Facile Synthesis of SiO2@C Nanoparticles Anchored on MWNT as High-Performance Anode Materials for Li-ion Batteries
© The Author(s). 2017
Received: 8 February 2017
Accepted: 9 July 2017
Published: 18 July 2017
Carbon-coated silica nanoparticles anchored on multi-walled carbon nanotubes (SiO2@C/MWNT composite) were synthesized via a simple and facile sol-gel method followed by heat treatment. Scanning and transmission electron microscopy (SEM and TEM) studies confirmed densely anchoring the carbon-coated SiO2 nanoparticles onto a flexible MWNT conductive network, which facilitated fast electron and lithium-ion transport and improved structural stability of the composite. As prepared, ternary composite anode showed superior cyclability and rate capability compared to a carbon-coated silica counterpart without MWNT (SiO2@C). The SiO2@C/MWNT composite exhibited a high reversible discharge capacity of 744 mAh g−1 at the second discharge cycle conducted at a current density of 100 mA g−1 as well as an excellent rate capability, delivering a capacity of 475 mAh g−1 even at 1000 mA g−1. This enhanced electrochemical performance of SiO2@C/MWNT ternary composite anode was associated with its unique core-shell and networking structure and a strong mutual synergistic effect among the individual components.
Due to its low lithium intercalation potential as well as excellent cycling performance, graphite has been widely adopted as a commercial anode for lithium-ion batteries (LIBs) . Nevertheless, the theoretical capacity of graphite is only 372 mAh g−1, which cannot fulfill the ever-growing demands for high-performance batteries. Therefore, the development of next-generation anode materials with a larger specific capacity is necessary [2, 3].
Due to a large theoretical capacity of 1965 mAh g−1 and a low electrochemical potential, SiO2 is considered as a potential alternative to traditional carbonaceous anode materials. Furthermore, environmental friendliness, low cost, and natural abundance make SiO2 a commercial viable electrode material for LIBs. However, its practical application in LIB is commonly hampered by its poor electronic conductivity as well as a drastic volume variation upon charge-discharge process, resulting in particle pulverization and electrode deterioration with cycling [4–6].
One of the effective approaches to overcome these issues is to design SiO2-based composites by confining SiO2 particles inside conductive and flexible matrixes [7, 8]. In our previous study, Cu/carbon was introduced into the SiO2 composite as a dispersive matrix due to its good conductivity and effective buffering of the volume change of SiO2 . It was shown by Yu et al.  that coating the SiO2 surface with carbon could be an efficient method to enhance its electrochemical performance, because such coating not only improves conductivity of the system but also accommodates the volume changes of the active material upon cycling.
Considering that the contact between SiO2@C particles is not good enough and the SiO2@C particles tend to agglomerate during charge/discharge  in this work, we report an effective and easy method to synthesize a core-shell SiO2@C anchored on MWNT via a sol-gel and pyrolysis route. In this composite, a carbon layer is homogeneously coated on the SiO2 particles, significantly improving the electronic conductivity of the system. Furthermore, formation of the 3D electron transportation pathways by a uniform dispersion of MWNT in the composite leads to outstanding electrochemical performance of the composite as an anode material for LIBs.
Nine cubic centimeter of tetraethyl orthosilicate (TEOS) ((C2H5O)4Si ≥ 99.5%) and 9 cm3 HCl (0.1 mol dm−3) were dispersed in ethanol (16 cm3) and stirred for 30 min. Meanwhile, 4 g citric acid (C6H8O7 · H2O ≥ 99.5%) and 2.2 cm3 ethylene glycol (C2H6O2 ≥ 99%) were dissolved in deionized water (10 cm3), and then 1.9 g MWNT dispersion (9 wt%, MWNT aqueous dispersion, Timesnano, Chengdu) (mass ratio of Si and MWNT = 6.6:1) was added into this solution with gentle stirring for 30 min. The two resulting solutions were thoroughly mixed and transferred into an evaporating dish and dried at 55 °C for 10 h. The resulting product was heated under Ar atmosphere for 1 h at 1100 °C to obtain SiO2@C/MWNT composite. A reference SiO2@C composite without MWNT was obtained following the same preparation route.
The crystal structure of the samples was characterized by X-ray diffraction (XRD D8 Discover, Bruker) employing Cu Kα radiation. Raman spectra were conducted with Ar-ion laser of 532 nm using the Via Reflex Raman imaging microscope system. The structure and morphology of the SiO2@C/MWNT composites were studied using scanning electron microscopy (SEM, Hitachi S-4800) and transmission electron microscopy (TEM, JEOL 2100), respectively. Surface elemental analysis was conducted by an energy-dispersive X-ray spectroscopy (EDX) attached to the TEM apparatus. The content of amorphous SiO2 in SiO2@C/MWNT composite was estimated by using a thermogravimetric analyzer (STD Q-600) under N2 flow (30 ml min−1).
The working electrodes were prepared by coating a homogeneous slurry containing 80 wt% active material, 10 wt% acetylene black (MTI, 99.5%), and 10 wt% polyvinylidene fluoride (PVDF) (Kynar, HSV900) binder dissolved in 1-methyl-2-pyrrolidinone (NMP, Sigma-Aldrich, 99.5%) onto a copper current collector by a doctor blade, and further drying at 65 °C for 12 h in a vacuum oven. The resulting SiO2@C/MWNT and SiO2@C composite electrode was punched into circular disks with a diameter of 10 mm and a mass loading of ~4 mg cm−2. The coin-type cells with high-purity lithium metal as the counter electrode were assembled in a glove box (MBraun) filled with argon (99.9995%). Galvanostatic charge and discharge tests were conducted on a multichannel battery tester (Neware, BTS-5 V5 mA) with the potential range of 0.01–2.5 V vs. Li/Li+ at various cycling rates. The Versa STAT electrochemical workstation was used to conduct cyclic voltammetry (CV) tests between 0.01 and 3 V vs. Li/Li+ at a scanning rate of 0.1 mV s−1 and electrochemical impedance spectroscopy (EIS) measurements in a frequency range from 100 kHz to 1 mHz.
Results and Discussion
Performance comparison of SiO2 and SiO2@C electrodes for LIBs
Reversible capacity (mAh g−1)
Initial discharge/charge specific capacity (mAh g−1)
Cutoff potential range (V)
Carbon-coated SiO2 nanoparticles
Above 500 (50th)
50 mA g−1
70 mA g−1
500 mA g−1
50 mA g−1
Ag-deposited 3D porous Si
50 mA g−1
100 mA g−1
The SiO2@C/MWNT ternary composite was successfully synthesized by a simple sol-gel method using low-cost citric acid and TEOS as starting materials, followed by heat treatment. Due to its unique core-shell and network structure and enhanced contact between its individual components, the resulting ternary composite cathode exhibited a remarkably enhanced electrochemical performance compared with the binary SiO2@C counterpart. Considering the simplicity and efficiency of the preparation process and outstanding electrochemical performance, the SiO2@C/MWNT composite can be considered as a promising anode material for the next generation lithium-ion batteries.
Energy-dispersive X-ray spectroscopy
Multi-walled carbon nanotube
Scanning electron microscope
- SiO2 :
Carbon-coated silica composite
SiO2@C nanoparticles anchored on MWNT
Transmission electron microscope
The authors acknowledge the financial support from the National Natural Science Foundation of China (Grant No. 21406052), the Program for the Outstanding Young Talents of Hebei Province (Grant No. BJ2014010), Scientific Research Foundation for Selected Overseas Chinese Scholars, Ministry of Human Resources and Social Security of China (Grant No. CG2015003002), and the targeted program 0143/PCF-14 «Fundamental bases of the processes, based on electrochemical formations» from the Ministry of Education and Science of the Republic of Kazakhstan.
The authors declare that they have no competing interests.
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