WO1994028563A1 - Supercapacitor and process for manufacturing same - Google Patents

Supercapacitor and process for manufacturing same Download PDF

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Publication number
WO1994028563A1
WO1994028563A1 PCT/CA1994/000275 CA9400275W WO9428563A1 WO 1994028563 A1 WO1994028563 A1 WO 1994028563A1 CA 9400275 W CA9400275 W CA 9400275W WO 9428563 A1 WO9428563 A1 WO 9428563A1
Authority
WO
WIPO (PCT)
Prior art keywords
current collector
container
carbon
electrode
collector substrate
Prior art date
Application number
PCT/CA1994/000275
Other languages
French (fr)
Inventor
Wojtek Halliop
Original Assignee
Alcan International, Ltd.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Alcan International, Ltd. filed Critical Alcan International, Ltd.
Priority to JP7500048A priority Critical patent/JPH09506209A/en
Priority to EP94915497A priority patent/EP0699337A1/en
Publication of WO1994028563A1 publication Critical patent/WO1994028563A1/en
Priority to US08/631,680 priority patent/US5649982A/en
Priority claimed from US08/631,680 external-priority patent/US5649982A/en

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Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/26—Electrodes characterised by their structure, e.g. multi-layered, porosity or surface features
    • H01G11/28—Electrodes characterised by their structure, e.g. multi-layered, porosity or surface features arranged or disposed on a current collector; Layers or phases between electrodes and current collectors, e.g. adhesives
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • H01G11/32—Carbon-based
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • H01G11/32—Carbon-based
    • H01G11/40—Fibres
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/13—Energy storage using capacitors

Definitions

  • This invention relates to an electrical double-layer capacitor and more particularly to an improved electrical double-layer supercapacitor and process for manufacturing same.
  • An electrolytic double-layer capacitor is comprised of a separate layer positioned between polarizable electrodes enclosed in a container including an electrolyte whereby when voltage is applied one electrode is negatively charged and the other electrode is positively charged, such as disclosed in U.S.P. 4,562,511 to Nishino et al . As disclosed therein, each electrode is in contact with a side of the container which is insulated from the other side thereof. A thus charged capacitor may be discharged over a period of time as a power source, and subsequently recharged again and again as a power source.
  • U.S.P. Nos. 4,597,028 and 4,626,964 are also illustrative of the prior art. In U.S.P. No.
  • a double layer capacitor including paired electrodes comprised of activated carbon fiber fabric impregnated with activated carbon particles.
  • Such capacitors are formed of costly materials of construction to achieve desired large surface areas on the fabric substrate. Additionally, attaching current collectors to the activated carbon fiber fabric requires plasma or flame spraying techniques limiting useful capacitor configurations.
  • An object of the present invention is to provide an improved double-layered supercapacitor.
  • Another object of the present invention is to provide an improved double-layered supercapacitor from less costly material of construction.
  • Still another object of the present invention is to provide an improved supercapacitor which may be readily manufactured without time consuming critical processing steps.
  • Yet another object of the present invention is to provide an improved process for manufacturing supercapacitors of bipolar configurations.
  • a still further object of the present invention is to provide supercapacitors of large surface areas.
  • a double-layer capacitor having electrodes formed of a current collector positioned against a nonwoven web of non-activated carbon fibers impregnated with carbon particles and positioned on either side of a porous layer within a container including a suitable electrolyte and having a conductor connected to each current collector of each electrode wherein the carbon fibers are of surface areas of less than 100 m 2 /g, preferably less than 5 m 2 /g.
  • a double-layer capacitor comprised of a housing member 12 defining a chamber 14 in which is positioned a separator member 16 disposed between electrode members, generally indicated as 18 and an electrolyte (not shown) .
  • Each electrode member 18 is a laminated structure comprised of a metal substrate 20 and reactive layers 22 laminated to the metal substrate 20, such as disclosed in U.S.P. No. 4,906,535 to Hoge.
  • the metal substrate 20 may be as metal mesh, foil or vapor or epoxy dependent layer and is connected to a conductor 24 to be attached to electrical elements as understood by one skilled in the art.
  • the metal substrate 20 is a current collector formed of a suitable metallic material, such as nickel, stainless steel and the like, formed for example by expanded metal techniques. Choice of the metallic material is a function of the electrolyte to be used, as more fully hereinafter discussed.
  • the reactive layer 22 is comprised of a nonwoven web of non-activated carbon fibers impregnated with a mixture of carbon particles and a nonfibrous polymeric substance for holding the carbon particles in the web.
  • the non-activated carbon fibers are of a length of from about 0.5 to 1.25 inches and a diameter of from about 5.0 to 15.O ⁇ .
  • the carbon fibers are of a surface area of less than 100 m 2 /g, preferably less than 5 m 2 /g.
  • the carbon content of such carbon fibers is preferably at least about 90 weight % exhibiting as resistance of less than about 20 ohms/cm 2 .
  • the nonwoven web of carbon fibers is formed into a thickness of from 5 to 50 mils exhibiting a pore volume of at least about 90%, to provide a high pick up of the impregnation mixture whether in suspension or in a coating format.
  • the impregnation mixture should increase the basic weight of the fibrous web of carbon fiber by about 20 to 200 g/m 2 as a function of solids content of the impregnation suspension or coating and pore volume of the fibrous web, and provide a front-to-back (F/B) electrical conductivity of less than about 1 ohm.
  • the impregnation mixture in the form of a suspension or coating, is comprised of carbon particles, generally in the form of carbon black, a nonfibrous polymeric material to bind the carbon particles to the web and a dispersion or mixing agents.
  • the carbon particles are sized, expressed as surface area (m 2 /g) , generally in excess of 1000, and preferably greater than about 1250, such as Black Pearls 2000, available from Cabot Corporation having a mean particle diameter of 0.015 ⁇ .
  • the nonfibrous polymeric materials include the polytetrafluoroethylenes, such as Teflon 0 T-30, a registered trademark of duPont.
  • the dispersion or mixing agents include the sodium salt of polymeric naphthalene sulfonic acid and those included with the polytetrafluoroethylene (PTFE) .
  • the nonwoven web of carbon fiber is impregnated by immersion, coating extrusion or the like, with the aqueous suspension of the impregnation mixture of the carbon particles, nonfibrous polymeric substance and other desired nonfibrous ingredients.
  • the impregnated conductive nonwoven web is preferably dried at a temperature of from about 150 to 400°F., (a temperature below the sintering temperature of the binder material, i.e., the PTFE) and a temperature high enough to ensure substantially complete moisture removal.
  • An electrode member is positioned on either side of a porous separator member 16 within the chamber 14 of the housing 12 and an electrolyte, such as potassium hydroxide (4M) is added to fill the void volume prior to encapsulating the members within the chamber 14.
  • the separator member 16 is formed of dielectric porous material, such as a sheet of hydrophilic polypropylene (Celgard, a registered trademark of Hoescht-Celanese) .
  • the electrolyte may be any suitable electrolyte for use in the generation of electricity in a battery configuration given the metal of the current collector.
  • Potassium hydroxide solutions may be used with a current collector in the form of nickel whereas sulfuric acid may necessitate the use of lead- based or tantalum-based current collector materials to withstand the corrosive effect of sulfuric acid.
  • Improved conductivity and an increase in voltage are achieved by use of sulfuric acid and lead-based current collector materials of construction. Still higher voltages may be achieved by use of organic-based electrolytes with aluminum-based current collectors.
  • a nonwoven web of carbon fibers (International Paper Company) is introduced into a continuous web machine to effect coating and drying operations.
  • the impregnated mixture (carbon/Teflon 0 is comprised of 36 gms. of an aqueous dispersion of Black Pearls 2000 (15% solids) and 0.9 gms. Teflon T-30 (60% 0 solids) applied at a solids content of 12.0%. Impregnation is effected to provide an add-on of 60 GSM.
  • the resulting impregnated layers and fine nickel mesh (Delker) precoated with an adhesive are passed through and over maintained at a temperature of from 200 to 300°F. and thence passed through laminating rolls at a nip pressure of 600 pounds per lineal inch at a temperature of 250°F. to form the electrode substrate.
  • Sheets of the electrode substrate connected to a conductor are positioned on either side of a slightly larger sheet of porous polypropylene to form a "Swiss roll" which is placed in a container of 9M KOH.
  • the total area of nonwoven is 680 cm 2 (i.e., 170 cm 2 per contacting surface between current collector and a layer of the nonwoven web) with a working volume below about 20 cm 3 .
  • the resulting capacitor assembly is repeatedly charged to 1 Volt and discharged to different resistors.
  • the apparent capacitance is 67 Farad at 20 ohm discharge and 81 Farad at 100 ohm discharge. Self discharge is nominal (78% of the charge retained after 60 hrs.).
  • a carbon black dispersion is prepared contained carbon black BP-2000, dispersant and Teflon 0 emulsion T-30 of total solids content of 14.7% by weight and solids Teflon 0 of 20 weight % on the amount of carbon.
  • a nonwoven web of carbon particles as in Example I is impregnated in the dispersion and dried to produce solids deposition by impregnation of 90 g/m 2 .
  • a nickel metal (M) mesh (Delco) is coated with an adhesive and after drying is laminated with impregnated nonwoven layers (CL) using hot rolling techniques to produce an electrode structure comprised of CL/CL/M/CL/CL. Adherence of the carbon layers is facilitated with solid adhesive powder.
  • the nickel mesh (M) layer is slightly larger to provide electrical contact. Two of such sheets (13.5 cm x 17.5 cm) are positioned on either side of a slightly larger sheet of porous polypropylene and positioned within a plastic container. 4M KOH is added and the container sealed with the nickel contacts extending from the container (total weight - 100 g.) to forma supercapacitor which when charged to 1.2 V and discharged at 10A shows a capacitance of about 240 Farads.

Abstract

There is disclosed a double-layer capacitor having electrodes formed of a current collector (20) positioned against a nonwoven web of non-activated carbon fibers (22) impregnated with carbon particles and positioned on either side of a porous layer (16) within a container (12) including a suitable electrolyte and having a conductor (24) connected to each current collector (20) of each electrode wherein the carbon fibers are of a surface area of less than 100 m2/g, preferably less than 5 m2/g.

Description

SUPERCAPACITOR AND PROCESS FOR MANUFACTURING SAME
BACKGROUND OF THE INVENTION
1. Field of the Invention
This invention relates to an electrical double-layer capacitor and more particularly to an improved electrical double-layer supercapacitor and process for manufacturing same.
2. Description of the Prior Art
An electrolytic double-layer capacitor is comprised of a separate layer positioned between polarizable electrodes enclosed in a container including an electrolyte whereby when voltage is applied one electrode is negatively charged and the other electrode is positively charged, such as disclosed in U.S.P. 4,562,511 to Nishino et al . As disclosed therein, each electrode is in contact with a side of the container which is insulated from the other side thereof. A thus charged capacitor may be discharged over a period of time as a power source, and subsequently recharged again and again as a power source. U.S.P. Nos. 4,597,028 and 4,626,964 are also illustrative of the prior art. In U.S.P. No. 4,626,964 to Azuma et al . , there is disclosed a double layer capacitor including paired electrodes comprised of activated carbon fiber fabric impregnated with activated carbon particles. Such capacitors are formed of costly materials of construction to achieve desired large surface areas on the fabric substrate. Additionally, attaching current collectors to the activated carbon fiber fabric requires plasma or flame spraying techniques limiting useful capacitor configurations. OBJECTS OF THE PRESENT INVENTION
An object of the present invention is to provide an improved double-layered supercapacitor.
Another object of the present invention is to provide an improved double-layered supercapacitor from less costly material of construction.
Still another object of the present invention is to provide an improved supercapacitor which may be readily manufactured without time consuming critical processing steps.
Yet another object of the present invention is to provide an improved process for manufacturing supercapacitors of bipolar configurations.
A still further object of the present invention is to provide supercapacitors of large surface areas. SUMMARY OF THE PRESENT INVENTION
These and other objects of the present invention are achieved by a double-layer capacitor having electrodes formed of a current collector positioned against a nonwoven web of non-activated carbon fibers impregnated with carbon particles and positioned on either side of a porous layer within a container including a suitable electrolyte and having a conductor connected to each current collector of each electrode wherein the carbon fibers are of surface areas of less than 100 m2/g, preferably less than 5 m2/g. BRIEF DESCRIPTION OF THE DRAWINGS
Other features and advantages of the present invention will become more readily apparent from the following detailed description when taken with the accompanying drawing of a schematic elevational view of a double-layer capacitor illustrating a preferred embodiment of the present invention. DETAILED DESCRIPTION OF THE PRESENT INVENTION
Referring now to the drawing, there is illustrated a double-layer capacitor, generally indicated as 10, comprised of a housing member 12 defining a chamber 14 in which is positioned a separator member 16 disposed between electrode members, generally indicated as 18 and an electrolyte (not shown) . Each electrode member 18 is a laminated structure comprised of a metal substrate 20 and reactive layers 22 laminated to the metal substrate 20, such as disclosed in U.S.P. No. 4,906,535 to Hoge. The metal substrate 20 may be as metal mesh, foil or vapor or epoxy dependent layer and is connected to a conductor 24 to be attached to electrical elements as understood by one skilled in the art.
The metal substrate 20 is a current collector formed of a suitable metallic material, such as nickel, stainless steel and the like, formed for example by expanded metal techniques. Choice of the metallic material is a function of the electrolyte to be used, as more fully hereinafter discussed.
The reactive layer 22 is comprised of a nonwoven web of non-activated carbon fibers impregnated with a mixture of carbon particles and a nonfibrous polymeric substance for holding the carbon particles in the web. The non-activated carbon fibers are of a length of from about 0.5 to 1.25 inches and a diameter of from about 5.0 to 15.Oμ. The carbon fibers are of a surface area of less than 100 m2/g, preferably less than 5 m2/g. The carbon content of such carbon fibers is preferably at least about 90 weight % exhibiting as resistance of less than about 20 ohms/cm2.
The nonwoven web of carbon fibers is formed into a thickness of from 5 to 50 mils exhibiting a pore volume of at least about 90%, to provide a high pick up of the impregnation mixture whether in suspension or in a coating format. The impregnation mixture should increase the basic weight of the fibrous web of carbon fiber by about 20 to 200 g/m2 as a function of solids content of the impregnation suspension or coating and pore volume of the fibrous web, and provide a front-to-back (F/B) electrical conductivity of less than about 1 ohm.
The impregnation mixture, in the form of a suspension or coating, is comprised of carbon particles, generally in the form of carbon black, a nonfibrous polymeric material to bind the carbon particles to the web and a dispersion or mixing agents. The carbon particles are sized, expressed as surface area (m2/g) , generally in excess of 1000, and preferably greater than about 1250, such as Black Pearls 2000, available from Cabot Corporation having a mean particle diameter of 0.015μ.
The nonfibrous polymeric materials include the polytetrafluoroethylenes,such as Teflon0 T-30, a registered trademark of duPont. The dispersion or mixing agents include the sodium salt of polymeric naphthalene sulfonic acid and those included with the polytetrafluoroethylene (PTFE) .
The nonwoven web of carbon fiber is impregnated by immersion, coating extrusion or the like, with the aqueous suspension of the impregnation mixture of the carbon particles, nonfibrous polymeric substance and other desired nonfibrous ingredients. The impregnated conductive nonwoven web is preferably dried at a temperature of from about 150 to 400°F., (a temperature below the sintering temperature of the binder material, i.e., the PTFE) and a temperature high enough to ensure substantially complete moisture removal.
An electrode member is positioned on either side of a porous separator member 16 within the chamber 14 of the housing 12 and an electrolyte, such as potassium hydroxide (4M) is added to fill the void volume prior to encapsulating the members within the chamber 14. The separator member 16 is formed of dielectric porous material, such as a sheet of hydrophilic polypropylene (Celgard, a registered trademark of Hoescht-Celanese) .
The electrolyte may be any suitable electrolyte for use in the generation of electricity in a battery configuration given the metal of the current collector. Potassium hydroxide solutions may be used with a current collector in the form of nickel whereas sulfuric acid may necessitate the use of lead- based or tantalum-based current collector materials to withstand the corrosive effect of sulfuric acid. Improved conductivity and an increase in voltage are achieved by use of sulfuric acid and lead-based current collector materials of construction. Still higher voltages may be achieved by use of organic-based electrolytes with aluminum-based current collectors. EXAMPLES OF THE INVENTION
The process of the present invention is set forth in the following specific examples which are intended to be merely illustrative and the present invention is intended not to be limited thereto.
EXAMPLE i
A nonwoven web of carbon fibers (International Paper Company) is introduced into a continuous web machine to effect coating and drying operations. The impregnated mixture (carbon/Teflon0 is comprised of 36 gms. of an aqueous dispersion of Black Pearls 2000 (15% solids) and 0.9 gms. Teflon T-30 (60% 0 solids) applied at a solids content of 12.0%. Impregnation is effected to provide an add-on of 60 GSM. The resulting impregnated layers and fine nickel mesh (Delker) precoated with an adhesive are passed through and over maintained at a temperature of from 200 to 300°F. and thence passed through laminating rolls at a nip pressure of 600 pounds per lineal inch at a temperature of 250°F. to form the electrode substrate.
Sheets of the electrode substrate connected to a conductor are positioned on either side of a slightly larger sheet of porous polypropylene to form a "Swiss roll" which is placed in a container of 9M KOH. The total area of nonwoven is 680 cm2 (i.e., 170 cm2 per contacting surface between current collector and a layer of the nonwoven web) with a working volume below about 20 cm3. The resulting capacitor assembly is repeatedly charged to 1 Volt and discharged to different resistors. The apparent capacitance is 67 Farad at 20 ohm discharge and 81 Farad at 100 ohm discharge. Self discharge is nominal (78% of the charge retained after 60 hrs.).
EXAMPLE II
A carbon black dispersion is prepared contained carbon black BP-2000, dispersant and Teflon0 emulsion T-30 of total solids content of 14.7% by weight and solids Teflon0 of 20 weight % on the amount of carbon. A nonwoven web of carbon particles as in Example I is impregnated in the dispersion and dried to produce solids deposition by impregnation of 90 g/m2. A nickel metal (M) mesh (Delco) is coated with an adhesive and after drying is laminated with impregnated nonwoven layers (CL) using hot rolling techniques to produce an electrode structure comprised of CL/CL/M/CL/CL. Adherence of the carbon layers is facilitated with solid adhesive powder.
The nickel mesh (M) layer is slightly larger to provide electrical contact. Two of such sheets (13.5 cm x 17.5 cm) are positioned on either side of a slightly larger sheet of porous polypropylene and positioned within a plastic container. 4M KOH is added and the container sealed with the nickel contacts extending from the container (total weight - 100 g.) to forma supercapacitor which when charged to 1.2 V and discharged at 10A shows a capacitance of about 240 Farads.
While the present invention has been described with reference to a double-layer capacitor, it will be understood that bipolar configurations are contemplated, e.g., M/CL/SL/CL/M/CL/S/CL/M/ wherein S is the porous separation layer.
In accordance with the present invention, it is believed that the surface area of the particulate carbon stores the charge compared to the charging of the nonwoven web of activated carbon fibers of the prior art. While the invention has been described in connection with an exemplary embodiment thereof, it will be understood that many modifications will be apparent to those of ordinary skill in the art; and that this application is intended to cover any adaptations or variations thereof. Therefore, it is manifestly intended that this invention be only limited by the claims and the equivalents thereof.

Claims

WHAT IS CLAIMED:
1. An improved capacitor comprising: a housing defining a chamber; a porous separator member disposed in said chamber of said housing; electrode member disposed on either side of said separator member, each electrode member comprised of a current-collecting substrate positioned against a nonwoven web of non-activated carbon fibers impregnated with carbon particles. a conductor connected to said current collector of each electrode member; and an electrolyte.
2. The improved capacitor as defined in Claim 1 wherein said surface area of said carbon fibers are less than 5 m2/g.
3. The improved capacitor as defined in Claim 1 wherein said electrode member is comprised of a nonwoven web of non- activated carbon fibers positioned on either side of said current collector substrate.
4. The improved capacitor as defined in Claim 1 wherein said electrode member is comprised of two (2) adhesively- connected carbon layers positioned on either side of said current collector substrate.
5. The improved capacitor as defined in Claim 1 and further including a plurality of electrodes disposed between a plurality of separator members within said container.
6. The process for preparing a supercapacitor, which comprises: impregnating a nonwoven web of non-activated carbon particles with a dispersion of carbon particles to form a carbon layer,- positioning said carbon layer against a current collector substrate to form an electrode,- positioning an electrode on either side of a porous separator plate within a container; adding an electrolyte to said container; and sealing said container.
7. The process as defined in Claim 6 and further including the step of forming a carbon layer on either side of said current collector substrate.
8. The process as defined in Claim 6 and further including the step of connecting a conductor to said current collecting substrate prior to sealing said container.
9. The process as defined in Claim 6 and further including a nonfibrous polymeric material in said dispersion prior to said impregnating step.
10. The process as defined in Claim 6 wherein said carbon layer is dried prior to positioning same against said current collector substrate.
11. The process as defined in Claim 6 wherein adhesive is applied to said current collector substrate prior to positioning said carbon layer against said current collector substrate.
PCT/CA1994/000275 1987-05-21 1994-05-19 Supercapacitor and process for manufacturing same WO1994028563A1 (en)

Priority Applications (3)

Application Number Priority Date Filing Date Title
JP7500048A JPH09506209A (en) 1993-05-21 1994-05-19 Improved supercapacitor and manufacturing method thereof
EP94915497A EP0699337A1 (en) 1993-05-21 1994-05-19 Supercapacitor and process for manufacturing same
US08/631,680 US5649982A (en) 1987-05-21 1996-04-10 Process for manufacturing super capacitor

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US08/065,987 1993-05-21
US08/065,987 US5581438A (en) 1993-05-21 1993-05-21 Supercapacitor having electrodes with non-activated carbon fibers
US08/631,680 US5649982A (en) 1987-05-21 1996-04-10 Process for manufacturing super capacitor

Publications (1)

Publication Number Publication Date
WO1994028563A1 true WO1994028563A1 (en) 1994-12-08

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US (1) US5581438A (en)
EP (1) EP0699337A1 (en)
JP (1) JPH09506209A (en)
CA (1) CA2161444A1 (en)
WO (1) WO1994028563A1 (en)

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JPH09506209A (en) 1997-06-17
US5581438A (en) 1996-12-03
CA2161444A1 (en) 1994-12-08

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