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  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D161/00—Coating compositions based on condensation polymers of aldehydes or ketones; Coating compositions based on derivatives of such polymers
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  • C01B32/00—Carbon; Compounds thereof
  • C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
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  • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
  • C04B35/515—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics
  • C04B35/52—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbon, e.g. graphite
  • C04B35/524—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbon, e.g. graphite obtained from polymer precursors, e.g. glass-like carbon material
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  • C04B38/00—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof
  • C04B38/0022—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof obtained by a chemical conversion or reaction other than those relating to the setting or hardening of cement-like material or to the formation of a sol or a gel, e.g. by carbonising or pyrolysing preformed cellular materials based on polymers, organo-metallic or organo-silicon precursors
• • C—CHEMISTRY; METALLURGY
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  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
  • C08G73/02—Polyamines
  • C08G73/0206—Polyalkylene(poly)amines
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  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G8/00—Condensation polymers of aldehydes or ketones with phenols only
  • C08G8/04—Condensation polymers of aldehydes or ketones with phenols only of aldehydes
  • C08G8/08—Condensation polymers of aldehydes or ketones with phenols only of aldehydes of formaldehyde, e.g. of formaldehyde formed in situ
  • C08G8/20—Condensation polymers of aldehydes or ketones with phenols only of aldehydes of formaldehyde, e.g. of formaldehyde formed in situ with polyhydric phenols
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G8/00—Condensation polymers of aldehydes or ketones with phenols only
  • C08G8/04—Condensation polymers of aldehydes or ketones with phenols only of aldehydes
  • C08G8/08—Condensation polymers of aldehydes or ketones with phenols only of aldehydes of formaldehyde, e.g. of formaldehyde formed in situ
  • C08G8/20—Condensation polymers of aldehydes or ketones with phenols only of aldehydes of formaldehyde, e.g. of formaldehyde formed in situ with polyhydric phenols
  • C08G8/22—Resorcinol
• • C—CHEMISTRY; METALLURGY
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  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J3/00—Processes of treating or compounding macromolecular substances
  • C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
  • C08J3/03—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
  • C08J3/075—Macromolecular gels
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
  • C08J9/28—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by elimination of a liquid phase from a macromolecular composition or article, e.g. drying of coagulum
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
  • C08L61/04—Condensation polymers of aldehydes or ketones with phenols only
  • C08L61/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
  • C08L61/12—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols with polyhydric phenols
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
  • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
  • H01G11/04—Hybrid capacitors
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
  • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
  • H01G11/22—Electrodes
  • H01G11/26—Electrodes characterised by their structure, e.g. multi-layered, porosity or surface features
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
  • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
  • H01G11/22—Electrodes
  • H01G11/26—Electrodes characterised by their structure, e.g. multi-layered, porosity or surface features
  • H01G11/28—Electrodes characterised by their structure, e.g. multi-layered, porosity or surface features arranged or disposed on a current collector; Layers or phases between electrodes and current collectors, e.g. adhesives
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
  • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
  • H01G11/22—Electrodes
  • H01G11/30—Electrodes characterised by their material
  • H01G11/32—Carbon-based
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
  • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
  • H01G11/54—Electrolytes
  • H01G11/58—Liquid electrolytes
  • H01G11/62—Liquid electrolytes characterised by the solute, e.g. salts, anions or cations therein
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  • C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
  • C04B2111/00474—Uses not provided for elsewhere in C04B2111/00
  • C04B2111/00844—Uses not provided for elsewhere in C04B2111/00 for electronic applications
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  • C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
  • C04B2111/00474—Uses not provided for elsewhere in C04B2111/00
  • C04B2111/00853—Uses not provided for elsewhere in C04B2111/00 in electrochemical cells or batteries, e.g. fuel cells
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  • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
  • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
  • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
  • C04B2235/48—Organic compounds becoming part of a ceramic after heat treatment, e.g. carbonising phenol resins
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J2201/00—Foams characterised by the foaming process
  • C08J2201/04—Foams characterised by the foaming process characterised by the elimination of a liquid or solid component, e.g. precipitation, leaching out, evaporation
  • C08J2201/05—Elimination by evaporation or heat degradation of a liquid phase
  • C08J2201/0504—Elimination by evaporation or heat degradation of a liquid phase the liquid phase being aqueous
• • C—CHEMISTRY; METALLURGY
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  • C08J2205/00—Foams characterised by their properties
  • C08J2205/02—Foams characterised by their properties the finished foam itself being a gel or a gel being temporarily formed when processing the foamable composition
  • C08J2205/028—Xerogel, i.e. an air dried gel
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J2205/00—Foams characterised by their properties
  • C08J2205/04—Foams characterised by their properties characterised by the foam pores
  • C08J2205/042—Nanopores, i.e. the average diameter being smaller than 0,1 micrometer
• • C—CHEMISTRY; METALLURGY
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  • C08J2361/00—Characterised by the use of condensation polymers of aldehydes or ketones; Derivatives of such polymers
  • C08J2361/04—Condensation polymers of aldehydes or ketones with phenols only
  • C08J2361/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
  • C08J2361/12—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols with polyhydric phenols
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
  • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
  • Y02E60/13—Energy storage using capacitors

Definitions

• the present invention relates to a gelled and non-crosslinked carbonaceous composition and a pyrolyzed composition respectively forming an organic polymeric gel and its pyrolyzate in the form of porous carbon, their process of preparation, a porous carbon electrode constituted by this pyrolyzed composition and a supercapacitor incorporating such electrodes.
• the invention applies in particular to supercapacitors adapted to equip electric vehicles.
• Supercapacitors are electrical energy storage systems of particular interest for applications requiring the conveyance of high power electrical energy. Their ability to charge and discharge fast, their longer life compared to a high power battery make them promising candidates for many applications.
• Supercapacitors generally consist of the combination of two conductive porous electrodes with a high specific surface area, immersed in an ionic electrolyte and separated by an insulating membrane called "separator", which allows ionic conductivity and avoids electrical contact between the electrodes. Each electrode is in contact with a metal collector for the exchange of electric current with an external system.
• the stored energy E within a supercapacitor is defined according to the conventional expression of the capacitors, namely:
• Capacity and potential are therefore two essential parameters that need to be optimized to promote energy performance.
• the capacity depends on the porous texture actually accessible by the electrolyte.
• it is necessary to have a high energy density to limit the onboard weight of the supercapacitor
• the potential of a supercapacitor depends mainly on the nature of the electrolyte used, which can be organic or aqueous.
• US-B2-63556432, US-A1-2007/0146967 and US-B2-7811337 disclose the dispersion of conductive porous carbons in a non-active organic binder and a solvent, and then coating the paste obtained on the collector current. This method has the disadvantage of using a binder that weighs down the system without being active to store energy.
• a carbon monolith in an aqueous electrolyte, in order to maximize the specific energy of the this electrode.
• the carbon monolith is very thin, having a thickness of a few hundred micrometers only and usually less than or equal to 0.5 mm, while being robust enough not to be brittle and not deform at these very small thicknesses.
• RF resins are particularly interesting for the preparation of high porosity carbon in the form of a monolith, because they are very inexpensive, can be implemented in water and allow different porosities and densities to be obtained depending on the conditions. of preparation.
• the mixture of precursor resorcinol R and formaldehyde F in water having a very low viscosity can not be coated with a sufficiently small thickness, ie typically less than 1 mm, and instead of such coating on chooses to arrange the mixture of precursors R and F in a closed mold to form a gel after the polymerization reaction.
• a sufficiently small thickness ie typically less than 1 mm
• Another disadvantage of this method lies in the mesoporous structure obtained for the carbon which, in the case of a supercapacitor, is unfavorable compared to a predominantly microporous structure which is preferred for having a specific energy and a capacity high.
• the use of a large amount of surfactant is expensive.
• a major disadvantage of the irreversible chemical gels presented in this article lies in their very low viscosity which makes them completely unfit to be coated with a thickness of less than 2 mm.
• An object of the present invention is to provide a gelled and uncrosslinked carbonaceous composition and a pyrolyzed composition respectively forming an aqueous polymeric gel and a pyrolyzate of said gel crosslinked in the form of porous carbon, which overcomes the aforementioned drawbacks by allowing in particular to implement directly by coating a RF-type gel of small thickness, and with a fast drying.
• a gelled and non-crosslinked carbonaceous composition according to the invention is thus based on a resin derived at least in part from polyhydroxybenzene (s) R and from formaldehyde (s) F and comprises at least one water-soluble cationic polyelectrolyte P, and the composition is such that it forms in the gelled and uncrosslinked state (ie before the crosslinking of the gelled composition) a rheofluidifying physical gel.
• this composition comprises said precipitated prepolymer forming said rheofluidifying gel which is the product of a pre-polymerization reaction and of precipitation of an aqueous solution containing poly (R) polyhydroxybenzene (s), formaldehyde (s) F, said at least one cationic polyelectrolyte P and a catalyst C dissolved in an aqueous solvent W.
• gel in known manner the mixture of a colloidal material and a liquid, which is formed spontaneously or under the action of a catalyst by flocculation and coagulation of a colloidal solution.
• rheofluidifying gel means a gel with non-Newtonian and time-independent rheological behavior, sometimes also called pseudoplastic and which is characterized by the fact that its viscosity decreases when the gradient shear rate increases.
• water-soluble polymer is meant a polymer which can be solubilized in water without the addition of additives (surfactants in particular), unlike a water-dispersible polymer which is capable of forming a dispersion when it is mixed with some water.
• the composition according to the invention has the advantage, in the gelled and non-crosslinked state where it consists of said precipitated pre-polymer forming a rheofluidifying reversible gel, that it can be used in the form of a thin layer and to possess improved mechanical properties.
• This intermediate physical gel is thus sufficiently viscous to be coated or molded to thicknesses less than 2 mm, and then crosslinked and dried more easily and quickly than a conventional RF gel to give a porous xerogel according to the invention.
• the unmodified RF resins of the prior art formed directly from their liquid precursors an irreversible chemical gel which could not be coated as a thin layer and which deformed to a small thickness during the pyrolysis of the gel.
• said Applicant has in fact discovered that said cationic polyelectrolyte P has a coagulating effect and makes it possible to neutralize the charge of the phenolates of the polyhydroxybenzene R and thus to limit the repulsion between pre-polymer colloids, favoring the formation and agglomeration of polymeric nanoparticles with low conversion of the polycondensation reaction.
• the precipitation occurring before the crosslinking of the composition according to the invention the mechanical stresses are lower at high conversion when the gel is formed.
• the gelled composition of the invention can be dried more easily and quickly - by simple curing - than the aqueous gels of the prior art.
• This drying in an oven is indeed much simpler to implement and penalizes less the cost of production of the gel than the drying carried out by solvent exchange and supercritical CO2.
• the Applicant has demonstrated that the gelled and dried composition (i.e. xerogel) does not deform during its pyrolysis even at thicknesses less than 1 mm, unlike pyrolysed gels of the prior art.
• said at least one polyelectrolyte P makes it possible to maintain the high porosity of the gel after drying in an oven and to give it a low density combined with a specific surface area and a high pore volume, it being specified that this gel according to The invention is mainly microporous which advantageously allows to have a specific energy and a high capacity for a supercapacitor electrode consisting of this pyrolyzed gel.
• said product of the prepolymerization and precipitation reaction may comprise:
• said at least one cationic polyelectrolyte P in a mass fraction of between 0.5% and 5%, and / or
• said at least one cationic polyelectrolyte P and said polyhydroxybenzene (s) R in an R / P mass ratio of less than 50 and preferably of between 10 and 25, and / or Said polyhydroxybenzene (s) R and said aqueous solvent W in a mass ratio R / W of between 0.2 and 2 and preferably of between 0.3 and 1.3.
• Said at least one polyelectrolyte P that can be used in a composition according to the invention may be any cationic polyelectrolyte totally soluble in water and of low ionic strength.
• said at least one cationic polyelectrolyte P is an organic polymer selected from the group consisting of quaternary ammonium salts, polyvinylpyridinium chloride, polyethyleneimine, polyvinylpyridine, poly (allylamine hydrochloride), poly (trimethylammonium chloride ethyl methacrylate), poly (acrylamide-dimethylammonium chloride) and mixtures thereof.
• said at least one cationic polyelectrolyte P is a salt comprising units derived from a quaternary ammonium chosen from poly (diallyldimethylammonium halide), and is preferably poly (diallyldimethylammonium chloride) or poly (diallyldimethylammonium halide). diallyldimethylammonium bromide).
• polyhydroxybenzenes that may be used are preferably di- or tri-hydroxybenzenes, and advantageously resorcinol (1,3-dihydroxybenzene) or the mixture of resorcinol with another compound chosen from catechol, hydroquinone and phloroglucinol.
• polyhydroxybenzene (s) R and formaldehyde (s) F can be used in a molar ratio R / F of between 0.3 and 0.7.
• a composition according to the invention may have, in the gelled and non-crosslinked state, a viscosity measured at 25 ° C. by a Brookfield viscometer which, at a shear rate of 50 revolutions / minute, is greater than 100 mPa.s. and is preferably included between 150 mPa.s and 10000 mPa.s, it being specified that at 20 rpm, this viscosity is greater than 200 mPa.s and preferably greater than 250 mPa.s.
• the composition is capable of being coated in the gelled and uncrosslinked state with a coating thickness of less than 2 mm and preferably less than 1.5 mm.
• a pyrolyzed carbonaceous composition according to the invention consisting of a carbon monolith preferably predominantly microporous, is characterized in that it is the product of a coating, a crosslinking, a drying and then a pyrolysis a gelled and non-crosslinked composition as defined above, said carbon monolith being able to constitute a supercapacitor electrode with a thickness of less than 1 mm and preferably less than or equal to 0.5 mm.
• this essentially microporous structure obtainable according to the invention is defined by pore diameters of less than 2 nm, in contrast to mesoporous structures such as those obtained in the above-mentioned article which are by definition characterized by diameters of inclusively between 2 nm and 50 nm pores.
• said composition has in the pyrolyzed state:
• a specific surface greater than 400 m 2 / g, and / or
• a composition according to the invention is capable of constituting in the pyrolyzed state a supercapacitor electrode with a thickness of less than 1 mm and preferably less than or equal to 0.5 mm.
• a method of preparation according to the invention of a carbonaceous composition as defined above comprises:
• said at least one cationic polyelectrolyte P in a mass fraction of between 0.5% and 5%;
• step b) is carried out in a reactor, for example immersed in an oil bath at between 50 and 70 ° C.
• catalyst usable in step a mention may be made for example of acidic catalysts such as aqueous solutions of hydrochloric acid, sulfuric acid, nitric acid, acetic acid, phosphoric acid, trifluoroacetic acid, trifluoromethanesulfonic acid, perchloric acid, oxalic acid, toluenesulfonic acid or dichloroacetic acid, or basic catalysts such as sodium carbonate, sodium hydrogencarbonate, potassium carbonate, ammonium carbonate, lithium carbonate, ammonia, potassium hydroxide and sodium hydroxide. sodium.
• this process for preparing the gelled and pyrolyzed composition according to the invention has the advantage of being simple and inexpensive to implement, in order to obtain a advantageously monolithic and essentially microporous carbon which makes it possible to obtain by coating thin flat plates.
• a porous carbon electrode according to the invention can be used to equip a supercapacitor cell by being immersed in an aqueous ionic electrolyte and covers a metal current collector, and this electrode is such that it consists of a carbon-based composition. pyrolyzed state as defined above and that it has a thickness of less than 1 mm and preferably less than or equal to 0.5 mm.
• a supercapacitor according to the invention comprises cells each comprising at least two porous electrodes, an electrically insulating membrane separating these electrodes from each other and an ionic electrolyte in which these electrodes are immersed, each cell comprising at least two collectors of respectively covered current of these electrodes, and this supercapacitor is such that at least one of these electrodes is as defined above.
• the single figure is a graph showing the evolution of the viscosity (in mPa.s) of a gelled and uncrosslinked composition G2 according to the invention and of a gelled and non-crosslinked GO "control" composition, measured at 25 ° C. C depending on the shear rate of a Brookfield viscometer.
• control G0 gelled composition consisting of a resorcinol R gel and of formaldehyde F was prepared by rigorously following the experimental protocol described in the aforementioned article of the prior art "A novel way to maintain resorcinol-formaldehyde porosity during drying: Stabilization of the sol-gel nanostructure using a cationic polyelectrolyte, Mariano M.
• R / P mass ratio between resorcinol and polyelectrolyte
• a prepolymerization of each aqueous solution thus obtained was carried out in a reactor immersed in an oil bath between 50 ° C. and 70 ° C. until precipitation of the prepolymer obtained after a reaction time of depending on the case from 5 minutes to 1 hour, to form an intermediate white gel of rheofluidifying nature, homogeneous and reversible.
• the viscosity of each rheofluidifying gel obtained using a Brookfield viscometer was measured at 25 ° C., and this viscosity was between about 200 mPa.s and 7100 mPa.s at a shear rate of 50 rpm. for compositions G1 to G4.
• control compositions G0 'and G0 were irreversibly crosslinked with a sudden jump in viscosity, without intermediate formation of rheofluidifying gel, unlike the compositions
• G1 to G4 gels exhibited polymer particle sizes of the order of 100 nm, measured by dynamic light scattering using a "zetasizer nano ZS, Malvern” device.
• compositions G1 and G4 were then film-coated using
• compositions G0 'and G0 were placed in Teflon® coated steel molds in a wet thickness of 2 mm. It will be noted that these gels G0 'and G0 "can be used only in a mold because they are not suitable for being coated. Subsequently, the coated gel compositions G1 to G4 were crosslinked in a humid oven at 90 ° C. for 24 hours. The gelled and crosslinked compositions thus obtained were then dried at 85 ° C. and 85% humidity for 6 hours.
• Planar monoliths which are considered useful for forming electrodes have been machined to fixed thickness and have been characterized by measuring the density of the carbons by the mass / volume ratio of the monolith, the specific surfaces and the porous volumes by means of TRISTAR 3020 from icromeritics.
• Surface area 640 640 630 715 650 680 specific (m 2 .g ⁇ 1 ) including, including, of which, of which portions 555 500 450 560 430 450 micro- and mesomicro micro micro micro micro micro porous 85 140 180 155 220 230 meso meso meso meso meso meso meso meso
• the Applicant has furthermore compared the rheofluidifying gels obtained for the gelled compositions G1-G4 of the invention to compositions not in accordance with the invention differing by the addition of various shear-thinning polymers in the gels obtained with the compositions G0 '. Whatever the rheofluidifying agent thus incorporated into these gels, this has each time led to a breakage of the monoliths subsequently obtained by pyrolysis of these gels.
• Electrochemical capacitance of the electrodes has been characterized, using the following device and electrochemical tests.
• Two identical electrodes isolated by a separator were placed in series in a supercapacitor measuring cell containing the aqueous electrolyte based on sulfuric acid (H 2 SO 4 1 M) and controlled by a potentiostat / galvanostat.
• Bio-Logic VMP3 "via a three-electrode interface. A first electrode corresponded to the working electrode and the second electrode constituted both the counter electrode and the reference.

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