氮掺杂碳包覆的蛋黄壳结构硅负极材料

doi:10.3969/j.issn.1000-5641.2022.01.004

摘要/Abstract

摘要：

采用间苯二酚-甲醛为碳源, 三聚氰胺为氮源, 以NaOH为蚀刻剂, 成功合成氮掺杂碳包覆的蛋黄壳结构硅(Si@void@N-C)锂离子电池复合负极材料. 对样品进行XRD、 SEM和X射线电子能谱, 透射电子显微镜(TEM)和电化学测试等表征及测试. 结果表明, 成功合成了蛋黄壳结构的Si@void@N-C复合负极材料. 同时, 该复合材料具有优异的电化学性能, 以0.1 A/g的电流密度进行充放电, 首次容量可达1282.3 mAh/g, 经过100次循环后, 其比容量仍高达994.2 mAh/g, 其容量保持率为77.5%, 表现出了良好的循环性能. Si@void@N-C材料中, 氮掺杂的碳壳可以增加复合材料的导电性, 同时, 蛋黄壳结构可有效缓解硅的体积效应, 有利于形成稳定的SEI膜, 从而提高电池的循环稳定性.

关键词: 锂离子电池, 氮掺杂碳, 硅负极, 蛋黄壳结构

Abstract:

Using resorcinol-formaldehyde resin as the carbon source, melamine as the nitrogen source, and NaOH as the etchant, a nitrogen-doped carbon-coated silicon (Si@void@N-C) anode material with a yolk-shell structure was synthesized. The samples were characterized and tested by XRD, SEM and X-ray photoelectron spectroscopy, TEM, and electrochemical tests; the results confirmed that a Si@void@NC composite anode material with a yolk-shell structure was successfully synthesized. The material was found to have excellent electrochemical performance. The initial capacity reached 1282.3 mA/g after charging and discharging at a current density of 0.1 A/g. After 100 cycles, its specific capacity was as high as 994.2 mAh/g with a capacity retention of 77.5%, demonstrating good cycle performance. The nitrogen-doped carbon shell of the Si@void@N-C material helps with the electrical conductivity of the composite material. Meanwhile, the yolk-shell structure effectively alleviates the volume effect of silicon; this feature is beneficial to the formation of a stable SEI film and improves the cycle stability of the battery.

Key words: lithium-ion battery, nitrogen-doped carbon, silicon-based anode, yolk-shell structure

中图分类号:

TM912.9

鲍恺婧, 张召凯, 朴贤卿, 孙卓. 氮掺杂碳包覆的蛋黄壳结构硅负极材料[J]. 华东师范大学学报（自然科学版）, 2022, 2022(1): 22-30.

Kaijing BAO, Zhaokai ZHANG, Xianqing PIAO, Zhuo SUN. Yolk-shell silicon anode material coated with nitrogen-doped carbon[J]. Journal of East China Normal University(Natural Science), 2022, 2022(1): 22-30.

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参考文献 25

1	RUFFO R, HONG S S, CHAN C K, et al. Impedance analysis of silicon nanowire lithium-ion battery anodes. The Journal of Physical Chemistry C, 2009, 113 (26): 11390- 11398. doi: 10.1021/jp901594g
2	WU J, MA F, LIU X, et al. Recent progress in advanced characterization methods for silicon-based lithium-ion batteries. Small Methods, 2019, 3 (10): 1900158. doi: 10.1002/smtd.201900158
3	WANG J, TANG H, ZHANG L, et al. Multi-shelled metal oxides prepared via an anion-adsorption mechanism for lithium-ion batteries. Nature Energy, 2016, (1): 1- 9.
4	LIAO D, KUANG X, XIANG J, et al. A silicon anode material with layered structure for the lithium-ion battery. Journal of Physics Conference Series, 2018, 986 (1): 12- 24.
5	KIM Y Y, LEE J H, KIM H J. Nanoporous silicon flakes as anode active material for lithium-ion batteries. Physica E: Low-dimensional Systems and Nanostructures, 2017 85, 223- 226.
6	XIAO J, XU W, WANG D, et al. Stabilization of silicon anode for Li-ion batteries. Journal of The Electrochemical Society, 2010, 157 (10): A1047- A1051. doi: 10.1149/1.3464767
7	MAGASINSKI A, DIXON P, HERTZBERG B, et al. High-performance lithium-ion anodes USING a hierarchical bottom-up approach. Nature Materials, 2010, (9): 353- 358.
8	DU F, WANG K, CHEN J. Strategies to succeed in improving the lithium-ion storage properties of silicon nanomaterials. Journal of Materials Chemistry, 2016, (A4): 32- 50.
9	YAO Y, MCDOWELL M T, RYU I, et al. Interconnected silicon hollow nanospheres for lithium-ion battery anodes with long cycle life. Nano Letters, 2011, (11): 2949- 2954.
10	PARK M H, KIM G, JOO J, et al. Silicon nanotube battery anodes. Nano Letters, 2009, 9 (11): 3844- 3847. doi: 10.1021/nl902058c
11	EPUR R, HANUMANTHA P J, DATTA M K, et al. A simple and scalable approach to hollow silicon nanotube (h-SiNT) anode architectures of superior electrochemical stability and reversible capacity. Journal of Materials Chemistry A, 2015, 3 (20): 11117- 11129. doi: 10.1039/C5TA00961H
12	WU H, CHAN G, CHOI J W, et al. Stable cycling of double-walled silicon nanotube battery anodes through solid–electrolyte interphase control. Nature Nanotechnology, 2012, 7 (5): 310- 315. doi: 10.1038/nnano.2012.35
13	XING Y, ZHANG L, MAO S, et al. Core-shell structure of porous silicon with nitrogen-doped carbon layer for lithium-ion batteries. Materials Research Bulletin, 2018 108, 170- 175.
14	AN W, GAO B, MEI S, et al. Scalable synthesis of ant-nest-like bulk porous silicon for high-performance lithium-ion battery anodes. Nature Communications, 2019, 10 (1): 1447- 1452. doi: 10.1038/s41467-019-09510-5
15	LIU N, WU H, MCDOWELL M T, et al. A yolk-shell design for stabilized and scalable Li-ion battery alloy anodes. Nano Letters, 2012, 12 (6): 3315- 3321. doi: 10.1021/nl3014814
16	ZHANG L, RANJUSHA R, GUO H P, et al. A green and facile way to prepare granadilla-like silicon-based anode materials for Li-ion batteries. Advanced Functional Materials, 2016, 26 (3): 440- 446. doi: 10.1002/adfm.201503777
17	CHEN L F, ZHANG X D, LIANG H W, et al. Synthesis of nitrogen-doped porous carbon nanofibers as an efficient electrode material for supercapacitors. ACS Nano, 2012, (6): 7092- 7102.
18	INAGAKI M, KONNO H, TANAIKE O. Carbon materials for electrochemical capacitors. Power Sources, 2010, 195, 7880- 7903. doi: 10.1016/j.jpowsour.2010.06.036
19	PODYACHEVA O Y, CHEREPANOVA S V, ROMANENKO A I, et al. Nitrogen doped carbon nanotubes and nanofibers: Composition, structure, electrical conductivity and capacity properties. Carbon, 2017, 122, 475- 483. doi: 10.1016/j.carbon.2017.06.094
20	JIN N, SU Z, YUE N, et al. Direct amination of Si nanoparticles for the preparation of Si@ultrathin SiOx@graphene nanosheets as high performance lithium-ion battery anodes. Journal of Materials Chemistry A, 2015, 3 (39): 19892- 19900. doi: 10.1039/C5TA05386B
21	CHEN Y, SHI L, GUO S, et al. A general strategy towards carbon nanosheets from triblock polymers as high-rate anode materials for lithium and sodium ion batteries. Journal of Materials Chemistry A, 2017, (5): 19866- 19874.
22	SHENG Z H, SHAO L, CHEN J J, et al. Catalyst-free synthesis of nitrogen-doped graphene via thermal annealing graphite oxide with melamine and its excellent electrocatalysis. Acs Nano, 2011, 5 (6): 4350- 4358. doi: 10.1021/nn103584t
23	ZHOU X S, YIN Y X, WAN L J, et al. Self-assembled nanocomposite of silicon nanoparticles encapsulated in graphene through electrostatic attraction for lithium-ion batteries. Advanced Energy Materials, 2012, (11): 1086- 1090.
24	WANG B, LI X, ZHANG X, et al. Adaptable silicon-carbon nanocables sandwiched between reduced graphene oxide sheets as lithium-ion battery anodes. Acs Nano, 2013, 7 (2): 1437- 1445. doi: 10.1021/nn3052023
25	YANG S, SONG H, CHEN X. Electrochemical performance of expanded mesocarbon microbeads as anode material for lithium-ion batteries. Electrochemistry Communications, 2006, 8 (1): 137- 142. doi: 10.1016/j.elecom.2005.10.035

[1]	张贤惠,陈珍莲,陈晓波. MoS2的电化学表征与探究(英)[J]. 华东师范大学学报(自然科学版), 2015, 2015(3): 105-115.
[2]	王斐，徐少辉，祝珊珊，楼薛锋，惠珂霜，杨平雄，王连卫. 覆银硅微通道板用于三维锂离子电池负极研究[J]. 华东师范大学学报(自然科学版), 2013, 2013(5): 110-118, 129.