随着全球电动汽车产业呈爆发式增长,由此引发的废旧锂离子电池规模化退役问题日益严峻。其中,凭借高安全性与低成本优势的磷酸铁锂电池在退役电池总量中占比已超60%,成为当前回收处理的主要对象。废旧磷酸铁锂电池的资源化回收不仅关乎锂、铁、磷等战略资源的循环再利用,更是推动锂离子电池产业实现“双碳”目标的关键环节。系统地梳理废旧磷酸铁锂电池回收技术体系,介绍了预处理工艺在杂质去除与有价组分富集中的基础作用,从火法冶金工艺的焙烧、湿法冶金工艺的浸出、生物浸出回收工艺的环保及废旧磷酸铁锂修复再生工艺方面,描述了各技术路线的核心工艺特性并分析其技术优势与应用局限。最后对废旧磷酸铁锂电池回收技术的发展趋势进行展望,旨在为行业技术突破提供思路,助力锂离子电池产业构建低碳、高效、可持续的循环发展模式。
With the explosive growth of the global electric vehicle industry,the problem of large-scale retirement of spent lithium-ion batteries has become increasingly severe.Among these spent batteries,lithium iron phosphate (LFP) batteries,which have the advantages of high safety and low cost,account for more than 60% of the total retired batteries and have become the main target of current recycling and disposal efforts.The resource-based recycling of spent LFP batteries is not only crucial for the circular reuse of strategic resources such as lithium,iron,and phosphorus,but also a key link in promoting the lithium-ion battery industry to achieve the “dual carbon” goals.This paper systematically sorted out the recycling technology system for spent LFP batteries,and introduced the fundamental role of pretreatment processes in impurity removal and enrichment of valuable components.From the aspects of roasting in pyrometallurgical processes,leaching in hydrometallurgical processes,environmentally friendly bioleaching recovery processes,and the repair and regeneration process of SLFP,it described the core process characteristics of each technical route and analyzed their technical advantages and application limitations.Finally,it looked forward to the development trends of spent LFP battery recycling technologies,aiming to provide ideas for technological breakthroughs in the industry and help the lithium-ion battery industry build a low-carbon,efficient,and sustainable circular development model.
[1] Murdock B E,Toghill K E,Tapia-Ruiz N.A perspective on the sustainability of cathode materials used in lithium-ion batteries[J].Advanced Energy Materials,2021,11(39):2102028.
[2] Wu X,Ma J,Wang J,et al.Progress,key issues,and future prospects for Li-ion battery recycling[J].Global Challenges,2022,6(12):2200067.
[3] Jiang Y,Zhang G,Zhou K,et al.Sequential separation and recovery of phosphorus and lithium from lithium phosphate slag by selective extraction-precipitation[J].Separation and Purification Technology,2024,333:125907.
[4] Kim S,Bang J,Yoo J,et al.A comprehensive review on the pretreatment process in lithium-ion battery recycling[J].Journal of Cleaner Production,2021,294:126329.
[5] Wang S,Tian Y,Zhang X,et al.A review of processes and technologies for the recycling of spent lithium-ion batteries[C]//IOP Conference Series:Materials Science and Engineering.IOP Publishing,2020.
[6] Deng Z,Huang Z,Shen Y,et al.Ultrasonic scanning to observe wetting and “unwetting” in Li-ion pouch cells[J].Joule,2020,4(9):2017-2029.
[7] Yao Y,Zhu M,Zhao Z,et al.Hydrometallurgical processes for recycling spent lithium-ion batteries:a critical review[J].ACS Sustainable Chemistry & Engineering,2018,6(11):13611-13627.
[8] Jie Y,Yang S,Li Y,et al.Waste organic compounds thermal treatment and valuable cathode materials recovery from spent LiFePO4 batteries by vacuum pyrolysis[J].ACS Sustainable Chemistry&Engineering,2020,8(51):19084-19095.
[9] Yang C,Zhang J,Jing Q,et al.Recovery and regeneration of LiFePO4 from spent lithium-ion batteries via a novel pretreatment process[J].International Journal of Minerals,Metallurgy and Materials,2021,28:1478-1487.
[10] Qiu R,Huang Z,Zheng J,et al.Energy models and the process of fluid-magnetic separation for recovering cobalt micro-particles from vacuum reduction products of spent lithium ion batteries[J].Journal of Cleaner Production,2021,279:123230.
[11] Cornelio A,Zanoletti A,Bontempi E.Recent progress in pyrometallurgy for the recovery of spent lithium-ion batteries:a review of state-of-the-art developments[J].Current Opinion in Green and Sustainable Chemistry,2024,46:100881.
[12] Xu Y,Zhang B,Ge Z,et al.Advances and perspectives towards spent LiFePO4 battery recycling[J].Journal of Cleaner Production,2024,434:140077.
[13] Lai Y,Zhu X,Xu M,et al.Recycling of spent LiFePO4 batte-ries by oxidizing roasting:kinetic analysis and thermal conversion mechanism[J].Journal of Environmental Chemical Engineering,2023,11(5):110799.
[14] Makuza B,Tian Q,Guo X,et al.Pyrometallurgical options for recycling spent lithium-ion batteries:a comprehensive review[J].Journal of Power Sources,2021,491:229622.
[15] Zhang B,Qu X,Chen X,et al.A sodium salt-assisted roasting approach followed by leaching for recovering spent LiFePO4 batteries[J].Journal of Hazardous Materials,2022,424:127586.
[16] 陈昱珏,张梁军,旷焕,等.磷酸铁锂废粉硫酸氢钠焙烧回收工艺研究[J].无机盐工业,2023,55(3):113-117;25.
[17] Jin H,Zhang J,Wang D,et al.Facile and efficient recovery of lithium from spent LiFePO4 batteries via air oxidation-water leaching at room temperature[J].Green Chemistry,2022,24(1):152-162.
[18] Zhang B,Qu X,Chen X,et al.A sodium salt-assisted roasting approach followed by leaching for recovering spent LiFePO4 batteries[J].Journal of Hazardous Materials,2022,424:127586.
[19] Cai G,Fung K Y,Ng K M,et al.Process development for the recycle of spent lithium ion batteries by chemical precipitation[J].Industrial & Engineering Chemistry Research,2014,53(47):18245-18259.
[20] Jing Q,Zhang J,Liu Y,et al.E-pH diagrams for the Li-Fe-P-H2O system from 298 to 473 K:thermodynamic analysis and application to the wet chemical processes of the LiFePO4 cathode material[J].The Journal of Physical Chemistry C,2019,123(23):14207-14215.
[21] Chen Y,Wang L,He H,et al.Preparation of FePO4 and LiH2PO4 from cathode mixture materials of scrapped LiFePO4 batteries[J].Journal of Materials Science:Materials in Electronics,2020,31:4083-4091.
[22] Yang C,Zhang J,Jing Q,et al.Recovery and regeneration of LiFePO4 from spent lithium-ion batteries via a novel pretreatment process[J].International Journal of Minerals,Metallurgy and Materials,2021,28:1478-1487.
[23] Zhang Y,Meng Q,Dong P,et al.Use of grape seed as reductant for leaching of cobalt from spent lithium-ion batteries[J].Journal of Industrial and Engineering Chemistry,2018,66:86-93.
[24] Li L,Bian Y,Zhang X,et al.A green and effective room-temperature recycling process of LiFePO4 cathode materials for lithium-ion batteries[J].Waste Management,2019,85:437-444.
[25] Li X,Li G D,Chen Y,et al.Resource sustainability application of lithium iron phosphate batteries via citric acid coupled recycling and regeneration[J].Rare Metals,2025,44:1-15.
[26] Gao T,Dai T,Fan N,et al.Comprehensive review and comparison on pretreatment of spent lithium-ion battery[J].Journal of Environmental Management,2024,363:121314.
[27] Cong J,Luo S,Sun Q,et al.Study on deep synergistic leaching mechanism of spent lithium iron phosphate under the H2SO4-H2O2 system and precise chemical precipitation recovery strategy of lithium carbonate[J].Separation and Purification Technology,2025,363:132326.
[28] Yan T,Zhong S,Zhou M,et al.High-efficiency method for recycling lithium from spent LiFePO4 cathode[J].Nanotechno-logy Reviews,2020,9(1):1586-1593.
[29] Fan E,Li L,Zhang X,et al.Selective recovery of Li and Fe from spent lithium-ion batteries by an environmentally friendly mechanochemical approach[J].ACS Sustainable Chemistry & Engineering,2018,6(8):11029-11035.
[30] Zhang J,Hu J,Liu Y,et al.Sustainable and facile method for the selective recovery of lithium from cathode scrap of spent LiFePO4 batteries[J].ACS Sustainable Chemistry & Engineering,2019,7(6):5626-5631.
[31] Li Z,He L,Zhu Y,et al.A green and cost-effective method for production of LiOH from spent LiFePO4[J].ACS Sustainable Chemistry & Engineering,2020,8(42):15915-15926.
[32] Zhang B,He L,Wang J,et al.Self-powered recycling of spent lithium iron phosphate batteries via triboelectric nanogenerator[J].Energy & Environmental Science,2023,16(9):3873-3884.
[33] Biswal B K,Balasubramanian R.Recovery of valuable metals from spent lithium-ion batteries using microbial agents for bioleaching:a review[J].Frontiers in Microbiology,2023,14:1197081.
[34] Xin Y,Guo X,Chen S,et al.Bioleaching of valuable metals Li,Co,Ni and Mn from spent electric vehicle Li-ion batteries for the purpose of recovery[J].Journal of Cleaner Production,2016,116:249-258.
[35] Mahandra H,Hein G,Faraji F,et al.A novel neutrophilic bacteria based process for selective LiFePO4 cathode recycling[J].Resources,Conservation and Recycling,2023,195:107015.
[36] Gu J,Nie Y,Li Z,et al.Efficient bioleaching of Li from waste lithium-iron phosphate batteries by acidophilic bacterial consortium:enrichment condition,Li recovery,and brief carbon footprint analysis[J].Chemical Engineering Journal,2025,509:161450.
[37] 聂思睿,陶志军,胡仁宗,等.废旧磷酸铁锂正极材料的绿色再生技术发展[J].材料热处理学报,2025,46(3):14-28.
[38] Jing Q,Zhang J,Liu Y,et al.Direct regeneration of spent LiFePO4 cathode material by a green and efficient one-step hydrothermal method[J].ACS Sustainable Chemistry & Engineering,2020,8(48):17622-17628.
[39] Fan M,Meng Q,Chang X,et al.In situ electrochemical rege-neration of degraded LiFePO4 electrode with functionalized prelithiation separator[J].Advanced Energy Materials,2022,12(18):2103630.
[40] Xu P,Dai Q,Gao H,et al.Efficient direct recycling of lithium-ion battery cathodes by targeted healing[J].Joule,2020,4(12):2609-2626.
[41] Yang D,Fang Z,Ji Y,et al.A room-temperature lithium-restocking strategy for the direct reuse of degraded LiFePO4 electrodes[J].Angewandte Chemie International Edition,2024,63(49):202409929.
[42] Zheng R,Zhao L,Wang W,et al.Optimized Li and Fe recove-ry from spent lithium-ion batteries via a solution-precipitation method[J].RSC Advances,2016,6(49):43613-43625.
[43] Wang Z,Wu D,Wang X,et al.Green phosphate route of regeneration of LiFePO4 composite materials from spent lithium-ion batteries[J].Industrial & Engineering Chemistry Research,2023,62(2):1181-1194.
[44] Li Haoyu,Ye Hua,Sun Mingcang,et al.Process for recycle of spent lithium iron phosphate battery via a selective leaching-precipitation method[J].Journal of Central South University,2020,27(11):3239-3248.
基金资助
河南省自然科学基金资助项目(242300420015);河南省科技攻关项目(242102321162,242102311241);河南工学院博士科研启动经费(KY1704);河南工学院教改项目(CLXY-2024001)
PDF
(1118KB)
