WO2019187943A1 - Matériau actif d'électrode négative pour batteries secondaires au fluorure-ion, électrode négative utilisant ledit matériau actif, batterie secondaire au fluorure-ion et procédé de production dudit matériau actif - Google Patents

Matériau actif d'électrode négative pour batteries secondaires au fluorure-ion, électrode négative utilisant ledit matériau actif, batterie secondaire au fluorure-ion et procédé de production dudit matériau actif Download PDF

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WO2019187943A1
WO2019187943A1 PCT/JP2019/007699 JP2019007699W WO2019187943A1 WO 2019187943 A1 WO2019187943 A1 WO 2019187943A1 JP 2019007699 W JP2019007699 W JP 2019007699W WO 2019187943 A1 WO2019187943 A1 WO 2019187943A1
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fluoride
ion secondary
negative electrode
active material
secondary battery
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森田　善幸
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Honda Motor Co Ltd
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Honda Motor Co Ltd
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Priority to DE112019001579.6T priority patent/DE112019001579B4/de
Publication of WO2019187943A1 publication Critical patent/WO2019187943A1/fr
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F7/00—Compounds of aluminium
    • C01F7/48—Halides, with or without other cations besides aluminium
    • C01F7/50—Fluorides
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
    • C01D15/00—Lithium compounds
    • C01D15/04—Halides
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F7/00—Compounds of aluminium
    • C01F7/48—Halides, with or without other cations besides aluminium
    • C01F7/50—Fluorides
    • C01F7/54—Double compounds containing both aluminium and alkali metals or alkaline-earth metals
    • 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
    • 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
    • H01M10/0561—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of inorganic materials only
    • H01M10/0562—Solid materials
    • 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
    • H01M10/058—Construction or manufacture
    • 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
    • H01M4/13—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
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/381—Alkaline or alkaline earth metals elements
    • H01M4/382—Lithium
    • 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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
    • C01P2002/85—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by XPS, EDX or EDAX data
    • 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
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/027—Negative electrodes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0065—Solid electrolytes
    • H01M2300/0068—Solid electrolytes inorganic
    • H01M2300/008—Halides
    • 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
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • 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 present invention relates to a negative electrode active material for a fluoride ion secondary battery, a negative electrode using the active material, a fluoride ion secondary battery, and a method for producing the active material.
  • lithium ion secondary batteries are widely used as secondary batteries having high energy density.
  • a lithium ion secondary battery has a structure in which a separator is present between a positive electrode and a negative electrode and a liquid electrolyte (electrolytic solution) is filled.
  • the fluoride ion secondary battery is a secondary battery using fluoride ions (F ⁇ ) as carriers, and is known to have high theoretical energy. And about the battery characteristic, there exists an expectation exceeding a lithium ion secondary battery.
  • Non-Patent Documents 1 and 2 As the negative electrode active material of the fluoride ion secondary battery, MgF 2, CaF 2, CeF 3 and the like have been reported (see Non-Patent Documents 1 and 2).
  • the currently reported fluoride ion secondary batteries using these negative electrode active materials have a problem that their charge / discharge efficiency is 10 to 20%, and energy efficiency as a secondary battery is low.
  • the charge / discharge capacity is only about 10 to 20% of the theoretical capacity, and the capacity has not been increased as compared with the current Li ion secondary battery or Ni-MH battery.
  • the reduction-side potential window of LBF is ⁇ 2.41 V vs.
  • La / LaF 3 potential calculated from Gibbs energy. Subject to constraints in the Pb / PbF 2.
  • the potential of the negative electrode active material of the fluoride ion secondary battery currently reported is that MgF 2 is ⁇ 2.35 to ⁇ 2.87 V vs. Pb / PbF 2 and CaF 2 are in a range of ⁇ 2.85 to ⁇ 2.89 V vs. Pb / PbF 2 and CeF 3 are in the range of ⁇ 2.18 to ⁇ 2.37 V vs. It is a Pb / PbF 2. Therefore, there has been a problem that the defluorination / refluorination reaction of the negative electrode active material under the restriction of -2.41 V, which is the reduction potential window of LBF, cannot be provided in consideration of the overvoltage.
  • the present invention has been made in view of the above-described background art, and an object of the present invention is for a fluoride ion secondary battery capable of expressing a reversible negative electrode reaction at a high utilization rate in a fluoride ion secondary battery.
  • the object is to provide a negative electrode active material, a negative electrode using the active material, a fluoride ion secondary battery, and a method for producing the active material.
  • AlF 3 -1.V
  • Aluminum fluoride (AlF 3 ) has a charge / discharge reaction (defluorination / refluorination reaction) within the constraint of the potential window of 2.41 V of LBF, which is a fluoride ion solid electrolyte. 78V vs. Pb / PbF2).
  • Aluminum fluoride (AlF 3 ) has a sufficient redox potential within the LBF reduction-side potential window ( ⁇ 2.41 V vs. Pb / PbF 2) even if the overvoltage of the negative electrode reaction is assumed to be about 0.5 V. .
  • AlF 3 aluminum fluoride
  • AlF 3 aluminum fluoride
  • F ⁇ fluoride ions
  • Negative electrode reaction does not occur.
  • AlF 3 aluminum fluoride
  • AlF 3 has a six-coordinate octahedral perfect crystal structure. The inventor considered that this crystal structure hinders the defluorination / refluorination reaction.
  • fluoride ions (F ⁇ ) are partially desorbed from aluminum fluoride (AlF 3 ) in advance, and aluminum fluoride (AlF 3 ) is modified so as to provide holes at positions where fluorine atoms existed.
  • the vacancies serve as a starting point for the defluorination / refluorination reaction, and it was found that a desired negative electrode reaction can be expressed with high utilization and reversibility, and the present invention has been completed.
  • the present invention is a negative electrode active material for a fluoride ion secondary battery, which is a modified aluminum fluoride having pores due to desorption of fluoride ions.
  • the vacancies may be the starting point for the defluorination reaction and the refluorination reaction.
  • the holes may be regions where fluorine atoms existed in the aluminum fluoride before modification.
  • the desorption of fluoride ions may be performed by contacting aluminum fluoride with an alkali metal or an alkaline earth metal.
  • Another embodiment of the present invention is a negative electrode for a fluoride ion secondary battery comprising the negative electrode active material for a fluoride ion secondary battery.
  • Another embodiment of the present invention is a fluoride ion secondary battery comprising the above-described negative electrode for a fluoride ion secondary battery, a solid electrolyte, and a positive electrode.
  • Another aspect of the present invention is a method for producing a modified aluminum fluoride to be a negative electrode active material for a fluoride ion secondary battery, wherein the aluminum fluoride is brought into contact with an alkali metal or an alkaline earth metal,
  • the alkali metal or alkaline earth metal may be a fluoride
  • the aluminum fluoride may be one in which some fluorine atoms are extracted and not an aluminum metal.
  • the ratio of the alkali metal or the alkaline earth metal may be 5 to 20 mol% with respect to the total with the aluminum fluoride.
  • the aluminum fluoride may be ⁇ -AlF 3 .
  • the alkali metal may be Li metal.
  • a reversible negative electrode reaction in a fluoride ion secondary battery can be expressed with high utilization and high reversibility.
  • the charge / discharge capacity of the fluoride ion secondary battery can be significantly increased.
  • ⁇ Negative electrode active material for fluoride ion secondary battery The negative electrode of the fluoride ion secondary battery, fluoride ions during discharge (F -) accommodates, fluoride ions during charging - should those capable of releasing (F).
  • the negative electrode active material for a fluoride ion secondary battery of the present invention is a modified aluminum fluoride having pores due to desorption of fluoride ions.
  • AlF 3 aluminum fluoride
  • AlF 3 aluminum fluoride
  • the negative electrode reaction due to (F ⁇ ) desorption and reinsertion (defluorination / refluorination reaction) does not proceed.
  • a prior example using aluminum fluoride (AlF 3 ) alone as an active material has been reported as a positive electrode active material for lithium ion batteries (see Reference 6), but fluoride ions (F ⁇ ) Has not been reported for fluoride ion secondary batteries.
  • Reference 6 J.A. Appl Electrochem (2017) 47 417-431
  • the modified aluminum fluoride serving as the negative electrode active material for the fluoride ion secondary battery of the present invention has pores in the aluminum fluoride (AlF 3 ) due to the elimination of fluoride ions (F ⁇ ).
  • the pores of the modified aluminum fluoride serve as starting points for the defluorination reaction and the refluorination reaction. That is, the presence of vacancies modifies aluminum fluoride (AlF 3 ), which is an ionic and electronically non-conductive insulator, and has high utilization and high reversibility. The reaction proceeds.
  • AlF 3 aluminum fluoride
  • FIG. 3 is a diagram showing the structure of ⁇ -AlF 3 which is one of the crystal structures of aluminum fluoride (AlF 3 ).
  • the structure of aluminum fluoride (AlF 3 ) serving as a structural unit of the crystal structure is a six-coordinate eight structure in which an Al atom 1 is arranged at the center and a vertex is composed of six fluorine atoms 2. It is a face.
  • the vacancies are formed in a region where fluorine atoms existed in the unmodified aluminum fluoride (AlF 3 ) used as a raw material. That is, as shown in FIG. 3, Al atom 1 is arranged at the center, and among the six fluorine atoms 2 existing at the apex, some fluorine atoms 2 are extracted, and there are fluorine atoms 2 that are extracted and desorbed. The position where it has become a hole.
  • the negative electrode for a fluoride ion secondary battery of the present invention includes the negative electrode active material for a fluoride ion secondary battery of the present invention. If the negative electrode active material for fluoride ion secondary batteries of this invention is included, another structure will not be specifically limited.
  • the negative electrode for a fluoride ion secondary battery of the present invention preferably has a structure that increases the contact area with the solid electrolyte as a structure having a high surface area such as a porous structure.
  • the negative electrode for fluoride ion secondary batteries of the present invention may contain other components in addition to the negative electrode active material for fluoride ion secondary batteries of the present invention.
  • other components include a conductive aid and a binder.
  • the negative electrode for a fluoride ion secondary battery of the present invention is obtained, for example, by applying a mixture containing the negative electrode active material for a fluoride ion secondary battery of the present invention, a conductive additive, and a binder onto a current collector. It can be obtained by drying.
  • the fluoride ion secondary battery of the present invention includes a negative electrode for a fluoride ion secondary battery containing the negative electrode active material for a fluoride ion secondary battery of the present invention, a solid electrolyte, and a positive electrode. If the negative electrode containing the negative electrode active material for fluoride ion secondary batteries of this invention is used for the fluoride ion secondary battery of this invention, another structure will not be specifically limited.
  • a positive electrode material that provides a sufficiently high standard electrode potential with respect to the standard electrode potential of the negative electrode for a fluoride ion secondary battery including the negative electrode active material for a fluoride ion secondary battery of the present invention is selected.
  • the characteristics as a fluoride ion secondary battery are high, and a desired battery voltage can be realized.
  • the method for producing a modified aluminum fluoride serving as a negative electrode active material for a fluoride ion secondary battery comprises contacting aluminum fluoride with an alkali metal or alkaline earth metal, and then converting the aluminum fluoride into a fluoride. By desorbing the ions, the aluminum fluoride is modified using the positions of the fluorine atoms desorbed as fluoride ions as vacancies.
  • Aluminum fluoride (AlF 3 ) has various crystal structures. Examples of the crystal structure include ⁇ -AlF 3 , ⁇ -AlF 3 , ⁇ -AlF 3 , and the like. However, in any crystal structure, the structural unit is the same structure.
  • FIG. 3 showing the structure of a is alpha-AlF 3 single crystal structure of aluminum fluoride (AlF 3), aluminum fluoride as the constituent unit of the crystal structure (AlF 3)
  • AlF 3 aluminum fluoride as the constituent unit of the crystal structure
  • the structure is a six-coordinate octahedron in which an Al atom is arranged at the center and a vertex is composed of six fluorine atoms.
  • the structure of the aluminum fluoride used as a starting material is not limited particularly, aluminum fluoride of any crystal structure (AlF 3) may also be used.
  • AlF 3 aluminum fluoride of any crystal structure
  • ⁇ -AlF 3 is preferably used from the viewpoint of availability and the lowest cost. Examples of commercially available alpha-AlF 3, for example, can be cited and Sigma-Aldrich AlF 3 (purity 99.9%), Alfa Aesar Co. AlF 3 (purity 99.9%), and the like.
  • Aluminum fluoride (AlF 3 ) absorbs moisture in the air and forms a more stable 0.5 hydrate or trihydrate. For this reason, it is more preferable to use aluminum fluoride (AlF 3 ) that has been subjected to dehydration treatment.
  • the dehydration method include a vacuum baking method at a temperature of about 250 to 300 ° C.
  • alkali metal or alkaline earth metal used for producing the negative electrode active material for fluoride ion secondary batteries of the present invention is not particularly limited.
  • alkali metal include lithium (Li), sodium (Na), potassium (K), rubidium (Rb), and cesium (Cs).
  • alkaline earth metal include magnesium ( Mg), calcium (Ca), strontium (Sr), barium (Ba), and the like.
  • lithium (Li) metal among alkali metals or alkaline earth metals. Since lithium (Li) metal is the lightest of all the metal elements, the capacity per active material weight (mAh / g) after mixing with aluminum fluoride can be kept high.
  • the shape of the lithium (Li) metal is not particularly limited, but is preferably a chip shape or a bead shape from the viewpoint of easy mixing with aluminum fluoride (AlF 3 ).
  • AlF 3 aluminum fluoride
  • reaction mechanism By contacting an alkali metal or alkaline earth metal having a lower potential with the defluorination / refluorination reaction potential of aluminum fluoride (AlF 3 ), the alkali metal or alkaline earth metal is converted to fluoride. And a reaction in which some fluorine atoms are extracted from aluminum fluoride (AlF 3 ) occurs. Such partial extraction of fluorine atoms from fluoride due to contact with a base metal has not been confirmed as a prior example.
  • the manufacturing method of the negative electrode active material for fluoride ion secondary battery of the present invention does not desorb all six fluorine atoms. That is, only some of the fluorine atoms are extracted, and the reaction is not performed until aluminum fluoride (AlF 3 ) becomes an aluminum metal.
  • AlF 3 aluminum fluoride
  • the reaction does not proceed to the stage of formula (2) and formula (3) in which aluminum fluoride (AlF 3 ) becomes an aluminum metal, and only a part of fluorine atoms is extracted. Stop the reaction in stages.
  • the method for contacting aluminum fluoride (AlF 3 ) with an alkali metal or alkaline earth metal is not particularly limited as long as the reaction is not allowed to proceed until the aluminum fluoride (AlF 3 ) becomes an aluminum metal. Absent.
  • AlF 3 aluminum fluoride
  • AlF 3 aluminum fluoride
  • Aluminum fluoride (AlF 3 ) and alkali metal or alkaline earth metal are both highly reactive with moisture, so contact in an environment that can avoid contact with moisture in the atmosphere, such as a glove box. It is preferable to implement.
  • the ratio of the alkali metal or alkaline earth metal to be used should be 5 to 20 mol% with respect to the total with aluminum fluoride. preferable. By setting the content to 5 to 20 mol%, a large charge / discharge capacity can be obtained, and at the same time, a fluoride ion secondary battery with reduced reaction overvoltage and increased charge / discharge efficiency can be formed.
  • the ratio of alkali metal or alkaline earth metal is more preferably from 5 to 15 mol%, most preferably from 10 to 15 mol%, based on the total amount with aluminum fluoride.
  • Examples 1 to 6 In Examples 1 to 6, aluminum fluoride (AlF 3 ) was used as modified aluminum fluoride using lithium (Li) metal.
  • the obtained raw material mixed powder was charged into a silicon nitride ball mill container (manufactured by Fritsch, Germany, internal volume: 80 cc, PL-7 exclusive container), and 40 g of silicon nitride balls having a diameter of 2 mm were charged and sealed.
  • the sealed container was rotated at 600 rpm for 15 hours, and a ball mill treatment was performed. After the ball mill treatment, the treated powder was recovered.
  • X-ray photoelectron spectroscopy spectrum The crystal structure of the modified aluminum fluoride obtained in Examples and Comparative Examples was analyzed using XPS (manufactured by ULVAC-PHI, PHI5000 Versa Probe II, Al-K ⁇ radiation source).
  • FIG. 5A shows a Li 1s spectrum
  • FIG. 5B shows an Al 2p spectrum.
  • the amount of lithium (Li) metal is preferably 20 mol% or less.
  • a fluoride ion secondary battery was produced by the following method using the following materials.
  • LBF Solid electrolyte
  • La 0.95 Ba 0.05 F 2.95 (LBF) which is a Tysonite solid electrolyte, was used.
  • LBF is a known compound (see References 7 to 9), and was prepared by the method described in Reference 7.
  • Reference 7 ACS Appl. Mater. Interfaces 2014, 6, 2103-2110
  • Reference 8 J.A. Phys. Chem. C 2013, 117, 4943-4950
  • Reference 9 J.M. Phys. Chem. C 2014, 118, 7117-7129
  • the aluminum fluoride (AlF 3 ) of the modified or comparative example 1 produced in the examples, the solid electrolyte (LBF) for imparting an ion conduction path, and acetylene black (manufactured by Electrochemical Industry) for imparting an electron conduction path ) was weighed at a mass ratio of 10:80:10, and thoroughly mixed using an agate mortar and pestle to obtain a negative electrode mixture powder.
  • a lead foil manufactured by Nilaco Corporation, purity: 99.99%, thickness: 200 um was processed into a diameter of 10 mm and used as a positive electrode.
  • a negative electrode mixture powder (20 mg), a solid electrolyte (400 mg), and a positive electrode prepared as described above are integrally molded at a pressure of 4 ton / cm 2 in a mold having a diameter of 10 mm ⁇ to form a fluoride ion secondary battery.
  • Got the body A gold wire for use as a terminal used for charge / discharge measurement was bonded to the positive / negative electrode surface of the obtained molded body with a carbon paste.
  • the fluoride ion secondary battery using the negative electrode active material of Comparative Example 1 that was not subjected to the modification treatment had a charge / discharge capacity of only several tens mAh / g, whereas the modification was It can be confirmed that the charge / discharge capacity of the fluoride ion secondary battery using the negative electrode active material of the example using aluminum fluoride is greatly increased. Moreover, compared with the fluoride ion secondary battery using the negative electrode active material of Comparative Example 1, the fluoride ion secondary battery using the negative electrode active material of Example has an increase in charge / discharge capacity, reaction All of the fact that the overvoltage is decreasing and the charging / discharging efficiency is increasing can be confirmed.
  • FIG. 7 shows the relationship between the charge / discharge capacity and the lithium (Li) metal blending amount in the AlF 3 reforming process for Examples 1 to 6 and Comparative Example 1. From FIG. 7, it can be confirmed that in the modification treatment of aluminum fluoride (AlF 3 ) according to the present invention, the particularly preferable blending amount of the lithium (Li) metal is 5 to 20 mol%.

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Abstract

L'invention concerne : un matériau actif d'électrode négative pour batteries secondaires au fluorure-ion, capable de provoquer une réaction d'électrode négative réversible avec un taux d'utilisation élevé dans une batterie secondaire au fluorure-ion ; une électrode négative qui utilise le matériau actif selon l'invention ; une batterie secondaire au fluorure-ion ; et un procédé de production du matériau actif selon l'invention. Le matériau actif d'électrode négative pour batteries secondaires au fluorure-ion selon l'invention est composé d'un fluorure d'aluminium modifié (AlF3) qui est obtenu par désintercalation partielle d'un ion fluorure (F-) à partir de fluorure d'aluminium (AlF3) à l'avance, ce qui permet une modification de telle sorte qu'une lacune soit présente dans une position où un atome de fluor utilisé doit être présent.
PCT/JP2019/007699 2018-03-27 2019-02-27 Matériau actif d'électrode négative pour batteries secondaires au fluorure-ion, électrode négative utilisant ledit matériau actif, batterie secondaire au fluorure-ion et procédé de production dudit matériau actif Ceased WO2019187943A1 (fr)

Priority Applications (3)

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CN201980022002.1A CN112042018B (zh) 2018-03-27 2019-02-27 氟化物离子二次电池用负极活性物质、使用了该活性物质的负极、及氟化物离子二次电池、以及该活性物质的制造方法
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JPWO2021070299A1 (fr) * 2019-10-09 2021-04-15
WO2021070300A1 (fr) * 2019-10-09 2021-04-15 本田技研工業株式会社 Composite de mélange pour électrode négative pour batterie rechargeable aux ions fluorure, électrode négative et batterie rechargeable pour batterie rechargeable aux ions fluorure utilisant ledit composite et procédé de production dudit composite
JPWO2021070298A1 (fr) * 2019-10-09 2021-04-15
JPWO2021070301A1 (fr) * 2019-10-09 2021-04-15
WO2022109229A1 (fr) * 2020-11-19 2022-05-27 Carnegie Mellon University Électrodes fluorées et batteries les contenant
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JPWO2023013390A1 (fr) * 2021-08-06 2023-02-09
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