Classifications

• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M10/00—Secondary cells; Manufacture thereof
  • H01M10/05—Accumulators with non-aqueous electrolyte
  • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
  • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
  • H01M10/0565—Polymeric materials, e.g. gel-type or solid-type
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M10/00—Secondary cells; Manufacture thereof
  • H01M10/05—Accumulators with non-aqueous electrolyte
  • H01M10/052—Li-accumulators
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
  • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
  • H01M50/409—Separators, membranes or diaphragms characterised by the material
  • H01M50/411—Organic material
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
  • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
  • H01M50/409—Separators, membranes or diaphragms characterised by the material
  • H01M50/44—Fibrous material
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
  • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
  • H01M50/463—Separators, membranes or diaphragms characterised by their shape
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M2300/00—Electrolytes
  • H01M2300/0085—Immobilising or gelification of electrolyte
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M2300/00—Electrolytes
  • H01M2300/0088—Composites
  • H01M2300/0091—Composites in the form of mixtures
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
  • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
  • Y02E60/10—Energy storage using batteries

Definitions

• the present invention relates to a specific separator comprising an electrolyte and, more specifically, an electrolyte trapped in a polymer matrix and forming a gel therewith, this separator being intended to be incorporated into electrochemical accumulators.
• the general field of the invention can be defined as that of energy storage devices, in particular that of electrochemical accumulators.
• 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, by means of which there is production of electrons at the origin of the electric current and production of ions which will circulate from one electrode to another by through an electrolyte.
• accumulators operating on the principle of insertion-removal of a metallic element intervening at the level of the electrodes (and more specifically, of the active materials of the electrodes) and known by the terminology of metal accumulators -ion (for example, Li-ion, Na-ion, K-ion, Ca-ion, Mg-ion or Al-ion) have supplanted other types of accumulators, such as lead-acid accumulators, Ni accumulators -MH, in particular for their performance in terms of energy densities.
• metal accumulators -ion for example, Li-ion, Na-ion, K-ion, Ca-ion, Mg-ion or Al-ion
• metal-ion accumulators such as Li-ion accumulators, make it possible, in particular, to obtain specific and volume energy densities (which may be greater than 180 Wh.kg -1 ) clearly greater than those of Ni-MH and Ni-Cd accumulators (which may range from 50 and 100 Wh.kg 1 ) and Lead-acid (which can range from 30 to 35 Wh.kg 1 ).
• the reaction at the origin of the production of current involves the transfer, by means of an electrolyte conductive of metal ions, of metal cations coming from a negative electrode which come to be inserted in the acceptor network of the positive electrode, while electrons resulting from the reaction at the electrode negative will feed the external circuit, to which the positive and negative electrodes are connected.
• the negative electrode may include, as lithium insertion materials, a carbonaceous material, such as graphite, a silicon-based compound, such as a silicon carbide SiC, a silicon-based composite, or an oxide of silicon. silicon, a lithiated titanium oxide, such as LUTiOsO ⁇ or 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.
• a carbonaceous material such as graphite
• a silicon-based compound such as a silicon carbide SiC, a silicon-based composite, or an oxide of silicon.
• silicon a lithiated titanium oxide, such as LUTiOsO ⁇ or a lithium-germanium alloy
• a mixture of several of these lithium insertion materials such as a mixture comprising graphite and a silicon-based compound.
• This electrolyte can be in liquid form and comprises, conventionally, one or more organic solvents (for example, a mixture of carbonate solvents), in which is (are) dissolved one or more metal salts (for example, one or more salts lithium, when the accumulator is a lithium-ion accumulator).
• organic solvents for example, a mixture of carbonate solvents
• metal salts for example, one or more salts lithium, when the accumulator is a lithium-ion accumulator.
• 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.
• an alternative consists of dispensing with the use of a liquid electrolyte by replacing it, for example, with the following solutions:
• a glass or a ceramic conductive of lithium ions 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 material composite comprising a polymeric matrix, for example, of polyvinylidene fluoride, and a filler made of a lithiated oxide, such as LbLasZ ⁇ O ⁇ ; a solid dry polymer electrolyte composed of a polymer of the polyethylene oxide (POE) type and of a lithium salt, for example, lithium trifluorosulfonylimide (LiTFSI).
• CVD chemical vapor deposition
• LiTFSI lithium trifluorosulfonylimide
• gelled electrolytes in which a liquid electrolyte is confined within a membrane conventionally formed of a or more polymers capable of gelling on contact with this liquid electrolyte. More specifically, these gelled electrolytes comprise a polymer matrix (in which case they can be qualified as gelled polymer electrolytes), a liquid phase and an ion-conducting salt (for example, a lithium salt, when the accumulator is an accumulator. lithium) and, optionally, one or more fillers, which may be inorganic.
• ion-conducting salt for example, a lithium salt, when the accumulator is an accumulator. lithium
• fillers which may be inorganic.
• polyvinylidene fluoride known by the abbreviation PVDF
• PVDF-HFP polyvinylidene fluoride
• PAN polyacrylonitrile
• PMMA poly (methyl methacrylate)
• the gelled polymer electrolytes generally exhibit an ionic conductivity of the order of 10 3 S. cm -1 , which represents approximately ten times the conductivity of a dry ionic polymer electrolyte.
• the mechanical properties are low, which makes them difficult to handle, especially during the manufacture of accumulators comprising them, in particular, in particular during the assembly step which consists of stacking and winding, according to the desired final format of the cell, the gelled polymer electrolyte with the positive electrode and the negative electrode, the gelled polymer electrolyte being interposed between two electrodes.
• One solution proposed for improving the mechanical properties of gelled polymer electrolytes may be to incorporate therein inorganic fillers, such as S1O2, T1O2, AI2O3 or else cellulosic fibers, these gelled polymer electrodes being however difficult to manufacture.
• inorganic fillers such as S1O2, T1O2, AI2O3 or else cellulosic fibers, these gelled polymer electrodes being however difficult to manufacture.
• the invention relates to a separator for an electrochemical accumulator comprising a substrate provided with cavities, said substrate consisting of one or more polymers, at least one of which is a polymer of the family of polyaryletherketones, all or part of said cavities being filled in whole or in part with a gelled polymer electrolyte.
• separator means an element or interface intended to ensure, in this context, the separation between a positive electrode and a negative electrode, this element or interface comprising, in addition, the electrolyte.
• electrochemical accumulator means a system which generates and / or stores energy based on a technique of reversible conversion of electrochemical energy, this type of system including primary batteries (corresponding to non-rechargeable batteries for single use ) or secondary batteries (corresponding to rechargeable batteries). Thanks to the presence of these specific substrates, the separators of the invention exhibit:
• these substrates being chemically inert with respect to the constituents conventionally used in electrochemical accumulators and in particular with respect to gelled polymer electrolytes, which allows stability over time of the mechanical and physical properties .
• the substrate is a substrate provided with cavities, said substrate consisting of one or more polymers, at least one of which is a polymer of the polyaryletherketone family.
• the substrate consists only of one or more polymers of the family of polyaryletherketones and, even more specifically, of a single polymer of the family of polyaryletherketones.
• polyaryletherketones comprise, in their backbone, aromatic groups, such as phenylene groups, linked together by oxygen atoms and aromatic groups, such as phenylene groups, linked together by carbonyl groups -CO-. .
• a polyaryletherketone can also be defined as a polymer comprising repeating units, of which more than 50% by moles of said repeating units are repeating units comprising a group of formula -Ar-C (0) -Ar'-, in which Ar and Ar ', identical or different from each other, are aromatic groups, these units being referred to below as units (RPAEK).
• the units (RPAEK) are chosen from the group consisting of the units of formulas (JA) to (JO) below:
• each R ' is chosen from the group consisting of halogen atoms, alkyl, alkylvinyl, alkenyl, alkynyl, aryl, ethers, thioethers, carboxylic acids, esters, amides, imides, sulfonates, phosphonates , alkali metal or alkaline earth metal alkylphosphonates, amines and quaternary ammonium;
• -j ' is zero or is an integer ranging from 1 to 4.
• the corresponding phenylene groups may have 1,2-, 1,4- or 1,3 bonds with groups other than the R 'substituents in the unit.
• these groups phenylenes have a 1,3- or 1,4- bond, and more preferably they have a 1,4- bond.
• j ' is preferably equal to zero, which means that the phenylene groups do not have any other substituents than those which allow bonding in the main chain of the polymer.
• repeating units are chosen from those of formulas (J'-A) to (J'-O) below:
• repeating units RPAEK
• RPAEK repeating units
• repeating units of the polyaryletherketone are repeating units (RPAEK), as described above. Defects in the polymer chain, or very limited amounts of other units could be present, provided that these do not substantially alter the properties of the polyaryletherketone concerned.
• the polyaryletherketone can in particular be a homopolymer or a random, alternating or block copolymer.
• the polyaryletherketone may in particular contain: - (i) repeating units (RPAEK) of at least two different formulas chosen from formulas (JA) to (JO); or (ii) repeating units (R PAEK ) according to one or more of formulas (JA) to (JO) and repeating units (R * PAEK ) different from the units (R PAEK ), described above.
• the polyaryletherketone can be a polyetheretherketone [polymer (PEEK), below].
• the polyaryletherketone may be a polyetherketoneketone [polymer (PEKK), below], a polyetherketone [polymer (PEK), below], a polyetheretherketoneketone [polymer (PEEKK), below], or a polyetherketoneetherketonketone polymer (PEKEKK), below].
• the polyaryletherketone can also be a mixture composed of at least two different polyaryletherketones, which are preferably chosen from the group consisting of a polymer (PEKK), a polymer (PEEK), a polymer (PEK), a polymer (PEEKK) ) and a polymer (PEKEKK), as defined below.
• PEKK polymer
• PEEK polymer
• PEK polymer
• PEEKK polymer
• PEKEKK polymer
• polymer PEEK
• PEEK polymer of which more than 50%, preferably more than 75%, even more preferably more than 85% and even more preferably more than 99% in moles of the repeating units are units (R PAEK ) of formula J'-A as defined above.
• R PAEK units of formula J'-A as defined above.
• the more preferred polymer (PEEK) is that in which all the repeating units are repeating units of formula (J'-A) as defined above.
• polymer in the context of the present invention, is used to denote any polymer of which more than 50%, preferably more than 75%, even more preferably more than 85% and even more preferably more than 99% in moles of the repeating units are units (R PAEK ) of formula J'-B as defined above.
• the more preferred polymer (PEKK) is that in which all the repeating units are repeating units of formula (J'-B) as defined above.
• polymer (PEK) is used to denote any polymer of which more than 50%, preferably more than 75%, even more preferably more than 85% and even more preferably more than 99% in moles of the repeating units are units (RPAEK) of formula (J'-C) as defined above.
• the more preferred polymer (PEK) is that in which all the repeating units are repeating units of formula (J'-C) as defined above.
• polymer PEEKK
• PEEKK polymer of which more than 50%, preferably more than 75%, even more preferably more than 85% and even more preferably more than 99% in moles of the repeating units are units (RPAEK) of formula (J'-M) as defined above.
• the more preferred polymer (PEEKK) is that in which all the repeating units are repeating units of formula (J'-M) as defined above.
• polymer PEEKK
• PEKEKK "is used to denote any polymer of which more than 50%, preferably more than 75%, even more preferably more than 85% and still more preferably more than 99% by moles of the repeating units are (RPAEK) units of formula (J'-L) as defined above
• the most preferred polymer (PEKEKK) is one in which all the repeating units are repeating units of formula (J'-L) as defined above.
• the polyaryletherketone is a homopolymer (PEEK), namely a polymer in which essentially all the repeating units are units of formula (J'-A), and in which defects of the polymer chain and / or very limited amounts ( ⁇ 1 mol% relative to all the units) of other units could be present, without the latter being able to significantly modify the properties of this homopolymer (PEEK).
• PEEK polyaryletherketone
• Examples of commercially available polyaryletherketone include notably polyetheretherketone KetaSpire ® available from Solvay Specialty Polymers USA, LLC.
• the substrate comprises (or even consists of) a polyetheretherketone (known by the abbreviation PEEK), this type of polymer having the particularity of exhibiting excellent tensile strength (of the order of 100 N / mm 2 measured according to DIN 53455) and lends itself to shaping as an open structure to accommodate the gelled polymer electrolyte.
• PEEK polyetheretherketone
• the substrate is not an ionic conductor.
• the substrate preferably has a porosity of at least
• porosity is used to denote the volumetric fraction of cavities relative to the total volume of the substrate.
• the porosity is determined by knowing the experimental density of the substrate and the density of the constituent polymer of the substrate and by the following relationship:
• the substrate can be in the form of a grid resulting from an interlacing of polymer strands, the grid being able to present a mesh square, circular, hexagonal, rhombic or any other shape.
• the substrate is in the form of a grid having a diamond-shaped mesh, each diamond possibly having a large diagonal ranging from 0.5 mm to 3 mm, preferably from 1 mm to 2 mm.
• FIG. 1 A photograph of a diamond-shaped mesh grid which can be used for the separators of the invention is illustrated in FIG. 1 attached in the appendix.
• the polymeric strands can have a square, rectangular, circular, diamond-shaped, hexagonal or any other shape with a preference for the polymeric strands with a rectangular cross-section.
• the strands preferably have a cross section of non-circular shape and a dimension ratio between the main axis of the cross section and the secondary axis of the cross section of between 1.5 and 15, in particular between 2 and 10.
• the major axis of the cross section has a length ranging from 0.1mm to 1mm, preferably 0.1mm to 0.3mm; and / or the secondary axis of the cross section has a length ranging from 20 ⁇ m to 60 ⁇ m, preferably 20 ⁇ m to 40 ⁇ m.
• All or part of the cavities of the substrate are filled in whole or in part with the gelled polymer electrolyte, the gelled polymer electrolyte being able, in addition, to occupy all or part of the surface of the substrate in the form of a layer.
• the gelled polymer electrolyte can be any type of gelled polymer electrolyte with or without an organic part, as described in WO 2017/220312 and, preferably, the gelled polymer electrolyte can comprise:
• (A1) an organic part comprising (or consisting of) at least one fluoropolymer (F) comprising at least one repeating unit resulting from the polymerization of a fluorinated monomer and at least one repeating unit resulting from the polymerization of a monomer comprising at least one hydroxyl group, optionally in the form of a salt; and
• A-2) an inorganic part formed, in whole or in part, of one or more oxides of at least one element M chosen from Si, Ti and Zr and combinations thereof;
• repeating unit (s) resulting from the polymerization of a fluorinated monomer and the repeating unit (s) resulting from the polymerization of a monomer comprising at least one hydroxyl 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 hydroxyl group (s), optionally in the form of a salt .
• the repeating unit (s) resulting from the polymerization of a fluorinated monomer can be, more specifically, one or more repeating units resulting from the polymerization of one or more ethylenic monomers comprising at least one atom of fluorine and optionally one or more other halogen atoms, examples of monomers of this type being the following:
• perfluoroolefins such as tetrafluoroethylene, hexafluoropropene (also known by the abbreviation HFP);
• C 2 -C 8 fluoroolefins such as vinylidene fluoride, vinyl fluoride, 1,2-difluoroethylene and trifluoroethylene;
• -perfluoroalkylethylenes of formula CH 2 CHR 1 , in which R 1 is a C 1 -C 6 perfluoroalkyl group;
• fluoroolefins comprising one or more other halogen atoms (such as chlorine, bromine, iodine), such as chlorotrifluoroethylene;
• the fluoropolymer (F) can comprise, as repeating units resulting from the polymerization of a fluorinated monomer, a repeating unit resulting from the polymerization of a monomer from the category of C 2 -C 8 perfluoroolefins, such as hexafluoropropene and a repeating unit resulting from the polymerization of a monomer from the category of hydrogenated C 2 -C 8 fluoroolefins, such as vinylidene fluoride.
• the repeating unit (s) resulting from the polymerization of a monomer comprising at least one hydroxyl group, optionally in the form of a salt can be, more specifically, one or more repeating units.
• a monomer of formula (I) below in which R 9 to R 11 represent, independently of one another, a hydrogen atom or a C 1 -C 3 alkyl group and R 12 is a C 1 -C 5 hydrocarbon group comprising at least one hydroxyl group, examples of such monomers being hydroxyethyl (meth) acrylate monomers, hydroxypropyl (meth) acrylate monomers.
• the fluoropolymer (F) can comprise, as repeating unit resulting from the polymerization of a monomer comprising at least one hydroxyl group, a repeating unit resulting from the polymerization of one of the monomers of formulas (II) to ( IV) following: and, preferably a repeating unit resulting from the polymerization of the monomer of above-mentioned formula (II), this monomer corresponding to 2-hydroxyethyl acrylate (also known by the abbreviation HEA).
• HEA 2-hydroxyethyl acrylate
• fluoropolymers (F) which can be used in the context of the invention to form the gelled polymer electrolyte can be polymers comprising, as repeating units resulting from the polymerization of a fluorinated monomer, a repeating unit resulting from the polymerization.
• C 2 -C 8 preferably vinylidene fluoride; -from 0.1 to 15 mol% of a C2-C8 perfluoroolefin, preferably hexafluoropropene; and
• the inorganic part formed, at least in part, of one or more oxides of at least one element M chosen from Si, Ti and Zr and the combinations thereof is, in whole or in part, chemically bonded to the organic part via hydroxyl groups.
• Gelled polymer electrolytes comprising a matrix, in which the organic part is chemically bonded to the inorganic part, as described above, are found in particular described in document WO 2013/072216.
• the liquid electrolyte trapped within the matrix is, conventionally, an ion-conducting electrolyte, which may comprise (or even consists of) at least one organic solvent, at least one metal salt and optionally a compound of the family of compounds. vinyls.
• the organic solvent (s) can be carbonate solvents and, more specifically:
• -cyclic carbonate solvents such as ethylene carbonate (symbolized by the abbreviation EC), propylene carbon (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 of these.
• DEC diethyl carbonate
• DMC dimethyl carbonate
• EMC ethylmethyl carbonate
• the organic solvent (s) can 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).
• ester solvents such as ethyl propionate, n-propyl propionate
• nitrile solvents such as acetonitrile
• ether solvents such as dimethyl ether, 1,2-dimethoxyethane
• the organic solvent (s) can also be ionic liquids, that is to say, conventionally, compounds formed by the combination of a cation and an anion, which is in the liquid state at temperatures below 100 ° C at atmospheric pressure.
• ionic liquids can include:
• a cation chosen from imidazolium, pyridinium, pyrrolidinium and piperidinium cations, said cations being optionally substituted with at least one alkyl group comprising from 1 to 30 carbon atoms;
• an anion chosen from halide anions, perfluorinated anions, imidazole anions, imide anions, phosphate anions and borate anions.
• the cation can be chosen from the following cations:
• the positively charged cation can be chosen from the following cations:
• the negatively charged anion can be chosen from: -4,5-dicyano-2- (trifluoromethyl) imidazole (known by the abbreviation TDI);
• a specific ionic liquid which can be used according to the invention can be an ionic liquid composed of a cation of formula (VI-A) as defined above and an anion of formula (SC ⁇ CFs N, PF 6 or BF 4 .
• the metal salt (s) can be chosen from the salts of the following formulas: Mel, Me (PFe) n , Me (BF4) n, Me (CI04) n, Me (bis (oxalato) borate) n (which may be designated by l 'abbreviation Me (BOB) n ), MeCF3S03, Me [N (FS02) 2] n, Me [N (CF 3 S0) 2] n, Me [N (CF 5 S02) 2] n, Me [N (CF 3 S02) (RFSC> 2)] n, where R F is -C 2 F 5 , -C 4 F 9 or -CF3OCF2CF3, Me (AsF 6 ) n , Me [C (CF 3 SC> 2) 3] n, Me 2 S n , Me (CeF3N4) (C6F3N4 corresponding to 4,5-dicyano-2- (trifluoromethyl) imidazole and, when Me is Li, the
• LiTDI lithium (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 a 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 Me (typically, 1, 2 or 3).
• Me is a metallic element and, preferably, a metallic transition element, an alkali
• the salt is preferably LÎPF 6 -
• concentration of the metal salt in the liquid electrolyte is preferably at least 0.01 M, preferably at least 0.025 M, and most preferably further, at least 0.05 M and, advantageously, at most 5 M, preferably at most 2 M and, more preferably, at most, IM.
• the liquid electrolyte may comprise an additive belonging to the category of vinyl 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, these specific additives possibly being included in the electrolyte at a content not exceeding, respectively, 5% by mass and 10% by mass of the total mass of the electrolyte.
• an additive belonging to the category of vinyl 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, these specific additives possibly being included in the electrolyte at a content not exceeding, respectively, 5% by mass and 10% by mass of the total mass of the electrolyte.
• a liquid electrolyte that can be used in the separators of the invention, in particular when it is a lithium-ion accumulator, is an electrolyte comprising a mixture of carbonate solvents (for example, a mixture of cyclic carbonate solvents, such as a mixture of ethylene carbonate and propylene carbonate and present, for example, in identical volume or a mixture of cyclic carbonate solvents and linear carbonate solvent (s), such as a mixture ethylene carbonate, propylene carbonate and dimethyl carbonate), a lithium salt, for example, LÎPF 6 (for example, at a concentration of 1M) and optionally an additive, such as vinylene carbonate (for example).
• a mixture of carbonate solvents for example, a mixture of cyclic carbonate solvents, such as a mixture of ethylene carbonate and propylene carbonate and present, for example, in identical volume or a mixture of cyclic carbonate solvents and linear carbonate solvent (s), such as a mixture ethylene carbonate, prop
• the separators of the invention are intended to be incorporated into electrochemical accumulators and, more specifically, to ensure physical separation and ionic conduction within an electrochemical accumulator cell between a positive electrode and a negative electrode.
• the invention also relates to an electrochemical cell for an electrochemical accumulator comprising a positive electrode, a negative electrode and a separator in accordance with the invention which is interposed between the positive electrode and the negative electrode.
• positive electrode is meant, conventionally, in what precedes and what follows, the electrode which acts as cathode, when the accumulator delivers current (that is to say when it is in the process of discharging ) and which acts as anode when the battery is charging.
• negative electrode is meant, conventionally, in what precedes and what follows, the electrode which acts as anode, when the accumulator delivers current (that is to say when it is in the process of discharge) and which acts as a cathode, when the accumulator is in the process of charging.
• Each of the electrodes conventionally comprises an active electrode material, namely a material capable of inserting and deinserting, in its structure, metal ions, such as alkali ions (for example, lithium ions, when the battery 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 l (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).
• alkali ions for example, lithium ions, when the battery 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 l (accumulator is a magnesium accumul
• chalcogenides of spinel structure such as LiMn2O4;
• MiM2 (J04) f Ei- f , in which Mi is lithium, which may be partially substituted by another alkaline element at a rate of substitution of less than 20%
• M2 is a transition metallic element of oxidation degree +2 selected from Fe, Mn, Ni and combinations thereof, which may be partially substituted by one or more other additional metallic elements of oxidation degree (s) (s) between +1 and +5 up to a substitution rate of less than 35%
• JO 4 is an oxyanion in which J is chosen from P, S, V, Si, Nb, Mo and combinations of those -ci
• E is a fluoride, hydroxide or chloride anion
• f is the molar fraction of the OJ 4 oxyanion and is generally between 0.75 and 1 (including 0.75 and 1).
• the lithiated or partially lithiated materials can be phosphorus-based (meaning, in other words, that the oxyanion has the formula PO4) and can have an ordered or modified olivine-like structure.
• the lithiated or partially lithiated materials can correspond to the specific formula Li3- x M ' y M''2-y (J04) 3, in which 0 ⁇ x ⁇ 3, 0 ⁇ y ⁇ 2, M' and M '' represent identical or different metallic elements, at least one of M 'and M "being a transition metallic element, JO4 is preferably PO4, which can be partially substituted by another oxyanion with J being chosen from S, V , Si, Nb, Mo and combinations thereof.
• the lithiated or partially lithiated materials can have the formula Li (Fe x Mni- x ) P04, in which 0 ⁇ x £ 1 and, preferably, x is equal to 1 (which means, in other words, that the corresponding material is LiFeP04).
• active electrode materials likely to enter 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);
• Carbonaceous materials comprising silicon Si or an oxide of silicon SiOx, such as graphitic carbon / C-Si silicon or graphitic carbon / C- SiOx silicon oxide, the graphitic carbon itself possibly being a mixture of one or more carbons capable of intercalating 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) M x Ti 5 0i 2 or Ü4MyTi (5-y) Oi2 in which x and y range from 0 to 0.2, M represents a element chosen from Na, K, Mg, Nb, Al, Ni, Co, Zr, Cr, Mn, Fe, Cu, Zn, Si and Mo, a specific example being LUTisO ⁇ , these oxides being lithium insertion materials exhibiting a low level of physical expansion after inserting lithium;
• M y Ti ( 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;
• the positive electrode or the negative electrode it can comprise electronic conductive additives, that is to say additives capable of giving the electrode, in which they are incorporated, a conductivity.
• electronic these additives possibly being, for example, carbonaceous materials such as carbon black, carbon nanotubes, carbon fibers (in particular, carbon fibers obtained in the vapor phase known by the abbreviation VGCF), graphite in powder form, graphite fibers and mixtures thereof.
• a negative electrode comprises, as active material, carbonaceous materials, such as graphite
• the negative electrode may advantageously be devoid of electronically conductive additive (s).
• the positive electrode and the negative electrode may comprise, in addition to the aforementioned ingredients, a liquid electrolyte trapped or confined within a polymer matrix, which liquid electrolyte advantageously meets the same specific characteristics as those set out above in subject of the separator, in terms of ingredients (organic solvents, salts, concentrations, etc.), such electrodes thus constituting gel electrodes.
• a liquid electrolyte trapped or confined within a polymer matrix
• which liquid electrolyte advantageously meets the same specific characteristics as those set out above in subject of the separator, in terms of ingredients (organic solvents, salts, concentrations, etc.), such electrodes thus constituting gel electrodes.
• ingredients organic solvents, salts, concentrations, etc.
• the polymeric matrix may be made of at least one gelling polymer (FF), the gelling polymer (s) (FF) being chosen (s) from fluoropolymers comprising at least one repeating unit resulting from the polymerization of a fluorinated monomer and, of 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.
• FF gelling polymer
• FF gelling polymer
• 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 include any carboxylic acid group (s), optionally in the form of a salt.
• the repeating unit or units resulting from the polymerization of a fluorinated monomer can be, more specifically, one or more repeating units resulting from the polymerization of one or more ethylenic monomers comprising at least one atom of fluorine 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);
• -C2-C8 hydrogenated fluoroolefins such as vinylidene fluoride, vinyl fluoride, 1,2-difluoroethylene and trifluoroethylene
• -perfluoroalkylethylenes of formula CH 2 CHR 1 , in which R 1 is a C 1 -C 6 perfluoroalkyl group;
• fluoroolefins comprising one or more other halogen atoms (such as chlorine, bromine, iodine), such as chlorotrifluoroethylene;
• CF 2 CFOR 2 , in which R 2 is a C 1 -C 6 fluoro- or perfluoroalkyl group, such as CF 3 , C 2 F 5 , C3F7;
• the gelling polymer (s) (FF) can comprise, as repeating unit (s) resulting from the polymerization of a fluorinated monomer, a repeating unit resulting from the polymerization of a monomer of the category C 2 -C 8 perfluoroolefins, such as hexafluoropropene and a repeating unit resulting from the polymerization of a monomer from the category of hydrogenated C 2 -C 8 fluoroolefins, such as vinylidene fluoride.
• 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 can be, more specifically, one or more repeating units resulting from the polymerization of a monomer of formula ( VIII) following: wherein R 5 to R 7 represent, independently of each other, a hydrogen atom or a C 1 -C 3 alkyl group and R 8 represents a hydrogen atom or a monovalent cation (for example, an alkali cation, an ammonium cation), particular examples of monomers of this type being acrylic acid or methacrylic acid.
• Particular gelling polymers which can be used in the context of the invention can 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 optionally 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).
• 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 optionally 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).
• gelling polymers (FF) which can be used as polymer matrix of the electrodes are gelling polymers, the aforementioned repeating units of which are obtained from the polymerization:
• the gelling polymer (s) (FF) advantageously exhibit an intrinsic viscosity measured at 25 ° C. in N, N-dimethylformamide ranging from 0.1 to 1.0 L / g, preferably from 0.25 at 0.45 L / g.
• the intrinsic viscosity is determined by the equation below based on the duration of fall, 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: in which :
• -h G corresponds to the relative viscosity, that is to say the ratio between the duration of the fall of the solution and the duration of the fall of the solvent;
• - q S p corresponds to the specific viscosity, that is to say h G - 1;
• the constituent ingredients of the positive electrode and the negative electrode may be the same.
• Each electrode can also be associated with a current collector.
• the current collectors conventionally used in industry and in research laboratories in the field of lithium-ion batteries are metallic. Generally the collectors used are in aluminum for the positive electrodes and for the negative electrode based on lithiated titanium oxides such as LUTisO ⁇ , and in copper, nickel-plated copper, nickel or stainless steel for the negative electrodes based on graphite, silicon or silicon oxide, and mixtures thereof.
• Current collectors can also be carbon-based such as woven or non-woven carbon fibers, carpets or felts based on carbon or carbon derivatives such as, for example, carbon nanotubes. These carbon based current collectors can be used at positive electrode and negative electrode.
• the current collectors can optionally be composites based on a polymer of thermoplastic or thermosetting type, on which a metallization is carried out or a metal layer is deposited, to make it conductive of electrons.
• the cells of the invention can be used alone to thus form a single-cell accumulator or be used with several to form an accumulator with several cells.
• the invention thus also relates to an electrochemical accumulator comprising at least one electrochemical cell as defined above.
• the accumulator may include packaging intended, as its name suggests, to package the various constituent elements of the accumulator.
• This packaging may be flexible (in which case it is, for example, made from a laminated film comprising a frame in the form of aluminum foil which is coated on its outer surface with a layer of polyethylene terephthalate ( PET) or a polyamide and which is coated on its inner surface with a layer of polypropylene (PP) or polyethylene (PE)) or else rigid (in which case it is, for example, in a light and inexpensive metal such stainless steel, aluminum or titanium, or a thermoset resin such as an epoxy resin) depending on the type of application targeted.
• PET polyethylene terephthalate
• PE polyethylene
• rigid in which case it is, for example, in a light and inexpensive metal such stainless steel, aluminum or titanium, or a thermoset resin such as an epoxy resin
• the accumulators of the invention can be prepared by a method comprising a step of assembling the various basic elements, which are, for each cell, the separator, the positive electrode and the negative electrode.
• the various basic elements can be prepared beforehand before assembly, in particular as regards the separator, the specific method of which is an object of the invention, which method comprises: a step of depositing in all or part of the cavities of the substrate as defined above of a gelled polymer electrolyte composition;
• the gelled polymer electrolyte composition can be prepared prior to the deposition step.
• the gelled polymer electrolyte comprises a matrix comprising:
• an organic part comprising (or consisting of) at least one fluoropolymer (F) comprising at least one repeating unit resulting from the polymerization of a fluorinated monomer and at least one repeating unit resulting from the polymerization of a monomer comprising at least a hydroxyl group, optionally in the form of a salt; and
• the gel polymer electrolyte further comprising a liquid electrolyte confined or trapped within the matrix, the preparation of the gel polymer electrolyte composition comprises the following steps:
• organometallic compound M1 of the following formula:
• the compound M1 can correspond to the following formula:
• C NR A -A- (OR b ) 3 in which A is a metallic element selected from Si, Ti, Zr and combinations thereof, R A is a hydrocarbon group, linear or branched, comprising from 1 with 12 carbon atoms and the R B's , identical or different, are hydrocarbon groups, more specifically, alkyl groups, linear or branched and comprising from 1 to 5 carbon atoms (for example, methyl or ethyl groups).
• Examples compound Ml include the triméthoxysilylméthylisocyanate the triéthoxysilylméthylisocyanate the triméthoxysilyléthylisocyanate the triéthoxysilyléthylisocyanate, triméthoxysilylpropylisocyanate the triéthoxysilylpropylisocyanate the triméthoxysilylbutylisocyanate the triéthoxysilylbutylisocyanate the triméthoxysilylpentylisocyanate the triéthoxysilylpentylisocyanate the triméthoxysilylhexylisocyanate the triéthoxysilylhexylisocyanate.
• the hydrolyzable group for compound M2 is preferably chosen so as to allow the formation of an -OA- bond, this group possibly being chosen from atoms d halogen (preferably chlorine), alkoxy groups, acyloxy groups and hydroxyl groups.
• reaction step (ii) is carried out, generally, at a temperature ranging from 20 to 100 ° C, preferably from 20 to 90 ° C and more preferably from 20 to 60 ° C and, preferably, under inert gas atmosphere (such as argon flow).
• This reaction step (ii) and the subsequent step (iii) can be carried out in the presence of a condensation catalyst, which can be introduced during step (i).
• the condensation catalyst can be an organotin compound. It can be introduced, during step (i), in an amount of 0.1% to 50% by moles, preferably from 1 to 25% by moles, more preferably from 5 to 15% by moles relative to to the total number of moles of compound M1 and, where appropriate, of compound M2.
• organotin compounds mention may be made of dibutyltin dilaurate, dibutyltin oxide, tributyltin oxide, dioctyltin oxide, tributyltin chloride and tributyltin fluoride.
• the hydrolysis-condensation step (iii) can be carried out at ambient temperature or by heating to a temperature below 100 ° C., the choice of temperature being dependent on the boiling point of the liquid electrolyte.
• This hydrolysis-condensation step can be carried out in the presence of an acid catalyst, which can be added during one of steps (i) to (iii), for example, in an amount of 0.5 to 10% by weight, preferably 1 to 5% by weight on the total basis of the composition.
• an acid catalyst which can be added during one of steps (i) to (iii), for example, in an amount of 0.5 to 10% by weight, preferably 1 to 5% by weight on the total basis of the composition.
• This acid catalyst can in particular be an organic acid, such as formic acid.
• the step of depositing the gelled polymer electrolyte composition on the substrate can be carried out by any compatible deposition techniques.
• the deposition of gelled material and, advantageously, according to a die coating technique or by extrusion slot (corresponding to the English terminology of "slot die coating"), the die or dies used may be in the form of distribution slots .
• the deposition step can be carried out on both sides of the grid and, more specifically, by the die coating technique and, more particularly, according to a continuous in-line process. Concretely, in this scenario and as illustrated in FIG.
• the substrate in the form of a grid (referenced 1) is placed between a pair of drive rollers (referenced 3 and 5), the substrate during scrolling being in contact via its first face (referenced 7) with a first die (referenced 9) delivering the composition of gelled polymer electrolyte and a second die (referenced 11) delivering the composition of polymer electrolyte gelled on a second face (referenced 13 ) opposite to the first face.
• the composition thus deposited continuously on the two faces will penetrate, by gravity and capillarity, inside the mesh of the grid.
• the positive and negative electrodes when they are gelled electrodes, can be produced by depositing a composition comprising the constituent ingredients of the electrodes (gelling polymer (FF), active material, liquid electrolyte and optionally at least one electronically conductive additive such as as defined above) on a current collector type substrate by a die coating technique or by an extrusion slot (corresponding to the English terminology of "slot die coating"), the die or dies used may be in the form of distribution slots, or through printing or casting technique, followed by drying when necessary.
• FF gelling polymer
• active material active material
• liquid electrolyte liquid electrolyte
• optionally at least one electronically conductive additive such as as defined above
• the positive and negative electrodes can be prepared by a process comprising the following steps: (i) providing a current collector type substrate;
• FF gelling polymer
• the electrode active material is a positive electrode active material, when the method relates to the preparation of a positive electrode or is a negative electrode active material, when the process relates to the preparation of a negative electrode;
• step (iii) the application of the composition of step (ii) on the current collector type substrate of step (i), whereby an assembly results comprising the substrate coated with at least one layer of said composition ;
• the composition can be applied to a collecting substrate type by all types of application methods, for example, by casting, printing, coating, for example, by roller or by coating by die.
• Step (iii) can typically be repeated one or more times, depending on the desired electrode thickness.
• step (iv) is preferably carried out online at a temperature which may, for example, range from 40 ° C to 60 ° C.
• the ingredients of the composition can correspond to the same variations as those already defined for these same ingredients in the context of the description of the electrodes as such.
• composition advantageously comprises an organic solvent chosen so as to allow the solubilization of the gelling polymer (s) (FF), this organic solvent possibly being that of the liquid electrolyte or being able to be added in addition to the other ingredients. mentioned above.
• the positive and negative electrodes of the accumulator can come from the same deposit layer (with a given composition for the positive electrode and a given composition for the negative electrode) deposited on a substrate composed of the material constituting the various current collectors followed by an appropriate cutting of this substrate to provide the various current collectors coated with electrode (s).
• the method of preparing the accumulators of the invention can comprise a step of placing a packaging around the accumulator, this positioning being able to be carried out by heat sealing in the case of a flexible packaging and by welding. laser in the case of rigid packaging.
• FIG. 1 is a photograph of a grid with a diamond-shaped mesh which can be used for the separators of the invention.
• FIG. 2 already described above, illustrates the die coating technique implemented for the preparation of a separator in accordance with the invention.
• Figure 3 illustrates, for training cycles in C / 20, the evolution of the voltage U (in V) as a function of the imposed current I (in A) over time t (in h) (respectively the curves a and b for the current and the curves c and d for the voltage) in the context of example 1.
• Figure 4 illustrates the evolution of the voltage U (in V) as a function of the discharge capacity C (in mAh ) (curve a for the accumulator according to the invention and curve b for the non-compliant accumulator) in the context of Example 1.
• FIG. 5 illustrates a tensile test (evolution of the force F (in N) as a function of the deformation D (in mm)) (curve a for the separator in accordance with the invention and curve b for the separator not in accordance with l invention) in the context of Example 1.
• This example relates to the preparation of an accumulator comprising a separator in accordance with the invention.
• PVdF -HEA-HFP VDF 96.8% in mole-HEA 0.8% in mole and HFP 2.4% in mole
• HFP hexafluoropropene
• DBTL dibutyltin dilaurate
• TSPI 3- (triethoxysilyl) propyl isocyanate
• the substrate used in this example is a substrate in the form of a polyetheretherketone grid of 50 ⁇ m thickness with a diamond-shaped mesh.
• the large diagonal of the mesh measures 1.96 mm and the polymer strand has a width of 0.114 mm.
• the PEEK grid used is marketed under the reference 2PEEK4.5-077F from the supplier Dexmet Corporation.
• the gelled electrolyte composition is deposited on one of the faces of the aforementioned substrate by a coating process comma bar in a dry atmosphere (dew point: -20 ° C) at a speed of 1 m / min.
• the composition thus deposited is subjected to in-line drying in an oven of 1.5 m length regulated between 40 to 60 ° C. depending on the drying zones.
• the mechanical properties of the separator according to the invention are evaluated on a traction bench of the brand Shimadzu AG-X equipped with a 50 N force sensor.
• the sample of the separator is precut in the form of a test piece of width 4 mm and gauge length of 25 mm.
• the pulling speed is 50 mm / min.
• Figure 5 shows that the tensile force of the separator according to the invention (a) is 2.53 N on average while the tensile force of the separator in the absence of the polyetheretherketone substrate (b) is 0, 18 N.
• the tensile strength is therefore much higher for the separator according to the invention.
• the same gelling polymer is used, whether for the positive electrode or the negative electrode.
• This is the polymer comprising repeating units resulting from the polymerization of vinylidene fluoride (96.7% in moles), acrylic acid (0.9% in moles) and hexafluoropropene (2.4% in moles). ) and exhibiting an intrinsic viscosity of 0.30 L / g in dimethylformamide at 25 ° C.
• This polymer is designated below by the terminology “Polymer 1”. This is incorporated into the ink intended for the manufacture of the electrodes in the form of an acetone solution in which 10% of polymer 1 has been dissolved at 60 ° C. * Preparation of the negative electrode
• liquid electrolyte composed of a mixture (EC: PC) in mass proportion (1: 1) (EC designating ethylene carbonate and PC designating propylene carbonate), vinylene carbonate (up to 2% by mass) and a lithium salt LÎPF 6 (1 M).
• the liquid electrolyte was added so as to obtain a mass ratio (m electrolyte / (meiectroiyte + m p0 iymer i)) x 100 equal to 85.7%.
• the separator is brought into contact with the negative electrode mentioned above and then the positive electrode is stacked on this assembly.
• the stack is packaged in a flexible “coffee bag” -type sachet and then hermetically sealed by thermal sealing.
• the characteristics of the accumulator in terms in particular of nominal voltage, cycling terminals, surface capacity and estimated practical capacity are set out in the table below in comparison with a similar accumulator, prepared using the same inks for the formation of the electrodes on a gelled polymer electrolyte film as described above, but said film not being impregnated on a polyetheretherketone substrate.
• Figure 3 illustrates, for training cycles in C / 20, the evolution of the voltage U (in V) as a function of the imposed current I (in A) over time t (in h) (respectively the curves a and b for the imposed current of the accumulator in accordance with the invention and the accumulator not in accordance with the invention and the curves c and d for the evolution of the voltage for the accumulator in accordance with the invention and the accumulator not in accordance with the invention ). It shows that the charge and discharge profiles during the training cycles at C / 20 are similar between the cell comprising a separator in accordance with the invention compared to that not in accordance with the invention. Only the charging and discharging times are slightly different.
• FIG. 4 illustrates the evolution of the voltage U (in V) as a function of the discharge capacity C (in mAh) (curve a for the accumulator according to the invention and curve b for the non-conforming accumulator). It shows that the measured capacities are close to the estimated capacities listed in the table above and that the presence of a separator in accordance with the invention does not alter these properties.
• FIG. 5 illustrates a tensile test (evolution of the force F (in N) as a function of the deformation D (in mm)) (curve a for the separator in accordance with the invention and curve b for the separator not in accordance with l 'invention). It demonstrates that the mechanical properties of the separator according to the invention are enhanced compared to the separator not according to the invention. This is because the tensile force is much higher when the substrate of the gelled polymer electrolyte is used.

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