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    • 专利摘要:
    The invention relates to a method for the production (1) of 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, and comprising at least one cyclic or aromatic organic compound in the molten state or in solution at a mass concentration of not more than 65%, of to obtain a combined precursor (20) corresponding to the structured precursor (10) covered by the unstructured precursor (15), said method further comprising the following steps: - a thermal and dimensional stabilization step (200) of the combined precursor ( 20) to obtain a fiber or a set of fibers covered with a cyclic or aromatic organic compound deposit (30), and - a carbonization step (300) of the fiber or set of fibers coated with a depot t cyclic or aromatic organic compound (30) so as to obtain a highly carbonaceous material (2).
    公开号:FR3058167A1
    申请号:FR1660536
    申请日:2016-10-28
    公开日:2018-05-04
    发明作者:Alexander Korzhenko；Celia Mercader
    申请人:Arkema France SA；
    IPC主号:
    专利说明:

    ® FRENCH REPUBLIC
    NATIONAL INSTITUTE OF INDUSTRIAL PROPERTY © Publication number:
    (to be used only for reproduction orders)
    ©) National registration number
    058 167
    60536
    COURBEVOIE © Int Cl 8 : D 01 F9 / 12 (2017.01), D 06 M 13/02, 15/01, 15/19,
    H 01 M 4/1393, 4/66, 4/96, H 01 G 11/40, C 23 F 13/14, B 32 B 5/02, B 01 J 32/00
    A1 PATENT APPLICATION
    ©) Date of filing: 28.10.16. (71) Applicant (s): ARKEMA FRANCE Public limited company (© Priority: - FR. @ Inventor (s): KORZHENKO ALEXANDER and MER- CADER CELIA. (43) Date of public availability of the request: 04.05.18 Bulletin 18/18. ©) List of documents cited in the report preliminary research: Refer to end of present booklet (© References to other national documents ©) Holder (s): ARKEMA FRANCE Société anonyme. related: ©) Extension request (s): (© Agent (s): A.P.I CONSEIL Société anonyme.
    FR 3 058 167 - A1
    04) NEW PROCESS FOR MANUFACTURING HIGH CARBON MATERIALS AND HIGH CARBON MATERIAL OBTAINED.
    The invention relates to a manufacturing process (1) of highly carbon 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, and comprising at least one cyclic or aromatic organic compound in the molten state or in solution at a mass concentration less than or equal to 65% , so as to obtain a combined precursor (20) corresponding to the structured precursor (10) covered by the unstructured precursor (15), said method further comprising the following steps:
    a step of thermal and dimensional stabilization (200) of the combined precursor (20) so as to obtain a fiber or a set of fibers covered with a deposit of cyclic or aromatic organic compound (30), and
    - A carbonization step (300) of the fiber or the set of fibers covered with a deposit of cyclic or aromatic organic compound (30) so as to obtain a highly carbonaceous material (2).
    NEW PROCESS FOR MANUFACTURING HIGH CARBON MATERIALS AND HIGH CARBON MATERIAL OBTAINED [0001] The invention relates to the field of highly carbonaceous materials, for the manufacture of parts made of composite materials or of part which can be used in electrochemical processes. The invention relates to a method for manufacturing a highly carbon material and the highly carbon material capable of being obtained by such a manufacturing process.
    Prior Art] [0002] The carbon fiber market is booming. In recent years, the carbon fiber industry has grown steadily to meet demands from different applications. The market is estimated today at around 60 kt / year and should evolve to 150-200 kt / year by 2020-2025. This strong forecast growth is mainly linked to the introduction of carbon fiber in composite materials used in the aeronautics, energy, construction, automotive and leisure sectors.
    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 include a polymer resin (matrix). The composite materials thus reinforced have excellent physical properties while retaining an advantageous lightness. Lightening is one of the key measures to reduce CO 2 emissions for transport. The automotive and aeronautical industry is in demand for compounds presenting, with equivalent performance, greater lightness. In this context, the automotive and aeronautical sectors, and more generally the industry, also need high-performance materials but at controlled costs.
    In addition, carbon fibers are also developing in the electrochemical field due to several qualities such as their high electrical conductivity and flexibility in terms of size and shape. However, in this area, carbon fibers still have drawbacks related to their low
    0509-Ark77 concentration of metallic charges. There is therefore always a need for 3D structures integrating a high conductivity and a high concentration of metallic charges making it possible to create an economical alternative to porous metals.
    Today carbon fibers are mainly made from acrylic precursors. Polyacrylonitrile (PAN) is the most widely used precursor today for the manufacture of carbon fibers. Briefly, the production of carbon fibers from PAN includes the stages of polymerization of PAN-based precursors, spinning of fibers, thermal stabilization, carbonization and graphitization. Carbonization takes place under a nitrogen atmosphere, at a temperature of 1000 to 1500 degrees. The carbon fibers obtained at the end of these stages consist of 90% carbon, approximately 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.
    With the aim of reducing the price of carbon fiber, one of the solutions proposed was to replace the petroleum-based precursors (for example PAN or Pitch) with bio-based materials, such as cellulose or lignin, contained in the woods. The cost price for manufacturing carbon fiber using cellulose precursor is much lower than that of fibers with PAN. In this perspective, several cellulosic precursors have been evaluated. Cellulose-based precursors have the advantage of producing well-structured carbonized structures, but they generally do not allow satisfactory carbon yields to be achieved. Nevertheless, application WO2014064373 published on May 01, 2014 filed by the applicant describes a process for the manufacture, from a bioresourced precursor, of continuous carbon fiber doped with carbon nanotubes (NTC). The presence of CNTs in the bio-resourced precursor makes it possible to increase the carbon yield of the precursor during carbonization, and also to increase the mechanical characteristics of carbon fibers. The bio-resourced precursor can be cellulose transformed into fibers by dissolution and coagulation / spinning, so as to form hydrocellulose (such as, for example, viscose, lyocell, rayon).
    Reference can be made to document FR2994968 which describes the manufacture of a carbon-based composite material comprising a carbon fiber based on Lyocell and a carbon matrix. However, the process described in this document
    0509-Ark77 requires the use of a carbon fiber which implies the implementation of several stages and in particular several carbonizations. Reference may also be made to document KR 20120082287 which describes a process for manufacturing carbon fiber from a precursor material comprising lyocell (cellulose fibers from wood or bamboo) and a nanocomposite - graphene material. Reference may also be made to document CN1587457, which describes a process for the preparation of a cellulosic precursor material for the manufacture of carbon fiber having improved properties and a lower manufacturing cost. The cellulosic preparation involves the insertion of nanoparticles of soot into the cellulosic solution. However, these methods do not allow an improvement in the carbon yield and an increase in the porosity of the materials obtained.
    The Applicant has noted that there is still a need for precursors which can be used in processes for the manufacture of carbonaceous materials capable of responding to the problems encountered with existing methods and which allow: i) a high carbon yield; ii) a combination of stable 3D structure and increased porosity, iii) reduced manufacturing cost.
    rTechnical problem [0009] The invention therefore aims to remedy the drawbacks of the prior art. In particular, the invention aims to provide a process for manufacturing a highly carbonaceous material which is very mechanically stable with an improved carbon yield. In addition, this highly carbon material has a higher porosity than that of carbon fibers allowing it to be more effectively combined with metals.
    f Brief description of the invention!
    Thus, the invention relates to a process for manufacturing highly carbonaceous material, mainly 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, and comprising at least one cyclic or aromatic organic compound in the molten state or in solution at a mass concentration less than or equal to 65%, so as to obtain a combined precursor corresponding to the precursor structured covered by the unstructured precursor, said method further comprising the following steps:
    0509-Ark77 a step of thermal and dimensional stabilization of the combined precursor so as to obtain a fiber or a set of fibers covered with a deposit of cyclic or aromatic organic compound, and a step of carbonization of the fiber or the set of fibers covered with a deposit of cyclic or aromatic organic compound so as to obtain a highly carbon material.
    This new method of manufacturing a highly carbon material has many advantages such as obtaining a carbon dioxide yield higher than that 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 thereby obtaining a highly carbon material with improved properties.
    The invention further relates to a fiber or a set of fibers covered with a deposit of cyclic or aromatic organic compound as an intermediate product, obtained after the step of thermal and dimensional stabilization of the manufacturing process 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 carbon material obtained by the process according to the invention. Advantageously, this highly carbonaceous material is bistructured, so as to comprise a structured part and an unstructured part, and it has an overall porosity greater than 5%, preferably greater than 10%. These products meet the expectations of industrialists looking for carbon materials with high porosity while retaining a structured part.
    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 which can be used in electrochemical processes.
    0509-Ark77 Other advantages and characteristics of the invention will appear on reading the following description given by way of illustrative and nonlimiting example, with reference to the appended figures which represent:
    • Figure 1 shows a diagram of an embodiment of the process for manufacturing a highly carbon material according to the invention. The dotted steps are optional.
    • Figures 2, represent two images obtained by microscopy of a section of a carbonaceous material. FIG. 2A represents a carbonaceous material comprising a hydrocellulose fiber treated with DAHP (Diammonium hydrogen phosphate), and FIG. 2B represents a highly carbonated material comprising a hydrocellulose fiber treated with lignin according to the process of the invention .
    rDescription of the inventionl The term “carbon nanofillers” according to the invention means a filler comprising an element from the group formed by carbon nanotubes, carbon nanofibers, graphene, fullerenes and carbon black, or a mixture of these in any proportion. Preferably, the carbon nanofillers are carbon nanotubes, alone or in admixture with graphene. This carbonaceous charge can have a smaller dimension of between 0.1 and 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.
    The term "graphene" according to the invention means a flat graphite sheet, isolated and individualized, but also, by extension, an assembly comprising between one and a few tens of sheets and having a planar structure or more or less wavy . This definition therefore includes FLG (Few Layer Graphene or weakly stacked graphene), NGP (Nanosized Graphene Plates), CNS (Carbon NanoSheets or graphene nano-sheets), GNR (Graphene NanoRibbons or graphene nano-ribbons). On the other hand, it excludes carbon nanotubes and nanofibers, which consist respectively of the winding of one or more graphene sheets coaxially and of the turbostratic stack of these sheets.
    0509-Ark77 The term “highly carbon material” according to the invention means a material whose mass of carbon represents more than 80% of the total mass of the non-metallic elements, preferably more than 90%, more preferred more than 95%, and even more preferred more than 98% (materials considered to be very high purity materials).
    The term "hydrocellulose fiber" according to the invention, cellulose fibers or cellulose derivatives, preferably continuous and of regular diameter, obtained after dissolution of cellulose from lignocellulosic material. As will be detailed in the following text, this combination can be achieved by several alternative methods. Hydrocellulose can, for example, be obtained after treatment with soda followed by dissolution with carbon disulfide. In this case, hydrocellulose is more particularly called viscose. Alternatively, the hydrocellulose fiber can be obtained from lignocellulosic material dissolved in a solution comprising N-methylmorpholine N-oxide to form Lyocell.
    The term "lignin" according to the invention means a plant aromatic polymer whose composition varies with the plant species and generally formed from three phenylpropanoid monomers: p-coumaryl, coniferyl and sinapylic alcohols.
    The term "lignin derivative" according to the invention means a molecule having a molecular structure of lignin type and which may contain substituents which have been added during the lignin extraction process or subsequently so as to modify its physicochemical properties . There are many methods for extracting lignin from lignocellulosic biomass and these can cause changes in lignin. 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 sulfite process, resulting in the formation of lignosulfonates. Organosolv pretreatment processes use an organic solvent or mixtures of organic solvents with water to dissolve the lignin before the enzymatic hydrolysis of the cellulose fraction. Preferably, by lignin derivative must be understood a lignin comprising substituents which can be selected from: Thiol, Sulfonate, Alkyl, or polyesther. The lignins or lignin derivatives used in the context of the present invention generally have a molecular weight greater than 1000 g / mol, for example greater than 10000 g / mol.
    0509-Ark77 In the following description, the same references are used to designate the same elements.
    According to a first aspect, the invention relates to a manufacturing process 1 for a highly carbon 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, and comprising at least one cyclic or aromatic organic compound in the molten state or in solution at a mass concentration less than or equal to 65%.
    This combining 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 schematically in Figure 1. It can be performed continuously or discontinuously. As part of a continuous production, industrial processes allow the sequence of different stages without interruption.
    Structured precursor (10) [0027] The structured precursor 10 comprises a fiber or a set of fibers. The fiber or the set of fibers may have undergone pretreatments making it possible to facilitate their handling in the context of the process according to the invention. However, being used as a precursor, this fiber or set of fibers has not undergone a carbonization step. Thus, preferably, the fiber or the set of fibers used in the structured precursor 10 has a mass concentration of carbon of less than 75%, advantageously less than 65%.
    Preferably, these fibers are cellulose fibers, hydrocellulose fibers, lignin fibers, pitch fibers or fibers of acrylic precursors (for example PAN). Even more preferably, 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 wood, flax, hemp, ramie, bamboo cellulose and preferably wood or lignocellulose cellulose, combination of cellulose and lignin, as in the fibers of wood, jute, cereal straw, corn legs, cork or lignin. This fiber can be obtained by various known manufacturing methods.
    0509-Ark77 Advantageously, the natural fibers are obtained from a cellulose solution; then extrusion into a die to form a continuous fiber such as a hydrocellulose fiber, or else obtained from lignin after extrusion to form a lignin fiber.
    In the case of a hydrocellulose fiber, it can for example be obtained according to the manufacturing process described in application WO2014064373. The hydrocellulose fibers used can also be Lyocell or viscose fibers, the cellulose of which comes, for example, from wood or bamboo. Most hydrocellulose fiber manufacturing processes are based on the preparation of a cellulosic preparation from dissolved cellulose, for example by carbon disulfide, 4-methylmorpholine 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 an immersion in a coagulation bath containing for example sulfuric acid. The hydrocellulose fiber used in the process of the present invention as a precursor has not been subject to prior carbonization.
    In addition, this fiber or this set of fibers can take very different forms. One of the advantages of the invention is that the process can be carried out with fibers having been previously shaped, for example in the form of a twisted multi-filament, of an untwisted multi-filament, of a set of non-woven fibers, or a set of woven fibers. When manufacturing carbon fiber fabrics, it is usually necessary to produce spools of carbon fibers, for example from charred PAN and then organize these fibers according to the desired weavings. Here, the invention makes it possible to directly use non-carbonized fibers having been previously organized, in the form of multi-filament or set of fibers. Thus, the method according to the invention has the advantage of reducing the costs of manufacturing multi-filaments or sets of carbon fiber (for example woven). For example, in the context of the process according to the invention, it is possible to manufacture a set of woven fiber (eg viscose, Lyocell, rayon, oxidized PAN) and to directly subject it to the manufacturing process according to the invention so forming a highly carbon material comprising a structured part such as for example a woven assembly of carbon fibers. Thus, preferably, the structured precursor 10 comprises a multi-filament or a set of fibers. Even more preferably, the precursor
    0509-Ark77 structured 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 of 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 pm and 300 pm, preferably between 1 pm and 50 pm. In addition, preferably 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 deposition of cyclic or aromatic organic compound and the fiber. By regular diameter, it should be understood that the diameter varies by less than 20%, preferably less than 10% over the length of the fiber.
    Unstructured precursor (151) 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 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 can be an aqueous solution, or an organic solution or a mixture of the two. These alternatives make it possible to adapt the unstructured precursor 15 as a function of the cyclic or aromatic organic compound used as well as any additives added. Preferably, the fluid is a mixture of water and an organic solvent.
    Alternatively, the fluid can be a molten material such as molten lignin. This is particularly suitable when the cyclic or aromatic organic compound used is not or sparingly soluble but fusible.
    The cyclic or aromatic organic compound can be in different forms in the fluid. It can be dissolved in solution, melted or even in the solid state in the form of a dispersion. This dispersion can equally well be carried out in a
    0509-Ark77 solution only in a melt. Preferably, the cyclic or aromatic organic compounds, neither fusible nor soluble, will be combined with the structured precursor in the form of a dispersion.
    Preferably, the fluid has a viscosity of less than 45,000 mPa.s-1 at the temperature at which the combining step 100 takes place. This allows during the combining step to associate a more significant amount of unstructured precursor 15 to the structured precursor and increase the porosity of the highly carbonaceous material 2 obtained. The viscosity of the fluid is measured at the temperature at which the combining step 100 takes place, for example using a free-flow viscometer, or capillary viscosity or the brookfield method.
    The cyclic or aromatic organic compound is an organic material which, after pyrolysis under an oxygen-free atmosphere, becomes carbonic remains preferably representing more than 5% by mass of the highly carbonaceous material 2 obtained in the context of the invention. A cyclic or aromatic organic compound according to the invention comprises a series of atoms linked successively by covalent bonds to form one or more rings. This cycle can be saturated or unsaturated and this cycle can be a heterocycle. Preferably, the cyclic or aromatic organic compound is an aromatic compound. That is to say, it has at least one aromatic cycle.
    The organic cyclic or aromatic compound can be selected from;
    - bio-based 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 alternatively polycyclic aromatic hydrocarbons such as naphthalene sulfonate;
    - synthetic products selected from phenolic resin, phenoplast resin, or polyepoxide resin; and
    - all other organic substances or formulations producing a carbon residue following pyrolysis under an inert atmosphere.
    0509-Ark77 Preferably, the cyclic or aromatic organic compound is an oligomer or a cyclic or aromatic organic polymer.
    Advantageously, 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.
    Even more preferably, the cyclic or aromatic organic compound is lignin or a lignin derivative.
    The unstructured precursor 15 may comprise several different cyclic or aromatic organic compounds.
    In solution, the cyclic or aromatic organic compound has a mass concentration less than or equal to 65%. Too high a concentration of a cyclic or aromatic organic compound solution could reduce the properties of the highly carbonaceous material obtained. Preferably, the unstructured precursor 15 comprises between 5 and 50% by mass of cyclic or aromatic organic compound. At such concentrations, the fibers of the structured precursor are completely covered with a cyclic or aromatic organic compound.
    Advantageously, the unstructured precursor 15 comprises lignin or a lignin derivative. Indeed, lignin represents 10 to 25% of the terrestrial biomass of lignocellulosic nature and it is today only little valued by industry. Each year, several hundred tonnes of lignin or lignin derivatives are produced without possible recovery. Lignin is mainly present 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: pcoumaryl, sinapylic and coniferyl alcohols as illustrated by the formulas below:
    ^ OH Z JOLMeoZ ^ OMe OH OH p-coumaryl alcohol sinapylic alcohol
    coniferyl alcohol
    Advantageously, the unstructured precursor 15 can also comprise at least one additional compound selected from: a metallic filler, compounds rich in carbon and organic particles. Adding additional compounds to the unstructured precursor 15 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 metallic filler can for example comprise 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. Preferably, the metallic filler can 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. These metals can be used, alone or as a mixture, in any form such as for example in the form of oxide, hydroxide, acid or also in the form of salts such as organic salts (for example nitrate salts , sulfate, acetate, carbonate, oxalate, benzoate or phosphates). The unstructured precursor contains for example a metallic filler and a cyclic or aromatic organic compound. The cyclic or aromatic organic compound then plays the double role of porous matrix and binder allowing the fixation of a large quantity of metals.
    The addition of such metals to the unstructured precursor 15 makes it possible to give the highly carbonaceous materials 2 according to the invention the physicochemical properties sought after, for example in the case of electrochemical applications.
    Preferably, the unstructured precursor 15 comprises several different metals. For example, the unstructured precursor 15 may include lithium, cobalt and nickel.
    The compounds rich in carbon can 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:
    0509-Ark77 cellulose nanofibers, cellulose microfibrils, cellulose nanocrystals, nanocellulose whiskers or bacterial nanocellulose), tannins, chitosan, or other biopolymers that are neither fusible nor soluble. Such compounds rich in carbon or organic particles, added to the unstructured precursor make it possible to increase the carbon dioxide yield of the material obtained and to improve its mechanical properties. Neither fusible nor soluble compounds can be added as a dispersion.
    Preferably, the unstructured precursor 15 may comprise between 0.001% and 50% by mass of additional compound. More preferably, it can comprise between 0.001% and 30% by mass of carbon-rich compounds, between 0.001% and 50% by mass of organic particles or a mixture of these in any proportion.
    Carbonaceous nanofillers. Advantageously, the structured precursor 10 and / or the unstructured precursor 15 can comprise carbon nanofillers, said carbon nanofillers being present at a concentration of between 0.0001% and 30% by mass. Preferably, these carbon nanofillers are present at a concentration of between 0.01% and 5% by mass. Adding carbon nanofillers to one or both of the precursors improves the carbon yield of the highly carbon material obtained. Indeed, when carbon nanofillers are added to the unstructured precursor 15, the latter acts as a binder and causes an increase in the quantity of carbon nanofillers being effectively inserted into the resulting material.
    Carbon nanotubes (CNTs) can 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 nanotubes with multiple walls can for their part be prepared as described in document WO 03/02456. 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, or even from 10 to 15 nm, and advantageously a length of 0.1 at 10 pm. Their length / diameter ratio is preferably greater than 10 and most often greater than 100. Their specific surface is for example between 100 and 300 m 2 / g, advantageously between 200 and 300 m 2 / g, and their apparent density can in particular be between 0.05 and 0.5 g / cm3 and more preferably between 0.1 and 0.2 g / cm3. The multi-wall nanotubes can for example comprise from 5 to 15 sheets (or walls) and more preferably from 7 to 10 sheets.
    0509-Ark77 An example of crude carbon nanotubes is in particular commercially available from the company ARKEMA under the trade name Graphistrength® C100. Alternatively, these nanotubes can be purified and / or treated (for example oxidized) and / or ground and / or functionalized, before being used in the process according to the invention. The purification of the crude or ground nanotubes can be carried out by washing with a sulfuric acid solution, so as to rid them of any residual mineral and metallic impurities. The oxidation of nanotubes is advantageously carried out by bringing them into contact with a solution of sodium hypoohlorite. 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 according to a process using a powdery catalyst based on a mixed oxide. It is typically in the form of particles with a thickness of less than 50 nm, preferably of less than 15 nm, more preferably of less than 5 nm and of lateral dimensions less than one 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. Various processes for the preparation of graphene have been proposed in the literature, including the so-called mechanical exfoliation and chemical exfoliation processes, consisting of removing successive layers of graphite sheets, respectively by means of an adhesive strip (Geim AK, Science, 306: 666, 2004) or using reagents, such as sulfuric acid combined with nitric acid, interposed between the graphite layers and the oxidizers, so as to form oxide graphite which can be easily exfoliated in water in the presence of ultrasound. Another exfoliation technique consists in subjecting graphite in solution to ultrasound, in the presence of a surfactant (US-7,824,651). Graphene particles can also be obtained by cutting carbon nanotubes along the longitudinal axis ("Micro-Wave Synthesis of Large Few-Layer Graphene Sheets in Aqueous Solution of Ammonia", Janowska, I. et al, NanoResearch, 2009 or "Narrow Graphene nanoribbons from Carbon Nanotubes", Jiao L. et al, Nature, 458: 877880, 2009). Yet another method of preparing graphene consists in decomposing silicon carbide at high temperature, under vacuum. Finally, several authors have described a process for synthesizing graphene by chemical phase deposition
    0509-Ark77 steam (or CVD), possibly associated with a radio frequency generator (RF-CVD) (DERVISHI et al., J. Mater. Soi., 47: 1910-1919, 2012).
    Fullerenes are molecules composed exclusively or almost exclusively of carbons which can take a geometric shape reminiscent of that of a sphere, an ellipsoid, a tube (called nanotube) or a ring. Fullerenes can for example be selected from: fullerene C60 which is a compound formed of 60 carbon atoms of spherical shape, C70, PCBM of formula [6,6] -phenyl-C61-methyl butyrate which is a derivative fullerene, the chemical structure of which has been modified to make it soluble, and PC 71 BM 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 made up of more or less organized graphitic zones (or turbostratic stacks) whose planes are inclined at variable angles relative to the axis of the fiber. These stacks can take the form of plates, fishbones or cups stacked to form structures having a diameter generally ranging from 100 nm to 500 nm or even more. Carbon nanofibers having a diameter of 100 to 200 nm, for example around 150 nm (VGCF® from SHOWA DENKO), and advantageously a length of 100 to 200 μm are preferred in the process according to the invention.
    In addition, carbon black can be used as carbon nanofillers, which is a colloidal carbon material produced industrially by incomplete combustion of heavy petroleum products, which is in the form of carbon spheres and of aggregates of these spheres and whose dimensions are generally between 10 and 1000 nm.
    Combination (100) The combination step 100 according to the invention corresponds to bringing the structured precursor 10 into contact with the unstructured precursor 15. This combination can be carried out by several alternative methods, generally at a temperature ranging from -10 ° C to 80 ° C, preferably 20 ° C to 60 ° C. For example, it is possible to realize
    0509-Ark77 soaking, spraying or impregnating (for example by padding). Preferably, the combining step 100 is an impregnation.
    Thermal and dimensional stabilization (200) 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 covered with a deposit of cyclic or aromatic organic compound 30.
    The thermal and dimensional stabilization step 200 may include drying allowing the solvent to evaporate and / or ventilation. The drying can be carried out via a rise in temperature, for example between 50 ° C and 250 ° C over a period of 1 to 30 min preferably. Indeed, when the structured precursor is treated with an unstructured precursor comprising a diluent or organic solvent, it is desirable to then remove the diluent or solvent, and for example to subject this article to a heat treatment to remove the diluent or the solvent in the form of vapor. For example, an infrared oven with ventilation can be used.
    Following this step, a deposit, similar to a solid film, of cyclic or aromatic organic compound is formed on the surface of the fiber. This deposit can have variable 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.
    Preferably, the combination steps 100 and thermal and dimensional stabilization 200 can be repeated one or more times. Repeating these steps increases 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 carbon material obtained at the end of the process.
    Carbonization (300) The manufacturing method 1 according to the invention further comprises a step of carbonization 300 of the fiber or of the set of fibers covered with a deposit of cyclic or aromatic organic compound 30 so as to obtain a highly carbon material 2.
    0509-Ark77 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 can for example last 2 to 60 minutes. This carbonization step may include a gradual rise in temperature or a rise and fall in temperature. Carbonization takes place in the absence of oxygen and preferably under a nitrogen atmosphere. The presence of oxygen during carbonization should preferably be limited 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.
    Pre-carbonization size (210) The manufacturing process according to the invention may further comprise, before the carbonization step 300, the following steps:
    a sizing step 210 consisting in bringing the fiber or the set of fibers covered with a deposit of cyclic or aromatic organic compound into contact with an aqueous solution comprising at least one flame retardant compound, said flame retardant compound being able to be selected from: potassium, sodium, phosphate, acetate, chloride, urea, and
    - a post-sizing drying step 220.
    This has the advantage of strengthening the physicochemical properties of the carbonaceous material obtained. Indeed, although the cyclic or aromatic organic compound, such as lignin or the 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 steps 210 for sizing and drying after sizing 220 can be repeated one or more times. It is therefore possible to increase the quantity of flame retardant associated with the fiber or to combine different treatments based on different substances.
    Shaping (400) The manufacturing method according to the invention may further comprise a shaping step 400, possibly coupled with a structuring step, of the
    0509-Ark77 highly carbonaceous material 2 by any shaping process such as: 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 can for example be carried out at a temperature below 400 ° C in the presence of a polymeric binder or at a temperature above 400 ° C in the context of stretching, 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 between 1000 ° C and 2800 ° C, preferably greater than or equal to 1100 ° C. The graphitization step 500 may for example last from 2 to 60 minutes, preferably from 2 to 20 minutes. This graphitization step 500 may include a gradual rise in temperature.
    Post carbonization sizing (600)
    The manufacturing method according to the invention may further comprise, after the carbonization step 300, a sizing step 600 consisting in bringing the highly carbonaceous material 2 into contact with a solution of an organic component which may comprise at least one Silane or derivative of Silane and / or at least one Siloxane or derivative of Siloxane. This size 600 can also be carried out 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.
    The size improves the integrity of the carbonaceous material and makes it possible to protect it from abrasion. The solution of the organic component is preferably an aqueous solution, an organic solution or an aqueous emulsion.
    This sizing step makes it possible to improve the physicochemical properties of the material (eg protection against abrasion and improvement of the integrity of the fibers composing it) and has the advantage, in the context of the invention of possibly be performed on a fiber assembly, i.e. for example on a carbon fiber fabric.
    In another aspect, 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 process according to the invention. 'invention. The organic deposit is a deposit of aromatic or cyclic organic compound.
    This intermediate product preferably has a ratio of the mass of fiber to the mass of aromatic or cyclic organic compound of between 1/5 and 100/1, preferably between 2/1 and 95/1.
    According to another aspect, the invention relates to a highly carbonaceous material 2 capable of being obtained by the manufacturing process according to the invention and preferably obtained by the manufacturing process according to the invention. Preferably and advantageously, 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 while the unstructured part corresponds to the material resulting from the carbonization of the structured precursor
    15. Advantageously, these two highly carbon-containing parts can have different physicochemical characteristics. The structured part can 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 available for the electronic reactions / exchanges.
    In addition, 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 which nevertheless have sufficient mechanical properties to meet the needs, for example of the aeronautical or automotive industries. In addition, the highly carbon material obtained by the process according to the invention has the advantage of having a greater porosity than the highly carbon materials obtained until now. This greater porosity has the advantage, as shown in the examples, of increasing the carbon dioxide yield which can be obtained from the addition of additives such as nanocarbon fillers. In addition, this greater porosity makes it possible to open the use of this material to numerous applications which can benefit from a larger overall specific surface. Porosity is for example measured by direct methods (tomography, radiography, micrograph on section
    0509-Ark77 of parts) or indirect (density measurement, weighing, ...). Preferably, the overall porosity is determined by density measurement with respect to the theoretical density.
    Advantageously, the structured part has a porosity of less than 40%, preferably less than 30%, and the unstructured part has a porosity of more than 7%, preferably more than 10%. These porosities are advantageously determined by micrograph on section of parts.
    Advantageously, 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 mastered by the person skilled in the art, for example the analysis of optical microscopy images of sections, obtained by microtome, of the highly carbonaceous material.
    Advantageously, the highly carbonaceous material 2 comprises additional compounds such as metals in its unstructured part. Metals can be present in the highly carbonaceous material at a mass concentration between 0.001% and 90%. More specifically, the metals can be present in the unstructured part 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 present, despite an absence of demarcation between its constituents, a heterogeneous structure which is particularly advantageous in the context of its use in electrochemical processes.
    Advantageously, 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. Indeed, this highly carbonaceous material comprises, in addition to the structured part, an unstructured part capable of creating stronger bonds at the level of the contacts between the fibers (for example crossings). Thus, such a highly carbonaceous material 2 has an improvement in the mechanical properties of the structured precursor (for example a tear resistance).
    According to another aspect, the invention relates to the use of the highly carbonaceous material 2 capable of being obtained via the manufacturing process according to the invention, and preferably obtained by the manufacturing process according to the invention. invention, for the manufacture of parts made of thermoplastic or thermosetting composite materials.
    [0085] Thus, according to another aspect, the invention relates to thermoplastic or thermosetting composite materials obtained from fibers produced by the manufacturing process according to the invention. Advantageously, these thermoplastic or thermosetting composite materials have, for an identical volume, a weight that is at least 5% less than the weight of conventional thermoplastic or thermosetting composite materials.
    Indeed, 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 manufacturing composite materials. It can be combined with a natural polymer resin or a synthetic polymer resin such as thermoplastic resins (for example polyamides, copolyamides, polyesthers, copolyesthers, polyurethanes, polyethylene, polyacetates, polyehtersulfonates, polyimides, polysulfones, polyphenlylene sulfones, polyolefins) or thermosetting resins (for example epoxides, unsaturated polyesters, vinyl esters, phenolic resins, polyimides).
    According to another aspect, the invention relates to the use of the highly carbonaceous material 2 capable of being obtained via the manufacturing process according to the invention, and preferably obtained by the manufacturing process according to the invention, for the manufacture of parts that can be used in electrochemical processes. The highly carbon materials according to the invention have low resistance and are very good electronic conductors. In addition, they have a porosity, and therefore a specific surface much greater than conventional carbon fibers. This is notably linked to the presence of a structured part and an unstructured part, each having a different role to play in the electrochemical process.
    The parts which can be used in electrochemical processes can for example be selected from the following list:
    anode for cathodic protection, electrode for fuel cells,
    0509-Ark77
    - electrode element for primary and rechargeable batteries, electric current collector for anodes or cathodes of lithium or sodium batteries, electric current collector for Lithium-Sulfur batteries
    - electric current collector for Lithium-Polymer batteries,
    - electrode element for lead acid batteries, especially for lead or carbon lead ultra-batteries,
    - electrode element for rechargeable lithium batteries,
    - supercapacitor electrode element,
    - catalytic support, in particular for air purification, and
    - catalytic support for Lithium-Air batteries.
    The following examples illustrate the invention, but are in no way limiting.
    Example 1 Description of the starting materials:
    The structured precursor used is based on Hydrocellulose fibers in multi filament with a linear density of 88 mg per meter.
    For the formation of the unstructured precursor, the lignin was dissolved in an Ethanol / Water mixture 60/40 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 mass of lignin.
    Preparation of the carbonaceous material [0095] Step 1: impregnation The hydrocellulose fibers, constituting the structured precursor, are impregnated in the lignin solution, the unstructured precursor, for 7 minutes.
    Step 2: drying The fibers impregnated with lignin were dried at 80 ° C. in a ventilated oven for 1 hour.
    0509-Ark77 Step 5: carbonization [00100] The carbonization was carried out in a vertical static oven under a nitrogen atmosphere. A temperature ramp of 5 ° C per minute was applied up to the temperature of 1200 ° C.
    Characteristics of the carbon material obtained The deposit of lignin on the hydrocellulose fiber was 9% by mass. The quantification of the mass lignin deposition can be obtained by weighing the hydrocellulose fiber before step 1 and then after step 2 of drying.
    Increasing the carbon dioxide yield The carbon dioxide yield (RC) was calculated after carbonization:
    RC = (m Carbonaceous material / m precursor) x 100
    Carbon performance results (after carbonization) are as follows:
    Hydrocellulose fibers, without lignin deposition or flame retardant(reference) 8% Hydrocellulose fibers, with 2% DAHP (Di Ammonium) depositionHydrogen Phosphate) 26% Hydrocellulose fibers, with 9% lignin deposition, according to the invention 25%
    These results show that lignin is a source of carbon during pyrolysis and also plays the role of flame retardant for hydrocellulose. Thus, the combination of hydrocellulose fibers with lignin so as to form, before carbonization, hydrocellulose fibers covered with a lignin deposit makes it possible to go from 8% to 25% of carbon yield, ie a multiplication by a factor of
    3 and more of the carbon yield. Lignin also achieves a carbon yield equivalent to the carbon yield achieved with a conventional chemical used with cellulose.
    Intimate deposit and constitution of a highly carbonaceous material [00104] FIG. 2A shows an image obtained by electron scanning microscopy of a section of a carbonaceous material, in the example a carbonaceous fiber, obtained after combination with DAHP ( A) and image 2B mounts an image obtained
    0509-Ark77 by scanning electron microscopy of the carbonaceous material obtained by the process according to the invention. FIG. 2B shows that the carbonic deposit originating from lignin is strongly linked to the surfaces of the fibers and that it is impossible to identify by microscopy the interface between the structured part, namely the fibers, and the unstructured part, namely the deposit. carbonic from lignin. On the contrary, FIG. 2A shows that the deposition of DAHP does not allow the creation of this unstructured carbon phase around the structured part.
    Thus the image of Figure 2B illustrates the creation of an agglomerate forming a bi-structured highly carbon material. There is no visible interface between carbon fiber from the hydrocellulose fiber and lignin after carbonization.
    The carbon fibers of the carbon material have a diameter between 6 and 7 μm which is larger than that of the hydrocellulose fibers used as a structured precursor.
    Example 2 The lignin deposition was carried out as in Example 1, but on hydrocellulose fibers added with 0.2% of CNT. The same protocol was also applied for carbonization.
    Characteristics of the carbonaceous material obtained The carbon dioxide yield results (after carbonization) are as follows:
    Hydrocellulose fibers, without lignin deposition or flame retardant (reference) 8% Hydrocellulose fibers, without lignin deposition or flame retardant, with 0.2% CNT (comparison) 9% Hydrocellulose fibers, with 9% lignin deposition, according to the invention 25% Hydrocellulose fibers, with 9% lignin deposition without flame retardant, with 0.2% CNT, according to the invention 35%
    These results show that the addition to the unstructured precursor of carbon nanofillers such as CNTs can be really effective and improve the carbon yield provided that the process according to the invention is respected, including the
    0509-Ark77 combination of an unstructured precursor comprising a cyclic or aromatic organic compound such as lignin.
    In addition, the addition of carbon nanotubes in the unstructured precursor containing lignin makes it possible to further increase the carbon yield and reach carbon yields of 35%, ie a multiplication by a factor of 4 and more of the carbon yield.
    These examples show that the treatment of structured precursor with an unstructured precursor comprising a cyclic or aromatic organic compound such as lignin makes it possible to increase the carbon yield and the fixation of additional compounds such as CNTs.
    [00112] Thus, 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.
    0509-Ark77
    权利要求:
    Claims (36)
    [1" id="c-fr-0001]
    Claims
    1. Manufacturing process (1) of highly carbon material (2), characterized in that it comprises the combination (100) of a structured precursor (10) comprising a fiber or a set of fibers and a non-precursor structured (15), in the form of a fluid, and comprising at least one cyclic or aromatic organic compound in the molten state or in solution at a mass concentration less than or equal to 65%, so as to obtain a combined precursor (20) corresponding to the structured precursor (10) covered by the unstructured precursor (15), said method further comprising the following steps:
    a step of thermal and dimensional stabilization (200) of the combined precursor (20) so as to obtain a fiber or a set of fibers covered with a deposit of cyclic or aromatic organic compound (30), and
    - a carbonization step (300) of the fiber or of the set of fibers covered with a deposit of cyclic or aromatic organic compound (30) so as to obtain a highly carbonaceous material (2).
    [2" id="c-fr-0002]
    2. Manufacturing process according to claim 1, characterized in that the cyclic or aromatic organic compound is selected from biobased products selected from: lignin, cellulose, starch, glycogen, amylose, amylopectin, dextran, hemicellulose, fructose or glucose, and their derivatives; products obtained from petroleum or mining resources selected from: pitch, naphthalene, phenanthrene, anthracene, pyrene or naphthalene sulfonate; and synthetic products selected from phenolic resin, phenoplast resin, or polyepoxy resin.
    [3" id="c-fr-0003]
    3. Manufacturing process according to one of claims 1 or 2, characterized in that the unstructured precursor (15) comprises between 5% and 50% by mass of cyclic or aromatic organic compound.
    [4" id="c-fr-0004]
    4. Manufacturing process according to any one of claims 1 to 3, characterized in that the fluid is an aqueous solution, or an organic solution or a mixture of the two.
    0509-Ark77
    [5" id="c-fr-0005]
    5. Manufacturing process according to any one of claims 1 to 3, characterized in that the fluid is a molten material.
    [6" id="c-fr-0006]
    6. Manufacturing process according to any one of the preceding claims, characterized in that the fluid has a viscosity of less than 45,000 mPa.s 1 at the temperature at which the combining step takes place (100).
    [7" id="c-fr-0007]
    7. Manufacturing process according to any one of the preceding claims, characterized in that the unstructured precursor (15) further comprises at least one additional compound selected from: metallic fillers, compounds rich in carbon and organic particles.
    [8" id="c-fr-0008]
    8. Manufacturing process according to claim 7, characterized in that the metallic fillers comprise metals selected from the following metals: Boron, Silicon, Germanium, Arsenic, Lithium, Sodium, Potassium, Titanium, Vanadium, Manganese, Iron, Cobalt, Nickel, Molybdenum, Aluminum and Lead
    [9" id="c-fr-0009]
    9. The manufacturing method according to claim 7, characterized in that the compounds rich in carbon are selected from the following compounds: activated carbon, natural anthracite, synthetic anthracite, carbon black, natural graphite or synthetic graphite.
    [10" id="c-fr-0010]
    10. The manufacturing method according to claim 7, characterized in that the organic particles are selected from the following compounds: nanocellulose, tannins, chitosan, or other biopolymers neither fusible nor soluble.
    [11" id="c-fr-0011]
    11. Manufacturing method according to any one of the preceding claims, characterized in that the structured precursor (10) comprises at least one regular fiber (11) whose diameter is between 0.5 and 300 µm, preferably between 1 pm and 50 pm.
    [12" id="c-fr-0012]
    12. Manufacturing method according to any one of the preceding claims, characterized in that the structured precursor (10) comprises a twisted multi-filament, a non-twisted multi-filament, a set of non-woven fibers, or a set of fibers woven.
    0509-Ark77
    [13" id="c-fr-0013]
    13. Manufacturing process according to any one of the preceding claims, characterized in that the structured precursor (10) comprises cellulose fibers, hydrocellulose fibers, lignin fibers, pitch fibers or PAN fibers. .
    [14" id="c-fr-0014]
    14. Manufacturing method according to any one of the preceding claims, characterized in that the structured precursor (10) and / or the unstructured precursor (15) comprises carbon nanofillers, said carbon nanofillers being present at a concentration between 0.0001% and 30% by mass, preferably between 0.01% and 5% by mass.
    [15" id="c-fr-0015]
    15. The manufacturing method according to any one of the preceding claims, characterized in that the steps of combining (100) and thermal and dimensional stabilization (200) are repeated one or more times.
    [16" id="c-fr-0016]
    16. Manufacturing process according to any one of the preceding claims, characterized in that it further comprises a shaping step (400) of the highly carbon material (2) by any shaping process such as: extrusion , compression, calendering, stretching or molding, at room temperature or with heat treatment.
    [17" id="c-fr-0017]
    17. The manufacturing method according to any one of the preceding claims, characterized in that it further comprises a graphitization step (500).
    [18" id="c-fr-0018]
    18. Fiber or 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 process according to any one of the preceding claims, characterized in that the ratio of the mass of fiber to the mass of cyclic or aromatic organic compound is between 1/5 and 100/1.
    [19" id="c-fr-0019]
    19. Highly carbon material (2) obtained by the method according to one of claims 1 to 17, characterized in that it is bi-structured, so as to comprise a structured part and an unstructured part, and in that 'It has an overall porosity greater than 5%, preferably greater than 10%.
    0509-Ark77
    [20" id="c-fr-0020]
    20. Highly carbon material (2) according to claim 19, characterized in that the structured part has a porosity of less than 40%, preferably less than 30%, and the unstructured part has a porosity of more than 7%, preferably greater than 10%.
    [21" id="c-fr-0021]
    21. High carbon material (2) according to any one of claims 19 or
    20, characterized in that the ratio of the volume of the structured part to the volume of the unstructured part is between 1/5 and 100/1.
    [22" id="c-fr-0022]
    22. Highly carbon material (2) according to any one of claims 19 to
    21, characterized in that it comprises additives such as metal fillers and / or metal salts introduced into its unstructured part according to claims 1 to 8 of the process.
    [23" id="c-fr-0023]
    23. High carbon material (2) according to any one of claims 19 to
    22, characterized in that it 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 a set of woven carbon fibers.
    [24" id="c-fr-0024]
    24. -Use of the highly carbon material according to any one of claims 19 to 23, for the manufacture of parts made of composite material of the thermoplastic or thermosetting type.
    [25" id="c-fr-0025]
    25. Use of the highly carbon material according to any one of claims 19 to 23, for the manufacture of parts which can be used as an electrode in electrochemical processes.
    [26" id="c-fr-0026]
    26. Use of the highly carbon material according to any one of claims 19 to 23, for the manufacture of parts which can be used as an anode for cathodic protection.
    [27" id="c-fr-0027]
    27. Use of the highly carbon material according to any one of claims 19 to 23, for the manufacture of parts which can be used as an electrode for fuel cells.
    0509-Ark77
    [28" id="c-fr-0028]
    28. Use of the highly carbon material according to any one of claims 19 to 23, for the manufacture of parts which can be used as an electrode element for primary and rechargeable batteries.
    [29" id="c-fr-0029]
    29. Use of the highly carbon material according to any one of claims 19 to 23, for the manufacture of parts which can be used as an electric current collector for the anodes or cathodes of lithium or sodium batteries.
    [30" id="c-fr-0030]
    30. Use of the highly carbon material according to any one of claims 19 to 23, for the manufacture of parts which can be used as an electric current collector for lithium-sulfur batteries
    [31" id="c-fr-0031]
    31. Use of the highly carbon material according to any one of claims 19 to 23, for the manufacture of parts which can be used as an electric current collector for Lithium-Polymer batteries.
    [32" id="c-fr-0032]
    32. Use of the highly carbon material according to any one of claims 19 to 23, for the manufacture of parts which can be used as electrode element for lead acid batteries, in particular for lead or carbon lead ultra-batteries.
    [33" id="c-fr-0033]
    33. Use of the highly carbon material according to any one of claims 19 to 23, for the manufacture of parts which can be used as an electrode element for rechargeable lithium batteries.
    [34" id="c-fr-0034]
    34. Use of the highly carbon material of any one of claims 19 to 23 for the manufacture of parts which can be used as a supercapacitor electrode element.
    [35" id="c-fr-0035]
    35. Use of the highly carbon material according to any one of claims 19 to 23, for the manufacture of parts which can be used as a catalytic support in particular for the purification of air.
    [36" id="c-fr-0036]
    36. Use of the highly carbon material according to any one of claims 19 to 23, for the manufacture of parts which can be used as catalytic support for Lithium-Air batteries.
    0509-Ark77
    1/2
    T
    500
    I_____________________________________
    Graphitization
    600 ~ yj Sizing with a solution of an organic component which can include! at least one Silane and / or at least one Siloxane, or their derivatives
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    同族专利:
    公开号 | 公开日
    RU2019116177A3|2021-02-19|
    US11214523B2|2022-01-04|
    IL266085D0|2019-06-30|
    JP2019535915A|2019-12-12|
    RU2019116177A|2020-11-30|
    CN110062825A|2019-07-26|
    RU2765203C2|2022-01-26|
    KR20190069540A|2019-06-19|
    CA3039721A1|2018-05-03|
    US20190270678A1|2019-09-05|
    WO2018078287A1|2018-05-03|
    EP3532660A1|2019-09-04|
    FR3058167B1|2019-11-22|
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    法律状态:
    2017-09-18| PLFP| Fee payment|Year of fee payment: 2 |
    2018-05-04| PLSC| Publication of the preliminary search report|Effective date: 20180504 |
    2018-09-13| PLFP| Fee payment|Year of fee payment: 3 |
    2019-09-13| PLFP| Fee payment|Year of fee payment: 4 |
    2020-09-14| PLFP| Fee payment|Year of fee payment: 5 |
    2021-09-13| PLFP| Fee payment|Year of fee payment: 6 |
    优先权:
    申请号 | 申请日 | 专利标题
    FR1660536|2016-10-28|
    FR1660536A|FR3058167B1|2016-10-28|2016-10-28|NEW PROCESS FOR MANUFACTURING HIGHLY CARBON MATERIALS AND HIGHLY CARBON MATERIAL OBTAINED|FR1660536A| FR3058167B1|2016-10-28|2016-10-28|NEW PROCESS FOR MANUFACTURING HIGHLY CARBON MATERIALS AND HIGHLY CARBON MATERIAL OBTAINED|
    CN201780065889.3A| CN110062825A|2016-10-28|2017-10-26|Prepare high-carbon material new method and prepared high-carbon material|
    RU2019116177A| RU2765203C2|2016-10-28|2017-10-26|New method for producing high-carbon materials and obtained high-carbon materials|
    JP2019521485A| JP2019535915A|2016-10-28|2017-10-26|New production method of high carbonaceous material and high carbonaceous material obtained|
    US16/344,976| US11214523B2|2016-10-28|2017-10-26|Process for producing highly carbonaceous materials and the highly carbonaceous material obtained|
    KR1020197014676A| KR20190069540A|2016-10-28|2017-10-26|A novel method for producing high-carbon materials and a method for producing the high-|
    CA3039721A| CA3039721A1|2016-10-28|2017-10-26|Novel method for producing high-carbon materials and high-carbon material produced|
    PCT/FR2017/052949| WO2018078287A1|2016-10-28|2017-10-26|Novel method for producing high-carbon materials and high-carbon material produced|
    EP17794393.3A| EP3532660A1|2016-10-28|2017-10-26|Novel method for producing high-carbon materials and high-carbon material produced|
    IL266085A| IL266085D0|2016-10-28|2019-04-17|New process for producing highly carbonaceous materials and the highly carbonaceous material obtained|
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