Hydrothermal-assisted synthesis of the Na7V4(P2O7)4(PO4)/C nanorod and its fast sodium intercalation chemistry in aqueous rechargeable sodium batteries

Abstract

Both high safety and low cost give aqueous rechargeable sodium-ion batteries (ARSB) the opportunity for application in stationary energy storage, but the low operating potential of the existing cathode materials limits its energy density. Here, we introduce a hydrothermal-assisted strategy to prepare the Na₇V₄(P₂O₇)₄(PO₄)/C nanorod and employ it as a novel high-property cathode material for ARSB. The hierarchical structure is formed by direct in situ carbonization of the surfactants (CTAB and oxalic acid) along with the crystallization of Na₇V₄(P₂O₇)₄(PO₄). The prepared Na₇V₄(P₂O₇)₄(PO₄) with a well-defined 1D nanostructure and uniform particle size is wrapped with a thin carbon layer. For the first time, its sodium intercalation chemistry in an aqueous electrolyte was investigated. Based on the reversible phase transformation and high sodium diffusion coefficient, it is demonstrated to be reliable in an aqueous electrolyte with the rapid ion transport capability. A pair of redox plateaus is observed in the charge and discharge curves at 0.961 and 0.944 V (vs. SCE) respectively with the capacity of 51.2 mA h g⁻¹ at 80 mA g⁻¹. Favored by the open ion channel and 1D morphology, the composite exhibits superior high rate capability and 72% of the capacity remains at 1000 mA g⁻¹. The results not only demonstrate a high-property cathode material for ARSB, but also are helpful for design and synthesis of mixed-polyanion electrode materials with tailored architecture.