| Citation: | ZHANG Junyu, SONG Chao, HOU Kai, LYU Chao. Research Status of Selective Recovery of Lithium from Cathode Materials of Spent Lithium-ion Batteries[J]. Multipurpose Utilization of Mineral Resources, 2025, 46(5): 19-30. doi: 10.12476/kczhly.202403190108 |
In recent years, with the rise and rapid development of new energy vehicles (EV), it is expected that a large number of lithium batteries will be scraped and disposed after 2025. Recycling valuable metals from spent lithium ion batteries can effectively reduce the environmental pollution of spent lithium batteries and realize the recycling of its resources, reducing the supply and demand conflict caused by the surge in the use of energy metals such as Li, Co and Ni. Selective lithium extraction from spent lithium-ion battery cathode materials can achieve short-flow recovery of lithium resources, and is conducive to the subsequent separation and extraction of cobalt and nickel high-value energy metals. Therefore, in recent years, the research on the selective extraction of lithium from spent lithium-ion batteries has attracted a lot of attentions. In this paper, we systematically sorted out the current research on selective lithium extraction by various recycling systems, including pyro-metallurgical processes such as high temperature smelting, thermal reduction and salting and roasting, and hydrometallurgical technologies of inorganic acid leaching, organic acid leaching, oxidative leaching et al. The advantages and disadvantages of different processes are also discussed in terms of environmental protection, leaching efficiency, energy consumption, and process feasibility. Finally, the development of efficient recovery of lithium from used lithium-ion batteries is prospected.
| [1] | SCHMUCH R, WAGENR R, HORPEL G, et al. Performance and Cost of Materials for Lithium-based Rechargeable Automotive Batteries[J]. Nature Energy, 2018, 3(4):267-78. doi: 10.1038/s41560-018-0107-2 |
| [2] | LI Y, ZHANG J W, CHEN Q G, et al. Emerging of heterostructure materials in energy storage: A Review[J]. Advanced Materials, 2021, 33(27):2100855. doi: 10.1002/adma.202100855 |
| [3] | NATARAJAN S, ARAVINDAN V. Burgeoning prospects of spent lithium-ion batteries in multifarious applications[J]. Advanced Energy Materials, 2018, 8(33):1802303. doi: 10.1002/aenm.201802303 |
| [4] | HARPER G,SOMMERVILLE R, KENDRICK E,et al. Recycling lithium-ion batteries from electric vehicles[J]. Nature,, 2019, 575(7781):75. doi: 10.1038/s41586-019-1682-5 |
| [5] | CHEN M Y,ZHENG Z F,WANG Q,et al. Closed loop recycling of electric vehicle batteries to enable ultra-high quality cathode powder[J]. Scientific Reports, 2019, 9:1654. doi: 10.1038/s41598-018-38238-3 |
| [6] | 刘光富,林锦灿,田婷婷. 新能源汽车动力电池报废量估算和资源潜力分析[J]. 中国资源综合利用, 2020, 38(1):96-99.LIU G F, LIN J C, TIAN T T. Quantity prediction and resources potential analysis of spent lithium-ion battery of new energy automobile[J]. China Resources Comprehensive Utilization, 2020, 38(1):96-99. LIU G F, LIN J C, TIAN T T. Quantity prediction and resources potential analysis of spent lithium-ion battery of new energy automobile[J]. China Resources Comprehensive Utilization, 2020, 38(1):96-99. |
| [7] | HUANG X. Research on short process recycling of ternary cathode materials for waste lithium-ion power battery[J]. Beijing General Research Institute for Nonferrous Metals, 2019. |
| [8] | 李波,张莉莉,洪秋阳,等. 废弃锂电池电极材料中有价金属的赋存状态[J]. 矿产综合利用, 2022(1):200-204.LI B, ZHANG L L, HONG Q Y, et al. Study on the occurrence state of valuable metals in waste lithium battery electrode material[J]. Multipurpose Utilization of Mineral Resources, 2022(1):200-204. doi: 10.3969/j.issn.1000-6532.2022.01.029 LI B, ZHANG L L, HONG Q Y, et al. Study on the occurrence state of valuable metals in waste lithium battery electrode material[J]. Multipurpose Utilization of Mineral Resources, 2022(1):200-204. doi: 10.3969/j.issn.1000-6532.2022.01.029 |
| [9] | SWAIN B. Recovery and recycling of lithium: A Review[J]. Separation and Purification Technology, 2017, 172:388. doi: 10.1016/j.seppur.2016.08.031 |
| [10] | LI L, LIANG Y, CHEN L, et al. Research progress on recovery of cobalt and nickel from waste batteries[J]. China Nonferrous Metallurgy, 2008, 3(4):57-60. |
| [11] | YUE L P, LOU P, XU G H, et al. Regeneration of degraded LiNi0.5Co0.2Mn0.3O2 from spent lithium-ion batteries[J]. Ionics, 2020, 26(6):2757-2761. doi: 10.1007/s11581-020-03479-8 |
| [12] | JOEY C Y, JUNG P C S, ZHANG J J. A review of recycling spent lithium-ion battery cathode materials using hydro-metallurgical treatments[J]. Journal of Energy Storage, 2021, 35:102217. doi: 10.1016/j.est.2020.102217 |
| [13] | DUNN J B, GAINES L, KELLY J C, et al. The significance of Li-ion batteries in electric vehicle life-cycle energy and emissions and recycling's role in its reduction[J]. Energy & Environmental Science, 2015, 8(1):158-168. |
| [14] | LV W, WANG Z, CAO H, et al. A critical review and analysis on the recyeling of spent lithium-ion batteries[J]. ACS Sustainable Chemistry & Engineering, 2017, 6(2):1504-1521. |
| [15] | CHEN M, MA X, CHEN B, et al. Recycling end-of-life electric vehicle lithium-ion batteries[J]. Joule, 2019, 3(11):2622-2646. doi: 10.1016/j.joule.2019.09.014 |
| [16] | LEE C K, RHEE K I. Preparation of LiCoO2 from spent lithium-ion batteries[J]. Journal of Power Sources, 2002, 109(1):17. doi: 10.1016/S0378-7753(02)00037-X |
| [17] | HU Y, DOEFF M M, KOSTECKI R, et al. Electro-chemical performance of Sol-gel synthesized LiFePO4 in lithium batteries[J]. Journal of Power Sources, 2004, 151(8):A1279. |
| [18] | 徐正震, 梁精龙, 李慧,等. 废旧锂电池正极材料中有价金属的回收工艺研究进展[J]. 矿产综合利用, 2022, 43(4):119-122,142.XU Z Z, LIANG J L, LI H,et al. Research progress of recovery process of valuable metals in cathode materials of waste lithium batteries[J]. Multipurpose Utilization of Mineral Resources, 2022, 43(4):119-122,142. doi: 10.3969/j.issn.1000-6532.2022.04.021 XU Z Z, LIANG J L, LI H,et al. Research progress of recovery process of valuable metals in cathode materials of waste lithium batteries[J]. Multipurpose Utilization of Mineral Resources, 2022, 43(4):119-122,142. doi: 10.3969/j.issn.1000-6532.2022.04.021 |
| [19] | DING L. Development review of cathode materials for lithium-ion power battery[J]. Chinese Journal of Power Sources, 2015, 39(8):1780-2,800. |
| [20] | XIA S B, ZHANG Y J, DONG P, et al. Developments and research of cathode materials for lithium-ion power batteries[J]. Chinese Journal of Power Sources, 2011, 35(12):1592-5. |
| [21] | 郑洲. 我国锂离子电池及其正极材料的产业化进展[J]. 新材料产业, 2020(6):49-52.ZHENG Z. Progress of industrialization of lithium ion battery and its cathode materials in China[J]. Advanced Materials Industry, 2020(6):49-52. ZHENG Z. Progress of industrialization of lithium ion battery and its cathode materials in China[J]. Advanced Materials Industry, 2020(6):49-52. |
| [22] | FERGUS J W. Recent developments in cathode materials for lithium-ion batteries[J]. Journal of Power Source, 2010, 195(4):1051. doi: 10.1016/j.jpowsour.2009.09.002 |
| [23] | FEY T K, CHANG C S, Kumar T P. Synthesis and surface treatment of LiNi1/3Co1- -/3Mn1/3O2 cathode materials for lion batteries[J]. Journal of Solid-State Electroche -mistry, 2010, 14(1):17. doi: 10.1007/s10008-008-0772-3 |
| [24] | QU G R, LI B, WEI Y G. A novel approach for the recovery and cyclic utilization of valuable metals by co-smelting spent lithium-ion batteries with copper slag[J]. Chemical Engineering Journal, 2023, 451:138897. doi: 10.1016/j.cej.2022.138897 |
| [25] | Hendrickson T P, Kavvada O, Shah N, et al. Life-cycle implications and supply chain logistics of electric vehicle battery recycling in California[J]. Research Letters, 2015, 10(1):014011. doi: 10.1088/1748-9326/10/1/014011 |
| [26] | 朱国辉, 还红先, 于大伟, 等. 废旧锂离子电池选择性提锂[J]. 化学进展, 2023, 35(2):287-301.ZHU G H, HUAN H X, YU D W, et al. Selective recovery of lithium from spent lithium-ion batteries[J]. Progress in Chemistry, 2023, 35(2):287-301. ZHU G H, HUAN H X, YU D W, et al. Selective recovery of lithium from spent lithium-ion batteries[J]. Progress in Chemistry, 2023, 35(2):287-301. |
| [27] | XING R G, BIN L C, HONG L Z, et al. Lithium and manganeseextraction from manganese-rich slag originated from pyrometallurgy of spent lithium-ion battery[J]. Trans Nonferrous Metals Soc China, 2022, 32:2746-2756. doi: 10.1016/S1003-6326(22)65981-8 |
| [28] | HU X, Mousa E, TIAN Y, et al. Recovery of Co, Ni, Mn, and Li from Li-ion batteries by smelting reduction - Part I: A laboratory-scale study[J]. J Power Sources 2021, 483. |
| [29] | 王玥, 郑晓洪, 陶天一, 等. 废锂离子电池正极材料中锂元素选择性回收的研究进展[J]. 化工进展, 2022, 41(8):4530-4543.WANG Y, ZHENG X H, TAO T Y,et al. Review on selective recovery of lithium from cathode materials in spent lithium-ion batteries[J]. Chemical Industry and Engineering Progress, 2022, 41(8):4530-4543. WANG Y, ZHENG X H, TAO T Y,et al. Review on selective recovery of lithium from cathode materials in spent lithium-ion batteries[J]. Chemical Industry and Engineering Progress, 2022, 41(8):4530-4543. |
| [30] | JAN O. B, SEAN P. C, Wolfgang G. Z, et al. A rapid and facile approach for the recycling of high performance LiNi1[J]. ChemSusChem, 2021, 14:441-448 doi: 10.1002/cssc.202001915 |
| [31] | QUAN Y, JING Z, QING X S, et al. Thermodynamic and experimental analysis of lithium selectively recovery from spent lithium-ion batteries by in-situ carbothermal reduction[J]. Journal of Environmental Chemical Engineering, 2023, 11(5):111029. doi: 10.1016/j.jece.2023.111029 |
| [32] | 王斌,邓小川,史一飞,等. 碳酸锂在水和NaCl-KCl 溶液体系中溶解度的在线测定[J]. 无机盐工业, 2021, 53(7):73-79.WANG B, DENG X C, SHI Y F,et al. On-line determination of the solubility of lithium carbonate in water and NaCl-KCl solution systems[J]. Inorganic Chemicals Industry, 2021, 53(7):73-79. WANG B, DENG X C, SHI Y F,et al. On-line determination of the solubility of lithium carbonate in water and NaCl-KCl solution systems[J]. Inorganic Chemicals Industry, 2021, 53(7):73-79. |
| [33] | HU J, ZHANG J, LI H, et al. A promising approach for the recovery of high value-added metals from spent lithium-ion batteries[J]. Journal of Power Sources, 2017, 351:192. doi: 10.1016/j.jpowsour.2017.03.093 |
| [34] | 廖财斌,任国兴,肖松文. 三元正极废粉还原焙烧——水浸提锂过程氟磷杂质的影响[J]. 有色金属(冶炼部分), 2020(12):42-47.LIAO C B,REN G X,XIAO S W. Effect of fluorine and phosphorus impurity on recovery of lithium from spent ncm cathode power by reduction roasting-water leaching process[J]. Nonferrous Metals(Extractive Metallurgy), 2020(12):42-47. LIAO C B,REN G X,XIAO S W. Effect of fluorine and phosphorus impurity on recovery of lithium from spent ncm cathode power by reduction roasting-water leaching process[J]. Nonferrous Metals(Extractive Metallurgy), 2020(12):42-47. |
| [35] | GHAMOUSS F, MALLOUKI M, BERTOLOTTI B,et al. Long lifetime in concentrated lioh aqueous solution of air electrode protected with interpenetrating polymer network membrane[J]. Journal of Power Sources, 2012, 197:267. doi: 10.1016/j.jpowsour.2011.09.052 |
| [36] | JIN X Y, ZHONG X Q, GAO H W,et al. Recycling Valuable metals from spent lithium-ion battery cathode materials based on microwave-assisted hydrogen reduction followed by grind-leaching and magnetic separation[J]. Journal of Cleaner Production, 2023, 428:139488. doi: 10.1016/j.jclepro.2023.139488 |
| [37] | Haruka P, Rajashekhar M, Peilin Y, et al. Reductive thermal treatment of LiCoO2 from end-of-life lithium-ion batteries with hydrogen[J]. ACS Sustainable Chem. Eng., 2021, 9:7447-7453. doi: 10.1021/acssuschemeng.0c08695 |
| [38] | HUANG Z, LIU F, MAKUZA B,et al. Metal reclamation fromspent lithium-ion battery cathode materials: directional conversion of metals based on hydrogen reduction[J]. ACS sustainable Chemistry & Engineering, 2022, 10(2):756. |
| [39] | PINEGAR H, MARTHI R, YANG P, et al. Reductive Thermal treatment of LiCoO2 from end-of-life lithium-ion batteries with hydrogen[J]. ACS Sustainable Chemistry & Engineering, 2021, 9(22):7447. |
| [40] | 郭苗苗, 席晓丽, 张云河, 等. 报废动力电池镍钴锰酸锂三元正极材料高温氢还原-湿法冶金联用回收有价金属[J]. 中国有色金属学报, 2020, 30(6):1415-1426.GUO M M, XI X L, ZHANG Y H,et al. Recovering valuable metals from waste ternary cathode materials of power battery by combined high temperature hydrogen reduction and hydrometallurgy[J]. The Chinese Journal of Nonferrous Metals, 2020, 30(6):1415-1426. doi: 10.11817/j.ysxb.1004.0609.2020-35823 GUO M M, XI X L, ZHANG Y H,et al. Recovering valuable metals from waste ternary cathode materials of power battery by combined high temperature hydrogen reduction and hydrometallurgy[J]. The Chinese Journal of Nonferrous Metals, 2020, 30(6):1415-1426. doi: 10.11817/j.ysxb.1004.0609.2020-35823 |
| [41] | WANG W, ZHANG T, LIU X,et al. A simplified process for recovery of Li and Co from spent LiCoO2 cathode using al foil as the in situ reductant[J]. ACS Sustainable Chemistry & Engineering, 2019, 7(14):12222. |
| [42] | LIN J, LI L, FAN E, et al. Conversion mechanisms of selective extraction of lithium from spent lithium-ion batteries by sulfation roasting[J]. ACS Applied Materials & Interfaces, 2020, 12(16):18482. |
| [43] | REN G X, LIAO C B, LIU Z H,et al. Environmentally benign process for selective recovery of valuable metals from spent lithium-ion batteries by using conventional sulfation roasting[J]. Green Chemistry, 2019, 21(21):5904. doi: 10.1039/C9GC01350D |
| [44] | BARRIOS O C, GONZÁLEZ Y C, BARBOSA L I,et al. Chlorination roasting of the cathode material contained in spent lithium-ion batteries to recover lithium, manganese, nickel and cobalt[J]. Minerals Engineering, 2022, 176:107321. doi: 10.1016/j.mineng.2021.107321 |
| [45] | ZHU X Y, CHEN C, GUO Q, et al. Improved recovery of cathode materials and enhanced lithium selective extraction from spent LiNi0.5Co0.2Mn0.3O2 batteries via CaCl2-assisted microwave roasting[J]. Journal of Environmental Chemical Engineering, 2024, 12(2):112037. doi: 10.1016/j.jece.2024.112037 |
| [46] | XIAO J, NIU B, SONG Q,et al. Novel targetedly extracting lithium: An environmental-friendly controlled chlorinating technology and mechanism of spent lithium ion batteries recovery[J]. Journal of Hazardous Materials, 2021, 404:123947. doi: 10.1016/j.jhazmat.2020.123947 |
| [47] | PENG C, LIU F, WANG Z,et al. Selective extraction of lithium (Li) and preparation of battery grade lithium carbonate (Li2CO3) from spent Li-ion batteries in nitrate system[J]. Journal of Power Sources, 2019, 415:179. doi: 10.1016/j.jpowsour.2019.01.072 |
| [48] | WANG R C, LIN Y C, WU S H. A Novel Recovery process of metal values from the cathode active materials of the lithium-ion secondary batteries[J]. Hydrometallurgy, 2009, 99(3):194. |
| [49] | Barik S P, Prabaharan G, Kumar L. Leaching and separation of Co and Mn from electrode materials of spent lithium-ion batteries using hydrochloric acid: Laboratory and pilot scale study[J]. Journal of Cleaner Production, 2017, 147:37-43. doi: 10.1016/j.jclepro.2017.01.095 |
| [50] | HUANG Y F, HAN G H, LIU J T, et al. A stepwise recovery of metals from hybrid cathodes of spent Li-ion batteries with leaching-flotation-precipitation process[J]. Journal of Power Sources, 2016, 325:555-564. doi: 10.1016/j.jpowsour.2016.06.072 |
| [51] | SONG S L, LIU R Q, SUN M M,et al. Hydrometallurgical recovery of lithium carbonate and iron phosphate from blended cathode materials of spent lithium-ion battery[J]. Rare Metals, 2024, 43:1275. doi: 10.1007/s12598-023-02493-9 |
| [52] | LIU T C, CHEN J, LI H L, et al. An integrated process for the separation and recovery of valuable metals from the spent LiNi0.5Co0.2Mn0.3O2 cathode materials[J]. Separation and Purification Technology, 2020, 245:116869. doi: 10.1016/j.seppur.2020.116869 |
| [53] | CHEN X,MAH, LUO C,et al. Recovery of valuable metals from waste cathode materials of spent lithium-ion batteries using mild phosphoric acid[J]. Hazardous Materials, 2017, 326:77. doi: 10.1016/j.jhazmat.2016.12.021 |
| [54] | HARSHIT M, AHMAD G. A sustainable process for selective eecovery of lithium as lithium phosphate from spent LiFePO4 batteries[J]. Resources, Conservation & Recycling, 2021, 175:105883. |
| [55] | HOU J H, MA X T, FU J Z, et al. A green closed-loop process for selective recycling of lithium from spent lithium-ion batteries[J]. Green Chem, 2022, 24:7049-7060. doi: 10.1039/D2GC01811J |
| [56] | Ankit V, Grant H. J, David R. C,et al. Separation of lithium and cobalt from LiCoO2: A unique critical metals recovery process utilizing oxalate chemistry[J]. ACS Sustainable Chemistry & Engineering, 2020, 8:6100-6108. |
| [57] | HUANG Z X, LIU X, ZHENG Y, et al. Boosting efficient and low-energy solid phase regeneration for single crystal LiNi0.6Co0.2Mn0.2O2 via highly selective leaching and its industrial application[J]. Chemical Engineering Journal, 2023, 451(4):139039. |
| [58] | YANG Y,MENG X, CAO H,et al. Selective recovery of lithium from spent lithium-iron phosphate batteries: a sustainable process[J]. Green Chemistry, 2018, 20(13):3121. doi: 10.1039/C7GC03376A |
| [59] | CHEN X P, FAN B L, XU L P, et al. An atom-economic process for the recovery of high value-added metals from spent lithium-ion batteries[J]. Journal of Cleaner Production, 2015, 10:132. |
| [60] | 卜祥宁, 任玺冰, 童正, 等. 功率超声对废旧锂离子电池资源化回收利用过程的影响研究进展[J]. 化工进展, 2024, 43(1):514-528.BU X N, REN X B, TONG Z,et al. Effect of power ultrasound on resource recycling and utilization of spent lithium-ion batteries: A review[J]. Chemical Industry and Engineering Progress, 2024, 43(1):514-528. BU X N, REN X B, TONG Z,et al. Effect of power ultrasound on resource recycling and utilization of spent lithium-ion batteries: A review[J]. Chemical Industry and Engineering Progress, 2024, 43(1):514-528. |
| [61] | CHU H, LIE J, LIU J C. Rapid leaching of valuable metals from spent lithium-ion batteries with microwave irradiation using organic and inorganic acid[J]. Journal of Sustainable Metallurgy, 2021, 7(2):630-41. doi: 10.1007/s40831-021-00362-2 |
| [62] | 贾智慧. 废弃电池的生物质浸出及金属回收研究[D].南充:西华师范大学,2018.JIA Z H. Study on the biomass leaching and metal recycling of waste battery [D]. Nanchong: China West Normal University, 2018. JIA Z H. Study on the biomass leaching and metal recycling of waste battery [D]. Nanchong: China West Normal University, 2018. |
| [63] | AKITOSHI H, NAOKI A, SYOUHEL N,et al. Selective recovery of lithium from cathode materials of spent lithium ion battery [J]. The Minerals, Metals & Materials Society, 2016, 10(68). |
Schematic diagram of selective extraction of lithium from waste lithium-ion batteries
Basic flowsheet of pyrometallurgy
Solubility-temperature of Li2CO3 in water
Flow chart of selective lithium extraction by carbothermal reduction
Flow chart of extraction and recovery of lithium from LFP/LMO mixed materials at HCl-H2O2 leaching system
Flow chart of extraction of lithium from waste LFP material and preparation of LiFePO4 by acetic acid-H2O2 leaching system