0001] The invention relates to highly carbonaceous materials for the manufacture of composite parts or parts that can be used in electrochemical processes. The invention relates to a method for manufacturing a highly carbonaceous material and the highly carbonaceous material obtainable by such a manufacturing method.

Prior Art!

[0002] The carbon fiber market is expanding. In recent years, the carbon fiber industry has been growing to meet the demands from different applications. The market is currently estimated at approximately 60 kt / year and should grow up to 150-200 kt / year by 2020-2025. This high growth forecast is primarily related to the introduction of carbon fiber in composites used in the aerospace, energy, construction, automotive and leisure.

[0003] The carbon fibers generally have excellent tensile properties, high thermal and chemical stabilities, good thermal and electrical conductivities, and excellent resistance to deformation. They can be used as reinforcements for composite materials which typically comprise a polymer resin (matrix). The thus reinforced composite materials have excellent physical properties while maintaining an advantageous lightness. The relief is a key measure of the reduction of CO2 emissions in transport. The automotive and aviation industry is in demand of compounds at equivalent performance, greater lightness. In this context, the automotive and aerospace sectors, and more broadly the industry, also,

[0004] Moreover, the 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 shapes. Nevertheless, in this area, carbon fibers still have drawbacks related to their low

concentration of metal fillers. There is always a need for 3D structures incorporating a high conductivity and a high concentration of metal fillers to create an economic alternative to porous metals.

[0005] Today the carbon fibers are predominantly made from acrylic precursor. Polyacrylonitrile (PAN) precursor is the most used today for the manufacture of carbon fibers. Briefly, the production of carbon fibers from PAN comprises the steps of polymerization of the precursor PAN-based, fiber spinning, thermal stabilization, carbonization and graphitization. Carbonization takes place under a nitrogen atmosphere at a temperature of 1 000 to 1 500 ° C. The carbon fibers obtained at the end of these steps are made in 90% carbon, about 8% nitrogen, 1% oxygen and less than 1% hydrogen. Pitch-based precursors have also been developed, but as acrylic precursors they consume fossil resources.

[0006] With the aim of reducing the price of carbon fiber, one of the proposed solutions was to replace petroleum precursors (eg PAN or Pitch) by bio-based materials, such as cellulose or lignin contained in the woods. The cost for manufacturing carbon fiber using as a precursor of the cellulose is much lower than that of the fibers with PAN. In this context, several cellulosic precursors were evaluated. The cellulose-based precursors have the advantage of producing well-structured charred structures but they generally fail to achieve satisfactory carbon yields. However, the document WO2014064373 filed by the applicant describes a manufacturing process, from a bioresourced precursor, of continuous carbon fiber doped with carbon nanotubes (CNTs). The presence of the CNTs in the bioresourced precursor allows to increase the carbon yield of the precursor during carbonization, as well as to increase the mechanical properties of carbon fibers. The bioresourced precursor can be converted to cellulose in the form of fibers by dissolution and coagulation / spinning, so as to form the hydrocellulose (e.g., viscose, lyocell, rayon). The method can include a sizing step before carbonization. increase the mechanical properties of carbon fibers. The bioresourced precursor can be converted to cellulose in the form of fibers by dissolution and coagulation / spinning, so as to form the hydrocellulose (e.g., viscose, lyocell, rayon). The method can include a sizing step before carbonization. increase the mechanical properties of carbon fibers. The bioresourced precursor can be converted to cellulose in the form of fibers by dissolution and coagulation / spinning, so as to form the hydrocellulose (e.g., viscose, lyocell, rayon). The method can include a sizing step before carbonization.

[0007] Reference may be made to the document FR2994968, which describes the manufacture of a carbon-based composite material comprising a carbon-based fiber and Lyocell a carbon matrix. However, the method described herein

requires the use of a carbon fiber which involves the implementation of several steps including several carbonization. One may also refer to the document KR 20120082287 which discloses a process for manufacturing carbon fiber from a precursor material comprising lyocell (cellulose fibers from wood or bamboo) and a nanocomposite material - graphenes. One may also refer to the document CN 1587457 which discloses a method for preparing a cellulose precursor material for the production of carbon fiber having improved properties and a lower cost of manufacture. The cellulosic preparation involves the insertion of nano soot particles in the cellulose solution. However, these methods do not allow an improved carbon efficiency and increase the porosity of the materials obtained. The US2009121380 discloses a method for obtaining carbon fibrous texture without using solvents from cellulose precursor having been spun and impregnated with an aqueous emulsion comprising an organosilicon additive.

[0008] The Applicant has noted that there is still a need for precursors used in carbon materials manufacturing processes capable of responding to the problems encountered with existing methods for: i) a high yield of carbon; ii) a combination stable 3D structure and increased porosity, iii) a reduced manufacturing cost.

Technical problem!

[0009] The invention therefore aims to overcome the disadvantages of the prior art. In particular, the invention aims to provide a method of manufacturing a highly carbonaceous material mechanically very stable with improved carbon efficiency. In addition, this highly carbonaceous material has a higher porosity than that of carbon fibers allowing it a more efficient combination with metals.

IBrève description of the invention]

[0010] Thus, the invention relates to a highly carbonaceous material manufacturing process, mainly characterized in that it comprises the combination of a structured precursor comprising a fiber or a fiber assembly and an unstructured precursor, being in the form of a fluid, said fluid preferably having a viscosity lower than 45 000 mPa · s "1 at the temperature at which occurs the combining step, and comprising at least one cyclic or aromatic organic compound

melt or in solution at a lower mass concentration 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 steps of:

a thermal and dimensional stabilization step of the combined precursor so as to obtain a fiber or an assembly of fibers coated with a deposit of cyclic or aromatic organic compound, and

a fiber carbonization stage or the assembly of fibers coated with a cyclic or aromatic organic compound deposition to obtain a highly carbonaceous material.

[001 1] This new process of manufacturing a highly carbonaceous material has many advantages such as obtaining a carbon yield higher than that observed with the methods of the prior art, the formation of a material having a high porosity while maintaining a structured part, and the ability to add additional compounds thus obtaining a highly carbonaceous material with improved properties.

[0012] The invention further relates to a fiber or an assembly of fibers coated 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 has advantageously a ratio of the fiber mass (s) of the mass of aromatic or cyclic organic compound between 1/5 and 100/1.

[0013] The invention further relates to a highly carbonaceous material obtained by the process according to the invention. Advantageously, this highly carbonaceous material is bi-structured so as to include a portion structured and unstructured part, and it comprises greater than 5% overall porosity, preferably greater than 10%. These products meet the expectations of manufacturers in search of carbon materials having a high porosity while maintaining a structured game.

[0014] The invention further relates to the use of highly carbonaceous material according to the invention for the manufacture of pieces in thermoplastic or thermoset composites.

[0015] The invention further relates to the use of highly carbonaceous material according to the invention for the manufacture of parts suitable for use in electrochemical processes.

[0016] Other advantages and features of the invention 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 one embodiment of the manufacturing process of highly carbonaceous material according to the invention. Dotted steps are optional.

· Figures 2 show two images obtained by microscopy of a section of a carbonaceous material. 2A shows a carbonaceous material comprising a fiber treated with hydrocellulose DAHP (Diammonium hydrogen phosphate), and Figure 2B is a highly carbonaceous material comprising a fiber hydrocellulose treated with lignin by the process of the invention .

R Description of the Invention!

[0017] The term "carbonaceous nanofillers" according to the invention, a filler comprising one of the group consisting of carbon nanotubes, carbon nanofibers, graphene, fullerenes and carbon black, or a mixture of these thereof in any ratio. Preferably, the carbon nano-filler are carbon nanotubes, alone or mixed with graphene. The carbonaceous filler may have a smallest dimension between 0.1 and 200 nm, preferably between 0.1 and 160 nm, more preferably between 0.1 and 50 nm. This dimension may be measured by light scattering.

[0018] The term "graphene" according to the invention, a graphite sheet plane, isolated and individualized, but also, by extension, an assembly comprising between one and a few tens of sheets and having a flat structure, more or less wavy . This definition encompasses FLG (Few Layer Graphene or poorly stacked graphene), the NGP (nanosized Graphene Plates or nanoscale graphene plates), CNS (Carbon NanoSheets or nano-graphene sheets), the GNR (Graphene NanoRibbons or nano-graphene ribbons). But exclude carbon nanotubes and nanofibers, which consist respectively of the winding of one or more layers of graphene coaxially and turbostratic stacking of the layers.

[0019] The term "highly carbonaceous material" according to the invention, a material having a mass of carbon is more than 80% of the total mass of nonmetallic elements, preferably more than 90%, more preferably more than 95%, and even more preferably more than 98% (materials considered materials of very high purity).

[0020] The term "fiber of hydrocellulose" according to the invention, cellulose fibers or cellulose derivatives, preferably continuous and regular diameter, obtained after dissolution of cellulose from lignocellulosic material. As detailed in the following text, this combination can be accomplished by several alternative methods. The hydrocellulose may, for example, be obtained after a treatment with sodium hydroxide followed by dissolution with carbon disulfide. In this case the hydrocellulose is specifically called viscose. Alternatively, the fiber hydrocellulose can be obtained from lignocellulosic material dissolved in a solution comprising N-methylmorpholine N-oxide to form lyocell.

[0021] The term "lignin" a plant according to the invention aromatic polymer whose composition varies with the plant species and generally formed from three phenylpropanoid monomers: p-coumaryl alcohol, coniferyl and sinapyl.

[0022] The term "lignin derivative" according to the invention a molecule having a molecular structure of lignin and may contain substituents having been added during the process for extracting lignin or subsequently so as to modify its physicochemical properties . There are numerous methods for extracting lignin from lignocellulosic biomass and these can lead to changes in the lignin. For example, the Kraft process uses a strong base with sodium sulfide to separate lignin from cellulose fibers. This process may form thio-lignins. The sulfite process, resulting lignosulfonates formation. Organosolv pretreatment processes use an organic solvent or mixtures of organic solvents with the water to solubilize the lignin prior to the enzymatic hydrolysis of the cellulosic fraction. Preferably by lignin derivative must include a lignin having substituents being selected from: thiol, sulphonate, Alkyl, or polyesther. 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 10,000 g / mol.

[0023] In the following description, the same references are used to designate the same elements.

[0024] According to a first aspect, the invention relates to a manufacturing method 1 of highly carbonaceous material 2, characterized in that it comprises the combination 100 of a structured precursor 10 having a fiber or fiber assembly and an unstructured precursor 15, which is in the form of a fluid, said fluid preferably having a viscosity lower than 45 000 mPa · s "1 at the temperature at which occurs the combining step, and comprising at least one cyclic or aromatic organic compound in the molten state or in solution in a lower mass concentration or equal to 65%.

[0025] This combination of step 100 provides a combined precursor 20 corresponding to the structured precursor 10 covered by the unstructured precursor 15.

[0026] One embodiment of this process is illustrated in Figure 1. It can be carried out continuously or batchwise. As part of a continuous production, industrial processes allow the sequence of steps without interruption.

structured precursor (10)

[0027] The structured precursor 10 comprises a fiber or an assembly of fibers. The fiber or the fiber assembly may have undergone pre-treatments to facilitate their handling within the process of the invention. Nevertheless, being used as a precursor, the fiber or set of fibers, has not undergone carbonization step. Thus, preferably, the fiber or set of fibers used in the structured precursor 10 has a concentration by mass of carbon of less than 75%, advantageously less than 65%.

[0028] Preferably, such fibers are cellulose fibers, hydrocellulose fibers, lignin fibers, pitch fibers or fiber acrylic precursors (e.g. PAN). Even more preferably, the structured precursor 10 comprises a natural fiber or a combination of natural fibers. Said natural fiber is obtained from at least one plant component, preferably cellulose, cellulose selected from wood, flax, hemp, ramie, bamboo, preferably wood cellulose or lignocellulose, cellulose and lignin combination, as in the wood fibers, jute, cereal straw, corn legs, cork or lignin. This fiber can be obtained by various known production processes.

[0029] Advantageously, the natural fibers are obtained from a solution of cellulose; then extrusion through a die to form a continuous fiber as a fiber hydrocellulose or obtained from lignin after extrusion to form a fiber lignin.

[0030] In the case of a fiber of hydrocellulose, it can for example be obtained according to the manufacturing method described in the application WO2014064373. The hydrocellulose used fibers may also be fibers of lyocell or viscose, the cellulose is derived for example of wood or bamboo. Most fiber manufacturing processes of hydrocellulose is based on achieving a cellulosic preparation from dissolved cellulose, for example carbon disulfide, 4-oxide, 4-methylmorpholine (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 fibers of hydrocellulose following immersion in a coagulation bath containing for example sulfuric acid.

[0031] In addition, the fiber or set of fibers may take many different forms. One advantage of the invention is that the method may be implemented with fibers having been previously formatted, for example in the form of a twisted multi-filament, untwisted multi-filament, of a set of non-woven fibers, or a set of woven fibers. In the manufacture of carbon fiber fabrics, it is usually necessary to produce coils of carbon fibers, for example from PAN carbonized then organize these fibers according to the desired weaving. Here, the invention enables direct use of non-carbonized fibers having previously been held in the form of multi-filament or fiber assembly. Thus, the method according to the invention has the advantage of reducing the manufacturing costs of multi-filaments or carbon fiber assemblies (for example woven). For example, under the method according to the invention, it is possible to manufacture a plurality of woven fiber (eg viscose, lyocell, rayon, PAN oxidized) and directly subjecting him the manufacturing process according to the invention so forming a material

highly carbonaceous having a structured part, such as a woven assembly of carbon fibers. Thus, preferably, the structured precursor 10 includes a multi-filament or a fiber assembly. Even more preferred, the structured precursor 10 is a twisted multi-filament untwisted multi-filament, a set of non-woven fibers, or a set of woven fibers.

[0032] The multi-filament twisted 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.

[0033] The structured precursor 10 according to the invention may comprise at least one fiber whose diameter is between 0.5 μηη and 300 μηη, preferably between 1 and 50 μηη μηη. In addition, preferably the structured precursor 10 according to the invention comprises at least one continuous fiber having a regular diameter along its 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 is understood that the diameter varies by less than 20%, preferably less than 10% along the length of the fiber.

unstructured precursor (15)

[0034] The informal precursor 15 is in the form of a fluid having at least one cyclic or aromatic organic compound in the molten state or in solution in a lower mass concentration or equal to 65%. The use of unstructured precursor in the form of a fluid improves the combination 100 between the unstructured and structured precursor 15 precursor 10.

[0035] The fluid may be an aqueous solution or an organic solution or a mixture of both. These alternatives allow to adapt the unstructured precursor 15 based on 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.

[0036] Alternatively, the fluid may be a molten material such as molten lignin. This is particularly suitable when the cyclic or aromatic organic compound used is not or poorly soluble but fuse.

[0037] The cyclic or aromatic organic compound may be in various forms in the fluid. It can be solubilized in the solution, molten or in the solid state in the form of a dispersion. This dispersion may also be carried out in a solution in a molten state material. Preferably, the cyclic or aromatic organic compounds or fusible or soluble, will be combined with the structured precursor in the form of a dispersion.

[0038] Preferably, the fluid has a viscosity less than 45 000 mPa · s "1 at the temperature at which occurs the combining step 100. This allows, during the combining step to combine an amount more significant unstructured precursor 15 to 10 structured precursor and increase the porosity of highly carbonaceous material 2 obtained. Advantageously, 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 suited to the technologies used for the combining step, particularly impregnation, and allows better control of the amount of fluid deposited during this step. A viscosity greater than 500 mPa.s "1 improves the yield carbonic carbonic performance of highly carbonaceous material obtained with respect to a lower viscosity. The viscosity of the fluid is measured, the temperature at which occurs the step of combination 100, for example using a viscometer free flowing or capillary viscosity or the Brookfield method.

[0039] The cyclic or aromatic organic compound is an organic material which, upon pyrolysis in an atmosphere devoid of oxygen, becomes preferably remains more than 5% by weight carbonic representative of highly carbonaceous material 2 obtained under of the invention. A cyclic or aromatic organic compound according to the invention comprises a series of atoms linked sequentially by covalent bonds to form one or more rings. This cycle may be saturated or unsaturated and the ring may be a heterocyclic ring. Preferably, the cyclic or aromatic organic compound is an aromatic compound. That is to say, it comprises at least one aromatic ring. Preferably, the cyclic or aromatic organic compound has a mass percentage of carbon greater than 40%, more preferably of greater than 45%, even more preferably greater than 60%. This allows it to best increase the carbon efficiency of highly carbonaceous material 2. Thus, compounds such as siloxanes or polysiloxanes

does not increase as effectively allow the carbon yield a cyclic or aromatic organic compound having a mass percentage of carbon greater than 40%.

[0040] The cyclic or aromatic organic compound may be selected from:

- biobased products selected from: the lignin or lignin derivatives, polysaccharides such as cellulose, starch, glycogen, amylose, amylopectin, dextran, hemicellulose, or other more simple sugars such as fructose or glucose and their derivatives;

- the products obtained from oil or mineral resources selected from: pitch, naphthalene, phenanthrene, anthracene, pyrene or polycyclic substituted aromatic hydrocarbons such as naphthalene sulfonate;

- synthesis of selected products from the phenolic resin, phenolic resin, or the polyepoxide resin; and

- all other organic substances or formulations producing a remainder carbon after pyrolysis under an inert atmosphere.

[0041] Preferably, the cyclic or aromatic organic compound is an oligomer or a cyclic or aromatic organic polymer.

[0042] Advantageously, the cyclic or aromatic organic compound has a molecular weight greater than 500 g / mol, preferably greater than 1000 g / mol and even more preferably greater than 5000 g / mol.

[0043] Even more preferably, the aromatic or cyclic organic compound is lignin or a lignin derivative.

[0044] The informal precursor 15 may comprise several different cyclic or aromatic organic compounds.

[0045] In solution, cyclic or aromatic organic compound having a lower mass concentration or equal to 65%. Too high a concentration in solution of cyclic or aromatic organic compound may reduce the properties of highly carbonaceous material obtained. Preferably, the unstructured precursor 15 comprises between 5 and 50% by weight of cyclic or aromatic organic compound. At such concentrations, the fibers of the structured precursor are completely covered with cyclic or aromatic organic compound.

[0046] Advantageously, the unstructured precursor 15 comprises lignin or a lignin derivative. Indeed, lignin represents 10 to 25% of the Earth's biomass lignocellulosic nature and it is now only undervalued by industry. Each year, hundreds of tons of lignin or lignin derivatives are produced without any possible recovery. Lignin is present mainly in vascular plants (or higher plants) and some algae. This is a plant aromatic polymer whose composition varies with the plant species and generally formed from three phenylpropanoid monomers: p-coumaryl alcohol, coniferyl and sinapyl as shown by the following formulas:

alcohol p-coumaryl alcohol sinapyl alcohol coniferyl

[0047] Advantageously, the unstructured precursor 15 may further comprise at least one additional compound selected from: a metal charge, compounds rich in carbon and organic particles. Adding additional compounds unstructured precursor 15 allows to benefit from the binding properties of the cyclic or aromatic organic compound and to form a highly carbonaceous material 2 with multiple properties.

[0048] The metallic filler may 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 metal filler may comprise at least one metal selected from the 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 in mixture with n '

alternatively in the form of salts such as organic salts (e.g. nitrate salts, sulfate, acetate, carbonate, oxalate, benzoate or phosphate). Unstructured precursor 15 contains for example a metal filler and a cyclic or aromatic organic compound. The cyclic or aromatic organic compound plays the dual role of porous matrix and binder for fixing a large quantity of metals.

[0049] The addition of such metals to unstructured precursor 15 allows to impart to highly carbonaceous materials 2 according to the invention physicochemical properties desired for example in the case of electrochemical applications.

[0050] Preferably, the unstructured precursor 15 comprises a plurality of different metals. For example, the unstructured precursor 15 may comprise lithium, cobalt and nickel.

[0051] The carbon-rich compounds may be selected from the following compounds: activated carbon, anthracite natural, synthetic anthracite, carbon black, natural graphite or synthetic graphite. The organic particles may be selected from the following compounds: nanocellulose (eg cellulose nanofibers, cellulose microfibril, cellulose nanocrystals nanocellulose whiskers nanocellulose or bacterial), tannins, chitosan, or other biopolymers neither fuses nor soluble. Such compounds rich in carbon or organic particles added to the precursor unstructured possible to increase the carbon yield of the resulting material and improve its mechanical properties. The compounds or soluble or fuses may be added in the form of a dispersion.

[0052] Preferably, the unstructured precursor 15 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 compounds rich in carbon, from 0.001% to 50% by weight of organic particles or a mixture thereof in any proportion.

[0053] Advantageously, the precursor 10 structured and / or unstructured precursor 15 may contain carbon nanofillers, said carbonaceous nanofillers being present at a concentration between 0.0001% and 30% by mass. Preferably, these carbon nanofillers are present at a concentration of between 0.01% and 5% by weight. The addition of carbon nano-filler to one of the two, or both precursors improves the carbon performance of highly carbonaceous material obtained. Indeed, when carbonaceous nanofillers are added to the unstructured precursor 15, the latter acts as a binder and causes an increase in the amount of carbonaceous nanofillers is actually inserted into the resulting material.

[0054] Carbon nanotubes (CNTs) can be of the single wall, double wall or multiwall. Double-wall nanotubes may especially be prepared as described by FLAHAUT et al in Chem. Corn. (2003), 1442. The multiwall nanotubes may in turn be prepared as described in WO 03/02456. Nanotubes typically have an average diameter ranging from 0.1 to 100 nm, preferably from 0.4 to 50 nm, and more preferably 1 to 30 nm, or 10 to 15 nm, and preferably a length of 0.1 10 μηη. 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, preferably between 200 and 300 m 2/ G, and their apparent density may in particular be between 0.05 and 0.5 g / cm3 and more preferably between 0.1 and 0.2 g / cm3. The multi-walled nanotubes may for example comprise 5 to 15 sheets (or walls) and more preferably from 7 to 10 sheets.

[0055] An example of crude carbon nanotubes is especially commercially available from Arkema under the trade name Graphistrength® C100. Alternatively, these nanotubes can be purified and / or treated (e.g., oxidized) and / or ground and / or functionalized, before their implementation in the process of the invention. The purification of raw or milled nanotubes may be carried out by washing with a sulfuric acid solution, so as to rid them of any residual mineral and metallic impurities. Oxidation of nanotubes is advantageously carried out by bringing the latter into contact with a sodium hypochlorite solution.

[0056] Graphene used in the process may be obtained by chemical vapor deposition or CVD, preferably by a method using a powdery catalyst of a mixed oxide. It arises, typically in particulate form having a thickness of less than 50 nm, preferably less than 15 nm, more preferably less than 5 nm and lower lateral dimensions

micron, 10 to 1000 nm, preferably from 50 to 600 nm, more preferably from 100 to 400 nm. Each of these particles generally contains from 1 to 50 layers, preferably 1 to 20 layers and more preferably from 1 to 10 layers. Graphene various preparation processes have been proposed in the literature, including the processes said mechanical exfoliation and chemical peels comprising tear by successive layers of graphite sheets, respectively by means of an adhesive strip (Geim AK, science, 306: 666, 2004) or with reagents such that the combined sulfuric acid with nitric acid, intercalated between the graphite layers and the oxidant so as to form oxide graphite which can be easily exfoliated in water in the presence of ultrasound. Another technique exfoliation comprises subjecting graphite solution to ultrasound in the presence of a surfactant (US 7,824,651). One can also obtain graphene particles by carbon nanotubes cut 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: 877-880, 2009). Yet another method for the preparation of graphene is to decompose at high temperatures, under vacuum, silicon carbide. Finally, several authors have described a graphene synthesis process by chemical vapor deposition (CVD), optionally associated with a radio frequency generator (RF-CVD) (DERVISHI et al., J. Mater. Sci., 47 :

[0057] The Fullerenes are molecules composed exclusively or almost exclusively of carbon may take a geometric shape reminiscent of a sphere, an ellipsoid, a tube (called nanotube) or ring. Fullerenes may for example be selected from: C60 fullerene which is a compound consisting of 60 carbon spherical carbon, C70, PCBM formula of [6,6] -phenyl-C61 methyl butyrate which is a derivative fullerene whose chemical structure was modified to make it soluble, and the PC 71 BM formula [6,6] -phenyl-C71 methyl butyrate.

[0058] The carbon nanofibers, like carbon nanotubes, nanowires produced by chemical vapor deposition (CVD) from a carbon source which is decomposed on a catalyst comprising a transition metal (Fe, Ni , Co, Cu), in the presence of hydrogen, at temperatures from 500 to 1200 ° C. The carbon nanofibers are composed of graphitic areas more or less organized (or turbostratic stacks) whose planes are inclined at angles

variable relative to the axis of the fiber. These stacks can take the form of chips, fish bone or cups stacked to form structures having a diameter generally ranging from 100 nm to 500 nm or more. carbon nanofibers having a diameter of 100 to 200 nm, e.g., about 150 nm (VGCF® SHOWA DENKO), and advantageously a length of 100 to 200 μηη are preferred in the process according to the invention.

[0059] Furthermore, carbon black can be used as carbonaceous nanofillers, which is a colloidal carbonaceous material manufactured industrially by incomplete combustion of heavy fuel, which is in the form of carbon spheres and aggregates of these spheres and whose dimensions are generally between 10 and 1000 nm.

Combining (100)

[0060] The combining step 100 according to the invention corresponds to the contacting of the precursor 10 with the structured unstructured precursor 15. This combination can be accomplished by several alternative methods, generally at a temperature ranging from -10 ° C at 80 ° C, preferably 20 ° C to 60 ° C. For example, it is possible to realize a dipping, spraying or impregnation (e.g., padding). Preferably, the combining step 100 is impregnation.

thermal and dimensional stabilization (200)

[0061] The production method 1 of the invention further comprises a thermal and dimensional stabilization step 200 the handset 20 precursor so as to obtain a fiber or an assembly of fibers coated with a deposit of cyclic or aromatic organic compound 30 .

[0062] The thermal and dimensional stabilization step 200 may comprise a drying for solvent evaporation and / or ventilation. Drying may be achieved via an increase 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, for example to subject this article to a heat treatment to remove the diluent or the solvent in vapor form. For example, an infrared oven with a ventilation can be used.

[0063] Following this step, a deposit, similar to a solid film, cyclic or aromatic organic compound is formed on the surface of the fiber. This deposition can have varying thicknesses depending on the parameters used in the method such that the viscosity of the solution or the concentration of cyclic or aromatic organic compound.

[0064] Preferably, the combination of steps 100 and thermal stabilization and dimensional 200 may be repeated one or more times. The repetition of these steps allows 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 increase the porosity of highly carbonaceous material obtained at the end of process.

Carbonisation (300)

[0065] The production method 1 of the invention further comprises a step 300 of carbonization of the fiber or set of fibers coated with a deposit of cyclic organic compound or aromatic 30 so as to obtain a highly carbonaceous material 2.

[0066] This carbonization step 300 may be performed at a temperature between 150 ° C and 2500 ° C, preferably between 250 and 1400 ° C. The charring 300 step can last, for example 2 to 60 minutes. This carbonization step may comprise a progressive rise in temperature or a rise and temperature lowering. The carbonization takes place in the absence of oxygen and preferably under a nitrogen atmosphere. The presence of oxygen during the carbonization should be preferably limited to 5 ppm.

[0067] This carbonization step may be carried out continuously and can be coupled to a step of stretching the fiber to improve the mechanical properties of the carbon fiber obtained.

Sizing the pre-carbonization (210)

[0068] The manufacturing method according to the invention may further comprise, before the carbonization step 300, the steps of:

- a sizing step 210 comprising contacting the fiber or set of fibers covered with a deposit of cyclic organic compound

aromatic or 30 with an aqueous solution comprising at least one flame retardant, said flame retardant being selected from: potassium, sodium, phosphate, acetate, chloride, urea, and a step of post-drying sizing 220 .

[0069] This has the advantage of strengthening the physicochemical properties of the resulting carbonaceous material. Indeed, although the cyclic or aromatic organic compound, such as lignin or lignin derivative, can exhibit flame retardant properties, the addition of a sizing step with a solution comprising at least one flame retardant compound is used to improve the characteristics of the obtained carbonaceous material.

[0070] The steps of sizing and sizing 210 220 post drying may be repeated one or more times. Thus, it is possible to increase the amount of flame retardant associated with the fiber or while combining different treatments based on different substances.

Formatting (400)

[0071] The manufacturing method according to the invention may further comprise a shaping step 400, optionally coupled to a patterning step, highly carbonaceous material 2 by any shaping method such as extrusion, compression, calendering, drawing or molding, at room temperature or with heat treatment. This shaping makes it possible to control accurately the final shape of highly carbonaceous material obtained by the process according to the invention. It can also help control the porosity of the material produced.

[0072] The shaping step can for example be carried out at a temperature below 400 ° C in the presence of a polymeric binder or a temperature higher than 400 ° C under a drawing, a compression or calendering.

Graphitisation (500)

[0073] The manufacturing method according to the invention may comprise, after the carbonization step 300, a step of graphitization 500. This step 500 of graphitization can be performed at a temperature between 1000 ° C and 2800 ° C, preferably greater than or equal to 1100 ° C. The graphitization step 500 may for example be from 2 to 60 minutes, preferably 2 to 20 minutes. This graphitization step 500 may comprise a progressive rise in temperature.

Ensimaqe post carbonisation (600)

[0074] The manufacturing method according to the invention may further comprise, after the step of carbonization 300, a sizing step 600 of putting into contact the highly carbonaceous material 2 with a solution of an organic component which can comprise at least one silane derivative or silane and / or at least one derivative siloxane or siloxane. This sizing composition 600 may also be performed after the step of graphitization 500. A plasma channel processing step, microwaves and / or electrochemical may also be formed between the graphitization step 500 and the sizing step 600.

[0075] The size improves the integrity of the carbonaceous material and helps protect from abrasion. The organic component of the solution is preferably an aqueous solution, an organic solution or an aqueous emulsion.

[0076] This sizing step can improve the physicochemical properties of the material (eg protection against abrasion and improving the integrity of the component fibers) and has the advantage, in the context of the invention of possibly be carried on a set of fiber, that is to say for example on a carbon fiber fabric.

[0077] According to another aspect, the invention relates to a fiber or an assembly of fibers coated 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. The organic deposit is a deposit of aromatic or cyclic organic compound. Preferably, the ratio of the fiber mass of the mass of aromatic or cyclic organic compound is between 1/5 and 100/1 and said organic deposit covering the fiber or set of fibers comprises at least one cyclic organic compound or aromatic selected from: the lignin or lignin derivatives, polysaccharides such as cellulose, starch, glycogen, amylose, amylopectin, dextran, hemicellulose, or fructose or glucose and their derivatives; pitch, naphthalene, phenanthrene, anthracene, pyrene or polycyclic substituted aromatic hydrocarbons such as naphthalene sulfonate; and the phenolic resin, phenolic resin, or the polyepoxide resin.

[0078] This intermediate product preferably has a ratio of the fiber mass of the mass of aromatic or cyclic organic compound between 1/5 and 100/1, preferably between 2/1 and 95/1.

[0079] According to another aspect, the invention relates to a highly carbonaceous material 2 capable of being obtained by the manufacturing method according to the invention, preferably obtained by the manufacturing method according to the invention.

[0080] Preferably and advantageously, this highly carbonaceous material 2 is bi-structured so as to include a portion structured and unstructured part. The structured portion corresponds to the resulting material from the carbonization of structured precursor 10 while the unstructured part corresponds to the resulting material from the carbonization of structured precursor 15. Advantageously, these two highly carbonaceous parts, can have different physico-chemical characteristics the part structured may be advantageous for the shape of the structure but also for electrical conductivity in combination with a non-structured portion providing a large surface area available for reactions / electronic exchanges. Thus, the invention advantageously provides a highly carbonaceous material 2,

[0081] In addition, the highly carbonaceous material 2 has a greater than 5% overall porosity, preferably greater than 10%. These products meet the expectations of manufacturers in search of lighter carbon fiber however with sufficient mechanical properties to meet the needs such as aeronautical and automotive industries. In addition, the highly carbonaceous material obtained by the process according to the invention has the advantage of including a larger porosity than the highly carbonaceous materials obtained until now. This higher porosity has the advantage as shown in the examples, to increase the carbon yield obtainable from the addition of additives such as nanocarbonées loads. In addition, This greater porosity to open the use of this material for many applications that can benefit from a larger overall surface area. The porosity is measured for example by direct methods (CT, X-ray, micrograph parts cut) or indirect (density measurement, weighing, ...). Preferably, the overall porosity is determined by density measurement with respect to the theoretical density. Advantageously, the structured portion has a porosity lower than 40%, preferably less than 30%, and the unstructured part has a porosity of greater than 7%, preferably greater than 10%. These porosities are advantageously determined by micrograph cutting inserts. use of this material for many applications that can benefit from a larger overall surface area. The porosity is measured for example by direct methods (CT, X-ray, micrograph parts cut) or indirect (density measurement, weighing, ...). Preferably, the overall porosity is determined by density measurement with respect to the theoretical density. Advantageously, the structured portion has a porosity lower than 40%, preferably less than 30%, and the unstructured part has a porosity of greater than 7%, preferably greater than 10%. These porosities are advantageously determined by micrograph cutting inserts. use of this material for many applications that can benefit from a larger overall surface area. The porosity is measured for example by direct methods (CT, X-ray, micrograph parts cut) or indirect (density measurement, weighing, ...). Preferably, the overall porosity is determined by density measurement with respect to the theoretical density. Advantageously, the structured portion has a porosity lower than 40%, preferably less than 30%, and the unstructured part has a porosity of greater than 7%, preferably greater than 10%. These porosities are advantageously determined by micrograph cutting inserts. micrograph parts cut) or indirect (density measurement, weighing, ...). Preferably, the overall porosity is determined by density measurement with respect to the theoretical density. Advantageously, the structured portion has a porosity lower than 40%, preferably less than 30%, and the unstructured part has a porosity of greater than 7%, preferably greater than 10%. These porosities are advantageously determined by micrograph cutting inserts. micrograph parts cut) or indirect (density measurement, weighing, ...). Preferably, the overall porosity is determined by density measurement with respect to the theoretical density. Advantageously, the structured portion has a porosity lower than 40%, preferably less than 30%, and the unstructured part has a porosity of greater than 7%, preferably greater than 10%. These porosities are advantageously determined by micrograph cutting inserts. preferably greater than 10%. These porosities are advantageously determined by micrograph cutting inserts. preferably greater than 10%. These porosities are advantageously determined by micrograph cutting inserts.

[0082] Advantageously, the ratio of the volume of the structured part of the unstructured part volume is between 1/5 and 100/1. More preferably, the ratio of the volume of the structured part of the volume of the unstructured portion is between 1/5 and 50/1. This ratio can be measured by various methods controlled by the skilled person as for example the analysis of optical sections microscopy images obtained by microtome, highly carbonaceous material.

[0083] Advantageously, the highly carbonaceous material 2 comprises additional compounds such as metals in the unstructured part. The metals may be present in the highly carbonaceous material in a mass concentration of between 0.001% and 90%. More specifically, the metals may be present in the unstructured part of highly carbonaceous material in a weight concentration of between 0.1% and 90%, while the same metal, or more generally the metals are present at a lower concentration of mass to 5% of the structured portion. This allows the highly carbonaceous material present, despite the absence of demarcation between its constituents, a particularly advantageous heterogeneous structure in the context of its use in electrochemical processes.

[0084] Advantageously, the highly carbonaceous material 2 is in the form of a carbon fiber, a twisted multi-filament, untwisted multi-filament, a plurality of carbon fibers or nonwoven a set of woven carbon fibers. Indeed, this highly carbonaceous material comprises, besides the structured portion, an unstructured part able to create stronger connections at the contacts between the fibers (e.g., crosses). Thus, such a highly carbonaceous material 2 shows an improvement of the mechanical properties of the structured precursor (e.g., tear strength).

[0085] According to another aspect, the invention relates to the use of highly carbonaceous material 2 can be obtained via the manufacturing process according

the invention, preferably obtained by the manufacturing method according to the invention for the manufacture of pieces in thermoplastic or thermoset composites.

[0086] Thus, according to another aspect, the invention relates to thermoplastic or thermoset composite materials obtained from fibers produced through the manufacturing method according to the invention. Advantageously, these thermoplastic or thermosetting composite materials have, for the same volume, a lower weight of at least 5% by weight of conventional thermoplastic or thermoset composites.

[0087] Indeed, the highly carbonaceous material 2 obtained by the method according to the invention can be used in conventional methods (e.g., injection, infusion, infiltration) of manufacturing composite materials. It can be associated with a natural polymer resin or a synthetic polymeric resin such as thermoplastic resins (e.g., polyamides, copolyamides, polyesthers, copolyesthers, polyurethanes, polyethylene, polyacetates, polyehtersulfonates, polyimides, polysulfones, polyphénlylène sulfones, polyolefins) or thermosetting resin (for example epoxy, unsaturated polyesters, vinyl esters, phenolic resins, polyimides).

[0088] According to another aspect, the invention relates to the use of highly carbonaceous material 2 can be obtained via the manufacturing process according to the invention, preferably obtained by the manufacturing method according to the invention, for the manufacture of parts suitable for use in electrochemical processes. The highly carbonaceous materials of the invention have low resistance and are very good electronic conductors. In addition, they have a porosity, and thus a surface area much greater than the conventional carbon fibers. This is particularly due to the presence of a structured portion and an unstructured portion, each having a different role in the electrochemical process.

[0089] The parts that can be used in electrochemical methods may for example be selected from the following list:

- anode for cathodic protection,

electrode for fuel cells,

electrode member for primary and rechargeable batteries,

electric current collector for the anodes or cathodes of lithium or sodium,

electrical current collector for Lithium-Sulfur electrical current collector for lithium-polymer batteries,

- electrode member for lead acid batteries, in particular for ultra-batteries lead or lead atoms,

element electrode for rechargeable lithium batteries,

element supercapacitor electrode,

catalyst support in particular for the purification of air, and

- catalytic support for Lithium-Air batteries.

[0090] The following examples illustrate the invention but have no limiting character.

example 1

Description of starting materials:

[0091] The structured precursor used is based on the hydrocellulose fiber multi filament with a linear density of 88 mg per meter.

[0092] For the formation of unstructured precursor, the lignin was solubilized in a mixture ethanol / water 60/40 at 60 ° C. After 2 h of stirring, the solution was cooled to room temperature. The precipitated fraction was filtered. The final solution contained 10% lignin mass.

Preparation of carbonaceous material

[0093] Step 1: impregnation

[0094] The fibers of hydrocellulose, constituting the structured precursor, are impregnated in the lignin solution, unstructured precursor for 7 minutes.

[0095] Step 2: drying

[0096] The lignin-impregnated fibers were dried at 80 ° C in a ventilated oven for 1 hour.

[0097] Step 5: carbonization

[0098] The carbonization was carried out in a vertical static oven under a nitrogen atmosphere. A temperature ramp of 5 ° C per minute was applied until the temperature of 1200 ° C.

Characteristics of the obtained carbonaceous material

[0099] The deposition of lignin on the fiber hydrocellulose was 9% by weight. Quantification of mass lignin deposition can be obtained by weighing the fiber before hydrocellulose step 1 then following step 2 of drying.

Increased carbon performance

[00100] The carbon efficiency (CR) was calculated after carbonization:

RC = (m carbonaceous material / precursor m) x 100

Carbon Performance Results (after carbonization) are:

Fibers hydrocellulose without lignin deposition or flame retardant

8% (reference)

Fibers hydrocellulose with dépôt de 2% DAHP (Di Ammonium

26% Hydrogéno Phosphate)

Fibers hydrocellulose, with deposit 9% lignin according to the invention 25%

[00101] These results show that the lignin is a carbon source during pyrolysis and also plays a role of flame retardant for hydrocellulose. Thus, the combination of hydrocellulose fibers with lignin to form, prior to carbonization, of hydrocellulose covered with a deposit of lignin fibers to switch from 8% to 25% carbon yield by a factor of a factor of 3 or more carbon performance. Lignin also achieves an equivalent carbon performance carbon performance achieved with conventional chemical used with cellulose.

intimate deposition and formation of a highly carbonaceous material

[00102] Figure 2A shows an image obtained by scanning electron microscopy of a section of a carbonaceous material, in the example a carbon fiber obtained after combination with DAHP (A) and the image 2B up an image obtained by scanning electron microscopy of the carbonaceous material obtained by the process according to the invention. Figure 2B shows that the carbon deposition resulting from the lignin is highly bound to surfaces of the fibers and it is impossible to identify it by microscopy the interface between the structured part i.e. the fibers and the unstructured part namely the deposit carbon from lignin. In contrast, Figure 2A shows that the deposit DAHP does not allow the creation of this unstructured carbon mass around the structured part.

[00103] Thus the image of Figure 2B illustrates the creation of an agglomerate forming a highly carbonaceous bi-structured material. There is no "visible interface between carbon fiber from the fiber after carbonization hydrocellulose and lignin.

[00104] The carbon fibers of the carbonaceous material have a diameter between 6 and 7 μηη which is larger than that of fibers used as hydrocelluloses structured precursor.

example 2

[00105] The lignin deposition was carried out as in Example 1, but of hydrocellulose additivated fiber 0.2% CNTs. The same protocol was also applied for carbonization.

Characteristics of the obtained carbonaceous material

[00106] Carbon Performance Results (after carbonization) are:

Fibers hydrocellulose without lignin deposition or flame retardant

8% (reference)

Fibers hydrocellulose without lignin deposition or flame retardant, with

9% 0.2% CNT (comparative)

Fibers hydrocellulose, with deposit 9% lignin according to the invention 25%

Fibers hydrocellulose, with deposition by 9% lignin insubstantial

35% flame retardant, with 0.2% of CNTs, according to the invention

[00107] These results show that the addition to the unstructured precursor carbonaceous nanofillers such that the CNTs can be really efficient and improve the carbon efficiency provided they respect the method according to the invention comprising a combination of an unstructured precursor comprising a cyclic or aromatic organic compound such as lignin.

[00108] Furthermore, the addition of carbon nanotubes in the informal precursor containing lignin possible to further increase the carbon yield and achieve carbonic yields of 35%, a multiplication by a factor 4 and most of the carbon performance.

[00109] These examples show that treatment of precursor structured by an unstructured precursor comprising a cyclic or aromatic organic compound such as lignin increases the carbon efficiency and the fixing of additional compounds such as CNTs.

[001 10] Thus, the present invention comprises using a combination of two precursors to obtain a highly carbonaceous material with a higher carbon yield.

claims

Production method (1) of highly carbonaceous material (2), characterized in that it comprises combining (100) a structured precursor (10) comprising a fiber or an assembly of fibers and a non-structured precursor ( 15), which is in the form of a fluid, said fluid having a viscosity less than 45 000 mPa · s "1 at the temperature at which occurs the combining step, and comprising at least one cyclic or aromatic organic compound melt or in solution at a lower mass concentration or equal to 65%, so as to obtain a combined precursor (20) corresponding to the structured precursor (10) covered by the non-structured precursor (15), said method comprising further the steps of:

a thermal and dimensional stabilization step (200) of the combined precursor (20) so as to obtain a fiber or an assembly of fibers coated with a deposit of cyclic or aromatic organic compound (30), and

a carbonization step (300) of the fiber or set of fibers coated with a deposit of cyclic or aromatic organic compound (30) so as to obtain a highly carbonaceous material (2).

A manufacturing method according to claim 1, characterized in that the cyclic or aromatic organic compound is selected from bio-based products selected from: lignin, cellulose, starch, glycogen, amylose, amylopectin, dextran , hemicellulose, fructose or glucose, and their derivatives; the products obtained from oil or mineral resources selected from: pitch, naphthalene, phenanthrene, anthracene, pyrene or naphthalene sulphonate; and synthetic products selected from phenolic resin, phenolic resin, or the polyepoxide resin.

Production method according to one of claims 1 or 2, characterized in that the unstructured precursor (15) comprises between 5% and 50% by weight of cyclic or aromatic organic compound.

A manufacturing method 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 both.

5. The manufacturing method according to any one of claims 1 to 3, characterized in that the fluid is a molten material.

6. The manufacturing method according to any one of the preceding claims, characterized in that the cyclic or aromatic organic compound has a molecular weight greater than 500 g / mol.

7. The manufacturing method according to any one of the preceding claims, characterized in that the non-structured precursor (15) further comprises at least one additional compound selected from: metallic fillers, carbon-rich compounds and organic particles.

8. The manufacturing method according to claim 7, characterized in that the metallic fillers include metals selected from the following metals:

Boron, Silicon, Germanium, Arsenic, Lithium, Sodium, Potassium, Titanium, Vanadium, Manganese, Iron, Cobalt, Nickel, Molybdenum, Aluminum and Lead

9. The manufacturing method according to claim 7, characterized in that the carbon rich compounds are selected from the following compounds: activated carbon, anthracite natural, synthetic anthracite, carbon black, natural graphite or synthetic graphite.

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 fuses nor soluble.

January 1. A manufacturing method according to any one of the preceding claims, characterized in that the structured precursor (10) has at least a regular fiber (1 1) whose diameter is between 0.5 and 300 μηι, preferably between 1 μηη and 50 μηη.

12. The manufacturing method according to any one of the preceding claims, characterized in that the structured precursor (10) comprises a twisted multi-filament untwisted multi-filament, a set of non-woven fibers, or an assembly of fibers woven.

13. The manufacturing method according to any one of the preceding claims, characterized in that the structured precursor (10) includes cellulose fibers, hydrocellulose fibers, lignin fibers, pitch fibers or PAN fibers .

14. The manufacturing method according to any one of the preceding claims, characterized in that the structured precursor (10) and / or unstructured precursor (15) comprises carbon nano-fillers, nano-fillers said carbon being present at a concentration between 0.0001% and 30% by weight, preferably between 0.01% and 5% by weight.

15. The manufacturing method according to any one of the preceding claims, characterized in that the combination of steps (100) and thermal and dimensional stabilization (200) are repeated one or more times.

16. The manufacturing method according to any one of the preceding claims, characterized in that it further includes a shaping stage (400) of highly carbonaceous material (2) by any shaping method such as extrusion , compression, calendering, drawing or molding, at room temperature or with heat treatment.

17. The manufacturing method according to any one of the preceding claims, characterized in that it further comprises a step of graphitization (500).

18. A fiber or set of fibers coated with an organic deposit (30) as an intermediate product, characterized in that said organic deposit comprises at least one cyclic or aromatic organic compound selected from:

lignin or lignin derivatives, polysaccharides such as cellulose, starch, glycogen, amylose, amylopectin, dextran, hemicellulose, or fructose or glucose and their derivatives,

pitch, naphthalene, phenanthrene, anthracene, pyrene or polycyclic substituted aromatic hydrocarbons such as naphthalene sulfonate, and

- phenolic resin, phenolic resin, or the polyepoxide resin,

and characterized in that the ratio of the fiber mass of the mass of aromatic or cyclic organic compound is between 1/5 and 100/1.

19. highly carbonaceous material (2) characterized in that it is bi-structured so as to include a structured portion having a carbonized fiber or set of carbonized fibers, and an unstructured part comprising a cyclic organic compound or aromatic carbonized and in that it comprises more than 5% overall porosity, preferably greater than 10%.

20. highly carbonaceous material (2) according to claim 19, characterized in that the structured portion has a porosity lower than 40%, preferably less than 30%, and the unstructured portion has a porosity greater than 7%, preferably greater than 10%.

21. highly carbonaceous material (2) according to any one of claims 19 or

20, characterized in that the ratio of the volume of the structured part of the unstructured part volume is between 1/5 and 100/1.

22. highly carbonaceous 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 in the unstructured part according to claims 1 to 8 of the process.

23. Nature hautement Coal (2) selon l'une des quelconque revendications 19 to 22, unfrankierte en ce qu'il se présente sous la forme d'une fibers of carbon, of a multi-filament torsade, a multi- filament not torsade, an ensemble of fiber carbon tissées or not of an ensemble fiber tissées coal.

24. Use of highly carbonaceous material according to any one of claims 19 to 23 for the manufacture of parts made of composite material of thermoplastic or thermosetting types.

25. Use of highly carbonaceous material according to any one of claims 19 to 23 for the manufacture of parts can be used as electrode in electrochemical processes.

26. Use of highly carbonaceous material according to any one of claims 19 to 23 for the manufacture of parts can be used as anode for cathodic protection.

27. Use of highly carbonaceous material according to any one of claims 19 to 23 for the manufacture of parts that can be used as an electrode for fuel cells.

28. Use of highly carbonaceous material according to any one of claims 19 to 23 for the manufacture of parts that can be used as an electrode member for primary and rechargeable batteries.

29. Use of highly carbonaceous material according to any one of claims 19 to 23 for the manufacture of parts that can be used as an electrical current collector for the anodes or cathodes of lithium or sodium.

30. Use of highly carbonaceous material according to any one of claims 19 to 23 for the manufacture of parts that can be used as an electrical current collector for Lithium-Sulfur

31. Use of highly carbonaceous material according to any one of claims 19 to 23 for the manufacture of parts that can be used as an electrical current collector for lithium-polymer batteries.

32. Use of highly carbonaceous material according to any one of claims 19 to 23 for the manufacture of parts that can be used as an electrode member for lead acid batteries, in particular for ultrabatteries the lead or lead atoms.

33. Use of highly carbonaceous material according to any one of claims 19 to 23 for the manufacture of parts that can be used as an electrode member for rechargeable lithium batteries.

34. Use of highly carbonaceous material according to any one of claims 19 to 23 for the manufacture of parts can be used as supercapacitor electrode element.

35. Use of highly carbonaceous material according to any one of claims 19 to 23 for the manufacture of parts that can be used as a catalyst support in particular for the purification of air.

36. Use of highly carbonaceous material according to any one of claims 19 to 23 for the manufacture of parts that can be used as a catalytic support for the lithium-air batteries.