CA2937869A1 - Electrode for an electric-energy storage system with collector including a protective conductive layer and corresponding manufacturing method - Google Patents
Electrode for an electric-energy storage system with collector including a protective conductive layer and corresponding manufacturing method Download PDFInfo
- Publication number
- CA2937869A1 CA2937869A1 CA2937869A CA2937869A CA2937869A1 CA 2937869 A1 CA2937869 A1 CA 2937869A1 CA 2937869 A CA2937869 A CA 2937869A CA 2937869 A CA2937869 A CA 2937869A CA 2937869 A1 CA2937869 A1 CA 2937869A1
- Authority
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- Canada
- Prior art keywords
- conductive
- copolymer
- vinyl chloride
- crosslinking
- current collector
- Prior art date
- Legal status (The legal status 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 status listed.)
- Abandoned
Links
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- 238000004132 cross linking Methods 0.000 claims abstract description 41
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- 239000011231 conductive filler Substances 0.000 claims abstract description 27
- 229920000642 polymer Polymers 0.000 claims abstract description 26
- 230000001681 protective effect Effects 0.000 claims abstract description 26
- 239000003792 electrolyte Substances 0.000 claims abstract description 25
- 239000008151 electrolyte solution Substances 0.000 claims abstract description 5
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- 239000011241 protective layer Substances 0.000 claims description 50
- 239000010410 layer Substances 0.000 claims description 45
- 125000002843 carboxylic acid group Chemical group 0.000 claims description 26
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 25
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical group CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims description 25
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- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 5
- 238000003860 storage Methods 0.000 claims description 5
- 239000007864 aqueous solution Substances 0.000 claims description 4
- KAKZBPTYRLMSJV-UHFFFAOYSA-N butadiene group Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 4
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- 238000010790 dilution Methods 0.000 claims description 4
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- 239000003125 aqueous solvent Substances 0.000 claims description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 3
- 229920002554 vinyl polymer Polymers 0.000 claims description 3
- 239000011521 glass Substances 0.000 claims description 2
- 125000004184 methoxymethyl group Chemical group [H]C([H])([H])OC([H])([H])* 0.000 claims description 2
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- 239000002987 primer (paints) Substances 0.000 description 33
- 238000009472 formulation Methods 0.000 description 21
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 14
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 14
- 238000005260 corrosion Methods 0.000 description 13
- 230000007797 corrosion Effects 0.000 description 13
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 8
- 229910052799 carbon Inorganic materials 0.000 description 6
- 239000011253 protective coating Substances 0.000 description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- 229910052802 copper Inorganic materials 0.000 description 5
- 239000010949 copper Substances 0.000 description 5
- 150000002978 peroxides Chemical class 0.000 description 5
- 229920003270 Cymel® Polymers 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 239000012736 aqueous medium Substances 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 125000000524 functional group Chemical group 0.000 description 4
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 4
- 150000002739 metals Chemical class 0.000 description 4
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- BJELTSYBAHKXRW-UHFFFAOYSA-N 2,4,6-triallyloxy-1,3,5-triazine Chemical compound C=CCOC1=NC(OCC=C)=NC(OCC=C)=N1 BJELTSYBAHKXRW-UHFFFAOYSA-N 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000004480 active ingredient Substances 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- IRLQAJPIHBZROB-UHFFFAOYSA-N buta-2,3-dienenitrile Chemical class C=C=CC#N IRLQAJPIHBZROB-UHFFFAOYSA-N 0.000 description 2
- 239000003990 capacitor Substances 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
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- 241000905957 Channa melasoma Species 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- GUWKQWHKSFBVAC-UHFFFAOYSA-N [C].[Au] Chemical compound [C].[Au] GUWKQWHKSFBVAC-UHFFFAOYSA-N 0.000 description 1
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- 230000002378 acidificating effect Effects 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- CREMABGTGYGIQB-UHFFFAOYSA-N carbon carbon Chemical compound C.C CREMABGTGYGIQB-UHFFFAOYSA-N 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
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- 230000005684 electric field Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
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- 230000009477 glass transition Effects 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000005486 organic electrolyte Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 description 1
- 229910052939 potassium sulfate Inorganic materials 0.000 description 1
- 235000011151 potassium sulphates Nutrition 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
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- 238000010408 sweeping Methods 0.000 description 1
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000010938 white gold Substances 0.000 description 1
- 229910000832 white gold Inorganic materials 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-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
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D109/00—Coating compositions based on homopolymers or copolymers of conjugated diene hydrocarbons
- C09D109/02—Copolymers with acrylonitrile
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D131/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid, or of a haloformic acid; Coating compositions based on derivatives of such polymers
- C09D131/02—Homopolymers or copolymers of esters of monocarboxylic acids
- C09D131/04—Homopolymers or copolymers of vinyl acetate
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-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
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-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
- H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for 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
- H01M4/665—Composites
- H01M4/667—Composites in the form of layers, e.g. coatings
-
- 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
-
- 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
- Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
- Y02T10/00—Road transport of goods or passengers
- Y02T10/60—Other road transportation technologies with climate change mitigation effect
- Y02T10/70—Energy storage systems for electromobility, e.g. batteries
Landscapes
- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Composite Materials (AREA)
- Electric Double-Layer Capacitors Or The Like (AREA)
- Cell Electrode Carriers And Collectors (AREA)
- Conductive Materials (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
La présente invention concerne une électrode conductrice pour système de stockage de l'énergie électrique (1) à solution d'électrolyte aqueuse, ladite électrode comprenant un collecteur de courant (3) métallique et une matière active (7), ledit collecteur de courant (3) comportant au moins une couche conductrice de protection (5) étanche aux électrolytes et placée entre ledit collecteur de courant (3) métallique et ladite matière active (7), ladite couche conductrice de protection (5) comprenant: -un liant polymère ou copolymère comportant au moins 50% d'unité de chlorure de vinyle, -un élastomère réticulé, -au moins un agent de réticulation dudit élastomère réticulé, -des charges conductrices.
Description
Electrode for an electric-energy storage system with collector including a protective conductive layer and corresponding manufacturing method The present invention relates to conductive electrodes having current collectors used in particular in energy storage systems, such as supercapacitors. More specifically, the present invention relates to a conductive electrode comprising a current collector comprising at least one conductive protective layer and also to the process for the manufacture of said current collector.
Supercapacitors are electrical energy storage systems which are particularly advantageous for applications requiring the conveyance of high-power electrical energy. The possibilities of rapid charges and discharges and the increased lifetime with respect to a high-power battery make supercapacitor s promising candidates for many applications.
Supercapacitors generally consist of the combination of two conductive electrodes having a high specific surface which are immersed in an ionic electrolyte and which are separated by an isolating membrane, known as "separator", which makes possible the ionic conductivity and prevents electrical contact between the electrodes.
Each electrode is in contact with a metal current collector, making possible exchange of the electrical current with an external system.
Under the influence of a potential difference applied between the two electrodes, the ions present within an electrolyte are attracted by the surface exhibiting an opposite charge, thus forming an electrochemical double layer at the interface of each electrode. The electrical energy is thus stored electrostatically by separation of the charges.
Supercapacitors are electrical energy storage systems which are particularly advantageous for applications requiring the conveyance of high-power electrical energy. The possibilities of rapid charges and discharges and the increased lifetime with respect to a high-power battery make supercapacitor s promising candidates for many applications.
Supercapacitors generally consist of the combination of two conductive electrodes having a high specific surface which are immersed in an ionic electrolyte and which are separated by an isolating membrane, known as "separator", which makes possible the ionic conductivity and prevents electrical contact between the electrodes.
Each electrode is in contact with a metal current collector, making possible exchange of the electrical current with an external system.
Under the influence of a potential difference applied between the two electrodes, the ions present within an electrolyte are attracted by the surface exhibiting an opposite charge, thus forming an electrochemical double layer at the interface of each electrode. The electrical energy is thus stored electrostatically by separation of the charges.
2 The expression of the capacitance of such supercapacitors is identical to that of conventional electrical capacitors, namely:
C = e.S/t with: E : the permittivity of the medium, S: the surface area occupied by the double layer, and t: the thickness of the double layer.
=
The capacitances achievable within supercapacitors are much greater than those commonly achieved by conventional capacitors, as a result of the use of porous electrodes having a high specific surface (maximization of the surface area) and of the extreme narrowness of the electrochemical double layer (a few nanometers).
The car.bon-based electrodes used within supercapacitor systems necessarily have to be:
- conductive, in order to provide for the transportation of the electric charges, - porous, in order to provide for the transportation of ionic charges and the formation of the electrical double layer over a large surface area, and - chemically inert, in order to prevent any energy-consuming side reactions.
The energy stored within the supercapacitor is defined according to the conventional expression for capacitors, i.e.:
E = 1/2.C.V2, in which V is.the electrical potential of the supercapacitor.
C = e.S/t with: E : the permittivity of the medium, S: the surface area occupied by the double layer, and t: the thickness of the double layer.
=
The capacitances achievable within supercapacitors are much greater than those commonly achieved by conventional capacitors, as a result of the use of porous electrodes having a high specific surface (maximization of the surface area) and of the extreme narrowness of the electrochemical double layer (a few nanometers).
The car.bon-based electrodes used within supercapacitor systems necessarily have to be:
- conductive, in order to provide for the transportation of the electric charges, - porous, in order to provide for the transportation of ionic charges and the formation of the electrical double layer over a large surface area, and - chemically inert, in order to prevent any energy-consuming side reactions.
The energy stored within the supercapacitor is defined according to the conventional expression for capacitors, i.e.:
E = 1/2.C.V2, in which V is.the electrical potential of the supercapacitor.
3 From this expression, the capacitance and the potential are two essential parameters which it is necessary to optimize in order to favor the energy performance. For example, for applications in transportation and in particular for an electric vehicle, to have a high energy density is necessary in order to limit the on-board weight of supercapacitors.
The potential depends mainly on the nature of the electrolyte.
There typically exist different types of electrolytes. One family is the family of organic electrolytes, that is to say comprising an organic salt dispersed in an organic solvent. Some of these electrolytes make it possible to achieve an operating potential of 2.7V. On the other hand, these electrolytes are expensive, flammable, toxic and potentially polluting. They thus present safety problems for use in a vehicle.
Aqueous electrolytes are less expensive and nonflammable; they are thus more advantageous for this application. In an aqueous medium, the applicable potential is 1.2V. Different aqueous electrolytes can be used, for example an aqueous solution of sulfuric acid, or of potassium chloride, or of potassium sulfate, or of other salts, in an acidic, basic or neutral medium.
In order to store a high energy density, it is therefore necessary to have a high mass capacitance. The capacitance depends on the porous texture really accessible by the electrolyte; for its part, the potential depends directly on the stability of the electrolyte under the influence of the electrical field.
In order to obtain a high mass capacitance, a known solution is to add active material to the supercapacitors. There exist different possibilities for incorporating the active material in a supercapacitor. In =
=
The potential depends mainly on the nature of the electrolyte.
There typically exist different types of electrolytes. One family is the family of organic electrolytes, that is to say comprising an organic salt dispersed in an organic solvent. Some of these electrolytes make it possible to achieve an operating potential of 2.7V. On the other hand, these electrolytes are expensive, flammable, toxic and potentially polluting. They thus present safety problems for use in a vehicle.
Aqueous electrolytes are less expensive and nonflammable; they are thus more advantageous for this application. In an aqueous medium, the applicable potential is 1.2V. Different aqueous electrolytes can be used, for example an aqueous solution of sulfuric acid, or of potassium chloride, or of potassium sulfate, or of other salts, in an acidic, basic or neutral medium.
In order to store a high energy density, it is therefore necessary to have a high mass capacitance. The capacitance depends on the porous texture really accessible by the electrolyte; for its part, the potential depends directly on the stability of the electrolyte under the influence of the electrical field.
In order to obtain a high mass capacitance, a known solution is to add active material to the supercapacitors. There exist different possibilities for incorporating the active material in a supercapacitor. In =
=
4 order to achieve operation with high powers, the resistance to the passage of the current in the system (ESR) has to be very low. This is because this.resistance brings about losses by the Joule effect, which reduce the output of the supercapacitor. This resistance is the sum of the resistances of the different components of the system and in particular the resistance of the electrolyte and the resistance of the current collectors. An essential contribution is the resistance of the interface between the current collector and the active material. This resistance is çlependent on the quality and on the nature of the contact.
In order to limit the contribution of the resistances of the current collectors, it is necessary to use metals of high conductivities.
Furthermore, for the sake of economy and of case of use, the metals used have to be inexpensive and to be able to be easily shaped.
Examples of metals which can be favorably used are thus typically copper and aluminum. However, the use of these materials in an aqueous medium presents problems of chemical and electrochemical stability. This is because, at a typical oxidation potential in an aqueous medium of 1.2V, the majority of metals corrode.
It is therefore necessary both to protect the metal collector from corrosion and to have a good electrical contact between the collector and the active material.
Different strategies have been used for this. The document EP 1 032 064 describes a current collector of a positive electrode composed of a paste of active material comprising a polymer layer comprising an oxalate and a compound based on silicon, on phosphate or on chromiurn. This solution makes it possible to protect the collector during the deposition of the paste of active material but has no effect on the characteristics of the electrode in use. It is thus necessary to use an interface between the metal current collector and the monolithic active material.
In order to limit the contribution of the resistances of the current collectors, it is necessary to use metals of high conductivities.
Furthermore, for the sake of economy and of case of use, the metals used have to be inexpensive and to be able to be easily shaped.
Examples of metals which can be favorably used are thus typically copper and aluminum. However, the use of these materials in an aqueous medium presents problems of chemical and electrochemical stability. This is because, at a typical oxidation potential in an aqueous medium of 1.2V, the majority of metals corrode.
It is therefore necessary both to protect the metal collector from corrosion and to have a good electrical contact between the collector and the active material.
Different strategies have been used for this. The document EP 1 032 064 describes a current collector of a positive electrode composed of a paste of active material comprising a polymer layer comprising an oxalate and a compound based on silicon, on phosphate or on chromiurn. This solution makes it possible to protect the collector during the deposition of the paste of active material but has no effect on the characteristics of the electrode in use. It is thus necessary to use an interface between the metal current collector and the monolithic active material.
5 To use an interface having a lower conductivity than the metal of the collector between the latter and the active material presents a problem as it is highly likely to increase the resistance of the system and thus to disrupt operation with high electric powers. Different interfaces have been tested between the collector and the active material.
One solution consists in coating the collector with a protective layer. The document FR2824418 describes a current collector covered with a layer of paint comprising conductive particles, such as graphite or carbon black. The paint is applied between the collector and the active material and is then heated in order to remove the solvent. The paint is epoxy-based or polyurethane-based. This layer of paint makes it possible to protect the collector in an organic medium but no information is given with regard to its effectiveness in protecting the collector from an aqueous electrolyte.
The document W02007/036641 describes a method for the deposition of a thin film of carbon by deposition of a dispersion of carbon-based particles in a polymeric sol-gel, followed by the removal of said polyrner1c sol-gel at high temperature. This additional layer makes it possible to improve the conductive properties at the level of the contact. Nevertheless, no information is given with regard to its leaktightness in an aqueous medium. Furthermore, the carbon-based
One solution consists in coating the collector with a protective layer. The document FR2824418 describes a current collector covered with a layer of paint comprising conductive particles, such as graphite or carbon black. The paint is applied between the collector and the active material and is then heated in order to remove the solvent. The paint is epoxy-based or polyurethane-based. This layer of paint makes it possible to protect the collector in an organic medium but no information is given with regard to its effectiveness in protecting the collector from an aqueous electrolyte.
The document W02007/036641 describes a method for the deposition of a thin film of carbon by deposition of a dispersion of carbon-based particles in a polymeric sol-gel, followed by the removal of said polyrner1c sol-gel at high temperature. This additional layer makes it possible to improve the conductive properties at the level of the contact. Nevertheless, no information is given with regard to its leaktightness in an aqueous medium. Furthermore, the carbon-based
6 films obtained by this method are delicate and subject to abrasion during the assembling of the electrodes.
One of the aims of the invention is thus to provide a current collector, and also its process of manufacture, having optimized longevity and conductivity properties.
The present invention thus relates to a conductive electrode for a system for the storage of electrical energy having an aqueous electrolyte solution, µsaid electrode comprising a metal current collector and an active material, said current collector comprising at least one conductive protective layer which is leaktight to electrolytes and which is placed between said metal current collector and said active material, said conductive protective layer comprising:
a polymer or copolymer binder comprising at least 50% of vinyl chloride unit, - à crosslinked elastomer, - at least one agent for crosslinking said crosslinked elastomer, conductive fillers.
According to one aspect of the invention, the proportions of the different components of the conductive protective layer are:
- from 10% to 50% of the polymer or copolymer binder comprising at least 50% of vinyl chloride unit, - from 10% to 50% of the crosslinked elastomer, - from 0.2% to 5% of the at least one agent for crosslinking said crosslinked elastomer, and - from 25% to 50% of conductive fillers, =
=
One of the aims of the invention is thus to provide a current collector, and also its process of manufacture, having optimized longevity and conductivity properties.
The present invention thus relates to a conductive electrode for a system for the storage of electrical energy having an aqueous electrolyte solution, µsaid electrode comprising a metal current collector and an active material, said current collector comprising at least one conductive protective layer which is leaktight to electrolytes and which is placed between said metal current collector and said active material, said conductive protective layer comprising:
a polymer or copolymer binder comprising at least 50% of vinyl chloride unit, - à crosslinked elastomer, - at least one agent for crosslinking said crosslinked elastomer, conductive fillers.
According to one aspect of the invention, the proportions of the different components of the conductive protective layer are:
- from 10% to 50% of the polymer or copolymer binder comprising at least 50% of vinyl chloride unit, - from 10% to 50% of the crosslinked elastomer, - from 0.2% to 5% of the at least one agent for crosslinking said crosslinked elastomer, and - from 25% to 50% of conductive fillers, =
=
7 as remainder. in order to achieve a total of 100% by weight of dry matter.
According to another aspect of the invention, the polymer or copolymer binder comprising at least 50% of vinyl chloride unit is a copolymer comprising vinyl chloride and/or vinyl acetate units and/or carboxylic acid groups.
According to another aspect of the invention, the copolymer comprising vinyl chloride and/or vinyl acetate units and/or carboxylic acid groups is crosslinked and the conductive protective layer additionally comprises:
an agent for crosslinking said copolymer comprising vinyl chloride and/or vinyl acetate units and/or carboxylic acid groups, a crosslinking catalyst.
According to another aspect of the invention, the proportion of the agent for crosslinking said copolymer comprising vinyl chloride and/or vinyl acetate units and/or carboxylic acid groups in the protective layer is from 2% to 8%, as remainder in order to achieve a total of 100% by weight of dry matter, and the proportion of the crosslinking catalyst is from 1% to 2%, as remainder in order to achieve a total of 100% by weight of dry manu.
According to another aspect of the invention, the agent for crosslinking said copolymer comprising vinyl chloride and/or vinyl acetate units and/or carboxylic acid groups is a mixture of methoxymethyl- and ethoxymethylbenzoguanamine.
=
According to another aspect of the invention, the polymer or copolymer binder comprising at least 50% of vinyl chloride unit is a copolymer comprising vinyl chloride and/or vinyl acetate units and/or carboxylic acid groups.
According to another aspect of the invention, the copolymer comprising vinyl chloride and/or vinyl acetate units and/or carboxylic acid groups is crosslinked and the conductive protective layer additionally comprises:
an agent for crosslinking said copolymer comprising vinyl chloride and/or vinyl acetate units and/or carboxylic acid groups, a crosslinking catalyst.
According to another aspect of the invention, the proportion of the agent for crosslinking said copolymer comprising vinyl chloride and/or vinyl acetate units and/or carboxylic acid groups in the protective layer is from 2% to 8%, as remainder in order to achieve a total of 100% by weight of dry matter, and the proportion of the crosslinking catalyst is from 1% to 2%, as remainder in order to achieve a total of 100% by weight of dry manu.
According to another aspect of the invention, the agent for crosslinking said copolymer comprising vinyl chloride and/or vinyl acetate units and/or carboxylic acid groups is a mixture of methoxymethyl- and ethoxymethylbenzoguanamine.
=
8 According to another aspect of the invention, the crosslinking catalyst is an acid catalyst blocked by an amine.
According to another aspect of the invention, the binder comprising at least 50% of vinyl chloride unit is a polyvinyl chloride.
According to another aspect of the invention, the crosslinked elastomer is a hydrogenated butadiene/acrylonitrile copolymer.
According to another aspect of the invention, the conductive protective layer additionally comprises an additive for adhesion to the current collector in a proportion of 2% to 7%, as remainder in order to achieve a total of 100% by weight of dry matter.
According to another aspect of the invention, the conductive electrode comprises a primer layer placed between the metal current collector and the protective layer, said primer layer comprising a water-dispersible binder and conductive fillers.
According to another aspect of the invention, the water-dispersible binder is a polyurethane latex.
According to another aspect of the invention, the proportions of the different .components of the primer layer are:
from 60% to 70% of water-dispersible binder, and from 30% to 40% of conductive fillers, as remainder in order to achieve a total of 100% by weight of dry matter.
=
According to another aspect of the invention, the binder comprising at least 50% of vinyl chloride unit is a polyvinyl chloride.
According to another aspect of the invention, the crosslinked elastomer is a hydrogenated butadiene/acrylonitrile copolymer.
According to another aspect of the invention, the conductive protective layer additionally comprises an additive for adhesion to the current collector in a proportion of 2% to 7%, as remainder in order to achieve a total of 100% by weight of dry matter.
According to another aspect of the invention, the conductive electrode comprises a primer layer placed between the metal current collector and the protective layer, said primer layer comprising a water-dispersible binder and conductive fillers.
According to another aspect of the invention, the water-dispersible binder is a polyurethane latex.
According to another aspect of the invention, the proportions of the different .components of the primer layer are:
from 60% to 70% of water-dispersible binder, and from 30% to 40% of conductive fillers, as remainder in order to achieve a total of 100% by weight of dry matter.
=
9 According to another aspect of the invention, the thickness of the =
primer layer is between 5 and 20 micrometers.
According to another aspect of the invention, the conductive fillers are chosen from carbon black and/or graphite and/or carbon nanotubes.
According to another aspect of the invention, the thickness of the conductive protective layer is between 5 and 30 micrometers.
The present invention also relates to a process for the manufacture of a conductive electrode having an aqueous electrolyte solution for a system for the storage of electrical energy, said electrode comprising a metal current collector, at least one conductive protective layer which is leaktight to electrolytes and a layer of active material, said process comprising the following stages:
- preparation of a protective composition comprising from 10% to 50% of a polymer or copolymer binder comprising at least 50% of vinyl chloride unit, from 10% to 50% of a crosslinked elastomer, from 0.2% to 5% of at least one agent for crosslinking said crosslinked elastomer and from 25% to 50% of conductive fillers, as rem.ainder in order to achieve a total of 100% by weight of dry matter, which are diluted in a solvent in order to achieve a proportion of 20% to 25%, - deposition of said protective composition on the metal current collector, - first heat treatment of the covered metal current collector at a temperature lower than the boiling point of the solvent, =
- second heat treatment of the covered metal current collector at a temperature greater than the glass transition temperature of the polymer or copolymer binder comprising at least 50% of vinyl chloride unit and than the boiling point of the solvent, said heat 5 treatment temperature being, however, lower than the decomposition temperature of said binder, - preparation and deposition of the layer of active material on the conductive protective layer.
primer layer is between 5 and 20 micrometers.
According to another aspect of the invention, the conductive fillers are chosen from carbon black and/or graphite and/or carbon nanotubes.
According to another aspect of the invention, the thickness of the conductive protective layer is between 5 and 30 micrometers.
The present invention also relates to a process for the manufacture of a conductive electrode having an aqueous electrolyte solution for a system for the storage of electrical energy, said electrode comprising a metal current collector, at least one conductive protective layer which is leaktight to electrolytes and a layer of active material, said process comprising the following stages:
- preparation of a protective composition comprising from 10% to 50% of a polymer or copolymer binder comprising at least 50% of vinyl chloride unit, from 10% to 50% of a crosslinked elastomer, from 0.2% to 5% of at least one agent for crosslinking said crosslinked elastomer and from 25% to 50% of conductive fillers, as rem.ainder in order to achieve a total of 100% by weight of dry matter, which are diluted in a solvent in order to achieve a proportion of 20% to 25%, - deposition of said protective composition on the metal current collector, - first heat treatment of the covered metal current collector at a temperature lower than the boiling point of the solvent, =
- second heat treatment of the covered metal current collector at a temperature greater than the glass transition temperature of the polymer or copolymer binder comprising at least 50% of vinyl chloride unit and than the boiling point of the solvent, said heat 5 treatment temperature being, however, lower than the decomposition temperature of said binder, - preparation and deposition of the layer of active material on the conductive protective layer.
10 According to one aspect of the process according to the invention, the polymer or copolymer binder comprising at least 50% of vinyl chloride unit is a copolymer comprising vinyl chloride and/or vinyl acetate units and/or carboxylic acid groups.
According to another aspect of the process according to the invention, the protective composition additionally comprises:
from 2% to 8% of an agent for crosslinking the copolymer comprising vinyl chloride and/or vinyl acetate units and/or carboxylic acid groups, from 1% to 2% of a crosslinking catalyst, as remainder in order to achieve a total of 100% by weight of dry matter before dilution in the solvent.
According to another aspect of the process according to the invention, the agent for crosslinking said copolymer comprising vinyl chloride and/or vinyl acetate units and/or carboxylic acid groups is a mixture of methoxymethyl- and ethoxymethylbenzoguanamine.
According to another aspect of the process according to the invention, the protective composition additionally comprises:
from 2% to 8% of an agent for crosslinking the copolymer comprising vinyl chloride and/or vinyl acetate units and/or carboxylic acid groups, from 1% to 2% of a crosslinking catalyst, as remainder in order to achieve a total of 100% by weight of dry matter before dilution in the solvent.
According to another aspect of the process according to the invention, the agent for crosslinking said copolymer comprising vinyl chloride and/or vinyl acetate units and/or carboxylic acid groups is a mixture of methoxymethyl- and ethoxymethylbenzoguanamine.
11 According to another aspect of the process according to the invention, the crosslinking catalyst is an acid catalyst blocked by an amine.
According to another aspect of the process according to the invention, the polymer or copolymer binder comprising at least 50% of vinyl chloride unit is a polyvinyl chloride.
According to another aspect of the process according to the invention, the crosslinked elastomer is a hydrogenated butadiene/acrylonitrile copolymer.
According to another aspect of the process according to the invention, the protective composition additionally comprises an additive for adhesion to the current collector in a proportion of 2% to 7%, as remainder in order to achieve a total of 100% by weight of dry matter before dilution in the solvent.
According to another aspect of the process according to the invention, the process additionally comprises the following stages:
preparation of a primer composition comprising from 60% to 70%
of water-dispersible binder and from 30% to 40% of conductive fillers, as remainder in" order to achieve a total of 100% by weight of dry matter, diluted in an aqueous solvent, - deposition of said primer composition on the metal current collector, drying of the metal current collector, before the deposition of the protective composition on the metal current collector.
According to another aspect of the process according to the invention, the polymer or copolymer binder comprising at least 50% of vinyl chloride unit is a polyvinyl chloride.
According to another aspect of the process according to the invention, the crosslinked elastomer is a hydrogenated butadiene/acrylonitrile copolymer.
According to another aspect of the process according to the invention, the protective composition additionally comprises an additive for adhesion to the current collector in a proportion of 2% to 7%, as remainder in order to achieve a total of 100% by weight of dry matter before dilution in the solvent.
According to another aspect of the process according to the invention, the process additionally comprises the following stages:
preparation of a primer composition comprising from 60% to 70%
of water-dispersible binder and from 30% to 40% of conductive fillers, as remainder in" order to achieve a total of 100% by weight of dry matter, diluted in an aqueous solvent, - deposition of said primer composition on the metal current collector, drying of the metal current collector, before the deposition of the protective composition on the metal current collector.
12 According to another aspect of the process according to the invention, the conductive fillers are choosing from carbon black and/or graphite and/or carbon nanotubes.
According to another aspect of the process according to the invention, the stage of deposition of the protective composition on the current collector is carried out using a film drawer.
According to another aspect of the process according to the invention, the first and second heat treatment stages each have a duration of 30 minutes.
Other characteristics and advantages of the invention will become more clearly apparent on reading the following description, given as illustrative and nonlimiting example, and the appended figures, among which:
- figure 1 shows a diagrammatic representation of the structure of à supercapacitor, and - figure 2 shows a flow chart of the stages of the manufacturing process according to the invention.
Figure 1 shows a diagrammatic representation of the structure of a supercapacitor 1.
The supercapacitor 1 comprises two conductive electrodes which are immersed in an aqueous .ionic electrolyte (not represented) and which are separated by an isolating membrane, known as separator 9,
According to another aspect of the process according to the invention, the stage of deposition of the protective composition on the current collector is carried out using a film drawer.
According to another aspect of the process according to the invention, the first and second heat treatment stages each have a duration of 30 minutes.
Other characteristics and advantages of the invention will become more clearly apparent on reading the following description, given as illustrative and nonlimiting example, and the appended figures, among which:
- figure 1 shows a diagrammatic representation of the structure of à supercapacitor, and - figure 2 shows a flow chart of the stages of the manufacturing process according to the invention.
Figure 1 shows a diagrammatic representation of the structure of a supercapacitor 1.
The supercapacitor 1 comprises two conductive electrodes which are immersed in an aqueous .ionic electrolyte (not represented) and which are separated by an isolating membrane, known as separator 9,
13 which makes possible the ionic conductivity and prevents electrical contact between the electrodes.
Each electrode comprises a metal current collector 3, for example made of copper or aluminum, covered with a conductive protective layer 5 which is leaktight to electrolytes, for example with a thickness of between 5 and 30 micrometers, and also an active material 7 in contact with the separator 9. This conductive protective layer 5 makes possible in particular an improvement in the electrical contact between said metal current collector 3 and the active material 7.
The conductive protective layer 5 comprises:
- a polymer or copolymer binder comprising at least 50% of vinyl chloride unit, - a crosslinked elastomer, at least one agent for crosslinking said crosslinked elastomer, conductive fillers.
Preferably, the proportions of these constituents of the conductive protective layer 5 are:
from 10% to 50% of the polymer or copolymer binder comprising at least 50% of vinyl chloride unit, - from 10% to 50% of the crosslinked elastomer, - from 0.2% to 5% of the agent for crosslinking said crosslinked elastomer, and - from 25% to 50% of conductive fillers, as remainder in order to achieve a total of 100% by weight of dry matter.
=
Each electrode comprises a metal current collector 3, for example made of copper or aluminum, covered with a conductive protective layer 5 which is leaktight to electrolytes, for example with a thickness of between 5 and 30 micrometers, and also an active material 7 in contact with the separator 9. This conductive protective layer 5 makes possible in particular an improvement in the electrical contact between said metal current collector 3 and the active material 7.
The conductive protective layer 5 comprises:
- a polymer or copolymer binder comprising at least 50% of vinyl chloride unit, - a crosslinked elastomer, at least one agent for crosslinking said crosslinked elastomer, conductive fillers.
Preferably, the proportions of these constituents of the conductive protective layer 5 are:
from 10% to 50% of the polymer or copolymer binder comprising at least 50% of vinyl chloride unit, - from 10% to 50% of the crosslinked elastomer, - from 0.2% to 5% of the agent for crosslinking said crosslinked elastomer, and - from 25% to 50% of conductive fillers, as remainder in order to achieve a total of 100% by weight of dry matter.
=
14 According to a first embodiment, the polymer or copolymer binder comprising at least 50% of vinyl chloride unit can be a copolymer comprising vinyl chloride and/or vinyl acetate units and/or carboxylic acid groups, Such as, for example, Vinnol H15/45 M.
According to an alternative form, the copolymer comprising vinyl chloride and/or vinyl acetate units and/or carboxylic acid groups can be crosslinked within the conductive protective layer 5. In order to do this, the latter comprises an agent for crosslinking said copolymer comprising vinyl chloride and/or vinyl acetate units and/or carboxylic acid groups. This crosslinking agent can be a mixture of methoxymethyl- and e thoxyme thylb en z oguanamine, for example Cymel 1123.
The proportion of the agent for crosslinking said copolymer comprising vinyl chloride and/or vinyl acetate units and/or carboxylic acid groups in the protective layer 5 is preferably from 2% to 8%, as remainder in'order to achieve a total of 100% by weight of dry matter.
In order for the crosslinking to take place, a catalyst for the crosslinking of the copolymer comprising vinyl chloride and/or vinyl acetate units and/or carboxylic acid groups is also added to the conductive protective layer 5. This catalyst can in particular be an acid catalyst blocked by an amine, such as Cycat 40-45. lis proportion within the conductive protective layer 5 is preferably from 1% to 2%, as remainder in order to achieve a total of 100% by weight of dry matter.
According to a second embodiment, the binder comprising at least 50% of vinyl chloride unit can be a polyvinyl chloride (PVC), in particular having a low molecular weight.
=
For ils. part, the crosslinked elastomer can be a hydrogenated butadiene/acrylonitrile copolymer (HNBr) crosslinked by peroxides, for example Luperox 231XL, which are accompanied by a cocrosslinking agent, for example based on silica and on triallyl cyanurate (TAC SIL).
The conductive fillers used are preferably carbon black, for example Ensaco 260G, and/or graphite, for Timcal or Timrex KS6L, or also carbon nanotubes.
10 The conductive protective layer 5 can additionally comprise an adhesion additive in a proportion of 2% to 7%, as remainder in order to achieve a total of 100% by weight of dry matter. This adhesion additive makes possible better adhesion of the protective layer 5 to the current collector 3. Tt can, for example, be a copolymer comprising acrylic
According to an alternative form, the copolymer comprising vinyl chloride and/or vinyl acetate units and/or carboxylic acid groups can be crosslinked within the conductive protective layer 5. In order to do this, the latter comprises an agent for crosslinking said copolymer comprising vinyl chloride and/or vinyl acetate units and/or carboxylic acid groups. This crosslinking agent can be a mixture of methoxymethyl- and e thoxyme thylb en z oguanamine, for example Cymel 1123.
The proportion of the agent for crosslinking said copolymer comprising vinyl chloride and/or vinyl acetate units and/or carboxylic acid groups in the protective layer 5 is preferably from 2% to 8%, as remainder in'order to achieve a total of 100% by weight of dry matter.
In order for the crosslinking to take place, a catalyst for the crosslinking of the copolymer comprising vinyl chloride and/or vinyl acetate units and/or carboxylic acid groups is also added to the conductive protective layer 5. This catalyst can in particular be an acid catalyst blocked by an amine, such as Cycat 40-45. lis proportion within the conductive protective layer 5 is preferably from 1% to 2%, as remainder in order to achieve a total of 100% by weight of dry matter.
According to a second embodiment, the binder comprising at least 50% of vinyl chloride unit can be a polyvinyl chloride (PVC), in particular having a low molecular weight.
=
For ils. part, the crosslinked elastomer can be a hydrogenated butadiene/acrylonitrile copolymer (HNBr) crosslinked by peroxides, for example Luperox 231XL, which are accompanied by a cocrosslinking agent, for example based on silica and on triallyl cyanurate (TAC SIL).
The conductive fillers used are preferably carbon black, for example Ensaco 260G, and/or graphite, for Timcal or Timrex KS6L, or also carbon nanotubes.
10 The conductive protective layer 5 can additionally comprise an adhesion additive in a proportion of 2% to 7%, as remainder in order to achieve a total of 100% by weight of dry matter. This adhesion additive makes possible better adhesion of the protective layer 5 to the current collector 3. Tt can, for example, be a copolymer comprising acrylic
15 functional groups and an olefinic base, such as, for example, Degalan VP 4174E.
Each electrode can also comprise a primer layer 11, with a thickness which can be between 5 and 20 micrometers, placed between the metal current collector 3 and the protective layer 5. This primer layer 11 comprises in particular a water-dispersible binder and conductive fillers. This primer layer 11 provides the metal current collector 3 with additional protection against corrosion.
The term "water-dispersible" is understood to mean that the binder can form a dispersion in an aqueous-based solution.
The water-dispersible binder can be a polyurethane latex or a polyurethane/polycarbonate latex and the conductive fillers chosen from the sanie conductive fillers as those used in the conductive protective layer 5.
=
= CA 02937869 2016-07-25
Each electrode can also comprise a primer layer 11, with a thickness which can be between 5 and 20 micrometers, placed between the metal current collector 3 and the protective layer 5. This primer layer 11 comprises in particular a water-dispersible binder and conductive fillers. This primer layer 11 provides the metal current collector 3 with additional protection against corrosion.
The term "water-dispersible" is understood to mean that the binder can form a dispersion in an aqueous-based solution.
The water-dispersible binder can be a polyurethane latex or a polyurethane/polycarbonate latex and the conductive fillers chosen from the sanie conductive fillers as those used in the conductive protective layer 5.
=
= CA 02937869 2016-07-25
16 The proportions of the different components of the primer layer 11 are preferàbly as follows:
from 60% to 70% of water-dispersible binder, and from 30% to 40% of conductive fillers, as remainder in order to achieve a total of 100% by weight of dry matter.
For its part, the active material 7 can be a carbon monolith or also result from an aqueous carbon-based composition, as, for example, described in the application FR2985598 filed on behalf of the applicant company.
The present invention also relates to a process for the manufacture of a conductive electrode having an aqueous electrolyte solution for a system for the storage of electrical energy, the conductive electrode comprising a metal current collector 3, at least one conductive protective layer 5 which is leaktight to electrolytes and a layer of active material 7.
The manufacturing process, illustrated in figure 2, comprises in particular the following stages:
a) Stage 101 of preparation of a protective composition This stage 101 is a stage of preparation of a protective composition comprising from 10% to 50% of a polymer or copolymer binder comprising at least 50% of vinyl chloride unit, from 10% to 50% of a crosslinked elastomer, from 0.2% to 5% of at least one agent for crosslinking said crosslinked elastomer and from 25% to 50% of =
= 17 conductive fillers, as remainder in order to achieve a total of 100% by weight of dry matter.
This protective composition is diluted in a solvent, for example methyl isobutyl ketone (MIBK), in order to achieve a proportion of 20%
to 25%.
As described above, according to a first embodiment, the polymer or copolymer binder comprising at least 50% of vinyl chloride unit can be a copolymer comprising vinyl chloride and/or vinyl acetate units and/or carboxylic acid groups, such as, for example, Vinnol H15/45 M.
According to an alternative form, the protective composition can also comprise an agent for crosslinking the copolymer comprising vinyl chloride and/or vinyl acetate units and/or carboxylic acid groups. This crosslinking agent can be a mixture of methoxymethyl- and ethoxymethylbenzoguanamine, for example Cymel 1123.
The proportion of the agent for crosslinking said copolymer comprising vinyl chloride and/or vinyl acetate units and/or carboxylic acid groups is preferably from 2% to 8%, as remainder in order to achieve a total of 100% by weight of dry matter.
In order for the crosslinking to take place, a catalyst for the crosslinking of the copolymer comprising vinyl chloride and/or vinyl acetate units and/or carboxylic acid groups is also added to the protective composition. This catalyst can in particular be an acid catalyst blocked by an amine, such as Cycat 40-45. Its proportion within the protective composition is preferably from 1% to 2%, as remainder in order to achieve a total of 100% by weight of dry matter.
According to a second embodiment, the polymer or copolymer binder comprising at least 50% of vinyl chloride unit can be a polyvinyl chloride (PVC).
Still as described above, for its part, the crosslinked elastomer can be a hydrogenated butadiene/acrylonitrile copolymer (HNBr) crosslinked by peroxides, for example Luperox 231XL, which are accompanied by a cocrosslinking agent, for example based on silica and on triallyl cyanurate (TAC SIL).
The conductive fillers used are preferably carbon black, for example Ensaco 260G, and/or graphite, for Timcal or Timrex KS6L, or also carbon nanotubes.
The protective composition can additionally comprise an adhesion additive in a proportion of 2% to 7%, as remainder in order to achieve a total of 100% by weight of dry matter. This adhesion additive makes possible, in the end, better adhesion of the protective layer 5 to the current collector 3. It can, for example, be a copolymer comprising acrylic functional groups and an olefinic base, such as, for example, Degalan VP 4174E.
b) Stage 102 of deposition of the protective composition This stage 102 is a stage of deposition of said protective composition on the metal current collector 3, for example using a film drawer.
c) Stage 103 of first heat treatment During this stage 103, the covered metal current collector 3 is subjected to a first heat treatment at a temperature lower than the boiling point of the solvent, for example for a period of time of 30 minutes.
This heat treatment stage thus makes it possible to remove the solvent from. the conductive protective layer 5 covering the metal current collector 3, while retaining the mechanical properties of this layer.
d) Stage 104 of second heat treatment During. this stage 103, the covered metal current collector 3 is subjected to a second heat treatment at a temperature greater than the glass transition temperature of the binder comprising at least 50% of vinyl chloride unit and than the boiling point of the solvent, said heat treatment temperature being, however, lower than the decomposition temperature of said binder, for example for a period of time of 30 minutes.
The term "decomposition temperature" is understood to mean the temperature at which the copolymer is destroyed and disappears from the conductive protective layer S.
This second heat treatment makes it possible to remove the surplus solvent and also to reinforce the leaktightness of the conductive protective layer S. In addition, this stage makes possible the crosslinking of the different crosslinkable components of the conductive protective layer 5.
=
e) Stage 105 of menaration and deposition of the laver of active material 7 During. this stage 105, the active material 7 is prepared and 5 deposited on the protective layer 5.
As described above, the active material 7 can be a carbon monolith or also result from an aqueous carbon-based composition, as, for example, described in the application FR2985598 filed on behalf of 10 the applicant. company.
In the case where the active material 7 results from an aqueous carbon-based composition, this stage 105 can in particular comprise the following substages:
preparation of an aqueous composition of active material, 15 for example starting from carbon black, from polyvinyl alcohol, from polyacrylic acid and from carboxymethylcellulo se, deposition of the active material composition on the protective layer 5, for example using a film drawer, drying heat treatment, for example for 30 min at a 20 temperature of 50 C, crosslinking heat treatment, for example for 30 min at a temperature of 140 C (this crosslinking can be carried out during stage 104 of second heat treatment of the conductive protective layer 5).
The manufacturing process can also comprise, before stage 102 of deposition of the protective composition on the metal current collector 3, the following stages:
- a stage 110 of preparation of a primer composition comprising from 60% to 70% of water-dispersible binder and from 30% to 40%
of conductive fillers, as remainder in order to achieve a total of 100% by weight of dry matter, diluted in an aqueous solvent, - a stage 111 of deposition of said primer composition on the metal current collector 3, - a stage 112 of drying the metal current collector, for example for a period of time of 30 min at a temperature of 50 C, so as to obtain a primer layer 11 with a thickness of between 5 and 20 micrometers.
Three examples of formulations for the manufacture of a conductive protective layer 5 within a metal current collector 3 of a conductive electrode are illustrated below.
The desired parameters of these conductive protective layers 5 are as follows:
- surface conductivity > 1 S/cm - volume resistivity < 80 mû
- dynamic corrosion time > 7 h at 0.8V at 60 C
- number of cycles of the closed cells at ambient temperature > 300 000 cycles (it is the number of cycles for which the equivalent series resistance (ESR) of the system remains less than twice its initial value).
- number of cycles of the closed cells at 60 C > 10 000 cycles (it is the number of cycles for which the equivalent series resistance (ESR) of the system remains less than twice its initial value).
FORMULATION 1:
Different components described in table 1 below are mixed to give a paste of a Protective composition.
Table 1: Compositions studied Vinnol/HNBr ratio 50/50 60/40 70/30 40/60 30/70 Formulation Example Example Example Example Example Vinnol H15/45 M 27.47 21.97 38.45 32.96 16.48 HNBr 27.47 32.96 16.48 21.97 38.45 Timrexe KS6L 12.60 12.60 12.60 12.60 12.60 Ensaco 260G 24.92 24.92 24.92 24.92 24.92 Luperox 231XL 40 2.08 2.08 2.08 2.08 2.08 TAC SIL 70 0.69 0.71 0.71 0.71 0.71 Degalan VP 4174E 4.76 4.77 4.77 4.77 4.77 The binder used is Vinnol H15/45 M. It is a copolymer comprising vinyl chloride and vinyl acetate units and carboxylic acid groups.
HNBr is an elastomer crosslinked by peroxides (Luperox 231XL
40) and a cocrosslinking agent (TAC SIL 70).
The conductive fillers are carbon black (Ensaco 260G) and graphite (Timcal , Timrex KS6L).
An additive, Degalan VP 4174E, is used to improve the adhesion between the conductive protective layer 5 and the metal current collector 3. Tt is a dispersion of a copolymer comprising acrylic functional groups and an olefinic base.
=
The solvent is methyl isobutyl ketone (MIBK).
The solids content is subsequently adjusted to 21% by addition of methyl isobutyl ketone (MIBK).
Deposition of the conductive protective laver 5:
140 microns of these compositions are subsequently deposited on the first face of a metal strip, acting as metal current collector 3, using a film drawer which makes possible homogenous and controlled deposition.
After drying at 50 C for 30 minutes, the covered strips are subsequently crosslinked at 140 C for 30 minutes.
The coating thickness is measured using a micrometer and is between 15 and 20 microns.
The metal strips can be covered with a primer layer 11 produced in the following way:
Different components described in table 2 are mixed to give a paste of a primer composition.
Table 2: components of the primer composition:
Formulation PU 6800 64.7 Ensaco 260G 11.76 Timr ex KS6L 23.53 =
The polymer or copolymer binder used is PU 6800; it is a latex of polyurethane in the aqueous phase.
The conductive fillers are carbon black (Ensaco 260G) and graphite (Timcal , Timrex KS6L).
Deposiiion of the primer laver 11:
55 microns of this primer composition is deposited on the first face of the metal strip using a film drawer which makes possible homogenous and controlled deposition.
After drying at 50 C for 30 minutes, the coating thickness is measured using a micrometer and is between 15 and 20 microns.
Characterization:
The covered metal strips are subsequently characterized in three different ways.
1) A deposition of the coating is carried out on glass according to the same method used on the metal current collector 3. A four-point conductivity measurement makes it possible to determinc the intrinsic electrical conductivity of the protective coating composed of the conductive protective layer 5 and with, if appropriate, the primer layer 11.
2) A volume resistivity test is carried out by placing under pressure a 3 cm2 square of two bands of covered strips. Pressure sweeping from 100N, 125N, 150N to 200N is carried out. This measurement makes it possible to perceive the compatibility at the interface of the different layers. The resistivity measured must be as low as possible in order to allow the supercapacitor to operate at high power. =
3) A dynamic corrosion measurement via a three-electrode 5 arrangement at 60 C under 0.8V. If the conductive protective coating holds for 7 h, that is to say if no corrosion of the metal current collector 3 is observed, then the test is validated. The objective of this measurement is to force the oxidation and thus the corrosion in order to evaluate the performance of the system under conditions as close as 10 possible to real cases.
Preparation of closed cells 1:
The evaluation of the overall performance of the system is carried 15 out within closed cells 1 as illustrated in figure 1.
The covered metal strips intended for the first electrode are subsequently coated with 305 um of aqueous solution of active material 7, as described in example 1 of the application FR2985598, with the aim of having 150 um after drying at 50 C for 30 min. The layers are 20 crosslinked at 140 C for 30 min.
The same process is carried out for the second electrode, with a dry weight of active material of 90 um, i.e. 155 um wet.
The closed cells 1 are obtained by assembling the two electrodes, 25 between which is placed a cellulose separator 9. The closed cells 1 are subsequently partially immersed in a 5M aqueous solution of lithium nitrate electrolyte and are protected between two heat-sealable plastic films with a thickness of 90 um.
Table 3: Properties of copper metal strips with a thickness of 12.5 Inn coated with formulation 1:
Formulation Ex. 1 Ex. 2 Ex. 3 Ex. 4 Ex. 5 Ex. 1 Ex. 7 With With With With With Without No . .
primer primer primer primer primer primer coating layer layer layer layer layer layer Electrical conductivity of the 1.60 1.24 1.76 2.62 1.57 ////// 59.104 P
protective coating (S/cm) .
Resistance at 200N (m) 20 24 28 20 20 17 8 , Dynamic corrosion at 60 C, 0.8V
, , +: test successful + + + +
+ -, , -: failure, corrosion observed ESR cell (mQ 15 Number of cycles at amblent temperature Number of cycles at 60 C 10 000 As is shown in table 3 of experimental results, the conductive protective layer 5 described in xamples 1 to 5 makes it possible not only to improve the contact with the metal collector but also, via the combination with the primer layer 11, to protect the metal current collector from degradation related to oxygenation in the presence of electrolyte.
Example 1 of formulation 1 was subsequently coated and characterized (table 4) on an aluminum metal strip with a thickness of 50 um.
Table 4: Properties of an aluminum metal strip with a thickness of 50 um coated with formulation 1:
Ex. 1 with Ex. 8 Formulation primer No coating layer Electrical conductivity of the 1.6 37.104 protective coating (S/cm) Resistance at 200N (me) 43 4 Dynamic corrosion at 60 C, 0.8V
ESR cell (mQ 17 Number of cycles at ambient temperature Just as for copper, the conductive protective layer described in example 1 makes it possible to protect the metal collector.
Likewise, "example 1 without primer layer" confirms that it is important to have a primer layer 11 between the metal current collector 3 and the conductive protective layer 5 in order to reduce the risks of corrosion.
FORMULATION 2:
Different components described in table 5 below are mixed to give a paste of a protective composition.
Table 5: Compositions studied Formulation Ex. 9 Vinnol H15/45 M 29.00 HNBr 29.00 Ensaco 260G 23.00 Luperox 231XL 40 0.88 Timrex KS6L 13.12 TAC SIL 70 0.74 Cymel 1123 4.26 Cycat 4045 1.5 The polymer or copolymer binder used is Vinnol H15/45 M. It is a copolymer comprising vinyl chloride and vinyl acetate units and carboxylic acid groups. This copolymer is crosslinked by a mixture of methoxymethyl- and ethoxymethylbenzoguanamine. The crosslinking agent used is Cymel 1123. The catalyst for the crosslinking of the polymer or copolymer binder used is an acid catalyst blocked by an amine (Cycat.40-45).
HNBr is an elastomer crosslinked by peroxides (Luperox 231X1 40) and a cocrosslinking agent (TAC SIL 70).
The conductive fillers are carbon black (Ensaco 260G) and graphite (Timcal, Timrex KS6L).
The solvent is methyl isobutyl ketone (MIBK).
The solids content ils subsequently adjusted to 21% by addition of methyl isobutyl ketone (MIBK).
The deposition of the conductive protective layer and the characterizations are carried out as for formulation 1.
Table 6: Properties of copper metal strips with a thickness of 12.5 um coated with formulation 2:
Formulation Ex. 9 With Ex. 7 No primer coating layer Electrical conductivity of the 2.2 59.104 protective coating (S/cm) Resistance at 200N (mû) 20 8 Dynamic corrosion 60 C, 0.8V
ESR cell (m0 15 Number of cycles at 60 C 60 000 0 Table 7: Properties of an aluminum metal strip with a thickness of 50 um coated with formulation 1:
Ex. 9 With Ex. 8 Formulation primer No coating layer Electrical conductivity of the 2.2 37.10' protective coating (S/cm) Resistance at 200N (mû) 77 4 Dynamic corrosion at 60 C, 0.8V
ESR cell (mQ 22 Number of cycles at 60 C 70 000 0 As shown in tables 6 and 7 of experimental results, the conductive 5 protective layer 5 described in example 9 makes it possible not only to improve the contact with the metal current collector 3 but also, via the combination with the primer layer 11, to protect the metal current collector 3 from degradation related to oxygenation in the presence of electrolyte.
= 31 FORMULATION 3:
Different components described in table 8 below are mixed to give a paste of a protective composition.
= Table 8: Compositions studied PVC/HNBr ratio 50/50 55/45 40/60 Formulation Example Example Example PVC 28.84 24.49 16.85 HNBR 2010 L 28.84 30.61 33.70 Graphite KS6L 13.24 14.05 15.47 Ensaco 260G 26.16 27.76 30.57 Luperox 231XL 40 2.19 2.33 2.56 TAC SIL 70 0.72 0.77 0.84 The binder used is a hydrophobic PVC polymer without a hydrolyzable functional group.
10 HNBr is an elastomer crosslinked by peroxides (Luperox 231XL) and a cocrosslinking agent (TAC SIL).
The conductive fillers are carbon black (Ensaco 260G) and graphite (Timcal , Timrex KS6L).
The solvent is methyl isobutyl ketone (MIBK).
The solids content is subsequently adjusted to 21% by addition of methyl isobutyl ketone (MIBK).
The deposition of the conductive protective layer 5 and the characterizations are carried out as for formulations 1 and 2.
Table 9: Properties of copper metal strips with a thickness of 12.5 um = coated with formulation 3:
Formulation Ex. 10 Ex. 11 Ex. 12 with Ex. 7 with with primer No primer primer layer coating layer layer Electrical conductivity of the protective 2.9 5.3 1.76 59.104 coating (S/cm) Resistance at 200N
(mû) Dynamic corrosion at 60 C, 0.8V
As shown in table 9 of experimental results, the conductive protective layer 5 described in examples 10 to 12 makes it possible flot only to improve the contact with the metal current collector 3 but also, via the combination with the primer layer 11, to protect the metal current collector 3 from degradation related to oxygenation in the presence of electrolyte.
from 60% to 70% of water-dispersible binder, and from 30% to 40% of conductive fillers, as remainder in order to achieve a total of 100% by weight of dry matter.
For its part, the active material 7 can be a carbon monolith or also result from an aqueous carbon-based composition, as, for example, described in the application FR2985598 filed on behalf of the applicant company.
The present invention also relates to a process for the manufacture of a conductive electrode having an aqueous electrolyte solution for a system for the storage of electrical energy, the conductive electrode comprising a metal current collector 3, at least one conductive protective layer 5 which is leaktight to electrolytes and a layer of active material 7.
The manufacturing process, illustrated in figure 2, comprises in particular the following stages:
a) Stage 101 of preparation of a protective composition This stage 101 is a stage of preparation of a protective composition comprising from 10% to 50% of a polymer or copolymer binder comprising at least 50% of vinyl chloride unit, from 10% to 50% of a crosslinked elastomer, from 0.2% to 5% of at least one agent for crosslinking said crosslinked elastomer and from 25% to 50% of =
= 17 conductive fillers, as remainder in order to achieve a total of 100% by weight of dry matter.
This protective composition is diluted in a solvent, for example methyl isobutyl ketone (MIBK), in order to achieve a proportion of 20%
to 25%.
As described above, according to a first embodiment, the polymer or copolymer binder comprising at least 50% of vinyl chloride unit can be a copolymer comprising vinyl chloride and/or vinyl acetate units and/or carboxylic acid groups, such as, for example, Vinnol H15/45 M.
According to an alternative form, the protective composition can also comprise an agent for crosslinking the copolymer comprising vinyl chloride and/or vinyl acetate units and/or carboxylic acid groups. This crosslinking agent can be a mixture of methoxymethyl- and ethoxymethylbenzoguanamine, for example Cymel 1123.
The proportion of the agent for crosslinking said copolymer comprising vinyl chloride and/or vinyl acetate units and/or carboxylic acid groups is preferably from 2% to 8%, as remainder in order to achieve a total of 100% by weight of dry matter.
In order for the crosslinking to take place, a catalyst for the crosslinking of the copolymer comprising vinyl chloride and/or vinyl acetate units and/or carboxylic acid groups is also added to the protective composition. This catalyst can in particular be an acid catalyst blocked by an amine, such as Cycat 40-45. Its proportion within the protective composition is preferably from 1% to 2%, as remainder in order to achieve a total of 100% by weight of dry matter.
According to a second embodiment, the polymer or copolymer binder comprising at least 50% of vinyl chloride unit can be a polyvinyl chloride (PVC).
Still as described above, for its part, the crosslinked elastomer can be a hydrogenated butadiene/acrylonitrile copolymer (HNBr) crosslinked by peroxides, for example Luperox 231XL, which are accompanied by a cocrosslinking agent, for example based on silica and on triallyl cyanurate (TAC SIL).
The conductive fillers used are preferably carbon black, for example Ensaco 260G, and/or graphite, for Timcal or Timrex KS6L, or also carbon nanotubes.
The protective composition can additionally comprise an adhesion additive in a proportion of 2% to 7%, as remainder in order to achieve a total of 100% by weight of dry matter. This adhesion additive makes possible, in the end, better adhesion of the protective layer 5 to the current collector 3. It can, for example, be a copolymer comprising acrylic functional groups and an olefinic base, such as, for example, Degalan VP 4174E.
b) Stage 102 of deposition of the protective composition This stage 102 is a stage of deposition of said protective composition on the metal current collector 3, for example using a film drawer.
c) Stage 103 of first heat treatment During this stage 103, the covered metal current collector 3 is subjected to a first heat treatment at a temperature lower than the boiling point of the solvent, for example for a period of time of 30 minutes.
This heat treatment stage thus makes it possible to remove the solvent from. the conductive protective layer 5 covering the metal current collector 3, while retaining the mechanical properties of this layer.
d) Stage 104 of second heat treatment During. this stage 103, the covered metal current collector 3 is subjected to a second heat treatment at a temperature greater than the glass transition temperature of the binder comprising at least 50% of vinyl chloride unit and than the boiling point of the solvent, said heat treatment temperature being, however, lower than the decomposition temperature of said binder, for example for a period of time of 30 minutes.
The term "decomposition temperature" is understood to mean the temperature at which the copolymer is destroyed and disappears from the conductive protective layer S.
This second heat treatment makes it possible to remove the surplus solvent and also to reinforce the leaktightness of the conductive protective layer S. In addition, this stage makes possible the crosslinking of the different crosslinkable components of the conductive protective layer 5.
=
e) Stage 105 of menaration and deposition of the laver of active material 7 During. this stage 105, the active material 7 is prepared and 5 deposited on the protective layer 5.
As described above, the active material 7 can be a carbon monolith or also result from an aqueous carbon-based composition, as, for example, described in the application FR2985598 filed on behalf of 10 the applicant. company.
In the case where the active material 7 results from an aqueous carbon-based composition, this stage 105 can in particular comprise the following substages:
preparation of an aqueous composition of active material, 15 for example starting from carbon black, from polyvinyl alcohol, from polyacrylic acid and from carboxymethylcellulo se, deposition of the active material composition on the protective layer 5, for example using a film drawer, drying heat treatment, for example for 30 min at a 20 temperature of 50 C, crosslinking heat treatment, for example for 30 min at a temperature of 140 C (this crosslinking can be carried out during stage 104 of second heat treatment of the conductive protective layer 5).
The manufacturing process can also comprise, before stage 102 of deposition of the protective composition on the metal current collector 3, the following stages:
- a stage 110 of preparation of a primer composition comprising from 60% to 70% of water-dispersible binder and from 30% to 40%
of conductive fillers, as remainder in order to achieve a total of 100% by weight of dry matter, diluted in an aqueous solvent, - a stage 111 of deposition of said primer composition on the metal current collector 3, - a stage 112 of drying the metal current collector, for example for a period of time of 30 min at a temperature of 50 C, so as to obtain a primer layer 11 with a thickness of between 5 and 20 micrometers.
Three examples of formulations for the manufacture of a conductive protective layer 5 within a metal current collector 3 of a conductive electrode are illustrated below.
The desired parameters of these conductive protective layers 5 are as follows:
- surface conductivity > 1 S/cm - volume resistivity < 80 mû
- dynamic corrosion time > 7 h at 0.8V at 60 C
- number of cycles of the closed cells at ambient temperature > 300 000 cycles (it is the number of cycles for which the equivalent series resistance (ESR) of the system remains less than twice its initial value).
- number of cycles of the closed cells at 60 C > 10 000 cycles (it is the number of cycles for which the equivalent series resistance (ESR) of the system remains less than twice its initial value).
FORMULATION 1:
Different components described in table 1 below are mixed to give a paste of a Protective composition.
Table 1: Compositions studied Vinnol/HNBr ratio 50/50 60/40 70/30 40/60 30/70 Formulation Example Example Example Example Example Vinnol H15/45 M 27.47 21.97 38.45 32.96 16.48 HNBr 27.47 32.96 16.48 21.97 38.45 Timrexe KS6L 12.60 12.60 12.60 12.60 12.60 Ensaco 260G 24.92 24.92 24.92 24.92 24.92 Luperox 231XL 40 2.08 2.08 2.08 2.08 2.08 TAC SIL 70 0.69 0.71 0.71 0.71 0.71 Degalan VP 4174E 4.76 4.77 4.77 4.77 4.77 The binder used is Vinnol H15/45 M. It is a copolymer comprising vinyl chloride and vinyl acetate units and carboxylic acid groups.
HNBr is an elastomer crosslinked by peroxides (Luperox 231XL
40) and a cocrosslinking agent (TAC SIL 70).
The conductive fillers are carbon black (Ensaco 260G) and graphite (Timcal , Timrex KS6L).
An additive, Degalan VP 4174E, is used to improve the adhesion between the conductive protective layer 5 and the metal current collector 3. Tt is a dispersion of a copolymer comprising acrylic functional groups and an olefinic base.
=
The solvent is methyl isobutyl ketone (MIBK).
The solids content is subsequently adjusted to 21% by addition of methyl isobutyl ketone (MIBK).
Deposition of the conductive protective laver 5:
140 microns of these compositions are subsequently deposited on the first face of a metal strip, acting as metal current collector 3, using a film drawer which makes possible homogenous and controlled deposition.
After drying at 50 C for 30 minutes, the covered strips are subsequently crosslinked at 140 C for 30 minutes.
The coating thickness is measured using a micrometer and is between 15 and 20 microns.
The metal strips can be covered with a primer layer 11 produced in the following way:
Different components described in table 2 are mixed to give a paste of a primer composition.
Table 2: components of the primer composition:
Formulation PU 6800 64.7 Ensaco 260G 11.76 Timr ex KS6L 23.53 =
The polymer or copolymer binder used is PU 6800; it is a latex of polyurethane in the aqueous phase.
The conductive fillers are carbon black (Ensaco 260G) and graphite (Timcal , Timrex KS6L).
Deposiiion of the primer laver 11:
55 microns of this primer composition is deposited on the first face of the metal strip using a film drawer which makes possible homogenous and controlled deposition.
After drying at 50 C for 30 minutes, the coating thickness is measured using a micrometer and is between 15 and 20 microns.
Characterization:
The covered metal strips are subsequently characterized in three different ways.
1) A deposition of the coating is carried out on glass according to the same method used on the metal current collector 3. A four-point conductivity measurement makes it possible to determinc the intrinsic electrical conductivity of the protective coating composed of the conductive protective layer 5 and with, if appropriate, the primer layer 11.
2) A volume resistivity test is carried out by placing under pressure a 3 cm2 square of two bands of covered strips. Pressure sweeping from 100N, 125N, 150N to 200N is carried out. This measurement makes it possible to perceive the compatibility at the interface of the different layers. The resistivity measured must be as low as possible in order to allow the supercapacitor to operate at high power. =
3) A dynamic corrosion measurement via a three-electrode 5 arrangement at 60 C under 0.8V. If the conductive protective coating holds for 7 h, that is to say if no corrosion of the metal current collector 3 is observed, then the test is validated. The objective of this measurement is to force the oxidation and thus the corrosion in order to evaluate the performance of the system under conditions as close as 10 possible to real cases.
Preparation of closed cells 1:
The evaluation of the overall performance of the system is carried 15 out within closed cells 1 as illustrated in figure 1.
The covered metal strips intended for the first electrode are subsequently coated with 305 um of aqueous solution of active material 7, as described in example 1 of the application FR2985598, with the aim of having 150 um after drying at 50 C for 30 min. The layers are 20 crosslinked at 140 C for 30 min.
The same process is carried out for the second electrode, with a dry weight of active material of 90 um, i.e. 155 um wet.
The closed cells 1 are obtained by assembling the two electrodes, 25 between which is placed a cellulose separator 9. The closed cells 1 are subsequently partially immersed in a 5M aqueous solution of lithium nitrate electrolyte and are protected between two heat-sealable plastic films with a thickness of 90 um.
Table 3: Properties of copper metal strips with a thickness of 12.5 Inn coated with formulation 1:
Formulation Ex. 1 Ex. 2 Ex. 3 Ex. 4 Ex. 5 Ex. 1 Ex. 7 With With With With With Without No . .
primer primer primer primer primer primer coating layer layer layer layer layer layer Electrical conductivity of the 1.60 1.24 1.76 2.62 1.57 ////// 59.104 P
protective coating (S/cm) .
Resistance at 200N (m) 20 24 28 20 20 17 8 , Dynamic corrosion at 60 C, 0.8V
, , +: test successful + + + +
+ -, , -: failure, corrosion observed ESR cell (mQ 15 Number of cycles at amblent temperature Number of cycles at 60 C 10 000 As is shown in table 3 of experimental results, the conductive protective layer 5 described in xamples 1 to 5 makes it possible not only to improve the contact with the metal collector but also, via the combination with the primer layer 11, to protect the metal current collector from degradation related to oxygenation in the presence of electrolyte.
Example 1 of formulation 1 was subsequently coated and characterized (table 4) on an aluminum metal strip with a thickness of 50 um.
Table 4: Properties of an aluminum metal strip with a thickness of 50 um coated with formulation 1:
Ex. 1 with Ex. 8 Formulation primer No coating layer Electrical conductivity of the 1.6 37.104 protective coating (S/cm) Resistance at 200N (me) 43 4 Dynamic corrosion at 60 C, 0.8V
ESR cell (mQ 17 Number of cycles at ambient temperature Just as for copper, the conductive protective layer described in example 1 makes it possible to protect the metal collector.
Likewise, "example 1 without primer layer" confirms that it is important to have a primer layer 11 between the metal current collector 3 and the conductive protective layer 5 in order to reduce the risks of corrosion.
FORMULATION 2:
Different components described in table 5 below are mixed to give a paste of a protective composition.
Table 5: Compositions studied Formulation Ex. 9 Vinnol H15/45 M 29.00 HNBr 29.00 Ensaco 260G 23.00 Luperox 231XL 40 0.88 Timrex KS6L 13.12 TAC SIL 70 0.74 Cymel 1123 4.26 Cycat 4045 1.5 The polymer or copolymer binder used is Vinnol H15/45 M. It is a copolymer comprising vinyl chloride and vinyl acetate units and carboxylic acid groups. This copolymer is crosslinked by a mixture of methoxymethyl- and ethoxymethylbenzoguanamine. The crosslinking agent used is Cymel 1123. The catalyst for the crosslinking of the polymer or copolymer binder used is an acid catalyst blocked by an amine (Cycat.40-45).
HNBr is an elastomer crosslinked by peroxides (Luperox 231X1 40) and a cocrosslinking agent (TAC SIL 70).
The conductive fillers are carbon black (Ensaco 260G) and graphite (Timcal, Timrex KS6L).
The solvent is methyl isobutyl ketone (MIBK).
The solids content ils subsequently adjusted to 21% by addition of methyl isobutyl ketone (MIBK).
The deposition of the conductive protective layer and the characterizations are carried out as for formulation 1.
Table 6: Properties of copper metal strips with a thickness of 12.5 um coated with formulation 2:
Formulation Ex. 9 With Ex. 7 No primer coating layer Electrical conductivity of the 2.2 59.104 protective coating (S/cm) Resistance at 200N (mû) 20 8 Dynamic corrosion 60 C, 0.8V
ESR cell (m0 15 Number of cycles at 60 C 60 000 0 Table 7: Properties of an aluminum metal strip with a thickness of 50 um coated with formulation 1:
Ex. 9 With Ex. 8 Formulation primer No coating layer Electrical conductivity of the 2.2 37.10' protective coating (S/cm) Resistance at 200N (mû) 77 4 Dynamic corrosion at 60 C, 0.8V
ESR cell (mQ 22 Number of cycles at 60 C 70 000 0 As shown in tables 6 and 7 of experimental results, the conductive 5 protective layer 5 described in example 9 makes it possible not only to improve the contact with the metal current collector 3 but also, via the combination with the primer layer 11, to protect the metal current collector 3 from degradation related to oxygenation in the presence of electrolyte.
= 31 FORMULATION 3:
Different components described in table 8 below are mixed to give a paste of a protective composition.
= Table 8: Compositions studied PVC/HNBr ratio 50/50 55/45 40/60 Formulation Example Example Example PVC 28.84 24.49 16.85 HNBR 2010 L 28.84 30.61 33.70 Graphite KS6L 13.24 14.05 15.47 Ensaco 260G 26.16 27.76 30.57 Luperox 231XL 40 2.19 2.33 2.56 TAC SIL 70 0.72 0.77 0.84 The binder used is a hydrophobic PVC polymer without a hydrolyzable functional group.
10 HNBr is an elastomer crosslinked by peroxides (Luperox 231XL) and a cocrosslinking agent (TAC SIL).
The conductive fillers are carbon black (Ensaco 260G) and graphite (Timcal , Timrex KS6L).
The solvent is methyl isobutyl ketone (MIBK).
The solids content is subsequently adjusted to 21% by addition of methyl isobutyl ketone (MIBK).
The deposition of the conductive protective layer 5 and the characterizations are carried out as for formulations 1 and 2.
Table 9: Properties of copper metal strips with a thickness of 12.5 um = coated with formulation 3:
Formulation Ex. 10 Ex. 11 Ex. 12 with Ex. 7 with with primer No primer primer layer coating layer layer Electrical conductivity of the protective 2.9 5.3 1.76 59.104 coating (S/cm) Resistance at 200N
(mû) Dynamic corrosion at 60 C, 0.8V
As shown in table 9 of experimental results, the conductive protective layer 5 described in examples 10 to 12 makes it possible flot only to improve the contact with the metal current collector 3 but also, via the combination with the primer layer 11, to protect the metal current collector 3 from degradation related to oxygenation in the presence of electrolyte.
Claims (28)
1. A conductive electrode for a system for the storage of electrical energy (1) having an aqueous electrolyte solution, said electrode comprising a metal current collector (3) and an active material (7), said current collector (3) comprising at least one conductive protective layer (5) which is leaktight to electrolytes and which is placed between said metal current collector (3) and said active material (7), characterized in that said conductive protective layer (5) comprises:
a polymer or copolymer brider comprising at least 50% of vinyl chloride unit, a crosslinked elastomer, - at least one agent for crosslinking said crosslinked elastomer, - conductive fillers.
a polymer or copolymer brider comprising at least 50% of vinyl chloride unit, a crosslinked elastomer, - at least one agent for crosslinking said crosslinked elastomer, - conductive fillers.
2. The conductive electrode as claimed in the preceding claim, characterized in that the proportions of the chifferent components of the conductive protective layer (5) are:
from 10% to 50% of the polymer or copolymer binder comprising at least 50% of vinyl chloride unit, - from 10% to 50% of the crosslinked elastomer, - from 0.2% to 5% of the at least one agent for crosslinking said crosslinked elastomer, and from 25% to 50% of conductive as remainder in order to achieve a total of 100% by weight of dry matter.
from 10% to 50% of the polymer or copolymer binder comprising at least 50% of vinyl chloride unit, - from 10% to 50% of the crosslinked elastomer, - from 0.2% to 5% of the at least one agent for crosslinking said crosslinked elastomer, and from 25% to 50% of conductive as remainder in order to achieve a total of 100% by weight of dry matter.
3. The conductive electrode as claimed in either of the preceding daims, characterized in that the polymer or copolymer binder comprising at least 50% of vinyl chloride unit is a copolymer comprismg vinyl chloride and/or vinyl acetate units and/or carboxylic acid groups.
4. The conductive electrode as claimed in the preceding claim, characterized in that the copolymer comprising vinyl chloride and/or vinyl acetate units and/or carboxylic acid groups is crosslinked and that the conductive protective layer (5) additionally comprises:
- an agent for crosslinking said copolymer comprising vinyl chloride and/or vinyl acetate units and/or carboxylic acid groups, - a crosslinking catalyst.
- an agent for crosslinking said copolymer comprising vinyl chloride and/or vinyl acetate units and/or carboxylic acid groups, - a crosslinking catalyst.
5. The conductive electrode as claimed in the preceding claim, characterized in that the proportion of the agent for crosslinking said copolymer comprismg vinyl chloride and/or vinyl acetate umts and/or carboxyhc açid groups in the protective layer is from 2% to 8%, as remainder in order to achieve a total of 100% by weight of dry matter, and that the proportion of the crosslinking catalyst is from 1% to 2%, as remainder in order to achieve a total of 100% by weight of dry matter.
6. The conductive electrode as claimed in either of claims 4 and 5, characterized in that the agent for crosslinking said copolymer comprising vinyl chloride and/or vinyl acetate units and/or carboxylic acid groups is a mixture of methoxymethyl- and ethoxymethylbenzoguanamine.
7. The conductive electrode as claimed in one of daims 4 to 6, characterized in that the crosslinking catalyst is an acid catalyst blocked by an amine.
8. The conductive electrode as claimed in either of claims 1 and 2, characterized in that the polymer or copolymer bmder comprising at least 50% of vinyl chloride unit is a polyvinyl chloride.
9. The conductive electrode as claimed in one of the preceding claims, characterized in that the crosslinked elastomer is a hydrogenated butadiene/acrylonitrile copolymer.
10. The conductive electrode as claimed in one of the preceding claims, characterized in that the conducnve protective layer (5) additionally comprises an additive for adhesion to the current collector in a proportion of 2% to 7%, as remainder in order to achieve a total of 100% by weight of dry matter.
11. The conducnve electrode as claimed in one of the preceding daims, characterized in that it comprises a primer layer (11) placed between the metal current collector (3) and the protective layer (5), said primer layer (11) comprising a water-dispersible binder and conductive
12. The conductive electrode as claimed in the preceding clann, characterized in that the water-dispersible binder is a polyurethane latex or a polyurethane/polycarbonate latex.
13. The conductive electrode as claimed in either of claims 11 and 12, characterized in that the proportions of the different components of the primer layer (11) are:
- from 60% to 70% of water-dispersible binder, and - from 30% to 40% of conductive as remainder in order to achieve a total of 100% by weight of dry matter.
- from 60% to 70% of water-dispersible binder, and - from 30% to 40% of conductive as remainder in order to achieve a total of 100% by weight of dry matter.
14. The conductive electrode as claimed in one of daims 11 to 13, characterized in that the thickness of the primer layer (11) is between 5 and 20 micrometers.
15. The conductive electrode as claimed in one of the preceding claims, characterized in that the conductive fillers are chosen from carbon black and/or graphite and/or carbon nanotubes.
16. The conductive electrode as claimed in one of the preceding claims, characterized in that the thickness of the conductive protective layer (5) is between 5 and 30 micrometers.
17. A process for the manufacture of a conductive electrode having an aqueous electrolyte solution for a system for the storage of electrical energy (1), said electrode comprising a metal current collector (3), at least one conductive protective layer (5) which is leaktight to electrolytes and a layer of active material (7), said process comprising the following stages:
- preparation of a protective composition comprising from 10% to 50% of a polymer or copolymer binder comprising at least 50% of vinyl chloride unit, from 10% to 50% of a crosslinked elastomer, from 0.2% to 5% of at least one agent for crosslinking said crosslinked elastomer and from 25% to 50% of conductive as remainder in order to achieve a total of 100% by weight of dry matter, which are diluted in a solvent in order to achieve a proportion of 20% to 25%, - deposition of said protective composition on the metal current collector (3), - first heat treatment of the covered metal current collector (3) at a temperature lower than the boiling point of the solvent, - second heat treatment of the covered metal current collector (3) at a temperature greater than the glass transition temperature of the binder comprismg at least 50% of vinyl chloride unit and than the boiling point of the solvent, said heat treatment temperature being, however, lower than the decomposition temperature of said binder, - preparation and deposition of the layer of active material (7) on the conductive protective layer (5).
- preparation of a protective composition comprising from 10% to 50% of a polymer or copolymer binder comprising at least 50% of vinyl chloride unit, from 10% to 50% of a crosslinked elastomer, from 0.2% to 5% of at least one agent for crosslinking said crosslinked elastomer and from 25% to 50% of conductive as remainder in order to achieve a total of 100% by weight of dry matter, which are diluted in a solvent in order to achieve a proportion of 20% to 25%, - deposition of said protective composition on the metal current collector (3), - first heat treatment of the covered metal current collector (3) at a temperature lower than the boiling point of the solvent, - second heat treatment of the covered metal current collector (3) at a temperature greater than the glass transition temperature of the binder comprismg at least 50% of vinyl chloride unit and than the boiling point of the solvent, said heat treatment temperature being, however, lower than the decomposition temperature of said binder, - preparation and deposition of the layer of active material (7) on the conductive protective layer (5).
18. The manufacturing process as claimed in the preceding claim, characterized in that the polymer or copolymer bmder comprising at least 50% of vinyl chloride unit is a copolymer comprismg vinyl chloride and/or vinyl acetate units and/or carboxylic acid groups.
19. The manufacturing process as claimed in the precedmg claim, characterized in that the protective composition additionally comprises:
- from 2% to 8% of an agent for crosslinking the copolymer comprising vinyl chloride and/or vinyl acetate units and/or carboxylic acid groups, - from 1% to 2% of a crosslinking catalyst, as remainder in order to achieve a total of 100% by weight of dry matter before dilution in the solvent.
- from 2% to 8% of an agent for crosslinking the copolymer comprising vinyl chloride and/or vinyl acetate units and/or carboxylic acid groups, - from 1% to 2% of a crosslinking catalyst, as remainder in order to achieve a total of 100% by weight of dry matter before dilution in the solvent.
20. The manufacturing process as claimed in claim 19, characterized in that the agent for crosslinking said copolymer comprising vinyl chloride and/or vinyl acetate units and/or carboxylic acid groups is a mixture of methoxymethyl- and ethoxymethylbenzoguanamme.
21. The manufacturing process as claimed in one of claims 18 to 20, characterized in that the crosslinking catalyst is an acid catalyst blocked by an amine.
22. The manufacturing process as claimed in claim 17, characterized in that the polymer or copolymer binder comprising at least 50% of vinyl chloride unit is a polyvinyl chloride.
23. The manufacturing process as claimed in one of claims 17 to 22, characterized in that the crosslinked elastomer is a hydrogenated butadiene/acrylonitrile copolymer.
24. The manufacturing process as claimed in the preceding claim, characterized in that the protective composition additionally comprises an additive for adhesion to the current collector in a proportion of 2% to 7%, as remainder in order to achieve a total of 100% by weight of dry matter before dilution in the solvent.
25. The manufacturing process as claimed in one of claims 17 to 24, characterized in that it additionally comprises the following stages:
- preparation of a primer composition comprising from 60% to 70%
of water-dispersible binder and from 30% to 40% of conductive fillers, as remainder in order to achieve a total of 100% by weight of dry matter, diluted in an aqueous solvent, - deposition of said primer composition on the metal current collector (3), - drying of the metal current collector, before the deposition of the protective composition on the metal current collector (3).
- preparation of a primer composition comprising from 60% to 70%
of water-dispersible binder and from 30% to 40% of conductive fillers, as remainder in order to achieve a total of 100% by weight of dry matter, diluted in an aqueous solvent, - deposition of said primer composition on the metal current collector (3), - drying of the metal current collector, before the deposition of the protective composition on the metal current collector (3).
26. The manufacturing process as claimed in one of claims 17 to 25, characterized in that the conductive fillers are chosen from carbon black and/or graphite and/or carbon nanotubes.
27. The manufacturing process as claimed in one of daims 17 to 26, characterized in that the stage of deposition of the protective composition on the current collector (3) is carried out using a film drawer.
28. The manufacturing process as claimed in one of claims 17 to 27, characterized in that the first and second heat treatment stages each have a duration of 30 minutes.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PCT/FR2014/050151 WO2015110715A1 (fr) | 2014-01-27 | 2014-01-27 | Electrode pour système de stockage de l'énergie électrique avec collecteur comportant une couche conductrice de protection et procédé de fabrication correspondant |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2937869A1 true CA2937869A1 (fr) | 2015-07-30 |
Family
ID=50933440
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA2937869A Abandoned CA2937869A1 (fr) | 2014-01-27 | 2014-01-27 | Electrode for an electric-energy storage system with collector including a protective conductive layer and corresponding manufacturing method |
Country Status (9)
| Country | Link |
|---|---|
| US (1) | US10079118B2 (fr) |
| EP (1) | EP3100293A1 (fr) |
| JP (1) | JP6371861B2 (fr) |
| KR (1) | KR20160113665A (fr) |
| CN (1) | CN106133862B (fr) |
| AR (1) | AR099192A1 (fr) |
| CA (1) | CA2937869A1 (fr) |
| TW (1) | TWI657466B (fr) |
| WO (1) | WO2015110715A1 (fr) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111092225A (zh) * | 2019-11-25 | 2020-05-01 | 华东理工大学 | 锂电池自支撑电极用多功能包覆层及其制备方法 |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP6540406B2 (ja) * | 2015-09-11 | 2019-07-10 | 株式会社ニコン | ビーム走査装置並びにパターン描画装置 |
| CN108155387B (zh) * | 2016-12-06 | 2020-08-25 | 华为技术有限公司 | 一种弹性集流体及其制备方法、电池电极极片和柔性锂离子电池 |
| CN109585904B (zh) * | 2017-09-29 | 2021-11-23 | 辉能科技股份有限公司 | 可挠式锂电池 |
| JP7004969B2 (ja) * | 2017-11-10 | 2022-01-21 | 国立研究開発法人産業技術総合研究所 | リチウムイオン二次電池用電極 |
| KR102358448B1 (ko) * | 2017-11-21 | 2022-02-04 | 주식회사 엘지에너지솔루션 | 리튬 이차전지용 음극 및 이의 제조 방법 |
| CN111668525B (zh) * | 2019-03-06 | 2021-10-12 | 清华大学 | 自充电储能装置 |
| WO2023097594A1 (fr) * | 2021-12-02 | 2023-06-08 | Guangdong Haozhi Technology Co. Limited | Collecteur de courant modifié pour batterie secondaire |
| TWI814650B (zh) * | 2022-11-25 | 2023-09-01 | 住華科技股份有限公司 | 儲能系統及製程系統 |
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| JPH02151645A (ja) * | 1988-12-03 | 1990-06-11 | Mitsubishi Kasei Vinyl Co | 塩化ビニル系熱可塑性エラストマー組成物 |
| US5478676A (en) * | 1994-08-02 | 1995-12-26 | Rexam Graphics | Current collector having a conductive primer layer |
| WO1997025728A1 (fr) * | 1996-01-12 | 1997-07-17 | Nippon Zeon Co., Ltd. | Collecteur pour condensateur electrique double couche |
| JP2000100441A (ja) * | 1998-09-25 | 2000-04-07 | Sekisui Chem Co Ltd | リチウム電池用負極電極及びその製造方法 |
| CA2268355A1 (fr) * | 1999-04-07 | 2000-10-07 | Hydro-Quebec | Revetement de collecteurs a base de lipo3 |
| JP2001026655A (ja) * | 1999-07-16 | 2001-01-30 | Nok Corp | 炭酸ガス用成形材料 |
| US6631074B2 (en) * | 2000-05-12 | 2003-10-07 | Maxwell Technologies, Inc. | Electrochemical double layer capacitor having carbon powder electrodes |
| US9206338B2 (en) * | 2002-01-16 | 2015-12-08 | Multi-Color Corporation | Heat-transfer label assembly and method of using the same |
| US7033698B2 (en) * | 2002-11-08 | 2006-04-25 | The Gillette Company | Flexible cathodes |
| EP1894215A1 (fr) | 2005-06-24 | 2008-03-05 | Universal Supercapacitors Llc. | Collecteur de courant pour des condensateurs electrochimiques a double couche electrique et son procede de fabrication |
| FR2891402B1 (fr) * | 2005-09-29 | 2010-03-26 | Univ Toulouse | Solution dispersee de materiaux carbones pour la fabrication de collecteurs de courant. |
| US8313571B2 (en) * | 2007-09-21 | 2012-11-20 | Microchem Corp. | Compositions and processes for manufacturing printed electronics |
| EP2212949B1 (fr) * | 2007-10-26 | 2016-12-07 | Sion Power Corporation | Primaire pour électrode de batterie |
| JP4403524B2 (ja) * | 2008-01-11 | 2010-01-27 | トヨタ自動車株式会社 | 電極およびその製造方法 |
| US20120237824A1 (en) * | 2009-09-25 | 2012-09-20 | Daikin Industries, Ltd. | Positive electrode current collector laminate for lithium secondary battery |
| JP5168395B2 (ja) * | 2010-09-17 | 2013-03-21 | ダイキン工業株式会社 | 非水二次電池などの集電積層体の導電性保護層形成用ペースト |
| WO2012165350A1 (fr) * | 2011-05-27 | 2012-12-06 | 日産化学工業株式会社 | Composition de résine |
| FR2977364B1 (fr) * | 2011-07-01 | 2015-02-06 | Hutchinson | Collecteur de courant et procede de fabrication correspondant |
| FR2977712A1 (fr) * | 2011-07-05 | 2013-01-11 | Hutchinson | Electrode transparente conductrice multicouche et procede de fabrication associe |
| WO2013018157A1 (fr) * | 2011-07-29 | 2013-02-07 | 古河スカイ株式会社 | Collecteur, structure d'électrodes, batterie à électrolyte non aqueux et composant accumulateur électrique |
| JP5942992B2 (ja) * | 2011-08-03 | 2016-06-29 | 日本ゼオン株式会社 | 電気化学素子電極用導電性接着剤組成物、接着剤層付集電体および電気化学素子電極 |
| DE102011085026A1 (de) * | 2011-10-21 | 2013-04-25 | Evonik Röhm Gmbh | Verfahren zur Herstellung von Korngrenzenhaftung von expandierten Copolymeren auf Basis von Methacryl- und Acrylverbindungen und Anhaftung diverser Deckschichten auf dem Schaumkern |
| FR2985857B1 (fr) * | 2012-01-17 | 2014-01-03 | Hutchinson | Cathode pour cellule de batterie lithium-ion, son procede de fabrication et cette batterie l'incorporant. |
-
2014
- 2014-01-27 WO PCT/FR2014/050151 patent/WO2015110715A1/fr active Application Filing
- 2014-01-27 KR KR1020167023244A patent/KR20160113665A/ko not_active Application Discontinuation
- 2014-01-27 CN CN201480077438.8A patent/CN106133862B/zh not_active Expired - Fee Related
- 2014-01-27 JP JP2016565572A patent/JP6371861B2/ja not_active Expired - Fee Related
- 2014-01-27 US US15/114,341 patent/US10079118B2/en not_active Expired - Fee Related
- 2014-01-27 EP EP14729700.6A patent/EP3100293A1/fr not_active Withdrawn
- 2014-01-27 CA CA2937869A patent/CA2937869A1/fr not_active Abandoned
-
2015
- 2015-01-27 TW TW104102713A patent/TWI657466B/zh not_active IP Right Cessation
- 2015-01-27 AR ARP150100222A patent/AR099192A1/es unknown
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111092225A (zh) * | 2019-11-25 | 2020-05-01 | 华东理工大学 | 锂电池自支撑电极用多功能包覆层及其制备方法 |
| CN111092225B (zh) * | 2019-11-25 | 2022-12-13 | 华东理工大学 | 锂硫电池自支撑电极及其制备方法 |
Also Published As
| Publication number | Publication date |
|---|---|
| US10079118B2 (en) | 2018-09-18 |
| JP6371861B2 (ja) | 2018-08-08 |
| WO2015110715A1 (fr) | 2015-07-30 |
| AR099192A1 (es) | 2016-07-06 |
| US20170011861A1 (en) | 2017-01-12 |
| CN106133862B (zh) | 2019-04-02 |
| KR20160113665A (ko) | 2016-09-30 |
| EP3100293A1 (fr) | 2016-12-07 |
| CN106133862A (zh) | 2016-11-16 |
| TW201546845A (zh) | 2015-12-16 |
| TWI657466B (zh) | 2019-04-21 |
| JP2017508307A (ja) | 2017-03-23 |
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