PROCESS FOR PREPARING A COMPOSITE ELECTRODE

专利摘要:
The invention relates to a method for preparing a composite electrode comprising a composite material deposited on a current collector, in particular on a flexible flexible collector, said composite electrode, its uses and an electrochemical storage system comprising such a composite electrode.
公开号:FR3038145A1
申请号:FR1555771
申请日:2015-06-23
公开日:2016-12-30
发明作者:Laurence Athouel；Thierry Brousse；Gregory Pognon
申请人:Centre National de la Recherche Scientifique CNRS；Universite de Nantes；
IPC主号:

专利说明:

[0001] The invention relates to a process for preparing a composite electrode comprising a composite material deposited on a current collector, in particular on a flexible and flexible collector, said composite electrode, its uses and an electrochemical storage system comprising such a composite electrode. . Existing electrochemical storage devices include fuel cells, batteries, supercapacitors and capacitors. The batteries are characterized by a high density of energy, to ensure the power supply of an electrical system over time, but suffer from a moderate power, while the capacitors have a very low energy density, but retain the advantage of great power. As opposed to batteries, the capacitors cyclically deliver very large powers but the associated energy density is very low. As an example of electrochemical batteries, we can mention the lithium-ion technology that already equips many new generation vehicles. Supercapacitors with lower capacities are used as energy converters. They are already used in the means of transport or lifting to convert the kinetic or potential energy into electrical energy. They also equip electric / hybrid vehicles where they are used to recover braking energy, in addition to a battery or fuel cell. At least one of the electrodes used in these electrochemical storage devices generally consists of a film or a paste of composite material deposited on a metal current collector, said composite material comprising at least one electrode active material, optionally a material generating an electronic conduction and optionally a polymeric binder. The electrode active substance is used in the form of particles, and it may be, for example, a transition metal oxide (eg MnO 2, Fe 3 O 4), in particular with a spinel or lamellar structure (eg oxides corresponding to the formula LiMPO 4 in which M represents at least one element selected from Mn, Fe, Co and Ni, in particular LiFePO4) or an activated carbon, in particular nanoporous carbon. The material generating an electronic conductivity is generally carbon, in the form of carbon black powder, graphite powder, carbon fiber or carbon nanofiber. The polymeric binder used is generally hydrophobic such as polyvinylidene fluoride (PVdF) or polytetrafluoroethylene (PTFE). The film or paste of composite material deposited on a metal current collector is generally prepared by coating, on a current collector, an ink comprising the electrode active material, the electron conduction generating material and the polymeric binder. The adhesion between the various constituents is therefore essentially mechanical and it only allows the coating of small amounts of active material (ie from a few hundred dag to a few mg per cm 2), while leading to a low mechanical strength of the film or dough on the current collector during deformation, or even zero hold when the current collector is a flexible or flexible material, such as a textile material, a carbon fabric or a glass fabric. The poor adhesion of the active material within the composite electrode also leads to a deterioration of electrochemical performance, particularly in terms of stability to cycling. In addition, the active material within the electrode obtained has an ionic and electronic accessibility to the limited aqueous or organic polar liquid electrolyte, especially when it is present in large quantities. In order to improve the performance of electrochemical storage systems, many research teams have focused on the preparation of new electrode materials and / or the synthesis or formulation of new electrolytes.
[0002] In particular, EP 2 417 657 B1 discloses a process for preparing a composite electrode comprising a mixture of functionalized functionalized material particles and functionalized electronic conductivity generating material particles, said mixture being supported by a collector metal stream optionally functionalized. The method comprises steps of functionalizing the particles of active material and particles of material generating an electronic conductivity by appropriate chemical groups, so that said particles can bind together covalently or electrostatically, and optionally a step of functionalizing the metal current collector with appropriate chemical groups so that the active material particles can be covalently or electrostatically bonded to the metal current collector. The functionalization of the material generating an electronic conductivity can be carried out by in situ formation of a diazonium salt R1-N-EN.Xcomprising a positively charged azo -1 1 + 1 1 function associated with an X-charged counter anion. negatively, said azo function being capable of being reduced quite easily, and leading to the formation of a very reactive aryl radical R ''. This radical R1 'can then be grafted by covalent bonding on said material generating an electronic conductivity. The diazonium salts can be obtained from aromatic amines having, in the para position of the amine function, numerous functional groups (-CO 2 H, -NO 2, -Br, -OH). They can also allow the functionalization of the metal current collector. By way of example, a mixture of carbon fibers and carbon nanotubes as a material generating electronic conductivity is functionalized by -Ph-CH 2 -CO 2 H groups from 4-amino-phenyl acid. acetic as aromatic amine. In addition, titanium oxide as the electrode active material is functionalized with -OO 2 -CH 2 -PN-NH 2 groups. Then, the particles of active material and of material generating an electronic conductivity are brought into contact in the presence of a coupling agent such as 4- (4,6-dimethoxy-1,3,5-triazin-2- yI) -4-methylmorpholinium (DMTMM) to bind said particles covalently (via formation of an amide function). The electrochemical performances of the composite electrode obtained are not described. Furthermore, the functionalization of the active ingredient can induce a decrease in the amount of available active material in order to ensure ionic and electronic exchanges within the electrochemical storage device and a modification of its physical properties (eg its wettability, its adhesion to a polymeric binder, its extrusionability, etc ...). The electrochemical performances of said device are therefore not optimized.
[0003] Moreover, the surface modification of a carbonaceous agent, in particular of carbon nanotubes, by any type of hydrophobic or hydrophilic polymer has been extensively studied in order to allow its homogeneous dispersion and / or its solubilization in various liquid media and thus making nanocomposite films. One of the most commonly used methods is to functionalize a carbonaceous agent (e.g., carbon nanotubes) with a polymerization initiator (e.g., α-bromoisobutyryl bromide), and then perform the polymerization (e.g. poly (methyl methacrylate)). This method makes it possible to obtain a high degree of grafting. However, the control of the molar mass of the graft polymer is difficult, the choice of the graftable polymers is limited and by-products may be formed, especially when the polymerization is radical. Another method is to first form the polymer, then in a second time to graft on the carbonaceous agent "bare" or previously oxidized surface (e.g. acid treatment). This method allows the total control of the molar mass of the graft polymer. However, it generally leads to very low grafting rates (less than 1%), particularly related to the steric hindrance of the polymer chains and / or the low reactivity of the carbonaceous agent previously oxidized on the surface. In addition, this method implements relatively severe reaction conditions (high temperatures and / or long reaction times) which may be incompatible with the molecules which are to be grafted onto the carbonaceous agent. For example, Lin et al. [Macromolecules, 2003, 36, 19, 7199-7204] have described the functionalization of acid-treated carbon nanotubes in order to present carboxylic functions on the surface, with polyvinyl alcohol (PVA) by a reaction of esterification. Films of about 50 to 200 amps thick were obtained by mixing the solution of functionalized carbon nanotubes with PVA in a viscous matrix of pure PVA. However, the presence of the ester functions has not been detected by carbon NMR, the degree of grafting is low (ie about 4%) and the content of the carbon nanotube film is not sufficient (0.1- 3% by weight) to ensure good electronic conduction.
[0004] Other more promising methods involve the addition of polymer radicals or anionic polymers on the surface of a carbonaceous agent comprising Tt (carbon nanotube) bonds since they avoid the prior functionalization of the carbonaceous surface.
[0005] The object of the present invention is to overcome the disadvantages of the aforementioned prior art and to provide a simple and economical method of preparing a composite electrode comprising a composite material deposited on a current collector (ie supported composite electrode). said method for immobilizing small or large amounts of active material in pulverulent form within the composite electrode, while optimizing its ionic and electronic accessibility and its mechanical strength, especially when the electrode is used in a device electrochemical storage. Another object of the invention is to provide a composite electrode 15 having improved mechanical strength, while ensuring good electrochemical performance, particularly in terms of cycling stability and specific capacity. These objects are achieved by the invention which will be described below. The invention therefore firstly relates to a process for preparing a composite electrode comprising a composite material deposited on an optionally functionalized DC current collector, said process comprising: 1) a step of functionalization of an EC carbonaceous agent with any of the following functional groups L: carboxylic acid [-CO 2 M], acyl halide [-COX], acid anhydride [-C (= O) 0 C (= O) -], sulfonic acid [-SO 2 (OM)], sulfonic acid halide [-SO2X], phosphonic acid halide [-PDX2], phosphonic acid monoester halide [-PDX (OR)], phosphonic acid monoester [-PO (OR) ) (OM)], phosphonic acid diester [-PO (OR) 2] or isocyanate [-N = C = O], with X representing a chlorine atom or a bromine atom, M representing a proton, a alkali metal cation or an organic cation and R representing a methyl or ethyl group, to form a functionalized carbonaceous agent CE-f, and said process characterized in that it further comprises the following steps: 2) a step of preparing an aqueous or organic paste comprising the functionalized carbonaceous agent CE-f of step 1), at least one active ingredient MA and at least one hydrophilic polymer PH comprising several alcohol functions, and 3) a step comprising contacting the aqueous or organic paste with an optionally functionalized DC-current collector and the thermal treatment of the aqueous or organic paste and the DC current collector possibly functionalized, in order to form a composite electrode comprising a composite material deposited on said DC current collector, it being understood that: * said optionally functionalized DC current collector has a surface resistance of less than or equal to about 50 ohms for 1 cm2 of surface (ie less than or equal to 50 ohms / square centimeter or approximately Q / cm 2), and said composite material comprises a functionalized carbonaceous agent CE-f, at least one active material MA and at least one crosslinked hydrophilic polymer PH-r comprising several functions alcohol and several ester functions selected from carboxylic acid esters, phosphonic acid esters, sulfonic acid esters and carbamates, said crosslinked hydrophilic polymer PH-r being covalently bound to the functionalized carbonaceous agent CE-f through said ester functions. The hydrophilic polymer PH may further comprise several hydrophilic functions different from the alcohol functions. The hydrophilic functions different from the alcohol functions can be chosen from carboxylic acid, amine, ketone and a mixture thereof.
[0006] Thanks to the method of the invention, the active ingredient MA is immobilized within the composite electrode. In particular, the MA is maintained within the composite material by virtue of the formation of numerous covalent bonds between the functionalized carbonaceous agent CE-f and the crosslinked hydrophilic polymer PH-r.
[0007] Said composite material therefore represents a hybrid carbon-polymer matrix ensuring the homogeneous distribution and maintenance of the active material which may be in the form of nanometric and / or micrometric particles. In addition, the method makes it possible to deposit an active ingredient MA on a flexible or rigid DC current collector having a large surface area (several hundreds of cm 2 approximately) and / or in the form of a relatively thick film (ie 50 about 1 mm). Therefore, any active material MA initially in the form of powder can thus be deposited on the DC current collector in large quantities and in a reproducible manner, while guaranteeing good accessibility both electronically and ionically, good mechanical strength of the Composite electrode, as well as good electrochemical performance, especially in aqueous medium and in polar organic medium. In addition, when the current collector is functionalized, a true anchoring of the carbon-polymer hybrid matrix comprising the MA electrode active material, on the surface of the DC collector is then obtained through the presence of additional covalent bonds between the functionalized current collector CC-f and the crosslinked hydrophilic polymer PH-r of the composite material. Step 1): Preparation of the functionalized carbon agent The carbonaceous agent CE used in step 1) acts as an agent generating electronic conduction in the composite material. The carbonaceous agent CE may be selected from carbon black, graphite, graphene, SP carbon, acetylene black, vitreous carbon, carbon nanotubes, carbon fibers, carbon nanofibers and the like. one of their mixtures. Carbon nanofibers are preferred.
[0008] In the present invention, the carbon nanotubes comprise both single-walled nanotubes (single wall carbon nanotubes, SWNTs) comprising a single sheet of graphene and multiwall or multiwall nanotubes (in English: Multi Wall Carbon 5). Nanotubes, MWNT) comprising several layers of graphene interlocked into each other in the manner of Russian dolls, or a single sheet of graphene rolled up several times on itself. In a particular embodiment, the carbon nanotubes have a mean diameter ranging from 1 to about 50 nm.
[0009] Carbon fibers are materials comprising very fine fibers of about 5 to 15 μm in diameter, of which carbon is the main chemical element. Other atoms are usually present such as oxygen, nitrogen, hydrogen, and less often sulfur. The carbon atoms are bonded together and form graphitic type crystals more or less parallel to the axis of the fiber. Carbon nanofibers (or carbon fibrils or carbon nanowires) consist of more or less organized graphitic zones (or turbostratic stacks) whose planes are inclined at variable angles with respect to the axis of the fiber. These stacks may take the form of platelets, fish bones or stacked cups to form structures generally ranging in diameter from about 100 nm to about 500 nm or more. As an example of carbon nanofibers, mention may be made of vapor phase growth carbon fibers (VGCF), in particular those having a diameter of about 100 nm and a length ranging from about 20 to 200 μm. When M is an organic cation in the functional groups L, it may be chosen from oxonium, ammonium, quaternary ammonium, amidinium, guanidinium, pyridinium, morpholinium, pyrrolidionium, imidazolium, imidazolinium, triazolium, sulfonium, phosphonium, iodonium and carbonium groups. . When M is an alkali metal cation in functional groups L, it is preferably lithium, sodium or potassium. According to a first variant of step 1), the functional group L as defined in the invention is directly grafted onto the carbonaceous agent CE. This variant is particularly suitable when the functional group L is any of the following groups: -CO 2 M, -SO 2 (OM) or -PO (OM) 2. Step 1) can be carried out by controlled oxidation of CE when L is -CO2M, by reaction of CE with SO3 when L is -503M or by reaction of CE with PCI3 followed by hydrolysis when L is -PO (0M) 2.
[0010] In particular, the grafting of the -CO 2 M functional group can be carried out by one of the following methods: - oxidation of EC with CO2 at a temperature of about 500 ° C.-900 ° C., or - treatment of CE by cold plasma under CO2.
[0011] According to a second variant of step 1), the functional group L as defined in the invention is grafted onto the carbonaceous agent CE via a compound bearing said functional group. In particular, the grafting of the -CO2M functional group may be carried out by one of the following methods: - diazotization of CE with a compound bearing a -CO2H group, - reaction of CE with maleic anhydride, followed by hydrolysis ; - Diels-Alder addition reaction of CE with an acid containing an unsaturated bond -C = C- or -CEC-, for example with fumaric acid or acetylene dicarboxylic acid (HCO2-CEC-CO2H); or - addition reaction with a compound bearing a -CO2H group such as a disulfide, a benzotriazole (e.g., benzotriazole-5-carboxylic acid) or an azo compound (e.g., azobenzene-4-carboxylic acid). In the -CO2H functional group, the hydrogen atom can then be replaced by cation exchange processes within the skill of the art to lead to the -CO2M functional group.
[0012] The grafting of the -SO 3 M functional group can be carried out by one of the following methods: EC reaction with a disulfide bearing two terminal -SO 3 M groups (e.g. LiSO 3 -Ph-S-S-Ph-SO 3 Li); reaction of CE with a benzotriazole bearing a -SO 3 H group (e.g., 8- (1-benzotriazolyl) -butanesulfonic acid); addition reaction with an azo compound bearing alkali metal sulfonate groups (e.g. (8Z) -7-oxo-8- (phenylhydrazinylidene) also known as "orange G"); or 15 - diazotization of CE with a compound bearing a -SO3H group. The grafting of the phosphonate functional group may be carried out by reactions similar to those used for the grafting of the sulphonate group, in particular by using precursors bearing phosphonate groups in the place of the sulphonate groups (benzotriazole, azo, -C = C-, -CEC-, diazonium). Stage 1) of functionalization makes it possible to introduce into the starting carbonaceous agent CE the functional groups L as defined in the invention. These functional groups L are then capable of reacting with at least a portion of the alcohol functions of a hydrophilic polymer PH comprising several alcohol functions in order to form covalent bonds via ester functions (eg carboxylic acid esters, acid esters phosphonic acid, sulfonic acid esters or carbamates). The formation of these covalent bonds leads to the crosslinking of the starting hydrophilic polymer PH and thus to the formation of a hydrophilic polymer PH-r (crosslinked hydrophilic polymer PH) comprising several alcohol functions and several ester functional groups chosen from among the esters. carboxylic acids, phosphonic acid esters, sulphonic acid esters and carbamates. According to a particularly preferred embodiment of the invention, the carbonaceous agent CE is functionalized in step 1) using a TXL reagent, in which: the group T is a functional group capable of react with CE to form a covalent bond or precursor functional group of a functional group capable of reacting with CE to form a covalent bond; the group X is a conjugated spacer group, that is to say a group which comprises a system of atoms linked by a covalent bond with at least one delocalized Tt bond; the group L is as defined in the invention. The conjugated spacer group X may be an aryl group, ie an optionally substituted aromatic or heteroaromatic, mono- or polycyclic group having 5 to 20 carbon atoms, especially 5 to 14 carbon atoms, in particular 6 to 8 carbon atoms. The heteroatom (s) likely to be present in the aryl group is (are) advantageously chosen from the group consisting of N, O and Pou S.
[0013] In the case of a polycyclic aromatic or heteroaromatic group, each ring may comprise from 3 to 8 carbon atoms. The spacer group X may also be a divalent group chosen from phenylene, oligophenylene, oligophenylenevinylene, oligophenyleneethynylene, oligothiophene and azo benzene groups.
[0014] The T group of a T-X-L reagent depends on the chemical nature of the EC carbonaceous agent to be modified in step 1). The T-X-L reagent may be a diazonium salt or a precursor of a diazonium salt. In the case where the T-X-L reagent is a diazonium salt, T is a diazonium cation. The counterion may be, for example, a BF4- or Cl- anion.
[0015] The reaction of the carbonaceous agent CE with an TXL reagent in which T is a diazonium cation is preferably carried out chemically, in particular in solution in acetonitrile or in water at pH 2, said solution containing 2 about 50 mM diazonium salt.
[0016] In particular, an TXL reagent in which T is a diazonium cation can be produced in situ from an NH2-XL precursor by addition of a nitrosating agent such as tert-butyl nitrite [(CH 3) 3 CONO or tBu-NO2] in organic medium (eg acetonitrile) or sodium nitrite (NaNO2) in acidic medium (eg medium at pH 1).
[0017] Generally, the nitrosation agent / NH 2 -X-L precursor molar ratio ranges from about 1 to about 5 and the NH 2 -X-L precursor / carbonaceous agent CE molar ratio ranges from about 0.1 to about 0.5. Then, formation of the X-L radical, derived from the T-X-L diazonium salt can be induced in several ways: spontaneously, by UV or microwave radiation, ultrasound, heat treatment or electrochemistry. The reaction of the carbonaceous agent CE with an TXL reagent in which T is a diazonium cation can also be carried out electrochemically in a cell with three electrodes, at a potential of less than 0 V vs SCE (calomel electrode saturated with KCl) wherein the electrolyte is a deaerated solution of 0.1 M NEt4BF4 or NBu4BF4 in acetonitrile, said solution containing from about 0.1 to about 50 mM of diazonium salt. T-X-L is preferably such that L is -CO2H or -CO2M and T is -NI-I2 (precursor functional group of the N2 + diazonium cation). In particular, the TXL reagent can meet one of the following formulas: ## STR1 ## ## STR2 ## Preparation of the aqueous or organic paste The active ingredient MA can be any type of material active electrode in powder form.
[0018] It may be in the form of micrometric and / or nanometric particles, especially in the form of particles having a size ranging from about 10 nm to about 10 μm. The active material may be a positive electrode active material or a negative electrode active material.
[0019] It is advantageously chosen from oxides, phosphates, borates, activated carbons, graphite, graphene and metal alloys of the LiyM type in which 1 <y <5 and M = Mn, Sn, Pb, Si, In or Ti. By way of examples of oxides, mention may be made of the simple oxides MnO 2, Fe 3 O 4, the complex oxides L 1 MnO 4 where 0 <x <2, 0 <y <2 and x + y = 3, LiCoO 2, LiAlxCoyNi, O 2 in where 0 <x <1, 0 <y <1, 0 <z <1 and x + y + z = 1, LiNi (i_y) Coy02in which 0y <1, oxides derived from lithium titanates by partial replacement of Li or of Ti. As examples of phosphates, mention may be made of lithium phosphates and of at least one transition metal preferably chosen from Fe, Mn, Ni and Co such as LiMPO4 in which M is Fe, Mn, Co or Ni . By way of examples of borates, mention may be made of Li borates and of at least one transition metal preferably chosen from Fe, Mn and Co. Activated carbons generally have a specific surface area ranging from about 200 m 2 / g to 3000 m2 / g approximately.
[0020] The amount of active material that can be deposited can be from about 1 to about 25 mg per cm 2 of collector area, and preferably from about 5 to about 20 mg per cm 2 of collector area. The hydrophilic polymer PH comprising several alcohol functions may have a molar mass ranging from about 5000 g / mol to about 300,000 g / mol, and preferably from about 10,000 g / mol to about 30,000 g / mol. The hydrophilic polymer PH comprising several alcohol functions may be chosen from polysaccharides, oligosaccharides and synthetic polymers comprising recurring units [-CH 2 -CH (OH) -], with 10 n ranging from 100 to 7000 approximately. As examples of polysaccharides, there may be mentioned cellulose, pectins, starch, glucoses, inulins, alginates, gelatins, dextrins, agar-agar, glycogen, chitin, and their derivatives. As examples of synthetic polymers, mention may be made of polyvinyl alcohol, copolymers of vinyl alcohol such as copolymers of vinyl alcohol and of acrylic acid, copolymers of vinyl alcohol and of methacrylic acid, copolymers of vinyl alcohol and maleic acid, copolymers of vinyl alcohol and vinyl ester. Synthetic polymers are preferred, especially polyvinyl alcohol. The paste of step 2) is preferably an aqueous paste. In a particular embodiment, step 2) is carried out according to the following substeps: 2-i) the preparation of an aqueous or organic solution comprising from 0.5% to 30% by weight approximately, and preferably from 0.5% to 15% by weight of hydrophilic polymer PH, 2-ii) the preparation of an aqueous or organic suspension comprising from 0.1% to 10% by weight, and preferably 0.5 about 5 to about 5% by weight of MA; and from about 0.1% to about 5% by weight, and preferably from about 0.1% to about 1.5% by weight of CE-f, the mixture of the aqueous or organic suspension of sub-step 2-ii) with the aqueous or organic solution of sub-step 2-i), and 2-iv) maintaining the resulting suspension at room temperature or heating, to obtain an aqueous paste or organic. When the solution of sub-step 2-i) is an organic solution, it preferably comprises from 0.5% to 5% by weight of hydrophilic polymer PH. When the solution of sub-step 2-i) is an aqueous solution, it preferably comprises from about 5% to about 15% by weight of hydrophilic polymer PH. The solution of sub-step 2-i) is preferably an aqueous solution. The sub-step 2-i) can be carried out with stirring and / or heating the aqueous or organic solution, in order to dissolve the hydrophilic polymer PH in said aqueous or organic solution. The heating of sub-step 2-i) can be carried out at a temperature ranging from about 20 ° C to 90 ° C. The suspension of the sub-step 2-ii) is preferably an aqueous suspension. The sub-step 2-ii) can be carried out by firstly dispersing the MA, in particular using ultrasound, and then dispersing the EC-f in a second step, in particular using ultrasound. Sub-step 2-iii) is preferably carried out by gradually adding the aqueous or organic solution of sub-step 2-i) to the aqueous or organic suspension of sub-step 2-ii) with stirring. The sub-step 2-iv) of maintenance or heating can last from 12 to about 48 hours. Sub-step 2-iv) is generally carried out with stirring.
[0021] The heating of sub-step 2-iv) can be carried out at a temperature ranging from about 70 ° C to 90 ° C, and preferably from about 75 ° C to 85 ° C. In a preferred embodiment, substep 2-iv) is a heating step. This sub-step 2-iv) makes it possible to evaporate a part of the liquid (water or organic solvent) from the aqueous or organic solution, in order to obtain the aqueous or organic paste with a viscosity suitable for performing step 3). In the present invention, the solvent of the "aqueous solution" or "aqueous suspension" comprises at least about 80% by volume of water, and preferably at least about 90% by volume of water, based on total volume of the solution. In the present invention, the solvent of the "organic solution" or "organic suspension" comprises at least about 80% by volume of about 15% organic solvent, and preferably at least about 90% by volume of organic solvent, based on total volume of the solution. The organic solvent may be chosen from cyclohexane and toluene. The solvent of the aqueous solution (respectively of the aqueous suspension) is advantageously only water, distilled water or ultrapure distilled water. According to a preferred embodiment of the invention, the solution and the suspension of substeps 2-i) and 2-ii) are aqueous and step 2) thus makes it possible to prepare an aqueous paste.
[0022] Step 3) The DC current collector may be selected from a metallic material, a carbonaceous material, a silicon-based material, a textile material, a metal material modified with a carbon layer, transition metal nitride or conductive polymer (eg polyaniline, polypyrrole, polythiophene) and a material consisting of a composite polymer layer and a layer of carbonaceous material. As examples of metallic material, mention may be made of stainless steel, aluminum, iron, copper, gold, nickel or one of the alloys of the abovementioned metals.
[0023] Examples of carbonaceous material include glassy carbon, graphite or carbon fibers, especially in the form of unidirectional fabric, canvas, taffeta, twill, paper or satin. Examples of silicon-based materials that may be mentioned are polycrystalline, monocrystalline or amorphous silicon, glass or glass fibers, in particular in the form of a unidirectional type fabric, a fabric, a taffeta, a twill, paper or satin. Examples of textile material include all types of unidirectional type fabric, canvas, taffeta, twill, paper or satin.
[0024] The current collector may be porous (e.g. grid, fibers, or more interlocking grids) or non-porous. DC can be flexible (i.e., flexible) or rigid. It may be in the form of a plate, sheet, unidirectional type fabric, canvas, taffeta, twill, paper or satin. The choice of the material used for the DC will depend on the intended application. In order to obtain a flexible composite electrode, a carbonaceous material such as carbon fibers, especially in the form of a fabric, as CC is preferred. To improve the mechanical strength of the composite electrode while ensuring good flexibility, a material consisting of a composite polymer layer and a layer of carbonaceous material can be used as DC. In this case, the electrode composite material will of course be applied to the layer of carbonaceous material.
[0025] The composite polymer may comprise an insulating polymer and a metal (e.g., metal powder). The insulating polymer may be selected from polyurethane, unsaturated polyester and an epoxy resin.
[0026] The metal may be selected from nickel, gold, aluminum and platinum. The carbonaceous material may be as defined above, and preferably carbon fibers, especially in the form of a fabric. According to a particularly preferred embodiment of the invention, the CC is functionalized.
[0027] In this case, the method then further comprises an additional step prior to step 3), during which the CC is functionalized to form a CC-f functionalized current collector. When the DC is functionalized to form a CC-f functionalized current collector, said cross-linked hydrophilic polymer PH-r of the composite material is also covalently bonded to CC-f through said ester functions selected from carboxylic acids, phosphonic acid esters, sulfonic acid esters and carbamates. When the current collector is a carbon material or a metal material modified by a carbon layer or a material consisting of a layer of composite polymer and a layer of carbon material, the functionalization methods as described in the invention to conduct to the functionalized carbonaceous agent CE-f can also be used.
[0028] In particular, the CC (carbonaceous surface or carbon portion of the CC) can be functionalized using a T'-X'-L 'reagent, in which: the group T' is a functional group capable of reacting with CC to form a covalent bond or precursor functional group of a functional group capable of reacting with CC to form a covalent bond; The group X 'is a conjugated spacer group, that is to say a group which comprises a system of atoms linked by a covalent bond with at least one delocalized Tt bond; the group L 'is chosen from the following functional groups: carboxylic acid [-CO2M], acyl halide [-COX], acid anhydride [-C (= O) 0C (= O) -], acid sulfonic acid [-SO2 (OM)], sulfonic acid halide [-SO2X], phosphonic acid halide [-PDX2], phosphonic acid monoester halide [-PDX (OR)], phosphonic acid monoester [ -PO (OR) (OM)], phosphonic acid diester [-PO (OR) 2] or isocyanate [-N = C = O], with X, M and R being as defined in the invention. The conjugated spacer group X 'may be an aryl group, ie an optionally substituted aromatic or heteroaromatic, mono- or polycyclic group having from 5 to 20 carbon atoms, especially from 5 to 14 carbon atoms, in particular from 6 to to 8 carbon atoms.
[0029] The heteroatom (s) likely to be present in the aryl group is (are) advantageously chosen from the group consisting of N, O and Pou S. In the case of a polycyclic aromatic or heteroaromatic group, each ring may comprise from 3 to 8 carbon atoms.
[0030] The spacer group X 'may also be a divalent group selected from phenylene, oligophenylene, oligophenylenevinylene, oligophenyleneethynylene, oligothiophene and azo benzene. The group T 'of a reagent T'-X'-L' depends on the chemical nature of the CC that must be modified.
[0031] The T'-X'-L 'reagent may be a diazonium salt or a precursor of a diazonium salt. In the case where the T'-X'-L 'reagent is a diazonium salt, T' is a diazonium cation. The counter ion may be for example a BF4 anion or CI-. The reaction of the current collector CC with a reagent T'-X'-L 'in which T' is a diazonium cation is preferably carried out chemically, especially in solution in acetonitrile or in water. pH 2, said solution containing from 2 to about 50 mM of diazonium salt. In particular, a T'-X'-L 'reagent in which T' is a diazonium cation can be produced in situ from an NH 2 -X'-L 'precursor by the addition of a nitrosating agent such as tert-butyl nitrite [(CH3) 3CONO or tBu-NO2] in an organic medium (eg acetonitrile) or sodium nitrite (NaNO2) in an acidic medium (eg pH 1 medium). Generally, the nitrosation agent / NH 2 -X'-L 'precursor molar ratio ranges from about 1 to about 5 and the NH 2 -X'-L' / CC precursor molar ratio ranges from about 0.005 to about 1. Then, the formation of the radical * X-L ', resulting from the diazonium salt T'-X'-L' can be induced in several ways: spontaneously, by UV or microwave radiation, by ultrasound, by heat treatment or by electrochemistry. The reaction of the current collector CC with a reagent T'-X'-L 'in which T' is a diazonium cation can also be carried out electrochemically in a cell with three electrodes at a potential less than 0 V vs SCE (KIC-saturated calomel electrode), wherein the electrolyte is a deaerated solution of 0.1 M NEt4BF4 or NBu4BF4 in acetonitrile, said solution containing from 0.1 to 50 mM diazonium salt.
[0032] When the DC is made of stainless steel or aluminum, the electrochemical path is indispensable. T'-X'-L 'is preferably such that L' is -CO2H or -CO2M and T 'is -NI-I2 (precursor functional group of the diazonium cation N2 +). In particular, the reagent T'-X'-L 'may correspond to one of the following formulas: ## STR2 ## The reagents TXL and T'-X'-L', respectively, allowing for Functionalize the CE and the CC may be the same or different. In step 3), the heat treatment of the aqueous or organic paste and the optionally functionalized DC collector is preferably carried out at a temperature of at least about 100 ° C. According to a first variant, step 3) comprises: 3-i) a substep during which the optionally functionalized DC is placed in a container such as a teflon mold, 3-ii) a substep during which the aqueous or organic paste obtained in step 2) is poured into the container comprising the CC optionally functionalized, and 3-iii) a sub-step of heat treatment of the container comprising the CC optionally functionalized and the aqueous paste or organic at a temperature of at least about 100 ° C, especially in an oven. According to a second variant, step 3) comprises: 3-a) a sub-step during which the aqueous or organic paste is poured into a container such as a Teflon mold, 3-b) a sub-step; heat treatment step of the container comprising the aqueous or organic paste at a temperature of at least about 100 ° C, especially in an oven, 3-c) a sub-step in which the optionally functionalized DC is placed in the container, on top of the thermally treated organic or aqueous paste, and 3-d) a sub-step of maintaining the heat treatment of the container comprising the optionally functionalized CC and the aqueous or organic paste at a temperature of at least 100 ° C. about, especially in an oven. The heat treatment according to the two variants of step 3) makes it possible to form covalent bonds between the functional groups L of CE-f and the alcohol functions of the hydrophilic polymer PH and possibly between the functional groups L 'of the CC-f and the alcohol functions of the hydrophilic polymer PH, and thereby lead to the formation of a completely crosslinked carbon-polymer hybrid matrix. The crosslinking during step 3) can be accelerated by the addition, in the aqueous or organic paste of step 2), coupling agents well known to those skilled in the art such as 1, 3-dicyclohexylcarbodiimide (DCC), N-hydroxybenzotriazole (HOBt), benzotriazol-1-yl-oxy-tris- (dimethylamino) -phosphonium hexafluorophosphate (BOP), 2- (1H-benzotriazol-1) tetrafluoroborate y1) -1,1,3,3-teramethyluronium (TBTU), 2- (1H-azabenzotriazol-1-yl) -1,1,3,3-tetramethyluronium (HAUT), etc ... The electrode composite obtained at the end of step 3) has improved mechanical strength and sufficient rigidity to maintain the AM particles in said composite electrode. In fact, the chemical reaction between CE-f and PH makes it possible to form a crosslinked carbon-polymer matrix trapping in situ the AM particles. In addition, the use of a hydrophilic polymer PH for the formulation of composite electrodes promotes the charge storage mechanism in an aqueous electrolytic medium, and allows a better grip of the different conductive elements of the composite electrode (CE and CC). ) by a grafting method on functionalized conductive surfaces.
[0033] Finally, the chemical reaction between the CC when it is functionalized and PH makes it possible to ensure the robust maintenance on the DC of the cross-linked carbon-polymer matrix trapping the MA via the formation of multiple additional covalent bonds.
[0034] In a particular embodiment of the process of the invention, the ester functions are carboxylic acid ester functions. The method of the invention does not preferably include a step (s) of functionalization of the active ingredient MA. The active ingredient MA is therefore used "as is", without chemical modification and / or introduction of 10 chemical groups on its surface. In this way, the ionic and electronic exchanges within the electrochemical storage device are optimized. The subject of the invention is a composite electrode comprising a composite material deposited on an optionally functionalized DC current collector, as obtained according to the process according to the first subject of the invention, characterized in that: optionally functionalized DC current has a surface resistance of less than or equal to approximately 50 ohms per 1 cm 2 of surface (ie less than or equal to 50 ohms / cm 2), and 20 * said composite material comprises a functionalized carbonaceous agent CE-f, at least an active material MA, and at least one hydrophilic crosslinked polymer PH-r comprising several alcohol functional groups and several ester functional groups chosen from carboxylic acid esters, phosphonic acid esters, sulphonic acid esters and carbamates, said Crosslinked hydrophilic polymer PH-r being covalently bound to the functionalized carbonaceous agent CE-f via say ester functions. The carbonaceous agent CE-f, the active material MA and the current collector CC are as defined in the first subject of the invention. When DC is functionalized, said crosslinked hydrophilic polymer PH-r of the composite material is also covalently bound to CC-f through said ester functions selected from carboxylic acid esters, acid esters, and the like. phosphonic acid, sulfonic acid esters and carbamates. In a particular embodiment, the ester functions are carboxylic acid ester functions.
[0035] The composite material preferably comprises from about 30% to about 90% by weight of MA, from about 5% to about 70% by weight of CE-f, and from about 5% to about 50% by weight of crosslinked hydrophilic polymer PH-R. . According to a particularly preferred embodiment of the invention, the composite material comprises from about 30% to 80% by weight of MA, from about 5% to about 40% by weight of CE-f, and from 10% to 45% by weight. in bulk about crosslinked hydrophilic polymer PH-r. The third subject of the invention is an electrochemical storage system comprising a positive electrode and a negative electrode separated by an electrolyte, characterized in that at least one of the electrodes 15 is a composite electrode as obtained according to the method according to the first object of the invention or according to the second object of the invention. Such an electrochemical storage system may be a fuel cell, an electric battery (e.g. lithium or lithium ion battery), a capacitor, a supercapacitor, an electrochromic window or a solar cell, and preferably a supercapacitor. The electrolyte may be a solution of a sodium or lithium salt in a solvent. The sodium salt is preferably selected from NaClO 4, NaBF 4, NaPF 6, Na 2 SO 4, NaNO 3, Na 3 PO 4, Na 2 CO 3 and NaTFSI.
[0036] The lithium salt is preferably selected from LiC104, LiBF4, LiPF6, Li2SO4, LiNO3, Li3PO4, Li2CO3 and LiTFSI. The solvent may be water. The solvent may also be a liquid organic solvent, optionally gelled with a polar polymer, or a polar polymer optionally plasticized with a liquid organic solvent.
[0037] The liquid organic solvent is preferably chosen for example from linear ethers and cyclic ethers, esters, nitriles, nitro derivatives, amides, sulfones, sulfolanes, alkylsulfamides and partially hydrogenated hydrocarbons. Particularly preferred solvents are diethyl ether, dimethoxyethane, glyme, tetrahydrofuran, dioxane, dimethyltetrahydrofuran, methyl or ethyl formate, propylene, ethylene, vinylene or fluoroethylene carbonate, carbonates and the like. alkyl (especially dimethyl carbonate, diethyl carbonate and methylpropyl carbonate), butyrolactones, acetonitrile, benzonitrile, nitromethane, nitrobenzene, dimethylformamide, diethylformamide, N-methylpyrrolidone, dimethylsulfone, tetramethylene sulfone, tetramethylene sulfone and tetraalkylsulfonamides having 5 to 10 carbon atoms. The polar polymer may be chosen from solvating polymers, cross-linked or otherwise, with or without grafted ionic groups. A solvating polymer is a polymer which comprises solvating units containing at least one heteroatom selected from sulfur, oxygen, nitrogen and fluorine. As examples of solvating polymers, mention may be made of polyethers of linear structure, comb or block, whether or not forming a network, based on poly (ethylene oxide), or copolymers containing the oxide-type unit. ethylene or propylene oxide or allylglycidylether, polyphosphazenes, crosslinked networks based on polyethylene glycol crosslinked with isocyanates or networks obtained by polycondensation and bearing groups that allow the incorporation of crosslinkable groups. Block copolymers may also be mentioned in which some blocks carry functions which have redox properties. Of course, the above list is not limiting, and all polymers having solvating properties can be used. The fourth subject of the invention is the use of the composite electrode 30 as obtained according to the method according to the first subject of the invention or according to the second subject of the invention in an energy storage system ( eg in a flexible or rigid supercapacitor or a battery, and preferably in a supercapacitor), in a sensor, a sensor or a detector of gases, ions or pollutants. EXAMPLES The raw materials used in the examples are listed below: tBuNO2 nitrosating agent, 90% pure, Sigma-Aldrich, NaNO2 nitrosating agent, 97% pure, Sigma-Aldrich, 4- acid aminobenzoic, 99% purity, Alfa Aesar, - carbon nanofibers, purity> 98%, vapor grown nanofiber 10 VGCF, Sigma-Aldrich, 100 nm x 20-200 μm, - carbon black, 99% purity, Superior Graphite, - acetonitrile, purity> 99.8%, Fisher Scientific, - N, N-dimethylformamide,> 99% purity, Acros Organics, - methanol, purity> 99.5%, Fisher Scientific, - distilled water , - acetone, purity> 99%, Fisher Scientific, - anhydrous Na2SO4, 99% purity, Fisher Scientific, - carbon fabric, Granoc Fabric PF-YSH70A-100, Nippon Graphite Fiber Corporation, 20 - MnO2, High Specific Surface Area, cryptomelane, Erachem Comilog, particle size of 2 to 5 μm, Fe304, 95% purity, Sigma-Aldrich, particle size <5 μm, - Fe304, pure 97% titer, Sigma-Aldrich, particle size <5 μm, - Fe304 "homemade", nanometer-sized particles <50 nm, 25 - fumaric acid, 99% purity, Sigma-Aldrich, - polyacrylic acid (PAA), purity > 85%, Poly (acrylic acid sodium), Sigma-Aldrich, Mw - 2100 g.mol1-1, 3038145 27 - polyvinyl alcohol, PVA, 98% hydrolyzed, Sigma-Aldrich, Mw = 13000-23000 g.mo1 -1, - polyaniline, PANI, (emeraldine base), Sigma-Aldrich, Mw = 5000 g.mo1-1, 5-polypyrrole, PPY, doped, dispersion of 5% by weight in H2O, Sigma Aldrich, - polyurethane resin for CC, Blend Dilpur 40-80 Isocyanate + Dilpur 40A Polyol, DIL France, Hardness 40 Shore A, - isocyanate for CC, Dilpur 40-80 Isocyanate, DIL France, density 10 of 1.05, viscosity of 5500 mPa.s , - polyol for DC, Dilpur 40A Polyol, DIL France, density of 1.04, viscosity of 350 mPa.s, - nickel powder for CC, purity 99.9%, Alfa Aesar, particles of size 3-7 pm.
[0038] Unless otherwise indicated, all materials were used as received. EXAMPLE 1 Method for Preparing a Composite Electrode E-1 According to the First Object of the Invention 1.1 Preparation of a Functionalized Carbonaceous Agent CE1-f (eg Functionalized Carbon Nanofibers) A solution A comprising 3.08 g terbutylnitrite as a nitrosating agent in 50 ml of acetonitrile was prepared. A solution B comprising 1.37 g of 4-aminobenzoic acid (0.05 mol / l) and 400 mg of carbon nanofibres (ie 3.33, 10-2 moles of carbon) in 200 ml of acetonitrile been prepared. Solution A was added dropwise to solution B to form a resulting solution which was stirred for 16 h and then filtered.
[0039] In the resulting solution, the molar ratio of nitrosation agent / 4-aminobenzoic acid was 3 and the molar ratio of 4-aminobenzoic acid / carbon of the carbon fibers was 0.3. The precipitate obtained was washed several times with portions of 200 ml of different solvents: the first washes were carried out in an aqueous medium with water (x5) and then with various organic solvents such as acetonitrile (x5 or until the filtrate is colorless), dimethylformamide (x5 or until the filtrate is colorless), acetone (x3) and methanol (x3).
[0040] The solid obtained was then dried under vacuum for 24 hours. Carbon nanofibers functionalized with benzoic acid (CE1-f) were thus prepared. 1.2 Preparation of Functionalized Carbon Fabric CC1-f A solution A comprising 0.616 g of terbutyl nitrite as a nitrosating agent in 50 ml of acetonitrile was prepared. A solution B comprising 0.274 g of 4-aminobenzoic acid (0.01 mol / l) and two pieces of carbon fabric of dimensions 10 cm x 5 cm (ie 0.205 mole of carbon) in 200 ml of acetonitrile was prepared . The two pieces of carbon fabric were thus immersed in said solution B and held in suspension by two clamps located above a container containing said solution B. Solution A was added dropwise to the solution B to form a resulting solution which was stirred for 16 h and then filtered.
[0041] In the resulting solution, the molar ratio of nitrosation agent / 4-aminobenzoic acid was 3 and the molar ratio of 4-aminobenzoic acid / carbon of the carbon fibers was 0.01. The resulting fabric was washed and then sonicated for 3-5 min in different solvents: acetonitrile (x3), methanol and acetone.
[0042] The fabric was then dried under vacuum for 24 hours.
[0043] A carbon fabric functionalized with benzoic acid (CC1-f) has thus been prepared and can be used as a current collector. Figure 1 (broad spectrum) shows X-ray photoelectron spectroscopy analysis (XPS analysis) of the unfunctionalized carbon fabric (curve with solid lines) and functionalized carbon fabric (curve with dashed lines). The curves represent the intensity (in number of photoelectrons) as a function of their binding energy (in eV). This analysis makes it possible to identify the chemical elements present on the surface of the carbon fabric.
[0044] Figure 2 (zone spectra) in X-ray photoelectron spectroscopy (XPS) of the unfunctionalized carbon fabric (solid line) and functionalized carbon fabric (dashed line). In particular, the enlarged figures 2a, 2b and 2c of FIG. 2 respectively represent the spectra of the peaks C1s, 01s and N1s. They show that the surface of the functionalized carbon fabric is chemically modified. In particular, FIG. 2a shows a decrease in the C1s peak at 284 eV relative to the CC bond (sp2 carbons at 284.3 eV and spi at 284.8 eV) and the presence of the COC bonds at 285.8 eV and OC = 0 to 288 eV at the surface of the functionalized carbon fabric, said groups being visible in Fig. 2b of the 01s peak at 232 eV and 234 eV. 1.3 Preparation of Composite Electrode E-1 A solution C comprising 10% by weight of PVA was prepared by dissolving PVA in water at 80 ° C. A solution D was prepared by dispersing 100 mg of MnO 2 in 10 ml of water using ultrasound for 30 min, then adding and dispersing 20 mg of modified carbon nanofibers as prepared in Example 1.1. using ultrasound for 30 min. 800 mg of solution C was then gradually added with stirring to solution D.
[0045] The resulting solution was maintained for at least 24 h with stirring at 80 ° C, so as to evaporate a portion of the water and obtain a composite material paste having a texture suitable for a homogeneous display on the carbon fabric. modified as prepared in Example 1.2.
[0046] The mass composition of the composite material thus prepared for the E-1 electrode was 50% MnO 2, 40% PVA and 10% functionalized carbon nanofibers CE1-f. The CC1-f modified carbon fabric as prepared in Example 1.2 was placed in the bottom of a removable teflon mold (10 cm x 10 cm in size) and specially designed to easily recover the tissue, and the paste of composite material was poured onto said fabric to promote the esterification reaction on the fabric surface. The mold containing the composite material and pulp material was held at 120 ° C in an oven to remove all traces of water and shift the equilibrium of the esterification reaction to the formation of the ester and total crosslinking of the carbon-polymer hybrid matrix. The current collector CC1-f coated with the paste of composite material was then recovered using a scalpel by peeling it from the walls of the mold.
[0047] It could then be used directly as composite electrode E-1 simply by making electrical contact on one end, while the other end was immersed in a liquid electrolyte. 1.4 Characteristics of the composite electrode E-1 The electrode E-1 was electrochemically tested by cyclic voltammetry over about ten cycles at room temperature in a three-electrode cell comprising: the electrode E-1 as a working, said electrode having a surface of 1 cm 2, an aqueous liquid electrolyte consisting of an aqueous solution of 0.5M Na 2 SO 4, an Ag / AgCl (saturated NaCl) electrode as a reference electrode, and a platinum electrode as counter-electrode. The measurement of current density I (in mA / cm 2) as a function of the imposed potential (ie of 0.0V to 0.9V) versus the Ag / AgCl reference electrode is shown in FIG. 3, using a speed cycling of 20 mV / s after 10 cycles. The hybrid carbon-polymer matrix trapping the active material, as well as the use of a functionalized current collector, makes it possible to obtain an electrode E-1 having good electrochemical performances as a positive electrode within a supercapacitor. . Indeed, the electrode E-1 has a surface capacity of 0.3 F / cm 2 and a specific capacity of 147 F / g. Electrode E-1 has been tested in galvanostatic cycling over 3000 cycles between 0.0V and 0.9V, at a constant current density of 7 mA.cm-2, at room temperature, in a three-electrode cell comprising the electrode E-1 as working electrode, said electrode having a surface of 1 cm 2, an aqueous liquid electrolyte consisting of an aqueous solution of Na 2 SO 4 at 0.5 M, an Ag / AgCl (saturated NaCl) electrode ) as the reference electrode, and - a platinum electrode as counter-electrode.
[0048] During galvanostatic cycling, the E-1 electrode was further tested by cyclic voltammetry at different charge-discharge cycles. After 1000 and 2000 cycles, the electrode E-1 and the assembly were washed, dried and then restarted by cycling with a renewed electrolyte.
[0049] The measurement of the current density I (in mA / cm 2) as a function of the imposed potential (ie between 0.0V and 0.9V) versus the Ag / AgCl reference electrode is shown in FIG. 4, using a cycling speed of 20 mV / s, after the various cycles of the galvanostatic cycling following: before cycling (curve with a solid line), after 100 cycles (curve with a broad dotted line), after 500 cycles (curve with a line dotted end), after 1000 cycles (curve with an alternating dotted line), after 2000 cycles (curve with a full fine line) and after 3000 cycles (curve with a very fine dotted line).
[0050] The functionalization of the current collector has allowed a durable adhesion over 3000 cycles of the carbon-polymer matrix trapping the active material on the functionalized current collector. EXAMPLE 2: Process for preparing composite electrodes E-2 and E-3 according to the first subject of the invention A composite electrode E-2 was prepared according to the method described in Example 1.3, using 200 mg of MnO2 active material instead of 100 mg of MnO2 and using an unmodified current collector CC1 (ie carbon fiber of dimensions 10 cm x 5 cm having not undergone functionalization).
[0051] The mass composition of the composite material thus prepared for the composite electrode E-2 was 67% MnO 2, 27% PVA and 6% functionalized carbon nanofibers CE1-f. A composite electrode E-3 was then prepared according to the method described in Example 1.3, using 200 mg of active ingredient MnO 2 instead of 100 mg of MnO 2 and using a modified current collector CC1-f such that prepared in Example 1.2. The mass composition of the composite material thus prepared for the composite electrode E-3 was 67% MnO 2, 27% PVA and 6% functionalized carbon nanofibers CE1-f.
[0052] The electrodes E-2 and E-3 were electrochemically tested by cyclic voltammetry over about ten cycles, at room temperature, in a three-electrode cell comprising: the electrode E-2 or E-3 as the electrode of each electrodes having a surface area of 1 cm 2, an aqueous liquid electrolyte consisting of an aqueous 0.5M Na 2 SO 4 solution, an Ag / AgCl (saturated NaCl) electrode as a reference electrode, and a platinum electrode, as counter-electrode. The measurement of the current density I (in mA / cm 2) of electrodes E-2 (solid line) and E-3 (dashed line) according to the imposed potential (ie from 0.0V to 0.9V) versus the reference electrode Ag / AgCl, is shown in FIG. 5 using a cycling speed of 20 mV / s after 10 cycles.
[0053] The surface modification of the carbon fabric causes a slight decrease in current density, but provides a more rectangular and less resistive pseudocapacitive signal, induced by a more durable adhesion of the paste to the current collector. EXAMPLE 3 Process for the Preparation of Composite Electrodes E-4 and E-5 in Accordance with the First Object of the Invention 3.1 Preparation of a Material Comprising a Composite Polymer Layer and a Carbonaceous Material Layer CC2 A Charged Polyurethane Resin with 80% by weight of PU-Ni nickel was prepared as follows: 4 g of isocyanate and 4 g of polyol were mixed to obtain a homogeneous viscous liquid. 32 g of nickel powder were gradually added (successive additions of 16 g, 8 g and 8 g) and mixed with the viscous liquid. A few drops of acetone (about fifty) were added to thin and homogenize the mixture.
[0054] The resulting mixture was spread with a spatula on a previously polished 15 x 23 cm 2 teflon plate (or glass plate) and allowed to crosslink for 2 to 3 hours at room temperature, until a tacky surface of polyurethane-nickel resin (PU-Ni) with a thickness of about 500 dam 5. Carbon (non-functionalized) fabric was then applied to the PU-Ni resin. The whole was left for about 24 hours at room temperature until complete resin crosslinking and was then recovered with a scalpel by peeling it off the teflon plate.
[0055] A material consisting of a PU-Ni filled resin layer and a nonfunctionalized carbon fabric layer has thus been obtained and can be used as a CC2 current collector useful for producing a composite electrode according to the invention. . The process can also be replicated using a functionalized carbon fabric such as that prepared in Example 1.2. This results in a functionalized current collector CC2-f consisting of a PU-Ni filled resin layer and a functionalized carbon fabric layer. The PU-Ni filled resin is flexible, conductive and lining the back of the optionally functionalized carbon fabric and makes it possible to improve its mechanical strength and facilitate its handling. The charged resin is sufficiently conductive to allow the assembly (optionally functionalized carbon fabric / charged resin) to be used as a current collector of an electrode for energy storage devices. The current collector thus obtained consists of a layer of composite polymer (PU-Ni) and a layer of carbon material (optionally functionalized carbon fabric). 3.2 Preparation of Composite Electrodes E-4 and E-5 Composite electrode E-4 was prepared according to the method described in Example 1.3, using an unmodified current collector CC1 (ie carbon fabric of dimensions 10 cm x 5 cm not functionalized).
[0056] The mass composition of the composite material thus prepared for the composite electrode E-4 was 50% MnO 2, 40% PVA and 10% functionalized carbon nanofibers CE1-f. Composite electrode E-5 was prepared according to the method described in Example 1.3, using an unmodified current collector CC2 as prepared in Example 3.2 (ie carbon fabric of dimensions 10 cm × 5 cm. having not undergone functionalization and coated with a PU-Ni resin). In the process for preparing the composite electrode E-5, the current collector CC2 is placed in the bottom of the demountable teflon mold (as described in Example 1.3), the face corresponding to the PU-Ni resin. being in contact with the mold while the face corresponding to the carbon fabric is able to directly receive the aqueous paste. The mass composition of the composite material thus prepared for the composite electrode E-5 was 50% MnO 2, 40% PVA and 10% functionalized carbon nanofibers CE1-f. The electrodes E-4 and E-5 were electrochemically tested by cyclic voltammetry over about ten cycles, at room temperature, in a three-electrode cell comprising: the electrode E-4 or E-5 as working electrode each of the electrodes having a surface area of 1 cm 2, an aqueous liquid electrolyte consisting of an aqueous 0.5M Na 2 SO 4 solution, an Ag / AgCl (saturated NaCl) electrode as the reference electrode, and a platinum as counter-electrode. The measurement of the current density I (in mA / cm 2) of electrodes E-4 (solid line) and E-5 (dashed line) according to the imposed potential (ie from 0.0V to 0.9V) versus the Ag / AgCl reference electrode, is shown in FIG. 6, using a cycling speed of 20 mV / s after 10 cycles.
[0057] The presence of the PU-Ni filled resin hardly modifies the electrochemical signal of the electrode and it makes it possible to improve the mechanical strength of the electrode over time and its flexibility. In addition, the manipulation of the carbon fabric is easier when said resin is used. EXAMPLE 4: Process for the preparation of composite electrodes E-6 and E-7 according to the first subject of the invention and of an E-8 composite electrode not according to the invention A composite electrode E-6 was prepared according to the invention. to the method described in Example 1.3, using 100 mg of CE1-f in place of 20 mg of CE1-f and using an unmodified current collector CC2 as prepared in Example 3.1 (ie carbon of dimensions 10 cm x 5 cm having not undergone functionalization and coated with a PU-Ni resin). The mass composition of the composite material thus prepared for the composite electrode E-6 was 36% MnO 2, 28% PVA and 36% functionalized carbon nanofibers CE1-f. Composite electrode E-7 was prepared according to the method described in Example 1.3, using 100 mg of CE1-f in place of 20 mg of CE1-f and using a modified current collector CC2-f such that described in Example 3.1 (ie 10 cm x 5 cm carbon fabric having functionalized as in Example 1.2 and coated with a PU-Ni resin). The mass composition of the composite material thus prepared for the composite electrode E-7 was 36% MnO 2, 28% PVA and 36% functionalized carbon nanofibers CE1-f. An E-8 composite electrode (not part of the invention) was prepared according to the method described in Example 1.3, using 100 mg of CE1-f in place of 20 mg of CE1-f and using a current collector CC3 consisting solely of the PU-Ni resin as prepared in Example 3.1. The current collector is not in accordance with the invention because it does not have a surface resistance of less than or equal to about 50 ohms / cm 2. The mass composition of the composite material thus prepared for the composite electrode E-8 was 36% MnO 2, 28% PVA and 36% functionalized carbon nanofibers CE1-f. The electrodes E-6, E-7 and E-8 were electrochemically tested by cyclic voltammetry over ten cycles, at room temperature, in a three-electrode cell comprising: the electrode E-6, E-7 or E-8 as a working electrode, each of the 10 electrodes having a surface of 1 cm 2, an aqueous liquid electrolyte consisting of an aqueous solution of Na 2 SO 4 at 0.5 M, an Ag / AgCl (saturated NaCl) electrode as the electrode of reference, and a platinum electrode as counter-electrode. The measurement of the current density I (in mA / cm2) of the electrodes E-6 (solid line), E-7 (broad dashed line) and E-8 (fine dashed line) according to the imposed potential (ie 0 0V to 0.9V) versus the Ag / AgCl reference electrode is shown in Figure 7, using a cycling rate of 20 mV / sec after 10 cycles. The current density of the carbonless E-8 electrode is much lower and the signal much more resistive than for the E-6 and E-7 electrodes, thus showing the strong influence of the conductive carbon fabric (functionalized or not) within the current collector. The surface modification of the carbon fabric (functionalization) is furthermore favorable to a good adhesion of the paste to the current collector and modifies only very little the electrochemical signal of the electrode.
[0058] EXAMPLE 5: Process for preparing a composite electrode E-9 according to the first subject of the invention A solution C comprising 10% by weight of PVA was prepared by dissolving PVA in water at 80 ° C. .
[0059] A solution D was prepared by dispersing 100 mg of MnO 2 in 10 ml of water using ultrasound for 30 minutes, and then adding and dispersing 100 mg of modified carbon nanofibers as prepared in Example 1.1. using ultrasound for 30 min. 800 mg of solution C was then gradually added with stirring to solution D. The resulting solution was maintained for at least 24 hours with stirring at 80 ° C. and then placed directly into the bottom of a removable Teflon mold. (Size 10 cm x 10 cm) as described in Example 1.3. The mold containing the solution was held at 120 ° C for 2 hours to allow PVA crosslinking. The mass composition of the composite material thus prepared for the electrode E-9 was 36% MnO 2, 28% PVA and 36% functionalized carbon nanofibers CE1-f. The current collector CC2 (ie 10 cm x 5 cm carbon fabric having not undergone functionalization and coated with a PU-Ni resin) as prepared in Example 3.1 was deposited on the crosslinked paste , the face corresponding to the carbon fabric being in contact with said reticulated paste. A few drops of water had been previously deposited on the crosslinked paste in order to allow a better contact with the cross-linked paste / carbon fabric and to promote the esterification reaction on the surface of the dough (ie in the opposite direction with respect to the process such as as described in Example 1.3). The assembly was maintained again at 120 ° C. in an oven until total evaporation of the water and total crosslinking of the hybrid carbon-polymer matrix.
[0060] The paste of composite material covered with the current collector CC2 was then recovered using a scalpel by peeling it from the walls of the mold. The electrode E-9 was tested [and by comparison electrodes E-6 and E-7 as prepared in Example 4)] electrochemically by cyclic voltammetry over ten cycles, at room temperature, in a cell with three electrodes comprising: - the electrode E-6, E-7 or E-9 as working electrode, each of the electrodes having a surface of 1 cm 2, 10 - an aqueous liquid electrolyte consisting of an aqueous solution of Na 2 SO 4 to 0.5M, an Ag / AgCl (saturated NaCl) electrode as the reference electrode, and a platinum electrode as counter-electrode.
[0061] The measurement of the current density I (in mA / cm 2) of the electrodes E-6 (solid line), E-7 (dashed fine line) and E-9 (dotted broad line) according to the imposed potential (ie 0.0V to 0.9V) versus the Ag / AgCl reference electrode, is reported in Figure 8, using a cycling speed of 20 mV / sec after 10 cycles.
[0062] The electrode E-9 has a density much higher than that of the electrodes E-6 and E-7, whatever the value of the potential, indicating that the method of depositing the current collector on the aqueous paste [second variant of step 3) of the invention, leads to improved electrochemical performance.
[0063] In addition, as shown in Example 4, the functionalization of the carbon fabric within the manifold hardly changes the electrochemical signal of the electrode but ensures improved adhesion of the paste to the current collector.
[0064] FIG. 9 shows images by scanning electron microscopy (SEM) of the composite material surface of the composite electrode E-9 not in contact with the current collector. FIG. 9 shows that the process carried out in this example allows a gravity displacement of the MnO 2 active material particles in the bottom of the mold during the crosslinking / gelling and thus the access to a larger quantity of MnO 2 at the free surface of the paste which will be in direct contact with the electrolyte of the electrochemical device. The microscopic images were made with an apparatus sold under the trade name Merlin by Zeiss. COMPARATIVE EXAMPLE 6 Process for the Preparation of EA and EB Composite Electrodes Not in Accordance with the First Object of the Invention The process for preparing electrode E-4 as described in Example 3.2 was reproduced using instead polyvinyl alcohol in the aqueous paste, other hydrophilic polymers not comprising alcohol functions. The functionalized carbonaceous agent CE1-f was identical to that prepared in Example 1.1. The active ingredient was identical to that used in Example 1.3 and the current collector was the unmodified current collector CC1 (i.e., 10 cm x 5 cm carbon fabric having not undergone functionalization). Table 1 below shows the mass concentrations of each of the constituents of the composite material of the various prepared electrodes EA and EB and by comparison with those of the electrode E-4 of Example 3.2: TABLE 1% in% in % by mass Type of polymer mass mass Hydrophilic polymer CE1-f MA hydrophilic PH PH E-4 10 50 40 Polyvinyl alcohol PVA EA (*) 10 50 40 Polyaniline PAN I EB (*) 10 50 40 Polypyrrole PPY (*): electrode Composite not part of the invention The two electrodes EA and EB not in accordance with the invention (and by comparison the electrode E-4 as prepared in Example 3.2) were electrochemically tested by cyclic voltammetry on a ten cycles, at room temperature, in a three-electrode cell comprising: - the electrode E-4, EA or EB as working electrode, each of the electrodes having a surface of 1 cm 2, 10 - an aqueous liquid electrolyte constituted 0.5M Na 2 SO 4 aqueous solution; Ag / AgCl (NaCl saturated) electrode as the reference electrode; and a platinum electrode as a counter electrode.
[0065] The measurements of the current density I (in mA / cm 2) as a function of the imposed potential (ie of 0.0V to 0.9V) versus the Ag / AgCl reference electrode for the E-4 electrode (solid line ), EA electrode (dashed fine line) and EB electrode (alternating dashed line) are reported in Figure 10, using a cycling speed of 20 mV / s after 10 cycles.
[0066] According to FIG. 10, the electrodes forming part of the invention EA and EB have a low current density regardless of the value of the potential, indicating that there is no creation of a hybrid carbon matrix. -polymer trapping the active material such as that of the invention.
[0067] Electrochemical tests by cyclic voltammetry of the "only" composite material of the EA and EB electrodes (ie without current collector CC1) or deposited on a current collector CC1-f did not make it possible to improve the electrochemical signal such as observed in FIG. 9 for EA and EB electrodes; while an electrochemical test by cyclic voltammetry of the "only" composite material of the electrode E-4 (i.e. without current collector CC1) gives an electrochemical signal, even if it is very resistive. COMPARATIVE EXAMPLE 7 Process for the Preparation of EC and ED Composite Electrodes 10 Not in Accordance with the First Object of the Invention The process for preparing the E-4 electrode as described in Example 3.2 was reproduced using the position of the functionalized carbonaceous agent CE1-f (ie carbon nanofibers functionalized with benzoic acid) in the aqueous paste, a carbonless NC2 non-functional carbonaceous agent CE2 (not in accordance with the invention) as well as an AL linker containing carboxylic acid functions (polyacrylic acid PAA or fumaric acid AcF). The active material and the hydrophilic polymer were identical to those used in Example 1.3, and the current collector was the unmodified current collector CC1 (ie, carbon fabric 10 cm x 5 cm in size which did not undergo functionalization). Table 2 below shows the mass concentrations of each of the constituents of the composite material of the various electrodes prepared EC and ED and by comparison with those of the electrode E-4 of Example 3.2: TABLE 2 in% in% added (for Mass AL Type of agent, type Type mass CE mass% by weight PH 200 mg of Carbon ratio of AL MA MA + PH + EC) molar CE AL / PH E-4 10 50 40 0 0 CE1-f - EC ( *) 10 50 40 1.88 mg 0.2 CE2 PAA ED (*) 10 50 40 5.2 mg 10 CE2 AcF (*): Composite electrode not part of the invention The two electrodes EC and ED not in conformity to the invention (and by comparison the E-4 electrode as prepared in Example 3.2) were electrochemically tested by cyclic voltammetry over about ten cycles at room temperature in a three-electrode cell comprising: electrode E-4, EC or ED as working electrode, each of the electrodes having a surface of 1 cm 2, 10 - an electrolyte an aqueous liquid consisting of an aqueous 0.5M Na 2 SO 4 solution, an Ag / AgCl (saturated NaCl) electrode as the reference electrode, and a platinum electrode as a counter-electrode.
[0068] The measurements of the current density I (in mA / cm 2) as a function of the imposed potential (ie of 0.0V to 0.9V) versus the Ag / AgCl reference electrode for the E-4 electrode (solid line ), the EC electrode (dashed fine line) and the ED electrode (alternating dashed line) are reported in FIG. 11, using a cycling speed of 20 mV / s after 10 cycles.
[0069] According to FIG. 11, the electrodes forming part of the invention EC and ED have a low current density, whatever the value of the potential, indicating that there is little or no creation of a hybrid matrix binding agent AL-polymer trapping the active material as well as the non-functional carbonaceous agent CE2. The hybrid matrix potentially associated with the AL-polymer bonding agent appears to be even less present with the low molecular weight (116.07 g.mol -1) fumaric acid AcF than with the high mass polyacrylic acid PAA polymer. molecular (-2100 g.mo1-1), as indicated by the electrochemical signal in Figure 10.
[0070] EXAMPLE 8: Process for the preparation of composite electrodes E-10, E-11, E-12 and E-13 according to the first subject of the invention The process for the preparation of electrode E-1 as described in FIG. Example 1.3 was repeated using instead of the active ingredient MnO 2 in the aqueous slurry, another active ingredient Fe 3 O 4 which can be used in particular as the negative electrode of a supercapacitor. The active ingredient Fe304 was used in the form of three different powders: a commercial Fe304 powder (Sigma-Aldrich) for the E-10 electrode, a commercial Fe304 powder (Alfa Aesar) for the E-11 electrode and a powder Fe304 prepared in the laboratory by the inventors of the present application according to the process as described in Kulkarni et al. [Ceramics International, 2014, 40 (1), part B, 1945-1949], for the E-12 electrode. The functionalized carbonaceous agent CE1-f (i.e., functionalized carbon nanofibers) was identical to that as prepared in Example 1.1 and the hydrophilic polymer (i.e. PVA) was identical to that used in Example 1.3. The current collector was the current collector CC1-f as prepared in Example 1.2 (i.e., functionally sized 10 cm x 5 cm carbon fabric). The amount of Fe304 active ingredient used for the preparation of the aqueous slurry was the same in number of moles as the amount of MnO 2 used in the process of Example 1.3 (i.e. 0.00115 moles), ie 266 mg Fe304. The mass concentrations of each of the constituents of the composite material of electrodes E-10, E-11 and E-12 were 73% Fe304 active material, 22% hydrophilic PVA polymer and 5% functionalized carbon nanofibers CE1-f.
[0071] An electrode E-13 of the same composition as the electrode E-12 (ie identical composite material and current collector) was prepared according to the method as described in Example 5 (ie by carrying out the second variant of the invention. step 3) of the process according to the invention). The four electrodes E-10, E-11, E-12 and E-13 were electrochemically tested by cyclic voltammetry over about 10 cycles at room temperature in a three-electrode cell comprising: the E-10 electrode, E-11, E-12 or E-13 as working electrode, each of the electrodes having a surface of 1 cm 2, an aqueous liquid electrolyte consisting of an aqueous solution of Na 2 SO 4 to 0.5M, an Ag / AgCl electrode (saturated NaCl) as the reference electrode, and - a platinum electrode as counter-electrode. Measurements of the current density I (in mA / cm 2) as a function of the imposed potential (ie from -0.8V to 0.2V for E-11, E-12 and E-13 and from -0.8V to 0.0V for E-10) versus the Ag / AgCl reference electrode for the E-10 electrode (solid line), the E-11 electrode (broad dotted line), the E-12 electrode (dashed line) fin) and the E-13 electrode (alternating dotted line) are reported in FIG. 12, using a cycling speed of 20 mV / s after 10 cycles of -0.8V to 0.2V (-0.8V). at 0.0V for E-12).
[0072] From Figure 12, the E-13 electrode has a higher current density than the other electrodes E-10, E-11 and E-12, confirming that the process of depositing the collector on the aqueous paste allows better contact of the active ingredient with the electrolyte resulting in better electrochemical performances. It should be noted that the electrodes E-12 and E-13 based on non-commercial Fe304 (ie prepared in the laboratory), and whose particle size is nanometric (ie approximately 10-20 nm in size), have a current density higher than commercially available Fe304 E-10 and E-11 electrodes with a particle size of less than 5 dBA.
[0073] EXAMPLE 9 Manufacture of an Asymmetric Supercapacitor in Accordance with the Fourth Object of the Invention Using Composite Electrodes in Accordance with the First Object of the Invention A SC-1 supercapacitor was prepared in a two-electrode asymmetric arrangement by assembling: the composite electrode E-9 as prepared in Example 5, as positive electrode based on MnO 2, a separator (Whatman filtration paper) impregnated with an aqueous liquid electrolyte consisting of an aqueous solution of Na 2 SO 4, 0.5M, and 10 - the composite electrode E-13 as prepared in Example 8, as Fe304-based negative electrode, the electrode / separator assembly being held between two Teflon plates, screwed together at a low pressure (ie slightly greater than a single contact, approximately 105-106 Pa), and the electrode / separator assembly being immersed in said liquid electrolyte consisting of an aqueous solution; use 0.5M Na2SO4. Electrodes E-9 and E-13 were directly used, making one electrical contact on one end with an alligator clip, while 1cm 2 on the other end was immersed in the liquid electrolyte, the clamp and the electrode surplus being surrounded by Teflon tape, to isolate them from the electrolyte. SC-1 was electrochemically tested, by constant current chronopotentiometry, in galvanostatic cycling over 1000 cycles at room temperature.
[0074] During galvanostatic cycling, SC-1 was further tested by cyclic voltammetry at different charge-discharge cycles. The evolution of the charge-discharge cycles as a function of time, during the galvanostatic cycling of SC-1 over 1000 cycles, at a constant current density of 3 mA.cm-2 and for a voltage of 1.6V, is shown in Figure 13: during the initial cycle (solid line) and during the 1000th cycle (alternating dotted line). The measurement of the current density I (in mA / cm 2) as a function of the imposed potential (ie between 0.0V and 0.9V) versus the Ag / AgCl reference electrode is shown in FIG. 14, using a cycling speed of 20 mV / s, after various cycles of galvanostatic cycling: before cycling (solid line) and after 1000 cycles (alternating dotted line). The SC-1 supercapacitor is stable over 1000 cycles with a loss of capacity of only 1% after 1000 cycles. 10

权利要求:
Claims (20)
[0001]
REVENDICATIONS1. A process for preparing a composite electrode comprising a composite material deposited on a DC current collector, said method comprising: 1) a step of functionalizing a carbonaceous agent CE with any one of the following functional groups L: carboxylic acid [ -CO2M], acyl halide [-COX], acid anhydride [-C (= O) 0C (= O) -], sulfonic acid [-SO2 (OM)], sulfonic acid halide [-SO2X] ], phosphonic acid dihalide [-PDX2], phosphonic acid monoester halide [-PDX (OR)], phosphonic acid monoester [-PO (OR) (OM)], phosphonic acid diester [-] PO (OR) 2] or isocyanate [-N = C = O], with X representing a chlorine atom or a bromine atom, M representing a proton, an alkali metal cation or an organic cation and R representing a methyl group or ethyl, to form a functionalized carbonaceous agent CE-f, and said method being characterized in that it further comprises the following steps:
[0002]
2) a step of preparing an aqueous or organic paste comprising the functionalized carbonaceous agent CE-f of step 1), at least one active material MA and at least one hydrophilic polymer PH comprising several alcohol functions, and
[0003]
3) a step comprising contacting the aqueous or organic paste with a DC current collector and the heat treatment of the aqueous or organic paste and the DC current collector, so as to form a composite electrode comprising a composite material deposited on said DC current collector, provided that: said DC current collector has a surface resistance of less than or equal to 50 ohms / cm 2, and said composite material comprises a functionalized carbonaceous agent CE-f, at least one active ingredient MA, and at least one cross-linked hydrophilic polymer PH-r comprising a plurality of alcohol functions and a plurality of ester functions selected from carboxylic acid esters, phosphonic acid esters, sulfonic acid esters and carbamates, said polymer hydrophilic crosslinked PH-r being covalently bonded to the functionalized carbon-based agent CE-f through said ester functions. 2. Method according to claim 1, characterized in that the carbonaceous agent CE is selected from carbon black, graphite, graphene, SP carbon, acetylene black, glassy carbon, carbon nanotubes, carbon fibers, carbon nanofibers and one of their mixtures. 3. Method according to claim 1 or claim 2, characterized in that the carbonaceous agent EC is functionalized in step 1) using a TXL reagent, wherein: - the group T is a group functional group capable of reacting with CE to form a covalent bond or precursor functional group of a functional group capable of reacting with CE to form a covalent bond; the group X is a conjugated spacer group; the group L is as defined in claim 1.
[0004]
4. Process according to claim 3, characterized in that the reagent T-X-L is a diazonium salt or a precursor of a diazonium salt.
[0005]
5. Process according to claim 4, characterized in that L is -CO2H or -CO2M and T is -N H2.
[0006]
6. Process according to any one of the preceding claims, characterized in that the active material MA is chosen from oxides, phosphates, borates, activated carbons and metal alloys of the LiyM type in which 1 <y <5 and M = Mn, Sn, Pb, Si, In or Ti.
[0007]
7. Method according to any one of the preceding claims, characterized in that the hydrophilic polymer PH comprising several alcohol functions has a molar mass ranging from 5000 g / mol to 300000 g / mol. 3038145 50
[0008]
8. Process according to any one of the preceding claims, characterized in that the hydrophilic polymer PH comprising several alcohol functional groups is chosen from polysaccharides, oligosaccharides and synthetic polymers comprising recurring units [-CH2-CH (01-1) -] n, 5 with n ranging from 100 to 7000.
[0009]
9. Process according to claim 8, characterized in that the hydrophilic polymer PH is polyvinyl alcohol.
[0010]
10. Process according to any one of the preceding claims, characterized in that step 2) is carried out according to the following substeps: 2-i) the preparation of an aqueous or organic solution comprising 0.5% at 30% by weight of hydrophilic polymer PH, 2-ii) the preparation of an aqueous or organic suspension comprising from 0.1% to 10% by weight of MA; and from 0.1% to 5% by weight of CE-f, 2-iii) mixing the aqueous or organic suspension of substep 2-ii) with the aqueous or organic solution of substep 2 -i), and 2-iv) maintaining the resulting suspension at room temperature or heating, to obtain an aqueous or organic paste.
[0011]
11. Method according to any one of the preceding claims, characterized in that step 3) comprises: 3-i) a sub-step during which the CC is placed in a container, 3-ii) a sub-step; step in which the aqueous or organic paste obtained in step 2) is poured into the container comprising the CC, and 3-iii) a sub-step of heat treatment of the container comprising the CC and the aqueous or organic paste at a temperature of at least 100 ° C. 3038145 51
[0012]
12. Method according to any one of claims 1 to 10, characterized in that step 3) comprises: 3-a) a sub-step during which the aqueous or organic paste is poured into a container, 5 3 b) a sub-step of heat treatment of the container comprising the aqueous or organic paste at a temperature of at least 100 ° C, 3-c) a substep during which the CC is placed in the container, on the heat-treated aqueous or organic pulp, and 3-d) a heat-maintaining sub-step of the container comprising the CC and the aqueous or organic pulp at a temperature of at least 100 ° C.
[0013]
13. Method according to any one of the preceding claims, characterized in that the current collector CC is selected from a metal material, a carbon material, a silicon-based material, a textile material, a metallic material modified with a carbon layer, transition metal nitride or conductive polymer and a material consisting of a composite polymer layer and a layer of carbon material.
[0014]
14. The method of claim 13, characterized in that the DC current collector is a material consisting of a composite polymer layer and a layer of carbonaceous material.
[0015]
15. Method according to any one of the preceding claims, characterized in that the current collector CC is functionalized and the method then further comprises an additional step prior to step 3), during which the CC is functionalized to form a functionalized current collector CC-f.
[0016]
16. Process according to any one of the preceding claims, characterized in that the ester functions are carboxylic acid ester functions.
[0017]
17. Composite electrode comprising a deposited composite material 3038145 52 on a DC current collector obtained by the method as defined in any one of claims 1 to 16, characterized in that: said DC current collector has a surface resistance less than or equal to 50 ohms / cm 2, and 5 * said composite material comprises a functionalized carbonaceous agent CE-f, at least one active material MA, and at least one hydrophilic crosslinked polymer PH-r comprising several alcohol functions and several ester functions selected among the carboxylic acid esters, the phosphonic acid esters, the sulphonic acid esters and the carbamates, the said crosslinked hydrophilic polymer PH-r being covalently bound to the functionalized carbonaceous agent CE-f by the intermediate of said ester functions, the carbonaceous agent CE, the active material MA and the current collector CC being as defined in any one of the claims cations 1 to 16.
[0018]
18. A composite electrode according to claim 17, characterized in that the composite material comprises from 30% to 90% by weight of MA, from 5% to 70% by weight of EC-f, and from 5% to 50% by weight. crosslinked hydrophilic polymer mass PH-r.
[0019]
19. An electrochemical storage system comprising a positive electrode and a negative electrode separated by an electrolyte, characterized in that at least one of the electrodes is a composite electrode obtained by the process as defined in any one of claims 1 to 16 or as defined in claim 17 or 18.
[0020]
20. Use of a composite electrode obtained according to the process as defined in any one of claims 1 to 16 or as defined in claim 17 or 18, in a system for storing energy, in a sensor , a sensor or a detector of gases, ions or pollutants.

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同族专利:

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公开号 | 公开日

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FR3038145B1|2017-07-21|

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US20180182566A1|2018-06-28|

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WO2016207497A1|2016-12-29|

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EP3314683A1|2018-05-02|

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法律状态:
2016-05-24| PLFP| Fee payment|Year of fee payment: 2 |

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2016-12-30| PLSC| Publication of the preliminary search report|Effective date: 20161230 |

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2017-05-23| PLFP| Fee payment|Year of fee payment: 3 |

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2018-06-27| PLFP| Fee payment|Year of fee payment: 4 |

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2020-03-13| ST| Notification of lapse|Effective date: 20200206 |

优先权:

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申请号 | 申请日 | 专利标题

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FR1555771A|FR3038145B1|2015-06-23|2015-06-23|PROCESS FOR PREPARING A COMPOSITE ELECTRODE|FR1555771A| FR3038145B1|2015-06-23|2015-06-23|PROCESS FOR PREPARING A COMPOSITE ELECTRODE|

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US15/738,673| US20180182566A1|2015-06-23|2016-06-22|Method for preparing a composite electrode|

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EP16735904.1A| EP3314683A1|2015-06-23|2016-06-22|Method for preparing a composite electrode|

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PCT/FR2016/000100| WO2016207497A1|2015-06-23|2016-06-22|Method for preparing a composite electrode|