METHOD FOR MANUFACTURING AN ASSEMBLY COMPRISING AN ELECTRODE AND A CURRENT COLLECTOR

Abstract

The invention relates to a method for manufacturing an assembly comprising a first planar electrode comprising a polymer matrix trapping an electrolyte and a current collector, said first electrode being deposited on one face of said current collector, said method comprising: a) a step of preparing a composition comprising the ingredients intended to be part of the constitution of the first electrode; b) a step of forming a strip by passing said composition through a die; c) a step of rolling the strip obtained in b), d) a step of co-rolling the rolled strip obtained in c) with a current collector, whereby the assembly comprising the first planar electrode and the current collector results.

Description

Title of the invention: METHOD FOR MANUFACTURING AN ASSEMBLY COMPRISING AN ELECTRODE AND A CURRENT COLLECTOR Technical field

[0001] The present invention relates to a method of manufacturing an assembly comprising at least one electrode comprising a polymer matrix trapping an electrolyte and a current collector, this assembly being intended to be incorporated into electrochemical accumulators.

[0002] The general field of the invention can be defined as that of energy storage devices, in particular, that of electrochemical accumulators. State of the art

[0003] Electrochemical accumulators operate on the principle of electrochemical cells capable of delivering an electric current thanks to the presence in each of them of a pair of electrodes (respectively, a positive electrode and a negative electrode) separated by an electrolyte, the electrodes comprising specific materials capable of reacting according to an oxidation-reduction reaction, whereby there is an exchange of electrons at the origin of the electric current and an exchange of ions which will circulate from one electrode to the other by means of an electrolyte.

[0004] Among the accumulators subscribing to this principle, the accumulators operating on the principle of insertion-deinsertion of a metallic element intervening at the level of the electrodes (and more specifically, of the active electrode materials) and known under the terminology of metal-ion accumulators (for example, Li-ion, Na-ion, K-ion, Ca-ion, Mg-ion or Al-ion) have supplanted the other types of accumulators, such as lead-acid accumulators, Ni-MH accumulators, in particular for their performances in terms of energy densities. Indeed, M-ion accumulators, such as Li-ion accumulators, allow, in particular, to obtain mass and volume energy densities (which can be greater than 180 Wh.kg ') which are significantly higher than those of Ni-MH and Ni-Cd accumulators (which can range from 50 and 100 Wh.kg ') and lead-acid accumulators (which can range from 30 to 35 Wh.kg ').

[0005] From a functional point of view, in metal-ion accumulators, the reaction at the origin of the production of current (i.e. when the accumulator is in discharge mode) involves the transfer, via an electrolyte conducting metal ions, of metal cations coming from a negative electrode which are intercalated in the acceptor network of the positive electrode, while electrons coming from the reaction at the negative electrode will supply the external circuit, to which the positive and negative electrodes are connected.

[0006] More specifically, in the case of a Li-ion accumulator, the positive electrode may comprise, as lithium insertion materials, lithium-based phosphate compounds (for example, LiFePO4), a lithium manganese oxide, optionally substituted (such as LiMn2O4), a lithium-nickel-manganese-cobalt material LiNixMnyCozO2 with x+y+z=1 (also known by the abbreviation NMC), such as LiNioj33Mnoj33Cooj3302 or LiNi0.6Mn0.2Co0.2O2 a lithium-nickel-cobalt-aluminum material LiNixCoyAlzO2 with x+y+z = 1 (also known by the abbreviation NCA), such as LiNio>8Cooji5Alojo502.

[0007] The negative electrode may comprise, as lithium insertion materials, a carbon material, such as graphite, a silicon-based compound, such as a silicon carbide SiC or a silicon oxide SiOx, a lithiated titanium oxide, such as Li4Ti5O i2, a lithium-germanium alloy or a mixture of several of these lithium insertion materials, such as a mixture comprising graphite and a silicon-based compound.

[0008] As mentioned above, between the negative electrode and the positive electrode, an electrolyte is arranged, which will allow the movement of ions (generally originating from a metal salt present in the electrolyte) from the positive electrode to the negative electrode during charging and vice versa during discharging.

[0009] This electrolyte may be in a liquid form and conventionally comprises one or more organic solvents (for example, a mixture of carbonate solvents), in which one or more metal salts are dissolved (for example, one or more lithium salts, when the accumulator is a lithium-ion accumulator).

[0010] However, the use of a liquid electrolyte has a number of disadvantages, including the following: - the problem of liquid electrolyte leaking out of the cell; - the possibility that the liquid electrolyte reacts chemically with the oxygen of the active material of the positive electrode, when thermal runaway occurs in the cell comprising this electrolyte, thus being able to generate a large volume of gas, the consequence of which may be the inflammation or even the explosion of the cell.

[0011] To circumvent these drawbacks, an alternative consists of avoiding the use of a liquid electrolyte by replacing it, for example, with the following solutions: - a lithium ion-conducting glass or ceramic in a purely solid form, for example, a thin layer deposited by chemical vapor deposition (CVD) such as a LIPON layer, or a layer of a composite material comprising a polymer matrix, for example, poly(vinylidene fluoride), and a filler consisting of a lithiated oxide, such as Li7La3Zr20i2; - a dry solid polymer electrolyte composed of a polymer of the poly(ethylene oxide) (PEO) type and a lithium salt, for example, lithium Z?z'5(trifluorosulfonyl)imide (LiTFSI).

[0012] However, these different solutions all currently have a certain number of drawbacks.

[0013] Concerning the use of lithium ion conductive glass or ceramic, this requires very complex implementation or synthesis techniques to be developed in an industrial context, which may prove prohibitive for the large-scale production of accumulators.

[0014] Concerning dry polymer solid electrolytes, their ionic conductivity, at room temperature, is generally less than 105 S.cm ', whereas, for a conventional liquid electrolyte, the ionic conductivity is of the order of 103 S.cm ', or even 102 S.cm 1 at room temperature. As a result, it may prove necessary to use accumulators comprising a dry polymer electrolyte at temperatures higher than room temperature, for example, a temperature ranging from 60 to 80°C to promote the diffusion of lithium ions within the electrolyte.

[0015] To overcome the drawbacks associated with the use of a liquid electrolyte and those of the aforementioned solid electrolytes, a new technology developed and illustrated in WO2015169835 consists of trapping the liquid electrolyte in a polymer matrix forming an integral part of the positive electrode and the negative electrode (these electrodes being able to be described as ionogel electrodes), this technology making it possible to obtain at room temperature electrochemical performances equivalent to those of a lithium-ion accumulator comprising a liquid electrolyte not trapped in a polymer matrix.

[0016] These electrodes are prepared in a conventional manner by a process successively comprising the following steps: - a step of manufacturing an ink (i.e. a liquid dispersion comprising in suspension the solid ingredients of the electrode) by mixing the different ingredients intended to enter into the constitution of the electrode, namely, the active material, the electronically conductive additive(s), a fluorinated (co)polymer which allows the trapping of the liquid electrolyte, at least one solvent of this fluorinated copolymer (for example, acetone), a lithium salt, one or more electrolyte solvents (such as carbonate solvents) to solubilize the lithium salt; - once the ink is obtained, a step of depositing it, generally by coating on a support forming the current collector; - a step of evaporation of the solvent(s) of the fluorinated (co)polymer followed optionally by a calendering step whereby the specific electrode remains.

[0017] The ink manufacturing step, which generally occurs in mixers Traditional inks, such as a disperser or planetary mixer, require a high proportion of solvent(s), which limits the percentage of solid mass in the ink. More specifically, the percentage of solid mass relative to the total mass of the ink is generally between 35 and 49% by mass, while the mass of the liquid electrolyte (salt + electrolyte solvent(s)) is between 6 and 13% of the total mass of the ink and the solvent(s) of the fluorinated (co)polymer is between 45 and 57% of the total mass of the ink.

[0018] The presence of such a quantity of solvent(s) constitutes a limiting factor for the implementation of such a process, in particular at the industrial level, because it involves setting up management of the effluents (here, the solvent used in significant quantity) both in terms of safety (in particular, due to the potential flammable nature of the chosen solvent(s) and / or the toxicity of the chosen solvent(s)) and elimination of the solvent(s), which also generates significant costs for implementing this process.

[0019] In this context, the inventors have therefore set themselves the objective of proposing a new method for manufacturing an assembly comprising an electrode comprising a polymer matrix containing an electrolyte and a current collector, which makes it possible to reduce or even eliminate the use of solvent(s) and which is, in fact, less expensive and limits the disadvantages linked to the use of solvent(s).Furthermore, the inventors have also set themselves the objective of developing a manufacturing process for an assembly as defined above, which no longer involves the prior preparation of an ink but rather the prior preparation of a composition in the form of a paste comprising the ingredients intended to form part of the electrode constitution, this preparation being made possible by the use of a specific mixer during this step and the shaping and association steps with a current collector being carried out in such a way as to avoid fouling of the elements used to implement said steps.. Disclosure of the invention

[0020] To do this, the inventors have developed a method for manufacturing an assembly comprising a first planar electrode comprising a polymer matrix trapping an electrolyte and a current collector, said first electrode being deposited on one face of said current collector, said method comprising the following steps: a) a step of preparing a composition comprising the ingredients intended to be used in the constitution of the first electrode, said step consisting of introducing and mixing the ingredients intended to be used in the constitution of the electrode in a mixer with two co-rotating interpenetrating screws rotating in a closed sheath, at a temperature below 100°C; b) from the composition obtained in a), a step of forming a strip by passing said composition through a die; c) a step of rolling the strip obtained in b), by passing it between a first roller, called the upper roller, and a second roller, called the lower roller, a first polymeric sheet being interposed between the first roller and the strip and a second polymeric sheet being interposed between the second roller and the strip (in order to avoid any direct contact between the rollers and the strip), the first polymeric sheet being separated from the strip at the end of the rolling step while the second polymeric sheet remains attached to the strip thus rolled at the end of the rolling step, whereby the result is a rolled strip coated on one face, called the lower face, with the second polymeric sheet and the face opposite the lower face, called the upper face, of which is free (i.e. not coated); d) a step of co-rolling the rolled strip obtained in c) with a current collector by passing it between a first roller, called the upper roller, and a second roller, called the lower roller, the lower face of the strip being in contact with the second roller via the second polymeric sheet and the upper face being in contact with the first roller via the current collector interposed between the first roller and the upper face, the second polymeric sheet being optionally separated from the strip at the end of the co-rolling step while the current collector remains attached to the upper face of the strip thus co-rolled at the end of the co-rolling step, whereby the assembly comprising the first flat electrode and the current collector results.

[0021] Thanks to this sequence of steps preserving in particular any contact between the rollers and the strip coming from the die, this makes it possible to avoid any damage to the latter by said rollers and also the fouling of the latter, which makes it possible to envisage a continuous implementation of said method.

[0022] Firstly, as mentioned above, the method of the invention comprises a step of preparing a composition comprising the ingredients intended to be part of the constitution of the electrode, said step consisting of an introduction and a mixing of the ingredients intended to be part of the constitution of the electrode in a mixer with two co-rotating interpenetrating screws rotating in a closed barrel, at a temperature below 100°C.

[0023] The introduction of the ingredients may be simultaneous or may be successive and this introduction may be carried out at separate locations (for example, the introduction of the solid constituents into a first introduction zone via one or more inlets of the mixer and the introduction of the liquid constituents into a second introduction zone via one or more inlets of the mixer), as may be the case with the mixer illustrated in [Fig.l] attached, which comprises: - a closed sheath 1; - two interpenetrating screws 3 and 5; - a first introduction zone 7 (called zone A) of the ingredients; - a second introduction zone 9 (called zone B) for the ingredients; and - an outlet 11 for the evacuation of the formed composition; - a motor 13 connected to the screws to generate their rotation.

[0024] Thanks to the use of this specific mixer, it is possible to cancel the presence of solvent(s) other than the solvent(s) present in the electrolyte, compared to a process using conventional mixers and therefore to limit the disadvantages linked to the management of effluents.

[0025] More specifically, this composition may comprise, as constituent ingredients of the electrode: -at least one active electrode material; -at least one polymer intended to be included in the constitution of the polymer matrix; -an electrolyte; - possibly at least one electronically conductive additive.

[0026] The active electrode material is a material capable of inserting and removing, in its structure, metal ions, such as alkali ions (for example, lithium ions, when the accumulator is a lithium accumulator, sodium ions, when the accumulator is a sodium accumulator, or potassium ions, when the accumulator is a potassium accumulator), alkaline-earth ions (for example, magnesium ions, when the accumulator is a magnesium accumulator, calcium ions, when the accumulator is a calcium accumulator), metal ions (for example, aluminum ions, when the accumulator is an aluminum-ion accumulator).

[0027] The nature of the active material is of course a function of its destination, namely whether it is intended for a positive electrode or a negative electrode.

[0028] Also, when the method of the invention is intended for the manufacture of a positive electrode, as examples of active electrode materials capable of entering into the constitution of a positive electrode of a lithium accumulator, mention may be made of: - metal chalcogenides of formula LiMQ2, in which M is at least one metallic element chosen from metallic elements, such as Co, Ni, Fe, Mn, Cr, V, Al and Q is a chalcogen, such as O or S, the preferred metal chalcogenides being those of formula LiM02, with M being as defined above, such that, in a manner preferred, LiCoO2, LiNiO2, LiNixCoi x02 (with 0 <x<l), un matériau à base de lithium-nickel-manganèse-cobalt LiNixMnyCozO2 avec x+y+z=l (connu également sous l’abréviation NMC), tel que LiNioj33Mnoj33Cooj3302j ou un matériau à base de lithium-nickel-cobalt-aluminium LiNixCoyAlzO2 avec x+y+z=l (connu également sous l’abréviation NCA), tel que LiNio> 8Cooji5Alojo502 ; - spinel-structured chalcogenides, such as LiMn2O4; - lithiated or partially lithiated materials of formula MiM2(JO4)fEi_f, in which Mi is lithium, which may be partially substituted by another alkali element up to a substitution rate of less than 20%, M2 is a transition metal element with oxidation state +2 selected from Fe, Mn, Ni and combinations thereof, which may be partially substituted by one or more other additional metal elements with oxidation state(s) between +1 and +5 up to a substitution rate of less than 35%, JO4 is an oxyanion in which J is selected from P, S, V, Si, Nb, Mo and combinations thereof, E is a fluoride, hydroxide or chloride anion, f is the mole fraction of the JO4 oxyanion and is generally between 0.75 and 1 (including 0.75 and 1).

[0029] More specifically, the lithiated or partially lithiated materials may be phosphorus-based (meaning, in other words, that the oxyanion has the formula PO4) and may have an ordered or modified olivine-type structure.

[0030] Lithiated or partially lithiated materials can correspond to the specific formula Li3 xM'yM”2 y(JO4)3, in which 0 <x<3, 0<y<2, M’ et M” représentent des éléments métalliques identiques ou différents, l’un au moins des M’ et M” étant un élément métallique de transition, JO4 est, de préférence, PO4, qui peut être partiellement substitué par un autre oxyanion avec J étant choisi parmi S, V, Si, Nb, Mo et les combinaisons de ceux-ci.

[0031] Lithiated or partially lithiated materials can correspond to the formula Li(FexMni x)PO4, in which 0 <x<l et, de préférence, x est égal à 1 (ce qui signifie, en d’autres termes, que le matériau correspondant est LiFePO4).

[0032] When the method of the invention is intended for the manufacture of a negative electrode, as examples of active electrode materials capable of entering into the constitution of a negative electrode of a lithium accumulator, mention may be made of: - carbonaceous materials, such as graphitic carbon capable of intercalating lithium which may exist, typically, in the form of a powder, flakes, fibers or spheres (for example, mesocarbon microbeads); - silicon-based compounds, such as silicon carbide SiC or silicon oxide SiOx; - metallic lithium; - lithium alloys, such as those described in US 6203944 and / or WO 00 / 03444; - lithiated titanium oxides, such as an oxide of formula Li(4 x)MxTi50i2 or Li4MyTi(5_y)Oi2 in which x and y range from 0 to 0.2, M represents an element chosen from Na, K, Mg, Nb, Al, Ni, Co, Zr, Cr, Mn, Fe, Cu, Zn, Si and Mo, a specific example being Li4Ti5O12, these oxides being lithium insertion materials exhibiting a low level of physical expansion after inserting lithium; - non-lithiated titanium oxides, such as TiO2; - oxides of formula MyTi(5_y)Oi2 in which y ranges from 0 to 0.2 and M is an element chosen from Na, K, Mg, Nb, Al, Ni, Co, Zr, Cr, Mn, Fe, Cu, Zn, Si and Mo; - lithium-germanium alloys, such as those comprising crystalline phases of formula Li44Ge; or - a mixture thereof, such as a mixture comprising graphite and a silicon-based compound.

[0033] The polymer(s) capable of forming part of the polymer matrix are advantageously chosen from gelling polymers capable of gelling on contact with the electrolyte and thus trapping the electrolyte (the resulting electrode thus forming an electrode commonly called an “ionogel electrode”) and, more specifically, may be chosen from fluorinated polymers comprising at least one repeating unit resulting from the polymerization of a fluorinated monomer and, preferably, at least one repeating unit resulting from the polymerization of a monomer comprising at least one carboxylic acid group, optionally in the form of a salt.

[0034] It is understood that the repeating unit(s) resulting from the polymerization of a fluorinated monomer and, where appropriate, the repeating unit(s) resulting from the polymerization of a monomer comprising at least one carboxylic acid group, optionally in the form of a salt, are chemically different repeating units and, in particular, the repeating unit(s) resulting from the polymerization of a fluorinated monomer do not comprise any carboxylic acid group(s), optionally in the form of a salt.

[0035] For gelling polymers, the repeating unit(s) resulting from the polymerization of a fluorinated monomer may be, more specifically, one or more repeating units resulting from the polymerization of one or more ethylenic monomers comprising at least one fluorine atom and optionally one or more other halogen atoms, examples of monomers of this type being the following: - C2-C8 perfluoroolefins, such as tetrafluoroethylene, hexafluoropropene (also known by the abbreviation HFP); - hydrogenated C2-C8 fluoroolefins, such as vinylidene fluoride, vinyl fluoride, 1,2-difluoroethylene and trifluoroethylene; - perfluoroalkylethylenes of formula CH2=CHR1, in which R1 is a group C1-C6 perfluoroalkyl; - C2-C6 fluoroolefins containing one or more other halogen atoms (such as chlorine, bromine, iodine), such as chlorotrifluoroethylene; - (per)fluoroalkylvinylethers of formula CF2=CFOR2, in which R2 is a C1-C6 fluoro- or perfluoroalkyl group, such as CF3, C2F5, C3F7; - monomers of formula CF2=CFOR3, in which R3 is a CrCi2 alkyl group, a CrCi2 alkoxy group or a CrCi2 (per)fluoroalkoxy group, such as a perfluoro-2-propoxypropyl group; and / or - monomers of formula CF2=CFOCF2OR4, in which R4 is a C1-C6 fluoro- or perfluoroalkyl group, such as CF2, C2F5, C3F7 or a C1_C6 fluoro- or perfluoroalkoxy group, such as -C2F5-O-CF3

[0036] More particularly, the gelling polymer(s) may comprise, as repeating unit(s) resulting from the polymerization of a fluorinated monomer, a repeating unit resulting from the polymerization of a monomer from the category of C2-C8 perfluoroolefins, such as hexafluoropropene and a repeating unit resulting from the polymerization of a monomer from the category of C2-C8 hydrogenated fluoroolefins, such as vinylidene fluoride.

[0037] The repeating unit(s) resulting from the polymerization of a monomer comprising at least one carboxylic acid group, optionally in the form of a salt, may be, more specifically, one or more repeating units resulting from the polymerization of a monomer of the following formula (I): [Chem. 1] (0 in which R5 to R7 represent, independently of each other, a hydrogen atom or a C1-C3 alkyl group and R8 represents a hydrogen atom, a monovalent cation (for example, an alkali cation, an ammonium cation) or a saturated or unsaturated C1-C5 hydrocarbon group comprising at least one carboxylic acid group, particular examples of monomers of this type being acrylic acid, methacrylic acid or 2-carboxyethyl acrylate.

[0038] Particular gelling polymers that can be used in the context of the invention may be polymers comprising a repeating unit resulting from the polymerization of vinylidene fluoride, a repeating unit resulting from the polymerization of a monomer comprising at least one carboxylic acid group, such as acrylic acid and even actually a repeating unit resulting from the polymerization of a fluorinated monomer other than vinylidene fluoride (and more specifically, a repeating unit resulting from the polymerization of hexafluoropropene).

[0039] More particularly still, gelling polymers which can be used in the context of the invention are gelling polymers, the above-mentioned repeating units of which are derived from the polymerization: - at least 70 mol% of a hydrogenated C2-C8 fluoroolefin, preferably vinylidene fluoride; - from 0.1 to 15 mol% of a C2-C8 perfluoroolefin, preferably hexafluoropropene; and - from 0.01 to 20 mol% of a monomer of formula (I) mentioned above, preferably acrylic acid.

[0040] Furthermore, the gelling polymer(s) advantageously have an intrinsic viscosity measured at 25°C in N,N-dimethylformamide ranging from 0.1 to 1.0 L / g, preferably from 0.25 to 0.45 L / g.

[0041] More specifically, the intrinsic viscosity is determined by the equation below based on the falling time, at 25°C, of ​​a solution obtained by dissolving the polymer concerned in a solvent (N,N-dimethylformamide) at a concentration of approximately 0.2 g / dL using an Ubbelhode viscometer:

[0042] [Math.l] r -] _ x 111 %) “(i+r)xc in which: - q corresponds to the intrinsic viscosity (in dL / g); - c corresponds to the polymer concentration (in g / dL); - qr corresponds to the relative viscosity, that is to say the ratio between the falling time of the solution and the falling time of the solvent; - qsp corresponds to the specific viscosity, i.e. pr - 1; - T corresponds to an experimental factor set at 3 for the polymer concerned.

[0043] The electrolyte is, advantageously, a liquid electrolyte and, more specifically, a liquid electrolyte, which can gel on contact with the polymer matrix, when the latter comprises one or more gelling polymers.

[0044] The liquid electrolyte may comprise (or even consist of) at least one organic solvent, at least one metal salt and possibly an additive belonging to the category of carbonate compounds (it being understood that this additive is different from the carbonate solvent(s) included, where appropriate, in the electrolyte).

[0045] The organic solvent(s) may be carbonate solvents and, more specifically: - cyclic carbonate solvents, such as ethylene carbonate (symbolized by the abbreviation EC), propylene carbonate (symbolized by the abbreviation PC), butylene carbonate, vinylene carbonate, fluoroethylene carbonate, fluoropropylene carbonate and mixtures thereof; - linear carbonate solvents, such as diethyl carbonate (symbolized by the abbreviation DEC), dimethyl carbonate (symbolized by the abbreviation DMC), ethylmethyl carbonate (symbolized by the abbreviation EMC) and mixtures thereof.

[0046] The organic solvent(s) may also be ester solvents (such as ethyl propionate, n-propyl propionate), nitrile solvents (such as acetonitrile) or ether solvents (such as dimethyl ether, 1,2-dimethoxyethane).

[0047] The organic solvent(s) may also be ionic liquids, that is to say, conventionally, compounds formed by the combination of a positively charged cation and a negatively charged anion, which is in the liquid state at temperatures below 100°C under atmospheric pressure.

[0048] More specifically, ionic liquids may comprise: - a cation chosen from imidazolium, pyridinium, pyrrolidinium, piperidinium, quaternary ammonium, quaternary phosphonium, pyrazolium cations, said cations being optionally substituted, for example, by at least one alkyl group comprising from 1 to 30 carbon atoms; - an anion chosen from halide anions, perfluorinated anions, borates.

[0049] Even more specifically, the cation can be chosen from the following cations: - a pyrrolidinium cation of the following formula (II): in which R13 and R14 represent, independently of each other, a C1-C8 alkyl group and R15, R16, R17 and R18 represent, independently of each other, a hydrogen atom or a C1-C30 alkyl group, preferably a C1-C18 alkyl group, more preferably a C1-C8 alkyl group; - a piperidinium cation of the following formula (III): [Chem. 3]

[0050] R1S r20 R23 (III) in which R19 and R20 represent, independently of each other, a C1-C8 alkyl group and R21, R22, R23, R24 and R25 represent, independently of each other, a hydrogen atom or a C1-C30 alkyl group, preferably a C1-C18 alkyl group, more preferably a C1-C8 alkyl group; - a quaternary ammonium cation; - a quaternary phosphonium cation; - an imidazolium cation; and - a pyrazolium cation. In particular, the positively charged cation can be chosen from the following cations: - a pyrrolidinium cation of the following formula (II-A): [Chem. 4] (II-A) - a piperidinium cation of the following formula (III-A): (1II-A)

[0051] When it is a quaternary ammonium cation, this can correspond to a tetraalkylammonium cation, a trialkylarylammonium cation or a tetraarylammonium cation, the alkyl groups, when present, being identical or different and which may correspond to alkyl groups, linear or branched, comprising from 4 to 12 carbon atoms, preferably from 4 to 6 carbon atoms and the aryl groups, when present, being identical or different and which may correspond to a phenyl group, a benzyl group or a naphthyl group. More specifically, it may be a tetraethylammonium cation, a tetrapropylammonium cation, a tetrabutylammonium cation, a trimethylbenzylammonium cation, a methyltributylammonium cation, an N,N-diethyl-N-methyl-N-(2-methoxyethyl)ammonium cation, an N,N-dimethyl-N-ethyl-N-(3-methoxypropyl)ammonium cation, an N,N-dimethyl-N-ethyl-N-benzylammonium cation, an N,N-dimethyl-N-ethyl-N-phenylethyl-ammonium cation, an N-tributyl-N-methylammonium cation, an N-trimethyl-N-butylammonium cation, an N-trimethyl-N-hexylammonium cation, an N-trimethyl-N-propylammonium cation.

[0052] When it is a quaternary phosphonium cation, this can correspond to a tetraalkylphosphonium cation, a trialkylarylphosphonium cation or a tetraarylammonium cation, the alkyl groups, when present, being identical or different and being able to correspond to linear or branched alkyl groups, comprising from 4 to 12 carbon atoms, preferably from 4 to 6 carbon atoms and the aryl groups, when present, being identical or different and being able to correspond to a phenyl group, a benzyl group or a naphthyl group. More specifically, it can be a trihexyl(tetradecyl)phosphonium cation, a tetrabutylphosphonium cation.

[0053] When it is an imidazolium cation, it can correspond to a 1,3-dimethylimidazolium cation, an l-(4-sulfobutyl)-3-methylimidazolium cation, an l-allyl-3H-imidazolium cation, an l-butyl-3-methylimidazolium cation, an l-ethyl-3-methylimidazolium cation, an l-hexyl-3-methylimidazolium cation, an l-octyl-3-methylimidazolium cation.

[0054] Specifically, the negatively charged anion may be selected from: - 4,5-dicyano-2-(trifluoromethyl)imidazole (known by the abbreviation TDI); - (Z?zXfluorosulfonyl)imide (known by the abbreviation FSI); - Z?zXtrifluoromethylsulfonyl)imide of formula (SO2CF3)2N; - hexafluorophosphate of formula PF6; - tetrafluoroborate of formula BF4; - the oxaloborate of the following formula (IV): [Chem. 6] (IV)

[0055] A specific ionic liquid that can be used according to the invention may be an ionic liquid composed of a cation of formula (II-A) as defined above and an anion of formula (SO2CF3)2N, PF6 or BF4.

[0056] The metal salt(s) may be chosen from the salts of the following formulae: Mel, Me(PF6)n, Me(BF4)n, Me(ClO4)n>Me(bis(oxalato)borate)n (which may be designated by the abbreviation Me(BOB)n), MeCF3SO3, Me[N(FSO2)2]n, Me[N(CF3SO2)2]n, Me[N(C2 F5SO2)2]n, Me[N(CF3SO2)(RFSO2)]n, in which RF is a group -C2F5, -C4F9 or -CF3OCF2CF3, Me(AsF6)n, Me[C(CF3SO2)3]n, Me2Sn, Me(C6F3N4) (C6F3N4 corresponding to 4,5-dicyano-2-(trifluoromethyl)imidazole and, when Me is Li, the salt corresponds to lithium 4,5-dicyano-2-(trifluoromethyl)imidazole, this salt being known by the abbreviation LiTDI), in which Me is a metallic element and, preferably, a metallic transition element, an alkali element or an alkaline-earth element and, more preferably, Me is Li (in particular, when the accumulator of the invention is a lithium-ion or lithium-air accumulator), Na (in particular, when the accumulator is a sodium-ion accumulator), K (in particular,when the accumulator is a potassium-ion accumulator), Mg (in particular, when the accumulator is an Mg-ion accumulator), Ca (in particular, when the accumulator is a calcium-ion accumulator) and Al (in particular, when the accumulator is an aluminum-ion accumulator) and n corresponds to the degree of valence of the metallic element (typically, 1, 2 or 3).

[0057] When Me is Li, the salt is preferably LiPF6.

[0058] The concentration of the metal salt in the liquid electrolyte is advantageously at least 0.01 M, preferably at least 0.025 M and more preferably at least 0.05 M and advantageously at most 5 M, preferably at most 2 M and more preferably at most 1 M.

[0059] Furthermore, the liquid electrolyte may comprise at least one additive belonging to the category of carbonate compounds (it being understood that this additive is different from the carbonate solvent(s) included, where appropriate, in the electrolyte), such as vinylene carbonate or fluoroethylene carbonate, this additive being included in the electrolyte at a content not exceeding 5% by mass of the total mass of the electrolyte.

[0060] A liquid electrolyte which can be used, in particular when the electrode manufactured according to the method of the invention is intended for a lithium-ion accumulator, is a electrolyte comprising a mixture of carbonate solvents (e.g., a mixture of cyclic carbonate solvents, such as a mixture of ethylene carbonate and propylene carbonate or a mixture of cyclic carbonate solvents and linear carbonate solvent(s), such as a mixture of ethylene carbonate, propylene carbonate and dimethyl carbonate), a lithium salt, e.g., LiPF6 (e.g., IM) and optionally an additive, such as vinylene carbonate, fluoroethylene carbonate.

[0061] As mentioned above, the composition may contain at least one electronically conductive additive, i.e. an additive capable of conferring electronic conductivity on the electrode in which it is incorporated, this additive being able to be, for example, chosen from carbon materials such as carbon black, carbon nanotubes, carbon fibers (in particular, vapor-formed carbon fibers known by the abbreviation VGCF), graphite in powder form, graphite fibers, graphene and mixtures thereof.

[0062] In addition, the composition may comprise at least one solvent (except, where appropriate, the possible organic solvent(s) of the electrolyte) of the polymer(s) intended to be part of the constitution of the polymer matrix, this solvent possibly being a solvent from the family of ketones (such as acetone), when the polymer(s) are chosen from the family of fluorinated polymers comprising at least one repeating unit resulting from the polymerization of a fluorinated monomer and, preferably, at least one repeating unit resulting from the polymerization of a monomer comprising at least one carboxylic acid group, optionally in the form of a salt. Thanks to the use of the specific mixer, this or these solvent(s) can be used in a smaller quantity compared to a process involving the use of a traditional mixer.

[0063] In the case where the composition comprises at least one solvent as mentioned above, the process advantageously comprises, after the preparation step, a step of evaporation, for example, selective, of the solvent(s) of the polymer(s) intended to enter into the constitution of the polymer matrix, for example, by in-line drying by selective evaporation.

[0064] The preparation step is carried out at a temperature below 100°C, preferably at a temperature below 80°C and, even more preferably, at a temperature below 70°C and, preferably, at a temperature greater than or equal to 5°C, more preferably, greater than or equal to 10°C, and even more preferably, greater than or equal to 15°C.

[0065] More specifically, the preparation step can be carried out at room temperature (i.e. the temperature of the environment in which the preparation step takes place, without the addition of heat by any heating element, for example, a temperature ranging from 15 to 35°C, and more specifically, a temperature equal to 25°C) or may be carried out at a temperature above room temperature, for example, a temperature above room temperature but below 100°C. More specifically, the preparation step may be carried out at a temperature above room temperature but below the boiling point of the solvent(s) of the polymer(s) intended to be part of the composition of the polymer matrix, when this or these solvent(s) are present in the composition or when this or these solvent(s) are not present, at a temperature above room temperature but below the melting point of the polymer(s) intended to be part of the composition of the polymer matrix (it being understood that the temperature at which the preparation step is carried out is always below 100°C).

[0066] The preparation step makes it possible to obtain a composition in the form of a homogeneous paste and having a very high dynamic viscosity, and more specifically, a dynamic viscosity greater than 5,000 Pa.s, preferably greater than 6,000 Pa.s and, more preferably still greater than 7,000 Pa.s, measured at a shear rate of 0.1 s 1 and at room temperature.

[0067] It is specified that, by ambient temperature, it is understood the temperature of the environment, in which the dynamic viscosity measurement takes place, without the supply of heat by any heating element, for example, a temperature ranging from 15 to 35°C, such as, for example, a temperature equal to 25°C.

[0068] More specifically, the dynamic viscosity of the composition is measured with a Bohlin CVO rheometer from Malvem equipped with a Peltier support and a cone-plate mobile with a diameter of 40 mm and an angle of 4°. To do this, the composition is deposited between the Peltier support and the mobile at a gap of 150 μm. Where appropriate, when the composition comprises at least one solvent for the polymer(s) constituting the polymer matrix, a solvent trap(s) is added to the system to prevent the solvent(s) from evaporating too quickly. The measurement is carried out in viscosimetry mode at a shear rate of 0.1 s 1 and at room temperature over an integration time of 5 seconds.

[0069] Furthermore, the composition in the form of a paste generally has a dynamic viscosity not exceeding 20,000 Pa.s, preferably not exceeding 18,000 Pa.s, under the conditions as defined above (namely, at a shear rate of 0.1 s 1 and at room temperature). Very advantageous results have been obtained when the composition is in the form of a paste having a dynamic viscosity ranging from 7,000 to 12,000 Pa.s under the conditions defined above (namely, at a shear rate of 0.1 s 1 and at room temperature).

[0070] A particularly advantageous aspect of this preparation step lies, in fact, in its ability to enable the preparation of an electrode-forming composition having a very high dynamic viscosity, thereby minimizing the use of liquid electrolyte and / or organic solvents. This is an advantage over well-established techniques for manufacturing electrodes from inks made from traditional mixers of the disperser or planetary mixer type, which have a dynamic viscosity of less than 5,000 Pa.s, or even less than 1,000 Pa.s measured under the conditions mentioned above.

[0071] When the compositions comprise at least one solvent for the polymer(s) intended to form part of the polymer matrix, these compositions may comprise, at the end of the preparation step, from 50 to 80% of solid mass relative to the total mass of the composition.

[0072] More specifically, when the compositions comprise, as constituent ingredients, at least one active electrode material, at least one polymer intended to be part of the constitution of the polymer matrix, an electrolyte and optionally at least one electronically conductive additive and at least one solvent for the polymer(s), the compositions obtained at the end of this preparation step advantageously have a percentage of solid mass relative to the total mass of the composition which can range from 50 to 80% (compared to 35 to 49% with processes involving traditional mixers). Furthermore, these compositions can comprise a mass of electrolyte at a level of 6 to 11% of the total mass of the composition and a mass of the solvent(s) of the polymer(s) at a level of 11 to 42% of the total mass of the composition (compared to 45 to 57% with processes involving traditional mixers).

[0073] According to a particular and advantageous embodiment, the composition may be free of solvent(s) of the polymer(s) intended to be part of the constitution of the polymer matrix. Under these conditions, the compositions may comprise, at the end of the preparation step, from 83 to 90% of solid mass relative to the total mass of the composition.

[0074] The compositions may comprise, at the end of the preparation step, from 83 to 90% of solid mass relative to the total mass of the composition.

[0075] More specifically, when the compositions comprise, as constituent ingredients, at least one active electrode material, at least one polymer intended to be part of the constitution of the polymer matrix, an electrolyte and optionally at least one electronically conductive additive but are devoid of solvent(s) of the polymer(s), the percentage of solid mass can represent from 83 to 90% of the total mass of the composition and the mass of electrolyte can represent from 10 to 17% of the total mass of the composition.

[0076] Under these conditions, the solvent evaporation step mentioned above is not necessary.

[0077] The preparation step can be carried out continuously, that is to say that the introduction of the ingredients and the mixing of these in the specific mixer is carried out continuously, that is to say during the entire duration of its implementation of the process.

[0078] After the preparation of the composition, it is subjected, at the outlet of the mixer, to a step of forming a strip by passing said composition through a die, such as a flat or cylindrical die (for example, with a circular or oblong section). Preferably, the die is a flat die, that is to say a die whose final section is rectangular, this section being able to advantageously have a height (which will give the thickness to the strip at the outlet of the die) ranging from 100 μm to 2,000 μm, preferably ranging from 300 μm to 1,500 μm and, more preferably, ranging from 500 μm to 1,000 μm.The section has a width, which will be a function of the desired strip width and therefore of the final width of the electrode, taking into account the spreading of the strip not only over the length but over the width inducing an increase in the width of the strip, which can be by a factor of 2, 3 or even 4 depending on the initial thickness of the strip resulting from step b).

[0079] The die is, advantageously, directly connected to the output of the mixer.

[0080] By way of example, [Fig.2] schematically illustrates this strip formation step via the passage of the composition obtained at the end of step a) through a die, the elements illustrated in this figure being the following: - the end 15 of the mixer through which the composition thus formed emerges; - a flat die 17, into which the composition from the mixer is introduced; - a strip 19 resulting from the shaping of the composition within the die 17.

[0081] The strip thus formed is then subjected to a rolling step or, in other words, a step of reducing its thickness by passing it between a first roller, called the upper roller, and a second roller, called the lower roller, a first polymeric sheet being interposed between the first roller and the strip and a second polymeric sheet being interposed between the second roller and the strip (in order to avoid any direct contact between the rollers and the strip), the first polymeric sheet being separated from the strip at the end of the rolling step while the second polymeric sheet remains attached to the strip thus rolled at the end of the rolling step, whereby the result is a rolled strip coated on one face, called the lower face, with the second polymeric sheet and the face opposite the lower face, called the upper face, of which is a free face, that is to say a face not coated with any element.

[0082] This step is illustrated schematically in [Fig.3], comprising the elements following: - band 19 from the previously described channel; - the upper roller 21; - the first polymeric sheet 23 arranged between the strip 19 and the upper roller 21; - the lower roller 25; - the second polymeric sheet 27 arranged between the strip 19 and the lower roller 25; it being understood that, as indicated by the arrow indicated on the upper roller indicating the direction of rotation of said roller and by the arrow indicated on the lower roller indicating the direction of rotation of said roller, said upper roller and said lower roller have opposite directions of rotation to induce a movement of the strip from right to left as well as of the polymeric sheets. In other words, the upper roller has a clockwise direction of rotation, while the lower roller has a counterclockwise direction of rotation. At the end of the rolling step, the strip has a free upper face 29 and a lower face 31 coated with the second polymeric sheet. In the foregoing and the following, it should be noted that the same numerical references will be used, since they designate the same elements in an identical or similar context.

[0083] The upper roller and the lower roller may belong to a rolling mill type device or a calender type device conventionally used to densify the electrodes in a conventional lithium-ion battery manufacturing process.

[0084] The first polymeric sheet and the second polymeric sheet may be polyester sheets and, more specifically, poly(ethylene terephthalate) or poly(ethylene naphthalate) sheets, preferably poly(ethylene terephthalate).

[0085] Advantageously, the first polymeric sheet and the second polymeric sheet may be of the same nature.

[0086] Advantageously, the first polymeric sheet and / or the second polymeric sheet has(have) at least one rough face, in particular, the face intended to be in contact with the strip. More specifically, the first polymeric sheet and / or the second polymeric sheet may have(have) an average surface roughness, called Ra, ranging from 0.01 pm to 1 pm, more preferably, ranging from 0.3 pm to 0.7 pm, these values ​​being particularly suitable, when the associated electrode is a negative electrode and, more particularly still, when the associated electrode is a negative electrode comprising, as active material, graphite.

[0087] The average surface roughness Ra, which can also be called roughness arithmetic mean, means the average roughness of the surface for the length of the measurement taken, that is to say the average deviation between the peaks and valleys, whereby the greater the roughness of the surface concerned, the greater the difference between the peaks and valleys of the latter.

[0088] The average surface roughness Ra is determined, conventionally, by means of a contact profilometer, for example, a Dektak 150 profilometer with a tip of radius 12.5 pm from the Bruker brand.

[0089] Furthermore, the first polymeric sheet and / or the second polymeric sheet advantageously has a thickness ranging from 6 μm to 75 μm, preferably from 10 μm to 30 μm.

[0090] As examples of sheets meeting the above-mentioned roughness and thickness criteria, mention may be made of the polyethylene terephthalate sheets supplied by the company Mitsubishi Polyester Film GmbH under the references PET HOSTAPHAN™ MK, these sheets having a thickness of 12 pm, 19 pm or 23 pm and a roughness Ra of 0.3 pm and PET HOSTAPHAN™ XMTK, these sheets having a thickness of 50 pm and a roughness Ra of 0.68 pm.

[0091] In particular, to achieve the required level of roughness, the first polymeric sheet and / or the second polymeric sheet may be a multi-layer sheet comprising a central polyester layer and on at least one of the faces of the central layer, a layer comprising a polymeric matrix, for example, a polyester polymeric matrix trapping inorganic particles, such as silica particles. Sheets of this type are those mentioned above under the reference PET HOSTAPHAN™ MK.

[0092] Furthermore, the first polymeric sheet and / or the second polymeric sheet advantageously have(s) a surface energy of less than 40 mN / m, this surface energy characteristic being particularly suitable when the associated electrode is a negative electrode and, more particularly still, when the associated electrode is a negative electrode comprising, as active material, graphite.

[0093] The surface energy can be determined - as known per se - by measuring the contact angle of a drop of a liquid deposited on the polymeric sheet according to the Owens-Wendt method. For example, it can be measured using a tensiometer, such as a tensiometer marketed by the company KRUSS under the reference DSA100™. In particular, three liquids of different polarity and known polar and dispersive components, namely water, diiodomethane and glycerol, can be used for this measurement.

[0094] Even more specifically, when the electrode is a negative electrode comprising, as active material, graphite, the first polymeric sheet and / or the second polymeric sheet advantageously has(have), a surface energy lower than the surface energy of the negative electrode, the latter having a surface energy lower than the current collector associated with the electrode.

[0095] The rolling step can be carried out hot and, more specifically, at a temperature ranging from 60°C to 120°C, more preferably, ranging from 80°C to 110°C, this temperature being able to be reached by heating the lower roller and the upper roller.

[0096] Whether for the first polymeric sheet or the second polymeric sheet, these can be supplied by a distributor roller located upstream of the upper roller for the first polymeric sheet and a distributor roller located upstream of the lower roller for the second polymeric sheet.

[0097] At the end of this step and, if necessary, once the cooling of the strip has been obtained, the first polymeric sheet is separated from the strip, that is to say that it does not remain attached to it, this separation being carried out, advantageously via a drive roller (reference 33 in [Fig. 4] similar to [Fig. 3] except for the presence of this drive roller) located downstream of the upper roller, preferably at a predetermined distance, and positioned on the first polymeric sheet and the strip and via a winding roller located downstream of the upper roller and the drive roller and in a raised position relative to them and connected to one end of the first polymeric sheet, the rotation of the winding roller causing the movement of the polymeric sheet towards the drive roller and then, a winding of the latter around the winding roller.More specifically, the drive roller is positioned at a predetermined distance defined according to the time required to cool the strip before removing the first polymeric sheet to prevent it from remaining stuck to the roller. For example, for a rolling temperature of 80°C and a line speed of 1 m / min, the predetermined distance must be greater than 20 cm.

[0098] After the rolling step, the method comprises a step of co-rolling the rolled strip obtained in c) with a current collector by passing it between a first roller, called the upper roller, and a second roller, called the lower roller, the lower face of the strip being in contact with the second roller via the second polymeric sheet and the upper face, called the free face, of the strip being in contact with the first roller via the current collector interposed between the first roller and the upper face, the second polymeric sheet being, optionally, separated from the strip at the end of the co-rolling step, while the current collector remains attached to the upper face of the strip thus co-rolled at the end of the co-rolling step, whereby the assembly comprising the first flat electrode and the current collector results.

[0099] This step is illustrated schematically in [Fig.5], comprising the elements following: - strip 19 resulting from the rolling step previously described; - the upper roller 35; - the current collector 37 arranged between the strip 19 and the upper roller 35; - the lower roller 39; - the second polymeric sheet 27 arranged between the strip 19 and the lower roller 39; it being understood that, as indicated by the arrow indicated on the upper roller indicating the direction of rotation of said roller and by the arrow indicated on the lower roller indicating the direction of rotation of said roller, said upper roller and said lower roller have a reverse direction of rotation to induce a movement of the strip from right to left as well as the second polymeric sheet and the current collector. In other words, the upper roller has a clockwise direction of rotation, while the lower roller has a counterclockwise direction of rotation.

[0100] As for the rolling step, the upper roller and the lower roller may belong to a rolling mill type device or a calender type device conventionally used to densify the electrodes in a conventional lithium-ion battery manufacturing process.

[0101] The co-laminating step can be carried out hot and, more specifically, at a temperature ranging from 60°C to 120°C, even more preferably ranging from 80°C to 110°C, this temperature being achievable by heating the lower roll and the upper roll.

[0102] At the end of this step and, if necessary, once the cooling of the strip has been obtained, the second polymeric sheet can be separated from the strip, that is to say that it does not remain attached to the lower face of the latter, this separation being carried out, advantageously via a drive roller (reference 41 in [Fig. 6] similar to [Fig. 5] except for the additional presence of this drive roller) located downstream of the lower roller, preferably at a predetermined distance, and positioned on the second polymeric sheet and the strip and via a winding roller located downstream of the lower roller and the drive roller and in a detached position relative to them and connected to one end of the second polymeric sheet, the rotation of the winding roller causing the movement of the polymeric sheet towards the drive roller and then, a winding of the latter around the winding roller.More specifically, the drive roller is positioned at a predetermined distance defined according to the time required to cool the strip before removing the second polymeric sheet to prevent it from remaining stuck to the roller. For example, for a rolling temperature of 80°C. and a line speed of 1 m / min, the predetermined distance must be greater than 20 cm. At the end of this co-rolling step, the strip is thus coated on the upper face by a current collector and has a free lower face, when the second polymeric sheet has been dissociated.

[0103] Regarding the current collector, it can be supplied by a distributor roller located upstream of the upper roller for the current collector.

[0104] The current collector may be, conventionally, a current collector in the form of a metal foil and, more specifically, an aluminum foil, when the prepared electrode is a positive electrode, or a copper, nickel or nickel-plated copper foil, when the prepared electrode is a negative electrode.

[0105] Advantageously, the current collector may be in the form of a metal sheet, at least the face of which (namely, the lower face of the current collector) intended to be in contact with the strip is modified to improve the adhesion of the strip to the current collector, this modification being able to consist of a surface treatment, for example, a treatment leading to the formation of a layer of particles on the surface, for example, particles which may be made of electrically conductive carbon, such as graphite, graphene, carbon nanotubes, activated carbon, non-activated carbon nanofibers; metal particles, for example, in the form of powder, fibers or flakes; particles of metal oxide(s) or electrically conductive polymeric particles. The modification may also consist of a surface treatment chosen from ablation or corrosion.

[0106] For example, a particular current collector is a chemically surface-treated aluminum collector known as SDX™-ZM from manufacturer Showa Denko.

[0107] Advantageously, the method of the invention is a continuous method, that is to say a method for which, throughout the duration of its implementation, there is no interruption between step a), step b), step c) and step d).

[0108] More specifically, the manufacturing process may be a continuous process, i.e. a process which takes place without interruption for the entire duration of its implementation, which means, in other words, that the assembly is manufactured without interruption for the entire duration of implementation of the process. In other words, this means that steps a) to d) are implemented concomitantly and without interruption for the entire duration of the process, which means, in other words, that at each instant t of the duration of the process, a fraction of the composition is subjected to the manufacturing step while another fraction of the composition is subjected to the strip formation step, that a fraction of the strip is subjected to the step of rolling and another fraction of the strip is subjected to the co-rolling step. It is also understood, in this case, that all optional steps of the process (for example, the drying step) are, when present, carried out continuously.

[0109] Different variants of implementation of a continuous method according to the invention are illustrated in figures 7, 8, 9 and 10 attached in the appendix. For these different figures, the numerical references identical to those used for the preceding figures designate the same elements and will not be systematically described, when they have already been described elsewhere.

[0110] [Fig.7] represents a first variant of implementation of the continuous process. More specifically, the strip 19 is formed at the outlet of the barrel 1 of the mixer with two co-rotating interpenetrating screws using a flat die 17. The thickness of the strip is then reduced by rolling between an upper roller 21 and a lower roller 25 of a first rolling mill, a first polymeric sheet 23 being interposed between the upper roller 21 and the strip 19, the first polymeric sheet being supplied via an unwinding roller 43 and a second polymeric sheet 27 being interposed between the strip 19 and the lower roller 25, said second sheet being supplied via an unwinding roller 45.At the end of the rolling, the first polymeric sheet is separated from the strip via a drive roller 33 located downstream of the upper roller at a predetermined distance and positioned on the first polymeric sheet attached to the strip and via a take-up roller 47 located downstream of the upper roller and the drive roller 33 and in a raised position relative to them and connected to one end of the first polymeric sheet. The predetermined distance is a function of the temperature of the aforementioned rollers and the rolling speed.The strip resulting from the rolling is then conveyed in the direction of movement of the arrow indicated in the figure to a second rolling mill for co-rolling with a current collector, this co-rolling consisting of passing the strip between an upper roller 35 and a lower roller 39, the current collector 37 being interposed between the upper roller 35 and the strip 19, the current collector being supplied via an unwinding roller 49. At the end of the co-rolling, the second polymeric sheet is separated from the strip via a drive roller 41 located downstream of the lower roller 39 positioned at a predetermined distance and positioned on the second polymeric sheet attached to the strip and via a take-up roller 51 located downstream of the lower roller and the drive roller and being detached from the strip and connected to one end of the second polymeric sheet.The predetermined distance is a function of the temperature of the aforementioned rollers and the rolling speed. After rolling, the strip coated with the current collector and freed from the second polymeric sheet is wound onto a winding roller 53.

[0111] To act on the tension of the strip 19 and of the first polymeric sheet and of the second polymeric sheet, one or more movable drive rollers can be added, which makes it possible to better control this tension and to ensure better alignment between the strip and the polymeric sheets, these implementation variants, respectively second, third and fourth variant, being illustrated in figures 8, 9 and 10 with: - for [Fig.8], a movable drive roller 55 in contact with the current collector and positioned between the upper roller 35 and the winding roller 53, the other elements being identical to those of [Fig.7] and being designated by the same numerical references; - for [Fig.9], in addition to the movable drive roller 55 of [Fig.8], another movable drive roller 57 in contact with the second polymeric sheet positioned between the lower roller 25 of the first rolling mill and the lower roller 39 of the second rolling mill, the other elements being identical to those of [Fig.7] and [Fig.8] and being designated by the same numerical references; - for [Fig. 10], in addition to the movable drive roller 55 and the other movable drive roller 57, another movable drive roller 59 in contact with the strip 19 downstream of the other movable drive roller 57 and upstream of the upper roller 35 of the second rolling mill.

[0112] The method of the invention is also suitable for the preparation of a bifacial electrode, in other words in the context of the invention an assembly comprising a first electrode deposited on a first face of the current collector and a second electrode deposited on a second face of the current collector, this method being able to adopt several variant embodiments.

[0113] According to a first variant embodiment, the method in addition to the steps already described comprises the following particularities: - for the aforementioned step d), the second polymeric sheet is not separated from the strip; - after step d), a step e) of co-laminating the assembly resulting from step d) with another strip, called the second strip, comprising a polymer matrix trapping an electrolyte, said second strip being coated on its upper face with a polymer sheet, called the third polymer sheet, by passing said assembly and the second strip between an upper roller and a lower roller, the lower roller being in contact with the second polymer sheet of the aforementioned assembly and, between the upper roller and the current collector of the assembly, is interposed the strip coated on its upper face with a polymer sheet, called the third polymer sheet, said third polymer sheet being in direct contact with the upper roller; - after step e), a step of dissociation of the second polymeric sheet and a step of dissociation of the third polymeric sheet, whereby the assembly results comprising a first electrode deposited on a first face of the current collector and a second electrode deposited on a second face of the current collector.

[0114] This variant is illustrated in [Fig. 11] which details the co-lamination step e) and the subsequent dissociation steps with the following elements: - the strip 19, called the first strip, coated on its lower face with the second polymeric sheet 27 and on its upper face with the current collector 37; - an upper roller 61 and a lower roller 63; - a second strip 65 coated on its upper face with a polymeric sheet 67, called the third polymeric sheet, and having its lower face free; - the lower roller 63 being in contact with the second polymeric sheet 27 and the upper roller 61 being in contact with the third polymeric sheet 67, the first strip 19 and the second strip 65 being brought into contact by passing between the upper roller 61 and the lower roller 63, which means, in other words, that the first strip 19 and the second strip 65 are brought into contact via the current collector covering the first strip 19 and via the free lower face 66 of the second strip; - downstream of the upper roller 61, a drive roller 69 in contact with the third polymeric sheet 67 covering the upper face of the second strip 65 and downstream of this drive roller 69, a winding roller 71 connected to one end of the third polymeric sheet and in a raised position relative to the drive roller 69, whereby the third polymeric sheet 67 is, on the one hand, driven and, on the other hand, detached from the second strip; - downstream of the lower roller 63, a drive roller 73 in contact with the second polymeric sheet 27 covering the lower face of the first strip 19 and downstream of this drive roller, a winding roller 75 connected to one end of the second polymeric sheet 27 and in a position detached from the second strip relative to the drive roller 73, whereby the second polymeric sheet is, on the one hand, driven and on the other hand, detached from the second strip; - a winding roller 77 connected to one end of the assembly comprising the first strip (which constitutes the first electrode) deposited on a first face of the current collector and the second strip (which constitutes the second electrode) deposited on a second face of the current collector.

[0115] [Fig. 12] illustrates a variant similar to that illustrated in [Fig. 11], except that a movable drive roller 79 is interposed between the upper roller 61 and the drive roller 69 to act on the web tension.

[0116] The second strip can be produced, up to the co-rolling step e), according to steps a), b) and c) as defined within the framework of the method of the invention.

[0117] According to a second variant embodiment, the method comprises the following features: - during step d), the upper face of the strip, called the first strip, is in contact with the first roller via the current collector itself in contact with the free face of another strip, called the second strip, comprising a polymer matrix trapping an electrolyte, said second strip being coated on another face with a polymer sheet, called the third polymer sheet. In other words, between the first roller and the upper face of the strip are interposed, in the direction going from the first roller towards the upper face of the first strip, the third polymer sheet deposited on the second strip, the second strip and the current collector.

[0118] The second strip, up to the co-rolling step d), can be produced by a method according to the invention comprising steps a), b) and c).

[0119] This variant is illustrated in [Fig. 13] which details the concomitant production of the two strips up to the contacting of these via the current collector with, more specifically, the framed parts a) and a') schematically representing the rolling step of the first strip (part a)) and the rolling step of the second strip (part a')). For each of these parts, similar references are used if possible, except that they differ by the affixing of a sign ' for the references of part a').

[0120] For each of parts a) and a'), the strip (19 or 19') is formed at the outlet of the barrel (1 or 1') of the mixer with two co-rotating interpenetrating screws using a flat die (17 or 17'). The thickness of the strip is then reduced by rolling between an upper roll (21 or 21') and a lower roll (25 or 25') of a first rolling mill, a first polymeric sheet (23 or 23') being interposed between the upper roll 21 and the strip 19 for part a) and between the lower roll 25' and the strip 19' for part a'), the first polymeric sheet being supplied via an unwinding roll (43 or 43') and a second polymeric sheet (27 or 27') being interposed between the strip 19 and the lower roll 25 for part a) and between the upper roll 21' and the strip 19' for part a'), said second sheet being supplied via an unwinding roll (45 or 45').At the end of the rolling, the first polymeric sheet is separated from the strip via two drive rollers 33 and 34 or 33' and 34' located downstream of the upper roller 21 for part a) or of the lower roller 25' for part a') and positioned on the first polymeric sheet attached to the strip and via a winding roller 47 or 47' located downstream of the upper roller for part a) and of the lower roller for part a') and of the drive rollers 33 and . 34 or 33' and 34' and in a detached position relative to these and connected to one end of the first polymeric sheet concerned.

[0121] In this [Fig.13], part b) illustrates the co-rolling step common to the two rolled strips, by passing them between an upper roller 35 and a lower roller 39 and interposing between them the current collector 37 supplied by means of an unwinding roller 49, the two strips being conveyed to the second rolling mill by means of the two drive rollers 55 and 55'. Downstream of the upper roller and the lower roller, the second polymeric sheets are detached from the strips by means of the respective drive rollers 41 and 41' and the winding rollers 51 and 51' connected to one end of said strips.

[0122] The resulting assembly thus formed is conveyed via a drive roller 55 to be wound and stored in a winding roller 53'.

[0123] Alternatively, still with the aim of producing an electrode-current collector assembly, the electrode of which comprises a polymer matrix trapping an electrolyte, the present invention also relates to a method of manufacturing an assembly comprising a first planar electrode comprising a polymer matrix trapping an electrolyte and a current collector, said method comprising the following steps: a) a step of preparing a composition comprising the ingredients intended to be used in the constitution of the first electrode, said step consisting of introducing and mixing the ingredients intended to be used in the constitution of the electrode in a mixer with two co-rotating interpenetrating screws rotating in a closed barrel, at a temperature below 100°C; b) from the composition obtained in a), a step of forming a strip by passing said composition through a die;c') a step of co-rolling the strip obtained in b), by passing it between a first roller, called the upper roller, and a second roller, called the lower roller, a polymeric sheet having an average surface roughness, called Ra, ranging from 0.01 pm to 1 pm being interposed between the first roller and the strip and a current collector being interposed between the second roller and the strip in order to avoid any direct contact between the rollers and the strip, the polymeric sheet being dissociated from the strip at the end of the co-rolling step while the current collector remains attached to the strip at the end of the co-rolling step, whereby the assembly comprising the first flat electrode and the current collector results.

[0124] This process variant is illustrated in [Fig. 14].In this figure, the strip 19 coming from the flat die (not shown) is rolled between an upper roller 81 and a lower roller 83 of a rolling mill, a polymeric sheet 85 being interposed between the strip 19 and the upper roller 81 and a current collector 87 being interposed. between the strip 19 and the lower roller 83. Downstream of the rollers, the polymeric sheet 85 is separated from the strip via a drive roller 89 positioned downstream of the upper roller on the polymeric sheet itself positioned on the strip.

[0125] This process variant is also suitable for the preparation of a bifacial electrode, otherwise in the context of the invention to an assembly comprising a first electrode deposited on a first face of the current collector and a second electrode deposited on a second face opposite to said first face of said current collector.

[0126] The characteristics relating to steps a) and b), to the polymeric sheet and to the current collector already described above are also valid for this variant.

[0127] In this case, the co-rolling step c') can be defined as a step of co-rolling the strip obtained in b), by passing it between a first roller, called the upper roller, and a second roller, called the lower roller; a polymeric sheet being interposed between the first roller and the strip, called the first strip, which is in contact, via its lower face, with a current collector; and between the second roller and the strip are interposed said current collector in contact, via its lower face with another strip, called second strip, comprising a polymer matrix trapping an electrolyte, this second strip being in contact via its lower face with another polymer sheet, the polymeric sheet being dissociated from the first strip and the other polymeric sheet being dissociated from the second strip at the end of the co-lamination step, whereby the aforementioned assembly results.

[0128] Before the co-rolling step, the second strip can be produced by a method comprising the aforementioned steps a) and b).

[0129] This variant is illustrated in [Fig. 15] with the co-rolling step common to the first strip 19 and the second strip 19' each resulting from a passage through a flat die (17 and 17') of a composition obtained from a mixer (1 and 1'), said first strip and said second strip being subjected to a passage in a rolling mill between an upper roller 81 and a lower roller 83 and interposition between them, of the current collector 87 supplied by means of an unwinding roller 49', said first strip being in contact with the upper roller via a polymeric sheet 85 supplied by an unwinding roller 43 and the second strip being in contact with the lower roller via a polymeric sheet 85' supplied by an unwinding roller 43'. Downstream of the upper roller and the lower roller, the polymeric sheets are detached from the strips concerned by means of the respective drive rollers 33 and 33' and to the winding rollers 47 and 47' connected to one end of said sheets. The resulting assembly is conveyed and stored on a winding roller 53.

[0130] The invention will now be described in light of the examples given below, given for illustrative and non-limiting purposes. Brief description of the figures

[0131] [Fig-1] is a diagram representing a mixer usable for implementing the method of the invention.

[0132] [Fig.2] is a diagram illustrating the strip formation step via the passage of the composition obtained at the end of step a) through a die.

[0133] [Fig.3] is a diagram illustrating the rolling step of the method of the invention.

[0134] [Fig.4] is a diagram illustrating the rolling step of the method of the invention with an additional specificity.

[0135] [Fig.5] is a diagram illustrating the co-rolling step of the method of the invention.

[0136] [Fig.6] is a diagram illustrating the co-rolling step of the process of the invention with an additional specificity.

[0137] [Fig.7] is a diagram illustrating a first variant of the implementation of the continuous method of the invention.

[0138] [Fig.8] is a diagram illustrating a second variant of the implementation of the continuous method of the invention.

[0139] [Fig.9] is a diagram illustrating a third variant of the implementation of the continuous method of the invention.

[0140] [Fig. 10] is a diagram illustrating a fourth variant of the implementation of the continuous method of the invention.

[0141] [Fig. 11] is a diagram illustrating the implementation of the continuous method of the invention for producing a bifacial electrode according to a first embodiment variant.

[0142] [Fig. 12] is a diagram illustrating the implementation of the continuous method of the invention for producing a bifacial electrode according to a first embodiment variant with an additional specificity.

[0143] [Fig. 13] is a diagram illustrating the implementation of the continuous method of the invention for producing a bifacial electrode according to a second embodiment variant.

[0144] [Fig. 14] is a diagram illustrating the implementation of a new form of the method of the invention.

[0145] [Fig. 15] is a diagram illustrating the implementation of this new form of the method of the invention for the continuous production of a bifacial electrode.

[0146] Detailed description of particular embodiments EXAMPLE 1

[0147] In the following example, the following ingredients are used: * Polymer-1: VDF-AA (0.9% by moles)-HFP (2.4% by moles) copolymer having an intrinsic viscosity of 0.28 L / g in dimethylformamide (DMF) at 25°C and a melting temperature of 148°C, VDF corresponding to vinylidene fluoride and AA corresponding to acrylic acid; *Polymer-2: VDF-HFP (2.5% by moles)-HEA (0.4% by moles) copolymer having an intrinsic viscosity of 0.117 L / g in DMF at 25°C and a melting temperature of 154.2°C, VDF corresponding to vinylidene fluoride and HFP corresponding to hexafluoropropene; * Polymer (Fl): VDF-AA (0.5% by moles)-HFP (6.5% by moles) copolymer having an intrinsic viscosity of 0.32 L / g in dimethylformamide (DMF) at 25°C and a melting temperature of 127°C, VDF corresponding to vinylidene fluoride and AA corresponding to acrylic acid; *Electronic Conductor (IEC): Super™ C65 carbon black marketed by IMERIS; *Electronic conductor (CE2): VGCF™-H carbon fibers marketed by SHOWA DENKO; *Graphite: 75% SMG-N-HE1 (Hitachi Chemical Co„ Ltd.) / 25% TIMREX™ SFG6; *NMC622 cathode material: HX12th marketed by UMICORE; *Liquid medium (Ll): ethylene carbonate (EC) / propylene carbonate (PC) (1:1) containing LiPF6 IM and 2% vinylene carbonate (VC); *TSPI: 3-(triethoxysilyl)propyl isocyanate; *DBTDL: dibutyltin dilaurate; and *TEOS: tetraethoxysilane Si(OC2H5)4.

[0148] Firstly, a negative electrode is prepared deposited on a current collector in accordance with the method of the invention.

[0149] To do this, the following components, in the proportions reported below, are introduced into a mixer with two co-rotating interpenetrating screws with a diameter of 24 mm from the manufacturer Thermofisher (reference TSE24): Graphite: mass proportion of 69.35%. Polymer (Fl): mass proportion of 3.65%. Liquid medium (Ll): mass proportion of 27%.

[0150] The mixing of the components is carried out at a temperature below 100°C with a screw rotation speed of 300 revolutions per minute and a total mass flow rate of 4.5 kg / h. A continuous strip is formed at the outlet of the mixer using a flat die with a 600 μm slot. Upon exiting the die, the continuous strip is passed between the rollers of a rolling mill from the manufacturer INGECAL, whose roller diameter is 150 mm, at 80°C and between a 23 μm thick HOSTAPHAN™ MK PET film fed by the upper roller and a copper current collector with a thickness 10 pm fed by the lower roller, the line speed being between 3.5 and 4.5 m / min and the gap between the rollers being set at 100 pm. The ionogel negative electrode thus produced has a final thickness of 115 pm and a total grammage of 19.2 mg / cm2 (including the electrolyte), which represents a surface capacity of 4.7 mAh / cm2.

[0151] In a second step, a positive electrode is prepared according to the following method. A solution of polymer-1 in acetone is prepared at 40°C and then cooled to room temperature. Then, 96.9% by mass proportion of NMC622, 2.1% by mass proportion of electronic conductor CEI and 1% by mass of electronic conductor CE2 were added to the solution of polymer-1 while respecting a mass proportion of 96 / 4 (active material + conductors / polymer-2). Subsequently, the liquid medium (Ll) is added to the mixture in a mass proportion [mLi / (mLi + mpoiymer l)] x 100 of 75.2%.

[0152] The mixture is then coated to a constant thickness on a 20 μm thick Al current collector using a comma bar type roll-to-roll coating machine. The solvent is then evaporated in-line at a temperature below 70°C, thus producing the ionogel positive electrode. The electrode is finally calendered to achieve a final thickness of 118 μm. The total grammage of the electrode is 28.4 mg / cm2 (including the electrolyte), which represents a surface capacity of 4.2 mAh / cm2.

[0153] In a third step, a membrane is prepared according to the following method. Polymer-2 (40 g) is dissolved in 275 g of acetone at 60°C, thus giving a solution containing 12.7% by mass of polymer-2. DBTDL (0.21 g) is added and the solution is homogenized at 60°C. TSPI (0.82 g) is then added. The amount of DBTDL is calculated to be in a molar proportion of 10% relative to TSPI. The amount of TSPI is itself calculated to be in a molar proportion of 0.55% relative to polymer-2. The solution is maintained at 60°C for 90 min while the isocyanate functional groups react with the hydroxyl groups of polymer-2.

[0154] Then, the liquid medium (Ll) is added to the solution in mass proportion [mLi / (mLi + m pOiymer-2)] x 100 of 80%. After homogenization at 60°C, formic acid is added followed by TEOS. The amount of TEOS is calculated by respecting the mass proportion (m(sio2) / m(pOiymer_2)) of 10%. The amount of formic acid is calculated from 1 equation. n(formicacid) / n(TEos) — 2.6.

[0155] All ingredients were introduced into the solution mixture under an argon atmosphere.

[0156] The mixture is then coated to a constant thickness onto a PET substrate using a comma bar type roll-to-roll coating machine. The solvent is then evaporated online at a temperature below 70°C, thus producing the membrane. The thickness of the membrane thus produced is 45 μm.

[0157] Finally, three flexible "Pouch Cell" type cells are prepared from the elements manufactured above. More specifically, three flexible cells are assembled using a negative ionogel electrode according to the invention of Example 1, characterized by a basis weight of 19.2 mg / cm2, i.e., a surface capacity of 4.7 mAh / cm2, a positive ionogel electrode characterized by a basis weight of 28.4 mg / cm2, i.e., a surface capacity of 4.2 mAh / cm2, and a membrane as described above.

[0158] The surface area of the negative ionogel electrode is 12.25 cm2 and that of the positive ionogel electrode is 10.24 cm2.

[0159] The discharge capacity values for these three cells were determined at different discharge rates. The results are reported in the table below, the three cells being named Cell 1, Cell 2, and Cell 3 respectively. [Tables 1] Cycling conditions Discharge capacity °C Regime Test number Cell 1 L ë l I il ? 6 2 Cell 3 22 C / 2O- D / 20 0 39.18 38.81 39.02 22 1 38.51 38.16 38.33 22 2 37.44 37.09 37.26 22 C / 10 - D / 10 37.11 36.79 36.73 22 4 35.41 35.36 34.93 22 5 35.11 35.17 34.65 22 6 34.87 35.06 34.45 22 7 34.57 34.88 34.16 22 C / 5- D / 5 3. 31.00 32.34 30.45 22 9: 30.71 32.23 30.19 22 10 30.42 32.14 30.00 22 11 30.0 7 32.00 29.73 22 12 29.79 31.92 29.43 22 C / 5-D / 2 13 24.45 28.68 24.31 22 14 24.43 28.74 w U 22 15 23.86 28.32 24.33 22 16 23.48 28.30 23.66 22 17 23.23 28.16 23.29 22 C / 5-D 18 9.94 14.41 8.93 22 19 9.79 14.50 8.60 22 20 9.71 14.50 8.58 22 21 9.56 14.53 8.52 22 22 8.68 14.30 8.49 22 C / 5-2D 23 5.04 2.65 22 24 2.75 4.96 2.79 22 25 2.73 4.96 2.81 22 26 2.71 4.98 2.84 22 27 2.73 5.00 2.87 22 Ç / 20- D / 20 28 34.23 35.20 34.37 22 29 34.14 35.18 34.03 22 30 33.97 35.09 33.66 22. 31 33.79 34.97 33.30 22 32 33.60 34.84 33.08 22 33 39.18 38.81 39.02 22 34 38.SI 38.16 38.33

[0160] It is clear from the above results that the cells are functioning correctly and the values ​​are repeatable. EXAMPLE 2

[0161] This example is a test aimed at optimizing the characteristics of the polymer sheets used as a function of the electrode and, in particular in terms of roughness and surface energy.

[0162] Indeed, in the context of the invention, in order to be able to remove, in an optimal manner, a polymeric sheet without detaching the electrode strip from its collector, the optimal characteristics of this polymeric sheet and, more particularly, of a polymeric sheet made of poly(ethylene terephthalate) were determined in this example.

[0163] Firstly, for a graphite-based electrode strip similar to that defined in Example 1 above, he tested different polyethylene terephthalate polymer sheets having different roughnesses, to determine, in an optimal manner, a range of roughnesses compatible with the rolling step and the co-rolling step. It emerges from these tests that sheets particularly compatible for these steps with a graphite-based electrode strip are sheets having a high average surface roughness (Ra) and, more specifically, between 0.01 pm and 1 pm and, more advantageously between 0.3 pm and 0.7 pm.

[0164] On the other hand, the polymeric sheets made of polyethylene terephthalate with low roughness (and, more particularly, less than 0.01 pm) tend to remain stuck to the graphite-based electrode strip, thus leaving, at the end of the process, the copper current collector separated from the electrode.

[0165] In a second step, with the high roughness sheets, tests were carried out to determine compatible surface energy ranges to allow simple removal of said sheets without causing detachment of the electrode strip from the current collector. It emerges from these tests that the surface energy of the polymeric sheet must advantageously be lower than the surface energy of the electrode strip and, preferably, must be lower than 40 mN / m.

[0166] Furthermore, it should be noted that the electrode strip must advantageously have a surface energy lower than that of the current collector, with which it is associated, in order to have optimal adhesion between them.

[0167] Therefore it can be deduced that advantageously, the surface energy of the polymeric film is lower than the surface energy of the electrode strip, which is lower than the surface energy of the current collector.

[0168] In a third step, with PET sheets of high roughness (around 0.30 pm) and surface energy lower than 40 mN / m (more precisely, 26.7), different thicknesses (respectively, 12, 19 and 125 pm) were tested and the impact of the latter on the adhesion and detachment properties of the sheets concerned. It appears that the polymeric sheet must be sufficiently thin to be able to be removed but it must also be thick enough to retain sufficient mechanical properties for the rolling step and the co-rolling step. Thus, it is deduced from these tests that a PET sheet can advantageously have a thickness ranging from 6 pm to 75 pm, preferably from 10 pm to 30 pm.

Claims

Claims

1. Method for manufacturing an assembly comprising a first planar electrode comprising a polymer matrix trapping an electrolyte and a current collector (37), said first electrode being deposited on one face of said current collector, said method comprising the following steps: a) a step of preparing a composition comprising the ingredients intended to enter into the constitution of the first electrode, said step consisting of an introduction and a mixing of the ingredients intended to enter into the constitution of the electrode in a mixer with two interpenetrating co-rotating screws (3, 5) rotating in a closed barrel (1), at a temperature below 100C; b) from the composition obtained in a), a step of forming a strip (19) by passing said composition through a die (17); c) a step of rolling the strip (19) obtained in b), by passing it between a first roller, called the upper roller (21), and a second roller, called the lower roller (25), a first polymeric sheet (23) being interposed between the first roller and the strip (19) and a second polymeric sheet (27) being interposed between the second roller and the strip (19), the first polymeric sheet (23) being separated from the strip (19) at the end of the rolling step while the second polymeric sheet (27) remains attached to the strip (19) thus rolled at the end of the rolling step, whereby the result is a laminated strip (19) coated on one face, called the lower face (31), with the second polymeric sheet (27) and the face of which opposite the lower face, called the upper face (29), is free; d) a step of co-rolling the laminated strip (19) obtained in c) with a current collector (37) by passing it between a first roller, called the upper roller (35), and a second roller, called the lower roller (39), the lower face (31) of the strip (19) being in contact with the second roller via the second polymeric sheet (27) and the upper face (29) being in contact with the first roller via the current collector (37) interposed between the first roller and the upper face (29), the second polymeric sheet (27) being optionally separated from the strip (19) at the end of the co-rolling step while the current collector (37) remains attached to the upper face (29) of the strip (19) thus co-laminated at the end of the co-laminated step, whereby the assembly comprising the first flat electrode and the current collector (37) results.

2. Manufacturing method according to claim 1, in which the composition comprises, as constituent ingredients of the electrode: - at least one active electrode material; - at least one polymer intended to enter into the constitution of the polymer matrix; - an electrolyte; - optionally at least one electronically conductive additive.

3. Manufacturing method according to claim 2, in which the polymer(s) are chosen from gelling polymers capable of gelling on contact with the electrolyte and thus trapping the electrolyte.

4. Manufacturing method according to claim 2 or 3, wherein the electrolyte is a liquid electrolyte comprising at least one organic solvent, at least one metal salt and optionally an additive belonging to the category of carbonate compounds.

5. A manufacturing method according to any one of claims 1 to 4, wherein the die (17) of step b) is a flat die.

6. A method according to any one of claims 1 to 5, wherein the first polymeric sheet (23) and the second polymeric sheet (27) are polyester sheets.

7. A method according to any one of claims 1 to 6, wherein the first polymeric sheet (23) and the second polymeric sheet (27) are sheets of polyethylene terephthalate or poly(ethylene naphthalate), preferably polyethylene terephthalate.

8. A method according to any one of claims 1 to 7, wherein the first polymeric sheet (23) and the second polymeric sheet (27) are of the same nature.

9. Method according to any one of claims 1 to 8, wherein the first polymeric sheet (23) and / or the second polymeric sheet (27) has(have) at least one rough face, in particular, the face intended to be in contact with the strip (19).

10. A method according to any one of claims 1 to 9, wherein the first polymeric sheet (23) and / or the second polymeric sheet (27) has an average surface roughness ranging from 0.01 pm to 1 pm, preferably ranging from 0.3 pm to 0.7 pm.

11. A method according to any one of claims 1 to 10, wherein the first polymeric sheet (23) and / or the second polymeric sheet (27) has a surface energy of less than 40 mN / m.

12. A method according to any one of claims 1 to 11, wherein the first polymeric sheet (23) and / or the second polymeric sheet (27) has a thickness ranging from 6 pm to 75 pm, preferably from 10 pm to 30 pm.

13. A method according to any one of claims 1 to 12, wherein the rolling step is carried out at a temperature ranging from 60°C to 120°C.

14. A method according to any one of claims 1 to 13, wherein the current collector (37) is in the form of a metal foil.

15. A method according to any one of claims 1 to 14, wherein the current collector (37) is in the form of a metal sheet, at least the face of which intended to be in contact with the strip (19) is subjected to a modification to improve the adhesion of the strip (19) to the current collector (37).

16. Method according to claim 15, in which the modification consists of a treatment leading to the formation of a layer of particles on the surface of the current collector (37) or a surface treatment chosen from ablation or corrosion.

17. A method according to any one of claims 1 to 16, which is a continuous method.

18. Method according to any one of claims 1 to 17, which is a method for preparing an assembly comprising a first planar electrode deposited on a first face of the current collector (37) and a second planar electrode deposited on a second face of the current collector, said second face being opposite the first face, whereby: - ​​for the aforementioned step d), the second polymeric sheet (27) is not dissociated from the strip (19); - after step d), a step e) of co-laminating the assembly resulting from step d) with another strip, called the second strip (65), comprising a polymeric matrix trapping an electrolyte, said second strip (65) being coated on its upper face with a polymeric sheet, called the third polymeric sheet (67), by passing said assembly and the second strip (65) between an upper roller (61) and a lower roller (63), the lower roller (63) being in contact with the second polymeric sheet (27) of the aforementioned assembly and, between the upper roller (61) and the current collector (37) of the assembly, is interposed the strip (65) coated on its upper face with a polymeric sheet, called third polymeric sheet (67), said third polymeric sheet (67) being in direct contact with the upper roller (61); - after step e), a step of dissociation of the second polymeric sheet (27) and a step of dissociation of the third polymeric sheet (67), whereby the assembly results in a first electrode deposited on a first face of the current collector (37) and a second electrode deposited on a second face of the current collector.

19. Method according to any one of claims 1 to 17, which is a method for preparing an assembly comprising a first planar electrode deposited on a first face of the current collector (37) and a second planar electrode deposited on a second face of the current collector, said second face being opposite the first face, in which, during step d), the upper face of the strip, called the first strip (19), is in contact with the first roller via the current collector itself in contact with the free face of another strip, called the second strip (19'), comprising a polymer matrix trapping an electrolyte, said second strip (19') being coated on another face with a polymer sheet, called the third polymer sheet.

20. A method of manufacturing an assembly comprising a first planar electrode comprising a polymer matrix trapping an electrolyte and a current collector (87), said method comprising the following steps: a) a step of preparing a composition comprising the ingredients intended to be part of the constitution of the first electrode, said step consisting of introducing and mixing the ingredients intended to be part of the constitution of the electrode in a mixer with two co-rotating interpenetrating screws rotating in a closed barrel, at a temperature below 100°C; b) from the composition obtained in a), a step of forming a strip (19) by passing said composition through a die; c') a step of co-rolling the strip (19) obtained in b), by passing

21.

22.

23. of the latter between a first roller, called upper roller (81), and a second roller, called lower roller (83), a polymeric sheet (85) having an average surface roughness ranging from 0.01 pm to 1 pm being interposed between the first roller and the strip (19) and a current collector (87) being interposed between the second roller and the strip (19) in order to avoid any direct contact between the rollers and the strip (19), the polymeric sheet (85) being dissociated from the strip (19) at the end of the co-rolling step while the current collector (87) remains attached to the strip (19) at the end of the co-rolling step, whereby the assembly comprising the first flat electrode and the current collector (87) results. Manufacturing method according to claim 20, wherein the die of step b) is a flat die. Method according to claim 20 or claim 21, which is a method of manufacturing an assembly comprising the first electrode deposited on a first face of the current collector (87) and a second electrode deposited on a second face opposite to said first face of said current collector, whereby step c') is a step of co-rolling the strip (19) obtained in b), by passing it between a first roller, called upper roller (81), and a second roller, called lower roller (83); a polymeric sheet (85) being interposed between the first roller and the strip, called first strip (19), which is in contact, via its lower face, with a current collector (87); and between the second roller and the strip (19) are interposed said current collector (87) in contact, via its lower face with another strip, called second strip (19'), the latter being in contact via its lower face with another polymeric sheet (85'), the polymeric sheet (85) being dissociated from the first strip (19) and the other polymeric sheet (85') being dissociated from the second strip (19') at the end of the co-lamination step, whereby the assembly results comprising the first electrode deposited on a first face of the current collector (87) and a second electrode deposited on a second face opposite said first face of said current collector. Method according to claim 22, wherein, before the co-rolling step, the second strip (19') is produced by a method comprising steps a) and b) as defined in claim 20.

Images