Stabilized aqueous anode composition

Abstract

The present invention relates to an aqueous anode composition stabilized by a polyurethane rheological agent comprising carbon graphite particles or metal particles or fibers and a binder. The invention also relates to a method for producing an anode using such an aqueous composition and to the anode produced.

Description

[0001] Details

[0002] The present invention relates to an aqueous anode composition stabilized by a polyurethane rheological agent, the composition further comprising a binder and metal or carbon graphite particles or fibers, a method for preparing an anode using the aqueous composition, and the anode obtained.

[0003] Known anode compositions typically comprise carbon or metal in particulate form combined with a binder composition. This binder composition must be able to effectively bond the carbon or metal to a substrate to form an anode. The most common binder composition comprises a styrene-butadiene polymer and allows the active particles to be fixed to a metal substrate. Adhesion, mechanical strength or electrochemical stability are particularly important during the preparation of the anode and during the use of the anode. In fact, the quality of the anode composition coating applied to the metal substrate is crucial for the optimal efficiency of the anode and its maximum durability. Therefore, the thixotropic behavior or rheological behavior of the aqueous anode composition over time must be controlled as much as possible. It is also advantageous to have a multifunctional anode composition that maintains its rheological properties when its conditions of use are different.

[0004] Simple and uniform application of the anode composition is essential to obtain a uniform layer and to limit or avoid defects on the anode surface, thereby obtaining a uniform and particularly efficient conductive layer.The surface leveling, reorganization and flow behavior of the aqueous anode composition must be well controlled.

[0005] Therefore, it is essential to have an anode composition whose rheology is well controlled. In fact, in addition to the application difficulties, too high a viscosity generally leads to many defects in the layer deposited on the anode surface. Insufficient viscosity leads to the same type of problems and also causes the anode composition to flow uncontrolled during its application.

[0006] The anode composition must also be stable and homogeneous during its preparation, storage or application. Therefore, sedimentation, formation of lumps or aggregates, and separation of the components must be limited or avoided.

[0007] Typically, these anode compositions contain silicon to increase the capacity of the resulting anode. During the charge-discharge cycles of batteries containing these anodes, deformation is often observed, which can lead to irreversible degradation of the anode, particularly due to the increase in silicon volume. Therefore, resistance to deformation is also a desirable property.

[0008] Compatibility of the various components of the anode compositions is also an important factor in preparing anode compositions and in using these compositions to prepare anodes.

[0009] JP 2015220170 relates to the use of a polymer binder made from a thermoplastic resin prepared using poly(tetramethylene glycol), diethylene glycol, IPDI, and N,N'-dimethylformamide in the preparation of battery anodes. WO 2021014054 describes an aqueous thickening composition made from a saccharide compound and a polyurethane polymer.

[0010] The anode compositions of the prior art are not always satisfactory. It is therefore desirable to have an anode composition which allows providing a solution to all or part of the problems of the anode compositions of the state of the art.

[0011] Thus, the present invention provides an aqueous anode composition T comprising:

[0012] At least one rheological agent R comprising at least one water-soluble nonionic polyurethane polymer P prepared by polymerization of:

[0013] a) at least one isocyanate compound (a) independently selected from diisocyanate compounds (a1), polyisocyanate compounds (a2), and combinations thereof;

[0014] b) at least one compound (b) of formula I:

[0015]

[0016] in:

[0017] -R independently represents a group selected from the following: straight chain C4-C 40 -alkyl, branched C4-C 40 -alkyl, C5-C 40 -Cycloalkyl, straight chain C4-C 40 -alkenyl, branched C4-C 40 -alkenyl, C5-C 40 -cycloalkenyl, C5-C 40 - aryl and combinations thereof,

[0018] -X independently represents an alkoxylated group selected from the group consisting of ethylene oxide, propylene oxide, butylene oxide, and combinations thereof,

[0019] -n represents 0 or a number from 1 to 500;

[0020] c) at least one polyhydroxylated and polyalkoxylated compound (c);

[0021] At least one material E selected from metal fibers, metal particles, carbon graphite fibers, carbon graphite particles, silicon particles, and combinations thereof; and

[0022] • At least one binder L for the material E, chosen from polymers L1 in the form of water-insoluble latexes, water-soluble polymers L2 and combinations thereof.

[0023] Essentially according to the invention, the anode composition comprises at least one rheological agent R comprising a polyurethane polymer P prepared with the aid of an isocyanate compound (a) selected from diisocyanate compounds (a1), polyisocyanate compounds (a2) and combinations thereof.

[0024] Preferably, for the composition T according to the invention, the diisocyanate compound (a1) is chosen from:

[0025] - Symmetrical aromatic diisocyanate compounds, preferably 2,2'-methylene diphenyl diisocyanate (2,2'-MDI); 4,4'-methylene diphenyl diisocyanate (4,4'-MDI); 4,4'-dibenzyl diisocyanate (4,4'-DBDI); 2,6-toluene diisocyanate (2,6-TDI); meta-xylylene diisocyanate (m-XDI);

[0026] - symmetrical alicyclic diisocyanate compounds, preferably methylenebis(4-cyclohexyl isocyanate)(H 12 MDI);

[0027] - symmetrical aliphatic diisocyanate compounds, preferably hexamethylene diisocyanate (HDI) and pentamethylene diisocyanate (PDI);

[0028] - an asymmetric aromatic diisocyanate compound, preferably 2,4'-methylenediphenyl diisocyanate (2,4'-MDI); 2,4'-dibenzyl diisocyanate (2,4'-DBDI); 2,4-toluene diisocyanate (2,4-TDI);

[0029] - an asymmetric alicyclic diisocyanate compound, preferably isophorone diisocyanate (IPDI). According to the present invention, preferably, compound (a1) is selected from IPDI, HDI, H 12 MDI and its combinations.

[0030] It is also preferred for the composition T according to the invention that the polyisocyanate compound (a2) contains strictly more than 2 isocyanate groups or more than 2.2 isocyanate groups or more than 2.5 isocyanate groups. More preferably, the polyisocyanate compound (a2) contains more than 2.6 isocyanate groups or more than 2.7 isocyanate groups or more than 3 isocyanate groups. More preferably, the polyisocyanate compound (a2) contains 2.2 to 6 isocyanate groups, 2.2 to 4 isocyanate groups, 2.2 to 3.5 isocyanate groups, 2.5 to 6 isocyanate groups, 2.2 to 5 isocyanate groups, 2.5 to 4 isocyanate groups, 2.5 to 3.5 isocyanate groups, in particular 2.6 to 3.3 isocyanate groups.

[0031] More preferably, the polyisocyanate compound (a2) is selected from:

[0032] -Triphenylmethane-4,4',4"-triisocyanate or 1,1',1"-methylenetris(4-isocyanatophenyl);

[0033] - an isocyanurate compound, in particular an isocyanurate compound selected from the group consisting of:

[0034] o Symmetrical aromatic diisocyanate compounds, preferably 2,2'-methylene diphenyl diisocyanate (2,2'-MDI); 4,4'-methylene diphenyl diisocyanate (4,4'-MDI); 4,4'-dibenzyl diisocyanate (4,4'-DBDI); 2,6-toluene diisocyanate (2,6-TDI); meta-xylylene diisocyanate (m-XDI);

[0035] o Symmetrical alicyclic diisocyanate compounds, preferably methylenebis(4-cyclohexyl isocyanate)(H 12 MDI);

[0036] o Symmetrical aliphatic diisocyanate compounds, preferably hexamethylene diisocyanate (HDI) and pentamethylene diisocyanate (PDI);

[0037] o Asymmetric aromatic diisocyanate compounds, preferably 2,4'-methylene diphenyl diisocyanate (2,4'-MDI); 2,4'-dibenzyl diisocyanate (2,4'-DBDI); 2,4-toluene diisocyanate (2,4-TDI);

[0038] - a biuret trimer compound, in particular a biuret trimer compound selected from the group consisting of:

[0039] o Symmetrical aromatic diisocyanate compounds, preferably 2,2'-methylene diphenyl diisocyanate (2,2'-MDI); 4,4'-methylene diphenyl diisocyanate (4,4'-MDI); 4,4'-dibenzyl diisocyanate (4,4'-DBDI); 2,6-toluene diisocyanate (2,6-TDI); meta-xylylene diisocyanate (m-XDI);

[0040] o Symmetrical alicyclic diisocyanate compounds, preferably methylenebis(4-cyclohexyl isocyanate)(H 12 MDI);

[0041] o Symmetrical aliphatic diisocyanate compounds, preferably hexamethylene diisocyanate (HDI) and pentamethylene diisocyanate (PDI);

[0042] o Asymmetric aromatic diisocyanate compounds, preferably 2,4'-methylene diphenyl diisocyanate (2,4'-MDI); 2,4'-dibenzyl diisocyanate (2,4'-DBDI); 2,4-toluene diisocyanate (2,4-TDI);

[0043] o An asymmetric alicyclic diisocyanate compound, preferably isophorone diisocyanate (IPDI).

[0044] According to the present invention, more preferably, compound (a2) is selected from triphenylmethane-4,4',4"-triisocyanate, 1,1',1"-methylenetris(4-isocyanatophenyl), HDI isocyanurate, IPDI isocyanurate, PDI isocyanurate, HDI biuret trimer, IPDI biuret trimer, PDI biuret trimer.

[0045] Preferably, for the composition T according to the invention, compound (b) is a compound of formula I in which:

[0046] -R independently represents a group selected from the following: straight chain C6-C 32 -alkyl, branched C6-C 32 -alkyl, C6-C 32 -Cycloalkyl, straight chain C6-C 32 -alkenyl, branched C6-C 32 -alkenyl, C6-C 32 -cycloalkenyl, C6-C 36 - aryl and combinations thereof, preferably

[0047] -R independently represents a group selected from the following: straight chain C6-C 24 -alkyl, branched C6-C 24 -alkyl, C6-C 24 -Cycloalkyl, straight chain C6-C24 -alkenyl, branched C6-C 24 -alkenyl, C6-C 24 -cycloalkenyl, C6-C 32 - aryl and combinations thereof; or

[0048] - X independently represents an alkoxylated group selected from the group consisting of an ethoxylated group, a propoxylated group, a butoxylated group, and a combination thereof; preferably X represents an ethoxylated group or a combination of an ethoxylated group and a propoxylated group, more preferably X represents an ethoxylated group; or

[0049] -n represents 0 or a number 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.

[0050] More preferably, for the composition T according to the invention, compound (b) is a compound of formula I, wherein:

[0051] -R independently represents a group selected from the following: straight chain C6-C 32 -alkyl, branched C6-C 32 -alkyl, C6-C 32 -Cycloalkyl, straight chain C6-C 32 -alkenyl, branched C6-C 32 -alkenyl, C6-C 32 -cycloalkenyl, C6-C 36 - aryl and combinations thereof, preferably

[0052] -R independently represents a group selected from the following: straight chain C6-C 24 -alkyl, branched C6-C 24 -alkyl, C6-C 24 -Cycloalkyl, straight chain C6-C 24 -alkenyl, branched C6-C 24 -alkenyl, C6-C 24 -cycloalkenyl, C6-C 32 - aryl and combinations thereof; and

[0053] - X independently represents an alkoxylated group selected from the group consisting of an ethoxylated group, a propoxylated group, a butoxylated group, and combinations thereof; preferably X represents an ethoxylated group or a combination of an ethoxylated group and a propoxylated group, more preferably X represents an ethoxylated group; and

[0054] -n represents 0 or a number 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.

[0055] According to the invention, the radical R may also represent a radical of the formula:

[0056]

[0057] Where R" represents the formula C 15 H 31-x wherein x represents 0, 2, 4, 6; and thus may contain 0, 1, 2 or 3 olefinic unsaturations (double bonds). Such a group is advantageously a cardanyl group derived from cardanol. According to the invention, the R group may also represent a pentastyrylcumylphenyl group, a tristyrylphenyl group (TSP) of the formula:

[0058]

[0059] or distyrylphenyl (DSP) of the formula:

[0060]

[0061] According to the invention, the polyurethane polymer P is prepared by at least one polyhydroxylated and polyalkoxylated compound (c). Preferably, for the composition T according to the invention, compound (c) may be a compound (c1) of formula II:

[0062] HO-Qm-OH

[0063] (II)

[0064] in:

[0065] -Q independently represents an oxyalkylene residue;

[0066] -m stands alone for a number from 30 to 1000.

[0067] More preferably, for the composition T according to the invention, compound (c) may be a compound (c1) of formula II, wherein:

[0068] -Q independently represents an ethylene oxide residue; or

[0069] -m independently represents a number from 50 to 600, preferably from 100 to 600.

[0070] More preferably, for the composition T according to the invention, compound (c) may be a compound (c1) of formula II, wherein Q independently represents an ethylene oxide residue and m independently represents a number ranging from 50 to 600, preferably from 100 to 600.

[0071] Also preferably, for the composition T according to the invention, compound (c) may be a compound of formula II (c1) combined with a non-alkoxylated compound (c2) comprising at least three hydroxyl groups. Preferably, for the composition T according to the invention, compound (c2) comprises three hydroxyl groups. More preferably, it is chosen from glycerol, pentaerythritol and combinations thereof.

[0072] Also preferably, for the 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. More preferably, compound (c3) is selected from polyethoxylated glycerol, polyethoxylated pentaerythritol, and combinations thereof.

[0073] According to the present invention, compound (c) may be used in the form of one or a combination of more than one of compounds (c1), (c2) and (c3).

[0074] In principle, according to the invention, the polyol (c) is a polyalkoxylated compound. Preferably, for the composition T according to the invention, compound (c) comprises from 10 to 500 alkoxylated groups, preferably from 20 to 400 alkoxylated groups or from 10 to 300 alkoxylated groups. More preferably, compound (c) comprises from 20 to 250 alkoxylated groups.

[0075] Also preferably, compound (c) is polyethoxylated or polyethoxylated-polypropoxylated or polyethoxylated-polybutoxylated. More preferably, compound (c) is polyethoxylated.

[0076] According to the present invention, compound (c) generally comprises 10 to 500 ethoxylated groups, preferably 20 to 400 ethoxylated groups or 10 to 300 ethoxylated groups. More preferably, compound (c) comprises 20 to 250 ethoxylated groups.

[0077] The molar mass of compound (c) can vary within a sufficiently wide range, in particular depending on the number of alkoxylated groups contained in compound (c). Preferably, compound (c), (c1) or (c3) independently has a molecular weight (Mw) of 1500 g / mol to 40,000 g / mol, as measured by CES. More preferably, its molecular weight is 2000 g / mol to 25,000 g / mol, more preferably 2000 g / mol to 20,000 g / mol or 2000 g / mol to 15,000 g / mol or 2000 g / mol to 12,000 g / mol. More preferably, its molecular weight is 4000 g / mol to 20,000 g / mol or 4000 g / mol to 15,000 g / mol or 4000 g / mol to 12,000 g / mol.

[0078] According to the present invention, the molecular weight or molecular mass is determined by stereo exclusion chromatography (CES) or in English "size exclusion chromatography" (SEC). A test portion of the compound solution corresponding to 90 mg of dry solids content is introduced into a 10 mL vial. A mobile phase supplemented with 0.04% dimethylformamide (DMF) is added to a total mass of 10 g. The composition of this mobile phase is as follows: NaHO3: 0.05 mol / L, NaNO3: 0.1 mol / L / L, triethanolamine: 0.02 mol / L, NaN3: 0.03 mass%. The CES chain consists of the following: a "Waters" 510 isocratic pump (with a flow rate set to 0.8 mL / min), a "Waters" 717+ injector, a column oven equipped with a "Waters" Guard Column Ultrahydrogel pre-column with a length of 6 cm and an inner diameter of 40 mm, followed by a "Waters" Ultrahydrogel linear chromatographic column with a length of 30 cm and an inner diameter of 7.8 mm. Detection is provided by a "Waters" 410RI differential refractometer. The column oven is heated to 60°C and the refractometer temperature is brought to 45°C. The CES instrument is calibrated using a series of sodium polyacrylate standards provided by Polymer Standards Service with peak molecular weights ranging from 900 g / mol to 2,250,000 g / mol and polydispersity indices ranging from 1.4 to 1.7. The calibration curve was linear and took into account the correction obtained using the flow rate marker: dimethylformamide (DMF). The chromatograms were acquired and processed using the "PSS WinGPCScientific" software v 4.02. The chromatograms obtained were integrated in the region corresponding to molecular weights greater than 250 g / mol.

[0079] The amounts of the various compounds used during the polymerization reaction in the preparation of the polymer P can vary within a sufficiently wide range. Preferably, for the 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).

[0080] More preferably, the polymerization reaction uses 25 mol% to 60 mol% of compound (a) or 35 mol% to 70 mol% of compound (b) or 5 mol% to 40 mol% of compound (c), relative to the total molar amount of compounds (a), (b) and (c).

[0081] Also preferably, the polymerization reaction uses, relative to the total molar amount of compounds (a), (b) and (c):

[0082] - 20 mol% to 74.9 mol%, preferably 25 mol% to 60 mol% of compound (a),

[0083] - 25 mol% to 79.9 mol%, preferably 35 mol% to 70 mol% of compound (b), and

[0084] - 0.1 to 55 mol %, preferably 5 to 40 mol %, of compound (c).

[0085] The molar mass of the polymer P can vary within a relatively wide range, depending in particular on the number of alkoxylated groups of compounds (b) and (c). Preferably, the polymer P has a molar mass (Mw), measured by CES, of 4,000 to 150,000 g / mol, preferably 6,000 to 100,000 g / mol, more preferably 10,000 to 80,000 g / mol.

[0086] Essentially, the polymerization reaction uses compounds (a), (b) and (c) in the preparation of the polymer P. Other monomers can also be used.

[0087] Preferably, for the composition T according to the invention, the polymerization reaction may also use at least one additional crosslinking compound (d), preferably compound (d) comprising at least three functional groups selected from OH, SH, primary amine, secondary amine, and combinations thereof. More preferably, compound (d) is selected from diethanolamine, triethanolamine, trimethylolpropane, glycerol, pentaerythritol, and combinations thereof.

[0088] Preferably, compound (d) is used in an amount of less than 5 mol %, preferably 0.01 to 5 mol %, particularly 0.1 to 5 mol %, relative to the total molar amount of monomers.

[0089] According to the present invention, the rheological agent R comprises at least one polyurethane polymer P, alone or in combination with one or more other ingredients. Agent R may comprise a carrier, in particular a liquid carrier selected from water, polar organic solvents, and combinations thereof. These solvents may be selected from glycols, butyl glycol, butyl diglycol, monopropylene glycol, ethylene glycol, methyl carbonate, ethyl carbonate, propylene carbonate, esters, ketones, ethylene diglycol, the product "Dowanol" with CAS No. 34590-94-8, the product "Texanol" with CAS No. 25265-77-4, and combinations thereof. Preferably, agent R comprises water in combination with polymer P. Agent R may also comprise at least one other ingredient selected from amphiphilic compounds, in particular surfactant compounds, preferably hydroxylated surfactant compounds, such as alkyl-polyalkylene glycols, in particular alkyl-polyethylene glycol and alkyl-polypropylene glycol; polysaccharide derivatives, such as cyclodextrins, cyclodextrin derivatives, polyethers, alkyl glycosides; hydrotropic compounds, defoamers, antimicrobial agents, and combinations thereof. According to the present invention, the defoaming agent is preferably selected from silicon dioxide, surface active compounds, organosilicon derivatives and combinations thereof.

[0090] 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 selected from silicon, carbon graphite or graphitic carbon, hexagonal carbon, rhombohedral carbon and combinations thereof, optionally doped with at least one element, preferably selected from lithium, silicon, germanium and combinations thereof.

[0091] Preferred material E is selected from carbon graphite, silicon and combinations thereof.

[0092] Also preferably, for the composition T according to the invention, the material E is in the form of particles, preferably particles having a volume average size of less than 200 μm, preferably less than 150 μm or less than 100 μm or ranging from 50 μm to 200 μm, as measured by dynamic light scattering (DLS). The volume average size is generally measured by dynamic light scattering.

[0093] In addition to the material E and the rheological agent R, the aqueous anodic composition T according to the invention comprises at least one binder L for the material E, which can be a water-insoluble latex-form polymer L1 or a water-soluble polymer L2.

[0094] Preferably, for the composition T according to the present invention, the polymer L1 is selected from styrene-butadiene rubber (SBR) polymer, phenyl-propane latex, ethylene / vinyl acetate (EVA) copolymer, acrylic latex, methacrylic latex, acrylonitrile latex, polymethyl methacrylate, water-insoluble ASE polymer latex, water-insoluble HASE polymer latex and combinations thereof.

[0095] Preferably, for the composition T according to the invention, the polymer L1 is a styrene-butadiene polymer.

[0096] Preferably, for composition T according to the present invention, water-soluble polymer L2 is an acrylic latex. Also preferably, for composition T according to the present invention, water-soluble polymer L2 is independently selected from water-soluble ASE polymers (alkali-swellable or alkali-swellable emulsions), water-soluble HASE (hydrophobically-modified alkali-swellable or hydrophobically-modified alkali-swellable emulsions), water-soluble acrylic acid polymers, polyvinyl alcohol (PVA), poly(ethylene oxide) (PEO), carboxymethyl cellulose (CMC), sodium polyacrylate, modified polyacrylic acid, acrylamide homopolymers, acrylamide copolymers, and combinations thereof. More preferably, water-soluble polymer L2 is prepared by emulsion polymerization with at least one water-soluble anionic monomer.

[0097] Preferably, for the composition T according to the invention, the polymer L2 is selected from water-soluble ASE polymers, sodium polyacrylate, modified polyacrylic acid, acrylamide copolymers and combinations thereof.

[0098] According to the present invention, polymer L2 is water-soluble, preferably water-soluble at a pH greater than or equal to 6 or greater than or equal to 7.

[0099] According to the present invention, the water-soluble polymer L2 can be prepared by polymerization of at least one anionic monomer M1 selected from acrylic acid, methacrylic acid, acrylic acid oligomers, acrylates, methacrylates, and combinations thereof, and optionally at least one monomer different from monomer M1, in the presence of at least one initiator compound. Preferably, the other monomer different from monomer M1 is independently selected from anionic monomer M2, organosulfur monomer M3, nonionic monomer M4, crosslinking monomer M5, and combinations thereof.

[0100] Preferably, the anionic monomer M2, which is different from the anionic monomer M1, is selected from maleic acid, maleate, itaconic acid, itaconic acid, crotonic acid, crotonate and combinations thereof.

[0101] Also preferably, the organosulfur monomer M3 is selected from the group consisting of sulfonated monomers M3a, sulfated monomers M3b, and combinations thereof. More preferably, the organosulfur monomer M3 is selected from the group consisting of 2-acrylamido-2-methylpropanesulfonic acid (AMPS), allylsulfonic acid, alkylenesulfonates, alkylenearylsulfonates, in particular styrenesulfonates, vinylsulfonates, methallylsulfonates, allylsulfonates, methallylsulfates, allylsulfates, 2-sulfoethylmethacrylate, 3-allyloxy-2-hydroxy-1-propanesulfonic acid, 3-sulfopropylmethacrylate, salts thereof, and combinations thereof.

[0102] Also preferably, the nonionic monomer M4 is selected from vinyl acetate, C1-C8 esters from compounds derived from acids 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), hydroxyethyl methacrylate, hydroxyethyl acrylate, hydroxypropyl methacrylate, hydroxypropyl acrylate, nitrogen-containing monomers (e.g. acrylonitrile, methacrylamide, acrylamide, vinyl-lactam, N-hydroxymethyl acrylamide), styrene and combinations thereof.

[0103] It is also preferred that the monomer M5 contains at least two polymerizable alkenyl groups. More preferably, the crosslinking monomer M5 is selected from polyvinyl aromatic monomers (e.g. divinylbenzene, diallyl phthalate); polyalkenyl ethers (triallyl pentaerythritol, diallyl pentaerythritol, diallyl sucrose, octaallyl sucrose, trimethylolpropane diallyl ether); polyunsaturated esters of polyols or polyunsaturated esters of polyacids (e.g. trimethylolpropane tri(meth)acrylate, trimethylolpropane, polyethylene glycol di(meth)acrylate); diacrylates, dimethacrylates derived from polyols, the polyols being in particular selected from pentaerythritol, sorbitol, sucrose; divinylnaphthalene, 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, triallyl cyanurate, diallyl phthalate, divinylbenzene; diallyl phthalate (DAP); ethylene glycol dimethacrylate (EGDMA); methylenebisacrylamide (MBA); divinylbenzene (DVB); biscyclopentenyl ethoxylated methacrylate (FRA); trimethylolpropane triallyl ether (APE) and combinations thereof.

[0104] According to the present invention, preferably, polymer L2 is prepared from the following substances:

[0105] - 2 to 100% by weight, preferably 5 to 98% by weight, of at least one monomer M1, and

[0106] 0 to 98% by weight, preferably 2 to 95% by weight, of at least one other monomer different from monomer M1, preferably at least one other monomer selected from the group consisting of monomer M2, monomer M3, monomer M4, monomer M5 and combinations thereof.

[0107] 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.

[0108] Also preferably, the water-soluble polymer L2 has a weight average molecular weight Mw (measured by CES) of greater than 2000 g / mol or greater than 5000 g / mol. More preferably, the water-soluble polymer L2 has a weight average molecular weight Mw (measured by CES) of 2000 g / mol to 1000000 g / mol, preferably 2000 g / mol to 800000 g / mol or 2000 g / mol to 500000 g / mol, more preferably 2000 g / mol to 100000 g / mol or 2000 g / mol to 50000 g / mol. More preferably, the water-soluble polymer L2 has a weight average molecular weight Mw (measured by CES) of 5000 g / mol to 1000000 g / mol, preferably 5000 g / mol to 800000 g / mol or 5000 g / mol to 500000 g / mol, more preferably 5000 g / mol to 100 000 g / mol or 5000 g / mol to 50000 g / mol.

[0109] According to the present invention, the polymer L2 can be prepared in a polar solvent, in particular a solvent selected from water, alcohols, toluene, ketones, chlorinated solvents, esters and combinations thereof.

[0110] Typically during the preparation of 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 below 75°C.

[0111] According to the present invention, polymer L2 is prepared in the presence of at least one initiator compound selected from the group consisting of peroxides (e.g., hydrogen peroxide), hydroperoxides (e.g., tert-butyl hydroperoxide), persulfates (e.g., sodium persulfate, ammonium persulfate, potassium persulfate), combinations thereof, and combinations thereof with metal salts, preferably metal salts selected from the group consisting of iron salts (e.g., Fe II or Fe III), copper salts (e.g., Cu I or Cu II), and combinations thereof.

[0112] According to the present invention, polymer L2 can be prepared in the presence of a chain transfer agent, preferably in the presence of a compound selected from isopropanol, mercaptans, dodecyl mercaptan, phosphorous acid, phosphites, such as sodium phosphite, hypophosphorous acid, hypophosphites, such as sodium hypophosphite, bisulfites, such as sodium bisulfite, alkyl iodides, and alkyl bromides.

[0113] Polymer L2 may be unneutralized or partially or fully neutralized, preferably with monovalent ions, divalent ions, or combinations thereof, more preferably with at least one compound selected from the group consisting of LiOH, NaOH, KOH, NH4OH, Ca(OH)2, Mg(OH)2, MgO, CaO, ZnO, and combinations thereof. Polymer L2 may also be partially or fully neutralized with an amine selected from the group consisting of tertiary amines, secondary amines, primary amines, and combinations thereof. The pH of polymer L2 is typically less than 12, or less than 11, or between 2 and 12, or between 5 and 11. Its pKa is typically less than 3.5, or between 1.5 and 2.5.

[0114] In the composition T according to the invention, the amounts of the ingredients may vary. Preferably according to the invention, the composition T comprises:

[0115] - 0.2% to 5% by dry weight of a rheological agent R,

[0116] -85% to 99.5% dry weight of material E, and

[0117] - 0.3% to 10% by dry weight of a binder, in particular binder L,

[0118] Calculated relative to the total dry weight of rheological agent R, binder, especially binder L and material E.

[0119] The composition T according to the invention comprises at least one binder L. Preferably, the composition T according to the invention may comprise at least one further binder compound different from the agent L, or it may not comprise any further binder compound than the binder L. Preferably, when a further binder compound different from the binder L is used, it is chosen from cellulose, in particular carboxymethylcellulose (CMC), hydroxycellulose (in particular hydroxymethylcellulose or hydroxyethylcellulose), alginates, poly(allylamine, HCl), pectin, amilopectine, guar gum and combinations thereof.

[0120] The composition T according to the invention may also contain at least one other compound chosen from (meth)acrylic comb polymers, polyethylene, fluorinated binder compounds, for example compounds chosen from polyvinylidene fluoride (PVDF), poly(vinyl-pyrrolidone), polytetrafluoroethylene (PTFE), chlorotrifluoroethylene (ECTFE), polyethylenetetrafluoroethylene (ETFE), fluorinated ethylene-propylene (FEP), perfluoroalkoxy (PFA), polychlorotrifluoroethylene (PCTFE), fluoroacrylates, fluorosilicones and combinations thereof.

[0121] The composition T according to the invention may also comprise at least one organic or inorganic acid, preferably one chosen from sulfuric acid, phosphoric acid, phosphorous acid, hypophosphorous acid, acetic acid, lactic acid and combinations thereof.

[0122] The composition T according to the present invention may also contain at least one dispersant for material E, preferably a dispersant selected from (meth)acrylic acid homopolymers, (meth)acrylic acid copolymers and at least one other monomer, and combinations thereof; more preferably a dispersant having a molecular weight, measured by CES, of 3,000 to 2,000,000 g / mol, in particular 5,000 to 900,000 g / mol. According to the present invention, the dispersant is advantageously used in an amount of 0.05 to 5% by weight, preferably 0.1 to 2% by weight, calculated on a dry weight basis, relative to the total dry weight of the rheological agent R, the binder, in particular the binder L, the material E, and the dispersant.

[0123] In a particularly advantageous manner, 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 greater than 2 mPa.s, preferably greater than 5 mPa.s, at 25°C and 0.01s according to the method of the embodiment. -1 Also preferably, the composition T according to the invention has a viscosity of less than 50 mPa.s or less than 100 mPa.s at 25°C and 0.01s according to the method of the embodiment. -1 The viscosity is measured below.

[0124] Also preferably, the composition T according to the present invention is heated at 25°C and 1000s according to the method of the embodiment. -1 The viscosity measured at 25°C and 1000s is greater than 0.1 mPa.s, preferably greater than 0.2 mPa.s. It is also preferred that the composition T according to the invention has a viscosity of less than 5 mPa.s or less than 1 mPa.s according to the method of the embodiment at 25°C and 1000s. -1 The viscosity is measured below.

[0125] It is also particularly advantageous that the rheological agents according to the invention make it possible to control the viscoelastic properties of the composition T according to the invention. According to the invention, the variation in the phase shift angle δ (°), obtained by the ratio of the loss modulus G″ to the elastic modulus G' (tan δ=G" / G'), is measured relative to the variation in shear stress. The elastic modulus G' and the loss modulus G" are quantified by viscoelasticity measurements performed at 1 Hz using a rheometer equipped with a cone-plate rotor (CP35) under applied stress.

[0126] Preferably, the composition T according to the present invention has a phase shift angle at 1 Hz measured according to the method of the embodiment at 25° C. and 0.01 Pa of greater than 30°, preferably greater than 50° or less than 90°. Also preferably, the composition T according to the present invention has a phase shift angle at 1 Hz measured according to the method of the embodiment at 25° C. and 100 Pa of greater than 60°, preferably greater than 70° or less than 90°.

[0127] Preferably according to the invention, the composition T is not an emulsion.

[0128] The present invention also relates to the preparation of an aqueous composition T according to the invention. Therefore, the present invention provides a method for preparing an aqueous composition T, comprising:

[0129] - prepare the adhesive L,

[0130] - Preparation of rheological agent R,

[0131] - Adding at least one material E selected from metal fibers, metal particles, carbon graphite fibers, carbon graphite particles and combinations thereof, preferably, material E selected from silicon, carbon graphite or graphite carbon, hexagonal carbon, rhombohedral carbon and combinations thereof, optionally doped with at least one element, preferably selected from lithium, silicon, germanium and combinations thereof.

[0132] The aqueous composition T according to the present invention may constitute an essential component in the preparation of an anode. Therefore, the present invention provides a method for preparing an anode, comprising:

[0133] - applying at least one composition T according to the invention to a substrate,

[0134] - Drying and then calendering the coated substrate.

[0135] According to the present invention, preferably, the substrate is a metal substrate, preferably a metal substrate selected from copper, titanium, silver, zinc, nickel and combinations thereof. According to the present invention, more preferably, the substrate is a copper substrate.

[0136] Preferably according to the invention, the preparation process according to the invention comprises applying the composition T obtained at a pH value below 7 or at a pH value ranging from 4 to 6.5.

[0137] According to the invention, the composition T is preferably applied to the substrate in a thickness of less than 500 μm, preferably less than 100 μm or less than 20 μm, measured after drying and calendering by a coating thickness gauge of 1 to 1000 μm.

[0138] It is also preferred according to the invention that the composition T is applied to the substrate in a thickness of greater than 5 μm, measured by a coating thickness gauge of 1 to 1000 μm after drying and calendering.

[0139] More preferably according to the invention, the composition T is applied to the substrate in a thickness of 5 to 500 μm, preferably 5 to 100 μm or 5 to 20 μm, measured after drying and calendering by a coating thickness gauge of 1 to 1000 μm.

[0140] According to the invention, it is particularly advantageous that the composition T is applied uniformly to the substrate. Preferably, the composition T is applied uniformly to the substrate according to the method described in the examples.

[0141] The present invention also provides an anode prepared according to the preparation method of the present invention.

[0142] According to the invention, the particular, advantageous or preferred features of the composition T according to the invention define the preparation method, the manufacturing method and the anode, which are also particular, advantageous or preferred.

[0143] The following examples serve to illustrate various aspects of the invention. Example

[0144] Preparation of the polyurethane polymer P according to the invention and the rheological agent R according to the invention

[0145] Copolymer P1 and rheological agent R1

[0146] In a 2L glass reactor equipped with a mechanical stirring rod, a vacuum pump, a nitrogen inlet and heated by a double jacket in which oil is circulated, compound (c) (polyethylene glycol-molecular weight 10000 g / mol) (260.8g) is introduced and heated to 95°C under vacuum. Then, under stirring and an inert atmosphere, 0.17g of DBU (1,8-diazabicyclo[5.4.0]undec-7-ene) catalyst is added, followed by the addition of compound (b) (Surfaline CL4 Arkema) (25g) of formula I over 15 minutes, wherein n represents 4, X represents an ethoxylated group and R represents a cashew group. Then, diisocyanate compound (a1) (isophorone diisocyanate, IPDI) (16.8g) is introduced by syringe and under stirring at 150 rpm. The reaction is continued at 100°C for 1 hour.

[0147] The isocyanate level is then checked by back titration to ensure it is zero. 1 g of the reaction medium is taken and an excess of dibutylamine (1 molar aqueous solution) is added, which reacts with any isocyanate groups present. Any unreacted dibutylamine is then quantified using 1N aqueous hydrochloric acid. The amount of isocyanate groups present in the reaction medium can then be deduced from this. If this amount is not zero, the reaction is extended for 15 minutes until the reaction is complete. The resulting copolymer P1 is formulated with an ethoxylated alcohol-type surfactant ("Emulan" HE51 "Basf") (202 g), 1000 ppm of an antimicrobial agent ("Biopol" SMV "Chemipol"), 1000 ppm of a defoamer ("Tego" 1488 "Evonik"), and water (495 g). This gives an aqueous rheology control composition R1 composed of 30% by mass of the copolymer P1 according to the invention, 20% by mass of the surfactant, and 50% by mass of water.

[0148] Copolymer P2 and rheological agent R2

[0149] In a 2 L glass reactor equipped with a mechanical stirring rod, a vacuum pump, a nitrogen inlet and heated by a double jacket in which oil is circulated, compound (c) (polyethylene glycol-molecular weight 10000 g / mol) (155.5 g) is introduced and heated to 95° C. under vacuum. Then, under stirring and inert atmosphere, 0.33 g of DBU catalyst is added to the medium, and then compound (b) of formula I, wherein n represents 0 and R represents a linear C, is added simultaneously over 15 minutes. 12-alkyl ("Nacol" 12-96 "Sasol") (3.5 g), another compound (b) of formula I in which n is 0 and R is 4-dodecyl-cyclohexyl ("Marlipal" VS18 "Sasol") (7.0 g) and a third compound (b) of formula I in which n is 0 and R is n-octyl ("Nacol" 8 "Sasol") (0.65 g). Then, the diisocyanate compound (a1) (IPDI) (11.0 g) was introduced via syringe while stirring at 150 rpm. The reaction was continued at 100° C. for 1 hour.

[0150] The isocyanate level was then checked by back titration to ensure it was zero. The resulting copolymer P2 was formulated with surfactant compounds of the ethoxylated alcohol type ("Emulan" HE51 "Basf") (48.3 g) and ("Simulsol" Ox1008 "Seppic") (48.3 g), 1000 ppm of an antimicrobial agent ("Biopol" SMV "Chemipol"), 1000 ppm of an antifoaming agent ("Tego" 1488 "Evonik"), and water (725 g). This gave an aqueous rheology control composition R2 composed of 17.5% by mass of the copolymer P2 according to the invention, 9.5% by mass of the surfactant compound, and 73% by mass of water.

[0151] Copolymer P3 and rheological agent R3

[0152] In a 2 L glass reactor equipped with a mechanical stirring rod, a vacuum pump, a nitrogen inlet and heated by a double jacket in which oil is circulated, compound (c) (polyethylene glycol - molecular weight 10000 g / mol) (271 g) is introduced and heated to 95 ° C. under vacuum. Then, under stirring and inert atmosphere, compound (b) of formula I ("Nacol" 16-95 "Sasol") (16.2 g) is added within 15 minutes, wherein n represents 0 and R represents a linear C 16 Then, diisocyanate compound (a1) (toluene diisocyanate, TDI) (11.6 g) was introduced through a syringe with stirring at 150 rpm. The reaction was continued at 100° C. for 1 hour.

[0153] The isocyanate level was then checked by back titration to ensure it was zero. The resulting copolymer P3 was formulated with a surfactant compound of the ethoxylated alcohol type ("Disponil" D8, "Cognis") (198 g), 1000 ppm of an antimicrobial agent ("Biopol" SMV, "Chemipol"), 1000 ppm of a defoamer ("Tego" 1488, "Evonik"), and water (500 g). This gave an aqueous rheology control composition R3 composed of 30% by mass of the copolymer P3 according to the invention, 20% by mass of the surfactant compound, and 50% by mass of water.

[0154] Copolymer P4 and rheological agent R4

[0155] In a 2 L glass reactor equipped with a mechanical stirring rod, a vacuum pump, a nitrogen inlet and heated by a double jacket in which oil is circulated, compound (c) (polyethylene glycol-molecular weight 10000 g / mol) (152.7 g) is introduced and heated to 95° C. under vacuum. Then, under stirring and inert atmosphere, 0.2 g of DBU catalyst is added to the medium, followed by the simultaneous addition of compound (b) over 15 minutes, which is a combination of branched and linear C 12 and C 13 A polybranched Guerbet alcohol (CAS No. 2041102-78-5 "Isofol" 2426S "Sasol") (6.7 g) obtained by dimerization of an alcohol, another compound (b) of formula I in which n is 3, X is an ethoxylated group, and R is a tristyrylphenyl group ("Simulsol" TS26 "Seppic") (4.8 g), and a third compound (b) of formula I in which n is 0 and R is a 2-butyl-1-octanol group (CAS No. 3913-02-8 "Isofol" 12 "Sasol") (3.4 g) were added. Then, the diisocyanate compound (a1) (IPDI) (10.2 g) was introduced via syringe with stirring at 150 rpm. The reaction was continued at 100° C. for 1 hour.

[0156] The isocyanate level was then checked by back titration to ensure it was zero. The resulting copolymer P4 was formulated with surfactant compounds of the ethoxylated alcohol type ("Emulan" HE51 "Basf") (48.3 g) and ("Simulsol" Ox1008 "Seppic") (48.3 g), 1000 ppm of an antimicrobial agent ("Biopol" SMV "Chemipol"), 1000 ppm of an antifoaming agent ("Tego" 1488 "Evonik"), and water (725 g). This gave an aqueous rheology control composition R4 according to the invention, composed of 17.5% by mass of the copolymer P4 according to the invention, 9.5% by mass of the surfactant compound, and 73% by mass of water.

[0157] Copolymer P5 and rheological agent R5

[0158] In a 2 L glass reactor equipped with a mechanical stirring rod, a vacuum pump, a nitrogen inlet and heated by a double jacket in which oil is circulated, compound (c) (polyethylene glycol-molecular weight 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 DBU catalyst is added, and then compound (b) of formula I, wherein n represents 0 and R represents tristyrylphenyl ("Simulsol" TS26 "Seppic") (15.7 g) is added over 10 minutes. Then, diisocyanate compound (a1) (IPDI) (9.8 g) is introduced by syringe and under stirring at 150 rpm. The reaction is continued at 100 ° C for 1 hour.

[0159] The isocyanate level was then checked by back titration to ensure it was zero. The resulting copolymer P5 was formulated with a surfactant compound of the ethoxylated alcohol type ("Simulsol" Ox1008 "Seppic") (118 g), 1000 ppm of an antimicrobial agent ("Biopol" SMV "Chemipol"), 1000 ppm of an antimicrobial agent ("Tego" 1488 "Evonik"), and water (700 g). This gave an aqueous rheology control composition R5 according to the invention, consisting of 18% by mass of the copolymer P5 according to the invention, 12% by mass of the surfactant compound, and 70% by mass of water.

[0160] Preparation and characterization of aqueous anodic compositions T1 to T4 according to the invention

[0161] 47 g of water and 2.06 g of a polyacrylic acid-based dispersant (molecular weight 600,000 g / mol, measured by CES) were placed in a 500 mL polypropylene container suitable for a stirrer ("Speedmixer" DAC 1100) and mixed at 800 rpm for 1 minute. 50 g of Material E (natural graphite powder with a D50 of 17 to 19 μm - "MSE Supply") was added and mixed at 1600 rpm for 1 minute and 30 seconds. The pH was adjusted to 6 using a 95% dry weight aqueous solution of AMP (2-amino-2-methyl-1-propanol). The mixture was stirred at 1600 rpm for 1 minute.

[0162] 2.08 g of rheological agent R1 were added and mixed at 1600 rpm for 1 minute. 1.56 g of binder L1 (styrene-butadiene latex-BM 451B "Zeon") were added and mixed at 800 rpm for 1 minute. The anode composition T1 according to the invention was obtained.

[0163] Similarly, aqueous anode compositions T2, T3, and T4 were prepared by replacing rheological agent R1 with rheological agents R2 (3.85 g), R3 (2.08 g), and R4 (3.85 g), respectively, and using water in amounts of 46 g, 47 g, and 46 g for compositions T2, T3, and T4, respectively.

[0164] A rheometer ("Haake Mars III") was used to analyze the flow of the fluid using a cone-plate rotor at 25°C and different shear rates. )(CP60) were used to determine their rheological properties by measuring their viscosity (mPa.s) under applied stress.

[0165] Their viscoelastic structure was also evaluated by measuring the change in the phase shift angle δ (°), which is obtained by the ratio of the loss modulus G" to the elastic modulus G' (tan δ = G" / G'), as a function of shear stress. The elastic modulus G' and loss modulus G" were quantified by viscoelastic measurements at 1 Hz using a rheometer ("Haake Mars III") equipped with a cone-plate rotor (CP35) under applied stress (Pa).

[0166] Their thixotropic behavior was also determined by evaluating the application efficiency using a three-stage thixotropic test (3-ITT), which stimulates the behavior of the anode composition at rest, during application, and during reconstitution after application. The viscosity measurements (mPa.s) were performed at 25° C. using a cone-plate rotor (CP35) in 3 stages:

[0167] - For 5 points, in 100s -1 Pre-cut for 10 seconds;

[0168] - For 5 points, let it stand for 60 seconds without shearing;

[0169] - in 0.1s -1 The viscosity of the composition at rest was determined by measuring at a low shear rate of 180s for 20 points;

[0170] -In the 1000s -1 The viscosity of the composition during its application was determined by measuring at a shear rate of 30s for 20 points;

[0171] - in 0.1s -1 The low shear rate was measured to reveal the speed of sample reconstruction, and 200s was measured for 150 points;

[0172] -0.1s -1 The low shear rate of 400 s was used to reveal the behavior of the structure over a longer acquisition time, with 50 points measured for 400 s.

[0173] The results are shown in Tables 1, 2 and 3, respectively.

[0174]

[0175] Table 1

[0176]

[0177] Table 2

[0178]

[0179] Table 3

[0180] Preparation and characterization of the anode according to the invention

[0181] The aqueous anode composition T1 according to the present invention was applied to a 12 μm thick copper foil using a 4-hole manual coater at a speed of 10 mm / s on a vacuum coating table with a wet coating of 200 μm. The coated foil was then dried in a constant temperature and humidity chamber at a temperature of 25° C. and a humidity of 50% for 24 hours. Once dried, the foil was rolled using a calender (“Gester”) at a pressure of 25 kg / cm 2 The coated foil was calendered on the front and back sides at a pressure of 1000 Å and a running speed of 0.1 m / s. Discs with a diameter of 12 mm were cut using a precision cutter.

[0182] Similarly, anodes were prepared using aqueous anode compositions T2, T3 and T4 by replacing composition T1 with one of these compositions according to the invention.

[0183] The uniformity and adhesion of the composition layer were evaluated by visual inspection of the prepared anodes immediately after preparation: when viewed from the front in daylight, no aggregates or surface unevenness were visible on the coating surface. The coating had no adhesion defects.

[0184] The aqueous anode composition T according to the invention comprising a rheological agent R has a thixotropic behavior which allows easy and efficient application during anode preparation.The aqueous anode composition according to the invention allows the preparation of anodes having a regular, uniform and stable active surface.

Claims

1. An aqueous anode composition T comprising: At least one rheological agent R comprising at least one water-soluble nonionic polyurethane polymer P prepared by polymerization of: a) at least one isocyanate compound (a) independently selected from diisocyanate compounds (a1), polyisocyanate compounds (a2), and combinations thereof; b) at least one compound (b) of formula I: R-X n -OH (I) in: -R independently represents a group selected from the following: straight chain C4-C 40 -alkyl, branched C4-C 40 -alkyl, C5-C 40 -Cycloalkyl, straight chain C4-C 40 -alkenyl, branched C4-C 40 -alkenyl, C5-C 40 -cycloalkenyl, C5-C 40 - aryl and combinations thereof, -X independently represents an alkoxylated group selected from the group consisting of ethylene oxide, propylene oxide, butylene oxide, and combinations thereof, -n represents 0 or a number from 1 to 500; c) at least one polyhydroxylated and polyalkoxylated compound (c); At least one material E selected from metal fibers, metal particles, carbon graphite fibers, carbon graphite particles, silicon particles, and combinations thereof; and • At least one binder L for the material E, chosen from polymers L1 in the form of water-insoluble latexes, water-soluble polymers L2 and combinations thereof.

2. The composition T according to claim 1, wherein: ●Diisocyanate compound (a1) selected from: - Symmetrical aromatic diisocyanate compounds, preferably 2,2'-methylene diphenyl diisocyanate (2,2'-MDI); 4,4'-methylene diphenyl diisocyanate (4,4'-MDI); 4,4'-dibenzyl diisocyanate (4,4'-DBDI); 2,6-toluene diisocyanate (2,6-TDI); meta-xylylene diisocyanate (m-XDI); - symmetrical alicyclic diisocyanate compounds, preferably methylenebis(4-cyclohexyl isocyanate)(H 12 MDI); - symmetrical aliphatic diisocyanate compounds, preferably hexamethylene diisocyanate (HDI) and pentamethylene diisocyanate (PDI); - an asymmetric aromatic diisocyanate compound, preferably 2,4'-methylenediphenyl diisocyanate (2,4'-MDI); 2,4'-dibenzyl diisocyanate (2,4'-DBDI); 2,4-toluene diisocyanate (2,4-TDI); - an asymmetric alicyclic diisocyanate compound, preferably isophorone diisocyanate (IPDI), According to the present invention, preferably, compound (a1) is selected from IPDI, HDI, H 12 MDI and its combinations; or the polyisocyanate compound (a2) strictly comprises more than 2 isocyanate groups or more than 2.2 isocyanate groups or even more than 2.5 isocyanate groups; preferably, the polyisocyanate compound (a2) comprises more than 2.6 isocyanate groups or more than 2.7 isocyanate groups or more than 3 isocyanate groups; more preferably, the polyisocyanate compound (a2) comprises 2.2 to 6 isocyanate groups, 2.2 to 4 isocyanate groups, 2.2 to 3.5 isocyanate groups, 2.5 to 6 isocyanate groups, 2.2 to 5 isocyanate groups, 2.5 to 4 isocyanate groups, 2.5 to 3.5 isocyanate groups and in particular 2.6 to 3.3 isocyanate groups; or The polyisocyanate compound (a2) is selected from: -Triphenylmethane-4,4',4"-triisocyanate or 1,1',1"-methylenetris(4-isocyanatophenyl); - an isocyanurate compound, in particular an isocyanurate compound selected from the group consisting of: o Symmetrical aromatic diisocyanate compounds, preferably 2,2'-methylene diphenyl diisocyanate (2,2'-MDI); 4,4'-methylene diphenyl diisocyanate (4,4'-MDI); 4,4'-dibenzyl diisocyanate (4,4'-DBDI); 2,6-toluene diisocyanate (2,6-TDI); meta-xylylene diisocyanate (m-XDI); o Symmetrical alicyclic diisocyanate compounds, preferably methylenebis(4-cyclohexyl isocyanate) (H 12 MDI); o Symmetrical aliphatic diisocyanate compounds, preferably hexamethylene diisocyanate (HDI) and pentamethylene diisocyanate (PDI); o Asymmetric aromatic diisocyanate compounds, preferably 2,4'-methylene diphenyl diisocyanate (2,4'-MDI); 2,4'-dibenzyl diisocyanate (2,4'-DBDI); 2,4-toluene diisocyanate (2,4-TDI); - a biuret trimer compound, in particular a biuret trimer compound selected from the group consisting of: o Symmetrical aromatic diisocyanate compounds, preferably 2,2'-methylene diphenyl diisocyanate (2,2'-MDI); 4,4'-methylene diphenyl diisocyanate (4,4'-MDI); 4,4'-dibenzyl diisocyanate (4,4'-DBDI); 2,6-toluene diisocyanate (2,6-TDI); meta-xylylene diisocyanate (m-XDI); o Symmetrical alicyclic diisocyanate compounds, preferably methylenebis(4-cyclohexyl isocyanate) (H 12 MDI); o Symmetrical aliphatic diisocyanate compounds, preferably hexamethylene diisocyanate (HDI) and pentamethylene diisocyanate (PDI); o Asymmetric aromatic diisocyanate compounds, preferably 2,4'-methylene diphenyl diisocyanate (2,4'-MDI); 2,4'-dibenzyl diisocyanate (2,4'-DBDI); 2,4-toluene diisocyanate (2,4-TDI); o an asymmetric alicyclic diisocyanate compound, preferably isophorone diisocyanate (IPDI); More preferably, compound (a2) is selected from triphenylmethane-4,4',4"-triisocyanate, 1,1',1"-methylenetris(4-isocyanatophenyl), HDI isocyanurate, IPDI isocyanurate, PDI isocyanurate, HDI biuret trimer, IPDI biuret trimer, PDI biuret trimer.

3. The composition T according to any one of claims 1 or 2, wherein compound (b) is a compound of formula I, wherein: -R independently represents a group selected from the following: straight chain C6-C 32 -alkyl, branched C6-C 32 -alkyl, C6-C 32 -Cycloalkyl, straight chain C6-C 32 -alkenyl, branched C6-C 32 -alkenyl, C6-C 32 -cycloalkenyl, C6-C 36 - aryl and combinations thereof, preferably -R independently represents a group selected from the following: straight chain C6-C 24 -alkyl, branched C6-C 24 -alkyl, C6-C 24 -Cycloalkyl, straight chain C6-C 24 -alkenyl, branched C6-C 24 -alkenyl, C6-C 24 -cycloalkenyl, C6-C 32 - aryl and combinations thereof; or - X independently represents an alkoxylated group selected from the group consisting of an ethoxylated group, a propoxylated group, a butoxylated group, and a combination thereof; preferably X represents an ethoxylated group or a combination of an ethoxylated group and a propoxylated group, more preferably X represents an ethoxylated group; or -n represents 0 or a number 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. The composition T according to any one of claims 1 to 3, wherein compound (c) is selected from: ●Compound (c1) of formula II: HO-Q m -OH (II) in: -Q independently represents an oxyalkylene residue; -m independently represents a number from 30 to 1000; a compound of formula II (c1) in combination with a non-alkoxylated compound (c2) comprising at least three hydroxyl groups; a polyalkoxylated compound (c3) comprising at least three hydroxyl groups; ●Their combination.

5. The composition T according to any one of claims 1 to 4, wherein compound (c) is selected from: ●Compound (c1) of formula II: HO-Q m -OH (II) in: -Q independently represents an ethylene oxide residue; or - m independently represents a number from 50 to 600, preferably from 100 to 600; or - wherein Q independently represents an ethylene oxide residue and m independently represents a number from 50 to 600, preferably from 100 to 600; a compound (c2) comprising three hydroxyl groups, preferably selected from glycerol, pentaerythritol and combinations thereof; • A polyalkoxylated compound (c3) different from compound (c2) and comprising three hydroxyl groups, preferably compound (c3) is selected from polyethoxylated glycerol, polyethoxylated pentaerythritol and combinations thereof.

6. The composition T according to any one of claims 1 to 5, wherein: Compound (c) comprises 10 to 500 alkoxylated groups, preferably 20 to 400 alkoxylated groups or 10 to 300 alkoxylated groups, more preferably 20 to 250 alkoxylated groups, or Compound (c) is polyethoxylated or polyethoxylated-polypropoxylated or polyethoxylated-polybutoxylated, preferably compound (c) is polyethoxylated, or Compound (c) comprises 10 to 500 ethoxylated groups, preferably 20 to 400 ethoxylated groups or 10 to 300 ethoxylated groups, more preferably 20 to 250 ethoxylated groups, or wherein: ●Compound (c), compound (c1) or compound (c3) independently has a molecular weight (Mw) measured by CES of 1500 g / mol to 40000 g / mol, preferably 2000 g / mol to 25000 g / mol, more preferably 2000 g / mol to 20000 g / mol or 2000 g / mol to 15000 g / mol or 2000 g / mol to 12000 g / mol, more preferably 4000 g / mol to 20000 g / mol or 4000 g / mol to 15000 g / mol or 4000 g / mol to 12000 g / mol.

7. The composition T according to any one of claims 1 to 6, wherein the polymerization reaction uses, relative to the total molar amount of compound (a), compound (b) and compound (c): - 20 mol% to 74.9 mol%, preferably 25 mol% to 60 mol% of compound (a), or - 25 mol% to 79.9 mol%, preferably 35 mol% to 70 mol% of compound (b), or - 0.1 to 55 mol %, preferably 5 to 40 mol %, of compound (c).

8. Composition T according to any one of claims 1 to 7, wherein the polymerization reaction further uses at least one additional crosslinking compound (d), preferably compound (d) comprises at least 3 functional groups selected from OH, SH, primary amine, secondary amine and combinations thereof, more preferably compound (d) is selected from diethanolamine, triethanolamine, trimethylolpropane, glycerol, pentaerythritol and combinations thereof, and the amount of compound (d) is preferably less than 5 mol%, preferably 0.01 mol% to 5 mol%, in particular 0.1 mol% to 5 mol%, relative to the total molar amount of monomers.

9. The composition T according to any one of claims 1 to 8, wherein: • Material E is selected from silicon, carbon graphite or graphitic carbon, hexagonal carbon, rhombohedral carbon and combinations thereof, optionally doped with at least one element, preferably an element selected from lithium, silicon, germanium and combinations thereof; or • Material E is in the form of particles, preferably particles having a volume average size measured by dynamic light scattering (DDL) of less than 200 μm, preferably less than 150 μm or less than 100 μm, or between 50 μm and 200 μm.

10. The composition T according to any one of claims 1 to 9, wherein: ● polymer L1 is selected from styrene-butadiene rubber (SBR) polymer, phenyl-propane latex, ethylene / vinyl acetate copolymer (EVA), acrylic latex, methacrylic latex, acrylonitrile latex, polymethyl methacrylate, water-insoluble ASE polymer latex, water-insoluble HASE polymer latex and combinations thereof; or ●The water-soluble polymer L2 is independently selected from water-soluble ASE polymers, water-soluble HASE polymers, water-soluble acrylic acid polymers, polyvinyl alcohol (PVA), polyethylene oxide (PEO), carboxymethyl cellulose (CMC), sodium polyacrylate, modified polyacrylic acid, acrylamide homopolymers, acrylamide copolymers and combinations thereof. Preferably, the water-soluble polymer L2 is prepared by an emulsion polymerization reaction with at least one water-soluble anionic monomer.

11. The composition T according to any one of claims 1 to 10, wherein: 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 by polymerization in the presence of at least one initiator compound of at least one anionic monomer M1 selected from acrylic acid, methacrylic acid, acrylic acid oligomers, acrylates, methacrylates 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 independently selected from the following: - an anionic monomer M2 different from the anionic monomer M1, which is selected from maleic acid, maleate, itaconic acid, itaconate, crotonic acid, crotonate and combinations thereof; - an organic sulfur monomer M3, preferably the monomer M3 is selected from the group consisting of sulfonated monomers M3a, sulfated monomers M3b and combinations thereof, more preferably, the organic sulfur monomer M3 is selected from the group consisting of 2-acrylamido-2-methylpropanesulfonic acid (AMPS), allylsulfonic acid, alkylenesulfonates, alkylenearylsulfonates, in particular styrenesulfonates, vinylsulfonates, methallylsulfonates, allylsulfonates, methallylsulfates, allylsulfates, 2-sulfoethyl methacrylate, 3-allyloxy-2-hydroxy-1-propanesulfonic acid, 3-sulfopropyl methacrylate, their salts and combinations thereof; - nonionic monomers M4 selected from vinyl acetate, C1-C8 esters from compounds derived from acids 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), hydroxyethyl methacrylate, hydroxyethyl acrylate, hydroxypropyl methacrylate, hydroxypropyl acrylate, nitrogen-containing monomers (e.g. acrylonitrile, methacrylamide, acrylamide, vinyl-lactam, N-hydroxymethyl acrylamide), styrene and combinations thereof; - crosslinking monomers M5, preferably monomers M5 comprising at least two polymerizable alkenyl groups, preferably crosslinking monomers M5 are selected from polyvinyl aromatic monomers (e.g. divinylbenzene, diallyl phthalate); polyalkenyl ethers (triallylpentaerythritol, diallylpentaerythritol, diallyl sucrose, octaallyl sucrose, trimethylolpropane diallyl ether); polyunsaturated esters of polyols or polyunsaturated esters of polyacids (e.g. trimethylolpropane tri(meth)acrylate, trimethylolpropane, polyethylene glycol di(meth)acrylate); diacrylates, dimethacrylates derived from polyols, in particular selected from pentaerythritol, sorbitol, sucrose; divinylnaphthalene, trivinylbenzene, 1,2,4-trivinylcyclohexane, triallylpentaerythritol, diallylpentaerythritol, 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, triallyl cyanurate esters, diallyl phthalate, divinylbenzene; diallyl phthalate (DAP); ethylene glycol dimethacrylate (EGDMA); methylenebisacrylamide (MBA); divinylbenzene (DVB); biscyclopentenyl ethoxylated methacrylate (FRA); trimethylolpropane triallyl ether (APE), and combinations thereof, and - a combination thereof, or -Polymer L2 was prepared from the following materials: o 2% to 100% by weight, preferably 5% to 98% by weight, of at least one monomer M1, and o 0 to 98 wt. %, preferably 2 to 95 wt. % of at least one other monomer different from monomer M1, preferably at least one other monomer selected from monomer M2, monomer M3, monomer M4, monomer M5 and combinations thereof, or 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, or • The water-soluble polymer L2 has a weight average molecular weight Mw (measured by CES) of greater than 2000 g / mol or greater than 5000 g / mol.

12. Composition T according to any one of claims 1 to 11, which contains no further binder compounds besides the binder L, or which further contains: at least one further binder compound different from the binder L, preferably the further binder compound is selected from cellulose, in particular carboxymethylcellulose (CMC), hydroxycellulose (in particular hydroxymethylcellulose or hydroxyethylcellulose), alginates, poly(allylamine, HCl), pectin, pullulan, guar gum and combinations thereof, or - at least one organic acid or at least one inorganic acid, preferably the acid is selected from sulfuric acid, phosphoric acid, phosphorous acid, hypophosphorous acid, acetic acid, lactic acid and combinations thereof; or further comprises: - at least one other compound selected from the group consisting of: (meth)acrylic comb polymers, polyethylene, fluorinated binder compounds, for example selected from the group consisting of polyvinylidene fluoride (PVDF), poly(vinyl-pyrrolidone), polytetrafluoroethylene (PTFE), chlorotrifluoroethylene (ECTFE), polyethylenetetrafluoroethylene (ETFE), fluorinated ethylene-propylene (FEP), perfluoroalkoxy (PFA), polychlorotrifluoroethylene (PCTFE), fluoroacrylates, fluorosilicones and combinations thereof.

13. The composition T according to any one of claims 1 to 12, further comprising at least one dispersant for material E, preferably selected from (meth)acrylic acid homopolymers, (meth)acrylic acid copolymers and at least one other monomer, and combinations thereof; more preferably the dispersant has a molecular weight measured by CES of 3000 to 2000000 g / mol, in particular 5000 to 900000 g / mol.

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

15. The composition T according to any one of claims 1 to 14, wherein: - According to the method in the manual, at 25°C and 0.01s -1 The viscosity measured at 1000 nm 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 - According to the instructions at 25 ° C and 1000s -1 The viscosity measured at 100 nm 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 - a phase shift angle at 1 Hz measured at 25°C and 0.01 Pa according to the method of the specification of greater than 30°, preferably greater than 50°; or less than 90°; or The phase shift angle at 1 Hz measured at 25° C. and 100 Pa according to the method of the specification is greater than 60°, preferably greater than 70°; or less than 90°.

16. The composition T according to claim 1 , wherein the polymer P has a molar mass (Mw), measured by CES, of 4000 to 150000 g / mol, preferably 6000 to 100000 g / mol, more preferably 10000 to 80000 g / mol.

17. A method for preparing the aqueous composition T according to claims 1 to 16, comprising: - prepare the adhesive L, - Preparation of rheological agent R, - Addition of at least one material E selected from metal fibers, metal particles, carbon graphite fibers, carbon graphite particles and combinations thereof, preferably, material E selected from silicon, carbon graphite or graphitic carbon, hexagonal carbon, rhombohedral carbon and combinations thereof, optionally doped with at least one element, preferably an element selected from lithium, silicon, germanium and combinations thereof.

18. A method for preparing an anode, comprising: - applying at least one composition T according to any one of claims 1 to 16 to a substrate, preferably a metal substrate selected from copper, titanium, silver, zinc, nickel and combinations thereof, more preferably a copper substrate, - Drying and then calendering the coated substrate.

19. The preparation method according to claim 18, wherein: - the application is carried out at a pH value below 7 or at a pH value between 4 and 6.5, or - the composition T is applied to the substrate in a thickness of less than 500 μm, preferably less than 100 μm or less than 20 μm, measured after drying and calendering by means of a coating thickness gauge of 1 μm to 1000 μm, or The composition T is applied to a substrate with a thickness of greater than 5 μm, measured after drying and calendering by a coating thickness gauge of 1 μm to 1000 μm, or wherein: - Apply the composition T evenly to the substrate. Preferably, apply the composition T evenly to the substrate according to the method described in the instructions.

20. An anode prepared by the method according to any one of claims 18 or 19.

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