Research Article
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Single-Walled Carbon Nanotube Film as an Efficient
Conductive Network for Si-Based Anodes
Ziying He, Zhexi Xiao, Hongjie Yue, Yaxin Jiang, Mingyu Zhao, Yukang Zhu, Chunhui Yu,
Zhenxing Zhu, Feng Lu, Hairong Jiang, Chenxi Zhang,* and Fei Wei*
Silicon-based anodes are considered ideal candidate materials for next-
generation lithium-ion batteries due to their high capacity. However, the low
conductivity and large volume variations during cycling inevitably result in
inferior cyclic stability. Herein, a dry method without binders is designed to
fabricate Si-based electrodes with single-walled carbon nanotubes (SWCNTs)
network and to explore the different mechanisms between SWCNT and mul-
tiwalled carbon nanotubes (MWCNTs) as a conductive network. As expected,
higher initial discharge capacity (1785 mAh g−1), higher initial Coulombic
efficiency (ICE, 81.52%) and outstanding cyclic stability are obtained from the
SiOx@C|SWCNT anodes. Furthermore, its lithium-ion diffusion coefficient
(DLi+) is 3–4 orders of magnitude higher than that of SiOx@C|MWCNT. The
underlying mechanism is clarified by in situ Raman spectroscopy and theo-
retical analysis. It is found that the SWCNTs can maintain good contact with
SiOx@C even under tensile stresses up to 6.2 GPa, while the MWCNTs lose
electrical contact due to alternating compressive stress up to 8.9 GPa and
tensile stress up to 2.5 GPa during long-term cycling. Under such very large
stresses, the more flexible SWCNTs and their stronger van der Waals forces
ensure that SiOx@C still has good contact with SWCNTs.
1. Introduction
Batteries are playing an integral role in the vital energy transi-
tion from fossil fuels to sustainable energies because intermit-
tent renewable energy can be efficiently stored and released as
needed with batteries.[1–4] Currently, rechargeable lithium-ion
batteries (LIBs) are the leading technology in the information
industry, which includes consumer electronics, environmen-
tally friendly power grids, aerospace applications, and electric
vehicles.[2,4–6]
Si has attracted attention in terms of the development of
high energy density LIBs due to its high theoretical capacity
Z. He, Z. Xiao, H. Yue, Y. Jiang, M. Zhao, Y. Zhu, C. Yu, Z. Zhu, F. Lu,
H. Jiang, C. Zhang, F. Wei
Beijing Key Laboratory of Green Chemical Reaction Engineering and
Technology
Department of Chemical Engineering
Tsinghua University
Beijing 100084, China
E-mail: cxzhang@mail.tsinghua.edu.cn; wf-dce@tsinghua.edu.cn
The ORCID identification number(s) for the author(s) of this article
can be found under https://doi.org/10.1002/adfm.202300094.
DOI: 10.1002/adfm.202300094
Adv. Funct. Mater. 2023, 33, 2300094 2300094 (1 of 9)
(≈4200 mAh g−1).[7–11] However, com-
mercial progress has been hindered by
the large volume expansion (≈400%) of
Si, which results in the destruction of
active materials and delamination from
the current collector, as well as unex-
pected solid electrolyte interphase (SEI)
growth.[7,12] SiOx (0 ≤ x ≤ 2) materials
exhibit a better trade-off in theoretical
capacity (≈2400 mAh g−1) and smaller
volumetric change (≈200%), making them
more promising candidates for practical
LIBs.[13] Nevertheless, the poor conduc-
tivity and volumetric expansion of SiOx
anodes result in capacity fading.[12,14] A
study found that single-walled carbon
nanotubes (SWCNTs) can greatly improve
the cyclic performance of SiOx/C, while
the improvement with multiwalled carbon
nanotubes (MWCNTs) is limited.[15] In
terms of carbon nanotube (CNT) proper-
ties, 2/3 of short SWCNTs are semicon-
ductor tubes, while most MWCNTs are
metallic; the conductivity of the latter is
5 times higher than that of the former.[16] Moreover, SWCNTs
are thin and long, and their perfect structure results in strong
van der Waals forces between tubes, and making them difficult
to disperse.[16,17] SWCNTs seem to offer no advantages in terms
of conductivity or dispersion, but their practical performance in
terms of stable cyclability is excellent, which implies that other
factors may play a role.
The poor cycling performance of SiOx is a result of the
volume expansion, which leads to separation from the con-
ductive network, and the formation of the SEI, which leads to
the loss of electrical contact with the conductive network.[18–23]
Thus, the flexibility of conductive CNT additives and their
strong interaction with SiOx are key to ensuring that no elec-
trical separation occurs. The flexibility is proportional to the 5th
power of the length-to-diameter ratio (l/d) when the length (l)
is fixed (Equations S1–S3, Supporting Information).[24–26] Thin
and long SWCNTs have a high length-to-diameter ratio, and
their flexibility and contact with SiOx/C is significantly better
than those of MWCNTs. Additionally, the van der Waals interac-
tions between nanosized CNTs and SiOx/C cannot be ignored,
and the different degrees of contact caused by flexibility directly
affect the van der Waals force (Equations S4 and S5, Supporting
Information). The van der Waals force is inversely proportional
to distance to the 7th power.[17] Thin SWCNTs with perfect
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structures and small diameters are expected to exhibit van der
Waals forces that are several orders of magnitude stronger than
those of MWCNTs.
The conductive network used in a silicon-based anode is
the key factor determining the stability and lifespan of a bat-
tery. Most previous work[27–31] is devoted to adjusting the mor-
phology and structure of silicon-based materials to improve
the performance of LIBs. These studies often focus on the
electrode behavior when the battery fails and lack real-time
quasi-deterministic and quantitative analyses of CNTs under
operando conditions. SiOx undergoes a volume change during
lithiation and delithiation. Our previous work[32–34] also found
that the occurrence of side reactions with the electrolyte results
in a thick SEI. These changes squeeze the CNTs and produce
significant stress changes, which may lead to the loss of elec-
trical contact between SiOx and the conductive network. The
Raman G-band shift is sensitive to the stress, exhibiting a linear
response; thus, Raman spectroscopy has become an effective
means for measuring and analyzing the stress on CNTs.[35–37] In
principle, by measuring the response of CNTs to Raman lasers
during lithiation and delithiation, the mechanism of the above
phenomena from a microscopic perspective can be revealed.
In addition, the insulating and inactive binders and residual
solvents inevitably hinder efficient electron/ion transport,
thereby decreasing the electrochemical performance of the elec-
trodes.[38,39] Thus, it is of great significance and urgent neces-
sity to develop binder-free and solvent-free Si-based electrode
with SWCNT network through dry method, no one has ever
reported the successful preparation of Si-based electrode just by
dry method without any solvent and binder before.
In this work, we fabricated a binder-free electrode by dry
methods utilizing the strong van der Waals force between
SWCNTs and SiOx@C. Benefiting from the unique struc-
ture and continuous ion/electron transport pathways, the
SiOx@C|SWCNT anode exhibits high initial Coulombic effi-
ciency, stable cyclic, and high-rate performances. Due to our
unique design, a facile strategy is proposed to measure the
change of stress and contact state in Si-anode. In situ Raman
spectroscopy was used to analyze the strain in CNTs during lith-
iation and delithiation to explain the underlying mechanisms
of the remarkable improvement in the cycling performance of
SiOx/C with SWCNTs. This work provides a new strategy to
characterize the electrical contact and a new concept to under-
stand why SWCNT distinguished from other conductive agents,
which is the most in-depth understanding in this field so far.
2. Results and Discussion
2.1. Fabrication and Characterization of the SiOx@C|SWCNT
Anode
We assembled an SWCNT network during the growth pro-
cess by applying an electric field (Figure 1a,b). The distribu-
tion of the diameters of the SWCNTs is shown in Figure S1
(Supporting Information). Approximately 60% of the SWCNT
diameters are within 1.2–1.8 nm. Figure 1c shows a SWCNT
with a 1.6 nm diameter (measured from the transmission elec-
tron microscopy (TEM) image), which is consistent with the
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diameter inferred from the radial breathing mode (RBM) in the
Raman spectrum (inset figure). The SWCNTs can be hundreds
of micrometres in length (Figure 1d), which results in a high
length-to-diameter ratio, so the SWCNT network has good flex-
ibility (Figure S2a, Supporting Information). A water drop is
placed on the film, which bends downward under the influence
of gravity, showing great flexibility (Figure 1e), and can be in
close contact with electroactive materials, such as SiOx@C. The
SiOx@C and SWCNT networks (Figure 1g) are combined with
direct contact (Figure 1f) without a binder or other solvents.
As shown in an image of the cross section of the integrated
SiOx@C|SWCNT electrode (Figure 1h), the upper SiOx@C par-
ticle (Figure 1f), the middle SWCNT network (Figure 1g), and
the bottom graphite paper (Figure S2b, Supporting Informa-
tion) layers are tightly packed, further indicating good contact
between these carbon materials.
2.2. Electrochemical Performance
Electrochemical performance tests were carried out to prove that
SWCNTs have a significant effect on electrode performance. As
a control sample, an SiOx@C electrode with a MWCNT con-
ductive additive (LB216-43) was fabricated by the traditional wet
coating method; this sample was named SiOx@C|MWCNT.
The above electrodes, SiOx@C|SWCNT and SiOx@C|MWCNT,
were assembled into half cells and tested under identical
conditions.
The cyclic voltammetry (CV) curves (0.1 mV s−1) showed
that the current rise of SiOx@C|SWCNT is significantly higher
than that of SiOx@C|MWCNT, indicating that using SWCNT
networks and a binder-free design result in better electrode
activation kinetics (Figure 2a). SiOx@C|MWCNT delivers a rela-
tively low initial discharge capacity (1514 mAh g−1) and initial
Coulombic efficiency (ICE) (72.35%), and such distinct decay
is attributed to the volume expansion and conductivity insuf-
ficiency. Surprisingly, the initial discharge capacity and ICE of
the SiOx@C|SWCNT electrode are 1785 mAh g−1 and 81.52%,
respectively (Figure 2b,c), confirming that the SWCNT network
and binder-free design can effectively increase the reversible
capacity of the electrode, possibly due to the improvement in
electronic contact. In the long-term cycling test at a current
density of 1 A g−1, the stability of SiOx@C|SWCNT is signifi-
cantly better than that of SiOx@C|MWCNT. After 200 cycles,
the capacity of the SiOx@C|SWCNT anode (915.89 mAh g−1)
is 3 times higher than that of the SiOx@C|MWCNT anode
(291.5 mAh g−1) (Figure 2d). Then, after 500 cycles, the
capacity of the SiOx@C|SWCNT anode (658.75 mAh g−1) is 3.5
times higher than that of the control sample (181.78 mAh g−1)
(Figure S10, Supporting Information). Long-term cycling per-
formance of the SiOx@C|SWCNT electrodes in areal capacity
is shown in Figure S15 (Supporting Information). In the
rate-capability test of current densities from 0.2 to 5.0 A g−1,
SiOx@C|SWCNT shows excellent high current resistance and
presents higher specific capacities than SiOx@C|MWCNT. In
detail, SiOx@C|MWCNT is almost incapable of contributing
any capacity at 5 A g−1, while the SiOx@C|SWCNT anode
can still offer a specific capacity of nearly 311 mAh g−1. When
recovering to a low current density of 0.2 A g−1, the capacity
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Figure 1. The fabrication and characterization of the SiOx@C|SWCNT anode. a) Schematic of the fabrication process. b) SWCNT network oriented
by the electric field. c) TEM image showing the diameter of an SWCNT. Inset, Raman spectrum, with RBM at 154 cm−1. d) SEM image of the SWCNT
film, in which the SWCNTs can be hundreds of micrometres in length. e) Optical image of the flexible SWCNT film with a water drop on it. f) SEM
image of the SiOx@C|SWCNT electrode in pseudo-colors (SiOx@C is in purple, SWCNT network is in blue). g) SEM image of the SWCNT network in
pseudo-color (blue). h) Cross sectional image of the SiOx@C|SWCNT electrode in pseudo-colors (SiOx@C is in purple, SWCNT network is in blue,
graphite paper is in grey).

of SiOx@C|SWCNT (1250 mAh g−1) is nearly 3 times that of
SiOx@C |MWCNT (Figure 2e).
Furthermore, the electrochemical impedance spectroscopy
(EIS) was employed to determine the diffusion coefficient of
Li+ (DLi+)after 3 (Figure 2f) and 500 cycles (Figure 2i). The corre-
sponding equivalent circuit model[40–42] is shown in Figure S14
(Supporting Information) and as inset figure in Figure 2f,h,i,k.
The equivalent circuit model includes the resistance for ohmic
contact (Re), surface film capacitance (CPE1), charge-transfer
resistance at the electrode and electrolyte interface (Rct), and
the Warburg impedance (Zw) that is related to the diffusion of
lithium-ions in solid electrode materials. After 3 cycles, the Rct
values of SiOx@C|SWCNT and SiOx@C|MWCNT are 17.85 and
80.69 Ω, respectively (Figure 2f). The DLi+ increases by approxi-
mately four orders of magnitude, from 3.83 × 10−17 cm2 s−1 to
72000 × 10−17 cm2 s−1, benefiting from the addition of the SWCNT
network and binder-free design (Figure 2g). After 500 cycles,
the Rct values of SiOx@C|SWCNT and SiOx@C|MWCNT
are 28.11 and 67.82 Ω, respectively (Figure 2i). DLi+ increases
from 7.34 × 10−15 cm2 s−1 to 1840 × 10−15 cm2 s−1 due to the
incorporation of the SWCNT network and binder-free design,
which is consistent with the excellent rate performance of the
SiOx@C|SWCNT anode (Figure 2e). Compared with the initial
cycling value, the long-term cycling DLi+ of the two anodes is
increased, which is due to the generation of an SEI (Figure 2j).
The Re value is the ohmic resistance of the cell, which can
express the contact state between the collector and the elec-
trode material and that between the electrode material and the
conductive network to a certain extent. In this work, it can be
used as a reference for measuring electrical contact. Compared
to that at 3 cycles, the Re value at 500 cycles is higher owing
to electrode polarization, nonconductive SEI growth, and elec-
trical separation of active materials and conductive networks.
In general, for the same cycle number, the Re value of SiOx@
C|SWCNT is lower than that of SiOx@C|MWCNT (Figure 2h,k).
2.3. In Situ Raman Spectroscopy Revealing the Stress During
Cycling
Next, we attempted to uncover the mechanism behind the
aforementioned improvement in electrochemical performance.

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Figure 2. Electrochemical performance. a) CV curves of SiOx@C|SWCNT and SiOx@C|MWCNT anodes at a scanning rate of 0.1 mV s−1. b) Charge/
discharge specific capacity-voltage profiles of SiOx@C|SWCNT and SiOx@C|MWCNT anodes at a current density of 0.2 A g−1 for the 1st cycle. c) The
initial capacity and ICE of SiOx@C|SWCNT and SiOx@C|MWCNT anodes. d) Long-term cycling performance of SiOx@C|SWCNT and SiOx@C|MWCNT
anodes, for 200 cycles. e) Rate performance of SiOx@C|SWCNT and SiOx@C|MWCNT anodes with discharge rates increasing from 0.2 to 5.0 A g−1.
f) Nyquist plots after 3 cycles and the equivalent circuit model inset. g) Apparent diffusion coefficients after 3 cycles. h) Fitting resistance results of
EIS spectra after 3 cycles and the equivalent circuit model inset. i) Nyquist plots after 500 cycles and the equivalent circuit model inset. j) Apparent
diffusion coefficients after 500 cycles. k) Fitting resistance results of EIS spectra after 500 cycles and the equivalent circuit model inset.

During lithiation and delithiation, SiOx@C suffers from a large
volume change, which squeezes the CNTs and significantly
changes their stress. The shifts in the G peak in the Raman
spectrum can accurately reflect the stress in CNTs. As shown
in previous work,[35,37,43,44] an 8 cm−1 G band shift (ΔG) approxi-
mately corresponds to 1% strain in a single CNT. Theoretically,
the Young’s modulus of the CNT is ≈1.1 TPa. The downshift
in the G-band frequency (ωG± ) corresponds to the generation
of strain, representing the elongation in the CC bond. The
upshift in the G-band frequency (ωG± ) corresponds to the relaxa-
tion of the residual strain, representing the shortening of the
CC bond. Therefore, based on the above CNT stress probe,
we performed in situ Raman experiments to detect the stress
change of the CNTs in the anode during charging and dis-
charging (Figure 3a).
We exclude the interference of voltage on the Raman G-band
of CNTs in this system (Figure S11, Supporting Information).
According to the shift in the G-band, we can obtain the change in
the strain in CNTs and then speculate about the volume expan-
sion of SiOx@C and its contact with CNTs. The results show that
the G-bands of the SWCNTs and MWCNTs both shift with the
progression of charging and discharging (voltage range from
1.5 V vs Li/Li+ to 0.01 V vs Li/Li+), which indicates that both expe-
rience stress (Figure 3b; Figure S12, Supporting Information).

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Figure 3. The stress in SWCNTs and MWCNTs during cycling under in situ Raman spectroscopy. a) Schematic illustration of stress monitoring in
the SiOx@C|SWCNT anode. b) The G-band positions in the in situ Raman spectra for SiOx@C|SWCNT during the initial cycling. c) The G-band shifts
and corresponding stress for the SWCNTs in the SiOx@C|SWCNT anode during the initial cycling. d) The G-band shifts and corresponding stress
for the MWCNTs in the SiOx@C|MWCNT anode during the initial cycling. e) The G-band shifts and corresponding stress for the SWCNTs in the
SiOx@C|SWCNT anode during long-term cycling. f) The G-band shifts and corresponding stress for the MWCNTs in the SiOx@C|MWCNT anode
during long-term cycling.

We sort the G-band shifts (compared with that under no
cycling) and the corresponding stress under different voltages.
The SWCNTs and MWCNTs continuously exhibit tensile stress
during the initial cycling (Figure 3c,d). We correlate the dif-
ferential capacity curve (dQ/dV curve) with the formed stress
and find that there is a close relationship between them. In the
dQ/dV curve, the peak value represents phase transformation,
which finally leads to expansion and shrinkage of SiOx. The left
panel shows the cathode peak, and the right panel shows the
anode peak. Among them, the cathode peak at ≈0.2 V is caused
by irreversible reactions to form Li2O and various lithium sili-
cates (such as Li4SiO4), and the peak at ≈0.05 V is assigned to
the reversible reactions forming LixSi (Li–Si alloy). During the
first lithiation of SiOx@C, the electrode is a mixed phase that
consists of Li2O, various lithium silicates and LixSi. The anode
peaks of ≈0.3 and 0.5 V are formed by the delithiation of LixSi.
With the expansion of SiOx@C, its electrical contact with the
conductive network and the collector worsens. As a result, some
LixSi species become inactive due to reversibility deterioration.
Therefore, any delithiation peak at 0.3 or 0.5 V may disappear,
and only one peak remains.
During the initial cycling of SiOx@C|SWCNT (Figure 3c),
the stress decreases intermittently at the beginning of lithia-
tion, but the SWCNT network retains tensile stress with a min-
imum value of 1.3 GPa. It is indicated that SiOx@C is still in
contact with the SWCNT network regardless of some slippage
that occurs between them. Irreversible and reversible reactions
(formation of Li–Si alloy) occur when the potential is lower than
0.2 V, and the capacity rises sharply and the volume increases,
but good electrical contact is maintained. With the progress of
delithiation, the stress on the CNTs increases rapidly, and the
maximum stress is 6.2 GPa. When the potential reaches ≈0.5 V,
the reversible reaction of Li–Si ends, the volume recovers to a
certain extent, and the stress decreases approximately linearly,

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which indicates that there is stable and good contact between
SiOx@C and the SWCNTs.
During the initial cycling of SiOx@C|MWCNT (Figure 3d),
compressive stress occurs at the beginning of lithiation, with
the maximum value of 1.1 GPa, indicating that SiOx@C exhibits
severe slippage with respect to the MWCNTs. When the poten-
tial reaches ≈0.2 V, the progress of lithiation leads to an increase
in capacity. Simultaneously, an irreversible reaction and revers-
ible reaction occur (forming Li–Si alloy), the volume increases,
the compressive stress changes to tensile stress, and the state
changes from slipping to contact. MWCNTs are stiffer than
SWCNTs. In the process of delithiation, there is tensile stress
with a maximum value of 2.7 GPa and compressive stress with
a maximum value of 2.0 GPa. The repeat switching between the
tensile stress and compressive stress indicates that the contact
between SiOx@C and MWCNTs is insufficient due to switching
between slipping and contact. It is easy to find that the diffu-
sion of Li+ and the conductance of MWCNTs decrease signifi-
cantly with increasing cycle numbers.
SiOx@C|SWCNT also shows stress during long-term cycling
(Figure 3e). There is a slight tensile stress during the lithiation
of SiOx@C. When the potential is lower than 0.2 V, an irrevers-
ible reaction and reversible reaction (forming Li–Si alloy) occur,
the volume expands, and the stress rises to the maximum value
of 0.6 GPa. In the process of delamination, lithium ions are
removed from SiOx, the volume recovers to a certain extent,
and the stress decreases approximately linearly, which indicates
that there is stable and good contact between SiOx@C and the
SWCNT network.
The compressive stress of the SiOx@C|MWCNT electrode
increases to 8.9 GPa during long-term cycling (Figure 3f), indi-
cating that the stiffness of MWCNTs is much higher than that
of SWCNTs and that serious slippage occurs between SiOx@C
and MWCNTs. When the potential is lower than 0.2 V, the
lithiation of SiOx leads to the formation of a Li–Si alloy and its
volume expansion. The compressive stress gradually changes
into tensile stress, and the state changes from slippage to con-
tact. During delithiation, there is a maximum tensile stress
of 2.5 GPa between MWCNTs and SiOx@C, and the stress
decreases linearly with the progress of delithiation. This indi-
cates that unlike the SWCNTs, with flexible contact and strong
van der Waals forces, the stress in the stiffer MWCNTs does
not decrease by orders of magnitude. In contrast, the stress of
MWCNTs increases rapidly, causing repeated slippage and poor
electrical contact during cycling, which is consistent with the
disappearance of the delithiation peak at 0.3 V in the dQ/dV
curve.
We correlate the above results with the electrochemical per-
formance in Figure 2 and analyze the following parameters: Rct
after the initial/long-term cycling (largely dependent on the dif-
ficulty of electron gain and loss in the electrode material itself,
which can reflect the carrier concentration and the thickness
of the SEI), Re (dependent on the contact between the collector
and the electrode material and the electrode material and the
conductive network and the polarization state of the electrode)
and DLi+ (the rate of lithium-ion diffusion from the bulk phase
into the electrolyte). The DLi+ values of the two anodes are tens
of thousands of times different after initial cycling (Figure 2g);
the difference decreases but is still hundreds of times after
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long-term cycling (Figure 2j). We think that the difference in
DLi+ results from different degrees of electrical contact. The dif-
ference in electrical contact is mainly caused by the following
two factors. First, the separation between the anode material
and conductive network due to the very large stress during
lithiation and delithiation and the deterioration of the electrical
contact decreases the electronic conductivity. Such analysis
coincides with the relative difference in Re for the same cycle
number and the increase in Re after long-term cycling. Second,
the dissolution of silicon leads to a thick SEI. Such analysis is
consistent with the difference between the Rct values of these
two anodes after initial cycling and the increase in Rct after
long-term cycling. Moreover, a thick SEI accelerates the elec-
trical separation between the conductive network and the anode
material under very large stress. Therefore, the great difference
in the performance of SiOx@C|SWCNT and SiOx@C|MWCNT
is due to the difference in the electric contact caused by the very
large stress during the charging and discharging process.
The above results can explain why SWCNTs have better elec-
trical contact with SiOx@C. Although the maximum stress of
the SWCNTs is reduced to 0.6 GPa after long-term cycling, the
tensile stress is maintained under different voltages. These
results suggest that even if a large volume expansion occurs,
SiOx@C and SWCNTs can still maintain good electrical contact.
Based on the above investigations, we next theoretically explain
why SWCNTs are so important to the cycling performance of
SiOx@C.
2.4. Different Behaviors of SWCNTs and MWCNTs in Si-Based
Anodes
As the flexibility is proportional to the length-to-diameter ratio
to the 5th power (Equations S1–S3, Supporting Information)
and SWCNTs are longer and thinner than MWCNTs, showing
a high length-to-diameter ratio, SWCNTs have better flexibility,
better contact with the Si-based material, and stronger van der
Waals interaction forces (Figure 4a). In the process of charging
and discharging, the in situ Raman results show that SWCNTs
and SiOx@C still maintain good contact even though the gener-
ated stress is as high as 6.2 GPa (Figure 4b). An SEI is gener-
ated on the SiOx@C and the conductive network after cycling
(Figure 4c), while good electrical contact is still maintained
between SiOx@C and the SWCNT network due to strong
van der Waals forces. Therefore, the SiOx@C|SWCNT anode
exhibits stable cycling performance, high ICE and excellent rate
performance. More importantly, such a difference in mecha-
nism leads to different electric contact, resulting in the DLi+
of the two anodes being tens of thousands of times different
during initial cycling and hundreds of times different after
long-term cycling, which results in remarkable improvements
in the cyclic stability and fast charging performance.
In contrast, the MWCNTs in the traditional wet electrode
have a wider diameter and are less flexible than SWCNTs; thus,
their electrical contact with SiOx@C and the corresponding
electrochemical performance are not as good as those of our
design (Figure 4d). In addition, the binder has difficulty with-
standing the tensile and compressive stress combination,
which is as high as 8.9 GPa during charging and discharging,
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Figure 4. Different behaviors of SWCNTs and MWCNTs in Si-based anodes. a) Schematic illustration of the contact mode between SiOx@C and
SWCNTs. b) Morphology of the SWCNT conductive network with volume expansion. c) Schematic illustration of the contact mode between SiOx@C
and SWCNTs when the SEI is generated. d) Schematic illustration of the contact mode between SiOx@C and MWCNTs. e) Morphology of the MWCNT
conductive network with volume expansion. f) Schematic illustration of the contact mode between SiOx@C and MWCNTs when the SEI is generated.

resulting in electrical separation between the conductive net- 4. Experimental Section

work and SiOx@C, even though the conductive network is still
intact (Figure 4e). After long-term cycling, a large amount of
SiOx@C breaks away from the conductive network, accelerating
the failure and degeneration of the battery and the electrochem-
ical performance (Figure 4f).
3. Conclusion
In this work, a facile dry method is designed to explore why
SWCNTs are important to the cyclic performance of SiOx/C.
Due to excellent conductivity, high length-to-diameter ratio
and excellent flexibility, SWCNTs have good electrical con-
tact with silicon-based materials. Benefiting from the unique
structure and continuous ion/electron transport pathways, the
SiOx@C|SWCNT anode exhibits high initial Coulombic effi-
ciency, stable cyclic and high-rate performances, which are dif-
ficult to achieve using conventional LIB electrode technologies.
Moreover, the study proposes a new approach to character-
izing electrical contacts and understanding the relationships
between contact and performance using Raman spectroscopy,
which is sensitive to the strain on CNT. There is a close cor-
respondence between the stress change and the differential
capacity (dQ/dV curves) during cycling, which is the key evi-
dence to correlate the stress and contact. The very large stress
on the MWCNTs readily leads to the separation of the conduc-
tive network and SiOx@C, resulting in rapid capacity decay.
The soft and slender SWCNTs, providing strong van der Waals
forces and good electrical contact, are the key to significantly
improving the cycling and rate performance of SiOx/C, offering
an efficient strategy for research on conductive additives and
electrode design.
Fabrication of the SiOx@C: The commercial SiOx powder (Flotu,
≈3 µm) was added to a glucose solution with a 60% solid content and
vigorously stirred for 1 h. Then, the suspension solution underwent a
spraying drying process to obtain secondary particles, which were
introduced into a Φ50 fluidized bed reactor. When the temperature
reached 800 °C under an Ar atmosphere, the carbon source (CH4) was
introduced at a ratio of 1:2 (CH4:Ar), in a total flux of 500h−1. Then, the
system temperature was held for 45 min until the CVD carbon coating
reaction was completed. After the system was cooled naturally to room
temperature, the solid product was collected.
Fabrication of the Electrodes: Carbon nanotubes were grown using
a floating-catalyst CVD technique with methane (CH4) as the carbon
source, and catalyst particles were produced by decomposition of
ferrocene vapor (FeCp2, 99%). The carbon nanotube network was
collected by the graphite paper (Tanyuan Technology Co., Ltd.) at room
temperature. Then, put a thin layer of active materials (SiOx@C) on it.
Finally, press the integration under the roller press at 10–20 MPa.
Material Characterization: Surface morphology of the electrodes was
observed under the field emission scanning electron microscopy (FE-
SEM, JSM 7401, JEOL Co. Ltd., Japan) at an operating voltage of 1.5 kV.
3D X-ray microscope is a nondestructive X-ray microscopy technique
that collects 2D radiographs of the sample as it rotates and then
reconstructs those into a 3D representation of the sample and its internal
structure. A small triangle was cut from the electrode and characterized
with a micro-CT instrument (Xradia Versa 620, Carl Zeiss Inc.), with
a 50 kV tube voltage and 40× optical magnification. 1801 projections
were captured with 1 s exposure time per projection. The radiographs
were reconstructed in a 3D volume using a filtered back-projection
algorithm (FDK46) implemented in the commercially available Zeiss
XMReconstructor (Carl Zeiss Inc.).
In situ Raman spectroscopy during galvanostatic cycling was
performed in a Raman Flow Cell 031–2H (Figure S13, Supporting
Information) to characterize the electrodes during cycling in 1 m LiPF6
with EC, DEC, and DMC (volume ratio = 2:1:2) with 10 wt.% FEC as
the electrolyte. The cell was assembled in an argon filled glovebox
(H2O and O2 content < 1 ppm) as described in previous studies. The

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confocal Raman microscope (HR Evolution) with a 532 nm wavelength
laser focused through a microscope (Olympus), via 50× long work
distance objective (Olympus). Filters were used to reduce the laser
power applied on the electrode surface to less 1% (ca. 0.3 mW) for in
situ characterization. A baseline correction was applied to all the spectra
for clarity, unless otherwise stated. Electrochemical measurements were
performed using a CHI 760E electrochemical workstation. An original
Raman spectrum was collected before cycling. After power on, collect
the spectrum every 0.1 V.
Electrochemical Measurements: The electrochemical measurements
were performed using CR2032-type coin cells assembled in an Ar-filled
glovebox (with O2 < 0.1 ppm and H2O < 0.1 ppm). For the assembly of
half-cells, several components were employed: Celgard 2500 film as the
separator, lithium foil as the counter electrode, and 1 m LiPF6 as solute
in a cosolvent of EC, DEC, and DMC (volume ratio = 2:1:2) with 10 wt.%
FEC as the electrolyte. The SiOx@C|SWCNT electrodes were already
fabricated by dry methods. The SiOx@C|MWCNT electrodes were
prepared by mixing 85% SiOx@C, 5% MWCNT conductive additives
(Cnano Technology), and 10% binder (carboxymethyl cellulose, CMC
and water-based binder, LA136D) into a uniform slurry, coating the
slurry onto Cu foil, and drying it at 80 °C for 12 h. Then, the wet film
was transformed into a dry film through a drying process in a vacuum
oven at 60 °C for 12 h to remove the residual oxygen and water. The
average mass loading of the electrodes was ≈1.7 mg cm−2. The cycling
performance was tested by a LANHE multichannel battery test system
(LAND-CT2001A) at room temperature. The galvanostatic voltage range
was 0.01–1.5 V for Li/Li+. Cyclic voltammetry (CV) measurements were
performed on a BioLogic Science Instruments VSP-300 potentiostat
system. The specific capacity was calculated based on the total mass of
the electrode. EIS measurements were performed on a BioLogic Science
Instruments VSP-300 electrochemical workstation in the frequency range
from 1 MHz to 0.01 Hz.
Supporting Information
Supporting Information is available from the Wiley Online Library or
from the author.
Acknowledgements
This work was supported by the National Natural Science Foundation of
China (Nos. 22278238, 22238004). The authors thank Dr Yan-Liang Wen
for helpful discussions.
Conflict of Interest
The authors declare no conflict of interest.
Data Availability Statement
The data that support the findings of this study are available from the
corresponding author upon reasonable request.
Keywords
carbon nanotubes, lithium-ion batteries, silicon anodes
Received: January 4, 2023
Revised: February 25, 2023
Published online: March 16, 2023
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