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Room-Temperature Rapid Self-Healing Polymer Binders for Si

Anodes in Highly Cycling-Stable and Capacity-Maintained Lithium-
Ion Batteries
Fei Wang, Xiang Ma, Yiren Li, Hongmei Liu, Qingping Wu, Xiang Guan, Hui Liu, Xiao Xia Wang,*
and Jun Xu*
Cite This: ACS Appl. Energy Mater. 2023, 6, 3538−3548 Read Online
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sı Supporting Information

ABSTRACT: Silicon (Si) with high specific capacity has received

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increasing attention for rechargeable battery anode materials.

However, particle pulverization as a result of the large volume
expansion of Si anodes further aggravated electrochemical perform-
ance degradation during the process of charging and discharging. In
this work, we report the room-temperature rapid self-healing
polymer binders (Al/Alg-TUEG) synthesized via dynamic coordi-
nation bonds (Al−O) and hydrogen bonds from poly(ether-
thioureas) (TUEG). The prepared polymer binders exhibit a
peeling force of 4.2 N, a swelling ratio of 9.5%, and a recovery of
90% in 2 h at room temperature. As a result, the Si@Al/Alg-TUEG
anodes stably cycle for 300 cycles at 0.5 C with a capacity retention
rate of 77.4%. A high initial Coulombic efficiency (CE) of 87.2%
and good rate performance are also achieved. In terms of full cell
performance, both LiFePO4//Si@Al/Alg-TUEG and NCM811//Si@Al/Alg-TUEG display stable cycling for 100 cycles at 0.5 C.
The capacity retention of both full cells reaches 93.8 and 92.5%. Good recoverability at high rates is also found. The superior
electrochemical performance of the Si anode indicates that Al/Alg-TUEG polymer with rapid self-healing capability at room-
temperature is one of the promising binder candidates for next-generation high-energy-density lithium-ion batteries.
KEYWORDS: lithium-ion battery, polymer binder, silicon anode, self-healing, full cell

■ INTRODUCTION
To further realize the rational application of renewable energy
sources, energy-storage batteries with high capacity are
urgently needed. However, at present, anode materials with a
relatively low theoretical specific capacity (372 mAh g−1) badly
restrict the development of high specific capacity batteries.
Consequently, much attention has been paid to seek high-
capacity anode materials for lithium-ion batteries (LIBs).1−6
Due to its high theoretical specific capacity (4200 mAh g−1), a
relatively low operating voltage (around 0.4 V vs Li+/Li), as
well as advantages of environmental friendliness and rich
abundance, Si has become one of the most promising anode
materials.7−12 Unfortunately, great volume change (around
300%) of Si particles occurs during the embedding and de-
embedding process of Li+, which results in squeezing and
pulverization of Si particles, destroying the electrode structure
and thus leading to an unstable solid electrolyte interphase
(SEI). In brief, the volumetric expansion/shrinking of the Si
anode largely reduces the cycling life of the electrode, which
indeed hurdles the practical application of the Si anode.10,12−14
To resolve these problems, several strategies have been
proposed. Among them, changing or modifying the Si anode
binders has attracted wide attention.13−29 Especially, polymer
binders play a vital role in stabilizing the inner structure of
electrode materials and shortening the transmission tunnel of
Li-ions.30,31 Many researchers predicted the future develop-
ment of binders for next-generation energy-storage devices.5,6
To date, besides commercial poly(vinylidene fluoride)
(PVDF),32 various binders consisting of rich hydroxyl
(−OH) or carboxyl (−COOH) have been widely reported,
e.g., poly(acrylic acid) (PAA),33 carboxymethyl cellulose
(CMC),34 and alginate (Alg),35 low-cost bio-derived materials
(BDMs),36 which can apparently improve the cycling life by
bonding with the surface of Si particles. However, these linear
Received: January 18, 2023
Accepted: February 22, 2023
Published: March 3, 2023

© 2023 American Chemical Society https://doi.org/10.1021/acsaem.3c00161

3538 ACS Appl. Energy Mater. 2023, 6, 3538−3548
ACS Applied Energy Materials
Figure 1. Inhibition of the volume expansion and crack generation of SiNPss through hydrogen bonding and metal coordination from Si@Al/Alg-
TUEG during lithiation and delithiation. (a) Structure and action mechanism of Al/Alg-TUEG, (b) hydrogen bond interaction between the Alg
and SiNPs surface, and (c) coordination bonds between Al3+ and Alg.
binders do not show ideal mechanical properties and stable
electrochemical behaviors for Si anodes during lithiation and
delithiation.37−39 On this basis, some conductive polymers are
adopted to enhance the ionic conductivity of Si anodes, such as
polyaniline (PANI),40 polypyrrole (PPy),41 polythiophen
(PTH), etc.10,42−44 Ionically and electronically conductive
polymers (c-PEOPEDOT:PSS/PEI) have also been widely
studied for high-performance Si anodes.45 However, these
polymers cannot assist in preserving the integrity of Si particles
in anodes, especially when they undergo severe volume change
during repeated charging/discharging processes. Consequently,
self-healing binders were proposed for their capability of
suppressing the volume expansion of Si particles and rapidly
impairing the deterioration of anodes. For instance, cycling
stability was improved by a self-healable polymer binder with
the reversible Diels-Alder reaction.46 Excellent capacity
retention for Si anodes was achieved by the polymer binders
(SHP-PEG) based on the combination of self-healing ability
and fast Li-ions conduction. However, the Si electrode with
SHP-PEG750 showed a low initial capacity at 0.5 C and a
cycling life of only 150 cycles.47 Self-healing poly(ether-
thioureas) (SHPET) polymer was synthesized by balanced
rigidity and softness for the Si anode, which achieved excellent
cycling life with a high capacity retention of 85.6% after 250
cycles at a high current rate of 4200 mA g−1. However,
applications in full cells have not been reported.48 The above
binders still cannot solve the problem resulted from the Si
particle volume expansion to achieve high capacity, long
cycling life, good rate performance, and applications in full
battery, due to their limited self-healing ability.48,49
Herein, we report a novel rapid room-temperature self-
healing polymer binder (Al/Alg-TUEG) composed of a
physical blend of alginate (Alg) polymer networks and
poly(ether-thioureas) (TUEG) polymers, where the Alg
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polymer network is formed by cross-linking Alg with Al3+
cations. The Al/Alg-TUEG is capable of reducing the volume
change of Si anodes through the dual polymer network during
the process of charging and discharging. Alg is a natural
polyanionic polysaccharide rich in gulonate units, which can
interact with the hydroxyl groups on the surface of Si
nanoparticles (SiNPs), thus enhancing the connection among
SiNPs, binders, and the current collector. After cross-linking
with Al3+, the Al-O bond endows a certain self-healing effect to
Alg. The isolated pair electrons on the oxygen in ether groups
contained in TUEG can help transport lithium ions; more
importantly, it has an excellent self-healing ability.50 Con-
sequently, Al/Alg-TUEG not only has a strong bonding force
(peeling force of 4.2 N at 25 °C), which limits the volume
expansion of SiNPs, but also the ability to self-heal rapidly. The
Si@Al/Alg-TUEG anode exhibits stable cycling performance
(capacity retention rate of 77.4% after 300 cycles) and a high
initial Coulombic efficiency (ICE) (77.4%) at 0.5 C, as well as
excellent rate performance in the range of 0.1−5 C. The
achieved performance of the assembled LiFePO4//Si@Al/Alg-
TUEG and NCM811//Si@Al/Alg-TUEG batteries confirms
the promising application potential of the Al/Alg-TUEG
binder.
■ RESULTS AND DISCUSSION
The Al/Alg-TUEG binder was prepared by a simple blending
approach. The chemical structure and action mechanism of Al/
Alg-TUEG are shown in Figure 1. Apparently, Alg is rich in
gulonate units, which can form hydrogen bonds with the
hydroxyl groups on the surface of SiNPs, thus enhancing the
adhesion between the SiNPs and the current collector (Figure
1a). The Al−O coordination bond is introduced by the
coordination of −COO− and −OH in Alg with Al3+, which
endows the binders with rapid self-healing ability (Figure 1b).
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ACS Applied Energy Materials
TUEG has been reported as a binder with a good self-healing
capacity, which can also help the transport of Li-ions for its
ether segments. The Al/Alg-TUEG can be used to a
considerable effect. On the one hand, guluronic acid units in
different alginate chains can well coordinate with dissociated
Al3+, acting as a recoverable and self-healing network during
energy dissipation. On the other hand, through the hydrogen
bond rearrangement, TUEG can also serve as a second
recoverable network.50 Both polymers have a self-healing
ability and promote each other to achieve a promising
performance. Furthermore, the doped Al3+ can improve Si
anode electrochemical activity, and the abundant Al−O metal-
chelated bonds enhance the overall mechanical strength of Al/
Alg-TUEG. With the help of multiple binding forces inside of
the binder, the Si anode can achieve satisfactory electro-
chemical performance.
Alg, TUEG, Alg-TUEG, and Al/Alg-TUEG were inves-
tigated using Fourier transform infrared (FT-IR) spectra
(Figure 2a). The characteristic peaks of Alg and TUEG are
Figure 2. (a) FT-IR spectra of the Alg, TUEG, Alg-TUEG, and Al/
Alg-TUEG. (b) XPS spectra of the Al/Alg-TUEG.
found in the spectrum of Alg-TUEG. The broad peaks at 2880
and 3290 cm−1 correspond to the deformation and stretching
vibrations of −NH− in the TUEG unit, respectively. The
characteristic peak at 2925 cm−1 is caused by the symmetric
and asymmetric vibrations of C−H in the Alg unit.51
Moreover, the peaks at 1037−1057 cm−1 and 1614 cm−1 are
attributed to the stretching vibrations of C−O−C and the
asymmetric stretching vibrations of COO−, respectively. In
contrast, the pattern of Al/Alg-TUEG contains all of the
mentioned characteristic absorptions. Besides, a new character-
istic peak at 812 cm−1 is also found in it, which is determined
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to be Al−O coordination bonds.52−54 As a result, these
evidences identify the successful preparation of Al/Alg-TUEG.
The presence of Al−O coordination bonds was further
verified using X-ray photoelectron spectroscopy (XPS) (Figure
2b) and proton nuclear magnetic resonance (1H NMR)
spectra (Figure S1). In XPS spectra of Al/Alg-TUEG, the
characteristic peaks at 72.9 and 75.7 eV are attributed to the
presence of Al−O coordination bonds. As well, in 1H NMR
spectra, the peaks at 3.56 and 7.52 ppm correspond to C−H
and N−H protons of TUEG, the peak at 5.32 ppm to −OH
protons of Alg, and the peak at 1.23 ppm to the Al−O bond.55
Therefore, the coordination between −COO− and −OH in
guluronic acid units and Al3+ ions actually exits in the binders.
The rheological properties of Al/Alg-TUEG and Alg were
analyzed by time-sweep tests at room temperature (Figure 3).
It can be seen that the loss module (G″) of Alg is always higher
than the energy-storage module (G′). Differently, G′ is always
greater than G″ and remains stable for Al/Alg-TUEG (Figure
3a). To investigate the self-healing properties of Al/Alg-
TUEG, a strain-sweep test was accomplished with strain
variations ranging from 1 to 1000%, followed by quick recovery
under 1% shear strain (Figure 3b,c). G′ and G″ remain
relatively stable until the strain reaches 600%, but after the
strain increases to 600%, G′ and G″ simultaneously drop
sharply (Figure 3b). It indicates that the hydrogen and
coordination bindings in Al/Alg-TUEG are able to remain
stable until the strain reaches 600%. Subsequently, time-scan
tests of Al/Alg-TUEG at 1% shearing strain reveal that G′ and
G″ are able to recover rapidly to their original state (Figure
3c). When the volume of SiNPs expands during the lithium
embedding process, although the inner stress is increased, the
SiNPs can be still firmly confined by the Al/Alg-TUEG
network. However, if the stress is increased too large, the
hydrogen bond and Al−O coordination in Al/Alg-TUEG will
also be partially destroyed. During the de-lithium process, the
stress relieves and the destroyed Al/Alg-TUEG network can
recover quickly. By this means, the integrity of the Si anodes is
preserved throughout the cycling of the battery. Therefore, Si
anodes with Al/Alg-TUEG as a binder show a long cycling life
and good cycling stability.
Simple experiments were designed to visualize the rapid self-
healing ability of Al/Alg-TUEG (Figure 3d). The original Al/
Alg-TUEG was stained and cut into small pieces, which was
then brought into contact. The Al/Alg-TUEG became an
integral piece again spontaneously after 2 h. A magnified view
of the interface shows the interpenetration of the different
colors, visually reflecting the excellent self-healing properties of
Al/Alg-TUEG. The original and self-healed Al/Alg-TUEG
samples were subjected to stress−strain tests to determine the
degree of self-healing (Figure 3e). The tensile strength of the
pristine Al/Alg-TUEG sample is 107 kPa, corresponding to a
maximum elongation of 585.29%. The tensile strength of the
self-healed Al/Alg-TUEG sample is 90 kPa, corresponding to a
maximum elongation of 567.96%, indicating that Al/Alg-
TUEG has a strong self-healing ability with a recovery
efficiency of 90%.
After the preparation of Si@Al/Alg-TUEG anodes, the
surface morphology of the anodes was observed by scanning
electron microscopy (SEM) (Figure S2a−c). The Si@Al/Alg-
TUEG anodes show a flat and uniform surface, in which SiNPs
are evenly dispersed without any agglomeration. In addition,
from the EDAX element mapping (Figure S2d−i), various
elements are also uniformly dispersed in the anodes. It
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ACS Applied Energy Materials
Figure 3. Rheological and self-healing properties of Alg and Al/Alg-TUEG at 25 °C (concentration: 35 wt %). (a) Time-sweep curves of the Al/
Alg-TUEG and Alg. (b) Strain-sweep curves of Al/Alg-TUEG. (c) Al/Alg-TUEG recovery from 1000% strain deformation under small shear strain.
(d) Schematic diagram of the self-healing properties of Al/Alg-TUEG. (e) Stress−strain curves of original and self-healed Al/Alg-TUEG.
indicates that the binder is well mixed with the SiNPs to form
an interpenetrating network.
The adhesion ability of the binder has been found as a
cardinal gauge to measure whether the binder material can
limit the rapidly violent volume expansion of SiNPs. Binders
with poor binding ability were apt to strip the active material
within the Si anodes, so the ideal binder must have high
adhesion. The force−displacement curves for Si@Alg, Si@Alg-
TUEG and Si@Al/Alg-TUEG under a 180° peeling test are
plotted (Figure 4a). The average adhesion forces of Si@Alg
and Si@Alg-TUEG electrodes are 2.22 and 3.49 N,
respectively, while that of the Si@Al/Alg-TUEG electrode
even reaches 4.41 N, which is much higher than that of other
two electrodes and twice as high as that of the Si@Alg
electrode. (Figure 4b). Additionally, the Si@Al/Alg-TUEG
electrode was stripped with little shedding of the electrode
material, whereas the Si@Alg electrode is exposed to the Cu
foil (Figure S3). It implies the stronger adhesion of the Al/Alg-
TUEG binder, which is resulted from both the hydrogen bond
and ionic coordination in Al/Alg-TUEG. Consequently, the
active material is tightly adhered to the Cu foil. Moreover, the
swelling ratio of the binder in the electrolyte is vital for
changing the morphology and electrochemical performance of
the electrode. The swelling ratio of Al/Alg-TUEG is 9.5%,
much lower than 23.5% of Alg (Figure S4), indicating that Al/
Alg-TUEG is crucial for the stability of the anode.56
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The electrochemical stability and smooth Li-ions diffusion of
Si@Al/Alg-TUEG anodes are demonstrated using cyclic
voltammetry (CV), as shown in Figure 5.57 In the CV curves
(Figure 5a), a stable redox reaction during lithiation and de-
lithiation over a voltage range of 0.01−2.5 V at a scan rate of
0.05 mV s−1 is found. Moreover, the perfect closure of the
curve and the absence of other current peaks indicate the good
reversibility of the Si@Al/Alg-TUEG anodes. As known for us,
the ionic conductivity of the anodes is considered to be crucial
for electrochemical performance. It was revealed that ether
oxygen groups can help the transport of Li-ions.58,59 The rate-
dependent CV curves of Si@Al/Alg-TUEG anodes and Si@
Alg anodes at scanning rates of 0.1, 0.3, and 0.5 mV s−1 are
displayed in Figure 5b,c. As well, the mathematical calculation
of the Li-ions diffusion coefficient is exhibited in Figure 5d. A
linear relationship between the peak current ( ip) and the
square root of the scan rate (v1/2 ) is revealed. The result
shows that the calculated diffusion constant of the Si@Al/Alg-
TUEG anodes (3.76 × 10−5 cm2 s−1) is larger than that of the
Si@Alg anodes (1.83 × 10−5 cm2 s−1). The specific calculation
formula is shown as follows:
i p = (2.69 × 105)n3/2AD1/2Cv1/2
where n is the number of electrons in the reaction (n = 4.4), ip
is the peak current, A is the anode area (0.64 cm2), C is the
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ACS Applied Energy Materials
Figure 4. (a) 180° peeling test and (b) average peeling force of Si@
Al/Alg-TUEG,Si@Alg-TUEG and Si@Alg anodes.
concentration of Li-ions (0.001 mol cm−3), v is the scanning
rate, and D is the Li-ions diffusion coefficient (cm2 s−1).60
The electrochemical performance of the Si@Al/Alg-TUEG
anodes was explored by galvanostatic charge/discharge (GCD)
measurements on coin-type half cells over a voltage range of
0.01−1.20 V (Figure 6). To activate the cell, the current
density was set to 0.05 C for cycles 1−4, followed by a long
cycle test at 0.5 C. The first-lap specific capacities of the Si@
Alg and Si@TUEG anodes are 3140 and 1500 mAh g−1,
respectively. However, the specific capacity of the Si@TUEG
anode decays sharply to 0 mAh g−1 within 100 cycles, and the
Si@Alg anode only has a capacity retention of 37.3%.
Differently, the Si@Al/Alg-TUEG anode exhibits a high
initial specific capacity of 3204 mAh g−1, which decreased to
2480 mAh g−1 after 300 cycles, with a capacity retention rate of
77.4% (Figure 6a). Due to the poor cycling performance of the
Si@TUEG anode, only Si@Alg and Si@Al/Alg-TUEG anodes
are chosen for subsequent tests. The initial discharge/charge
curves for the Si@Alg and Si@Al/Alg-TUEG anodes are
investigated (Figure S5). In contrast with Si@Alg anodes, the
Si@Al/Alg-TUEG anodes have a wider and flatter plateau,
which demonstrates its good self-healing and electrochemical
properties. To investigate the stability of Si anodes with
different binders during cycling, the impedance values of cells
were measured before and after cycling. As shown in Figure S6,
the impedance of the Si@Al/Alg-TUEG anodes is 70 Ω before
cycling and increased by 78 Ω after 100 cycles. However, the
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impedance of the Si@Alg anodes is 130 Ω before cycling and
increased by 120 Ω after 100 cycles, indicating that the Si@Al/
Alg-TUEG anode is more stable.
The CE of Si@Al/Alg-TUEG and the Si@Alg anodes are
tested and shown in Figure 6b. The Si@Al/Alg-TUEG anodes
have an exceptional ICE of 87.1%, which is much higher than
that of the Si@Alg anode (79.3%). The high ICE indicates that
the consumption of active ingredients and Li-ions for the
formation of the SEI in the Si@Al/Alg-TUEG anode is much
less than those in the Si@Alg anode during the initial cycle. In
addition to the good cycling stability, Si@Al/Alg-TUEG
anodes also exhibit excellent rate capability (Figure 6c). The
specific capacity of the Si@Al/Alg-TUEG anode is much
higher than that of the Si@Alg anode when the current density
is improved from 0.1 to 5 C, and the difference becomes larger
with the increase of current density. When the current density
is 5 C, the specific capacity of the Si@Alg anode drops to 0
mAh g−1, while the Si@Al/Alg-TUEG anode still maintains a
certain charge/discharge capacity (∼250 mAh g−1). Moreover,
when the current density changes from 5 to 0.1 C, the specific
capacity of the Si@Al/Alg-TUEG anode recovers to its initial
level, whereas the Si@Alg anode does not.
The good cycling performance of Si@Al/Alg-TUEG anodes
is due to the good ionic conductivity and the outstanding rapid
self-healing performance at room temperature, which suggests
that the Al/Alg-TUEG binder is able to repair the electrode in
time through the rearrangement of hydrogen bonds and
reconnection of metal coordination bonds, when the electrode
is mechanically damaged during repeated charging and
discharging. Furthermore, side reactions between the electro-
lyte and active substances are inhibited, and the integrity of the
electrode is maintained, which effectively improves the cycling
performance of the electrode.
The morphology of Si@Al/Alg-TUEG and Si@Alg anode
surfaces before and after 100 cycles at 0.5 C was observed by
SEM (Figure 7). As shown in Figure 7a,b, both anodes exhibit
a flat surface before cycling, but the surface of the Si@Al/Alg-
TUEG anode is more smooth. However, after 100 cycles, the
surface morphology of two anodes shows a dramatic difference.
Long and deep cracks are found on the surface of Si@Alg
anodes (Figure 7c,e). Differently, few and shallow cracks are
observed on the surface of Si@Al/Alg-TUEG anodes (Figure
7d,f). Apparently, rapid self-healing capability of Al/Alg-TUEG
endows Si@Al/Alg-TUEG anode with maintaining good
integrity even Si particle experiencing large volume expansion
and contraction. Furthermore, the electrode thickness before
and after cycling is investigated (Figure S7). The thickness of
Si@Al/Alg-TUEG anodes is 7.4 μm before cycling and
increases to 11.4 μm after cycling, with a swelling rate of
54.1%, much lower than 71.1% of the Si@Alg anodes. In
addition, the cross-section of the Si@Al/Alg-TUEG anodes is
smooth, but that of the Si@Alg anodes is rough and uneven. It
further indicates that self-healing inside the electrode is also
excellent.
The differences in composition between Si@Al/Alg-TUEG
and Si@Alg anodes after cycling and the formation of SEI
layers are characterized by XPS (Figure 8). Identical
characteristic peaks in the XPS spectra of C 1s and F 1s are
found for both anodes, including C−C/C−H (C 1s at 284.6
eV), C−O (C 1s at 286.6 eV), C�O (C 1s at 288.6 eV),
Li2CO3 (C 1s at 289.6 eV), LiF (F 1s at 685.0 eV), SiOF (F 1s
at 686.8 eV), and LixPFy (F 1s at 688.2 eV). The sources of
these substances are listed in Table S1.
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ACS Applied Energy Materials
Figure 5. CV curves of (a) Si@Al/Alg-TUEG anodes (0.05 mV s−1), (b) Si@Al/Alg-TUEG anodes (0.1, 0.3, 0.5 mV s−1), and (c) Si@Alg anodes
(0.1, 0.3, 0.5 mV s−1). (d) DLi coefficient in Si@Al/Alg-TUEG and Si@Alg anodes.
Although the composition of the surface for both anodes is
identical, the relative content of different substances can be
calculated from the intensity of these peaks. According to the F
1s pattern, from the lower intensity of the LiF peak and higher
intensity of SiOF and LixPFy peaks for the Si@Alg anode, more
electrolytes in the Si@Alg anode are decomposed during
cycling. In previous studies,61−65 it is revealed that the
formation of SiOF is originated from SiOx on the surface of
the Si anode, and the intensity reflects the thickness of the SEI
layer due to the inner SiOF layer. In the SEI layer, LiF plays a
crucial role in regulating the transport and deposition of Li-
ions homogenously. Accompanied with the observed SEM
images, it confirms that a more stable SEI layer with a smaller
thickness on the Si@Al/Alg-TUEG anode is formed during the
charge/discharge cycle.
To evaluate the potential of the Al/Alg-TUEG binder for
practical applications, Si@Al/Alg-TUEG anodes were paired
with LiFePO4 and NCM811 cathodes to assemble coin cells.
The first-lap specific capacity of the LiFePO4//Si@Al/Alg-
TUEG full cell is 156 mAh g−1 and the ICE is 89.4% at 0.5 C.
After 100 cycles, it still has a specific capacity of 147 mAh g−1
and a capacity retention of 94% (Figure 9a). In addition, the
LiFePO4//Si@Al/Alg-TUEG full cell also shows excellent rate
performance and ICE (90.1%) and is capable of stably cycling
in the 0.1−0.8 C interval (Figure 9b). As shown in Figure 9c,
the NCM811//Si@Al/Alg-TUEG full cell also performs well
at 0.5 C. It has a high ICE (88.5%) and fantastic capacity
retention of 92.5% within 100 cycles. The NCM811//Si@Al/
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Alg-TUEG full cell also has a stable rate capability in the 0.1−2
C ranges (Figure 9d). Consequently, the Al/Alg-TUEG binder
can significantly suppress the volume expansion of SiNPs and
has a great application potential.
■ CONCLUSIONS
In summary, we present a novel binder (Al/Alg-TUEG) with
rapid self-healing ability which can effectively inhibit the
volume expansion of SiNPs for highly cycling-stable and
capacity-maintained LIBs. The chemical and mechanical
characterization exhibits that Al/Alg-TUEG contains hydrogen
bonds and Al−O coordination bonds. The ether oxygen
groups of TUEG reduce the charge transfer resistance between
the electrolyte and SiNPs, allowing for faster Li-ions transport
and higher conductivity in the Si@Al/Alg-TUEG anode.
Therefore, the Si@Al/Alg-TUEG anode exhibits excellent
overall performance. After 300 cycles at 0.5 C, the capacity
retention of Si@Al/Alg-TUEG anodes reaches 77.4%. Due to
the formation of a uniform and stable SEI layer, the first-lap
specific capacity reaches 3204 mAh g−1 and the ICE is 87.2%.
Furthermore, the ICE of the LiFePO4//Si@Al/Alg-TUEG full
cell is 89.4% and the capacity retention reaches 94% within 100
cycles. The NCM811//Si@Al/Alg-TUEG full cell also shows
good performance, with 88.5% of ICE and 92.5% of capacity
retention. Consequently, polymer binders with a rapid self-
healing ability at room temperature consisting of both
hydrogen bonds and metal coordination already exhibit great
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Figure 6. (a) Cycling performance and (b) CE of Si@Al/Alg-TUEG, Si@TUEG and Si@Alg anodes (0.5 C). (c) rate performance of Si@Al/Alg-
TUEG and Si@Alg anodes.

Figure 7. SEM images of the Si anode surface, (a) Si@Alg and (b) Si@Al/Alg-TUEG before cycling, (c, e) Si@Alg, and (d, f) Si@Al/Alg-TUEG
after 100 cycles at 0.5 C.

potential for commercial applications in the Si anode with

enhanced cycling stability in LIBs.
3544 https://doi.org/10.1021/acsaem.3c00161
ACS Appl. Energy Mater. 2023, 6, 3538−3548
ACS Applied Energy Materials www.acsaem.org Article

Figure 8. XPS spectra (C 1s, F 1s) of anodes after 100 cycles: (a, c) Si@Alg, (b, d) Si@Al/Alg-TUEG.

Figure 9. (a, c) Cycling performance and (b, d) rate capability of LiFePO4//Si@Al/Alg-TUEG and NCM811//Si@Al/Alg-TUEG cells,
respectively.

3545 https://doi.org/10.1021/acsaem.3c00161
ACS Appl. Energy Mater. 2023, 6, 3538−3548
ACS Applied Energy Materials
■ EXPERIMENTAL SECTION
Materials. Silicon nanoparticles (SiNPs, diameter: 100 nm) and
carbon black (Super P) were purchased from Kejing Star Technology
Co., LTD (Shenzhen, China); Polythiourea (TUEG) was synthesized
according to previous work.66 Sodium alginate (Alg, Aladdin) and
aluminum trichloride (AlCl3, AR, Aladdin) were purchased.
Preparation of Polymer Binders (Al/Alg-TUEG). The Al/Alg-
TUEG binder was synthesized through two steps. In detail, Alg (0.8
g) and TUEG (0.2 g) were dissolved in deionized water and N-
methylpyrrolidone (NMP), respectively, and then mixed and stirred
at room temperature for 12 h to obtain homogeneous Alg-TUEG
solution; Subsequently, AlCl3 aqueous solution (1 mL, 1 M) was
added to the above solution and stirred continuously for 1 h, forming
transparent and uniform polymer binders (Al/Alg-TUEG).
Preparation of Al/Alg-TUEG Samples for the Self-Healing
Test. The Al/Alg-TUEG solution was poured into a mold and dried
to form a columnar gel of 5 mm in diameter. The Al/Alg-TUEG gels
were stained using water-soluble Bengal red and alkali blue. Then, the
gels were cut in half and the pieces with different colors were brought
into contact with each other for testing the self-healing performance.
The column gel before cutting and after self-healing was used to test
the tensile strength.
Preparation of Si@Al/Alg-TUEG Anodes and LiFePO4/
NCM811 Cathodes. SiNPs (0.8 g) and Super P (0.1 g) were well
ground and then stirred with an Al/Alg-TUEG solution in a mass
ratio of 80:10:10. After stirring uniformly, it was coated to the Cu foil
and dried in a vacuum oven at 90 °C for 24 h. The preparation of
cathodes is similar to the above method, except that SiNPs is replaced
by LiFePO4 or LiNi0.8Co0.1Mn0.1O2 (NCM811), and the binder is
replaced by PVDF.
Characterization. The existence of metal coordination bonds
(Al−O) and the cross-linking bond between Alg and TUEG were
gauged via XPS (ESCALAB 250Xi), 1H NMR, and FT-IR (Nicolet
7800 Infrared Spectrometer). SEM (Gemini SEM 500) was adopted
to analyze the microstructures and surface morphologies of the as-
prepared anodes before and after cycling. The MCR 501 rheometer
(Austria TA instrument) results were adopted to record the
rheological performances of Al/Alg-TUEG and Alg hydrogels, and
the tensile testing machine (Jinnan Hengpin Co. Ltd. HD-WDW,
China) with a 180° peeling mode was also used to measure the
peeling properties of Si@Al/Alg-TUEG and Si@Alg anodes. The
swelling rate test was conducted in the electrolyte of 1.0 M LiPF6 in
ethylene carbonate (EC), ethyl methyl carbonate (EMC), and
diethylene carbonate (DEC) (1:1:1 by volume).
Electrochemical Measurements. All electrochemical measure-
ments were performed using a CR2025-type coin, which were
fabricated by sandwiching polypropylene microporous diaphragm
(Celgard 2400) separators between the as-composed working anode
and lithium metal counter anode in an Ar-filled glovebox (oxygen
content <0.01 ppm, water content <0.01 ppm). The prepared anodes
and cathodes were cut into 12 mm diameter pieces and the electrolyte
was 1.0 M LiPF6 in a mixture of EMC, DEC, and EC (1:1:1 by
volume), with another 5 wt % FEC as additives. The GCD behavior
and rate performance were tested on a Land battery tester of
CT2001A (Wuhan LAND Electric Co., Ltd.) in a potential range
0.01−1.20 V at distinct current density (1 C = 4200 mAh g−1). The
prelithiated Si@Al/Alg-TUEG anodes were paired with LiFePO4 or
NCM811 cathodes to assemble full cells. The LiFePO4/Si@Al/Alg-
TUEG full cell was tested in the voltage range of 2.5−3.9 V. The
NCM811/Si@Al/Alg-TUEG full cell was tested in the voltage range
of 2.5−4.3 V.
■ ASSOCIATED CONTENT
* Supporting Information
sı
The Supporting Information is available free of charge at
https://pubs.acs.org/doi/10.1021/acsaem.3c00161.
1 Recent Progress on Silicon-Based Anode Materials for Practical
H NMR profile of Al/Alg-TUEG; SEM images and
EDAX element mapping of anodes; photograph of
3546
www.acsaem.org Article
anodes after the 180° peeling test; swelling ratio of the
binder; discharge−charge curves of anodes; Nyquist
plots of anodes; SEM images of anodes; and sources of
substances in XPS spectra (PDF)
■ AUTHOR INFORMATION
Corresponding Authors
Xiao Xia Wang − School of Mechanical and Power
Engineering, East China University of Science and
Technology, Shanghai 200237, China;
Email: wangxiaoxia@ecust.edu.cn; Fax: +86-21-64252874
Jun Xu − School of Chemical Engineering, East China
University of Science and Technology, Shanghai 200237,
China; orcid.org/0000-0002-0717-6194;
Email: xujun@ecust.edu.cn; Fax: +86-21-64252874
Authors
Fei Wang − School of Chemical Engineering, East China
University of Science and Technology, Shanghai 200237,
China; orcid.org/0000-0003-3402-1064
Xiang Ma − School of Chemical Engineering, East China
University of Science and Technology, Shanghai 200237,
China; orcid.org/0000-0002-6042-7845
Yiren Li − China Petroleum Pipeline Engineering Co., Ltd.
International, Langfang 065000, China
Hongmei Liu − School of Chemical Engineering, East China
University of Science and Technology, Shanghai 200237,
China; orcid.org/0000-0001-8383-3021
Qingping Wu − Chongqing Institute of Green and Intelligent
Technology, Chinese Academy of Sciences, Chongqing
400714, China
Xiang Guan − Department of Materials, University of
Manchester, Manchester M13 9PL, U.K.
Hui Liu − China Academy of Aerospace Science and
Innovation, Beijing 100176, China
Complete contact information is available at:
https://pubs.acs.org/10.1021/acsaem.3c00161
Notes
The authors declare no competing financial interest.
■ ACKNOWLEDGMENTS
Financial support by the Natural Foundation of China
(Funding number 52174023) and the China Petroleum
Engineering Corp., Ltd. (CPEC) (2021ZYGC-01-01) is
gratefully acknowledged.
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