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Titanium migration driven by Li vacancies in Li(1-x)Ti2O4 spinel.

A Kitada¹, A M Arevalo-Lopez, J P Attfield

¹Department of Materials Science and Engineering, Kyoto University, Yoshida-honmachi, Sakyo, Kyoto 606-8501, Japan.

Chemical Communications (Cambridge, England)

|June 4, 2015

Summary

Gentle oxidation of lithium titanate spinel (LiTi2O4) with water produces a Li-deficient material. This study reveals Ti cations migrate to alternative sites, limited by lithium vacancy concentration.

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Area of Science:

Materials Science
Solid-State Chemistry
Inorganic Chemistry

Background:

Lithium titanate spinel (LiTi2O4) is a material with potential applications in energy storage.
Understanding cation migration mechanisms is crucial for optimizing material properties.

Purpose of the Study:

To investigate the structural changes in lithium titanate spinel upon gentle oxidation with water.
To elucidate the cation migration pathways and their limiting factors.

Main Methods:

Gentle oxidation of LiTi2O4 with water at room temperature.
Combined X-ray and neutron Rietveld analysis for structural determination.

Main Results:

Formation of Li-deficient Li0.33Ti2O4.
Observation that 28% of titanium (Ti) cations are displaced to alternative octahedral sites.
Correlation of Ti migration with lithium (Li) vacancy concentration.

Conclusions:

The study provides a detailed structural model for the Li-deficient phase.
Ti-migration is confirmed to be a key process, limited by the concentration of Li vacancies.