Experimental study on electro-thermal characteristics of aged power batteries with ternary material

doi:10.11949/0438-1157.20190677

Abstract

Abstract:

The aging of power batteries is likely to cause problems such as inaccurate state of charge, difficult screening of retired batteries, and thermal safety, which limit the development of electric vehicles and the use of old batteries. Furthermore, it may offer theoretical foundation to solve the above problems by studying on the aging characteristics and analyze the variation of electro-thermal performance between fresh and aged batteries in a variety of environments or conditions by comparison. Therefore, it is researched and discussed based on the power battery test system through experiments. It is found that effective capacity, energy and energy efficiency reduces gradually as well as the increase of cycle numbers. Meanwhile, there is a slight swelling phenomenon accompanied by aging at the bottom section. The rate characteristics and the adaptability of ambient temperature become worse with the increase of aging degree. Moreover, the resistances and temperature sensitivity of resistances increase obviously. The variation of electrical performance affects its thermal performance directly so that working temperature and temperature gradient of battery increase obviously with comparison of fresh battery. The difference of working temperature between fresh and aged batteries is more serious especially for discharging under low ambient temperature or by high rate.

Key words: aged battery, capacity increment, rate characteristics, ambient temperature adaptability, internal resistance, working temperature

摘要：

动力电池老化容易引发荷电状态不准、退役电池筛选困难以及热安全性等问题，限制了电动汽车及废旧电池梯次利用的发展。而研究高比能量电池的老化特性，对比分析多种环境、多种条件下废旧电池的电热性能变化有助于为解决上述问题提供理论依据，因此基于动力电池测试系统对其进行了实验研究与讨论。研究表明：电池随着循环次数增加，有效容量和能量逐渐衰减，能量效率逐渐降低，底部截面发生膨胀；随着电池老化程度的增加，其倍率性能、环境温度适应性均会变差，内阻、内阻温度敏感度明显增大；电池电性能的变化直接影响其热性能，电池的工作温度以及温升速率与新电池相比明显增加，新旧电池工作温度的差异在低温环境或高倍率放电的条件下更为严重。

关键词: 废旧电池, 容量增量, 倍率特性, 环境温度适应性, 内阻, 工作温度

CLC Number:

TK 172.4

Shuai PAN, Changwei JI, Shuofeng WANG, Bing WANG, Jiejie SUN, Pengfei QI. Experimental study on electro-thermal characteristics of aged power batteries with ternary material[J]. CIESC Journal, 2020, 71(3): 1297-1309.

潘帅, 纪常伟, 汪硕峰, 王兵, 孙洁洁, 戚朋飞. 废旧三元动力电池电热特性的实验研究[J]. 化工学报, 2020, 71(3): 1297-1309.

Figures/Tables 17

Table 1 Specification of parameters for 21700 battery

名称	规格
正极材料	三元材料（NCA）
负极材料	层状石墨
半径	21 mm
高度	70 mm
质量	69 g
能量密度	268 W·h·kg^-1
标称容量	5000 mA·h
标称电压	3.63 V
最大充电电流	1.00 C
最大放电电流	1.50 C
充电截止电压	4.20 V
放电截止电压	2.50 V
工作适宜温度范围	0~45℃

Fig.1 Experimental device and test system

Fig.2 Pulse step at 100％SOC in HPPC test

Fig.3 Degradation of capacity and energy during accelerated aging

Fig.4 Variation of capacity at charging stage of CC-CV during accelerated aging

Fig.5 Variation of coulombic efficiency and energy efficiency during accelerated aging

Fig.6 Variation of discharging and charging voltage during accelerated aging

Fig.7 Swelling of lithium-ion battery during accelerated aging

Fig.8 Capacity increment curves of batteries with different aging degree

Table 2 Height variation of peak points

循环次数	SOH/%	峰高度
循环次数	SOH/%	峰①	峰②	峰③	峰④
0	100.0	6.057	9.832	6.057	14.112
50	94.5	6.057	9.528	6.057	14.072
100	88.0	5.980	8.934	5.984	13.973
150	77.8	5.582	7.483	5.625	11.940
200	59.7	峰形消失	6.231	5.234	11.129
250	29.8	峰形消失	5.056	5.056	8.647

Table 3 Area variation of curves

循环次数	SOH/%	曲线面积
循环次数	SOH/%	峰①	峰②	峰③	峰④
0	100.0	0.724	2.101	0.988	0.964
50	94.5	0.703	1.833	0.981	0.950
100	88.0	0.643	1.773	0.980	0.942
150	77.8	0.556	1.574	0.926	0.919
200	59.7	0.442	1.233	0.873	0.894
250	29.8	0.203	0.863	0.870	0.783

Table 4 Voltage variation corresponding to peak points

循环次数	SOH/%	峰顶点对应电压
循环次数	SOH/%	峰①	峰②	峰③	峰④
0	100.0	3.430	3.626	3.925	4.104
50	94.5	3.439	3.636	3.925	4.106
100	88.0	3.450	3.639	3.926	4.108
150	77.8	3.461	3.639	3.929	4.112
200	59.7	峰形消失	3.655	3.929	4.112
250	29.8	峰形消失	3.685	3.908	4.112

Fig.9 Effects of aging on rate characteristics and temperature adaptability of batteries

Fig.10 Effects of aging on ohmic resistance of batteries

Fig.11 Effects of aging on polarization resistance of batteries

Fig.12 Effect of aging on working temperature of batteries during 1.00C charge and discharge

Fig.13 Effects of aging on working temperature of batteries

References 40

1	Sack T, Matty T. Li-ion battery technology for compact high power sources (CHPS) [J]. J. Power Sources, 2001, 96(1): 47-51.
2	Gerssen-Gondelach S J, Faaij A P C. Performance of batteries for electric vehicles on short and longer term[J]. Journal of Power Sources, 2012, 212: 111-129.
3	Sakti A, Azevedo I M L, Fuchs E R H, et al. Consistency and robustness of forecasting for emerging technologies: the case of Li-ion batteries for electric vehicles[J]. Energy Policy, 2017, 106: 415-426.
4	叶飞鹏，王莉，连芳，等. 钠离子电池研究进展[J]. 化工进展, 2013, 32(8): 1789-1795.
	Ye F P，Wang L，Lian F，et al. Advance in Na-ion batteries[J]. Chemical Industry and Engineering Progress, 2013, 32(8): 1789-1795.
5	沈佳妮, 贺益君, 马紫峰. 基于模型的锂离子电池SOC及SOH估计方法研究进展[J]. 化工学报, 2018, 69(1): 309-316.
	Shen J N, He Y J, Ma Z F. Progress of model based SOC and SOH estimation methods for lithium-ion battery[J]. CIESC Journal, 2018, 69(1): 309-316.
6	贺理珀, 孙淑英, 于建国. 退役锂离子电池中有价金属回收研究进展[J]. 化工学报, 2018, 69(1): 327-340.
	He L P, Sun S Y, Yu J G. Review on processes and technologies for recovery of valuable metals from spent lithium-ion batteries[J]. CIESC Journal, 2018, 69(1): 327-340.
7	Li D, Danilov D L, Zwikirsch B, et al. Modeling the degradation mechanisms of C₆/LiFePO₄ batteries[J]. Journal of Power Sources, 2018, 375: 106-117.
8	Birkl C R, Roberts M R, Mcturk E, et al. Degradation diagnostics for lithium ion cells[J]. J. Power Sources, 2017, 341: 373-386.
9	Barré A, Deguilhem B, Sébastien G, et al. A review on lithium-ion battery ageing mechanisms and estimations for automotive applications[J]. Journal of Power Sources, 2013, 241(11): 680-689.
10	张克宇, 姚耀春. 锂离子电池磷酸铁锂正极材料的研究进展[J]. 化工进展, 2015, 34(1): 166-172.
	Zhang K Y, Yao Y C. Research progress in LiFePO₄ cathode material for lithium-ion batteries[J]. Chemical Industry and Engineering Progress, 2015, 34(1): 166-172.
11	王运灿，罗琳，刘钰，等. 锂离子电池聚合物正极材料研究进展[J]. 化工进展, 2013, 32(1): 134-139.
	Wang Y C，Luo L，Liu Y，et al. Research development on polymer cathode material for lithium ion batteries[J]. Chemical Industry and Engineering Progress, 2013, 32(1): 134-139.
12	Eddahech A, Briat O, Vinassa J M. Performance comparison of four lithium-ion battery technologies under calendar aging[J]. Energy, 2015, 84: 542-550.
13	徐晶. 梯次利用锂离子电池容量和内阻变化特性研究[D]. 北京: 北京交通大学, 2014.
	Xu J. Research on the variation characteristics of capacity and internal resistance of lithium-ion batteries echelon use[D]. Beijing: Beijing Jiaotong University, 2014.
14	Wang K, Gao F, Zhu Y, et al. Internal resistance and heat generation of soft package Li₄Ti₅O₁₂ battery during charge and discharge[J]. Energy, 2018, 149: 364-374.
15	时玮, 张言茹, 陈大分, 等. 锰酸锂动力电池寿命测试方法[J]. 汽车工程, 2015, 37(1): 67-71.
	Shi W, Zhang Y R, Chen D F, et al. Lifespan test method for LiMn₂O₄ traction batteries[J]. Automotive Engineering, 2015, 37(1): 67-71.
16	Gao Y, Jiang J, Zhang C, et al. Aging mechanisms under different state-of-charge ranges and the multi-indicators system of state-of-health for lithium-ion battery with Li(NiMnCo)O₂ cathode[J]. Journal of Power Sources, 2018, 400: 641-651.
17	Gao Y, Jiang J, Zhang C, et al. Lithium-ion battery aging mechanisms and life model under different charging stresses[J]. Journal of Power Sources, 2017, 356: 103-114.
18	Ma Z, Jiang J, Shi W, et al. Investigation of path dependence in commercial lithium-ion cells for pure electric bus applications: aging mechanism identification[J]. Journal of Power Sources, 2015, 274(3): 29-40.
19	Ouyang M, Chu Z, Lu L, 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.
20	Zhang Y, Wang C Y, Tang X. Cycling degradation of an automotive LiFePO₄, lithium-ion battery[J]. Journal of Power Sources, 2011, 196(3): 1513-1520.
21	Börner M, Friesen A, Grützke M, et al. Correlation of aging and thermal stability of commercial 18650-type lithium ion batteries[J]. Journal of Power Sources, 2017, 342: 382-392.
22	Doughty D H, Crafts C C. FreedomCAR: electrical energy storage system abuse test manual for electric and hybrid electric vehicle applications: SAND 2005-3123 [R]. Sandia National Laboratories, 2006.
23	Yang F, Wang D, Zhao Y, et al. A study of the relationship between coulombic efficiency and capacity degradation of commercial lithium-ion batteries[J]. Energy, 2018, 145: 486-495.
24	张熙贵, 张建, 杨传铮, 等. LiMeO₂材料中锂和镍原子混排的模拟和实验研究[J]. 无机材料学报, 2010, 25(1): 8-12.
	Zhang X G, Zhang J, Yang C Z, et al. Simulation and experimental study on mixed arrange of Li/Ni atoms in LiMeO₂ materials[J]. Journal of Inorganic Materials, 2010, 25(1): 8-12.
25	彭继明, 陈玉华, 刘世成, 等. 不同镍钴锰比对xLi₂MnO₃-(1-x)LiMO₂正极材料的结构和电化学性能的影响[J]. 化工学报, 2016, 67(7): 2950-2955.
	Peng J M, Chen Y H, Liu S C, et al. Effect of Ni/Co/Mn molar ratio on structure and electrochemical properties of xLi₂MnO₃-(1-x)LiMO₂ cathode material[J]. CIESC Journal, 2016, 67(7): 2950-2955.
26	肖忠良, 胡超明, 宋刘斌, 等. 正极材料LiNi_0.8Co_0.1Mn_0.1O₂的合成工艺优化及电化学性能[J]. 化工学报, 2017, 68(4): 1653-1659.
	Xiao Z L, Hu C M, Song L B, et al. Optimization for synthesis technology of LiNi_0.8Co_0.1Mn_0.1O₂ cathode material and electrochemical performance[J]. CIESC Journal, 2017, 68(4): 1653-1659.
27	Li W, Liu X, Celio H, et al. Mn versus Al in layered oxide cathodes in lithium-ion batteries: a comprehensive evaluation on long-term cyclability[J]. Advanced Energy Materials, 2018, 8(15): 1703154.
28	Shin J S, Han C H, Jung U H, et al. Effect of Li₂CO₃ additive on gas generation in lithium-ion batteries[J]. Journal of Power Sources, 2002, 109(1): 47-52.
29	颜雪冬, 马兴立, 李维义, 等. 浅析软包装锂离子电池胀气问题[J]. 电源技术, 2013, 37(9): 1536-1538.
	Yan X D, Ma X L, Li W Y, et al. Analysis of swollen problem in soft packing lithium-ion batteries[J]. Chinese Journal of Power Sources, 2013, 37(9): 1536-1538.
30	Anseán D, Dubarry M, Devie A, et al. Fast charging technique for high power LiFePO₄ batteries: a mechanistic analysis of aging[J]. Journal of Power Sources, 2016, 321: 201-209.
31	Han X, Ouyang M, Lu L, et al. A comparative study of commercial lithium ion battery cycle life in electrical vehicle: aging mechanism identification[J]. Journal of Power Sources, 2014, 251: 38-54.
32	郭琦沛, 张彩萍, 高洋, 等. 基于容量增量曲线的三元锂离子电池健康状态估计方法[J]. 全球能源互联网, 2018, 1(2): 82-89.
	Guo Q P, Zhang C P, Gao Y, et al. Incremental capacity curve based state of health estimation for LNMCO lithium-ion batteries[J]. Journal of Global Energy Interconnection, 2018, 1(2): 82-89.
33	张昊. 基于IC曲线特征参数的锂离子电池SOH估计及DSP实现[D]. 北京: 北京交通大学，2018.
	Zhang H. SOH estimation and DSP implementation of lithium ion battery based on characteristic parameters of IC curve[D]. Beijing: Beijing Jiaotong University, 2018.
34	Dubarry M, Truchot C, Cugnet M, et al. Evaluation of commercial lithium-ion cells based on composite positive electrode for plug-in hybrid electric vehicle applications (Part I): Initial characterizations[J]. Journal of Power Sources, 2011, 196: 10328-10335.
35	Zhang C, Jiang J, Gao Y, et al. Charging optimization in lithium-ion batteries based on temperature rise and charge time[J]. Applied Energy, 2017, 194: 569-577.
36	Dubarry M, Truchot C, Liaw B Y, et al. Evaluation of commercial lithium-ion cells based on composite positive electrode for plug-in hybrid electric vehicle applications (Part II): Degradation mechanism under 2C cycle aging[J]. Journal of Power Sources, 2011, 196(23): 10336-10343.
37	薛楠, 孙丙香, 白恺, 等. 基于容量增量分析的复合材料锂电池分区间循环衰退机理[J]. 电工技术学报, 2017, 32(13): 145-152.
	Xue N, Sun B X, Bai K, et al. Different state of charge range cycle degradation mechanism of composite material lithium-ion batteries based on incremental capacity analysis[J]. Transactions of China Electrotechnical Society, 2017, 32(13): 145-152.
38	Bandhauer T M, Garimella S, Fuller T F. Temperature-dependent electrochemical heat generation in a commercial lithium-ion battery[J]. Journal of Power Sources, 2014, 247: 618-628.
39	梁金华, 李建秋, 卢兰光, 等. 纯电动车电池组散热必要性的初步分析[J]. 汽车工程, 2012, 34(7): 589-591.
	Liang J H, Li J Q, Lu L G, et al. A preliminary analysis on the necessity of battery pack cooling for pure electric vehicles[J]. Automotive Engineering, 2012, 34(7): 589-591.
40	Waldmann T, Wilka M, Kasper M, et al. Temperature dependent ageing mechanisms in lithium-ion batteries - a post-mortem study[J]. Journal of Power Sources, 2014, 262: 129-135.

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