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1、Capacity Fade Mechanisms and Side Reactions inLithium-Ion Batteries锂离子电池容量衰减机机理和副反应Pankaj Arorat and Ralph E. White*作者：Pankaj Arorat and Ralph E. White*Center For Electrochemical Engineering, Department of Chemical Engineering, University of South Carolina,Columbia, South Carolina 29208, USA美国，南卡罗来纳
2、，年哥伦比亚29208，南卡罗来纳大学，化学工程系，中心电化学工程ABSTRACT The capacity of a lithium-ion battery decreases during cycling. This capacity loss or fade occurs due to several different mechanisms which are due to or are associated with unwanted side reactions that occur in these batteries. These reactions occur during
3、overcharge or overdischarge and cause electrolyte decomposition, passive film formation, active material dissolution, and other phenomena. These capacity loss mechanisms are not included in the present lithium-ion battery mathematical models available in the open literature. Consequently, these mode
4、ls cannot be used to predict cell performance during cycling and under abuse conditions. This article presents a review of the current literature on capacity fade mechanisms and attempts to describe the information needed and the directions that may be taken to include these mechanisms in advanced l
5、ithium-ion battery models.IntroductionThe typical lithium-ion cell (Fig. 1) is made up of a coke or graphite negative electrode, an electrolyte which serves as an ionic path between electrodes and separates the two materials, and a metal oxide (such as LiCoO2, LiMn2O4, or LiNiO2) positive electrode.
6、 This secondary (rechargeable) lithium-ion cell has been commercialized only recently.Batteries based on this concept have reached the consumer market, and lithium-ion electric vehicle batteries are under study in industry.The lithium-ion battery market has been in a period of tremendous growth ever
7、 since Sony introduced the first commercial cell in 1990.With energy density exceeding 130 Wh/kg (e.g., Matsushita CGR 17500) and cycle life of more than 1000 cycles (e.g., Sony 18650) in many cases, the lithium-ion battery system has become increasingly popular in applicationssuch as cellular phone
8、s, portable computers, and camcorders.As more lithium-ion battery manufacturers enter the market and new materials are developed,cost reduction should spur growth in new applications. Several manufacturers such as Sony Corporation, Sanyo Electric Company, Matsushita Electric Industrial Company, Moli
9、 Energy Limited, and A&T Battery Corporation have started manufacturing lithium-ion batteries for cellular phones and laptop computers. Yoda1 has considered this advancement and described a future battery society in which the lithium-ion battery plays a dominant role. Several mathematical models of
10、these lithium-ion cells have been published. Unfortunately, none of these models include capacity fade processes explicitly in their mathematical description of battery behavior. The objective of the present work is to review the current understanding of the mechanisms of capacity fade in lithium-io
11、n batteries. Advances in modeling lithium-ion cells must result from improvements in the fundamental understanding of these processes and the collection of relevant experimental data. Some of the processes that are known to lead to capacity fade in lithium-ion cells are lithium deposition (overcharg
12、e conditions), electrolyte decomposition, active material dissolution, phase changes in the insertion electrode materials, and passive film formation over the electrode and current collector surfaces. Quantifying these degradation processes will improve the predictive capability of battery models ul
13、timately leading to less expensive and higher quality batteries. Significant improvements are required in performance standards such as energy density and cycle life, while maintaining high environmental, safety, and cost standards. Such progress will require considerable advances in our understandi
14、ng of electrode and electrolyte materials, and the fundamental physical and chemical processes that lead to capacity loss and resistance increase in commercial lithium-ion batteries. The process of developing mathematical models for lithium ion cells that contain these capacity fade processes not on
15、ly provides a tool for battery design but also provides a means of understanding better how those processes occur.Present Lithium-Ion Battery Models The development of a detailed mathematical model is important to the design and optimization of lithium secondary cells and critical in their scale-up.
16、 West developed a pseudo two-dimensional model of a single porous insertion electrode accounting for transport in the solution phase for a binary electrolyte with constant physical properties and diffusion of lithium ions into the cylindrical electrode particles. The insertion process was assumed to be diffusion limited, and hence charge-transfer resistance at the interface between electrolyte and
