Research Article

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Carbon Nanotube-Reinforced Dual Carbon Stress-Buffering

for Highly Stable Silicon Anode Material in Lithium-Ion Battery
Xiaoming Fan,* Ting Cai, Shuying Wang, Zeheng Yang, and Weixin Zhang*

due to its large volume expansion during

Silicon (Si) anode suffers from huge volume expansion which causes poor lithiation (≈280% in Li15Si4 phase). Such
structural stability in terms of electrode material, solid electrolyte inter- a huge volume change causes a lot of
face, and electrode, limiting its practical application in high-energy-density issues including particle pulverization,
lithium-ion batteries. Rationally designing architectures to optimize the stress unstable solid electrolyte interface (SEI),
and electrical contact loss, resulting in
distribution of Si/carbon (Si/C) composites has been proven to be effective in sharp capacity fade and unsatisfied cycle
enhancing their structural stability and cycling stability, but this remains a big life.[6–8] Moreover, the semiconductor char-
challenge. Here, metal-organic frameworks (ZIF-67)-derived carbon nanotube- acteristics of Si further limit its commer-
reinforced carbon framework is employed as an outer protective layer to cial application due to the low electrical
encapsulate the inner carbon-coated Si nanoparticles (Si@C@CNTs), which conductivity.
To solve the problems mentioned above,
features dual carbon stress-buffering to enhance the structural stability of
the design of Si-based composites with
Si/C composite and prolong their cycling lifetime. Finite element simulation mechanically robust architecture and high
proves the structural advantage of dual carbon stress-buffering through sig- electrical conductivity becomes crucial
nificantly relieving stress concentration when Si lithiation. The outer carbon to enhancing the cycling performance of
framework also accelerates the charge transfer efficiency during charging/dis- the Si anode. A robust architecture for Si-
charging by the improvement of lithium-ion diffusion and electron transport. based composites could effectively accom-
modate volume expansion and relax the
As a result, the Si@C@CNTs electrode exhibits excellent long-term lifetime mechanical stress from the lithiated Si. To
and good rate capability, showing a specific capacity of 680 mAh g−1 even at this end, various architectures for Si-based
a high rate of 1 A g−1 after 1000 cycles. This work provides insight into the composites have been developed.[6,9–13] For
design of robust architectures for Si/C composites by stress optimization. instance, typical core/shell or yolk/shell
structured Si-based composites,[14–17] espe-
cially Si/carbon (Si/C) composites,[18,19]
1. Introduction have been widely investigated because the carbon layer not only
acts as a protective layer for buffering the stress and volume
Silicon (Si), as one of the alloy-type anode materials, displays change induced by Si expansion but also provides a high con-
a significantly higher specific capacity of 3579  mA h g−1 than ductive layer to increase the electrical conductivity of the com-
commercially used graphite with a low theoretical capacity posites. However, Si/C composites with a single carbon layer
of 372  mA h g−1. Besides, silicon anode material shows a low will still suffer from fracture and cracks formed with repeated
voltage platform (≈0.4  V vs Li/Li+), abundant reserves, and deformation during long-term Si lithiation/delithiation reac-
low cost, which makes it suitable to meet the demands of tion, leading to electrode failure. Thus, developing optimized
next-generation lithium-ion batteries (LIBs) with high-energy- and multifunctional outer carbon frameworks is still in high
density in the electric vehicle application.[1–5] However, for demand for Si/C composites.
practical use, Si anode material still remains many challenges Recently, Si/C composites with double carbon layers have
attracted much interest due to their multiple functions of
X. Fan, T. Cai, S. Wang, Z. Yang, W. Zhang
carbon layers in protecting the inner Si particles.[20–22] Yu et al.
School of Chemistry and Chemical Engineering, Anhui Province Key reported double carbon shells coated Si nanoparticles (Si NPs)
Laboratory of Advanced Catalytic Materials and Reaction Engineering with excellent rate capability and remarkable cycling perfor-
Hefei University of Technology mance.[23] The inner carbon shell allows big volume change
Hefei 230009, P. R. China and alleviates large stress of Si NPs and the outer carbon shell
E-mail: xmfan@hfut.edu.cn; wxzhang@hfut.edu.cn
promotes the formation of stable SEI film. Yang et al. prepared
X. Fan, W. Zhang
Institute of Energy micro-sized Si/C composites with inner chemical vapor deposi-
Hefei Comprehensive National Science Center tion carbon and outer dense and interlinked graphene network,
Hefei 230009, P. R. China which provides good mechanical and electrical robustness
for the electrode.[24] Metal-organic frameworks (MOFs), which
The ORCID identification number(s) for the author(s) of this article
can be found under https://doi.org/10.1002/smll.202300431.
consist of tunable chemical composition, porous structure,
and controlled morphology, have been employed as the pre-
DOI: 10.1002/smll.202300431 cursors to build multifunctional carbon frameworks for the

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fabrication of Si/C composites.[25–27] Chen et  al. used ZIF-8
derived multi-channel carbon as the inner carbon layer and
graphene-supported activated carbon generated from sucrose
as the outer carbon layer in the Si/C composite, which prom-
ises the Si-based anode good cycling stability and improved
rate capability.[28] Although some studies have focused on Si/C
composites with double carbon layers, little attention has been
given to the construction of multifunctional carbon frameworks
from the perspective of stress buffering, ion diffusion, and elec-
tron transport to improve the electrochemical performance of
Si anode.
Herein, we prepared Si/C composite as anode material with
MOFs (ZIF-67) derived carbon nanotube (CNT)-reinforced
multifunctional carbon frameworks as the outer carbon layer
to encapsulate the inner carbon-coated Si NPs. Citric acid (CA)
is adopted to modify the as-received Si NPs, which not only
facilitates the uniform growth of ZIF-67 on the surface of Si
NPs but also acts as a carbon precursor of the inner carbon
layer. The unique Si/C composite features CNT-reinforced dual
carbon stress-buffering, generated from the inner citric acid
and outer ZIF-67, to accommodate the volume expansion and
relieve the stress of lithiated Si. The finite element model is
also developed to simulate mechanical stress and proves the
advantage of a dual stress-buffering structure. Moreover, the
outer ZIF-67-derived carbon frameworks also improve the ion
diffusion kinetics and electron transport in the electrode.
Based on these benefits, the as-obtained Si/C composite with
novel architecture enables superior rate capability and excellent
cycling stability with a high specific capacity of 680 mAh g−1
(based on the mass of Si/C composite) at a high rate of 1 A g−1
for 1000 cycles.
Figure 1.  The synthesis and compositions of the Si/C composites. a) Graphical representation of the synthetic process of the Si@C@CNTs. b) XRD
patterns and c) Raman spectra of the precursor Si@CA@ZIF-67 and the Si@C@CNTs. d) TG and DSC analysis of the Si@C@CNTs under air condition.
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2. Results and Discussion
In order to address the issues of Si anode material, we design
and synthesize Si/C composite with the functional architecture
in which Si NPs are encapsulated in CNT-reinforced dual stress-
buffering layers. As illustrated in Figure  1a, Si NPs are first
modified by citric acid molecules, and the modified Si NPs are
then coated by ZIF-67 as a carbon precursor. It is worth noting
that citric acid molecules could increase the negative charge
density on the surface of Si NPs, which plays an important
role in the encapsulation process to ensure that Si NPs could
be involved in the ZIF-67 layers as much as possible. This will
be discussed in detail later. With heat treatment in a reduction
atmosphere, the citric acid and ZIF-67 dual coating layers are in
situ transformed into dual carbon stress-buffering layers to gen-
erate polyhedral Si/C microparticles, which feature core/shell
structured Si/C NPs inside and ZIF-67 derived carbon/CNTs
framework outside and are denoted as Si@C@CNTs.
As shown in Figure  1b, X-ray diffraction (XRD) patterns
reveal the presence of Si and ZIF-67 in the precursor of the
Si@C@CNTs (marked as Si@CA@ZIF-67). After heat treat-
ment, the obtained Si@C@CNTs show characteristic peaks of
crystalline Si (PDF No. 27–1402) and cubic cobalt (Co, PDF No.
15–0806).[29,30] The metallic Co is formed under the reduction
atmosphere during heat treatment and acts as a catalyst for the
growth of CNTs on the polyhedral Si@C@CNTs microparti-
cles.[31] Raman spectra further display the transformation from
the precursor Si@CA@ZIF-67 to the Si@C@CNTs during heat
treatment. Figure  1c shows that two peaks appear obviously
at ≈1342 and ≈1588 cm−1 corresponding to the D and G peaks
of carbon after thermal treatment,[32] caused by citric acid and
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ZIF-67 derived carbon/CNTs. Meanwhile, the peaks belonging
to crystalline Si could be observed at ≈292, ≈510, and ≈939 cm−1
for both the Si@CA@ZIF-67 and the Si@C@CNTs,[33] which
reveals that the phase of Si NPs undergoes no change with heat
treatment. Metallic Co also exists in the Raman spectrum of the
Si@C@CNTs, with a characteristic peak at ≈680 cm−1,[34] which
is consistent with the XRD result. Figure  1d demonstrates the
thermogravimetric (TG) and differential scanning calorimetry
(DSC) curve of the Si@C@CNTs under the air atmosphere.
Fast mass loss ranging from 260 to 280  °C in the TG curve
results from the combustion of carbon in the Si@C@CNTs.
Subsequently, the rate of mass loss obviously decreases between
280 and 380  °C, which arises from the oxidation of Co NPs
exposed in the air combined with the combustion of carbon.
DSC results also agree with the two main steps of mass loss
in the TG curves. Two exothermic peaks in the DSC curves at
about 276 and 333 °C are attributed to the combustion of carbon
and oxidation of Co NPs, respectively. The content of Co NPs in
the Si@C@CNTs is also determined to be ≈8  wt.% by induc-
tively coupled plasma spectroscopy. It should be pointed out
that Si NPs have a 5 wt.% increase in weight after the TG test
in air (Figure S1a, Supporting Information) and the residues of
the Si@C@CNTs after heat treatment in air consist of Si and
Co3O4 (Figure S1b, Supporting Information). According to the
above result, the content of carbon and Si in the Si@C@CNTs
is calculated to be 33.8 and 58.2 wt.%, respectively.
Citric acid plays an important role in the preparation pro-
cess of Si/C composite with dual carbon stress-buffering layers.
First, the adsorption of citric acid molecules on the Si NPs could
significantly increase the negative charge density on the surface
of Si NPs. As shown in Figure S2a, Supporting Information,
the as-received commercial Si NPs are negatively charged with
a small zeta potential value of −9.9 mV in methanol. After treat-
ment with citric acid, which has three carboxyl groups as illus-
trated in Figure 1a, the zeta potential value of modified Si NPs
increases obviously to −30.7  mV in methanol. The interaction
between Si NPs and citric acid was characterized by Fourier
transform infrared (FTIR) spectroscopy (Figure S3, Supporting
Information). In the case of bare Si NPs, two peaks at 3478 and
1633 cm−1 correspond to the OH groups on the surface of
Si NPs.[35] After modification with citric acid, the stretching
vibration of OH groups for the resulting product (Si@CA)
shifts to a lower wavenumber, revealing the formation of a
hydrogen bond.[36] The large negatively charged Si NPs could be
well dispersed in the methanol solvent, beneficial for the subse-
quent ZIF-67 coating process. As a result, more cobalt ions will
surround the citric acid-modified Si NPs due to the electrostatic
interaction, evidenced by a larger increase in zeta potential as
shown in Figure S2b,c, Supporting Information. This will be
in favor of the nucleation and growth of ZIF-67 around Si NPs
to ensure that Si NPs could be well encapsulated in the ZIF-67
layers. After heat treatment, the inside citric acid molecules are
transformed into an amorphous carbon layer on the Si NPs,
while the outside ZIF-67 layer is converted into a polyhedral
carbon framework composed of CNTs and graphitic carbon.
Such a dual carbon stress-buffering in the Si@C@CNTs could
offer a highly stable structure to accommodate the huge volume
change of silicon anode material during charging/discharging.
It is noteworthy that CNTs only exist under a reducing
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atmosphere (H2/Ar gas mixture) in this work. If the Si@CA@
ZIF-67 is thermally treated under a pure Ar atmosphere, the
outside ZIF-67 layers only could be converted into a carbon
framework without CNTs, represented as Si@C@C for com-
parison. CNTs with high mechanical strength will provide a
reinforced carbon stress-buffering in the Si@C@CNTs, which
will be discussed in detail later.
The morphologies and microstructures of the Si@C@CNTs
are further characterized by electron microscopy. With the
treatment of citric acid modification and ZIF-67 coating, the
as-obtained Si@CA@ZIF-67 shows a typical polyhedral struc-
ture similar to ZIF-67, with an average size of about 1.5  µm
(Figure  2a and Figure S4, Supporting Information). Due to
the electrostatic interaction as discussed above, most of the
citric acid-modified Si NPs could be encapsulated in the poly-
hedral ZIF-67 layers. In comparison, more aggregative bare Si
NPs are found in the sample prepared in the coating process
between the raw Si NPs and ZIF-67 in methanol (Figure S5,
Supporting Information). The citric acid-assisted uniform
ZIF-67 coating on Si NPs plays a key role in the construction
of stable structure for Si/C composite in this work. After heat
treatment, the Si@C@CNTs maintain the original polyhedral
structure of the precursor Si@CA@ZIF-67 (Figure  2b). The
average size of the Si@C@CNTs slightly decreases to ≈1  µm
as a result of the structural shrinkage during the pyrolysis of
the ZIF-67 skeleton. Moreover, dense CNTs could be found
on the surface of the polyhedral particle (Figure  2b). CNTs in
situ grow when ZIF-67 decomposes at high temperature and
assemble into carbon frameworks embedded with Si NPs. To
better illustrate the inner structure of the Si@C@CNTs, the
view of the cross section of the polyhedral particle is shown
by using the ion cross-section polishing technique. Obviously,
CNTs grow on both exterior and interior surfaces of the carbon
frameworks of the Si@C@CNTs and well connect with the Si
NPs inside the frameworks (Figure 2c). CNTs will not only sup-
port a stable carbon framework to accommodate the large Si
volume change during lithiation/delithiation but also provide
high electron transport pathways between the Si NPs and elec-
trodes. Many large pores are also found inside the polyhedral
particle observed from the sectional view (marked by the red
arrow in Figure  2c), which could serve as an electrolyte reser-
voir to enhance the lithium-ion diffusion in the electrochemical
reaction.[37] In addition, small Co NPs can be observed on the
carbon frameworks as well (Figure 2c), which act as the catalyst
for the growth of CNTs. Co NPs also play important role in the
improvement of the cycling stability of the Si@C@CNTs, and
this will be discussed further in the section below.
As a contrast, the Si@C@C derived from the precursor
Si@CA@ZIF-67 under Ar atmosphere exhibits a similar poly-
hedral morphology without any CNTs generated on the surface,
as shown in Figure S6a, Supporting Information. The connec-
tion between the outer carbon framework and inner Si NPs
exists in the Si@C@C as well (Figure S6b, Supporting Infor-
mation). The formation of different carbon frameworks in dif-
ferent atmospheres from the same precursor ZIF-67 may be
caused by the as-generated Co NPs with different sizes (Figure
S7, Supporting Information). Co acts as a catalyst that can cata-
lyze carbon atoms to form graphitic carbon or CNTs. Bulk diffu-
sion of carbon atoms on the large Co NPs in the Si@C@C will
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Figure 2.  The morphologies and microstructures of the Si@C@CNTs. SEM images of a) the Si@CA@ZIF-67, b) the Si@C@CNTs, and c) the cross-
section of Si@C@CNTs. d) TEM, e–g) HRTEM (inset: SAED pattern), and h–k) elemental mapping images of the Si@C@CNTs.
promote the layer-by-layer growth of graphitic carbon, while
surface diffusion is dominant for the small Co NPs in the
Si@C@CNTs, leading to the nucleation of carbon cap and
growth of CNTs with continuously supplied carbon atoms.[38–40]
Both the Si@C@CNTs and Si@C@C show typical mesoporous
structures according to the nitrogen adsorption/desorption
measurements (Figure S8, Supporting Information). The
Si@C@CNTs have higher specific surface area and total pore
volume than the Si@C@C according to the results in Table S1,
Supporting Information, which is beneficial for ion diffusion
during the electrochemical reaction.
Transmission electron microscopy (TEM) image and the
corresponding elemental mapping results prove that Si NPs
are indeed dispersed in the carbon matrix for the Si@C@
CNTs (Figure  2d,h). High-resolution TEM (HRTEM) image
shows that Si NPs are coated by a thin amorphous carbon layer
derived from citric acid molecules on the surface of Si NPs
(Figure  2e) compared with the raw Si NPs used in this work
(Figure S9, Supporting Information). A thin carbon layer could
be also observed in the case of the product obtained by direct
thermal treatment of the citric acid-modified Si NPs (marked
as Si@C, Figure S10, Supporting Information). This citric acid-
derived amorphous carbon layer could not only accommodate
the volume expansion of Si anode material to some extent but
also promote the electrical conductivity of Si as a semicon-
ductor.[41] Clear lattice fringes with an interplanar spacing of
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0.316  nm are ascribed to the (111) plane of Si.[42] The selected
area electron diffraction (SAED) pattern also identifies the poly-
crystalline Si as characterized by distinct diffraction rings with
bright spots related to (111), (220), and (311) facets.[43] The TEM
image in Figure  2f proves the existence of Co NPs at the end
of CNTs with an interplanar distance of 0.36 nm,[44] evidenced
by well-defined lattice fringes of 0.202  nm for the (111) plane
of Co (Figure 2g).[45] In addition, Co NP is surrounded by gra-
phitic carbon layers, as displayed in Figure  2f, confirming the
role of Co NP as a catalyst for the growth of CNTs. For com-
parison, CNTs have not been found on the Si@C@C according
to the TEM image shown in Figure S6c, Supporting Informa-
tion, which is consistent with the scanning electron microscopy
(SEM) result, confirming the key role of reduction atmosphere
in the generation of CNTs. Elemental mapping of the Si@C@
CNTs, as given in Figure  2h–k, illustrates the relatively uni-
form distribution of carbon, cobalt, and nitrogen elements
on a single Si@C@CNTs particle compared with the concen-
trated distribution of silicon element (Figure S11, Supporting
Information), and X-ray photoelectron spectroscopy (XPS) also
presents the coexistence of these elements (Figure S12, Sup-
porting Information), further proving the unique structure of
the Si@C@CNTs with Si NPs encapsulated in nitrogen-doped
carbon frameworks decorated with metallic Co.
The lithium storage properties of the Si@C@CNTs were
evaluated in a half-cell. Cyclic voltammetry (CV) was first tested
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Figure 3.  The electrochemical performances of the Si/C composites. a) CV curve and b) charge/discharge profiles of the Si@C@CNTs. c) Cycling
stability of the Si@C@CNTs, Si@C@C, and Si@C at 0.5 A g−1. d) High-rate cycling stability (1 A g−1) and Coulombic efficiency of the Si@C@CNTs.
e) Rate capability and f) Nyquist plots of the Si@C@CNTs, Si@C@C, and Si@C electrode after cycling.

to investigate the lithiation/delithiation reactions at a scan rate
of 0.1 mV s−1 (vs Li/Li+), as shown in Figure 3a. During the first
cathodic scan, an irreversible and broad peak at about 0.64  V
is shown in the CV curve, which is attributed to the decompo-
sition of electrolytes and the formation of SEI film.[46] The first
charge curve also has a small plateau at about 0.64  V which
disappears in the following two cycles (Figure S13a, Supporting
Information), which is consistent with the CV curves. A peak
around ≈0.16 V gradually increases in the cathodic scans, which
is related to the alloying reaction between Si NPs and lithium

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ions.[47] Ex situ XRD patterns of the Si@C@CNTs during the
lithiation process indicate that the peaks of crystalline Si dis-
appear at full discharge state, and only diffraction peaks of Co
could be found in the XRD pattern (Figure S13b, Supporting
Information). This reveals that crystalline Si is converted to
amorphous LixSi (a-LixSi) during the lithiation process. For
the anodic scans, two different peaks at about 0.32 and 0.53 V
can be observed, corresponding to the dealloying reaction of
a-LixSi.[48] All the diffraction peaks of crystalline Si could be
observed at full charge state. This reveals that a-LixSi is trans-
formed to crystalline Si again during the delithiation process.
HRTEM image of Si NPs after cycling also proves the existence
of crystalline Si (Figure S22, Supporting Information). More-
over, no obvious peaks belonging to the Co lithiation/delithia-
tion reactions could be found in the CV curves, and the peaks
corresponding to crystalline Co always exist in the ex situ XRD
patterns, suggesting that the metallic Co in the Si@C@CNTs
is electrochemically inactive. The inactive Co NPs in LIBs have
been reported previously.[49] The voltage profiles of the Si@C@
CNTs at different current densities are shown in Figure  3b.
It can be seen that the profiles at high current densities have
changed very little, which reveals the stable electrochemical
performance of the Si@C@CNTs. The electrode made from the
Si@C@CNTs exhibits excellent cycling stability, as shown in
Figure 3c, possessing a high specific capacity of 968 mAh g−1 at
a current density of 0.5 A g−1 after 500 cycles, corresponding to
a remarkably high capacity retention of 88% for a long cycling
test compared with recently reported results (Figure S14 and
Table S2, Supporting Information). The outer carbon frame-
work also shows high cycling stability with a capacity of 434
mAh g−1 after 300 cycles at 0.5 A g−1, corresponding to a capacity
retention of 90% (Figure S15, Supporting Information). In con-
trast, the specific capacity of the Si@C@C decreases sharply
to 434 mAh g−1 after more than 300 cycles at the same current
density. In comparison with the Si@C@C, abundant CNTs on
the carbon framework of the Si@C@CNTs could strengthen
the structure of the whole polyhedral particle to accommodate
the large volume expansion of inner Si NPs, which enables the
Si@C@CNTs to have better stability in long-term cycling test.
It should be pointed out that the outer carbon framework
without CNTs for the Si@C@C also significantly contributes
to the improvement of the cycling stability of the Si anode.
In the case of core/shell Si@C derived from citric acid-mod-
ified Si NPs, only a specific capacity of 269 mAh g−1 could be
maintained after cycling 300 times at 0.5 A g−1, which is obvi-
ously lower than that of the Si@C@C. Besides, the inner
carbon coating of core/shell Si@C is also important. Si NPs
were directly coated by ZIF-67 without citric acid modification
and the resulting product was calcined under H2/Ar atmos-
phere for comparison (denoted as Si@CNTs). As shown in
Figure S16, Supporting Information, although the Si@CNTs
have higher capacity than the Si@C@CNTs in the initial
period, the capacity rapidly decreases with cycling for the Si@
CNTs at the same current density. The inner carbon coating
and outer CNTs-supported carbon framework can act as dual
stress-buffering in the Si@C@CNTs to improve stability.
Moreover, the Si@C@CNTs exhibit a superior long lifetime
even after 1000 cycles at a high current density of 1 A g−1 and
possess a high reversible capacity of 680 mAh g−1 (Figure  3d),
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demonstrating the structural advantage of CNT-reinforced dual
stress-buffering in the Si@C@CNTs.
The rate capability of the above-mentioned Si/C composites
was compared at different current densities ranging from 0.1 to
3 A g−1 (Figure  3e). The Si@C@CNTs represent the best rate
performance compared with the Si@C@C and Si@C, with dis-
charge capacities of 1607, 1393, 1240, 1013, and 861 mAh g−1 at
different rates of 0.1, 0.5, 1, 2, and 3 A g−1, respectively. When
the current density is set back to 0.1 A g−1, the discharge capacity
of the Si@C@CNTs returns to 1511  mA h g−1. As a contrast,
the discharge capacities of the Si@C@C and Si@C electrodes
decay rapidly as the current density increases to a high value,
showing a low capacity of 323 and ≈0 mA h g−1 at 3 A g−1. Elec-
trochemical impedance spectroscopy (EIS) was further used to
evaluate the structural advantage of the Si@C@CNTs in terms
of charge transfer efficiency. Figure 3f shows the Nyquist plots
of the Si@C@CNTs, Si@C@C, and Si@C electrodes after
cycling. The semicircles in the medium-/high-frequency region
represent the charge transfer resistance (Rct) between electro-
lyte and electrode and the interfacial resistance of Li+ diffusion
across the SEI film (RSEI).[50–52] The Si@C@CNTs electrode
has the smallest semicircle in the medium frequency region,
corresponding to the lowest Rct value (21.3 Ω) (Table S3, Sup-
porting Information), demonstrating the fastest charge transfer
kinetics. The smallest semicircle related to the lowest RSEI value
(2.3 Ω) also could be observed in the high-frequency region
for the Si@C@CNTs electrode, suggesting a fast Li+ diffusion
through the stable SEI film. Moreover, if the metallic Co NPs
in the Si@C@CNTs are etched by acid (Figure S17, Supporting
Information), the cycling stability of the resulting product sig-
nificantly decreases at high current density (Figure S18a, Sup-
porting Information). EIS result reveals that the charge-transfer
impedance increases remarkably after the removal of Co NPs
from the Si@C@CNTs (Figure S18b, Supporting Information).
The inactive metallic Co NPs in the carbon framework of the
Si@C@CNTs will highly improve the electrical conductivity
and thus promote the charge transfer. In general, the unique
structure of the Si@C@CNTs, featuring high conductive CNTs
and Co NPs and opened porous structure, could enhance the
charge transfer efficiency in the lithium-ion extraction/inser-
tion reaction and thus exhibit good rate capability.
The diffusion of lithium ions in the Si@C@CNTs electrode
was further evaluated via galvanostatic intermittent titration
technique (GITT). Figure  4a,b show the GITT curves of the
Si@C@CNTs, Si@C@C, Si@C, and bare Si electrodes in the
first discharge and charge. Based on the above results and
Fick’s second law, the diffusion coefficient of lithium-ion (DLi + )
was calculated according to the following simplified equation.
2
4L2  ∆E s 
DLi + = (1)
πτ  ∆Eτ 
where L refers to the diffusion length of Li-ion (equal to the
electrode thickness). ΔEτ represents the voltage change and
ΔEs is the voltage change induced by pulse. The profile in a
single GITT titration for different electrodes and the linear
relationship between Eτ and τ1/2  are shown in Figure S19,
Supporting Information, revealing that Equation  (1) in our
calculation of diffusion coefficient is valid. Figure  4c displays
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Figure 4.  GITT curves of a) Si@C and bare Si, and b) Si@C@CNTs and Si@C@C. Lithium-ion diffusion coefficient of c) Si@C and bare Si, and
d) Si@C@CNTs and Si@C@C.
the DLi + values at different times in the first discharge/charge
cycle for the Si@C and bare Si, both of which do not have
outer carbon frameworks. It is obvious that the Si@C and bare
Si electrodes exhibit a similar situation during the lithiation/
delithiation reactions. The DLi + decreases sharply at the initial
lithiation stage and then almost maintains a stable and low
value of ≈10−13 cm2 s−1 until the alloying reaction between Si
and Li-ions is completed. During the delithiation process, the
DLi + descends gradually and then rises to the value of ≈10−11 cm2
s−1 at the end of the dealloying reaction of LixSi. Although the
Si@C is coated by a thin carbon layer, it still shows poor diffu-
sion kinetics similar to raw Si NPs. In the case of the Si@C@
CNTs and Si@C@C electrodes, the lithium-ion diffusion is
significantly different from the Si@C and bare Si electrodes
(Figure  4d). After a slight increase at the initial alloying stage,
the DLi + keeps a constant and high value of ≈10−10 cm2 s−1 and
then decreases to a relatively low value of ≈10−11 cm2 s−1 for both
Si@C@CNTs and Si@C@C in the following lithiation process.
It should be pointed out that the lithiation period with stable
and high DLi + for the Si@C@CNTs is significantly longer than
that for the Si@C@C. In the whole dealloying process, the DLi +
of the Si@C@CNTs electrode is also relatively constant with a
value as high as ≈10−10 cm2 s−1, which is higher than that of
the Si@C@C electrode. This result further demonstrates the
structural advantage of the Si@C@CNTs with CNTs-supported
carbon framework in the enhancement of lithium-ion diffu-
sion. Higher DLi + for the Si@C@CNTs could be resulted from
its higher surface area and porous structure which promotes
lithium-ion diffusion from the bulk electrolyte into the elec-
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trode and make easy access to the active materials. The Si@C@
CNTs with CNT-reinforced dual carbon stress-buffering also
enable the formation of stable SEI film to promote lithium-
ion diffusion across the SEI film, evidenced by EIS results.
Overall, it is obvious that the outer carbon frameworks in the
Si@C@CNTs and Si@C@C can promote lithium-ion diffusion
behavior compared with the Si@C and bare Si NPs and enable
faster lithiation/delithiation reaction kinetics.
The finite element model was adopted to simulate and com-
pare the mechanical stress distribution during the alloying
reaction for the Si@C@CNTs, Si@C@C, and Si@C, and the
initial models are shown in Figure S20, Supporting Informa-
tion. Figure 5a–c illustrates the stress distribution of these three
electrode materials after complete Si lithiation. Due to the large
volume expansion during Si lithiation, cracks will be formed
easily, leading to particle breakage. Crack formation is related to
the stress gradient in the particle. When a large stress gradient
occurs in a small localized area of a particle, the high stress is
considered as a stress concentration. In the case of the Si@C,
the volume of Si NPs expands seriously and these particles
show point-to-point contact. The stress occurs and increases
gradually close to the point-to-point contact during the lithia-
tion process. When Si NPs are completely lithiated, the stress
is obviously concentrated at the site near the point-to-point
contact (Figure 5a), which results in the crack formation on the
Si@C. The citric acid-derived amorphous carbon layer on the
Si NPs only could alleviate the volume expansion to a certain
extent, which agrees with the result in Figure  3c. As shown
in Figure S21, Supporting Information, the Si@C electrode
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Figure 5.  Stress distributions of the models with complete Si lithiation: a) Si@C, b) Si@C@C, and c) Si@C@CNTs. The front views of the electrodes
d–f) before and g–i) after cycling, and the lateral views of the electrodes j–l) before and m–o) after cycling. SEM images of the left, middle, and right
columns are collected from the front and lateral views of Si@C, Si@C@C, and Si@C@CNTs, respectively.

also has a slightly improved lifetime compared with the elec- been greatly alleviated (Figure  5b,c). A larger stress gradient
trode made of bare Si NPs. For the Si@C@C and Si@C@CNTs, exists in the Si@C@C compared with the Si@C@CNTs when
the stress concentration in the whole polyhedral particle has Si is completely lithiated, suggesting the Si@C@C has more

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concentration of stress in the whole particle. Carbon as filler
inside the whole particle changes the point-point contact mode
of Si@C NPs and increases the contact area by filling the
gaps between Si@C NPs, which reduces the cracks caused by
stress concentration. CNTs as filler in the Si@C@CNTs pos-
sess higher Young’s modulus and Poisson’s ratio due to their
intrinsic high mechanical property compared with carbon in
the Si@C@C, which is more conducive to relieving stress con-
centration. The change of stress distribution after Si lithiation
enables high mechanical stability of the Si@C@CNTs and thus
promotes cycling stability.
To further demonstrate the structural benefits of dual carbon
stress-buffering in the Si@C@CNTs, the crack and expan-
sion of the electrode film on the current collector caused by Si
volume expansion were measured from the front and lateral
views. Figure  5d–i show SEM images from the front views
of the electrodes before and after cycling. Before testing, no
obvious cracks could be observed for all these electrodes. When
the electrode is cycled 300 times, only a few and narrow cracks
(≈6  µm) appear on the surface of the Si@C@CNTs electrode.
In contrast, many large cracks formed after the long-term
cycling test in case of Si@C@C and Si@C electrodes. The
electrode film of the Si@C is destroyed more seriously, with
wider cracks generated on the surface (≈20  µm) compared
with the Si@C@C electrode film (≈15  µm). The expansion of
the electrode film on the current collector is also investigated
from the lateral views. The thickness of the Si@C@CNTs elec-
trode film increases from 75 to 110  µm, corresponding to the
volume expansion of ≈47% after 300 cycles. For comparison,
larger volume expansion of the Si@C@C and Si@C elec-
trodes could be detected after cycling, reaching up to ≈73%
and ≈108%, respectively. The structure of Si@C@CNTs after
cycling was also examined to evaluate the structure stability
(Figure S22, Supporting Information). SEM images show that
the polyhedral structure of Si@C@CNTs could be maintained
after cycling (Figure S22a,b, Supporting Information), which is
further proved by the TEM image in Figure S22c, Supporting
Information. Moreover, CNTs and surface carbon on the Si NPs
could be also observed after cycling (Figure S22c,d, Supporting
Information). These results agree with the excellent mechanical
structure stability of the Si@C@CNTs electrode, in which the
particles have low mechanical stress concentration under lithi-
ation state due to the existence of dual carbon stress-buffering.
The electrochemical performance of the Si@C@CNTs anode
in the pouch cell was also tested to evaluate the potential in
practical application. Commercial cathode material NCM523
was used in this pouch cell to prepare the cathode. As shown
in Figure S23, Supporting Information, the pouch cell exhibits
relatively high cycling stability at a voltage window of 2.8–4.3 V,
with a capacity retention of 70.3% for 100 cycles at 0.5 C
(1 C = 28 mA h). A LED display could be lighted up as well by the
self-made pouch cell. This result demonstrates the possibility of
the Si@C@CNTs as stable anode material for practical use.
3. Conclusion
In summary, a dual carbon stress-buffering strategy has been
developed in this work to accommodate the volume expansion
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and relieve the stress of Si NPs during lithiation. Citric acid is
adopted to increase the negative surface charge density of Si
NPs and ensures success in the subsequent ZIF-67 encapsula-
tion process. After thermal treatment, ZIF-67 could be success-
fully converted into CNTs supported carbon framework as the
outer protective layer, embedded with Si NPs coated by citric
acid-derived inner amorphous carbon layer. Benefiting from the
dual carbon stress-buffering, the stress concentration caused
by the lithiation of Si NPs has been greatly alleviated, which is
further proved by finite element simulation. The outer carbon
framework with dense CNTs and metallic Co contributes to the
enhancement of lithium-ion diffusion and electron transport,
thus boosting charge transfer for the Si@C@CNTs electrode.
The volume expansion of this electrode is also significantly sup-
pressed due to the unique structure of the Si@C@CNTs. The
Si@C@CNTs electrode shows improved cycling stability at a
high rate, possessing a capacity of 680 mAh g−1 for 1000 cycles
even at 1 A g−1. This work also offers insight into the fabrication
of robust Si-based anode by designing functional architectures
for Si/C composites in terms of stress optimization, ion diffu-
sion, and electron transport.
4. Experimental Section
Materials: All the reagents were purchased from Sinopharm Chemical
Reagent Co., Ltd and used as received without any purification.
Preparation of Si@CA: Citric acid (500 mg) was dissolved in deionized
water (40 mL) and then commercial Si NPs (150 mg) were dispersed in
the solution and stirred for 24 h at room temperature. After centrifuged
at 8000 r min−1 for 3 min and dried in vacuum at 80 °C overnight, brown
powder named Si@CA was obtained.
Preparation of Si@CA@ZIF-67: The Si@CA powder (150  mg) was
dispersed in a methanol solution (100  mL), in which Co(NO3)2·6H2O
(4  g) was dissolved first, with a treatment in an ultrasonic bath for
30 min (solution A). 2-Methylimidazole (4.512 g) was then dissolved in a
methanol solution (100 mL) and treated in an ultrasonic bath for 30 min
(solution B). The molar ratio of Co(NO3)2 to 2-methylimidazole was
1:4. Solution B was then rapidly mixed with solution A, and the mixture
was stirred strongly for 15  min and then stirred continuously at room
temperature for 24  h. Finally, the powder named Si@CA@ZIF-67 was
obtained after being centrifuged at 8000 r min−1 for 5 min, washed with
methanol at least three times, and dried in vacuum at 80 °C overnight.
Preparation of Si@C@CNTs and Si@C@C: The Si@CA@ZIF-67
powder was treated at 350 °C for 2 h and then further calcined at 700 °C
for 3 h under Ar/H2 atmosphere (95:5 in volume). The resulting product
was denoted as Si@C@CNTs. For comparison, the Si@C@C powder
was obtained by replacing Ar/H2 mixed gas with pure Ar gas under the
same heating procedure.
Preparation of Si@ZIF-67 and Si@CNTs: Si@ZIF-67 was prepared
in a similar process to the Si@CA@ZIF-67. Bare Si NPs instead of the
modified Si@CA were directly used in the ZIF-67 coating process. The
Si@ZIF-67 powder was then treated at 350  °C for 2  h and then further
calcined at 700 °C for 3 h under Ar/H2 atmosphere (95:5 in volume) to
obtain Si@CNTs.
Preparation of Si@C: The modified Si@CA powder was directly
calcined at 700 °C for 3 h to prepare Si@C.
Characterization: XRD (PANalytical, X-Pert PRO MPD and Rigaku,
SmartLab) with Cu Kα X-ray source was used for the characterizations of
Si-based anode materials and the precursors. Raman spectroscopy was
also measured by a confocal microprobe Raman spectrometer (Horiba
Jobin-Yvon, LabRam HR Evolution) to determine the compositions
of anode materials. The interaction between Si and citric acid was
characterized by FTIR spectroscopy (Thermo Fisher, Nicolet 6700).
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Morphologies and microstructures of anode materials and electrodes
were examined by field emission SEM (FESEM, Hitachi, SU8020) and
TEM(JEOL, JEM-1400flash), respectively. Cross-sectional views of the
polyhedral particle were obtained by using ion cross-section polishing
(JIT-CP-200E) and FESEM (FEI, Apreo 2C). HRTEM (JEOL, JEM-2100F)
operated at 200 kV was used for further microstructure analysis. Specific
surface area and pore volume were analyzed by nitrogen sorption (JWGB
Instruments, JW-BK100C). The surface chemistry was determined by
using XPS (Thermo Fisher, ESCALAB 250Xi). TG analysis (NETZSCH,
STA-449F5) was conducted from room temperature to 800  °C under
air condition with a heating rate of 5  °C min−1. A zeta potentiometer
(Malvern, Nano-ZS90) was used to analyze the surface charge of bare
Si and modified Si. An inductively coupled plasma mass spectrometer
(Agilent, A7900QMS) was adopted to determine the element ratios of
anode materials.
Chemomechanical Model: Finite element simulation was used to
calculate the volume expansion of the electrode materials, including
Si NPs, Si@C@C, and Si@C@CNT, after lithiation and the process of
structure mechanics related to intergranular extrusion. 2D simplified
models of three electrode materials were built, in which two boundary
condition constraints were included. One was set on the surface of
the carbon framework for the models of the Si@C@C and Si@C@
CNT to simulate the outside lumped constraint on the carbon
framework. The other one was the volume spring foundation that
was applied on all Si spheres to ensure the proper convergence of the
simulation. Moreover, the thin elastic layer was set on the surface of
the Si spheres, corresponding to the amorphous carbon layer coated
on the Si spheres. The pre-strain strength was set on the Si spheres,
and the volume expansion of Si spheres occurred due to the alloying
reaction. The contact surface of Si spheres was constrained by using
the penalty function when these spheres contacted each other, and
weak adhesion occurred between Si spheres. The shear stiffness
originated from contact penalty factor. A stress distribution pattern at
a lithiation state of 100% could be finally obtained according to the
above simulation.
Electrochemical Measurement: To prepare the electrodes, active
materials, sodium alginate (SA) and carbon black (Super P, SP) with
a weight ratio of 6:2:2 were uniformly mixed together with the solvent-
deionized water and continuously stirred for 12  h. The slurry was then
cast onto a piece of Cu foil with a doctor’s blade and dried at 80 °C under
vacuum. The mass loading of active materials is 1.3, 1.25, and 1.43  mg
cm−2 in the Si@C@CNTs, Si@C@C, and Si@C electrodes, respectively.
The electrodes were evaluated in the coin cells (CR2032) and assembled
in a glove box filled with argon gas. The coin cells were constructed with
the working electrode with active materials and lithium metal foil as
counter electrode. Celgard 2400 polypropylene membrane was employed
as a separator, and a mixture of 1.0 M LiPF6 in ethylene carbonate and
dimethyl carbonate (volume ratio of 1:1) was used as the electrolyte. CV
and EIS were conducted on an electrochemical workstation (Shanghai
Chenhua Instrument Co., Ltd., CHI-760E). In the EIS test, an applied
potential was 5  mV, and the frequency was set from 100  kHz to 100
mHz. The CV was achieved from 0.01 to 3.0 V at a scan rate of 0.1 mV s−1
(vs Li/Li+). Charge/discharge profiles at different current densities and
cycling test curves were obtained between 0.01 and 3.0 V at the battery
testing system (Shenzhen Neware Technology Co., Ltd., CT-4008T).
The GITT measurements were performed on the same device. The
cells were tested for 30  min with current flux followed by 150  min rest
(open circuit) to reach a steady state at 100  mA g−1 between 0.01 and
3.0  V. Pouch cell was assembled by using the Si@C@CNTs electrode
as the anode (mSi@C@CNTs:mSA:mSP:mSWCNTs  = 6:2:1:1) and commercial
NCM523 material as the cathode (mNCM523:mPVDF:mSP  = 8:1:1).
The voltage window was set from 2.8 to 4.3 V.
Supporting Information
Supporting Information is available from the Wiley Online Library or
from the author.
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Acknowledgements
X.F. and T.C. contributed equally to this work. This work was supported
by the National Natural Science Foundation of China (NSFC 21808046
and 22278107). The authors also acknowledge support from the Anhui
Provincial Development and Reform Commission (Grant 2021–442) and
the Institute of Energy, Hefei Comprehensive National Science Center
(Grant 21KZS210).
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, metal-organic frameworks,
silicon anodes, stress distribution
Received: January 15, 2023
Revised: March 19, 2023
Published online:
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