CA2389727A1 - Capacitor development - Google Patents
Capacitor development Download PDFInfo
- Publication number
- CA2389727A1 CA2389727A1 CA002389727A CA2389727A CA2389727A1 CA 2389727 A1 CA2389727 A1 CA 2389727A1 CA 002389727 A CA002389727 A CA 002389727A CA 2389727 A CA2389727 A CA 2389727A CA 2389727 A1 CA2389727 A1 CA 2389727A1
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- Prior art keywords
- current collector
- invention according
- electrolyte
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- Prior art date
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- Abandoned
Links
- 239000003990 capacitor Substances 0.000 title claims description 29
- 238000011161 development Methods 0.000 title description 2
- 239000003792 electrolyte Substances 0.000 claims abstract description 30
- 239000007772 electrode material Substances 0.000 claims abstract description 24
- 230000000694 effects Effects 0.000 claims abstract description 16
- 239000002904 solvent Substances 0.000 claims abstract description 9
- 230000000087 stabilizing effect Effects 0.000 claims abstract description 8
- 150000003839 salts Chemical class 0.000 claims abstract description 7
- 230000001965 increasing effect Effects 0.000 claims abstract description 6
- 239000000010 aprotic solvent Substances 0.000 claims abstract description 4
- 239000000463 material Substances 0.000 claims description 13
- -1 spirolactones Chemical class 0.000 claims description 13
- 239000000126 substance Substances 0.000 claims description 10
- 229910052782 aluminium Inorganic materials 0.000 claims description 9
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 8
- 239000004094 surface-active agent Substances 0.000 claims description 8
- 150000008064 anhydrides Chemical class 0.000 claims description 3
- 239000003575 carbonaceous material Substances 0.000 claims description 3
- 230000035515 penetration Effects 0.000 claims description 3
- 150000004649 carbonic acid derivatives Chemical class 0.000 claims description 2
- 239000000654 additive Substances 0.000 abstract description 4
- 230000000996 additive effect Effects 0.000 abstract description 3
- 239000000080 wetting agent Substances 0.000 abstract 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 17
- 229910052799 carbon Inorganic materials 0.000 description 11
- 229920000049 Carbon (fiber) Polymers 0.000 description 9
- 239000004698 Polyethylene Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 7
- 239000006184 cosolvent Substances 0.000 description 6
- 239000004917 carbon fiber Substances 0.000 description 5
- 239000011888 foil Substances 0.000 description 5
- 229920000573 polyethylene Polymers 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 230000014759 maintenance of location Effects 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- 239000002000 Electrolyte additive Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 239000004020 conductor Substances 0.000 description 3
- 239000004744 fabric Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 239000003989 dielectric material Substances 0.000 description 2
- 239000011263 electroactive material Substances 0.000 description 2
- 239000008151 electrolyte solution Substances 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- UWBICEKKOYXZRG-WNHSNXHDSA-N (8r,9s,10r,13s,14s,17r)-10,13-dimethylspiro[2,6,7,8,9,11,12,14,15,16-decahydro-1h-cyclopenta[a]phenanthrene-17,5'-oxolane]-2',3-dione Chemical compound C([C@H]1[C@H]2[C@@H]([C@]3(CCC(=O)C=C3CC2)C)CC[C@@]11C)C[C@@]11CCC(=O)O1 UWBICEKKOYXZRG-WNHSNXHDSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 125000005210 alkyl ammonium group Chemical group 0.000 description 1
- 230000003466 anti-cipated effect Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 239000012943 hotmelt Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000011255 nonaqueous electrolyte Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000013341 scale-up Methods 0.000 description 1
- GCLGEJMYGQKIIW-UHFFFAOYSA-H sodium hexametaphosphate Chemical compound [Na]OP1(=O)OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])O1 GCLGEJMYGQKIIW-UHFFFAOYSA-H 0.000 description 1
- 239000011877 solvent mixture Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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
- H01G11/54—Electrolytes
- H01G11/58—Liquid electrolytes
- H01G11/60—Liquid electrolytes characterised by the solvent
-
- 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
- H01G11/54—Electrolytes
- H01G11/58—Liquid electrolytes
- H01G11/64—Liquid electrolytes characterised by additives
-
- 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
- H01G11/66—Current collectors
- H01G11/68—Current collectors characterised by their material
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M14/00—Electrochemical current or voltage generators not provided for in groups H01M6/00 - H01M12/00; Manufacture thereof
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/029—Bipolar electrodes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/64—Carriers or collectors
- H01M4/66—Selection of materials
- H01M4/663—Selection of materials containing carbon or carbonaceous materials as conductive part, e.g. graphite, carbon fibres
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M6/00—Primary cells; Manufacture thereof
- H01M6/14—Cells with non-aqueous electrolyte
- H01M6/16—Cells with non-aqueous electrolyte with organic electrolyte
- H01M6/162—Cells with non-aqueous electrolyte with organic electrolyte characterised by the electrolyte
- H01M6/168—Cells with non-aqueous electrolyte with organic electrolyte characterised by the electrolyte by additives
-
- 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
- Y02E60/10—Energy storage using batteries
-
- 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
Abstract
The present invention is directed to super or ultracapacitors. The ultracapacitor includes at least one bipolar electrode plate (12), an electrolyte (14) and a separator (16). The bipolar electrode plate (12) includes a current collector and an electrode material associated with the current collector. The electrolyte (14), which is positioned between adjacently oriented bipolar plates, includes an organic aprotic solvent and a salt. A stabilizing additive is associated with the electrolyte for stabilizing electrochemical activity between the solvent and at least one of the current collector and the electrode material. In addition, the electroly te may further include a wetting agent for increasing wettability of the electrode.
Description
TITLE OF THE INVENTION
CAPACITOR DEVELOPMENT
BACKGROUND OF THE INVENTION
Field of the Invention The present invention is directed to capacitors, and, more particularly, super, or ultracapacitors of the type utilizing bipolar electrode plates.
CAPACITOR DEVELOPMENT
BACKGROUND OF THE INVENTION
Field of the Invention The present invention is directed to capacitors, and, more particularly, super, or ultracapacitors of the type utilizing bipolar electrode plates.
2. Background Art Ultracapacitors, also known as super-capacitors, are well known in the art.
These ultracapacitors store energy electrostatically by polarizing an electrolyte solution.
Although the ultracapacitor is indeed an electrochemical device, there are no chemical 1 ~ reactions involved in its energy storage mechanism. The historical background and operational characteristics and conventional structures can be found in Ultracapacitors For Portable Electronics, Xavier Andrieu, The Big Little Book of Capacitors, Chapter 1 ~, Pgs. 521-547.
An ultracapacitor is typically constructed from two or more bipolar electrode plates separated from each other by electrolyte and a separator positioned within the electrolyte. The bipolar plates include a current collector comprised of an electronically conductive material, and, an electrode material associated with the current collector. The components of the capacitor are operatively secured and encased in a surrounding housing. The housing exposes electrical leads for connection with an item to receive the 2~ electrical benefit of the capacitor.
In a conventional dielectric capacitor, energy is stored in the form of a separated electrical charge, wherein the greater the area for storing the charge, and the closer the separated charge, the greater the capacitance. In such a capacitor, the area for storing the charge is obtained from plates of a flat conductive material and the charged plates are separated with a dielectric material.
In an ultracapacitor, the area for storing a charge is conventionally obtained from a porous carbon material. The porous structure of the carbon allows the chargeable area to be much greater than the flat conductive plates of dielectric capacitors.
Furthermore, an ultracapacitor's charge separation distance is typically determined by the size of the ions in the associated electrolyte, which are attracted to the charged electrode. Such a charge separation is substantially smaller than that which can be obtained using conventional dielectric materials. Accordingly, the combination of the relatively large surface area and the small charge separation results in superior capacitance relative to conventional capacitors.
SUMMARY OF THE INVENTION
The present invention is directed to a capacitor, and, more particularly, a super capacitor comprising at least one bipolar electrode plate each comprising a current collector and an electrode material associated with the current collector; an electrolyte comprising an organic aprotic solvent, a salt and means for stabilizing electrochemical activity between the solvent and at least one of the current collector and/or the electrode material; and, a separator positionable in the electrolyte so as to prevent physical contact between adjacently positioned electrode plates.
In a preferred embodiment of the invention, the electrolyte further includes means for increasing wettability of the electrode. The wettability increasing means may comprise a surfactant.
In such a preferred embodiment, the surfactant is selected from the group comprising nonionic fluoro-alkanes.
In another preferred embodiment of the invention, the electrochemical activity stabilizing means comprises a chemical component which can be reduced in place of the solvent. In such a preferred embodiment, the electrochemical activity stabilizing means is selected from the group comprising carbonates, such as vinylene carbonate, spirolactones, anhydrides and oligomers.
In yet another preferred embodiment of the invention, the current collector is selected from the group of materials having low electrical resistance, substantial impermeability to electrolyte penetration, chemical compatibility with at least one of the electrode material and the electrolyte, and, chemical stability.
In one such preferred embodiment, the current collector includes carbon material, while in another preferred embodiment the current collector comprises aluminum.
In still another preferred embodiment of the invention, the capacitor further includes a substantially inert frame structure. In such a preferred embodiment, the frame structure includes end plates having a current collector associated therewith.
Ultracapacitors fabricated in accordance with the above, and, more particularly, with carbonlgraphite fiber electroactive materials, a non-aqueous electrolyte, and polymer coated aluminum bipolar current collector plates have demonstrated capacitance of up to 0.95 F/cm', energy of up to 1 mAh/cm'. These capacitors have been assembled using commercially available components. Materials and components have been selected in relation with known and anticipated manufacturing constraints and in order to enable manufacturing scale-up of the capacitor.
BRIEF DESCRIPTION OF THE DRAWINGS
Fig. 1 of the drawings is a schematic cross-sectional view of the present invention;
Fig. 2 of the drawings is a perspective view of a bipolar plate of the present invention;
Fig. 3 of the drawings is a cross-sectional view of Fig. 2, taken along lines 3-3, and showing the current collector material and the electrode material of the present invention;
Fig. 4 of the drawings is a graphical representation of the AC impedance of the present invention;
Fig. 5 of the drawings is a graphical representation of the normalized AC
impedance of the present invention;
Fig. 6 of the drawings is a graphical representation of the initial charge and discharge voltage-time profile for the ultracapacitor of the present invention;
Fig. 7 of the drawings is a graphical representation of the discharge voltage-time profile for the ultracapacitor of the present invention;
Fig. 8 of the drawings is a graphical representation of the discharge capacity retention as a function of cycle number;
Fig. 9 of the drawings is a graphical representation of the initial power performance, as illustrated by the voltage-time profile, for the capacitor of the present invention;
Fig. 10 of the drawings is a graphical representation of the normalized voltage-time profile during power testing of the capacitor of the present invention;
Fig. 11 of the drawings is a graphical representation of the Total Delivered Energy as of function of time during discharge at different power rates;
Fig. 12 of the drawings is a graphical representation of comparative AC
impedance;
Fig. 13 of the drawings is a graphical representation of an initial charge and discharge voltage-time profile;
Fig. 14 of the drawings is a graphical representation of comparative AC
impedance;
profile;
Fig. 1 ~ of the drawings is a graphical representation of comparative voltage-time Fig. 16 of the drawings is a graphical representation of comparative discharge voltage-time profile;
Fig. 17 of the drawings is a graphical representation of initial power performance;
Fig. 18 of the drawings is a graphical representation of normalized voltage-time profile during power testing;
Fig. 19 of the drawings is a graphical representation of the Total Delivered Energy as function of time during discharge at different power rates;
Fig. 20 of the drawings is a graphical representation of the effect of the electrolyte additive on the charge behavior of an ultracapacitor;
Fig. 21 of the drawings is a graphical representation of the effect of the maximum charge voltage;
Fig. 22 of the drawings is a graphical representation of the effect of co-solvent based electrolyte on the total cell resistance;
Fig. 23 of the drawings is a graphical representation of the effect of co-solvent based electrolyte on the total cell resistance; and Fig. 24 of the drawings is a graphical representation of initial charge-discharge voltage-time profile.
BEST MODE FOR PRACTICING THE INVENTION
While this invention is susceptible of embodiment in many different forms, there is shown in the drawings and will herein be described in detail, several preferred embodiments with the understanding that the present disclosure is to be considered an exemplification of the principles of the invention and is not intended to limit the invention to the embodiments so illustrated.
A schematic cross-sectional representation of ultracapacitor 10 is shown in Fig. 1 as comprising bipolar electrode plates 12, electrolyte 14, separators 16, housing 18, housing end plates 19, 19' and exposed current collector leads 20, 22, positioned through corresponding end plates. As can be seen, the separators are positioned in between adjacently positioned bipolar electrode plates, and, within the electrolyte, so as to prevent inadvertent contact between the bipolar plates. Although an ultracapacitor having five bipolar electrode plates is shown in Fig. l, it will be readily understood to those having ordinary skill in the art that any number of desired plates are contemplated by the present invention.
A bipolar electrode plate 12, of the type shown in Fig. l, is shown in Fig. 2 as comprising current collector 24 (Fig. 3) and electrode material 26 (see also Fig. 3) associated with the current collector. The combination of the current collector 24 and electrode material 26 are secured to and surrounded by frame structure 28.
Frame structure 28 is constructed from a substantially inert, non-electronically conducting material such as polyethylene and/or polypropylene. Alternatively, glass fiber filled polyethylene having a low temperature induced deformation and a low melting temperature may also be utilized. It is also contemplated that the frame structure be fabricated from other materials, such as low-density non-linear polyethylene and/or polypropylene. The frame structures can be manufactured through conventional techniques such as die-cutting, injection molding and even extrusion. The housing 18 (Fig. 1) can also be made out of the same material as the frame structure for the bipolar electrode plates. The end plates 19, 19' can further be fabricated from glass reinforced polyethylene sheets, and the associated end plate current collectors can be fabricated from the same material as the current collector itself, or for example, expended copper mesh or aluminum.
Current collector 24 is fabricated from materials having low electrical resistance, impermeability to electrolyte penetration and permeation, chemical compatibility, and electrochemical stability. A preferred material is polyethylene coated aluminum foil, commercially available under the trade name COER-Xal from a company called Rexam Graphics of South Hadley, Massachusetts. It has been observed that the use of such material provides several advantageous features. Specifically:
- aluminum foil provides absolute separation of electrolyte in the bipolar electrode construction;
- the PE coating onto the aluminum foil provides for additional mechanical and chemical stability to the aluminum foil;
- the PE coating onto the aluminum foil provides a "hot-melt" adhesive characteristic to the current collector, thus enhancing the adhesion of the carbon electrode onto the current collector; and - the COER-Xal provides good electrical conductivity and is available in fairly thin configurations (75 um Al, 25 um PE on each side).
As an alternative to the above, it is also contemplated that other materials, such as a polyethylene-carbon paper (25 um) and a polyethylene-carbon composite material can also be used.
With respect to electrode material 26, such material can be fabricated from conventional types of electrode materials presently available for the fabrication of super, ultracapacitors. One example of acceptable electrode material, and generally the most frequently described, is based on the utilization of a high surface area activated carbon powder. The surface area of the carbon is generally greater than 1,500 mZ/g.
These carbons generally have a total pore volume of 1 ml/g, and an average pore size of 20 A.
in order to fabricate an electrode material using these carbons, the selected carbon powder must be mixed with an appropriate "binder" and than applied onto a current collector to which the carbon powder must adhere.
A second acceptable type of carbon electrode material is based on activated carbon fibers, generally available in the form of woven and or non-woven felts, fabrics, foams, or webs. Carbon fibers having similar surface area than the ones measured for the activated carbons are available commercially. The use of carbon fiber webs simplifies the electrode assembly process by eliminating the need of compounding the activated carbon powder with a binder and by eliminating the need to apply, generally via a solvent coating process, the compounded carbon powder onto a current collector. It is believed that the main difference between the carbon powders and the carbon fibers reside in the trade off between the energy storage capacity of the carbon electrode and its ease of processing.
Electrolyte 14 as shown in Fig. 1 is comprised of an orUanic aprotic solvent, a salt, a stabilizer and a surfactant. The solvent can comprise conventionally known materials, such as the ones described by Dr. Ue In J. Electrochem. Soc. 141, 1 1 ( 1994) 2989-2996. For example only, propylene carbonate ("PC") can be used. Although PC
l 5 has proven to be a good solvent, it has a high viscosity (n = 2.5 cp) and consequently has a less than optimum conductivity. Accordingly, solvent mixtures have also been considered and tested. Acetonitrile (n=0.3 cp) and y-buryrolacrone (n=l .7 cp) have been initially selected as a co-solvent to PC.
The salt used in the electrolyte fornmlation comprises tetra ethylene ammonium tetra fluoroborate. However, other salts, such as fluorinated alkyl ammoniums, among several other conventional salts, are likewise contemplated for use.
Inasmuch as the electrochemical stability of organic aprotic electrolytes in contact with carbon powder/fiber anodes is of concern to the capacitor industry, the present invention addresses such a concern by utilizing an additive/chemical component that can preferentially be reduced in place of the solvent. For example, in a preferred embodiment, the additive may comprise a carbonate (vinylene carbonate), a spriolactone.
an anhydride and/or an oligomer.
In order to increase the wettability of the carbon electrode by the electrolyte, surfactants are added to the electrolyte solution. These surfactants are generally selected to be nonionic fluoro-alkanes (SaiNippon Ink F-142d, F177 and 3M FC-171 and FC
170C are examples).
In support of the advantageous benefits from the ultracapacitors constructed in accordance with the above, numerous analyses were performed and graphically depicted in Figs. 4 - 24, wherein the additives (stabilizers and surfactants) were used in combination with conventional electrode materials (i.e. TSW2, TSW3 carbon fiber electrode material, commercially available from a company called Toyobo in Japan, and, Satin based electrodes from a company called Calgon, located in the United Kingdom).
Further information regarding the analyses can be found in corresponding U.S.
Provisional Patent Application Serial No. 60/165,865, filed November 16, 1999, from which the present application depends, the entirety of which is incorporated herein by reference. In particular, and with respect to the graphs:
Fig. 4 of the drawings is a graphical representation of the AC impedance of the present invention based on TSW2 carbon fiber electrodes, as measured.
Fig. 5 of the drawings is a graphical representation of the normalized AC
impedance of the present invention based on TSW2, illustrating the effect of adhesion between the current collector and the electroactive material. Better adhesion provides for lower internal resistance.
Fig. 6 of the drawings is a graphical representation of the initial charge and discharge voltage-time profile for the ultracapacitor assembled using the TSW2 based electrodes. Although, some differences in charge time are observed, discharge time is almost constant for all systems. This behavior is further illustrated in Figure 7.
Fig. 7 of the drawings is a graphical representation of the discharge voltage-time profile for the ultracapacitor assembled using the TSW2 based electrodes.
Fig. 8 of the drawings is a graphical representation of the discharge capacity retention as a function of cycle number as illustrated for the initial 5 cycles for the capacitor assembled using the TSW2 based electrodes.
Fig. 9 of the drawings is a graphical representation of the initial power performance, as illustrated by the voltage-time profile, for the capacitor assembled using the YSW2 based electrodes.
Fig. 10 of the drawings is a graphical representation of the normalized voltage-time profile during power testing of the capacitor assembled using the TSW2 based electrodes. These results indicate a good capacity retention for these electrodes. This is further illustrated in Figure 11.
Fig. 11 of the drawings is a graphical representation of the Total Delivered Energy as of function of time during discharge at different power rates.
Fig. 12 of the drawings is a graphical representation of the comparative AC
impedance between the TSW2 and TSW3 electrode material considered by the manufacturer as "equivalents."
Fig. 13 of the drawings is a graphical representation of the initial charge and discharge voltage-time profile for the TSW2 and TSW3 electrode material.
Fig. 14 of the drawings is a graphical representation of the comparative AC
impedance between the TSW2 and TSW3 electrode material and the Satin electrode material.
1 ~ Fig. 15 of the drawings is a graphical representation of the comparative voltage-time profile between capacitor assembled using the TSW2 carbon paper and the Satin carbon fabric.
Fig. 16 of the drawings is a graphical representation of the comparative discharge voltage-time profile between capacitor assembled using the TSW2 carbon paper and the Satin carbon fabric.
Fig. 17 of the drawings is a graphical representation of the initial power performance, as illustrated by the voltage-time profile, for the ultracapacitor assembled using the Satin carbon fabric.
Fig. 18 of the drawings is a graphical representation of the normalized voltage-time profile during power testing of the ultracapacitor assembled using the Satin based electrodes. These results indicate a good capacity retention for these electrodes. This is further illustrated in Figure 19.
Fig. 19 of the drawings is a graphical representation of the Total Delivered Energy as function of time during discharge at different power rates.
Fig. 20 of the drawings is a graphical representation of the effect of the electrolyte additive on the charge behavior of an ultracapacitor. Capacitor #1 10103 has no electrolyte additive and shows long self decomposition behavior during the initial charge, while capacitor #102902 shows a normal charge behavior.
Fig. 21 of the drawings is a graphical representation of the effect of the maximum charge voltage.
Fig. 22 of the drawings is a graphical representation of the effect of co-solvent based electrolyte on the total cell resistance, for the ultracapacitor assembled using TSW3 electrode material.
Fig. 23 of the drawin~'s is a graphical representation of the effect of co-solvent based electrolyte on the total cell resistance, for the ultracapacitor assembled using Satin fabric. Tests performed using a 1:1 mixture of propylene carbonate and acetronitrile indicate that although the electrolyte conductivity is increased, as expected, the electrochemical stability of the electrolyte is reduced. This may be due in part to water contamination and to the presence of other residual impurities.
Fig. 24 of the drawings is a graphical representation of the initial charge-discharge voltage-time profile for capacitor assembled using the Satin fabric and co-solvent based electrolyte (#101501).
The foregoing description and drawings merely explain and illustrate the invention and the invention is not limited thereto except insofar as the appended claims are so limited as those skilled in the art who have the disclosure before them will be able to make modifications and variations therein without departing from the scope of the invention.
These ultracapacitors store energy electrostatically by polarizing an electrolyte solution.
Although the ultracapacitor is indeed an electrochemical device, there are no chemical 1 ~ reactions involved in its energy storage mechanism. The historical background and operational characteristics and conventional structures can be found in Ultracapacitors For Portable Electronics, Xavier Andrieu, The Big Little Book of Capacitors, Chapter 1 ~, Pgs. 521-547.
An ultracapacitor is typically constructed from two or more bipolar electrode plates separated from each other by electrolyte and a separator positioned within the electrolyte. The bipolar plates include a current collector comprised of an electronically conductive material, and, an electrode material associated with the current collector. The components of the capacitor are operatively secured and encased in a surrounding housing. The housing exposes electrical leads for connection with an item to receive the 2~ electrical benefit of the capacitor.
In a conventional dielectric capacitor, energy is stored in the form of a separated electrical charge, wherein the greater the area for storing the charge, and the closer the separated charge, the greater the capacitance. In such a capacitor, the area for storing the charge is obtained from plates of a flat conductive material and the charged plates are separated with a dielectric material.
In an ultracapacitor, the area for storing a charge is conventionally obtained from a porous carbon material. The porous structure of the carbon allows the chargeable area to be much greater than the flat conductive plates of dielectric capacitors.
Furthermore, an ultracapacitor's charge separation distance is typically determined by the size of the ions in the associated electrolyte, which are attracted to the charged electrode. Such a charge separation is substantially smaller than that which can be obtained using conventional dielectric materials. Accordingly, the combination of the relatively large surface area and the small charge separation results in superior capacitance relative to conventional capacitors.
SUMMARY OF THE INVENTION
The present invention is directed to a capacitor, and, more particularly, a super capacitor comprising at least one bipolar electrode plate each comprising a current collector and an electrode material associated with the current collector; an electrolyte comprising an organic aprotic solvent, a salt and means for stabilizing electrochemical activity between the solvent and at least one of the current collector and/or the electrode material; and, a separator positionable in the electrolyte so as to prevent physical contact between adjacently positioned electrode plates.
In a preferred embodiment of the invention, the electrolyte further includes means for increasing wettability of the electrode. The wettability increasing means may comprise a surfactant.
In such a preferred embodiment, the surfactant is selected from the group comprising nonionic fluoro-alkanes.
In another preferred embodiment of the invention, the electrochemical activity stabilizing means comprises a chemical component which can be reduced in place of the solvent. In such a preferred embodiment, the electrochemical activity stabilizing means is selected from the group comprising carbonates, such as vinylene carbonate, spirolactones, anhydrides and oligomers.
In yet another preferred embodiment of the invention, the current collector is selected from the group of materials having low electrical resistance, substantial impermeability to electrolyte penetration, chemical compatibility with at least one of the electrode material and the electrolyte, and, chemical stability.
In one such preferred embodiment, the current collector includes carbon material, while in another preferred embodiment the current collector comprises aluminum.
In still another preferred embodiment of the invention, the capacitor further includes a substantially inert frame structure. In such a preferred embodiment, the frame structure includes end plates having a current collector associated therewith.
Ultracapacitors fabricated in accordance with the above, and, more particularly, with carbonlgraphite fiber electroactive materials, a non-aqueous electrolyte, and polymer coated aluminum bipolar current collector plates have demonstrated capacitance of up to 0.95 F/cm', energy of up to 1 mAh/cm'. These capacitors have been assembled using commercially available components. Materials and components have been selected in relation with known and anticipated manufacturing constraints and in order to enable manufacturing scale-up of the capacitor.
BRIEF DESCRIPTION OF THE DRAWINGS
Fig. 1 of the drawings is a schematic cross-sectional view of the present invention;
Fig. 2 of the drawings is a perspective view of a bipolar plate of the present invention;
Fig. 3 of the drawings is a cross-sectional view of Fig. 2, taken along lines 3-3, and showing the current collector material and the electrode material of the present invention;
Fig. 4 of the drawings is a graphical representation of the AC impedance of the present invention;
Fig. 5 of the drawings is a graphical representation of the normalized AC
impedance of the present invention;
Fig. 6 of the drawings is a graphical representation of the initial charge and discharge voltage-time profile for the ultracapacitor of the present invention;
Fig. 7 of the drawings is a graphical representation of the discharge voltage-time profile for the ultracapacitor of the present invention;
Fig. 8 of the drawings is a graphical representation of the discharge capacity retention as a function of cycle number;
Fig. 9 of the drawings is a graphical representation of the initial power performance, as illustrated by the voltage-time profile, for the capacitor of the present invention;
Fig. 10 of the drawings is a graphical representation of the normalized voltage-time profile during power testing of the capacitor of the present invention;
Fig. 11 of the drawings is a graphical representation of the Total Delivered Energy as of function of time during discharge at different power rates;
Fig. 12 of the drawings is a graphical representation of comparative AC
impedance;
Fig. 13 of the drawings is a graphical representation of an initial charge and discharge voltage-time profile;
Fig. 14 of the drawings is a graphical representation of comparative AC
impedance;
profile;
Fig. 1 ~ of the drawings is a graphical representation of comparative voltage-time Fig. 16 of the drawings is a graphical representation of comparative discharge voltage-time profile;
Fig. 17 of the drawings is a graphical representation of initial power performance;
Fig. 18 of the drawings is a graphical representation of normalized voltage-time profile during power testing;
Fig. 19 of the drawings is a graphical representation of the Total Delivered Energy as function of time during discharge at different power rates;
Fig. 20 of the drawings is a graphical representation of the effect of the electrolyte additive on the charge behavior of an ultracapacitor;
Fig. 21 of the drawings is a graphical representation of the effect of the maximum charge voltage;
Fig. 22 of the drawings is a graphical representation of the effect of co-solvent based electrolyte on the total cell resistance;
Fig. 23 of the drawings is a graphical representation of the effect of co-solvent based electrolyte on the total cell resistance; and Fig. 24 of the drawings is a graphical representation of initial charge-discharge voltage-time profile.
BEST MODE FOR PRACTICING THE INVENTION
While this invention is susceptible of embodiment in many different forms, there is shown in the drawings and will herein be described in detail, several preferred embodiments with the understanding that the present disclosure is to be considered an exemplification of the principles of the invention and is not intended to limit the invention to the embodiments so illustrated.
A schematic cross-sectional representation of ultracapacitor 10 is shown in Fig. 1 as comprising bipolar electrode plates 12, electrolyte 14, separators 16, housing 18, housing end plates 19, 19' and exposed current collector leads 20, 22, positioned through corresponding end plates. As can be seen, the separators are positioned in between adjacently positioned bipolar electrode plates, and, within the electrolyte, so as to prevent inadvertent contact between the bipolar plates. Although an ultracapacitor having five bipolar electrode plates is shown in Fig. l, it will be readily understood to those having ordinary skill in the art that any number of desired plates are contemplated by the present invention.
A bipolar electrode plate 12, of the type shown in Fig. l, is shown in Fig. 2 as comprising current collector 24 (Fig. 3) and electrode material 26 (see also Fig. 3) associated with the current collector. The combination of the current collector 24 and electrode material 26 are secured to and surrounded by frame structure 28.
Frame structure 28 is constructed from a substantially inert, non-electronically conducting material such as polyethylene and/or polypropylene. Alternatively, glass fiber filled polyethylene having a low temperature induced deformation and a low melting temperature may also be utilized. It is also contemplated that the frame structure be fabricated from other materials, such as low-density non-linear polyethylene and/or polypropylene. The frame structures can be manufactured through conventional techniques such as die-cutting, injection molding and even extrusion. The housing 18 (Fig. 1) can also be made out of the same material as the frame structure for the bipolar electrode plates. The end plates 19, 19' can further be fabricated from glass reinforced polyethylene sheets, and the associated end plate current collectors can be fabricated from the same material as the current collector itself, or for example, expended copper mesh or aluminum.
Current collector 24 is fabricated from materials having low electrical resistance, impermeability to electrolyte penetration and permeation, chemical compatibility, and electrochemical stability. A preferred material is polyethylene coated aluminum foil, commercially available under the trade name COER-Xal from a company called Rexam Graphics of South Hadley, Massachusetts. It has been observed that the use of such material provides several advantageous features. Specifically:
- aluminum foil provides absolute separation of electrolyte in the bipolar electrode construction;
- the PE coating onto the aluminum foil provides for additional mechanical and chemical stability to the aluminum foil;
- the PE coating onto the aluminum foil provides a "hot-melt" adhesive characteristic to the current collector, thus enhancing the adhesion of the carbon electrode onto the current collector; and - the COER-Xal provides good electrical conductivity and is available in fairly thin configurations (75 um Al, 25 um PE on each side).
As an alternative to the above, it is also contemplated that other materials, such as a polyethylene-carbon paper (25 um) and a polyethylene-carbon composite material can also be used.
With respect to electrode material 26, such material can be fabricated from conventional types of electrode materials presently available for the fabrication of super, ultracapacitors. One example of acceptable electrode material, and generally the most frequently described, is based on the utilization of a high surface area activated carbon powder. The surface area of the carbon is generally greater than 1,500 mZ/g.
These carbons generally have a total pore volume of 1 ml/g, and an average pore size of 20 A.
in order to fabricate an electrode material using these carbons, the selected carbon powder must be mixed with an appropriate "binder" and than applied onto a current collector to which the carbon powder must adhere.
A second acceptable type of carbon electrode material is based on activated carbon fibers, generally available in the form of woven and or non-woven felts, fabrics, foams, or webs. Carbon fibers having similar surface area than the ones measured for the activated carbons are available commercially. The use of carbon fiber webs simplifies the electrode assembly process by eliminating the need of compounding the activated carbon powder with a binder and by eliminating the need to apply, generally via a solvent coating process, the compounded carbon powder onto a current collector. It is believed that the main difference between the carbon powders and the carbon fibers reside in the trade off between the energy storage capacity of the carbon electrode and its ease of processing.
Electrolyte 14 as shown in Fig. 1 is comprised of an orUanic aprotic solvent, a salt, a stabilizer and a surfactant. The solvent can comprise conventionally known materials, such as the ones described by Dr. Ue In J. Electrochem. Soc. 141, 1 1 ( 1994) 2989-2996. For example only, propylene carbonate ("PC") can be used. Although PC
l 5 has proven to be a good solvent, it has a high viscosity (n = 2.5 cp) and consequently has a less than optimum conductivity. Accordingly, solvent mixtures have also been considered and tested. Acetonitrile (n=0.3 cp) and y-buryrolacrone (n=l .7 cp) have been initially selected as a co-solvent to PC.
The salt used in the electrolyte fornmlation comprises tetra ethylene ammonium tetra fluoroborate. However, other salts, such as fluorinated alkyl ammoniums, among several other conventional salts, are likewise contemplated for use.
Inasmuch as the electrochemical stability of organic aprotic electrolytes in contact with carbon powder/fiber anodes is of concern to the capacitor industry, the present invention addresses such a concern by utilizing an additive/chemical component that can preferentially be reduced in place of the solvent. For example, in a preferred embodiment, the additive may comprise a carbonate (vinylene carbonate), a spriolactone.
an anhydride and/or an oligomer.
In order to increase the wettability of the carbon electrode by the electrolyte, surfactants are added to the electrolyte solution. These surfactants are generally selected to be nonionic fluoro-alkanes (SaiNippon Ink F-142d, F177 and 3M FC-171 and FC
170C are examples).
In support of the advantageous benefits from the ultracapacitors constructed in accordance with the above, numerous analyses were performed and graphically depicted in Figs. 4 - 24, wherein the additives (stabilizers and surfactants) were used in combination with conventional electrode materials (i.e. TSW2, TSW3 carbon fiber electrode material, commercially available from a company called Toyobo in Japan, and, Satin based electrodes from a company called Calgon, located in the United Kingdom).
Further information regarding the analyses can be found in corresponding U.S.
Provisional Patent Application Serial No. 60/165,865, filed November 16, 1999, from which the present application depends, the entirety of which is incorporated herein by reference. In particular, and with respect to the graphs:
Fig. 4 of the drawings is a graphical representation of the AC impedance of the present invention based on TSW2 carbon fiber electrodes, as measured.
Fig. 5 of the drawings is a graphical representation of the normalized AC
impedance of the present invention based on TSW2, illustrating the effect of adhesion between the current collector and the electroactive material. Better adhesion provides for lower internal resistance.
Fig. 6 of the drawings is a graphical representation of the initial charge and discharge voltage-time profile for the ultracapacitor assembled using the TSW2 based electrodes. Although, some differences in charge time are observed, discharge time is almost constant for all systems. This behavior is further illustrated in Figure 7.
Fig. 7 of the drawings is a graphical representation of the discharge voltage-time profile for the ultracapacitor assembled using the TSW2 based electrodes.
Fig. 8 of the drawings is a graphical representation of the discharge capacity retention as a function of cycle number as illustrated for the initial 5 cycles for the capacitor assembled using the TSW2 based electrodes.
Fig. 9 of the drawings is a graphical representation of the initial power performance, as illustrated by the voltage-time profile, for the capacitor assembled using the YSW2 based electrodes.
Fig. 10 of the drawings is a graphical representation of the normalized voltage-time profile during power testing of the capacitor assembled using the TSW2 based electrodes. These results indicate a good capacity retention for these electrodes. This is further illustrated in Figure 11.
Fig. 11 of the drawings is a graphical representation of the Total Delivered Energy as of function of time during discharge at different power rates.
Fig. 12 of the drawings is a graphical representation of the comparative AC
impedance between the TSW2 and TSW3 electrode material considered by the manufacturer as "equivalents."
Fig. 13 of the drawings is a graphical representation of the initial charge and discharge voltage-time profile for the TSW2 and TSW3 electrode material.
Fig. 14 of the drawings is a graphical representation of the comparative AC
impedance between the TSW2 and TSW3 electrode material and the Satin electrode material.
1 ~ Fig. 15 of the drawings is a graphical representation of the comparative voltage-time profile between capacitor assembled using the TSW2 carbon paper and the Satin carbon fabric.
Fig. 16 of the drawings is a graphical representation of the comparative discharge voltage-time profile between capacitor assembled using the TSW2 carbon paper and the Satin carbon fabric.
Fig. 17 of the drawings is a graphical representation of the initial power performance, as illustrated by the voltage-time profile, for the ultracapacitor assembled using the Satin carbon fabric.
Fig. 18 of the drawings is a graphical representation of the normalized voltage-time profile during power testing of the ultracapacitor assembled using the Satin based electrodes. These results indicate a good capacity retention for these electrodes. This is further illustrated in Figure 19.
Fig. 19 of the drawings is a graphical representation of the Total Delivered Energy as function of time during discharge at different power rates.
Fig. 20 of the drawings is a graphical representation of the effect of the electrolyte additive on the charge behavior of an ultracapacitor. Capacitor #1 10103 has no electrolyte additive and shows long self decomposition behavior during the initial charge, while capacitor #102902 shows a normal charge behavior.
Fig. 21 of the drawings is a graphical representation of the effect of the maximum charge voltage.
Fig. 22 of the drawings is a graphical representation of the effect of co-solvent based electrolyte on the total cell resistance, for the ultracapacitor assembled using TSW3 electrode material.
Fig. 23 of the drawin~'s is a graphical representation of the effect of co-solvent based electrolyte on the total cell resistance, for the ultracapacitor assembled using Satin fabric. Tests performed using a 1:1 mixture of propylene carbonate and acetronitrile indicate that although the electrolyte conductivity is increased, as expected, the electrochemical stability of the electrolyte is reduced. This may be due in part to water contamination and to the presence of other residual impurities.
Fig. 24 of the drawings is a graphical representation of the initial charge-discharge voltage-time profile for capacitor assembled using the Satin fabric and co-solvent based electrolyte (#101501).
The foregoing description and drawings merely explain and illustrate the invention and the invention is not limited thereto except insofar as the appended claims are so limited as those skilled in the art who have the disclosure before them will be able to make modifications and variations therein without departing from the scope of the invention.
Claims (11)
1. A capacitor comprising:
- at least one bipolar electrode plate each comprising a current collector and an electrode material associated with the current collector;
- an electrolyte comprising an organic aprotic solvent, a salt and means for stabilizing electrochemical activity between the solvent and at least one of the current collector and the electrode material; and - a separator.
- at least one bipolar electrode plate each comprising a current collector and an electrode material associated with the current collector;
- an electrolyte comprising an organic aprotic solvent, a salt and means for stabilizing electrochemical activity between the solvent and at least one of the current collector and the electrode material; and - a separator.
2. The invention according to Claim 1 wherein the electrolyte further includes means for increasing wettability of the electrode.
3. The invention according to Claim 2 wherein the wettability increasing means comprises a surfactant.
4. The invention according to Claim 3 wherein the surfactant is selected from the group comprising nonionic fluoro-alkanes.
5. The invention according to Claim 1 wherein the electrochemical activity stabilizing means comprises a chemical component which can be reduced in place of the solvent.
6. The invention according to Claim 5 wherein the electrochemical activity stabilizing means is selected from the group comprising carbonates, spirolactones, anhydrides and oligomers.
7. The invention according to Claim 1 wherein the current collector is selected from the group of materials having low electrical resistance, substantial impermeability to electrolyte penetration, chemical compatibility with at least one of the electrode material and the electrolyte, and, chemical stability.
8. The invention according to Claim 7 wherein the current collector includes carbon material.
9. The invention according to Claim 7 wherein the current collector comprises aluminum.
10. The invention according to Claim 1 wherein the capacitor further includes a substantially inert frame structure.
11. The invention according to Claim 10 wherein the frame structure include end plates having a current collector lead associated therewith.
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US16586599P | 1999-11-16 | 1999-11-16 | |
US60/165,865 | 1999-11-16 | ||
PCT/US2000/031588 WO2001037295A1 (en) | 1999-11-16 | 2000-11-16 | Capacitor development |
Publications (1)
Publication Number | Publication Date |
---|---|
CA2389727A1 true CA2389727A1 (en) | 2001-05-25 |
Family
ID=22600803
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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CA002389727A Abandoned CA2389727A1 (en) | 1999-11-16 | 2000-11-16 | Capacitor development |
Country Status (5)
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EP (1) | EP1230654A1 (en) |
JP (1) | JP2003515251A (en) |
AU (1) | AU1772101A (en) |
CA (1) | CA2389727A1 (en) |
WO (1) | WO2001037295A1 (en) |
Families Citing this family (9)
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JP5027540B2 (en) * | 2007-03-29 | 2012-09-19 | 富士重工業株式会社 | Lithium ion capacitor |
GB2482914A (en) * | 2010-08-20 | 2012-02-22 | Leclanche Sa | Lithium Cell Electrolyte |
US9178250B2 (en) | 2010-08-20 | 2015-11-03 | Leclanche' Sa | Electrolyte for a battery |
US10312028B2 (en) | 2014-06-30 | 2019-06-04 | Avx Corporation | Electrochemical energy storage devices and manufacturing methods |
US11043701B2 (en) * | 2016-05-17 | 2021-06-22 | Eos Energy Storage Llc | Zinc-halide battery using a deep eutectic solvent-based electrolyte |
MY195773A (en) * | 2016-05-20 | 2023-02-11 | Kyocera Avx Components Corp | Multi-Cell Ultracapacitor |
WO2017201167A1 (en) | 2016-05-20 | 2017-11-23 | Avx Corporation | Electrode configuration for an ultracapacitor |
KR102386805B1 (en) | 2016-05-20 | 2022-04-14 | 교세라 에이브이엑스 컴포넌츠 코포레이션 | Non-aqueous electrolyte for ultracapacitors |
EP3459094B1 (en) | 2016-05-20 | 2022-08-17 | KYOCERA AVX Components Corporation | Ultracapacitor for use at high temperatures |
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US5420747A (en) * | 1992-10-12 | 1995-05-30 | Econd | Capacitor with a double electric layer cell stack |
US5646815A (en) * | 1992-12-01 | 1997-07-08 | Medtronic, Inc. | Electrochemical capacitor with electrode and electrolyte layers having the same polymer and solvent |
US5581438A (en) * | 1993-05-21 | 1996-12-03 | Halliop; Wojtek | Supercapacitor having electrodes with non-activated carbon fibers |
US6010806A (en) * | 1995-06-09 | 2000-01-04 | Mitsui Chemicals, Inc. | Fluorine-substituted cyclic carbonate electrolytic solution and battery containing the same |
-
2000
- 2000-11-16 JP JP2001537753A patent/JP2003515251A/en active Pending
- 2000-11-16 CA CA002389727A patent/CA2389727A1/en not_active Abandoned
- 2000-11-16 EP EP00980465A patent/EP1230654A1/en not_active Withdrawn
- 2000-11-16 AU AU17721/01A patent/AU1772101A/en not_active Abandoned
- 2000-11-16 WO PCT/US2000/031588 patent/WO2001037295A1/en not_active Application Discontinuation
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AU1772101A (en) | 2001-05-30 |
JP2003515251A (en) | 2003-04-22 |
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