涉水锂离子电池的腐蚀与析氢风险研究

张青松; 李东琪; 连晓雪

doi:10.13700/j.bh.1001-5965.2022.0617

涉水锂离子电池的腐蚀与析氢风险研究

doi: 10.13700/j.bh.1001-5965.2022.0617

1.
中国民航大学民航热灾害防控与应急重点实验室，天津 300300
2.
中国民航大学理学院，天津 300300

基金项目: 国家自然科学基金民航联合基金(U1933109)；中国民航大学研究生科研创新资助项目(2022YJS009)

详细信息

通讯作者:
E-mail：nkzqsong@126.com

中图分类号: X951
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出版历程
- 收稿日期: 2022-07-13
- 录用日期: 2022-09-16
- 网络出版日期: 2022-11-11
- 整期出版日期: 2024-07-18

Study of corrosion and hydrogen evolution risk of waded lithium ion-battery

1.
Key Laboratory of Civil Aviation Thermal Hazards Prevention and Emergency Response，Civil Aviation University of China，Tianjin 300300，China
2.
College of Science，Civil Aviation University of China，Tianjin 300300，China

Funds: Civil Aviation Joint Fund of National Natural Science Foundation of China (U1933109); Civil Aviation University of China Postgraduate Research Innovation Project (2022YJS009)

More Information

Corresponding author: E-mail：nkzqsong@126.com

摘要

摘要:
锂离子电池涉水事件频发，特别是沿海地区及海事应用方面常常遇到高盐度涉水事件。以18650型电池为样本，进行不同盐度条件下涉水锂离子电池的腐蚀与析氢风险实验研究。结果表明：锂离子电池涉水时首先发生电解和电化学腐蚀现象，盐度越高，这种现象越显著；腐蚀主要发生在阳极帽处，随着腐蚀进行，腐蚀孔向内部深入，直至电池彻底损坏；涉水中锂离子电池的质量损失速率与电压降呈正相关关系；腐蚀产物主要为氢氧化亚铁、氢氧化铁和氢氧化铝；涉水过程中阴极析出大量氢气，氢气产生速率与盐溶液浓度呈正相关关系；对于较封闭的应用环境极易达到氢气爆炸下限；轻度腐蚀后电池热失控过程的喷射程度较为剧烈，燃爆危险性较高；而过度腐蚀则会直接破坏电池结构，进而使电池完全失效。
- 锂离子电池 /
- 安全 /
- 涉水 /
- 电池性能 /
- 热失控 /
- 析氢
Abstract:
Lithium-ion battery wading events occur frequently, especially, often suffering high salinity wading events in coastal areas and maritime operations. In this paper, 18650 model batteries were used as samples to carry out experiments on the risk of corrosion and hydrogen evolution of waded lithium-ion batteries under different salinity conditions. The findings indicate that soaking lithium-ion batteries in an aqueous sodium chloride solution triggers the onset of electrolytic and electrochemical corrosion. The higher the salinity of the solution, the more significant this phenomenon is. The corrosion mainly occurs at the anode cap. With corrosion developing, the corrosion hole goes deep into the interior until the battery is completely damaged. There is a positive correlation between the mass loss rate and voltage drop of lithium battery in the wading process. Aluminum hydroxide, ferrous hydroxide, and ferric hydroxide make up the majority of the corrosion products. In the process, a large amount of hydrogen emerges from the cathode, and the hydrogen generation rate has a positive linear relationship with the concentration of salt solution. For relatively narrow space, it is very easy to reach the lower limit of a hydrogen explosion. After mild corrosion, the injection degree of the thermal runaway process of the battery is more severe, and the risk of combustion and explosion is relatively high. Furthermore, extreme corrosion will directly damage the battery's construction, rendering it totally useless.
- lithium ion battery /
- safety /
- wading /
- battery performance /
- thermal runaway /
- hydrogen evolution

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图 1 涉水实验装置

Figure 1. Wading experiment device

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图 2 热失控试验装置

Figure 2. Thermal runaway test device

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图 3 锂离子电池涉水腐蚀过程

Figure 3. Wading corrosion process of lithiumion battery in water

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图 4 腐蚀产物

Figure 4. Corrosion products

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图 5 腐蚀产物扫描电镜照片和XRD图谱

Figure 5. SEM images and XRD patterns of corrosion products

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图 6 氢气体积分数与NaCl溶液质量分数的关系曲线

Figure 6. Relationship curve between hydrogen volume fraction and solution salinity

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图 7 锂离子电池涉水过程中质量损失与电压变化

Figure 7. Mass loss and voltage change of lithiumion battery during water wading

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图 8 涉水锂离子电池热失控后质量损失

Figure 8. Mass loss of wading lithiumion battery after thermal runaway

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图 9 不同浸泡时长电池燃爆后的形貌照片

Figure 9. Photo of lithium battery with different wading time after combustion and explosion

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图 10 锂离子电池热失控温度变化曲线

Figure 10. Temperature variation curve during thermal runaway of lithiumion battery

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图 11 涉水锂离子电池热失控中释放VOCs气体曲线

Figure 11. VOCs gas release curve during thermal runaway of water wading lithiumion battery

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表 1 电池参数

Table 1. battery parameters

品牌	标称电压/V	截止电压/V	容量/(mA·h)	长度/mm	高度/mm
三星UNG	3.6	2.75	2200	65.0	18.4

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表 2 A组实验电池样品的电压和质量数据

Table 2. Voltage and weight data of battery samples in A group

编号	浸泡时长/min	初始质量/g	初始电压/V
A21	10	40.99	4.09
A22	20	41.02	4.09
A23	30	41.36	4.08
A24	60	41.14	4.09
A25	120	41.07	4.09
A26	180	40.97	4.08
A27	240	41.17	4.08
A28	360	41.11	4.08
A29	480	40.98	4.09

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表 3 B组实验电池样品的电压和质量数据

Table 3. Voltage and weight data of battery samples in B group

编号	质量分数	初始质量/g	初始电压/V
B11	0	41.01	4.09
B12	0.01	40.97	4.09
B13	0.015	41.03	4.09
B14	0.02	41.13	4.08
B15	0.025	40.89	4.09
B16	0.03	40.98	4.09
B17	0.035	41.04	4.08

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表 4 氢气体积分数拟合方程

Table 4. Linear fitting equation of hydrogen concentration

NaCl质量分数	拟合曲线	相关系数r
0.01	C_H = 3.64t − 374.66	0.998 23
0.015	C_H = 6.36t + 1 053.76	0.999 39
0.02	C_H = 7.95t + 629.80	0.999 92
0.025	C_H = 9.30t + 800.29	0.999 92
0.03	C_H = 11.58t + 1 049.58	0.999 52
0.035	C_H = 13.77t + 654.06	0.999 75
注：C_H为氢气体积分数；t为反应时间，单位s。

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表 5 1 L受限空间中的NaCl溶液质量分数与析氢速率

Table 5. Relationship between hydrogen generation rate and solution salinity in 1 L confined space

NaCl溶液质量分数	析氢速率/(10⁻⁶·s⁻¹）
0.01	5.82
0.015	10.18
0.02	12.72
0.025	14.88
0.03	18.53
0.035	20.03

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