Mn~(2+)对Al/Pb-Ag-Co阳极在锌电积中电催化性能和耐蚀性能的影响
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摘要
为提高阳极材料的耐蚀性和电催化活性,以铝为基体,在其表面复合电沉积Pb-Ag-Co合金镀层制备Al/Pb-Ag-Co复合阳极。进一步分析了电积锌体系中不同浓度Mn2+对Pb-Ag-Co复合阳极的电化学性能、外观形貌、物相构成的影响,并确定了最佳Mn2+添加量。通过扫描电镜(SEM)、X射线衍射仪(XRD)、线性扫描伏安(LSV)曲线、循环伏安(CV)曲线及Tafel曲线进行了表征。结果表明:Mn2+掺杂阳极镀层表面形成一层晶粒细小、致密的PbO2-MnO2层,有利于改善阳极的耐腐蚀性能和电催化活性;当Mn2+的浓度为4 g/L时,复合阳极材料具有较低的腐蚀速率和析氧电位。
In order to improve the corrosion resistance and electrocatalytic activity of the anode material,the Al/Pb-Ag-Co composite anodes were prepared on the surface of aluminum substrate by electrodepositing of Pb-Ag-Co alloy coating. The effects of different concentrations of Mn~(2+)on the electrochemical properties,morphology and phase composition of the Pb-Ag-Co composite coatings were further characterized by scanning electron microscopy( SEM),X-ray diffractometer( XRD),linear sweep voltammetry( LSV),CV curve and Tafel curve,and the optimum addition of Mn~(2+)was determined. Results showed that a dense PbO_2-MnO_2 layer with fine grain was formed on the surface of Mn~(2+)doped alloy composite coating,which was beneficial to the improvement of the corrosion resistance and electrocatalytic activity of the anode.When the concentration of Mn~(2+)was 4 g/L,the composite anode material had lower corrosion rate and oxygen evolution potential.
In order to improve the corrosion resistance and electrocatalytic activity of the anode material,the Al/Pb-Ag-Co composite anodes were prepared on the surface of aluminum substrate by electrodepositing of Pb-Ag-Co alloy coating. The effects of different concentrations of Mn~(2+)on the electrochemical properties,morphology and phase composition of the Pb-Ag-Co composite coatings were further characterized by scanning electron microscopy( SEM),X-ray diffractometer( XRD),linear sweep voltammetry( LSV),CV curve and Tafel curve,and the optimum addition of Mn~(2+)was determined. Results showed that a dense PbO_2-MnO_2 layer with fine grain was formed on the surface of Mn~(2+)doped alloy composite coating,which was beneficial to the improvement of the corrosion resistance and electrocatalytic activity of the anode.When the concentration of Mn~(2+)was 4 g/L,the composite anode material had lower corrosion rate and oxygen evolution potential.
引文
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[25]衷水平,赖延清,蒋良兴,等.锌电积用Pb-Ag-Ca-Sr四元合金阳极极化行为[J].中国有色金属学报,2008,18(7):1 342-1 346.
[26]LAI Y Q,ZHONG S P,JIANG L S.et al.Effect of doping Bi on oxygen evolution potential and corrosion behavior of Pb-based anode in zinc electrowinning[J].Journal of Central South University of Technology,2009,16(2):236-241.
[2]TJANDRAWAN V.The role of manganese in the electrowinning of copper and zinc[D].Perth:Murdoch University,2010:1-2.
[3]潘君益,郭忠诚.锌电积用惰性阳极材料的研究现状[J].云南冶金,2004,33(6):31-34.
[4]CLAASSEN J O,MEYRR E H O,RENNIE J,et al.Iron precipitation from zinc-rich solutions:Defining the zinc or process[J].Hydrometallurgy,2002,67(1):87-108.
[5]张璋,陈步明,郭忠诚,等.湿法冶金中新型铅基阳极材料的研究进展[J].材料导报,2016,30(10):112-113.
[6]HUANG H,ZHOU J Y,GUO Z C.Effect of added cobalt ion on copper electrowinning from sulfate bath using doped polyaniline and Pb-Ag anodes[J].Transactions of the Nonferrous Metals Society of China,2010,20(S1):s55-s59.
[7]张玉萍.锌电积用阳极的研究与发展[J].湿法冶金,2001,20(4):169-171.
[8]李松瑞.铅及铅基合金[M].长沙:中南工业大学出版社,1996:329-330.
[9]REROLLE C,WIART R.Kinetics of Pb and Pb-Ag anodes for zinc electrowinning-I.Formation of PbSO4layers at low polarization[J].Electrochimica Acta,1995,40(8):939-948.
[10]张淑兰.锌电积铅基四元合金阳极的研究与应用[J].有色矿冶,1997(1):33-35.
[11]PETROVA M,STEFANOV Y,NONCHEVA Z,et al.Electrochemical behaviour of lead alloys as anodes in zinc electrowinning[J].British Corrosion Journal,1999,34(3):198-200.
[12]杨健,王帅,陈步明,等.铝基铅合金复合β-PbO2颗粒阳极在不同Mn2+浓度含Cl-锌电积液中的电化学行为[J].材料保护,2015,48(8):24-28.
[13]NEWNHAM R H.Corrosion rates of lead based anodes for zinc electrowinning at high current densities[J].Journal of Applied Electrochemistry,1992,22(2):116-124.
[14]PETITPIERRE J P,COMNINELLIS C,PLATTNER E.Oxydation Du MnSO4en dioxyde de manganese dans H2SO430%[J].Electrochimica Acta,1990,35(1):281-287.
[15]张永春,郭忠诚,杨海涛,等.Al/Pb-Ag-Co阳极中Co在锌电沉积过程中的催化机理[J].材料保护,2013,46(9):7-9.
[16]VEREECKEN J,WINAND R.Influence of manganese(II)ions on the anodic oxidation of methanol[J].Electrochimica Acta,1972,17(2):271-278.
[17]YU P,O'keefe T J.Evaluation of lead anode reactions in acid su lfate electrolytes---II.Manganese reactions[J].Journal of the Electrochemical Society,2002,149(5):A558-A569.
[18]LAI Y Q,LI Y,JIANG L X,et al.Electrochemical behaviors of co-deposited Pb/Pb-MnO2composite anode in sulfuric acid solution-Tafel and EIS investigations[J].Journal of Electroanalytical Chemistry,2012,671:16-23.
[19]YANG H T,CHEN B M,GUO Z C,et al.Effects of manganese nitrate concentration on the performance of an Al substrateβ-PbO2-MnO2-WC-Zr O2composite electrofe material[J].International Journal of Hydrogen Energy,2014,39(7):3 087-3 099.
[20]陈影,金炳界,陈步明,等.PbO2-Ti O2镀液中掺杂Ce对制备钛基锌电积阳极材料性能的影响[J].材料保护,2015,48(4):16-18.
[21]ZHANG W S,CHENG C Y.Manganese metallurgy review.PartⅢ:Mangnese control in zinc and copper electrolytes[J].Hydrometallurgy,2007,89(3/4):178-188.
[22]李宁,王旭东,吴志良.高速电镀锌用不溶性阳极[J].材料保护,1999,32(9):7-9.
[23]梅光贵,钟竹前,刘勇刚,等.锌电解中铅银阳极的电化学行为[J].中南工业大学学报,1998,29(4):337-340.
[24]ZHONG S P,LAI Y Q,JIANG L X,et al.Fabrication and anodic polarization behavior of lead-based porous anodes anodes in zinc electrowining[J].Journal of Central South University of Technology,2008,15(6):757-762.
[25]衷水平,赖延清,蒋良兴,等.锌电积用Pb-Ag-Ca-Sr四元合金阳极极化行为[J].中国有色金属学报,2008,18(7):1 342-1 346.
[26]LAI Y Q,ZHONG S P,JIANG L S.et al.Effect of doping Bi on oxygen evolution potential and corrosion behavior of Pb-based anode in zinc electrowinning[J].Journal of Central South University of Technology,2009,16(2):236-241.