钽电解电容器用新型聚合物电极材料
摘要
本文以新一代导电聚合物材料3，4—聚乙烯二氧噻吩（PEDT）为研究对象，研究了EDT单体合成路线及聚合物PEDT的最佳成膜条件，并以此为基础，讨论了以导电聚合物有机材料PEDT 取代传统的无机材料MnO2作阴极的固体钽电解电容器的制备工艺及相关机理。主要研究内容包括：（1）EDT单体合成路线的两种方案，以及具体的制备过程；（2）在玻璃基片上淀积PEDT膜层，研究了聚合温度、聚合物状态、聚合改良剂、烘干温度、溶剂含量等工艺及环境条件对PEDT材料电导率和成膜速度的影响。研究发现，当溶剂的含量一定时，反应速度可以由改变单体 M与氧化剂 C的比值来进行调节，当比值越小时，反应速度变越慢。降低烘干温度有利于提高膜的致密度。聚合改良剂的加入和PEDT掺杂都明显地提高了薄膜的导电性。（3）通过对PEDT阴极被膜工艺过程的研究，找到了较适合的单体M和氧化剂C配比，清洗液的配方和清洗时间，烘干温度和时间，被膜和补形成次数等工艺参数。对比两种被膜方法，选用一步法进行实验，创新使用了真空一步法，将真空干燥与真空浸渍结合使用，最终获得比一步法更均匀、致密的阴极膜层，样品的容量引出、损耗、漏电流和ESR等电性能参数也得到提高。
总之，本文以PEDT材料在固体钽电解电容器上的应用为背景，研究了其相关的机理和各种工艺条件，为有机钽电容器的研制提供了关键的先期研究基础。
By examining the new generation condutive polymer material 3，4—polyethylene dioxythiophene (PEDT), this paper investigated the EDT monomer synthetic path and the optimum filming conditions of the compound PEDT. Based on this research, I also discussed the manufacturing processes and the related principles of the solid tantalum capacitors, when replacing the conventional inorganic material MnO2 with the PEDT as the negative pole. (1) Two EDT monomer synthetic paths have been investigated. (2) Using the method of depositing the PEDT film on the glass base, the affect of processing and environmental conditions --such as the polymerizing temperature, the state of the polymer material, the polymerization correctives, the drying temperature, and the amount of the solution etc. -- to the PEDT material's electroconductivity has also been examined in this paper. (3) By exploring the filming processes of the PEDT negative pole, this paper, creatively using the vacuum single step method, has found a comparatively suitable processing condition.
In conclusion, based on the application of the PEDT material on the solid tantalum capacitors, this paper has investigated their related principles and varieties of processing conditions. This has provided an essential work for the further research on the organic tantalum capacitors and its manufacturing.
总之，本文以PEDT材料在固体钽电解电容器上的应用为背景，研究了其相关的机理和各种工艺条件，为有机钽电容器的研制提供了关键的先期研究基础。
By examining the new generation condutive polymer material 3，4—polyethylene dioxythiophene (PEDT), this paper investigated the EDT monomer synthetic path and the optimum filming conditions of the compound PEDT. Based on this research, I also discussed the manufacturing processes and the related principles of the solid tantalum capacitors, when replacing the conventional inorganic material MnO2 with the PEDT as the negative pole. (1) Two EDT monomer synthetic paths have been investigated. (2) Using the method of depositing the PEDT film on the glass base, the affect of processing and environmental conditions --such as the polymerizing temperature, the state of the polymer material, the polymerization correctives, the drying temperature, and the amount of the solution etc. -- to the PEDT material's electroconductivity has also been examined in this paper. (3) By exploring the filming processes of the PEDT negative pole, this paper, creatively using the vacuum single step method, has found a comparatively suitable processing condition.
In conclusion, based on the application of the PEDT material on the solid tantalum capacitors, this paper has investigated their related principles and varieties of processing conditions. This has provided an essential work for the further research on the organic tantalum capacitors and its manufacturing.
引文
1. 陈国光，电解电容器，西安交通大学出版社，1986
2. 蒋亚东，唐先忠，有机电子材料化学基础，电子科技大学出版社，2001
3. T.Nakata,K.Morimota, Y.Saiki,and T.Nishiyama, History of the Development of Tantalum Capacitor and Future Trend,International Symposium on Tantalum and Niobium, Goslar, Germany,Sept.1995
4. 姜节俭，电容器与电子器，电子科技大学出版社，1998
5. H. Shirakawa, E.J.Lewis,A.G.MacDiarmid,C.K.Chiang, A.J.Heeger, J.Chem.Soc.,
Chem.Commun.1977,578.
6. Roskill.Japanese tantalum powder demand drops.Met Powder Rep，1992；47(7/8)：4
7. P. 哈根穆勒著，陈立泉译，固体电解质，科学出版社，1984
8. Richard H,Heinrich H-J.Japanese tantalum demand falls in 1985.Inter Refract Hard
Met,1986；5(2)：70～73
9. 刘世友.高科技的多面手――钽.金属世界，1998；(2)：5
10. 叶方伟.钽及其合金.材料导报，1997；(2)：27～30
11. 黄金昌.世界钽及其合金的生产和消费.稀有金属快报，1996；(8)：2～3
12. 张小明.钽粉在世界范围内进入高CV时代.稀有金属快报，1995；(11)：2～3
13. J. Hong, I. H. Yeo, and W. Paik , Conducting Polymer with Metal Oxide for Electrochemical
Capacitor: PEDT-RuOx Electrode , J. Electrochem. Soc., 148(2), A156-163 (2001).
14. Raymond B. Seymour、Charles E. Carraher, POLYMER CHEMISTRY AN
INTRODUCTION,1988
15. 雀部博之，导电性高分子材料，科学出版社，1989
16. 张有纲，张永祥，许恒生，电子材料现代分析概论，国防工业出版社，1993
17. 杨邦朝，王文生，薄膜物理与技术，电子科技大学出版社，1994
18. R. Hahn and B. Melody, Process for Producing Low ESR Solid Tantalum Capacitors,
CART'S98 Program, 1998
19. J. Prymak,Conductive Polymer Cathodes-the Latest Step in Declining ESR in Tantalum
Capacitors, APEC2000 Program,IEEE Applied Power&Electronics Conference,Febrary 2000
20. Jonas, F;Schrader, L. Synth.Met. 1991,41-43,831
21. M. Sato, S. Tanaka, K. Kaeriyama, J. Chem. Soc., Chem. Comm. (1986)873
22. US patent, No. 5,035,926, Jul.30,1991
23. 宋永祥，固体电解质铝电解电容器，电子元件与材料，1995年6月第2期
24. Edward C. Jordan,Reference Data for Engineers: Radio, Electronics,Computers,and
Communications,7# Edition, Howard W. Sams&Co.,Inc., Inianapolis,1985
25. J. Prymak, New Tantalum Capacitors in Power Supply Applications, 1998 IEEE Industry Applications Society Annual Meeting,1998
26. A. Merz, R. Schropp, E. Dotterl, Synthesis 1995,795
27. Cletus J. Kaiser, THE CAPACITOR HANDBOOK, Second Edition, 1997
28. J. J. Svec, Capacitors from 0.01 ounce to 50 pounds, Ceram. Industry, pp, 32-34, Aug. 1979
29. J. Kammermaier and H. Hagedorn, chemical conversion processes during breakdowns in organic dielectrics, Siemens Forsch. U. Entwickl., vol. 2, pp. 26-33,1973.
30. 曲喜新，现代电容器，电子元件与材料，vol. 12，1993
31. R. D. Parker, Technological development of high energy density capacitors, Hughes Aircraft Rep., 1976
32. 朱树新、顾振军，导电高分子材料，上海科学技术文献出版社，1981
33. 布劳恩著，黄葆同译，聚合物合成和表征技术，科学出版社，1981
34. 张光敏，用导电聚合物电极的超电容器研究概况，电子元件与材料，vol. 18，1995
35. 陈国光，曹婉真，电解电容器，西安交通大学出版社，1993
36. 季锐，徐友龙，聚吡咯固体电解电容器，电子元件与材料，vol. 18，1999
37. 张光敏，阎康平，本征导电高分子材料的进展，电子元件与材料，vol. 18，1999
38. Warren L F, Walker J A, Anderson D P, A study of conducting polymer morphology, Electrochem Soc., 1989, 136(8):2286
39. Kuloh Y, Tsuchiya S, Fukuyama M, An aluminium solid electrolytic capacitor with an electroconducting-polymer,Synth Met, 1991
40. 闻立时，固体材料界面研究的物理基础，科学出版社，1991
41. 梁梦娥译，固体钽电容器的生产工艺，钽铌工业进展，1990，（3）：9－10
42. H. V. De Matos, Design of an internal fuse for a high-frequency solid tantalum capacitor, the 30th Annual Electronics Componets Conference, April 29-30,1980
43. 李荻，电化学原理，北京航空航天大学出版社，1989
44. Andrew Jones.Production and applications of tantalum powder.Int Refract Hard Met,1987,
6(3)：119～121
45. Cardonne S M.Tantalum and its alloys.Int J Refract Met Hard Mater,1995, 13(4)：187～194
46. J. R. Owen, Electrochemical Science and Technology of Polymer-1, Elsevier Applied Science, Chapter 3, p47
47. Hideyuku Masuda,Kyojj Kaeriyama,Synth met,1990,
48. John R Rcynolds,Paul A Poropatic,Rita L Toyooka.Macromolecules,1987(20):958
49. Menon R., in H.S. Nalwa, Handbook of Organic Conductive Molecules and Polymers, John Wiley&sons Ltd., Chichester, 1997, Chapter 2
50. 张声飞，高频固体钽电解电容器性能与钽粉，电子元件与材料，1999， 18（1）：39－41，47
51. Miinnstedt H., Properties of polypyrroles treated with base and acid, polymer, 1994(27):899-904
52. Takashi Saito, Development of high-power electric double layer capacitors,NEC 技报，1994，47（10）：91-97
53. A. J. Epstein, Y. Yang, Polymeric and Organic Electronic Merterias and Applications, MRS Bull. 1997,22(6), 13
54. C. A. Thomas, K. Zong, P. Schottland, Adv. Mater, 2000, 12, 222
55. M. D. Levi, Gofer, D. Aurbach, M. Lapkowski. E. Vieil, J. Serose, J. Electrochem. Soc. 147(2000)1096
56. I. Prymak, Replacing Mno2 with Condutive Polymer in Solid Tantalum Capacitors,CARTS '99 Program, The Components Technology Institute, Inc. March 1999
57. D. M. Welsh, A. Kumar, M. C. Morvant, J. R. Reynolds, Synth. Met. 1999, 102, 7629
58. A. N. Aleshin, S. R. Williams, A. J. Heeger, Synth. Met. 1998, 94, 173
59. A. C. Arias, M. Granstrom, D. S. Thomas, K. Petritsch, R. H. Friend, Phis. Rev. B: Condens.Matter. 1999, 60, 1854
60. T. Yamamoto, Bull. Chem. Soc. Jpn. 1999, 72, 621
61. 达马斯金，佩特里著，谷林瑛译，电化学动力学导论，科学出版社，1989
62. Seungwhan Chon and Woon-kie Paik, Adsorption Of Self-Assembling Sulfur Compounds Through Electrochemical Reactions: Effects Of Potential, Acid And Oxidizing Agents, Phys. Chem. Chem. Phys., 2001, 3, #16, 3405-3410
2. 蒋亚东，唐先忠，有机电子材料化学基础，电子科技大学出版社，2001
3. T.Nakata,K.Morimota, Y.Saiki,and T.Nishiyama, History of the Development of Tantalum Capacitor and Future Trend,International Symposium on Tantalum and Niobium, Goslar, Germany,Sept.1995
4. 姜节俭，电容器与电子器，电子科技大学出版社，1998
5. H. Shirakawa, E.J.Lewis,A.G.MacDiarmid,C.K.Chiang, A.J.Heeger, J.Chem.Soc.,
Chem.Commun.1977,578.
6. Roskill.Japanese tantalum powder demand drops.Met Powder Rep，1992；47(7/8)：4
7. P. 哈根穆勒著，陈立泉译，固体电解质，科学出版社，1984
8. Richard H,Heinrich H-J.Japanese tantalum demand falls in 1985.Inter Refract Hard
Met,1986；5(2)：70～73
9. 刘世友.高科技的多面手――钽.金属世界，1998；(2)：5
10. 叶方伟.钽及其合金.材料导报，1997；(2)：27～30
11. 黄金昌.世界钽及其合金的生产和消费.稀有金属快报，1996；(8)：2～3
12. 张小明.钽粉在世界范围内进入高CV时代.稀有金属快报，1995；(11)：2～3
13. J. Hong, I. H. Yeo, and W. Paik , Conducting Polymer with Metal Oxide for Electrochemical
Capacitor: PEDT-RuOx Electrode , J. Electrochem. Soc., 148(2), A156-163 (2001).
14. Raymond B. Seymour、Charles E. Carraher, POLYMER CHEMISTRY AN
INTRODUCTION,1988
15. 雀部博之，导电性高分子材料，科学出版社，1989
16. 张有纲，张永祥，许恒生，电子材料现代分析概论，国防工业出版社，1993
17. 杨邦朝，王文生，薄膜物理与技术，电子科技大学出版社，1994
18. R. Hahn and B. Melody, Process for Producing Low ESR Solid Tantalum Capacitors,
CART'S98 Program, 1998
19. J. Prymak,Conductive Polymer Cathodes-the Latest Step in Declining ESR in Tantalum
Capacitors, APEC2000 Program,IEEE Applied Power&Electronics Conference,Febrary 2000
20. Jonas, F;Schrader, L. Synth.Met. 1991,41-43,831
21. M. Sato, S. Tanaka, K. Kaeriyama, J. Chem. Soc., Chem. Comm. (1986)873
22. US patent, No. 5,035,926, Jul.30,1991
23. 宋永祥，固体电解质铝电解电容器，电子元件与材料，1995年6月第2期
24. Edward C. Jordan,Reference Data for Engineers: Radio, Electronics,Computers,and
Communications,7# Edition, Howard W. Sams&Co.,Inc., Inianapolis,1985
25. J. Prymak, New Tantalum Capacitors in Power Supply Applications, 1998 IEEE Industry Applications Society Annual Meeting,1998
26. A. Merz, R. Schropp, E. Dotterl, Synthesis 1995,795
27. Cletus J. Kaiser, THE CAPACITOR HANDBOOK, Second Edition, 1997
28. J. J. Svec, Capacitors from 0.01 ounce to 50 pounds, Ceram. Industry, pp, 32-34, Aug. 1979
29. J. Kammermaier and H. Hagedorn, chemical conversion processes during breakdowns in organic dielectrics, Siemens Forsch. U. Entwickl., vol. 2, pp. 26-33,1973.
30. 曲喜新，现代电容器，电子元件与材料，vol. 12，1993
31. R. D. Parker, Technological development of high energy density capacitors, Hughes Aircraft Rep., 1976
32. 朱树新、顾振军，导电高分子材料，上海科学技术文献出版社，1981
33. 布劳恩著，黄葆同译，聚合物合成和表征技术，科学出版社，1981
34. 张光敏，用导电聚合物电极的超电容器研究概况，电子元件与材料，vol. 18，1995
35. 陈国光，曹婉真，电解电容器，西安交通大学出版社，1993
36. 季锐，徐友龙，聚吡咯固体电解电容器，电子元件与材料，vol. 18，1999
37. 张光敏，阎康平，本征导电高分子材料的进展，电子元件与材料，vol. 18，1999
38. Warren L F, Walker J A, Anderson D P, A study of conducting polymer morphology, Electrochem Soc., 1989, 136(8):2286
39. Kuloh Y, Tsuchiya S, Fukuyama M, An aluminium solid electrolytic capacitor with an electroconducting-polymer,Synth Met, 1991
40. 闻立时，固体材料界面研究的物理基础，科学出版社，1991
41. 梁梦娥译，固体钽电容器的生产工艺，钽铌工业进展，1990，（3）：9－10
42. H. V. De Matos, Design of an internal fuse for a high-frequency solid tantalum capacitor, the 30th Annual Electronics Componets Conference, April 29-30,1980
43. 李荻，电化学原理，北京航空航天大学出版社，1989
44. Andrew Jones.Production and applications of tantalum powder.Int Refract Hard Met,1987,
6(3)：119～121
45. Cardonne S M.Tantalum and its alloys.Int J Refract Met Hard Mater,1995, 13(4)：187～194
46. J. R. Owen, Electrochemical Science and Technology of Polymer-1, Elsevier Applied Science, Chapter 3, p47
47. Hideyuku Masuda,Kyojj Kaeriyama,Synth met,1990,
48. John R Rcynolds,Paul A Poropatic,Rita L Toyooka.Macromolecules,1987(20):958
49. Menon R., in H.S. Nalwa, Handbook of Organic Conductive Molecules and Polymers, John Wiley&sons Ltd., Chichester, 1997, Chapter 2
50. 张声飞，高频固体钽电解电容器性能与钽粉，电子元件与材料，1999， 18（1）：39－41，47
51. Miinnstedt H., Properties of polypyrroles treated with base and acid, polymer, 1994(27):899-904
52. Takashi Saito, Development of high-power electric double layer capacitors,NEC 技报，1994，47（10）：91-97
53. A. J. Epstein, Y. Yang, Polymeric and Organic Electronic Merterias and Applications, MRS Bull. 1997,22(6), 13
54. C. A. Thomas, K. Zong, P. Schottland, Adv. Mater, 2000, 12, 222
55. M. D. Levi, Gofer, D. Aurbach, M. Lapkowski. E. Vieil, J. Serose, J. Electrochem. Soc. 147(2000)1096
56. I. Prymak, Replacing Mno2 with Condutive Polymer in Solid Tantalum Capacitors,CARTS '99 Program, The Components Technology Institute, Inc. March 1999
57. D. M. Welsh, A. Kumar, M. C. Morvant, J. R. Reynolds, Synth. Met. 1999, 102, 7629
58. A. N. Aleshin, S. R. Williams, A. J. Heeger, Synth. Met. 1998, 94, 173
59. A. C. Arias, M. Granstrom, D. S. Thomas, K. Petritsch, R. H. Friend, Phis. Rev. B: Condens.Matter. 1999, 60, 1854
60. T. Yamamoto, Bull. Chem. Soc. Jpn. 1999, 72, 621
61. 达马斯金，佩特里著，谷林瑛译，电化学动力学导论，科学出版社，1989
62. Seungwhan Chon and Woon-kie Paik, Adsorption Of Self-Assembling Sulfur Compounds Through Electrochemical Reactions: Effects Of Potential, Acid And Oxidizing Agents, Phys. Chem. Chem. Phys., 2001, 3, #16, 3405-3410
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