软包锂离子电池真空环境下循环性能特性

doi:10.19799/j.cnki.2095-4239.2021.0562

摘要/Abstract

摘要：

为研究飞行器和轨道空间站等低气压真空环境下，锂离子电池的循环安全性能。实验采用商用Li(NiCoMn)O₂软包锂电池，在球舱近似真空压力下，进行0.5 C倍率循环充放电实验，并与常压环境下进行对比分析。研究发现：真空循环后，电池出现严重的大面积不可恢复形变和褶皱且厚度增加。随着循环次数增加，容量加速衰减，循环10次后容量低于80 %。但恢复常压后，出现少部分容量的恢复；真空下扩大了充放电过程中的膨胀与收缩效应，加速了容量的衰减同时也造成部分容量的假性损失；电池周期性升温和降温速率加快，周期内温度不均匀性加剧，最大温差可达12.9 ℃，充放电的热稳定性和安全性变差，同时潜在的热灾害危害性变大。通过微分容量分析发现，低压真空环境下，所产生的活性锂的损耗和电极材料结构的损伤是降低电池循环充放性能的重要因素。

关键词: 软包锂离子电池, 真空环境, 循环安全性能, 不可逆形变, 容量衰减, 热稳定性

Abstract:

To investigate the cycle safety performance of batteries under low-pressure conditions, such as those found on the space station, aircrafts were used. The pouch batteries Li(NiCoMn)O₂ were cycled at 0.5 ℃ at a pressure of 0 kPa in a low-pressure cabin. After the experiment, the cycle characteristics changed greatly compared with the standard pressure environment. With the increase in cycles, severe large-scale areas of unrecoverable deformation occurred on the batteries, and the thickness increased. Furthermore, the capacity decreased rapidly, and it was >80% after 10 cycles. However, when the pressure is increased from 0 kPa to 95 kPa, a small portion of the cycle capacity is recovered. Under vacuum pressure, the processes of expansion and contraction within the battery during charging and discharging are accelerated. It hastens capacity attenuation and causes false loss of some capacity due to massive internal and external pressures. Besides, the battery periodic heating and cooling accelerates, and the temperature inhomogeneity deteriorates within the cycle. Therefore, the maximum temperature difference between the charge and the discharge is 12.9 ℃. Obviously, the battery's thermal stability and safety deteriorate, whereas the potential thermal hazard during charging and discharging increases under low-pressure conditions. Capacity differential analysis demonstrates that the loss of active lithium and the destruction of the electrode material structure are essential factors that decrease the cyclic charging and discharging performance of the battery in a low-pressure vacuum environment.

Key words: soft pack lithium-ion battery, vacuum pressure condition, cycle safety performance, irreversible deformation, capacity attenuation, thermal stability

中图分类号:

TM 912

刘杭鑫, 陈现涛, 孙强, 赵晨曦. 软包锂离子电池真空环境下循环性能特性[J]. 储能科学与技术, 2022, 11(6): 1806-1815.

LIU Hangxin, CHEN Xiantao, SUN Qiang, ZHAO Chenxi. Cycle performance characteristics of soft pack lithium-ion batteries under vacuum environment[J]. Energy Storage Science and Technology, 2022, 11(6): 1806-1815.

图/表 11

图1

图2

图3

图4

图5

图6

图7

表1

图8

图9

图10

参考文献 29

1	HOLLINGER A S, MCANALLEN D R, BROCKETT M T, et al. Cylindrical lithium-ion structural batteries for drones[J]. International Journal of Energy Research, 2020, 44(1): 560-566.
2	RODRIGUES M T F, BABU G, GULLAPALLI H, et al. A materials perspective on Li-ion batteries at extreme temperatures[J]. Nature Energy, 2017, 2: 17108.
3	NAGY A. Electric aircraft-present and future[J]. Production Engineering Archives, 2019, 23(23): 36-40.
4	Federal Aviation Administration. Lithium batteries & lithium battery-powered devices[R/OL].[[2021-10-01].https://www.faa.gov/hazmat/resources/lithium_batteries/media/Battery_incident_chart.
5	刘奕, 张旭, 陈现涛, 等. 不同压力下软包装锂离子电池的热失控研究[J]. 电池, 2020, 50(3): 237-241.
	LIU Y, ZHANG X, CHEN X T, et al. Study of thermal runaway of pouch Li-ion battery under different pressures[J]. Battery Bimonthly, 2020, 50(3): 237-241.
6	陈现涛, 张旭, 赵一帆, 等. 低气压及加热方式对锂离子电池热特性的影响[J]. 电池, 2021, 51(6): 558-562.
	CHEN X T, ZHANG X, ZHAO Y F, et al. Effect of low pressure and heating method on thermal characteristics of Li-ion battery[J]. Battery Bimonthly, 2021, 51(6): 558-562.
7	XIE S, REN L X, YANG X Y, et al. Influence of cycling aging and ambient pressure on the thermal safety features of lithium-ion battery[J]. Journal of Power Sources, 2020, 448: doi: 10.1016/j.jpowsour.2019.227425.
8	SU L S, ZHANG J B, WANG C J, et al. Identifying main factors of capacity fading in lithium ion cells using orthogonal design of experiments[J]. Applied Energy, 2016, 163: 201-210.
9	戴海峰, 周艳新, 顾伟军, 等. 电动汽车用动力锂离子电池寿命问题研究综述[J]. 电源技术, 2014, 38(10): 1952-1954, 1982.
	DAI H F, ZHOU Y X, GU W J, et al. Review on life studies of traction Li-ion batteries in electric vehicles[J]. Chinese Journal of Power Sources, 2014, 38(10): 1952-1954, 1982.
10	任东生, 冯旭宁, 韩雪冰, 等. 锂离子电池全生命周期安全性演变研究进展[J]. 储能科学与技术, 2018, 7(6): 957-966.
	REN D S, FENG X N, HAN X B, et al. Recent progress on evolution of safety performance of lithium-ion battery during aging process[J]. Energy Storage Science and Technology, 2018, 7(6): 957-966.
11	OUYANG M G, REN D S, LU L G, et al. Overcharge-induced capacity fading analysis for large format lithium-ion batteries with LiyNi_1/3Co_1/3Mn_1/3O₂+LiyMn₂O₄ composite cathode[J]. Journal of Power Sources, 2015, 279: 626-635.
12	吴静云, 侍成, 郭鹏宇, 等. 梯次利用阀控式铅酸电池过充安全特性[J]. 中国安全科学学报, 2020, 30(4): 14-20.
	WU J Y, SHI C, GUO P Y, et al. Overcharging safety characteristics of retired VRLA[J]. China Safety Science Journal, 2020, 30(4): 14-20.
13	OUYANG D X, WENG J W, CHEN M Y, et al. Impact of high-temperature environment on the optimal cycle rate of lithium-ion battery[J]. Journal of Energy Storage, 2020, 28: doi: 10.1016/j.est.2020.102420.
14	OUYANG M G, CHU Z Y, LU L G, et al. Low temperature aging mechanism identification and lithium deposition in a large format lithium iron phosphate battery for different charge profiles[J]. Journal of Power Sources, 2015, 286: 309-320.
15	ZHU G L, WEN K C, LV W Q, et al. Materials insights into low-temperature performances of lithium-ion batteries[J]. Journal of Power Sources, 2015, 300: 29-40.
16	王绥军, 傅凯, 官亦标, 等. 软包磷酸铁锂电池低温热安全性能研究[J]. 储能科学与技术, 2016, 5(2): 204-209.
	WANG S J, FU K, GUAN Y B, et al. Low temperature thermal safety performance of soft packaged lithium iron phosphate battery[J]. Energy Storage Science and Technology, 2016, 5(2): 204-209.
17	廖成龙, 王刘涛, 王健雁, 等. 动力锂电池系统运行环境条件对其性能影响的研究[J]. 化工新型材料, 2020, 48(7): 167-170.
	LIAO C L, WANG L T, WANG J Y, et al. Study on the influence of operating environment condition on the performance of REESS[J]. New Chemical Materials, 2020, 48(7): 167-170.
18	MUSSA A S, KLETT M, LINDBERGH G, et al. Effects of external pressure on the performance and ageing of single-layer lithium-ion pouch cells[J]. Journal of Power Sources, 2018, 385: 18-26.
19	CHOI Y H, LIM H K, SEO J H, et al. Development of standardized battery pack for next-generation PHEVs in considering the effect of external pressure on lithium-ion pouch cells[J]. SAE International Journal of Alternative Powertrains, 2018, 7(3): 195-205.
20	ZHANG J, . Effects of pressure evolution on the decrease in the capacity of lithium-ion batteries[J]. International Journal of Electrochemical Science, 2020: 8422-8436.
21	邹舜章. 压力对软包锂离子电池性能的影响及对策研究[D]. 长沙: 湖南大学, 2017.
	ZOU S Z. Effect of pressure on performance of soft-packaged lithium-ion battery and its countermeasures[D]. Changsha: Hunan University, 2017.
22	张军, 曾云路, 邹舜章, 等. 软包锂电池在适当压力下的膨胀及寿命研究[J]. 电源技术, 2019, 43(10): 1641-1644.
	ZHANG J, ZENG Y L, ZOU S Z, et al. Battery expansion and life study of soft-packaged lithium batteries under appropriate pressure[J]. Chinese Journal of Power Sources, 2019, 43(10): 1641-1644.
23	鲁怀敏, 方海峰, 何向明, 等. 压力对三元锂电池膨胀及充放电性能的影响[J]. 电源技术, 2017, 41(5): 686-688.
	LU H M, FANG H F, HE X M, et al. Effect of pressure on charge and discharge performance and expansion of ternary lithium battery[J]. Chinese Journal of Power Sources, 2017, 41(5): 686-688.
24	张军, 韩旭, 胡春姣, 等. 软包锂离子电池模块结构压力的优化[J]. 汽车工程, 2016, 38(6): 669-673, 715.
	ZHANG J, HAN X, HU C J, et al. An optimization of the pressing force applied onto the module structure of soft-package lithium-ion battery[J]. Automotive Engineering, 2016, 38(6): 669-673, 715.
25	LI J, DOWNIE L E, MA L, et al. Study of the failure mechanisms of LiNi_0.8Mn_0.1Co_0.1O₂Cathode material for lithium ion batteries[J]. Journal of the Electrochemical Society, 2015, 162(7): A1401-A1408.
26	YANG X G, ZHANG G S, GE S H, et al. Fast charging of lithium-ion batteries at all temperatures[J]. Proceedings of the National Academy of Sciences of the United States of America, 2018, 115(28): 7266-7271.
27	PELED E, MENKIN S. Review—SEI: Past, present and future[J]. Journal of the Electrochemical Society, 2017, 164(7): A1703-A1719.
28	LIU P, WANG J, HICKS-GARNER J, et al. Aging mechanisms of LiFePO₄ batteries deduced by electrochemical and structural analyses[J]. Journal of the Electrochemical Society, 2010, 157(4): A499.
29	KATO H, KOBAYASHI Y, MIYASHIRO H. Differential voltage curve analysis of a lithium-ion battery during discharge[J]. Journal of Power Sources, 2018, 398: 49-54.

电池编号	舱内循环次数	舱外循环次数	恢复率/%
1	30	7	16.32
2	35	5	14.92
3	42	5	9.95
4	33	6	13.15

[1]	李磊, 李钊, 姬丹, 牛慧昌. 过充电触发的LFP和NCM锂离子电池的热失控行为：差异与原因[J]. 储能科学与技术, 2022, 11(5): 1419-1427.
[2]	程广玉, 刘新伟, 梅悦旎, 顾洪汇, 杨丞, 王可. 锂离子电池高温贮存容量衰减分析[J]. 储能科学与技术, 2022, 11(5): 1339-1349.
[3]	赵鹤, 韩策, 程小露, 郝维健, 徐涵颖, 耿萌萌, 杨凯, 赵丰刚, 邱新平. 采用阳极预锂化技术的锂离子电池高倍率老化容量衰减机理研究[J]. 储能科学与技术, 2021, 10(2): 454-461.
[4]	任璞, 王顺利, 何明芳, 范永存, 曹文, 谢伟. 基于内阻增加和容量衰减双重标定的锂电池健康状态评估[J]. 储能科学与技术, 2021, 10(2): 738-743.
[5]	杜光超, 郑莉莉, 张志超, 冯燕, 王栋, 戴作强. 锂离子电池热安全性研究进展[J]. 储能科学与技术, 2019, 8(3): 500-505.
[6]	赵保国，李克锋，王冠，刘虹，史佳超，尤梅，张晓霞，谢巧. 锌银贮备电池加速寿命试验方法研究[J]. 储能科学与技术, 2018, 7(1): 141-.
[7]	王艳，白凤武，杨贝，王志峰. 高温显热-潜热复合储热系统传热特性研究[J]. 储能科学与技术, 2017, 6(4): 719-725.
[8]	朱教群，陈维，周卫兵，李儒光，张弘光. 三元硫酸熔盐的制备及其热稳定性能[J]. 储能科学与技术, 2016, 5(4): 498-502.
[9]	朱蕾，贾荻，俞超，吴勇民，吴晓萌，汤卫平. 锂离子电池LiFePO₄/LiNi_0.8Co_0.15Al_0.05O₂混合正极材料的电化学热稳定性能[J]. 储能科学与技术, 2016, 5(4): 478-485.