Yao, Yueping, A study of electro materials for lithium-ion batteries, PhD thesis, In-
stitute for Superconducting and Electronic Materials, University of Wollongong, 2008.
http://ro.uow.edu.au/theses/88
Doctor of Philosophy
University of Wollongong
2008
CANDIDATE’S CERTIFICATE
This is to certify that the work presented in this thesis is original and was carried out by
the candidate in the laboratories of the Institute for Superconducting & Electronic
Materials (ISEM) and the Faculty of Engineering at the University of Wollongong, New
South Wales, Australia. It has not been submitted for a degree to any other university or
institution.
Wollongong, Australia
2008
i
ACKNOWLEDGEMNENTS
I would firstly like to express my sincere gratitude and thanks to my research supervisors,
Professor H. K. Liu and Dr. K. Konstantinov, for their consistent academic supervision,
guidance and encouragement throughout may research. I also express my gratitude to the
Director of ISEM, Professor Shixue Dou, for support and financial assistance for my PhD
project. I am deeply indebted to the Australian Research Council (ARC) for the financial
I thank all the hard-working technical and administrative staff in ISEM and the Faculty of
Engineering, in particular Mr. Ron Kinnel, Mr. N. Mackie, and Mr. G. Tillman. They have
provided me with tremendous help in all my experiments. Thanks are also to Dr. T. Silver
Finally, I would like to express my gratitude to all other staff and to my fellow students at
the Institute for Superconducting and Electronic Materials for their constant
encouragement.
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Abstract
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Abstract
Lithium-ion batteries (or rechargeable lithium batteries) are most advanced battery
computers and cameracorders. There are also big potentials for lithium-ion batteries
to be used for electric vehicles (EVs), hybrid electric vehicles (HEVs) and stationary
power storage. In particular, the later will bring a significant contribution to reduce
green-house gas emissions and address global warming and climate change. Materials
lithium-ion batteries with high energy density, high power density, and long cycle
life.
This PhD thesis describes my exploration on developing new anode materials and
cathode materials for lithium-ion batteries. I firstly investigated silicon based anode
materials since silicon has the highest theoretical lithium storage capacity of about
4200 mAh/g when forming Li21Si5 alloys. The reversible lithium storage mechanism
is totally different from that of graphite based anode. It relies on a process called
formation of Li21Si5 alloys can induce more than 400% volume expansion. The
repeated expansion and shrinkage of the silicon electrode will cause cracking and
eventually failure of the battery system. A general strategy has been employed to
solve this problem. Firstly nanosize silicon powders were used to minimize the
carbon matrix to buffer the volume change during the reaction with lithium.
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(high capacity and satisfactory cyclability), compared to bare MCMB and bare
prepared by carbon aerogel method, through which nanosize silicon particles are
Si-C composite anodes was achieved. The good cyclability should be attributed to the
carbon matrix.
Carbon nanotubes have many unique and intriguing properties, including as anode
active to lithium insertion and extraction. A reversible lithium storage capacity of 950
mAh/g has been achieved for CNTs anodes. The solution-based chemical process
enables Sn2+ ions to penetrate into the inner cavity of the carbon nanotubes. The
Transition metal phosphides such as MnP4 and Zn3P2 were discovered to exhibit
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periods. After sintering, the products were purified by acid etching, which is a very
tedious process. Crystalline iron phosphide (FeP4) powders were directly prepared by
the reversible reactivity of FeP4 anodes towards lithium insertion and extraction. The
FeP4 anode exhibited a stable lithium storage capacity about 700 mAh/g.
Lithium iron phosphate has been emerging as a new cathode material for lithium-ion
batteries with low cost. However, lithium iron phosphate has a very lost electronic
Various cation dopings have been studied with the goal to improve the overall
phosphides and manganese phosphates were found to be formed during the sintering
process with the effect of enhancing the electronic conductivity of the materials. The
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Contents
CANDIDATE’S CERTIFICATE i
ACKNOWLEDGEMENTS ii
ABSTRACT iii
CONTENTS vi
CHAPTER 1 INTRODUCTION 1
2.1 Batteries 4
compounds 23
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CHAPTER 3 EXPERIMENTAL
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4.1 Introduction 72
4.2 Experimental 73
4.4 Conclusions 94
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MATERIALS
5.1 Introduction 96
5.2 Experimental 97
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CATHODE MATERIALS
MATERIALS
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FUTURE STUDY
materials 163
REFERENCES 167
PUBLICATIONS 189
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Chapter 1 Introduction
Our modern societies currently are heavily reliant on fossil fuels to supply energy for
all our daily lives. Global warming and climate change are among the most serious
concentrations, primarily due to the burning of fossil fuels. To protect the health and
economic well-being of our global society, we must reduce greenhouse gas emissions
by using clean energy and renewable energy. The combustion of fossil fuels in
vehicles is responsible for about 22% of global CO2 emissions. The rechargeable
Lithium-ion batteries have the highest energy density among all the secondary battery
Although lithium-ion batteries possess a high energy storage capability, they still
cannot meet the requirements for large-scale energy storage and electric vehicles
applications. On the other hand, the global market for small rechargeable batteries is
on an impressive scale and growing, mainly due to the spectacular increase in the use
of mobile communications and portable electronics. All of these factors drive the
performance characteristics, such as high energy density, long cycle life, and
mainly determined by the physical, chemical, and structural properties of the cathode
materials and anode materials used in the battery system. This PhD thesis aims at
exploring and investigating a number of new and innovative anode materials and
cathode materials for lithium-ion batteries. A systematic study has been performed,
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for the lithium-ion battery system. The basic concepts of batteries, rechargeable
batteries and lithium-ion batteries are reviewed. Then, the properties and current
status of all cathode materials for lithium-ion batteries are summarised. These include
LiCoO2 and doped LiCoO2, LiNiO2 and doped LiNiO2, layered LiMnO2, spinel
merits, disadvantages, and challenges of carbon based anode materials, alloy based
procedures are fully described, along with all materials, chemicals, and facilities used
in this work.
capacity element Si and carbon, the composite anode materials can deliver much
higher capacity than bare carbon and also maintain good cyclability.
Carbon nanotubes are a new emerging one dimensional materials with many unique
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vapour deposition (CVD) technique. Tin oxide – carbon nanotubes composites were
prepared to increase the specific capacity by utilizing the high capacity of SnO2.
active in lithium-ion cells and demonstrated a stable lithium storage capacity of about
700 mAh/g.
were obtained through Rietveld refinement on the X-ray diffraction patterns. The
phosphate and magnesium doped lithium iron phosphate cathode materials, in which
magnesium ions are doped into Li sites. It was found that the electrochemical
Finally, an overview and summary of this study are presented in Chapter 9, and
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2.1 Batteries
alternative green energy/power source. There is an increasing need for efficient, high
storage and conversion. In his 2006 State of the Union Address, the U.S. president
George W. Bush claimed, “We must change how we power our automobiles. We will
increase our research on better batteries for hybrid and electric cars.” The discovery of
new electrode materials for batteries could dramatically increase energy density,
reducing the cost of electrochemical power systems, and so open up the capacity to
Batteries are self-contained units that store chemical energy and convert it directly
into electrical energy to power various devices. Batteries are generally categorized
into three classes: (i) Primary batteries. They are discharged once and discarded, (ii)
Rechargeable batteries. They can be repeatedly discharged and charged many times.
The batteries can be restored to their original condition by charging with a reverse
current flow, (iii) Specialty batteries. They are designed to meet a special purpose.
Specialty batteries are mainly used for military and medical applications. Batteries
provide power sources serving all aspects of both our daily lives and industry. The
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(the anode). The cathode is an electron acceptor, such as lead oxide, manganese
dioxide, or lithium cobalt oxide. The anode is an electron donor, such as lead, zinc, or
lithium. The electrolyte usually is a pure ionic conductor that physically separates the
anode from cathode, allowing only ionic transport but not electronic conduction. A
schematic of battery operation is illustrated in Fig. 2.1 [1]. Battery electrolytes are
usually used in the form of a porous electrically insulating material soaked with
solid-state electrolytes. The aqueous electrolytes are normally salts of acids or bases,
and have high ionic conductivity, on the order of 1 S/cm. From the thermodynamic
limitation less than 2.0 V. The nonaqueous organic solvent-based electrolytes have
lower ionic conductivity, on the order of 10-2 – 10-3 S/cm. The operating voltage of an
polymer-based electrolytes and usually have low ionic conductivity in the range of
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charged again for many times over a long period. The chemical energy can be restored
generally divided into lead acid batteries, lithium-ion batteries, and nickel cadmium
batteries, nickel metal hydride batteries. The energy densities of those recharge able
battery systems are compared in Fig. 2.2 [2]. Among all the rechargeable battery
Fig. 2.2 Gravimetric and volumetric energy densities of different rechargeable battery
systems [2].
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In the past, the development of the lithium based battery system was motivated by the
(-3.04 V) element versus the standard hydrogen electrode (SHE) and also the lightest
(MW = 6.94 g/mol, ρ = 0.53g/cm3). Therefore, a battery system with lithium as the
electrode could deliver high energy density. The earliest version of the lithium battery
was the Li/(CF)n battery with a cell potential of 2.8 – 3.0 V. It was proposed that
lithium initially intercalates into the carbon mono fluoride lattice and then forms
Later, in the early 1970s, various primary lithium batteries were developed and
demonstrated in the United States. The Li/SOCl2 cell was one of primary lithium
battery systems [5]. Sanyo also successfully developed and marketed lithium batteries
with the Li/MnO2 cell [6]. Most primary lithium batteries have been developed for
medical and military applications. For example, implantable cardiac defibrillators use
Li/Ag2V4O11 batteries [7, 8]. The development of rechargeable lithium batteries came
from the discovery of some inorganic compounds that can react with lithium ions in a
reversible way. This led to the development of battery systems that use lithium as
and molybdenum sulfide (MoS3) as cathode [9, 10]. The discovery of so-called
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lithium batteries. The intercalation materials host lithium ions inside their crystalline
structure. The lithium ions can be reversibly inserted into and extracted from the hosts.
phase change and with no damage to the material structure. From that time, a new
electrochemistry for energy storage started to spring up, involving more and more
solid state chemistry. However, many difficulties were encountered during the early
containing lithium had to be identified. The electrolyte must consist of some lithium
to be found.
Lithium metal was initially used as the negative electrode in the rechargeable lithium
charge/discharge cycling, resulting in short cycle life and cell shorting. A short circuit
could cause serious safety problems such as fire and explosion, and the eventually led
batteries. Substituting Al for lithium metal solved the dendrite problem, but the
electrode could only be charged and discharged for a limited number of cycles due to
significant volume change [11]. Since then, many lithium alloys have been developed
as alternative anode materials. The energy densities of lithium alloys normally are
are quite substantial (200 – 600 %) [12-16]. These cause a fast disintegration of the
alloy anodes by cracking and crumbling. As a result, short cycle life and low cycling
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efficiency are induced. In the late 1980s, graphitic carbon was found to be
dimensionally stable for lithium insertion and extraction. Intercalation of lithium ions
corresponding to the composition LiC6 results in only about a 10% increase in the
layer distance [17, 18]. Therefore, graphite became the choice of anode materials for
The cathode material is also a critical electrode material for the development of
rechargeable lithium batteries. The search for cathode hosts has been continued for
more than two decades. Except for low-dimensional materials, the three dimensional
framework structure compound V6O13 was also found to function for lithium perfectly
intercalation and de-intercalation [19]. The family of lithium metal oxides LixMO2
(where M is Co, Ni, or Mn), was first reported as a source of cathode materials for
are based on organic systems, which consist of organic solvents and lithium salts. The
moisture is strictly controlled to avoid any side reaction. Polymer electrolytes have
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since 1990. This battery technology is also called rocking-chair technology. Sony
C/LiCoO2 in 1991 [24]. This new class of rechargeable batteries had a potential
exceeding 3.6 V (almost three times that of alkaline systems) and energy densities of
120 – 150 Wh/kg (two to three times that of Ni-Cd and Ni-MH batteries). Today,
lithium-ion batteries are becoming the dominant power sources for portable electronic
telecommunication.
Lithium metal free lithium batteries were originally termed “rocking chair” batteries
(RCB) by Armand [25]. The basic concept of operation for the RCB system was
electrodes in different reactant concentrations [26]. After the RCB concept was
revealed, this concept was demonstrated using transition metal compound anodes and
cathodes [27-28]. Later, new names for this technology appeared: lithium ion,
Shuttlecock and Swing Electrode System, etc., but the fundamental concept remained
the same.
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In a lithium-ion cell, the Li+ ions shuttle between the cathode and anode hosts during
the discharge and charge processes. The principles of lithium-ion battery operation
are shown in Fig. 2.3 [29]. Lithium ions are extracted from the cathode, go through
the electrolyte and separator and are inserted into the anode structure. The reverse
process happens during discharging. In order to achieve high cycling efficiency and
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long cycle life, the movement of Li ions in anode and cathode hosts should not change
or damage the host crystal structure. The design of a lithium-ion battery system
requires careful selection of electrode pairs to obtain a high operating voltage (Vc).
The operation of lithium-ion batteries obeys the thermodynamic laws. Therefore, the
equation:
ΔG = ΔH - TΔS (2.2)
ΔH – reaction enthalpy
ΔS – reaction entropy
The free energy ΔG is also related to cell voltage for the electrochemical reactions
ΔG = -nFE (2.3)
Where n is the number of electrons transferred; F is the Faraday constant (96500); and
E is the cell voltage (the potential difference between positive electrode and negative
electrode).
A high Vc can be realized with an anode and cathode that have, respectively, smaller
and larger work functions φa and φc. The open-circuit voltage Voc of the cell can be
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where e is the electronic charge. A schematic energy level diagram showing the work
E
Ec
ϕa
EF
φc Eg
Voc
EF
Ev
The Fermi energies (EF) of the anode and cathode must lie within the band gap (Eg) of
the electrolyte. Therefore, the anode and cathode materials are thermodynamically
stable in contact with the electrolyte, and there will be no side reduction or oxidation
of the electrolyte.
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They provide lithium ion sources (Li+) for the Li-ion “shuttle” between the cathode
and the anode. Since carbon materials are widely used as anodes in lithium-ion
batteries, which have a potential close to that of Li/Li+ reference electrode, the voltage
Therefore, cathode materials must meet some strict requirements: (i) The cathode host
must be structurally stable for repeated lithium ion intercalation and de-intercalation.
The variation of the lattice structure should be as small as possible during the battery
operation process to maintain long cycle life. (ii) The cathode materials must have a
high potential relative to Li/Li+ reference electrode to enable high operating voltage
(high energy density). (iii) The cathode materials should contain as great an amount of
from the host crystal structure (high capacity). (iv) The cathode materials should have
high electronic conductivity and high lithium chemical diffusion coefficient to keep
high rate capacity (high power density). (v) The cathode materials should be low cost,
compounds which are suitable as cathode hosts for lithium-ion batteries is quite
limited, due to the critical requirements such as high energy density, good cyclability,
and safety.
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battery production, currently, new layered and spinel structure cathode materials are
new generation of lithium-ion batteries for power storage and electric vehicle (EV)
applications. The layered and spinel structure cathode materials for lithium-ion
batteries mainly include layered structure LiCoO2, LiNiO2, LiMnO2, and spinel
compounds have also emerged as new cathode materials for lithium-ion batteries.
In 1980, J.B. Goodenough et al. proposed and tested LiCoO2 as cathode for lithium
batteries. It was surprisingly found that LiCoO2 cathode had a high charge and
discharge voltage in the range of 3.6 – 3.8 V in the cell configuration of LixCoO2 / Li
[30]. After almost 10 years, SONY made the first batch of lithium-ion batteries with
the combination of a LiCoO2 cathode and a carbon anode [31]. Since then, lithium-ion
batteries have been under massive commercial production and dominated the
LiCoO2 compound has a layered α-NaFeO2 type structure (SP: R3m), with the
oxygen in a cubic close-packed array. This structure is closely related to the rock-salt
structure. The Li+ and Co3+ ions are located at octahedral 3(a) and 3(b) sites and
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crystal lattice has lattice parameters of a = 2.816 Å and c = 14.08 Å. Fig.2.5 shows a
electrode in lithium cells using in situ X-ray diffraction (XRD) and concluded that the
reaction at the LiCoO2 electrode in lithium cells can be divided into three regions. In
the region 0 < x < 1/4 in Li1-xCoO2, the coexistence of two hexagonal phases was
observed. The reaction in terms of lithium insertion and extraction in this region is a
topotactic two-phase reaction. In the region 1/4 < x < 3/4 in Li1-xCoO2, the reaction
taken as a whole is a single phase reaction. In the region 3/4 < x < 1, the reaction is a
LiCoO2 delivers a theoretical capacity of about 274mAh/g. However, only part of the
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lithium can be reversibly extracted and inserted due to structural restriction [33]. If the
charging voltage is limited to 4.2 - 4.25 V versus Li/Li+, LiCoO2 cathode can provide
oxide (or cobalt carbonate) and lithium carbonate (or lithium hydroxide) at high
for the LiCoO2 compound have also been reported [5, 6]. In general, the different
synthesis methods using high temperature sintering have no significant impact on the
synthesized at low temperature demonstrated a high specific capacity in the initial few
An interfacial layer, called the solid electrolyte interphase (SEI), usually is formed on
the surface of the LiCoO2 electrode during the charge/discharge process. The
formation of this interfacial film, caused by the reaction between the electrolyte and
of the LiCoO2 electrode. The characterization of this interfacial film has been
conducted by many researchers via a.c. impedance, electron microscopy and atomic
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Since mineral resources of cobalt are very limited, it is better to partially replace Co
with other cheap transition metal elements in the LiCoO2 crystal structure to reduce
the cost of cathode materials. LiNiO2 can form a solid solution with LiCoO2 over the
investigated both Co rich and Ni rich LiNixCo1-xO2 compounds. It was found that the
electrochemical performance was poor, if prepared below 750 ºC. However, if the
sample was prepared at 750 ºC, it showed better reversibility, higher than that of a
Co-rich composition [40]. Tsutomu Ohzuku et al theoretically studied the solid- state
redox potentials of LiCoO2, LiCo1/2Ni1/2O2, and LiNiO2. They found that a one-to-one
mixture of Co and Ni in the layered structure induced a mixing effect on the redox
potential of 3.58 V [41]. Al, which is not a transition metal, can also substitute for Co
in the LiCoO2 structure, because the ionic radii of Al3+ (0.54 Å) and Co3+ (0.55 Å) are
very close, and α-LiAlO2 is isostructural with LiCoO2. LiAlxCo1-xO2 compounds (0.1
160mAh/g was observed for LiAl0.15Co0.75O2 cathode with stable cyclability [42].
The capacity and cyclability of LiCoO2 cathode can be further improved by coating a
metal oxide or phosphate on the surface of the cathode material particles. The coated
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between 2.75 V and 4.4 V. The mechanism could be attributed to minimizing the
reactivity of Co4+ with the acidic HF in the electrolyte in the fully charged state [43,
44]. It has also been identified that a coating of high-fracture-toughness metal oxide
such as ZrO2, Al2O3, TiO2 or B2O3 on LiCoO2 particles can effectively suppress the
change in the lattice constants during the lithium intercalation and de-intercalation
processes, and therefore suppresses the phase transition. The capacity retention of
LiCoO2 cathode can be dramatically enhanced through such a coating [45, 46].
The use of LiCoO2 as the cathode material in large scale lithium prototype batteries
having a flat plate construction inside, were assembled and tested [47]. Cylindrical
“C” size cells showed high capacity and a cycle life of more than 100 cycles.
material in lithium ion batteries, some drawbacks have to be addressed and cannot be
ignored. The major drawback is the high cost for LiCoO2 due to the high price and
limited natural abundance of Co. Another problem is the toxicity of Co, which causes
a serious environmental impact when batteries are disposed of. These two factors
forbid the application of LiCoO2 as the cathode material in any large batteries for
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LiNiO2 is an attractive candidate for lithium ion batteries because the natural
cathode is close to that of LiCoO2, i.e. 275 mAh/g. However, it can deliver a practical
specific capacity in the range of 185 – 210 mAh/g by charging up to 4.1 – 4.2 V vs.
LiNiO2 cathode suffers from a high capacity fading rate and poor thermal stability in
the highly oxidized state (Ni4+). LiNiO2 is isostructural with LiCoO2. The lattice
dimensions of the LiNiO2 unit cells (ah = 2.9 Å, ch = 14.2 Å, ch/ah = 4.9 Å in the
hexagonal setting) are very close to the parameters of a cubic unit cell (ac = ch / 2 3
= 4.1 Å), implying that nickel and lithium ions can easily displace each other in the
crystal structure. Once nickel ions occupy the Li ion position (3a) in the LiNiO2
structure, Ni3+/Ni4+ ions will block Li+ diffusion, resulting in a low lithium diffusion
Poor cycle ability of LiNiO2 electrode has been reported, but the cycle life of the
properly synthesized, the cycle life of LiNiO2 can be improved to an acceptable level.
No evolution of the structure of the LiNiO2 compound was observed even after 1200
cycles. Solid-state reactions are generally used to synthesize the LiNiO2 compound
which can be prepared by sintering a mixture of almost any Li, Co and O sources, the
precursors for the preparation of LiNiO2 have to be carefully chosen. The typical
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hydroxide), nickel hydroxide and lithium nitride, nickel oxide and lithium hydroxide
or by the use of Na2O2 and Ni sources, followed by ion exchange with LiNO3 at
elevated temperature. With careful control of all of the above factors, LiNiO2
batteries could be obtained. Li/LiNiO2 and C/LiNiO2 cells have been assembled using
liquid electrolyte. Results using personal area network (PAN) based hybrid polymer
electrolyte were also obtained [49]. Long cycle life, excellent high temperature
performance and low self-discharge rates have all been demonstrated using
including varied nominal Li: Ni ratios, different sintering temperatures and different
atmospheres [51]. When sintered at low temperatures such as 650 ºC or 700 ºC, the
impurity phases Li2O and NiO were present in the final product. It was also revealed
that too much excess Li (Li:Ni = 1.14:1) also induces the presence of Li2O impurity.
An appropriate amount of excess lithium in the precursors can compensate for the loss
product Li1-xNi1+xO2 has a disordered cation distribution, with nickel ions partially
occupying the lithium ion sites in the layered structure, resulting in very poor
electrochemical performance. So, the synthesis temperature for LiNiO2 should be kept
below 860 ºC to avoid any decomposition and oxygen evolution. The properly
prepared LiNiO2 cathode showed a discharge capacity of 180 mAh/g with good
reversibility. A.c. impedance analysis was performed on LiNiO2 cathode tostudy the
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in air has a high charge-transfer resistance (RCT) and low exchange current density.
Many efforts have been made to improve the electrochemical performance of LiNiO2
cathode by partial substitution of Ni by other metal elements such as Mg, Al, Mn, Cr,
Fe and Ti respectively [52 - 54]. LiCoxNi1-xO2 solid solutions ( x = 0, 0.25, 0.5, 0.75
and 1) were prepared by sintering the precursor reagents LiOH.H2O, NiO, and CoO at
750 ºC for 24 h under oxygen flow [55]. Electrochemical testing showed that LiNiO2
cathode had a higher initial capacity, but less stability on cycling comparing to
satisfactorily good, with a capacity fading rate of 0.3 and 0.18mAh/g per cycle
The structural integrity of the LiNiO2 cathode could be preserved via inert Al3+ cation
doping to prevent overcharge of the electrode, which is beneficial for extending the
cycle life of the cell. LiAlxNi1-xO2 ( x = 0, 0.1, 0.2 and 0.25) solid solutions were
stream for 24 – 40 h [56]. Single phase LiAlxNi1-xO2 solid solutions were obtained.
The Al doped LiAlxNi1-xO2 cathodes demonstrated almost the same charge and
discharge behavior as the LiNiO2 cathode. Both the initial charge and discharge
However, the cyclability of the cathode was improved for doped LiAlxNi1-xO2
cathodes in the voltage window of 3.0 – 4.3 V. This could be because the effects of
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Al3+ dopant prevent Li+ extraction in the voltage range of 4.1 – 4.3 V, thus avoiding
electrons of Al3+ and Ni4+ are 3S0, so that this material is an electronic insulator. Li+
electrons can be removed from either Al3+ or Ni4+. Residual Li+ and Al3+ are useful to
suppress the dimensional change of the interlayer distance due to the extraction of Li+
ions. This effect contributes to maintaining the structural integrity of the cathode and
The LiMnO2 system contains some of the most intensively investigated cathodic
materials for rechargeable lithium batteries, due to its low-cost, non-toxicity, and high
energy density. Theoretically, if all the lithium can be reversibly extracted from and
inserted into the LiMnO2 structure, it can deliver a specific capacity of about 270
mAh/g. LiMnO2 compound has two types of crystal structure e.g. a layered structure
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an ion exchange technique from NaMnO2 [57, 58]. Firstly, layered NaMnO2 was
– 730 ºC under flowing argon. Then, LiMnO2 was obtained by refluxing NaMnO2
with excess LiCl in n-hexanol at 145 – 150 ºC, during which Li+ ions replace Na+ ions.
Neutron diffraction confirmed the monoclinic layered structure with unit cell
º. The orthorhombic LiMnO2 has an ordered rock-salt structure in which LiO6 and
MnO6 octahedra are arranged in corrugated layers. It can be easily prepared via
lithium-ion cells. It was found that up to 0.95 lithium per formula of LiMnO2 can be
extracted from m-LiMnO2 cathode on the initial charging [31]. When lithium ions are
removed from LiMnO2, the Jahn-Teller Mn3+ ions are oxidized to Mn4+, inducing the
loss of the monoclinic distortion. X-ray diffraction has identified that the layered
LiMnO2 is converted to a spinel structure during the charge and discharge cycling
[60]. The mechanism for this structural conversion on cycling could be related to the
array of oxygen ions is much closer to the spinel structure, and also, the spinel
close-packed oxygen lattice and thus is thermodynamically stable. On the other hand,
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showed an initial reversible capacity of 170 mAh/g and exhibited little capacity loss
with cycle number when cycled either the 3 V or the 4 V plateau, but rapid capacity
loss when cycled over both voltage plateaus [61]. It was also found that the o-LiMnO2
was gradually converted to the single phase spinel structure on cycling [62]. The
metal elements such as Al, Co, Ni, Cr, etc.. The doped m-LiMxMn1-xO2 compounds
that LiAlO2 has a theoretical intercalation voltage plateau of 5.4 V vs. Li/Li+ reference
plateau and cathode energy density. Y. Jang et al. first reported the stabilization and
was found that m-LiMnO2 becomes the major phase when oxygen partial pressures
are below 10-5atm. Energy dispersive X-ray mapping using scanning and transmission
148mAh/g reversible capacity at C/5 rate and 182 mAh/g at the C/15 rate with
The stability of Co doped LiMnO2 was predicted by ab initio calculations using the
exact muffin-tin orbital (EMTO) method [64]. The calculations were performed for
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less stable than the orthorhombic structure in the DLM state. When there is 30 at. %
with ~ 60 at.% manganese replaced by Co, the desired layered R3m LiMnO2 structure
prepared by solid-state reaction. However, such a prediction does not represent the
successful preparation of Co doped LiMnO2 with the layered structure via soft
chemical approaches. P.G. Bruce et al. [65, 66] have successfully synthesized
LiCoxMn1-xO2 (0 ≤ x ≤ 0.5) using a solution based route coupled with ion exchange.
Five compositions of LiCoxMn1-xO2 ( x = 0.1, 0.2, 0.3, 0.4, and 0.5) were examined by
powder neutron diffraction. They were all identified as layered structure with the
space group R3m. The lattice parameter a decreases with increasing of Co content,
while c increases with increasing Co content. The Co doped LiMnO2 cathodes could
be charged and discharged over a wide voltage range of 2.6 – 4.8 V. The
general trend, with increasing Co dopant level, LiCoxMn1-xO2 cathodes exhibit lower
initial capacity, but better cyclability. Through analyzing the incremental capacity
plots, they found that the transformation to spinel is relatively facile for LiCoxMn1-xO2
with low Co content (< 30 at. %), but much slower above this composition. This could
be responsible for the increased stability as the Co doping content increases. They
also concluded that Co doping can significantly modify the structure chemistry and
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the capacity loss on the first cycle, and that higher Co level doping can suppress the
reported by Dahn et al. in 1992 [67]. The electrochemical properties deteriorated with
increasing Mn content. The optimum electrochemical behavior was found for the
existence of Ni2+ and Mn4+ rather than Ni3+ and Mn3+. Noguchi et al. [71]
Li2MnO3 can be prepared by the usual methods. They are rhombohedral (R3m) when
x ≤ 0.3, and have monoclinic symmetry (C2/m) when x ≥ 0.5. Ex situ XRD and
mA/cm2 and exhibited average discharge capacities of 165 mAh/g and 150 mAh/g
respectively.
The layered LiMnO2 structure can also be effectively stabilized at room temperature
by Cr doping. The groups of both Davidson and Ammundsen have described the
cathode materials [72 - 76]. The Li1.2Cr0.4Mn0.4O2 cathode compound was prepared
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diffraction confirmed the layered hexagonal structure in the R3m space group, with
unit cell parameters of a = 2.886 Å and c = 14.372 Å. k edge X-ray absorption near
edge specter (XANES) showed that Cr is trivalent and in octahedral sites, and Mn is
model for Li1.2Cr0.4Mn0.4O2, in which the transition metal layers consist of clusters of
cathodes exhibited very stable cyclability, both at room temperature (20ºC) and at an
elevated temperature of 55ºC, with average capacities of 135 mAh/g and 170 mAh/g,
and micro-Raman spectroscopy analysis [77]. It was identified that the trivalent Cr
ions are fixed to the octahedral site in the (Mn, Cr) O2 layer before and after
electrochemical cycling. The Cr doping can reduce the local structural variation of
The spinel-type oxide LiMn2O4 and its derivatives have been studied for more than a
decade as cathode materials for lithium ion batteries. The lithium insertion and
is similar to LiCoO2 and LiNiO2. Significant efforts have been made to extend the
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capacity. Spinel LiMn2O4 has the advantages over the Co- and Ni- containing
LiMn2O4 is only 148 mAh/g. The high rate of capacity fading on cycling is another
serious drawback for LiMn2O4 spinel electrodes. Fortunately, the problems related to
the capacity fading can be circumvented by doping Mn with other transition metals M
attractive cathode candidate for lithium ion batteries. Some doped LiMxMn2-xO4
Spinel LiMn2O4 belongs to the cubic system with a space group of Fd3m, in which Li+,
Mn3+/4+ and O2- ions occupy tetragonal 8a and octahedral 16d and 32e position in the
network of face-sharing tetrahedra and octahedra for lithium ion diffusion. In the [M2]
O4 spinel framework, 75% of the metal cations occupy alternate layers between the
ccp oxygen planes; the remaining 25% of the metal cations are located in the adjacent
sufficiently high binding energy to maintain an ideal ccp oxygen array when lithium
ions are extracted from the structure. The unit cell of the spinel structure expands and
contracts isotropically [78]. The electrodes with such a structure are likely to be more
stable under electrochemical cycling than those in which there is a large anisotropic
Li[M1.67Li0.33]O4 (M = Mn, Ti) are extremely tolerant to cycling, because the volume
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variation of the cubic unit cell is less than 1% within controlled compositional limits
[79, 80].
The LiMn2O4 spinel electrode offers a 4 V voltage versus lithium in the compositional
range 0 ≤ x ≤1 in LixMn2O4. Lithium ions can further insert into LiMn2O4 to form
phases: cubic phase LiMn2O4, and tetragonal phase Li2Mn2O4. The tetragonal phase
grows at the expense of the cubic phase. In the LiMn2O4 spinel structure, the strong
Mn-O bond maintains the structural integrity of the electrode during lithium ion
insertion and extraction. However, the Jahn-Teller distortion effect starts at Mnn+ =
3.5 (c/a = 1) and reaches a maximum at the valence of Mnn+ = 3 (c/a = 1.16), which
reduces the symmetry of the cubic spinel phase to tetragonal phase Li2Mn2O4 and
change of the unit cell would cause the crystal structure of the electrode to be
In practice, when the discharge voltage is close to 3.0 V, it is plausible that a few
average Mn oxidation state falls below 3.5. A Jahn-Teller distortion might occur at the
between the oxygen arrays of the cubic and tetragonal phases could then cause a
highly crystalline electrode particle to be degraded at the crystal surface, which would
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damaging effect can be reduced by suppressing the onset of the Jahn-Teller distortion
oxidation state slightly above 3.5 at the end of the 4.0 V discharge plateau.
To combat the Jahn-Teller distortion effect, doping the LiMn2O4 spinel structure with
LiMn2O4 is + 3.5, when partially replacing Mn with other low valence ions, the
the 4 V discharge (lithium insertion into the spinel structure), the average valence of
Mn will be kept slightly above +3.5. Because the Jahn-Teller distortion starts at Mnn+
= 3.5, low valence ion doping can suppress the Jahn-Teller effect in LiMn2O4 spinel.
amounts of dopant ions. It is believed that the redox reaction accompanying lithium
insertion and extraction relies on the valence change of Mn in LiMn2O4 spinel [80].
Doping Mn with other ions inevitably reduces the amount of lithium which can be
reversibly extracted from the spinel structure. So, a trade-off has to be made to achieve
the optimum balance between suppressing the Jahn-Teller effect and keeping an
appropriate capacity.
A series of alien cation doped spinel compounds with the general formula of
LiMδMn2-2δO4 (M = Co, Zn and Mg; δ = 0.02, 0.03, and 0.05) were synthesized [79].
In this type of doped LiMδMn2-2δO4 spinel, one fraction of M ion substitutes for 2
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partially substitute for Mnn+ ions at 16d sites. Thus, there are unoccupied 16d sites in
[79].
Compounds Lattice Theoretic Fully Oxidised Theoretic Initial The av. Rate
Constants Mn oxidation Composition al discharge of capacity
(A) state in ( n+Mn=4) Capacity capacity fade
LiMδMn2-2δO4 (mAh/g) (mAh/g) (mAh/g per
cycle)
As is shown, not all of the lithium can be electrochemically extracted from the doped
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could also help to suppress the chemical decomposition of the electrode at a high level
of the charge. The reasons for the degradation of spinel electrodes on cycling have
been identified as: (i) the structural damage to the electrode due to the volume change
in the unit cell caused by Jahn-Teller distortion in the 3V discharge regime; (ii) the
disproportionation reaction of Mn3+ from the cathode with the electrolyte: Mn3+ →
Mn2+ + Mn4+; and (iii) instability of the organic electrolyte at high voltage. The dopant
effect can combat (i) to suppress Jahn-Teller distortion and preserve the structural
integrity of the spinel electrode during cycling. Since we use LiPF6 electrolyte in
EC+DMC, which can resist oxidation even at 5 V, cause (iii) could be excluded. Co
doped spinel electrodes have demonstrated excellent cyclability. It is possible that the
Co dopant effect prevents the disproportionation reaction of Mn3+ with the electrolyte
[81]. Wakihara et al. proposed that the improvement in cycling behavior of the Co
spinel skeleton structure. This is because the binding energy of CoO is larger than that
of MnO [82].
The Co and Cr doped LiMn2O4 spinels synthesized by solid-state reaction have shown
the greatest improvement in cycle life without dramatically sacrificing the initial
capacity [83, 84]. However, the solid-state reaction produces heterogeneous spinels
0.04, 0.06 and 0.1) have been synthesised by the Pechini method, in which the cations
can be mixed on an atomic scale [85 – 87]. With more homogeneous distribution of
the dopant Cr ions in the spinel structure, the electrochemical properties of LiMn2O4
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whether there is a mixture of Li+ and Mn3+/4+ at the 8a and 16d sites and whether
dopant Cr ions are present instead of Mn ions at 16d sites. Consequently, Lu et al,
Fig. 2.6 shows the neutron diffraction patterns obtained for pure LiMn2O4 and
LiCr0.04Mn1.96O4 spinels. The Rietveld method and LHPM program were employed to
refine the neutron diffraction patterns [89]. The determination of the crystal structure
model of the crystal structure, and comparing the calculated diffraction pattern with
the observed one [90]. For undoped LiMn2O4, there is a substantial difference
between the experimental data and the calculated pattern. When we assumed that
there was some mixing of Li+ and Mn3+/4+ at 8a and 16d sites, when it was assumed
that all of the Li ions were in 8a sites and the Mn ions were in 16d sites, the best fit
was obtained. During the refinement of the LiCrxMn2-xO4 structure (x = 0.02 and
0.04), when we assumed that there were some Cr ions in 8a Li sites, the differences
between the experimental data and the calculated pattern were obvious. Only when it
was assumed that all Cr ions were in 16d Mn sites, did the calculated intensities best
fit the observed ones, and the differences were almost negligible. It was clearly
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elucidated that there was no mixing of Li and Mn ions in the LiMn2O4 spinel structure
and that the dopant Cr ions occupy 16d Mn sites in doped LiCrxMn2-xO4 spinels.
retention on cycling compared to the undoped LiMn2O4 spinel. The Cr doping effect
could also modify the surface states of the spinel electrode in the highly charged state,
0.6
0.4
0.2
0.0
-0.2
20 30 40 50 60 70 80 90 100 110 120 130
2 Theta (degree)
0.6
0.4
0.2
0.0
-0.2
20 30 40 50 60 70 80 90 100 110 120 130
2 T heta (degree)
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Iron based oxides have long been pursued as cathode materials for lithium-ion
batteries, because iron (Fe) is abundant, inexpensive, and less toxic than Co, Ni, or
Mn. LiFePO2 was initially prepared by ion-exchange from α-NaFePO2, but showed
little capability for reversible lithium intercalation and de-intercalation [91]. Later,
attention has been shifted to compounds with a NASICON (sodium super ionic
conductor) framework, allowing high mobility for lithium ion diffusion. This class of
compounds are built on corner-sharing MO6 octahedra (where M is Fe, Ti, V, or Nb)
and XO4n- tetrahedral anions (where X is S, P, As, Mo or W). The choice of the
dependent on the redox couple of the metal atom present in the structure. The
transition-metal redox couples are actually stabilized, and the potentials are made
more positive by the presence of the XO4 tetrahedra in the structure, due to strong
polarization of the oxygen atoms towards the X-cation and lowering of the covalent
In 1997, J.B. Goodenough et al. discovered the electrochemically active lithium iron
phosphate olivine compounds [92 -93]. This is a new cathode material with
friendliness. It is expected that lithium iron phosphate will have a significant impact
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metal
• Excellent stability during cycling when used with common organic electrolyte
systems (Since LiFePO4 does not react with the electrolyte) and long cycle life
overcharge, there is less heat released and thus less risk of fire or explosion;
• Environmentally benign;
• Low cost.
However, lithium iron phosphate cathode material also has several disadvantages,
which impede its industrial applications. These include: (i) very low electronic
conductivity in its pure form, on the order of 10-9 S cm-1; (ii) slow lithium diffusion in
the solid phase; and (iii) Low rate capacity. Those drawbacks can be overcome by
various strategies, including carbon coating, conductive additives, alien cation doping,
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MO6 octahedra (M = Mn, Fe, Co, Ni, etc.) to produce a 3D network [94, 95]. Amongst
the various polyanion compounds that are known, this olivine structure has the most
occupy half of the octahedral sites and X atoms one-eighth of the tetrahedral sites of a
According to Fig. 2.7, the two octahedral sites (M1 and M2) are crystallographically
distinct and have different sizes, which favors ordering in MM’XO4 olivines
containing M and M’ ions of different sizes and charges. In the actual structure
(Figure 1b), the M2 octahedron has mirror symmetry with M1, the M-O bond
distances are greater than in M1, and it is slightly distorted compared to the ideal
model. The M1 sites form linear chains of edge-sharing octahedra running parallel to
the c-axis in alternate a-c planes, and the M2 sites form zigzag planes of corner-shared
octahedra running parallel to the c-axis in the other a-c planes [16]. Each M1 site
shares its edges with two M2 sites and two X sites, while there is one edge shared by a
M2 site with an X site. The distortion of the array is related to the repulsion of positive
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Fig. 2. 7 The crystal structure of olivine LiFePO4 along [001]. Left: Expanded view of
the framework built on FeO6 octahedra and PO4 tetradedra. Right: Restricted view of
Li, Fe, and P distribution between two distorted h.c.p. (hexagonal close packed)
oxygen-dense layers (PTd[LiFe]octO4). LiO6 octahedra share edges and Li ions may
On the removal of lithium, FePO4 phase is formed. LiFePO4 and FePO4 have
conversion of the crystal structure between LiFePO4 and FePO4 is illustrated in Fig.
2.8 [97].
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Fig. 2.8 Crystal structures of orthorhombic LiFePO4 (left) and trigonal quartz-like
FePO4 (right).
The striking similarity in crystal structure similarity between LiFePO4 and FePO4 is
responsible for the superior reversibility of the cells on continuous cycling. The
connections among the different types of atoms are also shown. According to Fig. 2.8,
both phases have the same space group. On extraction of lithium from LiFePO4 [in
< x < 1), where x is the number of lithium ions that are extracted from a unit cell], the
host matrix structure changes slightly, with a contraction in the a and b lengths but a
small increase in the c length. The volume is reduced by 6.81% and the density by
2.59%. Even though the overall changes to the FePO4 framework are only slightly
displacive, there is still a limit to the reversible first-order transition reaction between
the two phases [98]. This is because the transition would require a cooperative elastic
deformation of the framework. In other words, the principal change in the framework
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on delithiation is an adjustment due to the coulombic repulsion between the O2- ion
Fig. 2.9 displays a 3D structural model of LiFePO4. The unit cell contains a total of 28
atoms [99, 100]. In the structure, the cations that occupy the M2 sites (Fe sites in
LiFePO4) form a corner-sharing network of octahedra in the (010) plane, and the
cations on M1 (Li) sites form octahedra edge-sharing chains in the [100] direction.
For LiFePO4, there are three different O sites, and the crystal can be viewed as
interconnected but distorted LiO6 and FeO6 octahedra, sharing oxygen vertices with
PO4 tetrahedra [3]. In particular, the O-O distance in the PO4 tetrahedron is small and
three of its edges are shared by the octahedra. Figure 4d shows that the FeO6
octahedra are linked through common corners in the bc plane and the LiO6 octahedra
form edge-sharing chains in the b direction. One FeO6 octahedron has common edges
with two LiO6 octahedra, while the PO4 groups share one edge with an FeO6
The separation between the octahedra and the tetrahedra hinders the ionic
conductivity, because the PO4 tetrahedra will bridge the two adjacent FeO6 octahedra
planes, which constrains the free volume in which the Li+ ions can move. Thus the
electrode supports only small current densities at room temperature compared to other
electrode materials. If the current density is increased, it will not reduce the open
circuit voltage Voc; rather it decreases, reversibly, the cell capacity (i.e. reducing the
current restores the capacity). Also, the low value of the electronic conductivity is
believed to be due to the large electron effective mass in the structure. Nevertheless,
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ideally up to 0.9 Li+ ions/formula unit can be reversibly intercalated when electronic
conductors (i.e. carbon and dopant atoms) are introduced. The ions will diffuse
tetrahedra [101-102].
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Fig. 2.9 Model displaying the connection among FeO6, LiO6, and PO4 structural
achieved by carbon coating. Carbon can be added into the bulk of the LiFePO4
material via either in situ (formed during the preparation process of the active
material) or ex situ (mixed with carbon powders) methods. Graphite was found to be
the best carbon source, and it offers the highest electronic conductivity for LiFePO4.
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electron transfer.
Carbon is often deposited on the surface of each LiFePO4 particle and forms a thin
that the lithium ions from the electrolyte solution can penetrate it to reach the surface
of the LiFePO4 particle with little resistance. Without carbon, the utilization of the
pure material, even at relatively low discharge rates, is poor, due to the voltage
reaching the cutoff potential much before any transport limiting factors such as
particle size become important; thus the electrode becomes ohmically limited. It has
been estimated that for solid-state synthesis techniques, approximately 20 wt% of the
cathode needs to be carbon in order for LiFePO4 to reach its theoretical capacity [12].
LiFePO4 materials were reported to reach conductivity values of > 10-2 S cm-1 at
rates, and retain significant capacity with little polarization at rates as high as 6000
mA g-1 (40C rate). Experiments have been carried out to study LiFePO4 samples
doped with various cations, including Mg2+, Al3+, Ti4+, and Zr4+.
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samples sintered at various temperatures and sectioned from pellets. They clearly
show that all doped compositions Li1-xMxFePO4 (M = Mg, Al, Ti, Nb or W) have
The study also examined the relationship between the conductivity and the dopant
concentration. For example, in the Nb sample, it was observed that doping levels of
0.1, 0.5 and 1.0 atom% Nb resulted in room temperature conductivities of 1.1 x 10-3,
4.1 x 10-2, and 2.2 x 10-2 S cm-1 respectively, for samples fired at 700°C. At higher
doping levels of 2 and 4 atom%, Nb-enriched impurity phases appeared, and the
conductivity was reduced to 2.8 x 10-3 and ~10-6 S cm-1 respectively. Thus, it seemed
that there was a lack of proportionality between the dopant level and the conductivity
crystal size, such as in the nanometer domain. Smaller crystals mean a higher surface
area for lithium insertion/extraction reactions and higher specific capacity due to
more utilization of the active material. Nanosize LiFePO4 powders have been
as the oxidizing agent. The as-prepared LiFePO4 powders have a relatively high BET
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electrochemical performance, with a capacity near the full theoretical capacity (170
mAh/g) when cycled at the C/10 rate [109]. Nanocomposites of LiFePO4 and
of the Fe redox centers in this insulating material. The resultant LiFePO4/C composite
achieves 90% theoretical capacity at C/2 rate, with very good rate capability and
excellent stability [110]. It was also found that the nanophase phosphide network that
Lithium metal (lithium foil) was traditionally used for anodes in lithium primary
charge/discharge cycles. These lithium dendrites are porous, have high surface area,
and are very reactive in organic electrolytes. Once lithium dendrites grow and
penetrate the separator after a certain number of cycles, it will cause short circuiting
and lead to fire or explosion. Therefore, this problem has driven research to find
The basic requirements for anode materials used in rechargeable lithium batteries
include:
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(i) The potential of lithium insertion and extraction in the anode versus
(ii) The amount of lithium which can be accommodated by the anode material
(iii) The anode hosts should endure repeated lithium insertion and extraction
Carbon materials are currently used in commercial lithium battery production. The
most widely used carbon anode materials are various types of graphitized carbon.
Graphite exists in various crystalline and amorphous forms. Carbon anode materials
can be produced from a variety of sources, such as natural graphite, oil, pitch, coal tar,
benzene, polymer resins, hydrocarbon gas, etc. In general, carbon anodes can be
categorized into:
(1) Graphite.
(2) Hard carbon - non-graphitized glass-like carbon which does not graphitized
Schematics of the structures of these three types of carbons are shown in Fig. 2.10.
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Graphite consists of ABAB layers (graphene layers), which are held together by van
der Waals forces. Each graphene layer contains sp2 bond. Lithium ions can intercalate
into the interlayer between graphene layers to form LiC6 intercalation compounds.
The theoretical capacity of graphite is 372 mAh/g (850 mAh.cm-3), based on the
The insertion compound LiC6 has a golden color and belongs to the graphite
intercalation compounds (GICs) of stage1, where the stage number corresponds to the
The intercalation of lithium into graphite and the related electrochemical properties
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discharging. This is because a thin lithium ion conductive film (solid electrolyte
interface, SEI) is formed on the surface of the graphite anode in the initial
relevant carbons [114-115]. One is graphitic carbons, which are normally prepared
well graphitized materials result. The second one is hydrogen containing carbons,
which are prepared from pyrolyzed organic precursors at temperatures near 700°C.
The third class of carbons are hard carbons or non-graphitized carbons. The structure
and chemistry of carbons strongly depends on the procedures of heating the organic
precursors. During the early stages of pyrolysis in inert gas (below 600 °C), organic
compounds decompose and emit gases that contain carbon, such as CO and CH4. The
remaining C atoms condense into planar aromatic structures (graphene sheets). If the
decomposing precursor forms a semifluid state, then these planar sheets can align in a
more parallel fashion that leads to easy graphitization upon heating to very high
organic precursor is sufficiently cross-linked, then a fluid state is not realized during
decomposition and the planar aromatic structure cannot align. These carbon materials
are difficult to graphitize at high temperature and thus are called “hard” or
1500 °C (so called soft carbon) have been shown to consist of small domains of
parallel stacking of two or three layers. These have been called basic structure units
(BSUs) [116,117].
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graphite having a high degree of plane orientation. The second classification scheme
relates to the axial orientation of layers, which consists of coaxial and radial cases. All
of the fibrous carbon materials have this scheme of orientation. The third scheme is
the orientation of the BSUs around a reference point (point orientation), in which two
cases have to be differentiated, radial and concentric. Most of the spherical carbon
The spherical graphite particles are obtained from pitches, so-called mesophase
The structure of carbon materials strongly depends on the precursors and the heat
between neighbouring hexagonal carbon layers, d002, the crystallite sizes along the c
and a axes, Lc and La, and the probability of graphitic AB stacking between adjacent
layers, P1, are commonly used as fundamental structural parameters. In general, the
degree of graphitization, P1, and the crystallite thickness, Lc(002), increase with the
The lithium insertion behavior in hard carbon electrodes such as coke is somewhat
different from that observed in graphite electrodes. In contrast with graphite, the
cycling profile of hard carbon electrode shows no evidence of staging plateaus but
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slope between 1.2 V and 0.2 V [118]. It is believed that the insertion of lithium in
lithium (relative to that in Li metal) and to show a very low plateau, consistent with
experimental results. Hard carbon materials consisted primarily of small single layers
of carbon arranged more or less like a house of cards. Lithium could be absorbed on
both surfaces of these single sheets, leading to more lithium per carbon than in
intercalated graphite, which would have the theoretical maximum capacity of Li2C6 or
740 mAh/g. In the structurally disordered coke electrodes, the intercalation process
does not promote formation of the staging phases, and due to its lack of crystallinity,
these electrodes are not as sensitive to the nature of the electrolyte as is the case for the
800 – 900 mAh/g. The hydrogen could be playing a crucial role in the mechanism of
lithium insertion. The reversible capacity increases with an increasing H/C atomic
ratio in this material. It has been suggested that lithium atoms can bind in the vicinity
the H-C bond, which would cause changes in the relative atomic positions of the C
and H atoms. Hydrogen-carbon electrodes do not maintain their large capacities over
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Carbon anode materials are still under intensive investigation to improve their
specific capacity and cycle life. Some super carbons prepared by pyrolsyzing special
precursors have demonstrated a capacity of more than 1000 mAhg-1 [121], but with
short cycle life. Nanocrystalline carbons prepared via high energy ballmilling had a
only half of this capacity was reversible during the first discharge. Such large
irreversible capacity in the first cycle is unacceptable for any practical application
[122, 123]. Nevertheless, it is expected that carbon materials will reach a capacity of
600 – 700 mAh/g with satisfactory cycle life and reversible capacity.
Many metallic elements (M) can react with lithium to form LixMy alloys. The
Fig. 2.11. Pure lithium has the largest specific capacity of all the metallic elements.
Silicon also has very high specific capacity when forming Li4.2Si alloys. However,
these metal anodes experienced a dramatic volume increase upon reacting with
lithium, causing cracking which eventually leads to the failure of the electrode.
In order to circumvent the problem of volume change upon lithium insertion, alloy
powders with small particle size have been synthesized by a chemical reaction
method. Powders of Sn, SnSb, and SnAg (typical grain size: 200-400 nm) were
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5000
4500
4000
3000
2500
2000
1500
1000
500
0
Li C(LiC6) Si As Al Sn Sb Pb
(Li21Si5) (Li As)
3
(LiAl) (Li21Sn5) (Li3Sb) (Li22Pb5)
[124]. A model for lithium insertion in alloys with small particle size has been
proposed. Many pores and cavities exist in a loosely packed small particle size
metallic matrix. During lithium insertion, even 100% volume expansion of individual
particles will not crack the electrode as the absolute changes in dimensions are still
small. In other words, the pores and cavities have the effect of buffering the expansion
of individual particles. During the extraction of lithium from LixM particles, the
expanded particles do not contract very much, thus the overall dimensions of the
electrode remain almost constant in the subsequent cycles. Wolfenstine [125] made a
prediction of the critical grain size below which microcracking does not occur, based
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critical grain size was less than the unit cell size for single-phase materials, which
suggests that decreasing the particle/grain size cannot fundamentally solve the
solve the mechanical instability problems were proposed: (i) incorporating within the
Li-alloys a ductile Li-ion conducting metal or polymer matrix, and (ii) embedding the
alloys within a matrix which places them under compressive stress [126]. The use of
intermetallic alloys is one choice to provide a ductile matrix for lithium alloying.
The intermetallic alloys MM’ have emerged as a new class of anode materials for
lithium-ion batteries. The operating voltage of these alloy anode materials is a few
and M’ is an “active” element which can react with lithium to form LixM’ alloy. The
The inactive M matrix is generated simultaneously. So, the reactions between lithium
which domains of lithium alloy LixM’ are created within the inactive M’ matrix.
It is well known that LixM’ alloy systems undergo several phase changes when the
active element M’ alloys with lithium to form a series of LixM’ alloys. For example,
Sn can alloy with lithium to form various LixSn alloys: Li5Sn2, Li7Sn2, Li13Sn5, and
eventually, if heavily lithiated, Li22Sn5. Severe volume expansion and contraction are
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cracking of alloy particles, damage the integrity of the electrode, and limit the cycle
life of the alloy electrode. This problem can be significantly improved by finely
believed that the inactive matrix provides structural stability to the composite
electrode and combats the volume change of the active element. Various intermetallic
lithium-alloying metal. For example, some intermetallic alloys such as Cu6Sn5 [127],
FeSn2, and FeSn [128] have demonstrated much improved cycling behavior
compared to pure Sn. These alloys were prepared by either powder sintering or
ball-milling. When lithium ions insert themselves into these anode materials, a
form a series of LixSn alloys within the inert Cu or Fe matrix. In situ x-ray diffraction
metallic Cu and Fe in Cu6Sn5 and FeSn2 electrodes after cycling. This displacement
reaction is partially reversible. The capacity fade on cycling has been attributed to the
performance of intermetallic MM’ alloy anode materials. Since there exist countless
pores and cavities within nanocrystalline materials, these cavities provide some free
room for the volume expansion of the active element when reacting with lithium to
form LixM’ alloys. The generated inactive matrix is also nanocrystalline in nature,
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which will be compatible with the original MM’ alloys if the starting materials are
nanocrystalline.
element, M’ and inactive element M, depending on their ability to react with lithium
to form lithium-alloy. Therefore, there will be many intermetallic alloys which have
the potential to be used as anode materials for lithium-ion batteries. Furthermore, the
intermetallic alloys can be ternary, or multi-element. This means that there can be
two, three, or more different active elements and vice versa for inactive elements.
Thus the possibilities for intermetallic alloys are many. Intensive research work is
batteries.
The tin-based amorphous composite oxide (TCO) anode materials were first
developed by Fujifilm Celltec [129, 130]. The TCO anode yields a specific capacity
for reversible lithium adsorption more than 50 percent higher than those of the carbon
adsorption and release, which corresponds in terms of reversible capacity per unit
volume to more than 2200 mAh cm-3. The tin-based composite oxide active material
- 56 -
Chapter 2 Literature Review
-------------------------------------------------------------------------------------------------------------------------
metallic elements whose total stoichiometric number is equal to or greater than that of
tin (x ≥ 1), and is typically comprised of a mixture of B (III), P (V), and Al (III). In the
oxide structure, Sn (III) forms the electrochemically active center for Li insertion and
inactive network of – (M-O)- bonding that delocalizes the Sn (II) active center. To
confer high reversibility in Li storage and release, the Sn-O framework is thus
and Al, in view of the enhancement of Li-ion mobility in the anisotropic glass
structure, which is favorable for ionic diffusion and release. The TCO
SnB0.5P0.4Al0.42O3.6 was prepared by mixing SnO, B2O3, Sn2P2O7, and Al2O3, sintering
at the high temperature of 1100 °C for more than 10 hours, and then quenching to
room temperature [130]. TCO anode can be coupled successfully with several
cathode materials, such as LiCoO2, LiNiO2, LiMn2O4, and LiMnO2. Such lithium-ion
batteries have been tested to have an energy density of more than 420 wh/l and good
cyclability. The major drawback for the TCO anode is the large irreversible capacity
in the first cycle (~ 40 percent of the first charge), which requires excess cathode
material to compensate.
Various tin oxides have been investigated as anode materials for lithium-ion batteries,
including SnO, SnO2, Li2SnO3, and SnSiO3 glass. All of these oxides can react
reversibly with lithium with a capacity from 1200 mAh/g to 1500 mAh/g in the first
charge, but with large irreversible capacity. In situ x-ray diffraction measurement
revealed that these tin oxides and tin oxide composites follow a similar mechanism for
lithium insertion. When lithium ions are inserted into these oxides, Li2O and Sn are
- 57 -
Chapter 2 Literature Review
-------------------------------------------------------------------------------------------------------------------------
generated simultaneously. Then the lithium alloys with Sn to form a series of LixSn
The formation of a Li2O and SiO2 matrix may act to retard the aggregation of tin
atoms into large coherent regions. When large tin regions form, the large volume
differences between coexisting bulk Li-Sn phases may introduce cracking and
doping. It was found that the Mo doping influences the habit of growth of the SnO2
crystallites and facilitates growth along the [hk0] direction. The presence of Mo in the
Li-Sn alloy as it is formed may favor Sn atom dispersion, which contributes to the
- 58 -
Chapter 2 Literature Review
-------------------------------------------------------------------------------------------------------------------------
Much work has been done on TCO and tin oxides. Although TCO glass and some
of large irreversible capacity related to oxygen in the first cycle is still not solved,
It was a surprise finding that MO-type compounds (where M is Co, Ni, Fe, Cu or Mn)
with a rock-salt structure and containing metal elements (M) that do not alloy with Li,
exhibited capacities two to three times those of carbon with 100% capacity retention
where M is Co, Ni, Cu, or Fe) have demonstrated electrochemical capacities of 700
mAh/g, with 100% capacity retention for up to 100 cycles and high recharging rates.
lithium-ion cells.
(a)
- 59 -
Chapter 2 Literature Review
-------------------------------------------------------------------------------------------------------------------------
(b)
voltage – composition profiles for MO/Li cells cycled between 0.01 V and 3 V of
CoO,NiO and FeO anodes at the C/5 rate. (b) Cyclability of Co3O4, CoO, FeO and
NiO anodes, with the data, also included demonstrating that the behaviour is not
specific to divalent oxides. The inset shows the rate capacity of a CoO electrode.
The reaction mechanism between Li and MO oxides differs from the classical Li
involves the formation and decomposition of Li2O accompanying the reduction and
oxidation of metal particles (in the range of 1 – 5 nanometers). For example, the
- 60 -
Chapter 2 Literature Review
-------------------------------------------------------------------------------------------------------------------------
situ extended X-ray absorption fine structure (EXAFS) measurements also revealed
the reversible nature of the process between CoO and Li ions. Since then, many metal
oxides have been investigated as anode materials for lithium-ion batteries [134-135].
- 61 -
Chapter 3 Experimental
--------------------------------------------------------------------------------------------------------------------------
Chapter 3 Experimental
3.1 Materials and chemicals
The materials, chemicals and reagents used in this study are listed in table 3-1.
- 62 -
Chapter 3 Experimental
--------------------------------------------------------------------------------------------------------------------------
Si-MCMB composites were prepared by high energy ball milling. The ball-milling
steel balls with a diameter of 10 mm were used. The weight ratio between the material
powders and the balls was 1: 8-10. Home-made stainless steel milling jars were
employed, equipped with ventilation valve to allow evacuation of the milling-jar and
purging with argon gas. During the ball-milling process, a speed of 120 - 140 rpm was
maintained.
Carbon aerogel was synthesized to prepare Si-Carbon composites. Carbon gel was
silicon powders were added and dispersed by ultrasonic probe and magnetic stirring.
- 63 -
Chapter 3 Experimental
--------------------------------------------------------------------------------------------------------------------------
The gel formation was accomplished by conducting the reaction at 85 °C. Finally,
carbon gel was sintered at high temperature (650 °C) to be converted into amorphous
carbon.
deposition (CVD) approach. The CVD reaction chamber consists of three different
controllers. Camphor was evaporated and carried by the flowing argon gas, and then
deposited on a silicon substrate downstream. The surface of the silicon wafer was
pre-deposited with iron carbonyl as catalyst. After deposition, carbon nanotubes were
Teflon lined autoclave (Parr Instrument Company, USA) was used with a maximum
temperature limitation of 300 °C. The ingredient reagents phosphorus, iron chloride
and de-ionized water were loaded in to an Autoclave. The autoclave was heated at 180
°C for 24 hours. After cooling down to room temperature, the reaction product was
taken out, washed thoroughly with distilled water, and dried in a vacuum oven.
- 64 -
Chapter 3 Experimental
--------------------------------------------------------------------------------------------------------------------------
Lithium iron phosphate and Mn and Mg doped lithium iron phosphate cathode
materials were prepared by the sol-gel synthesis method. Polyacrylic acid and citric
acid were used as complexing agents for the formation of a complex gel. The sol
solution was heated at 85 °C under vigorous stirring until forming a viscous gel was
formed. The gel was sintered at 500 °C to decompose the organic reagents into
carbon. The final products were obtained by sintering the intermediate product at 750
Lithium iron phosphate and alien cation doped lithium iron phosphate compounds
reagents were hand-mixed with ethanol using an agate mortar and pestle. Then the
mixture was dried in a vacuum oven. The dried mixtures were pre-sintered in alumina
boats at 500 °C. Then, the pre-sintered mixtures were mixed again via mortar and
pestle. The re-mixed reagents were sintered again at 750 °C for 12 hours. The final
products were ground and then used for characterization and electrochemical testing.
The phases and crystal structure of all material samples were identified and
- 65 -
Chapter 3 Experimental
--------------------------------------------------------------------------------------------------------------------------
1°/min and step size of 0.02 °. The crystallite sizes were calculated using the Scherrer
equation:
D = 0.9λ / β cosθ
Where λ is the x-ray wavelength, β is the observed full width at half maximum
All X-ray diffraction patterns were analyzed using the Difftech Traces V6 software
program and checked with the International Centre for Diffraction Data (ICDD)
database. X-ray diffraction patterns were also refined by the Rietveld method using
The morphologies of all the as-prepared powders were observed and analyzed using a
Surface element analysis and element mapping were performed using Energy
Dispersive X-ray Spectroscopy (EDXS) apparatus attached to the SEM. The SEM
facility is shown in Fig. 3.1. The morphologies and nanosize particles were analyzed
using transmission electron microscopy (TEM, JEOL 2011 TEM) and high resolution
TEM (HRTEM). The TEM apparatus is shown in Fig. 3.2. TEM samples were
- 66 -
Chapter 3 Experimental
--------------------------------------------------------------------------------------------------------------------------
- 67 -
Chapter 3 Experimental
--------------------------------------------------------------------------------------------------------------------------
The magnetic properties of lithium iron phosphate and transition metal doped lithium
the magnetization of the samples under zero magnetic field cooling (ZFC) and applied
magnetic field cooling (FC) were carried out in a magnetic field of 5000 Oe and over
a temperature range of 5 K – 300 K. The Curie and Néel temperatures, as well as the
spin state of the magnetic cations, were calculated from the inverse magnetic
χ = C/ (T-Өp) + χo (3.1)
temperature.
The electrode materials were hand mixed with 10 wt% carbon black and 5-10 wt%
PVDF binder in NMP solvent by mortar and pestle to form viscous slurry. Electrodes
aluminum foil. After coating, the electrodes were dried in a vacuum oven for 12 h at
120 o C and pressed between two steel plates at 3.0 × 106 Pa/cm2. The area of each
- 68 -
Chapter 3 Experimental
--------------------------------------------------------------------------------------------------------------------------
CR2032 coin cells were assembled for all electrochemical testing. A microporous
plastic film (Cellgard 2500, Cellgard Co., USA) was used as separator. The
ethylene carbonate (EC) and diethyl carbonate (DEC), and a 300 μm thick, 0.78 cm2
lithium foil for the negative electrode was also used. Coin cells were assembled in an
argon-filled glove box (Unilab, Mbraun, Germany) with both water and oxygen
Fig. 3.3 Atmosphere controllable glove box for assembling CR2032 coin cells.
- 69 -
Chapter 3 Experimental
--------------------------------------------------------------------------------------------------------------------------
switching between charge and discharge automatically, according to the cut off
potentials set.
- 70 -
Chapter 3 Experimental
--------------------------------------------------------------------------------------------------------------------------
elucidate the nature of the electrochemical process, and to provide insights into the
nature of processes beyond the electron-transfer reaction. It was used in the present
by scanning the voltage between two chosen cut-off voltages at a given sweep rate,
while simultaneously, the response current arising from the electron transference is
measured and recorded. In a cyclic voltammogram, the positive current represents the
lithium de-intercalation process, and the negative current the lithium intercalation
scan rate of 0.01-0.1 mV/s and a cut-off voltage of 0.0 V – 2.0 V for anode materials
and 2.5 V – 4.4 V for cathode materials. CHI 660B and CHI660C Electrochemical
Work Stations (CHI Instruments, USA) were employed for all CV measurement
- 71 -
Chapter 4 Preparation and characterization Si-MCMB and Si-carbon composite anode materials
--------------------------------------------------------------------------------------------------------------------------
Chapter 4
materials
4.1 Introduction
Silicon has a high theoretical lithium storage capacity of 4000mAh/g when forming
Li21Si5 alloys. Dahn et al. [136] synthesized nanodispersed silicon in carbon using
using the CVD approach. Lee et al. [137] dispersed crystalline silicon (325 mesh) in a
reversible capacity of 1700 mAh/g [138] have been prepared by hand mixing nano-Si
and carbon black. The lithium storage properties of nanostructured Si and Si film have
also been investigated [139, 140]. Since mesocarbon microbeads (MCMB) anode
materials have the best cyclability among all the various types of carbon anode
anode materials with high capacity and satisfactory rechargeability. Based on this
72
Chapter 4 Preparation and characterization Si-MCMB and Si-carbon composite anode materials
--------------------------------------------------------------------------------------------------------------------------
be changed when the crystals in the material have sizes on the tens of nanometers
originate from the unique mechanisms behind the lithiation and de-lithiation
4.2 Experimental
driven silane gas reaction). MCMB (MCMB-10 graphitizing) was supplied by Osaka
Gas Co. (Japan). MCMB powders have an average particle size of 10 μm.
73
Chapter 4 Preparation and characterization Si-MCMB and Si-carbon composite anode materials
--------------------------------------------------------------------------------------------------------------------------
Si-graphite [142]. The mixtures were ball-milled for 5, 10 and 20 hours respectively
Japan).
laser driven silane gas reaction). was purchased from Nanostructured & Amorphous
methanol, Sigma-Aldrich) were used for preparing carbon aerogel. A typical carbon
gel was formed by mixing 0.29 M resorcinol and 0.57 M formaldehyde. The pH value
was adjusted to be in the range of 6.5 – 7.4 by adding NH3.H2O solution. The mixture
solution was put in an ampoule, sealed, and heated on a hot plate. The temperature
was maintained at 85 °C. The solution changed progressively from clear to milk white
to yellow to orange as the reaction progressed. When the solution became viscous,
nanocrystalline Si powders were added, and dispersed through magnetic stirring. The
ampoule was kept at 85 °C for 10 hours, and then carbon aerogel was formed, with Si
dispersed inside the gel. The obtained gel was then sintered at 650 °C under flowing
argon to yield an Si-C composite, containing 40% carbon by weight. The carbon
74
Chapter 4 Preparation and characterization Si-MCMB and Si-carbon composite anode materials
--------------------------------------------------------------------------------------------------------------------------
were measured via coin cell testing. The Si-MCMB electrodes were made by
The slurry was spread onto a copper foil. The coated electrodes were dried in a
vacuum oven at 120 °C for 12 hours and then pressed to enhance the contact between
the active materials and the conductive carbons. The CR2032 coin cells were
metal foil as the counter electrode. The electrolyte was 1 M LiPF6 in a mixture of
ethylene carbonate (EC) and dimethyl carbonate (DMC) (1:1 by volume, provided by
MERCK KgaA, Germany). The cells were galvanostatically discharged and charged
MCMB particles have a spherical shape. Fig. 4.1 (a) shows an SEM image of MCMB
particles, which each consist of many small graphite particles. The images of the
Si-MCMB composites ball milled for different times are shown in Fig. 4.1 (b), (c) and
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Chapter 4 Preparation and characterization Si-MCMB and Si-carbon composite anode materials
--------------------------------------------------------------------------------------------------------------------------
(d). After ball milling for 5 and 10 hours, the spherical agglomerates were partially
broken. But most of the particles still retained a spherical shape. However, after 20
hours of extensive ball milling, most of the spherical MCMB agglomerates were
destroyed and formed finely ground graphite debris. Energy dispersive spectroscopy
(EDS) was performed on the bulk of the Si-MCMB composites and confirmed the
presence of Si. Fig. 4.2 shows the X-ray diffraction (XRD) pattern of Si-MCMB. As
a comparison, the XRD patterns of bare MCMB and nanocrystalline Si are also
presented in the insets. The intensities of the diffraction lines of nanocrystalline Si are
much weaker than for MCMB graphite, indicating the nanocrystalline nature of the Si.
The ball-milling process caused slight broadening of the (002) peak of MCMB
graphite. The full width at half maximum (FWHM) of the (002) diffraction peak of
the MCMB were calculated to be 0.248 °, 0.250 °, 0.278 °, and 0.296 ° for pristine
76
Chapter 4 Preparation and characterization Si-MCMB and Si-carbon composite anode materials
--------------------------------------------------------------------------------------------------------------------------
(a)
(b)
77
Chapter 4 Preparation and characterization Si-MCMB and Si-carbon composite anode materials
--------------------------------------------------------------------------------------------------------------------------
(c)
(d)
Fig. 4.1 SEM images of (a) bare MCMB graphite; (b) 20 wt% nano Si-MCMB ball
milled for 5 hours; (c) 20 wt% nano Si-MCMB ball-milled for 10 hours; and (d) 20
wt% nano-Si-MCMB ball-milled for 20 hours.
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Chapter 4 Preparation and characterization Si-MCMB and Si-carbon composite anode materials
--------------------------------------------------------------------------------------------------------------------------
Fig. 4.2 X-ray diffraction pattern of 20 wt% nano-Si-MCMB ball milled for 10 hours.
The insets show the XRD patterns of pristine MCMB and nanocrystalline Si for
comparison.
which a lithium foil was used as the counter electrode, and reference electrodes are
shown in Fig. 4.3 (a) and (b) respectively. In Fig. 4.3(a), the potential of the lithium
ion insertion peak in the cyclic voltammetric curve of the MCMB electrode is very
close to 0.0 V versus the Li/Li+ reference electrode, whereas the potential of lithium
extraction is in the range of 0.3 – 0.4 V versus the Li/Li+ reference electrode. In Fig.
4.3 (b), one pair of additional reduction and oxidation peaks appeared in the CV curve
of the Si-MCMB electrode, which are located at around 0.2 V and 0.51 V,
respectively versus the Li/Li+ reference electrode. This pair of redox peaks should
correspond to the lithiation and de-lithiation of Si in the MCMB matrix. The results of
79
Chapter 4 Preparation and characterization Si-MCMB and Si-carbon composite anode materials
--------------------------------------------------------------------------------------------------------------------------
lithium ions.
400
1st scanning cycle
300 25th scanning cycle
200
Current i (μA)
100
-100
-200
-300
-400
-500
(a)
2000
1500
-500
-1000
-1500
-2000
(b)
Fig. 4.3 Cyclic voltammograms of (a) MCMB electrode,
(b) nano-Si-MCMB electrode (sample E).
80
Chapter 4 Preparation and characterization Si-MCMB and Si-carbon composite anode materials
--------------------------------------------------------------------------------------------------------------------------
the discharge and charge capacities in the first cycle for different sample electrodes.
The bare MCMB electrode (sample A) delivered a reversible capacity of 325 mAh/g
in the first cycle with high efficiency. The bare nanocrystalline Si electrode (sample
B) delivered a very high lithium storage capacity of 3752 mAh/g, which is very close
to its theoretical capacity of 4000 mAh/g. However, this nanocrystalline Si anode had
a very high irreversible capacity of about 1821 mAh/g in the first cycle. The formation
of Li4.2Si alloy induces a 323% volume increase [143]. Such a high volume increase
could create microcracks and therefore destroy the integrity of the electrode, causing
μm)-MCMB composite prepared by ball milling for 10 hours. The sample C anode
shows a lower specific capacity and poorer rechargeability than for nanocrystalline Si
effect of the coarse particle size, the volume change in local domains in the sample C
anode could be much larger than for nanocrystalline Si when embedded in MCMB.
Therefore, it is not surprising that sample C demonstrated lower specific capacity and
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Chapter 4 Preparation and characterization Si-MCMB and Si-carbon composite anode materials
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Table 4.1 Specific capacity in the first cycle for bare MCMB, bare nanocrystalline Si,
It was found that the ball milling time has a significant impact on the specific capacity
hours) shows an optimal lithium storage capacity and capacity retention on cycling.
MCMB matrix. The longer the ball-milling time, the better the dispersing effect that
particles and destroys the graphite structure, therefore degrading the electrochemical
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Chapter 4 Preparation and characterization Si-MCMB and Si-carbon composite anode materials
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the MCMB powders. The irreversible capacity in the first cycle is considered to come
from the formation of a passivating film, which consumes lithium at the electrode
spherical MCMB particles were severely damaged after 20 hours of ball milling.
Therefore, the sample F (ball milling for 20 hours) anode exhibits a very high
MCMB matrix without damaging the spherical MCMB structure. Sample E seems to
In order to combat the problems caused by volume increase in the alloying process,
reducing the particle size of Si is an efficient way to minimize the volume change in
local domains due to the formation of LixSi alloys. Another approach to overcome this
problem is to embed the active element in an inactive matrix, to let the inactive matrix
absorb or buffer the volume expansion. The intermetallic MM’ alloys and tin
composite oxides (TCO) are exactly designed to utilise this principle. We embedded
lithium ions are inserted into Si-MCMB composites, nano-Si reacts with Li to form
LixSi alloys, and MCMB graphite reacts with Li to form LixC6. The intercalation of Li
in MCMB graphite causes only minor changes in the interlayer spacing and stacking
and extraction. Because Si particles are nanosize in nature, the volume increase in the
local environment is small, and can be easily absorbed by the ductile MCMB graphite
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Chapter 4 Preparation and characterization Si-MCMB and Si-carbon composite anode materials
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matrix surrounding the nano-Si clusters. As a result, the volume change in the
macro-domain is small and negligible for Si-MCMB electrodes. During the lithium
extraction process, a similar phenomenon occurs. This allows the integrity of the
model of the lithiation and de-lithiation processes in Si-MCMB composite has been
Fig. 4.4 Schematic model of the lithiation and de-lithiation process as in Si-MCMB
composites. The volume increases due to the formation of LixSi alloys are small in
84
Chapter 4 Preparation and characterization Si-MCMB and Si-carbon composite anode materials
--------------------------------------------------------------------------------------------------------------------------
Fig. 4.5 shows the discharge/charge profiles in the first cycle for bare nanocrystalline
electrode shows a flat discharge plateau in the 0.2 – 0.05 V range, corresponding to
the reduction peak in the CV curve (Fig.4.3 (b)), indicating the highly reactive nature
parabolic curve between 0.5 V and 0.2 V, and a flat plateau between 0.1 and 0.0 V,
which is typical for composite electrode materials. The cyclabilities of all the sample
anodes are shown in Fig. 4.6 The bare MCMB anode is very stable on cycling, but
with limited capacity. Although the bare nanocrystalline Si anode (sample B) had a
high initial capacity, its capacity decreased very quickly on cycling. Therefore, it is
(high capacity and satisfactory cyclability), compared to bare MCMB and bare
nano-Si electrodes. In particular, sample E shows stable cyclability, similar to the bare
MCMB electrode, but with much higher capacity. We believe that the electrochemical
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Chapter 4 Preparation and characterization Si-MCMB and Si-carbon composite anode materials
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2.0
1.5
Voltage (V)
1.0
0.5
0.0
(a)
2.0
1.5
Voltage (V)
1.0
0.5
0.0
(b)
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Chapter 4 Preparation and characterization Si-MCMB and Si-carbon composite anode materials
--------------------------------------------------------------------------------------------------------------------------
4000
1500
1000
500
-500
0 5 10 15 20 25
Cycle number
Fig. 4.6 The discharge capacity of the samples versus cycle number
derivatives of resorcinol, and these then further react with each other to form a
an enhanced electron density exists in the 2, 4, and 6 ring positions. However, the
number 2 position is sterically hindered by the adjacent hydroxyl groups. So, the
87
Chapter 4 Preparation and characterization Si-MCMB and Si-carbon composite anode materials
--------------------------------------------------------------------------------------------------------------------------
treatment at 650 °C, the gel was carbonized to become amorphous carbon. The final
Fig. 4.8 shows an X-ray diffraction pattern of typical Si-C composites. All diffraction
lines are indexed to Si. No diffraction lines from crystalline carbon (graphite) were
observed, indicating the amorphous nature of carbon in the composites. A TEM image
nanosize Si particles with a spherical shape. The size of individual particles ranges
from 20 nm to 80 nm. Some amorphous Si powders are also present. Fig. 4.9 (b)
shows a TEM image of nano Si-C composite powders. It clearly demonstrates that Si
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Chapter 4 Preparation and characterization Si-MCMB and Si-carbon composite anode materials
--------------------------------------------------------------------------------------------------------------------------
powders are surrounded by amorphous carbon. Spot EDX (energy dispersive x-ray)
analysis confirmed that the spherical black crystals in Fig. 4.9 (b) are Si. Therefore,
(111)
Intensity (a.u.)
(220)
(311)
(400)
20 30 40 50 60 70
2θ (degree)
cell, in which lithium foil was used as the counter electrode and reference electrode,
are shown in Fig. 4.10. The initial potential of the Si-C electrode is about 3.0 V in the
open-circuit state. In the first scanning cycle, there are two broad cathodic peaks
located at 0.60 V and 0.38 V, respectively, which disappear from the second cycle.
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Chapter 4 Preparation and characterization Si-MCMB and Si-carbon composite anode materials
--------------------------------------------------------------------------------------------------------------------------
interphase (SEI) passivation layer on the surface of the composite electrode, due to the
reaction of lithium with electrolyte. Once the SEI layer is formed, it will be stable
disappearance of these two reduction peaks from the second cycle. Two anodic peaks,
located at 0.38 V and 0.50 V, gradually evolve from the first scanning cycle and
become more distinct after the fourth cycle, which corresponds to the extraction of
lithium ions from the Si-C electrode. One additional cathodic peak at 0.20 V appears
from the fourth cycle. The two pairs of redox peaks remain stable from the fourth
scanning cycle until the twentieth cycle. We suggest that several cycles are required to
activate the Si-C composite electrode under a scanning rate of 0.1 mV/S. The
observed two redox peaks should be attributed to the reaction of lithium with Si to
[139].
90
Chapter 4 Preparation and characterization Si-MCMB and Si-carbon composite anode materials
--------------------------------------------------------------------------------------------------------------------------
(a)
(b)
91
Chapter 4 Preparation and characterization Si-MCMB and Si-carbon composite anode materials
--------------------------------------------------------------------------------------------------------------------------
600
1st scanning cycle
400 2nd scanning cycle
4th scanning cycle
200 20th scanning cycle
Current (μA) 0
-200
-400
-600
-800
-1000
-1200
0.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5
+
Potential vs. Li/Li (V)
discharge/charge profiles of a Si-C electrode at the rate C/10. The Si-C electrode
delivered a discharge capacity of about 2000 mAh/g in the first cycle, but with a
irreversible capacity of about 550 mAh/g. Part of this irreversible capacity was used to
form a SEI passivation layer on the surface of the electrode. The reversible capacity
was improved from the second cycle. In the first cycle, there is a discharge plateau in
the voltage range of 0.8 – 0.5 V, which corresponds to the formation of the SEI layer.
However, this discharge plateau disappears from the second cycle. This observation is
and 0.02 V is evolved from the second cycle and remains stable.
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Chapter 4 Preparation and characterization Si-MCMB and Si-carbon composite anode materials
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3.0
1st cycle
2.5 2nd cycle
1.5
1.0
0.5
0.0
2000
Discharge capacity (mAh/g)
1500
1000
500
0
0 5 10 15 20 25 30 35 40 45 50
Cycle number
Fig. 4.12 The discharge capacity versus cycle number for Si-C electrode.
93
Chapter 4 Preparation and characterization Si-MCMB and Si-carbon composite anode materials
--------------------------------------------------------------------------------------------------------------------------
The results of the cycling tests are shown in Fig. 4.12, with indicates good cyclability
of the nanostructured S-C composite electrodes. It is well known that a 300% volume
increase accompanies to the lithium alloying process with Si to form Li4.4Si. This
dramatic volume variation could pulverize the electrode, inducing poor cyclability.
amorphous carbon matrix. Through the synthesis of carbon aerogel, Si powders are
particles are nanosize in nature, the volume increase in the local sites is small and can
the volume change in the macro-domain will be negligibly small for the Si-C
composite electrode, which allows the integrity of the electrode to be preserved for
electrode demonstrates a high lithium storage capacity and good cycle life.
4.4 Conclusions
They are intended to utilise the high capacity of Si and the stable cyclability of
capacity of 1066 mAh/g for nanocrystalline Si-MCMB composites and fairly good
cyclability. A reaction model was proposed for the lithiation and de-lithiation
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Chapter 4 Preparation and characterization Si-MCMB and Si-carbon composite anode materials
--------------------------------------------------------------------------------------------------------------------------
associated with the lithiation and de-lithiation processes of LixSi alloys. A reversible
capacity of 1450 mAh/g for Si-C composite electrodes was achieved. The good
95
Chapter 5 Multiwalled carbon nanotubes (CNTs) anode materials
--------------------------------------------------------------------------------------------------------------------------
Chapter 5
anode materials
5.1 Introduction
Since the discovery of carbon nanotubes (CNTs) by Iijima [149], tremendous effort
nanotubes, for both multiwalled CNTs (MWCNTs) and single walled CNTs
(SWCNTs) [150, 151]. Carbon nanotubes can be produced using various techniques
such as electric arc discharge [152], laser vaporization [153], and chemical vapour
and electrical properties. They are an attractive system with potential uses in a wide
Carbon nanotubes have been proposed for application as lithium storage materials in
lithium-ion batteries. Carbon nanotubes have been reported with a reversible lithium
storage capacity in the range of 80 – 600 mAh/g [158 – 160]. The electrochemical
and disorder, and on the quality of the carbon nanotube bundles. Intermetallic alloy
(MM’) anodes rely on the reaction between lithium ions and the active element M to
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Chapter 5 Multiwalled carbon nanotubes (CNTs) anode materials
--------------------------------------------------------------------------------------------------------------------------
form LixM alloys. Transition metal oxides have been reported to exhibit high Li-ion
storage capacity in lithium-ion cells, which is based on the reversible reaction for the
formation of Li2O and metal oxide. Tin oxide (SnO2) has been extensively
electrochemical reaction of SnO2 anode in a Li-ion cell involves two steps: (i) the
formation of lithium oxide, and (ii) lithium alloying with Sn. The second step is an
mAh/g. However, the significant volume variation during lithiation induces poor
Vertically aligned carbon nanotubes were grown in this work on a planar quartz
substrate by a thermal CVD approach using camphor as the carbon source. The
5.2 Experimental
The vertically aligned carbon nanotubes were grown on planar quartz substrates with
nanocrystalline iron as the catalyst. Fig. 5.1 shows a schematic diagram of the CVD
97
Chapter 5 Multiwalled carbon nanotubes (CNTs) anode materials
--------------------------------------------------------------------------------------------------------------------------
quartz reactor, which consists of three different temperature zones heated by resistive
heating coils. The quartz substrate was placed in the hot zone and heated to 900 °C.
The low temperature zone was maintained at 350 °C. A quartz boat containing iron
carbonyl and another quartz boat containing camphor were also prepared. A small
piece of nickel wire was attached to the quartz boats for magnetic attraction. When the
temperatures in the heating zones reached the designated temperatures, the quartz
boat containing iron carbonyl was first moved into the low temperature zone with a
permanent magnet. The iron carbonyl was then evaporated and deposited on the
quartz substrate in the hot zone, to serve as a catalyst. The second quartz boat
containing camphor was then brought into the low temperature zone. The camphor
was then evaporated and decomposed in the high temperature zone, inducing carbon
nanotubes to grow on the quartz substrate. An argon gas flow was applied in the
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Chapter 5 Multiwalled carbon nanotubes (CNTs) anode materials
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(99.9%, Sigma-Aldrich), and ethanol were mixed homogeneously with a high speed
mixer. The molar ratio of Sn:C was 0.1:1 in the mixture, with a nominal weight
percentage of 55.6 wt% SnO2 in the final product. The mixed suspension was put into
a vacuum oven heated to 90 ºC to evaporate the ethanol. The dried mixture was then
heated to 600 ºC to form SnO2. The calcined product was washed with de-ionized
water to remove Cl- by filtering, and then dried at 100 ºC under vacuum to obtain a
SnO2-CNT composite.
electron microscope). The detailed structure of the CNTs was examined by HRTEM
99
Chapter 5 Multiwalled carbon nanotubes (CNTs) anode materials
--------------------------------------------------------------------------------------------------------------------------
SnO2-CNT composites was tested by fabricating CR2032 coin cells. The working
electrode was prepared by mixing the active materials with 10 wt% carbon black and
to form a slurry with appropriate viscosity. The slurry was then spread onto copper
foil, which was then cut out into φ12 mm electrodes. The thickness of each electrode
was approximately 60 – 80 μm, with a loading of 1.5 mg. The coin cells were
hand-operated closing tool (Hosen Co., Japan). The electrolyte was 1 M LiPF6 in a
mixture of ethylene carbonate (EC) and dimethyl carbonate (DMC) (1:1 by volume,
and discharged in the voltage range of 0 – 2.0 V versus Li/Li+. Cyclic voltammetry
(CV) measurements were carried out using a CHI660B Electrochemical Work Station
The configuration of the CNTs is shown in Fig. 5.2 (a) (b) (c) and (d). The as-prepared
CNTs are well-aligned over the quartz substrate. The CNTs have grown in a vertical
direction to the substrate and have a uniform distribution. The length of the CNTs is
about 70 - 80 μm. Fig. 5.2 (b) shows a vivid view of the vertically aligned CNTs
obtained by cutting the CNT layer with a razor. CNTs were then peeled off from the
100
Chapter 5 Multiwalled carbon nanotubes (CNTs) anode materials
--------------------------------------------------------------------------------------------------------------------------
substrate for further SEM study. Fig. 5.2 (c) shows the CNT bundles, which
demonstrate the feature of very long CNTs entangled with each other. Only very tiny
quantities of carbon clusters are present in Fig. 5.2 (c), indicating the high yield rate of
CNTs. Fig. 5.2 (d) shows a magnified view of the dispersed CNTs, which further
TEM and HRTEM analysis was performed on the CNTs grown on the quartz
substrate. The CNTs were peeled off and dispersed on a carbon coated microgrid. Fig.
5.3 (a) shows a TEM image of the CNTs. Except for some stand-alone multiwalled
carbon nanotubes, the CNTs are entangled together, forming bundles. Some catalyst
particles are encapsulated inside the CNTs. Spot EDS analysis confirmed that the
black dots are Fe catalyst. The outer diameter of the CNTs is about 40 – 60 nm. Fig.
5.3 (b) shows the HRTEM image of a single multiwalled carbon nanotube.
few curved chambers. The walls of the CNT consist of approximately 10 graphite
101
Chapter 5 Multiwalled carbon nanotubes (CNTs) anode materials
--------------------------------------------------------------------------------------------------------------------------
(a)
(b)
102
Chapter 5 Multiwalled carbon nanotubes (CNTs) anode materials
--------------------------------------------------------------------------------------------------------------------------
(c)
(d)
103
Chapter 5 Multiwalled carbon nanotubes (CNTs) anode materials
--------------------------------------------------------------------------------------------------------------------------
(a)
(b)
104
Chapter 5 Multiwalled carbon nanotubes (CNTs) anode materials
--------------------------------------------------------------------------------------------------------------------------
the electrochemical reactivity of the CNTs in lithium-ion cells, in which lithium metal
was used as both the working electrode and the reference electrode. Fig.5.4 shows
CV curves demonstrated that lithium ions can reversibly intercalate and de-intercalate
in carbon nanotubes. The lithium insertion potential is very low, close to 0.0 V versus
the Li+/Li reference electrode. However, the potential for lithium extraction is in the
range of 0.15 - 0.30 V. A slight voltage hysteresis between lithium insertion and
extraction in the CNT electrodes is similar to the situation with other carbonaceous
materials [164]. The intensity of the redox peaks remained stable for many scanning
cycles, indicating good reversibility of the carbon nanotubes for lithium insertion and
extraction.
60
2nd scanning cycle
40
20th scanning cycle
20
Current i (μA)
-20
-40
-60
-80
-100
-0.2 0.0 0.2 0.4 0.6 0.8 1.0 1.2 1.4 1.6
+
Potential (V) versus Li/Li
105
Chapter 5 Multiwalled carbon nanotubes (CNTs) anode materials
--------------------------------------------------------------------------------------------------------------------------
Fig. 5.5 shows the first discharge and subsequent discharge curves of a carbon
nanotube electrode. The first discharge curve shows a plateau at about 0.8 V, which is
associated with the formation of a SEI layer on the surface of the carbon nanotube
electrode. Carbon nanotubes usually have a large specific surface area. The
occur on the surface of carbon nanotubes during the first discharge process. The
capacity used for SEI formation is not reversible [165]. In the subsequent cycles, the
mAh/g was obtained from the second cycle and remained stable, indicating good
cyclability. Multiwalled carbon nanotubes consist of graphite sheets rolled into closed
concentric cylinders. The concentric tubes are separated by van der Waals gaps of ~
that lithium ions can only combine with every second hexagon on the external surface
950 mAh/g. We suggest that there are four possibilities for lithium intercalation in the
carbon nanotube electrode: (i) lithium ions intercalate into intratubal sites (the hollow
core); (ii) lithium ions intercalate into intertubal sites (the sites between individual
nanotubes ) through diffusion in the bundles; (iii) lithium ions intercalate into carbon
nanoclusters (since small quantities of carbon clusters have been identified in carbon
nanotubes); (iv) lithium ions intercalate into layered graphite structures, including
both nanotube structures and nanocluster structures. All these four possibilities could
contribute to the high lithium insertion capacity of carbon nanotube electrodes [166].
The lithium storage capacity versus cycle number is shown in the inset in Fig. 5.5.
106
Chapter 5 Multiwalled carbon nanotubes (CNTs) anode materials
--------------------------------------------------------------------------------------------------------------------------
After the first cycle, the carbon nanotube electrode exhibited stable cyclability for
2.0
1500
1000
1.5
500
Voltage (V)
0
5 10 15 20 25 30
1.0
0.5
3D
0.0 2D 1D
Fig. 5.5 Discharge curves of the carbon nanotube electrode. The inset shows the
discharge capacity versus cycle number for the carbon nanotube electrode.
The amount of SnO2 in the composite was determined by TGA analysis using air as
the carrying gas. The composite contains 55 wt % SnO2, which is consistent with the
nominal percentage. Fig. 5.6 shows the X-ray diffraction pattern of SnO2-CNT
composite. The SnO2 diffraction lines are clearly indexed, with broad diffraction
peaks indicating a nanocrystalline nature. The diffraction lines of CNTs are weak and
not distinguishable. The particle size of SnO2 was calculated to be in the range of 10 –
20 nm using the Scherrer equation. The distribution and morphology of the SnO2
107
Chapter 5 Multiwalled carbon nanotubes (CNTs) anode materials
--------------------------------------------------------------------------------------------------------------------------
(110)
Intensity (a.u.)
(101)
(211)
20 30 40 50 60 70
Angles (2θ)
Fig. 5.7 (a) presents a TEM image showing a general view of the SnO2-CNT
composite, which clearly demonstrates that nanosize SnO2 particles are distributed
homogeneously on the carbon nanotube matrix. Fig. 5.7 (b) further shows a high
magnification TEM image of the composite, from which it was found that some SnO2
particles formed, inside carbon nanotubes. Therefore, we can conclude that SnO2
particles were formed not only on the outside walls of CNTs (inter-), but also inside
108
Chapter 5 Multiwalled carbon nanotubes (CNTs) anode materials
--------------------------------------------------------------------------------------------------------------------------
(a)
(b)
109
Chapter 5 Multiwalled carbon nanotubes (CNTs) anode materials
--------------------------------------------------------------------------------------------------------------------------
(a)
(b)
110
Chapter 5 Multiwalled carbon nanotubes (CNTs) anode materials
--------------------------------------------------------------------------------------------------------------------------
(c)
(d)
111
Chapter 5 Multiwalled carbon nanotubes (CNTs) anode materials
--------------------------------------------------------------------------------------------------------------------------
Fig. 5.8 shows high resolution TEM images of SnO2-CNT composites. As shown in
Fig. 5.8 (a), a large number of SnO2 nanocrystals were formed, and they became
attached to the walls of the carbon nanotubes. Fig. 5.8 (b) shows the distribution of
SnO2 nanoparticles on a single carbon nanotube. The HRTEM images are shown in
Fig. 5.8 (c) and (d). We can see that the carbon nanotubes are multiwalled, with an
demonstrated in further detail in Fig. 5.8 (d), from which the sizes of the SnO2
nanocrystals are clearly visible, with a 3.4 Å interplanar distance. Although those
SnO2 nanocrystals are of very small size, of the same order as quantum dots, they
cyclic voltammetry (CV). Fig. 5.9 shows the CV curves of SnO2-CNT composite
electrodes. In the first cycle, there is a strong reduction peak at 0.85 V, which is
The strength of this reduction peak decreased substantially in the second scanning
cycle and gradually disappeared in the subsequent scanning cycles. Following the
formation of Sn and Li2O, there is a reduction peak at 0.15 V, which is associated with
112
Chapter 5 Multiwalled carbon nanotubes (CNTs) anode materials
--------------------------------------------------------------------------------------------------------------------------
The final reduction peak at 0.0 V is related to lithium insertion in carbon nanotubes:
During the charging process, three oxidation peaks appeared on the CV curves. The
first oxidation peak (a small hump), which is related to the extraction of Li from
inserted and extracted from the carbon nanotubes. The strongest oxidation peak is at
The last oxidation peak at 1.25 V is weak and decreases gradually. We suggest that
this oxidation line originates from the extraction of lithium from Li2O, which is
The specific capacity and cyclability of SnO2-CNT composite electrodes were tested
via galvanostatic charge and discharge cycling at the C/2 current rate using CR2032
coin cells. The voltage window was set between 0.0 V and 2.0 V vs. the Li/Li+ counter
electrode. Fig. 10 shows the charge and discharge curves of SnO2-CNT electrode in
the first and second cycles. In the first cycle, there is an irreversible capacity of about
390 mAh/g, which was caused by the formation of both Li2O and an SEI film on the
113
Chapter 5 Multiwalled carbon nanotubes (CNTs) anode materials
--------------------------------------------------------------------------------------------------------------------------
the second cycle. The cyclability of SnO2-CNTs is shown in Fig. 5.11. In the first ten
cycles, the lithium storage capacity decreased continuously, but the SnO2-CNT
storage capacity of 410 mAh/g after fifty cycles. The charging efficiency (the ratio of
charge capacity to discharge capacity) is shown in the inset in Fig. 5.11. The
SnO2-CNTs electrode demonstrated a very high charging efficiency (> 98%) after ten
cycles.
4.0x10-4
E
2.0x10-4
F
D
Current / A/cm2
0.0
-2.0x10-4
20th
2nd
-4.0x10-4
1st
-6.0x10-4 A
C
B
-8.0x10-4
0.0 0.5 1.0 1.5 2.0
Potential vs. Li/Li+ / V
114
Chapter 5 Multiwalled carbon nanotubes (CNTs) anode materials
--------------------------------------------------------------------------------------------------------------------------
2.5
2.0
Voltage (V)
1.5
1.0
0.5
1st
0.0 2nd
Fig. 5.10 The first and second discharge and charge curves of
SnO2-CNT composite electrode.
1100
1000 100
Discharge capacity / mAhg-1
90
80
Efficiency / ( /100)
900 70
60
800 50
40
30
700 20
10
600 0 10 20 30
Cycle number
40 50
500
400
300
200
100
0
0 10 20 30 40 50
Cycle number
Fig. 5.11 Discharge capacity vs. cycle number for SnO2-CNT composite electrode,
115
Chapter 5 Multiwalled carbon nanotubes (CNTs) anode materials
--------------------------------------------------------------------------------------------------------------------------
From TEM observation, we know that SnO2 crystals are very tiny (only a few
nanometers). They are well distributed and stick on both the inner and the outer
On the other hand, the volume expansion during the lithium reaction with SnO2 is
relatively small and limited due to the size of the SnO2 nanocrystals. Such a small
believe that these two factors contributed to the good cyclability of the SnO2-CNT
electrodes.
5.4 Conclusion
chemical vapour deposition. The carbon nanotubes have a typical diameter of several
lithium insertion and extraction. A reversible lithium storage capacity of 950 mAh/g
SnO2-CNT composite anode materials have been synthesized via chemical treatment
enables Sn2+ ions to penetrate into the inner cavity of the carbon nanotubes. SnO2
116
Chapter 5 Multiwalled carbon nanotubes (CNTs) anode materials
--------------------------------------------------------------------------------------------------------------------------
exhibited stable cyclability, with a lithium storage capacity of 410 mAh/g after fifty
cycles.
117
Chapter 6 Synthesis and electrochemical characterisation of iron phosphide as anode material for
lithium-ion batteries
--------------------------------------------------------------------------------------------------------------------------
Chapter 6
6.1 Introduction
Lithium-ion batteries using a carbon anode and a lithium cobalt oxide cathode are the
of new anode materials with high energy density is critical for the development of the
result in significant advances in the search for high capacity anode materials. Systems
intermetallic alloys, transition metal oxides, etc.. These anode materials have
demonstrated higher capacities than carbon anodes, but suffer from large irreversible
capacity and poor cycle life. For example, there have been intensive investigations on
tin, tin based alloys, and tin oxide composites [171,141,172]. The formation of Li4.4Sn
results in a theoretical capacity of 991mAh/g for elemental Sn. However, this alloying
inactive matrix to create a buffering effect. Silicon has the highest known theoretical
capacity of 4000 mAh/g when forming Li4.2Si alloys, far greater than that of carbon
118
Chapter 6 Synthesis and electrochemical characterisation of iron phosphide as anode material for
lithium-ion batteries
--------------------------------------------------------------------------------------------------------------------------
and Sn. However, this alloying process is also associated with a 300% volume
dilation, pulverizing the brittle electrode and inducing poor cyclability [173 - 175].
Transition metal phosphides such as MnP4 and Zn3P2 were discovered to exhibit
sintering at high temperature over long periods. After sintering, the products were
purified by acid etching [178-180]. Here we report the direct synthesis of transition
6.2 Experimental
Red phosphorus powders (99%, Aldrich) and FeCl2.4H2O (99%, Aldrich) were
compounds and loaded into a Teflon lined autoclave. De-ionised water was added as
solvent. The autoclave was inserted into an oven and kept at the reaction temperature
of 180 ˚C for 24 hours. The resulting product was filtered by vacuum suction and
washed with water, then dried at 110 ˚C. X-ray diffraction was performed on the
119
Chapter 6 Synthesis and electrochemical characterisation of iron phosphide as anode material for
lithium-ion batteries
--------------------------------------------------------------------------------------------------------------------------
assembling CR2032 coin cells. The electrodes were made by dispersing 92wt %
pyrolidone (NMP) solvent to form homogeneous slurry. The slurry was then spread
onto an Al foil to form the electrodes. The coated electrodes were dried in a vacuum
oven at 120 °C for 12 hours and then pressed to enhance the contact between the
active materials and the conductive carbon. The cells were assembled in an argon
filled glove-box (Mbraun, Unilab, Germany) using lithium metal foil as the counter
electrode. The electrolyte was 1 M LiPF6 in a mixture of ethylene carbonate (EC) and
The cells were galvanostatically charged and discharged over a voltage range of 0.02
– 1.5 V at a C/5 rate. Cyclic voltammetry (CV) measurements were performed using a
mV/s.
method. Crystalline FeP4 has a monoclinic structure (space group: p21/c). Fig. 6.1
shows the X-ray diffraction pattern of the as-prepared iron phosphide compound.
Most of the diffraction lines could be indexed as the monoclinic phase, but some
small amounts of unknown impurities were also present. In general, the diffraction
peaks are weak and broad, indicating the nanosize nature of the synthesized FeP4
powders.
120
Chapter 6 Synthesis and electrochemical characterisation of iron phosphide as anode material for
lithium-ion batteries
--------------------------------------------------------------------------------------------------------------------------
350
(-112)
(012)
300
(121)
Intensity (a.u.)
(-121)
(100)
(031)
250
200
(140)
(042)
150
100
50
20 25 30 35 40 45 50 55 60 65 70 75
Angles 2θ (degree)
SEM image of the FeP4 powders is shown in Fig. 6.2. The FeP4 powders
amorphous cotton-like phases. The sizes of the individual crystals were less than 100
nm. Those individual crystals were agglomerated together to form large composite
(EDS) analysis on the powder sample, which was spread onto a carbon tape without
any coating. The atomic ratio of Fe: P is 1:3.98, which confirmed the correct
121
Chapter 6 Synthesis and electrochemical characterisation of iron phosphide as anode material for
lithium-ion batteries
--------------------------------------------------------------------------------------------------------------------------
metal phosphides have been synthesized via a tin-flux method at high temperature.
reducing agent and a reactant. The possible reaction is proposed as equation (6.1).
The reaction product FeP4 is a precipitate, which can be easily separated via filtration.
Cyclic voltammetry measurements (CV) were performed on the FeP4 electrode using
122
Chapter 6 Synthesis and electrochemical characterisation of iron phosphide as anode material for
lithium-ion batteries
--------------------------------------------------------------------------------------------------------------------------
coin cell at a scanning rate of 0.1 mV/s in the voltage range of 0.0 V – 3.0 V. Fig. 6.3
shows the CV curves of FeP4. During the cathodic scanning process, there are three
in the anodic scanning process, there are two well-defined anodic peaks centred at 1.1
V and 1.3 V. Previously, it was proposed that the lithium insertion and extraction in
transition between different related crystal structures [176]. Our observed reaction
0.30
0.25
0.10
Current (mA)
0.05
0.00
-0.05
-0.10
-0.15
-0.20
-0.25
-0.30
0.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5
+
Potential vs. Li/Li
123
Chapter 6 Synthesis and electrochemical characterisation of iron phosphide as anode material for
lithium-ion batteries
--------------------------------------------------------------------------------------------------------------------------
Li + P → Li3P (6.4)
However, the confirmation and further analysis of the reactions between lithium ions
124
Chapter 6 Synthesis and electrochemical characterisation of iron phosphide as anode material for
lithium-ion batteries
--------------------------------------------------------------------------------------------------------------------------
2.5
2.0
1.5
Voltage (V)
1.0
0.5
The lithium storage capacity and reversibility of the FeP4 anodes were tested via
galvanostatic charge and discharge testing Fig. 6.4. The first discharge capacity of
FeP4 electrode reaches as high as 1130 mAh/g, which is equivalent to the intake of
4.33 mole lithium per formula FeP4. However, about 410 mAh/g of the capacity is
irreversible in the first charging process. After the first cycle, FeP4 electrode is fairly
stable for repeated charge and discharge, with a capacity of about 700 mAh/g. As
shown in Fig. 6.4, the FeP4 electrode showed the same charging and discharging
profile after the first cycle. During the charging process (lithium extraction), there are
two voltage plateaus, centred at 1.1 V and 1.3 V, respectively, which match the
observed oxidation peaks on the CV curves Fig. 6.3. During the discharging process
125
Chapter 6 Synthesis and electrochemical characterisation of iron phosphide as anode material for
lithium-ion batteries
--------------------------------------------------------------------------------------------------------------------------
(lithium insertion), the voltage of the electrode drops sharply from 2.0 V to 0.8 V, and
then gradually descends to a plateau centered at 0.5 – 0.6 V, followed by another steep
descent to 0.0 V. The 0.5 V plateau matches the reduction peak at 0.5 V that was
matching the reduction peaks at 1.5 V and 0.02 V. The cyclability of FeP4 with respect
to lithium insertion and extraction is shown in Fig. 6.5. In general, FeP4 electrode
exhibited stable cyclability after the first cycle, with a capacity of about 700 mAhg-1.
1200
1000
Discharge capacity (mAhg )
-1
800
600
400
200
0
0 10 20 30 40 50
Cycle number
Fig. 6.5 The discharge capacity of FeP4 anode vs. cycle number.
126
Chapter 6 Synthesis and electrochemical characterisation of iron phosphide as anode material for
lithium-ion batteries
--------------------------------------------------------------------------------------------------------------------------
6.4 Conclusion
We prepared nanosize FeP4 compound via the hydrothermal method. The as-prepared
products contain a majority of monoclinic FeP4 phase with some small amount of
towards lithium insertion and extraction. The FeP4 anode exhibited a stable lithium
127
Chapter 7 Characterisation of olivine-type LiMnxFe1-xPO4 cathode materials
--------------------------------------------------------------------------------------------------------------------------
Chapter 7
Characterisation of olivine-type
7.1 Introduction
Lithium polyanion compounds with the general formula LixMy(XO4)z (M: transition
materials for lithium-ion batteries [92,93,181 - 183]. Among them, LiFePO4 and
LiMnPO4 compounds are particularly interesting. Both LiFePO4 and LiMnPO4 have
an orthorhombic olivine structure (space group: Pnma), in which Li, Fe (Mn) and P
atoms occupy octahedral 4a, octahedral 4c,and tetrahedral 4c sites. The strong P-O
covalency stabilizes the anti-bonding Fe3+/Fe2+ (Mn3+/Mn2+) state through the Fe-O-P
(or Mn-O-P) inductive effects to generate a high operating potential. In the olivine
crystal structure, the oxygen atoms are in a slightly distorted, hexagonal close-packed
arrangement. The FeO6 (MnO6) octahedra share corners in the bc plane, and LiO6
octahedra form an edge sharing chain in the b-direction. The polyanion with strong
P-O covalency provides a stable crystal structure for lithium insertion and extraction,
inducing good cycle life and excellent safety when the compound is used as electrode
in lithium-ion cells. However, the separation of the FeO6 octahedra by PO4 polyanions
dramatically reduces the electronic conductivity of the material, causing poor rate
128
Chapter 7 Characterisation of olivine-type LiMnxFe1-xPO4 cathode materials
--------------------------------------------------------------------------------------------------------------------------
(x = 0.25, 0.50, 0.75, and 1.0), and found that the capacity rapidly decreases at x >
systems. They discovered that Mn-rich LiMnxFe1-xPO4 (x > 0.8) is not suitable as a
cathode material, due to the large anisotropic distortion of Mn3+. We report here the
conductive phosphides and manganese phosphates that were formed during the
sintering process, which could enhance the electronic conductivity of the materials.
7.2 Experimental
LiMnxFe1-xPO4 (x = 0, 0.1, 0.3, 0.5, 0.7, 0.9 and 1) compounds were synthesised by a
and citric acid were added as complexing agents for the formation of the gel. The
solution was heated at 85 °C under vigorous stirring until a viscous gel was formed.
The as-formed gel was calcined at 500 °C for 4 hours to decompose the organic
129
Chapter 7 Characterisation of olivine-type LiMnxFe1-xPO4 cathode materials
--------------------------------------------------------------------------------------------------------------------------
components under flowing argon gas. The decomposed precursors were then sintered
at 750 °C for 15 hours under a flowing gas mixture (10% H2 in Ar). The reducing
atmosphere was employed during the sintering process in order to prevent the
with Cu Kα radiation. The diffraction intensity was measured from 20 ° to 120 ° using
a step size of 0.02 ° with a counting time of 10 s per step. Rietveld refinement was
performed using the GSAS (General Structure Analysis System) program to obtain
the crystal structure parameters. Scanning electron micrographs were obtained with a
130
Chapter 7 Characterisation of olivine-type LiMnxFe1-xPO4 cathode materials
--------------------------------------------------------------------------------------------------------------------------
were made by dispersing 80 wt% active material, 10 wt% carbon black and 10 wt%
slurry was then coated onto an Al foil. The coated electrodes were dried in a vacuum
oven and then pressed at 1200 kg/cm2. The thicknesses of the electrodes were about
100 µm, and the mass of the active materials was about 2 mg. The coin cells were
assembled in an argon filled glove box (Mbraun, Unilab, Germany) with lithium foil
X-ray diffraction patterns of the LiMnxFe1-xPO4 (x = 0, 0.1, 0.3, 0.5, 0.7, 0.9 and 1.0)
samples are shown in Fig. 7.1 (a). The main diffraction lines are indexed as an
Rietveld refinement on the X-ray diffraction patterns using the GSAS program [193].
Fig. 7.1 (b) shows a typical Rietveld refinement on the XRD pattern of the
It is worth noting that the impurity phases in LiFePO4 are Fe2P, FeP, and Li4P2O7.
phosphides are usually formed during the sintering process under a reducing
131
Chapter 7 Characterisation of olivine-type LiMnxFe1-xPO4 cathode materials
--------------------------------------------------------------------------------------------------------------------------
atmosphere [194]. The selected bond distances and angles for all the LiMnxFe1-xPO4
(a) LiFePO4
(b) LiMn0.1Fe0.9PO4
(c) LiMn0.3Fe0.7PO4
(d) LiMn0.5Fe0.5PO4
(e) LiMn0.7Fe0.3PO4
(f) LiMn0.9Fe0.1PO4
(g) LiMnPO4
Intensity (a.u.)
(g)
(f)
(e)
(d)
(c)
(b)
(a)
20 25 30 35 40 45 50 55 60 65 70 75
2θ / degree
(a)
Intensity (a.u.)
LiFePO4
Mn2P2O7
Fe2P
FeP
(b)
Fig. 7.1 (a) X-ray diffraction patterns of LiMnxFe1-xPO4, (b) Rietveld refinement
132
Chapter 7 Characterisation of olivine-type LiMnxFe1-xPO4 cathode materials
--------------------------------------------------------------------------------------------------------------------------
Table 7.1 Phase composition and lattice parameters of olivine phase for
LiMnxFe1-xPO4 compounds
Fraction
Phase * a, Å b, Å c, Å V, Å3
Olivine 7.3366
Li3PO4 0.34292
LiFePO4 10.32559(7) 6.00463(4) 4.68908(3) 290.729(3)
Fe2P 0.70963
FeP 0.079816
Olivine 11.714
LiFe0.9
Fe2P 0.092737 10.3366(2) 6.0130(1) 4.69465(8) 291.791(9)
Mn0.1PO4
FeP 0.23027
Olivine 46.819
LiFe0.7
Fe2P 0.44832 10.3548(3) 6.0279(2) 4.7031(1) 293.56(1)
Mn0.3PO4
FeP 0.63682
Olivine 78.076
LiFe0.5 Fe2P 0.17978
10.3873(1) 6.05132(7) 4.71797(6) 296.557(6)
Mn0.5PO4 FeP 3.0864
Mn2P2O7 1.9555
Olivine 20.368
LiFe0.3
FeP 0.064183 10.4160(2) 6.07332(9) 4.73074(8) 299.262(8)
Mn0.7PO4
Mn2P2O7 1.1980
Olivine 6.9780
LiMnPO4 10.44723(9) 6.10279(5) 4.74778(5) 302.705(5)
Mn2P2O7 1.1349
*Phase fraction in the sample is the phase fraction coefficient in the GSAS program.
133
Chapter 7 Characterisation of olivine-type LiMnxFe1-xPO4 cathode materials
--------------------------------------------------------------------------------------------------------------------------
Table 7.2 Selected interatomic distances (Å) and angles (deg) for LiMnxFe1-xPO4
samples
134
Chapter 7 Characterisation of olivine-type LiMnxFe1-xPO4 cathode materials
--------------------------------------------------------------------------------------------------------------------------
However, the O-Fe-O and O-P-O bond angles vary with changing Mn content, but
compound. Therefore, taking into account the phase composition of the LiMnPO4
The variations in the lattice parameters of the olivine phases are shown in Table 7.1.
As the Mn content increases, the lattice parameters of the unit cell expand along all
the axes; a, b, and c, inducing an increase in the volume of the unit cell. This is in good
agreement with the fact that the Mn2+ ion (r = 0.84 Å) has a larger radius than that of
Fig. 7.2 shows SEM images of the LiFePO4, LiMn0.5Fe0.5PO4, and LiMnPO4 samples.
In general, all three samples have similar micromorphology and similar grain sizes,
regardless of the composition of the compounds. The average grain size is in the range
become cotton wool-like. For the LiMnPO4 sample, this characteristic becomes
samples. Our as-prepared samples contain about 2 % carbon, which was induced by
135
Chapter 7 Characterisation of olivine-type LiMnxFe1-xPO4 cathode materials
--------------------------------------------------------------------------------------------------------------------------
(a)
(b)
136
Chapter 7 Characterisation of olivine-type LiMnxFe1-xPO4 cathode materials
--------------------------------------------------------------------------------------------------------------------------
(c)
and LiMn0.5Fe0.5PO4 samples are shown in Fig. 7.3. The magnetic susceptibilities of
which is caused by the ferromagnetic impurities Fe2P and FeP. In the triphylite
Following the super and super-super exchange rule, the interactions between Fe(Mn)
137
Chapter 7 Characterisation of olivine-type LiMnxFe1-xPO4 cathode materials
--------------------------------------------------------------------------------------------------------------------------
0.026
0.024
0.022
χ emu/mol LiFePO4
0.020
0.018
0.016
0.014
0.012
0.010
0.008
0 50 100 150 200 250 300
Temperature (K)
(a)
0.040
0.035
0.030
χ emu/mol LiFe0.5Mn0.5PO4
0.025
0.020
0.015
0.010
0.005
0 50 100 150 200 250 300 350
Tem perature (K)
(b)
138
Chapter 7 Characterisation of olivine-type LiMnxFe1-xPO4 cathode materials
--------------------------------------------------------------------------------------------------------------------------
200
180
160
Discharge capacity (mAh/g) 140
120 LiFePO4
LiMn0.1Fe0.9PO4
LiMn0.3Fe0.7PO4
100
LiMn0.5Fe0.5PO4
LiMn0.7Fe0.3PO4
80 LiMn0.9Fe0.1PO4
60
40
20
0
0 10 20 30 40 50
Cycle number
Fig. 7.4 Discharge capacity vs. cycle number for LiMnxFe1-xPO4 sample electrodes.
constant current charge/discharge testing. Fig. 7.4 shows the specific capacities and
cyclabilities of all samples except for LiMnPO4 electrode. LiMnPO4 was found to
exhibit a general trend that the specific capacity and cycle life decrease with
increasing Mn content. For the pure LiMnPO4 sample, the electrochemical reactivity
139
Chapter 7 Characterisation of olivine-type LiMnxFe1-xPO4 cathode materials
--------------------------------------------------------------------------------------------------------------------------
7.4 Conclusions
LiMnxFe1-xPO4 (x = 0. 0.1, 0.3, 0.5, 0.7, 0.9 and1.0) compounds were prepared via a
characteristics. The electrochemical reactivity and cycle life degrade with increasing
140
Chapter 8 Electrochemical and magnetic characteristics of LiFePO4 and Li0.95Mg0.05FePO4 cathode
materials
-----------------------------------------------------------------------------------------------------------
Chapter 8
8.1 Introduction
Because of their high energy density lithium-ion batteries have become the dominant
power sources for portable electronic devices [2,197-199]. The current commercial
lithium-ion batteries use LiCoO2 as the cathode material, which limits their
applications to small batteries due to the high cost and toxicity of Co. In the past
decade, a number of new cathode materials, such as layer structured LiMnO2 [200,
201], LiMn2O4 spinels [202, 203], and LiMxNi1-xO2 compounds [204, 205], have been
cathode materials for lithium-ion batteries [206–210]. Among them, LiFePO4 olivines
have attracted particular interest because of the low cost and environmental
141
Chapter 8 Electrochemical and magnetic characteristics of LiFePO4 and Li0.95Mg0.05FePO4 cathode
materials
-----------------------------------------------------------------------------------------------------------
3.4 V – 3.5 V vs. Li/Li+ due to the tuning effect of the large polyanion [PO4]3+.
LiFePO4 is an ideal cathode materials for large-scale lithium-ion batteries for electric
vehicles (EVs) and stationary power storage. LiFePO4 has an ordered olivine
structure (space group: Pnma), in which Li, Fe, and P atoms occupy octahedral 4a,
octahedral 4c, and tetrahedral 4c sites. The oxygen atoms are arranged in a slightly
corners in the bc plane, and the LiO6 octahedra form an edge-shares chain in the
reduces the electrical conductivity of the material. This causes poor rate capacity and
low utilisation of Li in the LiFePO4 host structure. Extensive investigations have been
olivines by creating conductive iron phosphides has been reported as one efficient
performance of these olivines has not been described. Here we show the
compounds.
142
Chapter 8 Electrochemical and magnetic characteristics of LiFePO4 and Li0.95Mg0.05FePO4 cathode
materials
-----------------------------------------------------------------------------------------------------------
8.2 Experimental
and active acid were added as complexing agents for the formation of the gel. The
solutions were heated and maintained at 85 °C under vigorous stirring until a viscous
gel was formed. The as-formed gel was heated to 500 °C to decompose the organics
under flowing argon gas. The decomposed precursors were further sintered at 700 °C,
800 °C, and 850 °C, respectively, under a flowing gas mixture (10% H2 in Ar). A
slightly reducing atmosphere was employed during the sintering process in order to
prevent the oxidation of Fe2+ cations. Six samples were prepared, which are shown in
Table 8.1.
X-ray analysis and SEM observation. X-ray diffraction was performed on the
prepared lithium iron phosphates to determine the phase purity using Cu Kα radiation
143
Chapter 8 Electrochemical and magnetic characteristics of LiFePO4 and Li0.95Mg0.05FePO4 cathode
materials
-----------------------------------------------------------------------------------------------------------
Table 8.1 Sintering temperature, label, and average crystal size of lithium iron
phosphates
and 850 °C were studied using a Quantum Design MPMS XL SQUID magnetometer.
144
Chapter 8 Electrochemical and magnetic characteristics of LiFePO4 and Li0.95Mg0.05FePO4 cathode
materials
-----------------------------------------------------------------------------------------------------------
active material, 10 wt% carbon black, and 10 wt% polyvinylidene fluoride (PVDF) in
n-methyl pyrrolidone (NMP) to form a slurry. The slurry was then coated onto Al
foilto form the electrodes. The coated electrodes were dried in a vacuum oven and
then pressed at 1200 Kg/cm2. The coin cells were assembled in an argon filled glove
box (Mbraun, Unilab, Germany) with lithium foil as the counter electrode. The
carbonate (DMC).
X-ray diffraction was performed on the LiFePO4 and Li0.95Mg0.05PO4 powders. Fig.
8.1 shows the XRD patterns of LiFePO4 and Li0.95Mg0.05PO4 samples sintered at
different temperatures. Phase pure LiFePO4 and Li0.95Mg0.05PO4 were obtained after
145
Chapter 8 Electrochemical and magnetic characteristics of LiFePO4 and Li0.95Mg0.05FePO4 cathode
materials
-----------------------------------------------------------------------------------------------------------
o
(a) Sintered at 700 C
o
(b) Sintered at 800 C
o
(c) Sintered at 850 C
(b)
(a)
20 25 30 35 40 45
2θ / degree
(a)
o
(a) Sintered at 700 C
o
(b) Sintered at 800 C
o
(c) Sintered at 850 C
Fe2P
Intensity (a.u.)
(c)
(b)
(a)
20 25 30 35 40 45
2θ / degree
(b)
Fig. 8.1 X-ray diffraction patterns of (a) LiFePO4 and (b) Li0.95Mg0.05FePO4.
146
Chapter 8 Electrochemical and magnetic characteristics of LiFePO4 and Li0.95Mg0.05FePO4 cathode
materials
-----------------------------------------------------------------------------------------------------------
space group: Pnma). For LiFePO4 sintered at 850 °C, the main phase is still triphylite
LiFePO4, but there are substantial impurity phases such as FeP4 and Fe2P, as indicated
in Fig 1(a). However, for Li0.95Mg0.05PO4 sintered at 850 °C, the main phase is not
triphylite. There are numerous impurity phases that cannot be totally identified. The
strongest diffraction peak was identified as Fe2P. The x-ray diffraction analysis
confirmed a previous report [219] that iron phospides are formed in LiFePO4 and
analysis was performed on the LiFePO4 and Li0.95Mg0.05PO4 samples. All the samples
contained 2 – 3 wt% carbon, which was induced by the sol-gel synthesis process.
Fig. 8.2 (a)–(c) shows SEM images of Li0.95Mg0.05PO4 powders sintered at 700 °C,
800 °C, and 850 °C, respectively. The sample sintered at 700 °C has a small grain size
of about 0.5 – 1 μm. When sintered at 800 °C, the grain size increased to 3 – 5 μm,
while the 850 °C sintered sample exhibits the biggest grain size of 5 – 10 μm. The
crystal size of the lithium iron phosphates was significantly influenced by the
sintering temperature. Fig. 8.3 shows the EDS elemental mapping of Li0.95Mg0.05PO4
powders. Fig. 8.3 A is the secondary electron image. A very uniform element
distribution was observed for the main elements Fe, P, and O. For reasons of the
distributions of the trace dopant Mg and carbon are not shown. Trace dopant Mg2+
ions are also observed to be homogeneously distributed in the crystal structures. This
should be attributed to the chemical synthesis process. The ingredient Li+, Fe2+, Mg2+,
147
Chapter 8 Electrochemical and magnetic characteristics of LiFePO4 and Li0.95Mg0.05FePO4 cathode
materials
-----------------------------------------------------------------------------------------------------------
and PO43- ions were dissolved in water and mixed on the atomic scale in solution.
Following the subsequent gel formation and sintering, a uniform element distribution
(a)
(b)
148
Chapter 8 Electrochemical and magnetic characteristics of LiFePO4 and Li0.95Mg0.05FePO4 cathode
materials
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(c)
149
Chapter 8 Electrochemical and magnetic characteristics of LiFePO4 and Li0.95Mg0.05FePO4 cathode
materials
-----------------------------------------------------------------------------------------------------------
Fig. 8.3 EDS elemental mapping by SEM. (A) Secondary electron image,
samples sintered at 700 °C and 850 °C are shown in Fig. 8.4 (a) and (b) respectively.
The reciprocal susceptibilities are shown in the inset. The magnetic susceptibility of
150
Chapter 8 Electrochemical and magnetic characteristics of LiFePO4 and Li0.95Mg0.05FePO4 cathode
materials
-----------------------------------------------------------------------------------------------------------
called the Néel temperature (θN). A typical Curie-Weiss law behaviour was followed
above the Néel temperature. The two samples show similar dependences of the
lower molar susceptibility. The magnetic moments in LiFePO4 are attributed to Fe2+
amount of iron phosphides were formed in LiFePO4 when sintering was at 850 °C, but
these have no contribution to the antiferromagnetic behaviour. Fig. 8.5 (a) and (b)
700 °C and 850 °C, respectively. The Li0.95Mg0.05FePO4 sample sintered at 700 °C
sintered at 850 °C shows ferromagnetic behaviour, which is totally different from its
counterpart sintered at 700 °C. The main phases for Li0.95Mg0.05FePO4 sintered at 850
°C are iron phosphides. Most of these phosphides (Fe2P, Fe3P, FeP4, and Fe75P15C4)
151
Chapter 8 Electrochemical and magnetic characteristics of LiFePO4 and Li0.95Mg0.05FePO4 cathode
materials
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0.026
110
0.024 100
-1
70
60
50
0.020 40
χ emu/mol Fe
30
20
0.018 10
0
0 50 100 150 200 250 300
Temperature (K)
0.016
0.014
0.012
0.010
0.008
0 50 100 150 200 250 300
Temperature (K)
(a)
0.026
0.024 120
1/χ emu mol Fe
100
0.022
-1
80
χ emu/ mol Fe
0.020 60
0.018 40
Temperature (K)
0.016
0.014
0.012
0.010
0.008
0 50 100 150 200 250 300
Temperature (K)
(b)
samples (a) LFP-700 and (b) LFP-850. The insets are the reciprocal magnetic
susceptibilities.
152
Chapter 8 Electrochemical and magnetic characteristics of LiFePO4 and Li0.95Mg0.05FePO4 cathode
materials
-----------------------------------------------------------------------------------------------------------
0.026
120
0.024
0.022
-1
80
χ emu/mol Fe
0.020 60
0.018 40
0.014
0.012
0.010
0.008
0 50 100 150 200 250 300
Temperature (K)
(a)
0.16
0.14
0.12
χ emu/mol Fe
16
0.10
1/χ emu mol Fe
14
12
0.08
-1
10
0.06 8
6
0 50 100 150 200 250 300
0.02
0 50 100 150 200 250 300
Temperature (K)
(b)
153
Chapter 8 Electrochemical and magnetic characteristics of LiFePO4 and Li0.95Mg0.05FePO4 cathode
materials
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The effective magnetic moment was calculated using the paramagnetic formula μ =
(8χT)-1/2 [221], which is shown in Fig. 8.6. The measured μ values for the three
anti-ferromagnetic samples are in the range of 4.6 – 4.9 μB at room temperature. The
which is much higher than that of the other three samples. The Curie temperature θC
was obtained by linear fitting of the reciprocal magnetic susceptibility above the Néel
temperature. Table 8.2 shows the magnetic parameters of the four samples. All three
anti-ferromagnetic samples have the same Néel temperature. The Mg doped sample
In the triphylite structure of LiFePO4, Fe2+ ions occupy octahedral 4c sites with
coordinates x = 0.28, y = 0.25, and z = 0.96. Due to the influence of the octahedral
crystal field, the five 3d orbitals of the Fe2+ ion split into three t2g and two eg
configurations. There are six electrons in 3d orbitals for the Fe2+ ion. Among them,
four electrons are on the three t2g orbitals (dxy, dxz, and dyz), in which three electrons
are spin up and the fourth electron spin down. The magnetic moments for the paired
two electrons in one of the t2g orbitals cancel each other. Therefore, there are a net two
spin-up electrons in t2g orbitals. Two electrons occupy two eg orbitals (dx2-y2 and dz2),
in which one electron is in each orbital with spin-up configuration. The Fe2+ ion
presents net four spin-up electrons (high spin), with an expected magnetic moment of
4μB on the basis of the spin-only value. However, the measured magnetic moment is
in the range of 4.7 – 4.9 μB, which is higher than the theoretical value. Since the
154
Chapter 8 Electrochemical and magnetic characteristics of LiFePO4 and Li0.95Mg0.05FePO4 cathode
materials
-----------------------------------------------------------------------------------------------------------
angular momentum for the Fe2+ ion is not equal to 0, the Fe2+ ion could have a strong
The orbital momentum could contribute to the measured magnetic moment. The
corresponding to a spin sequence (+--+) with moments along [010]. Following the
super and super-super exchange rules, the interactions between Fe-O-Fe induce
orthorhombic phase, there is no Fe-O-Fe bonding, only Fe-O-P-O-Fe bonding. So, the
exchange [222–225].
4
o
LiFePO4 700 C sintered
μ / μB
o
LiFePO4 850 C sintered
3 o
Li0.95Mg0.05FePO4 700 C sintered
0
0 50 100 150 200 250 300
Temperature (K)
Fig. 8.6 The effective magnetic moment per mole of iron of LiFePO4 and
Li0.95Mg0.05FePO4 samples.
155
Chapter 8 Electrochemical and magnetic characteristics of LiFePO4 and Li0.95Mg0.05FePO4 cathode
materials
-----------------------------------------------------------------------------------------------------------
Effective
Magnetic Néel Curie
Properties Magnetic
Temperature Temperature
Moment μeff (μB)
TN (K) θC (K)
at 25°C
Sample
LiFePO4
50 ± 2 -96.2 4.77
700 °C sintered
LiFePO4
50 ± 2 -96.2 4.55
850 °C sintered
Li0.95Mg0.05FePO4
50 ± 2 -76.0 4.57
700 °C sintered
Li0.95Mg0.05FePO4
~ +110.5 12.61
850 °C sintered
156
Chapter 8 Electrochemical and magnetic characteristics of LiFePO4 and Li0.95Mg0.05FePO4 cathode
materials
-----------------------------------------------------------------------------------------------------------
materials
electrodes. In Fig. 8.7(a), the reduction and oxidation peak positions for the LFP-700
and LFP-800 samples are the same, at 3.30 V and 3.51 V vs Li/Li+ respectively. There
is a shift of the redox potentials for the LFP-850 sample to 3.12 V and 3.60 V vs
Li/Li+. The shift of the redox potential could be related to the formation of iron
phosphite impurities in the LFP-850 sample. Fig. 8.7 (b) shows the CV curves of
Li0.95Mg0.05PO4 electrodes. The redox potentials for doped samples are different from
those of the undoped one, indicating that the Mg doping has an influence on the redox
electrochemical reactivity due to the change of the main phase into iron phosphides as
157
Chapter 8 Electrochemical and magnetic characteristics of LiFePO4 and Li0.95Mg0.05FePO4 cathode
materials
-----------------------------------------------------------------------------------------------------------
300
250
200
150
100
Current i (μA)
50
-200
-250
-300
2.2 2.4 2.6 2.8 3.0 3.2 3.4 3.6 3.8 4.0 4.2 4.4 4.6 4.8
Potential E vs. Li/Li+ (V)
(a)
300
250
200
150
100
Current i (μA)
50
-150
-200
-250
-300
2.2 2.4 2.6 2.8 3.0 3.2 3.4 3.6 3.8 4.0 4.2 4.4 4.6 4.8
+
Potential E vs. Li/Li (V)
(b)
158
Chapter 8 Electrochemical and magnetic characteristics of LiFePO4 and Li0.95Mg0.05FePO4 cathode
materials
-----------------------------------------------------------------------------------------------------------
were tested by galvanostatic charge/discharge testing at a C/8 rate. Fig. 8.8 (a) and (b)
shows the voltage profiles in the first cycle for the LFP-700 and LFPMg-700 sample
electrodes, respectively, the cells were charged and discharged in the voltage range of
2.75 V – 4.2 V vs. Li/Li+. The profiles exhibit a flat charge and discharge plateau at
3.45 – 3.55 V, which matches the oxidation and reduction peaks in the CV curves.
The LiFePO4 electrode delivered a specific discharge capacity of 160 mAh/g in the
first cycle, whereas the Li0.95Mg 0.05FePO4 cathode shows a lower discharge capacity
of 150 mAh/g in the first cycle, which is due to the partial substitution of Li+ by
non-active Mg2+. The cyclabilities of all the sample electrodes are shown in Fig. 8.9.
5.0
4.5
4.0
Voltage (V)
3.5
3.0
2.5
2.0
0 50 100 150 200
Capacity (mAh/g)
(a)
159
Chapter 8 Electrochemical and magnetic characteristics of LiFePO4 and Li0.95Mg0.05FePO4 cathode
materials
-----------------------------------------------------------------------------------------------------------
5.0
4.5
4.0
Voltage (V)
3.5
3.0
2.5
2.0
0 20 40 60 80 100 120 140 160 180
Capacity (mAh/g)
(b)
Fig. 8.8 Charge/discharge curves in the first cycle for (a) LiFePO4 and (b)
200
Discharge capacity (mAh/g)
150
100 LFP-700
LFP-800
LFP-850
LFPMg-700
LFPMg-800
50
0
0 10 20 30 40 50
Cycle number
Fig. 8.9 Discharge capacity vs. cycle number for LiFePO4 and
160
Chapter 8 Electrochemical and magnetic characteristics of LiFePO4 and Li0.95Mg0.05FePO4 cathode
materials
-----------------------------------------------------------------------------------------------------------
mAh/g–160 mAh/g at the C/8 rate. The rate of degradation with cycling for the
temperature, which is due to the influence of the increased crystal size. The previously
proposed “Radial Model” and “Mosaic Model” for LiFePO4 can exactly explain the
observed phenomena [226, 227]. The process of lithium insertion and extraction in
LiFePO4 is a two-phase co-existing process. Therefore, the crystal size has a critical
influence on the transport of lithium ions and electrons into and out of the individual
crystals. The larger the crystal size, the greater the inefficiency of the full conversion
of LiFePO4 to FePO4 and back again, inducing a loss of capacity with cycling.
8.4 Conclusions
The sintering temperature has a significant influence on the crystal size of LiFePO4
triple exchange, due to the lack of direct Fe-O-Fe interactions. LiFePO4 and
161
Chapter 9 Conclusions and suggestions for future study
--------------------------------------------------------------------------------------------------------------------------
Chapter 9
Studies on the performance of various anode materials and cathode materials have
been presented in the previous chapters. The outcomes are summarized as follows.
This part of the work was intended to utilise the high capacity of Si and the stable
prepared via high energy ball-milling. A reversible capacity of 1066 mAh/g and fairly
good cyclability was been achieved for nanocrystalline Si-MCMB composite anode
materials. A reaction model was proposed for the lithiation and de-lithiation process
Cyclic voltammetry measurements showed two pairs of redox peaks associated with
the lithiation and de-lithiation processes of LixSi alloys. A reversible capacity of 1450
mAh/g for Si-C composite electrodes was achieved. The good cyclability should be
162
Chapter 9 Conclusions and suggestions for future study
--------------------------------------------------------------------------------------------------------------------------
attributed to the usage of nanosize Si powders and the buffering effect provided by the
9.1.2 Carbon nanotubes and tin oxide – carbon nanotubes anode materials
vapour deposition using iron carbonyl as the catalyst. A reversible lithium storage
capacity of 950 mAh/g has been achieved for the as-prepared vertically aligned
carbon nanotubes. SnO2-CNT composite anode materials were prepared via chemical
process enabled Sn2+ ions to penetrate into the inner cavity of the carbon nanotubes.
stable cyclability, with a lithium storage capacity of 410 mAh/g after fifty cycles.
Nanosize FeP4 compound was synthesised via the hydrothermal method. The
as-prepared products contain a majority of monoclinic FeP4 phase with some small
reactivity of FeP4 anodes towards lithium insertion and extraction. The FeP4 anode
163
Chapter 9 Conclusions and suggestions for future study
--------------------------------------------------------------------------------------------------------------------------
9.1.4 Lithium iron phosphate and manganese doped lithium iron phosphate
cathode materials
A series of LiMnxFe1-xPO4 (x = 0, 0.1, 0.3, 0.5, 0.7, 0.9 and 1) compounds were
increasing Mn content.
LiFePO4 and Li0.95Mg0.05PO4 compounds were synthesised via the sol-gel route
conductors, were formed when sintering took place at 850 °C. Magnetic susceptibility
50 ± 2 K for LiFePO4 and Li0.95Mg0.05PO4 sintered at temperatures below 850 °C. The
measured effective magnetic moments are in the range of 4.6 – 4.9 μB at room
electrochemical capacity in the range of 150 – 160 mAh/g on cycling. The cyclability
164
Chapter 9 Conclusions and suggestions for future study
--------------------------------------------------------------------------------------------------------------------------
deteriorates with increasing sample sintering temperature due to the increased crystal
size.
As an important energy storage system, lithium ion batteries will continue to attract
batteries. Therefore, exploration of new anode materials and cathode materials will
certainly provide synergy for the development of new generation lithium-ion batteries
Alloy based anode materials are a new direction with the potential to double or triple
the current carbon based anode materials used in lithium-ion batteries. In particularly,
tin and silicon or their alloy have high theoretical lithium storage capacities.
However, the problems related to volume expansion and contraction during the
lithiation and de-lithiation processes need to be overcome before any practical usage
is possible. Nanosize metal oxides are also candidate anode materials which can
Without a doubt, lithium iron phosphate is a very promising cathode material for
lithium ion batteries, particularly for large-scale lithium ion batteries, which are safe
in operation and cheap in terms of cost. However, low electronic conductivity induces
165
Chapter 9 Conclusions and suggestions for future study
--------------------------------------------------------------------------------------------------------------------------
low rate capacity and short cycle life. Carbon coating, metal ion doping, and the
166
References
--------------------------------------------------------------------------------------------------------------------------
References
[1] M.Winter and R.J. Brodd, Chem. Rev. 104 (2004) 4245.
[5] E.S. Takeuchi, W.C. Thiebolt, J. Electrochem. Soc. 135 (1988) 2691.
[6] A. Crespi, C. Schmidt, J. Norton, K. Chen, P.J. Skarstad, J. Electrochem. Soc. 148
1 (2001) A 30.
[7] K.M. Abraham, D.M. Pasquariello, and F.J. Martin, J. Electrochem. Soc. 133
(1986) 661.
[8] J.J. Auborn, Y.L. Barberio, K.J. Hanson, D.M. Schleich, and M.J. Martin, J.
[9] B.M.L. Rao, R.W. Francis, H.A. Christopher, J. Electrochem. Soc. 124 (1977)
1490 – 1492.
(1989) 421.
[11] A.S. Baranski, W.R. Fawset, J. Electrochem. Soc. 129 (1982) 901.
[12] J.O. Besenhard, P. Komenda, A. Paxines, E. Wudy and M. Josowices, Solid State
[13] A. Anani, S.C. Baker, R.A. Huggins, J. Electrochem. Soc. 134 (1987) 3098.
[14] A. Anani, S.C. Baker, R.A. Higgins, J. Electrochem. Soc.135 (1988) 2103.
167
References
--------------------------------------------------------------------------------------------------------------------------
551.
[17] D.W. Murphy, P.A. Christian, Science 205 (1979) 651 – 656.
[18] K. Mizushima, P.C. Jones, P.J. Wiseman and J.B. Goodenough, Mater. Res. Bull.
17 (1980) 783.
[19] J.L. Godman, R.M. Mank, J.H. Young, V.R. Koch, J. Electrochem. Soc., 127
(1980) 1461.
Broadhead and B.C.H. Steele (Plenum Press, New York, 1980) p. 145.
[30] K. Mizushima, P.C. Jones, P.J. Wiseman and J.B. Goodenough, Mater. Res. Bull.
15 (1980) 783.
168
References
--------------------------------------------------------------------------------------------------------------------------
389.
[36] J. N. Reimers, E. Rossen, C.D. Jones and J.R. Dahn, Solid State Ionics 61 (1993)
335.
[37] M.G.S.R. Thomas, P.G. Bruce and J.B. Goodenough, Solid State Ionics 17
(1985) 13.
[38] Y. Ma, M.M. Doeff, S.J. Visco and L.C. De Jonghe, J. Electrochem. Soc. 140
(1993) 2726.
[42] H.T. Huang, G.V. Subba Rao, B.V.R. Chowdari, J. Power Sources, 81-82 (1999)
690.
[44] J. Cho, J.G. Lee, B. Kim and B. Park, Chem. Mater. 15 (2003) 3190.
[45] L. Liu, Z. Wang, H. Li, L. Chen, and X. Huang, Solid State Ionics 152 (2002)
341.
[46] J. Cho, Y.J. Kim, T.J. Kim and B. Park, Angew. Chem. Int. Ed. 40 (2001) 3367.
[47] K.W. Beard, W.A. Depalma and J.P. Buckley, Proc. 1992 IEEE 35th Intern.
169
References
--------------------------------------------------------------------------------------------------------------------------
[48] T. Ohzuku, A. Ueda and M. Nagayama, J. Electrochem. Soc. 140 (1993) 1862.
[49] R. Koksbang, I.I. Olsen and D. Shackle, Solid State Ionics 69 (1994) 320.
[51] G. X. Wang, S. Zhong, D.H. Bradhurst, S.X. Dou and H.K. Liu, J. Power Sources
76 (1998) 141.
[53] W. Li, J. N. Reimers, J.R. Dahn, Solid State Ionics 67 (1993) 123.
[54] R.V. Moshtev, P. Zlatilova, V. Manev and A. Sato, J. Power Sources 54 (1995)
329.
[55] G.X.Wang, J. Horvat, D.H. Bradhurst, H.K. Liu and S.X. Dou, J. Power Sources
85 (2000) 279.
[56] G.X.Wang, S. Zhong, D.H. Bradhurst, S.X. Dou and H.K. Liu, Solid State Ionics
[57] A.R Armstrong and P.G. Bruce, Nature 381 (1996) 499.
[59] L. Croguennec, P. Deniard and R. Brec, J. Electrochem. Soc. 144 (1997) 3323.
[61] I. Koetschon, M.N. Richard, J.R. Dahn, J.B. Sonpart and J.C. Rousche, J.
[62] R. J. Gummow and M.M. Thackeray, J. Electrochem. Soc. 141 (1994) 1178.
[63] Y-II Jang, B.Y. Huang, Y.-M. Chiang, and D.R. Sadoway, Electrochem.
170
References
--------------------------------------------------------------------------------------------------------------------------
[64] A.I.Landa, C.-C. Chang, P.N. Kumta, L. Vitos, and I.A. Abrikosov, Solid State
[66] A.R. Armstrong, A.D. Robertson, R. Gitzendanner, and P.G. Bruce, J. Solid
[67] E. Rossen, C.D.W.Jones, and J.R. Dahn, Solid State Ionics 57 (1992) 311.
[68] M.E. Spahr, P. Novák, B. Schnyder, O. Haas, R.J. Nesper, J. Electrochem. Soc.
[69] Z. Lu, D.D. MacNeil, J.R. Dahn, Electrochem. Solid State Lett. 4 (2001) A191.
[71] L.Q. Zhang, H. Noguchi, M. Yoshio, J. Power Sources 110 (2002) 57.
[72] C. Storey, I. Kargina, Y. Grincourt, I.J. Davidson, Y.C. Yoo, D.Y. Seung, J.
[74] Y. Grincourt, C. Storey, I.J. Davidson, J. Power Sources 97-98 (2001) 711.
[75] B. Ammundsen, J. Paulsen, I. Davidson, R.-S. Liu, C.-H. Shen, J.-M. Chen,
[76] S.J. Hwang, H.S. Park, J.H. Choy, Solid State Ionics 151 (2002) 275.
[77] G.X. Wang, Z.P. Guo, X.Q. Yang, J. McBreen, H.K. Liu and S.X. Dou, Solid
[78] P. Arora, B.N. Popov and R.E. White, J. Electrochem. Soc.145 (1998) 807.
171
References
--------------------------------------------------------------------------------------------------------------------------
[79] G.X.Wang, D.H. Bradhurst, H.K. Liu, S.X. Dou, Solid State Ionics 120 (1999)
95.
[81] R. Bittihn, R. Herr and D. Hoge, J. Power Sources 43-44 (1993) 223.
[82] M.Wakihara, Li Guoha, H. Ikuta, T. Uchida, Solid State Ionics 86-88 (1996) 907.
[83] A.D. Robertson, S.H. Lu, W.F. Averill and W.F. Howard, Jr., J. Electrochem.
(1996)178.
[89] R.J. Hill and C.J. Howard, Australian Atomic Energy Commission Report,
AAEC/M112.
(1997) 1188.
[94] Y.N. Song, P.Y. Zavalij, M. Suzuki, M.S. Whittingham, Inorg. Chem. 41 (2002)
5778 – 5786.
172
References
--------------------------------------------------------------------------------------------------------------------------
[95] Y.N. Xu, S.Y. Chung, J.T. Bloking, Y.M. Chiang, W.Y. Ching, Electrochemical
[96] M.S. Islam, D.J. Driscoll, C.A.J. Fisher, P.R. Slater, Chem. Mater. 17 (2005)
5085.
[98] S.Y. Chung, J.T. Bloking, Y.M. Chiang, Nat. Mater. 1 (2002) 123.
(2003) 4082.
[101] A. Deb, U. Bergmann, E.J. Cairns, S.P. Cramer, J. Synchrotron Rad. 11 (2004)
497.
[103] H. Huang, S.C. Yin, L. F. Nazar, Electrochem. Solid State Lett. 4 (2001) A170.
[105] A.D. Spong, G. Vitins, J. R. Owen, J. Electrochem. Soc. 152 (2005) A2376.
[106] D.X. Gouveia, V. Lemos, J. A.C. de Paiva, A.G. Souza Filho, J. Mendes Filho,
[107] G.X. Wang, S. Bewlay, S. A. Needham, H.K. Liu, R.S. Liu, V. A. Drozd, J. F.
[108] H. Liu, Q. Cao, L.J. Fu, C. Li, Y.P. Wu, H.Q. Wu, Electrochem. Commun. 8
(2006) 1553.
173
References
--------------------------------------------------------------------------------------------------------------------------
[110] H. Huang, S.-C. Yin, and L.F. Nazar, Electrochem. Solid-state Lett. 4 (2001)
A170.
[111] P.S. Herle, B. Ellis, N. Coombs and L.F. Nazar, Nat. Mater. 3 (2004) 147.
[112] Z.X.Shu, R.S. McMillan, J.J. Murry, J. Electrochem. Soc.140 (1993) 922.
[115] J.R. Dahn, A.K. Sleigh, H. Shi, J.N. Reimers, Q. Zhong, B.M. Way,
[116] K. Sato, M. Noguchi, A. Demachi, N. Oki, M. Endo, Science 264 (1994) 556.
[117] J.R. Dahn, T. Zheng, Y.H. Liu, J.S. Xue, Science 270 (1995) 590.
[118] J.R. Dahn, A.K. Sleigh, H. Shi, B.M. Way, W.J. Wegdanz, J.N. Reimers, Q.
[119] T. Zheng, Y. Liu, E.W. Fuller, S. Tseng, U.V. Sacken and J.R. Dahn, J.
[121] G.T.-K. Fey and C.L. Chen, 10th International Meeting on Lithium Batteries,
[122] C.S. Wang, G.T. Wu, X.B. Zhang, Z.F. Qi and W.Z. Li, J. Electrochem.
[124] J.O. Besenhard, J. Yang and M. Winter, J. Power Sources 68 (1997) 87-90.
174
References
--------------------------------------------------------------------------------------------------------------------------
[126] K.D. Kepler, John T. Vaughey, and M.M. Thackeray, Electrochemical and
[127] O. Mao, R.A. Dunlap, and J.R. Dahn, J. Electrochem. Soc. 146 (1999) 405-423.
(1997) 1395.
[131] Ian A. Courtney and J.R. Dahn, J. Electrochem. Soc. 144 (1997) 2045.
[133] P. Poizot, S. Laruelle, S. Grugeon, L. Dupont and J-M. Tarascon, Nature 407
(2000) 496.
[134] P. Balaya, H. Li, L. Kienle, J. Maier, Adv. Funct. Mater. 13 (2003) 621.
[136] A. M. Wilson and J.R. Dahn, J. Electrochem. Soc. 142 (1995) 326.
[138] H. Li, X.J. Huang, L.Q. Chen, Z. G. Wu and Y. Liang, Electrochem. Solid-State
[139] J. Gratz, C.C. Ahn, R. Yazami, and B. Fultz, Electrochem. Solid-State Lett. 6
(1999) A194.
591.
175
References
--------------------------------------------------------------------------------------------------------------------------
[141] G.X. Wang, M.J. Lindsay, L. Sun, D.H. Bradhurst, S.X. Dou and H.K. Liu, J.
[142] C.S. Wang, G.T. Wu, X.B. Zhang, Z.F. Qi and W.Z. Li, J. Electrochem. Soc.
[144] J.O. Besenhard, J. Yang and M. Winter, J. Power Sources, 68 (1997) 87.
(1996) 3959.
[146] F.Disma, C. Lenain, B. Beaudoin, L. Aymard and J.-M. Tarascon, Solid State
[153] M.Yudasaka, T.Komatsu, T.Ichihashi, S.Iijima. Chem. Phys. Lett 278 102
(1997) 8.
[154] J.Kong, H.Soh, AM.Cassel, CF.Quate, H.Dai. Nature 395 (1998) 878-881.
176
References
--------------------------------------------------------------------------------------------------------------------------
[157] CJ.Lee, JH.Park, SY.Kang, JH.Lee. Chemical Physics Letters 326 (2000) 175 -
180.
(1999) 9.
[163] S.A. Needham, G.X. Wang, K. Konstantinov, Y. Tournayre, Z. Lao, H.K. Liu,
2122.
[166] R.Dominko, D.Arcon, A.Mrzel, A.Zorko, P.Cevc, P.Venturini, et al. Adv Mater
14 (2002) 1531 - 4.
(1993) 269.
[171] K. Sato, M. Noguchi, A. Demachi, N. Oki, and M. Endo, Science 264 (1994)
556.
177
References
--------------------------------------------------------------------------------------------------------------------------
[172] O. Mao, R.L. Turner, I.A. Countney, B.D. Fredericksen, M.I. Buckett, L.J.
[173] J.O. Besenhard, M. Hess and P. Komenda, Solid State Ionics 40/41 (1990) 525.
[174] G.X. Wang, J.H. Ahn, Jane Yao, Steve Bewlay and H.K. Liu, Electrochem.
[175] G.X. Wang, Jane Yao and H.K. Liu, Electrochem. Solid-state Lett. 7 (2004)
A250.
[176] D.C.S. Souza, V. Pralong, A.J. Jacobson and L.F. Nazar, Science 296 (2002)
2012.
[177] M.P. Bichat, J.L. Pascal, F. Gillot, F. Favier, Chem. Mater. 17 (2005) 6761.
[178] W. Jeitschko and D.J. Braun, Acta Cryst. B 34 (1978) 3196 – 3201.
[180] A. Dommam, R.E. Marsh and F. Hulliger, Journal of the Less-common Metals
152 (1989) 1.
- 1576.
178
References
--------------------------------------------------------------------------------------------------------------------------
[185] G.X. Wang, Steve Bewlay, Jane Yao, J.H. Ahn, S.X. Dou, and H.K. Liu,
[187] P.P. Prosini, D. Zane, and M. Pasquali, Electrochimica Acta, 46, (2001) 3517.
[188] S.Y. Chung, J.T. Bloking, and Y.M. Chiang, Nature Materials, 1 (2002) 123.
[189] P.S. Herle, B. Ellis, N. Coombs, and L.F. Nazar, Nature Materials, 3 (2004)
147.
[190] A. Yamada, Y. Kudo, and K.Y. Liu, J. Electrochem. Soc. 148 (2001) A747 –
A754.
[191] A. Yamada and S.C. Chung, J. Electrochem. Soc. 148 (2001) A960 – A967.
[192] A. Yamada, Y. Kudo, and K.Y. Liu, J. Electrochem. Soc. 148 (2001) A1153 –
A1158.
[193] A.C. Larson and R.B. Von Dreele, General Structure Analysis System, Los
[194] P.S. Herle, B. Ellis, N. Coombs, and L.F. Nazar, Nat. Mater. 3 (2004) 147.
[195] R.P. Santoro and R.E. Newnham, Acta Cryst. 22 (1967) 344.
[196] G. Rousse, J.R. Carvajal, S. Patoux, and C. Masquelier, Chem. Mater. 15 (2003)
4082.
179
References
--------------------------------------------------------------------------------------------------------------------------
[198] J.L. Tirado, Materials Sceince and Engineering R, 40 (2003) 103 – 136.
[200] A.R. Armstrong and P.G. Bruce, Nature, (1996) 499 – 500.
[203] G.H. Li, H. Ikuta, T. Uchida, M. Wakihara, J. Electrochem. Soc. 143 (1996)
178.
[205] A.R. Armstrong, A.J. Paterson, A.D. Robertson, P.G. Bruce, Chem. Mater., 14
(2002) 710.
[206] A.K. Padhi, K.S. Nanjundaswamy, and J.B. Goodenough, J. Electrochem. Soc.,
[208] K. Amine, H. Yasuda, and M. Yamachi, Electrochem. Solid State Lett. 3 (2000)
178 – 179.
[209] H. Huang, S.C. Yin, T. Kerr, N. Taylor, and L.F. Nazar, Adv. Mater., 14 (2002)
1525 – 1528.
180
References
--------------------------------------------------------------------------------------------------------------------------
[211] H. Huang, S.-C. Yin, and L.F. Nazar, Electrochem. Solid State Lett. 4 (2001)
A170 – A172.
[212] A.Yamada, S.C. Chung, and K. Hinokuma, J. Electrochem. Soc. 148 (2001)
A224 – A229.
[215] J. Barker, M.Y. Saidi, and J.L. Swoyer, Electrochem. Solid State Lett. 6 (2003)
A53 – A55.
[216] G.X. Wang, S. Bewlay, J. Yao, J.H. Ahn, S.X. Dou, and H.K. Liu, Electrochem.
[217] S. Franger, C. Bourbon, and F. Le Cras, J. Electrochem. Soc. 151 (2004) A1024
– A1027.
[218] C.H. Mi, X.B. Zhao, G.S. Cao, and J.P. Tu, J. Electrochem. Soc.152 (2005)
A483 – A487.
[219] P.S. Herle, B. Ellis, N. Coombs, and L.F. Nazar, Nature Materials, 3, (2004)
147 – 151.
[220] B.S. Berry and W.C. Pritchet, Solid State Commun. 26 (1978) 827 – 829.
[221] Y.N. Song, P.Y. Zavalij, N.A. Chernova, and M.S. Whittingham, Chem. Mater.
181
References
--------------------------------------------------------------------------------------------------------------------------
[222] R.P. Santoro and R.E. Newnham, Acta Cryst. 22 (1967) 344 – 347.
[223] Y.N. Song, P.Y. Zavalij, M. Suzuki, and M.S. Whittingham, Inorg. Chem. 41
[225] S.Y. Chung, J.T. Blocking, and Y.M. Chiang, Nature Materials, 1 (2002) 123 -
128.
[226] A.S. Andersson, B. Kalska, L. Häggström, J.O. Thomas, Solid State Ionics, 130
(2000) 41 – 52.
[227] A.S. Andersson, J.O. Thomas, J. Power Sources, 97 – 98 (2001) 498 – 502
182
Figure and table Captions
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Figure 2.7 The crystal structure of olivine LiFePO4 along [001]. Left:
Figure 2.8 Crystal structures of left: orthorhombic LiFePO4 and right: trigonal
quartz-like FePO4
Figure 2.9 a. Model displaying the connection among FeO6, LiO6 and PO4
183
Figure and table Captions
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CoO electrode.
cathodes
cells
Figure 4.1 SEM image of (a) bare MCMB graphite (b) 20 wt% nano
Si-MCMB ball milled for 5 hours. (c) 20 wt% nano Si-MCMB ball
hours
Figure 4.2 X-ray diffraction pattern of 20 wt% nano-Si-MCMB ball milled for
10 hours.
electrode (sample E)
184
Figure and table Captions
--------------------------------------------------------------------------------------------------------------------------
MCMB matrix.
Figure 4.5 The discharge/charge profiles of (a) bare nano-Si electrode (b)
Figure 4.6 The discharge capacity versus cycle number (Current density: 0.05
mAcm-2).
Figure 4.9 (a) TEM image of nanocrystalline Si powders. (b) TEM image of
Figure 4.12 The discharge capacity versus cycle number for Si-C electrode.
Table 4.1 Specific capacity in the first cycle for bare MCMB, bare
Figure 5.2 (a) (b) (c) and (d) SEM images of vertically aligned carbon
nanotubes.
Figure 5.3 (a) TEM image of carbon nanotubes. (b) HRTEM image of a
carbon nanotube.
185
Figure and table Captions
--------------------------------------------------------------------------------------------------------------------------
Figure 5.5 Discharge curves of the carbon nanotube electrode (The inset is the
electrode).
Figure 5.10 The first and second discharge and charge curves of SnO2-CNT
composite electrode.
Figure 5.11 Discharge capacity vs. cycle number for SnO2-CNT composite
number.
Figure 6.5 The discharge capacity of FeP4 anode vs. cycle number.
186
Figure and table Captions
--------------------------------------------------------------------------------------------------------------------------
Table 7.1 Phase composition and lattice parameters of olivine phase for
LiMnxFe1-xPO4 compounds.
Table 7.2 Selected interatomic distances (Å) and angles (deg) for
LiMnxFe1-xPO4 samples.
Figure 8.1 X-ray diffraction patterns of (a) LiFePO4 and (b) Li0.95Mg0.05FePO4.
Figure 8.2 SEM images of Li0.95Mg0.05FePO4 samples sintered at (A) 700 °C,
LiFePO4, samples (a) LFP-700 and (b) LFP-850. The insets are
Figure 8.6 The effective magnetic moment per mole of iron of LiFePO4 and
electrodes.
Figure 8.8 Charge/discharge curves in the first cycle for (a) LiFePO4 and (b)
187
Figure and table Captions
--------------------------------------------------------------------------------------------------------------------------
Figure 8.9 Discharge capacity vs. cycle number for LiFePO4 and
Table 8.1 Sintering temperature, label and average crystal size of lithium iron
phosphates.
samples.
188
Publications
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Publications
1. J. Yao, J.S Park, K. Konstantinov, G.X.Wang, J.H. Ahn, J. Wang and H.K. Liu
“Electrochemical performance of nanocrystalline SnO2-carbon nanotube
composites as anode in lithium-ion cells” Journal of Nanoscience and
Nanotechnology (in press).
2. J. Yao, K. Konstantinov, G.X. Wang, and H.K. Liu, “Electrochemical and magnetic
characterization of LiFePO4 and Li0.95 Mg0.05 FePO5 cathode materials” Journal of
Solid State Electrochemistry 11(5) (2007) 177 -185.
3. J. Yao, S. Bewlay, V.A. Drozd, R.S. Liu, X.L. Wang, H.K. Liu and G.X. Wang,
“Characterisation of olivine-type LiMnxFe1-xPO4 cathode materials” Journal of
Alloys and compounds 425 (2006) 362 – 366.
4. G.X. Wang, J. Yao, H.K. Liu, S.X. Dou and J.H. Ahn, “Growth and lithium storage
properties of vertically aligned carbon nanotubes” Metals and Materials
International 12(5) (2006) 413 – 416.
5. G.X. Wang, S. Needham, J. Yao, J.Z. Wang, R.S. Liu and H.K. Liu, “A study on
LiFePO4 and its doped derivatives as cathode materials for lithium-ion batteries”
Journal of Power Sources 159 (2006) 282 - 286.
6. G.X. Wang, Y. Chen, L. Yang, J. Yao, S. Needham, H.K. Liu and J.H. Ahn,
“Synthesis of nanocrystalline transition metal and oxides for lithium storage”
Journal of Power Sources 146 (2005) 487 - 491.
189
Publications
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7. G.X. Wang, S. Bewlay, J. Yao, J.H. Ahn, H.K. Liu and S.X. Dou,
“Characterisation of LiMxFe1-xPO4 (M=Mg, Zr, Ti) cathode materials prepared by
the sol-gel method” Electrochemical and Solid-state Letters 7(12) (2004) A503 –
A506.
8. G.X. Wang, J.H. Ahn, J. Yao, S. Bewlay and H.K. Liu, “Nanostructured Si-C
composite anodes for lithium-ion batteries” Electrochemistry Communication 6(7)
(2004) 689 – 692.
10. G.X. Wang, J. Yao, J.H. Ahn, H.K. Liu and S.X. Dou, “Electrochemical
properties of nanosize Sn-coated graphite anodes in lithium-ion cells” Journal of
Applied Electrochemistry 34 (2004) 187 – 190.
11. G.X. Wang, S. Bewlay, J. Yao, H. K. Liu, and S. X. Dou, “Tungsten Disulfide
Nanotubes for Lithium Storage”Electrochemical and Solid-State Letters 7 10
(2004) A321-A323.
190