LiFePO4锂离子动力电池45℃容量衰减机理

doi:10.11949/0438-1157.20210436

摘要/Abstract

摘要：

以电动汽车的方型LiFePO₄/石墨动力实验电池为研究对象，探究其在45℃恒温箱下1C充放电循环的失效机理。通过对电池进行解剖，系统分析了电池循环前后正负极片的厚度、形貌、结构和克容量的变化。随着电池在45℃高温下循环，电解液分解以及Fe溶出损失、SEI膜再生长，消耗大量的活性锂，交流内阻增加导致电化学极化增大，活性锂消耗引起负极容量损失为6.7%，负极结构变化造成的容量损失为22.64%。结果表明石墨负极动力学性能的衰减是电池失效的主要因素。

关键词: 动力电池, 磷酸铁锂, 电化学, 动力学, 膜

Abstract:

Taking the square LiFePO₄ (LFP) /graphite power battery as the research object, the failure mechanism is explored when the battery cycles with 1C current at 45℃. By dissecting the battery, the changes in the thickness, morphology, structure and gram capacity of the positive and negative plates before and after the battery cycle are systematically analyzed. With the continuous cycling of the battery at 45℃, the electrolyte in the battery is gradually decomposed, the loss of Fe dissolution is aggravated, and the growth of SEI film is accelerated, which leads to the large consumption of active lithium and the increase of EIS and battery polarization. The results indicate that the capacity loss of anode which is caused by active lithium consumption and structure change is higher than that in the cathode, which are 6.7% and 22.64%, respectively. Therefore, the battery failure is mainly resulted by the attenuation of dynamic performance of the graphite negative electrode.

Key words: power battery, LiFePO₄, electrochemistry, dynamics, film

中图分类号:

TM 912.9

张凯博,徐晓明,薛有宝,万柳,田威,曾涛,张亚婷. LiFePO₄锂离子动力电池45℃容量衰减机理[J]. 化工学报, 2021, 72(10): 5396-5401.

Kaibo ZHANG,Xiaoming XU,Youbao XUE,Liu WAN,Wei TIAN,Tao ZENG,Yating ZHANG. Analysis of mechanism of capacity attenuation of LiFePO₄ lithium-ion power battery at 45℃[J]. CIESC Journal, 2021, 72(10): 5396-5401.

图/表 10

图1 LiFePO4/石墨动力电池在45℃下的容量衰减曲线(a)和不同循环次数的恒流充放电曲线(b)

Fig.1 Capacity decay curve (a) and constant current charge-discharge curves of different cycles (b) of LiFePO4/graphite power battery at 45℃

表1 新鲜电池与失效电池的电解液、极片厚度对比

Table 1 Comparison of electrolyte and electrode thickness between fresh and failed batteries

电池	电解液	正极片厚度/μm	负极片厚度/μm
新鲜电池	大量	168	116
失效电池	无	184	142

图2 全电池在循环前后的电化学阻抗图和拟合等效电路图

Fig.2 EIS of the full battery before and after cycling and the fitted equivalent circuit diagram

表2 电池测试前后的EIS拟合数据

Table 2 EIS fitting data before and after battery test

电池	R_s/mΩ	R_SEI/mΩ	R_ct/mΩ
循环前	0.69	0.86	1.34
循环后	0.68	1.15	1.86

图3 正极磷酸铁锂新鲜极片[(a),(b)]，失效正极(c)及剖面(d)

Fig.3 Fresh pole piece [(a),(b)], faded cathode (c) and profile (d) of LiFePO4

图4 失效前后正极磷酸铁锂的XRD谱图

Fig.4 XRD patterns of LiFePO4 cathodes before and after failure

表3 新鲜电池与失效电池正极/Li半电池的平均容量

Table 3 Average capacity of fresh and failed battery cathodes/Li half-cell of LiFePO4

正极	新鲜电池容量		失效电池容量
正极	充电	放电	充电	放电
样品1	3.77	3.78	3.19	3.23
样品2	3.78	3.78	3.23	3.24
平均容量/(mA·h)	3.77	3.78	3.21	3.24
平均克容量/(mA·h/g)	151.34	152.48	140.10	143.82

图5 石墨负极新鲜极片[(a),(b)]和失效负极[(c),(d)]

Fig.5 Fresh [(a),(b)] and failed [(c),(d)] anodes of graphite

图6 失效前后负极石墨的XRD谱图

Fig.6 XRD patterns of graphite anodes before and after failure

表4 新鲜电池与失效电池负极/Li半电池的容量

Table 4 Average capacity of fresh and failed battery anodes/Li half-cell of graphite

负极	新鲜电池容量		失效电池容量
负极	充电	放电	充电	放电
样品1	3.27	3.29	2.74	2.79
样品2	3.25	3.27	2.71	2.73
平均容量/(mA·h)	3.26	3.28	2.72	2.76
平均克容量/(mA·h/g)	288.14	290.25	203.6	224.53

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LiFePO₄锂离子动力电池45℃容量衰减机理

Analysis of mechanism of capacity attenuation of LiFePO₄ lithium-ion power battery at 45℃

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