基于非线性动力学的锂沉积形貌模拟与预测

doi:10.11949/0438-1157.20200504

摘要/Abstract

摘要：

金属锂具有极高的理论能量密度，是新一代锂电池中最有潜力的负极材料之一。金属锂沉积时容易形成枝晶，极大影响了锂金属电池的安全性与使用寿命。但由于金属锂性质活泼，缺乏锂电极/电解液界面原位表征方法，锂枝晶生长机制尚不明确。通过有限元方法，基于非线性电极过程动力学，以三次电流模型定量研究了电极/电解液界面行为，并分析不同过程参数对表面电流的影响。结果表明，电极/电解质界面的浓度、电场差异是枝晶生长的主要原因，更大的扩散系数有利于提高界面浓度均匀性，更小的交换电流密度有利于减弱界面反应的敏感性。存在电化学极化区间是均匀沉积的必要条件，电化学极化区间越宽，均匀沉积操作窗口越宽。通过极化曲线可以判断体系是否具有均匀沉积的倾向。加深了对锂电极/电解液界面的电沉积过程的理解，对锂负极保护研究具有指导性意义。

关键词: 锂金属电池, 电化学, 动力学, 数值模拟, 锂枝晶

Abstract:

Lithium metal has a very high theoretical energy density and is one of the most promising anode materials for a new generation of lithium batteries. It is easy to form dendrites during the deposition of lithium metal, which greatly affects the safety and service life of lithium metal batteries. Mechanism of dendrite propagation in lithium metal batteries (LMB) is still to be fundamentally described. Herein, we studied the effects of electrochemical parameters on the behavior of lithium plating at the electrode/electrolyte interface using a tertiary current model by finite-element methods. The results show that dendrite growth is intrinsically influenced by differences in concentration and potential. A higher diffusion coefficient (D_e) of Li ion in electrolyte is effective to improve uniformity of local concentration and a smaller exchange current density (i⁰) is essential for reducing sensitivity of interface reaction. Activation polarization is beneficial for uniform plating of lithium. Thus, the polarization curve is extremely important to determine whether lithium deposits uniformly or not. This work results in a new understanding of principles for dendrite growth, and is expected to lead to new insights on strategies for dendrite suppression.

Key words: Li metal batteries, electrochemistry, kinetics, numerical simulation, Li dendrite

中图分类号:

TM 912

林振康, 乔耀璇, 王伟, 袁洪, 樊铖, 孙克宁. 基于非线性动力学的锂沉积形貌模拟与预测[J]. 化工学报, 2020, 71(9): 4228-4237.

Zhenkang LIN, Yaoxuan QIAO, Wei WANG, Hong YUAN, Cheng FAN, Kening SUN. Morphology prediction of lithium plating by finite element modeling and simulations based on non-linear kinetics[J]. CIESC Journal, 2020, 71(9): 4228-4237.

图/表 8

图1 锂对称电池二维模型示意图

Fig.1 Two-dimension scheme of Li symmetric cell

表1 仿真参数表

Table 1 Parameters in the model

模型参数	数值
温度T₀	298 K
电解液中Li⁺初始浓度c⁰	500 mol·m^-3
电解液中Li⁺扩散系数D_e	10^-9~10^-11 m²·s^{-1 [31,32,33]}
交换电流密度i⁰	10~10³ A·m^{-2 [34,35]}
阴极传递系数α	0.5
阳极传递系数β	0.5
极板间距d	18×10^-6 m
晶核曲率半径r	2×10^-6 m
晶核高度h	4×10^-6 m

图2 不同外加电流时，电解液的浓度与电位分布

Fig.2 Distributions of Li+ ion concentration and potential at different currents

图3 操作电流对沉积过程的影响

Fig.3 Influence of applied current

图4 i0为10 A·m-2时不同De体系恒电位沉积模拟

Fig.4 Potentiostatic simulations of cells with different De and the same i0 of 10 A·m-2

图5 De为10-10 m2·s–1时不同i0体系恒电流沉积模拟

Fig.5 Galvanostatic simulations of cells with different i0 and the same De of 10-10 m2·s–1

图6 不均匀电流影响因素

Fig.6 Factors in non-uniform current density

图7 极化曲线

Fig.7 Polarization curve

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