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