Preparation and electrochemical performance of self-supporting Si/graphene films

doi:10.16085/j.issn.1000-6613.2018-0950

Abstract

Abstract: Self-supporting Si/graphene nanocomposite films were prepared by a simple method combined with ultrasonication, filtration and chemical reduction. The effects of the ratio of Si on electrochemical performance of Si/graphene composite materials were investigated systematically. The results showed that the volume change of silicon can be effectively controlled due to the insertion of silicon between the layers of graphene, leading to the composite films with improved mechanical strength. It was found that the reversible capacity and first columbic efficiency of the composite films increased with increasing Si content. The film with 53% of Si loading showed higher reversible capacity of 492mA·h/g and better first columbic efficiency of 64.8% at 0.1C, which were 229 times and 9 times higher than pure Si, respectively. Moreover, the capacitance of these composites was 60.9% after 50 cycles when Si content was further increased to 67%, indicating that the graphene played an important role to improve the cycle performance of the composites.

Key words: graphene, Si nanoparticles, composite films, self-supporting, Li-ion battery

摘要： 采用简单的超声、抽滤和水合肼化学还原相结合的方法制备硅/石墨烯基自支撑薄膜，系统研究了硅含量对硅/石墨烯复合材料电化学性能的影响。结果表明：通过在石墨烯水凝胶的片层之间插入纳米硅颗粒，可以有效地控制硅体积变化，增加该复合膜的机械强度并提高其导电性。提高硅/石墨烯复合材料中硅含量的比例可以提升其可逆比容量和首次库仑效率，当硅质量分数为53%时，复合膜在0.1C倍率下的可逆比容量及首次库仑效率分别达到945.6mA·h/g和64.8%（纯硅的229倍和9倍）；继续提高硅含量的比例，可以提升其循环寿命（循环50次容量保持率60.9%、质量分数为67%的Si），但材料比容量有所下降，说明石墨烯在稳定硅基复合材料电化学性能方面发挥着非常重要作用。

关键词: 石墨烯, Si纳米颗粒, 复合薄膜, 自支撑, 锂离子电池

CLC Number:

TM912.9

MA Yan, LIN Zhen, JIA Qiurong, GAO Zhijie. Preparation and electrochemical performance of self-supporting Si/graphene films[J]. Chemical Industry and Engineering Progress, 2018, 37(10): 3974-3979.

马艳, 林振, 贾秋荣, 高志杰. 硅/石墨烯基自支撑薄膜的制备及电化学性能[J]. 化工进展, 2018, 37(10): 3974-3979.

References

[1] DING X L, LI Y T, FANG F, et al. Hydrogen-induced magnesium-zirconium interfaces coupling:enabling fast hydrogen sorption at lower temperature[J]. Journal of Materials Chemistry A, 2017, 5(10):5067-5076.
[2] LI Y T, DING X L, WU F L, et al. Enhancement of hydrogen storage in destabilized LiNH₂ with KMgH₃ by quick conveyance of N-containing species[J]. The Journal of Physical Chemistry C, 2016, 120(3):1415-1420.
[3] LI Y T, DING X L, ZHANG Q A. Self-printing on graphitic nanosheets with metal borohydride nanodots for hydrogen storage[J]. Scientific Reports, 2016, 6:31114.
[4] LI Y T, ZHANG L X, ZHANG Q A, et al. In situ embedding of Mg₂NiH₄ and YH₃ nanoparticles into bimetallic hydride NaMgH₃ to inhibit phase segregation for enhanced hydrogen storage[J]. The Journal of Physical Chemistry C, 2014, 118(41):23635-23644.
[5] LI Y T, FANG F, FU H L, et al. Carbon nanomaterial-assisted morphological tuning for thermodynamic and kinetic destabilization in sodium alanates[J]. Journal of Materials Chemistry A, 2013, 1(17):5238-5246.
[6] LI Y T, ZHOU G Y, FANG F, et al. De-/re-hydrogenation features of NaAlH₄ confined exclusively in nanopores[J]. Acta Materialia, 2011, 59(4):1829-1838.
[7] 李俊岭, 李涛, 李伟伟, 等. TiO₂基锂离子电池复合负极材料的研究进展[J]. 化工进展, 2017, 36(5):1755-1762. LI J L, LI T, LI W W, et al. Recent progress on TiO₂-based composites for Li-ion battery anodes[J]. Chemical Industry and Engineering Progress, 2017, 36(5):1755-1762.
[8] DUNN B, KAMATH H, TARASCON J M. Electrical energy storage for the grid:a battery of choices[J]. Science, 2011, 334(6058):928-935.
[9] 王仙宁, 凌锋, 潘薇, 等. 锂离子电池负极材料中国专利分析[J]. 化工进展, 2016, 35(1):336-339. WANG X N, LING F, PAN W, et al. Chinese patent analysis on anode materials for lithium-ion battery[J]. Chemical Industry and Engineering Progress, 2016, 35(1):336-339.
[10] BONACCORSO F, COLOMBO L, YU G H, et al. Graphene, related two-dimensional crystals, and hybrid systems for energy conversion and storage[J]. Science, 2015, 347(6217):1246501.
[11] CHANG J B, HUANG X K, CHEN J H, et al. Three-dimensional carbon-coated Si/rGO nanostructures anchored by nickel foam with carbon nanotubes for Li-ion battery applications[J]. Nano Energy, 2015, 15:679-687.
[12] XIAO Q Z, FAN Y, WANG X, et al. A multilayer Si/CNT coaxial nanofiber LIB anode with a high areal capacity[J]. Energy & Environmental Science, 2014, 7:655-661.
[13] LIANG B, LIU Y P, XU Y H. Silicon-based materials as high capacity anodes for next generation lithium ion batteries[J]. Journal of Power Sources, 2014, 267:469-490.
[14] CHAN C K, PENG H, CUI Y, et al. High-performance lithium battery anodes using silicon nanowires[J]. Nature Nanotechnology, 2008, 3:31-35.
[15] WU H, CHAN G, CUI Y, et al. Stable cycling of double-walled silicon nanotube battery anodes through solid-electrolyte interphase control[J]. Nature Nanotechnology, 2012, 7:310-315.
[16] WU H, ZHENG G, CUI Y, et al. Engineering empty space between Si nanoparticles for lithium-ion battery anodes[J]. Nano Letters, 2012, 12(2):904-909.
[17] BAGGETTO L, DANILOV G, NOTTEN P H L. Honeycombstructured silicon:remarkable morphological changes induced by electrochemical (De)lithiation[J]. Advanced Materials, 2011, 23(13):1563-1566.
[18] WU H, CUI Y. Designing nanostructured Si anodes for high energy lithium ion batteries[J]. Nano Today, 2012, 7(5):414-429.
[19] JIN Y, LI S, LI J, et al. Self-healing SEI enables full-cell cycling of a silicon-majority anode with a coulombic efficiency exceeding 99.9%[J]. Energy & Environmental Science, 2017, 10:580-592.
[20] CUI L F, YANG Y, CUI Y. Carbon-silicon core-shell nanowires as high capacity electrode for lithium ion batteries[J]. Nano Letters, 2009, 9(9):3370-3374.
[21] NG S H, WANG J Z, WEXLER D, et al. Highly reversible lithium storage in spheroidal carbon-coated silicon nanocomposites as anodes for lithium-ion batteries[J]. Angewandte Chemie International Edition, 2006, 45(41):6896-6899.
[22] WU H, YU G H, BAO Z N, et al. Stable Li-ion battery anodes by in-situ polymerization of conducting hydrogel to conformally coat silicon nanoparticles[J]. Nature Communications, 2013, 4:1943.
[23] 万武波, 赵宗彬, 邱介山, 等. 柠檬酸钠绿色还原制备石墨烯[J]. 新型炭材料, 2011, 26(1):16-20. WAN W B, ZHAO Z B, QIU J S, et al. "Green" reduction of graphene oxide to graphene by sodium citrate[J]. New Carbon Materials, 2011, 26(1):16-20.
[24] WAN W B, ZHAO Z B, QIU J S, et al. Highly controllable and green reduction of graphene oxide to flexible graphene film with high strength[J]. Materials Research Bulletin, 2013, 48(11):4797-4803.
[25] GEIM A K. Graphene:status and prospects[J]. Science, 2009, 324(5934):1530-1534.
[26] NOVOSELOV K S, GEIM A K, MOROZOV S V, et al. Two-dimensional gas of massless Dirac fermions in graphene[J]. Nature, 2005, 438:197-200.
[27] GEIM A K, NOVOSELOV K S. The rise of graphene[J]. Nature Materials, 2007, 6:183-191.
[28] MEYER J C, GEIM A K, NOVOSELOV K S, et al. The structure of suspended graphene sheets[J]. Nature, 2007, 446:60-63.
[29] LOZADA-HIDALGO M, ZHANG S, GEIM A K, et al. Giant photoeffect in proton transport through graphene membranes[J]. Nature Nanotechnology, 2018, 13:300-303.
[30] WANG Z L, XU D, ZHANG X B, et al. In situ fabrication of porous graphene electrodes for high-performance energy storage[J]. ACS Nano, 2013,7(3):300-303.
[31] ZHAO X, HAYNER C M, KUNG M C, et al. In-plane vacancy-enabled high-power Si-graphene composite electrode for lithium-ion batteries[J]. Advanced Energy Materials, 2011, 1(6):1079-1084.
[32] XIA F, KWON S, LEE W W, et al. Graphene as an interfacial layer for improving cycling performance of Si nanowires in lithium-ion batteries[J]. Nano Letters, 2015, 15(10):6658-6664.
[33] TANG H, ZHANG J, ZHANG Y J, et al. Porous reduced graphene oxide sheet wrapped silicon composite fabricated by steam etching for lithium-ion battery application[J]. Journal of Power Sources, 2015, 286:431-437.
[34] CHOCKLA A M, PANTHANI M G, HOLMBERG V C, et al. Electrochemical lithiation of graphene-supported silicon and germanium for rechargeable batteries[J]. The Journal of Physical Chemistry C, 2012, 116(22):11917-11923.
[35] YE Y S, XIE X L, RICK J, et al. Improved anode materials for lithium-ion batteries comprise non-covalently bonded graphene and silicon nanoparticles[J]. Journal of Power Sources, 2014, 247:991-998.
[36] HE D F, BAI F J, LI L X, et al. Fabrication of sandwich-structured Si nanoparticles-graphene nanocomposites for high-performance lithiumion batteries[J]. Electrochimica Acta, 2015, 169:409-415.
[37] YUN Q B, QIN X Y, LV W, et al. "Concrete" inspired construction of a silicon/carbon hybrid electrode for high performance lithium ion battery[J]. Carbon, 2015, 93:59-67.
[38] LUO Z P, XIAO Q Z, LEI G T, et al. Si nanoparticles/graphene composite membrane for high performance silicon anode in lithium ion batteries[J]. Carbon, 2016, 98:373-380.