Process for producing electrolytic capacitors with a polymeric outer layer

• US 8,882,856 B2
• Filed: 02/04/2010
• Issued: 11/11/2014
• Est. Priority Date: 02/05/2009
• Status: Active Grant

• Current Assignee: Heraeus Epurio GmbH
• Original Assignee: Heraeus Precious Metals GmbH & Co. KG (Einhorn Verwaltungsgesellschaft mbH)
• Inventors: Wussow, Klaus, Merker, Udo, Intelmann, Matthias
• Primary Examiner(s): NIKMANESH, SEAHVOSH J
• Application Number:
  US13/148,086
• Publication Number:
  US 20120057275A1
• Time in Patent Office: 1,741 Days
• Field of Search: None
• US Class Current: 29/25.03
• CPC Class Codes: H01G 9/0036 Formation of the solid electrolyte layer
• CPC Class Codes: H01G 9/028 Organic semiconducting electrolytes, e.g. TCNQ
• CPC Class Codes: H01G 9/15 Solid electrolytic capacitors H01G11/00 takes precedence
• CPC Class Codes: Y02E 60/13 Energy storage using capacitors

Abstract

The invention relates to a process for producing electrolytic capacitors with low equivalent series resistance, low residual current and high thermal stability, which consist of a solid electrolyte and an outer layer comprising conjugated polymers, to electrolytic capacitors produced by this process and to the use of such electrolytic capacitors.

Claims

1. A process for producing an electrolytic capacitor, in which at least one crosslinker e) is applied to a capacitor body at least comprising

an electrode body of an electrode material and a dielectric which covers the surface of this electrode material, and

a solid electrolyte at least comprising an electrically conductive material which completely or partially covers the dielectric surface,

and, after applying the crosslinker e), at least one solution a′

) of a conjugated polymer b) or a dispersion a) of a conjugated polymer b) is applied, and a polymeric outer layer is formed by at least partly removing a solvent d′

) or a dispersant d),

the crosslinker e), after applying the solution a) or dispersion a), forms at least one polyvalent cation.

2. The process according to claim 1, wherein the solution or dispersion a) comprises at least one polymer with a mean molecular weight (weight average) greater than 1000.

3. The process according to claim 2, wherein the polymer having a mean molecular weight greater than 1000 comprises at least the conjugated polymer b) of the solution a′

) or dispersion a), a polymeric anion or a polymeric binder.

4. The process according to claim 3, wherein the polymeric anion is an anion of a polymeric carboxylic or sulfonic acid.

5. The process according to claim 1, wherein the crosslinker c) is applied from a solution or dispersion whose pH measured at 25°

C. is less than 10.

6. The process according to claim 5, wherein the solvent or dispersant of the solution or dispersion from which the crosslinker e) is applied comprises at least water or at least one organic solvent or dispersant.

7. The process according to claim 1, wherein the crosslinker e), after being applied to the capacitor body, is in the form of a salt or of a salt solution.

8. The process according to claim 7, wherein that the salt of the crosslinker e) is soluble in solution a′

) or dispersion a).

9. The process according to claim 1, wherein the crosslinker and the solution a′

) or dispersion a) are applied sequentially and repeatedly.

10. The process according to claim 1, wherein the solution a′

) or dispersion a) comprises, as the conjugated polymer b), at least one polythiophcne, polyaniline or polypyrrole which is optionally substituted.

11. The process according to claim 1, wherein the conductive material of the solid electrolyte is a conductive polymer.

12. The process according to claim 1, wherein the electrode material of the electrode body is a valve metal or a compound having electrical properties comparable to a valve metal.

13. The process according to claim 1, wherein the parts of the solution a′

) or the dispersion a) which, after application of the crosslinker e), were in contact with the capacitor body but do not remain thereon and are reused are in contact with one or more ion exchangers continuously or in phases.

14. A process for producing an electrolytic capacitor, in which at least one crosslinker e) is applied to a capacitor body at least comprising

an electrode body of an electrode material and a dielectric which covers the surface of this electrode material, and

a solid electrolyte at least comprising an electrically conductive material which completely or partially covers the dielectric surface, and,

after applying the crosslinker e), at least one solution a′

) of a conjugated polymer b) or a dispersion a) of a conjugated polymer b) is applied, and a polymeric outer layer is formed by at least partly removing a solvent d′

) or dispersant d),

wherein the crosslinker e) comprises

at least one diamine, triamine, oligoamine or polymeric amine or derivatives thereof,

at least one cation and additionally at least one amine group, or

at least one polyvalent cation.

15. The process according to claim 14 wherein the solution a′

) or dispersion a) comprises at least one polymer with a mean molecular weight (weight average) greater than 1000.

16. The process according to claim 15, wherein the polymer having a mean molecular weight greater than 1000 comprises at least the conjugated polymer b) of the solution a′

) or dispersion a), a polymeric anion or a polymeric binder.

17. The process according to claim 16, wherein the polymeric anion is an anion of a polymeric carboxylic or sulfonic acid.

18. The process according to claim 14, wherein the crosslinker e) is applied from a solution or dispersion whose pH measured at 25°

C. is less than 10.

19. The process according to claim 18, wherein the solvent or dispersant of the solution or dispersion from which the crosslinker c) is applied comprises at least water or at least one organic solvent or dispersant.

20. The process according to claim 14, wherein the crosslinker e), after being applied to the capacitor body, is in the form of a salt or of a salt solution.

21. The process according to claim 20, wherein the salt of the crosslinker e) is soluble in solution a′

) or dispersion a).

22. The process according to claim 14, wherein the crosslinker and the solution a′

) or dispersion a) are applied sequentially and repeatedly.

23. The process according to claim 14, wherein the solution a′

) or dispersion a) comprises, as the conjugated polymer b), at least one polythiophene, polyaniline or polypyrrole which is optionally substituted.

24. The process according to claim 14, wherein the conductive material of the solid electrolyte is a conductive polymer.

25. The process according to claim 14, wherein the electrode material of the electrode body is a valve metal or a compound having electrical properties comparable to a valve metal.

26. The process according to claim 14, wherein the parts of the solution a′

) or the dispersion a) which, after application of the crosslinker e), were in contact with the capacitor body but do not remain thereon and are reused are in contact with one or more ion exchangers continuously or in phases.

27. The process according to claim 14, wherein the crosslinker is diamine.