Improved conductivity and ionic mobility in nanostructured thin films via aliovalent doping for ultra-high rate energy storage

通过异价掺杂提高纳米结构薄膜的电导率和离子迁移率以实现超高倍率储能

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作者:Clayton T Kacica, Pratim Biswas

Abstract

A high-rate lithium ion battery electrode consisting of nanostructured copper-doped TiO2 films, synthesized using a single-step, template-free aerosol chemical vapor deposition technique, is reported herein. A narrowing of the band gap of the copper-doped films from 2.92 to 1.93 eV corresponds to a large increase in electronic conductivity, overcoming a major drawback of pristine TiO2 in electronic applications. Lithium-ion batteries using copper-doped films as the negative electrode exhibit improved charge retention at ultra-high charge rates, up to 50C. Additionally, over 2000 charge-discharge cycles at a rate of 10C, the copper-doped TiO2 electrodes display higher stable cycling capacities. Cyclic voltammetry (CV) and a galvanostatic intermittent titration technique (GITT) provide insight into the chemical diffusion of Li+ in the TiO2 matrix, with copper-doped TiO2 electrodes exhibiting an order of magnitude higher value in CV measurements over pristine TiO2. GITT provided the state-of-charge (SoC) resolved chemical diffusion coefficient of Li+ and suggests that a minimum value occurs at a moderate SoC of 60%, with values near the extremes being over two orders of magnitude higher. Both techniques indicate increased Li+ mobility due to copper-doping, supporting improved electrochemical performance in ultra-high rate battery testing.

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