Pb-Al复合电极材料制备技术及性能的研究
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摘要
铅及铅合金被湿法冶金工业用来做电积铜、电积锌的不溶性阳极材料和作为铅蓄电池中的板栅材料,但其存在着机械强度低、抗蠕变性差、内阻大、质量大等缺陷。本文在Al与Pb之间引入第三组元金属,解决了Al、Pb的相容性问题,采用热浸渡和浇铸相结合的制备方法,制备出新型的铝-铅层状复合电极材料。利用扫描电子显微镜、万能材料测试机、电化学工作站等分析测试手段,对铝-铅复合材料的性能与界面进行分析,研究中间过渡层对铝-铅复合材料界面、性能的影响,结合力学性能和电化学性能测试,探索其作为电极材料应用的可行性和优势。
参阅相关文献,制定铝-铅复合材料的制备工艺,通过实验确定具体的工艺参数,并制备出三种不同界面结合方式的铝-铅复合材料。深入研究铝-铅复合材料的界面微观结构和物理性能,并应用人工神经网络技术建立起了铝-铅复合材料界面强度与第三组元过渡金属配比、热浸渡温度、热浸渡时间之间的关系,对界面结合力进行分析以得出最佳工艺方案。
研究结果表明,铝-铅层状复合电极材料与传统铅电极相对比,具有较强耐电化学腐蚀能力,内阻低,能耗低,抗弯性能好。当引入Sn或Bi作为第三组元金属,可在铝-铅界面可形成冶金式结合,使力学性能和电化学性能得到提高。通过人工神经网络技术建立起铝-铅复合材料界面与影响因素之间的关系模型,从而得出当第三组元金属为Sn,热浸渡温度为328℃,热浸渡时间为2min时,可制备出界面结合相对较好的铝-铅层状复合材料,此时的界面剪切力强度可达7.7304。纵观全文,本文的研究在综述前人工作的基础上,研究了非混溶体系的制备工艺和界面结构,并为新型能源材料的研发提供了新的思路与参考。
Lead and lead alloys were used for hydrometallurgical industrial electrowinning copper, zinc electrowinning anode insoluble materials and as a lead-acid batteries in the grid material, but there have the defect of low mechanical strength, poor creep resistance, large resistance, the heavy quality and so on. Based on introducing the third group metal between Al and Pb, solve the compatibility between Al and Pb,prepared Al-Pb composite material by the hot dipping and appends an the casting. The interfacial organization and microstructures of Al-Pb alloys had been investigated by SEM, The multi-purpose materials measure the testing and the electrochemistry workstation, study for the influences on Al-Pb composite material's interface by interim transition-layer. By electrochemistry experiments and mechanical experiments, the feasibility and advantages of apply Al-Pb composite material to Electrode material has been verified.
On basis of the related documents, technological process and parameter has been redefined by tests. And manufacture three kinds of Al-Pb compsite material, which have diffenernt interfacial structure. This paper mostly study for micstructures of interface and physical properties of Al-Pb compsite material. Application of artificial neural network technology to build the relationship between the aluminum-lead composite interface strength with the third element of transition metal ratio, hot-dip transition temperature and hot-dip crossing time, On an analysis of the interface bonding process to produce the best program in order to arrive at the best Technology program.
It was found that, Al-Pb composite material has a better corrosion-resistance and a low internal resistance, and a low energy consumption, and a good mechanical properties. The experimental results show that, when the introduction of Sn or Bi as the third element of metal, aluminum and lead can be to the formation of interface-type metallurgical combine, so that the mechanical properties and improved electrochemical properties, and Bi, Sn into the situation in different proportions under different performance reflected by the establishment of artificial neural network model obtained when the third element of metal is Sn, hot dip transition temperature is 328℃, hot-dip time is 2 minutes, can be relatively well prepared aluminum laminated composite lead, which has Interface shear force of 7.7304 strength. In sum, on basis of the related documents, the processing of Al-Pb composite material and micstructures of interface had been discussed. Moreover this study provided us a new choice and reference for power material and new grid material to Lead-acid Battery.
参阅相关文献,制定铝-铅复合材料的制备工艺,通过实验确定具体的工艺参数,并制备出三种不同界面结合方式的铝-铅复合材料。深入研究铝-铅复合材料的界面微观结构和物理性能,并应用人工神经网络技术建立起了铝-铅复合材料界面强度与第三组元过渡金属配比、热浸渡温度、热浸渡时间之间的关系,对界面结合力进行分析以得出最佳工艺方案。
研究结果表明,铝-铅层状复合电极材料与传统铅电极相对比,具有较强耐电化学腐蚀能力,内阻低,能耗低,抗弯性能好。当引入Sn或Bi作为第三组元金属,可在铝-铅界面可形成冶金式结合,使力学性能和电化学性能得到提高。通过人工神经网络技术建立起铝-铅复合材料界面与影响因素之间的关系模型,从而得出当第三组元金属为Sn,热浸渡温度为328℃,热浸渡时间为2min时,可制备出界面结合相对较好的铝-铅层状复合材料,此时的界面剪切力强度可达7.7304。纵观全文,本文的研究在综述前人工作的基础上,研究了非混溶体系的制备工艺和界面结构,并为新型能源材料的研发提供了新的思路与参考。
Lead and lead alloys were used for hydrometallurgical industrial electrowinning copper, zinc electrowinning anode insoluble materials and as a lead-acid batteries in the grid material, but there have the defect of low mechanical strength, poor creep resistance, large resistance, the heavy quality and so on. Based on introducing the third group metal between Al and Pb, solve the compatibility between Al and Pb,prepared Al-Pb composite material by the hot dipping and appends an the casting. The interfacial organization and microstructures of Al-Pb alloys had been investigated by SEM, The multi-purpose materials measure the testing and the electrochemistry workstation, study for the influences on Al-Pb composite material's interface by interim transition-layer. By electrochemistry experiments and mechanical experiments, the feasibility and advantages of apply Al-Pb composite material to Electrode material has been verified.
On basis of the related documents, technological process and parameter has been redefined by tests. And manufacture three kinds of Al-Pb compsite material, which have diffenernt interfacial structure. This paper mostly study for micstructures of interface and physical properties of Al-Pb compsite material. Application of artificial neural network technology to build the relationship between the aluminum-lead composite interface strength with the third element of transition metal ratio, hot-dip transition temperature and hot-dip crossing time, On an analysis of the interface bonding process to produce the best program in order to arrive at the best Technology program.
It was found that, Al-Pb composite material has a better corrosion-resistance and a low internal resistance, and a low energy consumption, and a good mechanical properties. The experimental results show that, when the introduction of Sn or Bi as the third element of metal, aluminum and lead can be to the formation of interface-type metallurgical combine, so that the mechanical properties and improved electrochemical properties, and Bi, Sn into the situation in different proportions under different performance reflected by the establishment of artificial neural network model obtained when the third element of metal is Sn, hot dip transition temperature is 328℃, hot-dip time is 2 minutes, can be relatively well prepared aluminum laminated composite lead, which has Interface shear force of 7.7304 strength. In sum, on basis of the related documents, the processing of Al-Pb composite material and micstructures of interface had been discussed. Moreover this study provided us a new choice and reference for power material and new grid material to Lead-acid Battery.
引文
[1]朱松然.蓄电池手册[M].天津：天津大学出版社,1998：83-84
[2]赵金珠,戴长松,王金玉,等.铅蓄电池极栅合金概述,电源技术,2002,26(2)：119-121.
[3]苏向东,罗宏,李鹏,等.电积铜用惰性Pb基合金阳极的工业试验,有色金属(冶炼部分),2002(4)：43-45
[4]李鑫,等.稀土在铅基合金中的应用,有色金属,2003,55(2)：15-17
[5]梅光贵,湿法炼锌学.长沙：中南大学出版社,2001：34-38
[6]K.Ichikawa and S.Ishizuka,Trans.Jpn.Inst.Met.,1987; 18:145
[7]朱敏等,难互溶体系中合金的机械合金化合成,功能材料,1992,23(6),346-34
[8]常志文,郭忠诚,潘君益,等.AI/Pb-WC-ZrO2-Ag和AI/Pb-WC-ZrO-CeO2复合电极材料的性能研究[J].昆明理工大学学报,2007,32(3)：13-17
[9]方芳,朱敏,袁斌,等.Al-Pb互不溶体系机械合金化过程中固溶度的计算[J].中国有色金属学报,2002年S1期：28-33
[10]左邻.材料工程[M].1995(1)：14-16
[11]K.I.Moore,D.L.Zhong and B.Cantor,Solidification of Pb particles embedded in A1[J],Acta metal.Mater,1990,Vol 38(7):1327-1342、
[12]胡劲,孙勇,姜东慧,等.Al-Pb体系研究进展昆明理工大学,2001
[13]刘兵.Al-Pb合金摩擦磨损性能研究[硕士学位论文].云南：昆明理工大学,2002
[14]赵九州.Al-Pb合金快速定向凝固的数值模拟[J],材料科学与工艺,2001,9(2)：154-156
[15]V I Dobatkin,V I Elangin. The structure of alloys of Montecito. [M]K I Moor,B Cantor,Oxford University,The insitute of metals, 1Cantlon b 1988:515-517
[16]Water T D,et al. US Pat 3 495 649,1970-02-17
[17]D.P.Howe,M.Mee,A.A.Torrance and J.D.Williams,Al-Pb-Si-In bearing alloy[J], Mater Sci Technol,1991 7:330-333
[18]Fedor R J, Smith W E. US Pat 4 069 369,1978-01-17
[19]L.Ratke.Coarsening of liquid Al-Pb dispersions under reduced gravity conditions [J].Materials Science and Engineering,1995, (A203):399-407
[20]H.Fujii, T. Ktaguchi, H. Kumakura, K. Togano, Fabrication of Uniform Al-Pb-Bi monotectic alloys under microgravity utilizing Space Shuttle, Microstructure and Superconducting Properties[J] Journal of Materials Science,1995(30):3429-3434
[21]赵九州,陈玉勇,张景辉,等.用电磁场减轻A1-Pb合金比重偏析[J].金属科学与工艺,1990,9(2)：77-82
[22]王闸.Al/Pb多层膜研究[硕士学位论文].云南：昆明理工大学,2003
[23]S.N.Ojha,O.P.Pandey,B.Tripathi,M.Kumar and C.Ramachandra, Microstructure and wear characteristics of an Al-4Cu-70Pb alloy produced by spray deposition Trans[J]. JIM,199233(5):514-525
[24]于春田.金属基复合材料[M],冶金工业出版社,1995
[25]丁W克莱因,P.J.威瑟斯,余永宁译.金属基复合材料导论,冶金工业出版社,1996
[26]陈荣,张国定,吴人杰,等.C/Al复合材料界面结合强度对拉伸性能的影响,复合材料学报,1993,Vol.10,No.2：121-125
[27]李道明,赵占国,不同界面结合强度条件下金属基复合材料拉伸断裂行为分析,复合材料学报,1993,V61.10,No.1：85-89
[28]George Durst.J Metals,1956, (3):328
[29]张鹏,杜玉慧,崔建忠,等.Al-20Sn合金半固态铸造的研究,金属学报,1997,33(8)：869
[30]Kim S T, et al. J Mater Sci,1990,25(2):5185
[31]张彩碚等,金属学报,1999,35(2)：117
[32]Kim S T, et al.J Mater Sci,1990,25(2)5185
[33]冷水孝夫,高木柳平,层状金属复合材料生产工艺及其新进展,焊接技术,1990,(9)：108
[34]Cam G, Bohm K H, Mullauer J, et al. JOM,1996,48(11):66
[35]Maehara Y.Mater Sci Technol,1998,4(8):669
[36]Richison R A,et al.Powder Met,1981,(1):1
[37]张鹏,曾大本,崔建忠,半固态铸造技术的发展状况及前景,等.金属学报,1997,33(8)：869
[38]Simon Haykin.神经网络原理[M].北京：机械工业出版社,2004.
[39]Martin T. Hagan, Howard B. Demuth, MarkH. beale.神经网络设计[M].北京：机械工业出版社,2002
[40]熊沈蜀.神经网络在动力学系统建模中的理论研究[J].清华大学学报,1998(8)：10-14
[41]Ghazi Zadeh A. Neural Network and Fuzzy Logic Ap-plications to Vehicle Systems: Literature Survey [J].Int J of Vehicle Design,1997,18 (2):132-193
[42]韩立群.人工神经网络理论、设计及应用.北京：化学工业出版社,2007
[43]郑君里,杨行峻.人工神经网络[M].北京：高等教育出版社,1992.
[44]冷飞.中国现代教育装备[M].2006(12)：53-54.
[45]朱敏,李伯林.不互溶Pb-Al二元系中纳米相复合结构的机械合金化合成及电镜分析[J],华南理工大学学报,Vol.28(6)：264-267
[46]刘兵.Al-Pb合金摩擦磨损性能研究[硕士学位论文].云南：昆明理工大学,2002
[47]S.Zhong, Characterization of a novel lead-aluminium alloy,Proceedings of the 2nd International Symposium on New Materials for Fuel Cell and Modern Battery Systems,178-184.Montreal,Canada,1997
[48]Zhu M et al. Mechanical Alloying of Immiscible Al-Pb Binary System by High Energy Ball Milling[J],Journal of Materials Science,1999,(33):5873-5881
[49]Hang-Moule Kim et al. Microstructure and Wear Characterstics of Rapidly Solidified Al-Pb-Cu Alloys[J].Materials Science and Engineering A,2000,(287):59-65
[50]Mohan S et al. Friction Characteristics of Stir-cast Al-Pb Alloy[J]. Wear,1992, (157):9-17
[51]Wang Jun et al. Trbological Behavior of Hot-Extruded Al-Si-Pb Bearing Alloy [J].Tribology,2002,22(4):268-273
[52]陈念贻.键参数函数及其应用[M].北京：科学出版社,1976
[53]李国斌,彭荣华,马淞江,铝基体电镀前浸锌工艺研究[J],电镀与精饰,2003,25(2)：24-26
[54]SCHMIDT J. Measureing oxygen overvoltage at lead-alloy anodes in sulphuric acid by means of AC impedence spectroscopy[J].Neue Huttle,1992,37(4):123-127
[55]于化顺.金属及复合材料及其制备技术[M].化学工业出版社,2006,10,第一版：107
[2]赵金珠,戴长松,王金玉,等.铅蓄电池极栅合金概述,电源技术,2002,26(2)：119-121.
[3]苏向东,罗宏,李鹏,等.电积铜用惰性Pb基合金阳极的工业试验,有色金属(冶炼部分),2002(4)：43-45
[4]李鑫,等.稀土在铅基合金中的应用,有色金属,2003,55(2)：15-17
[5]梅光贵,湿法炼锌学.长沙：中南大学出版社,2001：34-38
[6]K.Ichikawa and S.Ishizuka,Trans.Jpn.Inst.Met.,1987; 18:145
[7]朱敏等,难互溶体系中合金的机械合金化合成,功能材料,1992,23(6),346-34
[8]常志文,郭忠诚,潘君益,等.AI/Pb-WC-ZrO2-Ag和AI/Pb-WC-ZrO-CeO2复合电极材料的性能研究[J].昆明理工大学学报,2007,32(3)：13-17
[9]方芳,朱敏,袁斌,等.Al-Pb互不溶体系机械合金化过程中固溶度的计算[J].中国有色金属学报,2002年S1期：28-33
[10]左邻.材料工程[M].1995(1)：14-16
[11]K.I.Moore,D.L.Zhong and B.Cantor,Solidification of Pb particles embedded in A1[J],Acta metal.Mater,1990,Vol 38(7):1327-1342、
[12]胡劲,孙勇,姜东慧,等.Al-Pb体系研究进展昆明理工大学,2001
[13]刘兵.Al-Pb合金摩擦磨损性能研究[硕士学位论文].云南：昆明理工大学,2002
[14]赵九州.Al-Pb合金快速定向凝固的数值模拟[J],材料科学与工艺,2001,9(2)：154-156
[15]V I Dobatkin,V I Elangin. The structure of alloys of Montecito. [M]K I Moor,B Cantor,Oxford University,The insitute of metals, 1Cantlon b 1988:515-517
[16]Water T D,et al. US Pat 3 495 649,1970-02-17
[17]D.P.Howe,M.Mee,A.A.Torrance and J.D.Williams,Al-Pb-Si-In bearing alloy[J], Mater Sci Technol,1991 7:330-333
[18]Fedor R J, Smith W E. US Pat 4 069 369,1978-01-17
[19]L.Ratke.Coarsening of liquid Al-Pb dispersions under reduced gravity conditions [J].Materials Science and Engineering,1995, (A203):399-407
[20]H.Fujii, T. Ktaguchi, H. Kumakura, K. Togano, Fabrication of Uniform Al-Pb-Bi monotectic alloys under microgravity utilizing Space Shuttle, Microstructure and Superconducting Properties[J] Journal of Materials Science,1995(30):3429-3434
[21]赵九州,陈玉勇,张景辉,等.用电磁场减轻A1-Pb合金比重偏析[J].金属科学与工艺,1990,9(2)：77-82
[22]王闸.Al/Pb多层膜研究[硕士学位论文].云南：昆明理工大学,2003
[23]S.N.Ojha,O.P.Pandey,B.Tripathi,M.Kumar and C.Ramachandra, Microstructure and wear characteristics of an Al-4Cu-70Pb alloy produced by spray deposition Trans[J]. JIM,199233(5):514-525
[24]于春田.金属基复合材料[M],冶金工业出版社,1995
[25]丁W克莱因,P.J.威瑟斯,余永宁译.金属基复合材料导论,冶金工业出版社,1996
[26]陈荣,张国定,吴人杰,等.C/Al复合材料界面结合强度对拉伸性能的影响,复合材料学报,1993,Vol.10,No.2：121-125
[27]李道明,赵占国,不同界面结合强度条件下金属基复合材料拉伸断裂行为分析,复合材料学报,1993,V61.10,No.1：85-89
[28]George Durst.J Metals,1956, (3):328
[29]张鹏,杜玉慧,崔建忠,等.Al-20Sn合金半固态铸造的研究,金属学报,1997,33(8)：869
[30]Kim S T, et al. J Mater Sci,1990,25(2):5185
[31]张彩碚等,金属学报,1999,35(2)：117
[32]Kim S T, et al.J Mater Sci,1990,25(2)5185
[33]冷水孝夫,高木柳平,层状金属复合材料生产工艺及其新进展,焊接技术,1990,(9)：108
[34]Cam G, Bohm K H, Mullauer J, et al. JOM,1996,48(11):66
[35]Maehara Y.Mater Sci Technol,1998,4(8):669
[36]Richison R A,et al.Powder Met,1981,(1):1
[37]张鹏,曾大本,崔建忠,半固态铸造技术的发展状况及前景,等.金属学报,1997,33(8)：869
[38]Simon Haykin.神经网络原理[M].北京：机械工业出版社,2004.
[39]Martin T. Hagan, Howard B. Demuth, MarkH. beale.神经网络设计[M].北京：机械工业出版社,2002
[40]熊沈蜀.神经网络在动力学系统建模中的理论研究[J].清华大学学报,1998(8)：10-14
[41]Ghazi Zadeh A. Neural Network and Fuzzy Logic Ap-plications to Vehicle Systems: Literature Survey [J].Int J of Vehicle Design,1997,18 (2):132-193
[42]韩立群.人工神经网络理论、设计及应用.北京：化学工业出版社,2007
[43]郑君里,杨行峻.人工神经网络[M].北京：高等教育出版社,1992.
[44]冷飞.中国现代教育装备[M].2006(12)：53-54.
[45]朱敏,李伯林.不互溶Pb-Al二元系中纳米相复合结构的机械合金化合成及电镜分析[J],华南理工大学学报,Vol.28(6)：264-267
[46]刘兵.Al-Pb合金摩擦磨损性能研究[硕士学位论文].云南：昆明理工大学,2002
[47]S.Zhong, Characterization of a novel lead-aluminium alloy,Proceedings of the 2nd International Symposium on New Materials for Fuel Cell and Modern Battery Systems,178-184.Montreal,Canada,1997
[48]Zhu M et al. Mechanical Alloying of Immiscible Al-Pb Binary System by High Energy Ball Milling[J],Journal of Materials Science,1999,(33):5873-5881
[49]Hang-Moule Kim et al. Microstructure and Wear Characterstics of Rapidly Solidified Al-Pb-Cu Alloys[J].Materials Science and Engineering A,2000,(287):59-65
[50]Mohan S et al. Friction Characteristics of Stir-cast Al-Pb Alloy[J]. Wear,1992, (157):9-17
[51]Wang Jun et al. Trbological Behavior of Hot-Extruded Al-Si-Pb Bearing Alloy [J].Tribology,2002,22(4):268-273
[52]陈念贻.键参数函数及其应用[M].北京：科学出版社,1976
[53]李国斌,彭荣华,马淞江,铝基体电镀前浸锌工艺研究[J],电镀与精饰,2003,25(2)：24-26
[54]SCHMIDT J. Measureing oxygen overvoltage at lead-alloy anodes in sulphuric acid by means of AC impedence spectroscopy[J].Neue Huttle,1992,37(4):123-127
[55]于化顺.金属及复合材料及其制备技术[M].化学工业出版社,2006,10,第一版：107