分散体系对微米银粉微观形貌及粒径影响研究
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摘要
微米及亚微米级球形银粉具有良好的导电性,在太阳能电池正面银浆料中应用广泛。利用化学还原法制备球形银粉是目前主要的制备方法之一,但制备的银粉存在分散性差,粒径分布宽的缺点。因此为制备粉体粒径分布范围窄、球形度良好且分散性好的银粉,本实验在化学还原法基础上,选用聚乙二醇(PEG-6000)和乳液分散两种不同的分散体系制备球形银粉。以聚乙二醇为分散剂制备银粉,主要改变分散剂含量、反应温度、反应液pH值等制备因素,而以乳液作为分散剂制备银粉时,主要改变表面活性剂含量、O/W比(油/水比)和乳液的HLB值(亲水亲油平衡值)。通过调整制备条件比较银粉的粒径分布、球形度。发现利用聚乙二醇制备银粉在分散剂含量为7%、温度为50℃、pH为9时分散度较好,但是球形度较差,平均粒径在1.59μm;利用乳液法制备银粉时在分散剂含量为3%、乳化转速为11000 r·min-1、W/O比为1∶1、HLB=4.5时粉体分散度较好,且粉体球形度好,平均粒径为0.91μm。分析实验结果发现,利用乳液法制备的银粉粒径分布均一、球形度良好,且分散性明显提高。
Micron and sub-micron spherical silver powders are widely used in solar battery positive silver paste for its good electrical conductivity.Chemical reduction method is currently one of the main preparation methods to prepare spherical silver powders,but the silver powders are usually of poor dispersion and broad particle size distribution.In order to prepare silver powder with narrow particle size distribution,good sphericity and fine silver powder dispersion,the experiment was carried out based on the chemical reduction method.Polyethylene glycol(PEG-6000) and emulsion dispersion were selected as two different dispersing systems,and the silver powder particle size distribution and the spherical degree were compared by adjusting the experimental conditions.With polyethylene glycol(PEG) as dispersant to prepare silver powder,the main factors of dispersant content,reaction temperature and pH value were changed; with emulsion as dispersant to prepare silver powder,the main factors of surfactant content,ratio and O/W(oil/water) emulsion of HLB values(hydrophilic-lipophilic balance value) were changed.By adjusting the preparation conditions it was found that with polyethylene glycol(PEG-6000) as dispersant,the silver powder dispersion was good when the dispersing agent content was 7%,the temperature was 50 ℃,pH was 9,but the sphericity was poor and the average particle size was 1.59 μm; when silver powder was prepared by emulsion method with dispersing agent content of 3%,emulsifying speed of 11000 r·min-1,W/O ratio of 1∶ 1,HLB of4.5,the powder dispersion was good,and powder had good sphericity and the average diameter was 0.91 μm.The experiment results showed that silver powder prepared by emulsion method were with uniform particle size distribution,good sphericity,and obviously the dispersion was improved.
Micron and sub-micron spherical silver powders are widely used in solar battery positive silver paste for its good electrical conductivity.Chemical reduction method is currently one of the main preparation methods to prepare spherical silver powders,but the silver powders are usually of poor dispersion and broad particle size distribution.In order to prepare silver powder with narrow particle size distribution,good sphericity and fine silver powder dispersion,the experiment was carried out based on the chemical reduction method.Polyethylene glycol(PEG-6000) and emulsion dispersion were selected as two different dispersing systems,and the silver powder particle size distribution and the spherical degree were compared by adjusting the experimental conditions.With polyethylene glycol(PEG) as dispersant to prepare silver powder,the main factors of dispersant content,reaction temperature and pH value were changed; with emulsion as dispersant to prepare silver powder,the main factors of surfactant content,ratio and O/W(oil/water) emulsion of HLB values(hydrophilic-lipophilic balance value) were changed.By adjusting the preparation conditions it was found that with polyethylene glycol(PEG-6000) as dispersant,the silver powder dispersion was good when the dispersing agent content was 7%,the temperature was 50 ℃,pH was 9,but the sphericity was poor and the average particle size was 1.59 μm; when silver powder was prepared by emulsion method with dispersing agent content of 3%,emulsifying speed of 11000 r·min-1,W/O ratio of 1∶ 1,HLB of4.5,the powder dispersion was good,and powder had good sphericity and the average diameter was 0.91 μm.The experiment results showed that silver powder prepared by emulsion method were with uniform particle size distribution,good sphericity,and obviously the dispersion was improved.
引文
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[12]Gan W P,Luo J,Guo G Q,Xiang F,Liu H.Ultrafine silver powder for electronic paste prepared by chemical reduction[J].Electronic Components and Materials,2010,29(11):15.(甘卫平,罗贱,郭桂全,向锋,刘欢.化学还原法制备电子浆料用超细银粉[J].电子元件与材料,2010,29(11):15.)
[13]Gan W P,Chen Z B,Chen Y L,Guo G Q,Luo J.Polyacrylate as dispersing agent to prepare highly dispersed ultrafine silver powder[J].Electronic Components and Materials,2011,30(10):47.(甘卫平,陈志波,陈迎龙,郭桂全,罗贱.以聚丙烯酸为分散剂制备高分散超细银粉[J].电子元件与材料,2011,30(10):47.)
[14]Zhao S,Yan B.Research of micro/nano silver powder with high purity prepared by liquid phase reduction method[J].Journal of Taiyuan University of Technology,2015,46(3):263.(赵爽,严彪.液相还原法制备高纯度微纳米银粉的研究[J].太原理工大学学报,2015,46(3):263.)
[15]Zhang D,Dong Y H,Liang F X,Liu F Q,Song X M.Silver nanoparticles prepared by inverse emulsion[J].Journal of Liaoning University(Science and Technology),2007,3(3):273.(张丹,董奕含,梁福鑫,刘凤岐,宋溪明.反相乳液法制备银纳米粒子[J].辽宁大学学报(自然科学版),2007,34(3):273.)
[16]Shiomi H,Tanaka C.Preparation of spherical Sn O2particles by W/O type emulsion method[J].Journal of Materials Science,2002,37(21):4683.
[17]Wang J,Yang X Z.Emulsification and Micro Emulsion Technology[M].Version 1.Beijing:Chemical Industry Press,2012.23.(王军,杨许召.乳化与微乳化技术[M].第1版.北京:化学工业出版社,2012.23.)
[2]Li J,Huang H,Guo Z C.Preparation of ultrafine silver powder for solar battery positive electrode paste[J].Functional Materials,2012,44(2):206.(李纪,黄惠,郭忠诚.太阳能电池正极浆料用超细银粉的制备[J].功能材料,2012,44(2):206.)
[3]Wang Y,Cao J.Silver recovery from a zinc hydrometallurgy residue in Inner Mongolia[J].Metal Mine,2014,(11):164.(王宇,曹静.内蒙古某湿法炼锌渣选银试验[J].金属矿山,2014,(11):164.)
[4]Duan Z W,Zhang Z Z,Jiang C J,Wang C.Research of ultrafine Ag powder prepared by the DC arc plasma method[J].Casting Technology,2007,28(1):23.(段志伟,张振忠,江成军,王超.直流电弧等离子体法制备超细Ag粉研究[J].铸造技术,2007,28(1):23.)
[5]Chen Z W,Gan G Y,Yan J K,Liu J.Reseach of gelatin as dispersant to prepare spherical ultrafine silver powder[J].Rare Metal Materials and Engineering,2011,40(4):741.(陈忠文,甘国友,严继康,刘杰.明胶作分散剂制备球形超细银粉[J].稀有金属材料与工程,2011,40(4):741.)
[6]Shi C K,Liang S Y,Zhu X Y.Preparation of flake silver powder by photo-induced reducing method[J].Chinese Journal of Rare Metals,2015,39(6):533.(施昌快,梁诗宇,朱晓云.光诱导还原法制备片状银粉的研究[J].稀有金属,2015,39(6):533.)
[7]Liu S Z,Tan D S,LüC J.Ascorbic acid preparation of fine silver powder reduction research[J].Technology of Powder Metallurgy,2009,19(2):5.(刘书祯,谈定生,吕超君.抗坏血酸还原制备微细银粉的研究[J].粉末冶金工艺,2009,19(2):5.)
[8]Shuai Y,Wang X B,Zhai H X.Preparation of ultrafine spherical silver powders reduction by formaldehyde technology research[J].New Chemical Materials,2011,39(12):80.(帅英,王献彪,翟红侠.甲醛还原制备超细球形银粉的工艺研究[J].化工新型材料,2011,39(12):80.)
[9]Wang H,Wang W,Qiu X L,Tan F T,Chen J G,Qiao X L.Micron scale controllable preparation of spherical silver powders[J].Material Review,2011,25(17):147.(王辉,王维,邱小林,谈发堂,陈建国,乔学亮.微米级球形银粉的可控制备[J].材料导报,2011,25(17):147.)
[10]Xu L,Liu X J,Cheng G.Preparation of ultrafine silver powder for the electronic pastes[J].Marine Electric Technology,2013,33(5):61.(徐磊,刘显杰,程耿.电子浆料用超细银粉的制备[J].船电技术,2013,33(5):61.)
[11]Qin T,Ye H Q,Wu C,Dong H,Liu G G,Hao M Q.The influence of PVP to the micron grade silver powder particles prepared by the liquid phase reduction[J].Journal of Central South University(Science and Technology),2013,44(7):2675.(覃涛,叶红齐,吴超,董虹,刘贡钢,郝梦秋.PVP对液相还原法制备微米级银粉颗粒性能的影响[J].中南大学学报(自然科学版),2013,44(7):2675.)
[12]Gan W P,Luo J,Guo G Q,Xiang F,Liu H.Ultrafine silver powder for electronic paste prepared by chemical reduction[J].Electronic Components and Materials,2010,29(11):15.(甘卫平,罗贱,郭桂全,向锋,刘欢.化学还原法制备电子浆料用超细银粉[J].电子元件与材料,2010,29(11):15.)
[13]Gan W P,Chen Z B,Chen Y L,Guo G Q,Luo J.Polyacrylate as dispersing agent to prepare highly dispersed ultrafine silver powder[J].Electronic Components and Materials,2011,30(10):47.(甘卫平,陈志波,陈迎龙,郭桂全,罗贱.以聚丙烯酸为分散剂制备高分散超细银粉[J].电子元件与材料,2011,30(10):47.)
[14]Zhao S,Yan B.Research of micro/nano silver powder with high purity prepared by liquid phase reduction method[J].Journal of Taiyuan University of Technology,2015,46(3):263.(赵爽,严彪.液相还原法制备高纯度微纳米银粉的研究[J].太原理工大学学报,2015,46(3):263.)
[15]Zhang D,Dong Y H,Liang F X,Liu F Q,Song X M.Silver nanoparticles prepared by inverse emulsion[J].Journal of Liaoning University(Science and Technology),2007,3(3):273.(张丹,董奕含,梁福鑫,刘凤岐,宋溪明.反相乳液法制备银纳米粒子[J].辽宁大学学报(自然科学版),2007,34(3):273.)
[16]Shiomi H,Tanaka C.Preparation of spherical Sn O2particles by W/O type emulsion method[J].Journal of Materials Science,2002,37(21):4683.
[17]Wang J,Yang X Z.Emulsification and Micro Emulsion Technology[M].Version 1.Beijing:Chemical Industry Press,2012.23.(王军,杨许召.乳化与微乳化技术[M].第1版.北京:化学工业出版社,2012.23.)