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    废旧磷酸铁锂电池湿法回收工艺研究进展

    Progress in Hydrometallurgical Recycling Processes for Spent Lithium Iron Phosphate Batteries

    • 摘要: 湿法冶金回收废旧磷酸铁锂(LFP)电池因其金属回收率高和实现材料闭环再生的潜力,近年来备受关注。本文系统梳理了湿法回收工艺流程的研究进展,涵盖预处理、浸出、分离纯化与再生等关键环节。在预处理方面,重点介绍了工业规模下和实验室级别的预处理技术。讨论了无机酸(如硫酸)与有机酸(如柠檬酸、草酸)浸出体系,以及生物浸出和低共熔溶剂(DES)浸出等新兴绿色浸出方法,深入分析了其浸出机制与选择性回收潜力。综述了化学沉淀、溶剂萃取等分离纯化技术,以及制备碳酸锂、磷酸铁的最新研究进展。重点梳理了LFP的再生合成方法(包括固相法、水热法)及其向高价值材料(如磷酸锰铁锂LMFP)升级回收的策略。此外,从技术效能、环境影响和经济可行性等角度对各环节进行了综合比较,指出了废旧LFP电池湿法回收技术在试剂消耗、废物管理和工艺整合等方面的挑战和未来发展方向。

       

      Abstract: The rapid development of the electric vehicle and electrochemical energy storage sectors has created an urgent need for sustainable resource management in the lithium-ion battery sector, thereby drawing widespread attention to the recycling of spent lithium iron phosphate (LFP) batteries. Hydrometallurgy has become the mainstream recovery method due to its high metal recovery rate, low energy consumption, and high product purity. However, traditional processes are often associated with multi-step operations, high reagent consumption, and complex wastewater management, posing economic and environmental challenges that hinder large-scale industrial application. Therefore, a systematic review is necessary to integrate recent achievements and critically evaluate the recovery pathways of LFP batteries. This review comprehensively investigates the hydrometallurgical recovery processes of spent LFP batteries. First, pretreatment techniques are compared and analyzed, including discharging, mechanical crushing, and thermal or chemical treatment methods aimed at separating active materials from current collectors. A detailed analysis of various leaching systems follows, including inorganic acids, organic acids, bioleaching, and deep eutectic solvents (DESs), with a comparison of their mechanisms and efficiencies. Subsequently, methods for impurity removal and product purification are evaluated. Finally, material regeneration pathways are discussed, including the solid-state and hydrothermal synthesis of recovered iron phosphate and its upcycling into high-voltage lithium manganese iron phosphate (LMFP). This analysis highlights the trade-offs between different approaches. Specifically, inorganic acid leaching, especially using sulfuric acid, offers high efficiency but raises environmental concerns. Organic acid leaching and bioleaching are more environmentally friendly and exhibit higher lithium selectivity, though they often face challenges such as high reagent costs, slow reaction rates, or sensitivity to pulp density. DESs offer an innovative and tunable platform for selective metal dissolution, though issues of high viscosity and scalability remain. For separation, synergistic solvent extraction systems demonstrate impressive Fe/Li separation factors, while precise pH control is essential to minimize Fe loss during Al removal. The regeneration of cathode materials from purified solutions has proven feasible, with regenerated LFP exhibiting excellent electrochemical performance. Notably, upcycling LFP into materials with higher voltage and energy density enhances the economic viability of the recycling process. While hydrometallurgy effectively recovers valuable metals from spent LFP batteries, its industrialization is constrained by economic and environmental barriers related to process complexity, chemical consumption, and waste management. The future of sustainable LFP recycling lies in integrated innovations: developing short-process, closed-loop flowsheets; designing intelligent, adaptive leaching systems with minimal chemical input; and prioritizing upcycling strategies that directly convert waste into high-performance cathode materials. This transition from simple recovery to high-value regeneration is vital for establishing an economically viable and environmentally friendly circular economy for LFP batteries.

       

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