Polyanion Copolymers for Use with Conducting Polymers in Solid Electrolytic Capacitors

Patent metadata

Field	Value
Publication number	US-2021198469-A1
Application number	US-202117167176-A
Country	US
Kind code	A1
Filing date	Feb 4, 2021
Priority date	May 19, 2016
Publication date	Jul 1, 2021
Grant date	—

Abstract

An improved slurry of conductive polymer is provided. The slurry 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

1 . A formulation slurry 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 and 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 preferably 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 preferably 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, phos

Assignees

• Kemet Electronics Corp

Inventors

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

Classifications

• C08F212/30

  Sulfur · CPC title

• H01G9/042

  characterised by the material (H01G11/22 takes precedence) · CPC title

• Y02E60/10

  Energy storage using batteries · CPC title

• C08L25/18 Primary

  Homopolymers or copolymers of aromatic monomers containing elements other than carbon and hydrogen · CPC title

• H01G9/0036 Primary

  Formation of the solid electrolyte layer · CPC title