Mobile Small Polarons Explain Conductivity in Lithium Titanium Oxide Battery Electrodes

TL;DR

This paper demonstrates that small polarons, facilitated by oxygen vacancies, significantly enhance the electronic conductivity of lithium titanium oxide (LTO) electrodes, explaining experimental observations and guiding defect engineering strategies.

Contribution

It introduces a detailed theoretical analysis of polaronic charge transport in LTO using DFT+U, revealing how defect engineering can improve conductivity.

Findings

Polaronic states are crucial for charge transport in LTO.

Oxygen vacancies can increase electronic conductivity.

Polaron hopping barriers are key to understanding conductivity enhancement.

Abstract

Lithium titanium oxide Li$_4$Ti$_5$O$_{12}$ (LTO) is an intriguing anode material promising particularly long lived batteries, due to its remarkable phase stability during (dis)charging of the cell. However, its usage is limited by its low intrinsic electronic conductivity. Introducing oxygen vacancies can be one method to overcome this drawback, possibly by altering the charge carrier transport mechanism. We use Hubbard corrected density-functional theory (DFT+U) to show that polaronic states in combination with a possible hopping mechanism can play a crucial role in the experimentally observed increase of electronic conductivity. To gauge polaronic charge mobility, we compute relative stabilities of different localization patterns and estimate polaron hopping barrier heights. With this we finally show how defect engineering can indeed raise the electronic conductivity of LTO up to the level of its ionic conductivity, thereby explaining first experimental results for reduced LTO.