Stabilized aqueous anode composition

Abstract

The invention relates to an aqueous anode composition stabilized by means of a polyurethane rheological agent comprising carbon graphite or metallic particles or fibers and a binding agent. The invention also relates to a method for producing an anode using said aqueous composition, and to the resulting anode.

Description

[0001] STABILIZED AQUEOUS ANODE COMPOSITION

[0002] DESCRIPTION

[0003] The invention relates to an aqueous anode composition stabilized by means of a polyurethane rheological agent which also comprises a binding agent and metallic or carbon graphite particles or fibers. The invention also relates to a method for manufacturing an anode using this aqueous composition as well as the anode obtained.

[0004] Anode compositions are known that generally comprise carbon or a metal in particulate form associated with a binder composition. This binder composition must be able to effectively bind the carbon or metal to a substrate to form an anode. The most common binder compositions comprise a styrene-butadiene polymer and allow the active particles to be fixed on a metal substrate. The binding power, mechanical strength or electrochemical resistance are particularly sought after both during the manufacture and use of an anode. Indeed, the quality of the anode composition coating applied to the metal substrate is essential for the optimal efficiency of the anode as well as its maximum durability. The thixotropic behavior or rheological behavior over time of an aqueous anode composition must therefore be controlled as well as possible.

[0005] It is also advantageous to have anode compositions that are versatile and retain their rheological properties when their operating conditions differ.

[0006] Easy and homogeneous application of anode compositions is necessary to obtain a homogeneous layer and to limit or avoid defects on the anode surface, in order to achieve a homogeneous and particularly efficient conductive layer. The surface leveling, restructuring and flow behavior of an aqueous anode composition must be well controlled.

[0007] It is therefore essential to have anode compositions with very well-controlled rheology. Indeed, in addition to application difficulties, excessive viscosity generally leads to numerous defects in the layer deposited on the surface of the anode. Insufficient viscosity leads to the same types of problems and also results in uncontrolled flows of the anode composition during its application.

[0008] Anode compositions must also be stable and homogeneous during their preparation, storage or application. Sedimentation, formation of agglomerates or aggregates, and separation of ingredients must therefore be limited or avoided.

[0009] Often, these anode compositions include silicon to increase the capacity of the prepared anodes. During charge-discharge cycles of batteries containing these anodes, it is common to observe deformation that can lead to irreversible damage to the anode, particularly due to the increase in volume of silicon. Deformation tolerance is therefore also a sought-after property.

[0010] The compatibility of the different ingredients of the anode compositions is also an important factor when preparing the anode compositions as well as when preparing the anodes using these compositions.

[0011] Document JP 2015220170 relates to the use, during the preparation of a battery anode, of a polymeric binder based on a thermoplastic resin prepared from poly(tetramethylene glycol), diethylene glycol, IPDI and N,N'-dimethylformamide. Document WO 2021014054 describes an aqueous thickening composition based on an osidic compound and a polyurethane polymer.

[0012] 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. Thus, the invention provides an aqueous anode composition T comprising:

[0013] • at least one rheological agent R comprising at least one water-soluble, non-ionic urethane polymer P, prepared by a polymerization reaction: a) of at least one isocyanate compound (a) chosen independently from a diisocyanate compound (a1), a polyisocyanate compound (a2) and combinations thereof; b) of at least one compound (b) of formula I:

[0014] RX n -OH

[0015] (I) in which:

[0016] - R independently represents a group chosen from a linear C4-C40-alkyl group, a branched C4-C40-alkyl group, a Cs-C40-cycloalkyl group, a linear C4-C40-alkenyl group, a branched C4-C40-alkenyl group, a C5-C40-cycloalkenyl group, a C5-C40-aryl group and combinations thereof, - X independently represents an alkoxylated group chosen from oxyethylene, oxypropylene, oxybutylene and combinations thereof,

[0017] - n represents 0 or a number ranging from 1 to 500; c) at least one polyhydroxylated and polyalkoxylated compound (c);

[0018] • at least one material E chosen from metal fibers, metal particles, graphite carbon fibers, graphite carbon particles, silicon particles and combinations thereof; and

[0019] • at least one binding agent L of the material E chosen from a polymer L1 in the form of a non-water-soluble latex, a water-soluble polymer L2 and their combinations.

[0020] Essentially according to the invention, the anode composition comprises at least one rheological agent R comprising a urethane polymer P prepared by means of an isocyanate compound (a) chosen from a diisocyanate compound (a1), a polyisocyanate compound (a2) and combinations thereof.

[0021] Preferably for the composition T according to the invention, the diisocyanate compound (a1) is chosen from: symmetrical aromatic diisocyanate compounds, preferably 2,2'-diphenylmethylene diisocyanate (2,2'-MDI); 4,4'-diphenylmethylene diisocyanate (4,4'-MDI); 4,4'-dibenzyl diisocyanate (4,4'-DBDI); 2,6-toluene diisocyanate (2,6-TDI); m-xylylene diisocyanate (m-XDI); symmetrical alicyclic diisocyanate compounds, preferably methylene bis(4-cyclohexylisocyanate) (H12MDI); symmetrical aliphatic diisocyanate compounds, preferably hexamethylene diisocyanate (HDI), pentamethylene diisocyanate (PDI); unsymmetrical aromatic diisocyanate compounds, preferably 2,4'-diphenylmethylene diisocyanate (2,4'-MDI); 2,4'-dibenzyl diisocyanate (2,4'-DBDI); 2,4-toluene diisocyanate (2,4-TDI); unsymmetrical alicyclic diisocyanate compounds, preferably isophorone diisocyanate (IPDI).

[0022] Preferably according to the invention, the compound (al) is chosen from IPDI, HDI, H12MDI and their combinations.

[0023] Also preferably for the composition T according to the invention, the polyisocyanate compound (a2) strictly comprises more than 2 isocyanate functions or more than 2.2 isocyanate functions or even more than 2.5 isocyanate functions. More preferably, the polyisocyanate compound (a2) comprises more than 2.6 isocyanate functions or more than 2.7 isocyanate functions or more than 3 isocyanate functions. Much more preferably, the polyisocyanate compound (a2) comprises from 2.2 to 6 isocyanate functions, from 2.2 to 4 isocyanate functions, from 2.2 to 3.5 isocyanate functions, from 2.5 to 6 isocyanate functions, from 2.2 to 5 isocyanate functions, from 2.5 to 4 isocyanate functions, from 2.5 to 3.5 isocyanate functions, in particular from 2.6 to 3.3 isocyanate functions.

[0024] More preferably, the polyisocyanate compound (a2) is chosen from: triphenylmethane-4,4',4”-triisocyanate or 1,1',1”-methylidynetris (4-isocyanatobenzene); an isocyanurate compound, in particular an isocyanurate compound of a compound chosen from: o symmetrical aromatic diisocyanate compounds, preferably 2,2'-diphenylmethylene diisocyanate (2,2'-MDI); 4,4'-diphenylmethylene diisocyanate (4,4'-MDI); 4,4'-dibenzyl diisocyanate (4,4'-DBDI); 2,6-toluene diisocyanate (2,6-TDI); m-xylylene diisocyanate (m-XDI); o symmetrical alicyclic diisocyanate compounds, preferably methylene bis(4-cyclohexylisocyanate) (H12MDI); o symmetrical aliphatic diisocyanate compounds, preferably hexamethylene diisocyanate (HDI), pentamethylene diisocyanate (PDI); o unsymmetrical aromatic diisocyanate compounds, preferably 2,4'-diphenylmethylene diisocyanate (2,4'-MDI); 2,4'-dibenzyl diisocyanate (2,4'-DBDI);2,4-toluene diisocyanate (2,4-TDI); a trimeric biurea compound, in particular a trimeric biurea compound of a compound selected from: o symmetrical aromatic diisocyanate compounds, preferably 2,2'-diphenylmethylene diisocyanate (2,2'-MDI); 4,4'-diphenylmethylene diisocyanate (4, 4'-MDI); 4,4'-dibenzyl diisocyanate (4,4'-DBDI); 2,6-toluene diisocyanate (2,6-TDI); m-xylylene diisocyanate (m-XDI); o symmetrical alicyclic diisocyanate compounds, preferably methylene bis(4-cyclohexylisocyanate) (H12MDI); o symmetrical aliphatic diisocyanate compounds, preferably hexamethylene diisocyanate (HDI), pentamethylene diisocyanate (PDI); o unsymmetrical aromatic diisocyanate compounds, preferably 2,4'-diphenylmethylene diisocyanate (2,4'-MDI); 2,4'-dibenzyl diisocyanate (2,4'-DBDI); 2,4-toluene diisocyanate (2,4-TDI); o unsymmetrical alicyclic diisocyanate compounds, preferably isophorone diisocyanate (IPDI).;

[0025] More preferably according to the invention, the compound (a2) is chosen from triphenylmethane-4,4',4”-triisocyanate, 1,1',1”-methylidynetris (4-isocyanatobenzene), an HDI isocyanurate, an IPDI isocyanurate, a PDI isocyanurate, an HDI biurea trimer, an IPDI biurea trimer, a PDI biurea trimer.

[0026] Preferably for composition T according to the invention, compound (b) is a compound of formula I in which:

[0027] R independently represents a group selected from a linear C6-C32-alkyl group, a branched C6-C32-alkyl group, a C6-C32-cycloalkyl group, a linear C6-C32-alkenyl group, a branched C6-C32-alkenyl group, a C6-C32-cycloalkenyl group, a C6-C36-aryl group and combinations thereof, preferably

[0028] R independently represents a group selected from a linear C6-C24-alkyl group, a branched C6-C24-alkyl group, a C6-C24-cycloalkyl group, a linear C6-C24-alkenyl group, a branched C6-C24-alkenyl group, a C6-C24-cycloalkenyl group, a C6-C32-aryl group and combinations thereof; or

[0029] X independently represents an alkoxylated group selected from an ethoxylated group, a propoxylated group, a butoxylated group and combinations thereof; preferably X represents an ethoxylated group or a combination of ethoxylated groups and propoxylated groups, more preferably X represents an ethoxylated group; or n represents 0 or a number ranging from 1 to 300, preferably from 1 to 150 or from 1 to 100, more preferably from 1 to 50 or from 1 to 25.

[0030] More preferably for composition T according to the invention, compound (b) is a compound of formula I in which:

[0031] R independently represents a group selected from a linear C6-C32-alkyl group, a branched C6-C32-alkyl group, a C6-C32-cycloalkyl group, a linear C6-C32-alkenyl group, a branched C6-C32-alkenyl group, a C6-C32-cycloalkenyl group, a C6-C8-aryl group and combinations thereof, preferably

[0032] R independently represents a group selected from a linear C6-C24-alkyl group, a branched C6-C24-alkyl group, a C6-C24-cycloalkyl group, a linear C6-C24-alkenyl group, a branched C6-C24-alkenyl group, a C6-C24-cycloalkenyl group, a C6-C32-aryl group and combinations thereof; and

[0033] X independently represents an alkoxylated group selected from an ethoxylated group, a propoxylated group, a butoxylated group and combinations thereof; preferably X represents an ethoxylated group or a combination of ethoxylated groups and propoxylated groups, more preferably X represents an ethoxylated group; and n represents 0 or a number ranging from 1 to 300, preferably from 1 to 150 or from 1 to 100, more preferably from 1 to 50 or from 1 to 25.

[0034] According to the invention, the group R can also represent a radical of formula: in which R” represents a hydrocarbon group of formula C15H31-X in which x represents 0, 2, 4, 6; thus being able to comprise 0, 1, 2 or 3 ethylenic unsaturations (double bond). Such a radical is advantageously a cardanyl group derived from cardanol. According to the invention, the group R can also represent a pentastyrylcumylphenyl group, a tristyrylphenyl (TSP) group of formula: or a distyrylphenyl (DSP) group of formula: According to the invention, the urethane polymer P is prepared using at least one polyhydroxylated and polyalkoxylated compound (c). Preferably for the composition T according to the invention, the compound (c) may be a compound (cl) of formula II:

[0035] HO-Qm-OH

[0036] (II) in which:

[0037] Q independently represents an oxyalkylene residue; m independently represents a number ranging from 30 to 1,000.

[0038] More preferably for composition T according to the invention, compound (c) may be a compound (cl) of formula II in which:

[0039] Q independently represents an oxyethylene residue; or m independently represents a number ranging from 50 to 600, preferably from 100 to 600.

[0040] More preferably for composition T according to the invention, compound (c) may be a compound (cl) of formula II in which Q independently represents an oxyethylene residue and m independently represents a number ranging from 50 to 600, preferably from 100 to 600.

[0041] Also preferably for composition T according to the invention, compound (c) may be a compound (c1) of formula II associated with a non-alkoxylated compound (c2) comprising at least three hydroxyl groups. Preferably for composition T according to the invention, compound (c2) comprises three hydroxyl groups. More preferably, it is chosen from glycerol, pentaerythritol and their combinations.

[0042] Also preferably for composition T according to the invention, compound (c) may be a polyalkoxylated compound (c3) comprising at least three hydroxyl groups. The polyalkoxylated compound (c3) is different from compound (c2). More preferably, the polyalkoxylated compound (c3) comprises three hydroxyl groups. Even more preferably, compound (c3) is chosen from polyethoxylated glycerol, polyethoxylated pentaerythritol and combinations thereof.

[0043] According to the invention, compound (c) can be implemented in the form of one or more combinations of compounds (c1), (c2) and (c3).

[0044] Essentially according to the invention, the polyhydroxylated compound (c) is a polyalkoxylated compound. Preferably for the composition T according to the invention, the compound (c) comprises from 10 to 500 alkoxylations, preferably from 20 to 400 alkoxylations or from 10 to 300 alkoxylations. More preferably, the compound (c) comprises from 20 to 250 alkoxylations.

[0045] Also preferably, compound (c) is polyethoxylated or is polyethoxylated-polypropoxylated or is polyethoxylated-poly butoxylated. More preferably, compound (c) is polyethoxylated.

[0046] According to the invention, compound (c) generally comprises from 10 to 500 ethoxylations, preferably from 20 to 400 ethoxylations or from 10 to 300 ethoxylations. More preferably, compound (c) comprises from 20 to 250 ethoxylations.

[0047] The molar mass of compound (c) can vary quite widely, in particular depending on the number of alkoxylations that compound (c) comprises. Preferably, compound (c), (cl) or (c3) independently has a molecular mass by weight (Mw) measured by CES ranging from 1,500 g / mol to 40,000 g / mol. More preferably, their molecular mass by weight ranges from 2,000 g / mol to 25,000 g / mol, more preferably from 2,000 g / mol to 20,000 g / mol or from 2,000 g / mol to 15,000 g / mol or from 2,000 g / mol to 12,000 g / mol. Much more preferably, their molecular mass by weight ranges from 4,000 g / mol to 20,000 g / mol or from 4,000 g / mol to 15,000 g / mol or from 4,000 g / mol to 12,000 g / mol.

[0048] According to the invention, the molecular weight or mass is determined by Size Exclusion Chromatography (SEC). A sample of the compound 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: NaHCOs: 0.05 mol / L, NaNOs: 0.1 mol / L, triethanolamine: 0.02 mol / L, NaNs 0.03% by mass. The CES chain is composed of a “Waters” 510 isocratic pump, whose flow rate is set at 0.8 mL / min, a “Waters” 717+ sample changer, an oven containing a “Waters” Guard Column Ultrahydrogel precolumn of 6 cm length and 40 mm inner diameter, followed by a “Waters” Ultrahydrogel linear column of 30 cm length and 7.8 mm inner diameter.Detection is ensured by means of a differential refractometer type RI “Waters” 410. The oven is brought to the temperature of 60°C and the refractometer is brought to the temperature of 45°C. The CES device is calibrated with a series of sodium polyacrylate standards supplied by Polymer Standards Service with a peak molecular weight between 900 g / mol and 2,250,000 g / mol and a polydispersity index between 1.4 and 1.7. The calibration curve is of the linear type and takes into account the correction obtained thanks to the flow marker: dimethylformamide (DMF). The acquisition and processing of the chromatogram are carried out using the software “PSS WinGPC Scientific” v 4.02. The chromatogram obtained is integrated in the zone corresponding to molecular weights greater than 250 g / mol.

[0049] During the preparation of polymer P, the amounts of the different compounds used during the polymerization reaction can vary quite widely. Preferably for composition T according to the invention, the polymerization reaction uses from 20 mol% to 74.9 mol% of compound (a) or from 25 mol% to 79.9 mol% of compound (b) or from 0.1 mol% to 55 mol% of compound (c) relative to the total molar amount of compounds (a), (b) and (c).

[0050] More preferably, the polymerization reaction uses from 25 mol% to 60 mol% of compound (a) or from 35 mol% to 70 mol% of compound (b) or from 5 mol% to 40 mol% of compound (c) relative to the total molar quantity of compounds (a), (b) and (c).

[0051] Also preferably, the polymerization reaction uses: from 20 mol% to 74.9 mol%, preferably from 25 mol% to 60 mol%, of compound (a), from 25 mol% to 79.9 mol%, preferably from 35 mol% to 70 mol%, of compound (b), and from 0.1 mol% to 55 mol%, preferably from 5 mol% to 40 mol%, of compound (c), relative to the total molar quantity of compounds (a), (b) and (c).

[0052] The molar mass of the polymer P can vary quite widely, in particular depending on the number of alkoxylations of the compounds (b) and (c). Preferably, the polymer P has a molar mass (Mw) measured by CES ranging from 4,000 g / mol to 150,000 g / mol; preferably from 6,000 g / mol to 100,000 g / mol; more preferably from 10,000 g / mol to 80,000 g / mol.

[0053] Essentially, in the preparation of polymer P, the polymerization reaction involves compounds (a), (b) and (c). Other monomers can also be used.

[0054] Preferably for composition T according to the invention, the polymerization reaction can also use at least one additional crosslinking compound (d), preferably a compound (d) comprising at least 3 functional groups chosen from OH, SH, primary amine, secondary amine and combinations thereof. More preferably, compound (d) is chosen from diethanolamine, triethanolamine, trimethylolpropane, glycerol, pentaerythritol and combinations thereof.

[0055] Preferably, compound (d) is used in an amount of less than 5 mol%, preferably from 0.01 mol% to 5 mol%, in particular from 0.1 mol% to 5 mol% of compound (d), relative to the total molar amount of monomers.

[0056] According to the invention, the rheological agent R comprises at least one urethane polymer P alone or combined with one or more other ingredients. The agent R may comprise a support, in particular a liquid support which may be chosen from water, polar organic solvents and combinations thereof. These solvents may be chosen from glycol, butyl glycol, butyl diglycol, monopropylene glycol, ethylene glycol, methyl carbonate, ethyl carbonate, propyl carbonate, esters, ketones, ethylene diglycol, “Dowanol” products with CAS number 34590-94-8, “Texanol” products with CAS number 25265-77-4 and combinations thereof. Preferably, the agent R comprises water in combination with the polymer P.The agent R may also comprise at least one other ingredient chosen from an amphiphilic compound, in particular a surfactant compound, preferably a hydroxylated surfactant compound, for example alkyl-polyalkylene glycol, in particular alkyl-polyethylene glycol and alkyl-polypropylene glycol; a polysaccharide derivative, for example cyclodextrin, cyclodextrin derivative, polyethers, alkyl-glucosides; a hydrotropic compound, an anti-foaming agent, a biocidal agent and combinations thereof. Preferably according to the invention, the anti-foaming agent is chosen from silica, surfactant compounds, silicone derivatives and combinations thereof.

[0057] In addition to the rheological agent R, the aqueous anode composition T according to the invention comprises at least one material E. Preferably for the composition T according to the invention, the material E is chosen from silicon, graphite or graphitic carbon, hexagonal carbon, rhombohedral carbon and their combinations, optionally doped with at least one element, preferably chosen from lithium, silicon, germanium and their combinations.

[0058] The preferred material E is chosen from carbon graphite, silicon and their combinations. Also preferably for the composition T according to the invention, the material E is in the form of particles, preferably particles whose volume average size, measured by dynamic light scattering (DLS), is less than 200 pm, preferably less than 150 pm or less than 100 pm, or else ranges from 50 pm to 200 pm. The volume average size is generally measured by dynamic light scattering. In addition to the material E and the rheological agent R, the aqueous anode composition T according to the invention comprises at least one binding agent L of the material E which may be a polymer L1 in the form of a non-water-soluble latex or a water-soluble polymer L2.

[0059] Preferably for the composition T according to the invention, the polymer L1 is chosen from a styrene-butadiene gum polymer (SBR), phenyl-propane latex, ethylene / ethylene-acetate copolymer (EVA), acrylic latex, methacrylic latex, acrylonitrile latex, polymethyl-methacrylate, non-water-soluble ASE polymer latex, non-water-soluble HASE polymer latex and combinations thereof.

[0060] Preferably for composition T according to the invention, polymer L1 is a styrene-butadiene polymer.

[0061] Preferably for the composition T according to the invention, the water-soluble polymer L2 is an acrylic latex. Also preferably for the composition T according to the invention, the water-soluble polymer L2 is independently selected from a water-soluble ASE (alkali-swellable emulsion) polymer, a water-soluble HASE (hydrophobically-modified alkali-swellable emulsion) polymer, a water-soluble acrylic polymer, polyvinyl alcohol (PVA), poly(ethylene oxide) (PEO), carboxymethyl cellulose (CMC), sodium polyacrylate, modified polyacrylic acid, acrylamide homopolymer, acrylamide copolymer and combinations thereof. More preferably, the water-soluble polymer L2 is prepared by at least one emulsion polymerization reaction with a water-soluble anionic monomer.

[0062] Preferably for composition T according to the invention, the polymer L2 is chosen from a water-soluble ASE polymer, sodium polyacrylate, modified polyacrylic acid, acrylamide copolymer and their combinations.

[0063] According to the invention, the polymer L2 is water-soluble, preferably water-soluble at a pH greater than or equal to 6 or greater than or equal to 7.

[0064] According to the invention, the water-soluble polymer L2 can be prepared in the presence of at least one initiator compound, by a polymerization reaction of at least one anionic monomer M1 chosen from acrylic acid, methacrylic acid, an acrylic acid oligomer, an acrylic acid salt, a methacrylic acid salt and combinations thereof, and optionally at least one monomer different from the monomer M1. Preferably, the other monomer different from the monomer M1 is independently chosen from an anionic monomer M2, an organosulfur monomer M3, a non-ionic monomer M4, a crosslinking monomer M5 and combinations thereof. Preferably, the anionic monomer M2, different from the anionic monomer M1, is chosen from maleic acid, a maleic acid salt, itaconic acid, an itaconic acid salt, crotonic acid, a crotonic acid salt and combinations thereof.

[0065] Also preferably, the organosulfur monomer M3 is selected from a sulfonated monomer M3a, a sulfated monomer M3b, and combinations thereof. More preferably, the organosulfur monomer M3 is selected from 2-acrylamido-2-methylpropane sulfonic acid (AMPS), allyl sulfonic acid, alkylenesulfonates, alkylenearylsulfonates including styrene sulfonate, vinyl sulfonate, methallyl sulfonate, allyl sulfonate, methallyl sulfate, allyl sulfate, 2-sulfoethyl methacrylate, 3-allyloxy-2-hydroxy-1-propanesulfonic acid, 3 sulfopropyl methacrylate, their salts and combinations thereof.

[0066] Also preferably, the non-ionic monomer M4 is selected from vinyl acetate, a C1-C8 ester of a compound derived from an acid selected from acrylic acid, methacrylic acid, maleic acid, itaconic acid and crotonic acid (e.g. ethyl methacrylate, methyl methacrylate, butyl methacrylate, ethyl acrylate, methyl acrylate, butyl acrylate), hydroxyethylmethacrylate, hydroxyethylacrylate, hydroxypropylmethacrylate, hydroxypropylacrylate, a nitrogen-containing monomer (e.g. acrylonitrile, methacrylamide, acrylamide, vinyl-lactam, N-methylol acrylamide), styrene and combinations thereof.

[0067] Also preferably, the monomer M5 comprises at least 2 polymerizable ethylenic groups. More preferably, the crosslinking monomer M5 is chosen from polyvinyl aromatic monomers (for example divinylbenzene and diallyl phthalate); polyalkenyl ethers (triallyl pentaerythritol, diallyl pentaerythritol, diallyl sucrose, octaallyl sucrose, trimethylolpropane diallyl ether); polyunsaturated esters of polyalcohols or polyunsaturated esters of polyacids (for example trimethylolpropane tri(meth)acrylate, trimethylolpropane, polyethylene glycol di(meth)acrylates); diacrylic esters, dimethacrylic esters derived from polyols, in particular chosen from pentaerythritol, sorbitol, sucrose;Divinyl naphthalene, trivinylbenzene, 1,2,4-trivinylcyclohexane, triallyl pentaerythritol, diallyl pentaerythritol, diallyl sucrose, trimethylolpropane diallyl ether, 1,6-hexanediol di(meth)acrylate, allyl(meth)acrylate, diallyl itaconate, diallyl fumarate, diallyl maleate, butanediol dimethacrylate, ethylene di(meth)acrylate, poly(ethylene glycol) di(meth)acrylate, trimethylolpropane tri(meth)acrylate, methylenebis(meth)acrylamide, triallylcyanurates, diallyl phthalate, divinylbenzene; diallyl phthalate (DAP); ethylene glycol dimethacrylate (EGDMA); methylene bis acrylamide (MBA); divinylbenzene (DVB); bicyclopentenyloxyethyl-methacrylate (FRA); trimethylol propane triallyl ether (APE) and combinations thereof.;

[0068] Preferably according to the invention, the polymer L2 is prepared from: from 2% by weight to 100% by weight, preferably from 5% by weight to 98% by weight, of at least one monomer M1, and from 0 to 98% by weight, preferably from 2% by weight to 95% by weight, of at least one other monomer, different from the monomer M1, preferably from at least one other monomer chosen from monomer M2, monomer M3, monomer M4, monomer M5 and their combinations.

[0069] Also preferably, the water-soluble polymer L2 has a weight average molecular weight Mw (measured by CES) of less than 1,000,000 g / mol, preferably less than 800,000 g / mol or less than 500,000 g / mol, more preferably less than 100,000 g / mol or less than 50,000 g / mol.

[0070] Also preferably, the water-soluble polymer L2 has a weight average molecular weight Mw (measured by CES) greater than 2,000 g / mol or greater than 5,000 g / mol. More preferably, the water-soluble polymer L2 has a weight average molecular weight Mw (measured by CES) ranging from 2,000 g / mol to 1,000,000 g / mol, preferably from 2,000 g / mol to 800,000 g / mol or from 2,000 g / mol to 500,000 g / mol, more preferably from 2,000 g / mol to 100,000 g / mol or from 2,000 g / mol to 50,000 g / mol. Much more preferably, the water-soluble polymer L2 has a weight-average molecular weight Mw (measured by CES) ranging from 5,000 g / mol to 1,000,000 g / mol, preferably from 5,000 g / mol to 800,000 g / mol or from 5,000 g / mol to 500,000 g / mol, more preferably from 5,000 g / mol to 100,000 g / mol or from 5,000 g / mol to 50,000 g / mol.

[0071] According to the invention, the polymer L2 can be prepared in a polar solvent, in particular a solvent chosen from water, alcohol, toluene, a ketone, a chlorinated solvent, an ester and combinations thereof.

[0072] Generally, when preparing polymer L2, 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.

[0073] According to the invention, the polymer L2 is prepared in the presence of at least one initiator compound 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), their combinations and their associations 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 their combinations. According to the invention, the polymer L2 can be prepared in the presence of a chain transfer agent, preferably in the presence of a compound chosen from isopropyl alcohol, mercaptan, dodecyl mercaptan, phosphorous acid, phosphite, for example sodium phosphite, hypophosphorous acid, hypophosphite, for example sodium hypophosphite, bisulfite, for example sodium bisulfite, an alkyl iodide, an alkyl bromide.

[0074] The polymer L2 may be non-neutralized or may be partially or completely neutralized, preferably neutralized by means of a monovalent ion, a divalent ion or combinations thereof, more preferably by means of at least one compound selected from LiOH, NaOH, KOH, NH4OH, Ca(OH)2, Mg(OH)2, MgO, CaO, ZnO and combinations thereof. The polymer L2 may also be partially or completely neutralized by means of an amine selected from tertiary amine, secondary amine, primary amine and combinations thereof. The pH of the polymer L2 is generally less than 12 or less than 11 or ranges from 2 to 12 or from 5 to 11. Its pKa is generally less than 3.5 or ranges from 1.5 to 2.5.

[0075] Within the composition T according to the invention, the quantities of the ingredients may vary. Preferably according to the invention, the composition T comprises: from 0.2% by dry weight to 5% by dry weight of rheological agent R, from 85% by dry weight to 99.5% by dry weight of material E and from 0.3% by dry weight to 10% by dry weight of binding agent, in particular binding agent L, relative to the total quantity by dry weight of rheological agent R, binding agent, in particular binding agent L, and material E.

[0076] The composition T according to the invention comprises at least one binding agent L. Preferably, the composition T according to the invention may comprise at least one other binding compound different from the agent L or it may not comprise any other binding compound other than the binding agent L. Preferably, when using another binding compound, different from the binding agent L, it is chosen from cellulose, in particular carboxymethylcellulose (CMC), hydroxycellulose (in particular hydroxymethylcellulose or hydroxyethylcellulose), alginate, poly(allylamine, HCl), pectin, amilopectin, guar gum and combinations thereof.The composition T according to the invention may also comprise at least one other compound chosen from a (meth)acrylic comb polymer, polyethylene, a fluorinated binder compound, for example a compound chosen from polyvinylidene fluoride (PVDF), poly(vinyl-pyrrolidone), polytetrafluoroethylene (PTFE), chlorotrifluoroethylene (ECTFE), polyethylene tetrafluoroethylene (ETFE), fluorinated ethylene-propylene (FEP), perfluoro-alkoxy (PFA), polychlorotrifluoroethylene (PCTFE), fluoracrylates, fluorosilicones and combinations thereof.

[0077] The composition T according to the invention may also comprise at least one organic acid or one mineral acid, preferably an acid chosen from sulfuric acid, phosphoric acid, phosphorous acid, hypophosphorous acid, acetic acid, lactic acid and their combinations.

[0078] The composition T according to the invention may also comprise at least one dispersing agent for the material E, preferably chosen from a homopolymer of (meth)acrylic acid, a copolymer of (meth)acrylic acid and at least one other monomer and combinations thereof; more preferably a dispersing agent having a molecular mass by weight measured by CES ranging from 3,000 g / mol to 2,000,000 g / mol, in particular ranging from 5,000 g / mol to 900,000 g / mol. According to the invention, the dispersing agent is advantageously used in an amount by dry weight ranging from 0.05% by weight to 5% by weight, preferably from 0.1% by weight to 2% by weight, relative to the total amount by dry weight of rheological agent R, binder agent, in particular binder agent L, material E and dispersing agent.

[0079] Particularly advantageously, the rheological agent R according to the invention makes it possible to control the viscosity of the composition T according to the invention. Preferably, the composition T according to the invention has a viscosity, measured at 25°C and at 0.01 s 1 according to the method of the examples, greater than 2 mPa.s, preferably greater than 5 mPa.s. Also preferably, the composition T according to the invention has a viscosity, measured at 25°C and at 0.01 s 1 according to the method of the examples, less than 50 mPa.s or less than 100 mPa.s.

[0080] Also preferably, the composition T according to the invention has a viscosity, measured at 25°C and at 1000 s 1 according to the method of the examples, greater than 0.1 mPa.s, preferably greater than 0.2 mPa.s. Also preferably, the composition T according to the invention has a viscosity, measured at 25°C and at 1000 s 1according to the method of the examples, less than 5 mPa.s or less than 1 mPa.s. Also particularly advantageously, the rheological agent according to the invention makes it possible to control the viscoelasticity of the composition T according to the invention. According to the invention, the variation of the phase shift angle ô (°) is measured, obtained by the ratio of the loss modulus G' ' to the elastic modulus G' (tan ô = G” / G'), as a function of the variation of the shear stress. The elastic moduli G' and loss moduli G' ' are quantified by carrying out viscoelasticity measurements at 1 Hz using a rheometer equipped with a cone-plate spindle (CP35) under imposed stress.

[0081] Preferably, the composition T according to the invention has a phase shift angle at 1 Hz, measured at 25°C and at 0.01 Pa according to the method of the examples, greater than 30°, preferably greater than 50°; or less than 90°. Also preferably, the composition T according to the invention has a phase shift angle at 1 Hz, measured at 25°C and at 100 Pa according to the method of the examples, greater than 60°, preferably greater than 70° or less than 90°.

[0082] Preferably according to the invention, composition T is not an emulsion.

[0083] The invention also relates to the preparation of the aqueous composition T according to the invention. Thus, the invention provides a method for preparing an aqueous composition T comprising: the preparation of a binding agent L, the preparation of a rheological agent R, 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, graphite or graphitic carbon, hexagonal carbon, rhombohedral carbon and combinations thereof, optionally doped with at least one element, preferably chosen from lithium, silicon, germanium and combinations thereof.

[0084] The aqueous composition T according to the invention may constitute an essential ingredient during the manufacture of an anode. Thus, the invention provides a method for manufacturing an anode comprising: applying to a substrate at least one composition T according to the invention, drying and then calendering the coated substrate.

[0085] Preferably according to the invention, the substrate is a metal substrate, preferably a metal substrate chosen from copper, titanium, silver, zinc, nickel and combinations thereof. More preferably according to the invention, the substrate is a copper substrate. Preferably according to the invention, the manufacturing method according to the invention comprises the application of the composition T produced at a pH of less than 7 or at a pH ranging from 4 to 6.5.

[0086] Preferably according to the invention, the application of composition T to the substrate is carried out at a thickness after drying and calendering, measured by means of a coating thickness gauge of 1 μm to 1000 μm, which is less than 500 μm, preferably less than 100 μm or less than 20 μm.

[0087] Also preferably according to the invention, the application of composition T to the substrate is carried out at a thickness after drying and calendering, measured by means of a coating thickness gauge of 1 μm to 1000 μm, which is greater than 5 μm.

[0088] More preferably according to the invention, the application of composition T to the substrate is carried out at a thickness after drying and calendering, measured by means of a coating thickness gauge of 1 μm to 1000 μm, ranging from 5 μm to 500 μm, preferably from 5 μm to 100 μm or from 5 μm to 20 μm.

[0089] Particularly advantageously according to the invention, the application of composition T to the substrate is homogeneous. Preferably, the application of composition T to the substrate is homogeneous according to the method described in the examples.

[0090] The invention also provides an anode manufactured according to the manufacturing method according to the invention.

[0091] According to the invention, the particular, advantageous or preferred characteristics of the composition T according to the invention define methods of preparation, methods of manufacture and anodes which are also particular, advantageous or preferred.

[0092] The following examples illustrate the various aspects of the invention.

[0093] EXAMPLES

[0094] Preparation of urethane polymers P according to the invention and rheological agents R according to the invention

[0095] PI copolymer and RI rheological agent

[0096] In a 2 L glass reactor equipped with mechanical stirring, a vacuum pump, a nitrogen inlet and heated by means of a double jacket in which oil circulates, a compound (c) (polyethylene glycol - molecular mass 10000 g / mol) (260.8 g) is introduced and heated to 95°C under vacuum. Then, under stirring and in an inert atmosphere, 0.17 g of a DBU catalyst (1,8-diazabicyclo[5.4.0]undec-7-ene) is added and then a compound (b) of formula I in which n represents 4, X represents an ethoxylated group and R represents a cardanyl group (Surfaline CL4 Arkema) (25 g) is added over 15 minutes. Then, a diisocyanate compound (al) (isophorone diisocyanate, IPDI) (16.8 g) is introduced by means of a syringe and stirred at 150 rpm. The reaction is continued at 100°C for 1 hour.

[0097] Then, we check that the isocyanate level is zero by a back titration. We take 1 g of the reaction medium to which we add an excess of dibutylamine (1 molar aqueous solution) which reacts with any isocyanate functions present. Any unreacted dibutylamine is then titrated with a 1 N aqueous hydrochloric acid solution. We can then deduce the quantity of isocyanate functions present in the reaction medium. If it is not zero, the reaction is continued for periods of 15 minutes until the reaction is complete. The resulting PI copolymer is formulated using an ethoxylated alcohol surfactant compound (“Emulan” HE51 “Basf”) (202 g), 1000 ppm of a biocidal agent (“Biopol” SMV “Chemipol”), 1000 ppm of an antifoam agent (“Tego” 1488 “Evonik”) and water (495 g).An aqueous rheological control composition RI is obtained consisting of 30% by mass of copolymer PI according to the invention, 20% by mass of surfactant compound and 50% by mass of water.

[0098] Copolymer P2 and rheological agent R2

[0099] In a 2 L glass reactor equipped with mechanical stirring, a vacuum pump, a nitrogen inlet and heated by means of a double jacket in which oil circulates, a compound (c) (polyethylene glycol - molecular mass 10000 g / mol) (155.5 g) is introduced which is heated to 95°C under vacuum. Then, under stirring and in an inert atmosphere, 0.33 g of a DBU catalyst is added to the medium and then a compound (b) of formula I in which n represents 0 and R represents a linear Ci2-alkyl group (“Nacol” 12-96 “Sasol”) (3.5 g), another compound (b) of formula I in which n represents 0 and R represents a 4-dodecanyl-cyclohexyl group (“Marlipal” VS 18 “Sasol”) (7.0 g) and a third compound (b) of formula I in which n represents 0 and R represents an n-octanyl group (“Nacol” 8 “Sasol”) (0.65 g) are added simultaneously over 15 minutes.Then, a diisocyanate (al) compound (IPDI) (11.0 g) is introduced by means of a syringe and stirred at 150 rpm. The reaction is continued at 100°C for 1 hour.

[0100] Then, the isocyanate level is checked to be zero by back-dosing. The copolymer P2 obtained is formulated using ethoxylated alcohol surfactant compounds (“Emulan” HE51 “Basf”) (48.3 g) and (“Simulsol” 0x1008 “Seppic”) (48.3 g), 1000 ppm of a biocidal agent (“Biopol” SMV “Chemipol”), 1000 ppm of an anti-foaming agent (“Tego” 1488 “Evonik”) and water (725 g). An aqueous rheological control composition R2 is obtained, consisting of 17.5% by mass of copolymer P2 according to the invention, 9.5% by mass of surfactant compounds and 73% by mass of water. Copolymer P3 and rheological agent R3

[0101] In a 2 L glass reactor equipped with mechanical stirring, a vacuum pump, a nitrogen inlet and heated by means of a double jacket in which oil circulates, a compound (c) (polyethylene glycol - molecular mass 10,000 g / mol) (271 g) is introduced and heated to 95°C under vacuum. Then, under stirring and inert atmosphere, a compound (b) of formula I in which n represents 0 and R represents a linear Ci6-alkyl group (“Nacol” 16-95 “Sasol”) (16.2 g) is added over 15 minutes. Then, a diisocyanate compound (al) (toluene diisocyanate, TDI) (11.6 g) is introduced by means of a syringe and under stirring at 150 rpm. The reaction is continued at 100°C for 1 hour.

[0102] Then, the isocyanate level is checked to be zero by back-dosing. The copolymer P3 obtained is formulated using an ethoxylated alcohol surfactant compound (“Disponil” D8, “Cognis”) (198 g), 1000 ppm of a biocidal agent (“Biopol” SMV “Chemipol”), 1000 ppm of an anti-foaming agent (“Tego” 1488 “Evonik”) and water (500 g). An aqueous rheological control composition R3 is obtained, consisting of 30% by mass of copolymer P3 according to the invention, 20% by mass of surfactant compound and 50% by mass of water.

[0103] Copolymer P4 and rheological agent R4

[0104] In a 2 L glass reactor equipped with mechanical stirring, a vacuum pump, a nitrogen inlet and heated by means of a double jacket in which oil circulates, a compound (c) (polyethylene glycol - molecular mass 10000 g / mol) (152.7 g) is introduced which is heated to 95°C under vacuum. Then, under stirring and in an inert atmosphere, 0.2 g of a DBU catalyst is added to the medium and then a compound (b) which is a polybranched Guerbet alcohol obtained by dimerization of branched and linear alcohols in C12 and C13 (CAS No. 2041102-78-5 - "Isofol" 2426S "Sasol") (6.7 g), another compound (b) of formula I in which n represents 3, X represents an ethoxylated group and R represents a tristyrylphenyl group ("Simulsol" TS 26 "Seppic") (4.8 g) and a third compound (b) of formula I in which n represents 0 and R represents a 2-butyl-l-octanol group (CAS No. 3913-02-8 - "Isofol" 12 "Sasol") (3.4 g) are added simultaneously in 15 minutes.Then, a diisocyanate (al) compound (IPDI) (10.2 g) is introduced by means of a syringe and stirred at 150 rpm. The reaction is continued at 100°C for 1 hour.

[0105] Then, the isocyanate level is checked to be zero by back-dosing. The copolymer P4 obtained is formulated using ethoxylated alcohol surfactant compounds (“Emulan” HE51 “Basf”) (48.3 g) and (“Simulsol” 0x1008 “Seppic”) (48.3 g), 1000 ppm of a biocidal agent (“Biopol” SMV “Chemipol”), 1000 ppm of an anti-foaming agent (“Tego” 1488 “Evonik”) and water (725 g). An aqueous rheological control composition R4 according to the invention is obtained, consisting of 17.5% by mass of copolymer P4 according to the invention, 9.5% by mass of surfactant compounds and 73% by mass of water.

[0106] Copolymer P5 and rheological agent R5

[0107] In a 2 L glass reactor equipped with mechanical stirring, a vacuum pump, a nitrogen inlet and heated by means of a double jacket in which oil circulates, a compound (c) (polyethylene glycol - molecular mass 10000 g / mol) (151.3 g) is introduced and heated to 95°C under vacuum. Then, under stirring and inert atmosphere, 0.01 g of a DBU catalyst is added and then a compound (b) of formula I in which n represents 0 and R represents a tristyrylphenyl group (“Simulsol” TS 26 “Seppic”) (15.7 g) is added over 10 minutes. Then, a diisocyanate compound (al) (IPDI) (9.8 g) is introduced by means of a syringe and under stirring at 150 rpm. The reaction is continued at 100°C for 1 hour.

[0108] Then, the isocyanate level is checked to be zero by back-dosing. The copolymer P5 obtained is formulated using an ethoxylated alcohol surfactant compound (“Simulsol” 0x1008 “Seppic”) (118 g), 1,000 ppm of a biocidal agent (“Biopol” SMV “Chemipol”), 1,000 ppm of an anti-foaming agent (“Tego” 1488 “Evonik”) and water (700 g). An aqueous rheological control composition R5 according to the invention is obtained, consisting of 18% by mass of copolymer P5 according to the invention, 12% by mass of surfactant compound and 70% by mass of water.

[0109] Preparation and characterization of aqueous anode compositions T1 to T4 according to the invention

[0110] In a 500 mL polypropylene container suitable for a stirrer (Speedmixer DAC 1100), 47 g of water and 2.06 g of a polyacrylic acid dispersing agent (molecular weight 600,000 g / mol measured by CES) are introduced and mixed for 1 minute at 800 rpm. 50 g of material E (natural graphite powder of D50 17-19 pm - "MSE Supply") are added and mixed for 1 minute and 30 seconds at 1,600 rpm. The pH is adjusted using an aqueous solution of AMP (2-amino-2-methyl-l-propanol) at 95% by dry weight to a pH of 6. Stirring is carried out for 1 minute at 1,600 rpm.

[0111] 2.08 g of rheological agent RI are added and mixed for 1 minute at 1600 rpm. 1.56 g of binding agent L1 (styrene-butadiene latex - BM 45 IB "Zeon") are added and mixed for 1 minute at 800 rpm. The anode composition T1 according to the invention is obtained.

[0112] Similarly, the aqueous anode compositions T2, T3 and T4 are prepared by replacing the rheological agent RI respectively with the rheological agents R2 (3.85 g), R3 (2.08 g) and R4 (3.85 g) and by using respectively an amount of water of 46 g, 47 g and 46 g for the compositions T2, T3 and T4.

[0113] Using a rheometer ("Haake Mars III"), their rheological profiles are determined by measuring their viscosity (mPa.s) at 25°C and different speed gradients using a cone-plate mobile (CP60) under imposed stress.

[0114] Their viscoelastic structure is also evaluated by measuring the variation of the phase shift angle ô (°), obtained by the ratio of the loss modulus G' ' to the elastic modulus G' (tan ô = G” / G'), as a function of the variation of the shear stress. The elastic moduli G' and loss moduli G' ' are quantified by carrying out viscoelasticity measurements at 1 Hz using a rheometer ("Haake Mars III") equipped with a cone-plate mobile (CP35) under imposed stress (Pa).

[0115] Their thixotropic behavior is also determined by evaluating the application efficiency using 3-phase thixotropy tests (3-ITT) which stimulate the behavior of the anode composition at rest, during application and during restructuring after application. These viscosity measurements (mPa.s) were carried out at 25°C, in 3 phases using a cone-plate mobile (CP35): preliminary shear at 100 s 110 seconds for 5 points; 60 seconds rest without shear for 5 points; measurement at a low shear gradient of 0.1 s 1 to determine the viscosity of the composition at rest, with a measurement of 180 seconds for 20 points; measurement at a shear gradient of 1000 s 1 to determine the viscosity of the composition during its application, with a measurement of 30 seconds for 20 points; measurement at a low shear gradient of 0.1 s 1 to reveal how quickly the sample restructures, with a measurement of 200 seconds for 150 points; measurement at a low shear rate of 0.1 s 1 in order to reveal the behavior of the structure over a long acquisition time, with a measurement of

[0116] 400 seconds for 50 points.

[0117] The results are presented in Tables 1, 2 and 3 respectively.

[0118] Table 1

[0119] Table 2

[0120] Preparation and characterization of an anode according to the invention

[0121] A 12 μm thick copper foil is coated with a wet thickness of 200 μm of aqueous anode composition Tl according to the invention using a 4-opening manual applicator on a vacuum application table and at a speed of 10 mm / s. The coated foil is then dried for 24 hours in a climatic chamber at a temperature of 25 °C and a humidity of 50%. Once dried, the coated foil is calendered on both sides at a pressure of 25 kg / cm 2and at a running speed of 0.1 m / s using a calender ("Gester"). Discs with a diameter of 12 mm are cut using a precision cutter. In a similar manner, anodes are prepared using the aqueous anode compositions T2, T3 and T4 by replacing composition T1 with one of these compositions according to the invention.

[0122] Immediately after preparation, the homogeneity and adhesion of the composition layer are assessed by visual inspection of the prepared anodes: no aggregates or surface heterogeneities are visible on the surface of the layer observed from the front in daylight. The layer does not show any adhesion defects.

[0123] The aqueous anode composition T according to the invention comprising the rheological agent R has a thixotropic behavior which allows easy and effective application during the preparation of an anode. The aqueous anode composition according to the invention makes it possible to prepare an anode having a regular, homogeneous and stable active surface.

Claims

CLAIMS 1. Aqueous anode composition T comprising: • at least one rheological agent R comprising at least one water-soluble, non-ionic urethane polymer P, prepared by a polymerization reaction: a) of at least one isocyanate compound (a) chosen independently from a diisocyanate compound (a1), a polyisocyanate compound (a2) and combinations thereof; b) of at least one compound (b) of formula I: OH in which: R independently represents a group selected from a linear C4-C40-alkyl group, a branched C4-C40-alkyl group, a Cs-C40-cycloalkyl group, a linear C4-C40-alkenyl group, a branched C4-C40-alkenyl group, a C5-C40-cycloalkenyl group, a C5-C40-aryl group and combinations thereof, X independently represents an alkoxylated group chosen from oxyethylene, oxypropylene, oxybutylene and combinations thereof, n represents 0 or a number ranging from 1 to 500; c) at least one polyhydroxylated and polyalkoxylated compound (c); • at least one material E chosen from metal fibers, metal particles, graphite carbon fibers, graphite carbon particles, silicon particles and combinations thereof; and • at least one binding agent L of the material E chosen from a polymer L1 in the form of a non-water-soluble latex, a water-soluble polymer L2 and their combinations.

2. Composition T according to claim 1 for which: • the diisocyanate compound (a1) is chosen from: symmetrical aromatic diisocyanate compounds, preferably 2,2'-diphenylmethylene diisocyanate (2,2'-MDI); 4,4'-diphenylmethylene diisocyanate (4,4'-MDI); 4,4'-dibenzyl diisocyanate (4,4'-DBDI); 2,6-toluene diisocyanate (2,6-TDI); m-xylylene diisocyanate (m-XDI); symmetrical alicyclic diisocyanate compounds, preferably methylene bis(4-cyclohexylisocyanate) (H12MDI); symmetrical aliphatic diisocyanate compounds, preferably hexamethylene diisocyanate (HDI), pentamethylene diisocyanate (PDI); unsymmetrical aromatic diisocyanate compounds, preferably diphenylmethylene 2,4'-diisocyanate (2,4'-MDI); 2,4'-dibenzyl diisocyanate (2,4'-DBDI); toluene 2,4-diisocyanate (2,4-TDI); unsymmetrical alicyclic diisocyanate compounds, preferably isophorone diisocyanate (IPDI), preferably according to the invention, compound (a1) is chosen from IPDI, HDI, H12MDI and combinations thereof; or • the polyisocyanate compound (a2) strictly comprises more than 2 isocyanate functions or more than 2.2 isocyanate functions or even more than 2.5 isocyanate functions; preferably, the polyisocyanate compound (a2) comprises more than 2.6 isocyanate functions or more than 2.7 isocyanate functions or more than 3 isocyanate functions; much more preferably, the polyisocyanate compound (a2) comprises from 2.2 to 6 isocyanate functions, from 2.2 to 4 isocyanate functions, from 2.2 to 3.5 isocyanate functions, from 2.5 to 6 isocyanate functions, from 2.2 to 5 isocyanate functions, from 2.5 to 4 isocyanate functions, from 2.5 to 3.5 isocyanate functions, in particular from 2.6 to 3.3 isocyanate functions; or • the polyisocyanate compound (a2) is chosen from: triphenylmethane-4,4',4”-triisocyanate or 1,1',1”-methylidynetris (4-isocyanatobenzene); an isocyanurate compound, in particular an isocyanurate compound of a compound chosen from: o symmetrical aromatic diisocyanate compounds, preferably 2,2'-diphenylmethylene diisocyanate (2,2'-MDI); 4,4'-diphenylmethylene diisocyanate (4,4'-MDI); 4,4'-dibenzyl diisocyanate (4,4'-DBDI); 2,6-toluene diisocyanate (2,6-TDI); m-xylylene diisocyanate (m-XDI); o symmetrical alicyclic diisocyanate compounds, preferably methylene bis(4-cyclohexylisocyanate) (H12MDI); o symmetrical aliphatic diisocyanate compounds, preferably hexamethylene diisocyanate (HDI), pentamethylene diisocyanate (PDI); o asymmetrical aromatic diisocyanate compounds, preferably 2,4'-diphenylmethylene diisocyanate (2,4'-MDI); 2,4'-dibenzyl diisocyanate (2,4'-DBDI); 2,4-toluene diisocyanate (2,4-TDI); a trimeric biurea compound, in particular a trimeric biurea compound of a compound chosen from: o symmetrical aromatic diisocyanate compounds, preferably 2,2'-diphenylmethylene diisocyanate (2,2'-MDI); 4,4'-diphenylmethylene diisocyanate (4,4'-MDI); 4,4'-dibenzyl diisocyanate (4,4'-DBDI); 2,6-toluene diisocyanate (2,6-TDI); m-xylylene diisocyanate (m-XDI); o symmetrical alicyclic diisocyanate compounds, preferably methylene bis(4-cyclohexylisocyanate) (H12MDI); o symmetrical aliphatic diisocyanate compounds, preferably hexamethylene diisocyanate (HDI), pentamethylene diisocyanate (PDI);o unsymmetrical aromatic diisocyanate compounds, preferably 2,4'-diphenylmethylene diisocyanate (2,4'-MDI); 2,4'-dibenzyl diisocyanate (2,4'-DBDI); 2,4-toluene diisocyanate (2,4-TDI); o unsymmetrical alicyclic diisocyanate compounds, preferably isophorone diisocyanate (IPDI); • more preferably, the compound (a2) is chosen from triphenylmethane-4,4',4”-triisocyanate, 1,1',1”-methylidynetris (4-isocyanatobenzene), HDI isocyanurate, IPDI isocyanurate, PDI isocyanurate, HDI biurea trimer, IPDI biurea trimer, PDI biurea trimer.

3. Composition T according to one of claims 1 or 2 for which compound (b) is a compound of formula I in which: R independently represents a group selected from a linear C6-C32-alkyl group, a branched C6-C32-alkyl group, a C6-C32-cycloalkyl group, a linear C6-C32-alkenyl group, a branched C6-C32-alkenyl group, a C6-C32-cycloalkenyl group, a C6-C32-aryl group and combinations thereof, preferably R independently represents a group selected from a linear C6-C24-alkyl group, a branched C6-C24-alkyl group, a C6-C24-cycloalkyl group, a linear C6-C24-alkenyl group, a branched C6-C24-alkenyl group, a C6-C24-cycloalkenyl group, a C6-C32-aryl group and combinations thereof; or X independently represents an alkoxylated group selected from an ethoxylated group, a propoxylated group, a butoxylated group and combinations thereof; preferably X represents an ethoxylated group or a combination of ethoxylated groups and propoxylated groups, more preferably X represents an ethoxylated group; or n represents 0 or a number ranging from 1 to 300, preferably from 1 to 150 or from 1 to 100, more preferably from 1 to 50 or from 1 to 25.

4. Composition T according to one of claims 1 to 3 for which compound (c) is chosen from: • a compound (cl) of formula II: HO-Qm-OH (II) in which: Q independently represents an oxyalkylene residue; m independently represents a number ranging from 30 to 1,000; • a compound (cl) of formula II associated with a non-alkoxylated compound (c2) comprising at least three hydroxyl groups; • a polyalkoxylated compound (c3) comprising at least three hydroxyl groups; • their combinations.

5. Composition T according to one of claims 1 to 4 for which compound (c) is chosen from: • a compound (cl) of formula II: HO-Qm-OH (II) in which: Q independently represents an oxyethylene residue; or m independently represents a number ranging from 50 to 600, preferably from 100 to 600; or wherein Q independently represents an oxyethylene residue and m independently represents a number ranging from 50 to 600, preferably from 100 to 600; • a compound (c2) comprising three hydroxyl groups, preferably chosen from glycerol, pentaerythritol and their combinations; • a polyalkoxylated compound (c3) different from compound (c2) and comprising three hydroxyl groups, preferably a compound (c3) chosen from polyethoxylated glycerol, polyethoxylated pentaerythritol and their combinations.

6. Composition T according to one of claims 1 to 5 for which: • compound (c) comprises from 10 to 500 alkoxylations, preferably from 20 to 400 alkoxylations or from 10 to 300 alkoxylations, more preferably from 20 to 250 alkoxylations, or • compound (c) is polyethoxylated or is polyethoxylated-polypropoxylated or is polyethoxylated-polybutoxylated, preferably compound (c) is polyethoxylated, or • compound (c) comprises from 10 to 500 ethoxylations, preferably from 20 to 400 ethoxylations or from 10 to 300 ethoxylations, more preferably from 20 to 250 ethoxylations, or for which: • compound (c), (cl) or (c3) independently has a molecular weight (Mw) measured by CES ranging from 1,500 g / mol to 40,000 g / mol, preferably from 2,000 g / mol to 25,000 g / mol, more preferably from 2,000 g / mol to 20,000 g / mol or from 2,000 g / mol to 15,000 g / mol or from 2,000 g / mol to 12,000 g / mol, much more preferably from 4,000 g / mol to 20,000 g / mol or from 4,000 g / mol to 15,000 g / mol or from 4,000 g / mol to 12,000 g / mol.

7. Composition T according to one of claims 1 to 6 for which the polymerization reaction uses: from 20 mol% to 74.9 mol%, preferably from 25 mol% to 60 mol%, of compound (a) or from 25 mol% to 79.9 mol%, preferably from 35 mol% to 70 mol%, of compound (b), or from 0.1 mol% to 55 mol%, preferably from 5 mol% to 40 mol%, of compound (c), relative to the total molar quantity of compounds (a), (b) and (c).

8. Composition T according to one of claims 1 to 7 for which the polymerization reaction also uses at least one additional crosslinking compound (d), preferably a compound (d) comprising at least 3 functional groups chosen from OH, SH, primary amine, secondary amine and their combinations, more preferably a compound (d) chosen from diethanolamine, triethanolamine, trimethylolpropane, glycerol, pentaerythritol and their combinations, preferably less than 5 mol%, preferably from 0.01 mol% to 5 mol%, in particular from 0.1 mol% to 5 mol%, of compound (d) relative to the total molar quantity of monomers.

9. Composition T according to one of claims 1 to 8 for which: • the material E is chosen from silicon, graphite or graphitic carbon, hexagonal carbon, rhombohedral carbon and their combinations, optionally doped with at least one element, preferably chosen from lithium, silicon, germanium and their combinations; or • material E is in the form of particles, preferably particles whose average volume size, measured by dynamic light scattering (DLS), is less than 200 pm, preferably less than 150 pm or less than 100 pm, or else ranges from 50 pm to 200 pm.

10. Composition T according to one of claims 1 to 9 for which: • polymer L1 is chosen from a styrene-butadiene gum polymer (SBR), phenyl-propane latex, ethylene / ethylene-acetate copolymer (EVA), latex acrylic, methacrylic latex, acrylonitrile latex, polymethyl methacrylate, non-water-soluble ASE polymer latex, non-water-soluble HASE polymer latex and combinations thereof; or • the water-soluble polymer L2 is independently selected from a water-soluble ASE polymer, a water-soluble HASE polymer, a water-soluble acrylic polymer, polyvinyl alcohol (PVA), poly(ethylene oxide) (PEO), carboxymethyl cellulose (CMC), sodium polyacrylate, modified polyacrylic acid, acrylamide homopolymer, acrylamide copolymer and combinations thereof, preferably the water-soluble polymer L2 is prepared by at least one emulsion polymerization reaction with a water-soluble anionic monomer.

11. Composition T according to one of claims 1 to 10 for which: • polymer L1 is a styrene-butadiene polymer, or • the water-soluble polymer L2 is an acrylic latex, or • the water-soluble polymer L2 is prepared in the presence of at least one initiator compound, by a polymerization reaction of at least one anionic monomer M1 chosen from acrylic acid, methacrylic acid, an acrylic acid oligomer, an acrylic acid salt, a methacrylic acid salt and combinations thereof, and optionally at least one monomer different from the monomer M1, preferably at least one other monomer different from the monomer M1 and chosen independently from: an anionic monomer M2, different from the anionic monomer M1, chosen from maleic acid, a maleic acid salt, itaconic acid, an itaconic acid salt, crotonic acid, a crotonic acid salt and combinations thereof, an organosulfur monomer M3, preferably a monomer M3 chosen from a sulfonated monomer M3a, a sulfated monomer M3b, and combinations thereof, more preferably an organosulfur monomer M3 chosen from acid 2-acrylamido-2-methylpropane sulfonic acid (AMPS), allyl-sulfonic acid,alkylenesulfonates, alkylenearylsulfonates notamment le styrène- sulfonate, vinyl- sulfonate, methallyl- sulfonate, allyl-sulfonate, methallyl- sulfate, allyl- sulfate, 2- sulfoethyl méthacrylate, acide, 3-allyloxy-2-hydroxy-l-propanesulfonic acid, 3-sulfopropyl methacrylate, their salts and their combinations, a non-ionic monomer M4 selected from vinyl acetate, a C1-C8 ester of a compound derived from an acid selected from acrylic acid, methacrylic acid, maleic acid, itaconic acid and crotonic acid (for example ethyl methacrylate, methyl methacrylate, butyl methacrylate, ethyl acrylate, methyl acrylate, butyl acrylate), hydroxyethylmethacrylate, hydroxyethylacrylate, hydroxypropylmethacrylate, hydroxypropylacrylate, a nitrogen-containing monomer (for example acrylonitrile, methacrylamide, acrylamide, vinyl-lactam, N-methylol acrylamide), styrene and their combinations, a crosslinking monomer M5, preferably a monomer M5 comprising at least 2 groups polymerizable ethylenic monomers, preferably a crosslinking monomer M5 chosen from polyvinyl aromatic monomers (for example divinylbenzene and diallyl phthalate);polyalkenyl ethers (triallyl pentaerythritol, diallyl pentaerythritol, diallyl sucrose, octaallyl sucrose, trimethylolpropane diallyl ether); polyunsaturated esters of polyalcohols or polyunsaturated esters of polyacids (for example trimethylolpropane tri(meth)acrylate, trimethylolpropane, polyethylene glycol di(meth)acrylates); diacrylic esters, dimethacrylic esters derived from polyols, in particular chosen from pentaerythritol, sorbitol, sucrose; divinyl naphthalene, trivinylbenzene; 1,2,4-trivinylcyclohexane, triallyl pentaerythritol, diallyl pentaerythritol, diallyl sucrose, trimethylolpropane diallyl ether, 1,6-hexanediol di(meth)acrylate, allyl(meth)acrylate, diallyl itaconate, diallyl fumarate, diallyl maleate, butanediol dimethacrylate, ethylene di(meth)acrylate, poly(ethylene glycol) di(meth)acrylate, trimethylolpropane tri(meth)acrylate, methylenebis(meth)acrylamide, triallylcyanurates, diallyl phthalate, divinylbenzene; diallyl phthalate (DAP); ethylene glycol dimethacrylate (EGDMA); methylene bis acrylamide (MBA); divinylbenzene (DVB); bicyclopentenyloxyethyl- methacrylate (FRA); trimethylol propane triallyl ether (APE) and combinations thereof, and combinations thereof or the polymer L2 is prepared from: o from 2% by weight to 100% by weight, preferably from 5% by weight to 98% by weight, of at least one monomer M1, and o from 0 to 98% by weight, preferably from 2% by weight to 95% by weight, of at least one other monomer, different from the monomer M1, preferably from at least one other monomer chosen from monomer M2, monomer M3, monomer M4, monomer M5 and combinations thereof, or • the water-soluble polymer L2 has a weight-average molecular mass Mw (measured by CES) of less than 1,000,000 g / mol, preferably less than 800,000 g / mol or less than 500,000 g / mol, more preferably less than 100,000 g / mol or less than 50,000 g / mol, or • the water-soluble polymer L2 has a weight-average molecular mass Mw (measured by CES) greater than 2,000 g / mol or greater than 5,000 g / mol.

12. Composition T according to one of claims 1 to 11 not comprising any other binding compound other than the binding agent L or also comprising: at least one other binding compound, different from binding agent L, preferably another binding compound chosen from cellulose, in particular carboxymethylcellulose (CMC), hydroxycellulose (in particular hydroxymethylcellulose or hydroxyethylcellulose), alginate, poly(allylamine, HCl), pectin, amilopectin, guar gum and combinations thereof, or at least one organic acid or mineral acid, preferably an acid chosen from sulfuric acid, phosphoric acid, phosphorous acid, hypophosphorous acid, acetic acid, lactic acid and combinations thereof;or also comprising: at least one other compound selected from a (meth)acrylic comb polymer, polyethylene, a fluorinated binder compound, for example a compound selected from polyvinylidene fluoride (PVDF), poly(vinyl-pyrrolidone), polytetrafluoroethylene (PTFE), chlorotrifluoroethylene (ECTFE), polyethylene tetrafluoroethylene (ETFE), fluorinated ethylene-propylene (FEP), perfluoro-alkoxy (PFA), polychlorotrifluoroethylene (PCTFE), fluoracrylates, fluorosilicones and combinations thereof.; 13. Composition T according to one of claims 1 to 12 also comprising at least one dispersing agent for the material E, preferably chosen from a homopolymer of (meth)acrylic acid, a copolymer of (meth)acrylic acid and at least one other monomer and combinations thereof; more preferably a dispersing agent having a molecular mass by weight measured by CES ranging from 3,000 g / mol to 2,000,000 g / mol, in particular ranging from 5,000 g / mol to 900,000 g / mol.

14. Composition T according to one of claims 1 to 13 comprising: • from 0.2% dry weight to 5% dry weight of rheological agent R, • from 85% dry weight to 99.5% dry weight of material E and • from 0.3% by dry weight to 10% by dry weight of binding agent, in particular binding agent L, relative to the total quantity by dry weight of rheological agent R, binding agent, in particular binding agent L, and material E.

15. Composition T according to one of claims 1 to 14 including: the viscosity, measured at 25°C and at 0.01 s 1 according to the method of the description, is greater than 2 mPa.s, preferably greater than 5 mPa.s; or less than 50 mPa.s or less than 100 mPa.s; or the viscosity, measured at 25°C and 1000 s 1according to the method of the description, is greater than 0.1 mPa.s, preferably greater than 0.2 mPa.s; or less than 5 mPa.s or less than 1 mPa.s; or the phase shift angle at 1 Hz, measured at 25°C and 0.01 Pa according to the method of the description, is greater than 30°, preferably greater than 50°; or is less than 90°; or the phase shift angle at 1 Hz, measured at 25°C and 100 Pa according to the method of the description, is greater than 60°, preferably greater than 70°; or is less than 90°.

16. Composition T according to one of claims 1 to 15 for which the polymer P has a molar mass (Mw) measured by CES ranging from 4,000 g / mol to 150,000 g / mol; preferably from 6,000 g / mol to 100,000 g / mol; more preferably from 10,000 g / mol to 80,000 g / mol.

17. Method for preparing an aqueous composition T according to claims 1 to 16, comprising: the preparation of a binding agent L, the preparation of a rheological agent R, 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, graphite or graphitic carbon, hexagonal carbon, rhombohedral carbon and combinations thereof, optionally doped with at least one element, preferably chosen from lithium, silicon, germanium and combinations thereof.

18. Method for manufacturing an anode comprising: applying to a substrate, preferably a metal substrate chosen from copper, titanium, silver, zinc, nickel and their combinations, more preferably a copper substrate, at least one composition T according to one of claims 1 to 16, drying and then calendering the coated substrate.

19. A manufacturing method according to claim 18 wherein: the application is carried out at a pH of less than 7 or at a pH of from 4 to 6.5, or the application of composition T to the substrate is carried out at a thickness after drying and calendering, measured by means of a coating thickness gauge of 1 pm to 1000 pm, which is less than 500 pm, preferably less than 100 pm or less than 20 pm, or the application of composition T to the substrate is carried out at a thickness after drying and calendering, measured by means of a coating thickness gauge of 1 pm to 1000 pm, which is greater than 5 pm, or wherein: the application of composition T to the substrate is homogeneous, preferably the application of composition T to the substrate is homogeneous according to the method of the description.

20. Anode manufactured according to the manufacturing method according to one of claims 18 or 19.

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