Use of mixtures of self-doped and foreign-doped conductive polymers in a capacitor

Patent metadata

Field	Value
Publication number	US-9875852-B2
Application number	US-201314431418-A
Country	US
Kind code	B2
Filing date	Sep 25, 2013
Priority date	Sep 27, 2012
Publication date	Jan 23, 2018
Grant date	Jan 23, 2018

Abstract

Described are methods for the production of a capacitor, comprising the process steps:
a) the provision of an electrode body ( 1 ) of an electrode material ( 2 ), wherein a dielectric ( 3 ) covers one surface ( 4 ) of this electrode material ( 2 ) at least partly under formation of an anode body ( 5 ); b) the introduction of a dispersion comprising a dispersing agent, a foreign-doped conductive polymer and counter-ions which are not covalently bonded to the foreign-doped conductive polymer into at least a part of the anode body ( 5 ); c) the at least partial removal of the dispersing agent under obtaining a solid electrolyte ( 6 ) in a capacitor body;

wherein a self-doped conductive polymer is additionally introduced into at least a part of the anode body ( 5 ). Also described are capacitors obtainable by these methods, capacitors, electronic circuits, the use of these capacitors and dispersions.

First claim

The invention claimed is:

1. A method for the production of a capacitor, the method comprising:
(a) providing an electrode body of an electrode material, wherein a dielectric covers one surface of the electrode material at least partly thereby forming an anode body;
(b) introducing a dispersion comprising a dispersing agent, a foreign-doped conductive polymer and counter-ions which are not covalently bonded to the foreign-doped conductive polymer into at least a part of the anode body;
(c) removing at least part of the dispersing agent thereby obtaining a solid electrolyte in a capacitor body of the capacitor;
wherein a self-doped conductive polymer is additionally introduced into at least a part of the anode body.

2. The method of claim 1 , wherein the foreign-doped conductive polymer is poly(3,4-ethylenedioxythiophene).

3. The method of claim 1 , wherein the counter-ions are present as polyanions.

4. The method of claim 3 , wherein the polyanion is a polystyrenesulphonic acid.

5. The method of claim 1 , wherein the dispersion comprises ionic complexes of poly(3,4-ethylenedioxythiophene) and polystyrenesulphonic acid.

6. The method of claim 1 , wherein the self-doped polythiophene comprises recurring units of the formula (I)

in which
X, Y are identical or different and denote O, S, N—R 1 ,
Z denotes —(CH 2 ) m —CR 2 R 3 —(CH 2 ) n —,
R 1 denotes aryl, C 1 -C 18 -alkyl or hydrogen,
R 2 denotes hydrogen or —(CH 2 )s-O—(CH 2 ) p —SO 3 − M + ,
R 3 denotes —(CH 2 )s-O—(CH 2 ) p —SO 3 − M + ,
M + denotes a cation,
m, n are identical or different and denote an integer from 0 to 3,
s denotes an integer from 0 to 10 and
p denotes an integer from 1 to 18.

7. The method of claim 6 , wherein
X, Y denote O,
Z denotes —(CH 2 ) m —CR 2 R 3 —(CH 2 ) n —,
R 2 denotes hydrogen or —(CH 2 )s-O—(CH 2 ) p —SO 3 − M + ,
R 3 denotes —(CH 2 )s-O—(CH 2 ) p —SO 3 − M + ,
M + denotes a cation,
m, n are identical or different and denote an integer from 0 to 3,
s denotes an integer from 0 to 10 and
p denotes an integer from 1 to 18.

8. The method of claim 6 , wherein
X, Y denote O,
Z denotes —(CH 2 )—CR 2 R 3 —(CH 2 ) n —,
R 2 denotes hydrogen,
R 3 denotes —(CH 2 )s-O—(CH 2 ) p —SO 3 − M + ,
M + denotes Na + or K + ,
n denotes 0 or 1,
s denotes 0 or 1 and
p denotes 3, 4 or 5.

9. The method of claim 1 , wherein the self-doped conductive polymer is introduced into at least a part of the anode body in the form of a solution or dispersion, before the dispersion is introduced into at least a part of the anode body according to process step (b).

10. The method of claim 1 , wherein the self-doped conductive polymer is introduced into at least a part of the anode body in the form of a solution or dispersion, after the dispersion is introduced into at least a part of the anode body according to process step (b).

11. The method of claim 1 , wherein the self-doped conductive polymer is contained in the dispersion which is introduced into at least a part of the anode body according to process step (b).

12. The method of claim 1 , wherein the self-doped conductive polymer is introduced into at least a part of the anode body in an amount such that the weight ratio of self-doped polymer to foreign-doped polymer in the solid electrolyte is in a range of from 100:1 to 1:100.

13. A capacitor obtainable by the method of claim 1 .

14. A capacitor comprising an electrode body of an electrode material, wherein a dielectric at least partly covers the surface of this electrode material and forms an anode body, wherein the anode body is at least partly coated with a solid electrolyte which comprises a foreign-doped conductive polymer, counter-ions which are not covalently bonded to the foreign-doped conductive polymer and a self-doped conductive polymer.

15. The capacitor of claim 14 , wherein
the foreign-doped conductive polymer is poly(3,4-ethylenedioxythiophene);
the counter-ions are present as polyanions;
the self-doped conductive polymer comprises recurring units of the formula (I)

in which
X, Y are identical or different and denote O, S, N—R 1 ,
Z denotes —(CH 2 ) m —CR 2 R 3 —(CH 2 ) n —,
R 1 denotes aryl, C 1 -C 18 -alkyl or hydrogen,
R 2 denotes hydrogen or —(CH 2 )s-O—(CH 2 ) p —SO 3 − M + ,
R 3 denotes —(CH 2 )s-O—(CH 2 ) p —SO 3 − M + ,
M + denotes a cation,
m, n are identical or different and denote an integer from 0 to 3,
s denotes an integer from 0 to 10 and
p denotes an integer from 1 to 18.

16. The capacitor of claim 14 , wherein the weight ratio of self-doped polymer to foreign-doped polymer in the solid electrolyte is in a range of from 100:1 to 1:100.

17. An electronic circuit comprising the capacitor of claim 13 .

18. A dispersion comprising a self-doped conductive polymer, a foreign-doped conductive polymer and counter-ions which are not covalently bonded to the foreign-doped conductive polymer.

19. The dispersion of claim 18 , wherein
the foreign-doped conductive polymer is poly(3,4-ethylenedioxythiophene);
the counter-ions are present as polyanions;
the self-doped conductive polymer comprises recurring units of the formula (I)

in which
X, Y are identical or different and denote O, S, N—R 1 ,
Z denotes —(CH 2 ) m —CR 2 R 3 —(CH 2 ) n —,
R 1 denotes aryl, C 1 -C 18 -alkyl or hydrogen,
R 2 denotes hydrogen or —(CH 2 )s-O—(CH 2 ) p —SO 3 − M + ,
R 3 denotes —(CH 2 )s-O—(CH 2 ) p —SO 3 − M + ,
M + denotes a cation,
m, n are identical or different and denote an integer from 0 to 3,
s denotes an integer from 0 to 10 and
p denotes an integer from 1 to 18.

Assignees

• Heraeus Precious Metals Gmbh

Inventors

• Asteman Katrin
• Intelmann Matthias
• Merker Udo
• Reuter Knud
• Sautter Armin

Classifications

• H01G9/0036

  Formation of the solid electrolyte layer · CPC title

• Y02E60/13

  Energy storage using capacitors · CPC title

• H01G11/48 Primary

  Conductive polymers · CPC title

• Y02T10/7022

  Cross-Sectional Technologies · mapped topic

• H01G11/56

  Solid electrolytes, e.g. gels; Additives therein · CPC title