Applied Surface Science 511 (2020) 145609

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Applied Surface Science

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

Full Length Article

Novel bread-like nitrogen-doped carbon anchored nano-silicon as high- T

stable anode for lithium-ion batteries
⁎
Qin Weia, Yu-Mei Chena, Xu-Jia Honga, Chun-Lei Songa, Yan Yanga, Li-Ping Sib, Min Zhangb, ,
⁎
Yue-Peng Caia,
a
School of Chemistry, Guangzhou Key Laboratory of Materials for Energy Conversion and Storage, and Guangdong Provincial Engineering Technology Research Center for
Materials for Energy Conversion and Storage, South China Normal University, Guangzhou 510006, PR China
b
School of Materials Science and Energy Engineering, Foshan University, 528000, PR China

A R T I C LE I N FO A B S T R A C T

Keywords: Nano core-shell silicon/carbon (Si/C) composites can efficiently enhance the conductivity and accommodate the
Bread-like structure volume change for Si. However, new challenges of big specific surface area and high interparticle resistance still
Silicon weaken its advantages. In order to solve the above problems, we prepared a micron bread-like Si-based com-
ZIF-8 posite with high Si content in it, in which buffer space in clustered core-shell units are used to relieve the stress
Core-shell
caused by volume expansion, and the N-doped carbon skeleton derived from ZIF-8 is applied to enhance the
Anode
Lithium-ion batteries
electrical contact between adjacent core-shell units. Due to the stable bread-like structure, the integrity of stable
solid electrolyte interphase layer is maintained, and the lower external surface area retains the coulombic ef-
ficiency as high as 95.5% during cycling. The specific capacities of the obtained composite are 1155 mAh g−1 at
2 A g−1 and 815 mAh g−1 at 5 A g−1 in rate performance. After long-term cycling of 500 cycles, the composite
still maintains specific capacities of 1109 mAh g−1 at 3 A g−1 and 804 mAh g−1 at 5 A g−1 with ICE of 65.55%
in the first three activated cycles.

1. Introduction
In order to satisfy the ever-growing demands of lithium-ion batteries
(LIBs), materials with high energy density, good rate performance, and
stable cycle performance are urgently needed in recent years. As one of
the ideal anode materials for lithium-ion batteries (LIBs), silicon (Si)
has the advantages of the rich resources, high theoretical capacity
(4200 mAh g−1) and low operating voltage (below 0.5 V vs Li/Li+)
[1,2]. However, two inherent drawbacks still hinder their practical
application. Firstly, the volume change of Si (more than 300%) will
cause structural damage and form excess solid electrolyte interphase
(SEI) [3,4]. Secondly, poor conductivity will bring about insufficient
participation of Si in the electrochemical reaction, which will cause
rapid decay of reversible capacity during cycling [5,6]. Therefore, de-
signing multifunctional structure with high conductivity and stable
structure is the key to the development of Si-based anodes in LIBs.
In previous reports, nano-scale Si, such as Si NPs [7], Si nanowires
[8,9], and hollow Si [10,11], was used to relieve the stress caused by
volume expansion during lithiated/delithiated processes, and carbo-
naceous layers were designed to improve the conductivity and stability
of electrodes [12,13]. The requirement for a high Si content not only
increases the energy density of the electrode, but also increases the risk
of structural pulverization caused by the volume change of Si. Thereby,
void space in carbonaceous layers are needed, such as core-shell
structure [14,15], hollow carbon nanotubes [16], ball-in-ball hollow
spheres [17], to provide buffer space for Si NPs to maintain the stability
of SEI formed on the surface. Despite the enhanced conductivity and
cushion space, new challenge of a big external area and high inter-
particle resistance still discount its advantages [18]. On one hand, the
high surface area results the added formation of SEI, which will lead to
low initial coulombic efficiency (ICE) and reduced conductivity. On the
other hand, electronic transmission in electrode is easily affected by
structural changes during cycling. Therefore, it is valuable to design
durable Si/C materials with higher silicon content and lower external
area.
Metal-organic frameworks (MOFs), worked as carbon layer [19,20],
sulfur-loading [21–24], sandwich coating cushions [25,26], and self-
sacrificing template [27,28], have been proved to be an ideal carbo-
naceous part for lithium batteries. As one of the classical MOFs, zeolitic
imidazolate frameworks-8 (ZIF-8) has been used to enhance the elec-
trochemical performance of Si/C composites. For instance, wang et al.
used ZIF-8 NPs as a self-sacrificing template to build a hollow cube-like

⁎
Corresponding authors.
E-mail addresses: zhangmin@gic.ac.cn (M. Zhang), caiyp@scnu.edu.cn (Y.-P. Cai).

https://doi.org/10.1016/j.apsusc.2020.145609
Received 4 January 2020; Received in revised form 28 January 2020; Accepted 30 January 2020
Available online 01 February 2020
0169-4332/ © 2020 Elsevier B.V. All rights reserved.
Q. Wei, et al.
Si/SiO2@C composite with superior lithium storage performance [29].
Liu et al. obtained a ZIF-8 derived hierarchical porous nitrogen-doped
carbon coated Si/C microsphere by high voltage sputtering method,
which exhibits an improved lithium storage performance [30]. Due to
the composition of N-containing organic ligand and zinc ions, ZIF-8 can
be transformed into zinc oxide/nitrogen-doped carbon composite or
nitrogen-doped carbon at different temperature [31]. Therefore, ZIF-8
has great potential for producing durable Si/C composites with lower
external area due to its controllable configuration and high carbon
content.
Herein, we fabricate a ZIF-8 derived bread-like structure with
clustered core-shell Si/C unites anchored in it, in which buffer space in
clustered core-shell units are used to relieve the stress caused by volume
expansion, and the ZIF-8 derived micron N-doped carbon skeleton is
applied to maintain the electrical contact between adjacent core-shell
units. Compared to other similar investigations reported [18,30,32–34],
the micro structure with reduced external surface area can significantly
reduce the formation of SEI film on the surface of Si/C composite. The
reaction between zinc oxide and carbon at high temperature can
completely remove zinc oxide and consume a part of carbon to improve
the mass ratio of Si, in which the generated mesopores can promote the
penetration of lithium ions. The durable bread-like structure maintains
the integrity of SEI and exhibits high coulombic efficiency up to 95.5%
during long-term cycling. Thereby, the obtained micron bread-like Si/C
composite containing high Si content of 71 wt% can still presents good
rate performance with specific capacities of 1155 mAh g−1 at 2 A g−1
and 816 mAh g−1 at 5 A g−1. After long-term cycling of 500 cycles, the
composite maintains specific capacities of 1109 mAh g−1 at 3 A g−1
and 804 mAh g−1 at 5 A g−1 with ICE of 65.55% in the first three
activated cycles.
2. Experimental
2.1. Materials
All chemicals were directly used without purification.
Polyvinylpyrrolidone (PVP, Mw = 30000), tetraethyl orthosilicate
(TEOS, ≥98.0%), 2-methylimidazole (2-mim, ≥98.0%), zinc nitrate
hexahydrate (Zn(NO3)2⋅6H2O, ≥99.0%), ethanol (EtOH, ≥99.5%),
methanol (MeOH, ≥99.5%), hydrofluoric acid (HF, ≥40%), ammo-
nium hydroxide (NH3⋅H2O, 25–28%), and silicon (Si, ≥99%) were
purchased from Hua Xin Co., Ltd.
2.2. Synthesis of PVP-treated Si@Silica NPs
According to the classical method [35], Si (0.1 g) was ultrasonic
dispersed in a mixture of water (50 ml) and EtOH (300 ml). Then, TEOS
(2.15 ml) were dropwise added to the obtained yellow liquid under
vigorous stirring. After 5 min, NH3⋅H2O (2 ml) were dropwise added to
the liquid in about 1 min under vigorous stirring, and the mixture was
centrifugated and washed with EtOH for three times to obtain the
yellow solid of Si@SiO2. the obtained Si@SiO2 NPs were collected at
10000 rpm for 3 min by centrifugation, and then dispersed in a mixture
of PVP (0.7 g) and EtOH (40 ml). After ultrasonic treatment for 10mins,
PVP-coated Si NPs were centrifugated to remove the excess PVP.
2.3. Preparation of the Si@Z-1000
The obtained PVP-coated Si@SiO2 NPs were dispersed in the mix-
ture of MeOH (20 ml) and 2-methylimidazole (0.3 g) to form solution A,
and Zn(NO3)2⋅6H2O (0.1 g) was dissolved in MeOH (20 ml) to obtain
solution B. Then, the mixture of solutions A and B were stirred for
1 min, and then the mixture was grown at room temperature for 12 h
without stirring. The collected Si@SiO2@ZIF-8 particles were sequen-
tially carbonized at 700 °C for 2 h and 1000 °C for 2 h with heating rate
of 2 °C min−1 in an Ar-filled tube furnace. The obtained composite was
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Applied Surface Science 511 (2020) 145609
further washed with diluted HF to remove SiO2. Then, the micron-sized
Si/C composites named Si@Z-1000 were obtained and collected for
electrochemical test.
2.4. Preparation of the Si@Z-700
Si NPs (0.1 g) and PVP (0.7 g) were dissolved in EtOH (40 ml) by
ultrasonic method for 10 mins. After removing the excess PVP by
centrifugation, PVP-coated Si NPs were mixed with 2-methylimidazole
(0.3 g) and dispersed in MeOH (20 ml) to form solution A. Zn
(NO3)2⋅6H2O (0.1 g) was dissolved in MeOH (20 ml) to obtain solution
B. Then, the mixture of solutions A and B were stirred for 1 min, and
grown at room temperature for 12 h without stirring. The collected Si@
ZIF-8 particles were washed with EtOH for three times under ultrasonic
treatment and carbonized for 2 h at 700 °C in an Ar-filled tube furnace
with heating rate of 2 °C min−1. µm-sized Si/C composites named Si@
Z-700 were obtained and collected for electrochemical test.
2.5. Material characterization
X-ray diffraction (XRD) patterns were tested by Bruker d8
Diffractometer with Cu target tube. Thermogravimetric analysis (TGA)
were tested on a Netzsch TG 209 F3 Tarsus at a heating rate of 5 °C
min−1 with temperature range from room temperature to 900 °C. SEM
images and EDS mapping were obtained at TESCAN Brno, s.r.o. MIRA3
LMH field-emission scanning electron microscopy (SEM). Nitrogen ad-
sorption-desorption isotherms was carried out on automatic volumetric
adsorption device (Belsorp-max).
2.6. Electrochemical characterization
Electrochemical performances were tested via CR 2032 coin-cells
made in Ar-filled glove box (Mikrouna, China, < 0.1 ppm of O2
and < 0.1 ppm of H2O). The slurry was made with mixture of 90% Si@
Z-1000 (or Si@Z-700) composite and 10% sodium alginate in water.
The obtained slurry was pasted on Cu foil under vacuum drying at
100 °C overnight. The obtained electrodes were cut into a disk with a
diameter of 12 mm. Electrolyte are composed by 1 M LiPF6 in EC:DMC
(1:1, v/v). Galvanostatic charging and discharging cycles were tested
on LAND CT2001A instrument. Cyclic voltammetry (CV) measurements
were tested on electrochemical workstation (CHI660D) (CHI instru-
ment) with voltage range of 0.005–3 V at a scan rate of 0.1 mV s−1. The
electrochemical properties were calculated based on the overall mass of
the Si active material. Long-term cycling was tested at current densities
of 3 A g−1 and 5 A g−1 with voltage range of 0.005–3 V (vs. Li+/Li).
Rate performance was conducted at a current densities sequence of 0.5,
1, 2, 5, 2, 1 and 0.5 A g−1. Electrochemical impedance spectroscopy
(EIS) curves were tested on CHI660D electrochemical workstation with
frequency range of 1 mHz–100 kHz.
3. Results and discussion
3.1. Morphology and structure
As shown in Fig. 1g, the schematic illustration presents the synthesis
process of Si@Z-1000. Si NPs were firstly coated with silica and then
treated with PVP to obtain the PVP-treated Si@SiO2. Due to the co-
ordination effect between PVP and zinc ions, the PVP-treated Si@SiO2
can easily be encapsulated in micron ZIF-8 particles [35]. Fig. 1a–b
indicate that this obtained Si@SiO2@ZIF-8 composite possess an
average particle size of about 2 um. After treated by ultrasonic washing
to remove Si NPs on the surface, Fig. 1c–d exhibit a delicate dodeca-
hedral morphology of the obtained composite. In order to fabricate Si/C
composite with enhanced electrical conductivity and reinforced struc-
tural stability. This Si@SiO2@ZIF-8 composite was firstly carbonized at
700 °C for 2 h to transform the ZIF-8 from crystal state to the ZnO/C
Q. Wei, et al.
Fig. 1. (a, b) SEM images of Si@SiO2@ZIF-8 in fresh style. (c, d) SEM images of Si@SiO2@ZIF-8 composite after ultrasonic cleaning. (e, f) SEM images of Si@Z-1000
composite after calcination at 1000 °C for 2 h. (g) Schematic illustration of the synthesis process of Si@Z-1000.
composite thoroughly, and then calcinated at 1000 °C for 2 h to remove
ZnO by carbon reduction, in which silica layers can protect the Si NPs to
avid the formation of Si/C, and ZnO can generate more mesopores in
carbon reduction process at 1000 °C. After washing by diluted HF,
buffer space can be formed by removing the sacrificial template of si-
lica. Finally, Fig. 1e–f show that the obtained Si@Z-1000 composite
with wrinkled surface still maintains a dodecahedral morphology. In
comparison, Si@Z-700 composite with particle size of about 2 um has a
similar morphology in Fig. S1 after carbonized at 700 °C.
EDS analysis was carried out to provide information of elements
distribution and weight percentage. SEM image of Fig. 2a indicates that
the surface of Si@Z-1000 is wrinkled than that of Si@Z-700 in Fig. S2a,
and the corresponding STEM image of Fig. 2b shows that the Si@Z-
1000 has a looser structure than that of Si@Z-700 in Fig. S2b, which
can be attributed to the removing of silica layers and ZnO. At the same
time, elements of Si, C, N and O in Fig. 2c–f are uniformly distributed in
Si@Z-1000 composite, as well as the elements of Si, C, N, Zn and O in
Si@Z-700 of Fig. S2c–g. Line scan mode of EDS is to distinguish the
component changes from the edge to the center. Due to the low Si
content in the edge of composites, both Si@Z-1000 and Si@Z-700 ex-
hibit a low red Si line and a high black C line in Fig. 2g, S2h. However,
the higher black C line in the center position of Si@Z-1000 indicates
that the Si content is enhanced after removing ZnO and silica. Com-
pared with the element weight percentage of Si@Z-700 in Fig. S2i, ZnO
in micron Si@Z-1000 of Fig. 2h can be thoroughly removed by carbon
reduction, which is better than the method of acid washing.
HRTEM image was adopted to further investigate the internal
structure of Si@Z-1000. After removing ZnO and silica, TEM image of
Fig. 3b corresponded with SEM image of Fig. 3a shows that Si NPs are
uniformity dispersed in ZIF-8 derived NeC skeleton. Fig. 3c–f further
3
Applied Surface Science 511 (2020) 145609
demonstrate that silica template can successfully build cushion space
around Si NPs to form core-shell structure, and all these core-shell units
in the obtained micron Si@Z-1000 composite are tightly connected to
each other. The lattice fringes of 0.31 nm in HRTEM image of Fig. 3e
are matched with the (1 1 1) planes of the crystallized Si. In SAED
pattern of Fig. 3d, diffraction rings of (1 1 1), (2 2 0), and (3 1 1) planes
of Si are correspond to the XRD patterns of Si, indicating the poly-
crystalline nature of Si NPs.
XRD patterns of carbonized Si@Z-1000 and Si@Z-700 are shown in
Fig. 4a. The wide peaks around 25° belongs to the ZIF-8 derived
amorphous carbon [36]. Peaks at 28.4°, 47.3°, 56.1°, 69.1°, 76.4°, and
86.0° accord well with the (1 1 1), (2 2 0), (3 1 1), (4 0 0), (3 3 1), and
(4 2 2) crystal planes in the standard spectrum (JCPDS 27-1402) of
crystalline Si, respectively [37]. In addition, ZnO in Si@Z-1000 can be
absolutely removed by carbon reduction at 1000 °C, leading to no
corresponding peaks in XRD pattern of Si@Z-1000 [31]. Owning to the
protection of silica, there are no XRD peaks of SiC in Si@Z-1000. As
shown in Fig. S3, the XRD pattern of synthesized Si@ZIF-8 can perfectly
match the simulated peaks of ZIF-8, which indicates the existence of
ZIF-8. Raman spectrum of Si@Z-1000 and Si@Z-700 are shown in
Fig. 4b. Peaks at 515 and 950 cm−1 correspond to crystal Si. Two
broaden bands at 1352 cm−1 (D-band) and 1590 cm−1 (G-band) are
derived from the carbonized Si@ZIF-8 composite, in which the similar
value of ID:IG indicates the component of disorder SP2-carbon and CeC
carbon in all samples are similar [38]. Weight loss of Si@Z-1000 and
Si@Z-700 are caused by the decomposition of ZIF-8 at the temperature
range from 400 °C to 600 °C in Fig. 4c. In compared with the 71 wt% Si
content of Si@Z-1000, Si content of Si@Z-700 is less than 64% due to
the existence of small amount of ZnO.
The nitrogen sorption isotherms of Si@Z-1000 and Si@Z-700 were
Q. Wei, et al. Applied Surface Science 511 (2020) 145609

Fig. 2. (a, b) SEM image and STEM image of Si@Z-1000 composite. (c-f) EDS elemental mapping images of Si@Z-1000 composite. (g) The intensity distributions of
elements Si, C, N, and O tested by EDS line scan mode over the diagonal section of Si@Z-1000 composite. (h) Element weight percentage of Si@Z-1000 composite.

Fig. 3. (a, b) SEM image of Si@Z-1000. (b, c) TEM images of Si@Z-1000. (d) SAED pattern of Si. (e, f) HRTEM images of Si@Z-1000.

4
Q. Wei, et al.
Fig. 4. (a) XRD patterns of Si@Z-1000 and Si@Z-700; (b) Raman spectrums of Si@Z-1000 and Si@Z-700; (c) TG date of Si@Z-1000 and Si@Z-700; (d) Nitrogen
adsorption and desorption isotherms of Si@Z-1000.
calculated by Barrett-Joyner- Halenda (BJH) method. Fig. S4 shows
that the specific surface area of the Si@Z-700 composite is 53.8 m2 g−1
and the specific volume is 0.114 cm3 g−1. In contrast, Si@Z-1000 has a
higher specific surface area of 131.62 m2 g−1 with a specific volume of
0.198 cm3 g−1 in Fig. 4d, which can be attributed to the removal of ZnO
after carbon reduction. At the same time, after washing with diluted
HF, the silica layer can be removed to obtain large pores, and used as a
buffer space to buffer the unavoidable volume change [14,39].
The elemental composition and chemical state of Si@Z-1000 com-
posite was studied by XPS analysis. As shown in Fig. 5a, the measured
spectrum of Si@Z-1000 shows the peaks of Si 2p, Si 2s, C 1s, N 1s, and
O 1s, and these peaks match the EDS analysis. The high-resolution Si 2p
XPS spectrum in Fig. 5b is related to the two peaks of SieSi (99.4 eV)
and SieOeSi (103.5 eV). Due to the high activity of nano-silicon na-
noparticles, a small amount of oxide layer was formed on the surface of
Si [40]. Although calcined at 1000 °C for 2 h, the XPS spectrums of Si 2p
has no SieC peak, which is attributed to the protection of the sacrificial
silica layer. The high-resolution C 1s XPS spectrum in Fig. 5c shows four
peaks of CeC (284.4 eV), CeN (285 eV), CeOeC (285.9 eV) and C]O
(287.9 eV) [41]. The high-resolution N 1s XPS spectrum in Fig. 5d show
three peaks of pyridinic nitrogen (N-6) at 398.4 eV, pyrrolic nitrogen
(N-5) at 400.3 eV, and quaternary nitrogen (N-Q) at 402.7 eV. Ac-
cording to previous works, nitrogen doping in carbonaceous materials
can significantly incerase the conductivity of electrode [42].
3.2. Electrochemical LIB performance
The electrochemical properties of Si@Z-1000 and Si@Z-700 com-
posites were analyzed to distinguish the differences caused by the
structure. Fig. 6a–b illustrate the initial three CV curves for Si@Z-1000
and Si@Z-700 composites, and both composites exhibit characteristic
CV curves of Si. Two cathodic peaks at around 0.6 and 1.2 V are ap-
peared in the first cycle, and disappeared in the subsequent cycles,
5
Applied Surface Science 511 (2020) 145609
indicating the decomposition of electrolyte and the formation of SEI
film [43]. During the lithiated process, the cathodic peak at 0.19 V is
related to the formation of LixSi, and finally transformed to the fully
lithiated state of Li15Si4 at 0.1 V [44]. In the delithiated process, two
anodic peaks at 0.38 and 0.5 V belong to the dealloying procedure [45].
As the lithiation/delithiation cycle time increases, the activated Si
changes from the initial crystalline state to an amorphous state, ac-
companying with increased area in CV curves [46]. Except for the
characteristic peak of Si, the CV curves of Si@Z-700 still has the
characteristic peaks of ZnO. Fig. 6b shows two significant peaks at
0.54 V and 0.45 V due to the reaction between ZnO and Li to obtain Zn
and Li2O. Then in the subsequent reaction, Zn and Li-ions were con-
verted into LixZn at voltage around 0.24 V in the following reaction
[47]. Peaks at 0.53 V, 0.68 V and 1.26 V correspond to a series of re-
actions that transform LiZn to Li2Zn3, LiZn2, Li2Zn5 and Zn [48]. Al-
though peaks at similar position are overlapping, main typical peaks of
ZnO and Si in CV curves can be clearly distinguished.
Rate performances of Si@Z-1000 and Si@Z-700 composites were
tested at current densities of 0.5, 1, 2, 5, 2, 1 and 0.5 A g−1 in Fig. 6c.
This micron Si@Z-1000 composite has excellent rate performance with
a high specific capacity of 815 mAh g−1 (based on the weight of Si) at 5
A g−1. When the current density returns to 0.5 A g−1, the specific ca-
pacity of Si@Z-1000 is restored to 1639 mAh g−1. In contrast, Si@Z-
700 has a lower specific capacity of 679 mAh g−1 at 5 A g−1 and 1519
mAh g−1 at 0.5 A g−1, in which the attenuation of specific capacities at
high current density are larger than Si@Z-1000. Thus, the good rate
performance of Si@Z-1000 indicates that the bread-like NeC can con-
duct electrons and can withstand mechanical stress.
Galvanostatic discharge/charge (D/C) curves of Si@Z-1000 and Si@
Z-700 in Fig. 6d show the first two activated cycles at a current density
of 0.2 A g−1. The Si@Z-1000 sample delivers initial reversible D/C
specific capacities of 2990 and 2000 mA h g−1, corresponding to an ICE
of 65.55%. In comparison, the Si@Z-700 composite has an initial D/C
Q. Wei, et al.
Fig. 5. (a) XPS survey spectrum of Si@Z-1000. High-resolution XPS spectrum of (b) Si 2p, (c) C 1s, and (d) N 1s for Si@Z-1000.
reversible specific capacity of 3045 and 2009 mA h g−1, with similar
ICE of 65.9%. All initial discharge curves have a sloping voltage plateau
between 1.5 and 0.25 V, which can be ascribed to the formation of SEI
films [49]. The long plateau around 0.1 V are belonging to the trans-
formation from LixSi to the final phase of Li15Si4 during the lithiated
process [50]. The voltage plateau around 0.5 V is related to the de-
lithiated process, which corresponds to the two anodic peaks in CV
curves. Si@Z-700 has another electrochemical reaction plateau around
1.5 V in charge curves, which can be attributed to the existence of ZnO
[51].
In terms of the structure-induced differences, long-term cycling was
performed at high current densities of 3 and 5 A g−1 to compare the
lithium storage performance of Si@Z-1000 and Si@Z-700 composites.
When the current density increases from 0.2 A g−1 to 3 A g−1, the
specific capacities of the two activated Si@Z-1000 and Si@Z-700
samples were 1215 and 1231 mA h g−1, respectively. After 500 cycles,
the specific capacity of Si@Z-1000 anode maintains at 1109 mA h g−1,
and the attenuation rate was 0.017%, which is better than the specific
capacity of 792 mA h g−1 with a attenuation rate of 0.071% in the Si@
Z-700 anode. As a key parameter for LIBs, the coulombic efficiency (CE)
of Si@Z-1000 in Fig. 6e tend to be stable within 10 cycles and is higher
than 99.5% in the subsequent long-cycling. Thus, the high specific ca-
pacity and low capacity decay rate of the Si@Z-1000 anode can be
attributed to the buffer space in core-shell structure and high con-
ductive route in N-C skeleton derived from ZIF-8. To further highlight
the advantages of Si@Z-1000, two anodes were tested at a higher
current density of 5 A g−1 in Fig. 6f. In contrast to the initial specific
capacity of 607 mA h g−1 at 5 A g−1 of the activated Si@Z-700 anode,
the activated Si@Z-1000 anode still delivers an initial higher specific
capacity of 860 mA h g−1. When 500 cycles are completed under a
constant current of 5 A g−1, Si@Z-1000 keeps a specific capacity of
804 mA h g−1 with a decay rate of 0.013%, and Si@Z-700 maintains a
specific capacity of 316 mA h g−1 with an attenuation rate of 0.095%.
Meanwhile, the Si@Z-1000 anode still retains high CE around 99.5%
6
Applied Surface Science 511 (2020) 145609
during long-term cycling. Therefore, with the stable clustered core-shell
Si/C units and a high conductive ZIF-8 derived N-C, this micron Si@Z-
1000 anode can greatly improve the structural stability and electronic
conductivity for electrode during cycling. This Si@Z-1000 composite
has higher Si loading and superior electrochemical performance than
the recently reported micron-sized silicon-based materials in Table S1.
As shown in Fig. 7, In order to explain the reason of superior cycling
performance of Si@Z-1000, the electrochemical impedance spectro-
scopy (EIS) analysis was tested in fresh state, after 3 cycles and after
300 cycles. Compared with the composition of one semicircle and a
straight-line in impedance spectra in the fresh state, both the two
electrodes at the 3rd and 300th cycles have two semicircles at the high
frequency region and a straight-line portion in the range from medium-
to-low frequency, which can be attributed to the formation of SEI film
[52,53]. Insert images of these corresponding equivalent circuits in
Fig. 7a, c, and e are taken to evaluate the experiments date and provide
EIS parameters. The impedance parameters in Table 1 contain the
transportation resistance of Li ion in electrolyte (Re), the resistance of Li
ion shuttling through the SEI film (Rf), surface film capacitance (CPE1),
charge transfer capacitance (CPE2), charge transfer resistance (Rct) and
the diffusion process of Li ions in low frequency range corresponding to
the Warburg impedance (W) [54]. According to the Table 1, the two
Si@Z-1000 and Si@Z-700 anodes have a similar Re. Owning to ex-
istence of non-conducting ZnO in the ZIF-8 derived N-C skeleton, the Rct
of the Si@Z-700 anode is 71.6 Ω, which is higher than that of 45.41 Ω
of Si@Z-1000. After three activated cycles at small current density of
0.2 A g−1, the transformation from crystalline Si to amorphous Si can
reduce the Rct, thereby increasing the electrical conductivity for elec-
tron. At the same time, these emerging Rf with similar value are at-
tributed to the formation of SEI on the surface of the two anodes after 3
cycles. Due to the cushion space of clustered core-shell units in ZIF-8
derived N-C skeleton, values of Rf and Rct in the Si@Z-1000 anode are
lower than the corresponding one of the Si@Z-700 anode after 300
cycles. Thus, this stable micron structure Si@Z-1000 with higher
Q. Wei, et al.
Fig. 6. CV curves of (a) Si@Z-1000 and (b) Si@Z-700. (c) Rate performance of Si@Z-1000 and Si@Z-700 composites. (d) Charge-discharge profiles of Si@Z-1000 and
Si@Z-700 composites. (e–f) Cycle performance of Si@Z-1000 and Si@Z-700 at (e) 3 A g−1 and (f) 5 A g−1 (the first three cycles were performed at 0.2 A g−1).
electron conductivity can buffer the unavoidable volumetric variation
to reduce the redundant formation of SEI.
As shown in Fig. 7b, d, and f, the diffusion process of Li ions can be
analyzed by data group containing 11 data points in low frequency to
re-plotted a Z’/ω−1/2 plots. Based on the equations of (1) and (2),
structure-induced values of DLi between Si@Z-1000 and Si@Z-700 can
be calculated by the Warburg factor (σ) obtained from the slopes of the
fitting lines based on the date group.
Z′ = R e + R ct + σω−1/2 (1)
and
DLi = (R2T 2)/(2A2n4F 4C2σ 2) (2)
where ω, R, T, A, n, F and C are the angular frequency, gas constant,
absolute temperature, electrode area, number of transferred electrons,
Faraday constant and the concentration of Li-ions, respectively [52,55].
After finishing the activated process, the lower value of σ in the two
anodes indicate the formation of amorphous Si transformed from
crystalline Si, which make the diffusion of Li ions more feasible. Thanks
to stable structure with buffer space, the growing extent of σ in Si@Z-
1000 is lower than that of the Si@Z-700 anode during the long-term
cycling, which indicates the less formation of redundant SEI.
Based on the investigation of the structure-activity relationship in
the lithiated/delithiated cycling, Fig. 8 shows cross-section SEM images
of the two samples in fresh style and after 300 cycles. In Fig. 8a and c,
7
Applied Surface Science 511 (2020) 145609
both the two anodes of Si@Z-1000 and Si@Z-700 have a similar mor-
phology and thickness in fresh style, which is formed by stacking the
micron dodecahedral particles of Si@Z-1000 or Si@Z-700 layer by
layer. As shown in Fig. 8a and b, the thickness of the Si@Z-1000 anode
increases from 45 to 52um after 300 lithiated/delithiated cycles. In
contrast, the anode of Si@Z-700 has an initial thickness of 42 um in
Fig. 8c, and the increased thickness of 66 um in Fig. 8d are obtained
after 300 lithiated/delithiated cycles. Although the lithiation of (1 1 0)
surface in crystalline silicon is favorable than (1 0 0) and (1 1 1) sur-
faces, the theoretical specific capacity of Si with high anisotropic li-
thiation is still higher than that of silicon oxycarbide, which making it
ideal material for next-generation lithium-ion batteries [56,57]. In ad-
dition, carbon layer can short the nearest neighbor distance of Si-Li to
limit the volume change of silicon in lithiated/delithiated process and
improve the electronic conductivity to get good rate capability [58].
Based on the above analysis, we choose the crystalline silicon as the
main contribution of Li capacity to obtain a high theoretical specific
capacity, and use carbon layer derived from ZIF-8 to enhance the
conductivity of silicon. Buffer space formed by sacrificial template of
silica in the Si@Z-1000 composite can cushion the unwanted volu-
metric variation to maintain the stability of electrode and reduce the
formation of redundant SEI. Therefore, the bread-like silicon/carbon
composite are stable and exhibit good electrochemical performance
during long-term cycling.
Q. Wei, et al. Applied Surface Science 511 (2020) 145609

Fig. 7. Nyquist plots of the Si@Z-1000 and Si@Z-700 electrodes measured (a) before cycling, (c) after 3 cycles and (e) after 300 cycles. Relationship between Z’ and
ω−1/2 of the Si@Z-1000 and Si@Z-700 electrodes at the low-frequency region (b) before cycling, (d) after 3 cycles and (f) after 300 cycles.

Table 1 the stress caused by volume expansion to maintain the stability of

Impedance parameters of Si@Z-1000 and Si@Z-700 electrodes. electrode. Meanwhile, the ZIF-8 derived N-C skeleton woven with the
Samples Re(Ω) Rf(Ω) Rct(Ω) W(Ω S-1/ CPE1(F) CPE2(F) Chi-Sqr connected core-shell units supply a stable pathway for electron. Micro
2
) structure with reduced external surface area can significantly reduce
the formation of SEI film on the surface of Si/C composite. The reaction
Before cycling between zinc oxide and carbon at high temperature can completely
Si@Z-1000 4.62 45.41 0.444 1.28E-05 7.2E-04
Si@Z-700 4.75 71.6 0.442 1.86E-05 2.9E-04
remove zinc oxide and consume a part of carbon to improve the mass
ratio of Si, in which the generated mesopores can promote the pene-
After 3th cycle
tration of lithium ions. Thus, this micron Si@Z-1000 composite con-
Si@Z-1000 2.23 69.3 24.89 0.31 1.58E-07 0.0029 2.12E-05
Si@Z-700 2.51 77.9 60.15 0.5 2.13E-11 0.0018 9.41E-13 tains high Si content of 71 wt% and presents good specific capacities of
1155 mAh g−1 at 2 A g−1 and 815 mAh g−1 at 5 A g−1 in rate per-
After 300th cycle
Si@Z-1000 5.43 72.59 66.26 0.255 2.2E-05 0.0011 2.7E-06 formance. After long-term cycling of 500 cycles, the composite still
Si@Z-700 4.32 108.6 77.38 0.5 3.7E-05 0.0015 1.1E-12 maintains specific capacities of 1109 mAh g−1 at 3 A g−1 and 804 mAh
g−1 at 5 A g−1 with ICE of 65.55% in the first three activated cycles.
These superior electrochemical performances are better than the re-
4. Conclusions cently reported micron-sized silicon-based materials and provide a new
perspective of using MOFs for Si-based anodes.
In summary, we successfully fabricate a micron bread-like Si@Z-
1000 composite with clustered core-shell Si/C units distributed in the
ZIF-8 derived N-C skeleton. Buffer space in core-shell units can cushion

8
Q. Wei, et al.
Fig. 8. Cross-section SEM images of Si@Z-1000 (a) in fresh style and (b) after 300 cycles. Cross-section SEM images of Si@Z-700 (c) in fresh style and (d) after 300
cycles.
CRediT authorship contribution statement
Qin Wei: Conceptualization, Methodology, Software, Writing -
original draft. Yu-Mei Chen: Data curation. Xu-Jia Hong:
Visualization, Investigation. Chun-Lei Song: Visualization,
Investigation. Yan Yang: Visualization, Investigation. Li-Ping Si:
Supervision, Writing - review & editing, Software, Validation. Min
Zhang: Supervision, Writing - review & editing, Software, Validation.
Yue-Peng Cai: Supervision, Writing - review & editing, Software,
Validation.
Declaration of Competing Interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influ-
ence the work reported in this paper.
Acknowledgement
The authors are grateful for financial aid from the National Natural
Science Foundation of P. R. China (Grant No. 21471061 and
21671071), special funds for scientific and technological innovation
cultivation of undergraduate in Guangdong (special funds for “climbing
plan”) key project (No. pdjha0128), Scientific Research Foundation of
Graduate School of South China Normal University (Grant No.
2017LKXM006), Science and Technology Planning Project of
Guangdong Province, Guangzhou, China (No. 2015B010135009,
2017B090917002 and 2019A050510038), The cultivation foundation
of South China Normal University for young teachers (No. 17KJ07).
Innovation team project of Guangdong Ordinary University (No.
2015KCXTD005), the great scientific research project of Guangdong
Ordinary University (No. 2016KZDXM023).
Appendix A. Supplementary material
Supplementary data to this article can be found online at https://
doi.org/10.1016/j.apsusc.2020.145609.
9
Applied Surface Science 511 (2020) 145609
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