Synergistic Coupling Effect of Electronic Conductivity and Interphase Compatibility on High-Voltage Na₃V₂(PO₄)₂F₃ Cathodes

Na₃V₂(PO₄)₂F₃ (NVPF) has been considered an up-and-coming cathode material candidate for sodium (Na) ion batteries in light of its high specific capacity and working voltage. However, an erratic cathode/electrolyte interface layer is inevitably formed, accompanied by continuous electrolyte decomposition on the NVPF surface, when the voltage exceeds 4.2 V vs Na⁺/Na. Herein, the interphase features of NVPF are obviously enhanced owing to the ameliorated electronic conductivity obtained by combining it with carbon nanotubes (CNT). The NVPF with 3 wt % CNT (NVPF@3% CNT) reduces the Na⁺ diffusion kinetic energy barrier and electron transport resistance. Furthermore, the conducting network formed by CNT with sturdy structure strength can promptly accommodate the volumetric changes during sequential Na⁺ extraction/insertion and thus effectively improve the long-term cyclic performance of NVPF/hard carbon full cells. The initial discharge capacity approaches 105 mA h g^-1 at 0.5C, and it retains 94% capacity retention after 200 cycles at the temperature of −10 °C. The cathode/electrolyte interphase characterization results further demonstrate that the interphase layer on the NVPF@3% CNT cathode is thinner and more compact compared with pristine samples. This research provides a competitive strategy to facilitate the interfacial compatibility between the NVPF and electrolytes and accelerate the commercialization of high-performance Na-ion batteries.