High-entropy strategy to suppress volumetric strain and enhance diffusion rate of Na₃V₂(PO₄)₂F₃ cathode for durable and high-areal-capacity zinc-ion battery pouch cells

Aqueous zinc-ion batteries are pivotal contributors to the global energy transformation. Cathode materials with NASICON-type structures are promising candidates for zinc-ion batteries but are hindered by their low electrical conductivity, sluggish ionic diffusion, and structural instability. This work introduces a high-entropy, carbon-coated NASICON-type Na₃V₂(PO₄)₂F₃ (HE-NVPF@C) cathode by incorporating five metal elements (Al, Zn, Mn, Cr, and Nb) mainly into the V sites of the VO₄F₂ octahedral structure. Systematic experimental and simulation studies of the Zn²⁺ storage mechanism in high-entropy NASICON-type cathode are presented for the first time. The high-entropy doping strategy contributes to significantly enhanced cycling stability by suppressing Jahn-Teller distortion, reducing lattice change during Zn²⁺ extraction and insertion, and decreasing the Zn²⁺ migration energy barrier. As a result, the HE-NVPF@C cathode demonstrates exceptional cycling stability over 6000 cycles at 20 C with a capacity loss of a mere 0.0031 % per cycle and a high areal capacity retention of 2.17 mAh cm⁻². In addition, the pouch cell provides a long cycling lifespan with 90.8 % capacity retention at 5 C after 200 cycles. This feasible high-entropy approach broadens the perspective for developing practical zinc-ion batteries with a long cycle lifespan and high areal capacity.