# US 2018/0323015 A1 · Hybrid Capacitor and Method of Manufacturing a Capacitor

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- Number: US 2018/0323015 A1
- Document ID: US20180323015A1
- Status: Published application
- Kind: A1
- Application number: 16/038,609
- Filed: 2018-07-18
- Published: 2018-11-08
- Earliest claimed: 2015-02-13
- Assignees: Kemet Electronics Corporation
- Applicants: KEMET Electronics Corporation
- Inventors: Victor Andoralov; Débora Sá; Alexandre Guerreiro Fonseca; Antony P. Chacko; Yaru Shi; Philip M. Lessner
- Web page: https://patentgrep.com/patent/US20180323015A1

## CPC

- H01G 11/04: Hybrid capacitors
- H01G 11/26: characterised by their structure, e.g. multi-layered, porosity or surface features
- H01G 11/32: Carbon-based
- H01G 11/48: Conductive polymers
- H01G 11/52: Separators
- H01G 11/84: Processes for the manufacture of hybrid or EDL capacitors, or components thereof
- H01G 11/86: specially adapted for electrodes (carbonisation or activation of carbon for the manufacture of electrodes H01G11/34)
- H01G 11/58: Liquid electrolytes
- H01G 11/74: Terminals, e.g. extensions of current collectors
- Y02E 60/13: Energy storage using capacitors
- H01G: CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE (selection of specified materials as dielectric H01B3/00; capacitors having potential barriers H10D1/62, H10K10/10)
- Y02E: REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION

## Abstract

An improved capacitor is described wherein the capacitor comprises a working element. The working element comprises a first dielectric and an anode conductive polymer layer on the first dielectric. The working element also comprises a cathode and a separator between the anode conductive polymer layer and the cathode wherein the separator comprises a separator conductive polymer layer wherein at least one of the anode conductive polymer layer or the separator conductive polymer layer is crosslinked. The working element also comprises a liquid electrolyte.

## Claims

### Claim 1

A capacitor comprising:
a working element comprising:
an anode comprising a first dielectric and an anode conductive polymer layer on said first dielectric;
a cathode; and
a separator between said anode conductive polymer layer and said cathode wherein said separator comprises a separator conductive polymer layer wherein at least one of said anode conductive polymer layer or said separator conductive polymer layer is crosslinked; and
a liquid electrolyte.

### Claim 2 (depends on 1)

The capacitor of claim 1 wherein at least one of said anode, said separator or said cathode further comprises reactive functional groups.

### Claim 3 (depends on 2)

The capacitor of claim 2 wherein said separator comprises a reactive functional group of said reactive functional groups and said reactive functional group is reacted with a second reactive functional group of said reactive functional groups in said separator conductive polymer layer.

### Claim 4 (depends on 2)

The capacitor of claim 2 wherein a first reactive functional group of said reactive functional groups is crosslinked with a second reactive functional group of said reactive functional groups.

### Claim 5 (depends on 4)

The capacitor of claim 4 wherein said first reactive functional group and said second reactive functional group are in a common layer.

### Claim 6 (depends on 4)

The capacitor of claim 4 wherein said first reactive functional group and said second reactive functional group are in adjacent layers.

### Claim 7 (depends on 6)

The capacitor of claim 6 wherein one adjacent layer of said adjacent layers is said anode conductive polymer layer.

### Claim 8 (depends on 4)

The capacitor of claim 4 wherein one adjacent layer of said adjacent layers is said separator conductive polymer layer.

### Claim 9 (depends on 4)

The capacitor of claim 4 wherein said cathode comprises a cathode conductive layer and one adjacent layer of said adjacent layers is said cathode conductive polymer layer.

### Claim 10 (depends on 2)

The capacitor of claim 2 wherein at least one reactional functional group of said reactive functional groups is selected from the group consisting of epoxy, hydroxyl, amino, carboxylic, urethane, phosphate, silane, isocyanate, cyanate, nitro, peroxy, phosphio, phosphono, sulfonic acid, sulfone, nitro, acrylate, imide, amide, carboxyl, carboxylic anhydride, silane, oxazoline, (meth)acrylates, vinyls, maleates and maleimides itaconates, allyl alcohol esters, dicyclo-pentadiene-based unsaturations, unsaturated C12-C22 fatty esters or amides, carboxylic acid salts and quaternary ammonium salts.

### Claim 11 (depends on 10)

The capacitor of claim 10 wherein said reactive group is selected from the group consisting of epoxy, hydroxyl, amino, carboxylic, urethane, phosphate, silane, isocyanate, cyanate, nitro, peroxy, phosphio, phosphono, sulfonic acid, sulfone, nitro, acrylate, imide, amide, carboxyl, carboxylic anhydride, silane, oxazoline, (meth)acrylates, vinyls, maleates and maleimides itaconates, allyl alcohol esters, dicyclo-pentadiene-based unsaturations, unsaturated C12-C22 fatty esters or amides, carboxylic acid salts and quaternary ammonium salts.

### Claim 12 (depends on 1)

The capacitor of claim 1 wherein said liquid electrolyte is between said anode conductive polymer layer and said cathode.

### Claim 13 (depends on 12)

The capacitor of claim 12 comprising up to 50 wt % of said liquid electrolyte.

### Claim 14 (depends on 1)

The capacitor of claim 1 wherein said anode conductive polymer layer covers at least 80% of a surface area of said first dielectric or at least 80% of a surface area of said cathode comprises a cathode conductive polymer layer.

### Claim 15 (depends on 14)

The capacitor of claim 14 wherein said anode conductive polymer layer covers at least 90% of said surface area of said first dielectric or said cathode conductive polymer layer covers at least 90% of said surface area of said cathode.

### Claim 16 (depends on 1)

The capacitor of claim 1 comprising multiple anode leads or multiple cathode leads.

### Claim 17 (depends on 1)

The capacitor of claim 1 wherein at least one of said anode or said cathode comprises a valve metal.

### Claim 18 (depends on 17)

The capacitor of claim 17 wherein said valve metal is selected from the group consisting of tantalum, aluminum, niobium, titanium, zirconium, hafnium, alloys of these elements and a conductive oxide thereof.

### Claim 19 (depends on 18)

The capacitor of claim 18 wherein said valve metal is aluminum.

### Claim 20 (depends on 1)

The capacitor of claim 1 wherein at least one of said anode, said cathode or said separator has a conductive polymer coating of at least 0.1 mg/cm2 to no more than 10 mg/cm2.

### Claim 21 (depends on 1)

The capacitor of claim 1 having a rated voltage of at least 15 volts to no more than 250 volts.

### Claim 22 (depends on 1)

The capacitor of claim 1 wherein adjacent conductive polymer layers are in physical contact.

### Claim 23 (depends on 1)

The capacitor of claim 1 wherein at least one of said anode conductive polymer layer, said separator conductive polymer layer or a cathode conductive layer on said cathode is crosslinked with a crosslinker selected from the group consisting of silanes, epoxides, ethers, epoxy crosslinkers and hydrophilic coupling agents.

### Claim 24 (depends on 23)

The capacitor of claim 23 wherein said silanes are selected from the group consisting of glycidyl silane and organofunctional silane.

### Claim 25 (depends on 24)

The capacitor of claim 24 wherein said organofunctional silane is defined by the formula:
XR1Si(R3)3-n(R2)n
or
Y(Si(R3)3-n(R2)n)2
wherein X is an organic functional group;
Y is any organic moiety comprising reactive or nonreactive functional groups;
R1 is an aryl or alkyl (CH2)m wherein m is 0 to 14;
R2 is individually a hydrolysable functional group;
R3 is individually an alkyl functional group of 1-6 carbons; and
n is 1 to 3.

### Claim 26 (depends on 25)

The capacitor of claim 25 wherein said X is selected from the group consisting of amino, epoxy, anhydride, hydroxy, mercapto, sulfonate, carboxylate, phosphonate, halogen, vinyl, methacryloxy, ester and alkyl.

### Claim 27 (depends on 24)

The capacitor of claim 24 wherein said organofunctional silane is selected from the group consisting of 3-glycidoxypropyltrimethoxysilane, 3-aminopropytriethoxysilane, aminopropylsilanetriol, (triethoxysilyl)propylsuccinic anhydride, 3-mercaptopropyltrimethoxysilane, vinyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-trihydroxysilyl-1-propane sulfonic acid, octyltriethyoxysilane and bis(triethoxysilyl)octane.

### Claim 28 (depends on 24)

The capacitor of claim 24 wherein said organofunctional silane is defined by the formula:
wherein R1 is an alkyl of 1 to 14; and
each R2 is independently an alkyl or substituted alkyl of 1 to 6 carbons.

### Claim 29 (depends on 24)

The capacitor of claim 24 wherein said organofunctional silane is defined by the formula:

### Claim 30 (depends on 23)

The capacitor of claim 23 wherein said epoxy crosslinker is defined by the formula:
wherein the X is an alkyl or substituted alkyl of 0-14 carbons, an aryl or substituted aryl, an ethylene ether or substituted ethylene ether, polyethylene ether or substituted polyethylene ether with 2-20 ethylene ether groups.

### Claim 31 (depends on 23)

The capacitor of claim 23 wherein said epoxy crosslinker is selected from the group consisting of ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, 1,4-butanediol diglycidyl ether, pentylene glycol diglycidyl ether, hexylene glycol diglycidyl ether, cyclohexane dimethanol diglycidyl ether, resorcinol glycidyl ether, glycerol diglycidyl etherglycerol polyglycidyl ethers, diglycerol polyglycidyl ethers, trimethylolpropane polyglycidyl ethers, sorbitol diglycidyl ether, sorbitol polyglycidyl ethers, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, polytetramethylene glycol diglycidyl ether, di(2,3-epoxypropyl) ether, 1,3-butadiene diepoxide, 1,5-hexadiene diepoxide, 1,2,7,8-diepoxyoctane, 1,2,5,6-diepoxycyclooctane, 4-vinyl cyclohexene diepoxide, bisphenol A diglycidyl ether or maleimide-epoxy compounds.

### Claim 32 (depends on 23)

The capacitor of claim 23 wherein said ethers are glycidyl ether.

### Claim 33 (depends on 23)

The capacitor of claim 23 wherein said ethers are defined by the formula:
wherein R3 is an alkyl or substituted alkyl of 1-14 carbons, an ethylene ether, polyethylene ether with 2-20 ethylene ether groups; a alkyl substituted with a group selected from hydroxy,
or
—(CH2OH)xCH2OH wherein X is 1 to 14.

### Claim 34 (depends on 23)

The capacitor of claim 23 wherein said ether is selected from the group consisting of:
where n is an integer of 1 to 220;

### Claim 35

A method for forming a capacitor comprising:
forming a working element comprising:
forming an anode comprising a first dielectric and an anode conductive polymer layer on said first dielectric;
forming a cathode;
forming a separator wherein said separator comprises a separator conductive polymer layer;
forming a layered structure comprising said anode, said cathode and said separator wherein said separator is between said anode and said cathode;
forming a winding of said layered structure;
impregnating said winding with a liquid electrolyte; and
wherein at least one of said anode conductive polymer layer or said separator conductive polymer layer is crosslinked.

### Claim 36 (depends on 35)

The method for forming a capacitor of claim 35 wherein at least one of said anode conductive polymer layer or said separator conductive polymer layer is crosslinked prior to said forming of said winding.

### Claim 37 (depends on 35)

The method for forming a capacitor of claim 35 wherein at least one of said anode, said separator or said cathode further comprises reactive functional groups.

### Claim 38 (depends on 37)

The method for forming a capacitor of claim 37 wherein said separator comprises a reactive functional group of said reactive functional groups and said reactive functional group is reacted with a second reactive functional group of said reactive functional groups in said separator conductive polymer layer.

### Claim 39 (depends on 37)

The method for forming a capacitor of claim 37 wherein a first reactive functional group of said reactive functional groups is crosslinked with a second reactive functional group of said reactive functional groups.

### Claim 40 (depends on 39)

The method for forming a capacitor of claim 39 wherein said first reactive functional group and said second reactive functional group are in a common layer.

### Claim 41 (depends on 39)

The method for forming a capacitor of claim 39 wherein said first reactive functional group and said second reactive functional group are in adjacent layers.

### Claim 42 (depends on 41)

The method for forming a capacitor of claim 41 wherein one adjacent layer of said adjacent layers is said anode conductive polymer layer.

### Claim 43 (depends on 41)

The method for forming a capacitor of claim 41 wherein one adjacent layer of said adjacent layers is said separator conductive polymer layer.

### Claim 44 (depends on 41)

The method for forming a capacitor of claim 41 wherein said cathode comprises a cathode conductive layer and one adjacent layer of said adjacent layers is said cathode conductive polymer layer.

### Claim 45 (depends on 37)

The method for forming a capacitor of claim 37 wherein at least one reactional functional group of said reactive functional groups is selected from the group consisting of epoxy, hydroxyl, amino, carboxylic, urethane, phosphate, silane, isocyanate, cyanate, nitro, peroxy, phosphio, phosphono, sulfonic acid, sulfone, nitro, acrylate, imide, amide, carboxyl, carboxylic anhydride, silane, oxazoline, (meth)acrylates, vinyls, maleates and maleimides itaconates, allyl alcohol esters, dicyclo-pentadiene-based unsaturations, unsaturated C12-C22 fatty esters or amides, carboxylic acid salts and quaternary ammonium salts.

### Claim 46 (depends on 45)

The method for forming a capacitor of claim 45 wherein said reactive group is selected from the group consisting of epoxy, hydroxyl, amino, carboxylic, urethane, phosphate, silane, isocyanate, cyanate, nitro, peroxy, phosphio, phosphono, sulfonic acid, sulfone, nitro, acrylate, imide, amide, carboxyl, carboxylic anhydride, silane, oxazoline, (meth)acrylates, vinyls, maleates and maleimides itaconates, allyl alcohol esters, dicyclo-pentadiene-based unsaturations, unsaturated C12-C22 fatty esters or amides, carboxylic acid salts and quaternary ammonium salts.

### Claim 47 (depends on 35)

The method for forming a capacitor of claim 35 wherein said liquid electrolyte is between said anode conductive polymer layer and said cathode.

### Claim 48 (depends on 47)

The method for forming a capacitor of claim 47 comprising up to 50 wt % of said liquid electrolyte.

### Claim 49 (depends on 35)

The method for forming a capacitor of claim 35 wherein said anode conductive polymer layer covers at least 80% of a surface area of said first dielectric or at least 80% of a surface area of said cathode comprises a cathode conductive polymer layer.

### Claim 50 (depends on 49)

The method for forming a capacitor of claim 49 wherein said anode conductive polymer layer covers at least 90% of said surface area of said first dielectric or said cathode conductive polymer layer covers at least 90% of said surface area of said cathode.

### Claim 51 (depends on 35)

The method for forming a capacitor of claim 35 comprising multiple anode leads or multiple cathode leads.

### Claim 52 (depends on 35)

The method for forming a capacitor of claim 35 wherein at least one of said anode or said cathode comprises a valve metal.

### Claim 53 (depends on 52)

The method for forming a capacitor of claim 52 wherein said valve metal is selected from the group consisting of tantalum, aluminum, niobium, titanium, zirconium, hafnium, alloys of these elements and a conductive oxide thereof.

### Claim 54 (depends on 53)

The method for forming a capacitor of claim 53 wherein said valve metal is aluminum.

### Claim 55 (depends on 35)

The method for forming a capacitor of claim 35 wherein at least one of said anode, said cathode or said separator has a conductive polymer coating of at least 0.1 mg/cm2 to no more than 10 mg/cm2.

### Claim 56 (depends on 35)

The method for forming a capacitor of claim 35 having a rated voltage of at least 15 volts to no more than 250 volts.

### Claim 57 (depends on 35)

The method for forming a capacitor of claim 35 wherein adjacent conductive polymer layers are in physical contact.

### Claim 58 (depends on 35)

The method for forming a capacitor of claim 35 wherein at least one of said anode conductive polymer layer, said separator conductive polymer layer or a cathode conductive layer on said cathode is crosslinked with a crosslinker selected from the group consisting of silanes, epoxides, ethers, epoxy crosslinkers and hydrophilic coupling agents.

### Claim 59 (depends on 58)

The method for forming a capacitor of claim 58 wherein said silanes are selected from the group consisting of glycidyl silane and organofunctional silane.

### Claim 60 (depends on 59)

The method for forming a capacitor of claim 59 wherein said organofunctional silane is defined by the formula:
XR1Si(R3)3-n(R2)n
or
Y(Si(R3)3-n(R2)n)2
wherein X is an organic functional group;
Y is any organic moiety comprising reactive or nonreactive functional groups;
R1 is an aryl or alkyl (CH2)m wherein m is 0 to 14;
R2 is individually a hydrolysable functional group;
R3 is individually an alkyl functional group of 1-6 carbons; and
n is 1 to 3.

### Claim 61 (depends on 60)

The method for forming a capacitor of claim 60 wherein said X is selected from the group consisting of amino, epoxy, anhydride, hydroxy, mercapto, sulfonate, carboxylate, phosphonate, halogen, vinyl, methacryloxy, ester and alkyl.

### Claim 62 (depends on 59)

The method for forming a capacitor of claim 59 wherein said organofunctional silane is selected from the group consisting of 3-glycidoxypropyltrimethoxysilane, 3-aminopropytriethoxysilane, aminopropylsilanetriol, (triethoxysilyl)propylsuccinic anhydride, 3-mercaptopropyltrimethoxysilane, vinyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-trihydroxysilyl-1-propane sulfonic acid, octyltriethyoxysilane and bis(triethoxysilyl)octane.

### Claim 63 (depends on 59)

The method for forming a capacitor of claim 59 wherein said organofunctional silane is defined by the formula:
wherein R1 is an alkyl of 1 to 14; and
each R2 is independently an alkyl or substituted alkyl of 1 to 6 carbons.

### Claim 64 (depends on 59)

The method for forming a capacitor of claim 59 wherein said organofunctional silane is defined by the formula:

### Claim 65 (depends on 58)

The method for forming a capacitor of claim 58 wherein said epoxy crosslinker is defined by the formula:
wherein the X is an alkyl or substituted alkyl of 0-14 carbons, an aryl or substituted aryl, an ethylene ether or substituted ethylene ether, polyethylene ether or substituted polyethylene ether with 2-20 ethylene ether groups.

### Claim 66 (depends on 58)

The method for forming a capacitor of claim 58 wherein said epoxy crosslinker is selected from the group consisting of ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, 1,4-butanediol diglycidyl ether, pentylene glycol diglycidyl ether, hexylene glycol diglycidyl ether, cyclohexane dimethanol diglycidyl ether, resorcinol glycidyl ether, glycerol diglycidyl etherglycerol polyglycidyl ethers, diglycerol polyglycidyl ethers, trimethylolpropane polyglycidyl ethers, sorbitol diglycidyl ether, sorbitol polyglycidyl ethers, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, polytetramethylene glycol diglycidyl ether, di(2,3-epoxypropyl) ether, 1,3-butadiene diepoxide, 1,5-hexadiene diepoxide, 1,2,7,8-diepoxyoctane, 1,2,5,6-diepoxycyclooctane, 4-vinyl cyclohexene diepoxide, bisphenol A diglycidyl ether or maleimide-epoxy compounds.

### Claim 67 (depends on 58)

The method for forming a capacitor of claim 58 wherein said ethers are glycidyl ether.

### Claim 68 (depends on 58)

The method for forming a capacitor of claim 58 wherein said ethers are defined by the formula:
wherein R3 is an alkyl or substituted alkyl of 1-14 carbons, an ethylene ether, polyethylene ether with 2-20 ethylene ether groups; a alkyl substituted with a group selected from hydroxy,
or
—(CH2OH)xCH2OH wherein X is 1 to 14.

### Claim 69 (depends on 58)

The method for forming a capacitor of claim 58 wherein said ether is selected from the group consisting of:
where n is an integer of 1 to 220;