Mo Doping and Electrochemical Activation Co-Induced Vanadium Composite as High-Rate and Long-Life Anode for Ca-Ion Batteries

Abstract

Calcium-ion batteries have been considered attractive candidates for large-scale energy storage applications due to their natural abundance and low redox potential of Ca²⁺/Ca. However, current calcium ion technology is still hampered by the lack of high-capacity and long-life electrode materials to accommodate the large Ca²⁺ (1.00 Å). Herein, an amorphous vanadium structure induced by Mo doping and in-situ electrochemical activation is reported as a high-rate anode material for calcium ion batteries. The doping of Mo could destroy the lattice stability of VS₄ material, enhancing the flexibility of the structure. The following electrochemical activation further converted the material into sulfide and oxides co-dominated composite (defined as MoVSO), which serves as an active material for the storage of Ca²⁺ during cycling. Consequently, this amorphous vanadium structure exhibits excellent rate capability, achieving discharge capacities of 306.7 and 149.2 mAh g^-1 at 5 and 50 A g^-1 and an ultra-long cycle life of 2000 cycles with 91.2% capacity retention. These values represent the highest level to date reported for calcium ion batteries. The mechanism studies show that the material undergoes a partial phase transition process to derive MoVSO. This work unveiled the calcium storage mechanism of vanadium sulfide in aqueous electrolytes and accelerated the development of high-performance aqueous calcium ion batteries.

Keywords

calcium-ion batteries / electrochemical activation / phase transformation / vanadium sulfide

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2024 The Authors. Energy & Environmental Materials published by John Wiley & Sons Australia, Ltd on behalf of Zhengzhou University.