Bicontinuous hierarchical Na7V4(P2O7)4(PO4)/C nanorod–graphene composite with enhanced fast sodium and lithium ions intercalation chemistry

Abstract

Mixed polyanion materials with a 3D framework for battery electrodes have been attracting significant attention recently in view of the requirements to further improve energy storage and power densities. Herein, we present a design of a hierarchical Na₇V₄(P₂O₇)₄(PO₄)/C nanorod–graphene composite as sodium- and lithium-storage cathode materials. The hierarchical structure is composed of a 1D rectangular Na₇V₄(P₂O₇)₄(PO₄)/C nanorod, which is coated by in situ residual carbon and wrapped by a reduced graphene-oxide sheet. The open network of graphene and the surface carbon coating of the Na₇V₄(P₂O₇)₄(PO₄)/C nanorod provide bicontinuous electron and ion pathways, providing a three-dimensional conductive network for efficient electron and ion transfer. The flexible electrode built from the hierarchical composite free of binder or conductive additive exhibits improved electron conductivity and higher sodium/lithium ion migration coefficients than the pristine Na₇V₄(P₂O₇)₄(PO₄)/C nanorod. It approaches the initial reversible electrochemical capacities of 91.4 and 91.8 mA h g⁻¹ with high discharge potentials over 3.8 V (vs. Na/Na⁺ or Li/Li⁺) and good cycling properties with capacity retentions of 95% and 83% after 200 cycles at a 1 C rate in sodium and lithium intercalation systems, respectively. Even at 10 C, it still delivers 87.4% (for sodium) and 78.2% (for lithium) of the capacity and high cycling stability. Taking into consideration the compatibilities of both sodium/lithium ions and their superior electrochemical characteristics, the bicontinuous hierarchical composite is considered to be a promising high-rate capability electrode material for advanced energy storage applications.