Formulation for use with conducting polymers in solid electrolytic capacitors

Patent metadata

Field	Value
Publication number	US-11396594-B2
Application number	US-202117167176-A
Country	US
Kind code	B2
Filing date	Feb 4, 2021
Priority date	May 19, 2016
Publication date	Jul 26, 2022
Grant date	Jul 26, 2022

Abstract

An improved formulation of conductive polymer is provided. The formulation comprises a conductive polymer and a polyanion wherein the polyanion is a copolymer comprising groups A, B and C represented the ratio of Formula A:AxByCz  Formula Awherein:A is polystyrenesulfonic acid or salt of polystyrenesulfonate;B and C separately represent polymerized units substituted by a group selected from:—C(O)OR6 wherein R6 is selected from the group consisting of:—(CHR17)b—R18. All other groups are defined. The conductive polymer has an average particle size of at least 1 nm to no more than 10 microns.

First claim

The invention claimed is:

1. A formulation comprising:
a conductive polymer; and
a polyanion wherein said polyanion is a copolymer comprising groups A, B and C represented the ratio of Formula A:
A x B y C z   Formula A

wherein:
A is polystyrenesulfonic acid or salt of polystyrenesulfonate;
B and C separately represent polymerized units substituted by a group selected from:
—C(O)OR 6 wherein R 6 is selected from the group consisting of:
—(CHR 17 ) b —R 18 wherein:
R 17 is selected from a hydrogen or an alkyl of 1 to 7 carbons;
b is an integer from 1 to 10; and
R 18 is selected from the group consisting of phosphate, acrylate, hydroxyl, epoxy, thiol, alkene, alkyne, azide and anhydride;
—(CHR 7 CH 2 O) b —R 8 wherein:
R 7 is selected from a hydrogen or an alkyl of 1 to 7 carbons;
b is an integer from 1 to the number sufficient to provide a molecular weight of up to 200,000 for the —CHR 7 CH 2 O-group; and
R 8 is selected from the group consisting of hydrogen, silane, phosphate, acrylate, an alkyl of 1 to 9 carbons optionally substituted with a functional group selected from the group consisting of hydroxyl carboxyl, amine, epoxy, silane, amide, phosphate, imide, thiol, alkene, alkyne, azide, acrylate and anhydride;

—C(O)—NHR 9 wherein:
R 9 is a hydrogen or an alkyl of 1 to 20 carbons optionally substituted with a functional group selected from the group consisting of hydroxyl, carboxyl, amine, epoxy, silane, amide, phosphate, imide, thiols, alkene, alkyne, azide, acrylate and anhydride;

x, y and z, taken together are sufficient to form a polyanion with a molecular weight of at least 100 to no more than 500,000 and y/x is 0.01 to 100; z is 0 to a ratio z/x of no more than 100; and
with the proviso that C is not same as B and z is not zero when B is substituted with a group selected from:
—C 6 H 4 —R 10 wherein:
R 10 is hydrogen or an alkyl of 1-30 carbon; and

wherein said conductive polymer has an average particle size of at least 1 nm to no more than 10 microns.

2. The formulation of claim 1 further comprising at least one additive selected from the group consisting of crosslinking agents, surface-active agents, polymeric binders, polyols, organic solvents, organo metallic compounds, work function modifiers, colloidal particles, steric stabilizers and combinations thereof.

3. The formulation of claim 1 wherein said copolymer is a random copolymer.

4. The formulation of claim 1 wherein when B or C is —(CHR 7 CH 2 ) b R 8 and R 8 is selected from hydrogen and methyl.

5. The formulation of claim 1 wherein x represents 50-99%, y represents 1-50% and z represents 0-49% of the sum total of x+y+z.

6. The formulation of claim 5 where x represents 70-90%; y represents 10-30% and z represents 0-20% of the sum total of x+y+z.

7. The formulation of claim 1 wherein x represents 1-40%, y represents 60-99% and z represents 0-39% of the sum total of x+y+z.

8. The formulation of claim 7 where x represents 5-40%; y represents 60-95% and z represents 0-35% of the sum total of x+y+z.

9. The formulation of claim 1 wherein said conductive polymer is selected from the group consisting of polyaniline, polypyrrole and polythiophene.

10. The formulation of claim 9 wherein said conductive polymer comprises repeating units of Formula 1:

wherein:
R 1 and R 2 independently represent linear or branched C 1 -C 16 alkyl or C 2 -C 18 alkoxyalkyl; or are C 3 -C 8 cycloalkyl, phenyl or benzyl which are unsubstituted or substituted by C 1 -C 6 alkyl, C 1 -C 6 alkoxy, halogen or OR 3 ; or R 1 and R 2 , taken together, are linear C 1 -C 6 alkylene which is unsubstituted or substituted by C 1 -C 6 alkyl, C 1 -C 6 alkoxy, halogen, C 3 -C 8 cycloalkyl, phenyl, benzyl, C 1 -C 4 alkylphenyl, C 1 -C 4 alkoxyphenyl, halophenyl, C 1 -C 4 alkylbenzyl, C 1 -C 4 alkoxybenzyl or halobenzyl, 5-, 6-, or 7-membered heterocyclic structure containing two oxygen elements; R 3 represents hydrogen, linear or branched C 1 -C 16 alkyl or C 2 -C 18 alkoxyalkyl; or are C 3 -C 8 cycloalkyl, phenyl or benzyl which are unsubstituted or substituted by C 1 -C 6 alkyl; and
X is S, N or O.

11. The formulation of claim 10 wherein X is S.

12. The formulation of claim 10 wherein R 1 and R 2 are taken together to represent —O—(CHR 4 ) n —O— wherein:
n is an integer from 1 to 5;
R 4 is independently selected from hydrogen; a linear or branched C 1 to C 18 alkyl radical C 5 to C 12 cycloalkyl radical, C 6 to C 14 aryl radical C 7 to C 18 aralkyl radical or C 1 to C 4 hydroxyalkyl radical optionally substituted with a functional group selected from carboxylic acid, hydroxyl, amine, substituted amines, alkene, thiol, alkyne, azide, sulfate, sulfonate, sulfonic acid, imide, amide, epoxy, anhydride, silane, and phosphate; hydroxyl radical; or R 4 is selected from —(CHR 5 ) a —R 16 ; —O(CHR 5 ) a R 16 ; —OCH 2 (CHR 5 ) a R 16 ; —OCH 2 (CH 2 CHR 5 O) a R 16 ; or
R 4 is a functional group selected from the group consisting of hydroxyl, carboxyl, amine, epoxy, amide, imide, anhydride, hydromethyl, carboxylic acid, hydroxymethyl, alkene, thiol, alkyne, azide, sulfate, sulfonic acid, benzene sulfonic acid, SO 3 M, anhydride, epoxy, silane, acrylate and phosphate;
R 5 is H or alkyl chain of 1 to 5 carbons optionally substituted with a functional groups selected from carboxylic acid, hydroxyl, amine, alkene, thiol, alkyne, azide, epoxy, silane, acrylate, anhydride and phosphate;
R 16 is H or SO 3 M or an alkyl chain of 1 to 5 carbons optionally substituted with a functional groups selected from carboxylic acid, hydroxyl, amine, substituted amines, alkene, thiol, alkyne, azide, amide, imide, sulfate, SO 3 M, amide, epoxy, anhydride, silane, acrylate and phosphate;
a is from 0 to 10; and
M is a H or cation selected from ammonia, sodium or potassium.

13. The formulation of claim 12 wherein n is 2.

14. The formulation of claim 12 wherein said conductive polymer is 3,4-polyethylene dioxythiophene.

15. A formulation comprising:
a conductive polymer; and
a polyanion wherein said polyanion is a copolymer comprising groups A, B and C represented the ratio of Formula A:
A x B y C z   Formula A

wherein:
A is polystyrenesulfonic acid or salt of polystyrenesulfonate;
B and C separately represent polymerized units substituted by a group selected from:
—C(O)OR 6 wherein R 6 is selected from the group consisting of:
—(CHR 17 ) b —R 18 wherein:
R 17 is selected from a hydrogen or an alkyl of 1 to 7 carbons;
b is an integer from 1 to 10; and
R 18 is selected from the group consisting of phosphate, acrylate, hydroxyl, epoxy, thiol, alkene, alkyne, azide and anhydride;
—(CHR 7 CH 2 O) b —R 8 wherein:
R 7 is selected from a hydrogen or an alkyl of 1 to 7 carbons;
b is an integer from 1 to the number sufficient to provide a molecular weight of up to 200,000 for the —CHR 7 CH 2 O-group; and
R 8 is selected from the group consisting of hydrogen, silane, phosphate, acrylate, an alkyl of 1 to 9 carbons optionally substituted with a functional group selected from the group consisting of hydroxyl carboxyl, amine, epoxy, silane, amide, phosphate, imide, thiol, alkene, alkyne, azide, acrylate and anhydride;

—C(O)—NHR 9 wherein:
R 9 is a hydrogen or an alkyl of 1 to 20 carbons optionally substituted with a functional group selected from the group consisting of hydroxyl, carboxyl, amine, epoxy, silane, amide, phosphate, imide, thiols, alkene, alkyne, azide, a

Assignees

• Kemet Electronics Corp

Inventors

• Bunha Ajaykumar
• Chacko Antony P
• Shi Yaru
• Chen Qingping
• Lessner Philip M

Classifications

• H01M4/137

  Electrodes based on electro-active polymers · CPC title

• C08F212/30

  Sulfur · CPC title

• H01M4/136

  Electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy · CPC title

• H01G9/04

  Electrodes {or formation of dielectric layers thereon} · CPC title

• H01G9/028

  Organic semiconducting electrolytes, e.g. TCNQ · CPC title