过充循环老化电池产热特性

doi:10.19799/j.cnki.2095-4239.2022.0692

储能科学与技术 ›› 2023, Vol. 12 ›› Issue (3): 685-697.doi: 10.19799/j.cnki.2095-4239.2022.0692

过充循环老化电池产热特性

常修亮¹^,²^,³(), 李希超¹^,²^,³, 贾隆舟¹^,²^,³, 韦守李¹^,²^,³, 王敬豪¹^,²^,³, 戴作强¹^,²^,³, 郑莉莉¹^,²^,³()

^1.青岛大学机电工程学院
^2.青岛大学动力集成及储能系统工程技术中心
^3.电动汽车智能化动力集成技术国家地方联合工程技术中心（青岛），山东青岛 266071

收稿日期:2022-11-24 修回日期:2022-12-18 出版日期:2023-03-05 发布日期:2022-12-29
通讯作者: 郑莉莉 E-mail:x_l_chang@163.com;llzhengqdu@163.com
作者简介:常修亮（1996—），男，硕士研究生，研究方向为新能源汽车， E-mail：x_l_chang@163.com；
基金资助:
青岛市纵向科研基金项目(40518060027)

Heat generation characteristics of overcharged cyclic aging batteries

Xiuliang CHANG¹^,²^,³(), Xichao LI¹^,²^,³, Longzhou JIA¹^,²^,³, Shouli WEI¹^,²^,³, Jinghao WANG¹^,²^,³, Zuoqiang DAI¹^,²^,³, Lili ZHENG¹^,²^,³()

^1.College of Mechanical & Electronic Engineering, Qingdao University
^2.Power & Energy Storage System Research Center, Qingdao University
^3.National Engineering Research Centre for Intelligent Electrical;Vehicle Power System (Qingdao), Qingdao 266071, Shandong, China

Received:2022-11-24 Revised:2022-12-18 Online:2023-03-05 Published:2022-12-29
Contact: Lili ZHENG E-mail:x_l_chang@163.com;llzhengqdu@163.com

摘要/Abstract

摘要：

锂离子电池凭借其良好的性能，在新能源汽车的发展过程中备受青睐，但电池成组后因为电池的不一致性等原因会造成部分电池出现过充电现象，长期循环会影响电池的性能和寿命。本工作对某锂离子电池分别进行了4.3 V、4.4 V和4.5 V的过充循环试验，通过对新电池及过充循环后的电池进行开路电压温度系数测试、混合功率脉冲测试和等温量热测试获得了电池的熵热系数、等效直流内阻和产热功率及产热量，并利用Bernadi产热模型计算了电池的可逆热和不可逆热，综合分析过充循环对电池充放电产热特性的影响。结果表明，高的过充电压对电池性能影响更加明显，与新电池相比，4.3 V、4.4 V过充循环后的电池内阻增加并不明显，4.5 V过充循环后电池内阻最大增加了42.41%；过充循环后的电池熵热系数曲线波动更加明显且幅度随着循环电压的增大而增大；相比于放电，过充循环对电池的充电产热特性影响更明显；在电池产热的热源中，过充循环会先对可逆热产生影响，且随着过充电压的升高，可逆热占比呈现出增大的趋势。

关键词: 锂离子电池, 过充循环, 等效直流内阻, 熵热系数, 电池产热

Abstract:

Lithium-ion batteries are favored in developing new energy vehicles with good performance. However, due to the inconsistency of batteries and other reasons, some batteries become overcharged, and the long-term change cycle will affect their performance and life. This study conducted overcharge cycle tests of 4.3, 4.4, and 4.5 V for lithium-ion batteries. Entropy coefficient, direct current resistance, heat generation power, and heat generation of the battery were obtained by conducting an open-circuit voltage temperature coefficient test, a hybrid pulse power characteristic test, and an isothermal calorimetry test on a new battery and that after an overcharge cycle. The battery's reversible and irreversible heat were calculated using the Bernadi heat generation model. The overcharge cycle's influence on the battery's heat generation characteristic was analyzed comprehensively. Results show that a high overcharge voltage has a more noticeable impact on battery performance. Compared with the new battery, the direct current resistance of that after 4.3 and 4.4 V overcharge cycles did not increase significantly. However, the maximum internal resistance of the battery rose by 42.41% after 4.5 V overcharge cycles. After the overcharge cycle, the entropy coefficient curve of the battery fluctuates even more, and the amplitude increases with an increase in the cycle voltage. Compared with the discharge cycle, the overcharge cycle more obviously influences heat generation when charging. It first affects the reversible heat in the battery's heat source. An increase in overcharge voltage causes the proportion of reversible heat to increase.

Key words: lithium-ion batteries, overcharge cycle, DC resistance, entropy coefficient, heat generation

中图分类号:

TM 912

常修亮, 李希超, 贾隆舟, 韦守李, 王敬豪, 戴作强, 郑莉莉. 过充循环老化电池产热特性[J]. 储能科学与技术, 2023, 12(3): 685-697.

Xiuliang CHANG, Xichao LI, Longzhou JIA, Shouli WEI, Jinghao WANG, Zuoqiang DAI, Lili ZHENG. Heat generation characteristics of overcharged cyclic aging batteries[J]. Energy Storage Science and Technology, 2023, 12(3): 685-697.

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步骤	程序	设置条件
1	静置	t=1 h
2	脉冲放电	I=2 C，t=10 s
3	静置	t=40 s
4	脉冲充电	I=1.5 C，t=10 s
5	放电	放电容量=10%实际容量
6	循环1～5步骤	循环次数：11次

SOC	熵热系数/(mV/K)
SOC	新电池	4.3 V过充循环电池	4.4 V过充循环电池	4.5 V过充循环电池
0%	-0.457632187	0.009601148	0.010780082	0.281875018
10%	-0.000498757	0.123093975	0.182931605	0.472242308
20%	0.030525829	0.196617704	0.13185504	0.426139291
30%	0.211809699	0.243988919	0.284177807	0.10451674
40%	0.223622073	0.254646717	0.284445764	0.538850326
50%	0.243044865	0.284940573	0.355354014	0.139143562
60%	0.463981558	0.274904826	0.466202484	0.204868333
70%	0.056183366	0.163246772	0.344983242	0.073815324
80%	0.139989921	0.193519893	0.387118317	0.13060799
90%	0.141328652	0.275153646	0.488052715	0.657287266
100%	-0.000325855	0.11217643	0.132055479	-0.030355841

电池	脉冲充电电流/A	脉冲放电电流/A	放电电流/A
新电池	4.215	5.620	2.81
4.3 V过充循环电池	3.810	5.080	2.540
4.4 V过充循环电池	3.665	4.886	2.443
4.5 V过充循环电池	2.423	3.230	1.615

SOC/%	新电池		4.3 V过充电池		4.4 V过充电池		4.5 V过充电池
SOC/%	R_c/mΩ	R_d/mΩ	R_c/mΩ	R_d/mΩ	R_c/mΩ	R_d/mΩ	R_c/mΩ	R_d/mΩ
0	97.11	231.41	95.98	209.89	91.68	209.16	97.41	99.07
10	79.42	94.32	70.08	91.73	73.67	103.15	88.13	93.14
20	69.69	71.08	62.47	67.13	65.48	71.63	86.88	89.10
30	64.95	65.76	59.06	61.22	60.57	64.47	86.88	91.59
40	62.88	63.78	59.06	60.24	60.03	62.01	89.37	90.66
50	63.19	64.00	64.83	64.37	61.12	62.42	91.85	92.52
60	66.14	66.42	67.98	67.52	64.12	65.08	92.82	93.45
70	65.23	65.64	67.19	67.13	62.21	63.86	93.09	93.76
80	65.83	67.76	69.55	69.09	63.3	64.88	98.06	95.31
90	65.83	67.32	70.08	69.88	67.94	68.56	105.50	98.42
100	80.30	76.62	89.50	80.31	91.41	79.62	137.36	104.32

电池	参数	第一个峰值	第二个峰值	第三个峰值	Q/kJ
新电池	SOC	6.9%～9.4%	36.0%～60.0%	77.0%～82.0%	2.24
新电池	P/W	0.31	0.39	0.31	2.24
4.3 V过充电池	SOC	6.4%～9.3%	44.8%～47.7%	70.3%～73.2%	1.72
4.3 V过充电池	P/W	0.23	0.35	0.29	1.72
4.4 V过充电池	SOC	6.7%～17.4%	44.9%～53.6%	75.8%～78.5%	1.72
4.4 V过充电池	P/W	0.18	0.35	0.33	1.72
4.5 V过充电池	SOC	7.0%～11.2%	44.6%～51.4%	71.2%～73.6%	1.68
4.5 V过充电池	P/W	0.18	0.34	0.32	1.68

过充循环老化电池产热特性

Heat generation characteristics of overcharged cyclic aging batteries

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参考文献 21

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Metrics

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电池	参数	第一个峰值	第二个峰值	Q/kJ
新电池	DOD	18.4%～21.2%	100%	2.04
新电池	P/W	0.18	0.6	2.04
4.3 V过充电池	DOD	7.0%～9.6%	100%	1.50
4.3 V过充电池	P/W	0.23	0.35	1.50
4.4 V过充电池	DOD	29.6%～38.7%	100%	1.52
4.4 V过充电池	P/W	0.21	0.53	1.52
4.5 V过充电池	DOD	17.2%～19.1%	100%	1.36
4.5 V过充电池	P/W	0.32	0.81	1.36

项目	新电池		4.3 V过充循环电池		4.4 V过充循环电池		4.5 V过充循环电池
项目	充电	放电	充电	放电	充电	放电	充电	放电
总产热/kJ	1.94	1.81	1.58	1.46	1.55	1.39	1.33	1.19
可逆热/kJ	0.46	-0.34	0.61	-0.48	0.73	-0.57	0.57	-0.44
可逆热占比/%	23.71	18.78	38.61	32.88	47.10	41.01	42.86	36.97
不可逆热/kJ	1.48	2.15	0.97	1.94	0.82	1.96	0.76	1.63
不可逆热占比/%	76.29	81.22	61.39	67.12	52.90	58.99	57.14	63.03

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