Variation in surface energy and reduction drive of a metal oxide lithium-ion anode with stoichiometry: a DFT study of lithium titanate spinel surfaces

Abstract

Li₄Ti₅O₁₂ is a “zero-strain” lithium-ion anode material that shows excellent stability over repeated lithium insertion–extraction cycles. Although lithium (de)intercalation in the bulk material has been well characterised, our understanding of surface atomic-scale-structure and the relationship with electrochemical behaviour is incomplete. To address this, we have modelled the Li₄Ti₅O₁₂ (111), Li₇Ti₅O₁₂ (111) and α-Li₂TiO₃ (100), (110), and (111) surfaces using Hubbard-corrected density-functional theory (GGA+U), screening more than 600 stoichiometric Li₄Ti₅O₁₂ and Li₇Ti₅O₁₂ (111) surfaces. For Li₄Ti₅O₁₂ and Li₇Ti₅O₁₂ we find Li-terminated surfaces are more stable than mixed Li/Ti-terminated surfaces, which typically reconstruct. For α-Li₂TiO₃, the (100) surface energy is significantly lower than for the (110) and (111) surfaces, and is competitive with the pristine Li₇Ti₅O₁₂ (111) surface. Using these stoichiometric surfaces as reference, we also model variation in Li surface coverage as a function of lithium chemical potential. For Li₄Ti₅O₁₂, the stoichiometric surface is most stable across the full chemical potential range of thermodynamic stability, whereas for Li₇Ti₅O₁₂, Li deficient surfaces are stabilised at low Li chemical potentials. The highest occupied electronic state for Li₇Ti₅O₁₂ (111) is 2.56 eV below the vacuum energy. This is 0.3 eV smaller than the work function for metallic lithium, indicating an extreme thermodynamic drive for reduction. In contrast, the highest occupied state for the α-Li₂TiO₃ (100) surface is 4.71 eV below the vacuum level, indicating a substantially lower reduction drive. This result demonstrates how stoichiometry can strongly affect the thermodynamic drive for reduction at metal-oxide-electrode surfaces. In this context, we conclude by discussing the design of highly-reducible metal-oxide electrode coatings, with the potential for controlled solid-electrolyte-interphase formation via equilibrium chemistry, by electrode wetting in the absence of any applied bias.