Synthesis and electrochemical performance of nano-Ge-Sn/C composite material

doi:10.3969/j.issn.1674-1951.2021.07.004

Abstract

Abstract:

Ge has become the most promising anode material for lithium-ion batteries due to its high theoretical capacity.Our team has prepared a nano-Ge-Sn/C composite material：carbon can improve the conductivity of Ge and adapt to the change in its volume,and Sn can further improve the conductivity of the material.Since the electric potentials of Ge and Sn to deintercalate/intercalate lithium ion are different,the component that does not participate in the reaction can be used as a matrix to buffer the volume change led by the other component in charge and discharge processes,which can improve the structural stability of the electrode.The morphology,structure and composition of the material were analyzed by SEM,EDS and XRD.The capacity of the lithium-ion battery taking this composite as its anode material was 1 292 （mA·h）/g in the first cycle discharge at a current density of 0.5 A/g,and remained at 510 （mA·h）/g after 100 cycles’ discharge.When the current density was increased to 10 A/g,the battery kept a capacity of 460 （mA·h）/g.It indicates a good cyclical stability and rate performance of this composite.

Key words: lithium-ion battery, Ge-Sn/C anode material, specific capacity, current density, lithiumation reaction, rate performance

CLC Number:

TK02

QIAO Xue, YANG Xuebiao, HUANG Tingting, WANG Xinyue, JIA Zichen, WANG Hongqiang. Synthesis and electrochemical performance of nano-Ge-Sn/C composite material[J]. Huadian Technology, 2021, 43(7): 24-29.

Figures/Tables 10

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References 24

[1]	李小强, 陈欣, 李洪波, 等. 碳包覆CaSnO₃纳米纤维作为高性能锂离子电池负极材料[J]. 无机化学学报, 2021, 37(4):700-708.
	LI Xiaoqiang, CHEN Xin, LI Hongbo, et al. Carbon-coated CaSnO₃ nanofibers as high performance anode materials for lithium ion batteries [J]. Chinese Journal of Inorganic Chemistry, 2021, 37(4):700-708.
[2]	WANG Hongqiang, ZHANG Na, LI Ying, et al. Unique flexible NiFe₂O₄@S/rGO-CNT electrode via the synergistic adsorption/electrocatalysis effect toward high-performance lithium-sulfur batteries[J]. Journal of Physical Chemistry Letters, 2019, 10(21):6518-6524. doi: 10.1021/acs.jpclett.9b02649 pmid: 31596089
[3]	张林森, 郭春朵, 宋延华, 等. 原位合成Ni₃N/g-C₃N₄复合材料的储锂性能[J]. 电池, 2021, 51(1):13-16.
	ZHANG Linsen, GUO Chunduo, SONG Yanhua, et al. Lithium storage performance of in-situ synthesized Ni₃N/g-C₃N₄ composite [J]. Battery Bimonthly, 2021, 51(1):13-16.
[4]	CHEN Z, YANG X B, QIAO X, et al. Lithium-ion-engineered interlayers of V₂C MXene as advanced host for flexible sulfur cathode with enhanced rate performance[J]. Journal of Physical Chemistry Letters, 2020, 11(3):885-890. doi: 10.1021/acs.jpclett.9b03827
[5]	惠康龙, 傅继澎, 高湉, 等. 金属硫化物在可充电电池中的研究进展[J]. 应用化学, 2020, 37(12):1384-1402. doi: 10.11944/j.issn.1000-0518.2020.12.200190
	HUI Kanglong, FU Jipeng, GAO Tian, et al. Research progress of metal sulfides in rechargeable batteries[J]. Chinese Journal of Applied Chemistry, 2020, 37(12):1384-1402.
[6]	HU Zhenglin, ZHANG Shu, ZHANG Chuanjian, et al. High performance germanium-based anode materials[J]. Coordination Chemistry Reviews, 2016, 326:34-85. doi: 10.1016/j.ccr.2016.08.002
[7]	方华, 丰小华, 张林森, 等. 锂离子电池硅/碳复合负极材料的研究现状[J]. 电池, 2020, 50(6):580-584.
	FANG Hua, FENG Xiaohua, ZHANG Linsen, et al. Research status quo of silicon/carbon composite anode material for Li-ion battery[J]. Battery Bimonthly, 2020, 50(6):580-584.
[8]	XI Xiaoli, CHEN Guanglei, NIE Zuoren, et al. Preparation and performance of LiFePO₄ and LiFePO₄/C cathodes by freeze-drying[J]. Journal of Alloys and Compounds, 2010, 497(1-2):377-379. doi: 10.1016/j.jallcom.2010.03.078
[9]	KWON D, RYU J, SHIN M, et al. Synjournal of dual porous structured germanium anodes with exceptional lithium-ion storage performance[J]. Journal of Power Sources, 2018, 374:217-224. doi: 10.1016/j.jpowsour.2017.11.044
[10]	LIN N, LI T Q, HAN Y, et al. Mesoporous hollow Ge microspheres prepared via molten-salt metallothermic reaction for high-Pperformance Li-storage anode[J]. ACS Applied Materials & Interfaces, 2018, 10(10):8399-8404.
[11]	WANG Y, LUO S N, CHEN M, et al. Uniformly confined germanium quantum dots in 3D ordered porous carbon framework for high-performance Li-ion battery[J]. Advanced Functional Materials, 2020, 30(16):2000373. doi: 10.1002/adfm.v30.16
[12]	LIU Xin, LIU Yusi, HARRIS M M, et al. Germanium nanoparticles supported by 3D ordered macroporous nickel frameworks as high-performance free-standing anodes for Li-ion batteries[J]. Chemical Engineering Journal, 2018, 354:616-622. doi: 10.1016/j.cej.2018.08.056
[13]	MULLANE E, KENNEDY T, GEANEY H, et al. A rapid,solvent-free protocol for the synjournal of germanium nanowire lithium-ion anodes with a long cycle life and high rate capability[J]. Acs Applied Materials & Interfaces, 2014, 6(21):18800-18807.
[14]	KWON D, RYU J, SHIN M, et al. Synjournal of dual porous structured germanium anodes with exceptional lithium-ion storage performance[J]. Journal of Power Sources, 2018, 374:217-224. doi: 10.1016/j.jpowsour.2017.11.044
[15]	LI Dan, WANG Hongqiang, LIU Huakun, et al. A new strategy for achieving a high performance anode for lithium ion batteries encapsulating germanium nanoparticles in carbon nanoboxes[J]. Advanced Energy Materials, 2016, 6(5):1501666. doi: 10.1002/aenm.201501666
[16]	杨丽杰. 锂离子电池石墨类碳负极的容量衰减机制研究[D]. 哈尔滨:哈尔滨工业大学, 2014.
[17]	任永欢. 锂离子电池低温/高电压电解液研究[D]. 北京:北京理工大学, 2015.
[18]	QU J, YIN Y X, WANG Y Q, et al. Layer structured alpha-Fe₂O₃ nanodisk/reduced graphene oxide composites as high-performance anode materials for lithium-ion batteries[J]. Acs Applied Materials & Interfaces, 2013, 5(9):3932-3936.
[19]	许康力. 锂-硫电池电极材料制备及电化学反应动力学研究[D]. 合肥:中国科学技术大学, 2020.
[20]	张孝华. 层状P2型Na_2/3Ni_1/3Mn_5/9Al_1/9O₂钠离子电池正极材料的性能提升与电极动力学研究[D]. 长春:东北师范大学, 2017.
[21]	YE Xucun, LIN Zhihua, LIANG Shujie, et al. Upcycling of electroplating sludge into ultrafine Sn@C nanorods with highly stable lithium storage performance[J]. Nano Letters, 2019, 19(3):1860-1866. doi: 10.1021/acs.nanolett.8b04944 pmid: 30676748
[22]	QIAO X, YANG X B, ZHANG N, et al. One-step in situ encapsulation of Ge nanoparticles into porous carbon network with enhanced electron/ion conductivity for lithium storage[J]. Rare Metals, 2021, 40:2432-2439. doi: 10.1007/s12598-020-01662-4
[23]	于敬学. 硅和锗基纳米材料的合成及作为锂离子电池负极材料的研究[D]. 杭州:浙江大学, 2014.
[24]	王帮润. 高比能量锂离子电池硅/锗基负极材料的制备及其电化学性能研究[D]. 合肥:中国科学院大学(中国科学院上海硅酸盐研究所), 2019.

材料	x（C)	x（Ge）	x（Sn）
C@Ge	83.2	16.8	0
C@GS3	86.8	13.0	0.2
C@GS10	88.7	10.7	0.6

材料	电流密度/(mA⋅g^-1)
材料	0.20	0.50	1.00	2.00	5.00	8.00	10.00
C@GS3	0.25	0.24	0.26	0.29	0.35	0.39	0.40
C@GS10	0.26	0.25	0.26	0.30	0.36	0.40	0.44
C@Ge	0.26	0.28	0.31	0.35	0.41	0.48	0.52