废旧磷酸铁锂电池正极材料的回收研究现状
|
摘要
锂离子电池(LIBs)具有放电电压高、循环寿命长和无记忆效应等优点,广泛地应用于便携式电子设备、电动汽车、电化学储能等方面。电动汽车的快速发展带动了动力电池的爆发式增长,而磷酸铁锂电池(LFPBs)以其良好的安全性、成本低、无毒等优点,占据大量的市场份额。随之,废旧磷酸铁锂电池报废量也逐年增加,若不及时进行处理则会污染环境,浪费大量的金属资源。本文概述了废旧磷酸铁锂电池正极材料的回收方法,主要包括固相法、酸浸-沉淀法等,对比了诸方法的优缺点;并汇总了预处理、酸浸过程、再生磷酸铁锂(LFP)过程的条件及再生磷酸铁锂电化学性能;提出了废旧磷酸铁锂电池回收中存在的问题,且展望了废旧磷酸铁锂电池回收朝着自动化、绿色环保、低成本的方向发展。
Lithium-ion batteries( LIBs) are widely applied in portable electronic equipment, electric vehicles, space technology,defense industry etc.,because of their high energy density,excellent cycle performance and non-memory effect.Power batteries increase rapidly with the rapid development of electric vehicles industry,while LFPBs occupies a large market share due to good safety,low cost and non-toxicity etc. With the increase of their usage,the number of spent LFPBs is increasing with years. Spent LFPBs without treatment in time will pollute the environment,and waste a lot of metal resources.This paper summarizes recycling methods of spent LFPBs cathode materials,including pretreatment method,solid phase method,acid leaching-precipitation method etc. The advantages and disadvantages of several methods are compared. The process of pretreatment,acid leaching,LiFePO_4( LFP) regeneration and electrochemical properties are also summarized. The existing problems in the recovery of LFPs are put forward. Meanwhile,the development of spent LFPs recycling should be towards automatic,green initiative,low-cost in the future.
Lithium-ion batteries( LIBs) are widely applied in portable electronic equipment, electric vehicles, space technology,defense industry etc.,because of their high energy density,excellent cycle performance and non-memory effect.Power batteries increase rapidly with the rapid development of electric vehicles industry,while LFPBs occupies a large market share due to good safety,low cost and non-toxicity etc. With the increase of their usage,the number of spent LFPBs is increasing with years. Spent LFPBs without treatment in time will pollute the environment,and waste a lot of metal resources.This paper summarizes recycling methods of spent LFPBs cathode materials,including pretreatment method,solid phase method,acid leaching-precipitation method etc. The advantages and disadvantages of several methods are compared. The process of pretreatment,acid leaching,LiFePO_4( LFP) regeneration and electrochemical properties are also summarized. The existing problems in the recovery of LFPs are put forward. Meanwhile,the development of spent LFPs recycling should be towards automatic,green initiative,low-cost in the future.
引文
[1]孟奇,张英杰,董鹏.废旧锂离子电池中钴、锂的回收研究进展[J].化工进展,2017,36(9):3485-3491.
[2] Tian X,Zhou Y,Tu X,et al. Well-dispersed Li Fe PO4nanoparticles anchored on a three-dimensional graphene aerogel as high-performance positive electrode materials for lithium-ion batteries[J]. Journal of Power Sources,2017,340:40-50.
[3] Freitas M B J G,Celante V G,Pietre M K. Electrochemical recovery of cobalt and copper from spent Li-ion batteries as multilayer deposits[J].Journal of Power Sources,2010,195(10):3309-3315.
[4] Armand M,Tarascon J M. Building better batteries[J]. Nature,2008,451(7179):652-657.
[5] Evarts E C. Lithium batteries:To the limits of lithium[J]. Nature,2015,526(7575):93-95.
[6] Palacín M R,De G A. Why do batteries fail?[J]. Science,2016,351(6273):1253292.
[7] Guo Y,Li F,Zhu H,et al. Leaching lithium from the anode electrode materials of spent lithium-ion batteries by hydrochloric acid(HCl)[J].Waste Management,2016,51:227-233.
[8] Horeh N B,Mousavi S M,Shojaosadati S A. Bioleaching of valuable metals from spent lithium-ion mobile phone batteries using Aspergillus niger[J]. Journal of Power Sources,2016,320:257-266.
[9] Li L,Lu J,Ren Y,et al. Ascorbic-acid-assisted recovery of cobalt and lithium from spent Li-ion batteries[J]. Journal of Power Sources,2012,218(12):21-27.
[10] Zeng X L,Li J H,SINGH N. Recycling of Spent Lithium-Ion Battery:A Critical Review[J]. Critical Reviews in Environmental Science&Technology,2014,44(10):1129-1165.
[11]李洪枚,姜亢.废旧锂离子电池对环境污染的分析与对策[J].上海环境科学,2004,(05):201-203.
[12] Simon B,Ziemann S,Weil M. Potential metal requirement of active materials in lithium-ion battery cells of electric vehicles and its impact on reserves:Focus on Europe[J]. Resources Conservation&Recycling,2015,104:300-310.
[13] Li X,Zhang J,Song D,et al. Direct regeneration of recycled cathode material mixture from scrapped Li Fe PO4batteries[J]. Journal of Power Sources,2017,345:78-84.
[14] Chen J P,Li Q W,Song J H,et al. Environmentally friendly recycling and effective repairing of cathode powders from spent Li Fe PO4batteries[J]. Green Chemistry,2016,18:2500-2506.
[15] Bian D,Sun Y,Li S,et al. A novel process to recycle spent Li Fe PO4for synthesizing Li Fe PO4/C hierarchical microflowers[J]. Electrochimica Acta,2016,190:134-140.
[16] Wang L,Li J,Zhou H,et al. Regeneration cathode material mixture from spent lithium iron phosphate batteries[J]. Journal of Materials Science Materials in Electronics,2018:1-8.
[17] Song X,Hu T,Liang C,et al. Direct regeneration of cathode materials from spent lithium iron phosphate batteries using a solid phase sintering method[J]. RSC Advances,2017,7(4783):4783-4790.
[18]卞都成,刘树林,孙永辉,等.废旧Li Fe PO4正极材料的循环利用及电化学性能[J].硅酸盐学报,2015,43(11):1511-1516.
[19]卞都成,刘树林,田院.固相补锂法再利用废旧Li Fe PO4正极材料及电化学性能[J].无机盐工业,2016,48(2):71-74.
[20] Zheng R J,Zhao L,Wang W H,et al. Optimized Li and Fe recovery from spent lithiumion[J]. RSC Advances,2016,6:43613-43625.
[21]谢英豪,余海军,欧彦楠,等.从废旧动力电池中回收制备磷酸铁锂[J].电源技术,2014,(12):2239-2241.
[22]吴越,裴锋,贾蕗路,等.从废旧磷酸铁锂电池中回收铝、铁和锂[J].电源技术,2014,38(4):629-631.
[23] Shin E J,Kim S,Noh J K,et al. A green recycling process designed for Li Fe PO4[J]. The Royal Society of Chemistry,2015,3:11493-11502.
[24] Kim H S,Shin E J. Re-synthesis and Electrochemical Characteristics of Li Fe PO4Cathode Materials Recycled from Scrap Electrodes[J].Cheminform,2013,34(3):851-855.
[25] 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.
[26] Yang Y,Zheng X,Zhao C,et al. A closed loop process for selective metal recovery from spent lithium iron phosphate batteries through mechanochemical activation[J]. ACS Sustainable Chemistry&Engineering,2017,5(11):9972-9980.
[27]杨秋菊,赵世超,王楠,等.废旧动力锂离子电池中磷酸铁锂的再生[J].电池,2014,(1):60-62.
[28] 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):3121-3133.
[29] Li H,Xing S,Liu Y,et al. Recovery of Lithium,Iron,and Phosphorus from Spent Li Fe PO4Batteries Using Stoichiometric Sulfuric Acid Leaching System[J]. ACS Sustainable Chemistry&Engineering,2017,5(9):8017-8024.
[30] Fan E,Li L,Zhang X 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,2018,6:11029-11035.
[31] Chen X,Cao L,Kang D,et al. Recovery of valuable metals from mixed types of spent lithium ion batteries. Part II:Selective extraction of lithium[J]. Waste Management,2018,80:198-210.
[32] Huang Y,Han G,Liu J,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.
[33] Shangguana E,Fu S Q,Wu S Q,et al. Evolution of spent Li Fe PO4powders into Li Fe PO4-C-FeS composites-A facile and smart approach to make sustainable anodes for alkaline Ni-Fe secondary batteries[J]. Journal of Power Sources,2018,403:38-48.
[34] Shangguan E,Wang Q,Wu C K,et al. Novel Application of Repaired Li Fe PO4as a Candidate Anode Material for Advanced Alkaline Rechargeable Batteries[J]. ACS Sustainable Chemistry&Engineering,2018,6:13312-13323.
[35] Wang X,Wang X Y,Zhang R,et al. Hydrothermal preparation and performance of Li Fe PO4by using Li3PO4recovered from spent cathode scraps as Li source[J]. Waste Management,2018,78:208-216.
[36]杨则恒,张俊,吴情,等.废旧锂离子电池正极材料Li Fe PO4/C的电化学修复再生[J].硅酸盐学报,2013,(8):1051-1056.
[37] Kim S,Kim J,Kim S,et al. Electrochemical lithium recovery and organic removal from industrial wastewater of a battery recycling plant[J].Environmental Science Water Research&Technology,2017,4(2):199-205.
[2] Tian X,Zhou Y,Tu X,et al. Well-dispersed Li Fe PO4nanoparticles anchored on a three-dimensional graphene aerogel as high-performance positive electrode materials for lithium-ion batteries[J]. Journal of Power Sources,2017,340:40-50.
[3] Freitas M B J G,Celante V G,Pietre M K. Electrochemical recovery of cobalt and copper from spent Li-ion batteries as multilayer deposits[J].Journal of Power Sources,2010,195(10):3309-3315.
[4] Armand M,Tarascon J M. Building better batteries[J]. Nature,2008,451(7179):652-657.
[5] Evarts E C. Lithium batteries:To the limits of lithium[J]. Nature,2015,526(7575):93-95.
[6] Palacín M R,De G A. Why do batteries fail?[J]. Science,2016,351(6273):1253292.
[7] Guo Y,Li F,Zhu H,et al. Leaching lithium from the anode electrode materials of spent lithium-ion batteries by hydrochloric acid(HCl)[J].Waste Management,2016,51:227-233.
[8] Horeh N B,Mousavi S M,Shojaosadati S A. Bioleaching of valuable metals from spent lithium-ion mobile phone batteries using Aspergillus niger[J]. Journal of Power Sources,2016,320:257-266.
[9] Li L,Lu J,Ren Y,et al. Ascorbic-acid-assisted recovery of cobalt and lithium from spent Li-ion batteries[J]. Journal of Power Sources,2012,218(12):21-27.
[10] Zeng X L,Li J H,SINGH N. Recycling of Spent Lithium-Ion Battery:A Critical Review[J]. Critical Reviews in Environmental Science&Technology,2014,44(10):1129-1165.
[11]李洪枚,姜亢.废旧锂离子电池对环境污染的分析与对策[J].上海环境科学,2004,(05):201-203.
[12] Simon B,Ziemann S,Weil M. Potential metal requirement of active materials in lithium-ion battery cells of electric vehicles and its impact on reserves:Focus on Europe[J]. Resources Conservation&Recycling,2015,104:300-310.
[13] Li X,Zhang J,Song D,et al. Direct regeneration of recycled cathode material mixture from scrapped Li Fe PO4batteries[J]. Journal of Power Sources,2017,345:78-84.
[14] Chen J P,Li Q W,Song J H,et al. Environmentally friendly recycling and effective repairing of cathode powders from spent Li Fe PO4batteries[J]. Green Chemistry,2016,18:2500-2506.
[15] Bian D,Sun Y,Li S,et al. A novel process to recycle spent Li Fe PO4for synthesizing Li Fe PO4/C hierarchical microflowers[J]. Electrochimica Acta,2016,190:134-140.
[16] Wang L,Li J,Zhou H,et al. Regeneration cathode material mixture from spent lithium iron phosphate batteries[J]. Journal of Materials Science Materials in Electronics,2018:1-8.
[17] Song X,Hu T,Liang C,et al. Direct regeneration of cathode materials from spent lithium iron phosphate batteries using a solid phase sintering method[J]. RSC Advances,2017,7(4783):4783-4790.
[18]卞都成,刘树林,孙永辉,等.废旧Li Fe PO4正极材料的循环利用及电化学性能[J].硅酸盐学报,2015,43(11):1511-1516.
[19]卞都成,刘树林,田院.固相补锂法再利用废旧Li Fe PO4正极材料及电化学性能[J].无机盐工业,2016,48(2):71-74.
[20] Zheng R J,Zhao L,Wang W H,et al. Optimized Li and Fe recovery from spent lithiumion[J]. RSC Advances,2016,6:43613-43625.
[21]谢英豪,余海军,欧彦楠,等.从废旧动力电池中回收制备磷酸铁锂[J].电源技术,2014,(12):2239-2241.
[22]吴越,裴锋,贾蕗路,等.从废旧磷酸铁锂电池中回收铝、铁和锂[J].电源技术,2014,38(4):629-631.
[23] Shin E J,Kim S,Noh J K,et al. A green recycling process designed for Li Fe PO4[J]. The Royal Society of Chemistry,2015,3:11493-11502.
[24] Kim H S,Shin E J. Re-synthesis and Electrochemical Characteristics of Li Fe PO4Cathode Materials Recycled from Scrap Electrodes[J].Cheminform,2013,34(3):851-855.
[25] 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.
[26] Yang Y,Zheng X,Zhao C,et al. A closed loop process for selective metal recovery from spent lithium iron phosphate batteries through mechanochemical activation[J]. ACS Sustainable Chemistry&Engineering,2017,5(11):9972-9980.
[27]杨秋菊,赵世超,王楠,等.废旧动力锂离子电池中磷酸铁锂的再生[J].电池,2014,(1):60-62.
[28] 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):3121-3133.
[29] Li H,Xing S,Liu Y,et al. Recovery of Lithium,Iron,and Phosphorus from Spent Li Fe PO4Batteries Using Stoichiometric Sulfuric Acid Leaching System[J]. ACS Sustainable Chemistry&Engineering,2017,5(9):8017-8024.
[30] Fan E,Li L,Zhang X 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,2018,6:11029-11035.
[31] Chen X,Cao L,Kang D,et al. Recovery of valuable metals from mixed types of spent lithium ion batteries. Part II:Selective extraction of lithium[J]. Waste Management,2018,80:198-210.
[32] Huang Y,Han G,Liu J,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.
[33] Shangguana E,Fu S Q,Wu S Q,et al. Evolution of spent Li Fe PO4powders into Li Fe PO4-C-FeS composites-A facile and smart approach to make sustainable anodes for alkaline Ni-Fe secondary batteries[J]. Journal of Power Sources,2018,403:38-48.
[34] Shangguan E,Wang Q,Wu C K,et al. Novel Application of Repaired Li Fe PO4as a Candidate Anode Material for Advanced Alkaline Rechargeable Batteries[J]. ACS Sustainable Chemistry&Engineering,2018,6:13312-13323.
[35] Wang X,Wang X Y,Zhang R,et al. Hydrothermal preparation and performance of Li Fe PO4by using Li3PO4recovered from spent cathode scraps as Li source[J]. Waste Management,2018,78:208-216.
[36]杨则恒,张俊,吴情,等.废旧锂离子电池正极材料Li Fe PO4/C的电化学修复再生[J].硅酸盐学报,2013,(8):1051-1056.
[37] Kim S,Kim J,Kim S,et al. Electrochemical lithium recovery and organic removal from industrial wastewater of a battery recycling plant[J].Environmental Science Water Research&Technology,2017,4(2):199-205.