EP2731910A2 - Lithiumhaltiges manganphosphat und verbundmaterial damit - Google Patents

Lithiumhaltiges manganphosphat und verbundmaterial damit

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Publication number
EP2731910A2
EP2731910A2 EP12758609.7A EP12758609A EP2731910A2 EP 2731910 A2 EP2731910 A2 EP 2731910A2 EP 12758609 A EP12758609 A EP 12758609A EP 2731910 A2 EP2731910 A2 EP 2731910A2
Authority
EP
European Patent Office
Prior art keywords
lithium
manganese
phosphate
composite material
carbon
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Withdrawn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
EP12758609.7A
Other languages
English (en)
French (fr)
Inventor
Thibaud GUTEL
Etienne RADVANYI
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.)
Commissariat a lEnergie Atomique et aux Energies Alternatives CEA
Original Assignee
Commissariat a lEnergie Atomique et aux Energies Alternatives CEA
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Commissariat a lEnergie Atomique et aux Energies Alternatives CEA filed Critical Commissariat a lEnergie Atomique et aux Energies Alternatives CEA
Publication of EP2731910A2 publication Critical patent/EP2731910A2/de
Withdrawn legal-status Critical Current

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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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • 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
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/136—Electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • 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

  • the invention relates to a lithiated manganese phosphate, its manufacturing method and a composite material consisting of particles of this manganese phosphate coated in carbon and a method of synthesizing this composite material.
  • Lithium batteries are increasingly being used as an autonomous source of energy, particularly in portable equipment where they are gradually replacing nickel-cadmium (Ni-Cd) and nickel-metal hydride (Ni-MH) batteries.
  • Ni-Cd nickel-cadmium
  • Ni-MH nickel-metal hydride
  • lithium batteries are also called accumulators
  • Li-ion accumulators The increase in the use of Li-ion accumulators is due to the continuous improvement of their performances, conferring on them densities of energy mass and volume much higher than those proposed by the Ni-Cd and Ni-MH accumulators. .
  • Ni-MH accumulators where M is a metal peak at 100 Wh / kg and the Ni-Cd accumulators have an energy density of the order of 50 Wh / kg.
  • the new generations of lithium batteries are already under development for ever more diverse applications (hybrid or all-electric cars, energy storage of photo-voltaic cells, etc.).
  • Li-ion battery electrode materials are essential.
  • the active compounds of the electrodes used in commercial batteries have, for the positive electrode, lamellar compounds such as LiCo0 25 LiNi0 2 and mixed Li (Ni, Co, Mn, A1) 0 2 or spinel compounds of composition close to LiMn 2 0 4 .
  • the negative electrode is usually carbon (graphite, coke, ...) or possibly spinel Li 4 Ti 5 0i 2 or an alloying metal with lithium (Sn, Si, ).
  • the theoretical and practical specific capacities of the positive electrode compounds mentioned are respectively about 275 mAh / g and 140 mAh / g for the lamellar structure oxides (LiCoO 2 and LiNiO 2 ) and 148 mAh / g and 120 mAh / g for the spinel compound Li n 2 0 4 . In all cases, an operating potential relative to the lithium metal close to 4 volts is obtained.
  • this compound highlighting the Fe + / Fe 2+ electrochemical couple, operates at 3.4 V vs. Li + / Li. This low potential leads at most to a mass energy density of 580 Wh / kg of LiFePO 4 .
  • manganese, cobalt and nickel phosphates, isotypes of LiFePO 4 have higher extraction / insertion potentials of lithium ions, respectively 4.1 V, 4.8 V and 5, 1 vs. V Li + / Li.
  • the theoretical specific capacities of these three compounds are close to that of LiFeP0.
  • an experimental point of view significant progress remains to achieve in order to reach one specific practical skills satisfactory values.
  • the compounds obtained have an olivine-type structure and, as shown in the figures, the form of nanobaggets.
  • WO 2007/113624 also describes the solvothermal synthesis of lithium metal phosphate using a co-solvent polyol.
  • the method of manufacturing L1MPO 4 described herein includes heating (not by microwave) of the starting compounds in a water / diethylene glycol mixture for 1 to 3 hours at 100 to 150 ° C. This solvent is then removed to obtain an olivine crystalline phase, a heat treatment at a temperature between 300 and 500 ° C for 30 minutes to 1 hour in the air is applied.
  • European patent application 2,015,382 A1 describes, for its part, a process for preparing a carbon / lithium manganese phosphate composite.
  • the compounds obtained have a manganese layer at the carbon / lithium manganese phosphate interface.
  • L1MPO 4 type materials where M can be Co, Ni, Mn or Fe, and in particular LiMnPO 4 manganese phosphate, of olivine type structure, are of great interest as positive electrode active materials because of their relatively high operating potentials but remaining compatible with conventional electrolytes (4.1 V vs. Li + / Li) associated with a theoretical specific capacity of 171 m Ah / g.
  • the LiMPO 4 compound has a higher energy density than most known positive electrode materials (700 Wh / kg of LiMPO 4 ).
  • the object of the present invention is to obtain new positive electrode materials for lithium accumulator having a specific capacity greater than the positive electrode material of the prior art.
  • the object of the invention is to provide a lithiated carbon / metal phosphate composite having improved conductivity, low electrochemical polarization and high specific capacitance.
  • the inventors have discovered that by using a particular method of synthesis of lithiated metal phosphates LiMnPO 4 type and the composite C-LiMnPO 4 , the metal phosphate having a particular morphology beneficial to the electro-chemical performance of the composite.
  • the subject of the invention is a lithiated manganese phosphate of formula I below: in which :
  • D represents a doping element
  • olivine type characterized in that it is composed of non-agglomerated platelet-shaped particles having two dimensions between 100 nm and 1000 nm and whose thickness is between 1 nm and 100 nm, and in that it has a crystallographic structure of olivine type.
  • the lithium metal phosphate of the invention has a surface
  • the subject of the invention is also a composite material consisting of particles of lithiated manganese phosphate according to the invention previously described, coated on their external surfaces with a layer of carbon.
  • the carbon layer has a thickness of between
  • the composite material according to the invention has a specific surface area greater than 70 m 2 / g, preferably greater than or equal to 80 m 2 / g.
  • the invention also proposes a process for the synthesis of a lithium phosphate according to the invention, characterized in that it comprises the following stages:
  • the invention also proposes a process for synthesizing a composite material according to the invention, which comprises steps a) to d), previously described of the lithiated phosphate synthesis method according to the invention, followed by a step e) coating the particles obtained after step d) with carbon having a specific surface area of between 500 and 2000 m 2 / g, preferably between 700 and 1500 m 2 / g.
  • the lithium precursor can be chosen from lithium acetate (LiOAc 2H 2 O), lithium hydroxide (LiOH .H 2 O), lithium chloride (LiCl), lithium nitrate (L1NO3), and lithium hydrogenphosphate (LiH 2 PO 4 ).
  • the phosphate precursor it is chosen from ammonium hydrogen phosphate (NH 4 H 2 PO 4 ), diammonium hydrogen phosphate ((NH 4) 2 HPO 4 ), phosphoric acid (H 3 PO 4), and lithium hydrogen phosphate (Li3 ⁇ 4PO 4 ).
  • the precursor is manganese sulphate.
  • the washing solvent is water-based, preferably a mixture of water and ethanol. More preferably, the washing solvent in step c) is water.
  • step d it is preferably a drying step in an oven at a temperature of between 50 and 70 ° C. More preferably, it is a drying step in an oven at a temperature of 60 ° C.
  • step e) of coating the lithiated manganese phosphate particles of the invention in the method for synthesizing the composite according to the invention, it is preferably a step of grinding the particles under air. of manganese phosphate lithiated with carbon at room temperature.
  • this carbon is carbon black type carbon.
  • the invention also proposes a positive electrode comprising at least 50% by weight, with respect to the total mass of the electrode, of the composite material according to the invention or of the composite material obtained by the process according to the invention.
  • the invention finally relates to a lithium battery comprising at least one electrode according to the invention.
  • FIG. 1 represents the X-ray diffraction patterns (CuKa) of compounds of formula LiMnPO 4 prepared according to the invention and prepared according to the hydrothermal synthesis route
  • FIG. 2 is an image obtained by scanning electron microscope (SEM-FEG) of the LiMnPO compound obtained by the process of the invention at a magnification of 50000,
  • FIG. 3 represents the same LiMnPO 4 compound as in FIG. 2 but at a magnification of 200,000
  • FIG. 4 represents an image obtained by scanning electron microscopy - field emission gun (MEB-FEG) (Field Emission Gun), the final composite C-LiMnPO 4 prepared according to the process of the invention, at a magnification of 100000
  • FIG. 5 represents the same composite as in FIG. 4 but at a magnification of 300,000
  • FIG. 6 is a graph showing the first two charging / discharging cycles in intentio static mode (C / 10 regime, 20 ° C.) of the compound C-LiMnPO 4 (1% by mass of carbon) between 2.5 and 4.5 V,
  • FIG. 7 represents the evolution of the specific discharge capacity as a function of the number of cycles at a C / 10 regime; 20 ° C, carried out in the case of the compound C-LiMnPO 4 of the invention between 2.5 and 4.5 V,
  • FIG. 8 is a graph showing the first two charging / discharging cycles in intentio static mode (C / 10 regime, 20 ° C.) of the C-LiMnPO 4 (15% by weight carbon) composites prepared in various aqueous solvents. containing different glycol compounds, between 2.5 and 4.5 V, and
  • FIG. 9 is a graph showing the first two charging / discharging cycles in intentio static mode (C / 10 regime, 20 ° C.) of the C-LiMnPO 4 composites (15% by weight of Ketjen Black carbon EC300J and EC300JD). between 2.5 and 4.5 V,
  • the theoretical capacity of the electrochemical couple LiMnPO / MnPOn is 171 mAh / g.
  • the electrochemical potential for extraction / insertion of lithium is located at about 4.1 V vs. Li + / Li. These values lead to a mass energy density of 700 Wh / kg of LiMnPO.
  • Such a positive electrode material should allow, after optimization, to assemble Li-ion accumulators (conventional negative electrode based on graphite) of 250 Wh / kg, whereas the commercial accumulators currently the most efficient have a density energy consumption of about 200 Wh / kg, and the standard accumulators have a density of the order of 160-180 Wh / kg.
  • the syntheses are carried out in solid route at high temperature, greater than or equal to 600 ° C. It is necessary to use such temperatures to allow the decomposition of precursors of lithium, manganese and phosphorus, the reaction of complete formation of the product LiMnPO 4 and the total evaporation of the volatile species (carbonates, nitrates, ammonium, .,.).
  • LiMP0 4 phosphates are relatively electronically insulating. This is the reason why a deposit in situ (during the synthesis) or ex situ (post-treatment stage) of carbon on the surface of the particles of active material is often necessary for obtaining good electrochemical performances.
  • the carbon has a dual use, namely the increase of the electronic conductivity and a limitation of the agglomeration of the particles under the effect of the synthesis temperature. This carbon deposit is generally formed by thermal decomposition under a reducing atmosphere of an organic substance simultaneously with the synthesis of the compound. Despite the use of carbon, the electrochemical performances of LiMnP0 4 reported in the literature fall rapidly during high-speed cycling.
  • the polarization (or internal resistance of the electro-chemical cell) is relatively high.
  • Such a characteristic is significant poor conductivity (ionic and / or electronic) and is generally associated with poor electrochemical performance.
  • the undesired species such as sulphates and hydroxides, are removed at the end of synthesis other than by evaporation in an oven by a heat treatment at high temperature (of the order of 300 ° C).
  • the synthesis method of the invention involves a simple reaction, fast and low energy, in air and provides a compound that has a particular morphology.
  • the synthesis method of the invention makes it possible to obtain lithiated manganese phosphates of the following formula I: in which :
  • D represents a doping element
  • olivine type characterized in that it is composed of non-agglomerated platelet-shaped particles having two dimensions between 100 nm and 1000 nm and whose thickness is between 1 nm and 100 nm, and in that it has a crystallographic structure of olivine type.
  • This lithiated manganese phosphate is a first object of the invention.
  • this lithiated manganese phosphate has a surface area greater than 10m 2 / g, and more preferably a surface area greater than or equal to 20m 2 / g, typically between 25 and 35 m 2 / g.
  • the synthesis process of the invention is a microwave-assisted process for obtaining a compound of formula I and in particular LiMnPO 4 manganese phosphate .
  • the preparation of the compounds of formula I implements a first stage of solvent synthesis in a microwave reactor from a precursor of manganese, a lithium precursor and a phosphate precursor.
  • the various lithium precursors that can be used are: lithium acetate (LiOAc ⁇ LbO), lithium hydroxide (LiOH.IbO), lithium chloride (LiCl), lithium nitrate (L1NO3), and lithium hydrogenphosphate (LH2PO4).
  • the lithium precursor is lithium hydroxide hydrate LiOH.H 2 0.
  • the various phosphorus precursors that can be used are: ammonium hydrogen phosphate ( ⁇ 4 ⁇ 2 ⁇ 0 4 ), diammonium hydrogen phosphate ((NIL 2 HPO 4 ), phosphoric acid (H 3 PO 4 ), and lithium hydrogen phosphate (LiH 2 PO 4 ).
  • the metal M is manganese
  • the possible doping elements they may be vanadium, boron, aluminum, magnesium, etc.
  • They may be present in amounts of between 0 and 15%, preferably between 0 and 5% by moles relative to the number of moles of manganese present in the compound of the invention.
  • the various precursors are introduced in stoichiometric quantities into the microwave reactor.
  • the lithium precursor is LiOH.H 2 O
  • three equivalents of lithium are preferably used. This first stage of solvothermal synthesis takes place in a water / diethylene glycol mixture in the ratio 1/4 by volume.
  • diethylene glycol / water mixture comprising between 50% and 90% of diethylene glycol, by volume, relative to the total volume of the mixture, the remainder being advantageously composed of water.
  • the mixture contains about 80% ⁇ 5%, by volume, of diethylene glycol.
  • the diethylene glycol / water mixture does not comprise other glycols and in particular neither triethylene glycol nor tetraethylene glycol.
  • the temperature during this first step is between 90 and 250 ° C, preferably 160 ° C and the pressure in the reactor is between 1 and 15 bar but less than 4 bar.
  • the power of the microwave oven is set according to the mass of the sample to be treated (400, 800 or 1600W).
  • the temperature of the reaction medium is maintained for a period of between 1 and 30 minutes, preferably for 5 minutes.
  • the compound of formula I obtained is simply washed with ethanol and water to remove residual solvents and sulphates and then dried in an oven under air at a temperature between 50 and 60 ° C.
  • the third step consists in producing an intimate mixture by energetic grinding in air and at ambient temperature of the particles of the compound of formula I prepared previously with a carbon with a high specific surface area, preferably greater than 700 m. 2 / g, such as carbon Ketjen black ® ec600j.
  • the manganese concentration of the solution in the first step is chosen between 0.1 to 1 mol / L and the pH of this solution is between 10 and 11.
  • the compound of formula I obtained has a "platelet" type morphology, as shown in FIGS. 2 and 3.
  • the compound of formula I is in the form of unagglomerated or slightly agglomerated particles having a wafer shape, two of which are between 100 nm and 1000 nm in size and whose thickness is between 1 nm and 100 nm.
  • the thickness is between 10 and 35 nm.
  • the compound of formula I has an olivine type structure.
  • the latter is represented in cartridge in FIG.
  • FIG. 1 represents the X-ray diffraction spectrum of a LiMnPO 4 compound obtained by the method of the invention and the X-ray diffraction spectrum of a LiMnPO 4 compound obtained according to the synthetic method described in patent application WO 2007. / 113624. It is found that the compound according to the invention is free of impurities.
  • the LiMnPO 4 manganese phosphate of the invention crystallizes in the Pnma space group.
  • the mesh parameters are of the order of 10.44 ⁇ for parameter a, 6.09 ⁇ for parameter b, and 4.75 ⁇ for parameter c.
  • This compound is of olivine type structure. The latter consists of a compact hexagonal stack of oxygen atoms. Lithium ions and manganese ions are located in half of the octahedral sites while phosphorus occupies 1/8 of the tetrahedral sites.
  • a simplified representation of the structure of LiMnP0 4 is represented in a cartridge in FIG.
  • the LiMnPO 4 particles obtained have a flattened morphology and nanometric sizes.
  • the specific surface area of these particles is greater than 10 m 2 / g.
  • the lithiated manganese phosphate of the invention can then be covered on its outer surfaces with a layer of carbon, to obtain a lithiated carbon-phosphate composite of manganese having improved properties of conductivity and capacity.
  • the composite material of the invention has a specific surface area greater than 70 m 2, more preferably greater than or equal to 80 m 2 / g.
  • the carbon layer in the composite of the invention has a thickness of between 1 and 10 nm.
  • This composite material is shown in Figures 4 and 5.
  • the composite of the invention may be prepared by a process comprising the steps of synthesis of the lithiated manganese phosphate according to the invention, followed by a step of coating the lithiated manganese phosphate particles obtained by the process of the invention, with carbon having a specific surface area between 500 and 2000, preferably between 700 and 1500 m / g.
  • the process for synthesizing the composite material according to the invention may comprise steps of synthesis of the lithium manganese phosphate according to the invention, and in this case the same precursors of lithium, manganese and phosphate will be used, that in the method for synthesizing the lithiated manganese phosphate of the invention followed by a step of coating the lithiated manganese phosphate particles according to the invention with carbon or the method for synthesizing the composite according to the invention may comprise that step of coating the lithiated manganese phosphate particles obtained by the process according to the invention, the latter having been prepared beforehand.
  • transition element phosphates generally have low intrinsic conductivity.
  • the composite of the invention or obtained by the method of the invention, because of its particular morphology and its uniform coating of a carbon layer can deliver high capacities although its use is limited to charging regimes / relatively low discharge.
  • the invention also relates to a positive electrode comprising a composite material according to the invention and lithium batteries comprising such an electrode.
  • the electrodes according to the invention can be deposited on metal sheets serving as current collectors and are preferably composed of a dispersion of the composite material of the invention in an organic binder conferring a satisfactory mechanical strength.
  • the positive electrode consisting mainly of the composite of the invention or obtained by the method of the invention can be formed by any type of known means.
  • the material of the positive electrode may be in the form of an intimate dispersion comprising, inter alia, and for the most part, the composite of the invention and an organic binder.
  • the organic binder intended to provide good ionic conduction and satisfactory mechanical strength, may, for example, consist of a polymer chosen from polymers based on methyl methacrylate, acrylonitrile and vinylidene fluoride, as well as polyethers or polyesters or carboxymethy lcel lulo se.
  • Lithium accumulators containing a composite material prepared by the method of the invention at the positive electrode can be constructed and operated.
  • a mechanical separator between the two electrodes is impregnated with an electrolyte (ionic conductor) consisting of a salt whose cation is at least partly lithium ion and an aprotic polar solvent, which may be an organic solvent such as a carbonate or a mixture of carbonates (diethyl carbonate, ethyl carbonate, vinyl carbonate, etc.) or a solid polymer composite, POE (polyethylene oxide), PAN (polyacrylonitrile), PMMA (polymethylmethacrylate), PVdF (polyvinylidene fluoride) or a derivative thereof.
  • an electrolyte ionic conductor
  • an aprotic polar solvent which may be an organic solvent such as a carbonate or a mixture of carbonates (diethyl carbonate, ethyl carbonate, vinyl carbonate, etc.) or a solid polymer composite, POE (polyethylene oxide), PAN (polyacrylonitrile), PMMA (polymethylmeth
  • Accumulators according to the invention have good electrochemical characteristics, mainly in terms of polarization (potential difference between the charge curve and the discharge curve) and specific capacity restored to discharge.
  • This dispersion is then deposited on a metal sheet serving as a current collector, for example aluminum.
  • the negative electrode of the Li-ion accumulator may consist of any type of known material. Since the negative electrode is not a lithium source for the positive electrode, it must consist of a material that can initially accept the lithium ions extracted from the positive electrode, and then restore them.
  • the negative electrode may consist of carbon, most often in graphite form, or of a material of spinel structure such as Li 4 Ti 5 O 12. Thus, in a Li-ion battery, lithium is never in metallic form. Those are Li + cations that go back and forth between the two lithium insertion materials of the negative and positive electrodes, at each charge and discharge of the accumulator.
  • the active materials of the two electrodes are generally in the form of an intimate dispersion of said lithium insertion / extraction material with an electronic conductive additive and optionally an organic binder as mentioned above.
  • the electrolyte of the lithium battery made from the lithium metal phosphate or the composite of the invention is constituted by any type of known material. It may, for example, consist of a salt comprising at least the Li + cation.
  • the salt is, for example, chosen from LiClO 4 , LiAsF 6 , LiPF 6 , LiBF 4 , L 1 RFSO 3 , L 1 CH 3 SO 3, LiN (RFSO 2 ) 2. , LiC (RFS0 2 ) 3 , LiTFSI, LiBOB, LiBETI.
  • RF is selected from a fluorine atom and a perfluoroalkyl group having from one to eight carbon atoms.
  • LiTFSI is the acronym for lithium trifluoromethanesulphonylimide, LiBOB lithium bis (oxalato) borate, and LiBETI lithium bis (perfluoroethylsulfonyl) imide.
  • the lithium salt is preferably dissolved in an aprotic polar solvent and can be supported by a separator element disposed between the two electrodes of the accumulator; the separator element being soaked with electrolyte.
  • the lithium salt is not dissolved in an organic solvent, but in a solid polymer composite such as POE (polyethylene oxide), PAN (polyacrylonitrile) , PMMA (polymethylmethacrylate), PVdF (polyvinylidene fluoride) or a derivative thereof.
  • a solid polymer composite such as POE (polyethylene oxide), PAN (polyacrylonitrile) , PMMA (polymethylmethacrylate), PVdF (polyvinylidene fluoride) or a derivative thereof.
  • a precipitate is formed quickly from the beginning of the addition of the lithium salt.
  • the suspension After addition of 40 mL of diethylene glycol (DEG), the suspension is introduced into a 100 mL sealed reactor suitable for microwaves.
  • DEG diethylene glycol
  • the temperature is then brought to 160 ° C for 5 minutes in the microwave oven at a power of 400W.
  • the final solution (colorless) contains a white precipitate.
  • the precipitate is washed with water and the ethanol, centrifuged and dried 24h to
  • the recovered powder which is white in color, has the composition LiMnPO 4 .
  • FIG. 1 The X-ray diffraction spectrum of this compound is shown in FIG. 1 (upper curve).
  • the mixture is then ground for 4 hours at 500 rpm in air and at room temperature.
  • LiMnPO 4 in this example was carried out as in Example 1 but replacing the diethylene glycol with ethanol.
  • Example 2 The procedure was as in Example 1, but replacing the diethylene glycol with triethylene glycol.
  • Example 2 The procedure was as in Example 1, but replacing the diethylene glycol with triethylene glycol.
  • a "button cell” lithium battery is assembled with:
  • a positive electrode consisting of a disc of 14 mm in diameter taken from a 25 ⁇ m thick composite film comprising the composite material of the invention prepared according to Example 1 (90% by weight) and polyvinylidene fluoride; (10% by weight) as a binder, the whole being deposited on an aluminum current collector (20 micron thick sheet),
  • this system makes it possible to extract most of the lithium present in the positive electrode material, as shown in FIG. 7 on the curve indicated "grinding KB600". It can be seen from this figure and from FIG. 6 that the lithium phosphate compound of the invention is stable at least up to a hundred cycles.
  • Ketjen Black EC300J ® carbon has a specific surface of 1300m / g.
  • a "button cell” lithium battery is assembled with:
  • a positive electrode consisting of a disk 14 mm in diameter taken from a 25 ⁇ m thick composite film comprising the material of the invention prepared according to Example 3 (90% by weight) and polyvinylidene fluoride ( 10% by weight) as a binder, the whole being deposited on an aluminum current collector (20 micron thick sheet),
  • this system makes it possible to extract most of the lithium present in the positive electrode material, as shown in FIG. 9, on the KB300 milling curve.
  • Lithium accumulators were prepared as described in Example 2 but using respectively the compounds obtained in Comparative Examples 1 to 3.
  • the curve indicated “diethylene glycol solvents” corresponds to the curve obtained with the compound according to the invention of example 1
  • the curve denoted “Solvans triethylene glycol” corresponds to the curve obtained with the compound according to the example Comparative
  • the curve denoted “Ethylene glycol” corresponds to the curve obtained with the accumulator assembled with the composite of Comparative Example 2
  • the curve denoted “Ethanol” corresponds to the curve obtained with an accumulator assembled with the composite obtained at Comparative Example 1
EP12758609.7A 2011-07-12 2012-07-11 Lithiumhaltiges manganphosphat und verbundmaterial damit Withdrawn EP2731910A2 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR1156340A FR2977887B1 (fr) 2011-07-12 2011-07-12 Phosphate de manganese lithie et materiau composite le comprenant
PCT/IB2012/053541 WO2013008189A2 (fr) 2011-07-12 2012-07-11 Phosphate de manganese lithie et materiau composite le comprenant

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US (1) US20140295281A1 (de)
EP (1) EP2731910A2 (de)
KR (1) KR20140082635A (de)
FR (1) FR2977887B1 (de)
WO (1) WO2013008189A2 (de)

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US20140295281A1 (en) 2014-10-02
WO2013008189A3 (fr) 2013-05-23
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