Classifications

• • 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
  • H01M50/446—Composite material consisting of a mixture of organic and inorganic materials
• • 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
  • H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
• • 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
  • H01M10/00—Secondary cells; Manufacture thereof
  • H01M10/05—Accumulators with non-aqueous electrolyte
  • H01M10/052—Li-accumulators
  • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
• • 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
  • H01M10/056—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
  • H01M10/0566—Liquid materials
  • H01M10/0568—Liquid materials characterised by the solutes
• • 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
  • H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
  • H01M50/417—Polyolefins
• • 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
  • H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
  • H01M50/426—Fluorocarbon polymers
• • 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
  • H01M50/429—Natural polymers
• • 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
  • H01M50/431—Inorganic material
  • H01M50/434—Ceramics
• • 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
  • H01M50/431—Inorganic material
  • H01M50/434—Ceramics
  • H01M50/437—Glass
• • 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
• • 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 the general technical field of electrical energy storage systems.
• the present invention relates to a hybrid separator membrane consisting of a composite material comprising a non-porous polymer matrix and particles of an ion-conductive inorganic material dispersed in said polymer matrix, the use of such a membrane as a separator in an electrical energy storage system, as well as an electrical energy storage system, in particular an electrochemical accumulator such as a (rechargeable) lithium or sodium secondary battery comprising at least one such a separating membrane.
• an electrochemical accumulator such as a (rechargeable) lithium or sodium secondary battery comprising at least one such a separating membrane.
• Secondary lithium batteries are generally in the form of an assembly of superimposed thin films (winding or stacking of the following pattern (electrolyte/cathode/collector/cathode/electrolyte/anode) on n turns) or of n thin films stacked (cut and superimposed, i.e. n stacks of the aforementioned pattern).
• the electrolyte can be self-supporting or permeate a porous separator.
• This stacked/complexed unit pattern has a thickness of the order of a hundred micrometers.
• a negative electrode ensuring the supply of lithium ions during the discharge of the battery
• a self-supporting solid or gelled polymer electrolyte conductive of lithium ions or a separator porous material impregnated with an electrolytic solution
• a positive electrode cathode
• a current collector in contact with the positive electrode and making it possible to ensure the electrical connection.
• the negative electrode of Lithium Metal Polymer (LMP®) batteries generally consists of a sheet of pure metallic lithium or of a lithium alloy; the solid or gelled polymer electrolyte is generally composed of a polymer based on poly(ethylene oxide) (POE) and at least one lithium salt; the positive electrode is usually made of a material whose working potential is less than 4V vs Li7Li (ie the redox potential with respect to lithium is less than 4V) such as for example a metal oxide (such as for example V2O5, UV3O8, UC0O2, LiNiCte, LiMn204 and LiNio.5Mno.5O2...) or a phosphate of the L1MPO4 type, where M represents a metal cation selected from the group Fe, Mn, Co, Ni and Ti, or combinations of these cations, such as for example LiFeP0 4 , or a conversion material (eg sulfur) and also contains carbon and a polymer; and the current collector
• Na-ion Sodium-ion (Na-ion) technology appears to be a promising alternative for new generation batteries, particularly in the field of stationary energy storage due to the natural abundance of the element sodium and the low cost of it compared to lithium.
• Sodium batteries generally have a cathode in which the active material is a compound capable of reversibly inserting sodium ions, an electrolyte comprising an easily dissociable sodium salt, and an anode whose active material may in particular be a sheet of pure metallic sodium or a sodium-based alloy.
• US 2018/0230610 to protect the surface of the electrodes with a ceramic protective layer.
• This protection comprises 2 composite layers, each of the layers consisting of a porous polymer matrix whose pores are at least partially filled with a ceramic having an ionic conductivity, said ceramic being in contact with the surface of the electrode.
• the ceramic is in direct contact with the surface of the electrode, which implies that it is chemically stable with respect to it.
• the polymer constituting the matrix of the composite layer can be permeable to the solvents of the electrolyte and therefore does not prevent the diffusion of the chemical species present in the electrolyte to the electrode thus protected.
• the present invention has as its first object a hybrid separating membrane for an electrical energy storage system, said membrane comprising an organic phase and an inorganic phase, said inorganic phase being dispersed within the organic phase, said membrane being characterized in that:
• the organic phase constitutes a non-porous polymer matrix that is impermeable to electrolyte solvents
• the inorganic phase consists of a set of particles of at least one ion-conductive inorganic material
• the membrane is in the form of a film of thickness e
• the particles of said inorganic material have at least one smallest dimension / and at least one largest dimension L, said dimension L being greater than or equal to the thickness e of the polymer matrix, and
• the two faces of the membrane are ionically connected to each other either via a single particle of inorganic material, or via at least two particles of inorganic material in contact with each other.
• this membrane it is possible to design rechargeable batteries in which the diffusion of certain chemical species from one electrode to the other is prevented.
• This membrane thus allows the chemical decoupling of the electrodes by only allowing a transfer of the cationic species necessary for the operation of the battery (lithium or sodium ions). The other chemical species remain blocked on either side of the membrane, thus preserving the good electrochemical performance of the battery over time.
• the use of this separating membrane allows the use of very different electrolyte compositions at each electrode, whether for electrolyte salts, polymers or solvents, which makes it possible to adapt the nature of the electrolytes used to the nature of each of the electrodes.
• non-porous concerning the polymer matrix means that said matrix is essentially free of porosity, in other words that its pore volume is less than approximately 10%;
• the expression “impermeable to electrolyte solvents” concerning the polymer matrix means that said matrix exhibits swelling in the presence of said solvents of less than 5% by mass;
• ionic conductor concerning the inorganic material, means that said inorganic material has a higher ionic conductivity or equal to approximately 1.10 -5 S/cm, and preferably greater than or equal to approximately 3.10 -4 S/cm;
• the ionic conduction of said membrane is preferably greater than or equal to approximately 10 7 S/cm, and even more preferably greater than or equal to approximately 10 4 S/cm.
• the thickness e of the membrane is preferably less than approximately 30 ⁇ m, and even more preferably this thickness e is comprised inclusively between 3 and 20 ⁇ m approximately.
• the smallest dimension (/) of the particles of said inorganic material is inclusively between 3 and 15 ⁇ m approximately, more particularly between 5 and 8 ⁇ m approximately.
• the particles of inorganic material are oriented within the polymer matrix such that the axis passing through their largest dimension L is substantially perpendicular to the thickness of said membrane.
• the shape of the particles is not critical as long as they have, as indicated above, a largest dimension L greater than or equal to the thickness e of the polymer matrix.
• the particles of said inorganic material may be spherical, parallelepipedic, or even in the form of fibers or rods.
• the particles of said inorganic material are in the form of fibers or rods.
• the inorganic material is preferably chosen from ceramics that conduct lithium ions, glasses that conduct lithium ions or sodium ions, and ceramics that conduct sodium ions.
• LZS LhZrSieO-is ceramics
• LLZO LiyLa3Zr20i2
• LATP Lii,3Alo,3Tiij(P04)3
• LAGP LiAIGe2(P04)3
• LZS ceramic is particularly preferred.
• NASICON synchrom for “sodium (Na) Superlonic Conductor” which can be represented by the chemical formula Nai +x Zr2Si x P3- x Oi2, 0 ⁇ x ⁇ 3.
• the membrane preferably contains from 50% to 90% by mass approximately of ion-conductive inorganic material, from 10% to 50% by mass approximately of polymer matrix, relative to the total mass of said membrane.
• the non-porous polymer matrix is non-ionically conductive.
• the expression “ionically non-conductive” relating to the polymer matrix means that said matrix has an ionic conductivity of less than 10 7 S/cm approximately, and preferably less than 10 8 S/cm approximately.
• the non-porous polymer matrix contains at least one non-ionically conductive polymer preferably chosen from polyolefins, halogenated polymers, homopolymers and copolymers of epichlorohydrin, polyurethanes, homopolymers and styrene copolymers, vinyl polymers, polysaccharides, cellulose derivatives and mixtures thereof.
• polyolefins mention may more particularly be made of homopolymers or copolymers of ethylene and propylene, as well as mixtures of at least two of these polymers.
• halogenated polymers mention may in particular be made of homopolymers and copolymers of vinyl chloride, vinylidene fluoride (PVdF), vinylidene chloride, ethylene tetrafluoride, or chlorotrifluoroethylene, copolymers of fluoride vinylidene and hexafluoropropylene (PVdF-co-HFP) and mixtures thereof.
• PVdF vinylidene fluoride
• HFP chlorotrifluoroethylene
• the polymer or polymers of the polymer matrix are chosen from polyethylene and copolymers of vinylidene fluoride and hexafluoropropylene (PVdF-co-FIFP).
• the non-porous polymer matrix is ion-conductive.
• the polymer matrix then further comprises, in addition to the non-ionically conductive polymer(s) listed above, at least one ionically conductive polymer.
• the ionic-conducting polymer(s) can be chosen from polyethers, polycarbonates, polyamides, polyimides, polypyrroles and mixtures thereof.
• the hybrid separating membrane in accordance with the present invention may also contain one or more salt(s) such as a lithium salt or a sodium salt and/or one or more organic solvent(s).
• the salt(s) of lithium or sodium preferably represent from 0.1 to 5% by mass approximately relative to the total mass of said membrane and the solvent preferably represents from 0. 1 to 5% by mass approximately relative to the total mass of said membrane.
• the hybrid separator membrane in accordance with the present invention can be prepared according to the techniques known to those skilled in the art, and such as for example by mixing the various elements constituting it in a mixer in the presence of an organic solvent to obtain a paste which can then be rolled into a film. After lamination the film is dried. Such a membrane can then be used as a separator in an electrical energy storage system operating by circulation of lithium ions or sodium ions.
• the second object of the present invention is therefore the use of a hybrid separator membrane as defined according to the first object of the invention, as an electrode separator in an electrical energy storage system. operating by circulation of lithium or sodium ions and comprising at least one positive electrode, at least one negative electrode and at least one electrolyte.
• said membrane is placed between the positive electrode and the negative electrode and makes it possible to electrically isolate said electrodes from each other.
• the present invention has as a third object, an electrical energy storage system operating by circulation of lithium ions or sodium ions, said system comprising at least one positive electrode, at least one negative electrode, and at least one separator present between said positive and negative electrodes, said system being characterized in that said separator is a hybrid separator membrane as defined according to the first object of the invention.
• said storage system comprises at least one positive electrode, at least one negative electrode, at least two electrolytes E1 and E2 and at least one separator present between said electrolytes E1 and E2 .
• the energy storage system is preferably a lithium battery.
• said system comprises an assembly of at least one positive electrode, at least one electrolyte film E1, at least one hybrid separating membrane as defined according to the first object of the invention, of at least one second film of electrolyte E2 and of at least one negative electrode, said separating membrane being interposed between the two films of electrolyte E1 and E2.
• the positive electrode of a lithium battery generally consists of a current collector supporting a composite positive electrode comprising a positive electrode active material, optionally an electronic conduction agent such as carbon, and optionally a binder polymer.
• the current collector is generally made of a sheet of metal, for example an aluminum sheet.
• the negative electrode of a lithium battery is generally made of a sheet of metallic lithium or a lithium alloy.
• the electrolytes E1 and E2 may have an identical or different chemical composition from one another. They can be in the form of a solid polymer electrolyte which is generally composed of a solid polymer based on poly(ethylene oxide) (POE) and at least one lithium salt. They can also be in the form of a gelled electrolyte comprising at least one gelling polymer, at least one lithium salt and at least one solvent.
• a solid polymer electrolyte which is generally composed of a solid polymer based on poly(ethylene oxide) (POE) and at least one lithium salt.
• POE poly(ethylene oxide)
• a gelled electrolyte comprising at least one gelling polymer, at least one lithium salt and at least one solvent.
• the gelling polymers can be chosen from polyolefins such as homopolymers or copolymers of ethylene and propylene, or a mixture of at least two of these polymers; homopolymers and copolymers of ethylene oxide (e.g.
• POE POE copolymer
• methylene oxide propylene oxide
• carbonates epichlorohydrin or allylglycidyl ether
• halogenated polymers such as homopolymers and copolymers of vinyl chloride, vinylidene fluoride (PVdF), vinylidene chloride, ethylene tetrafluoride, or chlorotrifluoroethylene, copolymers of vinylidene fluoride and hexafluoropropylene (PVdF co HFP) and mixtures thereof
• PVdF co HFP hexafluoropropylene
• vinyl polymers electronic non-conductive polymers of anionic type such as poly(styrene sulfonate), poly(acrylic acid), poly(glutamate), alginate, pectin, carrageenan and mixtures thereof; polyacrylates; and one of their mixtures.
• the solvent(s) for the gelled electrolyte can be chosen from linear or cyclic ethers, carbonates, sulfur solvents (sulfolanes, sulfones, DMSO, etc.), linear or cyclic esters (lactones), nitriles , etc.
• dimethyl ether such as dimethyl ether, polyethylene glycol dimethyl ether (or PEGDME) such as tetraethylene glycol dimethyl ether (TEGDME), dioxolane, ethylene carbonate (EC), propylene carbonate (PC) , dimethylcarbonate (DMC), diethylcarbonate (DEC), methyl-isopropyl carbonate (MiPC), ethyl acetate, ethylbutyrate (EB), and mixtures thereof.
• PEGDME polyethylene glycol dimethyl ether
• TEGDME tetraethylene glycol dimethyl ether
• EC ethylene carbonate
• PC propylene carbonate
• DMC dimethylcarbonate
• DEC diethylcarbonate
• MiPC methyl-isopropyl carbonate
• EB ethyl acetate
• EB ethylbutyrate
• the electrolyte E1 has a different chemical composition from the chemical composition of the electrolyte E2.
• the electrolyte E1 between the separator and the positive electrode is an electrolyte based on PVdF, polycarbonate and a lithium salt such as lithium bis(trifluoromethylsulfonyl)imide (LiTFSI ) and the electrolyte E2 placed between the separator and the negative electrode is based on POE, PEGDME, and a lithium salt such as UNO3.
• FIG. 1 represents the change in capacity and efficiency as a function of the number of cycles of the battery of example 1 in accordance with the invention comprising a non-porous hybrid membrane;
• FIG. 2 represents the evolution of the internal resistance as a function of the number of cycles of the battery of Example 1 in accordance with the invention comprising a non-porous hybrid membrane;
• FIG. 3 represents the change in capacity and efficiency as a function of the number of cycles of the battery of Example 2 not in accordance with the invention comprising a porous membrane;
• FIG. 4 represents the evolution of the internal resistance as a function of the number of cycles of the battery of example 2 not in accordance with the invention comprising a porous membrane;
• FIG. 5 represents a scanning electron microscopy image of the electrolyte/membrane/electrolyte trilayer material of the battery of Example 2 not in accordance with the invention comprising a porous membrane ( Figure 5a), as well as a cartography of the chlorine of this same three-layer material (FIG. 5b);
• FIG. 6 represents the evolution of the capacity as a function of the number of cycles of the battery of example 3 in accordance with the invention comprising a dense and non-porous hybrid membrane;
• FIG. 7 represents the evolution of the internal resistance as a function of the number of cycles of the battery of Example 3 in accordance with the invention comprising a dense and non-porous hybrid membrane;
• FIG. 8 represents a scanning electron microscopy image of the trilayer material electrolyte/non-porous hybrid membrane in accordance with the invention/electrolyte of the battery of example 3 in accordance with the invention (FIG. 5a), as well as a cartography of the chlorine of this same three-layer material ( Figure 5b).
• EXAMPLE 1 Manufacture of a non-porous separating membrane based on poly(vinylidene fluoride-co-hexafluoropropene) and ceramic fibers in accordance with the invention and integration in a lithium battery
• a non-porous separating membrane consisting of a film of a composite material comprising a polymer matrix based on poly(vinylidene)-co-hexafluoropropene fluoride (PVdF-FIFP) and fibers of ceramic.
• PVdF-FIFP poly(vinylidene)-co-hexafluoropropene fluoride
• Second step preparation of solid polymer electrolyte films
• Solid polymer electrolyte films were prepared by mixing 40 g of poly(ethylene oxide) sold under the reference POE 1 L by the company
• a composite positive electrode film was prepared by mixing 74% by mass of LiFeP0 4 (Sumimoto Osaka Cernent), 19% by mass of POE 1L, 5% by mass of LiTFSI and 2% in mass of carbon black sold under the trade name Ketjenblack EC600JD (Akzo Nobel) in the Plastograph® EC mixer at a temperature of 80°C.
• the paste thus obtained was laminated on an aluminum current collector (3M).
• the films obtained above in the first step were used within a lithium battery.
• the assembly of the battery was carried out in a dry room (dew point -40°C).
• a film of the material obtained above in the first step was complexed by rolling between two films of polymer electrolytes as prepared above in the second step, at a temperature of 80° C. and under 0.5 MPa (5 bar) pressure.
• the assembly thus obtained was then interposed between the positive composite electrode film obtained above in the third step and a negative electrode of metallic lithium by lamination, still at a temperature of 80° C. under 0.5 MPa, in cells of small size, of the “pouch cell” type of around 15 mAh and having a surface area of around 10 cm 2 .
• FIG. 1 represents the evolution of the capacity (filled diamonds) and of the efficiency (empty diamonds) of the battery as a function of the number of cycles.
• FIG. 2 represents the evolution of the internal resistance of the battery of Example 1 in accordance with the invention as a function of the number of cycles.
• EXAMPLE 2 Manufacture of a porous separating membrane based on poly(vinylidene fluoride-co-hexafluoropropene) and ceramic fibers not in accordance with the invention and integration in a lithium battery
• a porous separator membrane not in accordance with the present invention was prepared, said membrane consisting of a film of a porous composite material comprising a polymer matrix based on poly(vinylidene) fluoride (PVdF ) and ceramic fibers.
• PVdF poly(vinylidene) fluoride
• Second step Preparation of a gelled electrolyte based on polv(ethylene glvcol) dimethyl ether
• a first film of gelled electrolyte was prepared by mixing 35 g of poly(ethylene oxide) sold under the reference POE 1L by the company Sumitomo Seika, 18 g of poly(ethylene glycol) dimethyl ether (PEGDME) at 240 g/mol (TCI Chemicals) and 17 g of LiCIC 4H2O (Sigma Aldrich) in the Plastograph® EC mixer at a temperature of 80°C.
• the paste thus obtained was laminated between 2 films of siliconed polyethylene at 80° C. in order to obtain films about 10 ⁇ m thick.
• Third step Preparation of a gelled electrolyte based on ethylene carbonate
• a second gelled electrolyte film was prepared by mixing 4 g of PVdF 5130 (Solvay), 2.6 g of 1.2M solution of LiTFSI (Solvay) in ethylene carbonate (Sigma Aldrich ), and 30 g of pure acetonitrile (Sigma Aldrich). The mixture was coated on a polypropylene support film. The acetonitrile was evaporated in the open air in a dry room (dew point -40°C) for 24 hours before use.
• a film composite positive electrode was prepared by mixing 71% by weight of LiNi 6 MnO 2 Coo 2 0 2 (also referred to as NMC; Umicore), 5% by weight of PVdF-HFP ( Solef® 21510 Solvay), 16% by mass of an equal volume mixture of ethylene carbonate and propylene carbonate, 6% by mass of LiTFSI and 2% by mass of carbon black sold under the trade name Ketjenblack EC600JS (Akzo Nobel) in the Plastograph® EC mixer at a temperature of 135°C.
• the paste thus obtained was laminated on an aluminum current collector (3M).
• the porous membrane obtained above in the first step was then complexed by lamination between the first and the second gelled electrolytes as obtained respectively in the second and third steps above, at 80° C., under 0 .5MPa of pressure.
• the "trilayer" assembly thus obtained was then interposed between a film of positive composite electrode as obtained above in the fourth step and a negative electrode of metallic lithium by lamination, still at a temperature of 80° C. under 0.5 MPa, in cells of small size, of the “pouch cell” type of around 15 mAh and having a surface area of around 15 cm 2 .
• Battery assembly was performed in a dry room (dew point -40°C).
• the cell thus obtained was cycled at 40° C. in galvanostatic cycling (rate C/10 + potentiostatic hold at 4.25 V for 1 hour 30 minutes; D/10; then C/10 + potentiostatic hold at 4.25 V for 1 hour 30 minutes; D/5 between 3 and 4.25 V).
• FIG. 3 represents the evolution of the capacity (filled diamonds) and of the efficiency (empty diamonds) of the battery as a function of the number of cycles.
• FIG. 4 represents the evolution of the internal resistance of the battery as a function of the number of cycles.
• the porous membrane not in accordance with the invention has insufficient cycling performance: it does not form a barrier to the solvents of the electrolytes, which results in a mixture of these and degradation of both electrodes. This results in an increase in the internal resistance of the battery (figure 4). Its malfunction leads to a drop in performance, which is the cause of premature end of life.
• the "trilayer" formed from the assembly of the non-porous membrane and the first and second gelled electrolytes was stored for 5 days at 40° C. and then analyzed by scanning electron microscopy associated with energy microanalysis dispersive X-ray (SEM/EDX Hitachi TM3000) on the edge of the assembly.
• SEM/EDX Hitachi TM3000 energy microanalysis dispersive X-ray
• the mapping of the chlorine element in the trilayer was analyzed, this being revealing of the permeability of the separating membrane, the chlorine element can only come from the lithium salt used in the PEGDME-based electrolyte, namely the LiCIC.
• Figure 5a is an SEM image of the trilayer in cross section.
• FIG. 5a there is a layer of the film of the second gelled electrolyte based on ethylene carbonate 51, a layer of porous separating membrane 52 and a layer of the film of the first gelled electrolyte based on poly(ethylene glycol) dimethyl ether. 53.
• Figure 5b shows the chlorine map.
• EXAMPLE 3 Manufacture of a dense and non-porous separating membrane based on poly(ethylene oxide) and ceramic fibers in accordance with the invention and integration in a lithium battery
• a dense and non-porous separating membrane according to the invention consisting of a film of a composite material comprising a polymer matrix comprising a plastomer based on ethylene, poly(oxide of ethylene (POE) and ceramic fibers.
• the membrane obtained was then integrated as a separator in a lithium battery.
• LZS ceramic fibers sold by Morgan Advanced Materials 60 g were mixed with 14.8 g of a plastomer (CAS-No. 26221-73-8, sold under the trade name Quéo ® 0201 by the company Boeralis), 2.2 g of poly(ethylene oxide) sold under the trade name ICPSEB (Nippon Shokuba ⁇ ), and 0.7 g of LiTFSI (Solvay) in a mixer sold under the trade name Plastograph® EC by the Brabender company at a temperature of 150°C.
• the paste thus obtained was then laminated between 2 siliconized polyethylene films at 130°C in order to obtain films approximately 22 ⁇ m thick. These films were then dried at 25°C for 24 hours under anhydrous air sweep (dew point -40°C).
• Second step Preparation of a gelled electrolyte based on diethylene glycol dimethyl ether
• a first film of gelled electrolyte was prepared by mixing 72 g of a copolymer of poly(ethylene oxide) and poly(propylene oxide) sold under the trade name Alkox EP10 by the company Meisei, of 8 g of a 3M LiNC solution (Alfa Aesar) in poly(ethylene glycol) dimethyl ether (PEGDME) at 240 g/mol (TCI Chemicals) in the Plastograph® EC mixer at a temperature of 80°C. The mixture thus obtained is laminated between 2 films of siliconed polyethylene at 60° C. in order to obtain films approximately 10 ⁇ m thick.
• the mixture was coated on a polypropylene support film.
• the acetonitrile was evaporated in the open air in a dry room (dew point -40°C) for 24 hours before use.
• a film composite positive electrode was prepared by mixing 71% by weight of LiNi 6 MnO 2 Coo 2 0 2 (also referred to as NMC; Umicore), 5% by weight of PVdF-HFP ( Solef® 21510 Solvay), 16% by mass of an equal volume mixture of ethylene carbonate and propylene carbonate, 6% by mass of LiTFSI and 2% by mass of carbon black sold under the trade name Ketjenblack EC600JS (Akzo Nobel) in the Plastograph® EC mixer at a temperature of 135°C. The paste thus obtained was laminated on an aluminum current collector (3M). [01081 Step Five: Battery Assembly
• the dense non-porous membrane obtained above in the first step was then complexed by lamination between the first and the second gelled electrolytes as obtained respectively in the second and third steps above, at 80° C., under 0.5MPa of pressure.
• the "trilayer" assembly thus obtained was then interposed between a film of positive composite electrode as obtained above in the fourth step and a negative electrode of metallic lithium by lamination, still at a temperature of 80° C. under 0.5 MPa, in cells of small size, of the “pouch cell” type of around 15 mAh and having a volume of around 15 cm 2 .
• Battery assembly was performed in a dry room (dew point -40°C). The cell thus obtained was cycled at 40° C. in galvanostatic cycling
• FIG. 6 represents the evolution of the capacity of the battery as a function of the number of cycles.
• FIG. 7 represents the evolution of the internal resistance of the battery as a function of the number of cycles.
• FIG. 8a is an SEM image of the trilayer in cross section.
• FIG. 8a there is a layer of gelled electrolyte based on poly(ethylene glycol) dimethyl ether and LiCIC 81, a layer of non-porous and dense separating membrane 82 in accordance with the invention and a layer of gelled electrolyte based on ethylene carbonate and LiTFSI 83.
• Figure 8b shows the chlorine map.

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