锂离子电池硅基负极比容量提升的研究进展

doi:10.19799/j.cnki.2095-4239.2020.0163

摘要/Abstract

摘要：

优化锂离子电池负极材料的首次库仑效率和循环稳定性对提升电池的可逆比容量具有重要意义。硅碳复合材料是目前公认的下一代锂离子电池负极材料，本文调研了硅碳二次粒子负极的工艺细节对电池性能的影响，介绍了硅碳二次粒子结构设计、硅基负极材料的预锂化及硅基负极黏结剂等研究进展及存在的不足。在综合分析硅基负极材料的基础科学问题与提升比容量的关键技术的基础上，对开发高性能、高稳定性硅基负极材料的结构、工艺、黏结材料体系方面提出明确要求。

关键词: 锂离子电池, 硅基负极材料, 首次库仑效率, 硅碳复合粒子结构, 预锂化, 硅基黏结剂

Abstract:

Optimizing the initial coulombic efficiency and cycling stability of anode materials is important to improve the specific capacity of lithium-ion batteries. Acknowledgedly, silicon-carbon composite material has been regarded as the most promising candidate for the next generation of lithium- ion batteries. In this paper, to the point of higher specific capacity, the structure design of secondary particles of silicon-based carbon anode material is detailed. Meanwhile, the up-to-date achievements and bottlenecks in secondary particles design, pre-lithiation strategies and binder explorations of silicon-based anodes are systematically reviewed, given their importance in electrochemical performance promotion and specific capacity upliftment. Based on many basic scientific issues and critical technologies for specific capacity of silicon-based anodes, the suitable design of structure, process and selection of binder are recommended to the achieve in higher power and better stability of anodes on lithium-ion batteries.

Key words: lithium-ion batteries, silicon-based anodes, initial coulombic efficiency, structure of secondary particles, pre-lithiation, binder

中图分类号:

TM 911

余晨露, 田晓华, 张哲娟, 孙　卓. 锂离子电池硅基负极比容量提升的研究进展[J]. 储能科学与技术, 2020, 9(6): 1614-1628.

Chenlu YU, Xiaohua TIAN, Zhejuan ZHANG, Zhuo SUN. Research progress of specific capacity improvements of silicon-based anodes in lithium-ion batteries[J]. Energy Storage Science and Technology, 2020, 9(6): 1614-1628.

图/表 11

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参考文献 71

1	周军华, 罗飞, 褚赓, 等锂离子电池纳米硅碳负极材料研究进展[J]. 储能科学与技术, 2020, 9(2): 569-571.
	ZHOU Junhua, LUO Fei, CHU Geng, et al. Research progress of nano silicon-carbon anode materials for lithium ion battery[J]. Energy Storage Science and Technology, 2020, 9(2): 569-571.
2	陆越. 锂离子电池硅基负极结构设计及其首次库仑效率研究[D]. 武汉: 华中科技大学, 2019: 52-53, 56
	-58.LU Yue. Structural design and initial coulombic efficiency of silicon-based anode materials for lithium-ion batteries[D]. Wuhan: Huazhong University of Science & Technology, 2019: 52-53, 56-58.
3	LIU Xiaohua, ZHONG Li, HUANG Shan, et al. Size-dependent fracture of silicon nanoparticles during lithiation[J]. ACS Nano, 2012, 6(2): 1522-1531.
4	TIAN Huajun, TAN Xiaojian, XIN Fengxia, et al. Micro-sized nano-porous Si/C anodes for lithium ion batteries[J]. Nano Energy, 2015, 11: 490-499.
5	HE Wei, TIAN Huajun, XIN Fengxia, et al. Scalable fabrication of micro-sized bulk porous Si from Fe-Si alloy as a high performance anode for lithium-ion batteries[J]. Journal of Materials Chemistry A, 2015, 3(35): 17956-17962.
6	CAO Weiyi, HAN Kai, CHEN Mengxun, et al. Particle size optimization enabled high initial coulombic efficiency and cycling stability of micro-sized porous Si anode via AlSi alloy powder etching[J]. Electrochimica Acta, 2019, 320: 134613.
7	ZHAO Tianting, ZHU Delun, LI Wenrong, et al. Novel design and synthesis of carbon-coated porous silicon particles as high-performance lithium-ion battery anodes[J]. Journal of Power Sources, 2019, 439: doi: 10.1016/j.jpowsour.2019.227027.
8	YI Ran, DAI Fang, GORDIN M L, et al. Micro-sized Si-C composite with interconnected nanoscale building blocks as high-performance anodes for practical application in lithium-ion batteries[J]. Advanced Energy Materials, 2013, 3(3): 295-300.
9	YI Ran, DAI Fang, GORDIN M L, et al. Influence of silicon nanoscale building blocks size and carbon coating on the performance of micro-sized Si-C composite Li-ion anodes[J]. Advanced Energy Materials, 2013, 3(11): 1507-1515.
10	SONG Jiangxuan, CHEN Shuru, ZHOU Mingjiong, et al. Micro-sized silicon-carbon composites composed of carbon-coated sub-10 nm Si primary particles as high-performance anode materials for lithium-ion batteries[J]. Journal of Materials Chemistry A, 2014, 2(5): 1257-1262.
11	LI Jinyi, LI Ge, ZHANG Juan, et al. Rational design of robust Si/C microspheres for high-tap-density anode materials[J]. ACS Applied Materials and Interfaces, 2019, 11(4): 4057-4064.
12	YI Ran, ZAI J, DAI Fang, et al. Dual conductive network-enabled graphene/Si-C composite anode with high areal capacity for lithium-ion batteries[J]. Nano Energy, 2014, 6: 211-218.
13	LU Zhenda, LIU Nian, Hyun Wook LEE, et al. Nonfilling carbon coating of porous silicon micrometer-sized particles for high-performance[J]. ACS Nano, 2015, 9(3): 2540-2547.
14	SOHN Hiesang, KIM Dong Hyeon, YI Ran, et al. Semimicro-size agglomerate structured silicon-carbon composite as an anode material for high performance lithium-ion batteries[J]. Journal of Power Sources, 2016, 334: 128-136.
15	LI Chao, JU Yuhang, QI Li, et al. A micro-sized Si-CNT anode for practical application: Via a one-step, low-cost and green method[J]. RSC Advances, 2017, 7(86): 54844-54851.
16	SUN Yanxian, GUAN Hongmin, JIANG Zhaohua, et al. Study on prelithiation technology of hard carbon electrode using stable metal lithium powder[J]. Journal of Electrochemical Energy Conversion and Storage, 2019, 16(2): 2018-2020.
17	JEONG Sookyung, LI Xiaolin, ZHENG Jianming, et al. Hard carbon coated nano-Si/graphite composite as a high performance anode for Li-ion batteries[J]. Journal of Power Sources, 2016, 329: 323-329.
18	FORNEY M W, GANTER M J, STAUB J W, et al. Prelithiation of silicon-carbon nanotube anodes for lithium ion batteries by stabilized lithium metal powder (SLMP)[J]. Nano Letters, 2013, 13(9): 4158-4163.
19	ZHAO Hui, WEI Yang, WANG Cheng, et al. Mussel-inspired conductive polymer binder for Si-alloy anode in lithium-ion batteries[J]. ACS Applied Materials and Interfaces, 2018, 10(6): 5440-5446.
20	PAN Qingrui, ZUO Pengjian, MU Tiansheng, et al. Improved electrochemical performance of micro-sized SiO-based composite anode by prelithiation of stabilized lithium metal powder[J]. Journal of Power Sources, 2017, 347: 170-177.
21	HAN Yuyao, LIU Xinyi, LU Zhenda. Systematic investigation of prelithiated SiO₂ particles for high-performance anodes in lithium-ion battery[J]. Applied Sciences (Switzerland), 2018, 8(8): 1245. 2-9.
22	ZHU Yuanchao, HU Wei, ZHOU Jianbin, et al. Prelithiated surface oxide layer enabled high-performance Si anode for lithium storage[J]. ACS Applied Materials and Interfaces, 2019, 11(20): 18305-18312.
23	栗欢欢, 刘成洋, 陈彪, 等. 一种扣式及软包全电池的制作方法: CN108493439A [P]. 2018-09-04.
	LI Huanhuan, LIU Chengyang, CHEN Biao, et al. Button battery and flexible package all-battery production method: CN108493439A [P]. 2018-09-04.
24	MENG Qinghai, LI Ge, YUE Junpei, et al. High-performance lithiated SiO_x anode obtained by a controllable and efficient prelithiation strategy[J]. ACS Applied Materials and Interfaces, 2019, 11(35): 32062-32068.
25	WU Hao, ZHENG Lihua, ZHAN Jing, et al. Recycling silicon-based industrial waste as sustainable sources of Si/SiO₂ composites for high-performance Li-ion battery anodes[J]. Journal of Power Sources, 2020, 449: doi: 10.1016/j.jpowsour.2019.227513.
26	RODRIGUES M T F, GILBERT J A, KALAGA K, et al. Insights on the cycling behavior of a highly-prelithiated silicon-graphite electrode in lithium-ion cells[J]. Journal of Physics: Energy, 2020, 2(2): doi: 10.1088/2515-7655/AB6B3A.
27	KIM Hye Jin, CHOI Sunghun, Seung Jong LEE, et al. Controlled prelithiation of silicon monoxide for high performance lithium-ion rechargeable full cells[J]. Nano Letters, 2016, 16(1): 282-288.
28	杨梢, 马卫. 预锂化硅碳负极材料及其制备方法与锂离子电池: CN109817953A [P]. 2019-05-28.
	YANG Shao, MA Wei. Pre-lithiated silicon-carbon negative electrode material and preparation method thereof and lithium ion battery: CN109817953A [P]. 2019-05-28.
29	刘静, 高秀玲, 王驰伟. 一种采用三维箔材的锂离子电池负极单面预锂化方法: CN108550780A [P]. 2018-09-18.
	LIU Jing, GAO Xiuling, WANG Chiwei. Lithium ion battery negative electrode single-side pre-lithiation method using three-dimensional foil: CN108550780A [P]. 2018-09-18.
30	杨玉洁. 金属锂带及其制备方法及使用该金属锂带的储能器件: CN104900841B [P]. 2018-03-30.
	YANG Yujie. Lithium metal strip, preparation method thereof, and energy storage device using lithium metal strip: CN104900841B [P]. 2018-03-30.
31	李良彬, 熊训满, 李玉成, 等. 一种金属锂带生产装置及方法: CN104759478A [P]. 2015-07-08.
	LI Liangbin, XIONG Xunman, LI Yucheng, et al. Metal lithium belt manufacturing device and method: CN104759478A [P]. 2015-07-08.
32	张杰. 金属锂带自动卷绕装置: CN207086594U [P]. 2018-03-13.
	ZHANG Jie. Automatic take -up device in lithium metal area: CN207086594U [P]. 2018-03-13.
33	陈强, 牟瀚波, 程滋平, 等. 一种超薄金属锂带生产线: CN206911938U [P]. 2018-01-23.
	CHEN Qiang, MOU Hanbo, CHENG Ziping, et al. Super thin metal lithium area production line: CN206911938U [P]. 2018-01-23.
34	曹乃珍, 邹崴, 刘强, 等. 3D打印制备金属锂带的方法: CN108145165A [P]. 2018-06-12.
	CAO Naizhen, ZOU Wai, LIU Qiang, et al. Method for preparing metallic lithium strip through 3D printing: CN108145165A [P]. 2018-06-12.
35	杨杰, 谭谋, 李正, 等. 一种超薄金属锂带的制备方法: CN109346680A [P]. 2019-02-15.
	YANG Jie, TAN Mou, LI Zheng, et al. Preparation method of ultrathin metal lithium belt: CN109346680A [P]. 2019-02-15.
36	李世玲. 一种金属锂带的生产方法: CN1644258A [P]. 2005-07-27.
	LI Shiling. Production for metal lithium bands: CN1644258A [P]. 2005-07-27.
37	陈强, 牟瀚波. 复合型金属锂带: CN201017936Y [P]. 2008-02-06.
	CHEN Qiang, MOU Hanbo. Composite type metal lithium strip: CN201017936Y [P]. 2008-02-06.
38	杨玉洁. 一种金属锂带及其制备方法及使用该金属锂带的储能器件: CN104868127A [P]. 2015-08-26.
	YANG Yujie. Metal lithium strip, preparation method thereof and energy storage device using metal lithium strip: CN104868127A [P]. 2015-08-26.
39	聂阳, 邹崴, 曹乃珍. 一种低品位锂源制备超薄金属锂带的系统: CN208949364U [P]. 2019-06-07.
	NIE Yang, ZOU Wai, CAO Naizhen. System for preparing ultrathin metal lithium strip from low-grade lithium source: CN208949364U [P]. 2019-06-07.
40	张杰. 超宽金属锂带的生产方法及系统: CN106914503A [P]. 2017-07-04.
	ZHANG Jie. Production method and system for ultra-wide metallic lithium strip: CN106914503A [P]. 2017-07-04.
41	唐胜利, 郑正坤, 刘右军. 一种锂离子电池负极材料补锂方法及电池的制备方法: CN110676427A [P]. 2020-01-10.
	TANG Shengli, ZHENG Zhengkun, LIU Youjun. Lithium ion battery negative electrode material lithium supplementing method and battery preparation method: CN110676427A [P]. 2020-01-10.
42	龚志杰, 徐永强, 谢斌, 等. 用于极片补锂的装置: CN210136958U [P]. 2020-03-10.
	GONG Zhijie, XU Yongqiang, XIE Bin. A device for electrode pre-lithiation: CN210136958U [P]. 2020-03-10.
43	王晓钰, 张渝, 马磊, 等. 锂离子电池硅基负极黏结剂发展现状[J]. 化学学报, 2019, 77(1): 25-26.
	WANG Xiaoyu, ZHANG Yu, MA Lei, et al. Recent development on binders for silicon-based anodes in lithium-ion batteries[J]. Acta Chimica Sinica, 2019, 77(1): 25-26.
44	FENG Kun, LI M, LIU Wenwen, et al. Silicon-based anodes for lithium-ion batteries: from fundamentals to practical applications[J]. Small, 2018, 14(8): doi: 10.1002/smll.201702737.
45	HOCHGATTERER N S, SCHWEIGER M R, KOLLER S, et al. Silicon/graphite composite electrodes for high-capacity anodes: influence of binder chemistry on cycling stability[J]. Electrochemical and Solid-State Letters, 2008, 11(5): A76-A80.
46	MAGASINSKI A, ZDYRKO B, KOVALENKO I, et al. Toward efficient binders for Li-ion battery Si-based anodes: polyacrylic acid[J]. ACS Applied Materials & Interfaces, 2010, 2(11): 3004-3010.
47	HERNANDEZ C R, ETIEMBLE A, DOUILLARD T, et al. A facile and very effective method to enhance the mechanical strength and the cyclability of Si-based electrodes for Li-ion batteries[J]. Advanced Energy Materials, 2018, 8(6): doi: 10.1002/aenm.201701787.
48	LI Jing, LEWIS R B, DAHN J R. Sodium carboxymethyl cellulose[J]. Electrochemical and Solid-State Letters, 2007, 10(2): 20-23.
49	MAZOUZI D, LESTRIEZ B, ROUÉ L, et al. Silicon composite electrode with high capacity and long cycle life[J]. Electrochemical and Solid-State Letters, 2009, 12(11): A215-A218.
50	LIU Jie, ZHANG Qian, WU Zhanyu, et al. A high-performance alginate hydrogel binder for the Si/C anode of a Li-ion battery[J]. Chemical Communications, 2014, 50(48): 6386-6389.
51	KURUBA R, DATTA M K, DAMODARAN K, et al. Guar gum: Structural and electrochemical characterization of natural polymer based binder for silicon-carbon composite rechargeable Li-ion battery anodes[J]. Journal of Power Sources, 2015, 298: 331-340.
52	LIU Jie, ZHANG Qian, ZHANG Tao, et al. A robust ion-conductive biopolymer as a binder for Si anodes of lithium-ion batteries[J]. Advanced Functional Materials, 2015, 25(23): 3599-3605.
53	LING Min, XU Yanan, ZHAO Hui, et al. Dual-functional gum arabic binder for silicon anodes in lithium ion batteries[J]. Nano Energy, 2015, 12: 178-185.
54	BIE Yitian, YANG Jun, NULI Yanna, et al. Natural karaya gum as an excellent binder for silicon-based anodes in high-performance lithium-ion batteries[J]. Journal of Materials Chemistry A, 2017, 5(5): 1919-1924.
55	JEONG You Kyeong, KWON Tae-woo, Inhwa LEE, et al. Millipede-inspired structural design principle for high performance polysaccharide binders in silicon anodes[J]. Energy and Environmental Science, 2015, 8(4): 1224-1230.
56	YOON Da Eun, HWANG Chihyun, KANG Na Ri, et al. Dependency of electrochemical performances of silicon lithium-ion batteries on glycosidic linkages of polysaccharide binders[J]. ACS Applied Materials and Interfaces, 2016, 8(6): 4042-4047.
57	ZHANG Li, ZHANG Liya, CHAI Lili, et al. A coordinatively cross-linked polymeric network as a functional binder for high-performance silicon submicro-particle anodes in lithium-ion batteries[J]. Journal of Materials Chemistry A, 2014, 2(44): 19036-19045.
58	Bonjae KOO, KIM Hyunjung, Younghyun CHO, et al. A highly cross-linked polymeric binder for high-performance silicon negative electrodes in lithium ion batteries[J]. Angewandte Chemie-International Edition, 2012, 51(35): 8762-8767.
59	SONG Jiangxuan, ZHOU Mingjiong, YI Ran, et al. Interpenetrated gel polymer binder for high-performance silicon anodes in lithium-ion batteries[J]. Advanced Functional Materials, 2014, 24(37): 5904-5910.
60	LIU Yajie, TAI Zhixin, ZHOU Tengfei, et al. An all-integrated anode via interlinked chemical bonding between double-shelled-yolk-structured silicon and binder for lithium-ion batteries[J]. Advanced Materials, 2017, 29(44): 1-11.
61	LOVERIDGE M J, LAIN M J, HUANG Qianye, et al. Enhancing cycling durability of Li-ion batteries with hierarchical structured silicon-graphene hybrid anodes[J]. Physical Chemistry Chemical Physics, 2016, 18(44): 30677-30685.
62	WEI Liangming, HOU Zhongyu. High performance polymer binders inspired by chemical finishing of textiles for silicon anodes in lithium ion batteries[J]. Journal of Materials Chemistry A, 2017, 5(42): 22156-22162.
63	Sun Young LEE, CHOI Yunju, HONG Kyong Soo, et al. Influence of EDTA in poly(acrylic acid) binder for enhancing electrochemical performance and thermal stability of silicon anode[J]. Applied Surface Science, 2018, 447: 442-451.
64	何旻雁, 杨志伟, 王振宇, 等. 聚酰亚胺黏结剂对锂离子电池用硅碳复合材料循环性能的影响[J]. 绝缘材料, 2019, 52: 21-24, 28.
	HE Minyan, YANG Zhiwei, WANG Zhenyu, et al. Effect of polyimide binder on cycling performance of Si/C composite for Li-ion battery[J]. Insulating Materials, 2019, 52: 21-24, 28.
65	TIAN Meng, CHEN Xiao, SUN Shengtong, et al. A bioinspired high-modulus mineral hydrogel binder for improving the cycling stability of microsized silicon particle-based lithium-ion battery[J]. Nano Research, 2019, 12(5): 1121-1127.
66	HIGGINS T M, PARK Sang Hoon, KING P J, et al. A commercial conducting polymer as both binder and conductive additive for silicon nanoparticle-based lithium-ion battery negative electrodes[J]. ACS Nano, 2016, 10(3): 3702-3713.
67	LIU Xuejiao, ZAI Jiantao, IQBAL A, et al. Glycerol-crosslinked PEDOT: PSS as bifunctional binder for Si anodes: Improved interfacial compatibility and conductivity[J]. Journal of Colloid and Interface Science, 2020, 565: 270-277.
68	TANG Ruixian, MA Lei, ZHANG Yu, et al. A flexible and conductive binder with strong adhesion for high performance silicon-based lithium-ion battery anode[J]. ChemElectroChem, 2020, 7: 1-10.
69	WU Hui, YU Guihua, PAN Lijia, et al. Stable Li-ion battery anodes by in-situ polymerization of conducting hydrogel to conformally coat silicon nanoparticles[J]. Nature Communications, 2013, 4: 1943-1946.
70	KIM Sang-Mo, KIM Myeong Hak, CHOI Sung Yeol, et al. Poly(phenanthrenequinone) as a conductive binder for nano-sized silicon negative electrodes[J]. Energy and Environmental Science, 2015, 8(5): 1538-1543.
71	ZHANG Peng, ZHU Qizhen, GUAN Zhaoruxin, et al. A flexible Si@C electrode with excellent stability employing an MXene as a multifunctional binder for lithium-ion batteries[J]. ChemSusChem, 2020, 13(6): 1621-1628.

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