EP1520309A2 - Particles comprising a non-conducting or semi-conducting core, which are coated with a hybrid conducting layer, production methods thereof and uses of same in electrical devices - Google Patents

Particles comprising a non-conducting or semi-conducting core, which are coated with a hybrid conducting layer, production methods thereof and uses of same in electrical devices

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Publication number
EP1520309A2
EP1520309A2 EP03763538A EP03763538A EP1520309A2 EP 1520309 A2 EP1520309 A2 EP 1520309A2 EP 03763538 A EP03763538 A EP 03763538A EP 03763538 A EP03763538 A EP 03763538A EP 1520309 A2 EP1520309 A2 EP 1520309A2
Authority
EP
European Patent Office
Prior art keywords
mixture
particles
carbon
conductive
type
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
EP03763538A
Other languages
German (de)
French (fr)
Inventor
Karim Zaghib
Patrick Charest
Abdelbast Guerfi
Michel Perrier
Kimio Kinoshita
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Hydro Quebec
Original Assignee
Hydro Quebec
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Hydro Quebec filed Critical Hydro Quebec
Priority to EP06023645A priority Critical patent/EP1775786B1/en
Publication of EP1520309A2 publication Critical patent/EP1520309A2/en
Ceased legal-status Critical Current

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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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Abstract

Particle mixture (I) comprises particles having a nonconducting or semiconducting core and a hybrid conductor coating, the particles being interconnected with hybrid conductor chains to form a network of electrical conductivity. Independent claims are also included for the following: (1) production of (I) by preparing a mixture of a nonconducting or semiconducting material with a conductive material and adding a second conductive material, preparing a mixture of a nonconducting or semiconducting material with at least two conductive materials, or preparing a mixture of conductive material and mixing it with a nonconducting or semiconducting material; (2) battery cathode and anode comprising (I); (3) lithium battery comprising a metallic lithium anode and a cathode comprising (I); (4) hybrid supercapacitor comprising an electrolyte, an anode comprising (I), and a high surface area carbon or graphite cathode.

Description

PARTICULES COMPORTANT UN NOYAU NON CONDUCTEUR OU SEMI PARTICLES COMPRISING A NON-CONDUCTIVE OR SEMI-CORE
CONDUCTEUR ENROBÉES PAR UNE COUCHE CONDUCTRICECONDUCTOR COVERED BY A CONDUCTIVE LAYER
HYBRIDE, LEURS PROCÉDÉS D'OBTENTION ET LEURSHYBRID, PROCESSES FOR OBTAINING THEM AND THEIR
UTILISATIONS DANS DES DISPOSITIFS ÉLECTROCHIMIQUESUSES IN ELECTROCHEMICAL DEVICES
DOMAINE DE L'INVENTIONFIELD OF THE INVENTION
La présente invention est relative à des mélanges de particules comportant un noyau non-conducteur ou semi-conducteur et un enrobage hybride conducteur ainsi qu'une connexion de chaînes conductrices hybrides.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.
La présente invention est également relative à des procédés permettant la préparation de ces particules et à leur utilisation notamment dans le domaine des dispositifs électrochimiques tels que les générateurs électrochimiques rechargeables.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.
Un objet de la présente invention est également constitué par les anodes et les cathodes comportant de telles particules et par les systèmes électrochimiques, notamment les supercapaciteurs ainsi obtenus.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.
ÉTAT DE LA TECHNIQUE:STATE OF THE ART:
La Société Hydro-Québec qui est à l'origine du brevet US-A-5.521.026 est l'un des pionniers dans le domaine des co-broyages de carbone avec les oxydes. Dans ce document, le co-broyage d'un carbone en présence de solvant est décrit comme pouvant être utilisé pour préparer des matériaux augmentant la conductivité électrique des cathodes pour les batteries lithium polymère. Ainsi, l'oxyde de type Vox est co-broyé avec du noir de carbone. Dans la demande de brevet PCT publiée sous le numéro WO 02/46101 A2, la synthèse du matériau Li Ti50ι2 est décrite comme pouvant être réalisée en présence du carbone. Dans ce cas, le rôle du carbone est principalement d'obtenir des nano-particules et d'empêcher la formation des agglomérats.Société Hydro-Québec, which is the source of patent US-A-5,521,026, is one of the pioneers in the field of co-grinding of carbon with oxides. In this document, the co-grinding of carbon in the presence of solvent is described as being able to be used to prepare materials increasing the electrical conductivity of cathodes for lithium polymer batteries. Thus, the Vox type oxide is co-ground with carbon black. In the PCT patent application published under the number WO 02/46101 A2, the synthesis of the material Li Ti 5 0ι 2 is described as being able to be carried out in the presence of carbon. In this case, the role of carbon is mainly to obtain nanoparticles and to prevent the formation of agglomerates.
BRÈVE DESCRIPTION DES DESSINSBRIEF DESCRIPTION OF THE DRAWINGS
Figure 1/7: est une représentation schématique d'une particule de Li Ti5θι2 à enrobage simple de carbone telle qu'obtenue par mise en œuvre du procédé de synthèse décrit dans WO 02/46101 A2.Figure 1/7: is a schematic representation of a particle of Li Ti 5 θι 2 with a simple coating of carbon as obtained by implementing the synthesis process described in WO 02/46101 A2.
Figure 2/7: est une représentation schématique d'un réseau simple de particules de Li4Ti5θι2 à enrobage simple de carbone telles qu'obtenues par mise en œuvre du procédé de synthèse décrit dans WO 02/46101 A2.Figure 2/7: is a schematic representation of a simple network of Li 4 Ti 5 θι 2 particles with a simple carbon coating as obtained by implementing the synthesis process described in WO 02/46101 A2.
Figure 3/7: est une représentation schématique d'un réseau de particules, selon la présente invention, comportant un noyau de Li TisOι2 et un enrobage hybride de carbone Cl et de carbone graphite C2.Figure 3/7: is a schematic representation of a network of particles, according to the present invention, comprising a core of Li TisOι 2 and a hybrid coating of carbon C1 and carbon graphite C2.
Figure 4/7: met en évidence le rôle bénéfique du Carbone 2 avec orientation du carbone, lors d'un calandrage.Figure 4/7: highlights the beneficial role of Carbon 2 with carbon orientation, during calendering.
Figure 5/7: illustre un dispositif de type High Energy Bail Milling utilisé pour la préparation de particules selon l'invention ayant un noyau deFigure 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
Li4Ti50ι2.Li 4 Ti 5 0ι 2 .
Figure 6/7: représente de façon schématique une particule dont le noyau est constitué de Li Ti50ι2, enrobée selon un mode de réalisation de la présente invention, dans lequel l'enrobage hybride conducteur mixte est constitué de particules de graphite et de noir de Kejen. Figure 7/7: représente de façon schématique un mélange de particules selon la Figure 6/7 et le réseau de conductivité créé au niveau de ces particules par des chaînes hybrides conductrices à base de graphite et de noir de Kejen.Figure 6/7: schematically represents a particle whose core consists of Li Ti 5 0ι 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.
RESUME DE L'INVENTIONSUMMARY OF THE INVENTION
La présente invention a trait à un mélange de particules comprenant un noyau non- conducteur ou semi-conducteur. Les noyaux de ces particules sont recouverts d'un enrobage hybride conducteur, et des chaînes conductrices hybrides situées entre les particules du mélange y constituent un réseau de conductivité.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.
Ces mélanges de particules peuvent être préparées par des procédés comportant au moins la préparation d'un mélange d'au moins un matériau non-conducteur ou semi-conducteur avec un matériau conducteur, puis l'ajout d'un deuxième matériau conducteur au mélange obtenu; ou au moins la préparation d'un mélange d'au moins un matériau non-conducteur ou semi-conducteur avec au moins deux matériaux conducteurs; ou au moins la préparation d'un mélange de matériaux conducteurs puis son mélange avec au moins un matériau non-conducteur ou semiconducteur.These 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.
Du fait d'une très bonne conductivité du réseau, d'une faible résistivité, d'une très bonne capacité à haut courant et/ou d'une bonne densité d'énergie, ces particules sont avantageusement incorporées dans des anodes et dans des cathodes de générateurs électrochimiques, résultant en des systèmes électrochimiques hautement performants. DESCRIPTION DE L'INVENTIONDue to very good network conductivity, low resistivity, very good high current capacity and / or good energy density, these particles are advantageously incorporated in anodes and in cathodes electrochemical generators, resulting in high performance electrochemical systems. DESCRIPTION OF THE INVENTION
Le premier objet de la présente invention est constitué par un mélange de particules comprenant un noyau non-conducteur ou semi-conducteur, les noyaux desdites particules étant au moins partiellement recouverts d'un enrobage hybride conducteur et lesdites particules étant au moins partiellement connectées entre elles par des chaînes conductrices hybrides, c'est-à-dire par des chaînes constituées par au moins deux types de particules conductrices de nature différente et qui créent un réseau de conductivité électrique..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.
La conductivité électrique, c'est-à-dire l'aptitude d'une substance à conduire un courant électrique peut être définie comme l'inverse de la résistivité par la formule suivante: σ= l/p Comme l'intensité d'un champ électrique dans un matériau peut être exprimée par la formule E = V/l, la loi Ohm's peut être réécrite dans les termes de courants de densité J - I/A et on arrive alors à la formule J = σ E.The electrical conductivity, i.e. the ability of a substance to conduct an electric current can be defined as the inverse of the resistivity by the following formula: σ = l / p As the intensity of a electric field in a material can be expressed by the formula E = V / l, the Ohm's law can be rewritten in terms of density currents J - I / A and we then arrive at the formula J = σ E.
Il est par ailleurs bien connu que la conductivité électronique varie suivant les matériaux utilisés selon un ordre d'amplitude de 27. On divise ainsi les matériaux comme en 3 grandes familles:It is also well known that the electronic conductivity varies according to the materials used according to an amplitude order of 27. The materials are thus divided as into 3 main families:
- les métaux conducteurs tel que σ > 105 (Ω.m) _1;- conductive metals such as σ> 10 5 (Ω.m) _1 ;
- les semis conducteurs avec 10 "6 < σ < 105 (Ω.m) _1 ;- conductive seedlings with 10 "6 <σ <10 5 (Ω.m) _1 ;
- les isolants tels que σ < 106 (Ω.m) _1.- insulators such as σ <10 6 (Ω.m) _1 .
Ces grandes familles sont celles auxquelles il est fait référence dans le cadre de la présente demande.These large families are those to which reference is made in the context of the present application.
On entend par ailleurs, dans le cadre de la présente invention, par enrobage hybride conducteur (aussi appelé mélange hybride) tout enrobage constitué d'au moins deux matériaux conducteurs différents. Le terme enrobage couvre notamment le dépôt d'une couche plus ou moins parfaite à la surface d'une particule et l'entourage des particules de façon plus ou moins uniforme par des particules conductrices au moins partiellement reliées entre elles.In the context of the present invention, the term “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.
On peut également citer comme enrobage ceux qui comprend un mélange d'au moins deux matériaux conducteurs différents et sous forme particulaire, des particules de l'enrobage d'un premier noyau étant interconnectées avec des particules de l'enrobage d'un deuxième noyau situé dans le mélange de particules à proximité dudit premier noyau.Mention may also be made as a coating those which comprises a mixture of at least two different conductive materials and in particulate form, particles of the coating of a first core being interconnected with particles of the coating of a second core located in the mixture of particles near said first nucleus.
On peut ainsi citer les enrobages hybrides conducteurs constitués d'une couche de particules d'au moins deux matériaux conducteurs différents, une partie au moins des particules d'un des matériaux conducteurs enrobant un premier noyau et étant interconnectées avec des particules conductrices enrobant un deuxième noyau situé à proximité du premier noyau dans le mélange de particules, et créant ainsi un réseau de conductivité électrique.Mention may thus be made of 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.
À titre d'exemple, de tels enrobages hybrides conducteurs on peut citer dans le cadre de la présente invention un enrobage hybride qui comprend: - une première couche de particules d'un premier matériau conducteur, ladite première couche couvrant au moins partiellement, de préférence entre 50 et 90 %, plus préférentiellement au moins 80 %, de la surface des desdits noyaux; et - d'une deuxième couche de particules d'un deuxième matériau conducteur, lesdites particules du deuxième matériau conducteur étant pour de préférence de 10 à 50 % (plus préférentiellement pour environ 20 %) connectées entre elles pour former un réseau de conductivité électrique. Avantageusement, les noyaux des particules comprennent un matériau choisi dans le groupe constitué par les phosphates, les nitrures, les oxydes ou les mélanges de deux ou de plusieurs de ces derniers.By way of example, 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. Advantageously, 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.
Selon un mode avantageux, le noyau des particules constitutives des mélanges de l'invention comprend de préférence pour au moins 70 % en poids, au moins un oxyde métallique tel un oxyde métallique constitué pour plus de 65 % en poids d'un oxyde de lithium.According to an advantageous embodiment, 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. .
L'oxyde de lithium est enrobé ou non de carbone et de préférence l'oxyde de lithium présente une structure spinelle.The lithium oxide may or may not be coated with carbon and preferably the lithium oxide has a spinel structure.
Des mélanges de particules particulièrement intéressants sont ceux dans lesquels l'oxyde de lithium est choisi dans le groupe constitué par les oxydes de formule: - Li4Ti5θι2 ; 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 θι 2;
- Li( -α)ZαTi50ι2 , dans laquelle α est supérieur à 0 et inférieur ou égal à 0,33; et- Li ( -α ) Z α Ti 5 0ι 2 , in which α is greater than 0 and less than or equal to 0.33; and
- Li ZβTi(5.β)Oι2 dans lequel β est supérieur à 0 et /ou inférieur ou égal à 0,5, Z représentant une source d'au moins un métal choisi de préférence dans le groupe constitué par Mg, Nb, Al, Zr, Ni, et Co.- Li ZβTi ( 5 .β) Oι 2 in which β is greater than 0 and / or less than or equal to 0.5, Z representing a source of at least one metal preferably chosen from the group consisting of Mg, Nb, Al, Zr, Ni, and Co.
De préférence, le noyau de ces particules est constitué pour au moins 65 %, de Li Ti5θi2, de Li(4-α)ZαTi5θι2, de Li ZpTi(5-β)Oι ou d'un mélange de ces derniers, les paramètres α et β étant tels que précédemment définis.Preferably, the core of these particles consists for at least 65% of Li Ti5θi2, Li ( 4-α ) Z α Ti5θι 2 , Li ZpTi ( 5- β) Oι or a mixture of the latter, the parameters α and β being as previously defined.
Une sous famille particulièrement intéressante de mélanges de particules selon l'invention est constituée par les mélanges dans lesquels le noyau des particules est constitué de Li Ti50ι2, de Li( -α)ZαTi5θι2, de Li ZβTi(5.β)Oι2 ou d'un mélange de deux ou de plusieurs de ces derniers, avec α et β étant tels que précédemment définis. Avantageusement dans ces particules, le matériau constitutif du noyau des particules est de type semi-conducteur et il est constitué par au moins un élément choisi dans le groupe constitué par Si, Si dopé de préférence de Ge, Ge, InSb et le mélange de ces derniers.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 0ι 2 , Li ( -α ) Z α Ti5θι 2 , Li ZβTi (5 . β) Oι 2 or a mixture of two or more of these, with α and β being as defined above. Advantageously in these particles, 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.
Selon une autre variante, le noyau des particules est non conducteur et il est constitué par au moins un matériau choisi dans le groupe constitué par les verres, le mica, Si02 et les mélanges de ces derniers.According to another variant, 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.
Dans les particules selon l'invention, les noyaux comportent avantageusement au moins un des oxydes de lithium enrobés de carbone décrits et/ou obtenus par un des procédés décrit dans la demande PCT WO 02/46101 A2, dont le contenu est incorporé par référence à la présente demande.In the particles according to the invention, 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.
Des propriétés, notamment des propriétés électrochimiques particulièrement intéressantes, sont obtenues en utilisant des oxydes métalliques de formule LiMn0;5Nio,5θ2, LiMn0,33Nio,33C0o,33θ2, Li4Ti50ι2, Li2TiC03, LiC002, LiNi02, LiMn20 ou des mélanges de ces derniers.Properties, in particular particularly advantageous electrochemical properties, are obtained by using metal oxides of formula LiMn 0; 5Nio, 5θ 2 , LiMn 0 , 33 Nio, 33 C 0 o, 3 3θ 2 , Li 4 Ti 5 0ι 2, Li 2 TiC0 3 , LiC 0 0 2 , LiNi0 2 , LiMn 2 0 or mixtures of these.
Dans les mélanges de particules de l'invention, les teneurs en carbone sont telles que le carbone total présent représente de 1 à 6%, et de préférence environ 2 % du poids total du mélange des particules.In the mixtures of particles of the invention, 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.
Selon un mode préférentiel, l'enrobage des particules de l'invention est constitué par un mélange hybride de carbones, et/ou par un mélange hybride carbone-métal.According to a preferred embodiment, the coating of the particles of the invention consists of a hybrid mixture of carbons, and / or by a hybrid carbon-metal mixture.
Dans le cas d'un mélange hybride carbone-métal, le métal peut être notamment choisi dans le groupe constitué par l'argent, l'aluminium et les mélanges correspondants. Lorsque l'enrobage hybride est de type carbone, il comprend avantageusement au moins deux formes différentes du carbone, ci-après appelées Carbone 1 et CarboneIn the case of a hybrid carbon-metal mixture, the metal can in particular be chosen from the group consisting of silver, aluminum and the corresponding mixtures. When the hybrid coating is of the carbon type, it advantageously comprises at least two different forms of carbon, hereinafter called Carbon 1 and Carbon
2.2.
Le Carbone 1 est alors avantageusement un carbone à faible cristallinité. La cristallinité des particules de Carbone 1 présentes dans les mélanges de particules objet de l'invention, est caractérisée par un do02, mesuré par diffraction des rayons- X ou par spectroscopie Raman, supérieur à 3,39 Angstroms.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.
Le Carbone 2 est habituellement de type graphite et/ou de type carbone à haute cristallinité. La cristallinité des particules de Carbone 2, mesurée par diffraction des rayons-X ou par spectroscopie Raman, est caractérisée par un doo2 inférieur à 3,36 Angstroms. De préférence, le Carbone 2 est de type graphite naturel, graphite artificiel ou graphite exfolié.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. Preferably, Carbon 2 is of the natural graphite, artificial graphite or exfoliated graphite type.
Le Carbone 2 est avantageusement choisi de façon à présenter une surface spécifique mesurée selon la méthode BET, qui est inférieure ou égale à 50 m2/g et/ou une taille moyenne variant de 2 à 10 micromètres.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.
On obtient aussi des propriétés électrochimiques particulièrement intéressantes pour des mélanges de particules dans lesquels le Carbone 2 est constitué d'au moins un graphite choisi dans le groupe des graphites artificiels, des graphites naturels, des graphites exfoliés ou des mélanges de ces graphites.Particularly advantageous electrochemical properties are also obtained for mixtures of particles in which Carbon 2 consists of at least one graphite chosen from the group of artificial graphites, natural graphites, exfoliated graphites or mixtures of these graphites.
Le Carbone 1 est avantageusement choisi de façon à présenter une surface spécifique, mesurée selon la méthode BET, supérieure ou égale à 50 m2/g.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.
Une sous-famille préférentielle de mélange de particules selon l'invention est constituée par les mélanges comportant des particules de Carbone 1 présentant une taille variant de 10 à 999 nanomètres. De préférence, le pourcentage en masse de Carbone 1 représente, dans l'enrobage composé de Carbone 1 et de Carbone 2, de 1 à 10 %, et, il est de préférence sensiblement identique à la quantité de Carbone 2.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. Preferably, 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.
Les sous-famillès constituées par les mélanges de poudres dans lesquels le diamètre moyen du noyau des particules, mesurée à l'aide du microscope électronique à balayage, varie de 50 nanomètres à 50 micromètres, est de préférence compris entre 4 et 10 micromètres, plus préférentiellement encore le diamètre moyen des particules et de l'ordre de 2 micromètres sont d'un intérêt particulier dans le cadre d'applications dans les systèmes électrochimiques.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.
Ces mélanges de particules sont caractérisés par au moins une des propriétés suivantes: une très bonne conductivité locale, une très bonne conductivité du réseau, une faible résistivité, une très bonne capacité à haut courant et une bonne densité d'énergie.These 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.
Ainsi la conductivité locale des mélanges de particules selon l'invention est habituellement, mesurée selon la méthode à quatre points, supérieure à 10" (Ohm- m) et elle est de préférence supérieure ou égale à 10"5 (Ohm-m).Thus, 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).
La conductivité de réseau, quant à elle, mesurée selon la méthode à quatre points, se situe habituellement entre 2,6x10"3 et 6.2x10"3 (Ohm-m), et elle est de préférence inférieure à 6,0xl0"3 (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).
Selon un mode avantageux, les poudres de l'invention ont une D50 d'environ 7 micromètres.According to an advantageous mode, the powders of the invention have a D50 of approximately 7 micrometers.
Un deuxième objet de la présente invention est constitué par les procédés de préparation de mélanges de particules conformes au premier objet de la présente invention. Ces procédés comprennent avantageusement au moins une des étapes suivantes: -a) la préparation d'un mélange d'au moins un matériau non- conducteur ou semi-conducteur avec un matériau conducteur, puis l'ajout d'un deuxième matériau conducteur au mélange obtenu;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;
-b) la préparation d'un mélange d'au moins un matériau non- conducteur ou semi-conducteur avec au moins deux matériaux conducteurs; etb) the preparation of a mixture of at least one non-conductive or semi-conductive material with at least two conductive materials; and
-c) la préparation d'un mélange de matériaux conducteurs puis son mélange avec au moins un matériau non-conducteur ou semiconducteur.-c) preparing a mixture of conductive materials and then mixing it with at least one non-conductive or semiconductor material.
Selon un mode avantageux de mise en œuvre des procédés de l'invention, le mélange de matériaux est réalisé par broyage mécanique de type HEBM, Jar milling, Vapor jet milling et de préférence par HEBM. Ces procédés sont habituellement mis en œuvre à une température inférieure à 300 degrés Celsius, de préférence à une température comprise entre 20 et 40° Celsius, plus préférentiellement encore à température ambiante.According to an advantageous embodiment of the methods of the invention, 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.
En effet des températures de synthèse trop élevées sont susceptibles de dégrader la structure des particules, notamment de les déformer de façon irréversible notamment par production de C02 à partir du carbone réactionnel.In fact, excessively high synthesis temperatures are liable to degrade the structure of the particles, in particular to deform them irreversibly, in particular by producing C0 2 from the reaction carbon.
Selon une autre variante, le mélange des carbones est réalisé par voie chimique avant l'étape de synthèse de Li Ti50ι2.According to another variant, the mixing of the carbons is carried out chemically before the synthesis step of Li Ti 5 0ι 2 .
Selon une autre alternative, l'un des matériaux conducteurs (Carbone 1) est obtenu par traitement thermique d'un précurseur de type polymère. Le polymère peut alors être choisi dans le groupe constitué par les polymères naturels et par les polymères naturels modifiés ainsi que par les mélanges de ces derniers. Ainsi, à titre d'exemple de polymère utilisables pour la préparation des mélanges de particules de l'invention, on peut mentionner les sucres, les sucres modifiés chimiquement, les amidons, les amidons modifiés chimiquement, les amidons gélatinisés, les amidons modifiés chimiquement, les amidons modifiés chimiquement et gélatinisés, les celluloses, les celluloses modifiées chimiquement et les mélanges de ces derniers. À titre d'exemple préférentiel, on mentionne l'acétate de cellulose.According to another alternative, one of the conductive materials (Carbon 1) 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. Thus, by way of example of 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. As a preferred example, cellulose acetate is mentioned.
Le mélange de carbones introduits dans le milieu réactionnel peut être également réalisé par mélange physique, après la synthèse de Li Ti50ι2.The mixture of carbons introduced into the reaction medium can also be produced by physical mixing, after the synthesis of Li Ti 5 0ι 2 .
Un troisième objet de la présente invention est constitué par les cathodes, notamment les cathodes de générateurs électrochimiques (de préférence de générateurs électrochimiques de type recyclables) comprenant un mélange de particules telles que celles définies dans le premier objet de la présente invention et/ou de particules susceptibles d'être obtenues par un procédé selon le deuxième objet de la présente invention.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.
Un quatrième objet de la présente invention est constitué par les anodes de générateur électrochimique (de préférence de générateurs électrochimiques recyclables) comprenant des particules telles que celles définies dans le premier objet de la présente invention et/ou des particules susceptibles d'être obtenues par un procédé selon le troisième objet de la présente invention.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.
Un cinquième objet de la présente invention est constitué par les générateurs électrochimiques de type lithium comportant au moins un électrolyte, au moins une anode de type lithium métallique et au moins une cathode de type Li4Ti50ι2 et/ou Li( -α)ZαTi502 et/ou Li4ZβTi(5-β)Oι2, la cathode dans ledit générateur étant telle que définie dans le troisième objet de la présente invention. Ces générateurs sont avantageusement de type rechargeable et/ou recyclable.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 0ι 2 and / or Li ( -α ) Z α Ti 5 0 2 and / or Li 4 Z β Ti (5-β) Oι 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.
D'un intérêt particulier, parmi ces générateurs électrochimiques, sont ceux de type lithium ion comprenant une anode est telle que définie dans le quatrième objet de l'invention, de préférence une anode de type Li4Ti5θι2 et/ou de type Li(4-α)ZαTi5θι2 et/ou de type Li4ZβTi(5-β)Oι2 et une cathode de type LiFeP0 , LiCo02, LiMn20 et/ou LiNi02.Of particular interest, among these electrochemical generators, are 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 Ti5θι 2 type and / or of the Li type ( 4-α ) Z α Ti5θι 2 and / or of Li 4 type ZβTi ( 5-β ) Oι 2 and a cathode of LiFeP0, LiCo0 2 , LiMn 2 0 and / or LiNi0 2 type .
De préférence, dans ces générateurs, l'anode et/ou la cathode sont équipées d'un collecteur de courant d'aluminium plein ou de type Exmet (expanded métal).Preferably, in these generators, the anode and / or the cathode are equipped with a current collector of solid aluminum or of the Exmet type (expanded metal).
De tels générateurs électrochimiques présentent en général l'intérêt de ne nécessiter aucune formation préalable de la batterie. Avantageusement, dans ces générateurs, l'électrolyte est de nature polymère sec, gel, liquide ou céramique.Such electrochemical generators generally have the advantage of not requiring any prior training of the battery. Advantageously, in these generators, the electrolyte is of dry polymer, gel, liquid or ceramic nature.
Un sixième objet de la présente invention est constitué par les supercapaciteurs de type hybride comprenant au moins un électrolyte, au moins une anode telle que définie dans le quatrième objet de l'invention, de préférence une anode de type Li4TisOi2 et/ou de type Li( -α)ZαTi5θι2 et/ou Li ZβTi(5.β)Oι2 et une cathode de type graphite ou carbone à grande surface spécifique.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 ( -α ) Z α Ti5θι 2 and / or Li ZβTi (5.β) Oι 2 and a graphite or carbon type cathode with large specific surface.
Ces supercapaciteurs ne nécessitent habituellement aucune formation préalable du supercapaciteur.These supercapacitors usually do not require any prior training of the supercapacitor.
De préférence, les supercapaciteurs de l'invention sont tels que l'anode et/ou la cathode sont équipées d'un collecteur de courant d'aluminium plein ou de type Exmet (expanded métal).Preferably, 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.
Avantageusement, également dans ces supercapaciteurs, l'électrolyte est de nature polymère sec, gel, liquide ou céramique. Les systèmes électrochimiques selon l'invention présentent, en outre, l'intérêt de pouvoir être préparés sans aucune addition d'autre carbone.Advantageously, also in these supercapacitors, 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.
Description de modes préférentiels de réalisation de l'invention:Description of preferred embodiments of the invention:
1- Addition des particules de carbone constitutive de l'enrobage hybride après la synthèse à partir de Li Ti5Oι2 1- Addition of the carbon particles constituting the hybrid coating after the synthesis from Li Ti 5 Oι 2
Le Li4Ti50ι2 est obtenu à partir d'un mélange binaire de Ti02 et de Li2C0 calciné à 850°C pendant 18 heures. Le Li4Ti50ι2 obtenu est alors mélangé avec deux types différents de carbones : un Carbone 1 aussi nommé Cl et un Carbone 2 aussi nommé C2.Li 4 Ti 5 0ι 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 0ι 2 obtained is then mixed with two different types of carbons: a Carbon 1 also called Cl and a Carbon 2 also called C2.
Carbone 1: il s'agit d'un carbone à faible cristallinité et ayant, de préférence, une surface spécifique BET ≥ 50 m2/g. Le Carbone 1 peut être un noir de carbone, ou tout autre type d'additif conducteur.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.
Carbone 2: il s'agit d'un carbone à haute cristallinité et ayant de préférence une surface BET < 50 m2/g. Le carbone 2 peut être un graphite naturel ou un graphite artificiel, éventuellement exfolié.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.
2 - Rôle des deux carbones:2 - Role of the two carbons:
Carbone 1: Le rôle de ce carbone est double. Le premier est d'enrober la particule afin d'assurer une conductivité locale de la particule comme cela apparaît sur la Figure 1/7.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.
Le second rôle du carbone à faible cristallinité est de former un réseau de conductivité entre les particules du type de celles représentées dans la Figure 1/7, ce qui assure la conductivité au niveau de l'électrode. En effet, la préparation de l'électrode se fait sans aucun additif de carbone.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.
Le réseau électronique et la conductivité inter-particules sont aussi assurés par le Carbone 1 comme cela ressort également de la Figure 2/7.The electronic network and the inter-particle conductivity are also provided by Carbon 1 as also shown in Figure 2/7.
Carbone 2: Le carbone 2 est de type graphite et il permet tout d'abord, de façon surprenante, d'améliorer la conductivité de l'électrode en formant des nœuds constitutifs de stations de distribution homogène de la conductivité électrique. Ces stations apparaissent dans la représentation de la Figure 3/7.Carbon 2: 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.
La bonne conductivité électronique du graphite permet d'abaisser la résistivité de l'électrode, ce qui permet avantageusement à la batterie d'opérer à hautes densités de courant.The good electronic conductivity of graphite lowers the resistivity of the electrode, which advantageously allows the battery to operate at high current densities.
Le second rôle du graphite est au niveau du procédé. Le graphite possède les caractéristiques d'un matériau lubrifiant et hydrophobe. Durant l'épandage de l'électrode, le graphite permet de contrôler la porosité de l'électrode. Un tel calandrage des électrodes permet, de plus, d'orienter les particules vers le plan basai, comme cela apparaît sur la Figure 4/7, c'est-à-dire parallèlement à la surface du support de l'électrode; ce qui induit une conductivité maximale de l'électrode.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.
Lors du procédé d'extrusion, le graphite, en raison de ses propriétés lubrifiantes, assure la facilité d'extrusion ainsi que l'homogénéité de l'épaisseur de l'électrode. De plus, il augmente la vitesse d'extrusion. Ces avantages techniques résultent en un coût de production réduit des électrodes. De plus, le graphite, lorsqu'il est utilisé pour la préparation d'électrodes par voie sèche, aide à lubrifier le buse de l'extrudeuse et permet d'éviter le dépôt des métaux à la surface de la buse. 3 -Préparation de particulesDuring the extrusion process, 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. In addition, 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
Mélange Ternaire:Ternary mixture:
Selon un mode avantageux de réalisation de la présente invention, un mélange ternaire (Mi) (Li4Ti50ι2 + Cl + C2) est obtenu par broyage à haute énergie HEMB (High Energy Bail Mill). A cet effet, un creuset en métal est utilisé. Dans ce creuset, le mélange Mi est introduit et des billes d'acier dans une proportion volumique 1/3, 1/3 et 1/3 de volume vide libre sont disposées dans le creuset comme représenté dans la Figure 5/7.According to an advantageous embodiment of the present invention, a ternary mixture (Mi) (Li 4 Ti 5 0ι 2 + Cl + C2) is obtained by high energy grinding HEMB (High Energy Bail Mill). For this purpose, a metal crucible is used. In this crucible, 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.
Les conditions de mélange par HEBM sont très importantes, l'une des plus cruciales est de ne pas détruire la, cristallinité du carbone C2. En effet, il ne faut pas réduire la taille de particule du carbone C2 en dessous de 1 micromètre.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.
4 - Préparation de l'électrode:4 - Preparation of the electrode:
L'électrode est préparée à partir du mélange de Mi et du PVDF. Ce mélange est réalisé dans un solvant ternaire N-méthylpyrrolydone (NMP), acétone, toluène) comme cela est décrit dans le brevet d'hydro-Québec WO 01/97303 Al dont le contenu est incorporé par référence à la présente demande.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.
La conductivité de la pâte obtenue est assurée intrinsèquement par le mélange Mi (Li4Ti5θι2 + Ci + C2), sans ajout de carbone additionnel ce qui a un impact positif sur la densité d'énergie de la batterie qui dans ce cas n'est pas pénalisée par le poids supplémentaire d'une autre source de carbone.The conductivity of the paste obtained is intrinsically ensured by the mixture Mi (Li 4 Ti5θι 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.
5 - Avantage de la synthèse de Li TisOi25 - Advantage of the synthesis of Li TisOi2
Dans ce cas, le mélange quaternaire (M2) comprend du Ti02, du Li2C03, du carbone C2 (graphite) et un précurseur de carbone (polymère ou autre). Le mélange M2 est alors introduit dans un creuset métallique. Un co-broyage de type HEBM est réalisé afin d'obtenir un mélange intime. Le mélange obtenu est ensuite placé dans un tube en quartz pour y être chauffé. La synthèse est alors finalisée en présence d'atmosphère inerte afin de carboniser le polymère.In this case, 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.
Une fois la synthèse finie, le produit de Li4TisOι2 est enrobé de carbone à faible cristallinité et de graphite à haute cristallinité. La fabrication des électrodes est équivalente à celle décrite dans le paragraphe 4 ci-dessus.Once the synthesis is complete, the Li 4 TisOι 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.
EXEMPLESEXAMPLES
Les exemples suivants sont donnés à titre purement illustratif et ne sauraient être interprétés comme constituant une quelconque limitation de la définition de l'invention.The following examples are given purely by way of illustration and should not be interpreted as constituting any limitation on the definition of the invention.
Exemple 1:Example 1:
Un mélange de Li Ti5θι2, d'un noir de Ketjen et de graphite naturel d'origine brésilienne, dans un ratio volumique de 80,77/ 7,32/ 2,5 est broyé par HEBM pendant 1 heure. Des particules ayant un noyau de Li Ti50ι2, d'une taille moyenne de 5 micromètres, et avec un enrobage hybride de graphite et de noir de Ketjen sont ainsi obtenues. Leur épaisseur moyenne est de 2 micromètres.A mixture of Li Ti 5 2ι 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 0ι 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.
Exemple 2:Example 2:
Un mélange de Li Ti5θι2,, de noir de Ketjen et de graphite dans un ratio volumique de 40/2,5/2,5 est préparé selon la méthode décrite dans l'exemple précédent 1. A mixture of Li Ti 5 θι 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.
Exemple 3 :Example 3:
Un mélange de Li TisOι2, de noir de Ketjen et de graphite dans un ratio volumique 81,06/ 3,51/ 2,5 est préparé comme dans l'exemple # 1 Le total massique de carbone ajouté correspond à environ 6% de la masse du mélange total.A mixture of Li TisOι 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.
Exemple 4:Example 4:
Un mélange de LiMno,5Nio,s02, non conducteur, un non de Ketjen et du graphite naturel d'origine brésilienne dans une proportion massique de 94/3/3 est broyé par Mechanofusion d'Hosokawa pendant 1 heure. Ces particules obtenues ont un noyau de LiMιin,5Nio,5θ , une taille moyenne de 7μm et un enrobage hybride de graphite + noir Ketjen et une épaisseur de 3μm. La résistivité du matériau enrobé, mesurée par la méthode de quatre points, est de 5 x 10" Ohm-m.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 LiMιin core, 5 Nio, 5 θ, an average size of 7 μm and a hybrid coating of graphite + Ketjen black and a thickness of 3 μm. The resistivity of the coated material, measured by the four-point method, is 5 x 10 " Ohm-m.
Les mesures des performances électrochimiques des particules préparées sont rapportés dans le tableau I suivant.The measurements of the electrochemical performance of the particles prepared are reported in Table I below.
Tableau 1 Les niveaux élevés de propriétés électrochimiques mis en évidence notamment par ces exemples sont utilisés pour préparer des systèmes électrochimiques hautement performants.Table 1 The high levels of electrochemical properties demonstrated in particular by these examples are used to prepare high performance electrochemical systems.
Bien que la présente invention ait été décrite à l'aide de mises en œuvre spécifiques, il est entendu que plusieurs variations et modifications peuvent se greffer aux dites mises en œuvre, et la présente invention vise à couvrir de telles modifications, usages ou adaptations de la présente invention suivant en général, les principes de l'invention et incluant toute variation de la présente description qui deviendra connue ou conventionnelle dans le champ d'activité dans lequel se retrouve la présente invention, et qui peut s'appliquer aux éléments essentiels mentionnés ci-haut, en accord avec la portée des revendications suivantes. Although the present invention has been described using specific implementations, it is understood that several variations and modifications can be grafted onto said implementations, and the present invention aims to cover such modifications, uses or adaptations of the present invention generally following the principles of the invention and including any variation of the present description which will become known or conventional in the field of activity in which the present invention is found, and which can be applied to the essential elements mentioned above, in accordance with the scope of the following claims.

Claims

REVENDICATIONS
Mélange de particules comprenant un noyau non-conducteur ou semiconducteur, les noyaux desdites particules étant au moins partiellement recouverts d'un enrobage hybride conducteur et lesdites particules étant au moins partiellement connectées par des chaînes conductrices hybrides qui créent un réseau de conductivité électrique.Mixture of particles comprising a non-conductive or semiconductor core, the nuclei of said particles being at least partially covered with a conductive hybrid coating and said particles being at least partially connected by hybrid conductive chains which create an electrical conductivity network.
2. Mélange selon la revendication 1, dans lequel les particules comprennent un noyau non-conducteur ou semi-conducteur et un enrobage, au moins partiellement fait d'un matériau hybride conducteur, et dans lequel lesdites particules sont au moins partiellement interconnectées par des chaînes conductrices hybrides.2. Mixture according to claim 1, in which the particles comprise a non-conductive or semi-conductive core and a coating, at least partially made of a conductive hybrid material, and in which said particles are at least partially interconnected by chains hybrid drivers.
3. Mélange selon al revendication 1 ou 2, dans lequel l'enrobage comprend un mélange d'au moins deux matériaux conducteurs différents et sous forme particulaire, des particules de l'enrobage d'un premier noyau étant interconnectées avec des particules de l'enrobage d'un deuxième noyau situé dans le mélange de particules à proximité dudit premier noyau.3. Mixture according to claim 1 or 2, wherein the coating comprises a mixture of at least two different conductive materials and in particulate form, particles of the coating of a first core being interconnected with particles of the coating of a second core located in the mixture of particles near said first core.
4. Mélange de particules selon la revendication 2 ou 3, dans lequel l'enrobage comprend: - un premier matériau conducteur couvrant au moins partiellement, de préférence entre 50 et 90 %, plus préférentiellement encore au moins 80 %, de la surface des desdits noyaux; et4. A mixture of particles according to claim 2 or 3, wherein the coating comprises: - a first conductive material covering at least partially, preferably between 50 and 90%, more preferably still at least 80%, of the surface of said cores; and
- un deuxième matériau conducteur dont les particules sont pour de préférence de 10 à 50 % (plus préférentiellement pour environ 20 %) connectées entre elles pour former un réseau de conductivité électrique. - A second conductive material, the particles of which are preferably from 10 to 50% (more preferably for approximately 20%) connected together to form an electrical conductivity network.
5. Mélange selon l'une quelconque des revendications 1 à 4, dans lequel les noyaux comprennent au moins un phosphate, un nitrure, un oxyde ou un mélange de deux ou de plusieurs de ces derniers.5. Mixture according to any one of claims 1 to 4, in which the cores comprise at least one phosphate, a nitride, an oxide or a mixture of two or more of the latter.
6. Mélange selon la revendication 5, dans lequel le noyau desdites particules est constitué majoritairement, et de préférence pour au moins 70 % en poids, d'au moins un oxyde métallique.6. Mixture according to claim 5, in which the core of said particles consists mainly, and preferably for at least 70% by weight, of at least one metal oxide.
7. Mélange selon la revendication 6, dans lequel l'oxyde métallique est constitué pour plus de 65 % en poids d'un oxyde de lithium.7. Mixture according to claim 6, in which the metal oxide consists for more than 65% by weight of a lithium oxide.
8. Mélange selon la revendication 7, dans lequel l'oxyde de lithium est enrobé de carbone.8. A mixture according to claim 7, in which the lithium oxide is coated with carbon.
9. Mélange de particules selon l'une quelconque des revendications 6 à 9, dans lequel le noyau est constitué par un oxyde de lithium de structure spinelle.9. A mixture of particles according to any one of claims 6 to 9, in which the nucleus consists of a lithium oxide of spinel structure.
10. Mélange de particules selon l'une quelconque des revendications 6 à 9, dans lequel l'oxyde de lithium est choisi dans le groupe constitué par les oxydes de formule: 10. Mixture of particles according to any one of claims 6 to 9, in which the lithium oxide is chosen from the group consisting of the oxides of formula:
- Li(4-α)ZαTi50i2 , dans laquelle α est supérieur à 0 et inférieur ou égal à 0,33, Z représentant une source d'au moins un métal; et- Li ( 4-α) Z α Ti 5 0i2, in which α is greater than 0 and less than or equal to 0.33, Z representing a source of at least one metal; and
- Li4ZβTi(5.β)Oι2 dans lequel β est supérieur à 0 et/ou inférieur ou égal à 0,5, Z représentant une source d'au moins un métal.- Li 4 ZβTi (5. Β) Oι 2 in which β is greater than 0 and / or less than or equal to 0.5, Z representing a source of at least one metal.
11. Mélange selon la revendication 10, dans lequel le noyau des particules est constitué pour au moins 65 % de Li Ti50ι2, de Li(4-α)ZαTi50ι2, de Li ZpTi(5- β)Oι2 ou d'un mélange de ces derniers, α et β ayant les valeurs définies dans la revendication 10. 11. A mixture according to claim 10, in which the nucleus of the particles consists for at least 65% of Li Ti 5 0ι 2 , of Li ( 4-α ) Z α Ti 5 0ι 2 , of Li ZpTi (5- β) Oι 2 or a mixture thereof, α and β having the values defined in claim 10.
12. Mélange selon la revendication 9, dans lequel le noyau des particules est constitué de Li4Ti5θι2, de Li(4-α)ZαTi5θι2, de Li ZβTi(5.β)Oι2 ou d'un mélange d'un ou de plusieurs de ces derniers, α et β ayant les valeurs définies dans la revendication 10.12. The mixture as claimed in claim 9, in which the particle core consists of Li 4 Ti 5 θι 2 , Li (4-α) Z α Ti 5 θι 2 , Li Z β Ti (5. Β) Oι 2 or a mixture of one or more of these, α and β having the values defined in claim 10.
13. Mélange selon la revendication 1, dans lequel le noyau desdites particules est semi-conducteur et il est constitué par un matériau choisi dans le groupe constitué par Si, Si dopé, ou Ge, Ge et InSb.13. A mixture according to claim 1, in which the core of said particles is semiconductor and it consists of a material chosen from the group consisting of Si, doped Si, or Ge, Ge and InSb.
14. Mélange selon la revendication 1, dans lequel le noyau desdites particules est non conducteur et est constitué par un matériau choisi dans le groupe constitué par les verres, le mica et le Si02.14. The mixture as claimed in claim 1, in which the core of said particles is non-conductive and consists of a material chosen from the group consisting of glasses, mica and Si0 2 .
15. Mélange selon la revendication 1, dans lequel les particules ont une D50 de 7 micromètres.15. The mixture of claim 1, wherein the particles have a D 50 of 7 micrometers.
16. Mélange selon l'une quelconque des revendications 9 à 11, dans lequel Z représente une particule de métal choisi dans le groupe constitué par Mg, Nb,16. Mixture according to any one of claims 9 to 11, in which Z represents a metal particle chosen from the group consisting of Mg, Nb,
Al, Zr, Ni et Co.Al, Zr, Ni and Co.
17. Mélange selon l'une quelconque des revendications 10 à 16, dans lequel l'oxyde métallique est de formule LiMno,5Nio,5θ2, LiMn0,33Nio,33Coo,3302, Li4Ti50ι2>Li2TiC03, LiC002, LiNi02, ou LiMn204.17. Mixture according to any one of claims 10 to 16, in which the metal oxide has the formula LiMno , 5 Nio, 5θ 2 , LiMn 0 , 33 Nio, 33 Coo , 33 0 2 , Li 4 Ti 5 0ι 2 > Li 2 TiC0 3 , LiC 0 0 2 , LiNi0 2 , or LiMn 2 0 4 .
18. Mélange selon l'une quelconque des revendications 1 à 17 contenant de 1 à 6% en poids de carbone dans ledit mélange.18. A mixture according to any one of claims 1 to 17 containing from 1 to 6% by weight of carbon in said mixture.
19. Mélange selon la revendication 18 contenant environ 2 % en poids de carbone dans ledit mélange. 19. The mixture of claim 18 containing about 2% by weight of carbon in said mixture.
20. Mélange selon l'une quelconque des revendications 1 à 19, dans laquelle l'enrobage est constitué par un mélange hybride de carbones, et/ou par un mélange hybride carbone-métal.20. Mixture according to any one of claims 1 to 19, in which the coating consists of a hybrid mixture of carbons, and / or of a hybrid carbon-metal mixture.
21. Mélange selon la revendication 20, dans lequel le métal est choisi dans le groupe constitué par l'argent, l'aluminium et les mélanges de ces derniers.21. A mixture according to claim 20, in which the metal is chosen from the group consisting of silver, aluminum and mixtures of these.
22. Mélange selon la revendication 20, dans lequel le mélange hybride de carbone comprend au moins deux formes conductrices différentes du carbone, ci-après appelées Carbone 1 et Carbone 2.22. The mixture as claimed in claim 20, in which the hybrid carbon mixture comprises at least two different conductive forms of carbon, hereinafter called Carbon 1 and Carbon 2.
23. Mélange selon la revendication 22, dans lequel le Carbone 1 est un carbone à faible cristallinité.23. A mixture according to claim 22, in which Carbon 1 is a carbon with low crystallinity.
24. Mélange selon la revendication 23, dans lequel la cristallinité des particules de Carbone 1, mesurée par diffraction des rayons-X et/ou par spectroscopie Raman, est caractérisée par un doo2 supérieur à 3,36 Angstroms.24. The mixture as claimed in claim 23, in which the crystallinity of the particles of Carbon 1, measured by X-ray diffraction and / or by Raman spectroscopy, is characterized by a doo 2 greater than 3.36 Angstroms.
25. Mélange selon l'une quelconque des revendications 22 à 24, dans laquelle le Carbone 2 est de type graphite et/ou de type carbone à haute cristallinité.25. A mixture according to any one of claims 22 to 24, in which the Carbon 2 is of the graphite type and / or of the carbon type with high crystallinity.
26. Mélange selon la revendication 25, dans laquelle la cristallinité des particules de Carbone 2, mesurée par diffraction des rayons-X, est caractérisée par un doo2 inférieur à 3,36 Angstroms.26. A mixture according to claim 25, in which the crystallinity of the particles of Carbon 2, measured by X-ray diffraction, is characterized by a doo 2 of less than 3.36 Angstroms.
27. Mélange selon la revendication 26, dans laquelle le Carbone 2 est de type graphite naturel, graphite artificiel ou graphite exfolié.27. A mixture according to claim 26, in which the Carbon 2 is of the natural graphite, artificial graphite or exfoliated graphite type.
28. Mélange selon l'une quelconque des revendications 22 à 27, dans lequel le Carbone 1 possède une surface spécifique, mesurée selon la méthode BET, supérieure ou égale à 50 m /g. 28. A mixture according to any one of claims 22 to 27, in which Carbon 1 has a specific surface, measured according to the BET method, greater than or equal to 50 m / g.
29. Mélange selon la revendication 28, dans lequel les particules de Carbone 1 utilisées ont une taille moyenne variant de 10 à 999 nanomètres.29. A mixture according to claim 28, in which the particles of Carbon 1 used have an average size varying from 10 to 999 nanometers.
30. Mélange selon l'une quelconque des revendications 22 à 29, dans lequel les particules de Carbone 2 ont une surface spécifique mesurée selon la méthode BET, inférieure ou égale à 50 m2/grammes.30. A mixture according to any one of claims 22 to 29, in which the particles of Carbon 2 have a specific surface area measured according to the BET method, less than or equal to 50 m 2 / grams.
31. Mélange selon l'une quelconque des revendications 22 à 30, dans lequel les particules de carbone 2 utilisées ont une taille variant de 2 à 10 micromètres.31. A mixture according to any one of claims 22 to 30, in which the carbon particles 2 used have a size varying from 2 to 10 micrometers.
32. Mélange selon l'une quelconque des revendications 22 à 31, dans lequel le Carbone 2 est constitué d'au moins un graphite choisi dans le groupe des graphites artificiels, des graphites naturels, des graphites exfoliés et des mélanges de deux ou de plusieurs de ces graphites.32. Mixture according to any one of claims 22 to 31, in which Carbon 2 consists of at least one graphite chosen from the group of artificial graphites, natural graphites, exfoliated graphites and mixtures of two or more of these graphites.
33. Mélange selon l'une quelconque des revendications 22 à 32, dans lequel le pourcentage en masse de Carbone 1 représente de 1 à 10 % de la masse totale de l'enrobage composé de Carbone 1 et de Carbone 2.33. Mixture according to any one of claims 22 to 32, in which the percentage by mass of Carbon 1 represents from 1 to 10% of the total mass of the coating composed of Carbon 1 and Carbon 2.
34. Mélange selon l'une quelconque des revendications 22 à 33, dans lequel la quantité de Carbone 1 est sensiblement identique à la quantité de Carbone 2.34. Mixture according to any one of claims 22 to 33, in which the amount of Carbon 1 is substantially identical to the amount of Carbon 2.
35. Mélange selon l'une quelconque des revendications 1 à 34, dans lequel le diamètre moyen du noyau desdites particules varie de 50 nanomètres à 30 micromètres.35. A mixture according to any one of claims 1 to 34, in which the average diameter of the core of said particles varies from 50 nanometers to 30 micrometers.
36. Mélange selon la revendication 35, caractérisée en ce que le diamètre moyen dudit noyau est de l'ordre de 2 micromètres. 36. Mixture according to claim 35, characterized in that the average diameter of said core is of the order of 2 micrometers.
37. Mélange selon l'une quelconque des revendications 1 à 36, dans lequel la taille moyenne desdites particules, mesurée selon la méthode du microscope électronique à balayage, est comprise entre 4 et 30 micromètres.37. Mixture according to any one of claims 1 to 36, in which the average size of said particles, measured according to the scanning electron microscope method, is between 4 and 30 micrometers.
38. Mélange selon l'une quelconque des revendications 1 à 37, présentant au moins une des propriétés suivantes: une très bonne conductivité locale, une très bonne conductivité du réseau, une faible résistivité, une très bonne capacité à haut courant, une bonne densité d'énergie.38. Mixture according to any one of claims 1 to 37, having at least one of the following properties: a very good local conductivity, a very good network conductivity, a low resistivity, a very good capacity at high current, a good density energy.
39. Mélange selon la revendication 36, présentant une conductivité locale, mesurée selon la méthode à quatre points, qui est supérieure à 10"6 (Ohm-m) et de préférence supérieure ou égale à 10"5 (Ohm-m).39. A mixture according to claim 36, having a local conductivity, measured according to the four-point method, which is greater than 10 "6 (Ohm-m) and preferably greater than or equal to 10 " 5 (Ohm-m).
40. Mélange de particules selon la revendication 38 ou 39 présentant une conductivité de réseau, mesurée selon la méthode à quatre points, qui est comprise entre 2,6x10"3 et 6,2x10"3 (Ohm-m), et de préférence inférieure à 6,0x10"3 (Ohm-m).40. A mixture of particles according to claim 38 or 39 having a network conductivity, measured according to the four-point method, which is between 2.6x10 "3 and 6.2x10 " 3 (Ohm-m), and preferably less at 6.0x10 "3 (Ohm-m).
41. Procédé de préparation d'un mélange de particules telles que définies dans l'une quelconque des revendications 1 à 40, comprenant au moins une des étapes suivantes:41. Process for the preparation of a mixture of particles as defined in any one of claims 1 to 40, comprising at least one of the following steps:
- a) préparation d'un mélange d'au moins un matériau non-conducteur ou semi-conducteur avec un matériau conducteur, puis ajout d'un deuxième matériau conducteur au mélange obtenu;a) preparation of a mixture of at least one non-conductive or semi-conductive material with a conductive material, then addition of a second conductive material to the mixture obtained;
- b) préparation d'un mélange d'au moins un matériau non-conducteur ou semi-conducteur avec au moins deux matériaux conducteurs; etb) preparation of a mixture of at least one non-conductive or semi-conductive material with at least two conductive materials; and
-c) préparation d'un mélange de matériaux conducteurs, puis mélange avec au moins un matériau non-conducteur ou semi-conducteur. -c) preparation of a mixture of conductive materials, then mixing with at least one non-conductive or semi-conductive material.
42. Procédé de préparation d'un mélange de particules selon la revendication 41, dans lequel le mélange de matériaux est obtenu par broyage mécanique, HEBM, Jar milling, Vapor jet milling et de préférence par HEBM.42. Process for preparing a mixture of particles according to claim 41, in which the mixture of materials is obtained by mechanical grinding, HEBM, Jar milling, Vapor jet milling and preferably by HEBM.
43. Procédé de préparation d'un mélange de particules selon la revendication 41 ou 42, réalisé a une température inférieure à 300 degrés Celsius, de préférence à une température comprise entre 20 et 40 degrés Celsius plus préférentiellement encore à température ambiante.43. A process for preparing a mixture of particles according to claim 41 or 42, carried out at a temperature below 300 degrees Celsius, preferably at a temperature between 20 and 40 degrees Celsius more preferably still at room temperature.
44. Procédé de préparation d'un mélange de particules selon l'une quelconque des revendications 41 à 43, dans lequel les noyaux desdites particules sont à base de Li4Ti5012 et l'enrobage à base d'un mélange de carbone, le mélange des carbones est réalisé par voie chimique, avant l'étape de synthèse de particules de Li Ti50ι2.44. Method for preparing a mixture of particles according to any one of claims 41 to 43, in which the cores of said particles are based on Li 4 Ti 5 0 12 and the coating based on a mixture of carbon , the mixing of the carbons is carried out chemically, before the stage of synthesis of particles of Li Ti 5 0ι 2 .
45. Procédé selon l'une quelconque des revendications 41 à 44, dans lequel au moins un des matériaux conducteurs (Carbone 1) est obtenu par traitement thermique d'un précurseur de type polymère.45. Method according to any one of claims 41 to 44, in which at least one of the conductive materials (Carbon 1) is obtained by heat treatment of a polymer type precursor.
46. Procédé selon la revendication 45, dans lequel le polymère est choisi dans le groupe constitué par les polymères naturels, par les polymères naturels modifiés ainsi que par les mélanges de ces derniers.46. The method of claim 45, wherein the polymer is selected from the group consisting of natural polymers, modified natural polymers as well as mixtures of the latter.
47. Procédé selon la revendication 46, dans lequel le polymère est choisi dans le groupe constitué par les sucres, les sucres modifiés chimiquement, les amidons, les amidons modifiés chimiquement, les amidons gélatinisés, les amidons modifiés chimiquement, les amidons modifiés chimiquement et gélatinisés, les celluloses, les celluloses modifiées chimiquement et les mélanges de ces derniers. 47. The method of claim 46, wherein the polymer is selected from the group consisting 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.
48. Procédé selon la revendication 47, dans lequel le polymère est un acétate de cellulose.48. The method of claim 47, wherein the polymer is cellulose acetate.
49. Procédé selon l'une quelconque des revendications 44 à 48, dans lequel, le mélange des carbones est réalisé par mélange physique, après la synthèse de49. Process according to any one of claims 44 to 48, in which the mixing of the carbons is carried out by physical mixing, after the synthesis of
Li4Ti5Oι2.Li 4 Ti 5 Oι 2 .
50. Cathode de générateur électrochimique comprenant un mélange de particules telles que celles définies dans l'une quelconque des revendications 1 à 40 et/ou de particules susceptibles d'être obtenues par un procédé selon l'une quelconque des revendications 41 à 49.50. An electrochemical generator cathode comprising a mixture of particles such as those defined in any one of claims 1 to 40 and / or of particles capable of being obtained by a process according to any one of claims 41 to 49.
51. Anode de générateur électrochimique comprenant des particules telles que celles définies dans l'une quelconque des revendications 1 à 40 et/ou des particules susceptibles d'être obtenues par un procédé selon l'une quelconque des revendications 41 à 49.51. An electrochemical generator anode comprising particles such as those defined in any one of claims 1 to 40 and / or particles capable of being obtained by a process according to any one of claims 41 to 49.
52. Générateur électrochimique de type lithium comportant au moins une anode de type lithium métallique et au moins une cathode telle que celles définies dans la revendication 50, de préférence l'anode est de type LLtTisOπ et/ou52. Electrochemical generator of lithium type comprising at least one anode of metallic lithium type and at least one cathode such as those defined in claim 50, preferably the anode is of LLtTisOπ type and / or
Li(4-α)ZαTi502 et/ou Li4ZβTi 5-β)Oι2.Li ( 4-α) Z α Ti 5 0 2 and / or Li 4 Z β Ti 5-β) Oι 2 .
53. Générateur électrochimique selon la revendication 52 de préférence de type rechargeable et/ou recyclable.53. An electrochemical generator according to claim 52, preferably of the rechargeable and / or recyclable type.
54. Générateur électrochimique selon la revendication 52 ou 53 de type Lithium ion comprenant au moins un électrolyte, au moins une anode telle que définie dans la revendication 50, de préférence l'anode est de type Li4Ti5θι2 et/ou de type Li 4.α)ZαTi5θι2 et/ou de type Li4ZβTi(5-β)Oι2 et au moins une cathode de type LiFePO4, LiCo02, LiMn204 et/ou LiNi02. 54. An electrochemical generator according to claim 52 or 53 of the Lithium ion type comprising at least one electrolyte, at least one anode as defined in claim 50, preferably the anode is of the Li 4 Ti 5 θι 2 type and / or type Li 4 . α) Z α Ti 5 θι 2 and / or of Li 4 type Z β Ti (5-β ) Oι 2 and at least one cathode of LiFePO 4 , LiCo0 2 , LiMn 2 0 4 and / or LiNi0 2 type .
55. Générateur électrochimique selon l'une quelconque des revendications 52 à 54, dont au moins une anode et/ou au moins une cathode sont équipées d'un collecteur de courant d'aluminium plein ou de type Exmet (expanded métal).55. An electrochemical generator according to any one of claims 52 to 54, at least one anode and / or at least one cathode are equipped with a current collector of solid aluminum or of the Exmet type (expanded metal).
56. Générateur électrochimique selon l'une quelconque des revendications 52 à 55 ne nécessitant aucune formation préalable de la batterie.56. An electrochemical generator according to any one of claims 52 to 55 not requiring any prior training of the battery.
57. Générateur selon l'une quelconque des revendications 52 à 57, dans lequel l'électrolyte est de nature polymère sec, gel, liquide ou céramique.57. Generator according to any one of claims 52 to 57, in which the electrolyte is of dry polymer, gel, liquid or ceramic nature.
58. Supercapacité de type hybride comprenant au moins un électrolyte au moins une anode, telle que définie dans la revendication 51, de préférence de type Li TisOι2 et/ou de type Li( -α)ZαTi5θι2 et/ou Li ZβTi(5.β)Oι2 et au moins une cathode de type graphite ou carbone à grande surface spécifique, ne demandant aucune formation préalable du supercapaciteur.58. Hybrid type supercapacitor comprising at least one electrolyte at least one anode, as defined in claim 51, preferably of Li TisOι 2 type and / or of Li ( -α) Z α Ti 5 θι 2 type and / or Li Z β Ti ( 5. Β ) Oι 2 and at least one cathode of the graphite or carbon type with a large specific surface, requiring no prior formation of the supercapacitor.
59. Supercapacité selon la revendication 58, dans lequel au moins une anode et/ou au moins une cathode sont équipées d'un collecteur de courant d'aluminium plein ou de type Exmet (expanded métal).59. Supercapacitor according to claim 58, in which at least one anode and / or at least one cathode are equipped with a current collector of solid aluminum or of the Exmet type (expanded metal).
60. Supercapacité selon la revendication 59, dans lequel l'électrolyte est de nature polymère sec, gel, liquide ou céramique.60. Supercapacity according to claim 59, in which the electrolyte is of dry polymer, gel, liquid or ceramic nature.
61. Système électrochimique selon l'une quelconque des revendications 52 à 60, caractérisé en ce que l'électrode est préparée sans aucune addition d'autre carbone. 61. An electrochemical system according to any one of claims 52 to 60, characterized in that the electrode is prepared without any addition of other carbon.
EP03763538A 2002-07-12 2003-07-10 Particles comprising a non-conducting or semi-conducting core, which are coated with a hybrid conducting layer, production methods thereof and uses of same in electrical devices Ceased EP1520309A2 (en)

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