ANODE COMPOSITION WITH CROSS-CUT BINDER

Abstract

The invention relates to an aqueous anode composition comprising carbon or metallic particles and a crosslinkable composition. This crosslinkable composition comprises a polycarboxylic polymer combined with an alcohol or an amine. The invention also relates to a method for manufacturing an anode using this aqueous composition.

Description

Title of the invention: ANODE COMPOSITION WITH CROSSLINKABLE BINDER

[0001] The invention relates to an aqueous anode composition comprising carbon particles or metal particles and a crosslinkable composition. This crosslinkable composition comprises a polycarboxylic polymer combined with an alcohol or an amine. The invention also relates to a method of manufacturing an anode using this aqueous composition.

[0002] Anode compositions are known which generally comprise carbon or a metal in the form of particles associated with a binder composition. The most common binder compositions comprise a styrene-butadiene polymer. After crosslinking, the composition makes it possible to fix the particles on a metal substrate. The binding power is therefore decisive when manufacturing an anode using these anode compositions. In addition, mechanical resistance or electrochemical resistance is particularly sought after.

[0003] Frequently, these anode compositions include silicon in order to increase the capacity of the prepared anodes. During charge-discharge cycles of batteries containing these anodes, it is common to observe deformation which can lead to irreversible alteration of the anode. Deformation tolerance is therefore also a sought-after property.

[0004] The reactions leading to the crosslinking of the composition must also be effectively controlled. Side reactions or inhibition of the reagents used must be avoided. The formation of degradation by-products or colored by-products, in particular due to excessive exposure to high temperatures, must be reduced or avoided. These crosslinkable compositions should have a high reactivity. They should allow high reaction kinetics.

[0005] The manufacturing time of these anodes is also an important factor. Improving the efficiency of the various reactions implemented, particularly during the crosslinking of the anode composition, must therefore be sought.

[0006] The number of ingredients used in the preparation of the anode compositions should also be able to be reduced.

[0007] Known crosslinkable compositions are used in many fields. However, certain compounds should be avoided or eliminated from these crosslinkable compositions, in particular for reasons of efficacy and safety but also for economic or environmental reasons. It may also be advantageous to be able to do without a phosphorus compound when preparing the reagents of a crosslinkable composition or when preparing a crosslinkable composition or when applying it before crosslinking. Thus, the esters or amides of the crosslinkable compositions should be able to be prepared in the absence of a compound that could be considered harmful from an environmental point of view or in the absence of a compound whose use is restricted by regulatory provisions. In particular, the preparation of these compounds in the absence of a compound comprising phosphorus could be preferred, in particular the absence of phosphorus in oxidation state I, III or V.

[0008] The reactions leading to the crosslinking of the composition present on a material must also be effectively controlled. Side reactions or inhibition of the reagents used must be avoided.

[0009] It is also important to have improved means, in particular crosslinkable aqueous compositions or crosslinking agents, necessary for the manufacture of anodes.

[0010] The manufacturing time of these composites is also an important factor. Improving the efficiency of the various reactions implemented, particularly during crosslinking, must therefore be sought.

[0011] The anode compositions of the state of the art are not always satisfactory. There is therefore a need to have anode compositions which make it possible to provide solutions to all or part of the problems of the anode compositions of the state of the art.

[0012] Thus, the invention provides an aqueous anode composition T comprising: * at least one crosslinkable aqueous composition R comprising: a) at least one polymer A prepared in water by a polymerization reaction of at least one monomer M chosen from acrylic acid, methacrylic acid, an acrylic acid salt, a methacrylic acid salt and combinations thereof, in the presence of at least one initiator compound, b) at least one compound B chosen from polyols, polyamines, amino alcohols, (polyamino) alcohols, amino(polyalcohols), oses, osides and combinations thereof, * at least one material E chosen from metal fibers, metal particles, graphite carbon fibers, graphite carbon particles and combinations thereof.

[0013] Essentially for the invention, the preparation of polymer A is carried out using monomer M. Preferably according to the invention, monomer M is chosen from acrylic acid, an acrylic acid salt and combinations thereof.

[0014] According to the invention, the monomer M can be combined with at least one other monomer, preferably another monomer selected from vinyl acetate, ethyl acrylate, methyl acrylate, hydroxyethylmethacrylate, hydroxyethylacrylate, hydroxypropylmethacrylate, hydroxypropylacrylate, 2-acrylamido-2-methylpropanesulfonic acid (AMPS), maleic acid, maleic anhydride, itaconic acid and combinations thereof. When combined with another monomer, monomer M may be selected from acrylic acid, an acid salt and combinations thereof, in combination with at least one other monomer selected from vinyl acetate, ethyl acrylate, methyl acrylate, hydroxyethylmethacrylate, hydroxyethylacrylate, hydroxypropylmethacrylate, hydroxypropylacrylate, 2-acrylamido-2-methylpropanesulfonic acid (AMPS), maleic acid, maleic anhydride, itaconic acid and combinations thereof. In combination with another monomer, the amount by weight of the other monomer is less than the amount by weight of monomer M.Preferably according to the invention, the monomer M is acrylic acid alone.

[0015] Preferably, the polymerization reaction is carried out at a temperature above 30°C and below 130°C, preferably below 100°C or below 90°C or below 80°C or 75°C. Preferably, during the polymerization reaction to prepare polymer A, the initiator compound is chosen from a peroxide (for example hydrogen peroxide), a hydroperoxide (for example tert-butyl hydroperoxide), a persulfate (for example sodium persulfate, ammonium persulfate, potassium persulfate), combinations thereof and associations thereof with a metal salt, preferably a metal salt chosen from an iron salt (for example Fe II or Fe III), a copper salt (for example Cu I or Cu II) and combinations thereof.

[0016] Preferably, polymer A has a weight average molecular weight Mw (measured by CES) of less than 20,000 g / mol, preferably less than 15,000 g / mol or less than 10,000 g / mol, more preferably less than 7,000 g / mol or less than 6,000 g / mol. Polymer A generally has a weight average molecular weight Mw (measured by CES) of greater than 1,000 g / mol or greater than 1,200 g / mol.

[0017] Preferably, polymer A has a polymolecularity index Ip (measured by CES) of less than 4 or ranging from 1.2 to 4 or from 1.5 to 4; from 1.2 to 3 or from 1.5 to 3; from 1.2 to 2.5 or even from 1.5 to 2.5.

[0018] According to the invention, the molecular weight or mass of polymer A is determined by Size Exclusion Chromatography (SEC). A test sample of the polymer solution corresponding to 90 mg of dry matter is introduced into a 10 mL flask. Mobile phase, containing 0.04% dimethylformamide (DMF), is added to a total mass of 10 g. The composition of this mobile phase is as follows: NaHCCU: 0.05 mol / L, NaNCU: 0.1 mol / L, triethanolamine: 0.02 mol / L, NaN3 0.03% by mass. The CES system consists of a Waters 510 isocratic pump with a flow rate set at 0.8 mL / min, a Waters 717+ autosampler, an oven containing a 6 cm long, 40 mm inner diameter Waters Guard Column Ultrahydrogel precolumn, followed by a 30 cm long, 7.8 mm inner diameter Waters Ultrahydrogel linear column. Detection is performed using a Waters RI 410 differential refractometer. The oven is heated to a temperature of 60°C and the refractometer is heated to a temperature of 45°C. The CES device is calibrated with a series of sodium polyacrylate standards supplied by Polymer Standard Service with peak molecular weights between 1000 g / mol and 1.106 g / mol and polydispersity indexes between 1.4 and 1.7.The calibration curve is linear and takes into account the correction obtained using the flow marker: dimethylformamide (DMF). The acquisition and processing of the chromatogram are carried out using the PSS WinGPC Scientific v 4.02 software. The chromatogram obtained is integrated into the area corresponding to molecular weights greater than 250 g / mol.

[0019] According to the invention, polymer A may be non-neutralized or it may be partially neutralized or totally neutralized. Preferably, polymer A is non-neutralized. According to the invention, the carboxylic groups of polymer A may be partially neutralized at a rate of 70 to 97 mol%, preferably at a rate of 90 to 95 mol%. Polymer A may be partially or totally neutralized by means of at least one monovalent ion or at least one divalent ion. According to the invention, polymer A may be partially or totally neutralized by means of a combination of at least one monovalent ion and at least one divalent ion. According to the invention, the total or partial neutralization of polymer A may then be carried out in variable relative molar proportions of the monovalent and divalent ions.Preferably according to the invention the molar proportions monovalent ion / divalent ion are between 90 / 10 and 10 / 90 or between 80 / 20 and 20 / 80, preferably between 80 / 20 and 60 / 40, for example 70 / 30 or 50 / 50.

[0020] According to the invention, the neutralization can be carried out by means of a primary amine, a secondary amine or a monovalent ion chosen from K+, Na+, Li+, NH4+ and combinations thereof. The preferred ion is NH4+. According to the invention, the neutralization can also be carried out by means of a divalent ion chosen from Ca2+, Mg2+ and combinations thereof. The preferred divalent ion is Ca2+.

[0021] According to the invention, polymer A can be neutralized by means of at least one compound chosen from NaOH, KOH, ammonium derivatives, ammonia, primary amine, secondary amine, CaO, Ca(OH)2, MgO, Mg(OH)2 and combinations thereof. Neutralization of polymer A by means of ammonia proves to be particularly advantageous. when implementing composition T or composition R at a pH below 7, preferably at a pH below 5. According to the invention, polymer A may be neutralized totally or partially by means of an amine base, for example a base chosen from ethylene diamine, 1,3-propanediamine, 1,4-butanediamine, 1,5-pentanediamine, 1,6-hexanediamine, a,a'-diaminoxylene, diethylenetriamine, trie-thylenetetramine, tetraethylenepentamine, triethanolamine, aminomethylpropanol or 2-amino-2-methyl-propanol (AMP) and combinations thereof. Advantageously according to the invention, the amine base may also be present in composition R as amine compound B.

[0022] Preferably according to the invention, polymer A can be prepared in the presence of at least one polymerization agent C chosen from compounds C1 to C6 and their combinations.

[0023] Preferably according to the invention, compound C is a sulfur compound Cl comprising sulfur in oxidation state IV, preferably a sulfur compound Cl chosen from lithium hydrogen sulfite, sodium hydrogen sulfite, potassium hydrogen sulfite, ammonium hydrogen sulfite, calcium di(hydrogen sulfite), magnesium di(hydrogen sulfite) and combinations thereof. Preferably according to the invention, compound Cl is a mono-hydrogen sulfite. Generally according to the invention, the molar quantity of sulfur compound Cl, preferably the molar quantity of sulfur IV, is between 1% and 15%, preferably between 1.5% and 12%, relative to the total molar quantity of monomers used, preferably the molar quantity of sulfur compound Cl, preferably the molar quantity of sulfur IV, is between 1% and 15%, preferably between 1.5% and 12%, relative to the total molar quantity of unsaturated groups of the monomers used.

[0024] According to the invention, compound C may be a phosphorus compound C2 comprising phosphorus in oxidation state I, preferably a phosphorus compound C2 chosen from hypophosphorous acid, sodium hypophosphite, potassium hypophosphite, lithium hypophosphite, ammonium hypophosphite, calcium hypophosphite, magnesium hypophosphite and combinations thereof. In particular, the molar amount of phosphorus compound C2, preferably the molar amount of phosphorus I, is between 1% and 15%, relative to the total molar amount of monomers used, preferably the molar amount of phosphorus compound C2, preferably the molar amount of phosphorus I, is between 1.5% and 12%, relative to the total molar amount of unsaturated groups of the monomers used.

[0025] According to the invention, compound C may be a phosphorus compound C3 comprising phosphorus in oxidation state III, preferably a phosphorus compound C3 chosen from phosphorous acid, a phosphorous acid salt and combinations thereof. In par In particular, the molar quantity of phosphorus compound C3, preferably the molar quantity of phosphorus III, is between 1% and 15%, relative to the total molar quantity of monomers used, preferably the molar quantity of phosphorus compound C3, preferably the molar quantity of phosphorus III, is between 1.5% and 12%, relative to the total molar quantity of unsaturated groups of the monomers used.

[0026] Preferably according to the invention, compound C may be a secondary alcohol C4, preferably isopropyl alcohol.

[0027] Also preferably according to the invention, compound C may be a sulfur compound C5, preferably chosen from primary thiols, mercaptans and their combinations, for example tert-dodecyl mercaptan, tert-nonyl mercaptan, thiolactic acid, mercaptopropionic acid, mercapto ethanol, thioglycolic acid, 1,8-dhnercapto-3,6-dioxaoctane (DMDO - CAS No. 14970-87-7).

[0028] Also preferably according to the invention, compound C is a RAFT polymerization agent C6, preferably dipropyl trithiocarbonate (DPTTC - CAS No. 6332-91-8) or its salts, for example its disodium salt (sodium dipropionate trithiocarbonate, CAS No. 86470-33-2). In particular, the molar amount of compound C6, preferably the molar amount of DPTTC, is between 1.5% and 12%, relative to the total molar amount of monomers used, preferably the molar amount of compound C6, preferably the molar amount of DPTTC, is between 1.5% and 12%, relative to the total molar amount of unsaturated groups of the monomers used.

[0029] Also preferably according to the invention, the polymer A is chosen from an a-co-disulfonated polymer A1, an a-monosulfonated polymer A2, a polymer A3 comprising phosphinate groups, a polymer A4 comprising phosphonate groups, a polymer A5 comprising phosphinate groups and phosphonate groups and combinations thereof.

[0030] According to the invention, composition T may also comprise, preferably within composition R, a compound D chosen from sulfo-carboxy-aromatic acids and sulfo-carboxy-alkyl acids, preferably 3-sulfopropionic acid, 3-sulfo-2-methyl-propionic acid, sulfo-succinic acid, their salts and their combinations. The preferred salts of compound D are chosen from sodium salt, potassium salt, lithium salt, calcium salt, magnesium salt and ammonium salt. The sodium salt and the ammonium salt of compound D are particularly preferred. Also preferably, composition T or composition R comprises a molar amount of compound D greater than 2% relative to the molar amount of sulfur IV of compound CL. Preferably according to the invention, composition T or composition R comprises a molar amount of compound D greater than 5%, preferably greater than 10% or 15%, more preferably greater than 20% or 25%, relative to the molar quantity of sulfur IV. Also preferably according to the invention, the molar quantity of compound D is less than 60%, preferably less than 50% or 40%, relative to the molar quantity of sulfur IV.

[0031] According to the invention, the molar quantity of compound D present in composition T or composition R relative to the molar quantity of sulfur IV is therefore generally within the ranges of 2% to 60% or 2% to 50% or 2% to 40%, preferably 5% to 60% or 5% to 50% or 5% to 40%. Also preferably, the molar quantity of compound D present in composition T or composition R relative to the molar quantity of sulfur IV is therefore generally within the ranges of 10% to 60% or 10% to 50% or 10% to 40%. Also preferably, the molar quantity of compound D present in composition T or composition R relative to the molar quantity of sulfur IV is within the ranges of 15% to 60% or 15% to 50% or 15% to 40% or 25% to 60% or 25% to 50% or 25% to 40% or 20% to 60% or 20% to 50% or 20% to 40%.

[0032] According to the invention, the composition T may also comprise, for example within the composition R, a compound F chosen from 2-sulfoacetic acid, para-toluenesulfonic acid (PTSA), sulfuric acid, methanesulfonic acid, their salts and their combinations.

[0033] De manière préférée selon l’invention, le composé B est choisi parmi glycérol, poly-alkylèneglycol (de préférence polyalkylèneglycol, polypropylèneglycol, polybutylè-neglycol), pentaérythrytol, triéthanolamine, ethanolamine, diethanolamine, 3-amino-l-propanol, l-amino-2-propanol, butanetriol, ethyleneglycol, 1,3-propanediol, l,4-butanediol,l,6-hexanediol, pentaerythritol, sorbitol 5-amino-l-pentanol, 2-(2-aminoethoxy)ethanol, N-(2-aminoethyl)ethanolamine, bis(N-hydroxyethyl)propane-1,3-diamine, diisopropanolamine, triisopropanolamine, N-methyldiethanolamine, N-butyldiethanolamine, ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2,3-propanetriol, 1,2-butanediol, 1,4-butanediol, 2,3-butanediol, neopentyl glycol, trimethylolpropane, trimethylolpropane 1,2,4 butanetriol, 1,2-pentanediol, 1,5-pentanediol, 1,6-hexanediol, 2,5-dimethyl-2,5-hexanediol, D-arabinose, L-arabinose, D-xylose, D-glucose, D-mannose, D-gallactose, D-glucosamine,D-fructose, maltose, sucrose, lactose, ethyl-nediamine, diethylenetriamine, triethylenetetramine, 1,3-propanediamine, 1,2-propanediamine, neopentyldiamine, hexamethylenediamine, octamethyl-nediamine, N-(2-aminoethyl)propane-1,3-diamine, 1,2,3-propanetriamine, N,N-bis(3-aminopropylamine) and combinations thereof, preferably chosen from, glycerol, triethanolamine, 1,2,4-trimethylolpropane, butanetriol, ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, pentaerythritol, sorbitol and combinations thereof. Also preferably, compound B has a molecular weight ranging from 50 g / mol to 1000 g / mol, preferably from 55 g / mol to 500 g / mol or from 55 g / mol to 250 g / mol.

[0034] Preferably according to the invention, the composition T comprises a molar quantity of functional groups of compound B ranging from 5% to 100%, preferably from 10% to 100% or from 10% to 90% or from 20% to 100% or from 20% to 80% relative to the total molar quantity of carboxylic groups of the polymer A.

[0035] Advantageously according to the invention, the composition R comprises a molar quantity of compound B ranging from 5% to 100%, preferably from 10% to 100% or from 10% to 90% or from 20% to 100% or from 20% to 80% relative to the total molar quantity of monomers.

[0036] In a particularly advantageous manner, the invention makes it possible to avoid the use of certain chemical compounds or substances. Preferably according to the invention, the composition T does not comprise a urea-formaldehyde compound or a formaldehyde compound. Advantageously, the composition T does not comprise a compound comprising phosphorus in oxidation state I or a compound comprising phosphorus in oxidation state III or a compound comprising phosphorus in oxidation state V. Also advantageously, the composition R does not comprise a urea-formaldehyde compound or a formaldehyde compound or does not comprise a compound comprising phosphorus in oxidation state I or a compound comprising phosphorus in oxidation state III or a compound comprising phosphorus in oxidation state V.

[0037] Preferably according to the invention, the composition T comprises a material E chosen from silicon, lithium, graphite or graphitic carbon, hexagonal carbon, rhombohedral carbon and their combinations, optionally doped with at least one element, preferably chosen from lithium, germanium, silicon and their combinations. The preferred material E is chosen from graphite carbon, silicon and their combinations.

[0038] The invention also provides a method of preparing a composition T. The method of preparation comprises: - the preparation of an aqueous composition R according to the invention, - the addition of at least one material E chosen from metallic fibers, metallic particles, graphite carbon fibers, graphite carbon particles and combinations thereof, preferably the material E is chosen from silicon, lithium, graphite or graphitic carbon, hexagonal carbon, rhombohedral carbon and their combinations, optionally doped with at least one element, preferably chosen from lithium, germanium, silicon and their combinations.

[0039] The invention also provides an aqueous composition R defined according to the invention as well as a method for its preparation. The method for preparing the aqueous composition R comprises the preparation of a polymer A according to the invention and then the addition of at least one polyfunctional compound B chosen from polyols, polyamines, amino alcohols, (polyamino) alcohols, amino (polyalcohols), oses, osides and combinations thereof.

[0040] The use during the preparation of polymer A of a sulfur compound Cl according to the invention leads to a method of preparing composition R comprising: - the preparation of a polymer A according to the invention, - optionally maintaining or adding in the aqueous dispersion of polymer A at least one compound D chosen from a sulfocarboxylic acid, a sulfocarboxylic acid salt and their combinations, - the addition of at least one polyfunctional compound B chosen from polyols, polyamines, amino alcohols, (polyamino) alcohols, amino (polyalcohols), oses, osides and combinations thereof.

[0041] The use during the preparation of polymer A of a phosphorus compound C2 or of a phosphorus compound C3 according to the invention leads to a method of preparing composition R comprising: - the preparation of a polymer A according to the invention in the presence of at least one compound C2 or at least one compound C3, - optionally maintaining or adding in the aqueous dispersion of polymer A at least one compound resulting from the reaction of monomer M with respectively compound C2 or at least one compound C3, - the addition of at least one polyfunctional compound B chosen from polyols, polyamines, amino alcohols, (polyamino) alcohols, amino (polyalcohols), oses, osides and combinations thereof.

[0042] The invention also provides a crosslinking agent for a polyfunctional compound B, a method for improving the crosslinking power of an aqueous composition R by means of a compound D according to the invention as well as the corresponding crosslinking improving agent.

[0043] The crosslinking agent according to the invention comprises at least one compound B chosen from polyols, polyamines, aminoalcohols, (polyamino)alcohols, amino(polyalcohols), oses, osides and combinations thereof, for the crosslinking of an aqueous composition R comprising: - at least one a-sulfonated polymer A prepared in water, preferably in the absence of phosphorus compound, by a polymerization reaction of at least one monomer M chosen from acrylic acid, methacrylic acid, an acrylic acid salt, a methacrylic acid salt and combinations thereof, in the presence of at least one initiator compound and at least one sulfur compound comprising sulfur in oxidation state IV, and - at least one compound D chosen from a sulfocarboxylic acid, a sulfocarboxylic acid salt and combinations thereof.

[0044] The method for improving the crosslinking power of an aqueous composition R comprises: - at least one aqueous dispersion of an a-sulfonated polymer A prepared in water, preferably in the absence of a phosphorus compound, by a polymerization reaction of at least one monomer M chosen from acrylic acid, methacrylic acid, an acrylic acid salt, a methacrylic acid salt and combinations thereof, in the presence of at least one initiator compound and at least one sulfur compound comprising sulfur in oxidation state IV, - at least one polyfunctional compound B chosen from polyols, polyamines, aminoalcohols, (polyamino)alcohols, amino(polyalcohols), oses, osides and combinations thereof, comprises maintaining or adding in the aqueous dispersion of polymer A or in the aqueous composition R at least one compound D chosen from a sulfocarboxylic acid, a sulfocarboxylic acid salt and combinations thereof.

[0045] The agent for this method comprises at least one compound B chosen from polyols, polyamines, aminoalcohols, (polyamino)alcohols, amino(polyalcohols), oses, osides and combinations thereof, for improving the crosslinking power of an aqueous composition R comprising: - at least one a-sulfonated polymer A prepared in water, preferably in the absence of a phosphorus compound, by a polymerization reaction of at least one monomer M chosen from acrylic acid, methacrylic acid, an acrylic acid salt, a methacrylic acid salt and combinations thereof, in the presence of at least one initiator compound and at least one sulfur compound Cl comprising sulfur in oxidation state IV, and - at least one compound D chosen from a sulfocarboxylic acid, a sulfocarboxylic acid salt and combinations thereof.

[0046] The aqueous anode composition T according to the invention can be used particularly effectively during the manufacture of an anode. Thus, the invention provides a method for manufacturing an anode comprising: - the application to a substrate of at least one composition T according to the invention, - crosslinking of the material E impregnated by means of composition R.

[0047] Preferably, when manufacturing an anode according to the invention, at least one of the application or crosslinking steps is carried out at a pH below 7, preferably at a pH below 5. Preferably, when manufacturing an anode according to the invention, the crosslinking is carried out at a temperature ranging from 100 to 250°C, preferably from 150 to 240°C or from 170 to 230°C.

[0048] The invention also provides an anode prepared according to the preparation method of the invention.

[0049] According to the invention, the particular, advantageous or preferred characteristics of the composition T according to the invention define aqueous compositions R, methods of preparation and corresponding agents as well as anodes according to the invention which are also particular, advantageous or preferred.

[0050] The following examples illustrate the different aspects of the invention.

[0051] Preparation and characterization of the AA polymer according to the invention

[0052] In a 1 liter glass reactor equipped with stirring, a thermometer and a cooling system, a charge of 6.66 g of sodium hypophosphite is introduced at room temperature into 182 g of water. Then, a solution of 0.01 g of iron sulfate heptahydrate is introduced into 0.74 g of water and 3 charges are prepared to be introduced in parallel for 2 hours. In a first beaker, 224.01 g of acrylic acid are introduced. In a second beaker, 23.12 g of hydrogen peroxide at 35% by mass are introduced into 19.9 g of water. In a third beaker, 6.03 g of sodium hypophosphite are introduced into 14 g of water. After 2 hours of addition at 97°C, a clear dispersion of AA polymer is obtained with a dry matter concentration of 45%, having a mass Mw of 3,855 g / mol and an Ip of 2.0.

[0053] Preparation and characterization of the polymer AB according to the invention

[0054] In a 1 liter glass reactor equipped with stirring, a thermometer and a cooling system, a charge comprising 0.006 g of iron sulfate heptahydrate and 380 g of water is prepared at room temperature. Then, 3 charges are prepared to be introduced in parallel for 3 hours. 623.5 g of acrylic acid are introduced into a first beaker, 5.086 g of sodium persulfate and 46.6 g of water into a second beaker and 122.86 g of an aqueous solution of sodium bisulfite at 40% by mass into a third beaker. After 3 hours of addition at 73°C, a clear dispersion of AB polymer is obtained with a dry matter concentration of 55.2%, having a mass Mw of 4,430 g / mol and an Ip of 2.2.

[0055] Preparation and characterization of the AC polymer according to the invention

[0056] In a 1 liter glass reactor equipped with stirring, a thermometer and a cooling system, a charge comprising 0.023 g of iron sulfate heptahydrate and 284.13 g of water is prepared at room temperature. Then, 3 charges are prepared to be introduced in parallel over 3 hours. First, a charge is introduced into the reactor heated to 80°C, a charge of 0.74 g of sodium persulfate and 19.68 g of water is added. Then, 450.99 g of acrylic acid are added to a first beaker, 1.96 g of sodium persulfate and 19.68 g of water to a second beaker and 94.23 g of a 40% by mass aqueous solution of sodium bisulfite to a third beaker. After 3 hours of addition at 80°C, a clear dispersion of AC polymer is obtained. This polymer is then neutralized by adding sodium hydroxide to a pH of 2.0. The dry matter concentration is 50.0%. The AC polymer has a mass Mw of 6,000 g / mol and an Ip of 2.7. Preparation of compositions R according to the invention

[0057] Preparation of the RAI composition according to the invention

[0058] 525.83 g of AA polymer dispersion, 2.30 g of sodium hypophosphite, 157.81 g of triethanolamine (polyfunctional compound B) and 321.60 g of water are mixed with stirring.

[0059] Preparation of the composition RA2 according to the invention

[0060] 614.07 g of AA polymer dispersion, 3.50 g of sodium hypophosphite, 129.41 g of a 70% by mass aqueous solution of sorbitol (polyfunctional compound B) and 309.34 g of water.

[0061] Preparation of the composition RB1 according to the invention

[0062] 131.34 g of polymer AB dispersion, 22.7 g of glycerol (polyfunctional compound B) and 24.2 g of water are mixed with stirring.

[0063] Preparation of the composition RC1 according to the invention

[0064] 146.46 g of AC polymer dispersion, 22.7 g of glycerol (polyfunctional compound B) and 24.2 g of water.

[0065] Preparation and characterization of anode compositions T according to the invention

[0066] Preparation of composition TA1 according to the invention

[0067] A homogeneous mixture comprising 3.07 g of composition RAI, 83.16 g of deionized water and 80.75 g of graphite carbon (Xiamen Tob tb-sup-c65 - CAS number 1333-86-4) is prepared under stirring at 2000 rpm (Speed ​​mixer DAC 400 FVZ Hauschild). The composition TA1 obtained has a dry extract of 60.6%.

[0068] Preparation of composition TA2 according to the invention

[0069] A homogeneous mixture comprising 3.18 g of composition RA2, 51.42 g of deionized water and 80.35 g of graphite carbon (Xiamen Tob tb-sup-c65 - CAS number 1333-86-4) is prepared under stirring at 2000 rpm (Speed ​​mixer DAC 400 FVZ Hauschild). The composition TA1 obtained has a dry extract of 60.5%.

[0070] Preparation of the composition TB1 according to the invention

[0071] A homogeneous mixture comprising 2.62 g of composition RB1, 49.02 g of deionized water and 70.39 g of graphite carbon (Xiamen Tob tb-sup-c65 - CAS number 1333-86-4). The TB1 composition obtained has a dry extract of 58.8%.

[0072] Preparation of the TCI composition according to the invention

[0073] A homogeneous mixture comprising 2.56 g of composition RC1, 49.02 g of deionized water and 70.22 g of graphite carbon (Xiamen Tob tb-sup-c65 - CAS number 1333-86-4) is prepared under stirring at 2000 rpm (Speed ​​mixer DAC 400 FVZ Hauschild). The TCI composition obtained has a dry extract of 58.7%.

[0074] On a copper substrate (copper foil for anode, thickness 12 μm), a continuous and homogeneous layer of composition TA1 (thickness 250 μm - wet) is applied using a Byko-Drive (BYK) automatic film applicator. It is dried at room temperature for 24 hours.

[0075] On a first sample at room temperature, the layer is manually wiped. A partial transfer of graphite onto the finger is visually observed, thus altering the layer of composition TA1 applied. On this sample, the composition TA1 did not adhere sufficiently to the copper substrate to resist mechanically.

[0076] A second sample is placed in an oven at 205°C for 10 minutes. After cooling to room temperature, the layer is manually wiped off. This does not result in any transfer of graphite onto the finger; the applied layer remained intact. On this second sample, the treated TA1 composition adhered correctly to the copper substrate to provide mechanical resistance.

[0077] These evaluations are reproduced using compositions TA2, TB1 and TCI. As with composition TA1, these compositions TA2, TB1 and TCI adhere well to the copper substrate to provide mechanical resistance.

Claims

Claims

1. Aqueous anode composition T comprising: * at least one crosslinkable aqueous composition R comprising: a) at least one polymer A having a weight-average molecular mass Mw (measured by CES) of less than 20,000 g / mol and prepared in water by a polymerization reaction of at least one monomer M chosen from acrylic acid, methacrylic acid, an acrylic acid salt, a methacrylic acid salt and combinations thereof, in the presence of at least one initiator compound, b) at least one compound B chosen from polyols, polyamines, amino alcohols, (polyamino) alcohols, amino (polyalcohols), oses, osides and combinations thereof, * at least one material E chosen from metal fibers, metal particles, graphite carbon fibers, graphite carbon particles and combinations thereof.

2. Composition T according to claim 1 for which: - the monomer M is chosen from acrylic acid, an acrylic acid salt and combinations thereof, or - the monomer M is combined with at least one other monomer chosen from vinyl acetate, ethyl acrylate, methyl acrylate, hydroxyethyl methacrylate, hydroxyethyl acrylate, hydroxypropyl methacrylate, hydroxypropyl acrylate, 2-acrylamido-2-methylpropane sulfonic acid (AMPS), maleic acid, maleic anhydride, itaconic acid and combinations thereof, or - the monomer M is chosen from acrylic acid, an acid salt and combinations thereof, combined with at least one other monomer chosen from vinyl acetate, ethyl acrylate, methyl acrylate, hydroxyethyl methacrylate, hydroxyethyl acrylate, hydroxypropyl methacrylate, hydroxypropyl acrylate, 2-acrylamido-2-methylpropane sulfonic acid (AMPS), maleic acid, maleic anhydride, itaconic acid and their combinations,or for which: - polymer A is non-neutralized or polymer A is partially or totally neutralized.,

3. Composition T according to one of claims 1 or 2 for which the polymer A is prepared in the presence of at least one polymerization agent C chosen from: - a sulfur compound Cl comprising sulfur in oxidation state IV,

4. preferably a sulfur compound Cl selected from lithium hydrogen sulfite, sodium hydrogen sulfite, potassium hydrogen sulfite, ammonium hydrogen sulfite, calcium di(hydrogen sulfite), magnesium di(hydrogen sulfite) and combinations thereof, or - a phosphorus compound C2 comprising phosphorus in oxidation state I, preferably a phosphorus compound C2 selected from hypophosphorous acid, sodium hypophosphite, potassium hypophosphite, lithium hypophosphite, ammonium hypophosphite, calcium hypophosphite, magnesium hypophosphite and combinations thereof, or - a C3 phosphorus compound comprising phosphorus in oxidation state III, preferably a C3 phosphorus compound selected from phosphorous acid, a phosphorous acid salt and combinations thereof, or - a C4 secondary alcohol, preferably isopropyl alcohol, or - a C5 sulfur compound, preferably chosen from primary thiols, mercaptans and combinations thereof, for example tert-dodecyl mercaptan, tert-nonyl mercaptan, thiolactic acid, mercaptopropionic acid, mercapto ethanol, thioglycolic acid, l,8-dimercapto-3,6-dioxaoctane (DMDO - CAS No. 14970-87-7), or - a RAFT C6 polymerization agent, preferably dipropyl trithiocarbonate (DPTTC - CAS No. 6332-91-8) or its salts, - and combinations thereof. Composition T according to one of claims 1 to 3 for which: - the molar quantity of sulfur compound Cl, preferably the molar quantity of sulfur IV, is between 1% and 15%, preferably between 1.5% and 12%, relative to the total molar quantity of monomers used, - preferably the molar quantity of sulfur compound Cl, preferably the molar quantity of sulfur IV, is between 1% and 15%, preferably between 1.5% and 12%, relative to the total molar quantity of unsaturated groups of the monomers used, or - the molar quantity of phosphorus compound C2, preferably the molar quantity of phosphorus I, is between 1% and 15%, relative to the total molar quantity of monomers used, preferably the molar quantity of phosphorus compound C2, preferably the molar quantity of phosphorus I, is between 1.5% and 12%, relative to the total molar quantity of unsaturated groups of the monomers used, or - the molar quantity of phosphorus compound C3, preferably the molar quantity of phosphorus III, is between 1% and 15%, relative to the total molar quantity of monomers used, preferably the molar quantity of phosphorus compound C3, preferably the molar quantity of phosphorus III, is between 1.5% and 12%, relative to the total molar quantity of unsaturated groups of the monomers used, or - the molar quantity of compound C6, preferably the molar quantity of DPTTC, is between 1.5% and 12%, relative to the total molar quantity of monomers used, preferably the molar quantity of compound C6, preferably the molar quantity of DPTTC, is between 1.5% and 12%, relative to the total molar quantity of unsaturated groups of the monomers used.

5. Composition T according to one of claims 1 to 4 for which: - polymer A is chosen from an a-co-disulfonated polymer A1, an a-monosulfonated polymer A2, a polymer A3 comprising phosphinate groups, a polymer A4 comprising phosphonate groups, a polymer A5 comprising phosphinate groups and phosphonate groups and combinations thereof, or - polymer A has a weight-average molecular mass Mw (measured by CES) of less than 15,000 g / mol, less than 10,000 g / mol, more preferably less than 7,000 g / mol or less than 6,000 g / mol, or - polymer A has a weight-average molecular mass Mw (measured by CES) greater than 1,000 g / mol or greater than 1,200 g / mol, or - polymer A has a polymolecularity index Ip (measured by CES) less than 4 or ranging from 1.2 to 4 or from 1.5 to 4; from 1.2 to 3 or from 1.5 to 3; from 1.2 to 2.5 or even from 1.5 to 2.

5.

6. Composition T according to one of claims 1 to 5 also comprising, preferably within composition R: - a compound D chosen from sulfo-carboxy-aromatic acids and sulfo-carboxy-alkyl acids, preferably the acid 3-sulfopropionic acid, 3-sulfo-2-methyl-propionic acid, sulfo-succinic acid, their salts and combinations thereof, or is selected from sodium salt, potassium salt, lithium salt, calcium salt,

7. magnesium and ammonium salt, preferably sodium salt and ammonium salt, also preferably: - a molar quantity of compound D greater than 2% relative to the molar quantity of sulfur IV of compound Cl, or - a compound F chosen from 2-sulfoacetic acid, para-toluenesulfonic acid (PTSA), sulfuric acid, methanesulfonic acid, their salts and their combinations. Composition T according to one of claims 1 to 6 for which: - compound B is chosen from glycerol, polyalkylene glycol (preferably polyalkylene glycol, polypropylene glycol, polybutylene glycol), pentaerythritol, triethanolamine, ethanolamine, diethanolamine, 3-amino-1-propanol, 1-amino-2-propanol, butanetriol, ethylenglycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, pentaerythritol, sorbitol 5-amino-1-pentanol, 2-(2-aminoethoxy)ethanol, N-(2-aminoethyl)ethanolamine, bis(N-hydroxyethyl)propane-1,3-diamine, diisopropanolamine, triisopropanolamine, N-methyldiethanolamine, N-butyldiethanolamine, ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2,3-propanetriol, 1,2-butanediol, 1,4-butanediol, 2,3-butanediol, neopentyl glycol, trime-thylolpropane, trimethylolpropane 1,2,4 butanetriol, 1,2-pentanediol, 1,5-pentanediol, 1,6-hexanediol, 2,5-dimethyl-2,5-hexanediol, D-arabinose, L-arabinose, D-xylose, D-glucose, D-mannose,D-gallactose, D-glucosamine, D-fructose, maltose, sucrose, lactose, ethylenediamine, diethylenetriamine, triethylenetetramine, 1,3-propanediamine, 1,2-propanediamine, neopentyldiamine, hexamethylenediamine, octa-methylenediamine, N-(2-aminoethyl)propane-1,3-diamine, 1,2,3-propanetriamine, N,N-bis(3-aminopropylamine) and combinations thereof, preferably selected from glycerol, triethanolamine, trimethylolpropane 1,2,4, butanetriol, ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, pentaerythritol, sorbitol and combinations thereof, or, - compound B has a molecular mass ranging from 50 g / mol to 1000 g / mol, preferably from 55 g / mol to 500 g / mol or from 55 g / mol to 250 g / mol, or - a molar quantity of functional groups of compound B ranging from 5% to 100%, preferably from 10% to 100% or from 10% to 90% or from 20% to 100% or from 20% to 80%, relative to the total molar quantity of carboxylic groups of polymer A, or for which: - the molar quantity of compound B ranges from 5% to 100%, preferably from 10% to 100% or from 10% to 90% or from 20% to 100% or from 20% to 80%, relative to the total molar quantity of monomers.

8. Composition T according to one of claims 1 to 7: - not comprising a urea-formaldehyde compound or a formaldehyde compound or not comprising a compound comprising phosphorus in oxidation state I or a compound comprising phosphorus in oxidation state III or a compound comprising phosphorus in oxidation state V, - preferably for which composition R does not comprise a urea-formaldehyde compound or a formaldehyde compound or not comprising a compound comprising phosphorus in oxidation state I or a compound comprising phosphorus in oxidation state III or a compound comprising phosphorus in oxidation state V.

9. Composition T according to one of claims 1 to 8 for which the material E is chosen from silicon, lithium, graphite or graphitic carbon, hexagonal carbon, rhombohedral carbon and their combinations, optionally doped with at least one element, preferably chosen from lithium germanium and their combinations.

10. Method for preparing an aqueous composition T according to claims 1 to 9, comprising: - the preparation of an aqueous composition R according to one of claims 1 to 9, - the addition of at least one material E chosen from metal fibers, metal particles, graphite carbon fibers, graphite carbon particles and combinations thereof, preferably the material E is chosen from silicon, lithium, graphite or graphitic carbon, hexagonal carbon, rhombohedral carbon and combinations thereof, optionally doped with at least one element, preferably chosen from lithium germanium and combinations thereof.

11.

12. Aqueous composition R defined according to one of claims 1 to 9. Method for preparing an aqueous composition R defined according to claims 1 to 9, comprising: - the preparation of a polymer A defined according to one of claims 1 to 6, - optionally maintaining or adding in the aqueous dispersion of polymer A at least one compound D chosen from a sulfo- carboxylic acid, a sulfocarboxylic acid salt and combinations thereof, - the addition of at least one polyfunctional compound B chosen from polyols, polyamines, aminoalcohols, (polyamino)alcohols, amino(polyalcohols), oses, osides and combinations thereof.

13. Crosslinking agent for an aqueous composition R comprising: - at least one a-sulfonated polymer A having a weight-average molecular mass Mw (measured by CES) of less than 20,000 g / mol and prepared in water, preferably in the absence of a phosphorus-containing compound, by a polymerization reaction of at least one monomer M chosen from acrylic acid, methacrylic acid, an acrylic acid salt, a methacrylic acid salt and combinations thereof, in the presence of at least one initiator compound and at least one sulfur-containing compound comprising sulfur in oxidation state IV, and - at least one compound D chosen from a sulfocarboxylic acid, a sulfocarboxylic acid salt and combinations thereof, comprising at least one compound B chosen from polyols, polyamines, aminoalcohols, (polyamino)alcohols, amino(polyalcohols), oses, osides and combinations thereof.

14. Method for improving the crosslinking power of an aqueous composition R comprising: - at least one aqueous dispersion of an a-sulfonated polymer A having a weight-average molecular mass Mw (measured by CES) of less than 20,000 g / mol and prepared in water, preferably in the absence of a phosphorus-containing compound, by a polymerization reaction of at least one monomer M chosen from acrylic acid, methacrylic acid, an acrylic acid salt, a methacrylic acid salt and combinations thereof, in the presence of at least one initiator compound and at least one sulfur-containing compound comprising sulfur in oxidation state IV, - at least one polyfunctional compound B chosen from polyols, polyamines, aminoalcohols, (polyamino)alcohols, amino(polyalcohols), oses, osides and combinations thereof,comprising maintaining or adding in the aqueous dispersion of polymer A or in the aqueous composition R at least one compound D chosen from a sulfocarboxylic acid, a sulfocarboxylic acid salt and combinations thereof.,

15. Agent for improving the crosslinking power of an aqueous composition R comprising: - at least one a-sulfonated polymer A having a molecular mass weight average Mw (measured by CES) less than 20,000 g / mol and prepared in water, preferably in the absence of a phosphorus compound, by a polymerization reaction of at least one monomer M chosen from acrylic acid, methacrylic acid, an acrylic acid salt, a methacrylic acid salt and combinations thereof, in the presence of at least one initiator compound and at least one sulfur compound Cl comprising sulfur in oxidation state IV, and - at least one compound D chosen from a sulfocarboxylic acid, a sulfocarboxylic acid salt and combinations thereof, comprising at least one compound B chosen from polyols, polyamines, aminoalcohols, (polyamino)alcohols, amino(polyalcohols), oses, osides and combinations thereof.

16. A method of manufacturing an anode comprising: - the application to a substrate of at least one composition T according to one of claims 1 to 9, - crosslinking the material E impregnated by means of composition R, preferably at least one of the application or crosslinking steps is carried out at a pH lower than 7, preferably at a pH lower than 5, or the crosslinking is carried out at a temperature ranging from 100 to 250°C, preferably from 150 to 240°C or from 170 to 230°C.

17. An anode prepared according to the method defined by claim 16.