Journal of Power Sources xxx (xxxx) xxx

Contents lists available at ScienceDirect

Journal of Power Sources

journal homepage: www.elsevier.com/locate/jpowsour

A conductive self-healing hydrogel binder for high-performance silicon

anodes in lithium-ion batteries
Shanming Hu, Leidanyang Wang, Tao Huang **, Aishui Yu *
Laboratory of Advanced Materials, Department of Chemistry, Shanghai Key Laboratory of Molecular Catalysis and Innovative Materials, Institute of New Energy,
Collaborative Innovation Center of Chemistry for Energy Materials, Fudan University, Shanghai, 200438, China

H I G H L I G H T S

� A conductive hydrogel binder with fast self-healing ability.

� Maintained a high capacity of 1786 mA h g 1 at 500 mA g 1 after 200 cycles.
� Achieved a superior areal capacity of 5.25 mA h cm 2 at ambient temperature.
� Exhibiting excellent cycling stability at elevated temperature.

A R T I C L E I N F O A B S T R A C T

Keywords: Although silicon has been viewed as the ideal anode material due to its superior specific capacity, silicon ma­
Conductive hydrogel terials easily break down because of its large volume changes during frequent charge-discharge cycles. Polymeric
3D network binders play key roles on maintaining the mechanical integrity of electrodes and contributing substantially to
Self-healing property
improving cycle lives. Here, we design and prepare that a novel conductive self-healing hydrogel (ESVCA) binder
Lithium-ion batteries
Si anodes
with 3D conductive network, excellent stretchablity and fast self-healing ability coating on the surface the Si
particle by in-situ polymerization method. The stretchable 3D self-healable network structure could effectively
restrain the huge volume change of Si particles during lithiation and delithiation cycles to maintain mechanical
integrity of the Si electrodes while 3D continuous electron transport pathways insuring the high conductivities
and better electric contacts among active Si particles. The Si-ESVCA electrode not only exhibits a reversible
capacity of 1786 mA h g 1 at 500 mA g 1 with a capacity retention of 71.3% after 200 cycles at ambient
temperature, but also maintains superior cycling stability with a capacity retention of 74.1% and remains a high
reversible capacity of 1743 mA h g 1 after 200 cycles at current density of 2000 mA g 1 at elevated temperature.

1. Introduction
Lithium-ion batteries have been widely applied in portable electronic
devices, electrical vehicles and renewable energy storage systems
because of its higher energy density and longer cycle life compared with
the other traditional secondary batteries [1,2]. Silicon (Si) anodes has
received much attention due to its high theoretical specific capacity
(over 3000 mA h g 1), a low discharge plateau (around 0.4 V vs Li/Liþ)
and huge reserves on earth [3,4]. However, a massive volume change
during repeated insertion and extraction lithium leads to cracking and
pulverization of Si electrode, loss of electrical contact of interphase
between active materials and current collectors and production of
unstable solid electrolytes interphase (SEI), which has been identified as
main obstacle of Si anodes in practical application [5–8]. Although it has
been recently reported that binders play a critical role in prolonging the
cycle life of Si anodes, traditional polyvinylidene difluride (PVDF)
binders are not suitable for Si anodes due to their weak van der Waals
interactions between Si powder and the copper current collector [9]. To
address above mentioned issues, various functional binders have been
developed, such as carboxymethyl cellulose (CMC) [10], alginate [11],
3D network binders [12], natural polysaccharide binders [13,14], and
self-healing binders [15–17]. Although these binders can provide robust
adhesion between Si particle and current collector because of the for­
mation of hydrogen bonds and covalent chemical bonds by the chemical

* Corresponding author.
** Corresponding author.
E-mail addresses: 17213010006@fudan.edu.cn (S. Hu), 17113010008@fudan.edu.cn (L. Wang), huangt@fudan.edu.cn (T. Huang), asyu@fudan.edu.cn (A. Yu).

https://doi.org/10.1016/j.jpowsour.2019.227472
Received 22 July 2019; Received in revised form 26 September 2019; Accepted 14 November 2019
0378-7753/© 2019 Elsevier B.V. All rights reserved.

Please cite this article as: Shanming Hu, Journal of Power Sources, https://doi.org/10.1016/j.jpowsour.2019.227472
S. Hu et al.
reaction between its carboxyl and hydroxyl groups and the SiO2 on the
surface of Si nanoparticle, there has no binding force between polymer
binder and conductive additives resulting in loss of electric connections
after repeated charge-discharge cycles [18–20]. To overcome this issue,
conducting binders have developed on Si anodes due to it has the
function of both binder and conductive additive. Conductive binders can
provide more stable electron transport compared with traditional ad­
ditives which will easily lose electric contact with Si particle during
charge and discharge cycles. Among the several conductive polymers,
such as polyaniline (PANI) hydrogels [20], poly (1-pyrenemethyl
methacrylate-co-triethylene oxide methyl ether methacrylate) (PPyE)
[19], poly (phenanthrenequinone) (PPQ) [18], and poly (3, 4-ethylene­
dioxythiophene): poly (styrenesulfonate) (PEDOT: PSS) [21]. PEDOT:
PSS has been designed various structural and functional binders because
of its high conductivity (1000 S cm 1) and good water solubility [22,
23]. However, these binders could not provide stable mechanical
stretchability and strong interaction with Si nanoparticles, especially the
generation of huge stress and strain leads to serious pulverization and
low conductivity because of the large volume change. A polymer with
self-healing property would possibly address this key issue [16,17].
Self-healing materials possess the ability of repairing cracks and me­
chanical damages, which is particularly suitable for restoring the cracks
or pulverization of electrodes by large volume changes and prolong the
lifetime of lithium batteries [16,24]. In recent years, most efforts in
self-healing polymers focused on the novel binders in silicon anodes. For
example, Bao et al. have reported a self-healing polymer with a double
hydrogen bonding as a Si anodes binder to improve cycling ability and
capacity retention [16]. Deng et al. have utilized a linear modified
polymer poly (acrylic acid) (PAA) chemical crosslinking a more stable
quadruplehydrogen-bonded unit (ureido-pyrimidinone) with high
healing efficiency and strong adhesion as self-healable binder to with­
stand huge volume change and improve cycle lives of Si anodes [15].
Although these conductive binders achieve good electric contact among
active materials or self-healing binders achieve mechanical integrity of
Si anodes, few binder possesses both conductivity and self-healing
properties to maintain the electric contact and the integrity of Si elec­
trodes at the same time during long-term charge-discharge cycles.
Herein, a novel three-dimensional conductive self-healing hydrogel
binder that possesses both high conductivity and fast self-healing ability
suitable for high-performance Si anodes is designed and described. As
illustrated in Fig. 1a, the self-healing conductive hydrogel binder
(ESVCA) is prepared by addition of gelation agents (ammonium per­
sulfate (APS)) in the composite solution by complexing PEDOT: PSS with
poly (vinyl alcohol) (PVA) followed by modification with
Fig. 1. a) Schematic illustration of the fabrication process for Si electrode with self-healing conductive hydrogel binder. b) Digital image of self-healing conductive
hydrogel. c) Digital image of Si electrode hydrogel slurry by in-situ polymerization of self-healing conductive hydrogel. d) TEM image of Si particle coated self-healing
conductive binder.
2
Journal of Power Sources xxx (xxxx) xxx
4-carbonxybenzaldehyde (CBA). APS initiates crosslinking polymeriza­
tion of PEDOT: PSS polymer chains to form 3D interpenetrating
hydrogel network architecture with more outstanding electrical
conductive ability compared with traditional liner conductive polymer
because of the special 3D network structure promotes more continuous
conduction pathways, enabling fast electron transport stability [25].
Fig. 1b shows a digital image of the self-healing conductive hydrogel
with stretchability, conductivity and self-healing capability. Fig. 1c
shows an image of Si electrode hydrogel slurry by in-situ polymerization
of self-healing conductive hydrogel to conformably coat silicon nano­
particles with the thickness of 2 nm (Fig. 1d). PVA is remarkable hy­
drophilic polymer having excellent chemical resistance and it can be
used for several practical applications such as adhesives in textile,
biomedical and pharmaceutical industries because of its nontoxic and
biodegradable properties [26,27]. PVA also can be easily modified by
chemical crossing-linking to improve the electrical and thermal prop­
erties [28]. Furthermore, PVA containing massive hydroxyl groups
usually can be made of gel polymer electrolytes exhibiting a good per­
formance of ion-conductivity because of its strong inter- and intra­
molecular interactions with Li ions [29,30]. In addition, the abundant
hydroxyl groups of PVA can act as hydrogen donors to form many dy­
namic hydrogen bonds with the sulfonate groups of PEDOT: PSS [31].
Thus, without the much complicated chemical modification process of
grafted special self-healing functional groups, the reversibility of dy­
namic covalent bonds and non-covalent crosslinking networks lead the
conductive hydrogel to achieve the intrinsic self-healing function [32].
As a result, the 3D conductive self-healing binder can not only effec­
tively accommodate the huge change of Si nanoparticle during insertion
and extraction of lithium repeated cycles to maintain the structural
integrity of Si electrode, but also extremely increase the electron
transport pathways resulting in high performance cyclability and
excellent rate capability.
2. Experimental section
2.1. Materials
Silicon nano-particles (SiNPs, 99.9%) with an average particle size of
~50 nm were purchased from Shanghai ST-nano Science & Technology
Co., Ltd. CMC was purchased from Hercules Chemicals Co., Ltd (China).
Polyvinyl alcohol (PVA) and 4-carbonxybenzaldehyde (CBA) was pur­
chased from J&K Sccientific Co., Ltd. Super P carbon black was obtained
from Hefei Ke Jing Materials Technology Co., Ltd. PEDOT: PSS was
purchased from Sigma-Aldrich Co., Ltd. ammonium persulfate (APS)
S. Hu et al.
was purchased from Sinopharm Chemical Reagent Co., Ltd.
2.2. Synthesis of ESVCA
An appropriate mass of the PVA was dissolved in deionized water at
90 � C, the homogeneous solution was mixed with PEDOT: PSS solution
while being added 5 wt% CBA solution and stirring half an hour at room
temperature. The (PEDOT: PSS): PVA: CBA mass ratio in the mixture
solution was 1:1:0.05. After mixing homogenous solution, 0.5 wt%
ammonium persulfate initiator (APS) was added to above precursor
solution. The complex solution was then slowly transferred into a poly
tetra fluoroethylene (PTFE, 5x1x1 cm3) mold used to control the shape
of hydrogel and the polymerization was performed at 30 � C. After 24 h,
the solution became viscous and gel-like, indicating the formation of
self-healing conductive hydrogel.
2.3. Electrode Preparation
To make a mixed Si-ESVCA electrodes, commercial Si nanoparticles
was poured into the above hydrogel precursor by sonication and poly­
merization, Si-ESVCA hydrogel was obtained. After amount of DI-water
washing the residual inorganic salt of the Si-ESVCA hydrogel, which was
dispersed by adding appropriate DI-water, heating and stirring at 90 � C
to form a uniform slurry. The weight ratio of the Si nanoparticles to
ESVCA was 6:4. For comparison, the PEDOT: PSS and PVA with a weight
ratio of 1:1 were stirred to form homogeneous solution, the Si nano­
particles were dispersed in mixture solution and stirred to form a uni­
form slurry. The weight ratio of the Si nanoparticles to PEDOT: PSS/PVA
was also 6:4. Si nanoparticles conductive agent (Super P) and binders
(CMC, PVA, or PEDOT: PSS) with a weight ratio of 6:2:2 was homoge­
neously dispersed into aqueous slurry. The electrodes were prepared by
spreading the slurry on the copper foil with a doctor blade manner and
dried at 80 � C for 12 h under a vacuum oven to remove water.
2.4. Materials Characterization
The structure of composites were characterized by X-ray diffraction
(SMART APEX II, BRUKER) with a Cu Kα radiation source (λ ¼ 0.154
nm). The morphology of the surfaces of the electrodes were measured on
field-emission scanning electron microscopy (S4800, Japan). X-ray
photoelectron spectroscopy (XPS) measurements were carried out on an
X-ray photoelectron spectrometer (PHI 5000&PHI 5300) with Mg/Al Kα
radiation. Fourier transform infrared spectra experiments were carried
out on a Nicolet 6700. Raman spectra were performed on a Raman
spectrometer (XploRA) with an excitation laser beam wavelength of 633
nm. The mechanical properties of self-healing conductive hydrogel were
conducted on Electronic universal testing machine (Instron 5966) and
the rate of extension was fixed at 50 mm min 1 for tensile test. Dynamic
mechanical analysis was measured by a SDTA861 dynamic mechanical
analysis appaeatus (DMA) at a temperature sweep rate of 5 � C/min and
the sinusoidal oscillation amplitude was 40 μm. The lithium-ion diffu­
sion coefficient (DLi) of binder was measured by biological EC-Lab with
GITT containing discharging/charging pulses 10 min each followed by
relaxation for 10 min. The thickness and sheet resistance of the polymer
films was measured by surface profilometry (Veeco Dektak 150) and a
four-point probe (RTS-8).
The conductivity was calculated by the following equation
σ ¼ ðRsr � tÞ 1 cm 1) corresponding to the acetal groups appears in the FTIR spectrum
where σ is the conductivity, Rsr is the sheet resistance, and t is the
thickness of the polymer films.
The lithium-ion diffusion coefficient (DLi) of binder was calculated
under the equation
3
Journal of Power Sources xxx (xxxx) xxx
0 12
� �2 B C � �
4 mB Vm B ΔEs C L2
DLi ¼ B .� �C ; τ≪
π MB A @τðdEt Þ pffiffi A DLi 2
d τ
Where mB is the binder mass, Vm is the molar volume of compound,
MB stands for the molar mass of the binder, A is the contact area between
the electrolyte and binder, ΔEs is the steady-state voltage change and the
.
ðdEt Þ ðdpffiτffi Þ is the slope of linearized curve of the voltage E(V) during
the current pulse of duration τ(s).
2.5. Electrochemical Measurements
The type of 2016 coin cells with metallic Li counter electrodes were
assembled in an argon-filled glove box to measure the electrochemical
performance of all the Si electrode. The electrolyte composites were
made up with 1 M lithium hexafluorophosphate (LiPF6) in the mixture of
ethylene carbonate and diethyl carbonate (1:1 by weight) with 10%
fluoroethylene carbonate additive. The charging and discharging mea­
surements were conducted on Land battery test system (Wu Han, China)
with the voltage cut off between 0.01 and 1.0 V versus Li/Liþ at room
temperature. EIS was measured on the Autolab Electrochemical Work­
station, the frequency range was from 100 kHz to 100 m Hz and the
amplitude was 5 mV. Cyclic voltammetry (CV) measurements were
performance on an electrochemical workstation (CHI 660D, Shanghai
Chenhua) at a scan rate of 0.20 mV s 1 between 0.01 and 1.20 V versus
Li/Liþ.
3. Results and discussions
To investigate the mechanical properties of self-healing conductive
hydrogel and the interactions among the polymer chains inside mixed
polymer, a series of experiments have been performed. Fig. 2a shows the
excellent stretchability of self-healing conductive hydrogel (ESVCA)
ruptured at a strain of about 300% and exhibits excellent mechanical
properties even after self-healing, which are ascribed to the robust
electrostatic interactions and the dynamically reversible hydrogen
bonds between the PEDOT: PSS and the PVA chains. When the stretch-
recovery cycles were repeated at 100% and 200% strain limits, ESVCA
hydrogel also exhibits robust behavior (Fig. 2b) because of the inter­
chain hydrogen bonds of PVA polymer break apart and releasing the
stress to some degree [33], indicating that ESVCA hydrogel can fully
tolerant the change of Si particle volume expansion during delithium
and insert-lithium process. Moreover, the ESVCA binder exhibits the
robust adhesive property and shows the highest peeling force among the
three binders, indicating a stronger adhesive of ESVCA binder compared
with other binders and a better electric contact between the active Si
particle and current collector (Fig. S1.). This increased adhesive of
ESVCA binder may be attributed to the formation of intermolecular
dynamic hydrogen bond networks caused by the crosslinking of polymer
networks. Fig. 2c shows the Fourier transform infrared (FTIR) spectra of
self-healing conductive hydrogel (ESVCA) and PEDOT: PSS membrane.
The FTIR spectrum of PEDOT: PSS shows a characteristic peak at 1060
cm 1, which is attributed to the symmetric stretching vibration of sul­
fonate groups. The peak of the sulfonate groups from PEDOT: PSS in the
ESVCA shifts to 1050 cm 1, suggesting that there are strong
hydrogen-bonding interactions between sulfonate groups of PEDOT: PSS
and hydroxyl groups of PVA [34]. At the same time, a new peak (1020
of the self-healing conductive hydrogel (ESVCA), indicating that CBA
groups have been successfully grafted on the PVA chains [32]. The X-ray
diffraction pattern (Fig. 2d) shows the structural change of polymer
composites. The peaks observed at 28.50� pointed at the crystalline
nature of Si nanoparticle with the reflection of (111) plane and the peaks
S. Hu et al.
Fig. 2. a) Stress-strain curve of self-healing conductive hydrogel. b) Stress-strain curves of self-healing conductive hydrogel for 10 stretch-recovery cycles. c) FTIR
spectra of ESVCA and PEDOT: PSS from 1100 to 1000 cm 1. d) XRD patterns of Si nanoparticle, Si-ESVCA, and PVA film. e) Electron conductivities and Lithium-ion
diffusion coefficient of several binders. (Error bars are based on maximum and minimum values from five different measurements) f) Raman spectra of Si particle,
ESVCA, and PEDOT: PSS/PVA.
appear at 19.36 and 21.20� corresponding to the crystalline atactic and
the (101 ) and (200) planes reflections of PVA because of the strong
intermolecular and intramolecular hydrogen bonding in its molecular
backbone [35]. The intensity of crystalline peak at 19.36� disappearing
corresponding to the PVA component of ESVCA was ascribed to crys­
talline atactic-to-amorphous transition, indicating that the enhanced
intercalation between PEDOT: PSS and PVA via hydrogen bonding [34].
In addition, the amorphous PVA chains also are more beneficial for the
transmission of Liþ than crystalline PVA and the contact angle test shows
that the Si-ESVCA electrode has a smaller contact angle (47.5� ) than
Si-PEDOT: PSS/PVA electrode (65.2� ) indicating a better wettability of
the modified self-healing conductive binder to electrolyte and facili­
tating Li-ion diffusion within electrode (Fig. S2) [36]. Fig. 2e shows the
electron conductivities of different binders (CMC/SP, PVA/SP, PEDOT:
PSS, PEDOT: PSS/PVA and ESVCA), ESVCA and PEDOT: PSS/PVA
binders based on the highly conductive PEDOT: PSS with 925 S cm 1
exhibit higher electro-conductivity compared with the simple mixed
composites (CMC/SP (31.6 S cm 1) and PVA/SP (30.2 S cm 1)). At the
same time, ESVCA (631.1 S cm 1) shows the higher electron conduc­
tivity than PEDOT: PSS/PVA (281.8 S cm 1) because of ESVCA forming
3D continuous electron pathways, enhancing the ability of fast electron
transport by doping and chemical crosslinking. At the same time, the
ESVCA (3.16 � 10 8 cm2 s 1) and the PEDOT: PSS/PVA (2.13 � 10 8
cm2 s 1) exhibits more excellent Li-ion diffusion coefficient compared
with the PEDOT: PSS (5.01 � 10 9 cm2 s 1), PVA (1.59 � 10 8 cm2 s 1)
and traditional CMC (3.66 � 10 9 cm2 s 1). Fig. S3 shows the GITT
curve of ESVCA, the Li-ion diffusion coefficients of the binders are
measured by the galvanostatic intermittent titration technique (GITT)
[21]. In addition, the curve of ESVCA hydrogel between the conductivity
and strain also exhibits the excellent conductive stability of ESVCA
hydrogel when it was stretched from 0 to 250% (Fig. S4). To further
study the change of conductivity of ESVCA by APS chemical cross­
linking, Raman spectroscopy were performed. Fig. 2f shows that the
characteristic peaks of PEDOT: PSS/PVA (ESVCX) were observed at
1069 cm 1 and 1424 cm 1, which are attributed to C–C single stretching
4
Journal of Power Sources xxx (xxxx) xxx
and C¼C symmetrical stretching. The characteristic peaks of Si-ESVCA
were observed at 521 cm 1 (Si–Si), 1365 cm 1 (C–C), 1421 cm 1
(C¼C). The Raman spectrum of Si-ESVCA shows broadening peak at
1421 cm 1 about the C¼C symmetrical stretching and the peaks of C–C
single stretching and C¼C symmetrical stretching appear red shift,
indicating that Si-ESVCA composite has higher electrical conductivity
than PEDOT: PSS/PVA sample due to PEDOT composites of ESVCA
having more abundant of qunoid structure than benzoid structure and
the quinoid structure having higher electric conductivity [37].
The self-healing performance of the stretchable 3D conductive
hydrogel is demonstrated in Fig. 3. The Fig. 3a exhibits the Schematic
illustration of the self-healing process because of dynamic hydrogen
bonds and electrostatic interactions. the Fig. 3b shows the pristine 3D
conductive self-healing hydrogel (the length is 1.0 cm, and the width is
0.5 cm) connected with a red light-emitting diode (LED) bulb powered
by a LiNi0.6Co02Al0.2O2//SiMP full cell and the LED is on, indicating
that the conductive of self-healing hydrogel is good and the practical
application of the SiNP-NCA full cell with 3D self-healing conductive
binder. When the 3D self-healing conductive hydrogel was stretched to
100% strain the LED was still on even 200% strain (Fig. 3c and d) sug­
gesting it’s intrinsically conductive with high stretchability [5]. The
Fig. 3e shows the conductive self-healing hydrogel was cut off and the
LED was off. However, when the two of pieces of conductive self-healing
hydrogel were fast brought together in an asymmetric way, subse­
quently, the conductive self-healing hydrogel was self-healing immedi­
ately and the LED also illuminated again (Fig. 3f). Furthermore, the
conductive self-healing hydrogel can be stretched about 200% strain
(Fig. 3g) after healing while maintaining excellent electrical conduc­
tivities, which indicates the fast electrical and mechanical healing
ability of 3D conductive self-healing hydrogel at room temperature.
The effect of the binder on the electrochemical performance were
evaluated by half-cell measurements using CR2016 type coin cells with
lithium metal as the counter electrode. ESVCA, PEDOT: PSS/PVA and
PEDOT: PSS electrodes are made of SiNPs (diameter, 50 nm on average),
binder in a weight ratio of 6:4, PVA and CMC electrodes are composed of
S. Hu et al. Journal of Power Sources xxx (xxxx) xxx

Fig. 3. Demonstration of stretchability

and healing process for self-healing
conductive hydrogel with an LED in se­
ries powered by a LiNi0.6­
Co02Al0.2O2//SiMP full cell and the Si
anode with self-healing conductive
binder. a) Schematic illustration of the
self-healing process. b) The length of
pristine self-healing conductive hydro­
gel is 1 cm. c) Stretched to two times of
its pristine length. d) Stretched to three
times of its pristine length. e) The self-
healing conductive hydrogel is cut off.
f) Electrical conductivity recovered
immediately when contacted in an
asymmetry way. g) The healed conduc­
tive hydrogel stretched to about three
times of its original length after 2 min.

Fig. 4. Electrochemical performance of Si electrodes with different binders. a) Cycling performance of the Si-ESVCA, Si-PEDOT: PSS/PVA, Si-PEDOT: PSS, Si-PVA, Si-
PVA electrodes at a current density of 2000 mA g 1. b) Cycling performance of the Si-ESVCA electrodes at different current densities of 500, 1000 and 2000 mA g 1.
c) Cycling performance of Si anodes with different binders at 55 � C. d) Cycling performance of the Si-ESVCA electrodes with different high mass loadings from 2.00 to
2.48 mg cm 2. e) Rate performance of the Si electrodes with different binders at different densities from 100 mA g 1 to 4 A g 1. f) CV curves of the Si-ESVCA
electrode at a scanning rate of 0.2 mV s 1.

5
S. Hu et al.
SiNPs, conductive additives (Super P) and binder in weight ratio of
6:2:2. Fig. 4a shows the long-term cycling performance of the Si elec­
trodes with different binders. At the current density of 2000 mA g 1, the
Si-ESVCA electrode exhibits the much higher reversible capacity of
1242 mA h g 1 for 200 cycles with the precycling at 100 mA g 1 for 2
cycles compared with 1092 mA h g 1 of the Si-PEDOT: PSS/PVA
(PEDOT: PSS mixed PVA in a weight ratio of 1:1) electrode due to self-
healing conductive hydrogel has 3D conductive network structure
maintaining the integrity of electron pathways and the excellent self-
healing ability instantly repairing the fragmentation caused by the
volume change of Si particle during repeated lithium/delithium [16,38].
At the same time, the Si-CMC (776 mA h g 1), Si-PVA (382 mA h g 1)
and Si-PEDOT: PSS (200 mA h g 1) electrodes exhibit a poorer cycling
performance, which may be ascribed to insufficient self-healing ability
and unrecoverable breakup of the conductive network caused by the
huge volume changes of Si particle during delithium and insert-lithium
processes. Fig. 4b shows the long-term cycling performance of Si-ESVCA
electrodes at a different current density of 500 mA g 1, 1000 mA g 1 and
2000 mA g 1, the Si-ESVCA electrode exhibits a reversible capacity of
1786 mA h g 1 at 500 mA g 1 with a capacity retention of 71.3% after
200 cycles and a reversible capacity of 1519 mA h g 1 at 1000 mA g 1
with a capacity retention of 66.6% after 200 cycles, furthermore, the
Si-ESVCA electrode shows a reversible capacity of 1250 mA h g 1 at a
current density of 1000 mA g 1 after 400 long-term cycles (Fig. S5),
suggesting that Si-ESVCA electrode also remains excellent cycling sta­
bility. Especially, at a very high current density of 4200 mA g 1, the
Si-ESVCA electrode remains reversible capacity of 1011 mA h g 1 after
100 cycles (Fig. S6). With respect to the application of lithium-ion bat­
tery, the performance of such electrodes is very important at elevated
temperatures which is related to its safe use in portable electronics or
electric vehicles. Fig. 4c shows the cycling performance of Si anodes
with different binders at elevated temperature (55 � C), Si-ESVCA elec­
trode maintains superior cycling stability with a capacity retention of
74.1% and remains a high reversible capacity of 1743 mA h g 1 after
200 cycles at current density of 2000 mA g 1 compared with Si-PEDOT:
PSS electrode and Si-CMC electrode which suffer from a fast capacity
fade at elevated temperature [39]. The formation of HF by the thermal
degradation of LiPF6 at 50 � C etching SiO2 layer on the surface of Si
nanoparticle, which has been considered as major reason causing the
capacity fading of Lithium-ion batteries at elevated temperature, espe­
cially, the exist of water will accelerate the formation of the HF
involving LiPF6 degradation [40,41]. Therefore, the content of water
absorbed of binders are important for battery cycling performance at
elevated temperature. The thermal gravimetric analysis of Fig. S7 show
that ESVCA absorbed fewer water (3%) compared with PEDOT:
PSS/PVA (5%) and CMC (10%), suggesting the Si-ESVCA electrode
facing fewer side reaction and maintaining cycling performance at
elevated temperature [42]. Furthermore, the XPS spectra of Si electrodes
with different binders after 200 cycles exhibit lower side reaction pro­
duced on the surface of Si-ESVCA electrode (Fig. S8), the C 1s spectrums
show a bulk binding energy peaks in the 288–292 eV region (orange),
corresponding to carbonate groups produced by reaction between sol­
vent and slice of water, at the same time, the Si 2p spectrums show the
appearance of SiOxFy species (green) in the 105–107 eV ensuing from
the reaction of HF with SiO2 at the surface of Si particles [43,44]. In
addition, dynamic mechanical analysis (DMA) exhibits that the ESVCA
hydrogel presents weak temperature-dependent mechanical behavior.
At the temperature range of 20–100 � C, the loss modulus (E00 ) of ESVCA
hydrogel slightly increased with increasing temperature while the
storage modulus (E0 ) decreases before 75 � C and fast increases from 75
�
C to 100 � C (Fig. S9). In the whole temperature range, the E” is always
much smaller than E’, indicating an excellent elastic response of ESVCA
[45]. The weak temperature-dependent mechanical and excellent elastic
properties of ESVCA binder ensure the superior cycling performance of
Si anodes at elevated temperature. Moreover, the charge-discharge
curves also reveal the smaller changes in its voltage curve and
6
Journal of Power Sources xxx (xxxx) xxx
capacity fade of Si-ESVCA electrode than the counter binders (Fig. S10).
High loading mass and current density are important to realize large and
fast charge-discharge process. The Si-ESVCA electrodes with a large
areal loading mass (Si loading mass varying from 2.00 to 2.48 mg cm 2)
remain good cycling ability and maintain excellent areal capacity over
5.0 mA h cm 2 at 0.5 mA cm 2 after 100 cycles (Fig. 4d). The superior
cycling stability and excellent reversible capacity of the Si-ESVCA
electrodes are attributed to the 3D conductive network leading to fast
electron transfer ability and the robust self-healing mechanical proper­
ties that can continuously repair the damage caused by the volume
change of Si particle during fast lithium-delithium procession and
maintain the electrical contacts among active materials [15,46]. Fig. 4e
shows the delithiation rate capacity of the Si electrodes with different
binders. Although the Si-PEDOT: PSS has the high reversible capacity at
a low current density of 100 mA g 1, it shows the worst capacity per­
formance when the charge current density are increased from 500 mA
g 1 to 4000 mA g 1. The Si-ESVCA electrode exhibits the highest rate
capacity of 1633 mA h g 1 with the best capacity retention of 51.5%. In
contrast, the Si-PEDOT: PSS/PVA electrode shows the capacity retention
of 42.8%, the Si-PVA and Si-CMC show the similar capacity retention of
only 18.2% when the current density is increased 40 times from 100 mA
g 1 to 4000 mA g 1. Furthermore, the voltage profiles also confirm the
rate performance of Si-ESVCA is superior to theses counter binders
(Fig. S11). The superior rate performance of the Si-ESVCA electrode is
ascribe to fast electron transport ability and robust electro contacts
during active materials produced by 3D conductive network [21,46].
Fig. 4f shows the cyclic voltammetry (CV) cures of Si-ESVCA corre­
sponding to a scanning rate of 0.2 mV s 1 over the potential range of
0.01–1.20 V versus Li/Liþ. The discharge curve displays a peak at 0.10 V
corresponding to crystalline Si to form an amorphous LixSi phase and the
formation of a solid electrolyte interphase (SEI). The peaks at 0.39 V and
0.52 V in the anodic scan process are attribute to the transformation of
amorphous α-LixSi to α-Si [47]. The increase of peak current from 1st to
4th cycles corresponding to a gradual activation process of more active
Si embed in the electrode [48]. The CV curve of ESVCA films suggest that
the contribution for the capacity of ESVCA compared with the capacity
of the whole Si electrode is negligible, thus the reversible capacity of
Si-ESVCA should mainly from SiNPs (Fig. S12).
To investigate the interfacial properties of Si electrodes with
different binders, AC impedance tests were shown in the Fig. 5a after 5
cycles, Fig. 5b after 50 cycles at 2000 mA g 1 and Fig. 5c after rate
cycles. The first and second semicircles are ascribe to the SEI layer
resistance in the high frequency region and the charge transfer resis­
tance in the middle frequency region [49]. Obviously, the Si-ESVCA
electrode presents the smallest semicircle diameter in the high and
middle frequency region after 5cycles even 50 cycles compared with the
Si-PEDOT: PSS/PVA, Si-PVA and Si-CMC electrodes, at the same time,
the curve of EIS with rate cycle further reveals that the rate performance
of the self-healing conductive binder is more than the other binders.
These results indicates that the fast electron transfer and self-repairing
property produced by 3D conductive network can efficiently decrease
the whole charge-transfer resistance of Si anodes [21,38].
The distinct effects of binders on the electro-chemical performance
was revealed by electron microscopy (SEM). At pristine states, all the
electrodes possess a smooth surface before delithation (Fig. 6a, b and c).
However, the electrodes present a drastic difference in the surface
morphology after 200 cycles, the Si-ESVCA exhibits some small spindly
cracks with a width about 1.2 μm (Fig. 6d), while the Si-PEDOT: PSS/
PVA and Si-CMC electrodes show much more severe cracks with widths
reaching 2.8 μm and 12 μm (Fig. 6e and f). These remarkable differences
can be related to the superior self-healing ability and 3D conductive
network structure of ESVCA binder which can continuous repair the
broken of active materials caused by the volume change of Si particle
and maintain the integrity of conductive pathway [15–17]. Moreover,
the thickness change of Si electrodes can also exhibit the advantage of
3D self-healing network restraining the volume expansion of Si particle
S. Hu et al.
Fig. 5. Nyquist plot of Si electrodes with various binders after a) 5cycles, b) 50 cycles and c) rate cycles.
Fig. 6. SEM images of Si electrodes with a, d) ESVCA, b, e) PEDOT: PSS/PVA, and c, f) CMC after 200 cycles.
after long-time cycles. The thickness of Si-ESVCA, Si-PEDOT: PSS/PVA,
and Si-CMC electrodes is about 14.3 μm (Fig. S13) before during lith­
iation and delithiation cycles, instead, the Si-ESVCA electrode increases
by 27.1 nm, in contrast to Si-PEDOT: PSS/PVA (30.5 nm), and Si-CMC
electrodes (51.5 nm), which indicates that the 3D network structure
and self-healing properties of conductive self-healing hydrogel coated
on Si particle effectively reduces the change of Si particles [5].
4. Conclusions
In conclusion, a novel 3D network conductive self-healing hydrogel
binder was designed and prepared by the chemical crosslinking, chem­
ical doping and electrostatic self-assembly between the high electron-
conductive PEDOT: PSS polymer and a cost-effective Li-ion conductive
PVA polymer for high performance silicon anodes. The 3D network self-
healing conductive hydrogel binder possesses excellent strechability,
high conductivity and fast self-healing ability at room temperature. The
stretchable 3D self-healable network structure coating on the surface of
active Si particle could efficiently restrain the huge volume change of Si
particles during lithiation and delithiation cycles to maintain mechani­
cal integrity of the Si electrodes while 3D continuous electron transport
pathways insuring the high conductivities and better electrical contacts
among active Si particles. The Si-ESVCA electrode exhibits a reversible
capacity of 1786 mA h g 1 at 500 mA g 1 with a capacity retention of
71.3% after 200 cycles and a reversible capacity of 1519 mA h g 1 at
1000 mA g 1 with a capacity retention of 66.6% after 200 cycles as well
as the highest rate capacity of 1633 mA h g 1 at the current density of
7
Journal of Power Sources xxx (xxxx) xxx
4000 mA g 1. Furthermore, the Si-ESVCA electrodes not only achieve a
superior areal capacity of 5.25 mA h cm 2 after 100 cycles even at the
high areal mass loading of 2.48 mg cm 2, but also maintains superior
cycling stability with a capacity retention of 74.1% and remains a high
reversible capacity of 1743 mA h g 1 after 200 cycles at current density
of 2000 mA g 1 at elevated temperature. The new binder embedding
both fast self-healing ability and 3D conductive pathways provides a
promising application for high-capacity electrode materials in next
generation high-energy LIBs.
Declaration of competing interest
The authors declare no conflict of interest.
Acknowledgements
The authors acknowledge funding is supported by the National
Natural Science Foundation of China (No. 21473040) and 973 Program
(2014CB932301).
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://doi.
org/10.1016/j.jpowsour.2019.227472.
References
[1] M. Armand, J.M. Tarascon, Nature 451 (2008), 652-628.
S. Hu et al. Journal of Power Sources xxx (xxxx) xxx

[2] J.B. Goodenough, K.S. Park, J. Am. Chem. Soc. 135 (2013) 1167–1176. [25] Z. Chen, J.W.F. To, C. Wang, Z. Lu, N. Liu, A. Chortos, L. Pan, F. Wei, Y. Cui, Z. Bao,
[3] H. Wu, Y. Cui, Nano Today 7 (2012) 414–429. Adv. Energy Mater. 4 (2014) 1400207–1400216.
[4] M.N. Obrovacz, L. Christensen, Electrochem. Solid State Lett. 7 (2004) A93–A96. [26] G.V. Kumar, R. Chandramani, Appl. Surf. Sci. 255 (2009) 7047–7050.
[5] S. Choi, T.-w. Kwon, A. Coskun, J.W. Choi, Science 357 (2017) 279–283. [27] E.F.d. Reisa, F.S. Campos, A.P. Lage, R.C. Leite, L.G. Heneine, W.L. Vasconcelosc,
[6] M.H. Ryou, J. Kim, I. Lee, S. Kim, Y.K. Jeong, S. Hong, J.H. Ryu, T.S. Kim, J. H.S. Mansur, Mater. Res. 9 (2006) 185–191.
K. Park, H. Lee, J.W. Choi, Adv. Mater. 25 (2013) 1571–1576. [28] M. Şenel, A. Bozkurt, A. Baykal, Ionics 13 (2007) 263–266.
[7] Y. Jin, S. Li, A. Kushima, X. Zheng, Y. Sun, J. Xie, J. Sun, W. Xue, G. Zhou, J. Wu, [29] Y.V. Baskakova, O.V. Yarmolenko, O.N. Efimov, Russ. Chem. Rev. , 81 367-380.
F. Shi, R. Zhang, Z. Zhu, K. So, Y. Cui, J. Li, Energy Environ. Sci. 10 (2017) [30] Y.N. Sudhakara, M. Selvakumara, D.K. Bhat, Mater. Sci. Eng. B 180 (2013) 12–19.
580–592. [31] Y. Li, X. Fang, Y. Wang, B. Ma, J. Sun, Chem. Mater. 28 (2016) 6975–6984.
[8] H. Wu, G. Chan, J.W. Choi, I. Ryu, Y. Yao, M.T. McDowell, S.W. Lee, A. Jackson, [32] Y. Li, L. Liang, C. Liu, Y. Li, W. Xing, J. Sun, Adv. Mater. 30 (2018)
Y. Yang, L. Hu, Y. Cui, Nat. Nanotechnol. 7 (2012) 310–315. 1707146–1707152.
[9] Y.K. Jeong, T.-w. Kwon, I. Lee, T.-S. Kim, A. Coskun, J.W. Choi, Energy Environ.l [33] Q. Rong, W. Lei, L. Chen, Y. Yin, J. Zhou, M. Liu, Angew Chem. Int. Ed. Engl. 56
Sci. 8 (2015) 1224–1230. (2017) 14159–14163.
[10] J.S. Bridel, T. Azaïs, M. Morcrette, J.M. Tarascon, D. Larcher, Chem. Mater. 22 [34] V. Mydhili, S. Manivannan, J. Appl. Polym. Sci. 134 (2017) 45079–45088.
(2010) 1229–1241. [35] R. Ricciardi, F. Auriemma, C.D. Rosa, F. Laupr^etre, Macromolecules 37 (2004)
[11] I. Kovalenko, B. Zdyrko, A. Magasinski, B. Hertzberg, Z. Milicev, R. Burtovyy, 1921–1927.
I. Luzinov, G. Yushin, Science 334 (2011) 75–79. [36] Y. Li, Q. Zeng, I.R. Gentle, D. Wang, J. Mater. Chem. A 5 (2017) 5460–5465.
[12] B. Koo, H. Kim, Y. Cho, K.T. Lee, N.S. Choi, J. Cho, Angew Chem. Int. Ed. Engl. 51 [37] S.W. Park, T.H. Oh, J.S. Hwang, Y.J. Lee, Fibers Polym. 17 (2016) 1171–1174.
(2012) 8762–8767. [38] T. Munaoka, X. Yan, J. Lopez, J.W.F. To, J. Park, J.B.H. Tok, Y. Cui, Z. Bao, Adv.
[13] S. Hu, Z. Cai, T. Huang, H. Zhang, A. Yu, ACS Appl. Mater. Interfaces 11 (2019) Energy Mater. 8 (2018) 1703138–1703148.
4311–4317. [39] S. Klamor, M. Schr€ oder, G. Brunklaus, P. Niehoff, F. Berkemeier, F.M. Schappacher,
[14] Y. Bie, J. Yang, Y. Nuli, J. Wang, J. Mater. Chem. A 5 (2017) 1919–1924. M. Wintera, Phys. Chem. Chem. Phys. 17 (2015) 5632–5641.
[15] G. Zhang, Y. Yang, Y. Chen, J. Huang, T. Zhang, H. Zeng, C. Wang, G. Liu, Y. Deng, [40] H. Gao, L. Xiao, I. Plümel, G.-L. Xu, Y. Ren, X. Zuo, Y. Liu, C. Schulz, H. Wiggers,
Small 14 (2018) 1801189–1801198. K. Amine, Z. Chen, Nano Lett. 17 (2017) 1512–1519.
[16] C. Wang, H. Wu, Z. Chen, M.T. McDowell, Y. Cui, Z. Bao, Nat. Chem. 5 (2013) [41] S.F. Lux, I.T. Lucas, E. Pollak, S. Passerini, M. Winter, R. Kostecki, Electroc. Comun.
1042–1048. 14 (2012) 47–50.
[17] Z. Xu, J. Yang, T. Zhang, Y. Nuli, J. Wang, S.-i. Hirano, Joule 2 (2018) 950–961. [42] M. Ling, Yanan Xu, Hui Zhao, Xingxing Gu, Jingxia Qiu, S. Li, Mingyan Wu,
[18] S.-M. Kim, M.H. Kim, S.Y. Choi, J.G. Lee, J. Jang, J.B. Lee, J.H. Ryu, S.S. Hwang, J.- Xiangyun Song, Cheng Yan, Gao Liu, S. Zhang, Nano Energy 12 (2015) 178–185.
H. Park, K. Shin, Y.G. Kim, S.M. Oh, Energy Environ. Sci. 8 (2015) 1538–1543. [43] V. Etacheri, O. Haik, Y. Goffer, G.A. Roberts, I.C. Stefan, R. Fasching, D. Aurbach,
[19] S.J. Park, H. Zhao, G. Ai, C. Wang, X. Song, N. Yuca, V.S. Battaglia, W. Yang, G. Liu, Langmuir 28 (2012) 965–976.
J. Am. Chem. Soc. 137 (2015) 2565–2571. [44] B. Philippe, R.m. Dedryvère, M. Gorgoi, H.k. Rensmo, D. Gonbeau, K. Edstr€ om,
[20] H. Wu, G. Yu, L. Pan, N. Liu, M.T. McDowell, Z. Bao, Y. Cui, Nat. Commun. 4 J. Am. Chem. Soc. 135 (2013) 9829–9842.
(2013) 1943–1947. [45] S. Shi, X. Peng, T. Liu, Y.-N. Chen, C. He, H. Wang, Polymer 111 (2017) 168–176.
[21] W. Zeng, L. Wang, X. Peng, T. Liu, Y. Jiang, F. Qin, L. Hu, P.K. Chu, K. Huo, [46] L. Wang, T. Liu, X. Peng, W. Zeng, Z. Jin, W. Tian, B. Gao, Y. Zhou, P.K. Chu,
Y. Zhou, Adv. Energy Mater. 11 (2018) 1702314–1702322. K. Huo, Adv. Funct. Mater. 28 (2018) 1704858–1704865.
[22] Y. Xia, K. Sun, J. Ouyang, Energy Environ. Sci. 5 (2012) 5325–5332. [47] M.N. Obrovac, L.J. Krause, J. Electrochem. Soc. 154 (2007) A103–A108.
[23] B. Lu, H. Yuk, S. Lin, N. Jian, K. Qu, J. Xu, X. Zhao, Nat. Commun. 10 (2019) [48] D. Liu, Y. Zhao, R. Tan, L.-L. Tian, Y. Liu, H. Chen, F. Pan, Nano Energy 36 (2017)
1043–1052. 206–212.
[24] Y. Sun, J. Lopez, H.W. Lee, N. Liu, G. Zheng, C.L. Wu, J. Sun, W. Liu, J.W. Chung, [49] D. Dees, E. Gunen, D. Abraham, A. Jansen, J. Prakash, J. Electrochem. Soc. 152
Z. Bao, Y. Cui, Adv. Mater. 28 (2016) 2455–2461. (2005) A1409–A1417.