Влияние варисторного эффекта и контактных явлений на характеристики твердотельных литий-ионных аккумуляторов с полупроводниковыми электродами

Александр Степанович Рудый, А. А. Мироненко, В. В. Наумов, А. Б. Чурилов, С. В. Курбатов, Ю. С. Егорова, Евгений Анатольевич Козлов
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Abstract

The results of measuring the charge-discharge characteristics of solid-state thin-film lithium-ion batteries with a nanocomposite anode based on a-Si(Al) solid solution are presented. The charging characteristics of batteries have a feature in the form of a step on the smooth branch of the charge curve. It is shown that the appearance of the step is associated with the compensation of a-Si(Al) and the change from hole to electron conductivity due to lithiation of the electrode during charging. As a result of lithiation, the electron over-barrier current becomes the main component of the charging current. To maintain a galvanostatic charge mode, the potentiostat increases the voltage by the height of the potential barrier, which leads to the appearance of a step on the charging curve. The impedance of a solid-state thin-film lithium-ion battery of the LiCoO2-LiPON-Si@O@Al electrochemical system was measured in the temperature range from -20°С to 50°С. A structural model of the accumulator is proposed and the parameters of the structural elements of the model are calculated which provide the best fit for experimental Nyquist diagrams. The obtained values of the electrodes’ resistivity are orders of magnitude higher than the results of direct measurements and data from literary sources. According to the IV-characteristics obtained by cyclic voltammetry the high resistance of the electrodes is due to the metal-semiconductor contact and the varistor effect of the electrode material. The results obtained make significant adjustments to the interpretation of the impedance spectra and structural models of solid-state lithium-ion batteries based on semiconductor materials
变容效应和接触现象对具有半导体半导体的固体锂离子蓄电池的影响
本文介绍了以a- si (Al)固溶体为基材的纳米复合负极对固态薄膜锂离子电池充放电特性的测量结果。电池的充电特性在充电曲线的光滑支路上以台阶的形式表现出来。结果表明,该阶跃的出现与a-Si(Al)的补偿以及充电过程中电极锂化引起的空穴电导率到电子电导率的变化有关。由于锂化,电子过势垒电流成为充电电流的主要组成部分。为了保持恒流充电模式,恒电位器通过电位势垒的高度来增加电压,从而导致充电曲线上出现一个台阶。测量了LiCoO2-LiPON-Si@O@Al电化学体系固态薄膜锂离子电池在-20°С ~ 50°С温度范围内的阻抗。提出了蓄能器的结构模型,并计算了模型中各结构单元的参数,得到了最适合实验奈奎斯特图的参数。所得的电极电阻率值比直接测量的结果和文献资料的数据高几个数量级。根据循环伏安法得到的iv特性,电极的高电阻是由金属-半导体接触和电极材料的压敏效应引起的。所得结果对基于半导体材料的固态锂离子电池的阻抗谱和结构模型的解释进行了重大调整
本文章由计算机程序翻译,如有差异,请以英文原文为准。
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