Classifications

• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
  • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
  • H01G11/22—Electrodes
  • H01G11/30—Electrodes characterised by their material
  • H01G11/46—Metal oxides
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B02—CRUSHING, PULVERISING, OR DISINTEGRATING; PREPARATORY TREATMENT OF GRAIN FOR MILLING
  • B02C—CRUSHING, PULVERISING, OR DISINTEGRATING IN GENERAL; MILLING GRAIN
  • B02C17/00—Disintegrating by tumbling mills, i.e. mills having a container charged with the material to be disintegrated with or without special disintegrating members such as pebbles or balls
  • B02C17/18—Details
  • B02C17/1815—Cooling or heating devices
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
  • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
  • H01G11/04—Hybrid capacitors
  • H01G11/06—Hybrid capacitors with one of the electrodes allowing ions to be reversibly doped thereinto, e.g. lithium ion capacitors [LIC]
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
  • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
  • H01G11/22—Electrodes
  • H01G11/30—Electrodes characterised by their material
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
  • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
  • H01G11/22—Electrodes
  • H01G11/30—Electrodes characterised by their material
  • H01G11/32—Carbon-based
• • 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
  • 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
  • H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
• • 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
  • H01M4/136—Electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
• • 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
  • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
  • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
• • 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
  • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
  • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
  • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
• • 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
  • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
  • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
  • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
• • 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
  • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
  • H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
• • 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
  • H01M4/625—Carbon or graphite
• • 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
  • H01M4/64—Carriers or collectors
  • H01M4/66—Selection of materials
  • H01M4/661—Metal or alloys, e.g. alloy coatings
• • 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
• • 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
  • 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
  • Y02E60/13—Energy storage using capacitors
• • 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

• the present invention relates to mixtures of particles comprising a non-conductive or semi-conductive core and a conductive hybrid coating as well as a connection of hybrid conductive chains.
• the present invention also relates to methods allowing the preparation of these particles and to their use in particular in the field of electrochemical devices such as rechargeable electrochemical generators.
• An object of the present invention is also constituted by anodes and cathodes comprising such particles and by electrochemical systems, in particular the supercapacitors thus obtained.
• Figure 1/7 is a schematic representation of a particle of Li Ti 5 ⁇ 2 with a simple coating of carbon as obtained by implementing the synthesis process described in WO 02/46101 A2.
• Figure 2/7 is a schematic representation of a simple network of Li 4 Ti 5 ⁇ 2 particles with a simple carbon coating as obtained by implementing the synthesis process described in WO 02/46101 A2.
• Figure 3/7 is a schematic representation of a network of particles, according to the present invention, comprising a core of Li TisO ⁇ 2 and a hybrid coating of carbon C1 and carbon graphite C2.
• Figure 4/7 highlights the beneficial role of Carbon 2 with carbon orientation, during calendering.
• Figure 5/7 illustrates a device of the High Energy Bail Milling type used for the preparation of particles according to the invention having a core of
• Figure 6/7 schematically represents a particle whose core consists of Li Ti 5 0 ⁇ 2 , coated according to an embodiment of the present invention, in which the hybrid conductive mixed coating consists of graphite particles and Kejen black.
• Figure 7/7 shows schematically a mixture of particles according to Figure 6/7 and the conductivity network created at the level of these particles by hybrid conductive chains based on graphite and Kejen black.
• the present invention relates to a mixture of particles comprising a non-conducting or semi-conducting core.
• the nuclei of these particles are covered with a conductive hybrid coating, and hybrid conductive chains located between the particles of the mixture constitute a network of conductivity there.
• mixtures of particles can be prepared by processes comprising at least the preparation of a mixture of at least one non-conductive or semi-conductive material with a conductive material, then the addition of a second conductive material to the mixture obtained ; or at least the preparation of a mixture of at least one non-conductive or semi-conductive material with at least two conductive materials; or at least the preparation of a mixture of conductive materials and then its mixture with at least one non-conductive or semiconductor material.
• the first object of the present invention consists of a mixture of particles comprising a non-conductive or semi-conductive core, the cores of said particles being at least partially covered with a conductive hybrid coating and said particles being at least partially connected together by hybrid conductive chains, that is to say by chains formed by at least two types of conductive particles of different nature and which create an electrical conductivity network.
• E V / l
• J ⁇ E.
• - conductive metals such as ⁇ > 10 5 ( ⁇ .m) _1 ;
• - insulators such as ⁇ ⁇ 10 6 ( ⁇ .m) _1 .
• conductive hybrid coating (also called hybrid mixture) is understood to mean any coating consisting of at least two different conductive materials.
• the term coating covers in particular the deposition of a more or less perfect layer on the surface of a particle and the surrounding of the particles in a more or less uniform manner by conductive particles at least partially connected together.
• conductive hybrid coatings consisting of a layer of particles of at least two different conductive materials, at least part of the particles of one of the conductive materials coating a first core and being interconnected with conductive particles coating a second nucleus located near the first nucleus in the mixture of particles, and thus creating an electrical conductivity network.
• such conductive hybrid coatings that may be mentioned in the context of the present invention a hybrid coating which comprises: a first layer of particles of a first conductive material, said first layer covering at least partially, preferably between 50 and 90%, more preferably at least 80%, of the surface of said cores; and - a second layer of particles of a second conductive material, said particles of the second conductive material preferably being from 10 to 50% (more preferably for approximately 20%) connected together to form an electrical conductivity network.
• the nuclei of the particles comprise a material chosen from the group consisting of phosphates, nitrides, oxides or mixtures of two or more of these.
• the core of the constituent particles of the mixtures of the invention preferably comprises, for at least 70% by weight, at least one metal oxide such as a metal oxide constituted for more than 65% by weight of a lithium oxide. .
• the lithium oxide may or may not be coated with carbon and preferably the lithium oxide has a spinel structure.
• Particularly interesting mixtures of particles are those in which the lithium oxide is chosen from the group consisting of the oxides of formula: - Li 4 Ti 5 ⁇ 2;
• Z representing a source of at least one metal preferably chosen from the group consisting of Mg, Nb, Al, Zr, Ni, and Co.
• the core of these particles consists for at least 65% of Li Ti5 ⁇ i2, Li ( 4- ⁇ ) Z ⁇ Ti5 ⁇ 2 , Li ZpTi ( 5- ⁇ ) O ⁇ or a mixture of the latter, the parameters ⁇ and ⁇ being as previously defined.
• a particularly interesting sub-family of mixtures of particles according to the invention consists of mixtures in which the core of the particles consists of Li Ti 5 0 ⁇ 2 , Li ( - ⁇ ) Z ⁇ Ti5 ⁇ 2 , Li Z ⁇ Ti (5 . ⁇ ) O ⁇ 2 or a mixture of two or more of these, with ⁇ and ⁇ being as defined above.
• the material constituting the nucleus of the particles is of the semiconductor type and it consists of at least one element chosen from the group consisting of Si, Si preferably doped with Ge, Ge, InSb and the mixture of these last.
• the core of the particles is non-conductive and it consists of at least one material chosen from the group consisting of glasses, mica, Si0 2 and mixtures of these.
• the cores advantageously comprise at least one of the carbon-coated lithium oxides described and / or obtained by one of the methods described in PCT application WO 02/46101 A2, the content of which is incorporated by reference to this application.
• LiMn 0 Metal oxides of formula LiMn 0; 5Nio, 5 ⁇ 2 , LiMn 0 , 33 Nio, 33 C 0 o, 3 3 ⁇ 2 , Li 4 Ti 5 0 ⁇ 2, Li 2 TiC0 3 , LiC 0 0 2 , LiNi0 2 , LiMn 2 0 or mixtures of these.
• the carbon contents are such that the total carbon present represents from 1 to 6%, and preferably approximately 2% of the total weight of the mixture of particles.
• the coating of the particles of the invention consists of a hybrid mixture of carbons, and / or by a hybrid carbon-metal mixture.
• the metal in particular be chosen from the group consisting of silver, aluminum and the corresponding mixtures.
• the hybrid coating is of the carbon type, it advantageously comprises at least two different forms of carbon, hereinafter called Carbon 1 and Carbon
• Carbon 1 is then advantageously a carbon with low crystallinity.
• the crystallinity of the Carbon 1 particles present in the mixtures of particles which are the subject of the invention is characterized by a DO 02 , measured by X-ray diffraction or by Raman spectroscopy, greater than 3.39 Angstroms.
• Carbon 2 is usually of the graphite type and / or of the high crystallinity carbon type.
• the crystallinity of Carbon 2 particles measured by X-ray diffraction or Raman spectroscopy, is characterized by a doo 2 of less than 3.36 Angstroms.
• Carbon 2 is of the natural graphite, artificial graphite or exfoliated graphite type.
• Carbon 2 is advantageously chosen so as to have a specific surface area measured according to the BET method, which is less than or equal to 50 m 2 / g and / or an average size varying from 2 to 10 micrometers.
• Carbon 2 consists of at least one graphite chosen from the group of artificial graphites, natural graphites, exfoliated graphites or mixtures of these graphites.
• Carbon 1 is advantageously chosen so as to have a specific surface, measured according to the BET method, greater than or equal to 50 m 2 / g.
• a preferred subfamily of mixture of particles according to the invention consists of mixtures comprising particles of Carbon 1 having a size varying from 10 to 999 nanometers.
• the percentage by mass of Carbon 1 represents, in the coating composed of Carbon 1 and Carbon 2, from 1 to 10%, and it is preferably substantially identical to the amount of Carbon 2.
• the subfamilies consisting of powder mixtures in which the average diameter of the particle nucleus, measured using the scanning electron microscope, varies from 50 nanometers to 50 micrometers, is preferably between 4 and 10 micrometers, more preferably still the average particle diameter and of the order of 2 micrometers are of particular interest in the context of applications in electrochemical systems.
• mixtures of particles are characterized by at least one of the following properties: very good local conductivity, very good network conductivity, low resistivity, very good high current capacity and good energy density.
• the local conductivity of the mixtures of particles according to the invention is usually, measured according to the four-point method, greater than 10 " (Ohm-m) and it is preferably greater than or equal to 10 " 5 (Ohm-m).
• the network conductivity meanwhile, measured according to the four-point method, is usually between 2.6x10 "3 and 6.2x10 " 3 (Ohm-m), and it is preferably less than 6.0xl0 "3 ( ohm-m).
• the powders of the invention have a D50 of approximately 7 micrometers.
• a second object of the present invention consists of the methods for preparing mixtures of particles in accordance with the first object of the present invention. These methods advantageously include at least one of the following steps: a) the preparation of a mixture of at least one non-conductive or semi-conductive material with a conductive material, then the addition of a second conductive material to the mixture obtained;
• the mixing of materials is carried out by mechanical grinding of the HEBM, Jar milling, Vapor jet milling type and preferably by HEBM. These processes are usually carried out at a temperature below 300 degrees Celsius, preferably at a temperature between 20 and 40 ° Celsius, more preferably still at room temperature.
• the mixing of the carbons is carried out chemically before the synthesis step of Li Ti 5 0 ⁇ 2 .
• one of the conductive materials is obtained by heat treatment of a polymer type precursor.
• the polymer can then be chosen from the group constituted by natural polymers and by modified natural polymers as well as by mixtures of the latter.
• a polymer which can be used for the preparation of the mixtures of particles of the invention mention may be made of sugars, chemically modified sugars, starches, chemically modified starches, gelatinized starches, chemically modified starches, chemically modified and gelatinized starches, celluloses, chemically modified celluloses and mixtures thereof.
• cellulose acetate is mentioned.
• the mixture of carbons introduced into the reaction medium can also be produced by physical mixing, after the synthesis of Li Ti 5 0 ⁇ 2 .
• a third object of the present invention consists of cathodes, in particular the cathodes of electrochemical generators (preferably of electrochemical generators of recyclable type) comprising a mixture of particles such as those defined in the first object of the present invention and / or particles capable of being obtained by a process according to the second object of the present invention.
• electrochemical generators preferably of electrochemical generators of recyclable type
• a fourth object of the present invention consists of the anodes of electrochemical generator (preferably of recyclable electrochemical generators) comprising particles such as those defined in the first object of the present invention and / or particles capable of being obtained by a method according to the third object of the present invention.
• a fifth object of the present invention consists of electrochemical generators of lithium type comprising at least one electrolyte, at least one anode of metallic lithium type and at least one cathode of type Li 4 Ti 5 0 ⁇ 2 and / or Li ( - ⁇ ) Z ⁇ Ti 5 0 2 and / or Li 4 Z ⁇ Ti (5- ⁇ ) O ⁇ 2 , the cathode in said generator being as defined in the third object of the present invention.
• These generators are advantageously of the rechargeable and / or recyclable type.
• electrochemical generators those of the lithium ion type comprising an anode is as defined in the fourth object of the invention, preferably an anode of the Li 4 Ti5 ⁇ 2 type and / or of the Li type ( 4- ⁇ ) Z ⁇ Ti5 ⁇ 2 and / or of Li 4 type Z ⁇ Ti ( 5- ⁇ ) O ⁇ 2 and a cathode of LiFeP0, LiCo0 2 , LiMn 2 0 and / or LiNi0 2 type .
• the anode and / or the cathode are equipped with a current collector of solid aluminum or of the Exmet type (expanded metal).
• electrochemical generators generally have the advantage of not requiring any prior training of the battery.
• the electrolyte is of dry polymer, gel, liquid or ceramic nature.
• a sixth object of the present invention consists of hybrid type supercapacitors comprising at least one electrolyte, at least one anode as defined in the fourth object of the invention, preferably an anode of Li 4 TisOi2 type and / or type Li ( - ⁇ ) Z ⁇ Ti5 ⁇ 2 and / or Li Z ⁇ Ti (5. ⁇ ) O ⁇ 2 and a graphite or carbon type cathode with large specific surface.
• the supercapacitors of the invention are such that the anode and / or the cathode are equipped with a current collector of solid aluminum or of the Exmet (expanded metal) type.
• the electrolyte is of dry polymer, gel, liquid or ceramic nature.
• the electrochemical systems according to the invention also have the advantage of being able to be prepared without any addition of other carbon.
• Li 4 Ti 5 0 ⁇ 2 is obtained from a binary mixture of Ti0 2 and Li 2 C0 calcined at 850 ° C for 18 hours. The Li 4 Ti 5 0 ⁇ 2 obtained is then mixed with two different types of carbons: a Carbon 1 also called Cl and a Carbon 2 also called C2.
• Carbon 1 it is a carbon with low crystallinity and preferably having a BET specific surface ⁇ 50 m 2 / g. Carbon 1 can be a carbon black, or any other type of conductive additive.
• Carbon 2 it is a carbon with high crystallinity and preferably having a BET surface ⁇ 50 m 2 / g. Carbon 2 can be natural graphite or artificial graphite, possibly exfoliated.
• Carbon 1 The role of this carbon is twofold. The first is to coat the particle to ensure local conductivity of the particle as shown in Figure 1/7.
• the second role of carbon with low crystallinity is to form a conductivity network between particles of the type of those represented in Figure 1/7, which provides conductivity at the electrode. Indeed, the preparation of the electrode is done without any carbon additive.
• the electronic network and the inter-particle conductivity are also provided by Carbon 1 as also shown in Figure 2/7.
• Carbon 2 is of the graphite type and it allows, first of all, surprisingly, to improve the conductivity of the electrode by forming nodes constituting stations of homogeneous distribution of the electrical conductivity. These stations appear in the representation of Figure 3/7.
• the good electronic conductivity of graphite lowers the resistivity of the electrode, which advantageously allows the battery to operate at high current densities.
• the second role of graphite is at the process level.
• Graphite has the characteristics of a lubricating and hydrophobic material. During the spreading of the electrode, graphite makes it possible to control the porosity of the electrode. Such calendering of the electrodes also makes it possible to orient the particles towards the basal plane, as appears in FIG. 4/7, that is to say parallel to the surface of the support of the electrode; which induces a maximum conductivity of the electrode.
• graphite due to its lubricating properties, ensures ease of extrusion as well as the homogeneity of the thickness of the electrode. In addition, it increases the extrusion speed. These technical advantages result in a reduced production cost of the electrodes.
• graphite when used for dry electrode preparation, helps lubricate the extruder nozzle and helps prevent the deposition of metals on the surface of the nozzle. 3 -Preparation of particles
• a ternary mixture (Mi) (Li 4 Ti 5 0 ⁇ 2 + Cl + C2) is obtained by high energy grinding HEMB (High Energy Bail Mill).
• HEMB High Energy Bail Mill
• a metal crucible is used.
• the mixture Mi is introduced and steel balls in a volume proportion 1/3, 1/3 and 1/3 of free empty volume are placed in the crucible as shown in Figure 5/7.
• the mixing conditions by HEBM are very important, one of the most crucial is not to destroy the crystallinity of the carbon C2. In fact, the particle size of carbon C2 should not be reduced below 1 micrometer.
• the electrode is prepared from the mixture of Mi and PVDF. This mixture is produced in a ternary solvent N-methylpyrrolydone (NMP), acetone, toluene) as described in the hydro-Québec patent WO 01/97303 A1, the content of which is incorporated by reference into the present application.
• NMP N-methylpyrrolydone
• acetone acetone
• toluene hydro-Québec patent WO 01/97303 A1
• the conductivity of the paste obtained is intrinsically ensured by the mixture Mi (Li 4 Ti5 ⁇ 2 + Ci + C 2 ), without adding additional carbon which has a positive impact on the energy density of the battery which in this case n is not penalized by the additional weight of another carbon source.
• the quaternary mixture (M 2 ) comprises Ti0 2 , Li 2 C0 3 , carbon C2 (graphite) and a carbon precursor (polymer or other).
• the mixture M 2 is then introduced into a metal crucible.
• HEBM-type co-grinding is carried out in order to obtain an intimate mixture.
• the mixture obtained is then placed in a quartz tube to be heated there.
• the synthesis is then finalized in the presence of an inert atmosphere in order to carbonize the polymer.
• the Li 4 TisO ⁇ 2 product is coated with carbon with low crystallinity and graphite with high crystallinity.
• the manufacture of the electrodes is equivalent to that described in paragraph 4 above.
• a mixture of Li Ti 5 2 ⁇ 2 , a Ketjen black and natural graphite of Brazilian origin, in a volume ratio of 80.77 / 7.32 / 2.5 is ground by HEBM for 1 hour.
• Particles having a core of Li Ti 5 0 ⁇ 2 , with an average size of 5 micrometers, and with a hybrid coating of graphite and Ketjen black are thus obtained. Their average thickness is 2 micrometers.
• a mixture of Li Ti 5 ⁇ 2 ,, Ketjen black and graphite in a volume ratio of 40 / 2.5 / 2.5 is prepared according to the method described in the previous example 1.
• Example # 1 A mixture of Li TisO ⁇ 2 , Ketjen black and graphite in a volume ratio 81.06 / 3.51 / 2.5 is prepared as in Example # 1
• the total mass of carbon added corresponds to approximately 6% of the mass of the total mixture.
• a mixture of LiMno, 5Nio, s0 2 , non-conductive, a non of Ketjen and natural graphite of Brazilian origin in a mass proportion of 94/3/3 is ground by Mechanofusion from Hosokawa for 1 hour.
• These particles obtained have a LiM ⁇ in core, 5 Nio, 5 ⁇ , an average size of 7 ⁇ m and a hybrid coating of graphite + Ketjen black and a thickness of 3 ⁇ m.
• the resistivity of the coated material, measured by the four-point method, is 5 x 10 " Ohm-m.
• Table 1 The high levels of electrochemical properties demonstrated in particular by these examples are used to prepare high performance electrochemical systems.

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