锂金属电池充放电过程中锂枝晶生长与溶解的相场模拟研究

doi:10.19799/j.cnki.2095-4239.2024.1125

储能科学与技术 ›› 2025, Vol. 14 ›› Issue (5): 1829-1840.doi: 10.19799/j.cnki.2095-4239.2024.1125

锂金属电池充放电过程中锂枝晶生长与溶解的相场模拟研究

梁辰¹(), 邢鹏飞², 吴孟武¹^,³(), 秦训鹏³

^1.武汉理工大学汽车工程学院，湖北武汉 430070
^2.智能农业动力装备全国重点实验室，河南洛阳 471039
^3.湖北隆中实验室，湖北襄阳 441000

收稿日期:2024-11-27 修回日期:2024-12-16 出版日期:2025-05-28 发布日期:2025-05-21
通讯作者: 吴孟武 E-mail:whutliangchen@163.com;wumw@whut.edu.cn
作者简介:梁辰（1998—），女，硕士研究生，研究方向为储能电池电化学及其模拟计算，E-mail：whutliangchen@163.com；
基金资助:
湖北省技术创新计划项目(2024BAB072);智能农业动力装备全国重点实验室开放课题资助项目(SKLIAPE2023014)

Phase-field simulation study on the growth and dissolution of lithium dendrites during the charging and discharging processes of lithium metal batteries

Chen LIANG¹(), Pengfei XING², Mengwu WU¹^,³(), Xunpeng QIN³

^1.School of Automotive Engineering, Wuhan University of Technology, Wuhan 430070, Hubei, China
^2.State Key Laboratory of Intelligent Agricultural Power Equipment, Luoyang 471039, Henan, China
^3.Hubei Longzhong Laboratory, Xiangyang 441000, Hubei, China

Received:2024-11-27 Revised:2024-12-16 Online:2025-05-28 Published:2025-05-21
Contact: Mengwu WU E-mail:whutliangchen@163.com;wumw@whut.edu.cn

摘要/Abstract

摘要：

随着锂金属电池(LMBs)在高能量密度电池中的应用潜力不断显现，其在电动汽车、便携式电子设备等领域的应用前景日益广阔。然而，锂金属电池充放电过程中锂枝晶的不可控生长及死锂的形成显著降低了电池的循环特性和安全性。本文采用相场方法建立了多物理场仿真模型，模拟了锂枝晶的生长与溶解过程，系统研究了充放电电压、循环周期数、温度等对锂枝晶形貌和死锂形成的影响。结果表明，充电时锂枝晶开始生长，放电时锂枝晶发生溶解，溶解从枝晶的主干与根部开始，在较窄区域出现缩颈进而逐渐与电极脱离形成死锂。锂沉积速率随着充电时间的增加而增大，而溶解速率随着放电时间的增加而减小，锂枝晶的溶解速率整体大于沉积速率。充电电压越高，锂枝晶的沉积速率越大，形貌越复杂；放电电压越高，锂枝晶溶解速率越大，但增加了死锂的形成；循环周期数的增加在减缓锂枝晶生长的同时，亦会导致死锂的累积；升高温度能够抑制锂枝晶的生长，同时促进锂的溶解反应，减少了死锂的形成。本研究对于提升锂金属电池的循环特性和安全性具有一定的指导意义。

关键词: 锂金属电池, 充放电, 锂枝晶, 死锂, 相场模拟

Abstract:

The potential of lithium metal batteries (LMBs) in high-energy-density applications such as electric vehicles, portable electronic devices, and other fields has become widely recognized. However, the cycling performance and safety of LMBs are degraded by uncontrolled growth of lithium dendrites and the formation of dead lithium during the charging and discharging processes. This paper establishes a multi-physics simulation model based on the phase-field method, which simulates the growth and dissolution of lithium dendrites. The effects of charging and discharging voltage, cycle number, and temperature on the dendrite morphology and dead lithium formation were systematically investigated. It was found that lithium dendrites begin growing during charging and dissolve during discharging. Dissolution begins at the trunk and root of the dendrite, leading to necking in narrow regions and eventual detachment from the electrode, forming dead lithium. The lithium deposition (dissolution) rates increase (decrease) with charging (discharging) time. Overall, the dissolution rate exceeds the deposition rate. Increasing the charging voltage increases the dendrite deposition rate and the morphological complexity, whereas increasing the discharging voltage increases the dendrite dissolution rate and the dead lithium formation. Increasing the number of cycles slows the dendrite growth but enhances the accumulation of dead lithium. Elevated temperatures suppress dendrite growth, promote lithium dissolution, and reduce dead lithium formation. This research provides valuable insights for enhancing the cycling performance and safety of LMBs.

Key words: lithium metal battery, charging and discharging, lithium dendrites, dead lithium, phase-field simulation

中图分类号:

TM 912

梁辰, 邢鹏飞, 吴孟武, 秦训鹏. 锂金属电池充放电过程中锂枝晶生长与溶解的相场模拟研究[J]. 储能科学与技术, 2025, 14(5): 1829-1840.

Chen LIANG, Pengfei XING, Mengwu WU, Xunpeng QIN. Phase-field simulation study on the growth and dissolution of lithium dendrites during the charging and discharging processes of lithium metal batteries[J]. Energy Storage Science and Technology, 2025, 14(5): 1829-1840.

图/表 10

表1

数值模型中的主要参数[32][35]"

参数符号	描述	数值[单位]
$δ$	各向异性强度	0.1
$ω$	各向异性模数	4
$L σ$	界面迁移率	2.5E-6[ $m 3 / (J ⋅ s)$ ]
$L η$	反应速率系数	1.0[ $s - 1$ ]
$α$	对称因子	0.5
$D e$	电极Li⁺扩散系数	7.5E-13[ $m 2 / s$ ]
$D m$	电解质Li⁺扩散系数	7.5E-10[ $m 2 / s$ ]
$σ e$	电极离子电导率	1.0E7[ $S / m$ ]
$σ m$	电解质离子电导率	1.0[ $S / m$ ]
$W$	势垒高度	3.75E5[ $J / m 3$ ]
$c p e$	电极比热容	3600[ $J / (k g ⋅ K)$ ]
$c p m$	电解质比热容	1200[ $J / (k g ⋅ K)$ ]
$ρ e$	电极密度	590 $[k g / m 3]$
$ρ m$	电解质密度	1290 $[k g / m 3]$
$R e$	电极热导率	84.8[ $W / (m ⋅ K)$ ]
$R m$	电解质热导率	0.45[ $W / (m ⋅ K)$ ]
h	对流换热系数	10[ $W / (m 2 ⋅ K)$ ]
$ε R$	发射速率	0.49
$σ R$	Stephen-Boltzmann常数	5.67E-8[ $W / (m 2 ⋅ K)$ ]
$E d$	活化能	3.3E4[ $J / m o l$ ]

表1

图1

图2

图3

图4

图5

图6

图7

图8

图9

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锂金属电池充放电过程中锂枝晶生长与溶解的相场模拟研究

Phase-field simulation study on the growth and dissolution of lithium dendrites during the charging and discharging processes of lithium metal batteries

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