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Small things make a big difference: binder effects

on the performance of Li and Na batteries
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Cite this: Phys. Chem. Chem. Phys.,

2014, 16, 20347
Shu-Lei Chou,* Yuede Pan, Jia-Zhao Wang, Hua-Kun Liu and Shi-Xue Dou

Li and Na batteries are very important as energy storage devices for electric vehicles and smart grids. It is
well known that, when an electrode is analysed in detail, each of the components (the active material, the
conductive carbon, the current collector and the binder) makes a portion of contribution to the battery
performance in terms of specific capacity, rate capability, cycle life, etc. However, there has not yet been a
review on the binder, though there are already many review papers on the active materials. Binders make up
only a small part of the electrode composition, but in some cases, they play an important role in affecting
the cycling stability and rate capability for Li-ion and Na-ion batteries. Poly(vinylidene difluoride) (PVDF) has
Received 5th June 2014, been the mainstream binder, but there have been discoveries that aqueous binders can sometimes make a
Accepted 17th June 2014 battery perform better, not to mention they are cheaper, greener, and easier to use for electrode fabrication.
DOI: 10.1039/c4cp02475c In this review, we focus on several kinds of promising electrode materials, to show how their battery
performance can be affected significantly by binder materials: anode materials such as Si, Sn and transitional
www.rsc.org/pccp metal oxides; cathode materials such as LiFePO4, LiNi1/3Co1/3Mn1/3O2, LiCoO2 and sulphur.

1. Introduction and energy crisis. The development of greener, cheaper, and

safer rechargeable batteries is considered today as a goal of
Electrochemical energy storage and conversion systems play a strategic importance for energy storage technology.1–4 One of
crucial role in our daily life and are also of great interest for our the most important types of rechargeable batteries in daily life is
future because they offer solutions to our environmental issues the Li-ion battery (LIB), which provides high energy density, long
cycle life, and relatively good power capability.5,6 The schematic
Institute for Superconducting and Electronic Materials, University of Wollongong,
drawing in Fig. 1 shows current and future promising energy
Wollongong, New South Wales, Australia. E-mail: [email protected]; storage systems plotted using cost vs. energy. The current Li-ion
Tel: +61 4298 1405 battery is suitable for portable devices. Cost and safety issues are

Shulei Chou is a Research Fellow in Yuede Pan received his BS and

the Institute for Superconducting MS degrees in Materials Physics
and Electronic Materials (ISEM) and Chemistry from Nankai
at Australian Institute of University in 2009 and 2012,
Innovative Materials, University respectively. He is currently a PhD
of Wollongong (UOW). He candidate under the supervision of
obtained his bachelor’s (1999) Prof. Shi Xue Dou, Prof. Hua Kun
and master’s degree (2004) from Liu, and Dr Shulei Chou at ISEM,
Nankai University, China. His University of Wollongong, Australia.
PhD degree was received from His research focuses on advanced
UOW with the best thesis award materials for novel binders, new
in 2010. He has also been separators, and electrode materials
Shu-Lei Chou awarded Australian Postdoctoral Yuede Pan in Li-ion and Li-S batteries.
Fellowship (2011) and UOW Vice-
Chancellor’s Award for Excellence Emerging Researcher (2014). His
research has been focused on energy storage materials for battery
applications, especially on novel composite materials, new binders,
and new electrolytes for Li-ion and Na-ion batteries.

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the major obstacles for Li-ion batteries to be used in electrical

vehicles and smart grids.7–9 A Li-ion supercapacitor with high rate
capability and relatively high energy density would be a good
candidate to replace the currently used lead acid batteries for power
tools and car starter batteries.10 Newly developed high energy
density systems such as Li–sulphur and Li–air batteries would be
more suitable for electric vehicles. However, safety issues would still
be a major concern for such systems due to the involvement of pure
Li metal.11 The sodium ion battery as one of the lowest cost systems
would be a good candidate for the storage of renewable energy.
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Further development is required as the current state-of-the-art

sodium ion batteries show poor rate capability, short cycle life,
and low energy density.12,13 As most previous reviews have been Fig. 1 Cost vs. energy plot for different energy storage systems.
intensively focused on the active materials for both anode and
cathode materials,1–13 with little attention to binders, here, we will
only focus on the effect of various binders on the performance of Batteries can rationally be divided into two types: the
electrode materials in Li-ion batteries and Na-ion batteries. primary battery and the rechargeable battery. The only differ-
ence between these two types of batteries is the rechargeability.
Therefore, the cycle life is a very important factor for recharge-
able batteries. As demonstrated in Fig. 2, both Li and Na ion
Jiazhao Wang was born in Harbin, batteries are composed of anode and cathode electrodes which
China, and received her PhD degree are soaked in an electrolyte and separated by a separator. Both
at the University of Wollongong, electrodes consist of active materials, a conductive agent, the
Australia in 2003. She is an current collector and a binder. The active materials determine
associate professor at the the energy of the electrode. The conductive agent can improve
University of Wollongong, and she the rate capability of the electrode owing to the enhanced
has been a team leader for three transportation of electrons. The binder is used to glue the
Discovery Projects, and one Linkage active materials and conductive agent together with the current
project, which are granted by collector. Therefore, the electrons can flow from/to the outside
Australia Research Council. She is circuit through the active materials–conductive agent–current
the author of more than 140 collector chain. Although binders only occupy 2–5% of the
publications. Her h-index factor is mass in a commercial electrode configuration, the binder
Jia-Zhao Wang 38. Her research has been focused material is one of the most crucial electrode components for
on energy storage materials for improved cell performance, especially for cycle life. Without the
battery applications, especially on conducting polymers, composite binder, the active materials will lose contact with the current
materials, and ionic liquid electrolytes for Li-ion and Li-S batteries. collector, resulting in capacity loss.

Hua Kun Liu is a Distinguished Shi Xue Dou is a distinguished

Professor and leader of the energy Professor and Director of the
materials research program at ISEM at UOW, Australia. He
ISEM, University of Wollongong, received his PhD in chemistry in
Australia, and a Fellow of 1984 at Dalhousie University,
Australian Academy of Techno- Canada. He was elected as a
logical Science and Engineering. Fellow of the Australian Academy
She received the UOW Vice- of Technological Science and
Chancellor’s Award for Research Engineering in 1994. He was
Excellence Senior Researcher in awarded a DSc by the University
2013, and won the most com- of New South Wales in 1998. He
petitive ARC Australian Professorial received the Australian Govern-
Hua-Kun Liu Fellowships in 17 years (1994–1998, Shi-Xue Dou ment’s Centenary Medal in 2003,
1999–2003, 2003–2005 and 2006– Vice-Chancellors Senior Excellence
2010). She has supervised 50 PhDs to completion and 30 postdoctoral Award in 2008, Vice-Chancellor Outstanding Partnership Award in
and visiting fellows, and published 2 Books, 10 review papers, and more 2012. His publications attracted over 15600 citations with a h-index
than 500 refereed journal papers with total citations 416600, h-index: >55. He specialises in energy and electronic materials for applications.
59 (Web of Science).

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solvents. On the other hand, the other three types of binder are
naturally abundant and can be dissolved in water, which makes the
electrode preparation process cheap and environmentally friendly.
Recently, aqueous binders have been gradually replacing PVDF
binder for the anode.20,21 The advantages of aqueous binders are
as follows: (1) low cost, (2) no pollution problem, (3) enhancement
of the active material ratio in a cell owing to the reduction of binder
content, (4) no requirement for strict control of the processing
humidity and (5) fast drying speed in electrode fabrication. Since the
binders’ function is different in different materials and systems, we
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will review the recent findings in details based on the major active
Fig. 2 Schematic drawing of a Li/Na ion battery. materials for both battery systems.

Typical binders used in the Li/Na ion battery are summarized in 2. Binders for lithium ion batteries
Table 1. Poly(vinylidene difluoride) (PVDF) binder is the most widely
used binder for Li-ion cells. This is due to its good electrochemical 2.1 Anode materials
stability and binding capability, as well as its ability to absorb 2.1.1 Carbon based materials. Graphite based materials
electrolyte for facile transport of Li to the active material surface.14–19 have been the most common commercially used anode materials
However, PVDF requires the usage of toxic and expensive organic for Li-ion batteries for more than 20 years. Lee et al. first reported

Table 1 Typical binders, their molecular structures and the corresponding electrode materials and references

Name Molecular structure Electrode materials Ref.

Graphite 25, 26 and 27
Si 31, 35 and 45
SnO2 46
SnCoC 47
Sn 48
Polyvinylidene fluoride (PVDF)
Fe2O3 49
NiO 51
CuO 52
Li4Ti5O12 54
Sulphur 97, 99–102 and 105

Graphite 22 and 23
Si 31–34 and 39
SnO2 46
SnCoC 47
Sn 48
Fe2O3 49 and 50
NiO 51
CuO 52
Carboxymethyl cellulose (CMC) Li4Ti5O12 54 and 55
LiCoO2 72
LiFePO4 74–79
Li2MnO3–LiMO2 (M = Ni, Mn, or Co) 80
LiNi0.4Mn1.6O4 81
LiNi1/3Mn1/3Co1/3O2 87
Sb 107a
Sulphur 104
Amorphous phosphorus 107b

Graphite 25, 27 and 28

Si–graphite 40
SnCoC 47
Polyacrylic acid (PAA) Sulphur 100 and 103
Amorphous phosphorus 107b

LiCoO2 73
Sulphur 92–98

Polyethylene glycol (PEG)

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the usage of CMC as a binder for graphite.22 CMC can lead to through electrostatic repulsion.28 With less polymer aggrega-
improved adhesion strength, giving the as-fabricated cell an tion, a more homogeneous coating may be obtained. The PAA
attractive cycle life with more than 90% of the initial discharge based binders resulted in brittle electrodes that showed macro-
capacity retained after 200 cycles. During the electrode prepara- size cracks upon drying; however, the cracks can be suppressed
tion, the important step is to make the slurry uniform and coat if small amounts of SBR (0.5–3%) are added to the electrode.
onto the current collector. Although the slurry can be homo- Unfortunately, the conductivity decreased monotonically with
geneous, after drying, it can be hard to maintain uniform the addition of SBR. Therefore, the rate capability of an
distributions of the binder and active materials. Wang et al. electrode would be limited.
proposed that the acetylene black and CMC binder may become 2.1.2 Silicon-based materials. Silicon is one of the most
concentrated near the contact points between two adjacent promising anode materials for Li-ion batteries because it has the
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graphite spheres because of the capillary effect of the binder highest theoretical capacity (3579 mA h g 1, Li3.75Si) and the raw
solution.23 The conductive bridge (acetylene black/binder) materials are abundant in nature. However, cycling stability is
between the graphite spheres is very effective for improving the the major problem for Si-based materials due to the large
electrical contact between the graphite spheres during long volume expansion, up to 270%, after lithiation.29,30 In this
cycling. Organic-based electrode sheets show more non- regard, the elastomer is an attractive binder because it permits
uniform distributions of the binder and the graphite. According a high active material ratio and high flexibility compared to the
to migration-controlled drying kinetics, the migration of the conventional PVDF binder. Buqa et al. first reported that a nano-
binder to the top surface of an electrode sheet is primarily caused Si electrode containing 1% sodium carboxymethyl cellulose
by the flow of solvent during drying. Because of the lower (CMC) as a binder showed the same cycling stability as an
evaporation rate of N-methyl pyrrolidone (NMP) and the longer identical electrode containing 10% conventional PVDF binder.31
drying time of the organic-based slurry, the uniformity of PVDF in Li et al. proposed that the CMC binder may act as a surface
the dried electrode sheet was found to be much poorer than that modifier promoting the formation of a stable SEI passive
for the water-based SBR/CMC.24 Therefore, the performance in layer.32 Lestriez et al. claimed that the extended conformation
terms of adhesion, resistance, and charge–discharge efficiency of CMC in solution facilitates an efficient networking process
was much poorer than that of the water-based electrode. between the conductive agent and the Si particles.33 Hochgat-
Chong et al.25 reported that lithium poly(acrylic acid) terer et al. reported that the chemical bonding between CMC
(PAALi) and sodium poly(acrylic acid) (PAANa) offered better binder and Si particles contributes to the enhanced capacity
cell performance for spherical natural graphite in terms of retention of Si/C composite electrodes.34 They suggested that
capacity and initial coulombic efficiency (Fig. 3) than PVDF, the cohesive strength between the binder and active particles is
which was attributed to a more favourable polymer conforma- an important factor. This hypothesis was supported by a
tion in the composite. The initial coulombic efficiency of the previous report where replacing the PVDF binder with a mod-
cells with PAALi and PVDF is 92.6% and 85%, respectively. For ified acrylic adhesive increased the capacity retention of a Si/C
PVDF, 70% of the solid electrolyte interphase (SEI) is formed in electrode from 67% to 90% (over 50 cycles). The peel strength of
the first cycle,26 and several subsequent cycles form a stable the acrylic adhesive (7 N) was much higher than that of PVDF
interface.27 A more effective and stable SEI layer appeared to (0.4 N).35 Choi et al. reported that the use of a high-strength
form in fewer cycles with the PAAX binders, where X = Li, Na, or polyamide-imide (PAI) binder can increase the initial coulombic
K.27 For PAAX, Li, Na, or K dissociates, leaving negative charges efficiency of a Si-based electrode from 29% to 75%.36 Garsuch
on the polymer chains that suppress aggregation of the polymer et al. reported that when lithium-exchanged Nafion was used as
a binder for a crystalline silicon and carbon composite, it
showed reversible specific capacities ranging from 800 to nearly
1000 mA h g 1 between 0.9 and 0.17 V.37 These results indicate
that the choice of binder system has a critical impact on the
performance of alloy anodes.
A simple model was proposed by Beattie et al. to explain the
excellent cycling results for low-Si-concentration electrodes.38
They used geometrical considerations to design an electrode
that can accommodate large changes in volume due to particle
lithiation and delithiation during cycling (Fig. 4). The largest Si
loading was calculated to be 20 vol% based on the theoretical
expansion of Si (270%). Since the electrode porosity was not
considered in the model, an electrode with 33 wt% Si (100 nm) +
33 wt% CMC + 33 wt% carbon was also shown to cycle well and
with a high capacity of 1200 mA h g 1. Our group reported a
simply mixed nano-sized Si and graphene composite using
Fig. 3 The cycle performance of a spherical natural graphite anode with CMC as a binder that could achieve a capacity of 1168 mA h g 1
different binders. Reproduced from ref. 25 with permission from Elsevier. based on the total composite weight and a capacity of more

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Fig. 4 Simple model to calculate the Si concentration in electrodes.

Reproduced from ref. 38 with permission from The Electrochemical
Society.
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than 2000 mA h g 1 based on the contribution of Si up to

30 cycles.39 Fig. 6 Reversible Li-extraction capacity of nano-Si electrodes with alginate,
Han et al. investigated the impact of the degree of neutra- CMC, and PVDF binders vs. cycle number. Reprinted from ref. 41 with
permission from AAAS.
lization of poly(acrylic acid) on electrode performance for
Si–graphite composite electrodes.40 Excellent capacity retention
for a 100 cycle test with a high reversible capacity of approxi- was far better than that for Si anodes using PVDF and Na–CMC
mately 1000 mA h g 1 is achieved with 80% neutralized as binders (Fig. 6). Such electrodes also show excellent high rate
(PAH0.2Na0.8) PAA as a binder for Si-based composite electro- capability. At a current density of 4200 mA g 1, the reversible Li
des. It was found that 80% neutralized PAA provides a moder- extraction specific capacity of an alginate-based Si anode is in
ately porous structure inside the composite electrode with the range of 1700 to 2000 mA h g 1 (Fig. 6). The surface
10 wt% binder content because of its unique rheological bonding between the binder and Si can be observed.
properties during the drying process after the slurry is coated The high concentration of functional (carboxylic) groups in
onto the current collector. The self-formed porous structure PAA and CMC is probably a major cause of their superior
arising from the partially neutralized PAA is beneficial for performance. A certain fraction of the COOH groups in PAA
buffering the volume expansion caused by lithiation of Si, as form strong hydrogen bonds with OH groups on the Si (or C)
shown in Fig. 5. surface. The remaining carboxy groups form ionically conduc-
So far, the highest performance that an aqueous binder can tive COOLi groups and, together with the solid electrolyte
achieve for Si materials was reported by Magasinski et al. interphase (SEI) formed during the first Li insertion, protect
Alginate, a high-modulus natural polysaccharide extracted the Si–C interface and thus the anode electrical connectivity
from brown algae, yields a remarkably stable Si-based anode.41 from degradation upon solvent intercalation. To see the influ-
Unlike many polysaccharides commonly found in terrestrial ence on mechanical properties of the binder, atomic force
plants, alginate, a major constituent of brown algae and many microscopy (AFM) was used to measure the mechanical proper-
aquatic microorganisms, contains carboxylic groups in each of ties of the binder and silicon surface. Magasinski et al. reported
the polymer’s monomeric units. An alginate binder allowed for that the moduli of PAA and Na–CMC do not change when
a stable capacity of B1800 mA h g 1 for up to 100 cycles, which exposed to diethyl carbonate (DEC). In contrast, the stiffness of
PVDF was significantly decreased by contact with DEC as
shown in Fig. 7.42

Fig. 5 Schematic illustration of the improved mechanism for Si–graphite Fig. 7 Results of AFM stiffness measurements for films made from PAA,
composite electrodes with PAH0.2Na0.8. Reproduced from ref. 40 with CMC, and PVDF. Reproduced from ref. 42 with permission from the
permission from The Royal Society of Chemistry. American Chemical Society.

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Fig. 8 Molecular structure of PF-type conductive polymers, with two key

functional groups in PFFOMB, carbonyl and methylbenzoic ester. Repro-
duced from ref. 43 with permission from John Wiley and Sons.
Fig. 9 Charge–discharge profiles of (a) a cross-linked PAA–CMC binder
(red line) and (b) a PVDF binder (blue line) at the current density of 175 mA
Through a combination of experimental and theoretical g 1 at 30 1C in the potential range of 0.005 to 2.0 V versus Li/Li+. The black
lines represent the electrode volume changes during Li insertion and
simulations, Liu et al.43 developed a new conductive binder, extraction processes. Reproduced from ref. 44 with permission from John
poly(9,9-dioctylfluorene-co-suorenone-co-methylbenzoic acid) Wiley and Sons.
(PFFOMB), as shown in Fig. 8, for a Si electrode showing a
high capacity of 2100 mA h g 1 for Si (1400 mA h g 1 for the
electrode) and a long cycle life of up to 650 cycles. The
molecular structures of PFFOMB were based on polyfluorene
(PF)-type polymers. Carbonyl, CQO, was introduced to tailor
the lowest unoccupied molecular orbital (LUMO) electronic
states so that the electrons could cathodically dope the polymer
to achieve adequate electronic conductivity during lithiation
and delithiation in the potential range of 0.01–1 V (Li/Li+).
Methylbenzoic ester, –PhCOOCH3 (MB), was added to improve
the polymer adhesion. The developed polymer features much
improved electric conductivity and a robust mechanical bind-
ing force, which maintains electrical connectivity and accom- Fig. 10 (a) Mussel; the inset shows the chemical structure of dopamine
modates the Si volume change simultaneously. However, the inspired by mussel foot proteins. (b) Structural formula of Alg–C and PAA–
toxic nature of the binder and the low initial coulombic C conjugated polymer binders. Reproduced from ref. 45 with permission
from John Wiley and Sons.
efficiency are still disadvantages.
Koo et al.44 reported that nano-sized silicon powder in a
three-dimensionally interconnected network of poly(acrylic
acid) and sodium carboxymethyl cellulose as binder exhibited Further studies to improve performance will be devoted to
a high reversible capacity of over 2000 mA h g 1 after 100 cycles exploring new binder materials and different types of carbons
at 30 1C and maintained a superior capacity of 1500 mA h g 1 to introduce artificial porosity and limit electrolyte decomposi-
for a high current density of 30 A g 1 at 60 1C. The use of a tion. The initial coulombic efficiency is also a crucial factor if Si
cross-linked polymer binder better accommodated the expan- materials are to be used commercially in a full cell. The large
sional strain of silicon in the fully lithiated state compared to amount of binder used in the electrode may reduce the volu-
the PVDF binder (Fig. 9) because the polymer chains were metric density of the electrode and bring in more side reactions
linked in three dimensions. to further lower the coulombic efficiency.
Ryou et al.45 demonstrated that cross-linked alginate (Alg) 2.1.3 Sn and other alloy based. CMC was also used as a
and catechol, which was a mussel-inspired adhesive material, binder to investigate its effects on the electrochemical perfor-
(Fig. 10) exhibited superior cycling performance compared to mance of Sn-based materials. Our group reported that using
Si-PVDF, indicating that binding based on catecholic adhesion CMC as a binder for commercial SnO2 nanoparticles showed
and hydrogen bonding was more effective for cycling perfor- much better performance than that of the carbon-coated com-
mance than simple van der Waals interactions. After 400 cycles, mercial SnO2 nanoparticles using PVDF as a binder in terms of
both Si–Alg–C and Si–Alg fully retained their initial capacities of cycling stability.46 The highest specific capacity reported was
around 2000 mA h g 1. The binders can be directly observed at 502 mA h g 1 up to 50 cycles at a current density of 100 mA g 1.
the peeling interface between the detached electrode film and Dahn et al.47 reported that a lithium polyacrylate (Li-PAA)
the Cu foils. At this interface, Si–Alg–C showed much more binder performed even better than the CMC binder. An amor-
elongated bridges than those observed for Si–Alg and Si–PVDF, phous SnCoC electrode using a Li-PAA binder showed an excel-
indicating the much better film adhesion resulting from Alg–C. lent capacity retention of 450 mA h g 1 for at least 100 cycles as

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Fig. 11 Cycle life of nano-Sn and nano-Sn–PPy composite electrodes

using CMC and PVDF as the binder, respectively. Reproduced from ref. 48
with permission from The Royal Society of Chemistry.
Fig. 12 SEM images of NiO electrodes with CMC binder (left) and PVDF
binder (right): (a and b) after cycling; (c and d) cross-sections of electrodes
after cycling. Insets in (e) and (f) show enlargements of the indicated areas.
compared to less than 20 cycles when using the PVDF or CMC Reproduced from ref. 51 with permission from Springer.
binders. The results indicated that the choice of binder system
has a critical impact on the performance of Sn-based alloy
anodes.
Our group demonstrated that a nano-Sn–polypyrrole com-
posite using CMC as the binder had both enhanced capacity
retention and good rate capability. Scanning electron micro-
scopy (SEM) images showed that both CMC and polypyrrole
(PPy) can work as composite binders and prevent the formation
of cracks in electrodes during the charge–discharge process,
leading to good cycling stability, as shown in Fig. 11, despite
the big volume changes.48
2.1.4 Transition metal oxide. Li et al. reported that Fe2O3
electrodes using a CMC binder and two other new binders show
better cycling performance (about 800 mA hg 1 for 100 cycles)
compared to electrodes made from the conventional PVDF Fig. 13 Typical cycling performance of Fe2O3 materials vs. Li. Reproduced
from ref. 50 with permission from The Royal Society of Chemistry.
binder.49 By combining the CMC binder and carbon composite,
our group demonstrated that Fe2O3 can deliver a high specific
capacity (1210 mA h g 1 at a current density of 0.1 C), enhanced 2.1.5 Li4Ti5O12. Spinel lithium titanate, Li4Ti5O12 (LTO),
rate capability and excellent cycling stability (720 mA h g 1 at a has attracted great interest as a safe anode material for
current density of 2 C up to 220 cycles).50 Other transition metal rechargeable Li-ion batteries because of its high and flat Li
oxides, such as NiO and CuO, were also investigated using CMC insertion voltage at B1.55 V versus Li/Li+, which prevents the
as binder and showed much enhanced cycling stability com- growth of lithium dendrites and the decomposition of electrolyte
pared with PVDF as binder.51,52 The active materials using as well as providing long cycle life and high rate capability.53 The
PVDF as binder detached themselves from the substrate very binder for high-capacity anode materials, such as silicon, tin, and
easily after cycling, while the electrode using CMC as the binder transition metal oxides, as we mentioned before, should have a
showed good adhesion. The gap between the electrode materials high adhesive capability to endure large volume changes during
and binder can be clearly observed in Fig. 12.51 the lithium intercalation and de-intercalation processes. The
Capacity increase during cycling has been commonly adhesion strength of the polymer is one of the most important
observed in many reports on transition metal oxides. One factors that should be considered when choosing the binder for
typical example is shown in Fig. 13. This is probably due to high-capacity anode materials. LTO experiences no volume
the decomposition of electrolyte during cycling and also related changes during cycling, indicating that the focus of using a new
to the formation of new SEI layers. This phenomenon is one of binder would be different. Our group reported that the high rate
the deadly drawbacks for transition metal oxides to be used for capability of LTO electrodes using CMC as binder is much better
commercial batteries as the anode because the electrolyte is a than that for those using PVDF as binder.54 The LTO electrodes
very limited amount in the commercial cell. The continuous using CMC as binder showed the highest specific capacity at
decomposition of electrolyte will lead to the battery dying after 62 mA h g 1 at a current density of 40 C, whereas those using
a certain number of cycles. Other disadvantages include big PVDF as binder showed a capacity of only 25 mA h g 1. The
charge and discharge potential separation, low initial coulombic charge curves of electrodes using PVDF as binder start to show
efficiency, and large volume expansion. sloping from 20 C, whereas those using CMC as binder still show

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the SEI film formed around the coating worked effectively in

synergy to separate LTO from the surrounding electrolyte
solution and prevent the interfacial gassing reactions. A future
direction is to design a new binder to coat the LTO surface to
both allow high ionic conductivity and separate LTO from the
electrolyte.

2.2 Cathode materials

Since the successful use of aqueous binders for anode materi-
als,60,61 a new trend is now being developed to replace the PVDF
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binder in the cathode. Many reasons have been provided: the

safety aspects of the battery, the high cost of cathode materials,
and a growing interest in high capacity and high energy.
Fluorine is one of the degradation products in the battery
leading to the production of stable LiF. Depending on the
liquid electrolyte, the formation reaction of LiF and other
Fig. 14 (a) Cycle life of Li4Ti5O12 microsphere electrodes at different harmful products is accelerated.62–64 Furthermore, a self-
current densities from 0.2 to 40 C using CMC (squares) and PVDF (circles) heating thermal runaway can be induced. With respect to safety
as binders. (b) Rate capability of Li4Ti5O12 microsphere electrodes at
and environmental concerns, it is better to find an alternative
different current densities using CMC (squares) and PVDF (circles) as
binders. (c and d) Charge and discharge curves of Li4Ti5O12 microsphere to PVDF. Thus, the switch from non-aqueous to aqueous
electrodes at different current densities from 0.2 to 40 C using CMC (c) systems is imperative. The research effort has started with the
and PVDF (d) as binders. Reproduced from ref. 54 with permission from the preparation of the cathode slurry,65 however, the transition
American Chemical Society. from the non-aqueous to aqueous coating process appears to
have encountered some unexpected difficulties related to the
instability of the cathode in water, slurry formulation, viscosity
a flat plateau, even at 40 C as shown in Fig. 14. This indicates the control, and film processing, which must be overcome for
kinetic difference between the two different binders. Further successful implementation in Li-ion batteries.
electrochemical impedance studies showed that the electrodes 2.2.1 LiCoO2. LiCoO2 is still the most important cathode
with CMC and PVDF as binder had the same lithium diffusion material since the first commercial Li-ion battery.66–68 Although
coefficient, but the electrode with CMC as binder had a much the use of a water-based binder is a new process expected to
lower charge transfer resistance, a lower apparent activation have high potential, aqueous binders are rarely used in the
energy, and a lower apparent diffusion activation energy than lithium-ion battery industry especially for the cathode, which
the electrode with PVDF as binder. may be due to the significant dissolution problems of LiCoO2 in
Lee and Oh55 reported an investigation of the influence of water69 and the difficulty in controlling the dispersion proper-
molecular weight and degree of substitution of CMC when used ties of oxides.70 Li et al.71 reported the effects of the pH of a
as the binder for LTO anodes. The results showed that the LTO water-based slurry on the dispersion homogeneity and cell
electrode that contained relatively low molecular weight and performance of LiCoO2 cathodes. The binder content increased
high degree of substitution CMC showed high specific capacity with the distance from the bottom to the top of the dried
and good rate capability owing to its low charge transfer electrode sheet for the LiCoO2 system when CMC was used as
resistance, high ionic conductivity, and good wettability with the binder.72 Thick electrode cathode films with active mass
the electrolyte. Recently, Tran et al.56 reported the fabrication of loadings of over 30 mg cm 2 were reported by Tran et al.73
200 mm thick LTO electrodes using a novel poly(PEGMA-co- using polyethylene glycol (PEG)-based binders. A high coulom-
MMA-co-IBVE) copolymer binder, containing methyl ether bic efficiency of 98.7% can be achieved, indicating that an
methacrylate (PEGMA), methyl methacrylate (MMA), and iso- aqueous binder could be used for a LiCoO2 cathode.
butyl vinyl ether (IBVE), and with active material loadings of up 2.2.2 LiFePO4. So far, only a few groups have reported on
to 28 mg cm 2, which can deliver an area specific capacity of using CMC as a slurry thickener or as a binder for LiFePO4
4.2 mA h cm 2 at the C/2-rate. cathodes.74–79 Guerfi et al.74 reported the usage of a water-
The major challenge for the use of LTO in large-scale soluble binder with an elastomer on saturated organic com-
applications is destructive gas generation with associated pounds and a thickener of CMC for LiFePO4 cathode materials.
swelling during charge and discharge.57,58 The generated gases The electrochemical performance shows that lower irreversible
mainly contain H2, CO2 and CO, which originate from inter- capacity losses were obtained with cathodes using the water-
facial reactions between LTO and the surrounding alkyl carbo- soluble binder. Porcher et al.75–77 investigated the usage of
nate solvents. The reactions occur at the very thin outermost CMC as a binder for LiFePO4. Their study revealed that LiFePO4
surface of the LTO (111) plane, and result in transformation slightly changes upon aging when it is brought into contact
from the (111) to the (222) plane and formation of the (101) with water. A Li3PO4 layer of a few nanometers grows at the
plane of anatase. He et al.59 reported that a carbon coating and grain surface (see high resolution transmission electron

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PCCP Perspective

Fig. 15 HRTEM images of LiFePO4 powders: (a) initial and (b) after
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immersion for 24 h in water. Reproduced from ref. 75 with permission

from Elsevier.

microscopy (HRTEM) image in Fig. 15), and at the same Fig. 17 Initial charge–discharge curves of LiNi1/3Mn1/3Co1/3O2 at various
time the Fe(III) percentage in the active material increases.75 current densities in the voltage range of 2.5–4.6 V using different binders:
The increase of Fe(III) content is less than 5% based on (a) CMC, (b) alginate, and (c) PVDF; (d) dQ/dV curves for LiNi1/3Mn1/3Co1/
3O2 with CMC, PVDF, and alginate binders. Reproduced from ref. 87 with
the Mössbauer results with a similar loss of capacity for
permission from Elsevier.
LiFePO4 when the processing time is limited to less than
24 h. Lee et al.78 reported that the addition of PAA significantly
decreased the viscosity of the LiFePO4 and CMC slurry, 2.2.3 Other cathode materials. Li et al.80 found that CMC
leading to an increased solid concentration and improved can be used as the binder for the high voltage (up to 4.8 V)
discharge capacity in terms of volumetric density. Lux cathode material Li2MnO3–LiMO2 (M = Ni, Mn, or Co) and
et al.79 reported that the high rate capability can be enhanced provide improved cycling stability and a very promising rate
by using CMC as binder via shortening the processing time capability compared to the PVDF binder. Wang et al. reported
to 30 min and using a higher drying temperature (170 1C) CMC as a binder in the high voltage (5 V) LiNi0.4Mn1.6O4
for the electrode, as shown in Fig. 16. The initial capacity cathode with close to the theoretical capacity (146 mA h g 1)
(140 mA h g 1) of the electrode using CMC as binder is and low self-discharge (B10%).81 LiNi1/3Mn1/3Co1/3O2 (NMC) is
lower than that of the one using PVDF as binder (155 mA h g 1), one of the most promising large-scale commercial cathodes for
but the capacity retention is significantly enhanced to lithium ion batteries, with the overwhelming advantages of high
105 mA h g 1 after 1000 cycles. The results reported show operating voltage, high specific capacity, cyclic stability, and struc-
that LiFePO4 can be processed in aqueous slurries and that tural stability.82–86 Our group reported that a LiNi1/3Mn1/3Co1/3O2
CMC could be used as an alternative binder for LiFePO4 electrode using CMC as a binder showed lower initial capacity
cathodes, as a water-soluble binder for Li-ion batteries. How- but improved high rate capability in comparison with the
ever, there is still no safety effects reported that are related to current commercial PVDF binder (Fig. 17).87 The possible
the aqueous binder. reason is that the lower activation energy of the electrode using
CMC as the binder facilitates the transport of lithium ions
compared with alginate and PVDF. Partial loss of lithium could
be found in both the LiNi0.4Mn1.6O481 and NMC87 samples
when mixed with the CMC binder in water. This is probably due
to the exchange of Li+ in the cathode material and protons in
the water, as confirmed by synchrotron X-ray diffraction refined
results. It is worth pointing out that many cathode materials
such as LiNi1/3Mn1/3Co1/3O2, LiMn2O4, and LiFePO4 have been
investigated as cathode materials in aqueous electrolytes with
excellent cycling stability.88–91 This again confirmed that the
cathode materials could be stable when in contact with water.
More work has to be done on cathode materials to evaluate the
possibilities for commercial application of aqueous binders for
lithium ion batteries from the safety aspect.

Fig. 16 Rate performance and the discharge voltage profiles of LiFePO4 3. Lithium sulphur battery
electrodes using (a) PVDF binder and CMC binder dried at (b) 120 1C and (c)
170 1C. Reproduced from ref. 79 with permission from The Electroche- Lithium sulphur (Li–S) batteries utilize sulphur as the cathode
mical Society. and lithium metal foil as the anode. Although most attention

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has been given to the cathode materials, there are some

interesting research papers on the binder. In our view, the
choice of binder relates to the cathode composition and the
electrolyte. As a whole, the binder, cathode materials, electro-
lyte and even the cell assembling technique decide the perfor-
mance of the cell. In other words, the function of the binder
cannot be judged only by the binder, it should be put in the
whole system of a cell and related to other components of the
cell. Bearing this concept in mind, we now might get some
inspiration from the following examples.
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The binder materials for Li–S batteries have been dominated

by two kinds of polymers: polyethylene oxide (PEO) and PVDF.
In the earlier stage of research on Li–S batteries, PEO was
widely used as the binder. Cheon et al.92 compared the sulphur Fig. 18 Cycle performance of PAN–S composite cathode with PTFE,
cathode with different amounts (8%, 13% and 18%) of PEO as b-CD, PVDF and C-b-CD (carbonyl b-CD prepared through treatment of
the binder, and found that with the binder taking up a larger b-CD with H2O2) at 0.2 C. Reproduced from ref. 105 with permission from
percentage in the cathode, the cycling performance improved John Wiley and Sons.
correspondingly. However, researchers made efforts to find a better
binder than PEO, and two successful cases were Gelatin93–95 and
poly(acrylamide-co-diallyldimethylammonium chloride) (AMAC).96 4. Sodium-ion battery
Regarding the composite binder carboxy methyl cellulose (CMC)
and styrene butadiene rubber (SBR), there have been two papers Sodium-ion batteries (SIBs) are similar in some ways to lithium-
reporting opposite results with Rao et al.97 claiming that CMC + ion batteries. In both types of battery, ions are shuttled between
SBR is better than PEO, while Lacey et al.98 reporting that PEO is the battery’s positive and negative electrodes during charging
better than CMC + SBR. Concerning these two inverse results, the and discharging, with the electrolyte serving as the medium for
factors that contribute might be the difference in varied aspects: moving those ions. Taking into account recent concerns about
sulphur materials (CNF–S composite vs. pure sulphur), current a possible lithium shortage with the spread of electric vehicles,
collectors (carbon coated Al foil vs. uncoated Al foil), electrolytes it is urgent to search for alternative energy storage systems that
(1 M kg 1 lithium bis(trifluoromethylsulfonyl)imide in N-methyl- could complement the existing Li-ion technology. For this
N-butylpyrrolidinium bis(trifluoromethanesulfonyl)imide/poly- purpose, Na-ion technology is a suitable choice in terms of
(ethylene glycol) dimethyl ether vs. 1 M LiTFSI and 0.25 M battery cost, safety, and raw material abundance. Due to the
LiNO3 in 1,2-dimethoxyethane/1,3-dioxolane) and electrode increased size and heavier weight of the Na atom compared to
preparing methods (unknown vs. ball milling for 2 h). the Li atom, the volumetric energy density and specific energy
Later, PVDF became the mainstream binder for Li–S density obtainable for the sodium-ion battery are significantly
batteries. However, when PVDF is applied as the binder, the less than those obtainable with the lithium-ion battery. How-
toxic dispersant NMP and longer heating time for electrodes are ever, recent computational studies by Ceder et al. on voltage,
two disadvantages. Therefore, researchers have been searching stability, and diffusion barriers to Na-ion and Li-ion materials
for environmentally friendly water soluble binders which can indicate that Na-ion systems can be competitive with Li-ion
contribute a better cell performance. Varied materials have systems.106 In any case, Na-ion batteries would be interesting
been proved to be better choices than PVDF, and they are for very low cost systems for grid storage, which could make
CMC + SBR,97,99 polyacrylic acid (PAA),100 Na–alginate101 and renewable energy a primary source of energy rather than just a
poly(vinylpyrrolidone) (PVP).102 A recent work103 also showed supplemental one. The foundations of Na-ion technology must
excellent performance of Li–S batteries with PAA as the binder. be deeply explored, however, in order to be ready to introduce
Through ball milling with polydopamine (PD), sulphur and new alternative energy storage systems onto the market. The
carboxylic acid functionalized multiwall carbon nanotubes search to develop commercially available Na-ion batteries
(MWCNT–COOH), covalent bonds formed through the cross- requires finding and optimizing new electrode materials and
linking between PD/PAA and PD/MWCNT–COOH demon- electrolytes, in order to obtain batteries that are more econom-
strated a strong binding effect with sulphur and a good ical, safer, and have a longer life.12,13
cycling performance for Li–S batteries was achieved. The binder effect has only been investigated for the anode of
Schneider et al.104 applied three kinds of water soluble sodium materials by several groups.107–111 There are three
binders (i.e. nafion, Teflon, polyacrylonitrile-CMC) in Li–S major kinds of anode materials, including carbon materials,
batteries, and demonstrated them as promising environmentally alloy-based materials such as those containing Sn, Sb, and P,
friendly binders. Carbonyl b-cyclodextrin (C-b-CD),105 which was and insertion type sodium metal oxide materials as reviewed in
prepared through treatment of b-cyclodextrin (b-CD) with H2O2, the latest review paper.12,13 The theoretical capacities and the
can be a better binder in Li–S batteries, compared with PVDF, volume expansion ratios are shown in Fig. 19. It can be found
polytetrafluoroethylene (PTFE) and b-CD (Fig. 18). that the expansion ratio for sodium based anode materials is

20356 | Phys. Chem. Chem. Phys., 2014, 16, 20347--20359 This journal is © the Owner Societies 2014
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PCCP Perspective

For big volume expansion anode materials in LIBs, a care-

fully designed elastomer binder with strong cohesive strength
in the interfaces of substrate–binder–active particles will be the
most promising next generation binder. Further research
should also focus on improving the initial coulombic efficiency
for anode materials and investigating the safety aspects. Since
the battery industry can only allow volume expansion of less
than 6% to keep the full battery functional, the expansion of
anode materials should also be reduced to lower than 10%.
For cathode materials in LIBs, aqueous binders could be
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used in water stable cathode like LiFePO4 to reduce the cost

and improve the cycle life and rate capability. However, the
processing time should be short to restrict the structural
Fig. 19 Theoretical specific capacity and volume expansion ratio of change in water. For some other lithium transition metal oxide
different anode materials for sodium batteries.
cathodes, there is still a big problem with the stability of such
materials in water, which lowers the specific capacity. The
more serious than for lithium based anode materials due to the safety aspects of binders are also worthy of investigation.
bigger size of Na+ ions leading to poor cycle life. Therefore, The sodium ion battery is only in its early stage of develop-
what we have learned about the binder effect on lithium anode ment. The binder effect on SIBs would be an interesting topic
materials could be useful for sodium anode materials. A good for research.
binder must ideally maintain adhesion of the electrode to the
current collector, maintain ionic contact, and facilitate the for-
mation of a stable interface with the electrolyte. Komaba et al.109 Acknowledgements
reported that Sn electrodes with high capacity (500 mA h g 1) for
more than 20 cycles were achieved by choosing an appropriate This work is supported by the Australian Research Council
binder and electrolyte additives. Qian et al.107a reported that a through a Discovery Project (DP110103909) and a Linkage
Sb–C nanocomposite with CMC as binder can deliver a rever- Project (LP120200432). The authors would also like to thank
sible capacity of 610 mA h g 1, high rate capability at a very Dr Tania Silver for critical reading of the manuscript.
high current of 2000 mA g 1 and long-term cycling stability
with 94% capacity retention over 100 cycles. Darwiche et al.108
found that commercial microsize Sb showed good cycling Notes and references
performance with Na, with a capacity of 600 mA h g 1 (theoretical
capacity 610 mA h g 1) up to 160 cycles and with a coulombic 1 M. Armand and J. M. Tarascon, Nature, 2008, 451, 652.
efficiency of 98% when using carboxymethyl cellulose (CMC) 2 C. Liu, F. Li, L.-P. Ma and H.-M. Cheng, Adv. Mater., 2010,
as binder and fluoroethylene carbonate (FEC) as an additive. 22, E28.
Qian et al.107b and Kim et al.110 reported independently that an 3 F. Y. Cheng, J. Liang, Z. L. Tao and J. Chen, Adv. Mater.,
amorphous phosphorus composite with carbon could deliver a 2011, 23, 1695.
high capacity of 1764 mA h g 1 at a current density of 250 mA g 1 4 L. L. Dai, D. W. Chang, J.-B. Baek and W. Lu, Small, 2012,
using CMC as binder and 1890 mA h g 1 at a current density of 8, 1130.
143 mA g 1 using PAA as binder, respectively. Although there is 5 P. G. Bruce, B. Scrosati and J.-M. Tarascon, Angew. Chem.,
no data comparison with PVDF, the binders play an important Int. Ed., 2008, 47, 2930.
role in long-term cycling stability. Great efforts need to be made to 6 H. Li, Z. X. Wang, L. Q. Chen and X. J. Huang, Adv. Mater.,
further develop appropriate low-cost active materials for SIBs. 2009, 21, 4593.
More work should be carried out to further improve the lower 7 J. B. Goodenough and K.-S. Park, J. Am. Chem. Soc., 2013,
initial coulombic efficiency. 135, 1167.
8 B. Dunn, H. Kamath and J.-M. Tarascon, Science, 2011, 334,
928–935.
5. Conclusions and outlooks 9 Z. Yang, J. Zhang, M. C. W. Kintner-Meyer, X. Lu, D. Choi,
J. P. Lemmon and J. Liu, Chem. Rev., 2011, 111, 3577.
Small things do make a big difference. The binder only makes 10 H. Zhang, G. Cao and Y. Yang, Energy Environ. Sci., 2009,
up a small part of the electrode composition, but it plays an 2, 932.
important role in the cycling stability and rate capability for the 11 J. Christensen, P. Albertus, R. S. Sanchez-Carrera, T. Lohmann,
Li-ion battery and the Na-ion battery. The additional advan- B. Kozinsky, R. Liedtke, J. Ahmed and A. Kojic, J. Electrochem.
tages of changing over from PVDF to aqueous binders are that Soc., 2012, 159, R1.
the aqueous binders are cheap, green, and easy to process for 12 B. L. Ellis and L. F. Nazar, Curr. Opin. Solid State Mater. Sci.,
electrode fabrication. 2012, 16, 168.

This journal is © the Owner Societies 2014 Phys. Chem. Chem. Phys., 2014, 16, 20347--20359 | 20357
 View Article Online

Perspective PCCP

13 (a) V. Palomares, P. Serras, I. Villaluenga, K. B. Hueso, 38 S. D. Beattie, D. Larcher, M. Morcrette, B. Simon and
J. Carretero-Gonzalez and T. Rojo, Energy Environ. Sci., 2012, J. M. Tarascon, J. Electrochem. Soc., 2008, 155, A158.
5, 5884; (b) V. Palomares, M. Casas-Cabanas, E. Castillo- 39 S. L. Chou, J. Z. Wang, M. Choucair, H. K. Liu, J. A. Stride
Martinez, M. H. Han and T. Rojo, Energy Environ. Sci., 2013, and S. X. Dou, Electrochem. Commun., 2010, 12, 303.
6, 2312. 40 Z. J. Han, N. Yabuuchi, K. Shimomura, M. Murase, H. Yui
14 H. Maleki, G. P. Deng, I. Kerzhner-Haller, A. Anani and and S. Komaba, Energy Environ. Sci., 2012, 5, 9014.
J. N. Howard, J. Electrochem. Soc., 2000, 147, 4470. 41 I. Kovalenko, B. Zdyrko, A. Magasinski, B. Hertzberg,
15 K. Zaghib, K. Striebel, A. Guerfi, J. Shim, M. Armand and Z. Milicev, R. Burtovyy, I. Luzinov and G. Yushin, Science,
M. Gauthier, Electrochim. Acta, 2004, 50, 263. 2011, 334, 75.
16 G. Liu, H. Zheng, A. S. Simens, A. M. Minor, X. Song and 42 A. Magasinski, B. Zdyrko, I. Kovalenko, B. Hertzberg,
Published on 25 June 2014. Downloaded by University of Warwick on 20/04/2017 18:24:37.

V. S. Battaglia, J. Electrochem. Soc., 2007, 154, A1129. R. Burtovyy, C. F. Huebner, T. F. Fuller, I. Luzinov and
17 J. Li, L. Christensen, M. N. Obrovac, K. C. Hewitt and G. Yushin, ACS Appl. Mater. Interfaces, 2010, 2, 3004.
J. R. Dahn, J. Electrochem. Soc., 2008, 155, A234. 43 G. Liu, S. Xun, N. Vukmirovic, X. Song, P. Olalde-Velasco,
18 D. W. Choi, D. H. Wang, V. V. Viswanathan, I. T. Bae, H. Zheng, V. S. Battaglia, L. Wang and W. Yang,
W. Wang, Z. M. Nie, J. G. Zhang, G. L. Graff, J. Liu, Z. G. Adv. Mater., 2011, 23, 4679.
Yang and T. Duong, Electrochem. Commun., 2010, 12, 378. 44 B. Koo, H. Kim, Y. Cho, K. T. Lee, N.-S. Choi and J. Cho,
19 A. Fedorkova, R. Orinakova, A. Orinak, I. Talian, A. Heile, Angew. Chem., Int. Ed., 2012, 51, 8762.
H. D. Wiemhofer, D. Kaniansky and H. F. Arlinghaus, 45 M.-H. Ryou, J. Kim, I. Lee, S. Kim, Y. K. Jeong, S. Hong,
J. Power Sources, 2010, 195, 3907. J. H. Ryu, T.-S. Kim, J.-K. Park, H. Lee and J. W. Choi,
20 S. S. Zhang, K. Xu and T. R. Jow, J. Power Sources, 2004, Adv. Mater., 2013, 25, 1571.
138, 226. 46 S. L. Chou, J. Z. Wang, C. Zhong, M. M. Rahman, H. K. Liu
21 J. H. Lee, S. Lee, U. Paik and Y. M. Choi, J. Power Sources, and S. X. Dou, Electrochim. Acta, 2009, 54, 7519.
2005, 147, 249. 47 J. Li, D. B. Le, P. P. Ferguson and J. R. Dahn, Electrochim.
22 J.-H. Lee, U. Paik, V. A. Hackley and Y.-M. Choi, Acta, 2010, 55, 2991.
J. Electrochem. Soc., 2005, 152, A1763. 48 S. L. Chou, X. W. Gao, J. Z. Wang, D. Wexler, Z. X. Wang,
23 H. Y. Wang, T. Umeno, K. Mizuma and M. Yoshio, J. Power L. Q. Chen and H. K. Liu, Dalton Trans., 2011, 40, 12801.
Sources, 2008, 175, 886. 49 J. Li, H. M. Dahn, L. J. Krause, D. B. Le and J. R. Dahn,
24 J. H. Jean and H. R. Wang, J. Am. Ceram. Soc., 2001, 84, 267. J. Electrochem. Soc., 2008, 155, A812.
25 J. Chong, S. D. Xun, H. G. Zheng, X. Y. Song, G. Liu, 50 S. L. Chou, J. Z. Wang, D. Wexler, K. Konstantinov,
P. Ridgway, J. Q. Wang and V. S. Battaglia, J. Power Sources, C. Zhong, H. K. Liu and S. X. Dou, J. Mater. Chem., 2010,
2011, 196, 7707. 20, 2092.
26 K. A. Hirasawa, K. Nishioka, T. Sato, S. Yamaguchi and 51 C. Zhong, J. Z. Wang, S. L. Chou, M. M. Rahman, S. X. Dou
S. Mori, J. Power Sources, 1997, 69, 97. and H. K. Liu, J. Appl. Electrochem., 2010, 40, 1415.
27 J. Li, D. B. Le, P. P. Ferguson and J. R. Dahn, Electrochim. 52 C. Zhong, J. Z. Wang, X. W. Gao, S. L. Chou,
Acta, 2010, 55, 2991. K. Konstantinov and H. K. Liu, J. Nanosci. Nanotechnol.,
28 S. Komaba, K. Okushi, T. Ozeki, H. Yui, Y. Katayama, 2012, 12, 1314.
T. Miura, T. Saito and H. Groult, Electrochem. Solid-State 53 T. Ohzuku, A. Ueda and N. Yamamoto, J. Electrochem. Soc.,
Lett., 2009, 12, A107. 1995, 142, 1431.
29 J. R. Szczech and S. Jin, Energy Environ. Sci., 2011, 4, 56. 54 S. L. Chou, J. Z. Wang, H. K. Liu and S. X. Dou, J. Phys.
30 U. Kasavajjula, C. Wang and A. J. Appleby, J. Power Sources, Chem. C, 2011, 115, 16220.
2007, 163, 1003. 55 B. R. Lee and E. S. Oh, J. Phys. Chem. C, 2013, 117, 4404.
31 H. Buqa, M. Holzapfel, F. Krumeich, C. Veit and P. Novak, 56 B. Tran, I. O. Oladeji, Z. Wang, J. Calderon, G. Chai,
J. Power Sources, 2006, 161, 617. D. Atherton and L. Zhai, Electrochim. Acta, 2013, 88, 536.
32 J. Li, R. B. Lewis and J. R. Dahn, Electrochem. Solid-State 57 I. Belharouak, G. M. Koenig Jr., T. Tan, H. Yumoto, N. Ota
Lett., 2007, 10, A17. and K. Amine, J. Electrochem. Soc., 2012, 159, A1165.
33 B. Lestriez, S. Bahri, I. Sandu, L. Roue and D. Guyomard, 58 K. Wu, J. Yang, Y. Zhang, C. Wang and D. Wang, J. Appl.
Electrochem. Commun., 2007, 9, 2801. Electrochem., 2012, 42, 989.
34 N. S. Hochgatterer, M. R. Schweiger, S. Koller, P. R. 59 Y. B. He, B. Li, M. Liu, C. Zhang, W. Lv, C. Yang, J. Li,
Raimann, T. Wohrle, C. Wurm and M. Winter, Electrochem. H. Du, B. Zhang, Q. H. Yang, J.-K. Kim and F. Kang, Sci.
Solid-State Lett., 2008, 11, A76. Rep., 2012, 2, 913.
35 L. Chen, X. Xie, J. Xie, K. Wang and J. Yang, J. Appl. 60 M. Fukunaga, K. Suzuki, A. Kuroda, The 44th Japan Battery
Electrochem., 2006, 36, 1099. Symposium, 2003, abst #1D19, pp. 462.
36 N. S. Choi, K. H. Yew, W. U. Choi and S. S. Kim, J. Power 61 S. S. Zhang, K. Xu and T. R. Jow, J. Power Sources, 2004,
Sources, 2008, 177, 590. 138, 226.
37 R. R. Garsuch, D.-B. Le, A. Garsuch, J. Li, S. Wang, A. Farooq 62 H. Maleki, G. Deng, I. K. Haller, A. Anani and J. N. Howard,
and J. R. Dahn, J. Electrochem. Soc., 2008, 155, A721. J. Electrochem. Soc., 2000, 147, 4470.

20358 | Phys. Chem. Chem. Phys., 2014, 16, 20347--20359 This journal is © the Owner Societies 2014
 View Article Online

PCCP Perspective

63 M. Gaberscek, M. Bele, J. Drofenik, R. Dominiko and 88 Q. Qu, L. Fu, X. Zhan, D. Samuelis, J. Maier, L. Li, S. Tian,
S. Pejovnik, Electrochem. Solid-State Lett., 2000, 3, 171. Z. Lia and Y. P. Wu, Energy Environ. Sci., 2011, 4, 3985.
64 G. Oskam, P. C. Searson and T. R. Jow, Electrochem. Solid- 89 F. Wang, S. Xiao, Z. Chang, Y. Yang and Y. P. Wu, Chem.
State Lett., 1999, 2, 610. Commun., 2013, 49, 9209.
65 A. Guerfi, P. Charest, H. Mori, M. Kaneko, K. Zaghib, 204 90 X. Wang, Y. Hou, Y. Zhu, Y. P. Wu and R. Holze, Sci. Rep.,
ECS Joint International Meeting, Honolulu, Hawaii, 2013, 3, 1401.
October 3–8, 2004. 91 W. Tang, Y. Zhu, Y. Hou, L. Liu, Y. P. Wu, K. P. Loh,
66 K. Mitzushima, P. C. Jones, P. J. Wiseman and J. B. H. Zhang and K. Zhu, Energy Environ. Sci., 2013, 6, 2093.
Goodenough, Mater. Res. Bull., 1980, 15, 783. 92 S. E. Cheon, J. H. Cho, K. S. Ko, C. W. Kwon, D. R. Chang,
67 T. Nagaura and K. Tozawa, Prog. Batteries Sol. Cells, 1990, H. T. Kim and S. W. Kim, J. Electrochem. Soc., 2002,
Published on 25 June 2014. Downloaded by University of Warwick on 20/04/2017 18:24:37.

9, 209. 149, A1437.

68 M. S. Whittingham, Chem. Rev., 2004, 104, 4271. 93 Y. Q. Huang, J. Sun, W. K. Wang, Y. Wang, Z. B. Yu,
69 S. Saeki, J. Lee, Q. Zhang and F. Saito, Int. J. Miner. Process., H. Zhang, A. B. Wang and K. G. Yuan, J. Electrochem.
2004, 74S, S373. Soc., 2008, 155, A764.
70 P. Nahass, W. E. Rhine, R. L. Pober, H. K. Bowen and 94 J. Sun, Y. Q. Huang, W. K. Wang, Z. B. Yu, A. B. Wang and
W. L. Robbins, in Ceramic transactions, vol 15, Materials K. G. Yuan, Electrochim. Acta, 2008, 53, 7084.
and processes in microelectronic systems, K. M. Nair, 95 Q. Q. Wang, W. K. Wang, Y. Q. Huang, F. Wang, H. Zhang,
R. Pohanka and R. C. Buchanan, American Ceramic Z. B. Yu, A. B. Wang and K. G. Yuan, J. Electrochem. Soc.,
Society, Westerville, OH, 1990, p. 355. 2011, 158, A775.
71 C. C. Li, J. T. Lee, Y. L. Tung and C. R. Yang, J. Mater. Sci., 96 S. S. Zhang, J. Electrochem. Soc., 2012, 159, A1226.
2007, 42, 5773. 97 M. M. Rao, X. Y. Song, H. G. Liao and E. J. Cairns, Electro-
72 C. C. Li and Y. W. Wang, J. Electrochem. Soc., 2011, chim. Acta, 2012, 65, 228.
158, A1361. 98 M. J. Lacey, F. Jeschull, K. Edstrom and D. Brandell, Chem.
73 B. Tran, I. O. Oladeji, Z. Wang, J. Calderon, G. Chai, Commun., 2013, 49, 8531–8533.
D. Atherton and L. Zhai, J. Electrochem. Soc., 2012, 99 M. He, L. X. Yuan, W. X. Zhang, X. L. Hu and Y. H. Huang,
159, A1928. J. Phys. Chem. C, 2011, 115, 15703.
74 A. Guerfi, M. Kaneko, M. Petitclerc, M. Mori and K. Zaghib, 100 Z. A. Zhang, W. Z. Bao, H. Lu, M. Jia, K. Y. Xie, Y. Q. Lai and
J. Power Sources, 2007, 163, 1047. J. Li, ECS Electrochem. Lett., 2012, 1, A34.
75 W. Porcher, P. Moreau, B. Lestriez, S. Jouanneau and 101 W. Z. Bao, Z. A. Zhang, Y. Q. Gan, X. W. Wang and J. Lia,
D. Guyomard, Electrochem. Solid-State Lett., 2008, 11, A4. J. Energy Chem., 2013, 22, 790.
76 W. Porcher, P. Moreau, B. Lestriez, S. Jouanneau, F. Le 102 Z. W. Seh, Q. F. Zhang, W. Y. Li, G. Y. Zheng, H. B. Yao and
Cras and D. Guyomard, Ionics, 2008, 14, 583. Y. Cui, Chem. Sci., 2013, 4, 3673.
77 W. Porcher, B. Lestriez, S. Jouanneau and D. Guyomard, 103 L. Wang, Z. H. Dong, D. Wang, F. X. Zhang and J. Jin, Nano
J. Electrochem. Soc., 2009, 156, A133. Lett., 2013, 13, 6244.
78 J. H. Lee, J. S. Kim, Y. C. Kim, D. S. Zang and U. Paik, 104 H. Schneider, A. Garsuch, A. Panchenko, O. Gronwald,
Ultramicroscopy, 2008, 108, 1256. N. Janssen and P. Novak, J. Power Sources, 2012, 205, 420.
79 S. F. Lux, F. Schappacher, A. Balducci, S. Passerini and 105 J. L. Wang, Z. D. Yao, C. W. Monroe, J. Yang and Y. Nuli,
M. Winter, J. Electrochem. Soc., 2010, 157, A320. Adv. Funct. Mater., 2013, 23, 1194.
80 J. Li, R. Klopsch, S. Nowak, M. Kunze, M. Winter and 106 S. P. Ong, V. L. Chevrier, G. Hautier, A. Jain, C. Moore,
S. Passerini, J. Power Sources, 2011, 196, 7687. S. Kim, X. Ma and G. Ceder, Energy Environ. Sci., 2011,
81 Z. L. Wang, N. Dupre, A. C. Gaillot, B. Lestriez, J. F. Martin, 4, 3680.
L. Daniel, S. Patoux and D. Guyomard, Electrochim. Acta, 107 (a) J. F. Qian, Y. Chen, L. Wu, Y. L. Cao, X. P. Ai and
2012, 62, 77–83. H. X. Yang, Chem. Commun., 2012, 48, 7070; (b) J. F. Qian,
82 T. Ohzuku, K. Ariyoshi, S. Yamamoto and Y. Makimura, X. Y. Wu, Y. L. Cao, X. P. Ai and H. X. Yang, Angew. Chem.,
Chem. Lett., 2001, 1270. Int. Ed., 2013, 52, 4633.
83 Z. H. Lu, D. D. MacNeil and J. R. Dahn, Electrochem. Solid- 108 A. Darwiche, C. Marino, M. T. Sougrati, B. Fraisse,
State Lett., 2001, 4, A200. L. Stievano and L. Monconduit, J. Am. Chem. Soc., 2012,
84 B. J. Hwang, Y. W. Tsai, D. Carlier and G. Ceder, Chem. 134, 20805.
Mater., 2003, 15, 3676. 109 S. Komaba, Y. Matsuura, T. Ishikawa, N. Yabuuchi,
85 Z. Wang, Y. Sun, L. Chen and X. Huang, J. Electrochem. W. Murata and S. Kuze, Electrochem. Commun., 2012, 21, 65.
Soc., 2004, 151, A914. 110 Y. Kim, Y. Park, A. Choi, N. S. Choi, J. Kim, J. Lee, J. H. Ryu,
86 K. M. Shaju and P. G. Bruce, Adv. Mater., 2006, 18, 2330. S. M. Oh and K. T. Lee, Adv. Mater., 2013, 25, 3045.
87 J. Xu, S. L. Chou, Q. F. Gu, H. K. Liu and S. X. Dou, J. Power 111 W. J. Li, S. L. Chou, J. Z. Wang, H. K. Liu and S. X. Dou,
Sources, 2013, 225, 172. Nano Lett., 2013, 13, 5480.

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