Solid electrolytic capacitor containing polyaniline

1. A solid electrolytic capacitor comprising a capacitor element, wherein the capacitor element comprises:

a sintered porous anode body;

a dielectric that overlies the anode body;

a pre-coat that overlies the dielectric, wherein the pre-coat contains an intrinsically conductive polymer with repeating thiophene units and an organometallic compound; and

a solid electrolyte that overlies the dielectric, wherein the solid electrolyte includes a conductive polymer having repeating units derived from an aniline monomer having the following general formula (I):

wherein,

R 5 and R 6 are independently hydrogen, alkyl, alkenyl, aryl, alkoxy, aryloxy, alkylthioalkyl, alkylaryl, arylalkyl, haloalkyl, amino, epoxy, silane, siloxane, alcohol, benzyl, carboxylate, ether, ether carboxylate, ether sulfonate, ester sulfonate, urethane, or a combination thereof.

2. The solid electrolytic capacitor of claim 1 , wherein R 5 and R 6 are hydrogen.

3. The solid electrolytic capacitor of claim 1 , wherein the solid electrolyte further includes a proton donor.

4. The solid electrolytic capacitor of claim 3 , wherein the proton donor is an organic acid compound.

5. The solid electrolytic capacitor of claim 4 , wherein the organic acid compound has the following general formula (VIII):

wherein,

m is an integer from 1 to 10;

M is hydrogen, an organic free radical group, an inorganic free radical group, or a combination thereof;

X is an anion;

R 4 , R 5 , and R 6 are independently hydrogen, a hydrocarbon group or a R 9 3 Si— group, wherein R 9 are each independently hydrogen or a hydrocarbon group; and

R 7 and R 8 are independently a hydrocarbon group or —(R 10 O) q —R″, wherein q is an integer equal to 1 or more, R 10 is a hydrocarbon group or a silylene group, R 11 is hydrogen, hydrocarbon group, or R 12 3 Si—, wherein R 12 are each independently a hydrocarbon group.

6. The solid electrolytic capacitor of claim 5 , wherein M is an alkali metal.

7. The solid electrolytic capacitor of claim 5 , wherein X is SO 3 .

8. The solid electrolytic capacitor of claim 5 , wherein R 4 , R 5 , and R 6 are each hydrogen.

9. The solid electrolytic capacitor of claim 5 , wherein R 7 and R 8 are independently a straight-chain or branched C 1 -C 24 alkyl.

10. The solid electrolytic capacitor of claim 1 , wherein the solid electrolyte further includes an external dopant.

11. The solid electrolytic capacitor of claim 10 , wherein the external dopant is a hydroxphenolic compound having one of the following structures (IX), (X), (XI), or (XII):

wherein,

n is an integer of 0 to 5; and

R is independently a C 1 -C 20 alkyl, alkenyl, cycloalkyl, aryl, alkylaryl, or a combination thereof.

12. The solid electrolytic capacitor of claim 10 , wherein the external dopant includes methoxyphenol, ethoxyphenol, propoxyphenol, isopropoxyphenol, butyloxyphenol, isobutyloxyphenol, tert-butyloxyphenol, hydroxynaphthalene, cresol, ethylphenol, propylphenol, butylphenol, pentylphenol,1,6-naphthanediol, 2,6-naphthalenediol, 2,7-naphthalenediol, or a combination thereof.

13. The solid electrolytic capacitor of claim 1 , wherein the solid electrolyte further includes a heat stabilizer.

14. The solid electrolytic capacitor of claim 13 , wherein the heat stabilizer includes an organic acid.

15. The solid electrolytic capacitor of claim 1 , wherein the solid electrolyte contains at least one inner layer that includes the conductive polymer.

16. The solid electrolytic capacitor of claim 1 , wherein the solid electrolyte contains at least outer layer.

17. The solid electrolytic capacitor of claim 16 , wherein the outer layer is formed from particles that contain a thiophene polymer.

18. The solid electrolytic capacitor of claim 1 , wherein the intrinsically conductive polymer contains repeating units of the following formula (V):

wherein,

R is (CH 2 ) a —O—(CH 2 ) b -L, where L is a bond or HC([CH 2 ] c H);

a is from 0 to 10;

b is from 1 to 18;

c is from 0 to 10;

M is an anion; and

X is a cation.

19. The solid electrolytic capacitor of claim 1 , wherein the intrinsically conductive polymer contains repeating thiophene units having the following general formula (VII):

wherein,

a is from 0 to 10;

b is from 1 to 18;

R 5 is an optionally substituted C 1 -C 6 linear or branched alkyl group or a halogen atom; and

X is a hydrogen atom, an alkali metal, NH(R 1 ) 3 , or HNC 5 H 5 , wherein R 1 is each independently a hydrogen atom or an optionally substituted C 1 -C 6 alkyl group.

20. The solid electrolytic capacitor of claim 19 , wherein a is 1 and b is 3 or 4.

21. The solid electrolytic capacitor of claim 19 , wherein R 5 is methyl.

22. The solid electrolytic capacitor of claim 19 , wherein X is an alkali metal.

23. The solid electrolytic capacitor of claim 1 , wherein the repeating thiophene units, are formed from sodium 3-[(2,3-dihydrothieno[3,4-b][1,4]dioxin-2−yl)methoxy]-1-methyl-1-propanesulfonate, sodium 3-[(2,3-dihydrothieno[3,4-b]-[1,4]dioxin-2−yl)methoxy]-1-ethyl-I-propanesulfonate, sodium 3-[(2,3-dihydrothieno[3,4-b]-[1,4]dioxin-2−yl)methoxy]-1-propyl-1-propane-sulfonate, sodium 3-[(2,3-dihydrothieno[3,4-b]-[1,4]dioxin-2−yl)methoxy]-I-butyl-I-propanesulfonate, sodium 3-[(2,3-dihydrothieno[3,4-b]-[1,4]dioxin-2−yl)methoxy]-1-pentyl-1-propane-sulfonate, sodium 3-[(2,3-dihydrothieno[3,4-b]-[1,4]dioxin-2−yl)methoxy]-1-hexyl-1-propanesulfonate, sodium 3-[(2,3-dihydrothieno[3,4-b]-[1,4]dioxin-2−yl)methoxy]-1-isopropyl-I-propanesulfonate, sodium 3-[(2,3-dihydrothieno[3,4-b]-[1,4]dioxin-2−yl)methoxy]-1-isobutyl-I-propanesulfonate, sodium 3-[(2,3-dihydrothieno[3,4-b]-[1,4]dioxin-2−yl)methoxy]-1-isopentyl-1-propanesulfonate, sodium 3-[(2,3-dihydrothieno[3,4-b]-[1,4]dioxin-2−yl)methoxy]-1-fluoro-I-propanesulfonate, potassium 3-[(2,3-dihydrothieno[3,4-b]-[1,4]dioxin-2−yl)methoxy]-1-methyl-I-propanesulfonate, 3-[(2,3-dihydrothieno[3,4-b]-[1,4]dioxin-2−yl)methoxy]-1-methyl-1-propanesulfonic acid, ammonium 3-[(2,3-dihydrothieno[3,4-b]-[1,4]dioxin-2−yl)methoxy]-1-methyl-1-propane-sulfonate, triethylammonium 3-[(2,3-dihydrothieno[3,4-b]-[1,4]dioxin-2−yl)methoxy]-i-methyl-1-propanesulfonate, or a combination thereof.

24. The solid electrolytic capacitor of claim 1 , wherein the intrinsically conductive polymer has a specific conductivity of about 20 S/cm or more.

25. The solid electrolytic capacitor of claim 1 , wherein the organometallic compound is a monoaminofunctional silane having the following general formula (II):

wherein,

R 1 , R 2 , and R 3 are independently alkyl, alkenyl, aryl, heteroaryl, cycloalkyl, heterocyclyl, halo, haloalkyl, or hydroxyalkyl;

R 4 and R 5 are independently hydrogen, alkyl, independently alkyl, alkenyl, aryl, heteroaryl, cycloalkyl, heterocyclyl, halo, haloalkyl, hydroxyalkyl, or alternatively N, R 4 , and R 5 together with one or more additional atoms form a ring structure; and

Z is an organic group.

26. The solid electrolytic capacitor of claim 1 , wherein the monoaminofunctional silane is a primary amine.

27. The solid electrolytic capacitor of claim 26 , wherein the primary amine is 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 4-aminobutyltriethoxysilane, m-aminophenyltrimethoxysilane, p-aminophenyltrimethoxysilane, aminophenyltrimethoxysilane, 3-aminopropyltris(methoxy-ethoxy)silane, 11-aminoundecyltriethoxysilane, 2(4-pyridylethyl)triethoxysilane, 2-(trimethoxysilylethyl)pyridine, N-(3-trimethoxysilylpropyl)pyrrole, 3-(m-aminophenoxypropyltrimethoxysilane, aminopropylsilanetriol, 3-aminopropylmethyldiethoxysilane, 3-aminopropyldiisopropylethoxysilane, 3-aminopropyldimethylethoxysilane, or a combination thereof.

28. The solid electrolytic capacitor of claim 1 , wherein the pre-coat contains a first layer that contains the organometallic compound and that overlies the dielectric, and further wherein the pre-coat contains a second layer that contains the intrinsically conductive polymer and that overlies the first layer.

29. The solid electrolytic capacitor of claim 1 , further comprising an external polymer coating that overlies the solid electrolyte and includes conductive polymer particles.

30. The solid electrolytic capacitor of claim 29 , wherein the conductive polymer particles in the external polymer coating include a thiophene polymer.

31. The solid electrolytic capacitor of claim 29 , wherein the external polymer coating further comprises a crosslinking agent.

32. The solid electrolytic capacitor of claim 1 , wherein the anode body includes tantalum.

33. The solid electrolytic capacitor of claim 1 , wherein the capacitor element further comprises a cathode coating that contains a metal particle layer that overlies the solid electrolyte, wherein the metal particle layer includes a plurality of conductive metal particles.

34. The solid electrolytic capacitor of claim 1 , wherein the capacitor exhibits a recovery of about 50% or more.

35. The solid electrolytic capacitor of claim 1 , wherein the capacitor exhibits a recovery of about 70% or more.

36. The solid electrolytic capacitor of claim 1 , wherein the capacitor exhibits a recovery of about 80% or more.