废旧锂电池中有价金属回收及三元正极材料的再制备
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摘要
探讨了磷酸体系下不同因素对废旧锂电池正极材料中有价金属浸出效率的影响,结果表明:在浸出时间60min,反应温度60℃,磷酸浓度2mol/L,液固比20mL/g,还原剂(H_2O_2)体积分数为4%时,可得最佳浸出效果,Co、Li、Mn、Ni浸出效率分别可达96.3%、100%、98.8%和99.5%;浸出液添加相应比例金属离子,采用草酸共沉淀法制备前体材料(Ni_(1/3)Co_(1/3)Mn_(1/3))C_2O_4,并得到相应再生磷酸溶液。再生磷酸进行循环浸出实验,实验研究结果表明:循环浸出5次之后Li的浸出率仍可保持在90.1%,而Co、Mn和Ni的浸出率在75.0%以上。前体添加锂源Li_2CO_3煅烧合成Li(Ni_(1/3)Co_(1/3)Mn_(1/3))O_2材料,考察了不同温度对Li(Ni_(1/3)Co_(1/3)Mn_(1/3))O_2材料合成的影响,结果显示,当合成温度为800℃时,得到的材料性能最优良,初次放电容量可达136.4mA·h/g。在0.2C下经过50圈循环后容量保持率为97.2%。
In this study, phosphoric acid was employed as efficient leaching reagent for the leaching of different valuable metals from waste cathode materials of spent lithium ion batteries(LIBs). Based on the leaching results, about 96.3% Co, 100% Li, 98.8% Mn and 99.5% Ni can be dissolved in phosphoric acidic medium under the optimized leaching conditions of acid concentration-2 mol/L, reductant dosage-4% H_2O_2, retention time-60 min, reaction temperature-60°C and pulp density-20 mL/g. After adjusting the molar ration with addition of a certain proportion of metal ions to the leachate, the precursor materials of(Ni_(1/3) Co_(1/3) Mn_(1/3))C_2O_4 can be obtained by co-precipitation method(adding stoichiometric oxalic acid to leaching solution). And phosphoric acid can be simultaneously regenerated during the above precipitating reaction. According to the circulating leaching results, it can be concluded that the regenerated acid can be reused to as leaching reagent with relatively sound leaching efficiencies for valuable metals(90.1% for Li and over 75.0% for Co, Mn and Ni) after 5 cycles of leaching. Finally, cathode materials of Li(Ni_(1/3) Co_(1/3) Mn_(1/3))O_2 can be reprepared by calcination the precursor materials of(Ni_(1/3) Co_(1/3) Mn_(1/3))C_2O_4 with pure Li_2 CO_3 in appropriate molar ratio. Analysis results of electrochemical performances of the regenerated cathode material indicated that the initial discharge capacity of Li(Ni_(1/3) Co_(1/3) Mn_(1/3))O_2 was 136.4 mA·h/g with a remained capacity rate of 97.2% after 50 cycles at 0.2 C under the optimized synthesis temperature of 800 oC.
In this study, phosphoric acid was employed as efficient leaching reagent for the leaching of different valuable metals from waste cathode materials of spent lithium ion batteries(LIBs). Based on the leaching results, about 96.3% Co, 100% Li, 98.8% Mn and 99.5% Ni can be dissolved in phosphoric acidic medium under the optimized leaching conditions of acid concentration-2 mol/L, reductant dosage-4% H_2O_2, retention time-60 min, reaction temperature-60°C and pulp density-20 mL/g. After adjusting the molar ration with addition of a certain proportion of metal ions to the leachate, the precursor materials of(Ni_(1/3) Co_(1/3) Mn_(1/3))C_2O_4 can be obtained by co-precipitation method(adding stoichiometric oxalic acid to leaching solution). And phosphoric acid can be simultaneously regenerated during the above precipitating reaction. According to the circulating leaching results, it can be concluded that the regenerated acid can be reused to as leaching reagent with relatively sound leaching efficiencies for valuable metals(90.1% for Li and over 75.0% for Co, Mn and Ni) after 5 cycles of leaching. Finally, cathode materials of Li(Ni_(1/3) Co_(1/3) Mn_(1/3))O_2 can be reprepared by calcination the precursor materials of(Ni_(1/3) Co_(1/3) Mn_(1/3))C_2O_4 with pure Li_2 CO_3 in appropriate molar ratio. Analysis results of electrochemical performances of the regenerated cathode material indicated that the initial discharge capacity of Li(Ni_(1/3) Co_(1/3) Mn_(1/3))O_2 was 136.4 mA·h/g with a remained capacity rate of 97.2% after 50 cycles at 0.2 C under the optimized synthesis temperature of 800 oC.
引文
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[24]谌谷春,唐新村,王志敏,等.废旧锂电池中镍钴锰的回收及正极材料LiCo1/3Ni1/3Mn1/3O2的制备[J].无机化学学报,2011,27(10):1987-1992.CHEN Guchun,TANG Xincun,WANG Zhimin,et al.Recovery of nickel,cobalt and manganese in waste lithium batteries and preparation of cathode material LiCo1/3Ni1/3Mn1/3O2[J].Journal of Inorganic Chemistry,2011,27(10):1987-1992.
[25]史红彩.废旧锂离子动力电池中镍钴锰酸锂正极材料的回收及再利用[D].郑州:郑州大学,2017.SHI Hongcai.Recovery and reuse of nickel-cobalt-manganate cathode materials in waste lithium ion power batteries[D].Zhengzhou:Zhengzhou University,2017.
[2]ZHANG T,HE Y,WANG F,et al.Chemical and process mineralogical characterizations of spent lithium-ion batteries:an approach by multi-analytical techniques[J].Waste Management,2014,34(6):1051-1058.
[3]JHA M K,KUMARI A,JHA A K,et al.Recovery of lithium and cobalt from waste lithium ion batteries of mobile phone[J].Waste Management,2013,33(9):1890-1897.
[4]CHEN X P,LUO C B,ZHANG J X,et al.Sustainable recovery of metals from spent lithium-ion batteries:a green process[J].ACSSustainable Chemistry&Engineering,2015,3(12):3104-3113.
[5]CHEN L,TABG X,ZHANG Y,et al.Process for the recovery of cobalt oxalate from spent lithium-ion batteries[J].Hydrometallurgy,2011,108(1/2):80-86.
[6]XU J,THOMAS H R,FRANCIS R W,et al.A review of processes and technologies for the recycling of lithium-ion secondary batteries[J].Journal of Power Sources,2008,177(2):512-527.
[7]CHEN X P,FAN B L,XU LP,et al.An atom-economic process for the recovery of high value-added metals from spent lithium-ion batteries[J].Journal of Cleaner Production,2016,112:3562-3570.
[8]ZENG X,LI J,SHEN B.Novel approach to recover cobalt and lithium from spent lithium-ion battery using oxalic acid[J].Journal of Hazardous Materials,2015,295:112-118.
[9]CHEN X,ZHOU T.Hydrometallurgical process for the recovery of metal values from spent lithium-ion batteries in citric acid media[J].Waste Management Research,2014,32(11):1083-1093.
[10]LI L,GE J,CHEN R J,et al.Environmental friendly leaching reagent for cobalt and lithium recovery from spent lithium-ion batteries[J].Waste Management,2010,30(12):2615-2621.
[11]PAULINO J F,BUSNARDO N G,AFONSO J C.Recovery of valuable elements from spent Li-batteries[J].Journal of Hazardous Materials,2008,150(3):843-849.
[12]ZENG G,DENG X,LUO S,et al.A copper-catalyzed bioleaching process for enhancement of cobalt dissolution from spent lithium-ion batteries[J].Journal of Hazardous Materials,2012,199/200:164-169.
[13]ERUST C,AKCIL A,GAHAN C S,et al.Biohydrometallurgy of secondary metal resources:a potential alternative approach for metal recovery[J].Journal of Chemical Technology&Biotechnology,2013,88(12):2115-2132.
[14]JOULIE M,LAUCOURNET R,BILLY E.Hydrometallurgical process for the recovery of high value metals from spent lithium nickel cobalt aluminum oxide based lithium-ion batteries[J].Journal of Power Sources,2014,247:551-555.
[15]OU Z,LI J,WANG Z.Application of mechanochemistry to metal recovery from second-hand resources:a technical overview[J].Environmental Science:Processes&Impacts,2015,17(9):1522-1530.
[16]SUN Z,CAO H,XIAO Y,et al.Toward sustainability for recovery of critical metals from electronic waste:the hydrochemistry processes[J].ACS Sustainable Chemistry&Engineering,2017,5(1):21-24.
[17]ZHANG X,XIE Y,CAO H,et al.A novel process for recycling and resynthesizing LiNi1/3Co1/3Mn1/3O2from the cathode scraps intended for lithium-ion batteries[J].Waste Management,2014,34(9):1715-1724.
[18]LEE C K,RHEE K I.Preparation of LiCoO2from spent lithium-ion batteries[J].Journal of Power Sources,2002,109(1):17-21.
[19]LI L,FAN E,GUAN Y,et al.Sustainable recovery of cathode materials from spent lithium-ion batteries using lactic acid leaching system[J].ACS Sustainable Chemistry&Engineering,2017,5(6):5224-5233.
[20]KIM D S,SOHN J S,LEE C K,et al.Simultaneous separation and renovation of lithium cobalt oxide from the cathode of spent lithium ion rechargeable batteries[J].Journal of Power Sources,2004,132(1-2):145-149.
[21]WENG Y,XU S,HUANG G,et al.Synthesis and performance of Li[(Ni1/3Co1/3Mn1/3)1-xMgx]O2prepared from spent lithium ion batteries[J].Journal of Hazardous Materials,2013,246-247:163-172.
[22]ZHANG X,CAO H,XIE Y,et al.A closed-loop process for recycling LiNi1/3Co1/3Mn1/3O2from the cathode scraps of lithium-ion batteries:process optimization and kinetics analysis[J].Separation and Purification Technology,2015,150:186-195.
[23]SAKULTUNG S,PRUKSATHORN K,HUNSOM M.Simultaneous recovery of valuable metals from spent mobile phone battery by an acid leaching process[J].Korean Journal of Chemical Engineering,2007,24(2):272-277.
[24]谌谷春,唐新村,王志敏,等.废旧锂电池中镍钴锰的回收及正极材料LiCo1/3Ni1/3Mn1/3O2的制备[J].无机化学学报,2011,27(10):1987-1992.CHEN Guchun,TANG Xincun,WANG Zhimin,et al.Recovery of nickel,cobalt and manganese in waste lithium batteries and preparation of cathode material LiCo1/3Ni1/3Mn1/3O2[J].Journal of Inorganic Chemistry,2011,27(10):1987-1992.
[25]史红彩.废旧锂离子动力电池中镍钴锰酸锂正极材料的回收及再利用[D].郑州:郑州大学,2017.SHI Hongcai.Recovery and reuse of nickel-cobalt-manganate cathode materials in waste lithium ion power batteries[D].Zhengzhou:Zhengzhou University,2017.