Classifications

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  • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
  • C04B35/71—Ceramic products containing macroscopic reinforcing agents
  • C04B35/78—Ceramic products containing macroscopic reinforcing agents containing non-metallic materials
  • C04B35/80—Fibres, filaments, whiskers, platelets, or the like
  • C04B35/83—Carbon fibres in a carbon matrix
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  • D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
  • D01F9/08—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
  • D01F9/12—Carbon filaments; Apparatus specially adapted for the manufacture thereof
  • D01F9/14—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments
  • D01F9/16—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from products of vegetable origin or derivatives thereof, e.g. from cellulose acetate
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01D—SEPARATION
  • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
  • B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
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  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
  • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
  • B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
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  • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
  • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
  • B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
  • B01J20/28023—Fibres or filaments
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  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
  • B01J20/30—Processes for preparing, regenerating, or reactivating
  • B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
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  • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
  • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
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  • C04B35/62204—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products using waste materials or refuse
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  • C04B35/62227—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products obtaining fibres
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  • C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
  • C04B35/628—Coating the powders or the macroscopic reinforcing agents
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  • C04B38/00—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof
  • C04B38/0022—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof obtained by a chemical conversion or reaction other than those relating to the setting or hardening of cement-like material or to the formation of a sol or a gel, e.g. by carbonising or pyrolysing preformed cellular materials based on polymers, organo-metallic or organo-silicon precursors
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  • D01F11/00—Chemical after-treatment of artificial filaments or the like during manufacture
  • D01F11/10—Chemical after-treatment of artificial filaments or the like during manufacture of carbon
  • D01F11/14—Chemical after-treatment of artificial filaments or the like during manufacture of carbon with organic compounds, e.g. macromolecular compounds
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  • D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
  • D01F9/08—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
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  • D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
  • D01F9/08—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
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  • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
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  • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
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  • C04B2235/656—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes characterised by specific heating conditions during heat treatment
  • C04B2235/6567—Treatment time
• • C—CHEMISTRY; METALLURGY
  • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
  • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
  • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
  • C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
  • C04B2235/74—Physical characteristics
  • C04B2235/77—Density
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
  • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
  • Y02E60/10—Energy storage using batteries
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
  • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
  • Y02E60/30—Hydrogen technology
  • Y02E60/50—Fuel cells

Definitions

• the invention relates to the field of highly carbonaceous materials for the manufacture of parts made of composite materials or parts that can be used in electrochemical processes.
• the invention relates to a method of manufacturing a highly carbonaceous material and the highly carbonaceous material obtainable by such a manufacturing method.
• Carbon fibers generally have excellent tensile properties, high thermal and chemical stability, good thermal and electrical conductivities, and excellent resistance to deformation. They can be used as reinforcements of composite materials which usually comprise a polymer resin (matrix). The composite materials thus reinforced exhibit excellent physical properties while maintaining an advantageous lightness. Lightening is one of the key measures in reducing CO2 emissions for transport.
• the automotive and aerospace industry is in demand for compounds presenting, with equivalent performance, a greater lightness. In this context, the automotive and aeronautics sectors, and more broadly the industry, also need high-performance materials but at controlled costs.
• carbon fibers are also developing in the field of electrochemistry due to several qualities such as their high electrical conductivity and flexibility in terms of size and shape. Nevertheless, in this field, carbon fibers still have disadvantages related to their low concentration in metallic charges. There is therefore still a need for 3D structures with high conductivity and a high concentration of metal charges to create an economical alternative to porous metals.
• PAN Polyacrylonitrile
• the production of carbon fibers from PAN includes the polymerization steps of PAN-based precursors, fiber spinning, thermal stabilization, carbonization and graphitization.
• the carbonization takes place under a nitrogen atmosphere at a temperature of 1000 to 1500 ° C.
• the carbon fibers obtained at the end of these steps consist of 90% carbon, about 8% nitrogen, 1% oxygen and less than 1% hydrogen.
• Precursors based on Brai have also been developed but, like acrylic precursors, they consume fossil resources.
• the presence of CNTs in the biosourced precursor makes it possible to increase the carbon yield of the precursor during carbonization, and also to increase the mechanical characteristics of the carbon fibers.
• the bio-resourced precursor may be cellulose transformed in the form of fibers by dissolution and coagulation / spinning, so as to form hydrocellulose (as for example, viscose, lyocell, rayon).
• the process may comprise a sizing step before carbonization.
• FR2994968 describes the manufacture of a carbon-based composite material comprising a carbon fiber based on Lyocell and a carbon matrix. Nevertheless, the process described in this document requires the use of a carbon fiber which involves the implementation of several steps including several carbonizations.
• KR 20120082287 describes a process for manufacturing carbon fiber from a precursor material comprising lyocell (cellulosic fibers from wood or bamboo) and a nanocomposite material - graphenes.
• CN 1587457 describes a process for preparing a cellulosic precursor material for the manufacture of carbon fiber having improved properties and a lower manufacturing cost.
• the cellulosic preparation involves inserting the soot nanoparticles into the cellulosic solution. Nevertheless, these processes do not allow an improvement in the carbon yield and an increase in the porosity of the materials obtained.
• the document US2009121380 describes a process for obtaining carbon fiber texture without using solvents from cellulosic precursor having been spun and impregnated with an aqueous emulsion comprising an organosilicon additive.
• the Applicant has noted that there is still a need for precursors used in carbon-based material manufacturing processes capable of responding to problems encountered with existing methods and allowing: i) a high carbon yield; ii) a combination of stable 3D structure and increased porosity; iii) reduced manufacturing cost.
• the object of the invention is to propose a method of manufacturing a highly carbonaceous material that is very mechanically stable with improved carbon yield.
• this highly carbonaceous material has a higher porosity than carbon fibers, allowing it to be more effectively combined with metals.
• the invention relates to a process for the production of highly carbonaceous material, characterized in that it comprises the combination of a structured precursor comprising a fiber or a set of fibers and an unstructured precursor, in the form of a fluid, said fluid preferably having a viscosity of less than 45,000 mPa ⁇ s -1 at the temperature at which the combining step takes place, and comprising at least one cyclic or aromatic organic compound in the molten state or in solution at a concentration by weight of less than or equal to 65%, so as to obtain a combined precursor corresponding to the structured precursor covered by the unstructured precursor, said method further comprising the following steps: a step of thermal and dimensional stabilization of the combined precursor to obtain a fiber or a set of fibers covered with a cyclic or aromatic organic compound deposition, and
• This new process for producing a highly carbonaceous material has many advantages such as obtaining a higher carbon yield than observed with the methods of the prior art, the formation of a material having a high porosity while retaining a structured part, and the possibility of adding additional compounds to obtain a highly carbonaceous material with improved properties.
• the invention further relates to a fiber or a set of fibers covered with a cyclic or aromatic organic compound deposition as an intermediate product, obtained after the thermal and dimensional stabilization step of the manufacturing method according to the invention.
• This intermediate product advantageously has a ratio of the mass of fiber (s) to the mass of cyclic or aromatic organic compound of between 1/5 and 100/1.
• the invention further relates to a highly carbonaceous material obtained by the process according to the invention.
• this highly carbonaceous material is bi-structured, having a structured portion and an unstructured portion, and has an overall porosity greater than 5%, preferably greater than 10%.
• the invention further relates to the use of the highly carbonaceous material according to the invention for the manufacture of parts made of thermoplastic or thermosetting composite materials.
• the invention further relates to the use of the highly carbonaceous material according to the invention for the manufacture of parts that can be used in electrochemical processes.
• FIG. 1 represents a diagram of an embodiment of the method for manufacturing a highly carbonaceous material according to the invention.
• the dotted steps are optional.
• Figures 2 show two images obtained by microscopy of a section of a carbon material.
• FIG. 2A shows a carbonaceous material comprising a hydrocellulose fiber treated with DAHP (Diammonium hydrogen phosphate)
• FIG. 2B represents a highly carbonaceous material comprising a hydrocellulose fiber treated with lignin according to the process of the invention. . rDescription of the invention!
• carbon nanofillers a charge comprising an element of the group consisting of carbon nanotubes, carbon nanofibers, graphene, fullerenes and carbon black, or a mixture of these in all proportion.
• the carbon nanofillers are carbon nanotubes, alone or mixed with graphene.
• This carbonaceous filler may have a smaller dimension of between 0.1 to 200 nm, preferably between 0.1 and 160 nm, more preferably between 0.1 and 50 nm. This dimension can be measured by light scattering.
• graphene a plane graphite sheet, 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 (Few Layer Graphene or Graphene NanoRibbons or Graphene NanoRibbons), NGP (Nanosized Graphene Plates), CNS (Carbon NanoSheets or nano-graphene sheets), and Graphene NanoRibbons. nano-ribbons of graphene).
• FLG Few Layer Graphene or Graphene NanoRibbons or Graphene NanoRibbons
• NGP Nanosized Graphene Plates
• CNS Carbon NanoSheets or nano-graphene sheets
• Graphene NanoRibbons Graphene NanoRibbons. nano-ribbons of graphene.
• carbon nanotubes and nanofibers which consist respectively
• highly carbonaceous material means a material whose carbon mass represents more than 80% of the total mass of the non-metallic elements, preferably more than 90%, more preferably more than 95%, and even more preferred more than 98% (materials considered materials of very high purity).
• hydrocellulose fiber cellulose fibers or cellulose derivatives, preferably continuous and regular diameter, obtained after dissolution of cellulose from lignocellulosic material.
• the hydrocellulose may, for example, be obtained after treatment with sodium hydroxide followed by dissolution with carbon disulphide. In this case, the hydrocellulose is more particularly called viscose.
• the hydrocellulose fiber can be obtained from lignocellulosic material dissolved in a solution comprising N-methylmorpholine N-oxide to form Lyocell.
• lignin a plant aromatic polymer whose composition varies with the plant species and generally formed from three phenylpropanoid monomers: p-coumaryl, coniferyl and sinapyl alcohols.
• lignin derivative a molecule having a lignin-type molecular structure and may include substituents having been added during the lignin extraction process or later so as to modify its physicochemical properties. .
• lignin modifications There are many processes for extracting lignin from lignocellulosic biomass and these can lead to lignin modifications. For example, the Kraft process uses a strong base with sodium sulfide to separate lignin from cellulose fibers.
• This process can form thio-lignins.
• the sulphite process resulting in the formation of lignosulfonates.
• the organosolv pretreatment methods use an organic solvent or mixtures of organic solvents with water to solubilize the lignin prior to the enzymatic hydrolysis of the cellulosic fraction.
• lignin derivative is meant a lignin having substituents that can be selected from: Thiol, Sulfonate, Alkyl, or Polyester.
• the lignins or lignin derivatives used in the context of this The invention generally has a molecular weight greater than 1000 g / mol, for example greater than 10000 g / mol.
• the invention relates to a method of manufacturing 1 a highly carbonaceous material 2, characterized in that it comprises the combination 100 of a structured precursor 10 comprising a fiber or a set of fibers and an unstructured precursor 15, in the form of a fluid, said fluid preferably having a viscosity of less than 45,000 mPa.s -1 at the temperature at which the combining step occurs, and comprising at least one cyclic or aromatic organic compound in the molten state or in solution at a mass concentration of less than or equal to 65%.
• This combination step 100 makes it possible to obtain a combined precursor 20 corresponding to the structured precursor 10 covered by the unstructured precursor 15.
• An embodiment of this process is shown diagrammatically in FIG. 1. It can be realized continuously or discontinuously. In the context of a continuous realization, the industrial processes allow the sequence of the various steps without interruption.
• the structured precursor 10 comprises a fiber or a set of fibers.
• the fiber or set of fibers may have undergone pretreatments to facilitate their handling in the context of the method according to the invention. Nevertheless, being used as a precursor, this fiber or set of fibers has not undergone a carbonization step.
• the fiber or set of fibers used in the structured precursor 10 has a carbon mass concentration of less than 75%, advantageously less than 65%.
• these fibers are cellulose fibers, hydrocellulose fibers, lignin fibers, Brai fibers or acrylic precursor fibers (for example PAN).
• the structured precursor 10 comprises a natural fiber or a set of natural fibers.
• Said natural fiber is obtained from at least one vegetable component, preferably cellulose, chosen from cellulose of wood, flax, hemp, ramie, bamboo and preferably the cellulose of wood or lignocellulose, a combination of cellulose and lignin, as in wood fibers, jute, cereal straw, corn stalks, cork or lignin. This fiber can be obtained by various known manufacturing processes.
• the natural fibers are obtained from a cellulose solution; then extruding into a die to form a continuous fiber such as a hydrocellulose fiber, or obtained from lignin after extrusion to form a lignin fiber.
• hydrocellulose fiber it may for example be obtained according to the manufacturing method described in WO2014064373 application.
• the hydrocellulose fibers used may also be Lyocell or viscose fibers, the cellulose of which comes for example from wood or bamboo.
• Most of the processes for producing hydrocellulose fibers are based on the production of a cellulosic preparation from dissolved cellulose, for example carbon disulfide, 4-methylmorpholine-4-oxide (N-Methylmorpholine-N-oxide). NMMO) or in an acid solution (eg ortho-phosphoric acid or acetic acid), which is then used to form the continuous hydrocellulose fibers following immersion in a coagulation bath containing, for example, sulfuric acid.
• an acid solution eg ortho-phosphoric acid or acetic acid
• the hydrocellulose fiber used in the process of the present invention as a precursor has not been prior carbonized.
• this fiber or this set of fibers can take very different shapes.
• One of the advantages of the invention is that the method can be implemented with fibers that have been previously shaped, for example in the form of a twisted multi-filament, a non-twisted multi-filament, a set of nonwoven fibers, or a set of woven fibers.
• the invention makes it possible to directly use non-carbonized fibers that have been previously organized, in the form of a multi-filament or set of fibers.
• the method according to the invention has the advantage of reducing the manufacturing costs of multi-filaments or sets of carbon fiber (for example woven).
• a set of woven fibers eg viscose, Lyocell, rayon, oxidized PAN
• the structured precursor 10 comprises a multi-filament or a set of fibers.
• the structured precursor 10 is a twisted multi-filament, a non-twisted multi-filament, a set of non-woven fibers, or a set of woven fibers.
• the twisted multi-filaments that can be used according to the invention have for example a number of turns per meter between 5 and 2000 turns per meter, preferably between 10 and 1000 turns per meter.
• the structured precursor 10 according to the invention may comprise at least one fiber whose diameter is between 0.5 ⁇ and 300 ⁇ , preferably between 1 ⁇ and 50 ⁇ .
• the structured precursor 10 according to the invention comprises at least one continuous fiber having a regular diameter over its entire length, and in particular the absence of fibril. This improves the cohesion between the cyclic or aromatic organic compound deposition and the fiber.
• regular diameter it should be understood that the diameter varies from less than 20%, preferably less than 10% over the length of the fiber.
• the unstructured precursor 15 is in the form of a fluid comprising at least one cyclic or aromatic organic compound in the molten state or in solution at a mass concentration of less than or equal to 65%.
• the use of the unstructured precursor in the form of a fluid makes it possible to improve the combination 100 between the unstructured precursor 15 and the structured precursor 10.
• the fluid may be an aqueous solution, or an organic solution or a mixture of both. These alternatives make it possible to adapt the unstructured precursor according to the cyclic or aromatic organic compound used as well as any added additives.
• the fluid is a mixture of water and an organic solvent.
• the fluid may be a melt such as melted lignin. This is particularly suitable when the cyclic or aromatic organic compound used is not soluble or poorly soluble.
• the cyclic or aromatic organic compound may be in different forms in the fluid. It can be solubilized in the solution, melted or in the solid state in the form of a dispersion. This dispersion can be carried out in a solution as well as in a melt.
• the cyclic or aromatic organic compounds neither fusible nor soluble, will be combined with the structured precursor in the form of a dispersion.
• the fluid has a viscosity of less than 45,000 mPa.s -1 at the temperature at which the combination step 100 takes place. This makes it possible, during the combination step, to associate a larger quantity. significant unstructured precursor 15 to 10 structured precursor and increase the porosity of highly carbonaceous material 2 obtained.
• the fluid has a viscosity greater than 500 mPa ⁇ s "1 and less than 45 000 mPa ⁇ s" 1, of Preferably, it has a viscosity greater than 1000 mPa ⁇ s -1 and less than 45 000 mPa ⁇ s ⁇ 1.
• This viscosity range corresponds to a viscosity suitable for the technologies used for the combination step, in particular the impregnation, and allows a better control of the quantity of fluid deposited during this step
• a viscosity higher than 500 mPa.s -1 makes it possible to improve the carbonic yield carbon yield of the highly carbonaceous material obtained u with respect to a lower viscosity.
• the viscosity of the fluid is measured at the temperature at which the combination step 100 takes place, for example by means of a free-flowing viscometer or capillary viscosity or the brookfield method.
• the cyclic or aromatic organic compound is an organic material which, following pyrolysis under an oxygen-free atmosphere, is converted into a carbon residue preferably representing more than 5% by weight of the highly carbonaceous material 2 obtained in the context of of the invention.
• a cyclic or aromatic organic compound according to the invention comprises a series of atoms successively linked by covalent bonds to form one or more rings. This cycle may be saturated or unsaturated and this ring may be a heterocycle.
• the cyclic or aromatic organic compound is an aromatic compound. That is, it has at least one aromatic ring.
• the cyclic or aromatic organic compound has a mass percentage of carbon greater than 40%, more preferably greater than 45%, even more preferably greater than 60%.
• the cyclic or aromatic organic compound may be selected from:
• biobased products selected from: lignin or lignin derivatives, polysaccharides such as cellulose, starch, glycogen, amylose, amylopectin, dextran, hemicellulose, or other simpler sugars such as fructose or glucose and their derivatives;
• products obtained from petroleum or mining resources selected from: pitch, naphthalene, phenanthrene, anthracene, pyrene or substituted polycyclic aromatic hydrocarbons such as naphthalene sulphonate;
• the cyclic or aromatic organic compound is an oligomer or a cyclic or aromatic organic polymer.
• the cyclic or aromatic organic compound has a molecular mass greater than 500 g / mol, preferably greater than 1000 g / mol and even more preferably greater than 5000 g / mol.
• the cyclic or aromatic organic compound is lignin or a lignin derivative.
• the unstructured precursor may comprise a number of different cyclic or aromatic organic compounds.
• the cyclic or aromatic organic compound has a mass concentration of less than or equal to 65%. Too high a solution concentration of cyclic or aromatic organic compound could reduce the properties of the highly carbonaceous material obtained.
• the unstructured precursor comprises between 5 and 50% by weight of cyclic or aromatic organic compound. At such concentrations, the structured precursor fibers are entirely covered with cyclic or aromatic organic compound.
• the unstructured precursor comprises lignin or a lignin derivative.
• lignin represents 10 to 25% of terrestrial biomass of lignocellulosic nature and it is currently little valorized by the industry. Thus, each year, several hundred tons of lignin or lignin derivatives are produced without any possible valorisation.
• Lignin is present mainly in vascular plants (or higher plants) and in some algae. It is a plant aromatic polymer whose composition varies with the plant species and generally formed from three phenylpropanoid monomers: p-coumaryl, sinapyl and coniferyl alcohols as illustrated by the formulas below:
• the unstructured precursor 15 may further comprise at least one additional compound selected from: a metal filler, carbon-rich compounds and organic particles.
• additional compounds selected from: a metal filler, carbon-rich compounds and organic particles.
• the addition of additional compounds to the unstructured precursor makes it possible to benefit from the binder properties of the cyclic or aromatic organic compound and to form a highly carbonaceous material 2 with multiple properties.
• the metal charge may for example include metalloids such as boron, silicon, germanium, arsenic; alkali metals such as lithium, sodium, potassium; transition metals such as titanium, vanadium, manganese, iron, cobalt, nickel, molybdenum; poor metals such as aluminum or lead; or halogens such as fluorine, chlorine, or bromine.
• the metal filler may comprise at least one metal selected from the following metals: boron, silicon, germanium, arsenic, lithium, sodium, potassium, titanium, vanadium, manganese, iron, cobalt, nickel, molybdenum, aluminum and lead.
• metals can be used, alone or as a mixture, in any form such as, for example, in the form of oxide, hydroxide, acid or still in the form of salts such as organic salts (for example salts of nitrate, sulfate, acetate, carbonate, oxalate, benzoate or phosphates).
• the unstructured precursor 15 contains, for example, a metal filler and a cyclic or aromatic organic compound. The cyclic or aromatic organic compound then plays the dual role of porous matrix and binder allowing the fixation of a large amount of metals.
• the unstructured precursor 15 allows to confer highly carbonaceous materials 2 according to the invention physicochemical properties sought for example in the case of applications in electrochemistry.
• the unstructured precursor 15 comprises several different metals.
• the unstructured precursor may include lithium, cobalt, and nickel.
• the carbon-rich compounds may be selected from the following compounds: activated carbon, natural anthracite, synthetic anthracite, carbon black, natural graphite or synthetic graphite.
• the organic particles can be selected from the following compounds: nanocellulose (for example: cellulose nanofibers, cellulose microfibrils, cellulose nanocrystals, nanocellulose whiskers or bacterial nanocellulose), tannins, chitosan, or other biopolymers neither fusible nor soluble.
• nanocellulose for example: cellulose nanofibers, cellulose microfibrils, cellulose nanocrystals, nanocellulose whiskers or bacterial nanocellulose
• tannins chitosan
• Such carbon-rich compounds or organic particles added to the unstructured precursor make it possible to increase the carbon yield of the material obtained and to improve its mechanical properties.
• the compounds neither soluble nor soluble can be added in the form of a dispersion.
• the unstructured precursor may comprise between 0.001% and 50% by weight of additional compound. More preferably, it may comprise from 0.001% to 30% by weight of carbon-rich compounds, from 0.001% to 50% by weight of organic particles or a mixture thereof in any proportion.
• the structured precursor 10 and / or the unstructured precursor 15 may comprise carbon nanofillers, said carbon nanofillers being present at a concentration of between 0.0001% and 30% by weight. Preferably, these carbon nanofillers are present at a concentration of between 0.01% and 5% by weight.
• the addition of carbon nanofillers to one or both precursors improves the carbon yield of the material highly carbonated obtained. Indeed, when carbon nanofillers are added to the unstructured precursor 15, the latter acts as a binder and causes an increase in the amount of carbon nanofillers being effectively inserted in the resulting material.
• the carbon nanotubes (CNTs) may be of the single wall, double wall or multiple wall type.
• the double-walled nanotubes can in particular be prepared as described by FLAHAUT et al in Chem. Corn. (2003), 1442.
• the multi-walled nanotubes may themselves be prepared as described in WO 03/02456.
• the nanotubes usually have an average diameter ranging from 0.1 to 100 nm, 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 ⁇ .
• 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 m 2 / g, advantageously between 200 and 300 m 2 / g, and their apparent density may in particular, be between 0.05 and 0.5 g / cm 3 and more preferably between 0.1 and 0.2 g / cm 3.
• the multiwall nanotubes may for example comprise from 5 to 15 sheets (or walls) and more preferably from 7 to 10 sheets.
• crude carbon nanotubes is in particular commercially available from ARKEMA under the trade name Graphistrength® C100.
• these nanotubes can be purified and / or treated (for example oxidized) and / or milled and / or functionalized before being used in the process according to the invention.
• the purification of the crude or milled nanotubes can be carried out by washing with a sulfuric acid solution, so as to rid them of any residual mineral and metal impurities.
• the oxidation of the nanotubes is advantageously carried out by putting them in contact with a solution of sodium hypochlorite.
• the functionalization of the nanotubes can be carried out by grafting reactive units such as vinyl monomers on the surface of the nanotubes.
• the graphene used in the process can be obtained by chemical vapor deposition or CVD, preferably in a process using a powder 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 lateral dimensions smaller than micron, from 10 to 1000 nm, preferably from 50 to 600 nm, and more preferably from 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.
• Fullerenes are molecules composed exclusively or almost exclusively of carbon that can take a geometric shape reminiscent of a sphere, an ellipsoid, a tube (called nanotube) or a ring.
• Fullerenes may for example be selected from: fullerene C60 which is a compound of 60 carbon atoms of spherical form, C70, PCBM of formula [6,6] -phenyl-C61-methyl butyrate which is a derivative fullerene whose chemical structure has been modified to make it soluble, and the PC 71 of formula [6,6] -phenyl-C71-methyl butyrate.
• Carbon nanofibers are, like carbon nanotubes, nanofilaments produced by chemical vapor deposition (or 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.
• Carbon nanofibers are composed of more or less organized graphitic zones (or turbostratic stacks) whose planes are inclined at angles variables relative to the axis of the fiber. These stacks can 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 nanofibers having a diameter of 100 to 200 nm, for example about 150 nm (VGCF® from SHOWA DENKO), and advantageously a length of 100 to 200 ⁇ are preferred in the process according to the invention.
• 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. whose dimensions are generally between 10 and 1000 nm.
• the combination step 100 corresponds to the contacting of the structured precursor 10 with the unstructured precursor 15.
• This combination can be carried out by several alternative methods, generally at a temperature ranging from -10 ° C. at 80 ° C, preferably from 20 ° C to 60 ° C.
• a soaking, spraying or impregnation for example by padding
• the combination step 100 is an impregnation.
• the manufacturing method 1 according to the invention further comprises a thermal and dimensional stabilization step 200 of the combined precursor 20 so as to obtain a fiber or a set of fibers coated with a deposit of cyclic or aromatic organic compound 30.
• the thermal and dimensional stabilization step 200 may comprise a drying allowing the evaporation of the solvent and / or a ventilation.
• the drying can be carried out via a rise in temperature, for example between 50 ° C. and 250 ° C. for a period of preferably 1 to 30 minutes.
• a heat treatment to expel the diluent or the solvent in the form of steam.
• an infrared oven with ventilation may be used.
• a deposit, similar to a solid film, of cyclic or aromatic organic compound is formed on the surface of the fiber. This deposit may have varying thicknesses depending on the parameters used in the process such as the viscosity of the solution or the concentration of cyclic or aromatic organic compound.
• the combination steps 100 and thermal and dimensional stabilization 200 can be repeated one or more times. Repetition of these steps makes it possible to increase the amount of cyclic or aromatic organic compound deposited on the fiber or set of fibers. It is thus possible to increase the carbon yield, to increase the diameter of the fibers obtained and / or to increase the porosity of the highly carbonaceous material obtained at the end of the process.
• the manufacturing method 1 according to the invention further comprises a carbonization step 300 of the fiber or set of fibers covered with a cyclic or aromatic organic compound deposit 30 so as to obtain a highly carbonaceous material 2.
• This carbonization step 300 can be carried out at a temperature between 150 ° C and 2500 ° C, preferably between 250 and 1400 ° C.
• the carbonization step 300 may for example last 2 to 60 minutes.
• This carbonization step may comprise a progressive rise in temperature or a rise and fall in temperature.
• the carbonization takes place in the absence of oxygen and preferably under a nitrogen atmosphere. The presence of oxygen during carbonization should be limited preferably to 5 ppm.
• This carbonization step can be carried out continuously and can be coupled to a drawing step of the fiber so as to improve the mechanical properties of the carbon fiber obtained.
• the manufacturing method according to the invention may further comprise, before the carbonization step 300, the following steps:
• a sizing step 210 consisting in bringing into contact the fiber or the set of fibers covered with a cyclic organic compound deposit or aromatic with an aqueous solution comprising at least one flame retardant compound, said flame retardant compound being selectable from: potassium, sodium, phosphate, acetate, chloride, urea, and a post-drying step 220
• the cyclic or aromatic organic compound such as lignin or lignin derivative, may have flame retardant properties
• the addition of a sizing step with a solution comprising at least one flame retardant compound makes it possible to improve the characteristics of the carbon material obtained.
• the sizing steps 210 and post-sizing drying 220 can be repeated one or more times. Thus, it is possible to increase the amount of flame retardant associated with the fiber or to combine different treatments based on different substances.
• the manufacturing method according to the invention may further comprise a shaping step 400, optionally coupled to a structuring step, of the highly carbonaceous material 2 by any shaping method such as that: extrusion, compression, calendering, stretching or molding, at room temperature or with heat treatment.
• This shaping allows precise control of the final shape of the highly carbonaceous material obtained by the process according to the invention. It can also make it possible to control the porosity of the material produced.
• the shaping step may for example be performed at a temperature below 400 ° C in the presence of a polymeric binder or at a temperature above 400 ° C in the context of a drawing, a compression or calendering.
• Graphitization 500
• the manufacturing method according to the invention can comprise, after the carbonization step 300, a graphitization step 500.
• This graphitization step 500 can be carried out at a temperature of between 1000 ° C. and 2800 ° C., preferably greater than or equal to 1100 ° C.
• the graphitization step 500 can for example last from 2 to 60 minutes, preferably from 2 to 20 minutes.
• This graphitization step 500 may comprise a gradual rise in temperature.
• the manufacturing method according to the invention may further comprise, after the carbonization step 300, a sizing step 600 of contacting the highly carbonaceous material 2 with a solution of an organic component that can comprise at least one silane or silane derivative and / or at least one siloxane or siloxane derivative.
• This sizing 600 can also be performed after the graphitization step 500.
• a plasma, microwave and / or electrochemical treatment step can also be performed between the graphitization step 500 and the sizing step 600.
• Sizing improves the integrity of the carbon material and protects it from abrasion.
• the solution of the organic component is preferably an aqueous solution, an organic solution or an aqueous emulsion.
• This sizing step improves the physicochemical properties of the material (eg protection against abrasion and improving the integrity of the fibers component) and has the advantage, in the context of the invention of possibly be performed on a set of fiber, that is to say for example on a carbon fiber fabric.
• the invention relates to a fiber or a set of fibers covered with an organic deposit 30 as an intermediate product obtained after the thermal and dimensional stabilization step 200 of the manufacturing method according to the invention.
• the organic deposit is an aromatic or cyclic organic compound deposit.
• the ratio of the mass of fiber to the mass of cyclic or aromatic organic compound is between 1/5 and 100/1 and the said organic deposit covering the fiber or the set of fibers comprises at least one cyclic organic compound.
• This intermediate product preferably has a ratio of the mass of fiber to the aromatic or cyclic organic compound mass of between 1/5 and 100/1, preferably between 2/1 and 95/1.
• the invention relates to a highly carbonaceous material 2 that can be obtained by the manufacturing method according to the invention and preferably obtained by the manufacturing method according to the invention.
• this highly carbonaceous material 2 is bi-structured so as to comprise a structured part and an unstructured part.
• the structured part corresponds to the material resulting from the carbonization of the structured precursor 10 while the unstructured part corresponds to the material resulting from the carbonization of the structured precursor 15.
• these two highly carbonaceous parts may have different physicochemical characteristics.
• the structured structure may be advantageous for the shape of the structure but also for the electrical conductivity, in combination with an unstructured part providing a large specific surface area available for the electronic reactions / exchanges.
• the invention advantageously relates to a highly carbonaceous material 2, bi-structured so as to comprise a structured part comprising a carbonized fiber or a set of carbonized fibers, and an unstructured part comprising a cyclic organic compound or carbonized aromatic and having an overall porosity greater than 5%, preferably greater than 10%.
• the highly carbonaceous material 2 has an overall porosity greater than 5%, preferably greater than 10%. These products meet the expectations of industrialists looking for lighter carbon fibers that nevertheless have sufficient mechanical properties to meet the needs of, for example, the aerospace or automotive industries.
• the highly carbonaceous material obtained by the process according to the invention has the advantage of having a greater porosity than the highly carbonaceous materials obtained until now. This greater porosity has the advantage, as shown in the examples, of increasing the carbon yield obtainable from the addition of additives such as nanocarbon feeds. In addition, this greater porosity opens the use of this material to many applications that can benefit from a larger overall surface area.
• Porosity is for example measured by direct methods (tomography, radiography, micrograph parts) or indirect (density measurement, weighing, ).
• the overall porosity is determined by density measurement with respect to the theoretical density.
• the structured part has a porosity of less than 40%, preferably less than 30%, and the unstructured part has a porosity greater than 7%, preferably greater than 10%. These porosities are advantageously determined by micrographs on cut pieces.
• the ratio of the volume of the structured part to the volume of the unstructured part is between 1/5 and 100/1. More preferably, the ratio of the volume of the structured part to the volume of the unstructured part is between 1/5 and 50/1.
• This ratio can be measured by various methods controlled by the person skilled in the art, such as, for example, optical microscope image analysis of microtome sections of the highly carbonaceous material.
• the highly carbonaceous material 2 comprises additional compounds such as metals in its unstructured part.
• the metals may be present in the highly carbonaceous material at a mass concentration of between 0.001% and 90%. More specifically, the metals may be present in the unstructured portion of the highly carbonaceous material at a mass concentration of between 0.1% and 90% while these same metals, or more broadly the metals, are present at a lower concentration. mass at 5% in the structured part. This allows the highly carbonaceous material to exhibit, despite a lack of demarcation between its constituents, a heterogeneous structure particularly advantageous in the context of its use in electrochemical processes.
• the highly carbonaceous material 2 is in the form of a carbon fiber, a twisted multi-filament, a non-twisted multi-filament, a set of non-woven carbon fibers or of a set of woven carbon fibers.
• this highly carbonaceous material comprises, in addition to the structured part, an unstructured part capable of creating stronger links at the level of the contacts between the fibers (for example crosses).
• a highly carbonaceous material 2 has an improvement in the mechanical properties of the structured precursor (for example a tear resistance).
• the invention relates to the use of the highly carbonaceous material 2 that can be obtained via the manufacturing process according to the invention, and preferably obtained by the manufacturing method according to the invention, for the manufacture of parts made of thermoplastic or thermosetting composite materials.
• the invention relates to thermoplastic or thermosetting composite materials obtained from the fibers manufactured via the manufacturing method according to the invention.
• these thermoplastic or thermosetting composite materials have, for an identical volume, a weight less than 5% by weight of conventional thermoplastic or thermosetting composite materials.
• the highly carbonaceous material 2 obtained by the process according to the invention can be used in conventional methods (for example injection, infusion, impregnation) of manufacture of composite materials.
• thermoplastic resins for example polyamides, copolyamides, polyesters, copolyesthes, polyurethanes, polyethylene, polyacetates, polyether sulfonates, polyimides, polysulfones, polyphenylenesulfones, polyolefins
• thermosetting resin for example epoxides, unsaturated polyesters, vinyl esters, phenolic resins, polyimides.
• the invention relates to the use of the highly carbonaceous material 2 obtainable via the manufacturing method according to the invention, and preferably obtained by the manufacturing method according to the invention, for the manufacture of parts that can be used in electrochemical processes.
• the highly carbonaceous materials according to the invention have a low resistance and are very good electronic conductors. In addition, they have a porosity, and therefore a specific surface much higher than conventional carbon fibers. This is particularly related to the presence of a structured part and an unstructured part, each having a different role to play in the electrochemical process.
• the parts that can be used in electrochemical processes may for example be selected from the following list:
• electrode element for primary and rechargeable batteries electric current collector for the anodes or cathodes of lithium or sodium batteries
• the structured precursor used is based on Hydrocellulose fibers in multi filament with a linear density of 88 mg per meter.
• the lignin was solubilized in an Ethanol / Water 60/40 mixture at 60 ° C. After 2 hours of stirring, the solution was cooled to room temperature. The precipitated fraction was filtered. The final solution contained 10% by weight of lignin.
• hydrocellulose fibers constituting the structured precursor are impregnated in the lignin solution, the unstructured precursor, for 7 minutes.
• the lignin impregnated fibers were dried at 80 ° C in a ventilated oven for 1 hour.
• the carbonization was carried out in a vertical static oven under a nitrogen atmosphere. A temperature ramp of 5 ° C per minute was applied to the temperature of 1200 ° C. Characteristics of the carbonaceous material obtained
• the lignin deposition on the hydrocellulose fiber was 9% by weight. Quantification of mass lignin deposition can be obtained by weighing the hydrocellulose fiber before step 1 and then after step 2 of drying.
• Hydrocellulose fibers no lignin deposit or flame retardant
• lignin is a carbon source during pyrolysis and also acts as a flame retardant for hydrocellulose.
• hydrocellulose fibers with lignin so as to form, before carbonization, hydrocellulose fibers coated with a lignin deposit makes it possible to go from 8% to 25% of carbon yield, ie a multiplication by one. factor of 3 and more of carbon yield.
• Lignin also achieves a carbon yield equivalent to the carbon yield achieved with a conventional chemical used with cellulose.
• FIG. 2A shows an image obtained by scanning electron microscopy of a section of a carbon material, in the example a carbon fiber, obtained after combination with DAHP (A) and image 2B mounts an image. obtained by scanning electron microscopy of the carbonaceous material obtained by the process according to the invention.
• FIG. 2B shows that the carbon deposition resulting from the lignin is strongly bound to the fiber surfaces and that it is impossible to identify by microscopy the interface between the structured part, namely the fibers, and the unstructured part, namely the deposition carbonic acid from lignin.
• FIG. 2A shows that the deposition of DAHP does not allow the creation of this unstructured carbonic mass around the structured part.
• FIG. 2B illustrates the creation of an agglomerate forming a bi-structured highly carbonaceous material. There is no visible interface between carbon fiber from the hydrocellulose fiber and lignin after carbonization. [00104]
• the carbon fibers of the carbonaceous material have a diameter of between 6 and 7 ⁇ which is greater than that of the hydrocellulose fibers used as structured precursor.
• Hydrocellulose fibers no lignin deposit or flame retardant
• Hydrocellulose fibers no lignin deposit or flame retardant substance
• carbon nanotubes in the unstructured precursor containing the lignin makes it possible to further increase the carbon yield and to reach carbon yields of 35%, ie a multiplication by a factor of 4 or more of carbon yield.
• the present invention comprises the use of a combination of two precursors so as to obtain a highly carbonaceous material with a higher carbon yield.

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