Understanding and illustrating the irreversible self-discharge in rechargeable batteries by the Evans Diagram

Xiangjun Pu, Yingping Zheng, Aiping Qi, Linlong Lyu, Guanqiang Ruan, Yuliang Cao, Zhongxue Chen, Zheng-Long Xu
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Abstract

As an intermediary between chemical and electric energy, rechargeable batteries with high conversion efficiency are indispensable to empower electric vehicles and stationary energy storage systems. Self-discharge with adverse effects on energy output and lifespan is a long-existing challenge and intensive endeavors have been devoted to alleviating it. Previous reports mainly focused on examining key factors influencing the rate of self-discharge, however, its origination has rarely been revealed from the viewpoint of fundamental electrochemistry. The Evans Diagram, which is a corrosion polarization diagram based on kinetics (corrosion current density) and thermodynamics (potential), is an informative method for analyzing the corrosion process of metals. In this perspective, after an introduction to electrochemical fundamentals, as well as the identical origination of battery self-discharging and metal corrosion, we first transferred the concept of the Evans Diagram to illustrate the origination and evolution of self-discharge in rechargeable batteries. The corresponding Evans Diagram has been proposed for different key factors, which were eventually used as guidance to exploit thermodynamical and kinetical solutions to alleviate the parasitic reactions induced by self-discharge. This contribution is believed to provide new insights towards understanding and regulating self-discharge problems, and promote the establishment of feasible protocols for battery storage in practice.

Abstract Image

通过埃文斯图理解和说明充电电池的不可逆自放电现象
作为化学能和电能的中介,具有高转换效率的可充电电池是电动汽车和固定储能系统不可或缺的能源。自放电会对能量输出和使用寿命产生不利影响,是一项长期存在的挑战,人们一直在努力缓解这一问题。以往的报道主要集中于研究影响自放电速率的关键因素,但很少从基础电化学的角度揭示自放电的起源。埃文斯图是基于动力学(腐蚀电流密度)和热力学(电位)的腐蚀极化图,是分析金属腐蚀过程的一种信息丰富的方法。从这个角度出发,在介绍了电化学基础知识以及电池自放电和金属腐蚀的相同起源后,我们首先将埃文斯图的概念用于说明充电电池自放电的起源和演变。我们针对不同的关键因素提出了相应的埃文斯图,并最终以此为指导,利用热力学和动力学解决方案来缓解自放电引起的寄生反应。相信这一贡献将为理解和调节自放电问题提供新的见解,并促进在实践中建立可行的电池存储协议。
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