Lithium Diffusion in Li4/3Ti5/3O4 Particles during Insertion and Extraction

Author:

Takami Norio,Hoshina Keigo,Inagaki Hiroki

Abstract

Lithium diffusion in a small Li4/3Ti5/3O4 (LTO) particle was investigated from kinetic viewpoints of two-phase transition process based on a core-shell model by means of galvanostatic and potentiostatic measurements of thin LTO composite electrodes. High-rate galvanostatic charge (insertion) – discharge (extraction) properties of the thin LTO composite electrode showed that the insertion into the LTO particle was significantly slower than the extraction. An apparent chemical diffusion coefficient (Dapp ) of lithium in the LTO particle during the insertion and extraction was evaluated from the results of potential step chronoamperometry (PSCA) with a spherical finite diffusion model. The phase-boundary movements between the two phases in the cathodic and the anodic potential steps for a long-time region were controlled by lithium diffusion through Li7/3Ti5/3O4 rock-salt (LTO-rock-salt) and Li4/3Ti5/3O4 spinel (LTO-spinel) shell, respectively. Dapp in the LTO-rock-salt and the LTO-spinel phase were estimated to be approximately 1 × 10−12 cm2/s and 1.6 × 10−11 cm2/s, respectively. The slower insertion was mainly due to a Dapp value one order of magnitude smaller in the LTO-rock-salt than that in the LTO-spinel phase. Electrochemical kinetic properties of the LTO particle with the core-shell structure were interpreted by lithium diffusion through the LTO-rock-salt shell during the insertion and the LTO-spinel shell with the low electron conductivity during the extraction.

Publisher

The Electrochemical Society

Subject

Materials Chemistry,Electrochemistry,Surfaces, Coatings and Films,Condensed Matter Physics,Renewable Energy, Sustainability and the Environment,Electronic, Optical and Magnetic Materials

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