Two-Phase Transition Induced Amorphous Metal Phosphides Enabling Rapid, Reversible Alkali-Metal Ion Storage.

Abstract

Metal phosphides as anode materials for alkali-metal ion batteries have captured considerable interest due to their high theoretical capacities and electronic conductivity. However, they suffer from huge volume expansion and element segregation during repetitive insertion/extraction of guest ions, leading to structure deterioration and rapid capacity decay. Herein, an amorphous Sn_0.5Ge_0.5P₃ was constructed through a two-phase intermediate strategy based on the elemental composition modulation from two crystalline counterparts and applied in alkali-metal ion batteries. Differing from crystalline P-based compounds, the amorphous structure of Sn_0.5Ge_0.5P₃ effectively reduces the volume variation from above 300% to 225% during cycling. The ordered distribution of cations and anions in the short-range ensures the uniform distribution of each element during cycles and thus contributes to durable cycling stability. Moreover, the long-range disordered structure of amorphous material shortens the ion transport distance, which facilitates diffusion kinetics. Benefiting from the aforementioned effects, the amorphous Sn_0.5Ge_0.5P₃ delivers a high Na storage capacity of 1132 mAh g^-1 at 0.1 A g^-1 over 100 cycles. Even at high current densities of 2 and 10 A g^-1, its capacities still reach 666 and 321 mAh g^-1, respectively. As an anode for Li storage, the Sn_0.5Ge_0.5P₃ similarly also exhibits better cycling stability and rate performance compared to its crystalline counterparts. Significantly, the two-phase transition strategy is generally applicable to achieving other amorphous metal phosphides such as GeP₂. This work would be helpful for constructing high-performance amorphous anode materials for alkali-metal ion batteries.