Polyurethane composition

Abstract

The invention relates to a composition prepared discontinuously by a polymerization reaction of a diisocyanate compound and a polyhydroxylated compound, followed by the termination reaction of the prepolymer of these compounds with a monoalcohol. This composition mainly comprises urethane polymers comprising strictly more than 3 residues of the polyhydroxylated compound. The invention also relates to the use of this polyurethane composition for bonding active electrode materials to a metal substrate.

Description

[0001] COMPOSITION OF POLYURETHANES

[0002] The invention relates to a composition prepared discontinuously by a polymerization reaction of a diisocyanate compound and a polyhydroxylated compound, followed by the termination reaction of the prepolymer of these compounds with a monoalcohol. This composition mainly comprises urethane polymers comprising strictly more than 3 residues of the polyhydroxylated compound. The invention also relates to the use of this polyurethane composition for bonding active electrode materials to a metal substrate.

[0003] Polyurethanes or polymers with urethane functions are widely used in many technical fields that can implement different types of foams, rigid or flexible for example, or even in the fields of adhesives, coatings, elastomers, binders, sealing, soles or lacquers.

[0004] The preparation of polyurethanes involves two essential reagents to form the polymer chain. The units or residues of these reagents are ultimately present within the structure of the resulting polymer. The ends of the polymer chain can be obtained using a third reagent. The ends of the polymer can notably be formed from hydrophobic groups, in particular alkyl or alkylene groups, often derived from a monoalcohol, while the polymer chain originates from a polyhydroxylated compound, in particular a polyalkylene glycol, combined with a polyisocyanate monomer, in particular a diisocyanate compound.

[0005] The preparation of these polyurethanes is carried out by step-by-step polymerization according to a mechanism of independent steps which is based on the reactivity of functional groups which react together to form a new group which will chemically link the respective chain ends by poly additions. The at least bifunctional monomers, in particular diisocyanates and diols, react and form prepolymers which can then react with a compound carrying the terminal group, for example a monoalcohol. Controlling the conditions of the reactions for preparing the prepolymer and then for reacting the monoalcohol is important and must make it possible to obtain urethane polymers with properties adapted to the different fields of use.

[0006] In particular, it is useful to be able to control the respective quantities of the different urethane polymers resulting from these preparation methods, in particular to be able to promote the production of certain polyurethanes, notably depending on the high proportion of diol residues present within the polymer.

[0007] It is also very useful to be able to control the production of urethane polymers comprising a high relative quantity of urethane functions compared to the molecular mass of the polyurethane obtained. The density of urethane functions in the polymer can therefore be increased.

[0008] The polyisocyanate monomer comprising a hydrocarbon chain, the urethane polymer can then also comprise a significant proportion of hydrocarbon residues within the polymer chain.

[0009] In addition to the advantages directly linked to their preparation, particularly in terms of yield or orientation towards preferred urethane polymers, better control of the conditions for preparing polyurethanes should also make it possible to promote the desired properties, particularly depending on the area of ​​use.

[0010] For example, for the preparation of secondary batteries, electrode compositions are known that generally comprise carbon or a metal in the form of particles associated with a binder composition. This binder composition must be able to effectively bind the carbon or the metal to a substrate to form an electrode. The most common binder compositions include a styrene-butadiene polymer for anode compositions or a polyvinylidene fluoride for cathode compositions, 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 during the use of an electrode. Indeed, the quality of the electrode composition coating applied to the metal substrate is essential for the optimal efficiency of the electrode as well as its maximum durability.

[0011] Typically, binder compositions also include various additives such as thickening agents, dispersing agents, for example, a cellulose derivative. The most common cellulose derivatives are carboxymethylcellulose, hydroxyethylcellulose, and hydroxymethylcellulose.

[0012] Furthermore, the number of ingredients used in the preparation of electrode compositions should be reduced. The compatibility of the different ingredients of the electrode compositions is also an important factor in the preparation of electrode compositions as well as when preparing electrodes using these compositions. The thixotropic behavior or rheological behavior over time of an aqueous electrode composition must therefore be controlled as well as possible.

[0013] It is also advantageous to have electrode compositions that are versatile and retain their rheological properties when their operating conditions differ. Easy and homogeneous application of electrode compositions is necessary to obtain a homogeneous layer and to limit or avoid defects on the electrode surface, in order to achieve a homogeneous and particularly efficient conductive layer. The surface leveling, restructuring and flow behavior of an aqueous electrode composition must be well controlled.

[0014] It is therefore essential to have electrode 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 electrode. Insufficient viscosity leads to the same types of problems and also results in uncontrolled flows of the electrode composition during its application.

[0015] Electrode 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.

[0016] Anode compositions often 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 desirable property.

[0017] JP 2015220170 describes the preparation of battery anodes with a polymeric binder based on a thermoplastic resin prepared from poly(tetramethylene glycol), diethylene glycol, IPDI and N,N'-dimethylformamide. EP 2444432 and EP 1940978 describe the preparation of polyurethanes from triisocyanate compounds or triols.

[0018] The electrode compositions of the prior art are not always satisfactory. There is therefore a need for electrode compositions that can provide solutions to all or some of the problems of the electrode compositions of the prior art. There is also a need for improved urethane polymer compositions and methods of preparation thereof that can provide solutions to all or some of the problems of the urethane polymer compositions and methods of preparation thereof of the prior art.

[0019] Thus, the invention provides a non-aqueous composition C comprising urethane polymers and prepared discontinuously:

[0020] • by a polymerization reaction, in the absence of a monohydroxylated compound: of at least one diisocyanate compound (a), of at least one polyhydroxylated compound (b), followed by:

[0021] • of the termination reaction of the prepolymer of compounds (a) and (b) with at least one compound (c) of formula I: in which R independently represents a group chosen from a linear C1-C40-alkyl group, a branched C3-C40-alkyl group, a Cs-C40-cycloalkyl group, a linear C3-C40-alkylene group, a branched C3-C40-alkylene group, a C5-C40-aryl group and combinations thereof; in which the urethane polymers comprising strictly more than 3 residues of compound (b) are in the majority in number measured by CES.

[0022] During the preparation of composition C according to the invention, the difunctional compounds (a) and (b) react, by addition of the isocyanate functions of compound (a) and the hydroxyl functions of compound (b), to form prepolymers comprising chemical residues or chemical units derived from these two compounds. Several compounds (a) can react with several compounds (b) to form prepolymers comprising several urethane functions. The termination reaction of these prepolymers with compound (c) leads to the presence of two residues of compound (c) in the urethane polymers of composition C according to the invention.

[0023] Finally, for 2 residues of compound (c), the urethane polymers according to the invention comprising a number 2N of residues of compound (b) comprise a number N+1 of hydrocarbon residues of compound (a) and a number 2N+2 urethane functions. According to the invention, the value of N is greater than 3.

[0024] Preferably according to the invention, the urethane polymers comprise strictly more than three residues of compound (b) representing at least 40% by number, preferably at least 50% by number or at least 55% by number, more preferably at least 60% by number or at least 65% by number or at least 70% by number, of all the urethane polymers.

[0025] According to the invention, the distribution of the polymeric entities present in the urethane polymers of composition C according to the invention, in particular the proportions by number of the residues of compound (b) present in the polymers, is determined by high-performance size exclusion chromatography (SEC), preferably using a high-performance size exclusion chromatograph (“Acquity” Advanced Polymer Chromatography APC, “Waters”) with refractometric detector and column system consisting of 3 “Waters” columns in series: “Acquity” APC XT 900 2.5 pm 4.6 mm x 150 mm, “Acquity” APC XT 450 2.5 pm 4.6 mm x 150 mm and “Acquity” APC XT 125 2.5 pm 4.6 mm x 150 mm. The solvent used for the mobile phase is tetrahydrofuran (THF HPLC grade). The calibration is carried out with polymethyl methacrylate (PMMA) standards with a molecular mass of up to 2,200,000 g / mol. The samples of composition C according to the invention are solubilized in THF.

[0026] Also preferably according to the invention, the urethane polymers have a molar mass Mw, measured by CES, greater than 20,000 g / mol, preferably greater than 30,000 g / mol, or a molar mass Mw less than 500,000 g / mol, preferably less than 300,000 g / mol. More preferably according to the invention, the urethane polymers have a molar mass Mw, measured by CES, ranging from 20,000 g / mol to 500,000 g / mol, preferably from 30,000 g / mol to 300,000 g / mol.

[0027] Also preferably according to the invention, the urethane polymers have a polymolecularity index Ip, measured by CES, of less than 4 or less than 3. More preferably according to the invention, this polymolecularity index is less than 2. Also preferably according to the invention, the urethane polymers have a polymolecularity index Ip greater than 1.3.

[0028] According to the invention, the molecular weight or mass as well as the polymolecularity index are determined by Size Exclusion Chromatography (SEC). A test sample of the compound solution corresponding to 90 mg of dry matter is introduced into a 10 mL flask. Mobile phase, supplemented with 0.04% dimethylformamide (DMF), is added up 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.

[0029] Preferably for composition C according to the invention, the diisocyanate compound (a) is chosen from:

[0030] • symmetrical aromatic diisocyanate compounds, preferably:

[0031] 2,2'-diphenylmethylene diisocyanate (2,2'-MDI) and 4,4'-diphenylmethylene diisocyanate (4,4'-MDI);

[0032] 4,4'-dibenzyl diisocyanate (4,4'-DBDI);

[0033] toluene 2,6-diisocyanate (2,6-TDI); m-xylylene diisocyanate (m-XDI);

[0034] • symmetrical alicyclic diisocyanate compounds, preferably methylene bis(4-cyclohexylisocyanate) (H12MDI);

[0035] • symmetrical aliphatic diisocyanate compounds, preferably hexamethylene diisocyanate (HDI), pentamethylene diisocyanate (PDI);

[0036] • asymmetric aromatic diisocyanate compounds, preferably:

[0037] 2,4'-diphenylmethylene diisocyanate (2,4'-MDI);

[0038] 2,4'-dibenzyl diisocyanate (2,4'-DBDI);

[0039] toluene 2,4-diisocyanate (2,4-TDI);

[0040] • asymmetric alicyclic diisocyanate compounds, preferably isophorone diisocyanate (IPDI). More preferably, compound (a) is chosen from IPDI, HDI, H12MDI and combinations thereof. Also preferably according to the invention, composition C does not comprise urethane polymers prepared in the presence of a branched polyisocyanate compound comprising at least 3 isocyanate groups. In particular, rheological control agent G does not comprise urethane polymers prepared in the presence of a cyanurate trimer compound or a biuret trimer, in particular in the absence of HDI isocyanurate trimer or IPDI isocyanurate trimer.

[0041] Preferably according to the invention, compound (b) is a dihydroxylated compound, more preferably a diol. Preferably for composition C according to the invention, the polyhydroxylated compound (b) is a compound of formula II: in which:

[0042] L independently represents an oxyalkylene residue; n independently represents a number ranging from 10 to 500.

[0043] Preferably for composition C according to the invention, the polyhydroxylated compound (b) is a compound of formula II in which L independently represents an oxyethylene residue.

[0044] Also preferably for composition C according to the invention, the polyhydroxylated compound (b) is a compound of formula II in which n independently represents a number ranging from 10 to 400, preferably from 10 to 150. More preferably for composition C according to the invention, the polyhydroxylated compound (b) is a compound of formula II for which L independently represents an oxyethylene residue and n independently represents a number ranging from 25 to 400, preferably from 30 to 300.

[0045] Also preferably for composition C according to the invention, compound (b) has a molar mass (Mw), measured by CES, ranging from 800 to 15,000 g / mol, preferably from 800 g / mol to 12,000 g / mol or from 800 g / mol to 10,000 g / mol. More preferably, compound (b) has a molar mass Mw ranging from 1,000 g / mol to 8,000 g / mol or from 1,000 g / mol to 6,000 g / mol.

[0046] Preferably for composition C according to the invention, compound (c) is a compound of formula I in which R independently represents a group chosen from a linear C1-C32-alkyl group, a branched C3-C32-alkyl group, a Cs-C32-cycloalkyl group, a linear C3-C32-alkylene group, a branched C3-C32-alkylene group, a Cs-C32-aryl group and combinations thereof.

[0047] More preferably for composition C according to the invention, compound (c) is a compound of formula I in which R independently represents a group chosen from a linear C1-C24-alkyl group or a linear C3-C24-alkylene group, preferably a linear C4-C20-alkyl group or a linear C4-C20-alkylene group, more preferably a linear C6-Cis-alkyl group or a linear C6-Cis-alkylene group, much more preferably a linear C6-Ci6-alkyl group or a linear C6-Ci6-alkylene group.

[0048] According to the invention, compound (c) may be different from n-decanol, a branched C12-C13 primary alcohol, a branched C14-C15 primary alcohol, 2-octyldodecanol.

[0049] Advantageously, during the preparation of the urethane polymers according to the invention, the respective quantities of compounds (a), (b) and (c) used can vary. Preferably for composition C according to the invention, the polymerization reaction uses: from 10 to 79.9 mol% or from 10 to 74.5 mol%, preferably from 10 to 68 mol% or from 10 to 60 mol%, of monomer (a) or from 20 to 89.9 mol% or from 25 to 89.5 mol%, preferably from 30 to 88 mol% or from 35 to 85 mol%, of monomer (b) or from 0.1 to 70 mol% or from 0.5 to 65 mol%, preferably from 2 to 60 mol% or from 5 to 55 mol%, of monomer (c), relative to the total molar quantity of monomers (a), (b) and (c).

[0050] More preferably for composition C according to the invention, the polymerization reaction uses: from 10 to 79.9 mol% or from 10 to 74.5 mol%, preferably from 10 to 68 mol% or from 10 to 60 mol%, of monomer (a), from 20 to 89.9 mol% or from 25 to 89.5 mol%, preferably from 30 to 88 mol% or from 35 to 85 mol%, of monomer (b) and from 0.1 to 70 mol% or from 0.5 to 65 mol%, preferably from 2 to 60 mol% or from 5 to 55 mol%, of monomer (c), relative to the total molar quantity of monomers (a), (b) and (c).

[0051] When preparing the urethane polymers according to the invention, the relative amounts of compounds (a) and (b) used may vary. Preferably, for composition C according to the invention, the polymerization reaction uses molar amounts of diisocyanate compound (a) and polyhydroxylated compound (b) in a molar ratio a / b ranging from 1.05 to 3.

[0052] More preferably for composition C according to the invention, the polymerization reaction uses molar quantities of diisocyanate compound (a) and polyhydroxylated compound (b) in a molar ratio a / b ranging from 1.1 to 2 or from 1.1 to 1.5. Much more preferably, this molar ratio a / b ranges from 1.1 to 1.45 or from 1.1 to 1.4.

[0053] Essentially according to the invention, composition C comprises urethane polymers which comprise strictly more than 3 residues of compound (b) are in the majority in number measured by CES. Preferably for composition C according to the invention, urethane polymers comprising strictly more than 4 residues, preferably more than 5 residues or more than 6 residues, of compound (b) are in the majority in number measured by CES.

[0054] Essentially according to the invention, the composition C according to the invention is prepared according to a method comprising a polymerization reaction, in the absence of monohydroxylated compound, then a termination reaction. Thus, the invention provides a method for the discontinuous preparation of a composition C according to the invention comprising:

[0055] • a polymerization reaction, in the absence of a monohydroxylated compound: of at least one diisocyanate compound (a), of at least one polyhydroxylated compound (b), followed by:

[0056] • of the termination reaction of the prepolymer of compounds (a) and (b) with at least one compound (c) of formula I:

[0057] HO-R (I)in which R independently represents a group chosen from a linear C1-C40-alkyl group, a branched C3-C40-alkyl group, a Cs-C40-cycloalkyl group, a linear C3-C40-alkylene group, a branched C3-C40-alkylene group, a C5-C40-aryl group and combinations thereof; in which the urethane polymers comprising strictly more than 3 residues of compound (b) are in the majority in number measured by CES.

[0058] Preferably for the preparation method according to the invention, the polymerization reaction is carried out in the polyhydroxylated compound (b), preferably in the molten medium of the compound (b). In particular, the polymerization reaction is carried out in the absence of organic solvent, preferably in the absence of organic hydrocarbon solvent such as xylene or toluene.

[0059] Also preferably for the preparation method according to the invention, the polymerization reaction uses molar amounts of diisocyanate compound (a) and polyhydroxylated compound (b) in a molar ratio a / b ranging from 1.05 to 3. More preferably, this molar ratio a / b ranges from 1.1 to 2 or from 1.1 to 1.5. Much more preferably, this molar ratio a / b ranges from 1.1 to 1.45 or from 1.1 to 1.4.

[0060] Also preferably for the preparation method according to the invention, the polymerization reaction is carried out for 10 min to 60 min, more preferably 10 min to 30 min, in particular depending on the compounds (a) and (b) or the catalyst.

[0061] The preparation method according to the invention makes it possible to prepare particular urethane polymers. Thus, the invention provides a urethane polymer P prepared according to the method defined according to the invention and which comprises strictly more than 3, preferably strictly more than 4 or strictly more than 5, more preferably strictly more than 6, residues of compound (b).

[0062] The urethane polymers according to the invention and the composition C according to the invention can be used in many technical fields. Preferably, the urethane polymers according to the invention and the composition C according to the invention can be used during the preparation of an electrode preparation composition T. Preferably, the urethane polymers according to the invention and the composition C according to the invention can be used in a binding agent of an active electrode material.Thus, the invention provides an electrode preparation composition T comprising: at least one material E chosen from: o at least one anode material E1 chosen from metal fibers, metal particles, graphite carbon fibers, graphite carbon particles, silicon particles and combinations thereof; o at least one cathode material E2 comprising carbon particles; o at least one electroactive cathode material E3; at least one binding agent L of the material E comprising at least one composition C according to the invention; a liquid support.

[0063] The invention also provides an electrode preparation composition T comprising: at least one material E chosen from: o at least one anode material E1 chosen from metal fibers, metal particles, graphite carbon fibers, graphite carbon particles, silicon particles and combinations thereof; o at least one cathode material E2 comprising carbon particles; o at least one electroactive cathode material E3; at least one binding agent L of the material E comprising urethane polymers P according to the invention; a liquid support.

[0064] The invention therefore provides a composition T according to the invention which is an aqueous anode preparation composition comprising: at least one anode material E1 chosen from metal fibers, metal particles, graphite carbon fibers, graphite carbon particles, silicon particles and combinations thereof; at least one binding agent L of the material E comprising urethane polymers P according to the invention or at least one composition C according to the invention; a liquid support, preferably water.

[0065] The invention also provides a composition T according to the invention which is a non-aqueous cathode preparation composition comprising: at least one cathode material E2 comprising carbon particles; at least one cathode electroactive material E3; at least one agent L binding materials E2 and E3 comprising urethane polymers P according to the invention or at least one composition C according to the invention or at least one polymer according to the invention; a liquid support, preferably an aprotic polar organic solvent, preferably chosen from pyrrolidone, N-methyl-pyrrolidone (NMP), alkyl carbonates and combinations thereof.

[0066] Preferably according to the invention, the electrode preparation composition according to the invention may be an anode preparation composition; the material El is then 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. Preferably, the material El 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 ranges from 50 pm to 200 pm.

[0067] Also preferably according to the invention, the electrode preparation composition according to the invention may be a cathode preparation composition; the material E2 is then chosen from carbon black, acetylene black, Ketjen black, carbon fibers, carbon nanotubes, carbon nanofiber, graphene and combinations thereof. And the electroactive material E3 is then chosen from lithium, iron, nickel, manganese, cobalt and combinations thereof, preferably chosen from iron, nickel, manganese, cobalt and combinations thereof, preferably chosen from LiFePCL (LFP), Li(Ni,Mn,Co)O2(NMC) and combinations thereof.

[0068] In addition to the binding agent L, the electrode preparation composition according to the invention may comprise one or more other binding agents. In this case, the composition T according to the invention also comprises at least one additional binding agent, preferably selected from an anode binding polymer L1 in the form of a non-water-soluble latex, preferably selected 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.

[0069] Polymer L1 is preferably a styrene-butadiene polymer.

[0070] The composition T according to the invention may also comprise a water-soluble anode binder polymer L2, preferably chosen 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. The polymer L2 is preferably an acrylic latex. 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.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. Preferably according to the invention, 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 Ml 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 Ml.

[0071] Preferably according to the invention, this other monomer, different from the monomer M1, is chosen independently from:

[0072] - 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,

[0073] - 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 2-acrylamido-2-methylpropane sulfonic acid (AMPS), allyl sulfonic acid, alkylenesulfonates, alkylenearylsulfonates, in particular styrenesulfonate, vinylsulfonate, methallylsulfonate, allylsulfonate, methallyl sulfate, allyl sulfate, 2-sulfoethyl methacrylate, 3-allyloxy-2-hydroxy-1-propanesulfonic acid, 3 sulfopropyl methacrylate, their salts and combinations thereof, a non-ionic monomer M4 chosen from vinyl acetate, a C1-C8 ester of a compound derived from an acid chosen 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 (e.g., acrylonitrile, methacrylamide, acrylamide, vinyl lactam, N-methylol acrylamide), styrene and combinations thereof,

[0074] - a crosslinking monomer M5, preferably a monomer M5 comprising at least 2 polymerizable ethylenic groups, preferably a 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 chosen in particular 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.;

[0075] Preferably, the polymer L2 is prepared from:

[0076] - from 2% by weight to 100% by weight, preferably from 5% by weight to 98% by weight, of at least one monomer Ml, and

[0077] - from 0 to 98% by weight, preferably from 2% by weight to 95% by weight, relative to the total quantity by weight of monomers, of at least one other monomer, different from monomer M1, preferably at least one other monomer chosen from monomer M2, monomer M3, monomer M4, monomer M5 and their combinations.

[0078] According to the invention, the composition T according to the invention may also comprise an anode binder polymer L3 chosen from cellulose, in particular carboxymethylcellulose (CMC), hydroxycellulose (in particular hydroxymethylcellulose or hydroxyethylcellulose), alginate, poly(allylamine, HCl), pectin, amilopectin, guar gum and combinations thereof. It may also comprise a cathode binder agent L4 chosen from polyvinylidene fluoride (PVDF) and combinations thereof, preferably PVDF.

[0079] Preferably according to the invention, the binding compound is not a (meth)acrylic polymer.

[0080] The anode 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 combinations thereof.

[0081] The amounts of the different ingredients of the composition T according to the invention may vary. Preferably, the composition T according to the invention comprises: from 85% by dry weight to 99.5% by dry weight of material E, from 0.5% by dry weight to 15% by dry weight of binding agent, in particular binding agent L, relative to the total amount by dry weight of binding agent, in particular binding agent L, and material E.

[0082] Also preferably, the composition T according to the invention comprises: from 70% by dry weight to 99.5% by dry weight of material E, from 0.3% by dry weight to 10% by dry weight of binding agent, in particular binding agent L, from 0.2% by weight to 10% by weight of liquid support, relative to the total quantity by dry weight of material E and binding agent, in particular binding agent L, and liquid support.

[0083] The invention also provides a method for preparing a composition T according to the invention, comprising the preparation of a binding agent L and the addition of at least one material E and the liquid support.

[0084] The composition T according to the invention can be used during the manufacture of an electrode. Thus, the invention provides a 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 anode composition T according to the invention, drying and then calendering the coated substrate.

[0085] More preferably for the method of manufacturing an anode according to the invention, the application is carried out at a pH lower than 7 or at a pH ranging from 4 to 6.5.

[0086] Also more preferably for the method of manufacturing an anode according to the invention, the application of the anode composition T on 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.

[0087] Also more preferably for the method of manufacturing an anode according to the invention, the application of the anode composition T on 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] Also more preferably for the method of manufacturing an anode according to the invention, the application of the anode composition T on the substrate is homogeneous, preferably the application of the anode composition T on the substrate is homogeneous according to the visual control method of the examples.

[0089] The invention also provides an anode manufactured according to the manufacturing method according to the invention.

[0090] The invention also provides a method for manufacturing a cathode comprising: applying at least one aqueous composition T according to the invention to a metal substrate, in particular a metal substrate comprising aluminum, drying and then calendering the metal substrate carrying the layer of composition T.

[0091] More preferably for the method of manufacturing a cathode according to the invention: the substrate is a purely metallic substrate or a composite substrate comprising at least one metal and at least one insulating support; or the electroactive compound is chosen from lithium, iron, nickel, manganese, cobalt and their combinations.

[0092] The invention also provides a cathode manufactured according to the manufacturing method according to the invention.

[0093] The advantageous, particular or preferred characteristics of composition C according to the invention define methane polymers, compositions T, methods of preparation or manufacture according to the invention, as well as anodes or cathodes, which are also advantageous, particular or preferred.

[0094] The various aspects of the invention may be illustrated by examples.

[0095] EXAMPLES

[0096] Preparation and characterization of urethane polymer compositions C1 to C8 according to the invention:

[0097] For the preparation of urethane polymers, the following compounds a, b and c are used: compound a1: diisocyanate H12MDI, compound a2: diisocyanate HDI, compound a3: diisocyanate IPDI, compound b1: polyethylene glycol with a molecular weight of 2,000 g / mol, compound b2: polyethylene glycol with a molecular weight of 4,000 g / mol, compound b3: polyethylene glycol with a molecular weight of 5,500 g / mol, compound b4: polyethylene glycol with a molecular weight of 8,000 g / mol, compound b5: polyethylene glycol with a molecular weight of 10,000 g / mol, compound c1: hydrophobic monoalcohol of formula I in which R represents a linear C6-alkyl group, compound c2: hydrophobic monoalcohol of formula I in which R represents a linear C12-alkyl group, compound c3: hydrophobic monoalcohol of formula I in which R represents branched C24-C26 alkyl groups derived from a Guerbet alcohol (" Isofol » 2426S from “Sasol”),

[0098] Compositions C1 to C8 according to the invention:

[0099] In a 2 L reactor equipped with mechanical stirring, compound (bl) (polyethylene glycol - molecular mass 2000 g / mol) (163.9 g) is introduced and heated to 90°C. 0.20 g of a bismuth catalyst (K-KAT XC-B221 “King Industries”) is added and then a diisocyanate compound (al) (H12MDI, 25.8 g) is introduced. The reaction medium is kept stirring for 30 minutes (reaction time, RT) at 95°C for the formation of the prepolymer. Then, compound (cl) is added. The reaction is continued at 95°C for 30 minutes with stirring.

[0100] In a manner analogous to the preparation of composition C1, compositions C2 to C8 are prepared according to the invention. The compounds and quantities (g) used as well as the reaction times TR are presented in Table 1.

[0101] Table 1

[0102] The compositions C1 to C8 according to the invention are characterized by high-performance size exclusion chromatography. The measurements of the molecular masses of the urethane polymer mixtures present in the compositions C1 to C8 according to the invention are carried out using a high-performance size exclusion chromatograph (“Acquity” Advanced Polymer Chromatography APC, “Waters”) with a refractometric detector. The column system used consists of 3 “Waters” columns in series:

[0103] “Acquity” APC XT 900 2.5 pm 4.6 mm x 15 0mm, “Acquity” APC

[0104] “Acquity” APC XT 125 2.5m 4.6mm x 150mm.

[0105] The solvent used for the mobile phase is tetrahydrofuran (THF HPLC grade). Calibration is carried out with polymethyl methacrylate (PMMA) standards with a molecular mass of up to 2,200,000 g / mol. The samples of polymers P according to the invention are solubilized in THF.

[0106] The analysis makes it possible to determine the number-average molecular masses Mn and mass Mw (g / mol) of the methane polymers of the compositions according to the invention. The polydispersity Ip and the degree of polymerization are also evaluated by discriminating the molecular weights of the different polymeric entities present in the samples of compositions according to the invention. The distribution of the polymeric entities is quantified in each sample, in particular the number proportions of PEG residues present in the polymers. The results obtained for the samples of urethane polymers present in the compositions C1 to C8 according to the invention are presented in Table 2.

[0107] Table 2

[0108] The compositions C1 to C8 according to the invention mainly comprise urethane polymers comprising strictly more than 3 PEG residues.

[0109] Furthermore, the composition C1 of urethane polymers according to the invention is formulated by mixing it in water at a concentration of 20% by mass and 80% by mass of water. In the same way, aqueous formulations are prepared with the compositions C2 to C8 according to the invention. The composition C8 according to the invention is formulated (17.5% by mass) in water (69.2% by mass) in the presence of a surfactant compound (“Emulan” HE51 “Basf”, polyethoxylated alcohol, 13.3% by mass).

[0110] Using an analog viscometer equipped with a spindle, the Brookfield viscosity (mPa.s) at 10 rpm was measured after storage for 24 hours at 25°C of these aqueous formulations comprising compositions C1 to C8. The results obtained are presented in Table 3.

[0111]

[0112] Table 3

[0113] The compositions according to the invention C1 to C8, in which the methane polymers comprising strictly more than 3 PEG residues are in the majority in number, make it possible to effectively control aqueous compositions.

[0114] Preparation of aqueous anode compositions T1 to T3 according to the invention:

[0115] In a 500 mL polypropylene container suitable for a stirrer (Speedmixer DAC 1100), 43 g of water and 2.1 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 (synthetic graphite powder of D50 15-19 pm - "S360") 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. 5.8 g of composition Cl according to the invention are added and mixed for 1 minute at 1600 rpm. 1.6 g of a styrene-butadiene latex (BM 45 IB “Zeon”) are added and mixed for 1 minute at 800 rpm. The anode composition Tl according to the invention is obtained.

[0116] Similarly, the aqueous anode compositions T2 and T3 are prepared by replacing composition Cl with compositions C2 (5.6 g) and C3 (5.3 g) respectively and using a quantity of water of 44 g.

[0117] Preparation and characterization of anodes according to the invention:

[0118] 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 2 and at a running speed of 0.1 m / s using a calender ("Gester"). 12 mm diameter discs are cut using a precision cutter.

[0119] In a similar manner, an anode is prepared by replacing the aqueous anode composition T1 with the composition T2 and T3 according to the invention. After preparation, the homogeneity and adhesion of the layer of composition T are evaluated 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 exhibit any adhesion defects.

[0120] The compositions according to the invention C1 to C3, in which the methane polymers comprising strictly more than 3 PEG residues are in the majority in number, make it possible to prepare an anode having a regular, homogeneous and stable active surface.

Claims

CLAIMS 1- Non-aqueous composition C comprising urethane polymers and prepared discontinuously: • by a polymerization reaction, in the absence of a monohydroxylated compound: of at least one diisocyanate compound (a), of at least one polyhydroxylated compound (b), followed by: • of the termination reaction of the prepolymer of compounds (a) and (b) with at least one compound (c) of formula I: in which R independently represents a group chosen from a linear C1-C40-alkyl group, a branched C3-C40-alkyl group, a Cs-C40-cycloalkyl group, a linear C3-C40-alkylene group, a branched C3-C40-alkylene group, a C5-C40-aryl group and combinations thereof; in which the urethane polymers comprising strictly more than 3 residues of compound (b) are in the majority in number measured by CES. 2- Composition according to claim 1 in which: the urethane polymers comprising strictly more than three residues of compound (b) represent at least 40% by number, preferably at least 50% by number or at least 55% by number, more preferably at least 60% by number or at least 65% by number or at least 70% by number, of all the urethane polymers; or for which: the urethane polymers have a molar mass Mw, measured by CES, greater than 20,000 g / mol, preferably greater than 30,000 g / mol, or a molar mass Mw less than 500,000 g / mol, preferably less than 300,000 g / mol; or for which: the urethane polymers have a molar mass Mw, measured by CES, ranging from 20,000 g / mol to 500,000 g / mol, preferably from 30,000 g / mol to 300,000 g / mol; or for which: the urethane polymers have a polydispersity index Ip, measured by CES, of less than 4 or less than 3, preferably less than 2; or have an Ip greater than 1.3 3- Composition according to one of claims 1 or 2 for which the diisocyanate compound (a) is chosen from: • symmetrical aromatic diisocyanate compounds, preferably: 2,2'-diphenylmethylene diisocyanate (2,2'-MDI) and 4,4'-diphenylmethylene diisocyanate (4,4'-MDI); 4,4'-dibenzyl diisocyanate (4,4'-DBDI); toluene 2,6-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); • asymmetric aromatic diisocyanate compounds, preferably: 2,4'-diphenylmethylene diisocyanate (2,4'-MDI); 2,4'-dibenzyl diisocyanate (2,4'-DBDI); toluene 2,4-diisocyanate (2,4-TDI); • asymmetric alicyclic diisocyanate compounds, preferably isophorone diisocyanate (IPDI), more preferably, compound (a) is chosen from IPDI, HDI, H12MDI and combinations thereof. 4- Composition according to one of claims 1 to 3 for which the polyhydroxylated compound (b) is a compound of formula II: HO- -OH (n) in which: - L independently represents an oxyalkylene residue; - n independently represents a number ranging from 10 to 500; preferably in which: - L independently represents an oxyethylene residue; or - n independently represents a number ranging from 10 to 400, preferably from 10 to 150; or - L independently represents an oxyethylene residue and n independently represents a number ranging from 25 to 400, preferably from 30 to 300. 5- Composition according to one of claims 1 to 4 for which the compound (b) has a molar mass (Mw), measured by CES, ranging from 800 to 15,000 g / mol, preferably from 800 g / mol to 12,000 g / mol or from 800 g / mol to 10,000 g / mol, more preferably from 1,000 g / mol to 8,000 g / mol or from 1,000 g / mol to 6,000 g / mol. 6- Composition according to one of claims 1 to 5 for which compound (c) is a compound of formula I in which: R independently represents a group selected from a linear C1-C32-alkyl group, a branched C3-C32-alkyl group, a C5-C32-cycloalkyl group, a linear C3-C32-alkylene group, a branched C3-C32-alkylene group, a Cs-C32-aryl group and combinations thereof; or R independently represents a group selected from a linear C1-C24-alkyl group or a linear C3-C24-alkylene group, preferably a linear C4-C20-alkyl group or a linear C4-C20-alkylene group, more preferably a linear C6-Cis-alkyl group or a linear C6-Cis-alkylene group, much more preferably a linear C6-Ci6-alkyl group or a linear C6-Ci6-alkylene group. 7- Composition according to one of claims 1 to 6 for which the polymerization reaction uses: from 10 to 79.9 mol% or from 10 to 74.5 mol%, preferably from 10 to 68 mol% or from 10 to 60 mol%, of monomer (a) or from 20 to 89.9 mol% or from 25 to 89.5 mol%, preferably from 30 to 88 mol% or from 35 to 85 mol%, of monomer (b) or from 0.1 to 70 mol% or from 0.5 to 65 mol%, preferably from 2 to 60 mol% or from 5 to 55 mol%, of monomer (c), relative to the total molar quantity of monomers (a), (b) and (c). 8- Composition according to one of claims 1 to 7 for which the polymerization reaction uses molar quantities of diisocyanate compound (a) and polyhydroxylated compound (b) in a molar ratio a / b ranging from 1.05 to 3, preferably from 1.1 to 2 or from 1.1 to 1.5, more preferably from 1.1 to 1.45 or from 1.1 to 1.

4. 9- Composition according to one of claims 1 to 8 in which the urethane polymers comprising strictly more than 4 residues, preferably more than 5 residues or more than 6 residues, of compound (b) are in the majority in number measured by CES. 10- Method for the discontinuous preparation of a composition C according to one of claims 1 to 9 comprising: • a polymerization reaction, in the absence of a monohydroxylated compound: of at least one diisocyanate compound (a), of at least one polyhydroxylated compound (b), followed by: • of the termination reaction of the prepolymer of compounds (a) and (b) with at least one compound (c) of formula I: in which R independently represents a group chosen from a linear C1-C40-alkyl group, a branched C3-C40-alkyl group, a Cs-C40-cycloalkyl group, a linear C3-C40-alkylene group, a branched C3-C40-alkylene group, a C5-C40-aryl group and combinations thereof; in which the urethane polymers comprising strictly more than 3 residues of compound (b) are in the majority in number measured by CES. 11- Method according to claim 10 for which: the polymerization reaction is carried out in the polyhydroxylated compound (b), preferably in a molten medium of the compound (b); or the polymerization reaction uses molar quantities of diisocyanate compound (a) and polyhydroxylated compound (b) in a molar ratio a / b ranging from 1.05 to 3, preferably from 1.1 to 2 or from 1.1 to 1.5, more preferably from 1.1 to 1.45 or from 1.1 to 1.4; or the polymerization reaction is carried out for 10 min to 60 min, preferably 10 min to 30 min, in particular depending on the compounds (a) and (b) or the catalyst. 12- Urethane polymer P prepared according to the method defined according to one of claims 10 and 11 comprising strictly more than 3, preferably strictly more than 4 or strictly more than 5, more preferably strictly more than 6, residues of compound (b). 13- Composition T for preparing an electrode comprising: at least one material E chosen from: o at least one anode material E1 chosen from metal fibers, metal particles, graphite carbon fibers, graphite carbon particles, silicon particles and combinations thereof; o at least one cathode material E2 comprising carbon particles; o at least one electroactive cathode material E3; at least one binding agent L of the material E comprising at least one composition C according to one of claims 1 to 9 or methane polymers P according to claim 12; a liquid support. 14- Composition T according to claim 13 in which: the material El 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 the material El is in the form of particles, preferably particles whose average size in volume, 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; or the material E2 is chosen from carbon black, acetylene black, Ketjen black, carbon fibers, carbon nanotubes, carbon nanofiber, graphene and their combinations; or the electroactive material E3 is chosen from lithium, iron, nickel, manganese, cobalt and their combinations, preferably chosen from iron, nickel, manganese, cobalt and their combinations, preferably chosen from LiFePCL (LFP), Li(Ni,Mn,Co)O2(N MC) and their combinations. 15- Composition T according to one of claims 13 or 14 also comprising at least one additional binding agent, preferably chosen from: an anode binder polymer L1 in the form of a non-water-soluble latex, preferably 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, a water-soluble anode binder polymer L2, preferably chosen 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, copolymer of acrylamide and their combinations,preferably the water-soluble polymer L2 is prepared by at least one emulsion polymerization reaction with a water-soluble anionic monomer, an anode binder polymer L3 chosen from cellulose, in particular carboxymethylcellulose (CMC), hydroxycellulose (in particular hydroxymethylcellulose or hydroxyethylcellulose), alginate, poly(allylamine, HCl), pectin, amilopectin, guar gum and combinations thereof, a cathode binder agent L4 chosen from polyvinylidene fluoride (PVDF) and combinations thereof, preferably PVDF., 16- Composition T according to one of claims 13 to 15 comprising: from 85% by dry weight to 99.5% by dry weight of material E, from 0.5% by dry weight to 15% by dry weight of binding agent, in particular binding agent L, relative to the total quantity by dry weight of binding agent, in particular binding agent L, and of material E or else comprising: from 70% by dry weight to 99.5% by dry weight of material E, from 0.3% by dry weight to 10% by dry weight of binding agent, in particular binding agent L, from 0.2% by weight to 10% by weight of liquid support, relative to the total quantity by dry weight of material E and binding agent, in particular binding agent L, and liquid support. 17- Method for preparing a composition T according to claims 13 to 16, comprising the preparation of a binding agent L and the addition of at least one material E and the liquid support. 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 anode composition T according to one of claims 13 to 16, drying and then calendering the coated substrate. 19- Manufacturing method according to claim 18 for which: the application is carried out at a pH of less than 7 or at a pH ranging from 4 to 6.5, or the application of the anode composition T on 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 the anode composition T on 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 for which: the application of the anode composition T on the substrate is homogeneous, preferably the application of the anode composition T on the substrate is homogeneous according to the visual control method of the description. 20- Anode manufactured according to the manufacturing method according to one of claims 18 or 19. 21- Method for manufacturing a cathode comprising: the application of at least one aqueous composition T according to one of the claims 13 to 16, on a metal substrate comprising aluminum, drying and then calendering the metal substrate carrying the layer of composition T. 22- Method according to claim 21 for which: the substrate is a purely metallic substrate or a composite substrate comprising at least one metal and at least one insulating support; or - the electroactive compound is chosen from lithium, iron, nickel, manganese, cobalt and their combinations. 23- Cathode manufactured according to the manufacturing method according to one of claims 21 or 22.

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