a,27,29a
sulfur melting diusion method,20,23a,25a,b,26,28a,c,e,f,30b,c,31b,33b
and sulfur vaporizing method.30a,33c During heat treatment, the
melting or vaporizing sulfur can diuse into the nanosized
porous substrates. These advanced processes eectively
encapsulate the sulfur into the narrow porous spaces of the
carbon host, resulting in a high initial discharge capacity and
stable cyclability. As a result, the heat treatment route has
dominated the preparation processes for SPC composites.
Wang et al.18 prepared SC composites by the two-step heat
treatment process. The rst step of heat treatment at 200 C is
to melt the elemental sulfur and to allow the melting sulfur to
diuse into the porous carbon substrates. The second step is to
vaporize and remove the sulfur that covers the outside surface
of the SC composites. The two-step heat treatment ensures a
strong sulfurcarbon bonding and no obvious sulfur coverage
on the surface of the composites. Following this concept,
various two-step heat treatments have been derived to obtain
higher active material utilization by modifying the following
three parameters: heat treatment temperature, dwell time, and
porous carbon substrates.22,24a,27,29a
In 2009, the sulfur melting diusion method for synthesizing
SMPC composites was reported by Ji et al.20 and involves a
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single-step heat treatment at 155 C. At this heat treatment
temperature, the melting sulfur has the lowest viscosity and can
easily diuse into the porous carbon substrates. After the sulfur
is imbibed into the interconnected porous spaces, the sulfur is
well absorbed into the composite, which suggests that no severe
sulfur covers the outside of the composite and the second step
of heat treatment is unnecessary. The melting diusion method
optimizes the morphology of the SPC composites well and
has become the most frequently used heat treatment
process.23a,25a,b,26,28a,c,e,f,30ac,31b,33b Jayaprakash et al. utilized
the sulfur vaporizing method to synthesize Sporous hollow
carbon composites. The encapsulating sulfur accomplishes
molecular contacts with the carbon host, providing an
enhanced cycle stability with 91% capacity retention after 100
cycles.
Solution-Based Synthesis: CS2, Na2S, and Water-Based
Solutions. The solution-based synthesis route starts from
preparing a sulfur-based solution and then mixing the carbon
host with the dissolved sulfur to achieve a close connection. By
going through a heterogeneous nucleation, the precipitated
sulfur is strongly held by or absorbed into the carbon substrate.
Currently, solution-based synthesis routes are supported by
CS2, Na2S, and water-based solutions.
Liang et al.23b utilized CS2 as the matrix solution to channel
the dissolved sulfur into the hierarchical micro/mesopores of
the activated MPC and to ll the micro/mesopores with the
sulfur-containing solution, resulting in an excellent sulfur
encapsulation within the porous carbon and thereby achieving
a high initial discharge capacity of 1584 mA h g1. The
improved electrochemical performance indicates that the CS2-
based solution may be an attractive method for preparing the
SPC composites.23a,25c However, the application of the toxic
CS2 may cancel the advantage from the environmentally
friendly sulfur. The Na2S solution method starts with Na2S
solution preparation by adding Na2S to distilled water and then
follows the chemical deposition method in an aqueous solution:
Sx2 + 2H+ (x 1)S + H2S. The sulfur nucleates on the
dispersed carbon substrates and accomplishes a strong
incorporation into the porous carbon host. The molecular
sulfur incorporated into the conductive carbon eliminates the
high cathode resistance and provides a high active material
utilization of above 70%.25b,32b However, the toxicity concern
still exists with the byproduct H2S.
In comparison with the two methods described above, a
water-based solution synthesis route may be safer, more
attractive, and more environmentally benign. The water-based
solution involves the precipitation of elemental sulfur on the
carbon nanoparticles29b or at the interspaces between carbon
nanoparticle clusters29c in aqueous solution at room temper-
ature. Both the coreshell carbonsulfur composites and the
carbon-wrapped sulfur network structure ensure that the
resultant sulfur contacts the carbon black closely due to the
heterogeneous nucleation of sulfur: (i) coreshell composites,
SO2 + 2S2 + 4H+ 3S + 2H2O, and (ii) carbon-wrapped
composites, S2O32 + 2H+ S + H2SO3. The chemical
precipitation process leads to a high sulfur utilization of 74% for
the coreshell composites and 67% for the carbon-wrapped
sulfur composites. Most importantly, the water-based synthesis
route avoids use of toxic raw materials and generation of toxic
products.
The heat treatment and solution-based syntheses have
received considerable attention in recent years because they
provide the best sulfur encapsulation conditions for SPC
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Chemical Reviews
composite syntheses. On the other hand, mechanical mixing
has mainly turned to serve as a support process: mixing the
synthesized SPC composites well with extra conductive
carbon and binder for further improving the cathode
conductivity. This synergy eect functions well and has made
several signicant improvements. However, there are some
disadvantages: (i) misleading calculation of the sulfur content
and (ii) low sulfur content/loading. First, the sulfur content
value presented should pertain to the sulfur content in the
whole cathode and not simply in the composite alone. For
example, the real sulfur content is only 49 wt % in a cathode
that is prepared by mixing 70 wt % SC composite (S:C ratio
in composite, 70:30), 15 wt % conductive carbon, and 15 wt %
binder. Second, according to the statistical table included in the
Supporting Information, several SPC composite cathodes
cannot reach a sulfur content of even 60 wt % and seem to
exhibit excellent cell performance because of low sulfur loading
in the cathode.10
5.3. SulfurGraphene Composite Materials
5.3.1. Graphene and Graphene Oxide. Graphene refers
to a single-atom-thick two-dimensional (2D) carbon material
with a honeycomb lattice. It could be the basic building block of
0D fullerenes, 1D nanotubes, and 3D graphite.34 There are
principally three representative methods to produce pristine
graphene: epitaxial growth method, micromechanical exfolia-
tion method, and solvent-assisted exfoliation method.37
Epitaxial graphene is grown on epitaxially matched surfaces,
and the method often involves chemical vapor deposition
(CVD) processes.37 The micromechanical exfoliation method
can be used to generate electrically isolated graphene of high
quality suitable for fundamental studies, but large-area
production has yet to be achieved.37 Moreover, exfoliation of
graphite could be achieved by exposing graphite powder to
organic solvents such as dimethylformamide (DMF) or N-
methyl-2-pyrrolidone (NMP) and applying high-intensity
ultrasound, but the yield is low.37
In contrast to graphene, graphene oxide (GO) is a
compound of carbon, oxygen, and hydrogen in variable ratios
and is rich in epoxide, carbonyl, hydroxyl, phenol, and
organosulfate functional groups, whose structure and properties
depend on the particular synthesis method and degree of
oxidation.38 In general, GO can be synthesized through the
Brodie,39 Staudenmaier,40 and Hummers38a methods, all of
which involve oxidation of graphite powder to various levels.37
Specically, a combination of potassium chlorate (KClO3) and
nitric acid (HNO3) is used in the Brodie and Staudenmaier
methods, while the Hummers method involves oxidizing
graphite by potassium permanganate (KMnO4) and sulfuric
acid (H2SO4).37 The synthesized GO is hydrophilic and easily
dispersed in water, making it suitable for the synthesis of
sulfurgraphene composites. In general, graphene-based
materials are less expensive to produce than some other carbon
nanomaterials such as carbon nanotubes, which is advantageous
when they are applied as raw materials for the synthesis of
graphene-based composite materials.34
5.3.2. SulfurGraphene/Graphene Oxide Composites.
With exceptional electronic conductivity and high mechanical
strength and exibility, graphene-based materials have been
successfully integrated into the sulfur cathode to enhance its
electrochemical reactivity and stability. To synthesize a sulfur
graphene composite, melting methods have been commonly
used. Wang et al.41 reported a sulfurgraphene composite
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electrode which exhibited a higher initial discharge capacity and
lower electrochemical impedance than the pure sulfur
electrode. However, severe capacity fading occurred in the
rst cycle with a low sulfur content of 17.6 wt % in the
electrode. Improved cycling performance with a higher sulfur
content was achieved by dissolving sulfur in an organic solvent
initially, e.g., CS2, followed by melting to lower the viscosity of
sulfur and improve the sulfur distribution.42 Through this
method, Cao et al.42 synthesized a functionalized graphene
sheetsulfur (FGSS) nanocomposite with a sandwich-type
architecture. The synthesized composite was further coated
with a cationic exchange Naon polymer lm that mitigated the
migration of polysulde anions. Improved capacity retention as
high as 84.3% over 100 cycles was obtained with a high sulfur
content of 57 wt % in the electrode.42
Herein, it is worth mentioning that polymers were usually
integrated into the sulfurgraphene composite to enhance the
exibility of the composite and assist the trapping of
polysuldes. Furthermore, graphene was rst decorated by
carbon black nanoparticles and coated onto the surface of
polyethylene glycol (PEG)-wrapped submicrometer sulfur
particles. The PEG/graphene composite coating accommo-
dated the volume expansion of the active material during
discharge and prevented the polysulde from diusing out of
the cathode, resulting in stable capacities of 600 mA h g1
over more than 100 cycles.33c Similarly, polyacrylonitrile43 and
polypyrrole44 have been incorporated into sulfurgraphene
composites. On the other hand, to produce a sulfurgraphene
composite cathode suitable for large-scale production and
industrial application, solution-based one-pot reaction syn-
theses have been developed. As mentioned in section 5.2.3, the
solution-based one-pot reaction synthesis is based on the redox
reaction of sulfur-containing compounds and heterogeneous
nucleation of sulfur on the surface of the conductive
matrix.33d,45 Following this strategy, Evers et al.33d synthesized
a graphene-wrapped sulfur composite with a high sulfur content
of 87 wt % (78 wt % in the electrode). However, the
reversible capacity dropped to 550 mA h g1 after 50 cycles at a
0.2C rate, indicating that further improvement of this method is
required. There seems to be a trade-o between the simple
synthesis strategies and the superior performance of the
graphenesulfur composite, and this calls for innovation in
materials synthesis.
In addition, the interaction between sulfur and the
functionalized graphene could be used to improve the
performance of sulfurgraphene composite cathodes. Sulfur
was anchored by a GO network through the CS bond,
resulting in enhanced cycling performance of LiS batteries.33b
The GOS nanocomposite cathodes exhibited a superior
reversible capacity of 1000 mA h g1 and a rate capability of
up to 2C in an ionic-liquid-based electrolyte.33b Nevertheless,
the functionalities on the GO network could only anchor sulfur
that is intimately in contact with the graphene substrate,
resulting in dissolution of outer layer sulfur species.46 To
address this problem, Song et al.46 developed this technology
by protecting the GOS nanocomposites with a cetyltrime-
thylammonium bromide (CTAB) coating layer and replacing
the conventional PVdF binder with an elastomeric styrene
butadiene rubber (SBR)/carboxymethyl cellulose (CMC)
binder. Cycling performance up to 1500 cycles with a low
decay rate of 0.039% per cycle was demonstrated, indicating the
feasibility of employing sulfurgraphene composite cathodes
for practical LiS batteries.
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Table 1. Overview of Some Selected SulfurGraphene Composite Electrodesa

S
material content method electrolyte (binder) performance ref
sulfurgraphene nanosheets 22/18 heat treatment LiTFSI in PEGDME 500 (PVdF) 600 mA h g1 41
(40th cycle, 0.03C)
Naon-coated FGSS 72/57 heat treatment LiTFSI in DOL + DME (PVdF) 960 mA h g1 42
(100th cycle, 0.1C)
sulfurpolyacrylonitrilegraphene 47/38 heat treatment LiPF6 in EC + DMC (PTFE) 1200 mA h g1 43a
composite (50th cycle, 0.1C)
sulfurgraphene oxide composite 66/46 heat treatment LiTFSI in PYR14TFSI + PEGDME () 954 mA h g1 (50th cycle, 33b
0.1C)
CTAB-coated sulfurgraphene oxide 80/56 heat treatment LiTFSI in PYR14TFSI + DOL + DME 740 mA h g1 46
composite (SBR/CMC) (1500th cycle, 0.02C)
graphene/PEG-wrapped sulfur 70/56 solution-based DOL + DME () 550 mA h g1 33c
method (140th cycle, 0.5C)
graphene-enveloped sulfur 87/78 solution-based LiTFSI in DOL + TEGDME () 550 mA h g1 33d
method (50th cycle, 0.2C)
sulfurhydroxylated graphene composite 50/40 solution-based LiCF3SO3 in DOL + DME (PVdF) 1021 mA h g1 (100th cycle, 33a
method 0.5C)
a
The sulfur content is presented as S concentration in the composite/S concentration in the electrode (wt %).

Figure 15. Schematic models, SEM observation (the SEM image of the carbon host is also shown), and cell performance of a representative binder-
free sulfurcarbon composite electrode: (a) SACF composites and (b) SVACNT composites. Part a reprinted with permission from ref 52.
Copyright 2011 Wiley-VCH Verlag GmbH & Co. KGaA. Part b reprinted with permission from ref 53. Copyright 2011 The Royal Society of
Chemistry.

Furthermore, to examine the interaction between the sulfur
species and a certain type of functional group on the graphene
substrate, our group selectively decorated the pristine graphene
with hydroxyl groups and achieved hydroxyl-group-induced
heterogeneous nucleation of bonded sulfur at room temper-
ature.33a Superior reversible capacities of 1021, 955, and 647
mA h g1 were retained, respectively, at C/2, 1C, and 2C rates
after 100 cycles.33a The stable high-rate performance was
attributed to (i) the homogeneously distributed hydroxyl
groups, which aided the formation of an amorphous sulfur
layer attached to graphene and retention of polysuldes, (ii)
small sulfur particles as a result of the enhanced interaction
between hydroxyl groups and sulfur species, providing short
pathways for ion and electron transport, and (iii) the exible
graphene-based substrate, which allowed complete electrolyte
penetration and absorption of the strain from cycling-induced
volume changes. Table 1 summarizes some selected major
achievements in the sulfurgraphene composite cathodes.
Recently, brous graphene has been fabricated into binder-
free self-standing electrodes for direct use in LiS batteries.47
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Huang et al.47a used a vapor treatment approach to introduce
amorphous sulfur homogeneously into mesoporous free-
standing graphene papers and obtained a high discharge
capacity of 1393 mA h g1. Moreover, Jin et al.47b reported a
exible graphene sheetsulfur paper electrode fabricated
through an in situ redox reaction of sulfur-containing
compounds and a vacuum-ltration procedure. The graphene
framework functioned as both a conductive network and a
supporting carrier for sulfur nanoparticles, leading to a high
capacity retention of 83% and an energy density of 804 W h
kg1 after 100 cycles. The binder- and current-collector-free
approach is environmentally friendly and benecial for
increasing the practical energy densities of LiS batteries,
which will be discussed in detail in the following section.
5.4. Binder-Free SulfurCarbon Composite Electrodes
Binders, which are usually polymeric materials (e.g., poly-
(tetrauoroethylene) (PTFE) or PVdF), are widely used in
conventional Li ion and other batteries in which they only act
as a binding additive to hold the active material and carbon
additives together without contributing any capacity. They are
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eective and interrupt the electrochemical processes in these
batteries less prominently. However, in LiS batteries, binders
could play a critical role in the cell performance. As the
structure and morphology change upon cycling, binders cannot
hold all the active materials, especially the soluble polysuldes.
In addition, they could become dead sites for the electro-
chemical reactions between lithium and sulfur which can
deteriorate the cell performance further. Therefore, functional
or smart binders become more important in LiS batteries
than in Li ion batteries, which will be discussed in later sections.
In this section, binder-free sulfur electrodes are discussed.
The binder-free electrode structure has shown unique
advantages in some electrodes in Li ion batteries, such as
Co3O4/graphene lms,48 TiO2 anodes,49 and silicon anodes.50
Some of these materials, like sulfur, also undergo signicant
compositional and structural changes upon cycling in Li ion
batteries. Without a binder, electrodes should be able to
maintain the supportive and integrated structures while
ensuring ecient electron and ion access to the active materials.
Carbon is the most eective additive in electrodes to provide
electron pathways. Carbon can also be fabricated into various
morphologies, e.g., spheres, particles, bers, tubes, etc., which
makes binder-free sulfurcarbon composite electrodes possible.
In addition, N-methyl-2-pyrrolidone (NMP) is a solvent
generally used in fabricating Li ion battery electrodes to
disperse the polymer binder and active materials. However,
NMP is harmful to human health and the environment.51
Without a binder, such solvents can be eliminated, facilitating
green fabrication processes with these binder-free electrodes.
Moreover, the active material loading and electrode con-
ductivity can also be increased without a binder.
Elazari et al.52 have utilized microporous activated carbon
bers as a binder-free substrate to impregnate sulfur, as shown
in Figure 15a. The carbon ber cloth provides sucient
mechanical strength and electron conduction pathways. In
addition, sulfur can diuse into the voids (2 nm) in the
carbon bers. The sulfur content, however, is relatively low (ca.
33 wt %), which is due to the large dense bers used. An
accessible capacity of 1250 mA h g1 and a reversible discharge
capacity higher than 800 mA h g1 after 80 cycles were
obtained. The authors suggested that the maximum accessible
capacity is limited by the electrochemical kinetics.
Dorer et al.53 utilized vertically aligned carbon nanotubes
(VACNTs) grown on a metal foil as a substrate to hold sulfur
(Figure 15b) with a high sulfur content of up to 70 wt %. The
VACNT was synthesized by a chemical vapor deposition
process. The CNT lms on the metal foil had a thickness of up
to 100200 m and a density of about 0.060.13 g cm3. The
calculated free volume in the CNT lms was about 94 vol %,
which can hold high sulfur loadings. In addition, CNTs have
high electronic conductivity and a high retention of the
integrity of the conductive network because of the high aspect
ratio. These favorable properties led to a discharge capacity of
over 1300 mA h g1 (800 mA h g1 based on the mass of the
electrode) with the binder-free sulfurCNT electrode. A
similar approach was developed by Hagen et al.,54 showing
an even higher sulfur loading of 90 wt % with reasonable
capacities and cyclability. Zhou et al.55 used a sulfate-containing
AAO template to directly grow aligned SCNTs without metal
substrates. Sulfur contents of 23 and 50 wt % in SCNTs have
been demonstrated with discharge capacities of, respectively,
712 and 520 mA h g1 over 100 cycles. Huang et al.56 modied
the aligned SCNT electrode by covering one end of the
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electrode with a PEG barrier to suppress the shuttle of
polysuldes. The electrode with the PEG barrier showed a
higher initial discharge capacity than that without the PEG
barrier. In addition, the electrode showed high cycling stability
with a degradation of 0.38% per cycle over 100 cycles without
LiNO3 in the electrolyte.
Our group developed a green process to fabricate binder-free
sulfurMWCNT electrodes (Figure 12).24b Sulfur was
deposited onto MWCNTs by the water-based solution method
(see section 5.2). The curly MWCNTs have a self-intertwining
behavior, which helps in forming a free-standing composite
electrode.57 The sulfur loading was up to 63 wt % in the
electrode. The highly conductive MWCNTs improved the
active material utilization at high rates. The absorption ability of
the cathode framework localized the electrolyte and suppressed
the migration of soluble polysuldes. The tortuous interspaces
in the network of MWCNTs provide a stable accommodation
of sulfur for rapid redox reactions and prevent sulfur/Li2S from
forming extensive agglomerates during cycling, leading to good
cyclability. Jin et al.58 developed a two-step process for
fabricating free-standing SCNT composite electrodes. A
slightly oxidized CNT lm was prepared rst by vacuum
ltration, and then sulfur was coated onto the surface of the
CNTs by a heating process. The authors believe the oxidized
CNTs contain oxygenic groups which can form strong covalent
bonds between sulfur and CNTs.
5.5. SulfurPolymer Composite Materials
Polymers are playing a more signicant role than binders in Li
S batteries, especially functional polymers with favorable
properties such as conductive polymers (e.g., polypyrrole,
polyaniline, poly(3,4-(ethylenedioxy)thiophene) (PEDOT),
etc.). Since polymers can be synthesized by dierent methods
and sulfur can be synthesized at low temperatures, a variety of
sulfurpolymer hybrid materials have been developed with the
target of reducing the dissolution and shuttle eect of
polysuldes, improving electronic conductivity, and controlling
the morphology of sulfurpolymer composite electrodes. A few
strategies exploring polymers as a conductive matrix and/or
barrier for blocking polysuldes are presented in the sections
below.
5.5.1. SulfurPolyacrylonitrile Composites. The rst
sulfurconductive polymer hybrid material was developed by
Wang et al.19a They used elemental sulfur as a dehydrogenating
reagent coheated with PAN at 280300 C. The CN groups
in PAN form heterocycles, while the main chain of the polymer
becomes like that of polyacetylene, which is a conductive
polymer. The composite is in the form of nanoparticles with an
average diameter of 200 nm. Extra sulfur (53.4 wt %) was
stabilized in the composite, which is electrochemically active.
However, the discharge voltage prole of the composite
consists of a voltage slope at ca. 2.11.8 V without the clear
upper discharge voltage (2.3 V) and lower discharge voltage
(2.1 V) plateaus that sulfur electrodes usually display. The
composite material showed a capacity of 850 mA h g1 in the
rst cycle, indicating almost all the sulfur was reduced to Li2S.
The cell showed decreasing cyclability with a remaining
capacity of 600 mA h g1 after 50 cycles in cells with a gel-
type polymer electrolyte. Yu et al.59 further characterized
chemically and physically such sulfurPAN composite
materials, which were prepared at dierent temperatures, and
examined their cycling performance. What they found was that
the carbon matrix and sulfur react with each other, forming
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CSSC bonds besides the dehydrogenation and
cyclization of PAN when a mixture of sulfur and PAN are
heated. The sample heated at 450 C showed a stable capacity
of ca. 480 mA h g1 over 240 cycles.
Fanous et al.60 advanced the understanding of the structure
and fading mechanism of the sulfurPAN composites in LiS
batteries. After removal of any remaining elemental sulfur in the
composites via an extraction with toluene, the analysis results
suggested that sulfur is exclusively covalently bound to carbon
and not to nitrogen, as shown in Figure 16. An ether-based
Figure 16. Proposed chemical structure of a sulfurPAN composite.
Reprinted from ref 60. Copyright 2011 American Chemical Society.
electrolyte which can dissolve polysuldes resulted in a
decrease in capacity upon cycling. With carbonate-based
electrolytes, a stable cycle life was obtained. In addition, the
polymer backbone, which consists of a conjugated -system,
aects the initial capacities obtained. Wang et al.61 found that
elemental sulfur nely dispersed in the PAN-derived network is
benecial for high capacity and cycle stability, so the optimized
synthesis temperature is 350 C. At this temperature, the
synthesized sulfurPAN composite showed a reversible
capacity of about 795 mA h g1 and capacity retention of
98.1% after 50 cycles based on the second discharge capacity. In
addition, the PAN-derived conjugated backbone contributes a
lithium storage capacity of about 156 mA h g1, which is
equivalent to 0.29 Li atom per acrylonitrile-derived C3N unit.
Yin et al.43a developed a PANgraphene composite as a
precursor to prepare SPANgraphene composites for high-
rate LiS batteries. PANgraphene composites were synthe-
sized by an in situ polymerization method, and the SPAN
graphene composite was prepared by pyrolyzing a mixture of
sulfur powder and PANgraphene composite at 300 C. It was
found that PAN nanoparticles less than 100 nm in size were
anchored onto the surface of graphene and this structure was
maintained after the SPANgraphene composite was formed.
The composite with only 4 wt % graphene exhibited a capacity
of ca. 1500 mA h g1 in the rst cycle and a capacity of ca. 800
mA h g1 at a high rate of 6C. The good battery performance
was attributed to the presence of graphene and the 3D structure
of PANgraphene, which acts as an electronically conductive
matrix.
5.5.2. SulfurPolypyrrole Composites. Wang et al.62
synthesized sulfurpolypyrrole (PPy) composites rst for LiS
batteries. The composite was synthesized by a chemical
polymerization method. Sulfur powder was dispersed in a
solution of sodium p-toluenesulfonate as a dopant, 4-
styrenesulfonic sodium salt as a surfactant, and pyrrole. FeCl3
was used as an oxidant to polymerize pyrrole to form the S
PPy composite. The PPy particles were in the range of 200
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500 nm, and the authors claimed that the sulfur particles were
uniformly coated with the PPy nanoparticles. The discharge
voltage prole showed the two typical plateaus of sulfur
electrodes. The capacities of the SPPy composite were higher
than those of bare sulfur electrodes, which was attributed to the
presence of PPy nanoparticles. Our group63 studied SPPy
composites that were synthesized by a two-step process. Sulfur
particles were formed and mixed with presynthesized PPy
nanoparticles by an oxidation method. It was found that the
presence of PPy nanoparticles prohibits the agglomeration of
sulfur during synthesis, resulting in small sulfur particles. In
addition, the PPy nanoparticles in the composite electrode
improved the electrochemical contact and rate capability as well
as the porosity of the electrodes. Liang et al.64 and Sun et al.65
studied SPPy composites with dierent morphologies, e.g.,
granular, tubular, and nanowire, in LiS batteries.
Our group has developed a strategy for fabricating core
shell-structured SPPy composites with the sulfur particles as
the core and a layer of PPy nanoparticles as the shell.66 Sulfur
particles could be formed into bipyramidal or spherical shapes
depending on the surfactant used by an in situ deposition
method. A layer of PPy nanoparticles could be self-assembled
onto the surface of sulfur particles due to the similar
hydrophobic properties of sulfur and PPy. The coating of
PPy on the sulfur particles can signicantly improve the
discharge capacities and cycling performance of sulfur while
decreasing the charge transfer resistance. However, the sulfur
particles are relatively large, resulting in low utilization of sulfur.
To further improve the performance of SPPy composites, a
mixed ionicelectronic conductor (MIEC) consisting of
conductive PPy and an ionic conducting polymer has been
developed.67 The ionic conducting component in the MIEC
can help transport lithium ions, retard polysulde dissolution,
and maintain a robust but porous electrode structure,
improving the cycling performance.
A variety of other approaches have also been developed to
utilize PPy in LiS batteries. For example, Qiu et al.68
synthesized poly(pyrrole-co-aniline) copolymer nanobers with
cetyltrimethylammonium chloride as a template, and they were
used as a conductive additive in sulfur composite cathodes.
Liang et al.69 synthesized a coreshell structure of a PPy
MWCNT composite by an in situ polymerization of Py in the
presence of MWCNT. Sulfur was introduced by heating the
sulfur powder and the PPyMWCNT composite at 155 C.
The SPPyMWCNT composite with 25 wt % PPy showed a
high discharge capacity of 726 mA h g1 after 100 cycles. Zhang
et al.70 prepared a SPPy composite by a simple one-step ball-
milling process without heat treatment. The electron micro-
scopic analysis showed that a uniform sulfur coating was
formed on the surface of PPy, and a rst discharge capacity of
1320 mA h g1 was obtained. Wang et al.71 prepared a ternary
composite consisting of a PPy-coated SCNT composite
synthesized by an in situ polymerization method. They found
that the PPy coating signicantly improves the performance of
the binary composites (SCNT and SPPy).
5.5.3. SulfurPolyaniline Composites. Polyaniline
(PANI) is another conductive polymer that has been widely
used in making SPANI composites. PANI can be used as
either a conductive coating of sulfur materials or a conductive
matrix after pyrolization. Wu et al.72 used an in situ
polymerization method to coat SMWCNT composites with
a layer of PANI. The sulfur-coated MWCNT composite was
prepared by ball-milling and thermal treatment. The initial
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discharge capacity was 1334.4 mA h g1, and the capacity was

932.4 mA h g1 after 80 cycles. Similarly, Li et al.73 coated a S
C composite with a nanolayer of PANI via a two-step process.
The electrochemical performance of the composite was
improved with high-rate performances, which was believed to
be due to a synergistic eect from both the conductive carbon
black in the matrix and the PANI coating. A discharge capacity
of 636 mA h g1 was obtained at a rate of 10C, and the
discharge capacity retention was >60% over 200 cycles. Duan et
al.74 introduced a layer-by-layer assembly technique to fabricate
PANI-coated sulfur particles. The positively charged poly-
(allylamine hydrochloride) and negatively charged poly-
(styrenesulfonate sodium salt) were rst alternatively adsorbed
onto the surface of sulfur particles, and then a layer of PANI
was formed on the outer shell of the polymer-coated sulfur by
an in situ polymerization method. The composite was
characterized, but no cell performance was presented.
Recently, Zhou et al.75 reported novel SPANI coreshell
and yolkshell nanocomposites, the yolkshell nanocomposite
being prepared through a heat treatment of the coreshell
composite, as shown in Figure 17. The yolkshell structure
Figure 17. (Top) Two-step synthesis route for the SPANI
nanocomposite with a yolkshell structure, with the yellow sphere
representing sulfur, the dark green shell representing PANI, and the
black shell representing vulcanized PANI. (Bottom) SEM image
showing the retained morphology of the SPANI composite with the
yolkshell structure after long-term cycling. Reprinted from ref 75.
Copyright 2013 American Chemical Society.
Figure 18. Schematic illustration of the construction and discharge/
charge process of the SPANI nanotubes. Reprinted with permission
from ref 76. Copyright 2012 Wiley-VCH Verlag GmbH & Co. KGaA.
polysuldes, which leads to superior cycle stability and rate
capability. A discharge capacity of 432 mA h g1 was obtained
at a 1C rate over 500 cycles. A follow-up study from the same
group presented an in-depth characterization of the SPANI
composite.77 It conrmed that part of the sulfur was grafted
onto PANI during heating and the PANI backbones were
connected with disulde bonds, forming a cross-linked
structure. The performance of the SPANI composite can be
further improved by reducing the particle size.
5.5.4. Other Sulfur-Conductive Polymer Composites.
Other conductive polymers, e.g., polythiophene (PTh) and
PEDOT, have also been used to obtain sulfurpolymer
composites. For example, Wu et al.78 coated sulfur particles
with a layer of PTh by an in situ polymerization method. An
initial discharge capacity of over 1100 mA h g1 and a capacity
of >800 mA h g1 over 50 cycles were obtained. To reduce the
sulfur particle size, Chen et al.79 used a membrane-assisted
precipitation technique to prepare ultrane sulfur nanoparticles
with diameters in the range of 1020 nm. The sulfur
nanoparticles were coated with PEDOT to form a core
shell-structured SPEDOT nanocomposite. An initial dis-
charge capacity of 1117 mA h g1 and a capacity of 930 mA h
g1 over 50 cycles were obtained. Yang et al.80 applied a
PEDOT/poly(styrenesulfonate) (PSS)-based conductive poly-
mer as a coating layer on a CMK-3 mesoporous carbonsulfur
composite, as shown in Figure 19. The polymer layer is not
only rigid and stable but also ionically and electronically

provides an internal void space to accommodate the volumetric

expansion of sulfur during lithiation, thereby preserving the
structural integrity and enhancing the cycling performance.
Stabilized capacities of 765 mA h g1 at a C/5 rate and 628 mA
h g1 at a C/2 rate were obtained. This study provides
important insights and a novel methodology to develop sulfur-
conductive polymer nanocomposites with favorable structures
and high performance.
In addition to the coreshell structure with PANI, some
other novel SPANI composites have been developed. For
example, Xiao et al.76 utilized self-assembled PANI nanotubes
for sulfur encapsulation, as shown in Figure 18. The PANI
nanotubes were treated at 280 C with sulfur, which resulted in
a partial reaction of sulfur with the polymer to form a 3D, cross-
linked, structurally stable SPANI composite in which the
PANI backbones are interconnected with inter- and/or Figure 19. Schematic of a PEDOT/PSS-coated CMK-3sulfur
intrachain disulde bonds. Such a structure provides an ideal composite. Reprinted from ref 80. Copyright 2011 American Chemical
connement for the active materials, e.g., sulfur and Society.

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Chemical Reviews
conductive, which can eectively block the dissolution of
polysuldes and provide pathways for ions and electrons. The
initial discharge capacity was 10% higher than that of the bare
counterpart, and a capacity of >600 mA h g1 was obtained
over 150 cycles.
Recently, Li et al.81 reported a novel polymer-encapsulated
hollow sulfur nanosphere cathode. The polymer can be
nonconductive poly(vinylpyrrolidone) (PVP) or conductive
PEDOT, which can minimize the polysulde dissolution. The
empty space in the sulfur nanosphere allows sulfur to expand
inward instead of outward upon lithiation. The nanosized sulfur
spheres facilitate electron and ion transport. All of these
features of the sulfurpolymer nanocomposites ensured
excellent performance (1000 cycles at a C/2 rate with a
capacity decay of 0.046% per cycle) and high rate capability
with the PEDOT coating (reversible capacities of 849 and 610
mA h g1 at, respectively, 2C and 4C rates). A follow-up study
from the same group compared dierent conductive polymers,
e.g., PPy, PANI, and PEDOT, as coating materials on sulfur
nanospheres. It was found that the capability of these three
polymers in improving the long-term cycle stability and high-
rate performance of the composite cathode decreased in the
order PEDOT > PPy > PANI.
5.6. SulfurMetal Oxide/Chalcogenide Composite
Materials
Not only conductive carbons/polymers but also other materials
could be applied in the composite synthesis with sulfur. The
alternative additive may serve as an absorbing agent for
trapping the soluble polysuldes or may function as a
supporting active material for generating extra capacity. To
function as the absorbing agent, the alternative material must
have a redox potential not overlapping with that of sulfur (1.5
2.8 V vs Li+/Li0) to prevent unwanted electrochemical
reactions and structural change during cell cycling. The density
and the amount of the alternative materials should not be too
large; otherwise, the energy density of the whole battery would
deteriorate. To work as the secondary active material in a
hybrid cathode, the alternative material must operate well
under a voltage window similar to that of the primary active
material, sulfur. The alternative materials should also have good
compatibility toward the same electrolyte system as the primary
sulfur active material.
5.6.1. Metal Oxide Additives/Composites. In 2001,
Gorkovenko et al.82 patented the application of vanadium
oxides, silicates, aluminum oxides, and transition-metal
chalcogenides to sulfur cathodes for suppressing polysulde
migration and diusion. However, the large particle size of
these absorbing agents limits the absorbing ability, especially
the electron transport properties, leading to limited improve-
ment.
Considering the size eect, Song et al.83 added nanosized
manganese nickel oxide particles (3050 nm) into sulfur
cathodes as an absorbing material, which led to good cell
performance with a high capacity retention of 85% for 50
cycles. In their analysis, they determined that a suitable
absorbing agent may need the following requirements: small
particle size, porous structure, and high surface area. Various
nanosized metal oxides that fulll these criteria and their
performances are summarized in Table S2 in the Supporting
Information. The representative metal oxides involve man-
ganese nickel oxide,83,84 -alumina,85 silica,86 and titania.87
These nanosized additives have a polysulde adsorbing eect
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for eectively addressing the polysulde diusion issue and
thereby improving the cycle stability. Most importantly, these
obvious improvements result from a small dosage of absorbing
additives from 3.6 wt % (TiO2) to 15 wt % (Mg0.6Ni0.4O) in the
whole cathode material.
5.6.2. Metal Oxide Coatings. Another attractive idea is S
metal oxide coreshell composites. Seh et al.88 designed a
TiO2sulfur yolkshell composite that exhibited prolonged
cyclability over 1000 cycles, showing that metal oxide shells
might replace a portion of carbon to trap polysuldes, although
the sulfur loading (0.40.6 mg cm2) needs to be increased for
practical applications. The idea of the yolkshell structure is to
avoid fracture of the TiO2 spheres during the volume expansion
of the active material, which could lead to serious leakage of
polysuldes. Extra void or pore space remaining in the cathode
structure is desirable not only to retain the dissolved
polysuldes but also to cushion the volume change during
the subsequent charge/discharge processes.
5.6.3. Intercalation Compounds/Chalcogenide Com-
posites. Dierent from the carbon additives and the metal
oxide additives described above, intercalation compounds could
participate in the discharge/charge reaction in a voltage range
similar to that of sulfur, functioning as a secondary active
material in the hybrid cathode. For example, TiS2 is an
attractive secondary active material because it can discharge/
charge in the same voltage range (1.53.0 V) as sulfur.89
Moreover, TiS2 is a semiconductor with a band gap of about 1.0
eV and becomes conductive on insertion of lithium. The
relatively conductive TiS2, in comparison with sulfur, may
enhance sulfur utilization in hybrid cathode systems, leading to
a better overall specic capacity.90 Various sulfurTiS2
composites have been investigated by our group. According
to our experimental data, TiS2 can cycle normally in the glyme-
based electrolyte just like that in the carbonate electrolytes,
ensuring good compatibility with sulfur. Other possibilities
(with the redox potential in parentheses) are VO2 (B) (2.03.0
V),91 TiO2 (B) (1.02.5 V),92 Li4Ti5O12 (1.22.0 V),93 and
Li2C6O6 (1.52.5 V),94 which all have an operating voltage
window that is compatible with that of sulfur.35
6. LITHIUM SULFIDE CATHODES
Li2S is the end discharge product of sulfur. Li2S has a
theoretical capacity of 1166 mA h g1, and it is more desirable
as the cathode material than sulfur because it allows the use of
lithium-free anodes such as silicon, tin, or metal oxides.
However, there are a number of challenges with utilizing Li2S,
e.g., low electronic and ionic conductivities, sensitivity to
moisture and oxygen, and limited synthesis routes. A number of
eorts have been made recently to understand the electro-
chemical behavior of Li2S and to develop Li2S cathodes.
6.1. Activation of Microsized Li2S Particles
Li2S is considered to be electrochemically inactive because of
some challenges. In a Li2S electrode, which is fabricated by a
slurry casting method, the size of the Li2S particles is usually in
the micrometer-scale range. Yang et al.95 found a potential
barrier of 1 V at the beginning of the rst charge of
microsized Li2S. When a higher cuto voltage is applied in the
rst charge to overcome this barrier, Li2S becomes active and
the barrier does not appear again in the following cycles, as
shown in Figure 20a. On the basis of the experimental
observations, a model was proposed by the authors and is
summarized in Figure 20b. In steps 1 and 2, it is a single-phase
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Chemical Reviews
Figure 20. (a) Voltage proles of a pristine Li2S electrode during the
initial three cycles showing the high cuto voltage in the rst charge
and (b) a model for the initial charging of Li2S. Reprinted from ref 95.
Copyright 2012 American Chemical Society.
reaction. Li2S is partially delithiated, forming Li2xS, which has
the same crystal structure as Li2S. The charge transfer of this
process is slow, resulting in a large charge-transfer resistance
(large potential barrier). In step 3, polysuldes are formed. The
coexistence of Li2S and polysuldes makes the charge transfer
easier than that in the previous steps. Once all the Li2S is
converted to polysuldes at the end of charge (step 4), charge
transfer among polysuldes is very easy. After the rst charge,
polysulde nuclei exist in the electrolyte, which signicantly
improves the charge transfer in the following cycles. This study
provided a practical approach to utilize Li2S as a cathode
material, and this approach has been used in other work with
microsized Li2S particles.96 For example, our group recently
developed a Li2SMWCNT sandwiched electrode which
consists of pristine Li2S powder between two layers of
MWCNT paper electrodes.96b The large Li2S particles in the
sandwiched electrode required a high cuto voltage in the rst
charge to activate Li2S. An initial discharge capacity of 838 mA
h g1 (based on the mass of Li2S) and a capacity of 680 mA h
g1 over 100 cycles have been obtained at a rate of C/10.
6.2. Li2SCarbon Composites
To enhance the electronic conductivity of Li2S, a usual
approach is to develop Li2SC composites. A simple way to
prepare a Li2Scarbon composite is ball-milling of pristine Li2S
powder and carbon under an inert-gas atmosphere.96a,97 Cai et
al.96a prepared a Li2SC composite by high-energy ball-milling
which showed an initial discharge capacity of 1144 mA h g1
(based on the mass of Li2S) and a capacity of 411 mA h g1
over 50 cycles at a rate of C/10. Spark-plasma sintering (SPS)
has also been used in making Li2SC composites.98 In this
process, Li2S and carbon powder were mixed and loaded into a
graphite die and then pressed uniaxially. A pulsed dc current
was simultaneously applied to generate a spark discharge
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between particles, which can generate an internal localized heat,
improving the contacts between particles. Recently, Jeong et
al.99 developed carbon-coated Li2S composites which were
prepared with either a dry coating process (mechanical milling
of Li2S and sucrose) or a wet coating process (PAN dissolved in
NMP). These composites showed a reasonable cycle life over
50 cycles.
6.3. Chemical Synthesis of Li2S Cathode Materials
A number of chemical synthesis approaches have been
developed to prepare Li2SC composite materials or electro-
des. Yang et al.100 developed a nanostructured Li2SC
composite by chemically lithiating a sulfurCMK-3 composite
with n-butyllithium. A sulfurCMK-3 electrode was rst
prepared, and then a solution of n-butyllithium in hexane was
drop-coated onto the electrode. After a drying process, a Li2S
CMK-3 composite electrode was obtained. More than 90% of
the sulfur in the composite electrode was converted to Li2S
based on the mass measurements. The initial discharge capacity
was 573 mA h g1 (based on the mass of Li2S), and the capacity
was stabilized between 300 and 400 mA h g1 after ve cycles.
The Li2SCMK-3 composite cathode was further demon-
strated in a full cell consisting of a silicon anode with a short
cycle life of 20 cycles. The use of n-butyllithium to lithiate
sulfur could increase the cost, and this approach may not be
easy to scale up. Zheng et al.101 developed a Li2Smicroporous
carbon (MC) composite by a scalable in situ lithiation method.
First, a sulfurMC composite electrode was fabricated, and
then the electrode was lithiated by spraying stabilized lithium
metal powder (SLMP), followed by compression. The Li2S
MC electrode provided a stable capacity of 650 mA h g1
(based on the mass of Li2S) over 900 cycles in half-cells. When
coupled with a lithium-free graphite electrode, the Li2SMC
electrode showed a stable capacity of around 600 mA h g1
over 150 cycles. This route could be close to practical
application to produce Li2Scarbon composite materials.
Recently, Archers group102 has reported two novel routes
toward Li2SC composite cathodes. The rst approach is to
utilize the strong interaction between lithium ions in Li2S and
electron-donating groups in carbon-precursor polymers such as
PAN.102a Li2S may function as a cross-linking agent between
PAN polymers in the mixture of Li2S and PAN. After
carbonization at elevated temperatures in an inert atmosphere,
a Li2SC composite can be obtained. After the rst charge,
which showed a high overpotential, the composite behaved
exactly like Li2S. A stabilized discharge capacity of over 500 mA
h g1 (based on the mass of Li2S) was obtained over 20 cycles.
The second approach is illustrated in Figure 21.102b Li2S is
formed via the reduction of sulfates by carbon, which has long
been used in the Leblanc process. First, resorcinol and
formaldehyde react under acidic conditions to form a cross-
linked resorcinolformaldehyde (RF) gel. The lithium ions in
Li2SO4 molecules could be linked with oxygen atoms in the RF
gel. After carbonization at 900 C, the Li2SC composite was
formed. The composite showed behavior similar to that of Li2S,
and performance over 40 cycles was demonstrated.
To further explore the synthesis methods for making Li2S
electrodes, our group recently reported an in situ formed Li2S
cathode in a lithiated graphite electrode,103 as illustrated in
Figure 22. This approach uses polysulde Li2S6 as a precursor
and a prelithiated carbon paper (graphite) electrode. The
porous carbon paper electrode acts as a lithium donor and a
matrix for holding the polysulde solution. As the potential of
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Figure 21. Synthesis scheme of a Li2SC composite. Reprinted with
permission from ref 102b. Copyright 2013 The Royal Society of
Chemistry.
Figure 22. Schematic showing the chemical reduction reaction of one
Li2S6 molecule by lithium to form six Li2S molecules involving the
diusion/driving of lithium out of the graphene layers in graphite.
Li2S6 represents the average molecular formula of polysuldes in the
liquid electrolyte, and 3.56 is the spacing of (002) planes in the
lithiated graphite. Reprinted from ref 103. Copyright 2013 American
Chemical Society.
lithium stored in the lithiated graphite is close to that of
metallic lithium, one polysulde Li2S6 molecule would react
with six lithium atoms in the lithiated graphite to form Li2S.
This reduction reaction occurs over 6 days under the
experimental conditions, and donation of lithium atoms is
evidenced by the up-shifts of the (002) peaks in the X-ray
diraction (XRD) pattern of the lithiated graphite. The formed
Li2S electrode exhibited a potential of 2.12 V vs Li/Li+ and a
low overpotential in the rst charge. On the basis of X-ray
photoelectron spectroscopy (XPS) analysis, about 48.4% of the
polysulde was converted to Li2S. The electrode exhibited a
stable capacity of about 800 mA h g1 over 50 cycles at a rate of
C/10.
A lithium-rich sulfur cathode, i.e., Li2S, is a promising
approach to advancing the LiS technology and avoiding the
safety concerns of a lithium metal anode. However, challenges
exist if Li2S is used directly in the cathode because of its
intrinsic low conductivity and reactivity. The lithiation
approaches developed hold the promise of providing alternative
ways to utilize Li2S in LiS batteries. Novel, easily scalable
chemical synthesis approaches are still needed to provide better
control over morphology and the degree of lithiation.
6.4. Solid-State Batteries with Li2S Cathodes
Besides the liquid electrolyte used with most Li2S cathodes,
solid-state electrolytes have also been studied. For example,
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Hassoun et al.97 rst reported a cell with a gel-type polymer
membrane as the electrolyte which was formed by trapping a
carbonate-based solution saturated with Li2S in a poly(ethylene
oxide)/lithium triuoromethanesulfonate (PEO/LiCF3SO3)
polymer matrix. With a Li metal anode, the cell operating at
60 C showed a reversible capacity of over 1000 mA h g1
(based on the mass of Li2S). With a Sn/C anode, the cell
operating at 25 C showed a reversible capacity of over 800 mA
h g1 over 30 cycles at a rate of C/20. A follow-up study from
the same group showed a solid-state battery with a hot-pressed
membrane of PEO/LiCF3SO3 complex containing nanosized
ZrO2 particles and Li2S as the electrolyte.16c With a Li2SC
composite cathode, the half-cell could be reversibly cycled over
50 cycles at dierent rates. Takeuchi et al.98b reported an all-
solid-state battery with a Li3PO4Li2SSiS2 solid-state electro-
lyte and a Li2SC composite cathode which was prepared by
the SPS process. The cell showed an initial discharge capacity
of 920 mA h g1 (based on the mass of Li2S) and a capacity of
>700 mA h g1 over 10 cycles. Nagao et al.104 utilized Li2S
P2S5 as a solid-state electrolyte with a conductivity of over 103
S cm1 in a solid-state battery with Li2SC composite
cathodes. The cell showed a reversible capacity of >600 mA
h g1 (based on the mass of Li2S) over 10 cycles at 25 C with
high rate capability (up to 3.5C).
7. CHARACTERIZATION TECHNIQUES AND
MECHANISTIC UNDERSTANDING
The LiS battery system is superior because of its high
theoretical energy density. However, the practical energy
density obtained with LiS batteries is usually much lower
than the theoretical value. This could result from the ineective
control of the complicated chemistry of the sulfur redox
process, involving both compositional and structural changes of
the electrodes. To better utilize the advantages of the LiS
battery system, a comprehensive understanding of the redox
reaction is demanded. Advanced characterization techniques
are introduced nowadays, and new reaction systems are
designed for LiS batteries. Parameters that inuence the
reaction kinetics could also be controlled to alleviate the
limitations of the LiS battery system.
7.1. In Situ Characterization
One of the most challenging issues with LiS batteries is
development of in situ probes to understand the working
mechanism of the redox reactions. For example, opinions on
the formation of Li2S and reappearance of sulfur, based on the
results from ex situ measurements, are debatable.105 Some
groups detected the formation of crystalline Li2S at the end of
discharge,14c,106 while others observed Li2S formation in the
middle of the lower discharge voltage plateau.107 On the other
hand, S8 was reported to exist at the end of charge,107b,108
whereas other groups claimed that polysuldes would never be
converted back to S8.5b,11,107a,109 To avoid the artifacts from
post-treatments and understand the real working mechanism, in
situ characterization methodologies are demanded. Nelson et
al. and Canas et al. used in situ XRD to study the structural
changes in LiS batteries.110 Both groups recorded the
formation of crystalline S8 at the end of charge. However,
Li2S was not detected at the end of discharge by Nelson et
al.,110a whereas Canas et al.110b observed the formation of Li2S
at 60% discharge in the lower discharge voltage plateau. It was
reasoned that Li2S was not detected in some previous work
because (i) the in situ cell was not airtight, (ii) the discharge
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capacity was low, or (iii) the penetration depth of the X-ray was
not high enough.110b To elucidate the aforementioned
contention, Walus et al.105 also conducted in situ XRD
characterization with high resolution. Their synchrotron-based
results indicated the formation of crystalline Li2S at the
beginning of the lower discharge voltage plateau and its
conversion to crystalline S8 during the following charge.105
Additionally, it was found that sulfur recrystallized into another
allotrope: monoclinic -sulfur.105 To obtain a more compre-
hensive overview of the redox mechanism, other complemen-
tary in situ characterizations are necessary.
In addition to in situ XRD, in situ X-ray absorption
spectroscopy (XAS) is another important in operando
characterization technique for probing LiS batteries. Gao et
al.111 studied seven liquid electrolytes and claimed that solvents
played a key role in the electrochemical performance of LiS
batteries while lithium salts had no signicant eect. In situ
sulfur K-edge XAS spectra of sulfur electrodes in dierent
electrolytes at the initial, discharged, and charged states were
analyzed. It was found that ether-based solvents with low
viscosity resulted in more complete polysulde reduction as
reected by the more complete conversion of the S peak to a
Li2S peak in the XAS spectra, whereas carbonate-based solvents
could react with the reduced sulfur species as revealed by the
possible presence of peaks of thioether and sulfonium
functionalities in the XAS spectra, indicating instability of the
cell.111 However, the cells were not studied under real-time in
operando conditions, and the polysulde spectral features were
not veried or quantied.112
To obtain more accurate information regarding the electro-
chemical redox processes of LiS batteries, Cuisinier et al.112
conducted in situ XAS characterizations of a cathode that had
sulfur imbibed into the spherical carbon shells with tailored
porosity, avoiding the overwhelming distortion of the XAS
spectra as a result of bulk particles. To gain insight into the
mechanism of sulfur dissolution and Li2S deposition, in situ
XAS spectra were interpreted by the linear combination of
some selected polysulde species (-S8, S62, S42, and S2).
Delay in Li2S precipitation was identied upon reduction owing
to supersaturation of S2, which was conrmed by the in situ
XAS results analyzed from the linear combination simula-
tion.112 The delayed Li2S formation could be a possible
explanation for the failure to identify Li2S in the previous in
operando XRD/tomography studies.110a On the other hand,
oxidation of Li2S proceeded straightforwardly to polysuldes.112
The dierent responses in the XAS spectra corresponding to
dierent steps in the reduction/oxidation evidenced the
potential hysteresis existing in the discharge/charge process.
7.2. Polysulde Dissolution
As mentioned previously, the intermediate lithium polysuldes
generated during the operation of LiS batteries are soluble in
common organic electrolytes.8b,c,113 To understand the solvent
eect on the polysulde dissolution and cycling characteristics
of LiS batteries, Barchasz et al.114a compared solvents with
dierent solvation abilities toward polysuldes. It was
concluded that LiS batteries require the use of high-
solvation-ability solvents to increase sulfur utilization, such as
tetraethylene glycol dimethyl ether (TEGDME)114b and 2-
ethoxyethyl ether (EEE). This is because solvents exhibiting
low polysulde solvation ability, e.g., 1,2-dimethoxyethane
(DME), diethylene glycol dibutyl ether (DEGDBE), or 1,3-
dioxolane (DOL), could lead to a passivation of the cathode by
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short-chain Li2S, which deteriorates the discharge capacity of
the lower discharge voltage plateau.114a
Nevertheless, polysulde dissolution into the bulk electrolyte
could negatively impact the cycle stability of LiS batteries due
to the parasitic reactions between polysuldes and the lithium
metal anode.5a To suppress polysulde dissolution into the bulk
electrolyte and its migration and contact with the lithium metal
anode, porous conductive substrates have been used to conne
polysuldes within the cathode through both physical and
chemical interactions.115 However, complete blocking of
polysuldes is not possible since the dissolution of polysulde
is thermodynamically favorable in organic electrolytes.
Recently, concentrated electrolytes have been reported to
eectively alleviate polysulde dissolution into the bulk
electrolyte through a common ion eect. Shin et al.116 showed
that a higher lithium salt (lithium bis((triuoromethyl)-
sulfonyl)imide (LiTFSI)) concentration of up to 5 M was
helpful in decreasing both the dissolution and diusion of
polysuldes. Furthermore, Suo et al.117 proposed a solvent-in-
salt (SIS) electrolyte in which the lithium salts had ultrahigh
concentrations up to 7 M and held a dominant position in the
lithium ion transport system. It was demonstrated that SIS
electrolytes not only inhibited the dissolution of lithium
polysuldes but also eectively protected the lithium metal
anode against the formation of lithium dendrites.117
On the other hand, Park et al.118a and Ueno et al.118b
revealed that polysulde dissolution was highly sensitive to the
anionic structure of the ionic liquids (ILs) in IL-based
electrolytes. Various binary mixtures of ILs and lithium salts
were studied as electrolytes for LiS batteries, and the solvent
eect of ILs was found to be related to its donor ability
(competition of the ILs anion against the polysuldes to
interact with the lithium ions).118 For example, polysuldes
were easily dissolved in the strongly basic N-butyl-N-
methylpyrrolidinium triuoromethanesulfonate ([P14][OTf])
electrolyte with high donor ability, whereas polysulde
dissolution was hampered in the ILs having bulky uorosul-
fonyl amide-type anions owing to the weak donor ability of
these anions to the lithium ions of lithium polysuldes.118
In addition to organic and IL-based electrolytes, polymer
electrolytes16c,36a,119 and inorganic solid electrolytes120 have
been studied to oer physical and kinetic barriers to polysulde
dissolution into the bulk electrolyte. For example, Hassoun and
Scrosati16c reported the synthesis of a polymer electrolyte
membrane consisting of a PEOLiCF3SO3 complex with nely
dispersed nanosized ZrO2 particles and Li2S, which was
believed to enhance the ionic conductivity and also prevent
sulde dissolution from the cathode. Reproducible cycles with
Coulombic eciency approaching 100% were obtained,
indicating that polysulde dissolution and shuttling were
controlled.16c Furthermore, an all-solid-state conguration
with an inorganic solid electrolyte was reported to realize
close solidsolid contact, prohibiting the dissolution of
polysuldes.120d Nagao et al.120d studied an all-solid-state
battery with a sulfurCMK-3 composite cathode and thio-
LISICON solid electrolyte and obtained stable cycling up to 30
cycles with high reversibility, indicating the feasibility of
applying an inorganic solid electrolyte to address the
polysulde dissolution issue. More detailed discussion regard-
ing the electrolytes used in LiS batteries and their inuence
on the performance of LiS batteries will be presented in
sections 8.18.3.
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7.3. Formation of the Passivation Layer
The high energy density of LiS batteries originates from the
use of a high-capacity sulfur cathode and a lithium metal anode.
Although metallic lithium has a large theoretical capacity of
3860 mA h g1, it suers from drawbacks such as dendrite
formation and poor cycling eciency as an anode for
rechargeable lithium batteries because of the unstable
passivation layer (solid electrolyte interphase, SEI) resulting
from parasitic reactions between organic electrolytes and the
lithium metal.
The chemical composition and microstructure of the
passivation layer on the lithium surface are greatly inuenced
by the electrolyte, which is comprised of the solvent and
lithium salts.121 For example, DOL is one of the most
commonly used electrolyte solvents in LiS batteries.122
During the discharge/charge electrochemical process, DOL is
reduced to several ROLi (R refers to alkyl) species and
oligomers with OLi edge groups, enhancing the exibility of
the passivation layer on the lithium surface, which assists the
passivation layers ability to accommodate lithium morpho-
logical changes upon cycling.121a,123 Moreover, uoroethylene
carbonate (FEC) solvent was identied to help the formation
of a robust protective layer by UV-curing polymerization.121c
The protective layer on the lithium anode surface formed in the
FEC-based electrolyte consists of LiF along with LixPFy and
LixPOFy, which eectively mitigates the overcharging related to
polysulde shuttling in LiS batteries.121c Recently, ILs have
been considered as a promising new class of electrolyte solvents
for LiS batteries. An IL-enhanced passivation layer on the
lithium surface is found to exhibit a smoother morphology and
less complicated surface chemistry compared to that formed
with the conventional organic electrolytes.84 Lithium metal was
reported to be protected from the continuous attack by
polysuldes with an N-methyl-N-butylpyrrolidinium bis-
((triuoromethyl)sulfonyl)imide (Py14TFSI)-modied passiva-
tion layer, leading to improved Coulombic eciency and cycle
stability.84 In terms of lithium salts, lithium triuoromethane-
sulfonate (LiCF3SO3) and LiTFSI used in LiS batteries have
high dissociation constants, high oxidation and temperature
stability, nontoxicity, and insensitivity to moisture.124 Unfortu-
nately, they seem to have no obvious positive eect on the
passivation layer that forms on the lithium metal surface.124
In addition to electrolyte solvents and lithium salts, additives
have been reported to eectively modify the physical and
chemical properties of the passivation layer on the lithium
surface.124 Recently, Mikhaylik125 patented an additive that
includes NO bonds, e.g., LiNO3. It was found that LiNO3 as
an electrolyte additive could prevent polysulde shuttling,
leading to higher reversible capacities of the LiS batteries.125
Aurbach et al.123 rigorously studied the eect of the presence of
LiNO3 on the Li surface through electrochemical and
spectroscopic analyses. With the combined use of Fourier
transform infrared (FTIR) spectroscopy and XPS, LiNO3 was
identied to suppress polysulde shuttling because of its direct
reduction by lithium to LixNOy species and its oxidation of
sulfur species to LixSOy moieties, passivating the lithium anode
surface and alleviating parasitic reactions between lithium and
sulfur species.123 A more stable passivation layer on the lithium
surface could thereby be expected. Moreover, the passivation
layer that forms in the presence of LiNO3 is benecial to the
lithium cycling eciency. Liang et al.64b studied the function of
LiNO3 on lithium deposition/dissolution and concluded that
the eciency increased with the concentration of LiNO3 and
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reached the highest value for an electrolyte containing 0.4 M
LiNO3, possibly due to the protective passivation layer formed
with the modied electrolyte compositions.
Recently, it was revealed that the polysulde is one essential
component to keep the stability of the passivation layer.126 The
stable passivation layer in LiS batteries was assumed to consist
of two sublayers, the top layer composed of oxidized products
of polysuldes and the bottom layer composed of the reduced
products of polysuldes and LiNO3,126 consistent with the
earlier work by Aurbach et al.123 In general, the ecacy of
forming an enhanced passivation layer in the presence of
LiNO3 has been conrmed by previous work. However, it is
worth mentioning that LiNO3 is progressively consumed with
the development of new lithium dendrites and the formation of
a new passivation layer during LiS cell operation, which limits
its ability to stabilize the lithium surface for long-term cycling or
in a polysulde-rich environment. Additionally, LiNO3 could be
irreversibly reduced on the cathode at potentials lower than 1.6
V, which negatively impacts the cycle stability of LiS
batteries.127 Therefore, further improvements to stabilize the
lithium surface passivation layer are demanded.
An alternative to LiNO3, lithium bisoxalatoborate (LiBOB),
was identied to modify the passivation layer on the lithium
surface in LiS batteries.128a Higher discharge capacity and
smoother lithium surface morphology were obtained in the
presence of LiBOB in the electrolyte.128a Finally, phosphorus
pentasulde (P2S5) disclosed by Lin et al.128b as an electrolyte
additive was found to passivate lithium surface, alleviating the
polysulde shuttling. The passivation layer that formed on
lithium surface consisting mainly of Li3PS4 was reported to have
fast lithium-ion conduction while blocking the direct contact
between lithium metal and polysuldes. The long-term cycle
stability of this passivation layer is still under investigation.
In contrast to the passivation layer on the metallic lithium
anode, the passivation layer that forms on the cathode surface
in LiS batteries is usually comprised of Li2S bulk particles, and
it negatively inuences the cycling performance of LiS
batteries.36b,114a,129 The formation of the Li2S passivation
layer on the cathode occurs at the lower discharge voltage
plateau36b and could decrease sulfur utilization by blocking
lithium ion transport toward the inside of the cathode.36b The
formation of this Li2S passivation layer is inuenced by the
electrolyte solvent selected and the discharge rate.36b,114a,129
Electrolytes with low polysulde-solvation ability and high-rate
discharge would result in more severe Li2S passivation on the
cathode surface, leading to the breakdown of the conductive
matrix, formation of irreversible Li2S, and deterioration of the
cycle stability.36b Further discussion regarding the formation
and properties of the Li2S passivation layer is available in
sections 7.2 and 7.4.
7.4. Kinetics
Yamin et al.113b studied the redox mechanism of polysuldes
with a glassy carbon electrode in THF by cyclic voltammetry
(CV), revealing one anodic peak and up to three cathodic
peaks. The anodic peak was reported to result from the
oxidation of polysuldes to elemental sulfur, in which the
charge-transfer stage was preceded by a slow chemical reaction.
The cathodic peaks were ascribed to reduction of high-order
polysuldes to Li2S6 in a diusion-controlled reaction,
reduction of Li2S6 to Li2S5 through a slow disproportionation
reaction, and reduction of Li2S5 to Li2S2 or Li2S. The kinetics of
the reduction from S8 to Li2S4 or Li2S5 corresponding to the
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upper discharge voltage plateau was believed to be fast.20,36b,113
Our group113c experimentally demonstrated that the long-chain
polysulde redox couple was able to deliver nearly full
theoretical capacity at a rate as high as 5C with a carbon
interlayer inserted between the cathode and separator, which
shows that the high-rate application of LiS batteries is not
hindered by reactions in the upper discharge voltage plateau.
In contrast, the reaction kinetics of the conversion from Li2S4
or Li2S5 to Li2S2 or Li2S corresponding to the lower discharge
voltage plateau was believed to be slow, attributed to the extra
energy required for nucleation of the solid phase and
sluggishness of solid-state diusion to convert Li2S2 to
Li2S.20,113a A systematic investigation on the rate capability
and cycling characteristics of LiS batteries was conducted by
Cheon et al.,36b and it was concluded that the lower discharge
voltage plateau where solid Li2S formed is highly sensitive to
the discharge rate. The combined use of electrochemical
characterization and morphology observation of the SC
composite cathode suggested that the thick Li2S layer formed at
the cathode surface was responsible for the diminution of the
lower discharge voltage plateau at a high discharge rate.36b It
was further reasoned that the diusional resistance of
polysuldes and lithium ions increased at high rates, leading
to more localized Li2S passivation on the cathode surface.36b
The localized Li2S passivation and its associated stress buildup
caused destruction of the carbon matrix and the formation of
irreversible Li2S, so the reversible capacity decreased. The slow
reaction kinetics of the low-order polysuldes and their
blockage of the cathode could be the major factor causing
low rate capability with LiS batteries.
To improve the kinetics of LiS batteries, major strategies
include decreasing the sulfur particle size and conning sulfur
into highly conductive substrates with high surface areas. Zhang
et al.22 encapsulated sulfur into microporous carbon and
obtained an enhanced rate capability, owing to the highly
dispersed elemental sulfur inside the narrow micropores of
carbon spheres with good electrical conductivity. In addition,
the micropores could trap elemental sulfur and subsequent
lithium polysuldes during cycling, avoiding the formation of a
thicker Li2S insulating layer on the composite surface. Similarly,
Xin et al.26b synthesized metastable small sulfur molecules of
S24 in the conned space of a conductive microporous carbon
matrix and achieved a favorable high-rate discharge capacity of
800 mA h g1 at a 5C rate. Superior high rate capability found
in this work was ascribed to the high-electronic-conductive core
of the carbon nanotube and the microporous carbon on the
surface that provided unperturbed lithium ion transport,
forming an ecient mixed-conducting 3D network.26b
It is worth mentioning that integrating sulfur with graphene
or graphene oxide is another important strategy to enhance the
reaction kinetics of LiS batteries. As mentioned previously,
with the high surface area, superior electronic conductivity, high
mechanical strength, and exibility, graphene-based material is a
suitable substrate to conne polysuldes and accommodate the
large volume expansion during lithiation, avoiding the
formation of irreversible Li2S. The graphene-based material
could be further fabricated as a free-standing electrode and used
in advanced cell congurations.130 More detailed discussion
regarding the use of sulfurgraphene/graphene oxide compo-
sites to improve LiS batteries was presented in section 5.3.
On the other hand, it was found that enhanced rate capability
could be achieved by using functional polymers to modify the
cathode architecture and retain a uniform nanocomposite
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structure. Our group replaced the conventional PVdF binder
with Pluronic F-127 block copolymer and stabilized the S
black pearl nanocomposite, preventing the formation of a dense
passivation layer of Li2S on the cathode.131 Stable cycling with
capability up to a 4C rate was obtained due to the uniformly
dispersed active material within the electrodes in the presence
of Pluronic F-127. Similarly, polymers (e.g., polyaniline,73,132
polyacrylonitrile133) were applied directly as a coating layer to
stabilize the cathode. The enhanced rate capability could be due
to the increased electronic conductivity of the composite
cathode and the superior electrolyte absorption ability of the
polymer coating, leading to a reduced lithium ion diusion
distance.
8. ELECTROLYTES AND SEPARATORS
Electrolytes act as the ion transport pathway between the anode
and cathode. Liquid electrolytes are widely used in batteries
because of their high ionic conductivity. In LiS batteries, the
electrolyte is critical because the intermediate polysuldes could
dissolve in the liquid electrolyte and shuttle between the
cathode and anode. The solubility of polysuldes in a liquid
electrolyte denitely aects the battery performance. In
addition, the passivation caused by the reduction or oxidation
of the electrolyte on the electrodes, which was discussed in
section 7.3, is also related to the composition of the electrolyte,
particularly the additives. A solid-state electrolyte could be
better than a liquid electrolyte in terms of reducing the
dissolution and shuttle of polysuldes. However, the low ionic
conductivity and interfacial instability associated with most
solid-state electrolytes lead to more issues when they are used
in LiS batteries.
Separators used in Li ion batteries are porous polymer lms,
e.g., expanded polypropylene. They physically separate the
anode and cathode, but allow ion movements in the liquid
electrolyte they absorb. In LiS batteries, functional separators
that can be ion selective become more promising in reducing
the shuttle of polysuldes. In this section, dierent electrolytes
and functional separators are discussed.
8.1. Liquid Electrolytes
The selection of liquid electrolyte solvents for LiS batteries
starts with aliphatic amines, carbonates, and then ethers. DOL
was rst demonstrated by Peled et al.8d in 1989 to be an
appropriate solvent in a liquid electrolyte for LiS batteries.
Presently, liquid electrolytes mainly containing DOL and other
solvents such as DME and lithium salts such as LiCF3SO3 or
LiTFSI are widely used in LiS batteries. A variety of other
solvents, including ionic liquids and short-chain PEO-based
polymers, have also been studied over the past several years;
however, it is dicult to compare them because of the
complexity of the LiS systems and dierent sulfur electrodes
prepared in dierent laboratories. Only a few representative
studies on liquid electrolytes are discussed here.
Chang et al.134 studied a mixed electrolyte of TEGDME and
DOL in LiS batteries. TEGDME can readily solvate the
lithium salt LiCF3SO3, and DOL can reduce the viscosity of the
electrolyte. What they found is that shorter polysuldes are
favorably formed in DOL-based electrolytes in the upper
discharge voltage plateau while the lower discharge voltage
plateau is dependent on the TEGDME:DOL ratio (30:70 is the
best) and sulfur utilization in the lower discharge voltage
plateau is related to the viscosity and conductivity of the
electrolyte. An electrolyte with high viscosity can cause
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passivation on the surface of sulfur electrodes because of the
low polysulde diusion. Ryu et al.14c investigated the self-
discharge behavior of LiS batteries with the TEGDME
electrolyte. What they found is the self-discharge of the cells
depends on the current collectors. With stainless steel current
collectors, the highest self-discharge rate is 59% per month.
With aluminum current collectors, the self-discharge rate is 34%
during the initial 80 days but only 36% after 360 days of
storage. Choi et al.106b,135 found that the addition of a small
amount of toluene in TEGDME has a remarkable eect of
increasing the initial discharge capacity and stabilizing the
cycling performance, which is attributed to the reduced lithium
metal interfacial resistance. Shin et al.136 found the addition of
TEGDME to N-methyl-N-butylpyrrolidinium bis-
((triuoromethyl)sulfonyl)imide (PYR14TFSI)-based electro-
lyte can signicantly enhance the ionic conductivity, particularly
at low temperatures. In addition, the mixed electrolyte has good
compatibility with lithium metal. Recently, Barchasz et al.137
revisited TEGDME/DOL binary electrolytes in LiS batteries.
By studying the electrochemical response of various solvent
ratios, lithium salt concentrations, and use of additives, it was
concluded that the solvation ability of the electrolyte is the key
factor in high electrochemical performance. High DOL
contents result in insucient solvation ability and DOL
polymerization.
Kolosnitsyn et al.138 studied sulfolane as a solvent in a liquid
electrolyte for LiS batteries. When sulfolane was used alone,
the cell showed a poor cycle life. The voltage prole presented
an obvious degradation in the upper and lower discharge
voltage plateaus. When sulfolane was used with ethers, e.g.,
DME, DOL, and THF, the cycling performances of these cells
were still poor. However, the cell with the mixed electrolyte
containing DOL showed the highest initial discharge capacity.
When sulfolane was used with linear ethers, e.g., glyme,
diglyme, and tetraglyme, the authors correlated the changes in
the cycling performance to the viscosity and solvation ability of
the solvents, which aect the reactions of dissociation of the
primary dianion S82 and disproportionation of lithium
polysuldes in the electrolyte solutions.
Kim et al.139 studied the mixed electrolytes of DME/DOL
with and without imidazolium salts (1-ethyl-3-methylimidazo-
lium bis((peruoroethyl)sulfonyl)imide (EMIBeti) and 1-
butyl-3-methylimidazolium hexauorophosphate (BMIPF6))
in LiS batteries. It was found that small amounts (5 or 10
vol %) of the imidazolium salts added to the electrolytes can
enhance the discharge capacity, rate capability, and low-
temperature performance, which may be related to the
enhancement of the electrochemical reaction of polysuldes
by the imidazolium cation and improved stability of the surface
morphology of the lithium metal anode. Xiong et al.128a studied
LiBOB as an additive in an electrolyte of LiTFSI in DME/
DOL. The cells with LiBOB in the electrolyte showed
improvements in discharge capacities and cycling performance,
which were attributed to the improvement of the lithium metal
anode in the presence of LiBOB.
ILs are promising electrolyte solvents for LiS batteries
because of their nonammability, good chemical stability, and
high ionic conductivity. In LiS batteries, ILs show interesting
properties and performance. Wang et al.140 used an ionic liquid
of N-methyl-N-propylpiperidinium bis((triuoromethyl)-
sulfonyl)imide (PP13-TFSI), a viscous solvent, to counteract
the high solubility and diusion rate of lithium polysuldes in
DME. With optimized ratios, superior battery performance in
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terms of capacity, eciency, and cycle stability was obtained. In
addition, Zheng et al.84 found that the ionic liquid Py14TFSI
can improve SEI layer formation on the lithium metal surface in
LiS batteries, which can suppress the corrosion of the lithium
metal anode by polysuldes and thereby improve the cycling
eciency and stability.
Park et al.141 studied the ionic liquid N,N-diethyl-N-methyl-
N-(2-methoxyethyl)ammonium bis((triuoromethyl)sulfonyl)-
amide ([DEME][TFSA]) as an electrolyte solvent in LiS
batteries. In comparison with the TEGDME solvent, [DEME]-
[TFSA] showed superior performance in terms of cycle stability
and eciency. The authors claimed that [DEME][TFSA] has a
low donor ability, which can signicantly suppress the
dissolution of lithium polysuldes, because of the weak Lewis
basicity of the [TFSA] anion. The follow-up study by Park et
al.118a showed that the solubility of lithium polysuldes in ILs is
strongly dependent on the anionic structure. The stronger the
donor ability of an IL, the higher the solubility of lithium
polysuldes. In addition, the battery performance is also
inuenced by side reactions of anions, such as BF4 and
[FSA], with polysuldes and mass transport in viscous ILs.
TFSI-based ILs show high capacities and cycling eciencies.
Another study from the same group118b reported the anionic
eects on solvated IL electrolytes in LiS batteries. Li salts
(LiX) with dierent anions (X = N(SO2C2F5)2 (BETI),
N(SO2CF3)2 (TFSA), CF3SO3 (OTf), BF4, and NO3) and
glymes were prepared as electrolytes. It was found that the
dissolution of lithium polysuldes in solvated IL electrolytes
Li[BETI] and Li[TFSA] in glymes as shown in Figure 23 was
Figure 23. Schematic illustrating the anionic eects on solvated ionic
liquids in suppressing the dissolution of polysuldes in LiS batteries.
Reprinted from ref 118b. Copyright 2013 American Chemical Society.
signicantly suppressed, leading to stable cycling performance.
However, NO3 anions can be irreversibly reduced at the
cathode, and BF4 anions can form unexpected byproducts with
polysulde anions. Li[OTf] in glyme is not a good electrolyte
for LiS batteries.
Suo et al.117 reported a new class of nonaqueous liquid
solvent-in-salt electrolytes for LiS batteries. The authors
chose the electrolyte containing LiTFSI in DME/DOL and
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Figure 24. Proposed nucleophilic reaction mechanism of EC and DMC with polysuldes. Reprinted with permission from ref 142. Copyright 2013
Elsevier.
studied the physicochemical properties of this electrolyte with
dierent ratios of salt to solvent. The lithium ion transference
number in 7 M electrolyte was 0.73, which is much higher than
that of traditional salt ionsolvent electrolytes (0.20.4).
However, the ionic conductivity of this electrolyte was 0.814
mS cm1 at room temperature, which is superior to that of an
all-solid-state dry polymer or most of the inorganic electrolytes,
although the viscosity was as high as 72 cP. Interestingly, the Tg
of this electrolyte is 77.3 C, which is much lower than that of
typical polymer-in-salt systems (Tg > 10 C) due to the
exible hinge in the SNS bond of TFSI. In LiS batteries,
such an electrolyte can inhibit the dissolution of lithium
polysuldes and protect the lithium metal anode against the
formation of lithium dendrites, which leads to excellent battery
performance.
8.2. Carbonate-Based Electrolytes
Carbonate-based electrolytes, such as LiPF6 in ethylene
carbonate (EC)/diethyl carbonate (DEC), are widely used in
Li ion batteries. It is desirable to use such electrolytes so that
graphite and other non lithium metal anodes can be used in
LiS batteries. However, carbonate-based electrolytes may be
inappropriate for use in LiS batteries because the intermediate
polysuldes could react with the carbonate solvent, resulting in
irreversible loss of active materials. Gao et al.111 studied
dierent electrolytes, including one with EC/DEC solvent, in
LiS batteries by in situ sulfur K-edge XAS. On the basis of the
dierent XAS results with the EC/DEC electrolyte, the authors
proposed that the nucleophilic sulde anions may chemically
react with carbonates to form methylated thiolate and
thioether. Similarly, Barchasz et al.114a also found instability
of carbonate-based electrolytes in LiS batteries. Yim et al.142
established the reaction mechanism of the carbonates with
polysuldes by studying the carbonate decomposition. A
plausible mechanism for the carbonate decomposition is
suggested, as shown in Figure 24. The polysuldes can react
with carbonates via nucleophilic addition or substitution to
form thiocarbonates and other small molecules.
Although the unsuccessful use of carbonate-based electro-
lytes in LiS batteries has been demonstrated by several
groups, a few studies show that carbonate-based electrolytes
can be used in cells with electrodes containing short-chain
sulfur species. Wang et al.18a studied a gel electrolyte membrane
containing a liquid electrolyte of 1 M LiPF6 in PC/EC/DEC
(1:4:5, v/v/v/) with a sulfurcarbon nanocomposite. The
voltage prole showed a single discharge voltage plateau after
the rst cycle. The sulfur composite electrode exhibited a
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reversible capacity of 400 mA h g1 over 20 cycles, and the
utilization of electrochemically active sulfur was about 90%.
Zhang et al.22,29a used 1 M LiPF6 in PC/EC/DEC (1:4:5, v/v/
v) with sublimed sulfur in acetylene black or carbon spheres.
The voltage prole showed only the lower discharge voltage
plateau at 1.8 V instead of the two voltage plateaus at 2.3 and
2.1 V. The authors attributed this potential hysteresis to sulfur
embedded in the narrow pores of carbon materials. The sulfur
in the carbon spheres showed a stable cycle life of 500 cycles.
Xin et al.26b demonstrated that metastable small sulfur
molecules of S24 in a microporous carbon matrix can work
with carbonate electrolytes, showing similar voltage proles and
a long cycle life. Wang et al.143 demonstrated that sulfur in a
microporousmesoporous carbon material can also work with
carbonate electrolytes. These results conrm that small sulfur
conned in a microporous carbon matrix can avoid the
irreversible reaction of polysuldes with carbonates in LiS
batteries. Recently, Lin et al.144 introduced a ame-retardant
additive (dimethyl methylphosphonate (DMMP)) to carbo-
nate-based electrolytes (LiPF6 in EC/EMC) for LiS batteries.
With 711 wt % DMMP in the electrolyte, the cells showed
good cyclability over 50 cycles.
8.3. Polymer/Solid-State Electrolytes
Polymer and solid-state electrolytes are more favorable than
liquid electrolytes in terms of their capability of reducing the
solubility of polysuldes and blocking the shuttle of polysuldes
in LiS batteries. In addition, they could protect the lithium
metal anode and minimize dendrite formation, which is
benecial for improving the safety and cycle life of LiS
batteries. However, polymer and solid-state electrolytes usually
have low ionic conductivity because of the high viscosity of
polymers and high energy barrier for lithium ion transport in
solid-state electrolytes. Short-chain polymers such as TEGDME
and polyethylene glycol dimethyl ether (PEGDME) have been
widely used in LiS batteries because of their liquidlike
property, which allowd good lithium ion transport. For
example, Marmorstein et al.119a compared three polymer
electrolytes, including PEO, poly(ethylenemethylene oxide)
(PEMO), and TEGDME. It was found that the cell with
TEGDME showed a much lower capacity fade rate than the cell
with the other two polymers. Kim et al.145 studied electrolytes
containing LiCF3SO3 in TEGDME with a sulfurmesoporous
hard carbon spherule composite cathode. The cell exhibited
high capacity with excellent retention during cycling. In
addition, the cell performed well at low temperatures, delivering
a capacity of 500 mA h g1 at 0 C over 170 cycles. Shim et al.17
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Chemical Reviews
compared three solvents with dierent molecular weights, i.e.,
triglyme, PEGDME 250, and PEGDME 500. The cells with
PEGDME 250 and 500 showed very reversible charging and
discharging behaviors with high Coulombic eciency, while the
cell with the triglyme solvent showed low eciency because of
the shuttle of polysuldes, indicating that polymers with high
molecular weights can indeed reduce the shuttle eect in LiS
batteries.
Long-chain PEO polymers have been widely used as a major
component in polymer electrolytes in LiS batteries. For
example, Shin et al.146 studied the electrochemical properties
and interfacial stability of (PEO)10LiCF3SO3 composite
polymer electrolytes with titanium oxide additive. The addition
of titanium oxide increased the ionic conductivity of the
composite electrolyte and improved the interfacial stability,
thereby improving the electrochemical performance. Hassoun
et al.16c,97 developed a solid-state LiS battery employing a
PEO-based gel-type polymer membrane containing a PEO/
LiCF3SO3 polymer matrix with nely dispersed nanosized
zirconia and a Li2SC composite cathode. A long cycle life and
high Coulombic eciency were obtained at elevated temper-
atures. Liang et al.147 studied a PEO18/Li(CF3SO2)2N polymer
electrolyte containing 10 wt % SiO2 with a sulfurmesoporous
carbon sphere composite in LiS batteries. A discharge
capacity of over 800 mA h g1 was obtained over 25 cycles
at 70 C.
Highly conductive glass-ceramic electrolytes based on thio-
LISICON have also been evaluated in LiS batteries. For
example, Hayashi et al.120b have developed an all-solid-state Li
S cell with Li2SP2S5 electrolytes which retained a capacity of
over 650 mA h g1 for 20 cycles at room temperature. Hakari et
al.120e from the same group studied Li2SP2S5 glasses and
acetyleneblack composite electrode materials in all-solid-state
batteries, which showed the largest charged capacity of 240 mA
h g1 (normalized by the weight of Li2SP2S5). The authors120a
also studied such electrolytes with Li2SCu composite
cathodes and an In metal anode. Cu is involved in the cathode
reaction by forming LixCuS. Nagao et al.104,120f also studied
Li2SP2S5 electrolytes with Li2S and sulfur composite cathodes.
Kobayashi et al.120c tested another thio-LISICON glass-ceramic
electrolyte with a composition of Li3.25Ge0.25P0.75S4 in LiS
batteries that showed a few reversible cycles. Yersak et al.120g
studied FeSS composite cathodes within all-solid-state
batteries with a 77.5Li2S:22.5P2S5 glass electrolyte and found
Li 2 S in the glass electrolyte can be involved in the
electrochemical processes and contribute to the capacity.
Recently, Lin et al.148 reported a novel class of sulfur-rich
cathode materials, lithium poly(suldophosphate)s, which
exhibited a high Li ion conductivity of 105106 S cm1.
They demonstrated this cathode material with the solid-state
Li3PS4 electrolyte to display a reversible capacity of over 1200
mA h g1 at C/10 over 300 cycles at 60 C. The lithium
superionic conductor Li10GeP2S12 with an ionic conductivity of
12 mS cm1 at room temperature demonstrated by Kamaya et
al.120h could be a promising solid electrolyte for LiS batteries.
8.4. Separators
Expanded polypropylene separators are widely used in LiS
batteries. Such separators have the limited ability to block the
shuttle of polysuldes since they are not functionalized. Some
eorts have been taken to evaluate other membranes with
functional groups in them with the goal of reducing the
transport of polysuldes. For example, Jin et al.149 applied
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lithiated Naon membranes in LiS batteries. Naon
membranes in hydrogen form are used in proton exchange
membrane fuel cells because of their high ionic conductivity
and good chemical stability. Once protons in Naon are
replaced by lithium ions, it becomes a lithium ion conductor. It
was found that the lithium ion conductivity of the lithiated
Naon membranes is 2.1 105 S cm1 at room temperature
and the Li ion transference number is 0.986, indicating high
lithium ion selectivity. The cell with the lithiated Naon
membrane exhibited better capacity retention and higher
Coulombic eciency than the cells with liquid electrolytes. A
recent work by Jin et al.150 demonstrated another peruori-
nated polymer membrane with lithium sulfonyl dicyanomethide
functional groups which showed a lithium ion conductivity on
the order of 104 S cm1 and a close-to-unity lithium ion
transference number. The cell with this membrane showed a
high initial discharge capacity of over 1100 mA h g1 and a
stable capacity of over 800 mA h g1 over 100 cycles with high
Coulombic eciency.
9. ANODES
The anode is an essential part of the LiS battery system
because the stability of the anode determines the long-term
cycle stability of LiS batteries. Metallic lithium may in
principle be the ultimate anode for Li ion batteries and the
primarily used anode in LiS batteries due to its low potential
and high capacity, leading to high energy density. However,
metallic lithium is unstable in contact with organic electrolytes,
which hampers the safety of rechargeable batteries based on
metallic lithium. The status and limitations of metallic lithium
anodes as well as alternative anodes are analyzed in the sections
below.
9.1. Lithium Metal Anode
As mentioned previously, although metallic lithium has a high
theoretical capacity of 3860 mA h g1, it suers from
drawbacks such as dendrite formation and low lithium cycling
eciency, which negatively inuence the cycling stability and
safety of rechargeable lithium batteries.124
The dendrite formation and low lithium cycling eciency
were believed to result from the instability of the passivation
layer (SEI layer) on the metallic lithium anode.124,151 The
unstable SEI cannot accommodate the shape and volume
changes of the lithium electrode during cycling, leading to
nonuniform lithium deposition and dissolution, resulting in
lithium dendrite formation.124 Moreover, the breakdown of the
SEI results in the exposure of the fresh lithium surface to the
electrolyte and parasitic reactions to form a new SEI layer,
which decrease the lithium cycling eciency.124 In contrast to
lithium ion batteries, LiS batteries involve the intermediate
polysuldes dissolved in an organic electrolyte, causing more
severe parasitic reactions on the lithium metal surface.
Consequently, conservation of a stable passivation layer is
more dicult, and degradation of the metallic lithium anode is
even more serious in LiS batteries.5a,123,152 Excess lithium is,
therefore, required to couple with the sulfur cathode, which
decreases the practical energy density of LiS batteries.
It is reasonable to comment that the success of LiS
batteries requires a reliable lithium metal anode. The reliability
of the lithium metal anode depends signicantly on the stability
of its passivation layer, which could be improved by changing
the electrolyte solvents and introducing additives as was
previously described in section 7.3. In addition, innovations
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in the electrode and cell conguration could be feasible
approaches for realizing safe lithium metal anodes for LiS
batteries.124 For example, Ji et al.151b reported an anisotropic,
spatially heterogeneous carbon-ber paper current collector
with SiO2 or SiC decoration. The rationally designed current
collectors were characterized to be dendrite-free by ex situ
scanning electron microscopy (SEM) observation after a deep
lithium deposition of 28.8 C cm2 at a high current density of 4
mA cm2. Furthermore, graphene sheets could be prepared as
3D current collectors and used to increase the anode surface
area, thereby reducing the eective current density and
suppressing lithium dendrite development.151c Despite the
advances in lithium metal protection in previous studies,
complete control of the stability of the passivation layer and the
roughness of the lithium metal surface during cycling, especially
in LiS batteries, has not been achieved, which hinders the
commercialization of LiS batteries.
9.2. Silicon Anode
Silicon with its high room temperature theoretical capacity of
3579 mA h g1 (Li15Si4) is a promising alternative for metallic
lithium as an anode for LiS batteries.153 The interest in Si-
based anodes dates back to the 1990s.153a,b Nevertheless,
application of Si-based anodes in rechargeable batteries was
hampered by the severe capacity fade due to the mechanical
failure of the active material caused by the huge volume
changes occurring during cycling.154 The huge volume change
of >300% could result in stresses exceeding the breaking stress
of Si, leading to cracking of the Si particles and loss of
interparticle contact and active Si for further reaction with
lithium.154,155 Recently, this problem has been alleviated and
stable cycling has been achieved by employing nanosized Si,
involving controlled volume changes and a shorter lithium ion
diusion length.156 However, it is worth mentioning that the
theretical gravimetric energy density of the Li15Si4S couple is
approximately 50% lower than that of the LiS couple
(assuming an average voltage of 1.8 V for the Li15Si4S couple
reaction).157159
For using Si-based anodes in LiS batteries, it is a
prerequisite that lithium be introduced into the cathode or
anode before assembly of the cell. One possible design is to
couple the Si-based anode with a Li2S cathode. Yang et al.100
prepared a Si nanowire anode and a Li2Smesoporous carbon
composite cathode and obtained an initial discharge energy
density of 630 W h kg1 (based on the mass of the active
electrode materials), suggesting the feasibility of a Li2S/CSi
cell conguration. The nanostructured design is essential for
both the electrodes to enhance the electronic conductivity and
alleviate the large volume changes. However, severe capacity
degradation occurred within 20 cycles.100
An alternative design is to couple a prelithiated Si electrode
with a sulfur cathode, which mitigated the aforementioned
technical problems associated with metallic lithium anode.124
Liu et al.157 demonstrated a rapid prelithiation of Si nanowires,
coupled it with a sulfurmesoporous carbon cathode, and
achieved a proof-of-concept S/CLi/Si full cell. Nevertheless,
the lithium cycling eciency was poor, weakening its practical
advantages compared to a metallic lithium anode.157 The poor
electronic conductivity of this cycled Si electrode with an
irregular blend of porous prelithiated Si nanowires and intact
nanowires could be one major reason for the inferior cycling
stability of the full cell. Elazari et al.158 also reported a
prelithiated silicon anode in combination with a sulfur cathode.
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With a prelithiated columnar structured -Si lm electrode,
they were able to achieve a reversible capacity of >380 mA h
g1 after 60 cycles, although the performance is still far from the
requirement for practical applications.158
To enhance the electronic conductivity of the Si-based
materials and suppress the volume expansion, the lithiated Si
could be conned into a carbon matrix.159 Hassoun et al.159a
disclosed a metal-free, S/CLi/Si/C full cell in which sulfur
was trapped in highly porous hard carbon spherules and
coupled with a lithiated Si/C nanocomposite anode and a
glycol-based electrolyte. A reversible capacity of 300 mA h g1
was obtained over 100 cycles. Improved performance was
further anticipated if problems such as mass balancing between
the electrodes or polysulde shuttling were addressed. Recently,
more promising results have been obtained by Yan et al.159b by
replacing the conventional organic electrolyte with an ionic
liquid, N-methyl-N-allylpyrrolidinium bis((triuoromethyl)-
sulfonyl)imide (RTIL P1A3TFSI) and employing a prelithiated
Si/C microsphere anode and a S/C composite cathode to
achieve a high initial discharge capacity of 1457 mA h g1 and a
capacity of 670 mA h g1 after 50 cycles. However, the sulfur
content in the cathode was only 32 wt %. Electrochemical
performances of the full cell with higher sulfur loadings and
charge/discharge rates need to be evaluated.
Similar to Li/Si alloys, Li/Sn alloys with a capacity of 993
mA h g1 are appealing as an anode for LiS batteries.122
Hassoun et al.97 demonstrated this concept with a Sn/C anode,
a Li2S/C nanocomposite cathode, and a gel-type electrolyte. A
reversible capacity of 800 mA h g1 (based on the mass of
Li2S) was obtained over 30 cycles.97 Furthermore, Kim et al.160a
synthesized a thin layer of Al on the lithium anode surface and
noticed better cycle stability with the Li/Al anode than similar
cells assembled with bare Li. It was concluded that the Li/Al
alloy layer was ecient in protecting the lithium anode and
mitigating the reaction between dissolved polysuldes and the
lithium anode. Li/B alloy was also identied to be benicial in
terms of restraining dendrite formation, reducing interfacial
impedance of the electrode, and improving the cycle perform-
ance to a certain degree in LiS batteries.160b Despite the high
capacities of Li-alloying materials, the huge volume changes
associated with the use of Li-alloying materials result in poor
capacity retention, which hampers their practical utility.124
9.3. Carbon Anode
Although graphite materials with the layered structure were
reported as the host lattice for lithium ion intercalation/
deintercalation as early as 1976,161 they have not been
successfully applied in LiS batteries. One major factor
preventing the use of graphite in LiS batteries is the
incompatibility of the supporting electrolyte systems. Similar
to the use of a metallic lithium anode, the use of graphite
materials as the anode in rechargeable lithium batteries requires
a choice of electrolyte solutions that could lead to surface
stabilization of the graphite particles, since the forces between
graphene planes in graphite are relatively weak.162 A
cointercalation of solvent molecules together with lithium
ions between the graphene planes could result in a
delamination of the graphene sheets and failure of the graphite
electrode.162 This failure mechanism was observed for graphite
electrodes processed in ether-based electrolytes, which are the
most commonly used electrolytes in LiS batteries.162
Recently, promising results have been obtained by Bruckner
et al.152 with the use of carbon-based anodes in LiS batteries.
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It was found that the hard carbon anode was stable in ether-
based electrolytes, making it possible to construct SLi/C full
cells. Cycling stability was obtained for more than 550 cycles
with capacity fading as slow as 0.08% per cycle.152 In contrast to
graphite materials, the nongraphitized hard carbon has a wider
interlayer spacing and cross-links between the domains of the
graphene planes, leading to good cycling stability in ether-based
electrolytes.
10. BINDERS
The binder is critical for fabricating battery electrodes.
However, conventional binders such as PTFE or PVdF are
not eective for sulfur cathodes because of the dissolution of
polysuldes as discussed before. In addition to the development
of binder-free electrodes discussed in section 5.4, alternative
binders have also been considered for LiS batteries. This
section summarizes the eorts on binders.
PEO is one of the earliest alternative binders that has been
studied in LiS batteries. Cheon et al.163 studied sulfur
cathodes with dierent PEO binder contents prepared by two
dierent methods, ball-milling and mechanical stirring. The
preparation methods aect the morphology of PEO and
porosity in the sulfur cathodes, which inuences the cycling
performance. In addition, roll-pressing improves the integrity of
sulfur cathodes containing a PEO binder, leading to a longer
cycle life. Lacey et al.164 found PEO- or PEG-modied cells
show improved electrochemical reversibility and suppressed
passivation of the cathode at the end of discharge. The reason is
that PEO can dissolve in the liquid electrolyte, modifying the
electrolyte similarly to PEGDME solvent.
Other polymers have also been studied as binders with sulfur
cathodes. For example, Sun et al.165 rst used gelatin, a natural
polymer, as a binder in sulfur cathodes. They compared sulfur
cathodes with gelatin and PEO binders and found that gelatin
can not only improve the adhesion but also enhance the
dispersion in sulfur cathodes, showing better performance than
the electrodes with a PEO binder. Later they166 studied sulfur
cathodes with a gelatin binder treated by a freeze-drying
method, which resulted in a porous electrode structure. Higher
initial and reversible capacities have been obtained with these
electrodes compared to the normal electrodes with a compact
structure. Huang et al.167 compared gelatin and PEO binders in
sulfur electrodes. It was found that gelatin could enhance the
redox reversibility of sulfur cathodes, resulting in better
electrochemical performance than with the PEO binder.
Wang et al.107b found the gelatin binder can maintain a porous
sulfur electrode structure even after prolonged cycles. A
capacity of 1235 mA h g1 was achieved in the rst discharge,
and a reversible capacity of 626 mA h g1 was retained after 50
cycles. Wang et al.168 also found that sulfur electrodes with
gelatin binder show high rate capability. In addition, the pH of
the gelatin solution was found to aect the battery cycling
performance. Zhang et al.169 found the electrode prepared with
a pH 10 gelatin solution showed higher discharge capacities and
a more stable cycle life than those prepared with pH 5.0 and 8.0
gelatin solutions. He et al.170 utilized a water-soluble binder
consisting of SBR and sodium CMC in sulfur electrodes. The
SBRCMC binder can not only act as an adhesion agent but
also facilitate the dispersion of active materials, maintaining a
uniform and electrochemically favorable structure in the sulfur
electrode and leading to better cycling performance than that
with the PVdF binder. Zhang171 at the U.S. Army Research
Laboratory introduced a cationic electrolyte, poly(acrylamide-
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co-diallyldimethylammonium chloride) (AMAC), as the binder
in high-loading sulfur electrodes. AMAC is a hydrophilic
polymer but is not soluble in organic electrolytes, retaining a
stable void structure in sulfur electrodes upon cycling. A high-
sulfur-loading (80 wt %) electrode with the AMAC binder
exhibited better cyclability than that with the PEO binder.
Wang et al.172 chemically converted -cyclodextrin to
carbonyl--cyclodextrin (C--CD) as a water-soluble binder
for sulfur electrodes. The cell with the C--CD binder and
carbonate-based electrolytes exhibited a high initial discharge
capacity of 1543 mA h g1 and a reversible capacity of 1456 mA
h g1 over 50 cycles. The high performance is related to the fact
that C--CD can tightly wrap the sulfur composite and
suppress its aggregation during cycling. Compared to other
binders such as PVdF and PTFE, C--CD oers the advantages
of high performance, low cost, and environmental benignity.
Recently, Seh et al.173 selected PVP as a good binder for Li2S
cathodes based on ab initio simulations. The results show that
the CO groups in PVP have high binding energies of 1.14
and 1.30 eV with Li2S and LiS species, respectively, which
are much higher than those with F groups in PVdF, as shown
in Figure 25. As a result, the Li2S electrode with PVP binder did
Figure 25. (a, b) Ab initio simulations showing the most stable
conguration and calculated binding energies of Li2S and LiS
species with (a) PVP and (b) PVdF binders. Optical microscopy
and digital camera images (inset) showing the electrode slurry of Li2S
electrodes with (c) PVP and (d) PVdF binders in NMP solvent.
Reprinted with permission from ref 173. Copyright 2013 The Royal
Society of Chemistry.
not show large aggregates that are usually observed in the
electrode with the PVdF binder and exhibited a stable cycle life
over 500 cycles.
11. CELL CONFIGURATIONS
As the LiS batteries owe their high capacity to the occurrence
of a chemical conversion reaction rather than an insertion
reaction unlike in conventional Li ion batteries, the adaptability
and the compatibility of the conventional cell conguration
need to be reconsidered. The cell conguration modication
has been determined as a crucial factor in improving the
performance of LiS batteries, especially the improvements in
the sulfur content/loading and active material utilization.
Several attractive novel congurations for the cathode/cell
have exhibited signicant enhancement in the electrochemical
performance of pure sulfur cathodes or dissolved polysulde
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Figure 26. (a) Schematic model of the bifunctional interlayer architecture. SEM observation and elemental S mapping of various bifunctional
interlayers: (b) microporous carbon, (c) MWCNTs, (d) metal foam, and (e) biomass. Part b reprinted with permission from ref 174a. Copyright
2012. Nature Publishing Group. Part c reprinted with permission from ref 16a. Copyright 2012 The Royal Society of Chemistry. Part d reprinted
with permission from ref 176. Copyright 2013 Springer Science and Business Media. Part e reprinted with permission from ref 177a. Copyright 2013
Wiley-VCH Verlag GmbH & Co. KGaA.

catholyte systems. The use of interlayers, porous current
collectors, and sandwiched structures is presented below. Some
of the physical/chemical parameters and cycling performances
are presented in Tables S3S5 in the Supporting Information.
11.1. Interlayers
Since commercial polymeric separators are perfect permeable
membranes for liquid electrolytes in a battery, they work well to
prevent an internal short circuit and permit lithium ion
diusion. However, even with a good cathode system, the LiS
battery might still have some polysuldes migrating from the
cathode to the anode, and the polymeric separator cannot stop
the free polysulde migration.
To tackle this challenge, our group introduced the concept of
inserting a bifunctional interlayer between the separator and the
cathode as a polysulde-diusion inhibitor.16a,d The bifunc-
tional interlayer has evidenced that it can eectively capture/
localize the migrating polysuldes within the cathode region of
the cell, resulting in long-term cycle stability with high sulfur
utilization, as shown in Figure 26a. Moreover, the bifunctional
interlayer oers additional electron pathways covering the top
surface of the cathode, enhancing the conductivity of pure
sulfur cathodes and assisting the reutilization of the trapped
active material. Therefore, the bifunctional interlayer can be
regarded as another kind of separator which aims to block the
penetration of soluble polysuldes, resulting in less shuttle
eect and better capacity retention.
This concept has now blossomed into a series of novel
interlayers based on various materials (Table S3 in the
Supporting Information): (i) micro/mesoporous carbon
(Figure 26b),113c,174 (ii) interwoven CNFs/CNTs (Figure
11777
26c),96b,175 (iii) porous metal foam (Figure 26d),176 and (iv)
porous biomaterials (Figure 26e).177 However, attention should
be paid to not impacting the energy density due to the
additional weight associated with the introduction of an
interlayer.10
11.1.1. Polysulde-Interception Mechanism. The bi-
functional interlayers listed above all fulll a fundamental
criterion: a layered porous architecture. The multilayer network
structure is necessary for intercepting the migrating poly-
suldes, transporting the lithium ions, and channeling the liquid
electrolyte. As a result, the active material and the electro-
chemical reaction can be stabilized within the cathode region of
the cell. The polysulde-interception mechanism is primarily
contributed by the microporous structure and the layered
porous network. First, the microporous structure in the
interlayer functions as the absorption site for immobilizing
the active material and limiting the soluble polysulde shuttling
into the electrolyte.174,175a,177 Second, the layered porous
structure that is composed of interwoven tubes/bers serves as
the host and as a shnet for accommodating and retaining the
dissolved polysulde species by its high electrolyte absorptivi-
ty.16a,177
Moreover, the interlayer must have high electrical con-
ductivity for achieving a high discharge capacity and, more
importantly, for reactivating the trapped polysuldes during
subsequent cycles. After capturing the migrating polysuldes,
the conductive interlayer matrix should freely transport the
electrons into the trapped polysuldes and reactivate them,
making them available to be reutilized even during long-term
cycling. With the interception, absorption, and reutilization
processes, the bifunctional interlayer system provides the LiS
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Chemical Reviews Review

Figure 27. (a) Schematic model of the porous current collector architecture. SEM observation and cycling performance of the bifunctional
interlayers with various preparation processes: (b) dissolved polysulde catholyte, (c) thermal sulfur impregnation, and (d) active material paste
absorption. Part b reprinted with permission from ref 180. Copyright 2013 Wiley-VCH Verlag GmbH & Co. KGaA. Part c reprinted with permission
from ref 52. Copyright 2011 Wiley-VCH Verlag GmbH & Co. KGaA. Part d reprinted with permission from ref 29d. Copyright 2013 The Royal
Society of Chemistry.

cells long-term cycle stability with a high sulfur content with
regular sulfur cathodes (i.e., no need to employ sulfurcarbon
composite cathodes). The high sulfur content in the cathode is
allowable with these cell congurations because the highly
conductive bifunctional interlayer works as the upper current
collector to reduce the cathode resistance.16a Our group has
made further progress by developing a bifunctional separator
that integrates the interlayer with the separator,16g,h which is
specially designed for LiS cells to allow lithium ion ow but
hinder polysulde migration.
11.1.2. Constructional Materials for Interlayers.
Although all the representative bifunctional interlayers
described above show good cell performance, the cyclability
of the cells is still inuenced by the raw material used for the
fabrication of the interlayers and its physical properties: (i)
layered porous architecture, (ii) pore size, (iii) electrolyte
absorptivity, (iv) electrical conductivity, and (v) structural
stability.
First, the multilayer porous network is a necessary factor for
intercepting the migrating polysuldes. Our group has analyzed
the thickness eect by designing a multilayer interlayer module
with a controllable thickness and a tunable number of layers.
The results demonstrate that a thicker interlayer provides better
interception ability and more stable cyclability than a thinner
interlayer. Thus, by taking a balance between cell performance
and the weight of the interlayer, a suitable thickness of the
multilayer porous network can be accomplished.175b Second,
considering that the soluble polysuldes have chain lengths
11778
smaller than 2 nm, micropores and small mesopores may have
better polysulde interception compared to macropores and
large mesopores.174,178 However, the large mesopores are
necessary for assisting fast lithium ion transport and
cooperating with macropores to form interconnected electro-
lyte pathways.113c,177 Third, the high electrolyte-absorption
ability is important for stabilizing the electrolyte containing the
dissolved polysuldes. Moreover, the excellent electrolyte
absorption suggests that there are plenty of interspaces for
accommodating the active material. Fourth, the conductivity of
the interlayer inuences sulfur utilization and reutilization,
which controls the reversible capacity during long-term cycling.
Therefore, the bifunctional interlayers should have a con-
tinuous carbon cluster framework113c,130,174 or interwoven ber
network16a,96b,175177 as the electron pathway. Fifth, the
structural stability of the interlayer requires both physical and
chemical stabilities. The structural stability requires high
mechanical strength, ensuring that the interlayer will not
break during cell assembly or during a long-term discharge/
charge process. Moreover, a exible porous network may
channel o the volume changes from the active material during
the charge/discharge process. The chemical structural stability
requires that the interlayer must avoid being corroded or
ruptured during cell cycling.
11.2. Porous Current Collectors
In most cases, a 2D aluminum foil is used as the current
collector for all types of lithium batteries. However, the
structure and morphology of sulfur change a lot during cycling
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Chemical Reviews Review

Figure 28. (a) Schematic model of the compound-sandwiched electrode. Cell conguration and cycling performance of various derived LiS cells:
(b) Li2S cathode, (c) dissolved polysulde catholyte, and (d) S cathode. Part b reprinted with permission from ref 96b. Copyright 2013 Wiley-VCH
Verlag GmbH & Co. KGaA. Part c reprinted with permission from ref 177a. Copyright 2013 Wiley-VCH Verlag GmbH & Co. KGaA. Part d
reprinted with permission from ref 130. Copyright 2013 Wiley-VCH Verlag GmbH & Co. KGaA.

because of its repeated dissolution and precipitation. Therefore,
a 3D porous current collector (PCC) may oer additional
benets: (i) serving as the container for holding the sulfur and
(ii) functioning as the absorbing points for conning soluble
polysuldes. As a result, the PCC is able to stabilize the active
material, liquid electrolyte, and electrochemical reaction within
the cathode region of the cell. The modication of the
necessary component that is already inside the cell should
support low active material loss and suppress polysulde
shuttling as shown in Figure 27a.
Moreover, the 3D conductive network improves the contact
between the active material and the current collector as well,
decreasing the cathode resistance. During cell operation, the 3D
PCCs behave as the inner electron pathway, facilitating fast
electron transport and reactivation of the inactivated areas.
Thus, use of PCCs could be a viable and facile approach to
improve the cycling performance of LiS batteries. For
example, metal foam,36c,179 porous carbon-
s,16b,21,29d,e,52,96b,130,179,180 AAO templates,25a,c,26c and porous
biomaterials177a have been studied to function as the 3D PCC
(Table S4, Supporting Information) and oer better cyclability
with a higher sulfur loading compared to those with the
conventional 2D at Al current collectors.
11779
11.2.1. Sulfur Impregnation Strategy. The PCC is a
cathode conguration modication that encapsulates the active
material into its porous spaces. There are three major categories
of sulfur impregnation processes: (i) dissolved polysulde
catholyte (Figure 27b; see section 11.4 for a detailed
discussion),16b,21,177a,179 (ii) thermal sulfur impregnation
(Figure 27c),25a,c,26c,52 and (iii) active material paste absorption
(Figure 27d).29d,e,36c
Dissolved Polysulde Catholyte. The combination of PCC
with the liquid-phase polysulde catholyte allows cells to have a
high discharge capacity with a high sulfur loading of >2 mg
cm2, which is hard to simultaneously achieve with cells having
the conventional cathode. When the catholyte is added to the
PCC, the PCC functions as the active material reservoir that
absorbs the electrolyte containing sulfur in its porous spaces,
realizing excellent active material encapsulation and uniform
sulfur coverage on the wall of the active material container.180
The excellent catholyte immersion and penetration in the PCC
can improve the connection among the active material, charges,
electrolyte, and conductive substrate. Moreover, the amount of
active material in the catholyte that is absorbed in the PCC is
more than the amount of active material in the SPC
composite cathode that is surface coated on a at current
collector.
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Chemical Reviews
Thermal Sulfur Impregnation. Elazari et al.52 synthesized a
sulfur-impregnated activated carbon ber cloth by a two-step
heat treatment process to encapsulate the melting sulfur into
the carbon substrate. This approach also oered a signicant
improvement in the cycle stability: a high capacity retention
approaching 95% after 80 cycles with a high discharge capacity
above 800 mA h g1 and a reasonable sulfur loading of around
1.6 mg cm2.52 Following this concept, several AAO hard
template-based approaches have been developed. Although
AAO templates oer LiS cells with high sulfur utilization
approaching 90% and a long cycle life over 1000 cycles, the
sulfur loading in the cathode declines back to as low as 1.0 mg
cm2.25a,c,26c
Active Material Paste Absorption. Active material paste
absorption is a facile and cost/time-eective process for
preparing high-performance porous sulfur cathodes. Our
group designed this method by modifying the conventional
slurry casting method.29d,e,36c The paste-absorption method
immerses the PCC into the active material paste, allowing the
PCC to absorb the paste by the capillary forces and forcing the
paste to penetrate into the porous substrate. The resultant
porous cathode achieves uniform sulfur coverage on the surface
of the conductive matrix, resulting in enhanced cathode
conductivity and high discharge capacities. The excellent sulfur
encapsulation in the porous spaces allows the absorbed active
material to occupy the electrochemically favorable positions
during subsequent cycles and leads to stable long-term
cyclability for over 100 cycles. Moreover, the PCC can function
as the active container to achieve a high sulfur loading of 80%
and 2.3 mg cm2.29e
11.2.2. Constructional Materials for Porous Current
Collectors. For promoting the application of PCCs, design
and development of promising substrates are critical. First, the
PCC must have high electrical conductivity to realize fast
election transport and thereby improve the utilization of the
active material. Second, the PCC must have abundant porous
spaces for accommodating the active material and the
polysuldes in the cathode region during the charge/discharge
process. According to these two criteria, metal foam,36c,179
porous carbon,16b,21,29d,e,52,96b,130,179,180 porous biomass,177a
and polymer substrates are suitable PCC candidates and are
introduced here. The AAO template method is not described
here because of its complex manufacturing procedures and low
sulfur loading.
Dierent from the interlayer, PCC may need a micro/meso/
macroporous structure.29d,e,36c The micropores in the PCC aim
to encapsulate and absorb the active material during cathode
preparation or during cell cycling. The small mesopores assist
micropores in enhancing sulfur encapsulation. The large
mesopores not only accelerate the charge accessibility but
also cooperate with the macroporous structure to absorb the
electrolyte containing the dissolved polysuldes into the
cathode.29d,e,36c,177a The macroporous structure is suggested
to be contributed by the interwoven ber architecture, which
can further provide electron pathways inside the cathode. As a
result, the electrochemical materials/reaction can be stabilized
within the cathode region, thereby limiting the loss of active
material.
11.3. Sandwiched Electrodes
In 2013, a compound-sandwiched electrode architecture that
includes a bifunctional interlayer on the top, the active material
in the middle, and a PCC at the bottom, which integrates the
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advantages of the bifunctional interlayer and the PPC as shown
in Figure 28a, was pursued by our group.96b This newly
developed cell conguration showed excellent electrochemical
performance with several derived LiS systems (Table S5 in
the Supporting Information): (i) Li2S cathode, (ii) polysulde
catholyte, and (iii) regular sulfur cathode.
Our group developed carbon-sandwiched electrodes (Figure
28b) that involve the Li2S active material powder within two
layers of self-weaving MWCNT electrodes.96b The upper
MWCNT electrode works as the bifunctional interlayer, and
the lower MWCNT electrode serves as the PCC. This unique
sandwiched electrode architecture enhanced ion/electron
transport and localized the cycled products within the
sandwiched electrodes, facilitating a high capacity and excellent
cyclability at high rates. Following this, our group has further
developed a carbonized eggshell membrane reservoir for
polysulde catholyte cells (Figure 28c), including two layers
of free-standing biomass carbon lm and the dissolved
polysuldes in between.177a The carbonized biomaterial
localizes the dissolved polysuldes within the sandwiched
electrode region, accomplishing a high discharge capacity, long-
term cycle stability, and high sulfur loading of 3.2 mg cm2.
Zhou et al.130 also designed a graphenesulfur sandwich
structure with regular sulfur cathodes which eectively reduces
the internal resistance and stores/reuses well the active material
in the compound electrodes (Figure 28d).
11.4. Dissolved Polysulde Catholytes
In 1979, Rauh et al.8b demonstrated the rst lithiumdissolved
polysulde cell, showing a high utilization of sulfur (1.83
electron per sulfur) in the initial discharge because of the
soluble polysuldes with high reactivity compared to solid
sulfur particles. Polysuldes can be dissolved in THF with high
concentrations (up to 10 M). However, the cyclability was not
satisfactory. Zhang et al.16b modied the dissolved polysulde
electrolyte with LiNO3 to promote Li anode passivation and
improve the cycling performance with a good capacity retention
over 70 cycles. However, the average discharge capacity was
only around 500 mA h g1. Xu et al.181 utilized a DME
electrolyte containing predissolved lithium polysuldes and
LiNO3 as the lithium salt to suppress the migration of
polysuldes into the electrolyte. A high capacity of 1450 mA h
g1 and almost 100% Coulombic eciency with excellent
cyclability were achieved. Chen et al.182 also found that the
polysulde-containing electrolytes can improve the cycling
performance of LiS batteries. Our group180 demonstrated a
high initial capacity of 1600 mA h g1 and a capacity of over
1400 mA h g1 over 50 cycles at a C/10 rate with lithium
dissolved polysulde cells with a binder-free MWCNT paper
current collector. The nanoscaled MWCNT electrode structure
signicantly improved the utilization of active material in the
polysulde electrolyte, leading to a highly reversible system.
Dissolved polysuldes can also be used in catholytes circulating
in a half-ow-mode redox ow battery, as proposed by our
group.35,113c To maintain the ow mode, the charge and
discharge voltage should be controlled within the dissolved
polysulde region (Li2Sx, x 4) to avoid clogging in the
electrode (see section 12.1).
12. VOLTAGE WINDOW
In most cases, LiS batteries are operated within a voltage
window of 1.53.0 V for utilizing the capacity generated by the
complete chemical reaction between the elemental sulfur and
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Chemical Reviews
its end product, lithium sulde. Currently, the cuto voltage
may shift from 1.5 to 1.8 V to avoid the irreversible capacity
loss from the LiNO3 additive that is often used in electrolytes
to passivate the metallic lithium anode and achieve high
discharge/charge eciency.10,127 In both voltage windows, two
discharge plateaus for the reduction reaction and two charge
plateaus for the oxidation reaction can be seen at moderate C
rates in ether-based electrolytes. However, the kinetics of the
upper and the lower discharge plateaus are quite dierent.20
The upper plateau (2.42.0 V) involves the transformation
from sulfur (S8) to long-chain polysuldes (Li2S4), and this step
is very fast in kinetics. The lower plateau, which is slow in
kinetics, involves the electrochemical reaction to generate solid
Li2S from the Li2S4 produced at the end of the upper plateau.
12.1. Upper Voltage Plateau
When utilizing only the upper plateau that has the voltage
range from 2.4 to 2.0 V in the half-ow-mode redox ow
battery, our group reported that the cell can achieve a very high
rate capability (6.3 A g1) and retain stable cyclability.35,113c In
2013, Yang et al.183 demonstrated this concept with a 5 M Li2S8
catholyte possessing energy densities of 97 W h kg1 and 108
W h L1. The half-ow-mode LiS cell without the ion-
selective membrane that inherited the same strategy and used
Li2S8 as a catholyte in the cell delivered a steady energy for
more than 2000 cycles, which may become a promising system
for large-scale storage of renewable energies.
12.2. Lower Voltage Plateau
174b
Our group conceived a recharge approach by controlling
the charge capacity for utilizing the lower plateau at 2 V.
Thus, the redox reaction can be conned within the solid-state
region, leading to highly reversible capacity output for extended
cycles. Cyclability with an extremely low capacity degradation
rate of 0.002% per cycle up to 500 cycles was obtained.
Additionally, high Coulombic eciency could be realized even
without the addition of LiNO3 to the electrolyte.
13. CONCLUSIONS AND FUTURE DIRECTIONS
In this review, we have provided a comprehensive account of
the developments in LiS batteries, including major historical
progress, associated technical obstacles, and component/
material developments. We also focused on the latest advent
of cell congurations, which hold promise for a leap in LiS
battery research. Moreover, advanced characterization techni-
ques that provide a better understanding of the mechanisms
involved in the LiS chemistry were introduced.
The application of nanostructured composites, facilitating
rapid ion/electron transport while trapping the polysulde
intermediates, have been intensively pursued with LiS
batteries. Sulfurcarbon nanocomposites, which are one
dominant type of composite cathode in LiS batteries, have
shown promising performances with high capacity, enhanced
rate capability, and long-term cycle stability. In addition,
sulfurpolymer composites have oered the advantage of a
versatile design of nanocomposite cathodes. Electrolytes also
play a critical role in solving the problems with LiS batteries.
For example, the LiNO3 additive enhances the Coulombic
eciency of LiS batteries and the stability of the lithium metal
anode. In addition, novel cell congurations, e.g., carbon
interlayer or porous current collector congurations, signi-
cantly improve the cycling performance of LiS batteries even
when coupled with a conventional pure sulfur electrode.
Furthermore, Lidissolved polysulde cells could regain
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Review
renaissance if stabilized lithium metal anode and advanced
carbon cathode current collectors are developed. With these
great achievements and eorts, the rechargeable LiS batteries
have become the most promising high-energy-density system
for next-generation electrical energy storage.
Despite the considerable improvements achieved during the
past few decades, it will still be a long time before the LiS
chemistry can be successfully employed in practical systems.
Realizing high capacities with long-term cycle stability, while
retaining a high sulfur loading/content essential for high
practical energy density, is challenging. Therefore, future eorts
should be directed toward basic science research and
approaches that can lead to viable high-performance practical
LiS batteries.
The eorts for developing high-performance LiS batteries
can be generalized as follows.
13.1. Appropriate Dispersion of Active Sulfur
Although the solid-phase sulfur transforms into soluble
polysuldes during cycling and changes its initial morphology,
the utilization of the active material will be low if sulfur has
insucient contact with conductive agents. Poor connection
between the insulating sulfur and the electrical conductor can
result in inactive regions in the cathode, leading to low cathode
conductivity and low capacity.
13.2. Ecient Absorbing Materials
Polysulde dissolution and diusion could lead to a series of
severe shuttle issues. Novel conductive and porous materials
need to be designed for eectively absorbing and accommodat-
ing the active material. Moreover, further improvement could
be expected with well-balanced additive:sulfur ratios.
13.3. Flexible Conductive Matrix
LiS batteries suer from large volume and structural changes
during the sulfur redox reactions. Flexible and robust
conductive matrixes are essential for accommodating the
Li2S/Li2S2 deposition during discharge and suppressing the
formation of irreversible Li2S to avoid deterioration of cycle
stability caused by a breaking down of the conductive substrate
through stresses induced by the large volume changes.
13.4. Stable Electrolyte Systems
The current liquid electrolyte is far from meeting the demands
of the practical utility of LiS batteries because of the side
reactions among polysuldes, electrolyte solvents, and lithium
metal. A more reliable electrolyte is preferred to have a
controlled dissolution of the polysuldes and to be compatible
with the lithium metal anode. Development of suitable polymer
or inorganic solid electrolytes may be a promising strategy.
13.5. Safe Anode Materials
A lithium metal anode in liquid electrolytes poses safety
concerns due to lithium dendrite development during cycling.
To address this problem, use of a protected lithium metal
anode or alternative Li/M (M = Si, Sn, C, etc.) alloys is a
feasible approach for building a safer LiS battery.
13.6. Li2S Cathode
Another approach to facilitate the use of a metallic lithium-free
anode is to employ Li2S rather than S as the cathode and couple
it with high-capacity anodes such as silicon, tin, or metal oxides.
This strategy, however, will need to overcome the initial
activation barrier associated with micrometer-sized Li2S
particles, possibly through the development alternative
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Chemical Reviews Review

chemical synthesis approaches with good control over Biographies

morphology and the degree of lithiation.
13.7. Novel Cell Congurations
Given the fact that LiS batteries involve conversion reactions,
and not insertion reactions, unlike those in the conventional Li
ion batteries, innovations in cell congurations should be
considered. Strategies involving interlayers, porous current
collectors, and sandwiched electrodes could be attractive
solutions to store the active material and conne the migrating
polysuldes. Moreover, these novel cell congurations can be
coupled with a pure sulfur cathode with high sulfur loadings.
However, caution should be exercised that the weight/volume
of these alternative porous/conductive substrates does not
sacrice the overall energy density. Coating the separator with a Arumugam Manthiram is the Joe C. Walter Chair in Engineering and

thin layer of carbon on the cathode side could potentially the Director of the Materials Science and Engineering Program and
alleviate the weight concern.16g,h
Texas Materials Institute at the University of Texas at Austin (UT-
13.8. Smart Recharge Settings
Utilizing only the lower voltage plateau at 2 V has been Austin). His research interests are in the area of materials for
proved eective in improving the cycle life of LiS batteries. rechargeable batteries, fuel cells, and solar cells, including novel
The only concern is that the utilization of the lower plateau
synthesis approaches for nanomaterials. He has authored 550
must be high (>1000 mA h g1); otherwise, the advantages of
the high energy density of the sulfur cathodes will be weakened. publications, including more than 470 journal papers. See www.me.
Overall, the commercial viability of LiS batteries could be
utexas.edu/manthiram for further details.
enhanced with further scientic and technical advances.
Development of advanced materials and characterization
methods together with a smart engineering design will have a
signicant impact in the LiS battery area. In addition, a
stabilized lithium metal anode needs to be developed to couple
with future long-cycle-life sulfur cathodes. With these improve-
ments, rechargeable LiS batteries could be the most
promising high-energy-storage system for supporting a
sustainable and mobile society.

ASSOCIATED CONTENT
*
S Supporting Information

Table S1, parameters of representative SPC composites, Yongzhu Fu is currently an assistant professor at Indiana University-
Table S2, parameters of representative metal oxide absorbing
Purdue University Indianapolis (IUPUI). He obtained his B.E. (2000)
agents, Table S3, parameters of representative bifunctional
interlayers, Table S4, parameters of representative porous and M.S. (2003) in chemical engineering from Tsinghua University
current collectors, and Table S5, parameters of representative
and the Dalian Institute of Chemical Physics, respectively, in China,
compound-sandwiched electrodes. This material is available
free of charge via the Internet at http://pubs.acs.org. and his Ph.D. (2007) in materials science and engineering from UT-

Austin. He was a chemist postdoctoral fellow at Lawrence Berkeley

AUTHOR INFORMATION
Corresponding Author National Laboratory, research scientist at Lynntech, Inc., and research
*E-mail: manth@austin.utexas.edu. Phone: 512-471-1791. Fax: associate at UT-Austin before joining IUPUI in 2014. His research is
512-471-7681.
Notes focused on new materials for electrochemical energy conversion and

The authors declare no competing nancial interest. storage.

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Chemical Reviews
Sheng-Heng Chung is currently a Ph.D. candidate in the Materials
Science and Engineering Graduate Program at UT-Austin. He
obtained his B.S. (2006) in resources engineering from the National
Cheng Kung University and M.S. (2008) in materials science and
engineering from the National Tsing Hua University in Taiwan. He
was a research assistant in the Safety and Health Technology Center in
Taiwan before joining UT-Austin. His research is focused on advanced
cell congurations for LiS batteries.
Chenxi Zu is currently a Ph.D candidate in the Materials Science and
Engineering Graduate Program at UT-Austin. She obtained her B.E.
(2011) in materials science and engineering from the Beijing
University of Aeronautics and Astronautics (Beihang University) in
China. Her research is focused on high-energy-density LiS batteries,
surface/interface studies, and metallic anode protection.
Yu-Sheng Su is currently working at Intel as a process engineer. He
obtained his B.S. (2005) and M.S. (2007) in materials science and
engineering from the National Tsing Hua University and his Ph.D.
(2013) in materials science and engineering from UT-Austin. His
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Review
research interests are in high-energy-density batteries, green chemistry,
and sustainable technology.
ACKNOWLEDGMENTS
Financial support by the U.S. Department of Energy, Oce of
Basic Energy Sciences, Division of Materials Sciences and
Engineering, under Award No. DE-SC0005397, Seven One
Ltd., and Welch Foundation Grant F-1254 is gratefully
acknowledged.
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