Classifications

• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M4/00—Electrodes
  • H01M4/02—Electrodes composed of, or comprising, active material
  • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
  • H01M4/134—Electrodes based on metals, Si or alloys
• • H—ELECTRICITY
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  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M4/00—Electrodes
  • H01M4/02—Electrodes composed of, or comprising, active material
  • H01M4/36—Selection of substances as active materials, active masses, active liquids
  • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
  • H01M4/40—Alloys based on alkali metals
  • H01M4/405—Alloys based on lithium
• • 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
  • H01M4/00—Electrodes
  • H01M4/02—Electrodes composed of, or comprising, active material
  • H01M4/04—Processes of manufacture in general
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M4/00—Electrodes
  • H01M4/02—Electrodes composed of, or comprising, active material
  • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
  • H01M4/139—Processes of manufacture
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M4/00—Electrodes
  • H01M4/02—Electrodes composed of, or comprising, active material
  • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
  • H01M4/139—Processes of manufacture
  • H01M4/1395—Processes of manufacture of electrodes based on metals, Si or alloys
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M4/00—Electrodes
  • H01M4/02—Electrodes composed of, or comprising, active material
  • H01M4/36—Selection of substances as active materials, active masses, active liquids
  • H01M4/362—Composites
  • H01M4/366—Composites as layered products
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M4/00—Electrodes
  • H01M4/02—Electrodes composed of, or comprising, active material
  • H01M4/36—Selection of substances as active materials, active masses, active liquids
  • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M4/00—Electrodes
  • H01M4/02—Electrodes composed of, or comprising, active material
  • H01M4/36—Selection of substances as active materials, active masses, active liquids
  • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
  • H01M4/381—Alkaline or alkaline earth metals elements
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M4/00—Electrodes
  • H01M4/02—Electrodes composed of, or comprising, active material
  • H01M4/36—Selection of substances as active materials, active masses, active liquids
  • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
  • H01M4/381—Alkaline or alkaline earth metals elements
  • H01M4/382—Lithium
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M4/00—Electrodes
  • H01M4/02—Electrodes composed of, or comprising, active material
  • H01M4/36—Selection of substances as active materials, active masses, active liquids
  • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
  • H01M4/40—Alloys based on alkali metals
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M4/00—Electrodes
  • H01M4/02—Electrodes composed of, or comprising, active material
  • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M4/00—Electrodes
  • H01M4/02—Electrodes composed of, or comprising, active material
  • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
  • H01M4/621—Binders
  • H01M4/622—Binders being polymers
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M4/00—Electrodes
  • H01M4/02—Electrodes composed of, or comprising, active material
  • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
  • H01M4/621—Binders
  • H01M4/622—Binders being polymers
  • H01M4/623—Binders being polymers fluorinated polymers
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M4/00—Electrodes
  • H01M4/02—Electrodes composed of, or comprising, active material
  • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
  • H01M4/624—Electric conductive fillers
• • 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
  • H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
• • 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
  • H01M10/058—Construction or manufacture
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M4/00—Electrodes
  • H01M4/02—Electrodes composed of, or comprising, active material
  • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
  • H01M2004/027—Negative electrodes
• • 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
• • 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
  • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
  • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
  • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

• Composite electrode comprising a metal and a polymer membrane, manufacturing process and battery containing it
• the present invention relates to the general technical field of electrical energy storage systems.
• the present invention relates to a composite negative electrode based on pure metallic lithium, pure metallic sodium or one of their alloys and a polymer membrane, a method of manufacturing such an electrode, as well as an electrical energy storage system, in particular an electrochemical accumulator such as a secondary (rechargeable) lithium or sodium battery comprising at least one such negative electrode. It is particularly applicable to Lithium-Metal-Polymer or LMP TM batteries.
• LMP TM 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) over n turns) or n thin films stacked (cut and superimposed, ie n stacks of the above-mentioned pattern).
• This stacked / complexed unitary 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 solid polymer electrolyte conductive of lithium ions iii) a positive electrode (cathode) made up of an active electrode material acting as a receptacle where the lithium ions are inserted
• a current collector in contact with the positive electrode and making it possible to ensure the electrical connection.
• the negative electrode of LMP TM batteries generally consists of a sheet of pure metallic lithium or of a lithium alloy; the solid 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 a material whose working potential is less than 4V vs Li7Li (ie the lithium insertion / deinsertion potential is less than 4V) such as for example an oxide metal (such as V2O5, UV3O8, UC0O2, LiNiCte, Limr C ⁇ Mno and LiNi .5 .5 O 2 ...) or a phosphate type L1MPO 4, wherein 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 , and also contains carbon and a polymer; and the current collector is generally made of a sheet of metal.
• the conductivity of the ions is ensured by the dissolution of
• Na-ion Sodium-ion (Na-ion) technology appears to be a promising alternative for new generation batteries, in particular in the field of fixed energy storage due to the high natural abundance and the low cost of sodium 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 of which the active material can in particular be a foil of pure metallic sodium or a sodium-based alloy.
• the negative electrodes have the common feature of being in the form of a very thin film, generally having a thickness of less than about 100 ⁇ m. It is difficult to industrially manufacture and handle films of metallic lithium or metallic sodium of significantly less thickness, in particular due to the very malleable and sticky nature of these metals.
• international application WO 2013/121164 describes a negative electrode based on lithium or sodium in the form of a thin film and comprising (i) a reinforcing layer formed by a porous substrate, and (ii ) a first and a second metallic film based on lithium or sodium, the reinforcing layer being sandwiched between the two metallic films based on lithium or sodium and bonded together by pressure to form a composite structure having a thickness total less than or equal to 100 ⁇ m in which the pores of the porous substrate are at least partly filled with the metal of the first and second metallic films.
• the porous substrate is an electrically non-conductive material in the form of a fibrous material, for example in the form of non-electrically conductive polymer fibers.
• This negative electrode is therefore in the form of a composite structure with at least 3 layers, in which the two metal films constitute the upper and lower outer faces of the electrode between which the porous substrate is trapped.
• the technology proposed in this international application is not entirely satisfactory insofar as the cohesion between the metallic films and the fibrous support is not always good.
• the metallic films present on each of the faces of the porous substrate can tear and / or electrically disconnect from the rest of the electrode thus formed, which has the consequence of impairing the performance of the electrode and of the battery. comprising such an electrode.
• the first subject of the present invention is therefore a negative electrode in the form of a composite material comprising:
• said at least one polymer is chosen from:
• electrically non-conductive polymers selected from the group comprising polyolefins; ethylene oxide homopolymers and copolymers (eg POE, copolymer of POE), of methylene oxide, of propylene oxide, of epichlorohydrin or of allyl glycidyl ether, and mixtures thereof; halogenated polymers; styrene homopolymers and copolymers and mixtures thereof; vinyl polymers; anionic polymers; polyacrylates; and one of their mixtures; and
• electrically non-conductive polymers selected from the group comprising polyolefins; ethylene oxide homopolymers and copolymers (eg POE, copolymer of POE), of methylene oxide, of propylene oxide, of epichlorohydrin or of allyl glycidyl ether, and mixtures thereof; halogenated polymers; styrene homopolymers and copolymers and mixtures thereof; vinyl polymers; anionic polymers;
• electrically conductive polymers chosen from the group comprising polyaniline, polypyrroles, polyfluorenes, polypyrenes, polyazulenes, polynaphthalenes, polycarbazoles, polyindoles, polyazepines, polythiophenes, poly (p- phenylene sulfides), polyacetylenes and poly (p-phenylene vinylene).
• this polymer membrane is chemically compatible with the metal of the metal layer with which it is in contact by at least one of its faces. It is flexible and follows the shape of lithium or sodium grains. In particular, it is able to flow between the lithium or sodium grains to maintain the mechanical integrity of the metal layer, even if the latter tears.
• the polymer membrane of the negative electrode in accordance with the invention has the particularity of being able to stretch at the same time as the metal layer with which it is in contact during the lamination of the electrode, each of the layers becoming thinner. then in the same proportion.
• the polymer membrane when it is indicated that the polymer membrane is non-porous, this means that it has a porosity less than or equal to 10% by volume, preferably less than or equal to 5% by volume per relative to the total volume of said membrane.
• the polymer membrane is chemically compatible with the metal of the layer metal with which it is in contact
• polystyrenes examples include polystyrene sulfonate, poly (acrylic acid), poly (glutamate), alginate, pectin, carrageenan and mixtures thereof.
• the electrically non-conductive polymers are preferably chosen from homopolymers and copolymers of ethylene oxide (eg POE, copolymer of POE), copolymers of vinylidene fluoride and of hexafluoropropylene (PVdF-co-FIFP) and mixtures thereof.
• ethylene oxide eg POE, copolymer of POE
• PVdF-co-FIFP hexafluoropropylene
• the polymer membrane of the negative electrode according to the invention may further contain at least one electronic conduction additive.
• an additive can in particular be chosen from carbonaceous fillers such as carbon black, graphite, carbon fibers and nanofibers, carbon nanotubes and graphene; particles of at least one conductive metal such as aluminum, copper, gold, silver, platinum, iron, cobalt and nickel; and one of their mixtures.
• the electronic conduction additive preferably represents from 5 to 80% approximately by mass, and even more preferably from 10 to 30% approximately by mass, relative to the total mass of the polymer membrane of the negative electrode.
• the polymer membrane of the negative electrode is preferably an electrically conductive polymer membrane.
• the polymer membrane is electrically conductive, either because it comprises a or more polymers which are not electrically conductive and at least one electronic conduction additive, or because it comprises at least one electrically conductive polymer optionally in the presence of at least one electronic conduction additive.
• the polymer membrane of the negative electrode according to the present invention is electrically conductive, the grain-to-grain electrical conduction can be maintained even in the event of mechanical breakage or tearing of the metal layer.
• the polymer membrane of the negative electrode according to the invention may further contain at least one salt comprising at least one anion and at least one metal cation M.
• the salts can in particular be chosen from MBF4, MPF 6 ,
• CF 3 SO 3 M triflate
• MTFSI metal cation M
• MFSI bis (fluorosulfonyl) imide of a metal cation M
• MFSI bis (fluorosulfonyl) imide of a metal cation M
• MBEI bis (pentafluoroethylsulfonyl) imide of a metal cation M
• MAsF 6 , MCF3SO3, MSbFe, MSbCle M 2 TiCI 6 , M 2 SeCI 6 , M 2 BioCho, M2B12CI12, MNOs, MCIO4, a trifluoroimidazole of a metal cation M (MTDI), a tetrafluoroborate of a metal cation M (MFOB), a bis (oxalato) borate of a metal cation M (MBOB), M3PO4, M 2 C0 3, and Na 2 S0 4.
• MTDI triflu
• the metal cation M can be chosen from lithium, beryllium, sodium, magnesium, aluminum, potassium, calcium, silver, rubidium, strontium, cesium, barium, radium and francium cations. Among such cations, lithium and sodium are preferred.
• lithium bis (trifluoromethylsulfonyl) imide LiTFSI is particularly preferred.
• the polymer membrane comprises a salt comprising at least one anion and at least one metal cation M
• the amount of said salt preferably represents from 5 to 30% by mass, and even more preferably from 10 to 25% by mass, relative to the total mass of the polymer membrane.
• the polymer membrane of the negative electrode according to the invention preferably has a thickness of approximately 2 to 50 ⁇ m, and even more preferably of approximately 2 to 10 ⁇ m.
• the metal layer of the negative electrode generally has a thickness of approximately 1 to 50 ⁇ m, preferably approximately 5 to 30 ⁇ m.
• the negative electrode further comprises at least one second metallic layer, said second metallic layer being in direct physical contact with the other face of said non-porous polymer membrane.
• the negative electrode is therefore composed of at least three layers, namely in this order a first metal layer, a layer of non-porous polymer membrane, and at least one second metallic layer.
• the first and the second metal layers are thus separated from each other by said non-porous polymer membrane.
• the first metal layer is preferably identical to the second metal layer.
• the term identical means that the first and the second metal layers are made of the same metal or the same alloy and that they have substantially the same thickness.
• the total thickness of the at least three-layer electrode according to the present invention preferably varies from approximately 10 to 100 ⁇ m, and even more particularly from approximately 15 to 60 ⁇ m.
• the negative electrode according to the invention may further comprise a current collector.
• said electrode comprises at least one non-porous electrically conductive polymer membrane and said current collector is in direct physical contact with said membrane.
• the current collector may for example consist of a sheet of copper or of a porous carbon-based material such as, for example, carbon fibers or a carbon grid.
• the negative electrode comprises 5 layers and consists in this order of a first metallic layer, preferably of metallic lithium or of an alloy of lithium, a first non-porous electrically conductive polymer membrane, a current collector, preferably copper, a second non-porous electrically conductive polymer membrane, preferably identical to the first polymer membrane non-porous electrically conductive, and a second metal layer, preferably identical to the first metal layer.
• said negative 5-layer electrode may have a thickness of 10 to 100 ⁇ m approximately, and preferably from 15 to 60 ⁇ m approximately.
• a second object of the present invention is a process for preparing a negative electrode as defined according to the first object of the invention.
• This method is characterized in that it comprises at least one step of applying a non-porous polymer membrane based on at least one polymer on at least one metal layer based on pure lithium, pure sodium or a lithium or sodium alloy, said polymer being chosen from:
• electrically non-conductive polymers selected from the group consisting of polyolefins; ethylene oxide homopolymers and copolymers
• electrically conductive polymers chosen from the group comprising polyaniline, polypyrroles, polyfluorenes, polypyrenes, polyazulenes, polynaphthalenes, polycarbazoles, polyindoles, polyazepines, polythiophenes, poly (p- phenylene sulfides), polyacetylenes and poly (p-phenylene vinylene).
• the polymer membrane is manufactured by extrusion and then deposited on said metal layer, for example by rolling.
• the negative electrode is composed of at least three layers, namely in this order a first metal layer, a layer of non-porous polymer membrane comprising two faces, and at least a second metal layer and it is obtained by complexing the first and second metal layers respectively on each of the faces of said non-porous polymer membrane.
• the method further preferably comprises a step of rolling the three-layer obtained between two rolls, optionally comprising co-winding films, in order to reduce the total thickness of the three-layer.
• the negative electrode is composed of at least five layers, and consists in this order, of a first metal layer, of a first non-porous polymer membrane conductor, a current collector, a second electrically conductive non-porous polymer membrane identical to the first electrically conductive non-porous polymer membrane, and a second metal layer identical to the first metal layer, and it is obtained according to a process comprising the following steps: i) the complexing of a metal layer on a non-porous electrically conductive polymer membrane, to obtain a bilayer, ii) the complexing of the bilayer obtained below above in step i) on each of the faces of a current collector, to obtain said negative electrode with at least 5 layers.
• the method further preferably comprises, between step i) and step ii), a step of rolling the bilayer obtained in step i) between two rolls, optionally comprising films co-winding, in order to reduce the total thickness of the bilayer.
• a composition comprising at least the constituent polymer (s) of the membrane, in solution in a solvent, is applied, for example by coating, directly to said metal layer or to a support film which is then complexed on said metal layer. Drying steps can then be implemented so as to cause the evaporation of the solvent and the formation of said membrane. Additional rolling steps can then be applied to the negative electrode according to the invention to reduce its total thickness. In this case, the thickness of each of the layers constituting the negative electrode in accordance with the invention becomes proportionately thinner.
• the rolling steps are preferably carried out at a temperature of 0 to 160 ° C, preferably 20 to 130 ° C.
• the lamination can be carried out in the presence of at least one co-winding film of polymer, for example of poly (ethylene terephthalate) (PET).
• PET poly (ethylene terephthalate)
• the force applied during the rolling steps can be chosen from a range going from 2.10 3 to 3.10 4 Pa, and preferably from 3.10 3 to 1.10 4 Pa approximately.
• a third object of the invention is an electrical energy storage system comprising at least one positive electrode, at least one electrolyte and at least one negative electrode, characterized in that said negative electrode is a negative electrode composite as defined according to the first subject of the invention.
• electrical energy storage systems include lithium batteries and sodium batteries.
• the energy storage system is preferably a lithium battery, and even more preferably an all-solid lithium battery comprising a solid polymer electrolyte such as, for example, Lithium-Metal-Polymer batteries. (LMP TM).
• LMP TM Lithium-Metal-Polymer batteries
• said lithium battery comprises at least one negative electrode composed of at least 3 layers, namely in this order a first metal layer, a layer of non-porous polymer membrane, and at least a second metallic layer.
• said lithium battery comprises at least one negative electrode composed of at least 5 layers, constituted in this order, of a first metal layer, of a first conductive non-porous polymer membrane. electricity, a current collector, a second electrically conductive non-porous polymer membrane, and a second metal layer.
• the first and second metal layers are identical to each other and the first and second non-porous electrically conductive polymer membranes are identical to each other.
• said battery is formed by the superposition, in this order, of the following elements:
• the positive electrode of a lithium battery is generally constituted by a current collector supporting a composite positive electrode comprising a positive electrode active material, optionally an electronic conduction agent, and optionally a binder.
• the active material of the positive electrode is usually a material whose working potential is less than 4V vs Li7Li (ie the lithium insertion / deinsertion potential is less than 4V) such as for example a metal oxide (as by example V2O5, L1V3O8, L1C0O2, LiNiC, LiMn204 and LiNio.5Mno.5O2 ...) or a phosphate of 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 , and also contains carbon and a polymer.
• the current collector is generally made of metal foil, for example aluminum foil.
• the electrolyte of a lithium battery is preferably a polymer electrolyte which is generally composed of a polymer based on poly (ethylene oxide) (POE) and at least one lithium salt.
• POE poly (ethylene oxide)
• FIG. 1 represents the evolution of the relative capacity and the efficiency of the battery of Example 3 compared to a control battery, as a function of the number of cycles;
• FIG. 2 shows the change in the internal resistance of the battery of Example 3, compared to a control battery, as a function of the number of cycles
• FIG. 3 shows the change in the relative capacity and the efficiency of the battery of Example 4, compared to a control battery, as a function of the number of cycles;
• FIG. 4 shows the change in the internal resistance of the battery of Example 4, compared to a control battery, as a function of the number of cycles;
• FIG. 5 represents the evolution of the relative capacity and the efficiency of the battery of Example 6, compared to a control battery, as a function of the number of cycles;
• FIG. 6 shows the change in the internal resistance of the battery of Example 6, compared to a control battery, as a function of the number of cycles;
• FIG. 7 is a schematic view of a composite negative electrode in accordance with the invention comprising 5 layers (pentacilayers): Lithium / Conductive polymer membrane / Copper collector / Conductive polymer membrane / Lithium;
• FIG. 8 represents the evolution of the relative capacity and the efficiency of the battery of Example 8, compared to a control battery, as a function of the number of cycles;
• FIG. 9 shows the change in the internal resistance of the battery of Example 8, compared to a test battery, as a function of the number of cycles.
• Example 1 Preparation of a negative lithium composite electrode comprising an electrically conductive polymer membrane
• Step 1 Preparation of a conductive polymer membrane electricity
• a polymer composition was prepared by mixing 90% by weight of polyethylene oxide sold under the reference POE 1 L by the company Sumitomo Seika and 10% by weight of carbon black under the trade name Ketjenblack EC600JD by the company Akzo Nobel using a Plastograph® (Brabender), at a temperature of 100 ° C. and at a speed of 80 revolutions per minute. The mixture obtained was then rolled at 110 ° C in the form of a membrane having a thickness of 10 ⁇ m.
• the three-layer thus obtained was then laminated between two rolls, using two co-winding films of poly (ethylene terephthalate) (PET), at room temperature under a pressure of 5.10 3 Pa to obtain films of a three-layer negative electrode having a total thickness of 15-20 ⁇ m, which corresponds to about 7 ⁇ m of lithium on each side of the polymer membrane, the latter having a thickness of about 5 ⁇ m.
• PET poly (ethylene terephthalate)
• Example 2 Preparation of a negative lithium composite electrode comprising an electrically conductive polymer membrane
• Example 2 was prepared according to the process described above in Example 1, a negative composite electrode identical in all points to that of Example 1 above, except that in this example the thickness of the polymeric membrane was set at 30 ⁇ m.
• a negative electrode was thus obtained composed of two sheets of lithium with a thickness of approximately 11 ⁇ m arranged on either side of the polymer membrane (approximately 30 ⁇ m), which corresponds to a total thickness of the electrode. about 52 pm.
• the composite negative electrode obtained above in Example 1 was used for the manufacture of a lithium-metal-polymer (LMP TM) battery.
• LMP TM lithium-metal-polymer
• a polymer electrolyte comprising 40% by weight of a copolymer of poly (vinylidene fluoride) and of hexafluoropropylene sold under the reference PVDF-HFP 21512 by the company Solvay, 48% by weight of poly (ethylene oxide) ) (POE 1 L) sold by the company Sumitomo Seika and 12% by mass of LiTFSI (Solvay) was prepared in a Plastograph® Brabender mixer at 130 ° C and at a speed of 80 revolutions per minute. The mixture thus obtained was then laminated at 130 ° C. between two silicone PET films. A polymer electrolyte film having a thickness of about 20 ⁇ m was obtained at the end of the lamination.
• a positive electrode comprising 74% by mass of LiFePC (LFP) sold by the company Sumitomo Osaka Cernent, 2% by mass of carbon black sold under the trade name Ketjenblack EC600JD by the company Akzo Nobel, 4.8% by weight.
• mass of LiTFSI (Solvay) and 19.2% by mass of POE was prepared in a Plastograph® Brabender mixer at 80 ° C. and at a speed of 80 revolutions per minute. The resulting mixture was then rolled at 80 ° C on a coated aluminum current collector (Armor).
• a battery according to the present invention was then assembled by successive rolling of the assembly formed by the composite negative electrode as obtained above in Example 1, the polymer electrolyte film and the positive electrode.
• the lamination was carried out at a pressure of 5.10 3 Pa and at a temperature of 80 ° C in air (dew point of -40 ° C) in small cells, of the "pouch cell” type having a volume of 10. cm 3 approximately.
• a control battery not in accordance with the invention, was assembled using the same positive electrode, the same polymer electrolyte but using, as negative electrode, a single sheet of lithium. 10 ⁇ m thick, stuck to a support film of PET to allow its handling.
• the assembly of the test battery was carried out under the same conditions as those of the battery according to the invention.
• the results obtained are given in FIG. 1 in which, for each of the two batteries, the relative capacity and the efficiency (%) are expressed as a function of the number of cycles.
• the gray curves correspond to the evolution of the relative capacity and the efficiency of the battery in accordance with the present invention and the black curves correspond to the evolution of the relative capacity and of the efficiency of the test battery not in accordance with the present invention.
• the solid diamond curves correspond to the change in capacity while the empty diamond curves correspond to the change in efficiency.
• FIG. 1 demonstrate that the efficiency and the relative capacity of the battery according to the present invention, that is to say comprising the composite negative electrode, are stable for approximately 120 cycles.
• the yield of the battery according to the invention begins to drop between the 120th and 150th cycles.
• the control battery not in accordance with the invention that is to say in which the negative electrode is a simple sheet of metallic lithium, has an efficiency and a relative capacity which are only stable over about twenty cycles. .
• FIG. 2 shows the evolution of the internal resistance (Ri in Ohm. Cm 2 ) as a function of the number of cycles, for the two batteries tested.
• the gray curve corresponds to the change in the internal resistance of the battery in accordance with the invention containing the composite negative electrode, while the black curve corresponds to the change in the internal resistance of the non-compliant control battery. to the invention.
• Example 4 Manufacture of a lithium battery according to the invention
• Example 2 The composite negative electrode obtained above in Example 2 was used for the manufacture of a lithium-metal-polymer (LMP TM) battery according to the present invention according to exactly the same process as that described below. above in Example 3.
• LMP TM lithium-metal-polymer
• the results obtained are given in FIG. 3 in which, for each of the two batteries, the relative capacity and the efficiency (%) are expressed as a function of the number of cycles.
• the gray curves correspond to the evolution of the relative capacity and the efficiency of the battery in accordance with the present invention and the black curves correspond to the evolution of the relative capacity and of the efficiency of the test battery not in accordance with the present invention.
• the solid diamond curves correspond to the change in capacity while the empty diamond curves correspond to the change in efficiency.
• FIG. 4 shows the evolution of the internal resistance (Ri in Ohm. Cm 2 ) as a function of the number of cycles, for the two batteries tested.
• the gray curve corresponds to the change in the internal resistance of the battery in accordance with the invention containing the composite negative electrode, while the black curve corresponds to the change in the internal resistance of the non-compliant control battery. to the invention.
• Figure 3 shows that the evolution of efficiency and capacity are comparable for the two batteries.
• the results presented in Figure 4 show that the development of internal resistance is slightly different. Indeed, the internal resistance of the test battery not according to the present invention increases more rapidly than that of the battery according to the present invention, that is to say comprising the composite negative electrode. The operation of the battery according to the present invention is therefore better than that of the control battery.
• Example 5 Preparation of a negative lithium composite electrode comprising a polymer membrane which is not electrically conductive
• Step 1 Preparation of a non-conductive polymer membrane of electricity
• a polymer composition was prepared by mixing 40% by mass of a copolymer of poly (vinylidene fluoride) and hexafluoropropylene sold under the reference PVDF-HFP 21512 by the company Solvay, 48% by mass of poly (ethylene oxide) (POE 1 L) sold by the company Sumitomo Seika and 12% in mass of LiTFSI (Solvay) using a Plastograph® (Brabender), at a temperature of 130 ° C. and at a speed of 80 revolutions per minute. The mixture thus obtained was then rolled at 130 ° C. until a membrane having a thickness of 14 ⁇ m was obtained.
• the three-layer thus obtained was then laminated between two rolls, using two co-winding films of poly (ethylene terephthalate) (PET), at room temperature, under a pressure of 5.10 3 Pa to obtain Three-layer negative electrode films having a total thickness of 15-20 ⁇ m, corresponding to about 7 ⁇ m of lithium on each side of the polymeric membrane, the latter having a thickness of about 2 ⁇ m.
• PET poly (ethylene terephthalate)
• Example 6 Manufacture of a lithium battery according to the invention
• Example 5 The composite negative electrode obtained above in Example 5 was used for the manufacture of a lithium-metal-polymer (LMP TM) battery.
• LMP TM lithium-metal-polymer
• a polymer electrolyte comprising 40% by weight of a copolymer of poly (vinylidene fluoride) and of hexafluoropropylene sold under the reference PVDF-FIFP 21512 by the company Solvay, 48% by weight of poly (ethylene oxide) ) (POE 1 L) sold by the company Sumitomo Seika and 12% by mass of LiTFSI (Solvay) was prepared in a Plastograph® Brabender mixer at 130 ° C. and at a speed of 80 revolutions per minute. The mixture thus obtained was then laminated at 130 ° C. between two silicone PET films. A polymer electrolyte film having a thickness of about 20 ⁇ m was obtained after the lamination.
• a positive electrode comprising 74% by mass of LiFeP0 4 (LFP) sold by the company Sumitomo Osaka Cernent, 2% by mass of carbon black sold under the trade name Ketjenblack EC600JD by the company Akzo Nobel, 4.8% by mass of LiTFSI (Solvay) and 19.2% by mass of POE (reference POE 1 L; Sumitomo Seika) was prepared in a Plastograph ® Brabender mixer at 80 ° C and at a speed of 80 revolutions per minute. The resulting mixture was then rolled at 80 ° C on a coated aluminum current collector (Armor).
• LFP LiFeP0 4
• a battery according to the present invention was then assembled by successive rolling of the assembly formed by the composite negative electrode as obtained above in Example 5, the polymer electrolyte film and the positive electrode.
• the rolling was carried out at a pressure of 5.10 3 Pa and at a temperature of 80 ° C. in air (dew point of -40 ° C.) in pouch cells.
• a control battery not in accordance with the invention, was assembled using the same positive electrode, the same polymer electrolyte but using, as negative electrode, a single sheet of lithium. 10 ⁇ m thick, stuck to a support film of PET to allow its handling.
• the assembly of the test battery was carried out under the same conditions as those of the battery according to the invention.
• the results obtained are given in FIG. 5 in which, for each of the two batteries, the relative capacity and the efficiency (%) are expressed as a function of the number of cycles.
• the gray curves correspond to the evolution of the relative capacity and the efficiency of the battery in accordance with the present invention and the black curves correspond to the evolution of the relative capacity and of the efficiency of the test battery not in accordance with the present invention.
• the solid diamond curves correspond to the change in capacity while the empty diamond curves correspond to the change in efficiency.
• FIG. 6 shows the evolution of the internal resistance (Ri in Ohm. Cm 2 ) as a function of the number of cycles, for the two batteries tested.
• the gray curve corresponds to the change in the internal resistance of the battery according to the invention containing the composite negative electrode while the black curve corresponds to the evolution of the internal resistance of the control battery not in accordance with the invention.
• Example 7 Manufacture of a negative lithium composite electrode comprising a current collector
• Step 1 Preparation of a conductive polymer membrane electricity
• a polymer composition was prepared by mixing 90% by weight of polyethylene oxide sold under the reference POE 1 L by the company Sumitomo Seika and 10% by weight of carbon black under the trade name Ketjenblack EC600JD by the company.
• Akzo Nobel company using a Plastograph ® (Brabender), at a temperature of 100 ° C and at a speed of 80 revolutions per minute.
• a 35 ⁇ m thick lithium strip was laminated on one of the faces of the polymer membrane obtained above in the previous step to obtain a composite electrode with two lithium layers / polymer membrane (bilayer) .
• the rolling was carried out under a pressure of 5.10 5 Pa and at a temperature of 80 ° C.
• the bilayer thus obtained was then laminated between two rolls, using two co-winding films of poly (ethylene terephthalate) (PET), at room temperature under a pressure of 5.10 3 Pa to obtain a film negative bilayer electrode having a total thickness of 10 ⁇ m, which corresponds to about 7 ⁇ m of lithium on a 3 ⁇ m membrane.
• PET poly (ethylene terephthalate)
• the bilayer thus obtained after this rolling was then applied to each of the two faces of a copper current collector having a thickness of 10 ⁇ m, by rolling at 80 ° C under a pressure of 5.10 3 Pa, so to get a 5-layer composite negative electrode (five-layer): Lithium / Conductive polymer membrane / Copper collector / Conductive polymer membrane / Lithium having a total thickness of about 30 ⁇ m.
• Example 8 Manufacture of a battery according to the invention comprising a negative lithium composite electrode comprising a current collector
• Example 6 The composite negative electrode obtained above in Example 6 was used for the manufacture of a lithium-metal-polymer (LMP TM) battery.
• LMP TM lithium-metal-polymer
• a polymer electrolyte comprising 40% by weight of a copolymer of poly (vinylidene fluoride) and of hexafluoropropylene sold under the reference PVDF-HFP 21512 by the company Solvay, 48% by weight of poly (ethylene oxide) ) (POE 1 L) sold by the company Sumitomo Seika and 12% by mass of LiTFSI (Solvay) was prepared in a Plastograph® Brabender mixer at 130 ° C. and at a speed of 80 revolutions per minute. The mixture thus obtained was then laminated at 130 ° C. between two silicone PET films. A polymer electrolyte film having a thickness of about 20 ⁇ m was obtained after the lamination.
• a positive electrode comprising 74% by mass of LiFeP0 4 (LFP) sold by the company Sumitomo Osaka Cernent, 2% by mass of carbon black sold under the trade name Ketjenblack EC600JD by the company Akzo Nobel, 4.8% by mass of LiTFSI (Solvay) and 19.2% by mass of POE (reference: POE 1 L ..; Sumitomo) was prepared in a Plastograph® Brabender mixer at 80 ° C. and at a speed of 80 revolutions per minute. The resulting mixture was then rolled at 80 ° C on a coated aluminum current collector (Armor).
• LFP LiFeP0 4
• a battery according to the present invention was then assembled by successive rolling of an assembly comprising in the center the negative electrode as prepared above in Example 6, surrounded on either side by two electrolytes and two positive electrodes as illustrated in FIG. 7 attached.
• the battery 1 comprises a composite negative electrode 2 comprising a copper current collector 21 comprising on each of its two faces a conductive polymer membrane 22, each of these two conductive polymer membranes 22 being in direct physical contact. with a lithium foil 23.
• Each lithium foil 23 is in contact with a film of polymer electrolyte 3 by the face opposite to the face being in contact with the conductive polymer membrane 22, said films of polymer electrolyte 3 being themselves each in contact with a positive electrode 4 comprising a layer of positive electrode material 41 in contact with one face of each polymer electrolyte 3, and a current collector 42 made of aluminum.
• the rolling was carried out at a pressure of 5.10 3 Pa and at a temperature of 80 ° C. in air (dew point of -40 ° C.) in pouch cells.
• a control battery not in accordance with the invention, was assembled using a single sheet of lithium 30 ⁇ m thick in place of the composite negative electrode 2, the other constituent elements of the control battery (electrolytes and positive electrodes) being otherwise identical to those of the battery according to the invention.
• the assembly of the test battery was carried out under the same conditions as those of the battery according to the invention.
• the results obtained are given in FIG. 8 in which, for each of the two batteries, the relative capacity and the efficiency (%) are expressed as a function of the number of cycles.
• the gray curves correspond to the evolution of the relative capacity and the efficiency of the battery in accordance with the present invention and the black curves correspond to the evolution of the relative capacity and of the efficiency of the test battery not in accordance with the present invention.
• the solid diamond curves correspond to the change in capacity while the empty diamond curves correspond to the change in efficiency.
• FIG. 9 shows the evolution of the internal resistance (Ri in Ohm. Cm 2 ) as a function of the number of cycles, for the two batteries tested.
• the gray curve corresponds to the evolution of the internal resistance of the battery according to the invention containing the composite negative electrode
• the black curve corresponds to the evolution of the internal resistance of the control battery not in accordance with invention.
• the results presented in FIG. 9 show that even if the internal resistance of the battery in accordance with the invention is initially higher than that of the control battery not in accordance with the invention, the internal resistance of the battery in accordance with the invention does not change during the charge and discharge cycles while that of the test battery increases, thus reflecting a degradation in the electrochemical performance of the battery.
• the use of a composite negative electrode in accordance with the present invention leads to better cycling stability of the battery comprising it.

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• 2019
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