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    • 专利摘要:
    Electrode (2) for storing electrical energy comprising a metal current collector (3) and an active material (7), the current collector (3) being coated on at least a part of one of its faces by at least one protective layer (5) placed between the current collector (3) and the active material (7), the protective layer (5) comprising: (A) a polymer matrix comprising: (Al) at least crosslinked epoxy polymer or copolymer, (A2) at least one elastomer, (B) conductive fillers. This system is used in aqueous electrolyte supercapacitors, the protective layer allowing a very significant reduction of the corrosion problems that are generally associated with the use of aqueous electrolytes, and to improve the adhesion of the active ingredient. on the metal collector.
    公开号:FR3028088A1
    申请号:FR1460575
    申请日:2014-11-03
    公开日:2016-05-06
    发明作者:Carole Buffry；Bruno Dufour；Elodie Morisset；Philippe Sonntag
    申请人:Hutchinson SA；
    IPC主号:
    专利说明:

    [0001] The invention relates to the field of electrochemical devices for storing electrical energy. It concerns in particular batteries and supercapacitors. It relates more particularly to electrodes comprising at least one metal current collector coated with one or more protection layers formulated in aqueous base, the protective layer being placed between the current collector and the active material. The formulation of the protective layer in aqueous base has the advantage of avoiding the use of flammable, toxic and environmentally harmful organic solvents. This system is used in aqueous electrolyte supercapacitors, the protective layer allowing a very significant reduction in the corrosion problems that are generally associated with the use of aqueous electrolytes. The protective layer improves the adhesion of the active ingredient to the metal collector.
    [0002] The electrodes of the invention can also be used as super-capacitor electrodes operating with an ionic liquid type electrolyte. In this case, the protective layer makes it possible to improve the adhesion and thus reduce the series equivalent resistance of the active material on the metal collector.
    [0003] State of the Prior Art 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 a separator, which allows ionic conductivity and avoids electrical contact between the electrodes. Each electrode comprises at least one metal current collector and one layer of active material. The metal current collector allows the exchange of electric current with an external system. Under the influence of a potential difference applied between the two electrodes, 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. The expression of the capacity of these supercapacitors is identical to that of conventional electrical capacitors, namely: C = ES / e with: E: the permittivity of the medium, S: the area occupied by the double layer, and e: the thickness of the double layer. ICG70035 EN Deposit text 3028088 2 The achievable capacitances in supercapacitors are much higher than those commonly achieved by conventional capacitors, due to the use of porous electrodes with high surface area (surface maximization) and the extreme narrowness of the electrochemical double layer (some 5 nanometers). The energy stored in the supercapacitor is defined according to the conventional expression of the capacitors, ie: E = 1 / 2.C.V2, in which V is the electrical potential of the supercapacity. Capacity and potential must therefore be high to optimize energy performance. The capacity depends on the porous texture actually accessible by the electrolyte. The carbon electrodes used in supercapacitive systems must necessarily be: conductive, in order to transport electrical charges, porous, in order to ensure the transport of the ionic charges and the formation of the electric double layer on a large scale. surface, and chemically inert, to avoid any energy-consuming parasitic reactions. The potential depends mainly on the nature of the electrolyte and in particular the stability of the electrolyte under the influence of the electric field. There are different types of electrolytes. Organic electrolytes, that is to say having an organic salt dispersed in an organic solvent make it possible to reach an operating potential of 2.7V. But 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. In 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. Since the layer of active material is porous, and at least a portion of the electrode is immersed in the electrolyte, the current collector is likely to be corroded by the aqueous electrolyte. Thus the life of the electrode is reduced by the lack of corrosion resistance of the current collector. Moreover, in the case where the collector is aluminum, in operation a passivation layer is formed composed of hydrated alumina A1203, xH20 which protects it from corrosion. However, this passivation layer, because of its ionic and electronic insulating properties, has the effect of increasing the resistance at the aluminum / active material interface. Furthermore, when aluminum is the positive current collector, this layer of alumina grows and densifies, as and when the electrical cycles to which the supercapacitor is subjected. Aluminum can even, in contact with certain electrolytes, lose its passive character, which causes its accelerated dissolution. The same problems have been observed with other materials forming the current collectors, such as titanium. To remedy all these problems, different solutions have been proposed. Most consist of coating the current collector with one or more layers of protection which are placed between the current collector and the active layer. To provide satisfactory protection of the current collector, the protective layer must be electrolyte-tight so as to prevent it from coming into contact with the metal collector and corroding it. It must be able to provide this protection over the entire operating temperature range of the system, typically up to 60 ° C. The protective layer must also ensure good electrical contact between the metal collector and the active material in order to have a series equivalent resistance (ESR) of the minimal supercapacitor. A low ESR is required for supercapacitor operation at high power. It must have a satisfactory adhesion to the metallic material of which the current collector is made. Finally, the weight and the volume of the protective layer must be as small as possible in order to limit the mass and the volume of the super-capacitor. A preferred configuration for supercapacitor electrodes being a wound configuration, another property of the electrodes must be their flexibility. Thus, the protective layer must also have flexibility properties. Several layers of current collector protection have been described in the prior art: To reduce corrosion and passivation problems, US 4,562,511 teaches covering the aluminum collector with a paint loaded with conductive particles. However this painting tends to increase the resistance of the system. In FR 2824418, a paint layer comprising conductive particles, such as graphite or carbon black is applied between the collector and the active material, and is then heated to remove the solvent. The paint is based on epoxy polymer and / or polyurethane. This paint is formulated in an organic solvent medium. This layer makes it possible to protect the collector in an organic environment. However, the behavior of such a collector is not known in the presence of an aqueous electrolyte. US 2009/0155693 discloses a method of forming a carbon thin film on a current collector by depositing a dispersion of carbonaceous particles in an organic sol-gel polymer matrix followed by removal of the gel by thermal degradation at high temperature. This layer makes it possible to improve the conduction properties at the level of the contact. No information is given on the water tightness. In addition, the carbon films obtained by this method are fragile and subject to abrasion during assembly of the electrodes.
    [0004] WO 200701201 and U52006 / 0292384 disclose a protective layer of a metal collector, consisting of a polymeric binder, which may be an epoxy, and carbon-based conductive fillers in powder form. The experimental part describes a lead-based collector and a protective layer based on polyvinyl chloride. This protective layer is waterproof with sulfuric acid. However, the protective compositions of the collector are formulated in an organic solvent medium. No information is given on the electrical contact between the metal collector and the active ingredient. No information is given on the watertightness in other aqueous electrolytes, especially 5M lithium nitrate in water. FR2977364 discloses metal current collectors covered by a protective layer consisting of conductive fillers dispersed in a copolymer matrix. The system described allows an improvement of the electrical contact between the metal collector and the active material, as well as a sulfuric acid seal. The copolymer used is based on vinyl chloride and / or vinyl acetate and the protective composition is prepared in an organic medium.
    [0005] U52012 / 0237824 discloses current collectors for lithium battery electrodes with corrosion resistance. The current collector is coated with a protective layer based on fluororesin. The protective layer may further contain as additives: fine rubber particles to improve flexibility, an adhesion promoter such as an epoxy resin, a fluororesin crosslinking agent to reduce its swelling. However, the protective compositions taught by this document are based on organic solvent. JPH0582396 discloses an assembly of a current collector made of a rubber-like material and a layer of active material, the assembly comprising an intermediate adhesive layer based on carbon black or graphite and a resin, which can be a polycarbodiimide resin, ABS, epoxy, polyphenylene sulfate, urethane, acrylic, polyester. The adhesive composition is formulated in a solvent medium ICG70035 EN Text for organic deposition 3028088. The active layer is attached to the current collector by hot pressing on the collector coated with the adhesive. EP2207188 discloses a supercapacitor electrode comprising an active material layer formulated in an aqueous medium and comprising a conductive material, a binder of carboxymethylcellulose and acrylic elastomer resin. JP2000100441 discloses a lithium battery electrode comprising a layer of active material comprising a conductive material, a binder based on a thermoplastic crosslinked elastomer, such as a polyester amide. However, a layer of active material does not exhibit the same characteristics as a protective layer of the current collector. In particular, the layer of active material must have a high porosity, unlike the protective layer. There are currently no electrodes for the operation of a supercapacitor in an aqueous electrolyte, with a protective coating of the current collector formulated in aqueous base, the electrode having both a low ESR , good corrosion resistance, high temperature stability over a large number of cycles, and satisfactory flexibility properties. The invention solved these problems found in the electrodes of the prior art.
    [0006] SUMMARY OF THE INVENTION The invention relates to an electrode for storing electrical energy comprising a metal current collector and an active material, the current collector being coated on at least a portion of one of its faces by at least one protective layer placed between the current collector and the active material, characterized in that the protective layer comprises: (A) a polymer matrix comprising: (A1) at least one crosslinked epoxy polymer or copolymer, (A2) At least one elastomer, (B) Conductive fillers.
    [0007] The invention also relates to a method of manufacturing an electrode comprising: 1 - The supply of a metal current collector, 2 - The preparation of an aqueous composition (G) comprising: (A1) At least one polymer or an epoxy copolymer and at least one crosslinking agent, (A2) At least one elastomer, ICG70035 EN Text for depositing 3028088 6 (B) Conductive fillers, 3-depositing the composition (G) on at least a part of a face of the current collector, a first heat treatment for drying the composition (G), a second heat treatment of the coated current collector at a temperature above the glass transition temperature of the epoxy polymer or copolymer crosslinked (Al), and lower than the degradation temperature of the crosslinked epoxy polymer or copolymer (Al), 6-depositing a layer of active material on the coated current collector.
    [0008] Another subject of the invention is a supercapacitor comprising two electrodes of which at least one part is immersed in an ionic electrolyte, the two electrodes being separated by an insulating membrane, at least one of the two electrodes being according to the invention described herein. above and illustrated in detail below. According to a preferred embodiment, the protective layer is obtained by drying and crosslinking an aqueous composition (G) comprising: - precursors of the polymer matrix (A) 20 - precursors of polymer (s) or crosslinked epoxy copolymer (s) (Al) - at least one elastomer (A2), - conductive fillers (B).
    [0009] According to a preferred embodiment, the protective layer is obtained by drying and crosslinking an aqueous composition (G) consisting essentially of: precursors of the polymer matrix (A): polymer precursors ( s) or crosslinked epoxy copolymer (s) (Al) - at least one elastomer (A2), - conductive fillers (B). According to a preferred embodiment, the current collector (3) is made of aluminum or copper. According to a preferred embodiment, (A2) is selected from: elastomers having a film-forming temperature below 20 ° C. According to a preferred embodiment, (A1) is chosen from: a crosslinked epoxy polymer, a crosslinked epoxy-alkyd copolymer, a mixture of epoxy polymer and crosslinked alkyd resin. According to a preferred embodiment, (A1) is a crosslinked epoxy-alkyd copolymer.
    [0010] According to a preferred embodiment, (A2) is chosen from butadiene-acrylonitrile (NBR) latices and polyurethane latices. According to a preferred embodiment, (B) is chosen from: mixtures of carbon black and graphite. According to a preferred embodiment, the polymer composition (A) represents from 50 to 70%, the conductive fillers (B) represent from 30 to 50%, and the sum of the masses of (A) and (B). ) represents from 95 to 100%, advantageously from 98 to 100%, and preferably from 99 to 100%, by mass of dry matter, relative to the total mass of dry matter of the protective layer.
    [0011] According to a preferred embodiment, the protective layer comprises: from 30 to 60% of at least one crosslinked epoxy polymer or copolymer (A1), from 10 to 30% of at least one elastomer (A2) from 30 to 50% of conductive fillers (B), the sum of the masses of (A1), (A2) and (B) represents from 95 to 100%, advantageously from 98 to 100%, and preferably from 99 to 100%, by mass of dry matter, relative to the total mass of dry matter of the protective layer.
    [0012] According to a preferred embodiment, the protective layer has a thickness ranging from 5 to 50 μm. According to a preferred embodiment, a primer layer is placed between the metal current collector and the protective layer. According to a preferred embodiment, the method of the invention further comprises a step of preparing the current collector before depositing the composition (G), this step comprising one or more steps chosen from: an abrasive treatment, a chemical treatment. According to a preferred embodiment of the process of the invention, the deposition of the composition (G) on the current collector is carried out using a film puller. According to a preferred embodiment of the process of the invention, the deposition step 3 followed by drying 4 is carried out one or more times until a deposition thickness after drying of 5 to 50 is obtained. .m.
    [0013] According to a preferred embodiment of the process of the invention, the treatment temperature in step 5- is 120 to 160 ° C, preferably 130 to 150 ° C. According to a preferred embodiment of the process of the invention, the preparation and the deposition of the active ingredient comprises the following sub-steps: (i) - preparation of an aqueous composition of active ingredient, (ii) - deposit of the active ingredient composition on the protective layer, (iii) - drying heat treatment.
    [0014] According to a preferred embodiment of the process of the invention, the step 6 of deposition of a layer of active material is carried out before step 5 of the second heat treatment. According to a preferred embodiment of the supercapacitor of the invention, the electrolyte is an aqueous electrolyte. According to a preferred embodiment of the supercapacitor of the invention, the electrolyte is an ionic liquid.
    [0015] According to a preferred embodiment of the supercapacitor of the invention, the two electrodes are according to the invention described above and illustrated in detail below. ICG70035 EN Deposited text 3028088 9 Detailed description The current collector: In known manner, the material used for the current collector may be, for example, aluminum and its alloys, copper and its alloys, stainless steel, nickel and its alloys, titanium and its alloys, and materials resulting from the treatment of the surface of aluminum or stainless steel or titanium with carbon. Of these, aluminum and its alloys, copper and its alloys are preferred examples. Advantageously, the current collector is made of aluminum or copper.
    [0016] These materials may also be subjected to oxidation treatment of the surface prior to use. The introduction of micro-reliefs on the surface of the current collector by a surface treatment is advantageous because it improves the adhesion of the material. The thickness of the current collector is generally in the range of 5 to 30 μm.
    [0017] The protective layer: The protective layer comprises a polymeric matrix (A) comprising at least at least one crosslinked epoxy polymer or copolymer (A1), and at least one elastomer (A2). It also comprises a conductive material of charge type (B). Preferably in the protective layer according to the invention: - the polymer matrix (A) represents from 50 to 70%, - the conductive fillers (B) represent from 30 to 50%, - the sum of the masses of (A) ) and (B) represents from 95 to 100%, by mass of dry matter, relative to the total solids mass of the protective layer.
    [0018] Preferably, the sum of the masses of (A) and (B) represents from 98 to 100%, even more preferably from 99 to 100%, by mass of dry matter, relative to the total mass of dry matter of the layer. protection. By polymer matrix is meant in the sense of the present invention a material resulting from the drying and optionally the crosslinking of polymers, copolymers, crosslinking agents, and additives, such as in particular crosslinking catalysts, surfactants , dispersing agents, wetting agents. The polymer matrix is obtained from a polymer composition, by drying and crosslinking. In practice, the polymer composition is mixed with the other components, including the electroconductive charges, to form a coating composition or protective composition (G) in the form of an aqueous dispersion. The protective composition is dried and then subjected to a treatment (heating for example) which triggers the crosslinking reaction. The ICG70035 EN Text for Deposition 3028088 Polymer matrix is formed as a result of this treatment. The protective layer is then obtained. Advantageously, the protective layer comprises: - from 30 to 60% of a crosslinked epoxy matrix (A1), 5 - from 10 to 30% of at least one elastomer (A2), - from 30 to 50% of conductive fillers (B) and the sum of the masses of (A1), (A2) and (B) represents from 95 to 100%, by mass of dry matter, relative to the total mass of dry matter of the protective layer.
    [0019] Preferably, the sum of the masses of (A1), (A2) and (B) represents from 98 to 100%, even more preferably from 99 to 100%, by mass of dry matter, relative to the total mass of dry matter. of the protective layer. The polymer matrix (A): The polymer matrix (A) comprises: (A1) at least one crosslinked epoxy polymer or copolymer, (A2) at least one elastomer. For the purposes of the present invention, polymer matrix is preferably understood to mean a material consisting essentially of polymers, copolymers, crosslinking agents and additives used for the manufacture of this matrix, such as, in particular, crosslinking catalysts. surfactants. Preferably, the polymer matrix (A) consists essentially of one or more crosslinked epoxy polymer (s) or copolymer (s), one or more elastomers (s), crosslinking agents, crosslinking catalysts, surfactants, dispersing agents, wetting agents.
    [0020] Preferably, (A1) is selected from: a crosslinked epoxy polymer, a crosslinked epoxy-alkyd copolymer, a mixture of epoxy polymer and crosslinked alkyd resin. Even more preferentially (A1) is a crosslinked epoxy-alkyd copolymer. As an example of an epoxy resin, mention may be made of: epoxy glycidyl resins which are prepared by a condensation reaction of the appropriate dihydroxy compound with a diacid or a diamine and with epichlorohydrin, such as, for example, bisphenol A diglycidyl ether (DGEBA) Novolac epoxy resins, which are glycidyl ethers of novolac phenolic resins. They are obtained by reacting phenol with formaldehyde in the presence of an acid catalyst to produce a Novolac phenolic resin, followed by reaction with epichlorohydrin. As an example of an epoxy-alkyd copolymer, there may be mentioned an alkyd resin containing a carboxyl group with which the epoxy resin has been reacted by a carboxy / epoxy esterification reaction. Among the crosslinking agents, mention may be made of amine crosslinking agents such as melamines, in particular hexamethoxymethylmelamine. Preferably, the crosslinking agent represents from 10 to 40%, preferably from 15 to 35%, more preferably from 20 to 30%, by weight relative to the weight of (A1) in dry matter. The catalyst is preferably used in an amount ranging from 0.1 to 2.5% by weight relative to the weight of crosslinking agent, in dry matter. Among the catalysts, mention may be made of paratoluene sulphonic acid. Preferably (A1) is a crosslinked epoxy matrix, i.e. a material resulting from the crosslinking of an epoxy polymer composition. Preferably (A1) is a material obtained from a polymer composition of which at least 30% by weight of dry matter is epoxy polymer or epoxy moieties in a copolymer. Preferably (A1) is a material consisting essentially of a crosslinked epoxy polymer or a crosslinked epoxy copolymer or a crosslinked mixture of an epoxy and another polymer, such as an alkyd resin. It may remain in (A1) greater or lesser amounts of uncrosslinked polymer or copolymer, unreacted crosslinking agent, catalyst, surfactant, wetting agents, dispersants. (A1) is implemented in the invention in the form of a polymer composition (CAO), which is an aqueous composition which comprises the (co) polymer or the mixture of (co) polymers, the agent crosslinker, the catalyst and optionally surfactants Such compositions are commercially available or can be readily prepared from commercially available products Preferably the elastomer (A2) is an elastomer or a mixture of elastomers selected from elastomers having a film-forming temperature of less than 20 ° C. (A2) may be chosen from cross-linked or non-crosslinked elastomers, it may be chosen from natural or synthetic latices, for example butadiene-acrylonitrile (NBR) latices, hydrogenated butadiene-acrylonitrile latexes (NBR), polyurethane latices, acrylic latices, styrene butadiene (SBR) latices, butyl latices, acrylonitrile-butadiene-styrene latices ( ABS), and mixtures thereof (A2) can be crosslinked simultaneously with the crosslinking of (A1), under the effect of the same crosslinking agent as (A1) or under the action of a specific crosslinking agent. Preferably, (A2) is selected from butadiene-acrylonitrile (NBR) latices and polyurethane latices. (A2) is used in the invention in the form of a latex composition (CA2). It is an aqueous composition that includes elastomer and surfactants. It may further comprise crosslinking agents. Such compositions are commercially available or can be readily prepared from commercially available products. According to a preferred embodiment, the protective layer comprises: from 30 to 60% of a matrix (Al) chosen from: a crosslinked epoxy polymer, a crosslinked epoxy-alkyd copolymer, a mixture of epoxy polymer and resin cross-linked alkyd, - from 10 to 30% of at least one elastomer (A2) chosen from: butadiene-acrylonitrile (NBR) latexes and polyurethane latices, - from 30 to 50% conductive fillers (B) and the sum masses of (Al), (A2) and (B) represent from 95 to 100%, advantageously 98 to 100%, even more preferably from 99 to 100% by weight of dry matter, relative to the total mass of material dry of the protective layer.
    [0021] Composition (G) According to the invention, the protective layer is obtained by drying and crosslinking an aqueous composition (G) comprising: precursors of the polymer matrix (A): polymer precursors (s) or cross-linked epoxy copolymer (s) (Al) - at least one elastomer (A2), - conductive fillers (B). Preferably, in the aqueous composition (G): the precursors of the polymer matrix (A) represent from 50 to 70%, the conductive fillers (B) represent from 30 to 50%, the sum of the masses of A) and (B) represent from 95 to 100%, by mass of dry matter, relative to the total dry mass of the aqueous composition (G). Preferably, the sum of the masses of (A) and (B) is from 98 to 100%, more preferably from 99 to 100% by weight of dry matter, based on the total solids content of the aqueous composition. (BOY WUT). Advantageously, the aqueous composition (G) comprises: - 30 to 60% of precursors of a crosslinked epoxy matrix (Al), - 10 to 30% of at least one elastomer (A2) from 30 to 50% of conductive fillers (B) and the sum of the masses of (Al), (A2) and (B) represents from 95 to 100% by weight of dry matter, relative to the total mass of dry matter of the aqueous composition (G). Preferably, the sum of the masses of (Al), (A2) and (B) represents from 98 to 100%, more preferably from 99 to 100% by weight of dry matter, relative to the total dry matter mass of the aqueous composition (G).
    [0022] According to a preferred embodiment, the aqueous composition (G) comprises: from 30 to 60% of precursors of a crosslinked epoxy matrix (Al), (Al) being chosen from: a crosslinked epoxy polymer, an epoxy copolymer, crosslinked alkyd, a mixture of epoxy polymer and crosslinked alkyd resin; from 10 to 30% of at least one elastomer (A2) chosen from: butadiene-acrylonitrile latexes (NBR) and polyurethane latices; 50% of conductive fillers (B) and the sum of the masses of (Al), (A2) and (B) represents from 95 to 100%, advantageously 98 to 100%, even more preferably from 99 to 100% by weight of dry matter, based on the total mass of dry matter of the aqueous composition (G). By precursors of the polymer matrix is meant the monomers, prepolymers, polymers and copolymers, the crosslinking agents and the additives used for the manufacture of this matrix, such as, in particular, crosslinking catalysts, surfactants, dispersants, wetting agents.
    [0023] The proportion of the components of the protective layer is controlled by the choice of the proportions of the components of the protective composition (G). In known manner, the heat treatment is carried out at a temperature and for a time sufficient to cause the crosslinking of the polymer (s) or copolymer (s) epoxy.
    [0024] The aqueous composition (G) can be prepared by mixing the various constituents of (CAO, (CA2) and (B) in any order: for example the conductive fillers can be introduced in part into (CAO and (CA2) before mixing them or they can be introduced after (CAO and (CA2) have been mixed.
    [0025] In order to facilitate the production of a stable and homogeneous composition, surfactants, dispersing agents, dispersing agents, dispersing agents, and dispersants may be incorporated in a manner known to those skilled in the art. water such as alcohols, especially ethanol or isopropanol. The aqueous composition (G) has a dry extract which is advantageously from 25 to 50%, preferably from 30 to 45% by weight. The choice of dry extract is adapted by those skilled in the art depending on the method of application of the composition. Conductive filler: For the purpose of the invention, the term "electrically conductive filler" means a filler having a volume resistivity of 1 × 10 -9 to 1 μcm. The preferred volume resistivity is from 1 x 10-6 to 1 x 10-1 cm -1.
    [0026] The electrically conductive charge may be selected for example from electrically conductive carbon charges. These electrically conductive fillers can be in the form of particles, in the form of fibers, or a mixture of different types of charges. Among the particulate carbon charges are carbon black, acetylene black, nanoporous carbon, graphite (natural graphite, artificial graphite). An average primary particle diameter of 0.002 to 20 μm, and in particular 0.025 to 10 μm, is preferred for obtaining a high electrical conductivity. Carbon fibers in the form of fibers include carbon fibers, carbon nanotubes and carbon nanofibers. The conductive filler preferably consists of at least one filler selected from the group consisting of carbon black, acetylene black, nanoporous carbon, graphite, carbon fibers, carbon nanotubes, and nanofibers of carbon. Preferably the invention is carried out with a filler selected from: mixtures of carbon black and graphite. Advantageously, the conductive filler is selected from mixtures having a carbon / graphite mass ratio of from 4/1 to 1/1. The electroconductive filler is preferably incorporated in amounts ranging from 30 to 50% by weight of dry matter relative to the dry substance mass of the protective composition or of the aqueous composition (G). It is preferable to use at least 30% by weight of electroconductive charges to obtain a satisfactory electrical conductivity of the protective layer. On the other hand, the manufacture of the composition is problematic when more than 50% by weight of electroconductive charges are used: ease of mixing, stability of the coating during deposition and during drying. Surfactants: ICG70035 EN Text for Deposition 3028088 Advantageously, the aqueous composition (G) comprises at least one surfactant. The surfactants may be used to fulfill several functions in the electroconductive protective layer. They can be introduced into (CAO, in (CA2) and / or after the mixing of (CAO, (CA2) and (B) .Their role is mainly in the formulation of the composition in the wet state, before and after during application to the current collector, for, without limitation: improving the dispersibility of the electrically conductive filler, improving the stability of the polymers and copolymers in the composition, improving the properties of the spreading of the coating Some surfactants evaporate during the heat treatment, others remain in the protective composition Other components: Non-conductive charges of electricity can also be used in the protective composition in addition to the electrically conductive filler Examples of non-electrically conductive filler are: electrically nonconductive carbon, inorganic oxides, resins, and the nature and quantity of electrically conductive filler. arges are chosen according to the properties of implementation (rheology) and properties of use (adhesion properties, electrical resistance) of the electroconductive protective layer.
    [0027] It is also possible to use in the protective composition, and without limitation: an adhesion promoter in order to improve the adhesion between the current collector and the electrically conductive layer. Among the adhesion promoters, there may be mentioned, for example, an acrylic polymer or an acrylic olefin copolymer.
    [0028] These components may be introduced into (CAO, in (CA2), mixed with the conductive fillers (B) and / or introduced after the mixing of (CAO, (CA2) and (B). at most 5% by weight of the total weight of the coating layer and the aqueous composition (G), in dry matter, advantageously they represent a maximum of 2% and even more preferably 1% by weight of the total mass of the coating layer and the aqueous composition (G), in dry matter Additional layers: The protective layer is placed between the current collector and the active material. placed between the metal current collector and the protective layer, the primer layer comprising a water-dispersible binder and conductive fillers, for example the water-dispersible binder may be a polyurethane latex. a primer layer may comprise: - from 60 to 70% of at least one water-dispersible binder, 5 - from 30 to 40% of conductive fillers, in mass relative to the total mass of the primer, in terms of dry, the water-dispersible binder and the conductive fillers representing from 95 to 100% of the dry matter of the primer layer. The invention also relates to a method of manufacturing an electrode 10 comprising: 1- The supply of a metal current collector, 2 - The preparation of an aqueous composition (G) comprising: At least one epoxy polymer or copolymer and at least one crosslinking agent, at least one elastomer, conductive fillers, 3-depositing the composition (G) on at least a portion of a face of the current collector A first heat treatment of the current collector coated with (G) at a temperature of 25 to 60 ° C; a second heat treatment of the current collector coated with the dried composition (G) at a temperature of greater than the glass transition temperature of the crosslinked epoxy polymer or copolymer, and less than the degradation temperature of the crosslinked epoxy polymer or copolymer, -the deposition of a layer of active material on the collector current coated with the protective layer or composition (G) simply dried. The aqueous composition (G) used in the process is as described above, the preferred variants of the process corresponding to the preferred variants for the selection of the components of (G).
    [0029] The process of the invention may comprise, prior to the deposition of the aqueous composition (G), a preparation of the current collector, this step comprising one or more steps chosen from: an abrasive treatment (silicon carbide paper for example), a chemical etching (for example, washing with acetone, washing with a mixture of hydrofluoric acid and nitric acid).
    [0030] In known manner, the deposition of the composition (G) on the current collector may be carried out using a film-puller, or by any other method known to those skilled in the art such as the application to the brushing, rolling ... ICG70035 EN Filing for deposit 3028088 17 The deposit can be made on the entire face of the current collector or on a part only. The deposit is made at least on the portion of the current collector which will be immersed in the electrolyte. After this deposition, the composition is dried by applying a heat treatment at a temperature of preferably 25 to 60 ° C, more preferably 30 to 50 ° C. The treatment is applied for a period of 15 minutes to 1 hour, preferably about 30 minutes. This step may for example be carried out in an oven so as to benefit from a controlled atmosphere. The deposition step 3 followed by drying 4 may be carried out only once or it may be repeated so as to increase the thickness of the deposit. Preferably, the deposition step (s) are performed so as to obtain a deposition thickness after drying of 5 to 50 μm. Once a deposit of the desired thickness has been obtained, a second heat treatment is carried out at a temperature above the glass transition temperature of the epoxy polymer or copolymer and below the degradation temperature of the polymer. or epoxy copolymer, so as to form a polymer network by reaction of the crosslinking agent with the polymer (s) or the copolymer (s). Advantageously, the treatment temperature in step 5- is 120 to 160 ° C, preferably 130 to 150 ° C. The active ingredient that is used can be chosen from the materials known from the prior art for this use, in particular those described in application FR 2985598. In the cases where the active ingredient is derived from an aqueous carbonaceous composition, the deposition and drying of the active material may comprise the following sub-steps: (i) - preparation of an aqueous composition of active material for example from carbon black, polyvinyl alcohol, poly (acrylic acid) and carboxymethylcellulose, (ii) - depositing the active ingredient composition on the protective layer for example with a film puller, (iii) - drying heat treatment, for example for 30 minutes at 50 ° C, (iv) - crosslinking heat treatment, for example for 30 minutes at 140 ° C. It can be provided that the step 6 of deposition of a layer of active material is carried out before step 5 of the second heat treatment. After carrying out steps 1-4, steps (i) to (iii) are carried out and then step 5 of the second thermal treatment is applied which allows the layer to be crosslinked simultaneously. protection and the active layer. The method of the invention may optionally include, between steps 1 and 2, the deposition of a primer layer, as described above, on the current collector, followed by drying of the layer primer. Such electrodes have advantageous properties when they are used in a supercapacitor. In a capacitor operating with an ionic liquid type electrolyte, the function of the protective layer is to improve adhesion and to reduce the equivalent series resistance of the active material to the metal collector. In a capacitor operating with an aqueous electrolyte, the function of the protective layer is to protect the current collector against corrosion, improve adhesion and reduce the equivalent series resistance of the active material to the metal collector. Thus, it helps to increase the life of the capacitor. Figures: Figure 1: schematic representation of the structure of a supercapacitor Figure 2: schematic representation of the assembly used to perform the transverse resistance measurement (ESR test) Figure 3: schematic representation of a sample for the corrosion test FIG. 4: Diagrammatic representation of a dynamic corrosion test assembly. In the figures, the same reference is used to designate the same element in different schemes. FIG. 1 is a schematic representation of the structure of a supercapacitor 1. The supercapacitor 1 comprises two conductive electrodes 2 immersed in an ionic electrolyte (not shown) and separated by an insulating membrane called separator 9, which allows the ionic conductivity and avoids the electrical contact between the electrodes 2. Each electrode 2 comprises a metal current collector 3, for example copper or aluminum, covered with a protective conductive layer 5, for example with a thickness of between 5 and 50 microns, and a monolithic active material 7, for example carbon, in contact with the separator 9.
    [0031] The protective layer 5 improves the contact between the current collector and the active layer 7, it protects the metal current collector 3 against the reactive species present in the electrolyte. ICG70035 EN Text for Deposition 3028088 19 The protective layer 5 is impervious to aqueous electrolytes, in particular in an acid medium, for example at a pH of less than or equal to 4, or in a neutral medium at a pH of 7. This sealing thus makes it possible to protect the metal current collector 3 against corrosion in aqueous media, thus preventing deterioration of the electrical contact between said metal current collector 3 and the monolithic active material 7. In addition, the protective conductive layer 5 also makes it possible to improve the electrical contact. between said metal current collector 3 and the monolithic active material 7.
    [0032] According to a first embodiment, an electrochemical energy storage device is formed by superimposing a plurality of multilayer unit assemblies in accordance with that shown in FIG. 1. This first embodiment typically corresponds to a structure supercapacitor. The device may be obtained by winding the multilayer unitary unit or by stacking a plurality of multilayer unitary units. The assembly thus has a repetitive pattern defined by the unitary unit shown in FIG. 1. Experimental part: Materials and methods: I - 1. Materials: - Binder (A1): it is obtained from RESYDROL AX resin 906We (CYTEC) by crosslinking. It is a 35% dispersed resin in aqueous phase, containing epoxy and alkyd functions. It is crosslinked with hexamethoxymethylmelamine to form a thermosetting polymer. The crosslinking agent used is CYMELe303 (CYTEC). This reaction is catalyzed by a para-toluene sulfonic acid, CYCAT 4040e (CYTEC) previously dispersed in ethanol. Binder (A2): LITEX NX 1200e (SYNTHOMER): butadiene-acrylonitrile latex dispersed at 45% in aqueous phase OR PU6800 (ALBERDINGK): polyurethane latex dispersed in aqueous phase at 33%. Fillers: The conductive fillers (B) used are carbon black (ENSACO 260Ge) and graphite (TIMCAL, Timrex KS6Le). ICG70035 EN Text for Deposition 3028088 20 - Additives: A silicone surfactant is added in the formulation in order to reduce the surface tension and thus to improve the wettability of the coating on the substrate. This agent is BYK e 349. - Metal strips: aluminum foil 201.1m thick 5 In the experimental part, unless otherwise indicated all the ratios are given in mass. I - 2. Methods of manufacturing the articles: - Coating of the protective coating: 55 microns of the protective composition are deposited on the first face 10 of a metal strip using a film puller via an Elcometere allowing homogeneous removal and controlled. After 30 minutes of drying at 50 ° C., the covered strips are then treated at 140 ° C. for 30 minutes. The coating thickness is measured using a micrometer, and is between 15 to 20 microns. A second layer is made in the same way to obtain a total thickness of about 35 pm. Cell Manufacture: The coating of the coating is the same as described above. Subsequently, the coated strips for the first electrode are coated with 305 microns of active material prepared according to Example 1 of Application FR 2985598, so that an active layer thickness of 1501.1m is obtained. after drying for 30 minutes at 50 ° C. All the layers are crosslinked simultaneously for 30 minutes at 140 ° C. The same process is carried out to manufacture the second electrode, with a dry thickness of active material of 90 μm, ie 155 μm wet. The model cells are obtained by assembling the two electrodes between which is placed a cellulosic separator. Aqueous Electrolyte Cell: The assembly is filled with 5M lithium nitrate electrolyte in water and protected between two 901.1m heat-sealable plastic films. Ionic liquid cell: the whole is filled, under a controlled atmosphere, 98% EMIM BF4 (1-ethyl-3-methylimidazolium tetrafluoroborate), protected between two 901.1m heat-sealable plastic films. I - 3. Methods of test and characterization: The covered strips are characterized by implementing four different test methods: ICG70035 EN Text for deposit 3028088 21 Test 1: A transverse strength test (in mS2) is carried out by putting under pressure (200N), a square 11 of 3 cm 2 of two strips of collector 3 coated with a protective layer 5 (Figure 2). 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. To evaluate the resistance of the system, Ohm's law U = RI is used. The intensity of the current is fixed at 1 ampere and a potential sweep is carried out. A straight line I = f (U) is then obtained. Resistance can be calculated. The software used to process the data is the EC-Lab ® software. The specifications are as follows: Collector transverse resistance + coating <50 mS2 Test 2: A winding test around a mandrel is used to examine the elongation and adhesion properties of a collector coated with a protective layer. Any damage such as cracks and / or scales is detected visually. The coating is applied to the metal collector under the same conditions as described above. During the test, the sample is folded uniformly for 1 to 2 seconds through 180 ° around the mandrel. The folding is started with the largest folding diameter and the test is continued to the diameter for which the coating reveals cracks. In the tests implemented in the context of the invention, this test must be validated for a 3 mm diameter mandrel. The PF 5710 ® reference mandrels come from BYK. The specification is as follows: Winding without cracks around a mandrel 3mm in diameter Test 3: A measurement of dynamic corrosion at ambient temperature This measurement is based on a 3-electrode assembly under 0.8V. The three electrodes used are (FIG. 4): - a saturated calomel reference electrode 15, - a working electrode 2 (shown in detail in FIG. 3) constituted by the collector 3 covered with the protective coating on a part of its surface 3.1 and uncoated on part 3.2 which is not immersed in the electrolyte, a coating with a plastic film 13 protects the back (not shown) and the edges of the collector 3 35 - a counter electrode 17 made of stainless steel . The three electrodes are immersed in a beaker filled with electrolyte 19 of 180 ml. ICG70035 EN Deposited text 3028088 22 A current is then sent to the electrodes. In the context of the present invention, the current sent is 0.8 V because the solution is an aqueous solution. The purpose of this test is to evaluate the variation of the intensity of the current as a function of time. If I is constant, there is no corrosion, if I is not constant, it is that a corrosion phenomenon is present. If the protective conductive coating holds 23h then the test is validated. The objective of this measure is to force the oxidation and therefore the passivation of aluminum to evaluate the system performance under conditions as close as possible to real cases. This test is performed only if all other tests are validated.
    [0033] 10 Test 3+: dynamic corrosion measurement at 60 ° C For certain applications, particularly in the automotive industry where the supercapacitor is to be placed near a hot spot, high temperature resistance, up to 60 ° C be necessary. This is why a dynamic corrosion test at 60 ° C has also been carried out in some cases. This test is optional at this time. Its implementation is identical with the exception of the temperature of the assembly which is brought to 60 ° C throughout the duration of the test. If the protective conductive coating holds 40h then the test is validated. Test 4: Measurement of the Performance of an Electrode in the Aqueous Electrolyte Cell From a cell comprising the electrodes according to the invention, cycling is carried out at room temperature and cycling at 60 ° C. Charge-discharge cycles of 0 to 1.5 V are used. An initial and final ESR test of the complete system is performed after 90,000 cycles for the room temperature test and after 10,000 cycles for the 60 ° C test.
    [0034] 25 The specification is: ESR final <2 x ESR initial for cycling at ambient temperature> 90,000 cycles ESR final <2 x ESR initial for cycling at 60 ° C> 10,000 cycles. Test 5: Measurement of the Performance of an Electrode in the Ion Electrolyte Cell The test proceeds as in Test 4 above, with charge-discharge cycles of 0 to 3V. The evaluation of the overall performance of the system (collector + protective coating + active ingredient) is carried out within closed cells. The specification is as follows: 35 - Voltage (V)> 3 - Capacity (F)> 10 - ESR (mS2) <70 ICG70035 EN Text for deposit 3028088 23 II- Production of coatings for the manufacture of a Super-capacitor operating with an aqueous electrolyte: Hereinafter are illustrated examples of formulations for the manufacture of a protective conductive layer for coating a metal current collector. II - 1. Formulations - Formulation 1 (F1.1 and F1.2): Epoxy resin dispersed in aqueous phase Various compositions described in Table 1 are mixed to give a paste. The formulation is 100% expressed before adding the dispersion catalyst in ethanol. The solvent is water. The dry extract of the complete formulation (including ethanol) is 40%. Formulation 1: F1.1 F1.2 RESYDROL AX906W 35% in water 42.45 43.18 BYK 349 0.30 0.31 WATER 31.40 31.94 TIMREX KS6L 6.73 6.85 ENSACO 260G 13.46 13.69 CYMEL 303 98% in water 5.66 4.03 Total wet 100.00 100.00 CYCAT 4040 40% in isopropanol 0.075 0.075 ETHANOL 10.00 10.00 Table 1: Composition of Formulation 1 The percent catalyst / crosslinking percentage was then varied from formulation F1.1 1CG70035 EN Text for deposit 3028088 24 Formulation 1 F1.3 F1.4 F1.1 F1.5 F1.6 F1.7 RESYDROL AX906W 35% in the water 42.45 42.45 42.45 42.45 42.45 42.45 BYK 349 0.30 0.30 0.30 0.30 0.30 0.30 WATER 31.40 31.40 31.40 31.40 31.40 31.40 TIMREX KS6L 6.73 6.73 6.73 6.73 6.73 6.73 ENSACO 260G 13.46 13.46 13.46 13.46 13.46 CYMEL 303 98% in water 5.66 5.66 5.66 5.66 5.66 5.66 Total wet 100.00 100.00 100.00 100.00 100.00 CYCAT 4040 0.019 0.034 0.075 0.150 0.226 0.301 ETHANOL 10.00 10.00 10.00 10.00 10.00 10.00 Table 2: Variants of formulation 1 with variati Percentage of Catalyst in Formula F1.1 Formulation 2: Selection and Formulation of a Latex That Will Be Added to Formulation To improve the performance of the epoxy resin formulation, a formulation of latex chosen from those described in Table 3. These two dispersions were used because they are compatible with the epoxy resin itself dispersed in aqueous phase. Formulation 2 F2.1 F2.2 LITEX NX 1200 to 45% 92.38 0 PU 6800 to 33% 0 84.35 TIMREX KS6L 5.07 5.21 ENSACO 260G 2.55 10.43 Total wet 100.00 100.00 Dry extract 49% 44% 10 Table 3: Latex composition Litex® and PU Formulation 3: Coating compositions from mixtures of Formulation 1 and Formulation 2 The wet mass ratio Formulation 1 / Formulation 2 is between 90/10 and 85/15. The coating composition comprising Formulation 1 + Formulation 2 is designated Formulation 3 and has a solids content of 37.6%. ICG70035 EN Text for deposit 3028088 25 Formulation 3: F3.1 F3.2 F3.3 F1.1 /F2.1 85/15 0 0 F1.2 / F / 1 0 85/15 0 F1.2 / F / 2 0 0 60/40 Isopropanol 1.5 1.5 1.5 Table 4: Compositions of formulation 3 From formulation F3.1, different catalyst ratios were tested Formulation 3: F3.4 F3.5 F3.1 F3.6 F3. 7 F3.8 F1.3 /F2.1 85/15 F1.4 / F / 1 85/15 F11 /F2.1 85/15 0 F1.5 / E / 1 0 85/15 F1.6 / F / 1 85/15 F1.7 / F / 1 85/15 Isopropanol 1.5 1.5 1.5 1.5 1.5 1.5 5 Table 5: Variants of formulation 3 (amount of catalyst) From formulation F3.1, various flexibilizing basic ratios were have been tested. Formulation 3: F3.1 F3.9 F1.1 /F2.1 85/15 90/10 Isopropanol 1.5 1.5 Table 6: Variations of formulation 3 (latex ratio) II - 2. Results: Formulation 1 (counter-examples): F1.1 F1.2 Control (*) Test 1: Resistance to 200N (me) 93 74 8.0 Test 2: Mandrel winding 0 = 3mm - + (*) Uncoated strand Table 7: Properties of 201.1m foils coated with formulation ICG70035 EN Text for Deposition 3028088 The flexibility of the coating is found to be unsatisfactory. In addition, its resistance to 200N is too high. Formulation 3: F3.1 F3.2 F3.3 Control (*) Test 1: Resistance to 200N according to drawing 1 (me) 30 45 31 8,0 Test 2: Mandrel winding 0 = 3mm + + + + Test 3: Dynamic Corrosion 23h, Tamb + + + - (*) Uncoated Strand 5 Table 8: Properties of 201.1m Coated Aluminum with Formula 3 In order to optimize the crosslinking, a catalyst / crosslinking percentage study was conducted from the formulation F3.1. Formulation 3: F3.4 F3.5 F3.1 F3.6 F3.7 F3.8 Control (*) Test 1: Resistance to 34 39 30 31 27 38 8.0 200N according to diagram 1 (me) Test 2: Winding + + + + + + + on mandrel 0 = 3mm Test 3: Corrosion + + + + + + - dynamic 23h, Tamb 10 (*) Strap without coating Table 9: Properties of 201.1m aluminum with different percentages of catalyst in formulation 3 15 ICG70035 EN Text for deposit 3028088 27 Formulation 3: F3.1 F3.9 Test 1: Resistance to 200N according to diagram 1 (me) 30 29 Test 2: Mandrel winding 0 = 3mm + + Test 3: Dynamic corrosion 23h, Tamb + + Test 3+: Dynamic Corrosion 40h 60 ° C 0.8V + + Table 10: Properties of 201.1m aluminum coated with different latex base ratio in the formulation As shown in the results in Tables 8, 9 and 10, the The aqueous conductive protective layer of formulation 3 makes it possible to reduce the resistance of the collector coated with a protective layer and to protect the metal collector from degradation related to oxygenation in the presence of aqueous electrolyte. As stipulated in the specifications, formulas F3.9 and F3.1 passed the 4 characterization tests. Formula F3.1 was evaluated for dynamic corrosion at 60 ° C. - Cell with aqueous electrolyte F3.1 Control (*) Test 5: ESR cells (me) 37 /////// Cycling at ambient temperature> 90 000 ,,, -,., 0 Cycling at 60 ° C 10 000 (*) Uncoated and active material layer Table 11: Characterizations of an aqueous electrolyte cell prepared from the coating F3.1 - Ionic electrolyte cell: F3.1 V max (V) 3 Capa discharge (F) 9.6 Energetic efficiency (%) 95.4 ESR (me) 61 (*) Uncoated and active material layer 20 Table 12: Characterizations of an ionic liquid cell prepared from the coating F3.1 ICG70035 FR Text for deposit
    权利要求:
    Claims (23)
    [0001]
    REVENDICATIONS1. Electrode (2) for storing electrical energy comprising a metal current collector (3) and an active material (7), the current collector (3) being coated on at least a part of one of its faces by at least one protective layer (5) placed between the current collector (3) and the active material (7), characterized in that the protective layer (5) comprises: (A) a polymer matrix comprising: Al) at least one crosslinked epoxy polymer or copolymer, (A2) at least one elastomer, (B) conductive fillers.
    [0002]
    Electrode (2) according to claim 1, wherein the protective layer (5) is obtained by drying and crosslinking an aqueous composition (G) comprising - precursors of the polymer matrix (A) - precursors of polymer (s) or crosslinked epoxy copolymer (s) (Al) - at least one elastomer (A2), - conductive fillers (B).
    [0003]
    An electrode (2) according to claim 1 or claim 2, wherein the current collector (3) is aluminum or copper.
    [0004]
    An electrode according to any one of the preceding claims, wherein (A2) is selected from: elastomers having a film-forming temperature of less than 20 ° C.
    [0005]
    An electrode (2) according to any one of the preceding claims, wherein (Al) is selected from: a crosslinked epoxy polymer, a crosslinked epoxy-alkyd copolymer, a mixture of epoxy polymer and crosslinked alkyd resin.
    [0006]
    An electrode (2) according to any one of the preceding claims, wherein (Al) is a cross-linked epoxy-alkyd copolymer. ICG70035 EN Text for deposit 3028088 29
    [0007]
    7. Electrode (2) according to any one of the preceding claims, wherein (A2) is selected from butadiene-acrylonitrile latex (NBR) and polyurethane latex. 5
    [0008]
    An electrode (2) according to any one of the preceding claims, wherein (B) is selected from: mixtures of carbon black and graphite.
    [0009]
    An electrode (2) according to any one of the preceding claims, wherein:
    [0010]
    The polymer composition (A) represents from 50 to 70%, the conductive fillers (B) represent from 30 to 50%, and the sum of the masses of (A) and (B) represents from 95 to 100%; , in mass of dry matter, relative to the total mass of dry matter of the protective layer (5). An electrode according to any one of the preceding claims, wherein the protective layer (5) comprises: - from 30 to 60% of at least one crosslinked epoxy polymer or copolymer (A1), 30% of at least one elastomer (A2), 30% to 50% of conductive fillers (B), the sum of the masses of (A1), (A2) and (B) represents from 95 to 100% by weight of dry matter, with respect to the total mass of dry matter of the protective layer (5). 25
    [0011]
    11. Electrode according to any one of the preceding claims, wherein the protective layer (5) has a thickness ranging from 5 to 50 lm.
    [0012]
    An electrode according to any one of the preceding claims, wherein a primer layer is placed between the metal current collector (3) and the protective layer (5).
    [0013]
    13. A method of manufacturing an electrode (2) comprising: 1 - providing a metal current collector (3), 2 - preparing an aqueous composition (G) comprising: (A1) at least one polymer or an epoxy copolymer and at least one crosslinking agent, ICG70035 EN Deposit text 3028088 (A2) At least one elastomer, (B) Conductive fillers, 3-deposition of the composition (G) on at least a part of a face of the current collector (3), a first heat treatment for drying the composition (G), a second heat treatment of the current collector (3) coated at a temperature above the transition temperature. glass fiber of the crosslinked epoxy polymer or copolymer (A1), and less than the degradation temperature of the crosslinked epoxy polymer or copolymer (A1), the deposition of a layer of active material on the current collector (3). coated.
    [0014]
    14. The method of claim 13, which further comprises a step of preparing the current collector (3) before the deposition of the composition (G), this step comprising one or more steps chosen from: an abrasive treatment, a treatment chemical.
    [0015]
    15. Method according to any one of claims 13 and 14, wherein the deposition of the composition (G) on the current collector (3) is carried out using a film puller. 20
    [0016]
    16. A process according to any one of claims 13 to 15, wherein the deposition step 3 followed by drying 4 is carried out one or more times until a deposition thickness after drying is obtained. at 50 1.1.m. 25
    [0017]
    17. A process according to any one of claims 13 to 16, wherein the treatment temperature in step 5 is 120 to 160 ° C, preferably 130 to 150 ° C.
    [0018]
    18. A process according to any one of claims 13 to 17, wherein the preparation and deposition of the active ingredient comprises the following substeps: (i) - preparation of an aqueous active ingredient composition, (ii) depositing the active material composition on the protective layer; (iii) drying heat treatment. 35
    [0019]
    19. A method according to any one of claims 13 to 18, wherein the step 6 of deposition of a layer of active material is carried out before step 5 of second heat treatment. ICG70035 EN Text for deposit 3028088 31
    [0020]
    20. Supercapacitor (1) comprising two electrodes (2), at least a part of which is immersed in an ionic electrolyte, the two electrodes (2) being separated by an insulating membrane (9), at least one of the two electrodes being one of claims 1 to 12.
    [0021]
    21. Supercapacitor (1) according to claim 20 wherein the electrolyte is an aqueous electrolyte. 10
    [0022]
    22. Supercapacitor (1) according to claim 20 or claim 21 wherein the electrolyte is an ionic liquid.
    [0023]
    23. Supercapacitor (1) according to any one of claims 20 to 22 whose two electrodes are according to any one of claims 1 to 12. 15
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    优先权:
    申请号 | 申请日 | 专利标题
    FR1460575A|FR3028088B1|2014-11-03|2014-11-03|CONDUCTIVE ELECTRODES AND METHOD FOR THE PRODUCTION THEREOF|FR1460575A| FR3028088B1|2014-11-03|2014-11-03|CONDUCTIVE ELECTRODES AND METHOD FOR THE PRODUCTION THEREOF|
    CN202010589656.7A| CN111785528B|2014-11-03|2015-10-30|Conductive electrode and method for manufacturing the same|
    PCT/EP2015/075209| WO2016071217A1|2014-11-03|2015-10-30|Conductive electrodes and their manufacturing process|
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    EP15800728.6A| EP3216040B1|2014-11-03|2015-10-30|Conductive electrodes and their manufacturing process|
    CA2966435A| CA2966435A1|2014-11-03|2015-10-30|Conductive electrodes and their manufacturing process|
    US15/522,981| US10438752B2|2014-11-03|2015-10-30|Conductive electrodes and their manufacturing process|
    KR1020177015216A| KR20170078829A|2014-11-03|2015-10-30|Conductive electrodes and their manufacturing process|
    JP2017523505A| JP2018501639A|2014-11-03|2015-10-30|Conductive electrodes and methods for producing them|
    JP2020108583A| JP7038760B2|2014-11-03|2020-06-24|Conductive electrodes and their manufacturing methods|
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