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Interpenetrated Gel Polymer Binder for High-Performance

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Silicon Anodes in Lithium-ion Batteries
Jiangxuan Song, Mingjiong Zhou, Ran Yi, Terrence Xu, Mikhail L. Gordin, Duihai Tang,
Zhaoxin Yu, Michael Regula, and Donghai Wang*

low-cost, and eco-friendly, which makes

Silicon has attracted ever-increasing attention as a high-capacity anode it more promising for low-cost, high-
material in Li-ion batteries owing to its extremely high theoretical capacity. energy LIBs. However, the silicon anode
materials suffer from substantial volume
However, practical application of silicon anodes is seriously hindered by its
change (>400%) during lithiation/delithia-
fast capacity fading as a result of huge volume changes during the charge/ tion. This will cause poor electrical contact
discharge process. Here, an interpenetrated gel polymer binder for high- of Si particles with the conducting matrix
performance silicon anodes is created through in-situ crosslinking of water- and severe pulverization of the silicon, as
soluble poly(acrylic acid) (PAA) and polyvinyl alcohol (PVA) precursors. This well as the excess growth of solid-electro-
gel polymer binder with deformable polymer network and strong adhesion lyte interphase (SEI).[24–31] As a result, the
silicon anodes show fast capacity fading,
on silicon particles can effectively accommodate the large volume change of
low Coulombic efficiency, and electrode
silicon anodes upon lithiation/delithiation, leading to an excellent cycling sta- deterioration upon cycling. The situation
bility and high Coulombic efficiency even at high current densities. Moreover, becomes even worse when fabricating
high areal capacity of ∼4.3 mAh/cm2 is achieved based on the silicon anode high energy cells where high mass loading
using the gel PAA–PVA polymer binder with a high mass loading. In view of of active materials (mg-Si/cm2) on current
collectors is necessary.[32]
simplicity in using the water soluble gel polymer binder, it is believed that this
Polymer binder, one of the major
novel binder has a great potential to be used for high capacity silicon anodes components in an electrode, is used to
in next generation Li-ion batteries, as well as for other electrode materials bind active materials and conducting
with large volume change during cycling. particles together onto the current
collector. The properties of polymer
binders play an important role in the
1. Introduction electrochemical performance of the electrodes, especially
for the cycle life and irreversible capacity losses.[33–35]
Lithium-ion batteries (LIBs) have been applied in a variety of Poly(vinylidene fluoride) (PVDF) is a conventional binder
portable electronic devices and are being pursued as power and widely used in traditional LIBs because of its acceptable
sources for hybrid electric vehicles and electric vehicles.[1–13] adhesion and wide electrochemical window.[36,37] However,
With respect to the anodes for LIBs, materials that can elec- the non-functionalized linear chain structure of the PVDF
trochemically form intermetallic alloys with Li have attracted binder cannot afford sufficient binding to high-capacity
tremendous attention as anode materials due to their much anode particles that exhibit huge volume changes.[33,38] This
higher capacities than that of conventional graphite anodes requires improved binding characteristics of binders to
based on intercalation chemistry.[10,14–17] Among these, silicon enable electrode integrity for long cycling life. Thus, novel
(Si) is particularly attractive because of its highest known the- polymer binders with the ability to accommodate substantial
oretical capacity of ∼4200 mAh/g and low charge-discharge volume changes during lithiation/delithiation of Si anodes
potential of ∼0.4 V vs Li/Li+.[18–23] In addition, Si is abundant, are highly desirable.
Recently, much attention has been devoted to developing
functional binders that can improve adhesion on silicon
Dr. J. Song, Dr. M. Zhou, R. Yi, Dr. T. Xu, M. L. Gordin, particles. For example, polymer binders that contain car-
Dr. D. Tang, Z. Yu, M. Regula, Prof. D. Wang boxyl groups and their derivatives, such as polyacrylic acid
Department of Mechanical and Nuclear Engineering
The Pennsylvania State University, University Park (PAA)[39] and carboxymethyl cellulose (CMC) based polymers
PA 16802, USA (e.g., CMC or NaCMC),[38,40] show better electrochemical
E-mail: dwang@psu.edu performance than non-functional polymers such as PVDF
Dr. M. Zhou and styrene-butadiene rubber (SBR).[39,41] These functional
The School of Material Science and Chemical Engineering binders show enhanced binding with silicon particles via
Ningbo University
Fenghua Road 818, Jiangbei District, Ningbo 315211, Zhejiang, PR China
hydrogen bonding and/or covalent chemical bonds between
the polar functional groups of the binder and the partially
DOI: 10.1002/adfm.201401269 hydrolyzed surface SiO2 layer of Si particles. Moreover,

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multi-functional polymer binders were further developed to 2. Results and Discussion

enhance the interaction of silicon and binder. For example,
high-modulus natural polysaccharidenatural (alginate)[33] The silicon electrodes with the interpenetrated gel polymer
containing hydroxyl and carboxyl groups and dopamine- binder were prepared by an in-situ thermo-induced polymeriza-
grafted PAA[42] containing catechol and carboxyl groups were tion approach. Commercial silicon nanoparticles in elliptical or
developed for high performance silicon anodes. Liu et al.[43] spherical shapes with diameters in the range of 30 to 100 nm
developed a new conductive polymer binder, integrating tri- were used for this study (see Figure S1 in Supporting Informa-
ethyleneoxide monomethyl ether, methyl benzoate ester, and tion). The silicon nanoparticles were covered with a thin layer
fluorenone moieties into a single-component n-type conduc- of amorphous SiO2 due to oxidation when exposed to air.[33]
tive polymer for silicon anode materials to improve mechan- This was confirmed by Fourier transform infrared spectroscopy
ical adhesion, ductility, and electrolyte-uptake. Indeed, the (FTIR) as shown in Figure S2. The spectra show typical vibra-
incorporation of the aforementioned functional groups to tion bands of silica materials such as the Si–O–Si asymmetric
the polymer chain presented higher adhesion associated stretching band at 1176 cm−1 and Si–O symmetric stretching
with improved performance of silicon anode. Nonetheless, band at 885 cm−1.[33,44] Moreover, the broad peak located in
the linear chain nature of these polymer binders is suscep- 3000–3600 cm−1 was also clearly observed, which is attributed
tible to sliding upon the continual volume change of silicon to the hydrogen bonding of Si-OH groups.[33] All of these char-
during cycling. As a result, the polymer chain together with acteristic peaks shown in the FTIR spectra support the exist-
the deformed electrode cannot recover to its original state ence of an SiO2 layer on the silicon surface, which agrees with
and irreversible change takes place. To combat this, three previous reports.[33] The aqueous solution of poly(acrylic acid)
dimensional polymer networks, including the cross-linked (PAA) and poly(vinyl alcohol) (PVA) (9:1, weight ratio) was used
CMC-PAA binder[44] and porous conductive gel polymer[34] as polymer precursor for the gel polymer network. The elec-
were sequentially developed for the silicon anodes, in which trodes were fabricated by a coating process of the slurry com-
the polymer chain was anchored by a cross-linking tech- prising of 60 wt.% Si nanoparticles and 20 wt.% carbon black,
nique. Another strategy of utilizing self-healing polymer via and 20 wt.% gel polymer binder precursor. These electrodes
a hydrogen bonding driving force was also recently adopted were heated at 100 °C for 5 h and then at 150 °C for another
for silicon binder.[35] These designs effectively enhanced 1 h under vacuum. In this manner, the esterification reaction
the electrochemical performance of Si anodes by sup- would take place between the carboxyl functional group of PAA
pressing the adverse effect from their large volume expan- and hydroxyl functional group of PVA. Simultaneously, the car-
sion. Despite promising progress, the current research on boxylic acid group of PAA would also react with the hydroxyl
polymer binders for silicon is still limited in the following groups of SiO2 on the surface of the Si particles to form cova-
ways. First, most of the literature reported a limited cycling lent ester bonds between the Si particles and polymer network.
for these binders (≤100 cycles) and a relatively low current To verify the chemical structure of the interpenetrated gel
density (∼400 mA/g), which is far from the practical applica- polymer binder, FTIR was conducted, as shown in Figure 1.
tion that needs at least 300 cycles and fast charge/discharge. After crosslinking PAA with PVA, the stretching vibration
Second, low-mass-loading electrodes (<1.0 mg-Si/cm2) peak (∼3300 cm−1) of the O–H bond in PVA was decreased and
were used for the evaluation of these binders, making shifted to a lower wavenumber. Moreover, the stretching vibra-
these results less attractive for practical application where tion peaks (1720 cm−1) of C=O band of PAA shifted to a lower
high mass loading is necessary for the high areal capacity wavenumber of 1714 cm−1. These peak changes demonstrated
(>4 mAh/cm2) to advance the energy density of LIBs. Third, the –COO– formation due to esterification reaction of PAA and
less attention has been paid to evaluating the developed PVA, resulting in a cross-linked gel polymer network.[47,48] Fur-
binders on silicon-graphite composite anodes that remain a thermore, in the presence of silicon in the interpenetrated gel
distinct approach for practical application of Si materials in PAA-PVA binder, the stretching vibration peak of C=O of PAA
current LIBs. became broader at a higher wavenumber (1730 cm−1), indi-
It is well known that super absorbent resin has an extra-large cating the occurrence of the condensation reaction between the
volume change (up to 500–1000 times) during solvent absorp- Si–OH of silicon particles and –COOH of PAA.[16] The strong
tion processes. Most interestingly, it can normally recover to its interactions between the PAA-PVA binder and the Si particles
original state after losing solvent from its three-dimensional are favorable for improving the electrode integrity and thus
flexible network.[45,46] Inspired by this smart flexible polymer mitigating destruction of the electrical network even under a
gel network, here, we report a novel deformable gel polymer large volume change during cycling, which has been previously
binder for Si anode materials through an in-situ thermal- identified as one of the most critical factors affecting the sta-
crosslinking of water soluble poly(acrylic acid) (PAA) and bility of Si-based electrodes.[39,43]
poly(vinyl alcohol) (PVA). This gel polymer binder contains car- The electrochemical properties of the silicon electrodes were
boxylic and hydroxyl functional groups, and can thus strongly evaluated by using CR2016 coin cells with lithium foil as the
bond with Si particles, exhibiting high mechanical strength of counter electrode. The charge/discharge processes of the silicon
adhesion on Si as well as a particularly recoverable deforma- electrodes were performed between 0.01 and 1.5 V by using
tion through the reversible morphology change with the silicon 1 M LiPF6 in a mixture of ethylene carbonate, diethyl carbonate
particles. This leads to an excellent cycling stability and high and dimethyl carbonate (EC: DEC: DMC, 1:1:1 by volume) as
Coulombic efficiency even at a high current density (4 A/g) or a electrolyte and fluoroethylene carbonate (FEC, 10 vol.%) as
high Si mass loading (∼2.4 mg-Si/cm2). additive. The silicon electrodes containing widely used NaCMC

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Figure 1. (a) The chemical structure and illustrative interaction between crosslined PAA-PVA and silicon particles; (b) FTIR spectra of PAA, PVA, PAA-
PVA gel binder, and silicon/PAA-PVA composites.

and PVDF binder were prepared as control electrodes by fol- cyclability with a high capacity of 1830 mAh/g remaining
lowing the same approach as the PAA-PVA binder. after 300 cycles, which corresponds to 68.6% capacity reten-
As seen in the voltage profiles of the silicon electrode made tion and only 0.1% capacity loss per cycle. The excellent battery
with PAA-PVA binder (Figure 2a), the first cycle lithiation
potential showed a plateau profile at 0.1−0.01 V, consistent
with the behavior of crystalline Si.[28,49] The cycling stability and
Coulombic efficiency of both the electrode and control elec-
trodes, cycled at a current density of 400 mA/g, are shown in
Figure 2b and c, respectively. For non-functional PVDF binder,
the cell shows fast capacity fading (180 mAh/g after 50 cycles)
with a very low initial Coulombic efficiency of 70.8%. The Si
anode with functional NaCMC binder showed an initial capacity
of 3282 mAh/g and a better cycling stability (1178 mAh/g after
100 cycles) compared to PVDF binder. Noticeably, the Si anode
with the PAA-PVA binder exhibited an excellent battery perfor-
mance. A specific capacity of 3616 mAh/g was achieved in the
initial cycle by using novel interpenetrated gel polymer binder,
which is about 86% of the theoretical capacity (4200 mAh/g).
Furthermore, this cell also gave an excellent cycling stability,
with a capacity of 2283 mAh/g remaining after 100 cycles.
Moreover, this novel binder also showed a relatively high initial
Coulombic efficiency of 83.9%, which increased to ∼97.7% at
the third cycle, and finally stabilized at ∼99.3% in subsequent
cycles. The high Coulombic efficiency of the silicon anode
made with this interpenetrated gel polymer binder indicated
a relatively stable SEI layer on the silicon particles, which pre-
vents the loss of some irreversible lithium storage sites. This
will also make the PAA-PVA gel binder more promising for the
application of full-cell configuration that requires high Cou-
lombic efficiency of both anodes and cathodes to advance the
overall energy density and cycle life.
The fast charge/discharge further validates the reliability of
the binders during a rapid substantial expansion and contrac-
tion for silicon nanoparticles.[50,51] Thus, we further evaluated
the silicon electrode with the PAA-PVA binder at a rather high
Figure 2. (a) The initial charge/discharge voltage profiles of the silicon
current density of 4 Ah/g as shown in Figure 3a. A high capacity anode using PAA-PVA gel polymer binder; (b) the cycling performance
of ∼2660 mAh/g was obtained at this high current density of 1C and (c) Coulombic efficiency of Si electrodes with PAA-PVA, NaCMC, and
(1C = 4000 mA/g). More importantly, the cell exhibited excellent PAA binders. Note that the specific capacity is calculated based on silicon.

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Areal capacity of electrodes, calculated as specific capacity

(mAh/g) of active materials × mass loading (g/cm2 of electrode
area), is widely used for evaluation of electrode performance
for practical application. It is clear that achieving a high areal
capacity requires high mass loading in the electrodes.[7,13] Com-
monly, the specific capacity is highly dependent on the silicon
loading, and will drop with increasing silicon loading because
of higher polarization of the electrodes and poor adhesion of
polymer binder.[32] Most of the high specific capacities reported
in the literature for Si electrodes fabricated using coating
techniques were obtained at a low silicon loading (below
1.5 mg-Si/cm2).[21,22,25,26,52–54] This loading is insufficient to
achieve an energy density greater than that of current graphite
anodes in commercial LIBs. For this work, the electrode
with a high mass loading of 2.4 mg/cm2 still presents great
cycling ability and the reversible capacity remains at around
1800 mAh/g up to 50 cycles. The silicon anode can deliver an
areal capacity of ∼4.3 mAh/cm2, which is much higher than
that of most reported silicon anode.[21,22,25,26,52–54]
To better understand the much-improved electrochemical
performance achieved by using the interpenetrated gel polymer
Figure 3. (a) The cycling stability and Coulombic efficiency of the silicon
anode with PAA/PVA binder at a current density of 4 A/g (1C); (b) The binder, scanning electron microscopy (SEM) was performed on
cycle stability of silicon anodes with a high mass loading of 2.4 mg-Si/cm2. the silicon electrodes with different binders before and after
cycling. Figure 4a–c show the morphology of pristine electrodes
performance characteristics of the silicon electrode with with PVDF, NaCMC, and PAA-PVA binders, respectively. It
PAA-PVA gel binder, such as high capacity retention and was found that silicon nanoparticles together with carbon black
high Coulombic efficiency with long extended cycling at high were relatively uniformly dispersed in the matrix in the three
current density, are outstanding compared to other silicon samples at their origin state. Obvious morphology changes
anodes using commercial Si nanoparticles reported in the were observed for these electrodes after 100 cycles, shown
literature.[21,22,25,26,52–54] in Figure 4d and 4e. The cycled electrodes using PVDF and
In practical applications, not only the specific capacity but also NaCMC binders show smooth surface topography on some
the mass loading of active material is crucial for achieving high areas of the electrode surface, as marked by arrows in Figure 4d
energy density in batteries. Increasing mass loading of active and 4e. The smooth surface is considered to be due to pulveri-
materials on current collector can minimize the weight portion zation of silicon particles from substantial volume change and
of the inactive parts (current collector, separator, and binder), consequent growth of SEI on newly exposed surfaces.[32,55] In
and thus enhances the overall energy density of batteries. comparison, neither obviously detectable morphology change

Figure 4. The surface morphology of silicon electrodes before and after 100th cycle using different binders. Scale bars in the images are 1 µm.

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Figure 5. Cross-sectional SEM images of the silicon electrodes with gel-polymer binder (a)before cycling; (b) at the end of the 5th discharge and (c) at
the end of the 5th charge; (d) proposed working mechanism of interpenetrated gel binder for silicon anodes.

nor microstructural failure was found for the electrode with binder after the cycle is due to the three-dimensional interpen-
the PAA-PVA binder, even after 100 deep cycles. Thus, the SEI etrated network of PAA-PVA binder which allows the revers-
layers on the silicon particles with PAA-PVA binder is believed ible deformable change upon the volume change of Si during
to be thinner and more stable than those formed when using cycling.
PVDF and NaCMC binder. The formation of the thin and To further evaluate the effect of PAA-PVA binder on Si
stable SEI could be attributed to the novel polymer binder composite anodes, the electrochemical properties of a silicon-
which accommodates the large volume change because of the graphite (Si-G) composite were also studied. The composite
deformable feature of the polymer network; furthermore, the composed of silicon and graphite with a mass ratio of 6:4 was
enhanced adhesion stemming from strong chemical bonding used as the active material. The electrode was fabricated using
between PAA-PVA and silicon nanoparticles should assist in an industrially used coating technique with the active mate-
constructing a stable SEI for Si electrodes. This bonding is sim- rial (Si-G composites), carbon black, and binder ratio of 90:5:5
ilar to the hydrogen bonds of reported functionalized polymer (weight ratio). Here, only 5% binder was used to achieve max-
binders for Si anodes.[33,39] The stable SEI is anticipated to play imum energy density for practical applications. Figure 6 shows
an active role in the cycle life and Coulombic efficiency, which the cycling stability of Si-G composite electrodes at a current
directly lead to the excellent capacity retention with Coulombic
efficiency over 99% of the Si anode with the PAA-PVA binder,
as mentioned before (Figure 2).
The thickness variation of the silicon electrode using PAA-
PVA binder with high silicon loading (∼2.4 mg/cm2) was fur-
ther measured to validate the ability of the binder for accom-
modating large volume changes during cycling. Figure 5a–c
show cross-section SEM images of electrodes before cycling, at
the end of the 5th discharge, and at the end of the 5th charge,
respectively. The thickness of discharged electrode (Figure 5b)
increased to ca. 85.3 µm from its origin state (ca. 64.5µm) after
lithiation, which is a ∼32% volume change. Upon charging, the
expanded silicon nanoparticles shrink as lithium is extracted;
the final thickness of the electrode (67.4 µm) almost returns
to its origin thickness with a volume variation of ∼4.5%. By
contrast, Figure S3 shows that the thickness of the silicon elec-
Figure 6. The cycling stability of silicon-graphite (Si-G) composite anode
trodes after cycling with PVDF and NaCMC binder increased (Si:Graphite = 6:4, mass ratio) using NaCMC and PAA-PVA gel polymer
by ∼19.7% and ∼16.5%, respectively, which are ∼4 times higher binder. The electrode was composed of Si-G composites (90%), super
than the increase with PAA-PVA gel polymer binder. The P (5%), and polymer binder (5%). Note that the specific capacity is
minimal thickness change of the electrodes with gel polymer calculated based on silicon.

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density of 400 mA/g. The PAA-PVA binder shows a high utili- Electrochemical tests were performed by using 2016 coin-type half
zation of active composites (Si-G) with a reversible capacity of cells assembled with lithium metal as the counter electrode in Argon
1880 mAh/g at the first cycle and a good capacity retention of filled glove box. The electrolyte consisted of 1 mol/L LiPF6 in a mixture
of ethylene carbonate, diethyl carbonate and dimethyl carbonate (EC:
70% after 70 cycles. In contrast, the cells using NaCMC binder DEC: DMC, 1:1:1 by volume) and fluoroethylene carbonate (FEC,
only show a capacity retention of 25%, much lower than PAA- 10 vol%). The FEC additive can increase the cycling efficiency of silicon
PVA. This result further demonstrated that the water soluble, anodes, due to the formation of a more stable SEI layer. Galvanostatic
interpenetrated gel polymer binder has a good compatibility cycling test was carried out at different constant current densities
with commercial Si-graphite mixture-based anodes, which between 0.01 and 1.5 V vs Li/Li+ on a BT2000 battery testing system
makes it more promising for practical application. (Arbin Instruments, USA). The specific capacity was calculated on the
basis of the weight of the active materials.

3. Conclusion
Supporting Information
We have developed an interpenetrated gel polymer binder Supporting Information is available from the Wiley Online Library or
for high performance silicon anodes by using a facile in-situ from the author.
thermal-crosslinking technique based on the low-cost water
soluble poly(acrylic acid) (PAA) and polyvinyl alcohol (PVA)
precursors. By having the advantages of a deformable polymer
network and strong binding between Si and the binder, this
Acknowledgements
designed binder can effectively accommodate the large volume J. Song and M. Zhou contributed equally to this work. This work was
change of silicon anode upon lithiation/delithiation, resulting supported by the Assistant Secretary for Energy Efficiency and Renewable
in an excellent cycling stability (1663 mAh/g after 300 cycles) Energy, Office of Vehicle Technologies of the U.S. Department of Energy
under Contract No. DE-EE0006447.
and high Coulombic efficiency (99.3%) even at a high current
density of 4 A/g. Furthermore, high-areal-capacity of 4.3 mAh/ Received: April 20, 2014
cm2 with good cycling stability was demonstrated at electrode Revised: June 2, 2014
level using the silicon anode based on the PAA-PVA binder. Published online:
This much improved electrochemical performance is attrib-
uted to the interpenetrated gel network of this binder and its
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Adv. Funct. Mater. 2014, © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim wileyonlinelibrary.com 7
DOI: 10.1002/adfm.201401269