Polyanion copolymers for use with conducting polymers in solid electrolytic capacitors

Patent metadata

Field	Value
Publication number	US-10947376-B2
Application number	US-201916411915-A
Country	US
Kind code	B2
Filing date	May 14, 2019
Priority date	May 19, 2016
Publication date	Mar 16, 2021
Grant date	Mar 16, 2021

Abstract

A capacitor and a method of making a capacitor, is provided with improved reliability performance. The capacitor comprises an anode; a dielectric on the anode; and a cathode on the dielectric wherein the cathode comprises a conductive polymer and a polyanion wherein the polyanion is a copolymer comprising groups A, B and C represented by Formula A x B y C z as described herein.

First claim

The invention claimed is:

1. A 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:

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.

2. The slurry of claim 1 wherein said copolymer is a random copolymer.

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

4. The slurry 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.

5. The slurry of claim 4 where x represents 70-90%; y represents 10-30% and z represents 0-20% of the sum total of x+y+z.

6. The slurry 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.

7. The slurry of claim 6 where x represents 5-40%; y represents 60-95% and z represents 0-35% of the sum total of x+y+z.

8. A slurry comprising:
a conductive polymer; and
a polyanion wherein said polyanion is selected from the group consisting of:

wherein each x, y and z, independently taken together for each said polyanion, 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
each b is independently an integer from 1 to 10.

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

10. The slurry 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 slurry of claim 10 wherein X is S.

12. The slurry 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 6 , —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 slurry of claim 12 wherein n is 2.

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

Assignees

• Kemet Electronics Corp

Inventors

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

Classifications

• C07C309/28

  having sulfo groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton · CPC title

• Y02E60/10

  Energy storage using batteries · CPC title

• C07C309/30

  of six-membered aromatic rings substituted by alkyl groups · CPC title

• H01G9/0036

  Formation of the solid electrolyte layer · CPC title

• H01M4/137

  Electrodes based on electro-active polymers · CPC title