Heat generation characteristics of overcharged cyclic aging batteries

doi:10.19799/j.cnki.2095-4239.2022.0692

Abstract

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

CLC Number:

TM 912

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