EP1878075A2 - Elektrodenmaterial mit einem lithium-/übergangsmetall-komplex-oxid - Google Patents

Elektrodenmaterial mit einem lithium-/übergangsmetall-komplex-oxid

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Publication number
EP1878075A2
EP1878075A2 EP06755473A EP06755473A EP1878075A2 EP 1878075 A2 EP1878075 A2 EP 1878075A2 EP 06755473 A EP06755473 A EP 06755473A EP 06755473 A EP06755473 A EP 06755473A EP 1878075 A2 EP1878075 A2 EP 1878075A2
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EP
European Patent Office
Prior art keywords
groups
particles
complex oxide
carbon
electrode
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.)
Withdrawn
Application number
EP06755473A
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English (en)
French (fr)
Inventor
Michel Gauthier
Christophe Michot
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.)
Universite de Montreal
Phostech Lithium Inc
Original Assignee
Universite de Montreal
Phostech Lithium Inc
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Publication date
Application filed by Universite de Montreal, Phostech Lithium Inc filed Critical Universite de Montreal
Priority to EP10185246A priority Critical patent/EP2320500A3/de
Publication of EP1878075A2 publication Critical patent/EP1878075A2/de
Withdrawn legal-status Critical Current

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    • 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
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
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    • 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
    • H01M4/04—Processes of manufacture in general
    • H—ELECTRICITY
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    • 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
    • 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
    • H01M4/58—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
    • H01M4/5805—Phosphides
    • 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
    • H01M4/581—Chalcogenides or intercalation compounds thereof
    • H01M4/5815—Sulfides
    • 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
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    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/621—Binders
    • H01M4/622—Binders being polymers
    • H—ELECTRICITY
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    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • H—ELECTRICITY
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    • 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
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    • 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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1397—Processes of manufacture of 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
    • H01M4/48—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
    • H01M4/582—Halogenides
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • Electrode material comprising a complex oxide of lithium and transition metal
  • the present invention relates to particulate redox compounds having a surface-modified carbon coating and their use as electrode material.
  • oxides In the field of lithium-ion batteries or metal-polymer lithium batteries, it is known to use oxides as cathode active material.
  • Mixed oxides of lithium and a transition metal such as LiMn 2 O 4 , LiCoO 2 , LiNi 3 / 3C ⁇ i / 3 Mni / 3O 2, Li 1 I + X) V 3 Os or LiNiO 2 are commonly used in batteries with sold in lithium, or in prototype batteries.
  • the structure of these composite electrodes is shown schematically in FIG. 1.
  • LiFePO 4 is a representative of a family of complex oxides LiMXO 4 in which M represents a metal and X is a non-metal such as P, S or Si.
  • this formula includes the complex oxides in which M represents a or more transition metals, and is eventually replaced in part by a metal other than a transition metal, X represents one or more elements of the "non-metal" type, and the XO anion 4 is partially replaced by one or more other oxyanions of formula XO 4 , as well as complex oxides whose atomic composition varies slightly around the stoichiometry. It has been demonstrated (US Pat. No. 5,910,382) that such complex oxides in which the polyanion phosphate or the polyanion sulfate have a certain crystalline structure (olivine or Nasicon, for example) have a high redox voltage for transition metals.
  • (1) denotes the binder
  • (2) denotes the carbon particles (agent generally used to confer an electronic conductivity in the composite electrode)
  • (3) designates the complex oxide particles
  • (4) denotes the current collector
  • (5) denotes the carbon particles bonded to the surface of the complex oxide particles.
  • LiFePO 4 coated or not with a carbonaceous layer is used in the form of particles of very small dimensions in order to increase the power characteristics and to compensate for the low diffusivity of lithium ions.
  • the specific surface area as determined by BET is therefore very high. It is generally of the order of 14 m 2 / g [more generally 5-20 m 2 / g for LiFePO 4 coated with a carbon layer and denoted LiFePO 4 -C]. Because of this high specific surface area, the amount of binder required to ensure the cohesion of the complex oxide particles within a composite electrode is greater than that required to ensure the cohesion of LiCoO 2 particles which are more large. In addition, because of the presence of carbon, the particles are more hydrophobic and therefore more difficult to process for the development of a composite electrode.
  • a cathode may be prepared by a process of dispersing a cathode material in a solvent, carbon particles as a conductivity-improving agent and a binder, at the same time. Apply to a current collector by coating.
  • the porous cathode thus obtained is then impregnated with a liquid electrolyte, including an electrolyte based on ionic liquids.
  • the porous cathode can be obtained by extruding a mixture comprising a cathode material, carbon particles and a binder.
  • a cathode in Lithium metal / polymer battery technology, can be obtained by a process of preparing a mixture comprising a cathode material, carbon particles and an ionically conductive polymer [e.g. a poly (ethylene oxide) derivative). solvant mixed with a lithium salt such as LiN (SO 2 CF 3 ) 2 ]], then to apply the mixture on a current collector, either by coating from a solution in a solvent, or by extrusion.
  • a lithium salt such as LiN (SO 2 CF 3 ) 2
  • the cathode can also be obtained by preparing a porous cathode by applying to a collector by coating or extrusion, a composition comprising the cathode material, carbon particles and a binder, then impregnating the porous cathode thus obtained with a conductive polymer. ionic in liquid form, and by cross-linking the polymer in situ.
  • aqueous compositions is widespread for the production of anodes, but more recent for the elaboration of cathodes.
  • the implementation of such processes in the aqueous route makes it possible in particular to overcome the use of N-methyl pyrrolidone as a coating solvent.
  • Aqueous binders are commercially available. Mention may be made in particular of LHO-108P from LICO Technology Corp. (Taiwan, product available from Pred Materials, USA) in the form of an aqueous suspension of a modified styrene-butadiene copolymer, or BM-400B product from Zeon Corporation (Japan), under the form of an aqueous dispersion of elastomer particles.
  • the inventors have found that it is possible to overcome these disadvantages while retaining the advantages of complex oxide particles simply coated with carbon.
  • the proposed solution consists in modifying the surface of the carbon by fixing functional groups by covalent bonding or by ionic bonding, so as to improve the use properties of the carbon-complex oxides by taking advantage of the numerous possibilities offered by the functions grafted to the carbon surface.
  • the complex oxides thus modified on the one hand provide new types of composite electrode material compositions, taking advantage of the wide variety of functional groups that can be used. On the other hand, they can improve electrode development processes.
  • the subject of the present invention is a new electrode material, a method for its preparation, and a composite electrode comprising said material and a generator comprising said electrode.
  • An electrode material according to the present invention consists of particles or aggregates of particles of a complex oxide which has redox properties and which can reversibly insert the lithium cation, wherein at least a portion of the surface of the particles or aggregates of complex oxide particles are coated with a carbon layer bonded by chemical bonds and / or physical bonds and optionally by mechanical bonding characterized in that: a) The complex oxide corresponds to the formula LiiM m M 'iZ m z 0 o N n F f (I) wherein:
  • Li, O, N and F respectively represent lithium, oxygen, nitrogen and fluorine
  • M represents one or more elements selected from transition metals
  • M ' represents one or more metals other than a transition metal
  • Z represents at least one non-metal
  • the coefficients i, m, m ', z, o, n and f are chosen so as to ensure the electroneutrality of the complex oxide, and respect the following conditions: i> 0, m> 0, z> 0, m '> 0, o> 0, n ⁇ O and f ⁇ O;
  • the carbon carries covalently attached GF functional groups;
  • the size of the particles and aggregates of carbonaceous oxide complex particles is such that at least 90% of the particles have a size between 1 nm and 5 ⁇ m, and if the particles are present as aggregates, at least 90 % of the aggregates of particles have a size between 10 nm and 10 ⁇ m.
  • the particle size and particle aggregate size is such that at least 90% of the particles have a dimension between nm and 1 ⁇ m, and, if the particles are present in the form at least 90% of the aggregates of particles have a size between 100 nm and 10 ⁇ m.
  • M represents one or more transition metals M1 selected from iron, manganese, vanadium, and titanium.
  • the metal or metals M1 are partially replaced by one or more transition metals M2 preferably selected from molybdenum, nickel, chromium, cobalt, zirconium, tantalum, copper, nickel, and the like. niobium, scandium, zinc and tungsten, it being understood that the ratio by weight of metals M1 to M2 is greater than 1.
  • M2 transition metals are chosen either for their redox properties complementary to those of the metals of transition M1, either for their influence on the properties of electronic or ionic conductivity of the complex oxide.
  • a metal M 'other than transition metal is preferably chosen from Li, Al, Ca, Mg, Pb, Ba, In, Be, Sr, Sn and Bi. Because M 1 is redox inert, its content m 'is preferably less than 10% by weight of the complex oxide.
  • a metal M ' is chosen for its influence especially on the electronic conduction or on the diffusivity of lithium ions in the structure of the partially substituted complex oxide.
  • the non-metal element Z is preferably selected from S, Se, P, As, Si, and Ge.
  • a family (II) of materials (I) according to the invention comprises the materials which contain a complex oxide corresponding to the general formula (I) above in which i> 0.
  • the presence of Li in the composition of the oxide complex of formula (I) allows the stabilization of certain structures of compounds that are produced during the synthesis of the material (II) and in particular during carbonization if the carbonization is used for the deposition of carbon on the complex oxide.
  • the materials (II) are particularly useful for the implementation of electrochemical generators prepared in the discharged or partially discharged state.
  • the materials of family (III) generally have relatively low electrode potentials with respect to a lithium anode, particularly when iron or titanium constitutes the transition metal M1.
  • a material (III) is therefore particularly useful for developing the anode of
  • a special case (HIa) of materials of the family (III) is constituted by a material in which M represents titanium.
  • M represents titanium.
  • titanate of formula LiiTi m M 'm .O 0 N n F f
  • titanate approximate formula Li 4 Ti 5 Oi2.
  • An anode constituted by a material of the family (HIa) has remarkable cyclability properties when the dimensions of the particles of titanate coated with carbon are from 1 to 100 nm for example.
  • the carbon is deposited by carbonization during the synthesis of the material (HIa), said carbon contributes to the control of the sizes of the elementary particles by preventing the sintering of the complex oxide.
  • a family (IV) of materials (I) according to the invention comprises materials which contain a complex oxide in which z ⁇ O.
  • the presence of a non-metal covalently bonded to the oxygen of the complex oxide contributes substantially to the increase of the voltage of the redox torque of the transition metal relative to a lithium anode, but it makes the complex oxide electrically insulating.
  • this low electrical conductivity is very clearly compensated by the presence of the carbon coating on the surface of the complex oxide.
  • the use of an oxide containing a non-metal consequently makes it possible to considerably widen the choice of electrode materials, in particular cathode materials, available for rechargeable lithium generators.
  • the materials of the family (IV) mention may be made in particular of the materials which contain a complex oxide of general formula LiMM 'ZO 4 of olivine structure and the materials of general formula Li 3 + X (MM') 2 (ZO 4 3 of Nasicon structure.
  • the two general formulas above include all complex oxides having stoichiometric deviations of less than 5%, a chemical impurity level of less than 2% and a level of substitution elements of the M lower crystalline sites. at 20% and complex oxides in which the ZO 4 polyanions are partially replaced by polyanions molybdenate, niobate, tungstate, zirconate or tantalate at a level of less than 5%.
  • Said formulas also include the complex oxides in which Z is phosphorus and a portion of the oxygen of the phosphate structures is replaced by nitrogen or fluorine (i.e., n> 0 and / or f> 0 ).
  • a particular case (IVa) of materials of the family (IV) is constituted by a material in which Z represents phosphorus.
  • a material (IVa) contains a phosphate, a pyrophosphate or an oxyphosphate.
  • a material (IVa) can be made especially with iron and manganese, which are abundant and inexpensive materials. The use of a material (IVa) as a complex electrode material nevertheless allows a high operating voltage.
  • the materials (IVa) which contain LiFe x Mg x PO 4 in which x varies between 0.1% and 5% at., In particular LiFePO 4 .
  • a material (IVa) can be made especially with iron and manganese, which are abundant and inexpensive materials.
  • the use of a material (IVa) as a complex electrode material nevertheless allows a high operating voltage
  • (IVa) are therefore particularly advantageous as substitutes for oxides based on cobalt, nickel or manganese currently used in rechargeable lithium-ion batteries.
  • the materials (IVa), especially when they contain iron and manganese, are therefore prime candidates for the new generations of accumulators for hybrid vehicles, electric vehicles, portable tools and stationary storage accumulators.
  • materials (IV) consist of materials that contain an oxide complex of formula (I) in which Z represents Si or S. Mention may in particular be made of materials (IVb) in which the complex oxide is a silicate, a sulphate or an oxysulphate in which M1 is Fe, Mg or one of their mixtures.
  • the materials (IVb) have substantially the same properties and the same advantages as the materials (IVa).
  • the crystal structures have excellent reversible insertion / reversal properties, and in addition they contribute with ZO 4 oxyanions to obtain high electrode potentials relative to a lithium anode. These materials are therefore particularly interesting for the development of cathodes.
  • a covalently attached GF functional group on the carbon which coats the complex oxide meets at least one of the following criteria: it has a hydrophilic character; it constitutes a polymer segment; it has redox properties and / or an electronic conductivity it carries or constitutes an FR function capable of reacting by substitution, addition, condensation or polymerization, or a function capable of initiating anionic, cationic or radical polymerization reactions.
  • a GF group having a hydrophilic character may be chosen from ionic groups and groups consisting of a hydrophilic polymer segment.
  • the presence of hydrophilic GF groups improves the character hydrophilic material itself, which leads to an improvement in the wettability of the material which then allows better impregnation of the material with a liquid (in particular by a liquid electrolyte, an ionic liquid or a low-mass liquid solvating polymer); the possibility of making deposits using aqueous compositions; the possibility of obtaining easily dispersed materials in an aqueous medium or in polar polymers; and improving the surface tension, which promotes the extrudability of the material.
  • a hydrophilic GF group of the ionic group type may be chosen in particular from the CO 2 M, -OH, -SM, -SO 3 M, -PO 3 M 2 , -PO 3 M 2 , -PO 2 M and NH groups. 2 , in which M represents a proton, an alkali metal cation or an organic cation.
  • An ionic GF group of hydrophilic nature can be bonded to the carbon either directly or via a polymer group.
  • the organic cation may be chosen from oxonium, ammonium, quaternary ammonium, amidinium, guanidinium, pyridinium, morpholinium, pyrrolidionium, imidazolium, imidazolinium, triazolium, sulfonium, phosphonium, iodonium and carbonium groups, said groups optionally bearing at least one substituent having a FR function capable of reacting by substitution, addition, condensation or polymerization, as defined above.
  • M is preferably H or an alkali metal.
  • the surface tension of the material is increased.
  • the ionic groups act as a buffer against acidic species that may be present in an electrochemical generator that contains an electrode material according to the invention.
  • HF may be present because it was initially introduced into the electrolyte or because it is formed during operation of the generator.
  • a hydrophilic group GF may be a group derived from a hydrophilic polymer.
  • the group GF may be, for example, a group derived from a polyalkylene containing heteroatoms such as oxygen, sulfur, nitrogen, in particular a group derived from poly (oxyethylene), poly (ethyleneimine) or polyvinyl alcohol, or a group derived from an ionomer having in its macromolecular chain acrylate groups, styrene carboxylate groups, styrene sulfonate groups, allylamine groups, or groups allylic alcohol.
  • a hydrophilic polymeric GF group also carries a FR function capable of reacting by substitution, addition, condensation or polymerization as defined below.
  • a GF group may be a group comprising at least one polymer segment optionally carrying one or more FR functions allowing either a subsequent crosslinking or a bond with another molecule.
  • a polymeric GF group may comprise one or more segments having the following definitions: • a poly (oxyethylene) segment which can act as a binder and an electrolyte;
  • a segment which has conjugated double bonds capable of providing electronic conduction A segment which has conjugated double bonds capable of providing electronic conduction.
  • the functions FR are as defined below.
  • an electrode material (I) according to the invention carries a GF group which is or which carries a FR function capable of reacting by addition, condensation or polymerization
  • the FR groups present on the surface of the carbonaceous coating of the particles complex oxide of the material (I) can bind the particles together if the FR groups are able to react with each other.
  • FR groups allow in addition to bonding the carbonaceous complex oxide particles of the material (I) to other constituents of the composite electrode if said constituents carry FR 'groups capable of reacting with the FR groups by addition, condensation or polymerization.
  • This embodiment is interesting insofar as it makes it possible to easily apply the complex electrode material to a collector by coating or extrusion, then to give a mechanical strength to the assembly by reaction of the groups FR and FR '.
  • FR groups allow the development of a material (I) modified by reaction with a compound that has a group FR '.
  • the determination of the FR functions and of the FR, FR 'pairs is within the abilities of those skilled in the art who can find the information useful in the basic textbooks of chemistry.
  • the physical characteristics of the carbon coating essentially depend on the application of the coating.
  • a non-powdery carbon coating adhering to the surface of the complex oxide particles is obtained when the carbon is applied by carbonising a precursor previously contacted with the oxide particles. complex, or when carbon deposition and synthesis of the complex oxide are carried out simultaneously.
  • the deposition of a carbon coating by carbonization of a precursor is described in particular in US Pat. No. 855,273 and US Pat. No. 962,666.
  • Particles or aggregates of complex oxide particles are contacted with an organic carbon precursor and then the mixture is subjected to a treatment to carbonize the precursor.
  • the precursor is preferably in liquid or gaseous form, for example in the form of a liquid precursor, a gaseous precursor or a solid precursor used in the molten state or in solution in a liquid solvent.
  • the carbonization may be CO disproportionation, hydrocarbon dehydrogenation, dehalogenation or dehydrohalogenation of a halogenated hydrocarbon, gas phase carbonization of preferably carbon-rich hydrocarbons.
  • Such a process gives a carbon deposit which has good hiding power and good adhesion to the complex oxide particles.
  • Charging carried out by cracking a hydrocarbon such as acetylene, butane, 1-3-butadiene, propane as described in particular in US 2004/0157126, is favorable to obtaining carbon nanotubes in the coating of carbon.
  • the precursor is mixed, prior to carbonization, with particles or carbon fibers, including carbon nanotubes, optionally containing GF groups, in particular sulfonates or carboxylates, allowing obtain a composite coating.
  • the oxide is at least slightly porous, the organic precursor can penetrate the particles to a certain depth which ensures good mechanical anchoring before or during carbonization.
  • a partial or total surface covering by the precursor can be observed from the residual carbon after carbonization as illustrated in FIGS. 3 and 4.
  • FIGS. 3 and 4 each represent a TEM micrograph obtained using a GIG spectrometer. from Gatan for a LiFePO 4 carbon.
  • the carbon coating comprises carbon nanotubes.
  • This embodiment promotes the anchoring of a polymer with the carbon coating of the complex oxide.
  • the nanotube structure of a carbonaceous coating is described in more detail by Henry J. Liu et al, Applied Physics Letters, Vol. 85, 5, pp 807-809, 2004], and SH Jo et al, [Applied Physics Letters, vol. 85, 5, pp 810-812, 2004].
  • the presence of nanotubes is visible on the micrograph of FIG. 5.
  • the synthesis of nanotubes on the surface of the material can be carried out simultaneously with the carbonization or after the carbonization.
  • a carbon coating which comprises carbon nanotubes can be obtained by carbonization or cracking of gaseous hydrocarbons in the presence of the complex oxide, preferably in the presence of iron, cobalt or nickel under conditions known to the skilled in the art (see [Lee CJ, Kim DW, Lee TJ, et al., Applied Physics Letters, Vol 75, 12, pp. 1721-1723, 1999], [Chen Yuan, Dragos Ciuparu, Yanhui Yang, Sangyun Lim, Chuan Wang, Gary L Haller and Lisa D Pfefferle, Nanotechnology, Vol 16, 2005, S476-S483], and [Mark Meier, Energeia, Vol.12, No. ⁇ , 2001, published by the University of Kentucky ]).
  • the carbon coating in intimate contact with the surface of the complex oxide particles is mechanofused.
  • a mechanofusion deposited coating has a powdery character which is not observed on a carbon coating deposited by carbonization of an organic precursor.
  • the adhesion of the mechanofusion deposited carbon to the surface of the complex oxide is obtained by mechanical bonding of the carbon with the surface of the complex oxide.
  • Mechano-liaison is done probably inter alia by physical bonds or chemical bonds which result from the intense mechanical work and the renewal of the surface of the complex oxide in intimate contact with the carbon.
  • a mechanofusion process is described in detail in US Pat. No. 5,789,114.
  • Particles or aggregates of complex oxide particles are brought into contact with a carbon powder, and the mixture is subjected to a mechanical treatment which creates mechanizations. between the complex oxide particles and the carbon particles.
  • a particular embodiment of the mechanofusion process consists in using carbon particles which carry GF functional groups, in particular carboxylate or sulphonate groups.
  • Devices for performing such a mechanofusion are commercially available, in particular from Hosokawa Micron Group (Japan) and Nara Machinery Co., Ltd. (Japan). .
  • the qualitative determination of the functional groups on the surface of the carbon coating of the complex oxide particles can be carried out by the XPS technique for the oxygen groups such as COOH, OH and CHO, the phosphonate group or the sulfur groups -SH, -SO 3H (see Pantea, D., Darmstadt, H., Kaliaguine, S., Summchen, L. Roy, C, Carbon, Vol. 39, pp 1147-1158, 2001). Grafting rates of from 0.0001 to 1 meq of GF functions per gram of graft material, preferably from 0.001 to 0.2 meq / g, and more particularly from 0.01 to 0.1 meq / g, are considered effective. . However, the invention is not limited to these rates.
  • the evaluation of the change of properties is a good indicator of the sufficiency or not of the degree of grafting.
  • a material I according to the invention comprises from 0.1 to 10% of carbon, more particularly from 0.5 to 5%.
  • the carbon coating is more or less covering and adhering to the surface of the particles or particle agglomerates of complex oxide.
  • the thickness of the carbon coating is generally in the nanometer range to a few hundred nanometers.
  • the distribution of carbon on the surface of the complex oxide or in the mass of the complex oxide can be controlled by the shape of the organic precursor: liquid precursor, gaseous, polymerizable or in the form of organometallic.
  • a material I consisting of particles of a complex oxide or aggregates of complex oxide particles in which at least a part of the surface of the particles or aggregates of complex oxide particles is coated with carbon attached by bonds and / or physical bonds and possibly by mechanical attachment, can be obtained by a process characterized in that it comprises: a) The preparation of particles or aggregates of particles of a complex oxide such as at least 90% of the particles have a size between 1 nm and 5 microns and at least 90% of particle aggregates have a size between 10 nm and 10 microns, said complex having oxide formula Liim m m 'm - Z z 0 o N n F f in which:
  • Li, O, N and F respectively represent lithium, oxygen, nitrogen and fluorine
  • M represents one or more elements selected from transition metals
  • M ' represents one or more metals other than a transition metal
  • Z represents at least one element other than a metal; the coefficients i, m, m ', z, o, n and f are chosen so as to ensure the electroneutrality of the complex oxide, and comply with the following conditions: i> 0, m> 0, z> 0, m '> 0, o> 0, n ⁇ O and f ⁇ O; b) depositing carbon on at least a part of the surface of the particles or aggregates of complex oxide particles or on at least a part of the surface of the precursors of the particles or aggregates of particles of the complex oxide; c) the attachment of GF functional groups by formation of a covalent bond with carbon; it being understood that the steps can be performed successively or simultaneously.
  • phases a), b) and c) are performed in three successive steps.
  • the era complex oxide is prepared.
  • the carbon coating is applied to the particles or aggregates of complex oxide particles.
  • a 3 rd step subjecting the particles or carbonaceous particles aggregate to a treatment to fix GF functional groups.
  • the step of preparing the complex oxide can be suppressed for complex commercially available oxides.
  • the preparation of complex oxides is within the reach of those skilled in the art, in view of the many publications of the prior art. (See WO-05/062 404, US-5, 910, 382, US-6,514,640, US-2002/0124386, US- ⁇ , 855,462 and US-6,811,924).
  • the carbon coating is applied by carbonization of a precursor.
  • the precursor is mixed, prior to carbonization, with carbon particles or fibers, including carbon nanotubes, optionally containing GF groups, in particular sulphonates or carboxylates. This gives a composite carbon coating.
  • the application of the carbon coating can be performed by mechanofusion.
  • the preparation of the particles or aggregates of complex oxide particles and the deposition of carbon are carried out simultaneously, and the attachment of the GF groups is carried out on the "carbonaceous complex oxide” material thus obtained.
  • the "carbonaceous complex oxide” material can be obtained for example by carrying out the thesis of the complex oxide from the precursors of the complex oxide and one or more precursors of carbon.
  • the carbon precursor may be chosen so as to also constitute a precursor of the complex oxide, for example a salt or an organometallic compound comprising one or more of the constituents of the oxide
  • carbon deposition and GF groups are simultaneously formed on previously prepared particles or aggregates of complex oxide particles.
  • This embodiment is particularly useful when the desired GF groups are carboxylate, hydroxyl, ketone or aldehyde groups.
  • the result is obtained by appropriate choice of synthesis and carbonization conditions and organic precursors.
  • the grafting of the carboxylate, hydroxyl, ketone or aldehyde groups is obtained by oxidation of carbon with CO 2 , optionally in the presence of water vapor. It may be interesting in this case to choose more easily oxidizable carbon precursors to promote the grafting of GF groups.
  • the carbon precursor may also be mixed with metal salts which facilitate the oxidation of the carbon coating and which may optionally serve as doping agent for the complex oxide [Cf. "Chemically modified carbon fibers and their applications” in Ermolenko, IP Lyubliner, and NV Gulko, translated by Tivovets, EP ([VCH, New York and Germany, 1990, pp 155-206)]
  • Steps a), b) and c) of the process for preparing material I can be carried out simultaneously when the desired GF groups are carboxylate, hydroxyl, ketone or aldehyde groups.
  • the process then consists of preparing a precursor mixture of the complex oxide and a carbon precursor and oxidizing C with CO 2 .
  • titanates Li 4 Ti 5 Oi 2 which are complex oxides stable in air at high temperatures, carbonization can be carried out under air or oxygen optionally in the presence of water vapor, unlike compounds like LiFePO, ⁇ .
  • carboxylate functions or hydroxyl functions by oxidation in air or oxygen at 500-900 ° C., ie titanate previously formed and subsequently coated with a carbon precursor, or during the synthesis of titanate. , for example by reaction of TiO 2 with LiOH in the presence of a precursor of carbon around 800 ° C.
  • GF1 groups may be grafted directly onto a carbonaceous material.
  • GF1 groups include COOM, CO, CHO, SO 3 M (where M is H or an alkali metal) and amino groups.
  • Other GF functional groups designated GF2 may be obtained from GF1 groups by conversion, substitution, addition, condensation or polymerization reactions.
  • GF1 groups such as the ketone function, the aldehyde function, the quinone function, the -COOH function or the -OH function can be obtained directly on the carbon surface by controlled oxidation.
  • a -SO 3 H function, or an NH 2 amine function can be obtained directly on the carbon surface, for example by a reaction with SO 3 or NH 3 .
  • the GF1 groups above make it possible to set GF groups useful for the electrode materials.
  • the -COOH, -OH, -SO 3 H, -PO 3 H 2 , -PO 2 H and -NH 2 functions are directly useful as hydrophilic GF groups for electrode materials.
  • -COOH can be obtained for example by treatment of the carbon-based complex oxide with water vapor under a current of a CO / CO 2 mixture at 700 ° C., or by a cold plasma treatment under O 2 .
  • An -SO 3 M group wherein M is H or an alkali metal may be attached to the carbon surface of the complex oxide by different routes. M can then be replaced by known ion exchange reactions.
  • the following procedures are given as examples. a) reaction of the carbonaceous complex oxide with a disulfide bearing two terminal -SO 3 M groups; b) reacting the carbonaceous complex oxide with a benzotriazole bearing a SO 3 H group; c) addition reaction with an azo compound bearing alkali metal sulfonate groups.
  • a ketone, aldehyde or quinone group can be attached to a carbonaceous complex oxide by reacting the carbonaceous complex oxide with CO 2 or water vapor respectively, and mixing them.
  • the carbon-containing complexed oxide groups carrying carboxyl, hydroxyl, sulfonate, phosphonate or amine GF1 groups may be used to prepare carbon-containing complex oxides bearing GF2 GF groups, by reaction with a compound carrying the GF2 group and a reactive function. Examples of reactions involving a GF1 group can be found in Table I above. Many other reactions can be considered, including:
  • An ion exchange reaction using an appropriate halide makes it possible to replace the initial ion of an ionic group (for example a group -COOLi or a group -SO3Li) fixed on the carbon of the carbonaceous complex oxide, with an organic ion comprising the desired GR2 substituent.
  • an ionic group for example a group -COOLi or a group -SO3Li
  • Each of the above reactions thus makes it possible, for example, to bind a group GF 2 comprising a terminal ethylenic double bond, a terminal epoxy group, or a group GF 2 constituted by a polymer segment, optionally carrying a reactive group.
  • the modification of the surface of a carbonaceous material by grafting polymer groups is known in particular by N. Tsubokawa ["Functionalization of carbon black by surface grafting of polymers", Prog. Polym. Sci., 17, 417 (1992)] and ["Functionalization of Carbon Material by Surface Grafting of Polymers", Bulletin of the Chemical Society of Japan, Vol. 75, No. 10 (October, 2002)].
  • a material I according to the present invention consisting of particles or aggregates of GF group-carrying carbon-oxide particles is particularly useful for the preparation of composite electrodes, which constitute another object of the present invention.
  • a composite electrode according to the invention consists of a composite material deposited on a current collector, said composite material comprising a material I, and optionally a binder and / or an agent conferring electronic conductivity and / or an agent conferring ionic conductivity .
  • the material I used for producing the electrode carries hydrophilic GF groups.
  • the compound which imparts electronic conductivity is preferably selected from carbon black, acetylene black, graphite and mixtures thereof.
  • the electronically conductive carbon can be introduced in the form of powder, microfibres or nanotubes, as well as their mixtures.
  • the compound which confers ionic conductivity may be chosen from the lithium salts used in the electrolytes of lithium batteries, for example LiClCU, LiPF 6 , LiFSI or LiTFSI in solution in an aprotic liquid solvent (such as EC, DEC, DMC, PC, ...), an ionic liquid solvent (such as, for example, an imidazolium bis (trifluorosulfonyl) imide or a pyrrolidinium fluorosulfonylimide) or a solvating polymer such as, for example, a poly (oxide) derivative. ethylene), or a mixture of these solvents used for the production of gelled electrolytes.
  • an electrode according to the invention is constituted by a composite material deposited on a current collector, said composite material comprising a material I, a binder, and optionally an electronic conductivity-imparting agent
  • the binder is incorporated in the I material by mechanical mixing in the presence of a solvent.
  • the binder is preferably chosen from natural rubbers and synthetic rubbers such as SBR (styrene butadiene rubber), NBR (butadiene-acrylonitrile rubber), HNBR (hydrogenated NBR), CHR (epichlorohydrins rubber) and ACM (acrylate-rubber) rubbers. rubber).
  • SBR styrene butadiene rubber
  • NBR butadiene-acrylonitrile rubber
  • HNBR hydrogenated NBR
  • CHR epichlorohydrins rubber
  • ACM acrylate-rubber
  • the material I is incorporated into the binder dispersion.
  • the electrode is obtained by a process characterized in that: •
  • the material I carries groups GF which are or which carry a function FR facilitating the dispersion of the particles or aggregates of functionalized carbon complex oxides, and groups GFa which are or which carry a FRa function capable of reacting by addition or condensation;
  • the binder carries reactive groups GA capable of reacting by addition or condensation with the groups FRa of the material I;
  • the particles or aggregates of particles of material I are dispersed in a colloidal suspension of nanoparticles of binder
  • the dispersion is coated on a substrate which constitutes the current collector of the electrode;
  • the dispersion is subjected to a treatment aimed at reacting the FR functions with the GA groups.
  • the binder is preferably selected from natural rubbers and synthetic rubbers such as SBR (styrene butadiene rubber), NBR (butadiene) rubbers acrylonitrile-rubber), HNBR (hydrogenated NBR), CHR
  • An electrode constituted by a layer of composite material on a current collector is thus obtained, said composite material consisting of particles or aggregates of carbonaceous complex oxide particles connected to nanoparticles. binder particles by the bonds created by the reaction between the FR functions and the GA groups.
  • the structure of such a composite material is shown schematically in FIG. 5.
  • (3) represents the complex oxide particles
  • (5) represents the carbon coating
  • (4) represents the current collector
  • (6) represents the binder nanoparticles.
  • the binder nanoparticles have a diameter ⁇ 50 nm, and more particularly ⁇ 25 nm.
  • the nanoparticles of binder preferably have a T g ⁇ 0 0 C, and more particularly ⁇ -20 0 C.
  • Nanoparticles derived from silicone polymers form a particular class for obtaining low T g polymers.
  • the binders of the latex type are commercially available, and can be obtained by emulsion polymerization of ethylenic, acrylic, styrenic monomers (see US Pat. No. 6,656,633).
  • the material I further comprises GF groups hydrophilicity that promote its wettability, which facilitates the dispersion of the material I in the solvent (organic or aqueous) of the binder suspension.
  • an electrode according to the invention is constituted by a composite material deposited on a current collector and comprising a material I which carries the groups GF polymer type and optionally GF groups which have a hydrophilic character.
  • the composite material forming the electrode it is not necessary for the composite material forming the electrode to contain a binder, because the GF groups of the polymer type themselves act as binders.
  • the structural integrity of the electrode during cycling is ensured by the polymeric GF groups.
  • the said GF polymer groups are chosen for their mechanical and elastomeric properties in order to ensure the mechanical strength of the composite electrode and the maintenance of the electrical contacts during the discharge and charge cycles.
  • the appropriate choice of monomers used to form the polymer group further provide other useful functions to the electrode material and thus optimize the characteristics of the composite electrode.
  • the polymers are preferably constituted by a poly (oxyethylene) segment, which in the presence of a lithium salt will play the role of electrolytic conductor.
  • the choice of a polymer having conjugated double bonded segments will give the electrode material electron conduction properties, which will partially remove the carbon powders generally used as electronic conduction additives.
  • the appropriate GF groups to optimize the energy and power densities of the composite electrode by reducing the amount of the non-active material (binder, electronic conduction additives, electrolyte, etc.), as well as to optimize the mechanical properties, the cycling properties and the use thereof.
  • the non-active material binder, electronic conduction additives, electrolyte, etc.
  • an electrode according to the invention consists of a composite material which is deposited on a current collector and which is composed of complex oxide particles coated with carbon and interconnected by covalent bonding or by ionic bond.
  • the structure of such a composite material is shown schematically in FIG. 4.
  • (3) designates the complex oxide particles
  • (5) designates the carbon coating
  • (4) designates the current collector.
  • the complex oxide particles are interconnected at a very short distance by the carbon-bonded linking groups.
  • these linking groups have elastomer properties in order to ensure the maintenance of the electrochemical contacts between the constituents of the composite electrode.
  • the material I carries GR groups constituted by a solvating link or a conjugated link bearing the reactive function FR.
  • This embodiment of a composite electrode according to the invention minimizes or eliminates the constituents other than the complex oxide in order to maximize the energy and power density of the composite electrode and the generator which comprises it.
  • Such an electrode is obtained by a method characterized in that:
  • a composite material is prepared from a material I carries groups GF which are or which carry a function FR able to react by addition or condensation with an identical function;
  • the composite material is applied to a substrate which constitutes the current collector of the electrode;
  • the composite material is subjected to a treatment aimed at reacting the FR functions with each other.
  • the complex oxide of the electrode material is LiFe x Mg x PO 4 in which x varies between 0.1% and 5% at., In particular LiFePO 4
  • an electrode according to the present invention is particularly useful as a cathode.
  • an electrode according to the invention is particularly useful as anode.
  • hydrophilic groups especially carboxylic acid, sulfonic acid, sulfonate or carboxylate groups (preferably sulfonate or lithium carboxylate) on the carbon surface facilitates dispersion of the complex oxide and development of composite electrodes Whether in the form of solvent preparation, including aqueous solvents, or by extrusion, the presence of these hydrophilic functions during extrusion makes it possible to reduce the dynamic viscosity of the mixture containing the additive. electronic conduction and the solvating polymer, which facilitates the implementation and improves the electrochemical properties of the electrodes thus obtained.
  • the binder of the cathode is used in the form of an aqueous colloidal suspension of polymer nanoparticles
  • the possibility of obtaining good dispersions of the electrode material makes it possible to prepare electrodes in which the nanoparticles are uniformly distributed on the surface of the particles or aggregates of complex oxides, which improves the performance of the electrodes as well as obtained.
  • hydrophilic groups especially carboxylic acid, sulfonic acid, sulfonate or preferably lithium carboxylate groups
  • hydrophilic groups improve the wettability of the carbonaceous complex oxide particles, which facilitates the penetration of electrolytes (liquids, ionic liquids, low mass solvating polymers) into porous electrodes. Optimization of the formulations is facilitated to the extent that the surface-carbon-containing complex oxide comprising hydrophilic groups can make it possible to reduce or even eliminate the conduction carbon generally used in dispersion with the binder of the composite electrode. .
  • ionic groups such -COOH, -PO 2 H 2 , -PO 3 H 2 , -NH 2 , -SO 3 H, or -OH, also allows ion exchange on the carbon surface.
  • polymerizable, condensable, or crosslinkable GF groups opens up numerous possibilities of optimizing the binder properties of the composite electrode. These functions make it possible in particular to chemically bond the particles or aggregates of particles of the active material to the binder of the composite, thus making it possible to minimize the necessary quantities.
  • Polymerizable GF groups can also act directly as a mechanical binder between the particles within the composite electrode.
  • Polymeric GF groups may also be selected to add a second useful function to the electrode material.
  • a polymeric GF group of polyethylene oxide type can play an electrolyte role in the presence of a lithium salt; a conjugated type GF polymer group makes it possible both to ensure electronic exchanges with the electrode material and to act as a mechanical binder for the composite electrode.
  • the presence of polymer moieties on the electrode material of the present invention improves the dispersibility of carbonaceous composite oxide particles in organic or aqueous solvents, as well as in polymeric solvents, depending on the nature of the polymer segments. In some cases, it is thus possible to obtain stable suspensions over time of ultrafine carbon particles.
  • the chemical bonding of the electrode material to the binder of the composite makes it possible to reduce the amount necessary for its mechanical strength and its cycling behavior.
  • the additional role of electrolytic or electronic conductor played by the binder and made possible by the present invention makes it possible to optimize the energy, power and cyclability densities of the composite electrodes and the generators.
  • the present invention opens a new way of producing electrodes that retain the advantages of the electrodes of the prior art, while eliminating or at least reducing their disadvantages.
  • the interesting redox potentials of the complex oxides are preserved, but without the low electronic conductivity.
  • the good electronic conductivity provided by the carbon coatings is retained, without the disadvantages related to their hydrophobicity.
  • the good diffusivity of the Li + ions in the very fine particles of complex oxide is conserved, without the weak cohesion of the materials inherent to the small dimension of the particles.
  • the use of carbon oxides functionalized with crosslinkable groups allows to ensure the cohesion of the material, with zero or very small amounts of added binder, in favor of the active ingredient.
  • Examples 1a to 14a describe the preparation of carbon-modified complex oxides modified by grafting of groups of the GF1 type.
  • Examples Ib to 12b describe the modification of GF1 functions grafted onto a carbonaceous complex oxide.
  • Examples Ic to 9c describe the preparation of electrode materials, and their use in batteries.
  • C-LiFePO 4 generally denotes a material consisting of particles or aggregates of Fe and Li phosphate particles bearing a carbon coating
  • C-LiFePO 4 (PL) denotes a material consisting of particles or aggregates of Fe and Li phosphate particles bearing a carbon coating, the particles of which have an average dimension (d 50 ) of 2.7 ⁇ m and which is provided by Phostech Lithium Inc, Canada
  • C-LiFePO 4 (Al) denotes a material consisting of particles or aggregates of Fe and Li phosphate particles bearing a carbon coating, whose particles have a mean dimension (dso) of 2.9 ⁇ m and which is provided by Aldrich
  • C-Li 4 Ti 5 O 12 generally denotes a material consisting of particles or aggregates of Li titanate particles carrying a carbon coating
  • MC-LiFePO 4 generally denotes a material consisting of particles or aggregates of Fe and Li phosphate particles bearing a carbon coating carrying GF groups.
  • the nanometric titanate Li ⁇ isO ⁇ , whose particles have a surface of the order of 130 m 2 / g, is provided by Altair Nanotechnologies, USA;
  • microporous separator is provided by the company Celgard;
  • LiPF ⁇ EC DMC electrolyte is supplied by Tomiyama Pure Chemicals; • Carbon Black FW200 is supplied by Degussa, Germany;
  • Acetylene black is supplied by Chevron Phillips Chemical Company;
  • 5-Amino-benzotriazole is supplied by Lancaster Synthesis Ltd .; • The monallyl polyalkylene glycol A 20-20 ether is supplied by Clariant;
  • Noigen® RN-40 polyoxyethylene alkylphenyl ether is supplied by Dai-Ichi Kogyo Seiyaku Co., Japan;
  • TYZOR TPT® tetraisopropyl titanate
  • Epichlorohydrin is supplied by ABCR GmbH & Co. KG;
  • Polyethylene glycol diacrylate (600) is supplied by Sartomer, France;
  • EPOCROS WS-700 polyoxazoline is supplied by Nippon Shokubai, Japan;
  • Modified LHB-108P styrene-butadiene copolymer is produced by LICO Technology Corp., Taiwan, and marketed by Pred Materials International Inc., USA)
  • Aziridine is supplied by ABCR GmbH & Co, KG;
  • BM-400B latex is produced by Zeon Corporation, Japan.
  • C-LiFePO 4 (PL) 100 g were introduced into an aqueous solution containing 5 g of LiSO 3 - ⁇ -SS- ⁇ -SO 3 Li disulfide and mixed thoroughly. After removal of the water, the product was heated for 4 hours at 180 ° C. under argon, then it was washed with Soxhlet under argon overnight, and then dried under vacuum at 80 ° C. for 24 hours. An MC-LiFePO 4 material carrying lithium sulfonate groups was obtained.
  • LiFePO 4 was prepared by melting in a graphite crucible at 1000 ° C. under argon for 1 h, 1 mole of Fe 2 O 3 , 2 moles of (NH 4 ) 2 HPO 4 , and 1 mole of Li 2 CO 3. . LiFePO 4 was obtained with a purity level of 94% (determined by XRD).
  • This compound was then converted into particles having a size of 2 ⁇ m in a planetary mill.
  • the powder obtained was mixed in an alumina mortar with 4% by weight of acetylene black and then the mixture was mechanofused at 1000 rpm for 1 hour to produce a coated C-LiFePO 4 material. of acetylene black.
  • the material C-LiFePO 4 was then treated for 2 hours at 700 ° C. with water vapor under a gas flow of CO / CO 2 . There was thus obtained an MC-LiFePO 4 carrying -OH groups and -COOH groups.
  • Example 3a The procedure of Example 3a was repeated using 3% by weight of FW200 carbon black instead of 4% acetylene black. There was thus obtained a MC-LiFePO 4 bearing -COOH groups.
  • a LiFePO 4 powder was prepared according to the procedure of Example 3, and then this powder was mixed with a dispersion of carbon black FW200 in an aqueous solution of PVA, the amount of FW200 and the amount of PVA representing respectively 2% and 5% by weight of the amount of LiFePO 4 . After removal of water, the residual mixture was treated at 600 ° C for 1 h under argon. An MC-LiFePO 4 carrying -COOH groups was obtained.
  • LiFePO 4 powder was mixed with 4% by weight of acetylene black, and the mixture was mechanofused at a rotation speed of 1000 rpm to obtain LiFePO 4 .
  • 50 g of material were then refluxed for 8 h in 300 ml of a degassed aqueous solution containing 2 g of ⁇ - (1-benzotriazolyl) -butanesulfonic acid.
  • the residue obtained after filtration was washed several times with water, and a MC-LiFePO 4 carrying -SO 3 H groups was obtained.
  • LiFePO 4 was prepared by precipitation from LiH 2 PO 4 , Fe (SO 4 ) 2 '7H 2 O and LiOH as precursors, as described in Example 4 of US 2004/0151649.
  • the LiFePO 4 material obtained was impregnated with lactose, and then subjected to carbonization by a heat treatment consisting of heating from room temperature to 725 ° C. with a speed of 3 ° C./min under atmospheric pressure. nitrogen, and maintaining at a temperature of 725 ° C under nitrogen for 12 h.
  • sample 1 The procedure of sample 1 was repeated using 13.7 g of 4-aminobenzoic acid, and there was obtained a MC-LiFePO 4 material carrying -CO 2 K. 3rd sample
  • sample 1 The procedure of sample 1 was repeated, using lithium nitrite. An MC-LiFePO 4 material having -SO 3 Li groups was obtained.
  • sample 4 The procedure of sample 1 was repeated using 13.7 g of 4-aminobenzoic acid and lithium nitrite, and there was obtained a MC-LiFePO 4 material carrying -CO 2 Li groups.
  • a C-Li 4 Ti 5 O 12 material was prepared by the sol-gel technique using titanium tetra (isopropoxide) (28.42 g), and lithium acetate dehydrated (35.7 g in 300 ml of a mixture). isopropanol-water 80:20 The resulting white gel was dried in an oven at 80 0 C and calcined at 800 0 C in air for 3 hours, then under argon comprising 10% hydrogen at 850 0 C for 5 hours 10 g of the resulting powder was mixed in 12 ml of a 13% by weight solution of cellulose acetate in acetone The slurry was dried and the polymerized carbonized under an inert atmosphere at 700 ° C. 2nd sample
  • Example 9a The procedure of the 1st sample was reproduced using a nanometric titanate Li 4 Ti 5 O 2 (130 m 2 / g instead of that obtained by a sol-gel, to prepare a C-material Li 4 Ti 5 O 2 .
  • the 4 samples of Example 9a were reproduced by replacing C-LiFePO 4 (PL) with the material C-Li 4 Ti 5 O 12 obtained by the two processes above, to obtain MC-materials.
  • Li 4 Ti 5 Oi 2 respectively bearing groups SO 3 K, COOK, SO 3 Li and
  • Example 12a The 3 samples of Example 12a were reproduced by replacing C-LiFePO 4 (PL) with C-Li 4 Ti 5 O 12 prepared according to the procedure described in Example 10a, to obtain MC-Li 4 Ti materials. 5 O 2 respectively carrying groups SO 3 H and COOH.
  • Example 12a The procedure of Example 12a was repeated using different aminobenzene derivatives instead of 4-aminobenzene sulfonic acid. This resulted in an MC-
  • EXAMPLE Ib 10 g of a carboxy-bearing MC-LiFePO 4 were dispersed in 50 ml of a solution of 4 g of 20-20 monallyl polyalkylene glycol A ether. The mixture was cooled to 0 ° C., then 5 ml of a solution of 200 mg of 1,3-dicyclohexyl carbodiimide (DCC) in ethyl acetate and then pyridine were slowly added over 30 minutes. as a catalyst. The reaction mixture was stirred overnight. The powder recovered after filtration was washed several times with ethyl acetate and water. The MC-LiFePO 4 obtained carries allyl groups.
  • DCC 1,3-dicyclohexyl carbodiimide
  • the above procedure was repeated replacing the A20-20 ether successively with 2 mmol of the following compounds: allyl alcohol, 1, ⁇ -hexanediol vinyl ether, 2-hydroxyethyl methacrylate, N- (hydroxymethyl) acrylamide, N - (4- hydroxyphenyl) maleimide, polyoxyethylene alkylphenyl ether Noigen ® RN-40.
  • MC-LiFePO 4 carrying -SO 3 Li groups were reacted with 100 mg of 1-ethyl-3-methylimidazolium chloride (EMI). After filtration, the product was washed several times with water. The treatment was repeated five times, then the product was dried under vacuum at 80 ° C.
  • EMI 1-ethyl-3-methylimidazolium chloride
  • BMP 1-butyl-1-methylpyrrolidinium chloride
  • EXAMPLE 9b 10 g of azo-bearing MC-LiFePO4 material obtained according to the method of Example 8b and 2 g of sodium methacrylate were dispersed in 50 ml of dimethylformamide (DMF). glycidyl. A stream of argon was passed into the reaction medium for 1 h and then heated at 100 0 C for 3 h.
  • DMF dimethylformamide
  • the product recovered by filtration was washed several times with DMF and with acetone, and then dried under vacuum at room temperature for 24 hours.
  • the MC-LiFePO 4 material obtained carries polyacrylate groups which have pendant epoxy groups.
  • LiFePO 4 carrying COOK groups 1.42 g of glycidyl methacrylate and 20 mg 18-crown-6.
  • the reaction medium was heated with stirring at 100 ° C. for 4 h.
  • the product recovered by filtration was washed several times with DMF and with acetone, and then dried under vacuum at room temperature for 24 hours.
  • the MC-LiFePO 4 material obtained carries polyester groups which have pendant methacrylate groups.
  • MC-LiFePO 4 prepared according to Example Ib was mixed in 15 ml of ethyl acetate; 250 mg of EBN-1010 graphite particles; 1.7 g of an ethylene oxide terpolymer, methyl glycidyl ether and allyl glycidyl ether (molar ratio 80: 15: 5); and 500 mg of polyethylene glycol diacrylate (600).
  • composition thus obtained is applied in the form of a 30 ⁇ m thick film on an aluminum strip (which will serve as a current collector for an electrode), then heated under an inert atmosphere at 80 ° C. for 24 hours.
  • An electrode (cathode) for a battery is thus obtained, comprising a MC-LiFePO 4 in an interpenetrating network formed between MC-LiFePO 4 and polymers.
  • a battery comprising a MC-Li 4 TIsOi 2 in an interpenetrating network formed between the MC-Li 4 TIsOi 2 and polymers.
  • EPOCROS WS-700 oxazoline EPOCROS WS-700 oxazoline.
  • composition thus obtained is applied in the form of a film of 60 .mu.m thick on a substrate, then heated under an inert atmosphere for 12O 0 C for 1 h.
  • a lithium-ion battery cathode is thus obtained, in which the
  • the binder is attached to MC-LiFePO 4 via a linkage formed by the reaction of oxazoline and -COOH groups.
  • a mixture containing 1.8 g of water, 2.82 g of MC-LiFePO 4 bearing COOH groups and OH groups, 12 mg of EBN-1010 graphite particles and an aqueous suspension containing 40 mg is prepared. of a modified styrene-butadiene copolymer LHB-108P.
  • composition thus obtained is applied as a film 50 .mu.m thick on a substrate and then heated in air for 25 60 0 C for 2 h, then under an inert atmosphere at 80 ° C for 24 h.
  • a battery cathode is thus obtained.
  • tetrahydrofuran THF
  • MC-LiFePO 4 material carrying COOH groups 1 g of freshly distilled aziridine
  • the product recovered by filtration was washed several times with THF and then dried under vacuum at room temperature for 24 hours.
  • the MC-LiFePO 4 material obtained carries amino groups.
  • a dispersion of 300 mg of poly (glycidyl methacrylate) nanoparticles, having a diameter of 10-20 nm in 5 ml of water was prepared by emulsion polymerization by the method described in "Synthesis and curing of poly (glycidyl) methacrylate) Nanoparticles, Jyongsik Jang, Joonwon Bae, Sungrok Ko, Journal of Polymer Science Part A: Polymer Chemistry, Volume 43, Issue 11, 2005, Pages 2258-2265 ".
  • a mixture containing 10 g of amino-bearing MC-LiFePO 4 , 1 g of EBN-1010 graphite particles and the dispersion of poly (glycidyl methacrylate) nanoparticles is prepared.
  • composition thus obtained is applied as a film 60 .mu.m thick on a substrate and then heated to 120 0 C in dry air for I h.
  • a cathode material for lithium-ion battery is thus obtained, in which the MC-LiFePO 4 material is bound to a polymer by the bond formed between an epoxy group and an amino group.
  • EXAMPLE 5c 10 g of an azo-bearing MC-LiFePO4 material obtained by the method of Example 8b and 1 g of 4-styrene sulfonic acid (obtained from 4 g) were dispersed in 50 ml of water. sodium styrenesulfonate). A stream of argon was passed through the reaction medium through a septum for 1 h, then heated at 70 ° C. for 4 h.
  • the product recovered by filtration was washed several times with water and then dried under vacuum at room temperature for 24 hours.
  • the MC-LiFePO 4 material obtained carries poly (sulfonic acid) groups. This material was dispersed with stirring in 50 ml of water containing 1 g of 3,4-ethylenedioxythiophene (EDOT). After 10 min, 2 g of ammonium persulfate was added. After 24 h of reaction at 30 0 C, a powder was recovered which was washed several times with water and methanol, and then dried under vacuum for 24 h at room temperature.
  • EDOT 3,4-ethylenedioxythiophene
  • LiFePO 4 doped with molybdenum was synthesized by melting for one hour, under argon at 1000 ° C. and in a graphite crucible, 1 mole of Fe 2 O 3 , 2 moles of (NH 4 ) 2 HPO 4 , 1 mole of Li 2 CO 3 and 0.06 mole Li 2 MoO 4 .
  • LiFeMoPO 4 molybdenum-doped LiFePO 4 (94% x-ray purity) was then milled to an average size of 1 ⁇ m. 50 g of the LiFeMoPO 4 powder was then mixed in a mortar with 2.5 g of cellulose acetate dissolved in water.
  • a button cell was assembled in a glove box using a cathode as prepared in the first sample of Example Ic, a poly (ethylene oxide) electrolyte film 5.10 6 containing 30% by weight of
  • LiTFSI and a lithium pellet as anode were tested using a VMP2 potensiostat (Bio-Logic - Science Instruments) at 80 ° C. and a scanning speed of
  • a button cell was assembled with a composite cathode as prepared in example 4c, a separator 25 .mu.m in Celgard ®, a metallic lithium anode and an electrolyte IM LiPF 6 in ECiDMC (1: 1) impregnating the whole.
  • a first cyclic voltammetry between 3 V and 3.7 V vs Li + / Li ° is performed at room temperature to determine the electrode capacity.
  • power tests were performed intensiostatically to determine the energy / power characteristic of the battery as described in Figure 9.

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Publication number Priority date Publication date Assignee Title
EP2430690B1 (de) * 2009-05-11 2019-11-06 Johnson Matthey PLC Verbundmaterial enthaltend ein gemischtes lithium-metalloxid

Families Citing this family (124)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2395059B (en) 2002-11-05 2005-03-16 Imp College Innovations Ltd Structured silicon anode
GB0601319D0 (en) 2006-01-23 2006-03-01 Imp Innovations Ltd A method of fabricating pillars composed of silicon-based material
GB0601318D0 (en) 2006-01-23 2006-03-01 Imp Innovations Ltd Method of etching a silicon-based material
JP2010503606A (ja) * 2006-09-13 2010-02-04 ヴァレンス テクノロジー インコーポレーテッド 二次電気化学セルで用いる活性材料を処理する方法
US8097361B2 (en) * 2006-10-18 2012-01-17 Dow Global Technologies Llc Nanotube wiring
CA2569991A1 (en) * 2006-12-07 2008-06-07 Michel Gauthier C-treated nanoparticles and agglomerate and composite thereof as transition metal polyanion cathode materials and process for making
JP5190916B2 (ja) * 2007-03-15 2013-04-24 独立行政法人産業技術総合研究所 電極用複合粉末及びその製造方法
GB0709165D0 (en) 2007-05-11 2007-06-20 Nexeon Ltd A silicon anode for a rechargeable battery
CN101333650B (zh) * 2007-06-27 2010-08-11 中国科学院金属研究所 在LiFePO4颗粒表面均匀、可控包覆导电性碳层的方法
EP2015382A1 (de) * 2007-07-13 2009-01-14 High Power Lithium S.A. Kohlenstoffbeschichtetes Lithium-Mangan-Phosphat-Kathodenmaterial
GB0713896D0 (en) 2007-07-17 2007-08-29 Nexeon Ltd Method
GB0713895D0 (en) 2007-07-17 2007-08-29 Nexeon Ltd Production
GB0713898D0 (en) 2007-07-17 2007-08-29 Nexeon Ltd A method of fabricating structured particles composed of silcon or a silicon-based material and their use in lithium rechargeable batteries
US20090148377A1 (en) * 2007-12-11 2009-06-11 Moshage Ralph E Process For Producing Electrode Active Material For Lithium Ion Cell
JP4834030B2 (ja) * 2008-04-22 2011-12-07 第一工業製薬株式会社 リチウム二次電池用正極及びこれを用いたリチウム二次電池
KR101463957B1 (ko) * 2008-07-16 2014-11-26 주식회사 뉴파워 프라즈마 전기 전도성 복합 소재로 구성되는 전기 단자 및 이를구비한 전기 장치
CA2638410A1 (en) * 2008-07-28 2010-01-28 Hydro-Quebec Composite electrode material
KR100938138B1 (ko) * 2008-09-03 2010-01-22 대정이엠(주) 도전성이 우수한 리튬 이차전지용 양극 활물질 및 그 제조방법과 이를 포함하는 리튬 이차전지
JP2010111565A (ja) * 2008-10-07 2010-05-20 Toyota Motor Corp 窒化リン酸リチウム化合物の製造方法
FR2937185B1 (fr) * 2008-10-09 2011-02-25 Batscap Sa Electrode comprenant un oxyde complexe modifie comme matiere active.
GB2464158B (en) 2008-10-10 2011-04-20 Nexeon Ltd A method of fabricating structured particles composed of silicon or a silicon-based material and their use in lithium rechargeable batteries
US20110262809A1 (en) * 2008-11-04 2011-10-27 Incorporated National University Iwate University Non-stoichiometric titanium compound, carbon composite of the same, manufacturing method of the compound, active material of negative electrode for lithium-ion secondary battery containing the compound, and lithium-ion secondary battery using the active material of negative electrode
WO2010053328A2 (ko) * 2008-11-10 2010-05-14 주식회사 엘지화학 고전압 특성이 향상된 양극 활물질
JP5381115B2 (ja) * 2009-01-20 2014-01-08 住友大阪セメント株式会社 リン酸リチウム粉体とリン酸リチウム含有スラリー及び電極活物質の製造方法並びにリチウムイオン電池
FR2943463B1 (fr) * 2009-03-19 2011-07-01 Arkema France Materiaux composites a base de liants fluores et nanotubes de carbone pour electrodes positives de batteries lithium.
FR2944149B1 (fr) * 2009-04-06 2011-04-29 Centre Nat Rech Scient Electrode composite.
GB2470056B (en) 2009-05-07 2013-09-11 Nexeon Ltd A method of making silicon anode material for rechargeable cells
GB2470190B (en) 2009-05-11 2011-07-13 Nexeon Ltd A binder for lithium ion rechargeable battery cells
US9853292B2 (en) 2009-05-11 2017-12-26 Nexeon Limited Electrode composition for a secondary battery cell
JP5671831B2 (ja) 2009-05-21 2015-02-18 トヨタ自動車株式会社 窒化リチウム−遷移金属複合酸化物の製造方法、窒化リチウム−遷移金属複合酸化物およびリチウム電池
JP5391832B2 (ja) * 2009-05-26 2014-01-15 株式会社デンソー 二次電池及びその製造方法
JP5659352B2 (ja) * 2009-06-01 2015-01-28 クラリアント （カナダ） インコーポレイテッド 有機電子導電性ポリマーの重合を誘導する方法
JP5534363B2 (ja) * 2009-06-25 2014-06-25 国立大学法人 長崎大学 複合ナノ多孔電極材とその製造方法、及びリチウムイオン二次電池
TWI403374B (zh) * 2009-07-28 2013-08-01 Univ Nat Taiwan Polymeric Polymer Containing Polyvinyl Ether Amines and Its Application in the Production of Nanometer Silver Particles
US9178215B2 (en) * 2009-08-25 2015-11-03 A123 Systems Llc Mixed metal olivine electrode materials for lithium ion batteries having improved specific capacity and energy density
JP5594656B2 (ja) * 2009-09-30 2014-09-24 国立大学法人名古屋大学 リチウムイオン二次電池の正極材の製造方法
JP5515665B2 (ja) * 2009-11-18 2014-06-11 ソニー株式会社 固体電解質電池、正極活物質および電池
KR101093697B1 (ko) * 2009-11-20 2011-12-15 삼성에스디아이 주식회사 리튬 이차 전지용 양극 및 이를 포함하는 리튬 이차 전지
JP5445841B2 (ja) * 2009-11-27 2014-03-19 トヨタ自動車株式会社 電極活物質の製造方法
JP2011113924A (ja) * 2009-11-30 2011-06-09 Univ Of Fukui チタン酸リチウム負極物質の製造方法
CA2784686C (en) * 2009-12-17 2018-02-20 Phostech Lithium Inc. Method for improving the electrochemical performances of an alkali metal oxyanion electrode material and alkali metal oxyanion electrode material obtained therefrom
KR101613498B1 (ko) * 2009-12-23 2016-04-20 삼성에스디아이 주식회사 양극 활물질, 이를 채용한 양극과 리튬 전지 및 이의 제조방법
WO2011084003A2 (ko) * 2010-01-07 2011-07-14 주식회사 엘지화학 4v 영역과 3v 영역에서 우수한 충방전 특성을 발휘할 수 있는 리튬 망간 산화물을 포함하는 양극 활물질
CN102792495B (zh) * 2010-03-12 2015-10-21 丰田自动车株式会社 电极活性物质和电极活性物质的制造方法
GB201005979D0 (en) 2010-04-09 2010-05-26 Nexeon Ltd A method of fabricating structured particles composed of silicon or a silicon-based material and their use in lithium rechargeable batteries
CN102893432B (zh) 2010-04-21 2016-01-13 株式会社Lg化学 碳包覆的具有橄榄石晶体结构的锂铁磷酸盐和使用所述锂铁磷酸盐的锂二次电池
JP5836568B2 (ja) 2010-05-04 2015-12-24 日本ケミコン株式会社 チタン酸リチウム結晶構造体とカーボンの複合体、その製造方法、その複合体を用いた電極及び電気化学素子
GB201009519D0 (en) 2010-06-07 2010-07-21 Nexeon Ltd An additive for lithium ion rechargeable battery cells
WO2012006725A1 (en) * 2010-07-15 2012-01-19 Phostech Lithium Inc. Battery grade cathode coating formulation
JP5918236B2 (ja) 2010-08-20 2016-05-18 ロディア オペレーションズＲｈｏｄｉａ Ｏｐｅｒａｔｉｏｎｓ ポリマー組成物、ポリマーフィルム、ポリマーゲル、ポリマーフォーム、並びに当該フィルム、ゲル及びフォームを含有する電子デバイス
GB201014707D0 (en) 2010-09-03 2010-10-20 Nexeon Ltd Electroactive material
GB201014706D0 (en) 2010-09-03 2010-10-20 Nexeon Ltd Porous electroactive material
JP5634184B2 (ja) * 2010-09-14 2014-12-03 東洋アルミニウム株式会社 導電層被覆アルミニウム材とその製造方法
FR2965107A1 (fr) * 2010-09-22 2012-03-23 Commissariat Energie Atomique Encre aqueuse pour l'impression d'electrodes pour batteries au lithium
US9643842B2 (en) 2011-03-14 2017-05-09 Imra America, Inc. Nanoarchitectured multi-component electrode materials and methods of making the same
JP6057893B2 (ja) 2011-04-28 2017-01-11 昭和電工株式会社 リチウム二次電池用正極材料及びその製造方法
CN103828099B (zh) 2011-07-25 2018-04-20 A123系统有限责任公司 掺混的阴极材料
US20130029227A1 (en) 2011-07-26 2013-01-31 Toyota Motor Engineering & Manufacturing North America, Inc. Polyanion active materials and method of forming the same
US20130045423A1 (en) * 2011-08-18 2013-02-21 Hong Kong Applied Science and Technology Research Institute Company Limited Porous conductive active composite electrode for litihium ion batteries
JP2013047161A (ja) * 2011-08-29 2013-03-07 Asahi Glass Co Ltd ケイ酸化合物、二次電池用正極および二次電池の製造方法
JP5696008B2 (ja) * 2011-09-07 2015-04-08 株式会社日立製作所 被覆活物質およびそれを用いたリチウム二次電池
JP5535160B2 (ja) 2011-09-20 2014-07-02 株式会社東芝 非水電解質電池及び電池パック
US8956688B2 (en) * 2011-10-12 2015-02-17 Ut-Battelle, Llc Aqueous processing of composite lithium ion electrode material
FR2983466B1 (fr) * 2011-12-06 2014-08-08 Arkema France Utilisation de melanges de sels de lithium comme electrolytes de batteries li-ion
FR2985857B1 (fr) * 2012-01-17 2014-01-03 Hutchinson Cathode pour cellule de batterie lithium-ion, son procede de fabrication et cette batterie l'incorporant.
SG11201403892QA (en) * 2012-02-01 2014-10-30 Univ Nanyang Tech An anode material for ultrafast-charging lithium ion batteries and a method of its synthesis
US10135068B2 (en) * 2012-03-09 2018-11-20 Nippon Electric Glass Co., Ltd. Cathode active material for sodium secondary battery and method for manufacturing the cathode active material for sodium secondary battery
CN103715429B (zh) * 2012-09-28 2016-04-27 王复民 锂电池
KR101470090B1 (ko) * 2012-11-30 2014-12-05 삼성정밀화학 주식회사 리튬이차전지용 양극 활물질 복합체, 이의 제조방법 및 이를 이용한 리튬이차전지
JP5861650B2 (ja) * 2013-01-29 2016-02-16 住友大阪セメント株式会社 電極材料及び電極並びにリチウムイオン電池
DE102013206007A1 (de) * 2013-04-04 2014-10-09 Chemische Fabrik Budenheim Kg Amorphisiertes Eisen(III)phosphat
KR101459736B1 (ko) * 2013-04-25 2014-11-20 주식회사 포스코 리튬 이차전지용 양극 활물질 제조방법
US10135071B2 (en) 2013-06-21 2018-11-20 Cabot Corporation Conductive carbons for lithium ion batteries
WO2015006058A1 (en) 2013-07-09 2015-01-15 Dow Global Technologies Llc Mixed positive active material comprising lithium metal oxide and lithium metal phosphate
KR102214826B1 (ko) * 2013-07-31 2021-02-10 삼성전자주식회사 복합 양극 활물질, 이를 포함하는 리튬 전지, 및 이의 제조방법
EP3695899B1 (de) * 2013-08-27 2025-01-15 Nissan Chemical Corporation Dispersion von elektrisch leitfähigen kohlenstoffmaterial
JP6136765B2 (ja) * 2013-08-28 2017-05-31 住友金属鉱山株式会社 非水系電解質二次電池用正極活物質の製造方法、非水系電解質二次電池用正極活物質および非水系電解質二次電池
JP2015176831A (ja) * 2014-03-17 2015-10-05 トヨタ自動車株式会社 リチウムイオン二次電池用正極、およびリチウムイオン二次電池
JP6026457B2 (ja) * 2014-03-31 2016-11-16 古河電気工業株式会社 正極活物質、二次電池用正極、二次電池及び正極活物質の製造方法
DE102014217727A1 (de) * 2014-09-04 2016-03-10 Wacker Chemie Ag Polymerzusammensetzung als Bindersystem für Lithiumionenbatterien
US10283776B2 (en) 2014-09-11 2019-05-07 Kabushiki Kaisha Toshiba Electrode material, and electrode layer, battery, and electrochromic device using the electrode material
JP6139780B2 (ja) 2014-12-02 2017-05-31 株式会社東芝 負極活物質、非水電解質電池、電池パック及び車
EP3235028B1 (de) 2014-12-18 2021-05-12 Dow Global Technologies LLC Lithiumionenbatterie mit erhöhter wärmestabilität
JP6326366B2 (ja) * 2014-12-25 2018-05-16 信越化学工業株式会社 リチウムリン系複合酸化物炭素複合体及びその製造方法並びに、電気化学デバイス及びリチウムイオン二次電池
JP6058836B2 (ja) 2015-01-30 2017-01-11 株式会社東芝 活物質、非水電解質電池、電池パック、組電池、及び車両
EP3147974B1 (de) 2015-01-30 2019-02-27 Kabushiki Kaisha Toshiba Batteriemodul und batteriepack
JP6067902B2 (ja) 2015-03-13 2017-01-25 株式会社東芝 活物質、非水電解質電池、電池パック、組電池、及び自動車
FR3038145B1 (fr) * 2015-06-23 2017-07-21 Centre Nat Rech Scient Procede de preparation d'une electrode composite
KR102203636B1 (ko) * 2015-11-30 2021-01-15 주식회사 엘지화학 리튬 전이금속 산화물 입자를 포함하는 양극 활물질, 이의 제조 방법, 및 이를 포함하는 리튬 이차 전지
US10987735B2 (en) 2015-12-16 2021-04-27 6K Inc. Spheroidal titanium metallic powders with custom microstructures
CA3009630C (en) 2015-12-16 2023-08-01 Amastan Technologies Llc Spheroidal dehydrogenated metals and metal alloy particles
KR102753477B1 (ko) * 2016-02-22 2025-01-10 주식회사 엘지에너지솔루션 리튬 전이금속 인산화물 입자를 포함하는 양극 활물질, 이의 제조 방법, 및 이를 포함하는 리튬 이차 전지
CN105529458B (zh) * 2016-03-02 2018-09-18 合肥国轩高科动力能源有限公司 一种锂离子电池的镍钴锰酸锂/磷酸锰铁锂复合正极材料的制备方法
JP6702564B2 (ja) * 2017-03-21 2020-06-03 株式会社東芝 活物質、電極、二次電池、組電池、電池パック、及び車両
CN107394169B (zh) * 2017-07-27 2020-02-14 山东大学 一种钼酸钠改性钛酸锌锂负极材料及其制备方法
JP6497461B1 (ja) * 2018-03-30 2019-04-10 住友大阪セメント株式会社 リチウムイオン二次電池用電極材料、リチウムイオン二次電池用電極材料造粒体、リチウムイオン二次電池用電極、リチウムイオン二次電池
DE102018206799A1 (de) * 2018-05-03 2019-11-07 Robert Bosch Gmbh Elektrode für eine Lithium-Ionen-Batterie und Verfahren zum Herstellen einer Elektrode für eine Lithium-Ionen-Batterie
CN112654444A (zh) 2018-06-19 2021-04-13 6K有限公司 由原材料制造球化粉末的方法
JP7026252B2 (ja) * 2018-09-27 2022-02-25 株式会社村田製作所 リチウムイオン二次電池用電解液およびリチウムイオン二次電池
US12148915B2 (en) 2018-11-02 2024-11-19 Nissan Chemical Corporation Composition for forming an active material composite, an active material composite, and a method for producing an active material composite
KR102757221B1 (ko) 2018-11-28 2025-01-21 현대자동차주식회사 리튬 이차전지 및 리튬 이차전지의 제조방법
KR102803819B1 (ko) * 2018-12-10 2025-05-08 주식회사 엘지에너지솔루션 음극 활물질, 이를 포함하는 음극 및 리튬 이차전지
SG11202111576QA (en) 2019-04-30 2021-11-29 6K Inc Mechanically alloyed powder feedstock
CN112751140B (zh) * 2019-10-16 2023-09-15 珠海冠宇电池股份有限公司 一种提高锂离子电池电解液保液量和安全性能的隔膜功能涂层材料
CN114641462A (zh) 2019-11-18 2022-06-17 6K有限公司 用于球形粉末的独特原料及制造方法
KR102330086B1 (ko) * 2019-12-05 2021-11-24 한국전력공사 확산방지층을 포함하는 아연-이산화망간 이차전지
US11590568B2 (en) 2019-12-19 2023-02-28 6K Inc. Process for producing spheroidized powder from feedstock materials
JPWO2021229802A1 (de) * 2020-05-15 2021-11-18
CA3180426A1 (en) 2020-06-25 2021-12-30 Richard K. Holman Microcomposite alloy structure
CN111808814B (zh) * 2020-09-03 2021-01-08 朗姿赛尔生物科技（广州）有限公司 一种促进神经干细胞增殖的方法
AU2021349358A1 (en) 2020-09-24 2023-02-09 6K Inc. Systems, devices, and methods for starting plasma
CA3196653A1 (en) 2020-10-30 2022-05-05 Sunil Bhalchandra BADWE Systems and methods for synthesis of spheroidized metal powders
CN112687837B (zh) * 2020-12-19 2023-06-20 贵州贵航新能源科技有限公司 一种高安全高化学性能高倍率充电锂电池及其制造方法
AU2022206483A1 (en) 2021-01-11 2023-08-31 6K Inc. Methods and systems for reclamation of li-ion cathode materials using microwave plasma processing
WO2022212291A1 (en) 2021-03-31 2022-10-06 6K Inc. Systems and methods for additive manufacturing of metal nitride ceramics
CN113293300B (zh) * 2021-05-21 2022-04-12 江苏中南锂业有限公司 一种盐湖提锂用冠醚改性电极的制备方法
WO2023229928A1 (en) 2022-05-23 2023-11-30 6K Inc. Microwave plasma apparatus and methods for processing materials using an interior liner
US12040162B2 (en) 2022-06-09 2024-07-16 6K Inc. Plasma apparatus and methods for processing feed material utilizing an upstream swirl module and composite gas flows
WO2024044498A1 (en) 2022-08-25 2024-02-29 6K Inc. Plasma apparatus and methods for processing feed material utilizing a powder ingress preventor (pip)
CN115528296B (zh) * 2022-09-29 2023-12-29 欣旺达动力科技股份有限公司 一种二次电池
US12195338B2 (en) 2022-12-15 2025-01-14 6K Inc. Systems, methods, and device for pyrolysis of methane in a microwave plasma for hydrogen and structured carbon powder production
CN118974974A (zh) * 2023-03-31 2024-11-15 昆明理工大学 一种电池正极材料及其处理方法和电池
EP4585299A1 (de) * 2024-01-11 2025-07-16 Johannes Gutenberg-Universität Mainz Polyethercopolymere für membrananwendungen
CN118539085B (zh) * 2024-05-22 2024-11-22 吉林师范大学 离子型共价有机骨架修饰的锂硫电池改性隔膜的方法、改性隔膜及含有该改性隔膜的电池

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1049182A2 (de) * 1999-04-30 2000-11-02 Hydro-Quebec Elektrodenmaterialen mit erhöhter Oberflächenleitfähigkeit
JP2003151533A (ja) * 2001-11-08 2003-05-23 Denso Corp 電極、その製造方法及び電池

Family Cites Families (40)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6265029B1 (en) 1995-05-04 2001-07-24 William Lewis Low-cost, user-friendly hardcoating solution, process and coating
JP3237472B2 (ja) * 1995-07-06 2001-12-10 松下電器産業株式会社 ２次電池用電極の製造方法
JP3601124B2 (ja) 1995-09-22 2004-12-15 株式会社デンソー 非水溶液を用いる二次電池の正極活物質、および正極。
JP3286516B2 (ja) 1995-12-06 2002-05-27 三洋電機株式会社 非水電解液二次電池
US5910382A (en) 1996-04-23 1999-06-08 Board Of Regents, University Of Texas Systems Cathode materials for secondary (rechargeable) lithium batteries
US6514640B1 (en) 1996-04-23 2003-02-04 Board Of Regents, The University Of Texas System Cathode materials for secondary (rechargeable) lithium batteries
US6447951B1 (en) 1996-09-23 2002-09-10 Valence Technology, Inc. Lithium based phosphates, method of preparation, and uses thereof
JP4823401B2 (ja) * 1996-12-30 2011-11-24 イドロ―ケベック 過フッ化アミド塩及びイオン伝導物質としてのその使用方法
US6096101A (en) 1997-03-05 2000-08-01 Valence Technology, Inc. Method of preparing electrochemical cells
US6153333A (en) 1999-03-23 2000-11-28 Valence Technology, Inc. Lithium-containing phosphate active materials
EP1078960A1 (de) 1999-08-27 2001-02-28 Degussa-Hüls Aktiengesellschaft Metall-behandelter Russ
DE19954260A1 (de) 1999-11-11 2001-06-28 Degussa Wäßrige Rußdispersionen
DE10012784A1 (de) 2000-03-16 2001-09-27 Degussa Ruß
US6660075B2 (en) 2000-03-16 2003-12-09 Degussa Ag Carbon black
US6387568B1 (en) 2000-04-27 2002-05-14 Valence Technology, Inc. Lithium metal fluorophosphate materials and preparation thereof
US6399246B1 (en) 2000-05-05 2002-06-04 Eveready Battery Company, Inc. Latex binder for non-aqueous battery electrodes
DE10030703A1 (de) 2000-06-23 2002-01-10 Degussa Ruß
US6656633B2 (en) * 2000-07-26 2003-12-02 Zeon Corporation Binder for electrode for lithium ion secondary battery, and utilization thereof
JP2002075375A (ja) * 2000-08-31 2002-03-15 Nippon Shokubai Co Ltd 電池用電極
CA2320661A1 (fr) 2000-09-26 2002-03-26 Hydro-Quebec Nouveau procede de synthese de materiaux limpo4 a structure olivine
JP4491946B2 (ja) 2000-09-29 2010-06-30 ソニー株式会社 正極活物質の製造方法及び非水電解質電池の製造方法
TW513822B (en) 2000-10-06 2002-12-11 Sony Corp Method for producing cathode active material and method for producing non-aqueous electrolyte cell
US7250147B2 (en) 2001-01-29 2007-07-31 Tour James M Process for derivatizing carbon nanotubes with diazonium species
DE10117904B4 (de) 2001-04-10 2012-11-15 Zentrum für Sonnenenergie- und Wasserstoff-Forschung Baden-Württemberg Gemeinnützige Stiftung Binäre, ternäre und quaternäre Lithiumeisenphosphate, Verfahren zu ihrer Herstellung und ihre Verwendung
DE10136043A1 (de) 2001-07-25 2003-02-13 Degussa Verfahren zur Herstellung von modifiziertem Ruß
US6758891B2 (en) 2001-10-09 2004-07-06 Degussa Ag Carbon-containing material
JP3959708B2 (ja) 2001-11-19 2007-08-15 株式会社デンソー リチウム電池用正極の製造方法およびリチウム電池用正極
DE10211098A1 (de) 2002-03-14 2003-10-02 Degussa Verfahren zur Herstellung von nachbehandeltem Ruß
CA2394056A1 (fr) 2002-07-12 2004-01-12 Hydro-Quebec Particules comportant un noyau non conducteur ou semi conducteur recouvert d'un couche conductrice, leurs procedes d'obtention et leur utilisation dans des dispositifs electrochimiques
DE10238149A1 (de) 2002-08-15 2004-02-26 Degussa Ag Kohlenstoffhaltiges Material
US7632317B2 (en) 2002-11-04 2009-12-15 Quallion Llc Method for making a battery
CA2411695A1 (fr) 2002-11-13 2004-05-13 Hydro-Quebec Electrode recouverte d'un film obtenu a partir d'une solution aqueuse comportant un liant soluble dans l'eau, son procede de fabrication et ses utilisations
JP4553619B2 (ja) * 2003-04-03 2010-09-29 パナソニック株式会社 電気化学素子用電極の製造方法
JP4061586B2 (ja) * 2003-04-11 2008-03-19 ソニー株式会社 非水電解質二次電池用正極活物質及びそれを用いた非水電解質二次電池
JP2005050669A (ja) 2003-07-28 2005-02-24 Tdk Corp 電極、及び、それを用いた電気化学素子
JP3930002B2 (ja) * 2003-07-28 2007-06-13 昭和電工株式会社 高密度電極及びその電極を用いた電池
EP1652247A4 (de) * 2003-07-28 2009-08-19 Showa Denko Kk Hochdichte elektrode und batterie mit der elektrode
JP4338489B2 (ja) * 2003-09-26 2009-10-07 関西熱化学株式会社 二次電池電極用黒鉛、該電極用黒鉛を含む二次電池用電極、該電極を用いたリチウムイオン二次電池
CA2791156C (en) 2003-12-23 2015-12-15 Universite De Montreal Process for preparing electroactive insertion compounds and electrode materials obtained therefrom
JP4819342B2 (ja) * 2004-11-08 2011-11-24 エレクセル株式会社 リチウム電池用正極及びこれを用いたリチウム電池

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1049182A2 (de) * 1999-04-30 2000-11-02 Hydro-Quebec Elektrodenmaterialen mit erhöhter Oberflächenleitfähigkeit
JP2003151533A (ja) * 2001-11-08 2003-05-23 Denso Corp 電極、その製造方法及び電池

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of WO2006120332A2 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2430690B1 (de) * 2009-05-11 2019-11-06 Johnson Matthey PLC Verbundmaterial enthaltend ein gemischtes lithium-metalloxid

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US20090305132A1 (en) 2009-12-10
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