机械压力对锂电池性能影响的研究进展

doi:10.11949/0438-1157.20210145

摘要/Abstract

摘要：

锂电池在充放电过程中，由于锂离子的嵌入/脱出或沉积/剥离，SEI膜持续生长及产气等副反应的发生会造成电池产生内压。压力能够通过界面作用影响锂电池的各项性能。回顾并总结了近年来压力，包括电池内压及外加压力对锂电池性能影响的研究。从压力作用下电池材料的形变、界面阻抗及金属锂负极的沉积模式及电池的循环和倍率性能的改变等角度出发，详细介绍了压力对锂电池隔膜及电解质、插层电极材料、合金电极材料及锂金属电极性能的影响及作用机理。同时对合理利用压力改善电池性能以及相关锂电池的设计策略进行展望，为从事相关研发的工作者提供一些借鉴。

关键词: 锂电池, 电池压力, 电解质, 力学性能, 金属锂负极, 界面, 弹性

Abstract:

During the charging and discharging process of the lithium battery, due to the intercalation/extraction or deposition/stripping of lithium ions, the continuous growth of the SEI film and the occurrence of gas production will cause the battery to generate internal pressure. Pressure can affect the performance of lithium batteries through interface effects. This paper reviews the research progress of the effect and influence mechanism of pressure on the performance of lithium batteries, including the interface resistance, the deformation of the material, and the cyclic and rate performance of the batteries. Furthermore, the paper brings on the prospect of the improvement of battery using pressure and tries to provide some references to the research in this area.

Key words: lithium batteries, battery pressure, electrolyte, mechanical properties, lithium metal anode, interface, elasticity

中图分类号:

TQ 028.8

崔锦,石川,赵金保. 机械压力对锂电池性能影响的研究进展[J]. 化工学报, 2021, 72(7): 3511-3523.

CUI Jin,SHI Chuan,ZHAO Jinbao. Research progress on the effect of mechanical pressure on the performance of lithium batteries[J]. CIESC Journal, 2021, 72(7): 3511-3523.

图/表 9

图1 根据应力-应变特性泡沫结构隔膜可分为弹性、塑性和致密化三个特性区域[21-22]

Fig.1 Stress-strain schematic demarcating domains of elastic, plastic, and densification characteristics for a foam-based separator[21-22]

图2 在0~3 MPa压力下隔膜的交流阻抗曲线（a）和隔膜电阻值（b）[25]

Fig.2 Alternating current (AC) impedance spectra (a) and resistance (b) of the separators under 0—3 MPa[25]

图3 在60℃（a）、80℃（b）、100℃（c）下，以0.1 mA·cm-2充放电，Li/PEO-LiTFSI/Li对称电池在约束压力下的体相电阻及界面电阻的变化[43]

Fig.3 Variation of bulk and interfacial impedance with stack pressure of a typical Li/PEO-LiTFSI/Li cell during cycling at 0.1 mA·cm-2 at 60℃ (a), 80℃ (b) and 100℃ (c) [43]

图4 LPSC对称电池的阻抗谱图[46]

Fig.4 Nyquist plots of LPSC symmetry cells[46]

图5 施加压力装置示意图（a）；约束压力随循环次数的变化，电池后期压力演化与初始压力有关（b）[53]

Fig.5 Schematic diagram of the constraint fixture used to maintain and measure compressive stack stress (a); Stack stress evolution as a function of cycle number. Changes in the initial stack pressure have a profound effect on the nature of the subsequent stress evolution in the cell (b)[53]

图6 电池在不同压力下的充放电容量和库仑效率（a）；相对于首圈容量的电池容量保持率（b）[58]

Fig.6 Electrochemical performance and CE of solid-state nano-Si composite anodes cycled at a rate of C/20 under compressive pressures of 3, 150 and 230 MPa (a); Specific charge (delithiation) capacity retention as a percentage of initial specific capacity (b) [58]

图7 软包电池中锂负极的结构演变[80](a)电池的体积膨胀与循环周期的函数关系;(b)~(d)两种不同区域,300 W·h·kg-1电池锂负极的结构演变示意图

Fig.7 Structural evolution of the Li metal anode in high-energy Li metal pouch cells[80]

图8 Li/LLZO界面在多次Li剥离/沉积过程中的动态变化示意图[83]

Fig.8 Schematic illustration of the dynamic changes at the Li/LLZO interface during repeated Li dissolution/deposition cycles[83]

图9 不同压力下电压对恒定电流密度的响应（a）；0.1 mA·cm-2循环时压力诱发应变率与电流诱发应变率比较（b）[84]

Fig.9 The potential response to a constant current density at varying stack pressures(a); Comparison of the pressure-induced strain rate and the current-induced strain rate for cycling at 0.1 mA·cm-2 (b) [84]

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