Ru‐ and Cl‐Codoped Li₃V₂(PO₄)₃ with Enhanced Performance for Lithium‐Ion Batteries in a Wide Temperature Range

Abstract

Li₃ V₂ (PO₄ )₃ (LVP) is a promising cathode material for lithium-ion batteries, especially when used in a wide temperature range, due to its high intrinsic ionic mobility and theoretical capacity. Herein, Ru- and Cl-codoped Li₃ V₂ (PO₄ )₃ (LVP-Ru_x -Cl₃ _x ) coated with/without a nitrogen-doped carbon (NC) layer are synthesized. Among them, the optimized sample (LVP-Ru_0.05 -Cl_0.15 @NC) delivers remarkable performances at both room temperature and extreme temperatures (-40, 25, and 60 °C), indicating temperature adaptability. It achieves intriguing capacities (49 mAh g^-1 at -40 °C, 128 mAh g^-1 at 25 °C, and 123 mAh g^-1 at 60 °C, all at 0.5 C), long cycle life (94% capacity retention after 2000 cycles at 25 °C and 5 C), and high-rate capabilities (up to 20 C). The structural evolution features and capacity loss mechanisms of LVP-Ru_0.05 -Cl_0.15 @NC are further investigated using in situ X-ray diffraction (XRD) at different temperatures (-10, 25, and 60 °C) during redox reactions. Theoretical calculations elucidate that Ru- and Cl-codoping can greatly improve the intrinsic diffusion coefficient of LVP by reducing its bandgap energy and lowering the energy barrier of lithium-ion diffusion. In "all-weather" conditions, the dual-element co-doping strategy is critical for increasing electrochemical performance.