利用废旧三元锂离子电池制备锰催化剂及其催化性能研究
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摘要
以废旧锂离子电池的正极材料为原料,利用氧化沉淀法制备锰催化剂,考察反应温度、pH、反应时间以及过硫酸铵用量对产物的影响,并分析制备的锰催化剂催化H_2O_2降解亚甲基蓝(MB,methylene blue)溶液的效果。结果表明:pH对锰催化剂晶型影响明显,在pH=1时,所制得锰催化剂属于γ-Mn O2,10 min即可完全降解MB;而在pH=4的条件下,所制得锰催化剂属于δ-MnO_2,1 h后MB去除率可达82%;pH=2或3条件下,所得锰催化剂为混合晶型,MB降解率分别为93%和77%(1 h)。因此,通过过硫酸铵氧化沉淀法能成功从锂离子电池中制备出具有良好催化性能的锰催化剂,实现了"以废治废",也为废旧三元锂离子电池资源化提供了新的思路。
Manganese catalysts were prepared by oxidation precipitation from cathode material of the spent li-ion batteries.Parameters including reaction temperature,time,pH and concentration of(NH_4)_2S_2O_8 were investigated,and then catalytic performances of the recovered Mn catalysts were also studied in catalytic degradation of methylene blue(MB) in the presence of H_2O_2.The results showed that: pH had significant impact on the crystal-forms of the recovered Mn catalysts.At pH = 1,the recovered Mn catalyst,which was able to remove 100% MB in 10 min,was assigned to γ-MnO_2; the XRD patterns of Mn catalyst recovered at pH = 4 corresponded to δ-MnO_2,MB degradation rate was only 83%; products prepared in pH = 2 and 3 were found in mixed crystal-forms with MB degradation rate of 93% and 77%,respectively in 1 h.Therefore,oxidation precipitation using(NH_4)_2S_2O_8 could recover Mn products with excellent catalytic performance from spent li-ion batteries,which provided a new way to recover the spent li-ion batteries.
Manganese catalysts were prepared by oxidation precipitation from cathode material of the spent li-ion batteries.Parameters including reaction temperature,time,pH and concentration of(NH_4)_2S_2O_8 were investigated,and then catalytic performances of the recovered Mn catalysts were also studied in catalytic degradation of methylene blue(MB) in the presence of H_2O_2.The results showed that: pH had significant impact on the crystal-forms of the recovered Mn catalysts.At pH = 1,the recovered Mn catalyst,which was able to remove 100% MB in 10 min,was assigned to γ-MnO_2; the XRD patterns of Mn catalyst recovered at pH = 4 corresponded to δ-MnO_2,MB degradation rate was only 83%; products prepared in pH = 2 and 3 were found in mixed crystal-forms with MB degradation rate of 93% and 77%,respectively in 1 h.Therefore,oxidation precipitation using(NH_4)_2S_2O_8 could recover Mn products with excellent catalytic performance from spent li-ion batteries,which provided a new way to recover the spent li-ion batteries.
引文
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[19]Zhang W,Wang H,Yang Z,et al.Promotion of H2O2decomposition activity overβ-Mn O2nanorod catalysts[J].Colloids and Surfaces A:Physicochemical and Engineering Aspects,2007,304(1/2/3):60-66.
[2]Millner A.Modeling lithium ion battery degradation in electric vehicles[C]∥Innovative Technologies for an Efficient and Reliable Electricity Supply(CITRES).2010 IEEE Conference,2010:349-356.
[3]Xu J,Dou S,Liu H,et al.Cathode materials for next generation lithium ion batteries[J].Nano Energy,2013,2(4):439-442.
[4]王刚,赵光金.动力锂电池梯次利用与回收处理[M].北京:中国电力出版社,2014.
[5]Fergus J W.Recent developments in cathode materials for lithium ion batteries[J].Journal of Power Sources,2010,195(4):939-954.
[6]Joo S H,Shin D J,Oh C,et al.Selective extraction and separation of nickel from cobalt,manganese and lithium in pretreated leach liquors of ternary cathode material of spent lithium-ion batteries using synergism caused by Versatic 10 acid and LIX 84-I[J].Hydrometallurgy,2016,159:65-74.
[7]Lin K,Liu W,Gan J.Oxidative removal of bisphenol A by manganese dioxide:Efficacy,products,and pathways[J].Environmental Science&Technology,2009,43(10):3860-3864.
[8]Devaraj S,Munichandraiah N.Effect of crystallographic structure of Mn O2on its electrochemical capacitance properties[J].The Journal of Physical Chemistry C,2008,112(11):4406-4417.
[9]Zhang J,Li Y,Wang L,et al.Catalytic oxidation of formaldehyde over manganese oxides with different crystal structures[J].Catalysis Science&Technology,2015,5(4):2305-2313.
[10]Liang S,Teng F,Bulgan G,et al.Effect of phase structure of Mn O2nanorod catalyst on the activity for CO oxidation[J].The Journal of Physical Chemistry C,2008,112(14):5307-5315.
[11]Zhang W,Yang Z,Wang X,et al.Large-scale synthesis ofβ-Mn O2nanorods and their rapid and efficient catalytic oxidation of methylene blue dye[J].Catalysis Communications,2006,7(6):408-412.
[12]Cui H J,Huang H Z,Yuan B,et al.Decolorization of Rh B dye by manganese oxides:Effect of crystal type and solution p H[J].Geochemical Transactions,2015,16(1):10.
[13]Liu Y,Chen Z,Shek C H,et al.Hierarchical mesoporous Mn O2superstructures synthesized by soft-interface method and their catalytic performances[J].ACS Applied Materials&Interfaces,2014,6(12):9776-9784.
[14]Gallegos M V,Falco L R,Peluso M A,et al.Recovery of manganese oxides from spent alkaline and zinc-carbon batteries.An application as catalysts for VOCs elimination[J].Waste Management,2013,33(6):1483-1490.
[15]Meshram P,Pandey B D,Mankhand T R.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,2015,281418-427.
[16]Zhang W,Tay H L,Lim S S,et al.Supported cobalt oxide on Mg O:Highly efficient catalysts for degradation of organic dyes in dilute solutions[J].Applied Catalysis B:Environmental,2010,95(1/2):93-99.
[17]Xu H,Qu Z,Zhao S,et al.Different crystal-forms of onedimensional Mn O2nanomaterials for the catalytic oxidation and adsorption of elemental mercury[J].J Hazard Mater,2015,29986-29993.
[18]宋灿.不同晶型与形貌锰氧化物的合成及催化燃烧氯苯的研究[D].武汉:武汉工程大学,2012.
[19]Zhang W,Wang H,Yang Z,et al.Promotion of H2O2decomposition activity overβ-Mn O2nanorod catalysts[J].Colloids and Surfaces A:Physicochemical and Engineering Aspects,2007,304(1/2/3):60-66.
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