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首页> 外文期刊>The journal of physical chemistry, C. Nanomaterials and interfaces >Kinetics of LixFePO4 Lithiation/Delithiation by Ferrocene-Based Redox Mediators: An Electrochemical Approach
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Kinetics of LixFePO4 Lithiation/Delithiation by Ferrocene-Based Redox Mediators: An Electrochemical Approach

机译：二茂铁基氧化还原介体对LixFePO4锂化/脱锂的动力学：一种电化学方法

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摘要

An electrochemical approach for studying the kinetics of reactions between redox mediators and Li-ion battery electrode materials has been developed. The approach is based on a simple diffusion-reaction model, similar to that used to describe the classical catalytic electrochemical-chemical (EC') reaction mechanism. Using this approach it is possible to determine the diffusion length of redox mediators in a porous film made from a Li-ion battery electrode material. The rate constant for reaction between redox species and the porous electrode may then be calculated. The approach is applied to determine rate constants for the disappearance of ferrocene and dibromoferrocenium due to reaction with excess pristine and carbon-coated LixFePO4 (0 <= x <= 1) nanoparticulate films (porosity similar to 0.63, BET surface area 20-30 m(2) g(-1)) and excess Li+ (0.1 M), which are of relevance to the operation of the recently introduced redox-flow Li-ion battery. Pseudo-first-order volumetric rate constants in the range 1-6 s(-1) were obtained, corresponding to apparent heterogeneous rate constants in the range 2.2 x 10(-6) - 4.4 x 10(-6) cm s(-1), which we show are fast enough not to limit the charge/discharge rate of redox flow Li-ion batteries constructed from these materials.
机译：已经开发出一种用于研究氧化还原介体和锂离子电池电极材料之间反应动力学的电化学方法。该方法基于简单的扩散反应模型，类似于用来描述经典的催化电化学反应（EC'）的机理。使用这种方法，可以确定氧化还原介体在由锂离子电池电极材料制成的多孔膜中的扩散长度。然后可以计算氧化还原物质与多孔电极之间反应的速率常数。该方法适用于确定由于与过量的原始和碳包覆的LixFePO4（0 <= x <= 1）纳米颗粒薄膜（孔隙度近似于0.63，BET表面积为20-30 m）反应而导致的二茂铁和二溴二茂铁消失的速率常数。 （2）g（-1））和过量的Li +（0.1 M），这与最近推出的氧化还原流式锂离子电池的运行有关。获得了1-6 s（-1）范围内的伪一阶体积速率常数，对应于2.2 x 10（-6）-4.4 x 10（-6）cm s（-）范围内的表观异质速率常数。 1），我们展示的速度足够快，不会限制由这些材料制成的氧化还原液流锂离子电池的充电/放电速率。

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