Abstract

The discharge characteristics of a heat activated battery containing NiCl₂–CoCl₂ mixtures as a positive electrode are studied. The battery cell discharge temperature is found to decrease when the mixtures are used instead of individual nickel(II) and cobalt(II) chlorides. The minimum temperature at which a stable discharge plateau is detected is 480°C. The maximum capacity of the discharge plateau is 0.33 A h g^–1. The optimum composition of the cathode mixture contains 20 wt % CoCl₂. The composition and morphology of the reduction products of the cathodic materials are determined. The initial nickel and cobalt chlorides are reduced to metals during battery cell discharge. The reduction process is accompanied by the diffusion of lithium halides from the separator to the cathodic space. The reduced metals (Ni, Co) form a network of branched dendrites covered with a salt film based on lithium chloride. The density and morphology of the dendritic deposit is determined by the composition of the initial cathodic mixture. The salt film consists of solid solutions and peritectics of the Li, Co, Ni||Cl, Br, F system. The reduction of M²⁺ (where M = Ni, Co) to the M⁰ metal is shown to proceed via a melt mechanism in the diffusion kinetics mode.

中文翻译：

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热活化电池中氯化镍 (II) 和氯化钴 (II) 混合物的电还原

摘要

研究了含有 NiCl ₂ -CoCl ₂混合物作为正极的热激活电池的放电特性。当使用混合物代替单独的镍 (II) 和钴 (II) 氯化物时，发现电池放电温度会降低。检测到稳定放电平台的最低温度为 480°C。放电平台的最大容量为 0.33 A hg ^–1。正极混合物的最佳组成包含 20 wt % CoCl ₂. 确定阴极材料的还原产物的组成和形态。最初的镍和钴氯化物在电池放电过程中被还原为金属。还原过程伴随着卤化锂从隔膜扩散到阴极空间。被还原的金属 (Ni, Co) 形成支链状枝晶网络，上面覆盖着基于氯化锂的盐膜。树枝状沉积物的密度和形态由初始阴极混合物的组成决定。盐膜由Li、Co、Ni||Cl、Br、F系的固溶体和包晶组成。M ²⁺ (其中M = Ni, Co)还原为M ⁰金属被证明是通过扩散动力学模式中的熔化机制进行的。