Influence of slight over-discharge on aging behavior of lithium-ion batteries in high-temperature environments
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摘要:
近年来全球范围内出现的极端高温天气造成锂离子电池高温环境运行概率显著增加，而运行环境及系统管理引起的电池一致性差异问题使得电池易发生轻微过放电现象，高温环境与过放电现象耦合显著增大电池触发安全事故的风险。为探究高温环境与轻微过放电耦合对锂离子电池老化行为的影响，在60 ℃高温和25 ℃常温环境下对三元锂离子电池进行了轻微过放电实验研究，结果表明：60 ℃和25 ℃轻微过放电循环100次后电池容量衰减率分别为28.46%和2.54%。与常温环境相比，高温环境轻微过放电显著增加了电池的容量衰减；电池电化学分析表明，高温使电池内部锂脱嵌反应受限，活性锂损失增多，动力学性能衰退；电池拆解照片、扫描电镜和元素分析结果表明，高温环境下轻微过放电电池形变严重，电池副反应造成的沉积物增多。因此，高温环境与轻微过放电耦合将加剧正极结构的破坏和内部副反应，导致电池性能下降。研究结果可对锂离子电池材料的开发和电动汽车的安全运行提供实验参考和理论依据。
Abstract:The extreme high-temperature weather that has occurred worldwide in recent years has significantly increased the probability of lithium-ion batteries operating in high-temperature environments. The battery consistency difference caused by the operating environment and system management makes the battery prone to slight over-discharge. The coupling between high-temperature environment and over-discharge phenomenon significantly increases the risk of battery safety accidents. In order to study the influence of high-temperature environment and slight over-discharge coupling on the aging behavior of lithium-ion batteries, this paper carried out a slight over-discharge experiment on ternary lithium-ion batteries at 60 °C (high temperature) and 25 °C (normal temperature). The results show that the battery capacity attenuation rates after 100 cycles of slight over-discharge at 60 °C and 25 °C are 28.46% and 2.54%, respectively. Compared with that in normal temperature environments, slight over-discharge in high-temperature environments significantly increases the battery capacity attenuation. The electrochemical analysis of the battery shows that high temperatures limit the lithium deintercalation reaction inside the battery, increase the loss of active lithium, and degrade the kinetic performance. Battery disassembly photos, scanning electron microscopy, and elemental analysis results prove that slightly over-discharged batteries in high-temperature environments are severely deformed, and more sediments are produced by battery side reactions. Therefore, the coupling of a high-temperature environment and slight over-discharge will aggravate the damage of the cathode structure and internal side reactions, leading to a decline in battery performance. The research results can provide an experimental reference and theoretical basis for the development of lithium-ion battery materials and the safe operation of electric vehicles.
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图 1 不同环境温度下正常充放电与轻微过放电电池的充放电曲线
Figure 1. Curves of batteries with normal charging and discharging and slight over-discharge at different ambient temperatures
图 2 不同温度下轻微过放电电池容量保持率、放电中值电压、直流放电内阻及健康状态变化曲线
Figure 2. Variation of capacity retention rate, median discharge voltage, internal resistance of DC discharge, and SOH of slightly over-discharged batteries at different temperatures
图 3 不同环境温度下过放电电池的EIS及等效电路图
Figure 3. EIS and equivalent circuit diagram of over-discharged batteries at different ambient temperatures
图 4 新电池及不同温度下轻微过放电电池放电状态下的dQ/dV、−Q0dV/dQ曲线
Figure 4. dQ/dV and −Q0dV/dQ curves of new battery and slightly over-discharged battery at different temperatures
图 5 不同温度下100次循环的电池拆解图
Figure 5. Battery disassembly photos after 100 cycles at different temperatures
图 6 不同温度下过放电电池的正极和负极的SEM图像
Figure 6. SEM images of cathode and anode of over-discharged batteries at different temperatures
图 7 不同环境下电池正极和负极的XPS结果
Figure 7. XPS results of battery cathode and anode in different environments
表 1 实验所用锂离子电池参数
Table 1. Lithium-ion battery parameters in experiment
参数 规格 电池类型 软包 额定容量/mAh 5000 重量/ g ≤90 标称电压/V 3.7 截止电压/V 2.75～4.2 工作温度最佳范围/℃ 20～45 
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表 2 负极表面元素的原子质量分数
Table 2. Atomic content of elements on anode surface
不同环境工况 质量分数 碳元素 氧元素 氟元素 新电池 0.94 0.030 0.017 60 ℃过放电 0.87 0.075 0.031 25 ℃过放电 0.80 0.13 0.048
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