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Abstract

Lithium-ion batteries are without a doubt a key technology in the coming energy revolution. It is thus all the more surprising that one of the more prevalent Li battery anode materials, reduced lithium titanium oxide (LTO, Li₄Ti₅O₁₂), is still poorly understood on a microscopic level. While recent theoretical and experimental evidence suggests that a polaron hopping mechanism is responsible for the increased electronic conductivity of reduced LTO, no such explanation exists for the concurrent improvements to the ionic mobility. In this computational study, we show that the presence of polaronic Ti³⁺ centers can indeed lead to a significant lowering of Li hopping barriers in both bulk and surface reduced LTO. For the latter, we find a reduced barrier height of roughly 40 meV compared to that of our pristine reference. This is in accordance with experimental findings showing that lithium-ion diffusion in reduced LTO is twice as high as that for pristine LTO. Finally, we show that—in accordance with experimental observations—polaron formation upon lithiation of LTO leads to a similar behavior. Altogether, our analysis hints at a correlated movement of Li ions and polarons, highlighting LTO’s potential for rational defect engineering.