Localized Electron Density Redistribution in Fluorophosphate Cathode: Dangling Anion Regulation and Enhanced Na-Ion Diffusivity for Sodium-Ion Batteries

Polyanionic transition metal polyphosphate (TMPO)-type Na3V2(PO4)(2)O2F (NVPO2F) is promising as cathode for large-scale sodium-ion batteries (SIBs) on account of its considerable capacity and highly stable structure. However, the redox of transition metal and phase transitions along with the (de)intercalation of Na+ lead to its slow kinetics and inferior rate performance. Herein, chlorine (Cl) is applied as a heteropical dopant to obtain Cl-doped NVPO2F (NVPO2-xClxF) cathode material for SIBs. Density functional theory investigation reveals that Cl doping tunes the localized electronic density and structure in NVPO2F lattice, causing the electron redistribution on vanadium center and dangling anions. Hence, the NVPO2-xClxF cathode exhibits a revised redox behavior of vanadium for Na+ extraction/insertion, increases Na+ diffusion rate, as well as lowers charge transfer resistance. A Na+ storage mechanism of reversible transformations between three phases and V4+/V5+ redox couple for NVPO2-xClxF cathode is verified. The NVPO2-xClxF cathode reveals a high rate capacity of approximate to 63 mAh g(-1) at 30C and great cycle stability over 1000 cycles at 10C. More importantly, outstanding rate property (314 Wh kg(-1) at 5850 W kg(-1)) and cycling capability are obtained for the NVPO2-xClxF//3DC@Se full cell. This study demonstrates a brand-new strategy to prepare advanced cathode materials for superior SIBs.

Automated summary

This study demonstrates a new strategy to prepare advanced cathode materials for superior SIBs by doping chlorine, which improves the redox behavior of the cathode, enhances Na+ diffusion rate, and reduces charge transfer resistance. The Cl-doped NVPO2-xClxF cathode exhibits high rate capacity and cycle stability, and shows outstanding rate property and cycling capability in full cell configuration.