锂离子在三维骨架复合锂金属负极中的沉积规律

doi:10.11949/0438-1157.20200120

摘要/Abstract

摘要：

锂金属具有极高的理论比容量和极低的氧化还原电极电势，成为了新一代高比能二次电池最理想的负极材料。然而，锂金属负极其走向大规模应用仍存在诸多问题与挑战。三维骨架复合负极可以控制金属锂均匀形核，低电流密度下均匀沉积，有望推动锂金属负极的实用化。为了更高效地指导锂金属负极设计和优化，采用相场理论，对三维骨架锂金属负极中比表面积对金属锂沉积过程的作用机制进行了定量分析和探究，发现了比表面积调控金属锂沉积的两阶段作用机理，并提出了基于比表面积参数的三维骨架负极设计与优化方向，从而最大程度发挥三维骨架在调控稳定金属锂负极上的积极作用。

关键词: 数学模拟, 电化学, 纳米材料, 相场, 锂金属电池, 锂金属负极

Abstract:

Lithium metal has a very high theoretical specific capacity and a very low redox electrode potential, making it the most ideal anode material for a new generation of high specific energy secondary batteries. However, the large-scale practical applications of lithium metal batteries have been hindered by several issues on lithium metal anodes, such as uncontrollable lithium electroplating morphology and unstable solid electrolyte interphase (SEI) layer. Researchers have proposed plenty of strategies including three-dimensional (3D) structured lithium metal anodes to settle these challenges. The rational design of 3D structured lithium metal anodes requires a deep understanding of the mechanisms behind lithium metal batteries, which are extremely deficient at current initial stage. In this work, the mechanism of the areal surface area in 3D structured lithium metal anode on the electroplating process of lithium metal is quantitatively explored, and the two-stage mechanism of the areal surface area regulating lithium metal electroplating was revealed. At the early stage, higher areal surface area can provide more activated sites for electrochemical reactions, which can reduce the reaction resistance. While at the later stage, higher areal surface area may bring more narrow pores, which may hinder the lithium ion transport. In order to maximize the positive effect of 3D structured lithium metal anode in the early stage, the areal surface area and pore structure should be rational designed.

Key words: mathematical modeling, electrochemistry, nanomaterials, phase field, lithium metal batteries, lithium metal anodes

中图分类号:

TM 912

张睿, 沈馨, 王金福, 张强. 锂离子在三维骨架复合锂金属负极中的沉积规律[J]. 化工学报, 2020, 71(6): 2688-2695.

Rui ZHANG, Xin SHEN, Jinfu WANG, Qiang ZHANG. Plating of Li ions in 3D structured lithium metal anodes[J]. CIESC Journal, 2020, 71(6): 2688-2695.

图/表 6

表1 相场模型计算参数

Table 1 Parameters in phase field model

参数符号	参数名称	值	单位
L_σ	界面迁移系数	1.0×10^-8	m³·J^-1·s^-1
L_η	电化学反应系数	0.2	s^-1
κ₀	相场梯度能量系数	5.0×10^-5	J·m^-1
δ	各向异性系数	0.03	无量纲
α	电荷转移系数	0.5	无量纲
c₀	电解液体相锂离子浓度	1.0×10³	mol·m^-3
c_s	锂金属锂原子浓度	7.69×10⁴	mol·m^-3
W	固液相平衡势垒	1.2×10⁷	J·m^-3
D₊_l	电解液相扩散系数	6.0×10^-12	m²·s^-1
D_+s	金属锂相扩散系数	1.0×10^-15	m²·s^-1
σ_l	电解液相电导率	1.0	S·m^-1
σ_s	金属锂相电导率	1.0×10⁷	S·m^-1
φ_s0	电化学反应固相电势	-0.1	V

图2 三维骨架金属锂负极沉积过程锂离子浓度分布

Fig.2 Li ion concentration evolution during electroplating process in 3D structured lithium metal anode

图1 三维骨架金属锂负极沉积过程相场序参数分布

Fig.1 Phase field order parameter evolution during electroplating process in 3D structured lithium metal anode

图3 不同比表面积的三维骨架金属锂负极金属锂沉积形貌

Fig.3 Lithium electroplating morphology in 3D structured lithium metal anodes with different areal surface area

图4 电化学沉积阻力随沉积容量变化曲线

Fig.4 Electroplating resistance varies with electroplating capacity

图5 电化学沉积阻力随比表面积变化曲线

Fig.5 Electroplating resistance varies with areal surface area

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