Insights into the ternary substitution Na2.96+xK0.04 V2-xNix(PO4)2.98F0.06 with superior rate capability and near-zero strain property

Abstract

Na3V2(PO4)3 (NVP) is considered the most favorable cathode for sodium-ion batteries due to its solid NASICON skeleton. Nevertheless, poor intrinsic conductivity is insufficient for its further commercialization. In this paper, we present a promising K/Ni/F co-doped and carbon nanotubes (CNTs) encapsulated Na2.96+xK0.04 V2-xNix(PO4)2.98F0.06 (KNF@CNTsx) cathode materials. The synthesis of KNF@CNTsx is achieved using a facile sol-gel method. The replacement of Na+ with K+ broadens the migratory pathway and supports the crystal skeleton, while F− substitution reduces the average grain dimension, thereby increasing the diffusion rate of Na+. Furthermore, the reduction of resistance by Ni2+ doping enables optimization of the transport of electrical charge, while also facilitating the optimization of chemically-defined properties. Concurrently, the optimal quantity of carbon capping and wrapping of CNTs facilitate the formation of efficacious conductive network, which diminishes the size of grains and shortens the pathway for the diffusion of Na+. This network could also serve as a buffer against crystal deformation. In conclusion, the modified KNF@CNTsx samples exhibit notable enhancements in their conductivity, ion diffusion capacity, and structural stability. Among them, the KNF@CNTs0.04 sample exhibits a capacity for reversibility of 93.3 mAh g−1 at 50C, with a remaining capacity of 68.5 mAh g−1 after 4000 successive long charge-discharge cycles. Ex-situ electrochemical XRD demonstrates the V3+/V4+ redox reaction occurs accompanied by the phase transfer reaction, during which Na+ prefers to diffuse along c-axial in the crustal structure. Moreover, volume alteration of this KNF@CNTs0.04 cellular entity is miniscule and reversible during the charge-discharge process, further confirming the stabilized construction and near-zero strain property. The after-cycled XRD/SEM/XPS certify the improved chemical and structural stability of KNF@CNTs0.04, indicating the constructive effects of K/Ni/F ternary substitution.