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

Definitions

• the present invention relates to current-collector conductive electrodes in particular used 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 protective conductive layer and the method of manufacturing said current collector.
• Supercapacitors are electrical energy storage systems of particular interest for applications requiring the conveyance of high power electrical energy.
• the ability to charge and discharge fast, the longer life compared to a high power battery make supercapacitors promising candidates for many applications.
• Supercapacitors generally consist of the combination of two conductive electrodes with a high specific surface area, immersed in an ionic electrolyte and separated by an insulating membrane called "separator", which allows ionic conductivity and avoids electrical contact between the electrodes.
• Each electrode is in contact with a metal current collector for the exchange of electric current with an external system.
• the ions present in an electrolyte are attracted by the surface having an opposite charge thus forming a double electrochemical layer at the interface of each electrode. The electrical energy is thus stored electrostatically by separating the charges.
• e the thickness of the double layer.
• the carbon electrodes used in supercapacitive systems must necessarily be:
• the energy stored in the supercapacitor is defined according to the conventional expression of the capacitors, namely:
• capacity and potential are two essential parameters that must be optimized to promote energy performance.
• the potential depends mainly on the nature of the electrolyte.
• electrolytes There are typically different types of electrolytes.
• a family is the family of organic electrolytes, that is to say comprising an organic salt dispersed in an organic solvent. Some of these electrolytes allow to reach a potential of operation of 2.7V.
• these electrolytes are expensive, flammable, toxic and potentially polluting. They thus pose security problems for use in a vehicle.
• Aqueous electrolytes are inexpensive and non-flammable, so they are more interesting for this application.
• aqueous medium the applicable potential is 1.2V.
• Various aqueous electrolytes may be used, for example an aqueous solution of sulfuric acid, or potassium chloride, or potassium sulfate, or other salts in acidic, basic or neutral medium.
• the capacity depends on the porous texture actually accessible by the electrolyte, the potential depends directly on the stability of the electrolyte under the influence of the electric field.
• a known solution is to add active material to the supercapacitors. There are different possibilities for incorporating the active ingredient into a supercapacitor.
• ESR resistance to current flow in the system
• This resistance is the sum of the resistances of the various components of the system, and in particular the resistance of the electrolyte, and the resistance of the current collectors.
• a key contribution is the resistance of the interface between the current collector and the active ingredient. This resistance is dependent on the quality and nature of the contact.
• metals of high conductivities In addition for the sake of economy and ease of use, the metals used must be inexpensive and can be shaped easily. Examples of metals that can be favorably used are therefore typically copper and aluminum.
• the use of these materials in an aqueous medium poses problems of chemical and electrochemical stability. Indeed, at a typical oxidation potential in an aqueous medium of 1.2V, most metals corrode.
• EP1032064 discloses a current collector of a positive electrode consisting of a paste of active material comprising a polymer layer comprising an oxalate and a compound based on silicon, phosphate or chromium. This solution makes it possible to protect the collector during the removal of the paste of active material but has no effect on the characteristics of the electrode in use. It is therefore necessary to use an interface between the metal current collector and the monolithic active material.
• FR2824418 describes a current collector covered with a paint layer comprising conductive particles, such as graphite or carbon black.
• the paint is applied between the collector and the active ingredient and is then heated to remove the solvent.
• the paint is epoxy base or polyurethane base. This layer of paint protects the collector in an organic medium, but no information is given on its effectiveness to protect the collector of an aqueous electrolyte.
• WO2007 / 036641 discloses a method of depositing a carbon thin film by depositing a particle dispersion carbonaceous in a sol-gel polymer followed by the removal of said sol-gel polymer at high temperature. This additional layer makes it possible to improve the conduction properties at the contact. Nevertheless, no information is given on its watertightness in an aqueous medium. In addition, the carbon films obtained by this method are fragile and subject to abrasion during assembly of the electrodes.
• One of the aims of the invention is therefore to provide a current collector and its manufacturing method, having properties of optimized durability and conductivity.
• the present invention thus relates to a conductive electrode for an aqueous electrolyte solution electrical energy storage system, said electrode comprising a metal current collector and an active material, said current collector comprising at least one conductive protective layer to the electrolytes and placed between said metal current collector and said active material, said protective conductive layer comprising:
• a polymer or copolymer binder comprising at least 50% vinyl chloride unit
• the proportions of the various components of the protective conductive layer are:
• the polymer or copolymer binder comprising at least 50% vinyl chloride unit is a copolymer comprising vinyl chloride and / or vinyl acetate units and / or carboxylic acid groups.
• the copolymer comprising vinyl chloride and / or vinyl acetate units and / or carboxylic acid groups is crosslinked and that the protective conductive layer further comprises:
• an agent for crosslinking said copolymer comprising vinyl chloride and / or vinyl acetate units and / or carboxylic acid groups
• the proportion of the crosslinking agent of said copolymer comprising units of vinyl chloride and / or vinyl acetate and / or carboxylic acid groups in the protective layer is from 2 to 8% in addition to achieve a total of 100% by weight of dry matter and the proportion of the crosslinking catalyst is 1 to 2% in addition to achieve a total of 100% by weight of dry matter.
• the crosslinking agent of said copolymer comprising vinyl chloride and / or vinyl acetate units and / or carboxylic acid groups is a mixture of methoxymethyl and ethoxymethyl benzoguanamine.
• the crosslinking catalyst is an acid catalyst blocked by an amine.
• the binder comprising at least 50% vinyl chloride unit is a polyvinyl chloride.
• the crosslinked elastomer is a hydrogenated butadiene-acrylonitrile copolymer.
• the protective conductive layer further comprises an adhesion additive to the current collector in a proportion of 2 to 7% in addition to achieve a total of 100% by weight of dry matter.
• 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.
• the water-dispersible binder is a polyurethane latex.
• the proportions of the various components of the primer layer are: 60 to 70% of water-dispersible binder, and
• the thickness of the primer layer is between 5 and 20 microns.
• the conductive fillers are chosen from carbon black and / or graphite and / or carbon nanotubes.
• the thickness of the protective conductive layer is between 5 and 30 micrometers.
• the present invention also relates to a method for manufacturing a conductive electrode with an aqueous electrolyte solution for an electrical energy storage system, said electrode comprising a metal current collector, at least one conductive electrolytic-tight protective layer and a layer of active material,
• said method comprising the following steps:
• a protective composition comprising from 10 to 50% of a polymeric or copolymer binder comprising at least 50% vinyl chloride unit, from 10 to 50% of a crosslinked elastomer, from 0.2 to 5% at least one crosslinking agent of said crosslinked elastomer, and 25 to 50% of conductive fillers, in addition to achieve a total of 100% by weight of material dried, and diluted in a solvent to reach a proportion of 20 to 25%,
• the polymer or copolymer binder comprising at least 50% vinyl chloride unit is a copolymer comprising vinyl chloride and / or vinyl acetate units and / or carboxylic acid groups.
• the protective composition further comprises:
• the crosslinking agent of said copolymer comprising vinyl chloride and / or vinyl acetate units and / or carboxylic acid groups is a mixture of methoxymethyl and ethoxymethyl benzoguanamine.
• the crosslinking catalyst is an acid catalyst blocked by an amine.
• the polymer or copolymer binder comprising at least 50% vinyl chloride unit is a polyvinyl chloride.
• the crosslinked elastomer is a hydrogenated butadiene-acrylonitrile copolymer.
• the protective composition additionally comprises an additive for adhesion to the current collector in a proportion of 2 to 7% in addition in order to reach a total of 100% by weight of dry matter. before dilution in the solvent.
• the latter further comprises the following steps:
• preparing a primer composition comprising 60 to 70% water-dispersible binder, and 30 to 40% conductive fillers, complement to achieve a total of 100% by weight of dry matter, diluted in an aqueous solvent,
• the conductive fillers are chosen from carbon black and / or graphite and / or carbon nanotubes.
• the step of depositing the protective composition on the current collector is carried out using a film puller.
• the first and second heat treatment stages have a duration of 30 minutes each.
• FIG. 1 shows a schematic representation of the structure of a supercapacitor
• Figure 2 shows a flowchart of the steps of the manufacturing method according to the invention.
• Figure 1 shows a schematic representation of the structure of a supercapacitor 1.
• the supercapacitor 1 comprises two conductive electrodes immersed in an aqueous ionic electrolyte (not shown) and separated by an insulating membrane called separator 9, which allows the ionic conductivity and avoids electrical contact between the electrodes.
• Each electrode comprises a metal current collector 3, for example copper or aluminum, covered with an electrolytic-tight protective conductive layer 5, for example with a thickness of between 5 and 30 microns, as well as an active substance 7 in contact with the separator 9.
• This conductive protective layer 5 makes it possible in particular to improve the electrical contact between said metal current collector 3 and the active material 7.
• the protective conductive layer 5 comprises:
• a polymer or copolymer binder comprising at least 50% vinyl chloride unit
• At least one crosslinking agent of said crosslinked elastomer, conductive fillers is selected from at least one crosslinking agent of said crosslinked elastomer, conductive fillers.
• the proportions of these constituents of the protective conductive layer 5 are:
• the polymer or copolymer binder comprising at least 50% 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 ® H 15/45 M.
• the copolymer comprising units of vinyl chloride and / or vinyl acetate and / or carboxylic acid groups may be crosslinked within the protective conductive layer 5.
• the latter comprises a crosslinking agent.
• This crosslinking agent may be a mixture of methoxymethyl and ethoxymethyl benzoguanamine, e.g., CYMEL ® 1123.
• the proportion of the crosslinking agent of said copolymer comprising vinyl chloride and / or vinyl acetate units and / or carboxylic acid groups in the protective layer 5 is preferably 2 to 8% in addition in order to achieve a total of 100% by weight of dry matter.
• a catalyst for crosslinking the copolymer comprising vinyl chloride and / or vinyl acetate units and / or carboxylic acid groups is also added to the protective conductive layer 5.
• This catalyst may in particular be a acid catalyst blocked by a amin like CYCAT 40-45. Its proportion within the protective conductive layer 5 is preferably 1 to 2% in addition to achieve a total of 100% by weight of dry matter.
• the binder comprising at least 50% vinyl chloride unit can be a polyvinyl chloride (PVC) especially low molecular weight.
• the crosslinked elastomer can be in turn be hydrogenated butadiene-acrylonitrile copolymer (HNBR) crosslinked with peroxides, e.g. Luperox ® 231XL accompanied by crosslinking co-agent, e.g. silica and triallyl cyanurates of agent (TAC SIL).
• the conductive fillers used are preferably carbon black, for example ® ENSACO 260G and / or graphite by the ® TIMCAL or Timrex KS6L ® or carbon nanotubes.
• the protective conductive layer 5 may further comprise an adhesion additive in a proportion of 2 to 7% in addition to achieve a total of 100% by weight of dry matter.
• This adhesion additive allows a better adhesion of the protective layer 5 to the current collector 3, it may be for example a copolymer comprising acrylic functions and an olefinic base such as DEGALAN ® VP 4174E.
• Each electrode may also comprise a primer layer 11, with a thickness that may be between 5 and 20 micrometers, placed between the metal current collector 3 and the stripping layer. protection 5.
• This primer layer 11 comprises in particular a water-dispersible binder and conductive fillers. This primer layer 11 provides additional protection against corrosion at the metal current collector 3.
• hydrodispersible is meant that the binder can form a dispersion in an aqueous base solution.
• the water dispersible binder may be a polyurethane latex or a polyurethane / polycarbonate latex and the conductive fillers chosen from the same conductive fillers as those used in the protective conductive layer 5.
• the proportions of the various components of the primer layer 11 are preferably as follows:
• the active substance 7, for its part, may be a carbon monolith or may be derived from an aqueous carbonaceous composition, as for example described in application FR2985598 filed in the name of the applicant.
• the present invention also relates to a method of manufacturing a conductive electrode with an aqueous electrolyte solution for a system for storing electrical energy.
• the conductive electrode comprising a metal current collector 3, at least one electrolytic-tight protective conductive layer and a layer of active material 7.
• the manufacturing method, illustrated in FIG. 2, notably comprises the following steps: a) Step 101 for preparing a protection composition.
• This step 101 is a step 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 crosslinking agent of said crosslinked elastomer, and 25 to 50% of conductive fillers, in addition to achieve a total of 100% by weight of dry matter.
• This protective composition is diluted in a solvent, for example methylisobutyketone (MIBK), in order to reach a proportion of 20 to 25%.
• MIBK methylisobutyketone
• the polymer or copolymer binder comprising at least 50% vinyl chloride unit may be a copolymer comprising vinyl chloride and / or vinyl acetate units and / or carboxylic acid groups, such as Vinnol ® H15 / 45 M.
• the protective composition may also comprise a crosslinking agent for the copolymer comprising vinyl chloride and / or vinyl acetate units and / or carboxylic acid groups.
• This crosslinking agent may be a mixture of methoxymethyl and ethoxymethyl benzoguanamine, e.g., CYMEL ® 1123.
• the proportion of the crosslinking agent of said copolymer comprising vinyl chloride and / or vinyl acetate units and / or carboxylic acid groups is preferably from 2 to 8% in addition in order to reach a total of 100% by weight. dry matter.
• a crosslinking catalyst 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 may especially be an acid catalyst blocked by an amine such as CYCAT 40-45. Its proportion within the protective composition is preferably 1 to 2% in addition to achieve a total of 100% by weight of dry matter.
• the polymer or copolymer binder comprising at least 50% vinyl chloride unit may be a polyvinyl chloride (PVC).
• the crosslinked elastomer can be in turn be hydrogenated butadiene-acrylonitrile copolymer (HNBR) crosslinked with peroxides, e.g. Luperox ® 231XL accompanied by crosslinking co-agent, e.g. silica and agent triallyl cyanurates (TAC SIL).
• HNBR hydrogenated butadiene-acrylonitrile copolymer
• peroxides e.g. Luperox ® 231XL accompanied by crosslinking co-agent, e.g. silica and agent triallyl cyanurates (TAC SIL).
• TAC SIL agent triallyl cyanurates
• the conductive fillers used are preferably carbon black, for example ® ENSACO 260G and / or graphite by the ® TIMCAL or Timrex KS6L ® or carbon nanotubes.
• the protective composition may further comprise an adhesion additive in an amount of 2 to 7% in addition
• This adhesion additive ultimately allows a better adhesion of the protective layer 5 to the current collector 3, it may be for example a copolymer comprising acrylic functions and an olefinic base such as DEGALAN ® VP 4174E.
• Step 102 of depositing the protective composition it may be for example a copolymer comprising acrylic functions and an olefinic base such as DEGALAN ® VP 4174E.
• This step 102 is a step of depositing said protective composition on the metal current collector 3, for example by means of a film puller.
• Step 103 of first heat treatment is a step of depositing said protective composition on the metal current collector 3, for example by means of a film puller.
• the coated metal current collector 3 undergoes a first heat treatment at a temperature below the boiling point of the solvent, for example for a period of 30 minutes.
• Step 104 of the second heat treatment thus makes it possible to remove the solvent from the protective conductive layer 5 covering the metal current collector 3, while retaining the mechanical properties of the latter.
• the covered metallic current collector 3 undergoes 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 at the boiling point of the solvent, said heat treatment temperature being however lower than the degradation temperature of said binder, for example during a duration of 30 minutes.
• degradation temperature is meant the temperature at which the copolymer is destroyed and disappears from the protective conductive layer 5.
• the active material 7 is prepared and deposited on the protective layer 5.
• the active material 7 may be a carbon monolith or may be derived from an aqueous carbonaceous composition, for example described in the application FR2985598 filed in the name of the applicant.
• this step 105 may in particular comprise the following sub-steps:
• an aqueous composition of active material for example from carbon black, polyvinyl alcohol, poly (acrylic acid) and carboxymethylcellulose, depositing the active material composition on the protective layer 5, for example using a film puller,
• drying heat treatment for example for 30 min at a temperature of 50 C
• the manufacturing process may also comprise, before the step 102 of depositing the protective composition on the metal current collector 3, the following steps:
• a step 110 of preparing a primer composition comprising 60 to 70% of water-dispersible binder, and 30 to 40% of conductive fillers, in addition to achieving a total of 100% by weight of dry matter, diluted in an aqueous solvent,
• a step 112 of drying the metal current collector for example for a period of 30min at a temperature of 50 C so as to obtain a primer layer 11 having a thickness of between 5 and 20 microns.
• TAC SIL 70 0.69 0.71 0.71 0.71 0.71 0.71
• the binder used is Vinnol ® H15 / 45 M. It is a copolymer comprising vinyl chloride units, vinyl acetate, and carboxylic acid groups.
• HNBr is an elastomer crosslinked by peroxides (LUPEROX ®
• the conductive fillers are carbon black (ENSACO ® 260G) and graphite (TIMCAL ® , Timrex ® KS6L).
• DEGALAN ® VP 4174E is used to improve the adhesion between the protective conductor layer 5 and the metal current collector 3. This is a dispersion of a copolymer comprising acrylic functions and an olefinic base.
• the solvent is methylisobutylketone (MIBK).
• the dry extract is then adjusted to 21% by addition of methylisobutylketone (MIBK).
• MIBK methylisobutylketone
• Deposition of the protective conductive layer 5 140 microns of these compositions are then deposited on the first face of a metal strip, acting as a metal current collector 3, using a film puller for homogeneous and controlled removal.
• the covered strips are then crosslinked at 140 ° C. for 30 minutes.
• the coating thickness is measured using a micrometer, and is between 15 to 20 microns.
• the metal strips may be covered with a primer layer 11 made as follows:
• the polymer or copolymer binder used is PU 6800, it is a polyurethane latex in aqueous phase.
• Conductive fillers are carbon black (ENSACO ®
• the coating thickness is measured using a micrometer, and is between 15 to 20 microns. Characterization :
• coated metal strips are then characterized in three different ways.
• a deposition of the coating is performed on glass according to the same method used on the metal current collector 3.
• a four-point conductivity measurement makes it possible to determine the intrinsic electrical conductivity of the protective coating composed of the protective conductive layer 5 and, if appropriate, the primer layer 11.
• a transverse strength test is carried out by putting under pressure, a square of 3 cm 2 of two strip of strips covered.
• the pressure sweep is 100N, 125N, ON at 200N. This measurement makes it possible to understand the compatibility at the interface of the different layers.
• the measured resistance should be as low as possible to allow high power operation of the supercapacitor.
• the covered metal strips intended for the first electrode are then coated with 305 ⁇ m of aqueous solution of active substance 7, as described in Example 1 of Application FR2985598 in order to have 150 ⁇ m after drying for 30 minutes at 50.degree.
• the layers are crosslinked for 30 minutes at 140 C.
• the closed cells 1 are obtained by assembling the two electrodes between which is placed a cellulose separator 9. The closed cells 1 are then partially immersed in an aqueous solution of lithium nitrate electrolyte 5M and protected between two heat-sealable plastic films of 90 ⁇ d 'thickness.
• the protective conductive layer 5 described in Examples 1 to 5 not only improves 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 then coated and characterized (Table 4) on an aluminum foil 50 ⁇ thick.
• Example 1 As for copper, the protective conductive layer described in Example 1 protects the metal collector. Similarly, “Example 1 without a primer” confirms that it is important to have a primer layer 11 between the metal current collector 3 and the protective conductive layer 5 in order to reduce the risks of corrosion. .
• the binder polymer or copolymer used is Vinnol ® H15 / 45 M. It is a copolymer comprising vinyl chloride units, vinyl acetate, and carboxylic acid groups. The latter is cross-linked by a mixture of methoxymethyl and ethoxymethyl benzoguanamine.
• the crosslinker used was CYMEL ® 1123.
• the crosslinking catalyst binder polymer or copolymer used is an acid catalyst blocked with an amine (CYCAT 40-45).
• HNBR is a crosslinked elastomer with peroxide (Luperox ® 231XL 40) and a crosslinking coagent (TAC SIL 70).
• the conductive fillers are carbon black (ENSACO ® 260G) and graphite (TIMCAL, Timrex KS6L).
• the solvent is methylisobutylketone (MIBK).
• the dry extract is then adjusted to 21% by addition of methylisobutylketone (MIBK).
• MIBK methylisobutylketone
• the deposition of the protective conductive layer and the characterizations are as for the formulation 1.
• the protective conductive layer 5 described in Example 9 not only improves contact with the metal current collector 3 but also, via the association with the stratum primer 11, to protect the metal current collector 3 from the degradation associated with the oxygenation in the presence of electrolyte.
• the binder used is PVC, a hydrophobic polymer with no hydrolysable function.
• HNBR is a crosslinked elastomer with peroxide (Luperox ® 231XL) and a crosslinking coagent (TAC SIL).
• the conductive fillers are carbon black (ENSACO ® 260G) and graphite (TIMCAL ® , Timrex ® KS6L).
• the solvent is methylisobutylketone (MIBK).
• the dry extract is then adjusted to 21% by addition of methylisobutylketone (MIBK).
• MIBK methylisobutylketone
• the protective conductive layer 5 described in Examples 10 to 12 not only makes it possible to improve contact with the metal current collector 3 but also, via the association with the stripping layer. primer 11, to protect the metal current collector 3 from the degradation associated with the oxygenation in the presence of electrolyte.

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• 2014
  • 2014-01-27 US US15/114,341 patent/US10079118B2/en not_active Expired - Fee Related
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  • 2014-01-27 EP EP14729700.6A patent/EP3100293A1/de not_active Withdrawn
  • 2014-01-27 WO PCT/FR2014/050151 patent/WO2015110715A1/fr not_active Ceased
  • 2014-01-27 KR KR1020167023244A patent/KR20160113665A/ko not_active Ceased
  • 2014-01-27 CA CA2937869A patent/CA2937869A1/fr not_active Abandoned
  • 2014-01-27 CN CN201480077438.8A patent/CN106133862B/zh not_active Expired - Fee Related
• 2015
  • 2015-01-27 AR ARP150100222A patent/AR099192A1/es unknown
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