Classifications

• • 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
  • H01M4/36—Selection of substances as active materials, active masses, active liquids
  • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
  • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
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  • H01M4/04—Processes of manufacture in general
  • H01M4/0402—Methods of deposition of the material
  • H01M4/0404—Methods of deposition of the material by coating on electrode collectors
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  • H01M10/00—Secondary cells; Manufacture thereof
  • H01M10/24—Alkaline accumulators
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B15/00—Layered products comprising a layer of metal
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
  • B32B7/04—Interconnection of layers
  • B32B7/10—Interconnection of layers at least one layer having inter-reactive properties
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  • H01M10/00—Secondary cells; Manufacture thereof
  • H01M10/05—Accumulators with non-aqueous electrolyte
  • H01M10/052—Li-accumulators
  • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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  • H01M4/00—Electrodes
  • H01M4/02—Electrodes composed of, or comprising, active material
  • H01M4/04—Processes of manufacture in general
  • H01M4/0402—Methods of deposition of the material
  • H01M4/0421—Methods of deposition of the material involving vapour deposition
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  • H01M4/00—Electrodes
  • H01M4/02—Electrodes composed of, or comprising, active material
  • H01M4/04—Processes of manufacture in general
  • H01M4/0402—Methods of deposition of the material
  • H01M4/0421—Methods of deposition of the material involving vapour deposition
  • H01M4/0423—Physical vapour deposition
  • H01M4/0426—Sputtering
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  • H01M4/00—Electrodes
  • H01M4/02—Electrodes composed of, or comprising, active material
  • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
  • H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
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  • H01M4/02—Electrodes composed of, or comprising, active material
  • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
  • H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
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  • H01M4/02—Electrodes composed of, or comprising, active material
  • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
  • H01M4/134—Electrodes based on metals, Si or alloys
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  • H01M4/00—Electrodes
  • H01M4/02—Electrodes composed of, or comprising, active material
  • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
  • H01M4/136—Electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
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  • H01M4/00—Electrodes
  • H01M4/02—Electrodes composed of, or comprising, active material
  • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
  • H01M4/139—Processes of manufacture
  • H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
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  • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
  • H01M4/139—Processes of manufacture
  • H01M4/1393—Processes of manufacture of electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
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  • H01M4/00—Electrodes
  • H01M4/02—Electrodes composed of, or comprising, active material
  • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
  • H01M4/139—Processes of manufacture
  • H01M4/1395—Processes of manufacture of electrodes based on metals, Si or alloys
• • H—ELECTRICITY
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  • H01M4/00—Electrodes
  • H01M4/02—Electrodes composed of, or comprising, active material
  • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
  • H01M4/139—Processes of manufacture
  • H01M4/1397—Processes of manufacture of electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
• • H—ELECTRICITY
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  • H01M4/00—Electrodes
  • H01M4/02—Electrodes composed of, or comprising, active material
  • H01M4/36—Selection of substances as active materials, active masses, active liquids
  • H01M4/362—Composites
  • H01M4/366—Composites as layered products
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  • H01M4/00—Electrodes
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  • H01M4/36—Selection of substances as active materials, active masses, active liquids
  • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
  • H01M4/40—Alloys based on alkali metals
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  • H01M4/36—Selection of substances as active materials, active masses, active liquids
  • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
  • H01M4/5805—Phosphides
• • H—ELECTRICITY
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  • H01M4/36—Selection of substances as active materials, active masses, active liquids
  • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
  • H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
• • H—ELECTRICITY
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  • H01M4/00—Electrodes
  • H01M4/02—Electrodes composed of, or comprising, active material
  • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
  • H01M4/621—Binders
• • H—ELECTRICITY
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  • H01M10/00—Secondary cells; Manufacture thereof
  • H01M10/05—Accumulators with non-aqueous electrolyte
  • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
  • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
  • H01M10/0565—Polymeric materials, e.g. gel-type or solid-type
• • H—ELECTRICITY
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  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M10/00—Secondary cells; Manufacture thereof
  • H01M10/05—Accumulators with non-aqueous electrolyte
  • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
  • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
  • H01M10/0566—Liquid materials
  • H01M10/0568—Liquid materials characterised by the solutes
• • H—ELECTRICITY
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  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M10/00—Secondary cells; Manufacture thereof
  • H01M10/05—Accumulators with non-aqueous electrolyte
  • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
  • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
  • H01M10/0566—Liquid materials
  • H01M10/0569—Liquid materials characterised by the solvents
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  • H01M2300/00—Electrolytes
  • H01M2300/0085—Immobilising or gelification of electrolyte
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  • H01M2300/00—Electrolytes
  • H01M2300/0088—Composites
  • H01M2300/0091—Composites in the form of mixtures
• • 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
  • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
  • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
  • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

• the present invention relates to multi-layer materials comprising a solid support and at least two solid superimposed layers which contain particles of an electrochemically active material. These multilayer materials are characterized in particular by a low interpenetration between adjacent solid layers.
• the present invention also relates to processes for preparing the multi-layer materials of the invention, especially those comprising a step of spreading a mixture comprising particles of electrochemically active materials.
• the present invention also relates to the multi-layer electrodes obtained by the process of the invention and which have remarkable mechanical and electrochemical properties.
• the present invention relates to electrochemical generators which incorporate at least one electrode based on a multi-layer material of the invention and which are characterized by exceptional security. These generators are particularly suitable for use in portable electronic systems and in hybrid vehicles, in particular because of their high resistance in the presence of overload.
• the invention firstly relates to the family of multi-layer materials comprising a solid support and at least two superimposed solid layers which contain particles of an electrochemically active material, the first solid layer adhering to the solid support and the second adhering solid layer. to the first solid layer.
• This multi-layer material is further characterized in that it exhibits at least one of the following properties:
• a thickness of the first solid layer which is, measured according to the electron microscope method, constant at 95% or more, and preferably constant at 97% or more;
• a thickness of the second solid layer which is, measured according to the scanning electron microscope method, constant at 95% or more, and preferably constant at 97% or more;
• the electrochemically active material may be a complex oxide corresponding to the general formula A a MMZ 2 O 0 N n F f wherein:
• - A comprises an alkali metal
• M comprises at least one transition metal, and optionally a metal other than a transition metal, or mixtures thereof;
• Z comprises at least one non-metal
• N is nitrogen and F is fluorine
• the coefficients a, m, z, o, n, f ⁇ 0 being chosen so as to ensure electroneutrality.
• a preferred subfamily of multi-layer materials of the invention may be multi-layer materials in which the first solid layer is of a different nature from that of the electrochemically active material present in the second solid layer.
• Another preferred subfamily of multi-layer materials of the invention may be constituted by the materials in which the first and second solid layers each contain a binder of the electrochemically active particles present in said first and second solid layers and the binder present. in a solid layer representing, preferably, between 0 and 99%, more preferably still, between 1 and 95% of the weight of the solid layer in which it is present.
• the binder present in the first solid layer may be of a different nature from that of the binder present in the second solid layer.
• one of the solid layers may contain a thickener, the thickener present in a solid layer preferably representing between 0 and 98%, more preferably between 0 and 94%, of the weight of the solid layer in which it is present. present. - AT -
• the binder present in the first layer may be, at 25 ° C., soluble in an Si solvent at a concentration greater than 1 gram per liter and the binder present in the second solid layer may be soluble at 25 ° C. in the solvent Si at a concentration of less than 1 gram per liter.
• the binder present in the second layer may be, at 25 ° C., soluble in a solvent S 2 at a concentration greater than 1 gram per liter and the binder present in the second layer may be, at 25 ° C., soluble in the solvent S 2 at a concentration of less than 1 gram per liter.
• a preferred subfamily of multi-layer materials of the invention may consist of multi-layer materials comprising a third protective layer, preferably based on a solid material LJ 3 PO4 type adhering to the second solid layer on the surface of the second layer that is not in contact with the first layer.
• a preferred subfamily of multi-layer materials of the invention may be multi-layer cathode materials.
• the first solid layer may be based on a material chosen from the group consisting of materials of LiFePO 4 , LiFePO 4 type coated with carbon, FePO 4 , FePO 4 coated with carbon, and of the mixture type of at least two of these; more preferably, the first layer may be of LiCoO 2, LiMn 2 O 4, LiMn 1 Z 3 COiZ 3 Ni 1 Z 3 O 2, LiNi ⁇ Co ⁇ Al 2 O 2 (O ⁇ x, y, z ⁇ 1) or of a mixture of at least two of these materials; and or
• the second solid layer may be based on a LiCoO 2 material , LiMn 2 O 4 , LiMn 1Z 3 Co 1 Z 3 Ni 1 Z 3 O 2 , LiNi x Co ⁇ Al z O 2 , (O ⁇ x, y, z ⁇ 1), or a mixture of at least two of these materials; more preferably still, the second layer may be LiFePO 4 , LiFePO 4 coated with carbon, FePO 4 , FePO 4 coated with carbon, or a mixture of at least two of these.
• the binder in the first solid layer may be of the water-soluble binder type.
• the binder in the second solid layer may be of PVDF or PTFE type.
• the binder in the first layer may be of PVDF or PTFE type.
• the binder in the second layer may be of the water-soluble binder type.
• the thickener may be Cellogen® type.
• the binder in the first solid layer may be of the water-soluble binder type and the binder of the second solid layer may be of the NMP or cyclopentanone type.
• the binder in the first layer may be of the NMP or cyclopentanone type and the binder of the second layer may be of water-soluble binder type.
• a preferred subfamily of multi-layer materials of the invention may be the multi-layer anode materials.
• these multi-layer materials preferably:
• the first solid layer may be of the natural graphite type, of the artificial graphite type or of the mixture type of at least two of these
• the second solid layer may be of the Li 4 Ti 5 O 12 , Sn, Al, Ag type; , Si, SiO x , SiO ⁇ -graphite, SiO x -Carbone, or a mixture type of at least two of these, with x greater than 0 and less than or equal to 2; or the first solid layer may be of the Li 4 TIsO 2, Sn, Al 1 Ag, Si, SiO x, SiO 2-graphite or SiO 2 -carbon type, and the second solid layer may be of the natural graphite, artificial graphite or type type; mixing at least two of these, with x greater than 0 and less than or equal to 2.
• the binder present in the first solid layer may then be soluble in water.
• the first solid layer may contain a Cellogene® type thickener.
• the binder present in the second solid layer of the multi-layer material may be PVDF.
• the binder present in the first solid layer may be PVDF or PTFE.
• the binder used in the first solid layer may be PVDF or PTFE and NMP or cyclopentanone.
• the binder present in the second solid layer may be soluble in water.
• the binder used in the second solid layer may be PVDF or PTFE and NMP.
• the binder used in the second solid layer may be soluble in water.
• a preferred subfamily of multi-layer materials of the invention may be constituted by the materials in which the solid support consists of a chosen material: in the case of an anode: in the group consisting of copper and copper Exmet, aluminum and nickel, and preferably in the group consisting of copper and copper Exmet; and
• a cathode in the group consisting of aluminum, carbon aluminum, Exmet aluminum, Exmet carbonated aluminum, titanium and platinum, preferably in the group consisting of aluminum , carbon aluminum and Exmet aluminum.
• the thickness of: the first layer may be between 1 and 200 ⁇ m, preferably between 10 and 120 ⁇ m;
• the second layer may be between 1 and 200 ⁇ m, preferably between 10 and 120 ⁇ m;
• the protective layer may be between 500 nanometers and 16 microns, preferably between 1 and 5 microns.
• a particularly interesting subfamily of materials of the invention may be composed of multi-layer materials for anode comprising a solid support and two superimposed solid layers: the first solid layer comprising:
• the second solid layer comprising:
• a particularly interesting subfamily of materials of the invention may be composed of multi-layer cathode materials comprising a solid support and two superimposed solid layers:
• the first solid layer comprising: between 1 and 100, preferably between 15 and 97% by weight, of an active material
• the second solid layer comprising:
• Another particularly interesting sub-family of multilayer anode materials may comprise a solid support, two superimposed solid layers and a protective layer:
• the first solid layer comprises: between 1 and 100, preferably between 15 and 97%,% by weight of an active material
• the second solid layer comprising: between 1 and 100, preferably between 15 and 97% by weight of an active material;
• the protective layer comprising: between 1 and 100, preferably between 15 and 97% by weight of an active material;
• Another preferred subfamily may consist of multi-layer cathode materials comprising a solid support, two superimposed solid layers and a protective layer:
• the first solid layer comprising:
• the second solid layer comprising:
• the protective layer comprising:
• Another preferred subfamily of multi-layer materials according to the invention may be constituted by the materials in which:
• the support has a thickness of between 1 and 100 ⁇ m; the first layer has a thickness of between 1 and 200 ⁇ m;
• the second solid layer has a thickness of between 1 and 200 ⁇ m
• the protective layer has, when present, a layer of between 0.5 and 5 ⁇ m.
• a second object of the present invention is constituted by the processes for the preparation of a multi-layer material comprising a solid support and at least two superimposed solid layers, the first solid layer which contains particles of a first electrochemically active material, bound together or not by a binder of said particles, adhering to the solid support; and
• the second solid layer which contains particles of a second electrochemically active material, bound together or not by a binder of said particles, being of a different nature from that of the electrochemically active material present in the first solid layer,
• the two solid layers comprise a binder
• a ') of preparation on the solid support by a physical or chemical method, of a solid layer consisting of a first active material and not containing a binder; b ') spreading on the solid layer formed in step a'), a mixture comprising the particles of a second electrochemically active material and of a different nature from that present in the solid layer without a binder, a binder of second electrochemically active material, and a solvent of the binder; and c ') evaporating the solvent present in the second layer after spreading and forming the second solid layer in step b'), or else the steps of: a ") spreading on the solid support a mixture comprising the particles of a first electrochemically active material, a binder of the first electrochemically active material, and a solvent of the binder; evaporating the solvent present in the first layer after spreading and forming the first solid layer; and c ") for preparing, by
• a "" preparation outside the solid support by a physical or chemical method, a first solid layer consisting of a first electrochemically active material and not comprising a binder; b "") of applying the first solid layer obtained in step a "") on the solid support; and c "") of preparation directly on the first solid layer attached to the solid support in step b ""), by a physical or chemical method, of a solid layer consisting of a second electrochemically active material and not comprising binder,
• a "" ") preparation outside the solid support by a physical or chemical method, a first solid layer consisting of a first electrochemically active material and not comprising a binder; ") of application of the first layer obtained in step a" "") on the solid support; c) of preparation outside the solid support material covered with the first solid layer, by a physical or chemical method, a second solid layer made of a second electrochemically active material and having no binder and the application of the second solid layer thus obtained on the solid support covered with the first solid layer obtained in step a "" "); and d “") for applying the second layer obtained in step c "" ") to the solid support covered with the first layer in step b" "").
• the binder solvent mixture used in stage c) can not dissolve the first solid layer or can dissolve it only very slightly, and this preferably at a value of less than 1 gram per liter at 25 ° C.
• the methods of the invention can be advantageously used for the manufacture of cathodes.
• the manufacture of the first solid layer can be advantageously carried out by Doctor Blade or by extrusion on an aluminum collector and the second layer can be spread on the first layer.
• the manufacture of the first layer can be obtained by vertical spreading on an "expanded metal” type collector - "Exmet", the second layer being able to be obtained by vertical spreading on the first layer .
• the manufacture of the second layer can be advantageously obtained by Doctor Blade or by extrusion on the first layer.
• the second layer may preferably be spread on a PP (polypropylene) support, then transferred by rolling to the first layer.
• the binder used to make the two layers may be of PVDF or PTFE type and the solvent used may be of the NMP or cyclopentanone type, the solvent used to prepare the second layer not having to dissolve the binder of the first layer.
• At least one of the layers can be prepared by at least one of the techniques chosen from the group consisting of the following techniques: plasma, evaporation, CVD, sputtering, and mixtures of at least two of these techniques.
• the binder used for the manufacture of the first layer may be different from the binder used for the manufacture of the second layer.
• the methods of the invention can be advantageously used for the manufacture of multilayer cathode materials.
• the first solid layer may then advantageously be based, preferably consisting of materials of LiFePO 4 type.
• the second solid layer may then be based, preferably consisting of a material selected from the group consisting of materials of LiCoO 2 , LiMn 2 O 4 , LiMn 3 / 3C ⁇ i / 3 Nii / 3O 2, LiNi ⁇ Co type. ⁇ Al z O 2 , (O ⁇ x, y, z ⁇ 1), and by the mixed-type materials of at least two of these.
• the first layer may be of the LiCoO 2 , LiMn 2 O 4 , LiMnI / 3C ⁇ i / 3IMii / 3O 2 , LiNi ⁇ C ⁇ AlzO 2 , (O ⁇ x, y, z ⁇ 1) type, or their mixture
• the second layer is LiFePO 4 , LiFePO 4 coated with carbon, FePO 4 , FePO 4 coated with carbon, or mixtures of at least two of these.
• the binder of the first solid layer may advantageously be of the water-soluble binder type.
• the binder in the second solid layer may preferably be of the PVDF or PTFE type.
• the solvent used for spreading may advantageously be of the aqueous type.
• the solvent used for spreading may be of the NMP or cyclopentanone type.
• the binder of the first solid layer may preferably be of PVDF or PTFE type.
• the binder in the second solid layer may advantageously be of the water-soluble binder type.
• the solvent used for spreading may be of the NMP or cyclopentanone type.
• the solvent used for spreading may be of the water type.
• the method may be particularly advantageous when the binder of the first solid layer is of the water-soluble binder type and the binder of the second solid layer is of the NMP or cyclopentanone type.
• the method may be particularly advantageous when the spreading of the first solid layer is of the water type and that used for the spreading of the second solid layer of NMP or cyclopentanone type.
• the binder of the first solid layer may be of the NMP or cyclopentanone type and the binder of the second water-soluble binder type solid layer.
• that used for spreading the second solid layer may advantageously be of the solvent-free type.
• the first solid layer may advantageously be of the natural or artificial graphite type and the second solid layer may be of Li 4 Ti 5 O 12 , Sn, Al, Ag, Si, SiO x , SiO x -graphite, SiOx type. - carbon with x greater than 0 and less than or equal to 2.
• the first solid layer may be of Li 4 TJsO 12 , Sn, Al, Ag, Si, SiO x, SiO 2 -graphite or SiO 2 -carbon type, with x greater than 0 and less than or equal to 2, and the second solid layer may be of natural or artificial graphite type.
• the binder and solvent used in the first layer may be respectively a binder soluble in water and water.
• the binder and the solvent used for the preparation of the first layer may be respectively PVDF or PTFE and NMP or cyclopentanone.
• the binder and the solvent used for the preparation of the second layer may be respectively PVDF or PTFE and NMP or cyclopentanone.
• the binder and the solvent used in the second layer may be respectively a water-soluble binder and water.
• a third object of the present invention is the multi-layer materials obtained by implementing one of the methods defined in the second subject of the present invention.
• a fourth object of the present invention is constituted by electrochemical generators comprising at least one anode, at least one cathode and at least one electrolyte. These generators are characterized in that they contain at least one electrode containing one of the materials defined in the first subject of the invention or as obtained by one of the methods defined in the second subject of the invention.
• Preferred sub-families of generators of the invention correspond to: electrochemical generators of cathode / electrolyte / anode type; and electrochemical generators of the liquid electrolyte type, advantageously then the electrolyte being of the gel type.
• the electrolyte may be composed of at least one salt and a solvent.
• the salt may be chosen from the group consisting of the salts of LiFSI, LiTFSI, LiBF 4 , LiPF 6 , LiClO 4 , LiCl 3 SO 2 , LiBETI, LiBOB, LiDCTA, and mixtures. at least 2 of these.
• the solvent may be selected from the group of EC, DEC, PC, DMC, EMC, GBL, and mixtures of at least two of these solvents.
• the gel electrolyte may be formed of at least one polymer, a salt and a plasticizer.
• the polymer may be preferentially chosen from the group of polyether-type polymers, PVDF, PAN, PMMA, and from mixtures of at least two of these.
• the salt may be chosen from the group of salts of LiFSI, LiTFSI, LiBF 4 , LiPF 6 , LiClO 4 , LiCl 3 SO 2 , LiBETI, LiBOB, LiDCTA, and mixtures of at least two of these.
• the plasticizer may be chosen from EC type plasticizers, DEC, PC, DMC, EMC, GBL, TESA, VC, and mixtures of at least two of these.
• the formation of the gel can then be carried out thermally by IR, UV, "Electron-Beam” or by a mixture of at least two of these techniques.
• the electrochemical generators of the invention are characterized by the fact that they are safe and resistant to overloads.
• electrochemical generators are also characterized in that the temperature in the generator, in the presence of an overload greater than or equal to 12 volts, is less than 80 ° C.
• a preferred sub-family of generators of the invention may be constituted by generators which have less than 100 ppm, and preferably no trace of deposition of lithium metal during a fast charge.
• a fifth object of the present invention is constituted by the cathodes based on at least one cathode multilayer material previously defined in the first and the second object or as obtained by the methods of the third subject of the invention. .
• a preferred subfamily of these cathodes may be those in which at least one of the electrochemically active materials present in the multilayer material is basic and, preferably, selected from the group consisting of LiFePO 4 , Li 3 PO 4 particles. and mixtures thereof.
• At least one of the electrochemically active materials present in the multi-layer material may be coated with a layer of a basic material.
• a sixth object of the present invention is constituted by the anodes based on at least one anode multi-layer material previously defined in the first and the second object or as obtained by the methods of the third subject of the invention.
• a preferred subfamily of these anodes may be those in which at least one of the electrochemically active materials present in the multi-layer material is a capacity reservoir having a capacity of at least 10% of the total capacity of the material. 'anode.
• the capacity reservoir material may be selected from the group consisting of Li 4 Ti 5 O 12 , Ag, Sn, Si, Al, SiO x , SiO x -graphite, SiO ⁇ -carbon, with x greater than 0 and lower or equal to 2, and mixtures of at least two of these.
• a seventh object of the present invention is constituted by the multi-layer materials according to the first object, or as obtained by one of the methods according to the second subject of the invention, and in which the electronic conductive material is of the type carbon, graphite, fiber, or a mixture of at least two of these.
• the carbon may preferably be of the Ketjen, Shawinigan or Denca type, or of the mixture type of at least two of these.
• the graphite may be artificial or natural type.
• the fiber may be VGCF ("vapor growth carbon fiber"), exmesophase, expal (polvinylacronitrile), or a mixture type of at least two of these.
• An eighth object of the present invention consists of the processes according to the second object for the preparation of a material according to one of the first, fourth and fifth objects, using: an aqueous solution particularly suitable for spreading on a support anode which is formulated as follows, the percentages being formulated by weight:
• the aqueous solution used for the spreading contains by weight:
• Figure 1 shows one of the multi-layer material configurations of the invention according to the variants I, II, III and IV explained.
• Figure 2 shows one of the possible configurations for the multi-layer materials of the invention, for the anode and for the cathode and in which the adjacent layers have been prepared with different aqueous / organic systems; these configurations differ from those shown in FIG. 1 in that the active material present in layers A and A 'is now present in layers B and B' respectively.
• Figure 3 shows the preparation of a multi-layer material of the invention by transfer of the layer B, initially attached to the support PP, on the layer A.
• FIG. 4 represents a multi-layer material of the invention in which the layer A has been obtained by spraying (without binder) of the active material A onto the solid support 1.
• FIG. 5 represents, for case 1, a multi-layer material of the invention in which the active material incorporated in the second layer consists of particles of an active material coated with particles of smaller sizes of LiFePO 4 , in case 2 and case 3 which represents an enlargement of the case 2, a comparison of the shape of a section of multi-layer material of the prior art in which the same binder is present in both layers with the shape of a material of the invention (case 1) in which the binder is not the same in both layers.
• FIG. 6 represents a multi-layer material of the invention in which an electrochemically active material consists of particles coated with a layer of basic particles.
• Figure 7 shows a multi-layer material of the invention in which electrochemically active material present in at least one solid layer is ionic conductor.
• multi-layer electrode is similar to an electrode characterized by a superposition of at least two layers on its surface.
• the SEM used is a HITACHI S-3500N with integrated calculator.
• the apparatus is provided with a program that gives the measurement of the thickness of each linear millimeter of the sample.
• the values obtained are exploited using the Excel® program and presented in the form of two-dimensional curves: length of the sample and thickness measured on each millimeter of the segment. Measuring the differences between the average value of the thickness of the sample and the measured extreme values makes it possible to determine the constancy.
• an average sample thickness of 40 microns constant at 95% means that the average thickness varies between 38 and 42 microns.
• the "average depth of penetration of one layer into another” is measured by the scanning electron microscope (SEM) method, and represents the statistical average of the penetrations measured every linear millimeter of the sample.
• the term “spreading” represents an electrode coating method on a support.
• a binder has the function of chemically bonding the particles of an electrochemically active material present in a solution and also when they are present in the solid layer.
• a thickener has the function of increasing the viscosity of the solution of the mixture to be spread and which contains the particles of an electrochemically active material and the binder, as well as the solvent.
• binders are usable. Those described in the international application PCT / CA03 / 01739 and in the corresponding European application bearing the number EP 1, 573,834 (HYDRO-QUÉBEC), the contents of which are incorporated by reference in the present application, are particularly advantageous in the context of the preparation of multilayer structures of the invention, and more particularly in the context of solid layer preparation techniques by spreading from at least one aqueous mixture of an electrochemically active material.
• the binder and the thickener retained are generally at least 20% soluble in water when introduced at room temperature, at a rate of 20 grams in 100 grams of water. Preferably, they are soluble for at least 50% and more preferably at least 90%. More preferably, the thickener is soluble in water and may be selected from the group consisting of natural celluloses, physically and / or chemically modified celluloses; natural polysaccharides, polysaccharides chemically and / or physically modified and which have a molecular weight between 27000 and 250000.
• the thickener is advantageously chosen from the group consisting of carboxymethylcelluloses, hydroxymethylcelluloses, and methylethylhydroxy celluloses.
• the thickener is chosen from the group consisting of carboxymethylcelluloses of Cellogen® type sold by the company Dai-lchi Kogyo Seiaku Co. Ltd. in Japan, especially under the trade names EP, 7A, WSC, BS- H and 3H.
• the soluble binder is advantageously selected from the group consisting of natural and / or synthetic rubbers.
• the binder is of the non-fluorinated or weakly fluorinated type. Indeed, by way of example, since LiF is not soluble in water, it can not be used in the context of the invention.
• those of synthetic type and more particularly those selected from the group consisting of SBR, (Butadiene Rubber Styrene), NBR (butadiene-acrylonitrile rubber), HNBR (hydrogenated NBR), CHR (epichlorohydrins rubber) and ACMs (acrylate rubber) are particularly advantageous.
• SBR Silicon Rubber Styrene
• NBR butadiene-acrylonitrile rubber
• HNBR hydrogenated NBR
• CHR epichlorohydrins rubber
• ACMs acrylate rubber
• the soluble rubbers used are preferably in the form of a paste.
• SBR marketed by the company Nippon ZEON 1 S BINDER BATTERY GRADE under the trade name (BM-400B) or equivalent and cellogen thickeners known as EP and / or 3H abbreviations. .
• the thickener / binder ratio ranges from 10 to 70%, preferably from 30 to 50%.
• the binder content is advantageously between 1 and 70%, and that by thickening between 1 and 10%, in an aqueous solution.
• An aqueous solution particularly suitable for spreading on an anode support can be formulated as follows, the percentages being formulated by weight:
• An aqueous solution particularly suitable for spreading on a cathode support can be formulated as follows, the aqueous solution used for the spreading contains by weight:
• the electrode is dried by eliminating, preferably at least 95%, the water present in the solution used to carry out the spreading step.
• Various techniques known to the person of the technique in question are used to remove traces of H 2 O present on the surface of the electrode, after the recovery of the latter by the aqueous solution. These traces are in particular eliminated thermally online process EXT, DBH and / or DB or infrared at a temperature advantageously between 80 and 130 ° C for a period of between 1 and 12 hours.
• collector is similar to an electrode support that is electrochemically inactive and electronically conductive.
• Doctor Blade represents a method of spreading in vertical mode.
• the term "extrusion” represents a particular method of spreading in which the spreading mixture is sent under pressure in a die in order to accelerate the spreading process.
• the term "calendering” represents an electrode pressing to obtain an optimum electrode density that is expressed in grams per cm 3 .
• the pH of an MEA represents the measured value, using a conventional glass electrode, in a solution of MEA obtained by dissolution, under normal conditions of temperature and pressure, of 0.15 grams of MEA in 10 cc of water. It is allowed to stand for a week under normal temperature conditions, then stirred just before taking the measurement with an OAKTON 2100 series apparatus, marketed by OAKTON.
• acidic MEA is defined as any sample having a pH less than 7 and as basic MEA any sample having a pH greater than 7.
• physical techniques include techniques such as plasma, evaporation, sputtering, and any other similar techniques well known to those skilled in the art.
• chemical techniques include those such as: Chemical Vapor Deposition (CVD) or spin coating.
• a particularly advantageous embodiment of the invention lies in a multi-layer spreading process using two binders having different chemistries: one being based on a non-aqueous system and the other based on a system. aqueous.
• Cathode - The cathode consists of at least two layers of active materials A and B, respectively, as described in Figure 1.
• I 1 layer A is of LiFePO 4 type with a binder soluble in water.
• the thickness of the layer A may be greater or less than that of the layer B.
• the spreading of the cathode A is 100% water-based.
• the cathode B consists of either LiCoO 2 , LiMn 2 O 4 , LiNiO 2 , LiMn 1 Z 3 Co 1 Z 3 Ni 1 Z 3 O 2 or a mixture of at least two of these.
• the binder used for layer B is based on PVDF or PTFE.
• the thickness of this layer B may be greater or less than the layer A.
• the solvent used for the spreading of the layer B is organic, preferably of the NMP or cyclopentanone type.
• the binder of the inner layer A is not solubilized by the solvent of the outer layer B. In addition, it gives mechanical stability. and chemical at layer A ( Figure 1), particularly since the binder is not soluble in the solvent used to prepare the second layer.
• the layer A ' is of the LiFePO 4 type, and a binder of PVDF or PTFE type soluble in an NMP or cyclopentanone type solvent is used.
• the thickness of the layer A ' may be greater or less than that of the layer B'.
• Layer B is formed either of LiCoO 2, LiMn 2 O 4, LiNiO 2, LiMn Co 1Z3 1Z3 NJI Z3 O 2 or a mixture thereof.
• the binder used for the spreading of the layer B is water-based and the solvent used consists of 100% water.
• the thickness of this layer B ' may be greater or less than the layer A' (FIG. 2).
• the manufacturing process is done by the Doctor Blade technique or by extrusion on an aluminum collector.
• the first layer is spread on the aluminum collector, the second layer is spread on the first layer without dissolution or significant deformation of the inner layer A or A '.
• the first layer A or A ' is spread on the aluminum grid
• the second layer B or B' is extended on the first layer A or A 'without dissolution or significant deformation of the inner layer A or A'.
• the two layers are prepared from the same binder and the same solvent.
• the first layer A is spread on the aluminum collector.
• the layer B is spread on a polypropylene (PP).
• PP polypropylene
• Both layers are prepared from PVDF or PTFE dissolved in NMP or cyclopentanone.
• the two layers are prepared from a binder soluble in water and the solvent used consists of 100% water (Figure 3).
• the thickness of layer A may be greater or less than that of layer B.
• the first layer A is spread on a copper film.
• the second layer B is spread on a PP film. Then this last layer B is transferred to the first layer A by rolling without any deformation of the inner layer A.
• the first layer A is of natural or artificial graphite type
• the binder is of the water-soluble type.
• the solvent used for the spreading of the layer A consists of 100% water.
• the thickness of this layer A may be greater or less than the layer B.
• the layer B is composed of hard carbon, Li 4 Ti 5 O 12 , Sn, Al 1 Ag, Si, SiO x , SiO 2 graphite, SiO ⁇ -carbon, with x greater than 0 and less than or equal to 2.
• the binder used in this layer B is of PVDF or PTFE type and the solvent used is of the NMP or cyclopentanone type (FIG. 1).
• the layer A ' is of natural or artificial graphite type used with a PVDF or PTFE type binder soluble in an NMP or cyclopentanone type solvent.
• the thickness of the layer A ' may be greater or less than that of the layer B'.
• the layer B ' is composed of hard carbon ("hard carbon"), Li 4 Ti 5 O 4 , Sn, Al, Ag, Si, SiO 2, SiO 2 -graphite, SiO 2 -carbon or other, with x greater than 0 and lower or 2.
• the binder used in this layer B ' is water-based and the solvent used consists of 100% water.
• the thickness of this layer B ' may be greater or less than the layer A'.
• the manufacture of the multi-layer anode is done by the Doctor Blade technique or by extrusion on a copper collector.
• the first layer is spread on the copper collector, the second layer B or B 'is spread on the first layer without any dissolution or deformation of the inner layer A or A'.
• the first layer A or A ' is spread on the copper grid
• the second layer B or B' is extended on the first layer A or A 'without any significant dissolution or deformation of the inner layer A or A'.
• the two layers are prepared from the same binder and the same solvent.
• the first layer A is spread on the copper collector.
• the layer B is spread on a polypropylene (PP).
• PP polypropylene
• layer B is transferred to layer A by rolling.
• Both layers are prepared from PVDF or PTFE dissolved in NMP or cyclopentanone.
• the two layers are prepared from the binder soluble in water and the solvent used is 100% water.
• the thickness of layer A may be greater or less than that of layer B.
• Other spreading methods may be used such as vertical spreading on expanded copper.
• the first layer A is spread on a copper film.
• the second layer B is spread on a PP film. Then this last layer B is transferred to the first layer A by rolling without any deformation of the inner layer A.
• At least one of the layers of the anode or of the cathode is deposited by physical techniques such as: plasma, evaporation, sputtering, or chemical such as: CVD, "spin coating” or other technique ( Figure 5).
• the particles of the multi-layers of the cathode material (LiCoO 2, LiM ⁇ O 4, L ⁇ mni / 3 C ⁇ i / 3Ni- ⁇ / 3 ⁇ 2) are coated with the material LiFePO 4 to the using techniques such as mechanofusion, plasma, evaporation, sputtering, or chemical such as: CVD, "spin coating” or other equivalent techniques.
• the material of the anode (natural or artificial graphite or carbon) is advantageously coated with one of the elements: Li 4 Ti 5 O 4 , Sn, Al, Ag, or Si or a mixture of at least two of these.
• coated materials are used to make the cathode or anode with a binder of either PVDF or PTFE type or with a water-soluble binder.
• the application of 10 micrometers of electrode is carried out on a carbon aluminum collector by Doctor Blade.
• the LiFePO 4 ZAI film obtained constitutes the first solid layer.
• LiCoO 2 cathode is carried out on the LiFePO 4 / Al film, the LiCoO 2 layer has a thickness of 40 microns, the cathode is double-layered, LiCoO 2 / LiFePO 4 / AI type and called Configuration 1.
• the constancy measured for the thickness of the layer 1 is 95%, that is to say that the average thickness of the layer is 40 microns and the thickness of the layer varies between 38 and 42 microns. It is the same for the solid layer 2.
• the 10 micron application of the first layer of LiFePO 4 / AI is obtained by Doctor Blade.
• the second layer is prepared from 33.11 grams of LiCOi Z Sni I ZsMn 1 ZSO 2, 2.13 grams of carbon black and 83 grams of PVDF in NMP mixed.
• the second layer is deposited by Doctor Blade on the first layer of LiFePO 4 / AI.
• the second layer has a thickness of 40 micrometers.
• the multi-layer material thus obtained is of the type LiN 1ZS CO 2 Z sMn IZ sOaZLiFePO 4 ZAL and is called Configuration 2.
• the constancy measured for the thickness of the layer 1 is 95%, that is to say that the average thickness of the layer is 40 microns and the thickness of the layer varies between 38 and 42 microns. It is the same for the solid layer 2.
• Example 3 Multilayer Material Graphite: SNG12ZLi 4 TiOi 2 ZCuivre
• the second layer of graphite is deposited on Li 4 Ti 5 Oi 2 Zcuivre by Doctor Blade.
• the thickness of the second layer is 50 microns.
• the Graphite SNG12ZLi 4 TiO 12 ZCuivre configuration is called Configuration 3.
• the constancy measured for the thickness of the layer 1 is 95%, that is to say that the average thickness of the layer is 40 microns and the thickness of the layer varies between 38 and 42 microns. It is the same for the solid layer 2.
• the thickness of the layer 1 is 45 plus or minus 2 microns which corresponds to a constancy of 95.6%.
• the thickness of the layer 1 is 45 plus or minus 2 microns which corresponds to a constancy of 95.6%.
• Example 5 Lithium battery with multi-layer material according to Configuration 1
• a Configuration 1 / LiPF 6 / EC + DEC / Li type battery is charged up to 12 volts. The temperature of the battery is raised to 75 ° C. and returns to 25 ° C. after 1 minute.
• a battery of LiCOO 2 / LiPF 6 / EC + DEC / Li type is charged up to 12 volts, the temperature is raised to 150 ° C. and returns to 60 ° C. after 1 minute.
• Example 7 Lithium battery Configuration i / LiPF ⁇ / EC + DEC / Configuration 3
• a Configuration 1 / l_iPF 6 / EC + DEC / Configuration 2 type battery is charged in 2 C (30 minutes) and the voltage is maintained at 4.2 Volts for 24 hours.
• Example 8 Lithium battery Configuration 2 / LiPF 6 / Configuration 4
• a Configuration 2 / LiPF 6 / Configuration 4 type battery is charged in 2C (30 minutes) and the voltage is maintained at 4.3 Volts for 24 hours.
• One of the determining advantages of multi-layer materials of the invention resides in the improved resistance to overloading that they confer on the generators in which they are incorporated as an electrode component.
• the cathode of the generator becomes very acidic and reacts with the electrolyte, in particles with the salt, to form acids of HF (LiPF 6 ) or HCl (LiClO 4 ) type.
• HF LiPF 6
• HCl LiClO 4
• LiFePO 4 type cathodes or very basic pH, considerably secures the battery, in particular by avoiding the formation of acid and by preventing the generation of oxygen.
• Another possibility of further optimizing the overload resistance capacity lies in the coating of the particles of electrochemically active material with a layer of a very basic material such as Li 3 PO 4 or others. This in particular prevents the acid contact of the cathode with the electrolyte during charging.
• electrochemically active particles having a pH greater than 7 are used, such as LiFePO 4 particles having a pH of 9.9 and those of LiCoO 2 having a pH of 8.6.

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