直接回收锰酸锂制备超级电容器MnS材料的研究
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摘要
通过将锂离子电池正极锰酸锂废料直接回收制备超级电容器MnS材料的方法,研究锰酸锂废料的再生利用.将正极废料溶解浸出后,调整废料浓度并加入硫源,经水热反应得到MnS材料.采用X射线衍射分析(XRD)、扫描电子显微镜(SEM)观察、透射电子显微镜(TEM)观察、比表面积分析(BET)等表征手段和电化学性能测试对MnS材料进行了研究.结果显示:水热法制备的MnS具有良好的晶体结构和较好的电容器特性;浸出液中Mn~(2+)浓度对最终产物的形貌、比表面积均有影响,其中当Mn~(2+)浓度为0.5 mol/L时,可以得到三维花状辐射结构,该辐射结构有利于提升电解液与材料之间的表面接触性能,从而促进材料的电容性能.该研究为锂离子电池正极材料的回收提供了新的思路.
The LiMn_2O_4 scraps recovered from spent Lithium ion batteries is converted into MnS,which can be used as an active material for manufacturing supercapacitors. The cathode scrap is dissolved and leached firstly,then the concentration of the leaching solution is adjusted with S-sources,and finally the MnS material is obtained by heating the leaching solution. The XRD,SEM,TEM and BET results show that the MnS can exhibit excellent crystal structure and good capacitor property. Some interesting results are obtained by investigating the impacts of Mn~(2+) concentration on the performance of the final products. The Mn~(2+) concentration has vital impact on the morphology and specific surface area of the MnS product. When the Mn~(2+) concentration equals to 0.5 mol/L,MnS with 3D flower-like radiating structure can be obtained. This structure can enhance the contact between the material and the electrolyte,resulting in better electrochemical performance. This study can provide a new way for recycling of cathode scraps,which is worth further investigation.
The LiMn_2O_4 scraps recovered from spent Lithium ion batteries is converted into MnS,which can be used as an active material for manufacturing supercapacitors. The cathode scrap is dissolved and leached firstly,then the concentration of the leaching solution is adjusted with S-sources,and finally the MnS material is obtained by heating the leaching solution. The XRD,SEM,TEM and BET results show that the MnS can exhibit excellent crystal structure and good capacitor property. Some interesting results are obtained by investigating the impacts of Mn~(2+) concentration on the performance of the final products. The Mn~(2+) concentration has vital impact on the morphology and specific surface area of the MnS product. When the Mn~(2+) concentration equals to 0.5 mol/L,MnS with 3D flower-like radiating structure can be obtained. This structure can enhance the contact between the material and the electrolyte,resulting in better electrochemical performance. This study can provide a new way for recycling of cathode scraps,which is worth further investigation.
引文
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[13]林赞锐,沈家东,沈楷翔,等.不同锂源对富锂锰基Li1.133Mn0.466Ni0.2Co0.2O2正极材料性能的影响研究[J].华南师范大学学报(自然科学版),2015,47(6):37-41.LIN Z R,SHEN J D,SHEN K X,et al.Influence of different sources of lithium on the performance of lithium-rich manganese-based Li1.133Mn0.466Ni0.2Co0.2O2cathode materials[J].Journal of South China Normal University(Natural Science Edition),2015,47(6):37-41.
[14]陶锋,於孝朋,王志俊,等.Mn S纳米线阵列上Mn S花状球的水热合成[J].无机化学学报,2010,26(4):603-608.TAO F,YU X M,WANG Z J,et al.Hydrothermal synthesis of MnS flower-like spheres sitting on MnS nanowirearrays[J].Chinese Journal of Inorganic Chemistry,2010,26(4):603-608.
[15]ZHANG X H,CHEN Y Q,JIA C,et al.Two-step solvothermal synthesis ofα-Mn S spheres:growth mechanism and characterization[J].Materials Letters,2008,62:125-127.
[16]TANG Y F,CHEN T,GUO W F,et al.Reduced graphene oxide supported MnS nanotubes hybrid as a novel nonprecious metal electrocatalyst for oxygen reduction reaction with high performance[J].Journal of Power Sources,2017,362:1-9.
[17]LUO F L,LI J,YUAN H Y.Rapid synthesis of three-dimensional flower-like cobalt sulfide hierarchitectures by microwave assisted heating method for high-performance supercapacitors[J].Electrochimica Acta,2014,123:183-189.
[18]HUANG X,ZHANG Z G,LI H,et al.Novel fabrication of Ni3S2/MnS composite as high performance supercapacitor electrode[J].Journal of Alloys and Compounds,2017,17:1-19.
[2]JOO S H,SHIN D J,OH C H,et al.Extraction of manganese by alkyl monocarboxylic acid in a mixed extractant from a leaching solution of spent lithium-ion battery ternary cathodic material[J].Journal of Power Sources,2016,305:175-181.
[3]MESHRAM P,PANDEY B D,MANKHAND T R,et al.Hydrometallurgical processing of spent lithium ion batteries(LIBs)in the presence of a reducing agent with emphasis on kinetics of leaching[J].Chemical Engineering Journal,2015,281:418-427.
[4]QINA S,ERIC G,MEINAN H,et al.Synthesis of high performance Li Ni1/3Mn1/3Co1/3O2from lithium ion battery recovery stream[J].Journal of Power Sources,2015,282:140-145.
[5]SONG D W,WANG X Q,ZHOU E L,et al.Recovery and heat treatment of the Li(Ni1/3Co1/3Mn1/3)O2cathode scrap material for lithium ion battery[J].Journal of Power Sources,2013,232:348-352.
[6]ZHANG X H,XIE Y B,CAO H B,et al.A novel process for recycling and resynthesizing Li Ni1/3Co1/3Mn1/3O2from the cathode scraps intended for lithium-ion batteries[J].Waste Management,2014,34:1715-1724.
[7]ZHANG X X,XUE Q,LI L,et al.Sustainable recycling and regeneration of cathode scraps from industrial production of lithium ion batteries[J].ACS Sustainable Chemistry and Engineering,2016,7:7041-7049.
[8]ZHANG R J,WANG W H,DAI Y K,A closed-loop process for recycling Li NixCo Mn(1-x-y)O2from mixed cathode materials of lithium-ion batteries[J].Green Energy and Environment,2017,2:42-50.
[9]NIE H H,XU L,SONG D W,et al.Li Co O2:recycling from spent batteries and regeneration with solid state synthesis[J].Green Chemistry,2015,17:1276-1280.
[10]YAO L,FENG Y,XI G X.A new method for the synthesis of Li Ni1/3Co1/3Mn1/3O2from waste lithium ion batteries[J].RSC Advance,2015,5:44107-44114.
[11]YAO L,YAO H S,XI G X,et al.Recycling and synthesis of Li Ni1/3Co1/3Mn1/3O2from waste lithium ion batteries using D,L-malic acid[J].RSC Advance,2016,6:17947-17954.
[12]赵瑞瑞,杨子莲,杜鹏,等.锂源对固相合成Li Ni0.5Co0.2Mn0.3O2正极材料性能的影响[J].华南师范大学学报(自然科学版),2015,47(2):48-52.ZHAO R R,YANG Z L,DU P,et al.Effects of lithium sources on the performance of Li Ni0.5Co0.2Mn0.3O2cathode material derived by solid state method[J].Journal of South China Normal University(Natural Science Edition),2015,47(2):48-52.
[13]林赞锐,沈家东,沈楷翔,等.不同锂源对富锂锰基Li1.133Mn0.466Ni0.2Co0.2O2正极材料性能的影响研究[J].华南师范大学学报(自然科学版),2015,47(6):37-41.LIN Z R,SHEN J D,SHEN K X,et al.Influence of different sources of lithium on the performance of lithium-rich manganese-based Li1.133Mn0.466Ni0.2Co0.2O2cathode materials[J].Journal of South China Normal University(Natural Science Edition),2015,47(6):37-41.
[14]陶锋,於孝朋,王志俊,等.Mn S纳米线阵列上Mn S花状球的水热合成[J].无机化学学报,2010,26(4):603-608.TAO F,YU X M,WANG Z J,et al.Hydrothermal synthesis of MnS flower-like spheres sitting on MnS nanowirearrays[J].Chinese Journal of Inorganic Chemistry,2010,26(4):603-608.
[15]ZHANG X H,CHEN Y Q,JIA C,et al.Two-step solvothermal synthesis ofα-Mn S spheres:growth mechanism and characterization[J].Materials Letters,2008,62:125-127.
[16]TANG Y F,CHEN T,GUO W F,et al.Reduced graphene oxide supported MnS nanotubes hybrid as a novel nonprecious metal electrocatalyst for oxygen reduction reaction with high performance[J].Journal of Power Sources,2017,362:1-9.
[17]LUO F L,LI J,YUAN H Y.Rapid synthesis of three-dimensional flower-like cobalt sulfide hierarchitectures by microwave assisted heating method for high-performance supercapacitors[J].Electrochimica Acta,2014,123:183-189.
[18]HUANG X,ZHANG Z G,LI H,et al.Novel fabrication of Ni3S2/MnS composite as high performance supercapacitor electrode[J].Journal of Alloys and Compounds,2017,17:1-19.
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