The low-temperature molten Na₃AlF₆–K₃AlF₆–AlF₃ salts was evaluated in order to perform the electrochemical reduction of vanadium sesquioxide. By using cyclic voltammetry and constant potential electrolysis, the cathodic reduction reactions were determined and the promoting effect of oxygen concentration in the electrolyte on the process was proved. A rapid electro-reduction of vanadium sesquioxide was achieved under a constant voltage of 4 V at 850 °C, the vanadium metal with an oxygen content of 0.3 mass% was obtained. The corresponding current efficiency was around 60%. The reaction kinetic pathway was systematically investigated by analyzing the phase transformations and microstructure evolutions of the products prepared at different electrolysis durations. The reduction mechanism was concluded to start by the direct electro-reduction of V₂O₃ accompanied with the implantation of aluminium ions to form AlV₂O₄ intermediate, which was then reduced to vanadium directly through aluminothermic reduction, with aluminium reductant being generated from the electrodeposition reaction. Additionally, by using the low-temperature fluoride salts as the electrolyte, the formed AlV₂O₄ showed a porous structure composed of small and uniform intermediate particles, which is obviously different from the observations in traditional molten Na₃AlF₆ salt. This structure could provide more active sites for the reduction reaction and shorten the diffusion path for O²⁻ ion in the solid phase. The possible microstructure transformation mechanisms were also discussed.

低温熔融Na ₃ AlF ₆ –K ₃ AlF ₆ –AlF ₃为了进行三氧化二钒的电化学还原，评估了其盐。通过循环伏安法和恒电位电解，确定了阴极还原反应，并证明了电解液中氧浓度对该工艺的促进作用。在850℃下于4 V的恒定电压下，可快速电解还原倍半氧化钒。制得的氧含量为0.3质量％的钒金属。相应的电流效率约为60％。通过分析在不同电解时间下制备的产物的相变和微观结构演变，系统地研究了反应动力学路径。还原机理的结论是通过直接电还原V ₂ O开始的₃与铝离子的注入形成AlV ₂ O ₄中间体，然后通过铝热还原直接还原成钒，而电沉积反应生成铝还原剂。另外，通过使用低温氟化物盐作为电解质，所形成的AlV ₂ O ₄显示出由小的且均匀的中间颗粒组成的多孔结构，这与在传统的熔融Na ₃ AlF ₆盐中的观察结果明显不同。这种结构可以为还原反应提供更多的活性位点，并缩短O ^2-的扩散路径。固相中的离子 还讨论了可能的微观结构转变机制。