微米级SiO合成多孔氧化硅/硅/碳储锂复合材料

doi:10.11944/j.issn.1000-0518.2017.01.160101

摘要/Abstract

摘要：

以微米级SiO为原料,通过简单的高温煅烧、碳包覆和酸刻蚀制备多孔氧化硅/硅/碳复合材料,复合材料比表面积和平均孔径分别为32.9 m²/g和3 nm。纳米硅分散在缓冲介质氧化硅多孔体系中,表面包覆一层薄而均匀的碳层。所得的复合材料具有较好的循环稳定性,在0.3 mA/g下,50次循环后可逆容量保持在645.1 mA·h/g。多孔结构、氧化硅缓解了硅在脱嵌锂过程的体积膨胀,碳层提高了复合材料的导电性和结构稳定性。

关键词: 氧化亚硅, 多孔结构, 电化学性能, 锂离子电池

Abstract:

Porous silicon oxide/silicon/carbon composite was derived from micro-silicon monoxide with simple calcination, chemical vapor deposition and HF etching. The obtained c-SiO_x/Si/C(c-refers to calcination) composite after etching possesses a high specific surface area of 32.9 m²/g and an average/mean pore distribution of 3 nm. The atomic ratio of Si/O in c-SiO_x/Si/C is increased comparing to that of c-SiO/C without etching. The Si nano-crystallites were embedded in porous Si-suboxide, and the particles are covered by a uniform carbon layer with a thickness of 6 nm on the surface. The c-SiO_x/Si/C with this particular structure exhibits a stable reversible capacity of ca. 645.1 mA·h/g after 50 cycles with the current density at 0.3 mA/g. In contrast, c-SiO/C composite without pores presents a reversible capacity of only ca. 466 mA·h/g under the same carbon coating condition. The different cycling performances of c-SiO_x/Si/C and c-SiO/C may be consequences of their structural differences. It is believed that the rich nanopores of the c-SiO_x/Si/C can endure and buffer the severe volume change of silicon upon lithium insertion and extraction and improve the mechanical integrity of composite.

Key words: silicon monoxide, porous structure, electrochemical performance, lithium ion battery

冯雪娇, 崔红敏, 肖正强, 晏南富, 李敏. 微米级SiO合成多孔氧化硅/硅/碳储锂复合材料[J]. 应用化学, 2017, 34(1): 76-82.

FENG Xuejiao, CUI Hongmin, XIAO Zhengqiang, YAN Nanfu, LI Min. Synthesis of Porous Silicon Oxide/Silicon/Carbon Composite Material from Micro-SiO for Lithium Storage[J]. Chinese Journal of Applied Chemistry, 2017, 34(1): 76-82.

参考文献

[1]	LI Zhijie,LIANG Qi,CHEN Dongliang,et al. Cooperation Action of Carbon Nanotubes and Graphite During Lithium Electrochemical Intercalation[J]. Chinese J Appl Chem,2001,18(4):269-271(in Chinese). 李志杰,梁奇,陈栋梁,等. 碳纳米管和石墨在电化学嵌锂过程中的协同效应[J]. 应用化学,2001,18(4):269-271.
[2]	Liang B,Liu Y,Xu Y.Silicon-Based Materials as High Capacity Anodes for Next Generation Lithium Ion Batteries[J]. J Power Sources,2014,267:469-490.
[3]	Wang W,Datta M K,Kumta P N.Silicon-Based Composite Anodes for Li-ion Rechargeable Batteries[J]. J Mater Chem,2007,17(30):3229-3237.
[4]	Bao Q,Huang Y H.,Lan C K,et al. Scalable Upcycling Silicon from Waste Slicing Sludge for High-Performance Lithium-Ion Battery Anodes[J]. Electrochim Acta,2015,173:82-90.
[5]	Park H,Choi S,Lee S,et al. Novel Design of Silicon-Based Lithium-ion Battery Anode for Highly Stable Cycling at Elevated Temperature[J]. J Mater Chem A,2014,3(3):1325-1332.
[6]	Lin H,Weng W,Ren J,et al. Twisted Aligned Carbon Nanotube/Silicon Composite Fiber Anode for Flexible Wire-shaped Lithium-Ion Battery[J]. Adv Mater,2014,26(8):1217-1222.
[7]	Wang J,Wang H,Zhang B,et al. A Stable Flexible Silicon Nanowire Array as Anode for High-Performance Lithium-Ion Batteries[J]. Electrochim Acta,2015,176:321-326.
[8]	Wang W,Ruiz I,Ahmed K,et al. Silicon Decorated Cone Shaped Carbon Nanotube Clusters for Lithium Ion Battery Anodes[J]. Small,2014,10(16):3389-3396.
[9]	FAN Xuge,LI Guocai,CHENG Chaoqun,et al. Progress in Controlled Fabrication Techniques and Applications of Silicon Nanowires Associated with Metal-Assisted Chemical Etching[J]. Chinese J Appl Chem,2013,30(11):1257-1264(in Chinese). 范绪阁,李国才,程超群,等. 金属辅助化学刻蚀法制备硅纳米线及应用[J]. 应用化学,2013,30(11):1257-1264.
[10]	Si Q,Hanai K,Ichikawa T,et al. Improvement of Cyclic Behavior of a Ball-Milled SiO and Carbon Nanofiber Composite Anode for Lithium-Ion Batteries[J]. J Power Sources,2011,196(22):9774-9779.
[11]	Liu Y H,Okano M,Mukai T,et al. Improvement of Thermal Stability and Safety of Lithium Ion Battery Using SiO Anode material[J]. J Power Sources,2016,304:9-14.
[12]	Doh C H,Park C W,Shin H M,et al. A New SiO/C Anode Composition for Lithium-ion Battery[J]. J Power Sources,2008,179(1):367-370.
[13]	Hou X,Wang J,Zhang M,et al. Facile Spray-Drying/Pyrolysis Synthesis of Intertwined SiO@CNFs&G Composites as Superior Anode Materials for Li-Ion Batteries[J]. RSC Adv,2014,4(65):34615-34622.
[14]	Wu W,Liang Y,Ma H,et al. Insights into the Conversion Behavior of SiO-C Hybrid with Pre-treated Graphite as Anodes for Li-ion Batteries[J]. Electrochim Acta,2016,187:473-479.
[15]	Doh C H,Park C W,Shin H M,et al. A New SiO/C Anode Composition for Lithium-Ion Battery[J]. J Power Sources,2008,179(1):367-370.
[16]	Liu W R,Yen Y C,Wu H C,et al. Nano-Porous SiO/Carbon Composite Anode for Lithium-Ion Batteries[J]. J Appl Electrochem,2009,39(9):1643-1649.
[17]	Lee J I,Lee K T,Cho J,et al. Chemical-Assisted Thermal Disproportionation of Porous Silicon Monoxide into Silicon-Based Multicomponent Systems[J]. Angew Chem Int Ed,2012,51(11):2767-2771.
[18]	Feng X,Yang J,Lu Q,et al. Facile Approach to SiOx/Si/C Composite Anode Material from Bulk SiO for Lithium Ion Batteries[J]. Phys Chem Chem Phys,2013,15(34):14420-14426.
[19]	Etacheri V,Haik O,Goffer Y,et al. Effect of Fluoroethylene Carbonate(FEC) on the Performance and Surface Chemistry of Si-Nanowire Li-Ion Battery Anodes[J]. Langmuir,2012,28(1):965-976.
[20]	Doh C H,Veluchamy A,Lee D J,et al. Comparative Study on Performances of Composite Anodes of SiO, Si and Graphite for Lithium Rechargeable Batteries[J]. Bull Korean Chem Soc,2010,31(5):1257-1261.