Classifications

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  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J3/00—Processes of treating or compounding macromolecular substances
  • C08J3/20—Compounding polymers with additives, e.g. colouring
  • C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
  • C08J3/226—Compounding polymers with additives, e.g. colouring using masterbatch techniques using a polymer as a carrier
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
  • B29B7/00—Mixing; Kneading
  • B29B7/30—Mixing; Kneading continuous, with mechanical mixing or kneading devices
  • B29B7/34—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices
  • B29B7/38—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices rotary
  • B29B7/40—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices rotary with single shaft
  • B29B7/42—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices rotary with single shaft with screw or helix
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
  • B29B7/00—Mixing; Kneading
  • B29B7/30—Mixing; Kneading continuous, with mechanical mixing or kneading devices
  • B29B7/34—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices
  • B29B7/38—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices rotary
  • B29B7/46—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices rotary with more than one shaft
  • B29B7/48—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices rotary with more than one shaft with intermeshing devices, e.g. screws
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
  • B29B9/00—Making granules
  • B29B9/02—Making granules by dividing preformed material
  • B29B9/06—Making granules by dividing preformed material in the form of filamentary material, e.g. combined with extrusion
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
  • B29B9/00—Making granules
  • B29B9/12—Making granules characterised by structure or composition
  • B29B9/14—Making granules characterised by structure or composition fibre-reinforced
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
  • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
  • B29C48/25—Component parts, details or accessories; Auxiliary operations
  • B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
  • B29C48/395—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders
  • B29C48/40—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders using two or more parallel screws or at least two parallel non-intermeshing screws, e.g. twin screw extruders
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
  • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
  • B29C48/25—Component parts, details or accessories; Auxiliary operations
  • B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
  • B29C48/395—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders
  • B29C48/40—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders using two or more parallel screws or at least two parallel non-intermeshing screws, e.g. twin screw extruders
  • B29C48/405—Intermeshing co-rotating screws
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
  • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
  • B29C48/25—Component parts, details or accessories; Auxiliary operations
  • B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
  • B29C48/395—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders
  • B29C48/40—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders using two or more parallel screws or at least two parallel non-intermeshing screws, e.g. twin screw extruders
  • B29C48/41—Intermeshing counter-rotating screws
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
  • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
  • B29C48/25—Component parts, details or accessories; Auxiliary operations
  • B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
  • B29C48/50—Details of extruders
  • B29C48/505—Screws
  • B29C48/625—Screws characterised by the ratio of the threaded length of the screw to its outside diameter [L/D ratio]
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/02—Elements
  • C08K3/04—Carbon
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/02—Elements
  • C08K3/04—Carbon
  • C08K3/041—Carbon nanotubes
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/02—Elements
  • C08K3/04—Carbon
  • C08K3/042—Graphene or derivatives, e.g. graphene oxides
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/02—Elements
  • C08K3/04—Carbon
  • C08K3/046—Carbon nanorods, nanowires, nanoplatelets or nanofibres
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
  • C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
  • C08L27/12—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
  • C08L27/22—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers modified by chemical after-treatment
  • C08L27/24—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers modified by chemical after-treatment halogenated
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D11/00—Inks
  • C09D11/52—Electrically conductive inks
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
  • C09D5/24—Electrically-conducting paints
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
  • C09D7/40—Additives
  • C09D7/60—Additives non-macromolecular
  • C09D7/61—Additives non-macromolecular inorganic
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J139/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen; Adhesives based on derivatives of such polymers
  • C09J139/04—Homopolymers or copolymers of monomers containing heterocyclic rings having nitrogen as ring member
  • C09J139/06—Homopolymers or copolymers of N-vinyl-pyrrolidones
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
  • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
  • H01B1/20—Conductive material dispersed in non-conductive organic material
  • H01B1/24—Conductive material dispersed in non-conductive organic material the conductive material comprising carbon-silicon compounds, carbon or silicon
• • 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
  • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
  • H01M4/624—Electric conductive fillers
  • H01M4/625—Carbon or graphite
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M4/00—Electrodes
  • H01M4/02—Electrodes composed of, or comprising, active material
  • H01M4/64—Carriers or collectors
  • H01M4/66—Selection of materials
  • H01M4/668—Composites of electroconductive material and synthetic resins
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
  • B29B9/00—Making granules
  • B29B9/12—Making granules characterised by structure or composition
  • B29B2009/125—Micropellets, microgranules, microparticles
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B82—NANOTECHNOLOGY
  • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
  • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K2201/00—Specific properties of additives
  • C08K2201/001—Conductive additives
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M10/00—Secondary cells; Manufacture thereof
  • H01M10/05—Accumulators with non-aqueous electrolyte
  • H01M10/052—Li-accumulators
  • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
• • 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
  • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
  • H01M4/621—Binders
  • H01M4/622—Binders being polymers
• • 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

Definitions

• the present invention relates to a process for preparing a pasty composition containing carbon-containing conductive fillers, at least one polymeric binder, at least one solvent and at least one polymeric dispersant separate from the binder. It also relates to the dough likely to be obtained and to its uses, in particular for the manufacture of Li ⁇ ion battery electrodes and. supercapacities.
• a Li-ion battery comprises at least one negative electrode or anode coupled to a copper current collector, a positive electrode or cathode coupled to a current collector, aluminum, a separator, and an electrolyte.
• the electrolyte consists of a lithium salt, generally lithium hexafluorophosphate, mixed with a solvent which is a mixture of organic carbonates, chosen to optimize the transport and dissociation of the ions.
• a high dielectric constant favors the dissociation of the ions, and therefore the number of available ions in a given volume, whereas a low viscosity is favorable for the ionic diffusion which plays a key role, among other parameters, in the rates of charge and discharge of the electrochemical system.
• the electrodes generally comprise at least one current collector on which is deposited a composite material which is constituted by: a so-called active material because it has an electrochemical activity with respect to lithium, a polymer which plays the role of binder and which is generally a copolymer of vinylidene fluoride for the positive electrode and water-based binders of carboxymethylcellulose type or styrene-butadiene latexes, for the negative electrode, plus an electronically conductive additive which is generally the carbon black Super P or acetylene black, and possibly a surfactant,
• the lithium is inserted into the negative electrode active material (anode) and its concentration is kept constant in the solvent by the deintercalation of an equivalent quantity of the active material of the positive electrode (cathode).
• the insertion in the negative electrode results in a reduction of lithium and it is therefore necessary to provide, via an external circuit, the electrons to this electrode, from the positive electrode.
• the reactio s in erses have 1 ieu.
• CNTs are generally in the form of agglomerated powder grains whose average dimensions are of the order of a few hundred microns. Differences in size, shape, and physical properties mean that the toxicological properties of CNT powders are not yet fully known. The same is true of other conductive carbonaceous fillers, such as carbon black or carbon nanofifores. It would be it is therefore preferable to be able to work with carbon-conducting charges in a form that is more easily manipulated.
• the document US2 04/0160156 describes a method for preparing a battery electrode from a masterbatch, in the form of granules composed of CNTs and a binder resin, to which is added an electrode active material suspension.
• the resin is. present in a large quantity within the masterbatch, since the CNTs are present in proportions ranging from 5 to 20 parts by weight per 100 parts by weight of resin.
• This high level of binder is problematic for the electrode material formulator who wishes to use "universal" masterbatches in predefined compositions without causing formulation constraints, in particular without limiting the choice of the binder used in these compositions.
• the presence of a large amount of binder in the formulation of the electroconductive ink decreases the proportion of usable electrode active material, and therefore the overall capacity of the battery.
• an agglomerate solid masterbatch comprising: from 15 to 40% by weight of CNT, at least one solvent and from 1 to 40% by weight of at least one polymeric binder ( WO 2011/117530).
• the document EP 2 081 244 describes a liquid dispersion based on MTC, a solvent and a binder, which is intended to be sprayed on a layer of electrode active material, It is.
• the solutions proposed in these documents are still imperfect, in that they do not always make it possible to avoid the persistence of CNT aggregates in these compositions, so that a fraction of the CNTs It is not used opimally to improve the electrical conductivity of the electrode obtained from these compositions.
• document US 2011/171364 suggests another solution for reducing the amount of binder in electroconductive ink formulations. It describes a paste based on agglomerates of CNT mixed with a dispersant such as polyvinyl pyrrolidone) or PVT, with an aqueous or organic solvent, and optionally with a binder whose presence here is optional.
• the process for producing this paste comprises a step, presented as crucial, of grinding (or ultrasonic passage) of entangled clusters of CNTs, having an average diameter of about 100 ⁇ m, produced by a catalytic decomposition process.
• This step makes it possible to obtain CNT agglomerates having a size of less than 10 ⁇ m in at least one dimension, ie a degree of dispersion, on the Hegman scale, which is greater than 7. Grinding can be performed before or after mixing the CNTs with the dispersant, solvent, and any binder.
• a paste of this type is. especially commercially available from C ANO under the trade name LB ® 100.
• the solution proposed in this document has the disadvantage of using a manufacturing method comprising a grinding step, preferably by spraying, which is likely to present risks of environmental pollution or even health risks.
• the paste obtained has a viscosity of at least 5,000 cPs, which can cause dispersion difficulties in some cases.
• the present invention specifically relates, in a first aspect, to a process for preparing a pasty composition based on carbon-containing conductive fillers, comprising:
• step (iii) the dilution of said masterbatch in a solvent identical or different from that of step (i), to obtain a pasty composition.
• the invention also relates, according to a second aspect, to the pasty composition obtainable by this process.
• It also relates, in a third aspect, to the use of said pasty composition for the preparation of thin films, inks or conducting coatings, in particular for the manufacture of Li-ion battery electrodes or supercapacitors; or for the preparation of conductive composite materials.
• the method according to the present invention makes it possible to make the conductive carbon charges easily manipulable for applications in the liquid phase, by effectively dispersing them in a medium containing a solvent and a binder, suitable in particular for the manufacture of an electrode, without having recourse to a step comprising grinding (in particular in a ball mill or by spraying.) . , the ultrasonic passage or the passage in a rotor-stator system conductive carbon charges, and without using tenstoactif.
• carbonaceous conductive filler means a filler comprising at least one element of the group consisting of nanotubes and nanofibers of carbon and carbon black, and graphene, or a mixture of these in all proportions.
• the carbon nanotubes may be of the rnoncparox type, double-walled or multi-walled.
• the double-walled nanotubes can in particular be prepared as described by LAHAOT et al. In Chem. Com. (2003), 1442.
• the multi-walled nanotubes may themselves be prepared as described in WO 03/02456.
• multi-walled carbon nanotubes obtained according to a chemical vapor deposition (or CVD) method, by catenary decomposition of a carbon source (preferably of plant origin), as described above, are preferred. especially in the application EP 1 980 530 of the Applicant.
• the nanotubes usually have an average diameter ranging from 0.1 to 100 ⁇ m, preferably from 0.4 to 50 nm and better still from 1 to 30 nm, indeed from 10 to 15 nm, and advantageously a length of 0.1. at 10 ⁇ m.
• Their length / diameter ratio is preferably greater than 10 and most often greater than 100.
• Their specific surface area is for example between 100 and 300 rn g, advantageously between 200 and 300 m 2 / g, and bulk density may especially be between 0.05 and 0.5 / / CTTV 5 and more preferably between 0.1 and 0.2 10 g / cm "5.
• the multiwall nanotubes may for example comprise from 5 to 15 sheets (or walls) and more preferably from 7 to 10 sheets, these nanotubes may or may not be treated.”
• crude carbon nanotubes is especially commercially available from Arkema under the trade name Graphistrength® ® C100.
• nanotubes can be purified and / or treated (for example oxidized) and / or functionalized before being used in the process according to the invention.
• the purification of the nanotubes can be carried out by washing with a sulfuric acid solution, so as to rid them of any residual mineral and metal impurities, such as iron, originating from their preparation process.
• the weight ratio of the nanotubes to the sulfuric acid may especially be between 1: 2 and 1: 3.
• the purification operation may also be carried out at a temperature ranging from 90 to 120 ° C., for example for a period of 5 to 10 hours. This operation may advantageously be followed by rinsing steps with water and drying the purified nanotubes.
• Nanotubes can. alternatively be purified by heat treatment at high temperature, typically above 1000 ° C.
• 1 / oxidation of nanotubes is advantageously carried out by putting them in contact with a sodium hypochlorite solution containing from 0.5 to 15% by weight NaOCl and preferably 1 to 10% by weight of NaOCl, for example in a weight ratio of nanotubes to sodium hypochlorite ranging from 1: 0.1 to 1: 1.
• 1 / oxidation is preferably carried out at a temperature below 60 ° C and preferably at room temperature, for a period ranging from a few minutes to 24 hours. This oxidation operation may advantageously be followed by filtration and / or cen.tr.ifugation, washing and drying steps of the oxidized nanotubes.
• the functionalization of the nanotubes can be carried out by grafting reactive units such as vinyl monomers on the surface of the nanotubes.
• the material constituting the nanotubes is used as a radical polymerization initiator after having been subjected to a heat treatment at over 900 ° C., in an anhydrous and oxygen-free medium, which is intended to eliminate the oxygenated groups from its surface. It is thus possible to polymerize methyl methacrylate or hydroxyethylmethacrylate on the surface of carbon nanotubes in order, in particular, to facilitate their dispersion in PVDF.
• nanotubes that is to say nanotubes that are neither oxidized nor purified nor functionalized and have undergone no other chemical and / or thermal treatment.
• purified nanotubes may be used, in particular by high temperature heat treatment.
• the carbon nanotubes are not ground.
• the carbon nanofibers like carbon nanotufoes, of nanofllaments produced by chemical vapor deposition (CVD) from a carbon source which is decomposed on a catalyst comprising a transition metal (Fe, Ni? Co, Cu); in the presence of hydrogen, at temperatures of 500 to 1200 ° C.
• CVD chemical vapor deposition
• the carbon nanotubes consist of one or more sheets of graphene wound concentrically around the axis of the fiber to form a cylinder having a diameter of 10 to 100 nm.
• carbon nanofibers consist of more or less organized graphitic zones (turbostratic stacks) whose planes are inclined at variable angles with respect to the axis of the fiber. These stacks may take the form of platelets, fish bones or stacked cups to form structures generally ranging in diameter from 100 nm to 500 nm or more.
• carbon black is a colloidal carbon material produced industrially by incomplete combustion of heavy petroleum products, which is in the form of carbon spheres and aggregates of these spheres and. whose dimensions are generally between 10 and 1000 nm.
• Carbon nanofiber is preferably used having a diameter of 100 to 200 nm, e.g., about 150 nm (VGCF ® from SHOWA DENKO), and advantageously a length of 100 to 200 .mu.m.
• graphene ors denotes a sheet of graphite yolk, isolated and individualized, - but also, by extension, an assembly comprising between one and a few tens of sheets and having a flat structure or more or less wavy.
• This definition therefore includes FLG ⁇ Fe Layer Graphene or graphene with low stacking ⁇ , NGP (Nanosized Graphene Plates), CNS (Carbon NanoSheets or nano-graphene), GNR (Graphene).
• graphene used according 1f invention is not subjected to an additional step of chemical oxidation ormputationnai ization.
• the graphene used according to the invention is advantageously obtained by chemical vapor deposition or CVD, preferably in a process using a powdery catalyst based on a mixed oxide. It is typically in the form of particles having a thickness of less than 50 nm, preferably less than 15 nm, more preferably less than 5 nm and less than one micron side dimensions, preferably 10 nm less than 1000 nm, more preferably 50 to 600 m, or even 100 to 400 nm. Each of these particles generally contains from 1 to 50 sheets, preferably from 1 to 20 sheets, and more preferably from 1 to 10 sheets, or even from 1 to 5 sheets, which are likely to be separated from each other. each other in the form of independent sheets, for example during an ultrasound treatment.
• the carbon-containing conductive fillers comprise carbon nanotubes, preferably multistage nanotubes obtained by a chemical vapor deposition process, and possibly carbon nanofibers. and / or carbon black and / or graphene.
• the conductive carbonaceous fillers represent from 15 to 40% by weight, preferably from 20 to 35% by weight, relative to the weight of the masterbatch.
• the polymeric binder used in the present invention is advantageously chosen from the group consisting of polysaccharides, modified polysaccharides, polyethers, polyesters, acrylic polymers, polycarbonates, polyimines, polyamides, polyacrylamides, polyurethanes and polyepoxides. polyphosphazenes, polyisulfones, halogenated polymers, natural rubbers, functionalized or non-functionalized elastomers, in particular elastomers based on styrene, butadiene and / or isoprene, and mixtures thereof.
• These polymeric binders may be used in solid form or in the form of a solution, or a liquid dispersion (latex type) or else in the form of a supercritical solution.
• the polymeric binder is selected from the group consisting of halogenated polymers and even more preferably from the fluorinated polymers defined in particular in the following manner;
• X 1 , X 2 and X 3 independently denote a hydrogen or halogen atom (in particular fluorine or chlorine), such as pol (vinylidene fluoride) (PVDF), preferably in gold form, pol (trifluoroethylene) (P F3), polytetrafluoroethylene (P ' T ' FR), vinyiidene fluoride copolymers with either hexafluoropropylene (HFP) or trifluoroethylene (VF3) or tetrafluoroethylene (TFE), or chlorotrifluoroethylene (CTFE), fluoroethylen / propene copolymers (FEP), copolymers of ethylen with either fluoroethylene / propylene (FEP), tetrafluoroethylene (TFE) or chlorotrifluoroethylene (CTFE);
• PVDF pol (vinylidene fluoride)
• PVDF polytetrafluoroethylene
• R denotes a perhalogenated (in particular perfluorinated) alkyl radical, such as perfluoropropyl vinyl ether (PPVE), perfluoroethyl vinyl ether (PEVE) and copolymers of ethylene with perfluoromethylvinyl ether (PMVE),
• PPVE perfluoropropyl vinyl ether
• PEVE perfluoroethyl vinyl ether
• PMVE perfluoromethylvinyl ether
• the masterbatch according to the invention advantageously contains, as binder. at least one modified polysaccharide such as a modified cellulose, in particular carfooxymethylcellulose.
• This may be in the form of a solution, aqueous or in solid form or in the form of a liquid dispersion,
• the polymeric binder may represent from 1 to 15% by weight, preferably from 2 to 10% by weight, relative to the weight of the masterbatch.
• the ratio by weight of the polymeric binder to the conductive carbonaceous fillers is between 0.04 and 0.40. and 0.4, and it is further preferred that it be between 0.05 and 0.12 inclusive.
• the polymeric dispersant used in the masterbatch prepared according to the invention is a polymer chosen from poly (vinyl pyrrolidone) or PVP, poly (phenyl acetylene) or PAA, poly (meta-phenylene vinylidene) or P PV, the polypyrole or PPy, poly (para-phenylene benzobisoxazole) or PBO, polyvinyl alcohol or PVA, and mixtures thereof.
• the polymeric dispersant may represent from 1 to 40% by weight, preferably from 2 to 10% by weight, relative to the weight of the masterbatch.
• the ratio by weight of the polymeric dispersant to the conductive carbonaceous fillers is between 0.1 and 1 inclusive, and it is furthermore preferred that it be between 0.25 and 0.8 inclusive.
• solvents used in step (i) and in step (iii) may be chosen from an organic solvent or water or mixtures thereof in all proportions.
• Organic solvents include N-methyl pyrrolidone (NMP), diroethyl sulfoxide (DMSO), dimethylformamide (DMF), ketones, acetates, furans, alkylcarbonates, alcohols and mixtures thereof.
• NMP, DMSO and BMF are preferred for use in the present invention, with NMP being particularly preferred.
• the amount of solvent present in the masterbatch is from 20 to 85% by weight, more preferably from 50 to 75% by weight and most preferably from 60 to 75% by weight, inclusive, based on weight. total of the masterbatch.
• the conductive carbonaceous fillers, the polymeric binder, the polymeric dispersant and the solvent are introduced and then kneaded in a kneader.
• a compounding device as a kneader.
• Compounding devices are well known to those skilled in the art and generally comprise feed means, in particular at least one hopper for pulverulent materials and / or at least one injection pump for liquid materials; means of high shear mixing, for example a co-rotating or counter-rotating twin-screw extruder or a com-sorber, usually comprising a worm disposed in a heated tube (tube); an outlet head which gives shape to the outgoing material; and cooling means, in air or with the aid of a water circuit, of the material.
• feed means in particular at least one hopper for pulverulent materials and / or at least one injection pump for liquid materials
• means of high shear mixing for example a co-rotating or counter-rotating twin-screw extruder or a com-sorber, usually comprising a worm disposed in a heated tube (tube); an outlet head which gives shape to the outgoing material; and cooling means, in air or with the aid
• co-kneaders of the invention are co-kneaders Buss MDK 46 and those of the series BUSS ® MRS or MX, sold by the company BUSS AG, which are constituted by a screw shaft provided with fins, disposed in a heating sleeve possibly t consists of several parts and whose inner wall is provided with kneading teeth adapted to cooperate with the fins to produce shear of the kneaded material. 1 / shaft is rotated, and provided with an oscillation movement in the axial direction, by a motor.
• These co-kneaders may be equipped with a pellet manufacturing system, adapted for example to their outlet orifice, which may be constituted by an extrusion screw and a granulation device.
• co-kneaders that can be used according to the invention preferably have an L / D screw ratio ranging from 7 to 22, for example from 10 to 20, advantageously from 11, while Co-rotating extruders preferably have an L / D ratio of from 15 to 56, for example from 20 to 50.
• a preferred embodiment of the "step (i) is to carry out kneading of the mixture with a co-rotating twin screw extruder had against-rotating or more Introduceentielle ⁇ ent using a co- mixer (in particular BUSS type) comprising a rotor provided with fins adapted to cooperate with teeth mounted on a stator, said co-kneader being advantageously equipped with an extrusion screw and a granulation device.
• a co- mixer in particular BUSS type
• a rotor provided with fins adapted to cooperate with teeth mounted on a stator
• said co-kneader being advantageously equipped with an extrusion screw and a granulation device.
• the constituents of the master liquor may be introduced separately into the kneader, or in the form of premixes of at least two of these constituents.
• the powder of the binder polymer may be previously dissolved in the solvent before introduction into the kneader.
• the carbonaceous conductive fillers, the polyraeric binder and the polymeric dispersant can be introduced separately, or as a premix, into the feed hopper of the co-kneader, while the solvent is injected in liquid form into the first zone of the co-kneader.
• the masterbatch is extruded in solid form and then optionally cut, especially in the form of granules.
• a step of shaping granules from the masterbatch can thus be provided between steps (II) and (iii) of the process according to 1 ! inventio.
• the masterbatch is then diluted in a solvent which is identical to or different from that of stage (1), in order to obtain a pasty composition.
• This step (iii) may preferably be carried out in a kneader such as that used in step (i), or alternatively in another mixing device such as a loculator, the dilution ratio in the step (iii), i.e. the weight ratio of the solvent to the masterbatch, may be from 2: 1 to 10, preferably from 3: 1 to
• the above method may comprise other preliminary, intermediate or subsequent steps, as long as they do not adversely affect. obtaining the desired pasty composition. It may in particular comprise one or more steps of adding one or more organic or inorganic additives. However, it is preferred that this method does not include any step of grinding the conductive carbonaceous fillers, the passage of conductive carbonaceous charges to ultrasound or in a rotor-stator device and / or addition of surfactant (s).
• the pasty composition thus obtained has a greater or lesser viscosity depending on the intended applications, ranging from the consistency of a liquid to that of a tar-like paste. It can thus be between 200 and 1,000 mPa.s, for example between about 400 and 600 ⁇ Pa.s, as measured using a Lamy model Rhéomat RM100 viscometer equipped with a D.IK22 measuring system and driven by an acquisition software Lamy VISCO-R Soft, according to the following protocol: 20 ml of paste are introduced into the measuring cylinder, which is then assembled with the mobile on the apparatus. A viscosity curve is then plotted by varying the gradient between 1.2 and 1032 sec- 1 at a temperature of 23 ° C., and the viscosity corresponding to a 100s- 1 gradient is noted (see Figure 1).
• This pasty composition is distinguished in particular from a solid, insofar as it is not possible to measure its Young's modulus at room temperature, and where its softening point is. less than room temperature.
• the pasty composition obtained according to the invention preferably contains from 0.5 to 20% by weight, preferably from 1 to 15% by weight and more preferably from 4 to 7% by weight of conductive carbonaceous fillers.
• This paste can in particular be used for the preparation of thin films, inks or conductive coatings, in particular for the manufacture of Li-ion battery electrodes or supercapacitors; or for the preparation of conductive composite materials by introducing it, for example, into a polyurethane-based polymer matrix; or in the manufacture of paints, lubricants or textiles.
• the process for preparing an electrode from the pasty composition according to the invention may comprise the following steps:
• step (c) optionally, adding an electrode active material to the product of step (c); e) depositing said coating composition on a substrate to form a film;
• the second solvent refers to that used in the manufacture of the masterbatch and the third solvent refers to the solvent used to make the pasty composition from the masterbatch, it being understood that the first, second and third solvents, as well as that the dilution solvent, may be identical or different from each other, and selected from the list mentioned above. It is preferred that they all be identical.
• the first binder may be identical to the second binder or different from this one. It is also preferred that they be identical.
• step f 1 (a) agitators "flocculator" are preferred for the implementation of step f 1 (a).
• the active electrode material may be dispersed with powdering in the mixture from step (a) or (c), respectively.
• electrode active material may be selected from the group consisting of:
• transition metal oxides with a spinel structure of where M represents a metal atom containing at least one of the metal atoms selected from the group consisting of Mn, Fe, Co, Ni, Cu, Mg, Zn, V, Ca, Sr, Ba, Ti, Al, Si, B and Mo said oxides preferably containing at least one Mn and / or Ni atom;
• transition metal oxides with lamellar structure of LiMQj type where M represents a metal atom containing at least one of the metal atoms selected from the group formed by Mn, Fe, Co, Ni, Cu, Mg, Zn, V , Ca, Sr, Ba, Ti, Al, Si, B and Mo, said oxides preferably containing at least one of the atoms selected from the group consisting of Mn, Co and Ni;
• M represents a metal atom containing at least one of the metal atoms selected from the group formed by Mn, Fe, Co, Cu, Mg, Zn, V, Ca, Sr, Ba, Ti, Al, Si, o X represents one of the selected atoms in the group formed by P, Si, Ge, S and s,
• the electrode active materials i) to iv ⁇ are more suitable for the preparation of cathodes, and preferred according to the invention, while the active materials of electrodes v ⁇ and vi) are more suitable for the preparation of anodes.
• the dispersion of the first binder is mixed with the pasty composition according to the invention in step ⁇ c ⁇ .
• This mixing can be carried out using any mechanical means, provided that they make it possible to obtain a homogeneous dispersion. According to the invention, it is preferred that the mixture of 1 / step (c) be carried out using a "flocculator" type mixer,
• step (e) the film obtained from the suspension resulting from step (c) or (d) can be deposited on a substrate by any conventional means, for example by extrusion, spreading ⁇ tape casting ), by coating or spray drying followed by a drying step (step (f)).
• the substrate may in particular be a current collector. An electrode is thus obtained.
• the carbon nanotubes With the method according to the invention, it is in particular possible to distribute the carbon nanotubes in such a way that they form a mesh around the particles of active material and thus play a role of both a conductive additive but also a mechanical support , important for accommodating volume variations during charge-discharge steps.
• they distribute electrons to the particles of active material and, on the other hand, because of their length and their flexibility, they form electric bridges between the particles of active material that move as a result of their volume variation.
• the usual conductive additives carbon 59, acetylene black and graphite
• the electrical paths are formed by the juxtaposition of grains and the contacts between them are easily broken due to the voluminal expansion of the particles of the active material.
• FIG. 1 illustrates the viscosity curve of a paste according to the invention as a function of shear
• Figure 2 is a SEM image at magnification; 50,000 times) showing the dispersion of the CNTs, obtained from the paste according to the invention, around particles of LiFePO 4 / C,
• Figure 3 is a SEM image (magnification:
• Figure 4 illustrates the viscosity curves of a paste according to the invention and a commercial pulp, depending on the shear.
• NTCs Graphistrength ® C100 from ARKEMA
• a BU ' SS® MDK 46 co-reamer L / D - 11
• PVDF poly (vinylidene fluoride)
• AR EMA Kynar ® HSV 900 AR EMA Kynar ® HSV 900
• pol vinyl pyrrolidone
• NMP N ⁇ methyl pyrrolidone
• the slurry had the following composition: 5% by weight of TC, 0.4% by weight of PVDF, 1.4% by weight of PVP and 93.2% by weight of NMP.
• Example 2 Use of a coissposition dough s ⁇ oux s fabiTicati-Oîi d. ' Noxecfcxocte Step a) A pasty composition was prepared as described in Example 1, except that it contained 5% by weight of CNT, 1% by weight of PVP, 0.8% by weight of PVDF and 93.2% by weight of PVDF. NMP weight. 40 g of this composition were poured into 85.6 g of NMP and mixed with a 50 m diameter stirrer at 850 rpm for 1 hour. The resulting solution has been designated "Preraix NTC".
• Step h a PVDF solution was prepared (HSV ynar ® 900 ARKEM) to 12% in NMP, using a type stirrer flocuiateur for 4 hours at 50 ° C.
• Step c) 30.9 g of the PVDF solution was dispersed in the "Premix NTC" at 1,100 rpm for 5 minutes.
• Step d) 93.6 g of LiFePO4 / C (LFP) powder (Prayon grade 2B) were gradually dispersed in the above dispersion while maintaining the stirring speed at 1,100 rpm. The increase in viscosity of the medium then made it possible to increase the stirring speed to 1,700 rpm. This stirring speed was maintained for one hour.
• LFP LiFePO4 / C
• composition of the dry ink was as follows: 2% by weight of CNT; 4% by weight of PVDF, 0.4% by weight of PVP and 93.6% by weight of LiFePO4 / C, with a solids content of 40% in the NMP solvent.
• Step e) Using a Sheen type filmography and an adjustable BYK-Gardner e> applicator , a film of Thickness was achieved on an aluminum sheet of 25 ⁇ m.
• Step f) The film made in step e) was dried at 55 ° C. for 4 hours in a ventilated oven and then compressed at 200 bar to obtain a final thickness of active material of about 60 ⁇ m. SEM observations (see Figure 2) have. It has been shown that the CNTs are well dispersed around the micrometric particles of LiFePO 4 / C. Moreover, the electrical completeness of the electrode obtained is equal to 2 ⁇ S / cm. jEggsgle 3 (coi>& tf): Analysis of a NC ⁇ ⁇
• Example 2 Starting from a paste prepared as described in Example 1 but not containing PVP, a film containing 2% by weight of CNT, 4% by weight of the product, was prepared in accordance with the process described in Example 2. PVDF and 94% by weight of LiFePO4 / C with a solids content of 40% in the MMP.
• the CNTs are in the form of non-dispersed aggregates around the micrometric particles of LiFePO4 / C, which results in a significant decrease in electrical conductivity, which is 0.05 pS / cro, compared to that measured in Example 2.
• the two pastes were subjected to a viscosity measurement using a Lamy model Rheomat M100 viscometer equipped with a DIN22 measurement system and controlled by a Lamy ViSCG-RM Soft acquisition software, following the following protocol: 20 ml of dough is introduced into the measuring cylinder, which is then assembled with the mobile on the apparatus. Then draws a viscosity curve by varying the gradient between 1.2 and 1032 s "A to a temperature of 23 ° C.
• the viscosity of the paste according to the invention r is from about 500 mPa.s, while it is of about 3,000 mPa.s to pulp commercial.
• the dough obtained according to the process according to the invention is more fluid, and therefore easier to handle, than the commercial dough.

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