锂离子电池化成技术研究进展

doi:10.19799/j.cnki.2095-4239.2020.0270

摘要/Abstract

摘要：

锂离子电池生产过程中需要进行化成，实现对电极的浸润及对电极材料进行充分激活。同时，在首次充电过程中，随着锂离子在负极的嵌入，电解液成分在负极发生还原反应形成一层稳定的固体电解质界面膜(SEI膜)，以防止后续循环过程中电解液和锂离子的不可逆消耗，因此该技术对电池性能的意义非同寻常，化成的效果直接影响锂离子电池的后续性能表现，包括存储性能、循环寿命、倍率性能和安全性等。然而，对于电动汽车电池组中的每个单体电池，都需要耗时几天甚至几星期的化成和老化工序，导致较低的电池生产效率；大量的充放电设备、控温设备和环境空间提高了电池的生产成本；传统的化成方式无法完全满足容量，寿命和安全等高性能需求。目前已有很多研究通过优化锂离子电池化成技术来提高电池性能，降低化成时间，从而降低电池生产成本。本综述针对锂离子化成技术优化展开评述，介绍电池化成的意义、成本分析、各种技术参数和化成方法，并对未来的研究和改进方向进行展望。

关键词: 锂离子电池, 化成技术, 固体电解质界面膜, 生产效率, 生产成本

Abstract:

In the process of LIB production, the formation processes aim at achieving the wetting of the electrodes and the activation of the electrode materials. Meanwhile, during the initial charge, with the insertion of lithium ions, the electrolyte components are reduced in the anode and form a stable solid electrolyte interface film on the anode for preventing the irreversible consumption of the electrolyte and lithium ions in the subsequent cycling. Consequently, these techniques are of great significance for the battery performance; the formation effect directly affects the subsequent performance of LIBs, including storage performance, cycle life, rate performance and safety. However, for each single battery in the battery pack of electric vehicles, it takes days or even weeks to carry out the formation and conditioning processing, resulting in low battery production efficiency. A large amount of charge/discharge equipment, temperature control equipment, and environmental space increases the cost of battery production. The traditional formation method cannot completely meet the requirements of high performance, such as capacity, life, and safety, in LIBs. To date, there have been many studies on improving the battery performance and reducing the formation time and the cost of battery production by optimizing the formation technique of LIBs. This review focuses on the optimization of the lithium-ion formation technique, introducing the significance of battery formation, cost analysis, and various technological parameters and forecasting the future research and improvement directions.

Key words: lithium ion batteries, formation technique, SEI films, production efficiency, cost of production

中图分类号:

TM 912

林乙龙, 肖敏, 韩东梅, 王拴紧, 孟跃中. 锂离子电池化成技术研究进展[J]. 储能科学与技术, 2021, 10(1): 50-58.

Yilong LIN, Min XIAO, Dongmei HAN, Shuanjin WANG, Yuezhong MENG. Research progress in formation technique for LIBs[J]. Energy Storage Science and Technology, 2021, 10(1): 50-58.

图/表 7

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参考文献 42

1	DUNN B, KAMATH H, TARASCON J. Electrical energy storage for the grid: A battery of choices[J]. Science, 2011, 334(6058): 928-935.
2	LI Wei, LIU Jun, ZHAO Dongyuan. Mesoporous materials for energy conversion and storage devices[J]. Nature Reviews Materials, 2016, 1: 16023-16039.
3	LIU Wen, OH Pilgun, LIU Xien, et al. Nickel-rich layered lithium transition-metal oxide for high-energy lithium-ion batteries[J]. Angewandte Chemie International Edition, 2015, 54(15): 4440-4457.
4	HE Yu, YU Xiqian, WANG Yanhong, et al. Alumina-coated patterned amorphous silicon as the anode for a lithium-ion battery with high coulombic efficiency[J]. Advanced Materials, 2011, 23(42): 4938-4941.
5	CHO Taehyung, TANAKA M, OHNISHI H, et al. Composite nonwoven separator for lithium-ion battery: Development and characterization[J]. Journal of Power Sources, 2010, 195(13): 4272-4277.
6	LIN Yilong, XU Mengqing, WU Suping, et al. Insight into the mechanism of improved interfacial properties between electrodes and electrolyte in the graphite/LiNi_0.6Mn_0.2Co_0.2O₂ cell via incorporation of 4-propyl-[1,3,2]dioxathiolane-2,2-dioxide (PDTD)[J]. ACS Applied Materials & Interfaces, 2018, 10(19): 16400-16409.
7	WOOD D L, LI J L, DANIEL C. Prospects for reducing the processing cost of lithium ion batteries[J]. Journal of Power Sources, 2015, 275: 234-242.
8	LI J L, DANIEL C, WOOD D L. Materials processing for lithium-ion batteries[J]. Journal of Power Sources, 2011, 196(5): 2452-2460.
9	PATHAN T S, RASHID M, WALKER M, et al. Active formation of Li-ion batteries and its effect on cycle life[J]. Journal of Physics: Energy, 2019, 1(4): doi: 10.1088/2515-7655/ab2092.
10	ANTONOPOULOS B K, STOCK C, MAGLIA F, et al. Solid electrolyte interphase: Can faster formation at lower potentials yield better performance?[J]. Electrochimica Acta, 2018, 269(10): 331-339.
11	LI J L, DU Z J, RUTHER R E, et al. Toward low-cost, high-energy density, and high-power density lithium-ion batteries[J]. JOM, 2017, 69(9): 1484-1496.
12	DAVOODABADI A, LI J L, ZHOU H, et al. Effect of calendering and temperature on electrolyte wetting in lithium-ion battery electrodes[J]. Journal of Energy Storage, 2019, 26: doi: 10.1016/j.est.2019.101034.
13	WOOD D L, LI J L, AN S J. Formation challenges of lithium-ion battery manufacturing[J]. Joule, 2019, 3(12): 2884-2888.
14	AN S J, LI J L, DU Z J, et al. Fast formation cycling for lithium ion batteries[J]. Journal of Power Sources, 2017, 342: 846-852.
15	LEE Hsianghwan, WANG Yungyun, WAN Chichao, et al. A fast formation process for lithium batteries[J]. Journal of Power Sources, 2004, 134: 118-123.
16	MAO C Y, AN S J, MEYER H M, et al. Balancing formation time and electrochemical performance of high energy lithium-ion batteries[J]. Journal of Power Sources, 2018, 402: 107-115.
17	BHATTACHARYA S, ALPAS A T. Micromechanisms of solid electrolyte interphase formation on electrochemically cycled graphite electrodes in lithium-ion cells[J]. Carbon, 2012, 50(15): doi: 10.1016/j.carbon.2012.07.009.
18	WANG Renheng, LI Xinhai, WANG Zhixing. Electrochemical analysis graphite/electrolyte interface in lithium-ion batteries: p-toluenesulfonyl isocyanate as electrolyte additive[J]. Nano Energy, 2017, 34: 131-140.
19	XU Kang. Electrolytes and interphases in Li-ion batteries and beyond[J]. Chemical Reviews, 2014, 114(23): 11503-11618.
20	XU Mengqing, ZHOU Liu, DONG Yingnan, et al. Improving the performance of graphite/LiNi/_0.5Mn_1.5O₄ cells at high voltage and elevated temperature with added Lithium bis(oxalato) borate (LiBOB)[J]. Journal of the Electrochemical Society, 2013, 160(11): A2005-A2013.
21	GILBERT J A, BARENO J, SPILA T, et al. Cycling behavior of NCM523/graphite lithium-ion cells in the 3～4.4 V range: Diagnostic studies of full cells and harvested electrodes[J]. Journal of the Electrochemical Society, 2016, 164(1): A6054-A6065.
22	GLAZIER S L, LI J, LOULI A J, et al. An analysis of artificial and natural graphite in lithium ion pouch cells using ultra-high precision coulometry, isothermal microcalorimetry, gas evolution, long term cycling and pressure measurements[J]. Journal of the Electrochemical Society, 2017, 164(14): A3545-A3555.
23	AGUBRA V A, FERGUS J W. The formation and stability of the solid electrolyte interface on the graphite anode[J]. Journal of Power Sources, 2014, 268(5): 153-162.
24	LOPEZ I R, LAIN M J, KENDRICK E. Optimisation of formation and conditioning protocols for lithium ion EV batteries[J]. Batteries & Supercaps, 2020, 3(9): 900-909.
25	杜强, 张一鸣, 田爽, 等. 锂离子电池SEI膜形成机理及化成工艺影响[J]. 电源技术, 2018, 42(12): 1922-1926.
	DU Qiang, ZHANG Yiming, TIAN Shuang, et al. Formation mechanism of solid electrolyte interphase (SEI) and effect of formation process on it in lithium ion batteries[J]. Chinese Journal of Power Sources, 2018, 42(12): 1922-1926.
26	杨娟. 锂离子电池化成条件对化成效果的影响[J]. 河南科技, 2017(19): 139-140.
	YANG Juan. Influence of formation conditions of lithium ion battery on formation efficiency[J]. Henan Science and Technology, 2017(19): 139-140.
27	DAVOODABADI A, LI J L, LIANG Y F, et al. Analysis of electrolyte imbibition through lithium-ion battery electrodes[J]. Journal of Power Sources, 2019, 424: 193-203.
28	JEON D H. Wettability in electrodes and its impact on the performance of lithium-ion batteries[J]. Energy Storage Materials, 2019, 18: 139-147.
29	HE Yanbing, TANG Zhiyuan, SONG Quansheng, et al. Effects of temperature on the formation of graphite/LiCoO₂ batteries[J]. Journal of the Electrochemical Society, 2008, 155(7): A481-A487.
30	GERMAN F, HINTENNACH A, LACROIX A, et al. Influence of temperature and upper cut-off voltage on the formation of lithium-ion cells[J]. Journal of Power Sources, 2014, 264: 100-107.
31	YAN Chong, YAO Yuxing, CAI Wenlong, et al. The influence of formation temperature on the solid electrolyte interphase of graphite in lithium ion batteries[J]. Journal of Energy Chemistry, 2020, 49: 335-338.
32	HUANG Chenghuan, HUANG Kelong, WANG Haiyan, et al. The effect of solid electrolyte interface formation conditions on the aging performance of Li-ion cells[J]. Journal of Solid State Electrochemistry, 2011, 15(9): 1987-1995.
33	CANNARELLA J, ARNOLD C B. Stress evolution and capacity fade in constrained lithium-ion pouch cells[J]. Journal of Power Sources, 2014, 245: 745-751.
34	PETZL M, KASPER M, DANZER M A. Lithium plating in a commercial lithium-ion battery—A low-temperature aging study[J]. Journal of Power Sources, 2015, 275: 799-807.
35	MAO Z Y, FARKHONDEH M, PRITZKER M, et al. Calendar aging and gas generation in commercial graphite/NMC-LMO lithium-ion pouch cell[J]. Journal of the Electrochemical Society, 2017, 164(14): A3469-A3483.
36	RUBINO R S, GAN Hong, TAKEUCHI E S. A study of capacity fade in cylindrical and prismatic lithium-ion batteries[J]. Journal of the Electrochemical Society, 2001 148(9): A1029-A1033.
37	PEABODY C, ARNOLD C B. The role of mechanically induced separator creep in lithium-ion battery capacity fade[J]. Journal of Power Sources, 2011, 196(19): 8147-8153.
38	HEIMES H H, OFFERMANNS C, MOHSSENI A, et al. The effects of mechanical and thermal loads during lithium-ion pouch cell formation and their impacts on the process time[J]. Energy Technology, 2020, 8(2): doi: 10.1002/ente.201900118.
39	STEINHAUER M, RISSE S, WAGNER N, et al. Investigation of the solid electrolyte interphase formation at graphite anodes in lithium-ion batteries with electrochemical impedance spectroscopy[J]. Electrochimica Acta, 2017, 228: 652-658.
40	WANG A P, KADAM S, LI H, et al. Review on modeling of the anode solid electrolyte interphase (SEI) for lithium-ion batteries[J]. Computational Materials, 2018, 3(4): 1-26.
41	OTA H, SATO T, SUZUKI H, et al. TPD-GC/MS analysis of the solid electrolyte interface (SEI) on a graphite anode in the propylene carbonate/ethylene sulfite electrolyte system for lithium batteries[J]. Journal of Power Sources, 2001, 97: 107-113.
42	ZHU Taohe, HU Qiyang, YAN Guochun, et al. Manipulating the composition and structure of solid electrolyte interphase at graphite anode by adjusting the formation condition[J]. Energy Technology, 2019, 7(9): 1900273-1900281.

成本分布	总成本/$·(kW·h)^-1	化成成本/$·(kW·h)^-1
复合电极材料	101.7	145.3
电池收集器及分离器	80.2	114.6
电极处理	36.1	51.6
电解质	24.6	35.1
润湿和成型循环	22.6	32.3
装袋和贴标材料	6.7	9.6
模块硬件，电力电子和组件冷却	46	65.7
人工成本(电极加工和电池/封装)	34	48.6
总计	351.9	502.8

T/℃	容量衰减 (a)/%		容量衰减 (b)/%		总容量衰减/%
T/℃	NCM	Graphite	NCM	Graphite	NCM	Graphite
15	26.4	9.5	-3.9	0.2	22.5	9.7
25	19.7	9.9	-0.6	0.5	19.1	10.4
35	17.2	10.8	5.1	0.6	22.3	11.4
45	15.0	13.3	8.5	0.8	23.5	14.1

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