V-substituted pyrochlore-type polyantimonic acid for highly enhanced lithium-ion storage

Abstract

Pyrochlore-structured polyantimonic acid (PAA) is a potential high-capacity electrode material, but its innately poor electroconductivity (∼10−10 S/cm) seriously impairs its electrochemical reversibility for lithium-ion storage. Herein, we report design and synthesis of a novel V-substituted PAA (PAA-V), where V5+ are introduced to partially replace Sb5+. Owing to identical valence and close ionic radius relative to Sb5+, the V5+ cation can constitute the covalent VO6 octahedra framework without changing the pyrochlore crystal structure of PAA. As a result, the V5+-substitution is capable to modulate the electronic structure of PAA with significantly improved electrical conductivity (∼10−6 S/cm for PAA-V) and meanwhile decreases the size of crystals with reduced diffusion length for Li+-ions. With varying the ratio of V5+-substitution, the PAA-V with optimized substitution molar ratio (18%) exhibits the best lithium-ion storage performance, delivering a long cycling life with high reversible capacity (731 mAh/g after 1200 cycles at 1 A/g) and outstanding rate capability (279 mAh/g at 15 A/g). More importantly, by pairing the PAA-V as anode and commercial LiFePO4 as cathode, the full cell with a limited negative/positive capacity ratio of 1.2 exhibits decent cycling stability at 1 C after 150 cycles with 85.5% capacity retention.