Classifications

• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M4/00—Electrodes
  • H01M4/02—Electrodes composed of, or comprising, active material
  • H01M4/36—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
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
  • C01B25/00—Phosphorus; Compounds thereof
  • C01B25/16—Oxyacids of phosphorus; Salts thereof
  • C01B25/26—Phosphates
  • C01B25/37—Phosphates of heavy metals
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
  • C01B25/00—Phosphorus; Compounds thereof
  • C01B25/16—Oxyacids of phosphorus; Salts thereof
  • C01B25/26—Phosphates
  • C01B25/45—Phosphates containing plural metal, or metal and ammonium
• • 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
  • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
  • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
  • H01M10/0565—Polymeric materials, e.g. gel-type or solid-type
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • 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
  • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
  • H01M4/621—Binders
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M4/00—Electrodes
  • H01M4/02—Electrodes composed of, or comprising, active material
  • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
  • H01M4/621—Binders
  • H01M4/622—Binders being polymers
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M4/00—Electrodes
  • H01M4/02—Electrodes composed of, or comprising, active material
  • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
  • H01M4/624—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
  • H01M2004/021—Physical characteristics, e.g. porosity, surface area
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
  • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
  • Y02E60/10—Energy storage using batteries
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
  • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
  • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

• the present invention relates to a method of optimizing a cathode material which thus has improved electrochemical properties.
• the present invention also relates to a material which has improved electrochemical properties.
• intercalation compound LiCoO 2 has very good electrochemical properties.
• the limited quantity, the cobalt price and the safety problems hamper the generalization of such lithium-ion accumulators in applications requiring high storage capacities.
• the safety problems are thus solved, thanks to the covalent bond P-0 which stabilizes the fully charged cathode with respect to the release of oxygen.
• Some materials such as LiFePO 4 , exhibit non-optimal kinetics, induced by the low intrinsic electronic conductivity, which results from the fact that the PO 4 polyanions are covalently bonded.
• the use of a thin layer of pyrolytic carbon on the surface of such materials (as described in EP 1049182, CA 2,307,19, US 6,855,273, US 6,962,666, US 7,344,659, US 7,457,018, WO 02/27823 & WO 02/27824) has made it possible to develop and commercialize a phosphate product carrying a pyrolytic carbon deposit electronic conductor (eg C-LiFeP0 4 ) of battery grade which has high capacity and which can provide high power.
• a phosphate product carrying a pyrolytic carbon deposit electronic conductor eg C-LiFeP0 4
• this material may also be modified by partial replacement of the Fe cations by isovalent or aliovalent metal cations, such as for example and without limitation, Mn, Ni, Co, Mg, Mo , Nb, Ti, Al, Ta, Ge, La, Y, Yb, Sm, B, Ce, Hf, Cr, Zr, Bi, Zn, Ca and W, or by partial replacement of the oxyanion P0 with Si0, S0 or M0O 4 (as described in US 6,514,640).
• isovalent or aliovalent metal cations such as for example and without limitation, Mn, Ni, Co, Mg, Mo , Nb, Ti, Al, Ta, Ge, La, Y, Yb, Sm, B, Ce, Hf, Cr, Zr, Bi, Zn, Ca and W, or by partial replacement of the oxyanion P0 with Si0, S0 or M0O 4 (as described in US 6,514,640).
• C-LiFePO 4 the potential of the cathode C-LiFePO at 3.5 V vs Li + / Li ° makes it also an ideal candidate for lithium metal polymer (LMP) technology batteries using an anode of metallic lithium, replacing vanadium oxides.
• LMP lithium metal polymer
• These batteries use in effect as ionic electrolyte conductive dry polymer of the family of polyethers in which is dissolved a lithium salt, the window of electrochemical stability is of the order of 4 V vs Li + / Li °.
• the use of C-LiFeP0 4 makes it possible to design LMP batteries for electric vehicles with excellent cycling performance and improved safety.
• the present invention is directed to an oxyanion material of lithiated or partially lithiated metal having a pyrolytic carbon deposition on the surface which has improved electrochemical properties, such as when used as a cathode in an LMP battery.
• the present invention also provides an electrode that contains the material defined above and the use of this electrode in an LMP battery.
• the present invention also aims at a material CA x M (X0 4 ) y constituted by particles of a compound having the formula A x M (XO) y , where the particles comprise on at least one part of their surface a deposit of carbon deposited by pyrolysis, where: A represents Li, alone or partially replaced by not more than 10 atomic% of Na or K; M represents Fe (II), or Mn (II), or mixtures thereof, alone or partly replaced by not more than 30 atomic% of one or more other metals selected from Ni and Co, and / or by at most 10 at% d one or more aliovalent or isovalent metals other than Ni or Co, and / or not more than 5 at% Fe (III); X0 4 represents PO 4 alone or partially replaced by at most 10 mol% of at least one group selected from SO 4 , SiO and MoO 4 ; 0 ⁇ x ⁇ 2 and 0 ⁇ y ⁇ 2, the coefficients x and y being chosen independently to
• the present invention is directed to a method for improving the electrochemical properties of a lithium metal polymer (LMP) battery, wherein the battery comprises an oxyanion material of lithiated or partially lithiated metal comprising particles.
• LMP lithium metal polymer
• the battery comprises an oxyanion material of lithiated or partially lithiated metal comprising particles.
• A represents Li, alone or partially replaced by at most 10 at% of Na or K ;
• M represents Fe (II), or Mn (II), or mixtures thereof, alone or partly replaced by not more than 30 atomic% of one or more other metals selected from Ni and Co, and / or by at most 10 at% d one or more aliovalent or isovalent metals other than Ni or Co, and / or not more than 5 at% Fe (III);
• X0 4 represents P0 alone or partially replaced by at most 10 mol% of at least one group selected from SO 4 , SiO 4 and Mo
• the method defined above comprises, during the synthesis of the materials and / or during washing steps, the use of a water which is little or not calcareous so that in the product CA x M (X0 4 ) y the calcium content present as impurity is less than about 1000 ppm, preferably less than about 500 ppm, more preferably less than about 300 ppm, more preferably less than about 100 ppm.
• the carbon film is a uniform, adherent, non-powdery deposit. It represents about 0.03 to about 15% by weight, preferably about 0.5 to about 5% by weight based on the total weight of the material.
• the material of the present invention when used as a cathode material, has at least one discharge tray / charge at about 3.4-3.5 V vs. Li + / Li °, characteristic of torque Fe +2 / Fe +3 .
• the present invention is directed to a MPO 4 material, optionally hydrated, for the synthesis of C-LiMP0 4 by a thermal process, wherein the material has a calcium content present as an impurity of less than about 1000 ppm, M is a metal representing at least 70 at% Fe (II).
• the MPO 4 material for the synthesis of C-UMP0 by a thermal process is characterized by a calcium content present as an impurity of less than about 500 ppm, preferably less than about 300 ppm, more preferably less than about 100 ppm.
• the impurity comprising calcium is essentially present on the surface of the MPO 4 material.
• M represents Fe (II)
• the material FePO 4 optionally hydrated, for the synthesis of C-LiFePO by a thermal process, is characterized by a calcium content present as an impurity of less than about 1000 ppm, preferably less than about 500 ppm, preferably less than about 300 ppm, more preferably less than about 00 ppm.
• the impurity comprising calcium is essentially present on the surface of FePO 4 material.
• C-LiFePO 4 synthesized by a thermal method in the solid state.
• This solid state thermal process consists of mixing sources of Li, Fe and PO 4 with an organic compound. More precisely, lithium carbonate (Li 2 CO 3 ), iron phosphate (FePO 4 ) and a polymer are mixed, then this mixture is cooked under a reducing atmosphere in a rotary kiln at the outlet of which the cathode material C is obtained.
• -LiFeP0 4 .
• the inventors have correlated the origin of the calcium present as impurity to the raw material FePO 4 , which may contain calcium-based impurities, in particular calcium phosphates or calcium carbonates poorly soluble in aqueous medium. These impurities comprising calcium are found ultimately in the product C-LiFePO.
• the inventors have observed an increase in the ASI during the cycling of LMP batteries with batches of C-LiFePO 4 containing only very small amounts of calcium present as impurity, ie a few hundred ppm as determined by chemical microanalyses (plasma torch, etc.). Explanations can be advanced for this surprising purpose without this being a limit to the invention.
• LiTFSI bis (trifluoromethanesulfonyl) imide
• TFSI anion is able to take in solution many cations, including the divalent cations like calcium.
• a polymer electrolyte is conductive only if it has an amorphous structure, that is to say disorganized structure most able to dissociate and solvate the salt. Any crystallization primer increases the cohesion energy of the polymer and has adverse consequences on the ionic conductivity of the material. Such an amorphous structure is obtained only by placing itself at a temperature greater than the glass transition temperature T g, which must therefore be as low as possible.
• T g can vary depending on the amount of solvated salt in the polymer, and also depending on the nature of the cation for a given anion.
• the method of the invention comprises, during the synthesis of the materials and / or during washing steps, the use of water that is little or not calcareous so that in the product CA x M (X0) y the calcium content present as impurity is less than about 1000 ppm, preferably less than about 500 ppm, more preferably less than about 300 ppm, more preferably less than about 100 ppm.
• the skilled person will be able to obtain water that is little or no limestone without abnormal effort.
• CA x M (X0 4 ) y material, consists of particles of a compound having the formula A x M (X0 4 ) y which have an olivine structure and which bear on at least a part of their surface a deposit of carbon deposited by pyrolysis, where:
• - A represents Li, alone or partially replaced by at most 10 atomic% of Na or K;
• M represents Fe (II), or Mn (II), or mixtures thereof, alone or partly replaced by at most 30 atomic% of one or more other metals selected from Ni and Co, and / or by at most 10 at% one or more aliovalent or isovalent metals other than Ni or Co, and / or not more than 5 at% Fe (III); and
• - X0 4 is an oxyanion and represents PO 4 alone or partially replaced by at most 10 mol% of at least one group selected from SO 4 , SiO 4 and MoO 4 ;
• the coefficients x and y being chosen independently to ensure the electroneutrality of the complex oxide, the material being characterized in that it has a calcium content present as lower impurity at about 1000 ppm.
• the material CA x M (X0 4 ) y preceded is characterized in that it has a calcium content present as impurity of less than about 500 ppm, preferably less than about 300 ppm, and more particularly less than about 100 ppm.
• the material CA x M (X0) y of the present invention consists of particles of a compound having the formula A x M (XO 4 ) y which have an olivine structure and which cover at least one part of their surface a deposit of carbon deposited by pyrolysis, where:
• - A represents Li, alone or partially replaced by at most 10 atomic% of Na or K;
• M represents Fe (II), alone or partly replaced by at most 30 atomic% of one or more other metals selected from Mn, Ni and Co, and / or by at most 10 atomic% of one or more aliovalent metals or isovalents selected from Mg, Mo, Nb, Ti, Al, Ta, Ge, La, Y, Yb, Sm, Ce, Cu, Hf, Cr, Zr, Bi, Zn, B, Ca and W, and / or by plus 5 atomic% of Fe (III); and
• - X0 4 is an oxyanion and represents PO 4 alone or partially replaced by at most 10 mol% of at least one group selected from SO 4 , SiO 4 and MoO 4 ;
• the coefficients x and y being chosen independently to ensure the electroneutrality of the complex oxide, the material being characterized in that it has a calcium content present as lower impurity at about 1000 ppm.
• the material CA x M (X0 4 ) y preceded is characterized in that it has a calcium content present as impurity less than about 500 ppm, preferably less than about 300 ppm, more particularly lower at about 100 ppm.
• the CA x M material (X0 4) is C-UMPO 4 consisting of particles of a compound of formula L1MPO 4 which has an olivine structure and which carries on at least one part of its surface a deposit of carbon deposited by pyrolysis, M representing at least 70 atomic% of Fe (II), and characterized in that it has a calcium content present as impurity less than about 1000 ppm, preferably less than about 500 ppm, preferably less than about 300 ppm, and more preferably less than about 100 ppm.
• the CA x M material (X0 4) is C-LiFePO 4 consisting of particles of a compound having the formula LiFePO which has an olivine structure and which bears on at least a portion of its surface a deposit of carbon deposited by pyrolysis, and characterized in that it has a calcium content present as impurity less than about 1000 ppm, preferably less than about 500 ppm, preferably less than about 300 ppm, and more particularly less than about 00 ppm.
• the calcium content present as impurity of a material according to the invention can be measured using equipment commonly used in industry, in particular plasma torches for carrying out chemical microanalyses (inductively coupled plasma, etc.), for example the ICP spectrometers of Horiba Scientific.
• the analysis often consists of wet digestion, acid dissolution of the sample, and the resulting solution is injected into the plasma as an aerosol.
• the content of the various elements is then determined by means of detectors based on optical emission spectrometry or mass spectrometry.
• the properties of the materials according to the invention can be adapted by appropriately selecting the element or elements that partially replace Fe.
• the choice of M 'from Mn, Ni and Co makes it possible to adjust the mean discharge potentials of the cathode material .
• the choice of M" among, for example, Mg, Mo, Nb, Ti, Al , B, Zr, Ca and W can be used to adjust the kinetic properties of the cathode material.
• the expression "particles” includes both elementary particles and agglomerates of elementary particles, also called secondary particles.
• the size of the elementary particles is preferably between 10 nm and 3 m.
• the size of the agglomerates is preferably between 100 nm and 30 ⁇ .
• the CA x M material (X0 4) is composed of primary particles of micron sizes, mostly greater than about 1 pm and preferably between about 1 micron and about 5 microns.
• the size of the secondary particles is preferably between about 1 ⁇ m and about 10 ⁇ m.
• the CA x M material (X0 4) is composed of primary particles with a distribution of particle sizes D 50 of between about 1 pm to about 5 pm, and such that the distribution of The size of the secondary particles D 50 is from about 1 ⁇ m to about 10 ⁇ m.
• the CA x M material (X0 4) is characterized in that the size of the elementary particles is between 10 nm and 3 microns and the size of the agglomerates is between 100 nm and 30 pm.
• the material CA x M (XO 4 ) y may be prepared by various methods, it may be obtained for example by hydrothermal route (see WO 05/051840), by thermal solid state (see WO 02/027823 and WO 02/027824), or by melting (see WO 05/062404).
• the synthesis is carried out by reacting by equilibrium, thermodynamic or kinetic, a gaseous atmosphere with a mixture in the required proportions of the source compounds a) , (b), (c) (d) and (e): (a) one or more source compounds of the A-forming element (s); b) a source or several sources of the element or elements forming M; c) a source compound of the X element (s); d) an oxygen source compound; and e) a conductive carbon source compound; the synthesis is carried out continuously in an oven by controlling the composition of the gaseous atmosphere, the temperature of the synthesis reaction and the level of the source compound c) relative to the other source compounds a), b) d) and e), to impose the oxidation state of the transition metal at the desired valence level for the constitution of the compound of type A x M (X0) y the process comprising a step of pyro
• the gas stream and the flow of solids circulate against the current, under optimal conditions, the CA x M material (X0 4) are recovered at the outlet of the furnace contains less than about 200 ppm water.
• the source compound a) is a lithium compound chosen for example from the group consisting of lithium oxide or hydroxide, lithium carbonate, neutral phosphate Li 3 PO 4 , phosphate LiH 2 PO 4 acid, ortho, meta or lithium poly silicates, lithium sulfate, lithium oxalate and lithium acetate, and any mixture thereof.
• the source compound b) is an iron compound chosen, for example, from the group consisting of iron oxide (III) or magnetite, trivalent iron phosphate, iron lithium hydroxyphosphate or trivalent iron nitrate.
• the source compound c) is a phosphorus compound chosen, for example, from the group consisting of phosphoric acid and its esters, Li 3 PO 4 neutral phosphate, LiH 2 PO 4 acid phosphate and mono- or di-ammonic phosphates. , trivalent iron phosphate, ammonium manganese phosphate (NH 4 MnPO 4 ).
• All these compounds are furthermore oxygen source and some of them are sources of at least two elements among Li, Fe and P.
• Carbon deposition on the surface of the complex oxide particles A x M (X0 4 ) is obtained by pyrolysis of a source compound e).
• the Pyrolysis of the compound e) can be carried out simultaneously with the synthesis reaction between the compounds a) to d) to form the compound A x M (X0 4 ) y . It can also be carried out in a step subsequent to the synthesis reaction.
• the deposition of the conductive carbon layer on the surface of the complex oxide particles A x M (X0 4 ) y can be obtained by thermal decomposition of source compounds e) very varied.
• a suitable source compound is a compound that is in a liquid state or a gaseous state, a compound that can be used in the form of a solution in a liquid solvent, or a compound that goes into the liquid or gaseous state. during its thermal decomposition, so as to coat the complex oxide particles more or less completely.
• the source compound e) can be chosen for example from the group consisting of liquid hydrocarbons, solid or gaseous, and their derivatives (in particular polycyclic aromatic species such as tar or pitch), perylene and its derivatives, the compounds polyhydric (eg, sugars and carbohydrates, and derivatives thereof), polymers, cellulose, starch and their esters and ethers, and any mixture thereof.
• polymers examples include polyolefins, polybutadienes, polyvinyl alcohol, polyvinyl butyral, condensation products of phenols (including those obtained from reaction with aldehydes), polymers derived from alcohol furfuryl, styrene, divinylbenzene, naphthalene, perylene, acrylonitrile, and vinyl acetate.
• the compound e) is CO or a gaseous hydrocarbon, it is subjected to disproportionation, advantageously catalyzed by a transition metal element present in at least one of the precursors a) to c), or by a transition metal compound added to the precursor mixture.
• the thermal decomposition is carried out by cracking in an oven at a temperature between about 100 and about 1300 ° C, and more particularly between about 400 and about 1200 ° C, preferably in the presence of an inert carrier gas.
• an inert carrier gas See, for example, US 2002/195591 and US 2004/15726.
• Carbon deposition may further be effected by CVD from hydrocarbons as described in JP 2006-302671.
• the C-LiFePO 4 material is prepared by a solid-state thermal process from iron phosphate (FePO 4 ), lithium carbonate (Li 2 CO 3 ) and an organic compound. carbon source.
• a CA x M material (X0 4 ) y according to the invention is particularly useful as a cathode in a lithium metal polymer (LMP) technology battery, using a lithium metal anode and a solid electrolyte polymer plasticized or not.
• LMP lithium metal polymer
• the cathode is preferably constituted by a composite material applied to a collector, the composite material comprising CA x M (X0 4 ) y , a solvating polymer salified or not as a binder, preferably the polymer which forms the solvent of the electrolyte, and a material promoting electronic conduction.
• the material promoting electronic conduction is advantageously chosen from carbon black (Ketjenblack, etc.), graphite, carbon fibers (for example in the form of carbon nanotubes or VGCF fibers (Vapor Grown Carbon Fiber) whose growth is performed in gas phase, carbon nanotubes and graphene.
• the solvating polymer is advantageously chosen from polymers comprising polyether segments, the dissolution of a lithium salt in this polymer making it possible to prepare a solid polymer electrolyte.
• polyethers that can be used in the context of the present invention to form the electrolyte include poly (ethylene oxide) and copolymers which are obtained from ethylene oxide and at least one oxirane. substituted, and which comprise at least 60% of recurring units -CH 2 -CH 2 O- derived from ethylene oxide.
• the repeating units derived from a substituted oxirane may be -O-CH2-CHR- units (derived from an oxirane CH 2 -CHR-O) in which R is a alkyl radical, preferably chosen from alkyl radicals having from 1 to 16 carbon atoms, more preferably from alkyl radicals having from 1 to 8 carbon atoms.
• the repeating units derived from a substituted oxirane may furthermore be -O-CH 2 -CHR'- units (derived from an oxirane CH 2 -CHR'-O), in which R 'is a group capable of polymerizing by radical way.
• Such a group may be chosen from those which comprise a double bond, for example a vinyl, allyl, vinylbenzyl or acryloyl group.
• a polyether useful for the present invention may comprise recurring units derived from various substituted oxiranes.
• the polyether used according to the present invention comprises repeating units derived from at least one substituted oxirane wherein the substituent comprises a polymerizable function.
• the substituent comprises a polymerizable function.
• the polymer electrolyte may also consist of a mixture of polymers, for example without limitation, by mixing a solvating polymer and a non-solvating polymer and / or at least partially soluble in the solvating polymer (see FR). 2,881,275 and WO 2009/079757).
• the lithium salt may be chosen in particular from LiPF 6 , LiAsF 6 , LiClO 4 , LiBF 4 , LiC 4 B0 8 , Li (C 2 F 5 SO 2 ) 2N, Li [(C 2 F 5 ) 3PF3], LiCF 3 SO 3 > UCH 3 SO 3 , LiN (SO 2 F) and LiN (SO 2 CF 3 ) 2 .
• the polymer electrolyte thus formed may optionally be plasticized by at most 30% by weight of a liquid solvent, a plasticizer or a low-mass polymer.
• the capacity of the cathode is commonly expressed in mg of electroactive material per cm 2 of the surface of the cathode.
• the cathode is made from a material CA x M (X0 4 ) y of this invention having a calcium content present as an impurity of less than about 1000 ppm, preferably less than about 500 ppm, preferably less than about 300 ppm, more preferably less than about 100 ppm.
• a C-LiFePO 4 material and a C-LiMPO 4 material in which M represents at least 70 at% Fe partially replaced by Mn, Nb or Mg are particularly preferred as the cathode active material.
• the process according to the invention was carried out in a comparative manner with the techniques of the prior art, in order to demonstrate that a very low calcium content present as an impurity had a favorable effect on the performance of the CA x M material ( X0 4 ) y used as a cathode material in a lithium metal polymer technology battery.
• a mixture containing FePO 4 '(H 2 O) 2 (1 mole) and Li 2 CO 3 (1 mole, purity level: 99.9%) and 5% polyethylene-block-poly (ethylene glycol) was prepared. ) containing 50% ethylene oxide, was introduced into isopropyl alcohol and mixed for about 10 hours, after which the solvent was removed. In the material thus obtained, the polymer together holds the particles of phosphate and carbonate.
• the mixture was treated under a stream of nitrogen at 700 ° C for 2 hours, to obtain a battery grade C-LiFePO material, and then dried under vacuum at room temperature. 100 ° C and the final material was stored in a glove box under an argon atmosphere at a dew point of -90 ° C.
• the material has a surface area of 13.4 m 2 / g and a carbon content of 1.7% by weight.
• the cathodes are made with the C-LiFePO cathode materials obtained in Example 1.
• the LMP batteries were prepared according to the following procedure. 2.06 g of C-LiFePO 4 , 1.654 g of poly (ethylene oxide) having a molecular weight of 100,000 (supplied by Aldrich) and 334 mg of carbon powder were carefully mixed for 1 hour. Ketjenblack (supplied by Akzo-Nobel) in acetonitrile, using zirconia beads in a Turbula® mixer.
• the resulting mixture was then deposited on a carbon-coated aluminum sheet (supplied by Exopack Advanced Coatings TM), using a Gardner® device, the deposited film was dried under vacuum at 80 ° C. 12 hours, then stored in a glove box.
• the cathodes contain 4 mg / cm 2 of C-LiFePO.
• Button type batteries A1, B1, C1 and D1 were assembled and sealed in a glove box for each samples A, B, C and D, using the carbonaceous aluminum foils bearing the coating containing these phosphates as the cathode a metal lithium film as anode and a polyethylene oxide film containing 30% by weight of LiTFSI (supplied by the company 3M).
• the batteries A1, B1, C1 and D1 were subjected to an intentiostatic cycling at a C / 4 regime at 80 ° C between 2 and 3.8 Volts vs Li + / Li °.
• the UPS was determined in start of discharge at a C / 4 rate by the commonly used current interruption method (1 second in this case) at the 5 th and 100 th cycles.
• the results indicated (ASI in Ohm.cm 2 ) in the table below confirm the harmful role of calcium present as impurity in C-LiFeP0 4 used as cathode of a lithium metal polymer technology battery.
• A1-Mg, B1-Mg, C1-Mg and D1-Mg and A1-Mn, B1-Mn, C1-Mn and D1-Mn batteries of the "button" type were assembled and sealed in a glove box for each samples A-Mg, B-Mg, C-Mg and D-Mg and respectively A-Mn, B-Mn, C-Mn and D-Mn, using the carbonaceous aluminum sheets bearing the coating containing these phosphates as cathode a metal lithium film as anode and a polyethylene oxide film containing 30% by weight of LiTFSI (supplied by the company 3M).

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