Electrochimica Acta 317 (2019) 583e593

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Electrochimica Acta
journal homepage: www.elsevier.com/locate/electacta

Novel honeycomb silicon wrapped in reduced graphene oxide/CNT

system as high-stability anodes for lithium-ion batteries
Qin Wei a, Gui-Cheng Liu a, Chi Zhang c, Xu-Jia Hong a, Chun-Lei Song a, Yan Yang a,
Min Zhang b, Wei Huang a, Yue-Peng Cai a, b, *
a
School of Chemistry and Environment, Guangzhou Key Laboratory of Materials for Energy Conversion and Storage, Guangdong Provincial Engineering
Technology Research Center for Materials for Energy Conversion and Storage, and Theoretical Chemistry of Environment, Ministry of Education, South China
Normal University, Guangzhou, 510006, PR China
b
School of Materials Science and Energy Engineering, Foshan University, 528000, PR China
c
Nanjing Institute of Environmental Sciences of the Ministry of Environmental Protection of China, Jiangsu, Nanjing 210042, PR China

a r t i c l e i n f o a b s t r a c t

Article history: Silicon (Si) has been regarded as one of the next-generation anode materials due to its ultrahigh theo-
Received 20 April 2019 retical capacity, low equilibrium potential, abundant resources and superior safety performance. Herein,
Received in revised form we fabricated a novel honeycomb Si composed of many Si nanoparticles (NPs), which can be refined from
5 June 2019
the urchin-like crude product obtained through the magnesiothermic reduction process. Via the elec-
Accepted 5 June 2019
trostatic attraction, rapid freeze-drying process and further thermal treatment, the honeycomb Si can be
Available online 6 June 2019
tightly encapsulated in a thin layer composed of reduced graphene oxide and carbon nanotube (indi-
cating as Si-rGO/CNT) to avoid direct exposure to the electrolyte. Si NPs with the wrinkled rGO/CNT
Keywords:
Honeycomb silicon
wrapping layer containing mesopores can not only shorten the pathway of Liþ ions and electrons but also
Magnesiothermic reduction accommodate the unavoidable expansion/contraction and buffer the excessive stress. Meanwhile, the
Graphene oxide/carbon nanotube CNT intertwined throughout the electrode can effectively repair those areas that lost conductivity during
Self-standing anode long-term cycling. Therefore, the self-supported Si-rGO/CNT electrode having a high Si content of 76 wt%
Lithium ion battery exhibits capacities of 1304 mAh g1 at 2 A g1 and 1053 mAh g1 at 5 A g1 in rate performance, and
maintain a capacities of 1899 mAh g1 at 0.5 A g1 after 250 cycles and 1003 mAh g1 at 4 A g1 after
1000 cycles accompanying with a stable coulombic efficiency (CE) up to 99.5%.
© 2019 Published by Elsevier Ltd.

1. Introduction big volume change (~360%) during the lithiation/delithiation pro-

cesses, Si-based anode materials are known to suffer from the
Accompanying the ever-growing demands of energy storage pulverization of electrodes, losing interparticle electrical contact
equipment, rapid charge/discharge ability and high stability of the and regenerated solid electrolyte interphase (SEI) on the crack
lithium-ion batteries (LIBs) have become the key standard [1,2]. In surfaces, which results in a low actual capacity and hinders their
comparison with the theoretical capacity (372 mAhg1) of com- practical application [6e8].
mercial graphite anode in LIBs, Silicon (Si) has been regarded as one Thus, alleviating volume effect and improving the conductivity
of the next-generation anode materials due to its specific charac- of Si materials are crucial to the development of Si-based anodes for
teristics, including ultrahigh theoretical capacity of 4200 mAh g1, LIBs. One effective strategy is primarily designed to decrease the
low equilibrium potential (~0.3 V versus Li/Liþ), abundant re- size to nanoscale. The representative nanostructures, including
sources, and superior safety performance [3e5]. However, owing to nanoparticles [9e11], hollow nanoparticles [12,13], nanowires
[14,15], nanoporous [16e18], and nanotubes [19e21], can relieve
the mechanical stress caused by volumetric change and facilitate
* Corresponding author. School of Chemistry and Environment, Guangzhou Key the diffusion of Liþ ion along surface of Si NPs. Manufacturing
Laboratory of Materials for Energy Conversion and Storage, Guangdong Provincial processes, such as chemical vapor deposition [19,22], magnetron
Engineering Technology Research Center for Materials for Energy Conversion and
co-sputtering [23], and plasma deposition [24], are often used to
Storage, and Theoretical Chemistry of Environment, Ministry of Education, South
China Normal University, Guangzhou, 510006, PR China.
produce diverse and complex structures. In comparison with those
E-mail address: caiyp@scnu.edu.cn (Y.-P. Cai). above methods, magnesiothermic reduction reaction (MRR)

https://doi.org/10.1016/j.electacta.2019.06.024
0013-4686/© 2019 Published by Elsevier Ltd.
584 Q. Wei et al. / Electrochimica Acta 317 (2019) 583e593

method offers a relatively feasible and low-cost way for the con- 1003 mAh g1 at 4 A g1 after 1000 cycles.
version from SiO2 to Si [25]. For instance, Zuo et al. reported a three-
dimensional (3D) hierarchical macro-/mesoporous Si, which 2. Experimental
showed a superior cycling with a reversible capacity of
632 mAh g1 at the large current density of 2 A g1 after 300 cycles 2.1. Materials
[26]. Ren et al. obtained Si with homogeneous mesoporous struc-
ture through the zinc assisted MRR method, which delivers high All chemicals were used without purification. Ethanol (EtOH,
reversible capacity and good cycling stability [27]. Wang et al. 99.5%), magnesium (Mg, 100200 mesh, 99%), ammonium hy-
converted zeolite SSZ-13 template to the mesoporous Si microcube droxide (NH3$H2O, 25e28%), hydrochloric acid (HCl, 36.0e38.0%),
(CM-Si) through the MRR method and demonstrated a capacity Polydiallyldimethylammonium chloride (PDDA, 99.5%), Tet-
retention of 77.6% after 200 cycles [28]. Among those diversified raethyl orthosilicate (TEOS, 96%), Conductive carbon black (Super
structures of Si, porous structure made by MRR method can pref- P, 99%), and hydrofluoric acid (HF, 40%) were purchased from
erably buffer the inherent defects of volume expansion and shorten Hua Xin Co., Ltd.
the pathway of Liþ ion. Furthermore, in order to enhance the
conductivity, Si can be wrapped by carbon layer to form Si-carbon 2.2. Synthesis of SiO2 sphere
(Si/C) composites, such as Si-hollow carbon [29e31], Si-graphene
[32e34], Si-mesoporous carbon [35e37], and Si-carbon nano- The SiO2 sphere was synthesized by a modified Sto € ber process
tubes [38], which can significantly enhance the conductivity of the [47]. Firstly, deionized water (50 mL), NH3$H2O (18 mL) and ethanol
electrode. Among these carbon materials, graphene has been (32 mL) were mixed at room temperature to form solution A. Then,
widely used because of its high electronic conductivity, good me- TEOS (9 mL) and ethanol (90 mL) were stirred to get solution B.
chanical strength, big Liþ diffusion efficiency (108 cm2s1), as well Finally, solution B was added into solution A with vigorous stirring
as high thermal stability. For example, Bao and co-workers for 12 h at room temperature. The products were collected by
encapsulated Si microparticles (1e3 mm) using conformally syn- centrifugation and washed with ethanol for four times, followed by
thesized cages of multilayered graphene to achieve the graphene- drying at 80  C for 24 h.
caged Si microparticles and showed a 90% capacity retention after
100 cycles [39]. Nie et al. grow graphene cages onto the composite 2.3. Synthesis of honeycomb Si
particles of magnesium oxide and silicon for the formation of
hollow graphene-encapsulated Si particles, which displayed high In a stainless-steel reactor, the upper layer of the as-prepared
specific capacity and remarkable rate capability of 890 mAh g1 at SiO2 powder (0.3 g) and the lower layer of Mg power (0.36) were
5 A g1 [40]. Shan et al. use graphene oxide (GO) as a new “dual- put together (Fig. S1) and then heated in a tube furnace at 800  C
role” binder to synthesis the GO/Si-NPs electrode, exhibiting a for 12 h with the heating rate of 5  C min1 in Ar atmosphere
better specific capacity of 2400 mAh g1 at the 50th cycle and [48,49]. After finishing the MRR process, the collected brown
2000 mAh g1 at the 100th cycle [41]. Nevertheless, several obsta- powder was soaked in dilute HCl solution to remove the byproducts
cles still exist in the utilization of GO. Firstly, the capacity decay of of MgO and Mg2Si. Thereby, the acquired yellow powder was
Si/G composites still exists due to the exposed Si direct contact with collected by centrifugation and washed with three times with
the electrolyte under the condition of incomplete encapsulation of ethanol, then treated with diluted hydrofluoric acid (HF) solution
Si in two-dimensional carbon material during lithiation/delithia- for 0.5 h to remove the unreacted SiO2. Finally, pure porous Si
tion process [42,43]. Secondly, excessive accumulation of graphene having a honeycomb structure was collected after the ethanol
and uneven distribution of Si always lengthen the transfer distance washing and drying treatment.
of electrons and hamper the diffusion of Liþ ion, leading to a poor
rate performance of Si/G anode [44e46]. Thereby, choosing a sec- 2.4. Preparation of self-supported electrode of Si-rGO and Si-rGO/
ond carbon material to combine with the Si/G system could be a CNT
promising way to fabricate a more stable Si/C composite, bring
about long cycle life and good rate performance for LIBs. The electrostatic coating and freeze-drying process can uni-
Inspired by previous work, we fabricated a honeycomb silicon formly and tightly enclose graphene oxide on the rugged surface of
and encapsulated it in the reduced graphene oxide (rGO) layer, honeycomb Si [46,50]. Firstly, graphene oxide (20 mg) and CNT
where the carbon nanotube (CNT) penetrated and wrapped (5 mg) were dispersed by ultrasonic method in deionized water
throughout the composite. Firstly, the pristine SiO2 sphere were (200 mL) for 1 h to obtain dispersion and then centrifuged at
converted into a novel urchin-like crude product by MRR process. 4000 rpm to remove unpeeled graphene oxide, obtaining the GO/
After removing the byproducts of Mg2Si, MgO and unreacted SiO2, a CNT suspension. Secondly, the synthesized porous Si (100 mg) and
graceful honeycomb Si composed of many Si NPs can be obtained PDDA solution (40 wt%, 2 mL) were mixed in deionized water
(Fig. 1i). Secondly, in virtue of the electrostatic attraction, rapid (150 mL) by sonication at room temperature for 20 min to obtain Si-
freeze-drying process and further thermal treatment, the undu- PDDA suspension. Thirdly, the obtained GO/CNT suspension and Si-
lating surface of Si can be tightly encapsulated in a thin reduced PDDA turbid liquid were transferred into the polyethylene plastic
graphene oxide/carbon nanotube (indicated as rGO/CNT) layer to pipe and heated to 90  C for 5 min to obtain Si-GO/CNT composite.
avoid direct exposure to the electrolyte and simultaneously help to Fourthly, the remaining PDDA around Si-GO/CNT was removed by a
the infiltration of electrolyte. Thirdly, both the wrinkled rGO/CNT repeat centrifugation (10000 rpm), and the heated polyethylene
layer and the numerous buffer space in honeycomb Si can syner- plastic tube was then quickly placed in the liquid nitrogen. The
gistically alleviate excessive stress of volume change. Meanwhile, turbid liquid was lyophilized in a freezedryer for 24 h and then the
CNT in rGO/CNT can repair those areas that lost conductivity during mixture was calcined in a tube furnace at 700  C for 2 h with the
long cycling, which ensures and enhances the conductivity of the heating rate of 2  C min1 under Ar atmosphere to obtain the Si-
entire electrode. Therefore, the Si-rGO/CNT self-standing electrode rGO/CNT composite. The obtained composite was distributed in
containing 76 wt% of honeycomb Si exhibits a good rate perfor- ethanol to prepare a self-supported Si-rGO/CNT electrode by
mance, a stable coulombic efficiency up to 99.5%, and a reversible filtration method and the as-made electrode was dried in a vacuum
specific capacity of 1899 mAh g1 at 0.5 A g1 after 250 cycles and chamber at 60  C for 1 h. The self-supported Si-rGO electrode was
 Q. Wei et al. / Electrochimica Acta 317 (2019) 583e593 585

Fig. 1. SEM images of (aeb) pristine SiO2 and (ced) urchin-like crude product containing Si after MRR processes; (eef) Honeycomb Si composed of numerous Si NPs after removing
byproducts; (g) TEM and (h) HRTEM (the inset in Fig. 1h shows the corresponding SAED pattern) images of the honeycomb Si; (i) Schematic illustration of the synthesis process for
the honeycomb Si; (j) XRD patterns of the rough product after MRR process.

synthesized with the same process except for the addition of car- instrument.
bon nanotube.
2.6. Electrochemical measurements
2.5. Material characterization
The round self-supported electrodes of Si-rGO and Si-rGO/CNT
The X-ray powder diffraction patterns were measured on a with a diameter of 1 cm along with a thickness of 8 mm were
Bruker D8 Advance diffractometer at 40 mA and 40 kV with a directly used as an anode for LIBs. The area loading of Si in Si-rGO/
graphite monochromator and a Cu target tube. Thermogravimetric CNT and Si-rGO are 1.1 mg cm2 and 1.19 mg cm2, respectively.
analyses (TGA) were carried out on a Netzsch TG 209 F3 Tarsus from Honeycomb Si electrode was prepared in a typical procedure. The
room temperature to 900  C with a heating rate of 5  C min1 under mixture of 70 wt% the synthesized Si, 10 wt% super P and 20 wt%
air atmosphere. The nitrogen physisorption was played on auto- sodium alginate binder was dispersed in deionized water to form a
matic volumetric adsorption equipment (Belsorp-max); the surface slurry, and then the slurry was coated on a copper current collector
area analysis was based on Brunauer-Emmett-Teller (BET) theory. and dried at 50  C for 24 h by vacuum drying method, in which the
The EDS mapping and SEM morphology were investigated using area loading of Si is 1 mg cm2. As a comparison, commercial bulk
TESCAN Brno, s.r.o. MAIA3 LMH field-emission scanning electron Si electrode was made in the same way. The CR2032 type coin cells
microscopy (SEM) with an Oxford Instruments Nano Analysis INCA were assembled in an argon-filled glove box (Mikrouna, China)
Energy 150 X-ACT energy dispersive spectrometer (EDS). Galva- (<0.1 ppm of H2O and <0.1 ppm of O2) using the lithium foil as the
nostatic charge discharge cycles were taken with a LAND CT2001A counter electrode. Cyclic voltammetry (CV) measurements were
586 Q. Wei et al. / Electrochimica Acta 317 (2019) 583e593

recorded on a CHI660D electrochemical workstation (CHI instru- Fig. 2c are scanned from room temperature to 900  C in an air at-
ment) at a scan rate of 0.1 mV s1 in the voltage range of mosphere. The weight loss ranging from 400 to 600  C can be
0.005e3.0 V. The electrochemical impedance spectroscopy (EIS) ascribed to the oxidation and combustion of carbon and the Si
was tested on CHI660D electrochemical workstation in the fre- content for Si-rGO and Si-rGO/CNT composites are 83.5% and 76%,
quency range from 0.01 Hz to 1  106 Hz. The cycle performance respectively. The N2 adsorption curve of the Si-rGO/CNT composite
test was carried out at a current density of 0.5 A g1 and 4 A g1. The in Fig. 2d displays a typical type III adsorption/desorption isotherm,
rate performance was measured at a series of current densities in a indicating the existence of a mesoporous structure [58]. The BET
sequence of 0.2, 0.5, 1.0, 2.0, 5.0, 1, and 0.5 A g1. surface area of the micron honeycomb-like Si is 50.30 m2 g1 in
Fig. S2, while the distribution of the corresponding pore size
3. Results and discussion worked out by the Barrett-Joyner-Halenda (BJH) method falls
mainly on 6.6 nm and 23 nm, exhibiting the existence of meso-
The synthesis process of honeycomb Si is presented in Fig. 1i. pores. After combined with the rGO or rGO/CNTs, the BET surface
Firstly, pristine SiO2 spheres were converted into a novel urchin- areas of Si-rGO in Fig. S3 and Si-rGO/CNT in Fig. 2d are increased to
like rough product containing Si by MRR process. After removing 64.83 m2 g1 and 93.92 m2 g1, respectively. The self-supported Si-
the byproducts of Mg2Si, MgO and unreacted SiO2, a graceful rGO/CNT electrode was further investigated by X-ray photoelectron
honeycomb Si composed of many Si NPs can be obtained. Fig. 1aeb spectroscopy (XPS) in Fig. S10. The survey spectrum in Fig. S10a
shows that the mono-disperse SiO2 spheres synthesized by the indicates that the self-supported Si-rGO/CNT electrode is
Sto€ber method have a smooth surface with a diameter of 200 nm. In composed of Si, C and O. The high-resolution XPS spectra of Si2p in
classical MRR reaction of using silica to synthesize Si, several re- Fig. S10b shows that there are three peaks located at 99.08 eV (Si
actions occur simultaneously, leading to complex byproducts and 2p3/2), 99.8 eV (Si 2p1/2) and 103.4 eV (SieO). The existence of SiOx
difficult separation processes [48,51]. Therefore, the compartment in Si-rGO/CNT is mainly attributed to the high activity of honey-
in the stainless-steel reactor of Fig. S1 is designed to avoid the direct comb Si, resulting in the formation of a small amount of oxide on
contact of SiO2 with Mg to reduce the possible side reaction. In the the surface.
reduction process using magnesium vapor, Si is formed via the After the electrostatic coating and freeze-drying processes, SEM
redox reaction between SiO2 and Mg, and the XRD analysis in Fig. 1j images of Fig. 3aeb indicates that two samples of Si-rGO and Si-
further confirmed the presence of crystalline Si and impurities of rGO/CNT are well coated by rGO and rGO/CNTs, respectively. At
MgO and Mg2Si. The reactions can be summarized as follows the same time, the honeycomb structure of Si can be clearly seen
equation (1) under a thin rGO or rGO/CNTs layer. To further study the two
samples, the TEM image shows more details inside the sample. In
SiO2(s) þ 2 Mg(g) ¼ 2MgO(s) þ Si(s) DH ¼ 546.42 kJ mol1 (1) Fig. 3ced, numerous Si NPs having a particles size of about 20 nm
are distributed under the rGO layer in these two samples. Mean-
If the amount Mg is more, the following reaction (2) will occur while, the Si-rGO/CNT sample is combined with the second carbon
simultaneously. material of CNT to enhance the performance of the electrode. In the
TEM images of Fig. 3eef, rGO can tightly wrap Si NPs in the two
Si(s) þ 2 Mg(g) ¼ Mg2Si(s) DH ¼ 318.91 kJ mol1 (2) samples, and CNT in Si-rGO/CNT can also intimately imbed between
rGO and Si. HRTEM images combined with SAED pattern (inset) in
The Mg2Si in the obtained urchin-like coarse product (Fig. 1ced) Fig. 3geh indicates that the lattice fringes of 0.31 nm match the
is essential for the formation of the granular surface of Si and the (111) planes of the crystallized Si. Diffraction rings of (111), (220),
unreacted SiO2 is a template for constructing macropores with an and (311) planes of Si in Si-rGO/CNT electrode correspond to the
inner diameter of about 200 nm. After removal of these byproducts, XRD patterns of honeycomb Si, indicating the polycrystalline na-
the honeycomb Si composed of many Si NPs on the surface can be ture of Si NPs.
seen in Fig. 1eef. TEM of Fig. 1g further exhibits the existence of Si The self-supported Si-rGO/CNT electrode in Fig. 4a has a thick-
NPs on the surface of honeycomb Si. Moreover, HRTEM in Fig. 1h ness of 8 mm and Si can be well wrapped by the rGO/CNT conductive
displays distinct crystal lattice fringes of crystalline Si, and the layer of Fig. 4b, exhibiting good flexibility and favorable toughness
0.31 nm interlayer spacing is an index of (111) plane of Si. in Fig. 4c. The obvious wrinkles on the surface of the self-supported
SiO2 spheres with particle-size of 200 nm were fabricated by a Si-rGO/CNT electrode in Fig. S4 can provide extra buffer space for
modified Sto € ber process. As showed in Fig. 2a, the X-ray diffraction volume expansion of Si, and the intertwined CNT can serve to form
(XRD) patterns of the obtained amorphous SiO2 powder exhibits a a 3D conductive network [43]. In comparison with Si-rGO in Fig. 4d,
weak and broad diffraction peak at 23 . According to the cubic a crack with a width of 2 mm in the self-supported Si-rGO/CNT
phase of Si (JCPDS 27e1402), the XRD peaks at 28.4 , 47.3 , 56.1, electrode can be connected by CNT in Fig. 4f, which confirms that
69.1, 76.4 , and 86.0 are well matched with the (111), (220), (311), CNT can ensure stability and conductivity during cycling. EDS
(400), (331), and (422) planes after removing the byproducts of mapping images of Si-rGO in Fig. 4e and Si-rGO/CNT in Fig. 4g
unreacted SiO2, Mg2Si and MgO, confirming the purity of the as- clearly demonstrate that Si is uniformly distributed under the self-
synthesized honeycomb-like Si powder. In comparison with the supported conductive layer of rGO and rGO/CNT, where yellow
bare Si, the weak broad peak around 23 in the two samples of Si- represents the distribution of Si and red represents the distribution
rGO and Si-rGO/CNT is associated with the existence of reduced of carbon.
graphene and CNT [52e54]. Fig. 2b shows the Raman spectra of The electrochemical performance of the above three samples
honeycomb Si, Si-rGO and Si-rGO/CNT composites and the peak at was studied in 2032-type coin half-cell. Fig. 5a shows the CV curves
519 cm1 of crystallized Si represents the pure honeycomb Si of the first 3 cycles of the self-supported Si-rGO/CNT electrode. In
existed in Si/C composites [55]. Moreover, Raman peaks at 1355 and the initial discharge cycle, a broad reduction peak at around 0.7 V
1597 cm1 are corresponding to the D band (the disorder degree) indicates the formation of SEI layers, which disappears in following
and the G band (the graphitic degree), respectively [56,57]. The cycles [59]. Two reductive peaks at 0.02 and 0.19 V are attributed to
similar ID/IG value for the electrode of Si-rGO and Si-rGO/CNT im- the lithiation process of Si and two oxidative peaks at 0.32 and
plies that those two samples have a similar degree of graphitization 0.53 V are ascribed to the delithiation process [60]. Moreover, since
after thermal treatment. The TGA curves of these three samples in the crystallized Si is converted to amorphous Si, the self-supported
 Q. Wei et al. / Electrochimica Acta 317 (2019) 583e593 587

Fig. 2. (a) The XRD patterns of SiO2, honeycomb-like Si, Si-rGO and Si-rGO/CNT; (b) The Ramam spectrums and (c) the TG curves of honeycomb-like Si, Si-rGO and Si-rGO/CNT; (d)
The N2 adsorption and desorption isotherms of Si-rGO/CNT.

Si-rGO/CNT electrode can be gradually activated in the first 3 cycles, charge capacity of 1645 mAh g1 are matched with the initial
accompanying with an increasing current in CV curves [29]. coulombic efficiency (CE) of 79% of the self-supported Si-rGO/CNT
The rate performance of these three electrodes at different electrode in Fig. 5e.
current densities is exhibited in Fig. 5b. The self-supported Si-rGO/ The cycling performances of the honeycomb Si, Si-rGO and Si-
CNT electrode has reversible capacity of 2529, 1871, 1620, 1304 and rGO/CNT electrodes at a current density of 0.5 A g1 are presented
1053 mAh g1 in different current densities of 0.2, 0.5, 1, 2, and in Fig. 5d. The specific capacity of commercial bulk Si in Fig. S6
5 A g1, respectively. Under the same test conditions, the self- decay rapidly due to the large volume change, poor conductivity
standing Si-rGO electrode displays 2089, 1414, 1049, 684, and and redundant SEI layer. Compared with bulk Si, the specific ca-
450 mAh g1, respectively. Furthermore, the electrode of honey- pacity of honeycomb Si maintains a value of 569 mAhg1 at
comb Si exhibits relatively poor rate performance with specific 0.5 A g1 after 250 cycles, indicating that the honeycomb Si can
capacities of only 1591, 1137, 780, 546, and 393 mAh g1, respec- effectively buffer volume expansion than micron silicon [62]. In
tively. When the current density switches back from 5 to 0.5 A g1, order to enhance the conductivity of Si, honeycomb Si was
the discharge capacity of the self-supported Si-rGO/CNT electrode encapsulated in a thin GO layer to avoid the direct contact with
can restore to 1750 mAh g1, while the electrodes of honeycomb Si electrolyte. After the thermal reduction process, the self-supported
and self-supported Si-rGO only reach a specific capacity of Si-rGO electrode can maintain a specific capacity of 1443 mAh g1
1219 mAh g1 and 1432 mAh g1, respectively. Compared to the after 250 cycles at 0.5 A g1. When the second carbon of CNT
rate performance of commercial bulk micron silicon in Fig. S5, this intertwined throughout the thin rGO layer, the obtained self-
honeycomb Si can significantly enhance the rate performance, supported Si-rGO/CNT electrode demonstrates a very high spe-
owing to the existence of numerous Si NPs and abundant buffer cific capacity of 1899 mAh g1 under the same test conditions,
space in the honeycomb-like structure. which means that CNTs as the second carbon material can not only
Galvanostatic discharge/charge curves of the self-supported Si- boost the conductivity but also reinforce the integrity of electrode,
rGO/CNT electrode in Fig. 5c shows the 10th, 200th, and 1000th which is beneficial to retain the stability of SEI film.
cycles at a current density of 4 A g1 with voltage ranging from In order to further investigate the electrochemical performance
0.005 to 3.0 V (the first 3 cycles are activated at 0.2 A g1). In the of those electrodes at a larger current density. These two self-
first discharge cycle, a sloping voltage plateau between 1.5 and 0.1 V standing electrodes of Si-rGO and Si-rGO/CNT were tested at a
matches the broad reduction peak at 0.5 V in the CV curve, corre- current density of 4 A g1 in Fig. 5e. After finishing the first 3
sponding to the formation of SEI layer [36]. The long and flat activation cycles, two discharge specific capacities in the 4th cycle
voltage plateaus below 0.1 V is consistent with the formation of are 1010 mAh g1 for Si-rGO and 1456 mAh g1 for Si-rGO/CNT,
Li15Si4 phase in the lithiation processes [61]. Moreover, voltage respectively. After the 200th cycle, the specific capacity of Si-rGO/
plateaus around 0.5 V during the delithiation process is also CNT electrode can maintain 1049 mAh g1 with a decay rate of
consistent with the two oxidative peaks in the CV curve. After 1000 0.13% per cycle, which is better than that of 324 mAh g1 for Si-rGO
cycles, the discharge/charge plateaus still maintain the above fea- with a decay rate of 0.33% per cycle. Therefore, the second carbon
tures, indicating a relatively stable electrochemical reaction pro- material of CNT can significantly reinforce the stability of the self-
cess. The initial discharge capacity of 2070 mAh g1 and initial supported Si-rGO/CNT electrode. After finishing 1000 cycles, the
588 Q. Wei et al. / Electrochimica Acta 317 (2019) 583e593

Fig. 3. SEM image of (a) Si-rGO and (b) Si-rGO/CNT; TEM image of (c,e) Si-rGO and (d,f) Si-rGO/CNT; HRTEM image of (g) Si-rGO and (h) Si-rGO/CNT.
 Q. Wei et al. / Electrochimica Acta 317 (2019) 583e593 589

Figure 4. (aeb) Cross-sectional SEM image and (c) digital image of self-supported Si-rGO/CNT electrode; (d) SEM image and (e) EDS elemental mapping image of self-supported Si-
rGO electrode; (e) SEM image and (f) EDS elemental mapping image of the self-supported Si-rGO/CNT electrode.

Si-rGO/CNT electrode still maintains a specific capacity of morphology maintained the honeycomb-like structure in Fig. 6d,
1003 mAh g1 at a current density of 4 A g1. To the best of our but its crystalline Si NPs became amorphous deriving from volume
knowledge, this Si-rGO/CNT anode with high silicon loading and expansion and contraction during cycling. After 300 cycles, the
long cycle life has good stability compared to the recent studies of wrinkled surface in Fig. 6e covered by the SEI film is still visible. The
Si-graphene composite in Table S1. As a critical parameter of internal Si in Fig. 6f still maintains a honeycomb-like profile, also
judgment for LIBs, the coulombic efficiency (CE) in Fig. 5e of the Si- supported by the TEM image of Fig. S11, which indicates that the
rGO/CNT self-standing electrode reaches 99% at the second cycle rGO/CNT carbon system can well maintain the stability of the in-
and retain upon 99.5% during the following cycles at a current tegral electrode, and the honeycomb structure composed of many
density of 4 A g1, here the high CE benefits from the stable struc- Si NPs can well accommodate the volume expansion. In contrast,
ture with good conductivity and numerous buffer space in honey- bare honeycomb Si coated directly on copper foil must suffer from a
comb Si. In comparison with Si, the overall specific capacity large volume change. At the same time, the continuously formed
contribution of the rGO/CNT layer is negligible due to its low SEI film in Fig. 6geh destroys the initial organized structure and
theoretical specific capacity and a low weight ratio in the self- affects its electrochemical performance.
supporting electrode. Both the self-supported Si-rGO electrode To further explain the function of the second carbon material
and the honeycomb Si electrode have a similar trend of capacity worked in the electrode of Si-rGO/CNT, the electrochemical
decay in a high current density because of the rGO layer may not impedance spectroscopy (EIS) of the two electrodes of Si-rGO and
supply rapid electronic exchange lonely in the electrode of the Si-rGO/CNT before cycling is shown in Fig. 6i. The EIS of the two
honeycomb Si. electrodes after 300 cycles and 600 cycles is shown in Fig. 6j and
To explain this superior electrochemical performance of the Fig. S9, respectively. Both Nyquist plots consist of two semicircles
self-supported Si-rGO/CNT electrodes, SEM images and EIS analysis and a slope line, in comparison, there is only one semicircle in
of the electrode after cycling are further investigated. As shown in Fig. 6i due to no SEI layer formed before cycling. The corresponding
Figs. S7aeb and Fig. 6a, the self-supported Si-rGO/CNT electrode in equivalent circuit diagram includes the transfer resistance of
fresh style are tightly piled up. After treated with an acid wash to lithium ions in the electrolyte (Re), charge transfer resistance (Rct),
remove SEI film, honeycomb Si in activated self-supported Si-rGO/ SEI resistance (Rf), surface film capacitance (CPE1), charge transfer
CNT electrode in Figs. S7ced still be encapsulated in a thin rGO/CNT capacitance (CPE2) and diffusion impedance (W). The high-to-
layer and the honeycomb structure of Si can be simultaneously medium-frequency range semicircle belongs to the interfacial
maintained in Fig. S8. In comparison with the cross-sectional SEM charge transfer impedance (Rct) formed on the electrode surface
image of the fresh Si-rGO/CNT electrode in Fig. 6a, the thickness of and SEI film resistance (Rf) fabricated from the electrode/electrolyte
the electrode in Fig. 6b increases from 8 to 27 mm after 3 activation interface charge transfer impedance, while the oblique line in the
cycles. The increased thickness is mainly attributed to the relaxed low frequency range is related to Liþ ions diffusion process, asso-
structure with large gap between the components caused by the ciating with Warburg impedance (W) [64,65]. The corresponding
infiltration of electrolyte [43,63]. In addition, SEM images of the parameters are listed in Table 1. In the fresh state in Fig. 6i, the two
self-supported Si-rGO/CNT electrode in different cycle can provide electrodes have similar Re, but the Rct of Si-rGO/CNT is relatively
more detail regarding the electrode surface and internal Si low compared with the electrode of Si-rGO, indicating that CNT can
morphology. After 30 cycles, the wrinkled surface of the electrode enhance the conductivity of Si-rGO/CNT. By comparison with the
in Fig. 6c was covered with a SEI film, and the internal Si self-supported Si-rGO electrode after 300 cycles and 600 cycles, the
590 Q. Wei et al. / Electrochimica Acta 317 (2019) 583e593

Fig. 5. (a) CV curve of self-supported Si-rGO/CNT electrode; (b) Rate performance of the honeycomb Si, self-supported Si-rGO and self-supported Si-rGO/CNT electrode; (c) Charge/
discharge profiles of self-supported Si-rGO/CNT at 4 A g1 (the first 3 cycles are activated at 0.2 A g1); Cyclic performances of Si, self-supported Si-rGO electrode and self-supported
Si-rGO/CNT electrode at (d) 0.5 A g1 and (e) 4 A g1 (the first 3 cycles are activated at 0.2 A g1).

Si-rGO/CNT electrode has a lower Rf and Rct. After 600 cycles, the calculated from the slopes of the fitting lines. The anti-proportional
increasing degree of Rf and Rct in the Si-rGO/CNT electrode is relationship between the diffusion coefficient of Li ions, D, and u
significantly smaller than that of the self-supported Si-rGO elec- can be seen from equation (2) [64,65].
trode. The lower Rf demonstrates that the CNTs can effectively
maintain the stability of the structure and avoid the formation of Z 0 ¼ Re þ Rct þ su1=2 (1)
redundant SEI film. The lower Rct indicates that the CNTs can well
increase the conductivity of the electrode. Therefore, CNTs as the and
second carbon material, can enhance the conductivity and maintain
the stability of the electrode to reduce the formation of redundant .
DLi ¼ ðR2 T 2 Þ ð2A2 n4 F 4 C 2 s2 Þ (2)
SEI film.
Diffusion process can be descripted by five date points in the
low-frequency region to re-plotted a Z’/u1/2 plots along with a where R, T, A, n, F and C are the gas constant, absolute temperature,
fitted line in Fig. 6k, in which u represents the angular frequency. electrode area, number of electrons transferred, Faraday constant
According to equation (1), the values of Warburg factor, u, can be and the concentration of lithium-ions, respectively. Obviously, the
s of Si-rGO/CNT (1.07) is much lower than that of Si-rGO (1.96).
 Q. Wei et al. / Electrochimica Acta 317 (2019) 583e593 591

Fig. 6. Cross-sectional SEM images of the self-supported Si-rGO/CNT electrode (a) in fresh style and (b) after 3 cycles. Surface SEM images of the self-supported Si-rGO/CNT
electrode after (c) 30 cycles and (e) 300 cycles. SEM images of the honeycomb Si inside the self-supported Si-rGO/CNT electrode after (d) 30 cycles and (f) 300 cycles. (geh) Surface
SEM images of the honeycomb Si electrode in different magnification. Nyquist plots of the Si-rGO and Si-rGO/CNT electrodes measured (i) before cycling and (j) after 300 cycles. (k)
Relationship between Z0 and u1/2 of the Si-rGO and Si-rGO/CNT electrodes at the low-frequency region after 300 cycles.

Table 1
Impedance parameters of self-supported Si-rGO and Si-rGO/CNT electrodes.

Samples R e ( U) Rf(U) Rct(U) W (U S1/2) CPE1(F) CPE2(F) Chi-Sqr

Before cycling
Si-rGO 5.93 29.2 0.45 1.4E-05 9.6E-08
Si-rGO/CNT 5.88 22.9 0.47 5.2E-06 1.9E-04
After 300th cycle
Si-rGO 6.93 36.49 20.3 0.46 8.6E-06 0.00178 1.8E-07
Si-rGO/CNT 6.89 20.82 6.35 0.31 1.3E-05 0.00344 3.1E-07
After 600th cycle
Si-rGO 5.65 78.81 28.7 0.5 1.8E-05 0.0011 2.9E-12
Si-rGO/CNT 7.2 37.77 7.31 0.49 5.0E-05 0.00269 2.9E-06

Therefore, the Si-rGO/CNT self-supporting electrode has the higher schematic diagram of those two self-supported electrodes of Si-
D of diffusion coefficient of Li ions, which is corresponded with the rGO and Si-rGO/CNT is shown in Fig. 7. The huge volume change
electrochemical performance. caused by Li-ion insertion, may lead to pulverization and decreased
In order to better understand the superiority of Si-rGO/CNT, a conductivity of Si electrode, consequently, a honeycomb-like
592 Q. Wei et al. / Electrochimica Acta 317 (2019) 583e593

Fig. 7. Schematic of the lithiation/delithiation process of the self-supported electrodes of Si-rGO and Si-rGO/CNT.

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