Attempts to Improve the Behavior of Li Electrodes in Rechargeable Lithium Batteries

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Abstract
In this work we studied properties of modified lithium electrodes in an attempt to improve the high rate performance of rechargeable Li (metal) batteries containing liquid electrolyte solutions. Li (metal)- Li0.3MnO2Li0.3MnO2 AA batteries with solutions containing 1,3-dioxolane (DN), LiAsF6,LiAsF6, and a basic stabilizer became commercial several years ago but failed to compete with Li-ion battery technology because of a very limited cycle life at high charging rates. The problem relates to intensive reactions between Li deposited at high rates and the electrolyte solutions, which dry the batteries. The lithium-solution reactivity was modified through several approaches. Li anodes doped by Li3N,Li3N, Al, and Mg were tested, as well as solutions containing derivatives of DN that are expected to be less reactive toward lithium than DN. It was concluded that reduction of the Li anode-solution reactivity by these approaches cannot solve the problem, because it is impossible to modify the rough morphology, high surface of lithium electrodes when charging (Li deposition) rates are high (>1 mA/cm2). Since there is no hermetic passivation of any Li surface in liquid electrolyte solutions, the high-surface-area Li deposits react with solution components. Therefore, upon charge-discharge cycling of practical Li (metal) batteries, the electrolyte solution is consumed in these reactions. Hence, the future of Li (metal) rechargeable batteries lies either in the use of solid electrolyte matrices instead of the liquid solutions, or in applications where low charging rates are tolerable. © 2002 The Electrochemical Society. All rights reserved.