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This invention belongs to the field of lithium-ion battery technology, specifically relating to a Ni-doped molybdenum carbide / lithium oxalate composite lithium replenisher. The invention first obtains a Ni molecular catalyst through a liquid-phase reaction of triethanolamine and nickel chloride in ethanol, followed by calcination with Mo₂C to form a composite Ni-doped molybdenum carbide catalyst. Then, using an anti-solvent crystallization method, the lithium replenisher solution is dropwise into an organic solvent containing the catalyst, stirred, and then vacuum dried. The lithium replenisher particles adhere to the catalyst surface and / or pores, forming the composite lithium replenisher. This composite lithium replenisher, by combining lithium oxalate with the Ni-doped molybdenum carbide catalyst, utilizes the highly active catalytic sites, excellent electronic conductivity, and synergistic catalytic effect of Ni-doped molybdenum carbide to reduce the decomposition voltage of lithium oxalate, improve its conductivity and decomposition rate, thereby significantly improving the battery's initial efficiency, capacity, and cycle performance. Furthermore, the preparation process is simple, highly compatible, and has good commercial application prospects.