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

doi:10.19799/j.cnki.2095-4239.2024.1125

Abstract

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

CLC Number:

TM 912

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.

Figures/Tables 10

Table 1

Parameters used in numerical model[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[ $J / m o l$ ]

Table 1

Fig. 1

Fig. 2

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Fig. 4

Fig. 5

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Fig. 8

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