A Tremella-Like Nanostructure of Silicon@void@graphene-Like Nanosheets Composite as an Anode for Lithium-Ion Batteries
© Mi et al. 2016
Received: 14 January 2016
Accepted: 4 April 2016
Published: 16 April 2016
Graphene coating is receiving discernable attention to overcome the significant challenges associated with large volume changes and poor conductivity of silicon nanoparticles as anodes for lithium-ion batteries. In this work, a tremella-like nanostructure of silicon@void@graphene-like nanosheets (Si@void@G) composite was successfully synthesized and employed as a high-performance anode material with high capacity, cycling stability, and rate capacity. The Si nanoparticles were first coated with a sacrificial SiO2 layer; then, the nitrogen-doped (N-doped) graphene-like nanosheets were formed on the surface of Si@SiO2 through a one-step carbon-thermal method, and the SiO2 layer was removed subsequently to obtain the Si@void@G composite. The performance improvement is mainly attributed to the good conductivity of N-doped graphene-like nanosheets and the unique design of tremella nanostructure, which provides a void space to allow for the Si nanoparticles expanding upon lithiation. The resulting electrode delivers a capacity of 1497.3 mAh g−1 at the current density of 0.2 A g−1 after 100 cycles.
To meet the further demands driven by the rapid development of portable electronics hybrid and electric vehicles, novel anode materials with higher energy density, low-cost, and long cycle life for lithium-ion batteries (LIBs) are of great interest [1–3]. Silicon has been recognized as one of the most promising and appealing anode materials, owing to the high natural abundance, low discharge potential, and especially its high theoretical specific capacity (4200 mAh g−1) which is ten times greater than that of a traditional graphite (~372 mAh g−1) [4, 5]. Unfortunately, Si suffers from the low conductivity and the severe volume fluctuation during the Li+ insertion/extraction, which can fracture the materials and lead to fast capacity fading. Moreover, the thickness of the insulating solid electrolyte interphase (SEI) film increases upon charge/discharge process, further degrading the capacity and cycling stability of Si electrode [6, 7]. These shortages cause much difficulty in the development of the silicon-based materials as commercial anode materials.
Many approaches have been developed to mitigate the above–mentioned challenges, including to decrease the Si particle sizes [8–13] and fabricate hollow or porous structure to confine volume expansion [14–18]. Tao et al.  prepared hollow core-shell structured Si/C nanocomposites to adapt for the large volume change. In addition, many Si-based materials were modified by new binder or conductive polymer [19–21], carbonaceous materials, such as amorphous carbon [22, 23], carbon nanotubes , graphite [25, 26], and graphene [27–32]. Graphene has been applied in LIBs in recent years, mainly due to its outstanding flexibility, electrical conductivity, and excellent mechanical strength [33–36]. For example, Wu et al.  synthesized the three-dimensional (3D) interconnected network of graphene-wrapped porous silicon spheres, and this electrode delivered a high reversible capacity of 1299.6 mAh g−1 after 20 cycles, exhibiting markedly enhanced performance compared with bare Si spheres.
Taking advantages of which offered by both hollow structure and graphene, we herein design a tremella-like nanostructure of silicon@void@graphene-like nanosheets (Si@void@G) composite as an anode for LIBs. The tremella-like structure with an internal void space can accommodate the large volumetric expansion of Si during lithiation. Moreover, nitrogen-doped (N-doped) graphene-like nanosheets can increase the electronic conductivity of the electrode. As an anode material for LIBs, the Si@void@G electrode delivers a reversible capacity of 1497.3 mAh g−1 at the current density of 0.2 A g−1 after 100 cycles, with the initial coulombic efficiency of 73.8 %, which exhibits significantly improved electrochemical performance than bare Si and silicon@graphene (Si@G) composite.
Materials and Preparation
Silicon nanoparticles (100 nm, Shanghai ST-NANO Science & Technology Co. Ltd., People’s Republic of China) were firstly dispersed into 400 mL of deionized alcohol-water (3:1 by volume) solution by sonication at room temperature for an hour. Then, 10 mL ammonia was added into this solution. After 5 min, tetraethoxysilane (TEOS) was added dropwise under vigorous magnetic stirring for 24 h to form the SiO2 layers. Si@SiO2 composites were collected by filtering and washed thoroughly with distilled water. Subsequently, a certain amount of liquid-polyacrylonitrile (LPAN) were mixed with Si@SiO2 composite and ground in a QM-3SP2 planetary ball mill for 10 h. The mixtures were cured in air at 220 °C for 3 h and carbonized at 1000 °C in an argon atmosphere for 5 h to form Si@SiO2@G composites. Finally, the Si@void@G composites were obtained by washing the products with HF to remove the SiO2 layers. As a comparison, bare Si nanoparticles were also coated with N-doped graphene-like sheets without SiO2 layer to obtain Si@G composite.
The morphology and structure of the samples were observed by using a LEO1530 scanning electron microscope (SEM, Germany) and a Tecnai G2 transmission electron microscope (TEM, FEI, USA). The crystalline structures were obtained by a D8 advance X-ray diffraction spectrometer (XRD, Bruker, Germany) using Cu Kα radiation. Thermogravimetric analysis (TGA) results were obtained with a STA409PC TG-DSC/DTA instrument (Netzsch, Germany) from 30 to 800 °C with a heating rate of 10 °C min−1 in air. Raman measurements were carried out at room temperature using a Jobin Yvon/Atago Bussan T64000 triple spectrometer equipped with micro-optics. X-ray photoelectron spectroscopy (XPS) was carried out on the ESCAlab220iXL electron spectrometer from VG scientific using 300-W Al Kα radiation.
Electrochemical tests were performed by coin-type 2032 cells (Shenzhen Kejingstar Technology Co. Ltd., People’s Republic of China) which were assembled in an Ar-filled glove box (MBRAUN, Germany) with oxygen and moisture contents of less than 0.1 ppm. For preparing the working electrode, a slurry mixture of prepared active materials, carbon black, and sodium alginate in a weight ratio of 6:2:2 in water was coated on a copper (Cu) foil by an automatic film applicator (AFA-II, Shanghai Pushen Chemical Machinery Co., Ltd., People’s Republic of China). The Cu foil was dried at 70 °C for 12 h and then cut into pieces with a diameter (ϕ) of 14 mm. The loading of active material was ~0.42 mg cm−2. Subsequently, the pieces were dried at 110 °C for 6 h in vacuum. A solution of 1 M LiPF6 in ethylene carbonate (EC) and dimethyl carbonate (DMC) (1:1 v/v) was served as electrolyte.
The galvanostatic charge-discharge performance was assessed on a battery testing system (LAND-CT2001A, People’s Republic of China) at room temperature between cut-off potentials of 1.00 and 0.01 V at different densities. Cyclic voltammetry (CV) was recorded on an electrochemical workstation (1470E Cell Test System, Solartron, UK), with a scanning of rate of 0.1 mV s−1 at room temperature. Electrochemical impedance spectroscopy (EIS) was measured with a Solartron Impedance analyzer 1260A by applying an alternating current (AC) voltage of 5 mV in the frequency range from 100 kHz to 0.1 Hz.
Results and Discussion
Structure and Characterization
Kinetic parameters of Si, Si@G, and Si@void@G electrodes
Samples and cycle numbers
Si 5 cycles
Si 50 cycles
Si@G 5 cycles
Si@G 50 cycles
Si@void@G 5 cycles
Si@void@G 50 cycles
In summary, inspired by nature, a tremella structure of Si@void@G electrode with high capacity, cycling stability, and rate capacity was obtained. The Si@void@G electrode can deliver a capacity of 1497.3 mAh g−1 at the current density of 0.2 A g−1 after 100 cycles, showing better electrochemical performance than bare Si and Si@G electrodes. These results are mainly attributed to the following reasons: the unique design of tremella nanostructure provides a large void space between Si nanoparticles and graphene-like sheets to allow for the expansion and contraction of Si during the lithiation/delithiation process; the N-doped graphene-like nanosheets provide excellent electrical conductivity throughout the electrode; moreover, the Si nanoparticles are encapsulated by the thin graphene-like nanosheets, limiting the amount of SEI, which also confirms the successful design of Si@void@G materials.
We appreciate the financial support from the NSF of China (no. 21374064, 21571131, 51502177), Key Project of Natural Science Foundation of Guangdong Province (no. 2014A030311028, 2014A030310323), the foundation for Emerging Industries of Strategic Importance of Shenzhen (no. JCYJ20150324141711692, JCYJ20140418182819158), Major Programs for Science and Technology Development of Shenzhen (no. XCL201110060), and Student’s Platform for Innovation and Entrepreneurship Training Program (no. 201510590017).
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