Journal of New Materials for Electrochemical Systems 10, 101-104 (2007)

J. New Mat. Electrochem. Systems

The Impact of Nanomaterials on Li-ion Rechargeable Batteries

*
Hua Kun Liu, Guo Xiu Wang, Zai Ping Guo, Jia Zhao Wang and Kosta Konstantinov

Institute for Superconducting and Electronic Materials, ARC Centre of Excellence for Electromaterials Science
University of Wollongong, NSW 2522, Australia

Received: May 30, 2006, Accepted: December 20, 2006

Abstract: In this paper we report on the impact of nanomaterials on lithium rechargeable battery performances. Nanotubes (single wall
carbon nanotube and multi wall carbon nanotube, NiO and WS2), nano-intermetallic alloys (Cu6Sn5, Sn/SnSb and Sn/SnNi), nano-oxides
(NiO, CoO, SnO2 and Co3O4), nano-composites (C-LiFePO4, Si-C, Si-MCMB (mesocarbon microbeads), Si-TiC, Si-PPY (polypyrrole) and
MWNT(multiwalled nanotubes)/Sn/SnNi), as well as other nanoparticles (TiO2, SiO2 and Al2O3) have been used in lithium rechargeable
batteries in our studies. Free-standing single wall carbon nanotube (SWNT) papers produced without any binder and metal substrate
shows a capacity slightly lower than that of the conventional electrode. Carbon-coated Si nanocomposites produced by a spray-pyrolysis
technique can reversibly store lithium with a high capacity of 1489 mAh/g and a high coulumbic efficiency above 99.5%, even after 20
cycles. Nanosize 10 wt% TiO2 increased the ionic conductivity of PEO-LiClO4 polymer electrolyte by a factor of 2 at room temperature
and at elevated temperature.

Keywords: nanotubes, nanointermetallic alloys, nanooxides, nanocomposites, lithium rechargeable batteries

1. INTRODUCTION next generation of lithium rechargeable batteries.

High performance of a lithium rechargeable battery depends
strongly on the electrode and electrolyte materials. Metallic lith-
ium as an anode material has an excellent specific capacity of 3860
mAh/g. However, lithium dendrites will grow on anode during
charging, and if they reach the cathode, an internal short circuit
occurs. The replacement of lithium metal by carbonaceous materi-
als solves the dendrite problem but brings lower specific capacity
(since the theoretical specific capacity of graphite is 372 mAh/g).
Li-alloys have higher lithium storage capacities than carbonaceous
materials, however, the major drawback for lithium alloy elec-
trodes is their poor cyclability, which is caused by mechanical
cracking or crumbling due to the volume expansion of alloys ac-
companying lithium insertion [1]. In the new battery technology,
there is a renewed interest in metal alloys and intermetallic com-
pounds for replacing graphic carbon as the anode of choice in
lithium-ion batteries [2]. Nanotubes, nanostructured intermetallic
alloys, nano-oxides and nano-composites as electrode materials
may solve the volume expansion problem, avoid the high irreversi-
ble capacity and improve the electrochemical properties for the
*To whom correspondence should be addressed: Email: hua_liu@uow.edu.au
Fax: 61242215731
Among the polymer electrolyte systems reported, conventional
polyethylene oxide (PEO)-based electrolytes are the most com-
monly used, a very few literatures are available on other composite
polymer electrolytes. The objection to their use is that the conduc-
tivity is too low to satisfy the general requirement of batteries, or
of other practical electrochemical devices. It was reported that the
addition of TiO2 to polymer electrolyte has a good absorption ca-
pability, and enables plasticising liquid electrolyte to be loaded
onto the polymer electrolyte film. It would be very useful to inves-
tigate the influence of nano-size TiO2 on the ionic conductivity of
polymer electrolyte.
2. EXPERIMENTAL
Nanocrystalline NiSi, FeSi-Si and Ni3Sn4 powders were synthe-
sized by high-energy ball milling. WS2 nanotubes were synthe-
sized by sintering amorphous WS3 at high temperature under flow-
ing hydrogen. Free-standing single wall carbon nanotube
(SWNT) papers were synthesized by simple filtration method via
positive pressure. Nanostructured Si-C composite materials were
prepared by dispersing nanocrystalline Si in carbon aerogel and
subsequent carbonization or by a spray-pyrolysis technique. Si-

101
102 Hua Kun Liu et al. / J. New Mat. Electrochem. Systems

disordered carbon (DC) nanocomposites were synthesized by

high-energy ball-milling of Si-sucrose and Si-polyvinyl alcohol
followed by pyrolysis under flowing argon. Nanocrystalline Si-
mesocarbon microbeads (MCMB) composite anode materials
were prepared by ball milling. Nanocrystalline multi-walled car-
bon nanotube (MWNT)-Sn and MWNT-SnNi composite anode
materials were prepared by chemical reduction of SnCl2 and NiCl2
precursors in the presence of MWNTs. Phase-pure LiMxFe1-xPO4
(M = Mg, Zr, Ti) compounds were prepared by sol-gel synthesis.
A layer of carbon was coated on the surface of the lithium crys-
tals. Nanoparticles (TiO2, SiO2 and Al2O3) were dispersed in poly-
mer electrolytes of polyethylene oxide (PEO) under soft magnetic
stirring with lithium salt (LiCF3SO3, LiClO4 and LiPF6) or by ball
milling.

3. RESULTS AND DISCUSSION

3.1. Nanomaterials used in anode
3.1.1. Nanocrystalline intermetallics
Nanocrystalline intermetallic NiSi alloy prepared by high en-
ergy ball milling showed a high lithium storage capacity of 1180
mAh/g in the initial discharge, in which Si acted as an active ele-
ment to combine with Li to form LixSi. This reaction was partially Figure 1. TEM image of nanocrystalline Si-C composites
reversible and its capacity declined with each cycle [3].
Nanocrystalline intermetallic Ni3Sn4 alloy prepared by high
energy ball-milling exhibited a very high initial lithium capacity
tubes), which is much higher than for WS2 powders (where the
of 1515 mAh/g which can not be explained by only the lithium
lithium insertion capacity was only 0.6 mol Li+ per mole of crys-
intercalated in the alloy and formed Li4.4Sn phase, corresponding
talline WS2). After the first cycle, the WS2 nanotube electrode
to the maximum lithium storage capacity of 724 mAh/g. So some
exhibited stable cycling behaviour over a wide voltage range of
supplementary reactions (Li-Sn, Li-Ni-Sn etc) must be considered.
0.1 3.1 V versus Li/Li+[7].
However, the capacity declined quickly after the first cycle (775
mAh/g) [4].
3.1.3. Nanocomposites
Si-C composites prepared by dispersing nanocrystalline Si in
3.1.2. Nanotubes
carbon aerogel and subsequent carbonization exhibit a reversible
A conventional SWNT slurry coated electrode was fabricated to
lithium storage capacity of 1450 mAh/g [8]. Fig. 1 shows a TEM
compare with the SWNT papers. The capacity of the free-
image of nanostructured Si-C composite powders. It can be clearly
standing electrode was slightly lower than that of the conven-
seen that Si particles are surrounded by amorphous carbon. The
tional electrode, but the free-standing electrode was produced
nanosize spherical Si particles are in the range of 20 nm to 80 nm.
without any binder, and metal substrate, so that the weight of elec-
Carbon-coated Si nanocomposites produced by a spray-pyrolysis
trode was reduced significantly. Also, the procedure for SWNT
technique can reversibly store lithium with a high capacity of
electrode preparation was simplified and the cost of the manufac-
1489 mAh/g and a high coulumbic efficiency above 99.5%, even
ture could be reduced [5].
after 20 cycles [9], which are better than the capacities of Si-Ni-C
Multiwall carbon nanotubes (MWNTs) synthesized by chemical
composite (1000 mAh/g) and Si-Ni alloy-C composite (800
evaporation deposition demonstrated a reversible lithium storage
mAh/g) [10].
capacity of 340 mAh/g at moderate current density. MWNTs con-
The optimized Sidisordered carbon (DC) nanocomposite an-
sist of graphitic sheets rolled into closed concentric cylinders [6].
ode demonstrated a reversible capacity of 754 mAh/g over 20
Lithium ions only can combine with every second hexagon on the
cycles (Fig. 2) [11]. In Si-DC nanocomposites, the nano-sized Si
external surface of rolled grapheme sheet. The limiting
particles are separated and coated by disordered carbon, which
stoichiometry would be less than LiC6 and the maximum lithium
could not only suppress the decomposition of electrolyte on the
storage capacity should be less than the theoretical capacity of 372
surface of Si-based electrode, but also provide integral and con-
mAh/g.
tinuous electric contact network around the Si particles even when
WS2 nanotubes were synthesised by sintering amorphous WS2
they are slightly expanded after lithium insertion [12].
at high temperature under flowing hydrogen. High resolution
Nano-Si-MCMB anode in lithium rechargeable batteries shows
TEM observation revealed that the as-prepared WS2 nanotubes
superior performance. MCMB graphite is almost dimensionally
have an open end with an inner hollow core of about 4.6 nm.
invariable during lithium insertion and extraction. The volume
Compared to the crystalline WS2 powders, WS2 nanotubes demon-
change is small as the Si particles are nanosize in nature. The an-
strate significant different electrochemical properties. WS2 nano-
odic performance is greatly improved either by applying pressure
tube electrodes show a lithium insertion capacity of about 915
on the cells or by loading a larger amount of conductive carbon in
mAh/g (corresponding to 8.6 mol lithium per mole of WS2 nano-
 The Impact of Nanomaterials on Li-ion Rechargeable Batteries / J. New Mat. Electrochem. Systems
Figure 2. Cycle life behavior of Si-disordered carbon nanocompo-
sites. The current density was 50mA/g. Z.P. Guo, E. Milin, J.Z.
Wang, J. Chen, H.K. Liu, J. Electrochem. Soc., 152, A2211 (2005)
with permission of the Electrochemical Society.
Figure 3. The discharge capacity vs cycle number. The current
density was 50 mA/g. Z.P. Guo, Z.W. Zhao, H.K. Liu, S.X. Dou,
Carbon 43, 1392 (3005) with permission of Elsevier.
the composite electrodes [13].
MWNT-Sn and MWNT-SnNi anodes have demonstrated a high
first discharge capacity (570 and 512 mAh/g for MWNT-Sn and
MWNT-SnNi anodes, respectively), high charge/discharge effi-
ciency in the first cycle (77.5% and 84.1% for MWNT-Sn and
MWNT-SnNi anodes, respectively) (Fig. 3), and good cyclability
(0.99 loss%/cycle for MWNT/SnNi anode) [14].
3.2. Nanomaterials used in cathode
Nanocrystalline LiMxFe1-xPO4 (M = Mg, Zr, Ti) compounds
prepared by sol-gel synthesis dramatically enhance the electronic
conductivity. High Resolution Electron Transmission Spectroscopy
image and EDS analysis of a LiFePO4 particle confirmed that the
103
Figure 4. (a) TEM image of LiFePO4 powder (40 nm - 150 nm)
and (b) HRTEM image of a single LiFePO4 crystal. (A thin layer
of unorganized carbon was coated on the surface of the LiFePO4
crystals.) G.X. Wang, S. Bewlay, J. Yao, J.H. Ahn, S.X. Dou,
H.K. Liu, Electrochem. Solid-State Letter, 7, A503 (2004) with
permission of the Electrochemical Society.
outside layers are amorphous carbon and the inside crystallites are
lithium iron phosphates (Fig. 4). This means that a thin layer of
unorganised carbon was coated on the surface of the LiFePO4 crys-
tals. During the sol-gel process, the gel complexes and precursors
were sintered in an inert atmosphere. Carbon was formed from the
decomposition of the organic compounds. The Ti-doped and un-
doped lithium iron phosphates demonstrated a stable discharge
capacity of approximately 160 165 mAh/g [15], almost approach-
ing the theoretical capacity, at the low rate of C/8. The good elec-
tronic conductivity and nanocrystallinity could contribute to the
excellent electrochemical performance of the lithium iron phos-
phates.
Conducting HClO4-doped poly(aniline) nanotubes and nanofi-
bers prepared through a template route and a spray technique re-
spectively exhibited higher electrical conductivity, large charge-
discharge capacity, and better cycling capability than the commer-
cial doped PANI powders. The electrochemical results showed the
promising application of the doped PANI nanostructures in
Li/PANI rechargeable batteries [16].
3.3. Nanomaterials used in electrolytes
Nanosize TiO2 powders can effectively improve the conductivity
of PEO-LiClO4 by a factor of 2 both at room temperature and at
elevated temperature [17]. This is because nanoparticles with large
surface area can prevent the PEO chain reorganisation at room
temperature and thus enhance the ionic conductivity. Nanosize
TiO2 powders are highly polar chemicals with many hydrophilic
groups on the surface of the grains, such as COOH and OH.
These highly polar groups can react with the anions and the PEO
segments, and thus reduce the ion aggregation, increase the fraction
of free lithium cations and enhance the ionic conductivity. The
incorporation of the inert filler reduces the crystallinity of the poly-
mer host and acts as solid plasticizer capable of enhancing the
transport properties [18]. Also, fast ion conduction can proceed at
the highly conductive interface layer between the PEO matrix and
the nanoparticles, according to the effective medium theory [19].
104 Hua Kun Liu et al. / J. New Mat. Electrochem. Systems

4. CONCLUSIONS
High performance of a lithium rechargeable battery depends
strongly on the electrode and electrolyte materials. Our results
show that the nanomaterials used in electrodes and electrolytes can
improve the performance of lithium rechargeable batteries.
Nanocrystalline intermetallic alloys, nanosize composite materials,
nanotubes and nano-oxides are promising materials for use in lith-
ium-ion rechargeable batteries.

5. ACKNOWLEDGEMENTS
The authors would like to acknowledge financial support from
the Australian Research Council through the ARC Centre of Excel-
lence for Electromaterials Science and also Dr. T. Silvers great
help in improving the manuscript.

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