Oxygen Vacancy Enhanced Two-Dimensional Lithium Titanate for Ultrafast and Long-Life Bifunctional Lithium Storage

Abstract

Boosting sufficient Li⁺ ion mobility in Li₄Ti₅O₁₂ (LTO) is crucial for high-rate performance lithium storage. Here, an ultrafast charge storage oxygen vacancy two-dimensional (2D) LTO nanosheet was successfully fabricated through a one-pot hydrothermal method. The selectively doped Al³⁺ into octahedron Li⁺/Ti⁴⁺ 16d sites not only provide bulk oxygen vacancy and appropriate distorted TiO₆ octahedra to facilitate Li⁺ ions diffusion, but also serve as a "pillar" to stabilize the Ti-O framework. The oxygen vacancy lowers Li⁺ ion diffusion energy barrier. Moreover, the 2D structure provides open diffusion channels for fast Li⁺ ion transport. As a result, the sample shows excellent electrochemical performance for bifunctional lithium storage. As a lithium-ion battery anode, the capacity retention reaches 112.8 mA h g^-1 after 5000 cycles at 40 C with a fading rate of 0.288% per 100 cycles. Meanwhile, as a lithium-ion capacitor anode, it exhibits an excellent rate capacity of 120 mA h g^-1 after 5000 cycles at 500 C with nearly 100% Coulombic efficiency. The produced LTO shows much higher rate capacity and longer lifetime than the reported LTO. Density functional theory calculations also demonstrate that oxygen vacancy can facilitate Li⁺ ion diffusion kinetics. The relationship between oxygen vacancy content and Li⁺ ions diffusion energy barrier in LTO is quantified. This work pioneers a defect engineering strategy for synthesized high-performance electrode materials.