Research on toxicity of gases of thermal runaway released from ternary lithium-ion batteries featuring cyclic aging process
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摘要:
为研究高能量密度锂离子电池循环老化过程中热失控特性变化及释放气体的毒性危害，对不同循环老化程度的三元锂离子电池进行热滥用实验，利用气体传感器阵列，基于有效剂量分数模型对热失控气体毒性危害进行定量分析。结果表明，高镍含量三元锂离子电池循环性能差，200次循环老化后，电池健康状态低于70%。老化电池更容易进入热失控状态，热失控反应更剧烈但释放能量少，释放气体燃烧效率低。在密闭空间内，电池热失控释放窒息性气体危害性比刺激性气体更高，150次循环老化电池的窒息性气体毒性累积效应比新鲜电池早638 s达到临界值1。随老化程度增加，最终电池的刺激性气体毒性即时效应与气体致死毒性即时效应降低，与新鲜电池相比，100次循环老化后，电池的刺激性气体毒性即时效应降低0.34，气体致死毒性即时效应降低0.19。研究结果可为老化电池安全性评估及热失控预警提供数据支撑。
Abstract:Thermal abuse experiments were carried out on ternary lithium-ion batteries with a range of cyclic aging degrees in order to investigate the changes in thermal runaway characteristics and the harmful effects of released gases during the cyclic aging process of high-energy-density lithium-ion batteries. Additionally, a gas sensor array was used to carry out quantitative analysis on the toxicity of pyrolysis gases based on fraction model of effective dose. The results demonstrated that the ternary lithium-ion battery with high nickel content was equipped with poor cyclic performance since the health state of the battery was lower than 70% after 200 cycles of aging. Aging batteries tended to transform into a state of thermal runaway, which reacted more drastically with less energy released, consequently, the combustion efficiency of the released gas is low. The detriments of asphyxiating gases released during the thermal runaway of batteries were more harmful than irritating gases in a confined space, and the cumulative effect of asphyxiating gas toxicity of batteries after 150 times of cyclic aging process tended to reach the critical value, which is one, 638 s earlier than fresh batteries. With the aging degree increasing, immediate toxic effects of irritant gases and immediate effects of gas lethal toxicity weakened. Compared with fresh batteries, immediate toxic effects of irritant gases after 100 times of cyclic aging process decreased by 0.34, and immediate effects of gas lethal toxicity decreased by 0.19. The study’s findings can offer data support for the assessment of safety and the aging process’s thermal runaway warning.
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图 1 循环老化过程中锂离子电池容量和能量的动态变化
Figure 1. Dynamic changes of lithium battery capacity and energy during cyclic aging
图 3 不同老化程度电池热滥用全过程气体分析
Figure 3. Gas analysis in whole process of thermal abuse of batteries with different aging degrees
图 4 不同老化程度电池热失控气体毒性动力学模型
Figure 4. Thermal runaway gas toxicity kinetic model for batteries with different aging degrees
表 1 容量和能量衰减曲线的线性拟合
Table 1. Linear fitting of capacity and energy decay curves
参数 截距 斜率 R2 充电容量 3.3919 −0.00629 0.92781 放电容量 3.3823 −0.00629 0.93436 充电能量 13.3120 −0.02305 0.92683 放电能量 11.8847 −0.02317 0.93194 
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表 2 电池主要性能参数
Table 2. Main performance parameters of battery
循环次数 H/% $ {\eta }_{Q} $/% $ {\eta }_{E} $/% 内阻/mΩ 0 100.0 99.75±0.41 88.7±0.3 27.2±0.2 50 91.3±1.3 99.97±0.11 88.0 27.7±0.3 100 77.3±1.7 99.80±0.24 85.3±0.7 28.6±0.5 150 72.9±2.9 99.85±0.18 84.3±0.7 29.7±0.6 200 66.8±3.2 99.71±0.41 83.5±0.5 30.5±0.5
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表 3 不同老化程度电池关键参数
Table 3. Key parameters of batteries with different aging degrees
循环次数 Δt/s Tdrop/℃ Tvent/℃ TTR/℃ Tgmax/℃ Pmax/MPa ΔM/g 0 153±41 138.19±4.73 149.22±2.63 206.24±3.54 878.55±29.23 0.2787±0.0272 27.86±0.22 50 135±23 133.43±3.24 146.24±2.98 198.97±3.25 671.65±23.61 0.3002±0.0327 29.45±0.19 100 106±16 130.78±4.65 144.39±3.21 186.43±2.97 646.96±58.48 0.3064±0.0416 30.67±0.21 150 71±20 130.37±2.79 150.49±3.87 181.48±4.12 474.63±47.37 0.3174±0.0372 31.34±0.16 200 63±13 121.70±2.37 142.81±2.10 179.82±2.67 355.93±37.92 0.2871±0.0118 19.70±0.24
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表 4 不同老化程度电池热失控后气体分析
Table 4. Gas analysis after thermal runaway of batteries with different aging degrees
循环次数 $C_{{\mathrm{CO}}_2} $/10−2 CCO/10−2 $C_{{\mathrm{CH}}_4} $/10−2 CHF/10−6 CHCN/10−6 $C_{{\mathrm{SO}}_2} $/10−6 $C_{{\mathrm{O}}_2} $/10−2 Cmax,CO/10−2 $C_{{\mathrm{max,CH}}_4} $/10−2 0 17.29±0.82 0.28±0.07 0.52±0.08 2.61±0.29 3.06±0.24 56.34±15.66 4.13±0.85 6.87±1.49 6.12±0.34 50 18.14±0.46 0.63±0.10 0.47±0.05 6.26±0.41 1.02±0.34 34.96±13.64 2.32±0.70 7.09±1.63 7.25±0.21 100 17.71±0.43 0.44±0.14 0.41±0.01 6.59±0.65 2.57±0.22 20.95±8.52 2.27±0.30 10.44±1.59 7.50±0.47 150 19.18±0.75 0.54±0.12 0.37±0.02 2.79±0.32 1.15±0.29 <0.01 0.88±0.57 10.56±1.35 8.72±0.39 200 15.71±0.55 0.67±0.09 0.48±0.14 1.95±0.29 1.76±0.35 <0.01 4.76±0.68 2.84±0.62 1.05±0.03
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