废旧三元动力电池电热特性的实验研究

doi:10.11949/0438-1157.20190677

摘要/Abstract

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

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

中图分类号:

TK 172.4

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.

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.

图/表 17

表1 21700电池的参数规格

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℃

图1 实验测试设备与系统

Fig.1 Experimental device and test system

图2 HPPC测试中100％SOC时的脉冲步骤

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

图3 加速老化过程中的容量和能量衰减

Fig.3 Degradation of capacity and energy during accelerated aging

图4 老化过程中恒流恒压阶段容量的变化

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

图5 加速老化过程中库仑效率及能量效率的变化

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

图6 加速老化过程中充放电电压的变化

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

图7 加速老化过程中锂离子电池的膨胀

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

图8 不同老化程度电池的容量增量曲线

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

表2 峰顶点高度的变化

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

表3 曲线面积的变化

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

表4 峰顶点对应电压的变化

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

图9 电池老化对倍率特性以及温度适应性的影响

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

图10 电池老化对欧姆内阻的影响

Fig.10 Effects of aging on ohmic resistance of batteries

图11 电池老化对极化内阻的影响

Fig.11 Effects of aging on polarization resistance of batteries

图12 1.00C充放电过程中电池老化对其工作温度的影响

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

图13 电池老化对工作温度的影响

Fig.13 Effects of aging on working temperature of batteries

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