升温和脉冲充电对锂枝晶生长抑制作用的数值分析

doi:10.19799/j.cnki.2095-4239.2021.0629

摘要/Abstract

摘要：

金属锂被认为是具有高理论比容量的电池负极材料。然而，锂枝晶的生长可能会连接正负极导致爆炸等事故。因此，抑制锂枝晶对提高锂电池的安全性至关重要。本工作通过非线性相场模型与热模型耦合，首先探究了不同初始条件下的锂枝晶形貌及其温度场分布。由于反应放热，随着反应的进行，锂枝晶区域的温度高于电解质区域的温度，并在二者界面处形成温度梯度。然后，研究了不同温度下锂枝晶的形貌特征并量化了抑制效果。研究发现，温度越低，充电过程中生成的锂枝晶越长，数目越多，侧枝越多，从而在放电过程中形成“死锂”的可能性越大。通过改变脉冲电流的频率，分析了不同充电频率下的枝晶长度和形貌特征。研究结果表明，5 ms的脉冲之后接10 ms的休息周期是抑制锂枝晶的合适频率，在此频率下可以得到较为均匀的沉积表面。通过探究在不同过电位和扩散系数下的枝晶平均生长速率，引入了一个无量纲数Da来阐明扩散与电极反应之间的竞争关系，得出减小反应速率和扩散速率之间的差距是抑制锂枝晶的必要条件。

关键词: 相场模型, 电沉积, 锂枝晶, 脉冲电流, 温度

Abstract:

Lithium is considered a battery anode material with high theoretical energy. However, the growth of lithium dendrites can connect the positive and negative poles, causing disasters, such as explosions. Therefore, the inhibition of lithium dendrite is essential to improve the safety of lithium metal batteries. Herein, the dendrite morphology and temperature field distribution under different initial conditions are studied by coupling the nonlinear phase-field model with a thermal model. As the reaction progresses, the temperature of the lithium dendrite region exceeds that of the electrolyte region due to exothermic reaction, and a temperature gradient is formed at the interface between the lithium dendrite and electrolyte region. Then, the morphology characteristics of lithium dendrites at different temperatures were studied and the inhibition effect was quantified. It was found that the lower the temperature, the longer the lithium dendrites, the more the number of lithium dendrites, and the more the side branches are generated during charging, and thus the more likely "dead lithium" is formed during discharge. The dendrite length and morphology at different charging frequencies were analyzed by changing the frequency of the pulse current. The results show that a 5 ms pulse followed by a 10 ms rest period is the appropriate frequency for restraining lithium dendrites, and a relatively uniform deposition surface can be obtained at this frequency. By investigating the average dendrites growth rate under different overpotential and diffusion coefficients, a dimensionless number Da is introduced to illustrate the competition between diffusion and electrode reaction. It can be concluded that reducing the difference between the reaction and diffusion rates is a necessary condition for restraining lithium dendrites.

Key words: phase-field model, electrodeposition, lithium dendrite, pulse current, temperature

中图分类号:

TM 912

乔东格, 刘训良, 温治, 豆瑞峰, 周文宁. 升温和脉冲充电对锂枝晶生长抑制作用的数值分析[J]. 储能科学与技术, 2022, 11(3): 1008-1018.

Dongge QIAO, Xunliang LIU, Zhi WEN, Ruifeng DOU, Wenning ZHOU. Numerical analysis of inhibition of lithium dendrite growth by heating and pulse charging[J]. Energy Storage Science and Technology, 2022, 11(3): 1008-1018.

图/表 7

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参数	数值	参考文献
界面迁移率L_σ	2.5×10^-6 m³/(J·s)	[28, 30]
反应常数L_η	1.0 s^-1	[28, 30]
势垒高度W_ξ	3.75×10⁵ J·m³	[28, 30]
梯度能系数κ	5×10^-5 J/m	[28, 30]
电极中Li⁺扩散系数D^s	7.5×10^-13 m²/s	[28, 30]
电解液中Li⁺扩散系数D^l	7.5×10^-10 m²/s	[28, 30]
电极电导率σ^s	1.0×10⁷ S/m	[28, 30]
电解液电导率σ^l	1.0 S/m	[28, 30]
电极比热容c_p_s	3600 J/(kg·K)	—
电解液比热容c_p_l	1200 J/(kg·K)	[29, 32]
电极质量密度ρ_s	590 kg/m³	—
电解液质量密度ρ_l	1290 kg/m³	[29, 32]
电极热导率λ^s	84.8 W/(m·K)	—
电解液热导率λ^l	0.45 W/(m·K)	[29, 32]
对称因子α	0.5	[28, 30]
各向异性强度δ	0.05	[28, 30]
各向异性模数ω	4	[28, 30]
锂体积浓度c₀	1×10³ mol/m³	[28, 30]
锂物质的量浓度c_s	7.64×10⁴ mol/m³	[28, 30]
活化能E_d	3.3×10⁴ J/mol	[29, 31-32]

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