Layer compositions with improved electrical parameters comprising PEDOT/PSS and a stabilizer

Patent metadata

Field	Value
Publication number	US-11600449-B2
Application number	US-201816017165-A
Country	US
Kind code	B2
Filing date	Jun 25, 2018
Priority date	Oct 1, 2010
Publication date	Mar 7, 2023
Grant date	Mar 7, 2023

Abstract

The present invention relates to a process for the production of a layer composition (10) with an electrically conductive layer (11), comprising the process steps:a) provision of a substrate (12) with a substrate surface (13);b) formation of a polymer layer (14) comprising an electrically conductive polymer (15) on at least a part of the substrate surface (13);c) application of a liquid stabilizer phase, comprising a stabilizer and a liquid phase, to the polymer layer (14) from process step b), wherein the stabilizer phase comprises less than 0.2 wt. %, based on the stabilizer phase, of the electrically conductive polymer,wherein the stabilizer is an aromatic compound with at least two OH groups, and a layer composition (10) and uses thereof.

First claim

The invention claimed is:

1. A capacitor which comprises a layer composition, the layer composition comprising
S1. a substrate with a substrate surface, wherein the substrate comprises an electrode body of an electrode material, the surface of this electrode material being at least partly covered by a dielectric;
S2. a polymer layer following the substrate surface and serving as a layer of a solid electrolyte, the polymer layer comprising an electrically conductive polymer;
S3. a stabilizer layer following the polymer layer, comprising a stabilizer which is an aromatic compound with at least two OH groups.

2. The capacitor according to claim 1 , wherein the electrically conductive polymer comprises at least one polythiophene, polypyrrole or polyaniline or one of their derivatives or a mixture of at least two of these.

3. The capacitor according to claim 1 , wherein the electrically conductive polymer comprises at least one polythiophene with recurring units chosen from the group consisting of the general formula (I), the general formula (II) or the general formula (III) or a combination of at least two of these

wherein
A represents an optionally substituted C 1 -C 5 -alkylene radical,
R represents a linear or branched, optionally substituted C 1 -C 18 -alkyl radical, an optionally substituted C 5 -C 12 -cycloalkyl radical, an optionally substituted C 6 -C 14 -aryl radical, an optionally substituted C 7 -C 18 -aralkyl radical, an optionally substituted C 1 -C 4 -hydroxyalkyl radical or a hydroxyl radical,
x represents an integer from 0 to 8 and

in the case where several radicals R are bonded to A, these can be identical or different.

4. The capacitor according to claim 1 , wherein the electrically conductive polymer is poly(3,4-ethylenedioxythiophene).

5. The capacitor according to claim 1 , wherein the electrically conductive polymer additionally comprises at least one polymeric anion.

6. The capacitor according to claim 5 , wherein the polymeric anion is polystyrenesulphonic acid.

7. The capacitor according to claim 1 , wherein the electrode material is a valve metal or NbO.

8. The capacitor according to claim 1 , wherein the electrode material is aluminum.

9. The capacitor according to claim 1 , wherein the stabilizer is at least one compound selected from the group consisting of 1,3-dihydroxybenzene, 1,4-dihydroxybenzene, 2,3-dihydroxybenzene, dihydroxyalkylbenzene, trihydroxybenzene, dihydroxynaphthalene and derivatives thereof.

10. The capacitor according to claim 9 , wherein the stabilizer is a gallic acid ester.

11. The capacitor according to claim 10 , wherein the gallic acid ester is a tannine.

12. The capacitor according to claim 1 , wherein the electrically conductive polymer has an electrical conductivity of at least 0.1 S cm −1 .

13. A process for the production of a layer composition with an electrically conductive layer, comprising the process steps:
a) providing a substrate with a substrate surface;
b) forming a polymer layer comprising an electrically conductive polymer on at least a part of the substrate surface;
c) application of a liquid stabilizer phase, comprising a stabilizer and a liquid phase, onto the polymer layer from process step b), wherein the stabilizer phase comprises less than 0.2 wt. %, based on the stabilizer phase, of the electrically conductive polymer,

wherein the stabilizer is an aromatic compound with at least two OH groups,
wherein the layer composition is a capacitor and wherein the substrate comprises an electrode body of an electrode material, and a dielectric at least partly covers a surface of this electrode material.

14. The process according to claim 13 , wherein after application of the stabilizer phase in process step c) the liquid phase is at least partly removed in a further process step d).

15. The process according to claim 13 , wherein the stabilizer is at least one compound selected from the group consisting of 1,3-dihydroxybenzene, 1,4-dihydroxybenzene, 2,3-dihydroxybenzene, dihydroxyalkylbenzene, trihydroxybenzene, dihydroxynaphthalene and derivatives thereof.

16. The process according to claim 15 , wherein the stabilizer is a gallic acid ester.

17. The process according to claim 16 , wherein the gallic acid ester is a tannine.

18. The process according to claim 13 , wherein the liquid phase in process step c) comprises water or an alcohol or a mixture thereof.

19. The process according to claim 13 , wherein the stabilizer phase in process step c) comprises the stabilizer in a concentration in a range of from 0.1 to 50 wt. %, based on the stabilizer phase.

20. The process according to claim 13 , wherein the electrically conductive polymer comprises at least one polythiophene, polypyrrole or polyaniline or one of their derivatives or a mixture of at least two of these.

21. The process according to claim 13 , wherein the electrically conductive polymer comprises at least one polythiophene with recurring units chosen from the group consisting of the general formula (I), the general formula (II) or the general formula (III) or a combination of at least two of these

wherein
A represents an optionally substituted C 1 -C 5 -alkylene radical,
R represents a linear or branched, optionally substituted C 1 -C 18 -alkyl radical, an optionally substituted C 5 -C 12 -cycloalkyl radical, an optionally substituted C 6 -C 14 -aryl radical, an optionally substituted C 7 -C 18 -aralkyl radical, an optionally substituted C 1 -C 4 -hydroxyalkyl radical or a hydroxyl radical,
x represents an integer from 0 to 8 and

in the case where several radicals R are bonded to A, these can be identical or different.

22. The process according to claim 21 , wherein the electrically conductive polymer is poly(3,4-ethylenedioxythiophene).

23. The process according to claim 13 , wherein the electrically conductive polymer additionally comprises at least one polymeric anion.

24. The process according to claim 23 , wherein the polymeric anion is polystyrenesulphonic acid.

25. The process according to claim 13 , wherein the formation of a polymer layer in process step b) is carried out by application of a dispersion containing particles of an electrically conductive polymer and a dispersing agent and the at least partial removal of this dispersing agent.

26. The process according to claim 25 , wherein the particles of the dispersion in process step b) have a size (d 50 ) of 70 nm and less.

27. The process according to claim 26 , wherein the dispersion containing particles of an electrically conductive polymer in process step b) comprises organic solvents, water or mixtures of an organic solvent and water as the dispersing agent.

28. The process according to claim 13 , wherein the electrode material is a valve metal or NbO.

29. The process according to claim 13 , wherein the electrode material is aluminum.

30. The process according to claim 13 , wherein the electrically conductive polymer has an electrical conductivity of at least 0.1 S cm −1 .

Assignees

• Heraeus Deutschland Gmbh & Co Kg
• Heraeus Precious Metals Gmbh

Inventors

• Ishikawa Akio
• Merker Udo
• Wussow Klaus
• Asteman Katrin

Classifications

• C09D165/00

  Coating compositions based on macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain (C09D107/00 - C09D157/00, C09D161/00 take precedence); Coating compositions based on derivatives of such polymers · CPC title

• H01G9/025 Primary

  Solid electrolytes (H01G11/54 takes precedence) · CPC title

• C09D5/24

  Electrically-conducting paints {(conductive materials H01B1/00)} · CPC title

• H01G9/00

  Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture · CPC title

• Y02E60/13

  Energy storage using capacitors · CPC title