A Li+ and PANI co-intercalation strategy for hydrated V2O5 to enhance zinc ion storage performance

Layered vanadium-based oxides are regarded as promising cathode materials for zinc-ion batteries (ZIBs) due to their open-framework crystal structure and high theoretical specific capacity. However, the sluggish Zn2+ diffusion and poor structural stability limit their wide application in ZIBs. Herein, a new strategy is proposed to introduce metal ions and conjugated conductive polymers into layered hydrated V2O5 as a cathode material for ZIBs. For demonstration, Li+ and polyaniline (PANI) are co-intercalated into hydrated V2O5 (LPVO) resulting in an enlarged spacing of 14.4 angstrom. A ZIB with this LPVO cathode exhibits a capacity of 377 mA h g(-1) at a current density of 0.1 A g(-1), which is higher than that of a single Li+ pre-intercalated hydrated V2O5 (LVO) or PANI pre-intercalated host (PVO). Besides, a long-term cycling stability (94% capacity retention after 800 cycles at 5 A g(-1)) is achieved. The synergistic effect of pre-intercalated Li+ and PANI in LPVO originates from the weak electrostatic interactions between Zn2+ and the host O2-. Density functional theory (DFT) calculation results clearly show that LPVO possesses the lowest binding energy of 1.67 eV for Zn2+ insertion into the host (2.41 eV for LVO, 1.84 eV for PVO), indicating favorable reaction kinetics in LPVO, which is also confirmed by the fastest Zn2+ diffusion coefficient of LPVO among the three samples. The enlarged lattice space and stabilized host structure also improve the cycling performance. Our study elucidates the advantages of co-intercalated alien species in the host and provides a facile strategy to obtain high performance ZIBs.