WO2021070299A1 - フッ化物イオン二次電池用負極合材複合体、当該複合体を用いたフッ化物イオン二次電池用負極および二次電池、ならびに当該複合体の製造方法 - Google Patents
フッ化物イオン二次電池用負極合材複合体、当該複合体を用いたフッ化物イオン二次電池用負極および二次電池、ならびに当該複合体の製造方法 Download PDFInfo
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- WO2021070299A1 WO2021070299A1 PCT/JP2019/039885 JP2019039885W WO2021070299A1 WO 2021070299 A1 WO2021070299 A1 WO 2021070299A1 JP 2019039885 W JP2019039885 W JP 2019039885W WO 2021070299 A1 WO2021070299 A1 WO 2021070299A1
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- negative electrode
- secondary battery
- ion secondary
- fluoride ion
- fluoride
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- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 title claims abstract description 199
- 239000000203 mixture Substances 0.000 title claims abstract description 109
- 239000002131 composite material Substances 0.000 title claims abstract description 92
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 26
- 239000007773 negative electrode material Substances 0.000 claims abstract description 51
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 45
- 229910001512 metal fluoride Inorganic materials 0.000 claims abstract description 36
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 33
- KLZUFWVZNOTSEM-UHFFFAOYSA-K Aluminum fluoride Inorganic materials F[Al](F)F KLZUFWVZNOTSEM-UHFFFAOYSA-K 0.000 claims abstract description 27
- 239000002245 particle Substances 0.000 claims abstract description 26
- 238000006243 chemical reaction Methods 0.000 claims abstract description 20
- 238000002156 mixing Methods 0.000 claims description 28
- 238000010298 pulverizing process Methods 0.000 claims description 21
- REYHXKZHIMGNSE-UHFFFAOYSA-M silver monofluoride Chemical group [F-].[Ag+] REYHXKZHIMGNSE-UHFFFAOYSA-M 0.000 claims description 17
- 239000006229 carbon black Substances 0.000 claims description 16
- -1 fluorine ions Chemical class 0.000 claims description 15
- 239000007784 solid electrolyte Substances 0.000 claims description 15
- 229910052751 metal Inorganic materials 0.000 claims description 13
- 239000002184 metal Substances 0.000 claims description 13
- 229940096017 silver fluoride Drugs 0.000 claims description 9
- 229910052731 fluorine Inorganic materials 0.000 claims description 7
- 239000011737 fluorine Substances 0.000 claims description 6
- 238000013329 compounding Methods 0.000 claims description 4
- IRPGOXJVTQTAAN-UHFFFAOYSA-N 2,2,3,3,3-pentafluoropropanal Chemical compound FC(F)(F)C(F)(F)C=O IRPGOXJVTQTAAN-UHFFFAOYSA-N 0.000 abstract description 7
- 238000007599 discharging Methods 0.000 abstract description 3
- 238000004220 aggregation Methods 0.000 abstract description 2
- 230000002776 aggregation Effects 0.000 abstract description 2
- 239000011248 coating agent Substances 0.000 abstract description 2
- 238000000576 coating method Methods 0.000 abstract description 2
- 238000004334 fluoridation Methods 0.000 abstract 2
- 230000015572 biosynthetic process Effects 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 10
- 238000000034 method Methods 0.000 description 10
- 239000012752 auxiliary agent Substances 0.000 description 8
- 238000006115 defluorination reaction Methods 0.000 description 8
- 150000002500 ions Chemical class 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 239000000843 powder Substances 0.000 description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- 238000003487 electrochemical reaction Methods 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 5
- 239000006230 acetylene black Substances 0.000 description 5
- 229910001416 lithium ion Inorganic materials 0.000 description 5
- 238000006722 reduction reaction Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 239000000470 constituent Substances 0.000 description 4
- 238000003411 electrode reaction Methods 0.000 description 4
- 229910052744 lithium Inorganic materials 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 230000009257 reactivity Effects 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 230000002441 reversible effect Effects 0.000 description 3
- 229910052709 silver Inorganic materials 0.000 description 3
- 229910016569 AlF 3 Inorganic materials 0.000 description 2
- 229910004261 CaF 2 Inorganic materials 0.000 description 2
- 229910016509 CuF 2 Inorganic materials 0.000 description 2
- 229910052581 Si3N4 Inorganic materials 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- 239000011149 active material Substances 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 239000008151 electrolyte solution Substances 0.000 description 2
- 238000003682 fluorination reaction Methods 0.000 description 2
- 125000001153 fluoro group Chemical group F* 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- 239000011244 liquid electrolyte Substances 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 239000007774 positive electrode material Substances 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 229910017768 LaF 3 Inorganic materials 0.000 description 1
- 229910018095 Ni-MH Inorganic materials 0.000 description 1
- 229910018477 Ni—MH Inorganic materials 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000011246 composite particle Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002222 fluorine compounds Chemical group 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 239000006232 furnace black Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 229910003480 inorganic solid Inorganic materials 0.000 description 1
- 239000003273 ketjen black Substances 0.000 description 1
- YAFKGUAJYKXPDI-UHFFFAOYSA-J lead tetrafluoride Chemical compound F[Pb](F)(F)F YAFKGUAJYKXPDI-UHFFFAOYSA-J 0.000 description 1
- 230000028161 membrane depolarization Effects 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000011812 mixed powder Substances 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 239000007779 soft material Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- YUOWTJMRMWQJDA-UHFFFAOYSA-J tin(iv) fluoride Chemical compound [F-].[F-].[F-].[F-].[Sn+4] YUOWTJMRMWQJDA-UHFFFAOYSA-J 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—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
-
- 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
- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
-
- 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
- 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
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
-
- 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
-
- 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
-
- 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
-
- 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 mixture composite for a fluoride ion secondary battery, a negative electrode and a secondary battery for a fluoride ion secondary battery using the composite, and a method for producing the composite.
- the lithium ion secondary battery has been widely used as a secondary battery having a high energy density.
- the lithium ion secondary battery has a structure in which a separator is present between the positive electrode and the negative electrode and is filled with a liquid electrolyte (electrolyte solution).
- the fluoride ion secondary battery is a secondary battery using fluoride ion (F ⁇ ) as a carrier, and is known to have high theoretical energy. The battery characteristics are expected to exceed those of lithium-ion secondary batteries.
- the negative electrode active material of the fluoride ion secondary battery for example, MgF 2 , CaF 2 , CeF 3 and the like have been reported (see Non-Patent Documents 1 and 2).
- the fluoride ion secondary battery using these negative electrode active materials has a problem that the charge / discharge efficiency is 10 to 20% and the energy efficiency as the 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 lithium ion secondary batteries and Ni-MH batteries.
- the reduction side potential window of the LBF is the potential of La / LaF 3 calculated from the Gibbs energy, as shown in FIG. 1, -2.41 V vs. Constrained by Pb / PbF 2.
- the potential of the negative electrode active material of the fluoride ion secondary battery currently reported is that MgF 2 has -2.35 to -2.87 V vs. Pb / PbF 2 and CaF 2 are -2.85 to -2.89 V vs. Pb / PbF 2 and CeF 3 are -2.18 to -2.37V vs. It is Pb / PbF 2 . Therefore, under the constraint of -2.41 V, which is the reduction potential window of LBF, the defluorination / refluorination reaction of the above-mentioned negative electrode active material cannot be provided in consideration of its overvoltage.
- a negative electrode active material that exhibits a reversible negative electrode reaction with a high utilization rate is required in order to establish a practical all-battery reaction that combines a positive / negative electrode reaction.
- Patent Document 5 aluminum fluoride in which a charge / discharge reaction (defluorination / refluorination reaction) exists within the constraint of the potential window -2.41V of LBF which is a fluoride ion solid electrolyte Focusing on (AlF 3 : -1.78V vs.
- the pores provided at the positions where the fluorine atoms were present serve as the starting point of the defluorination / refluorination reaction, and the desired negative electrode reaction can be obtained with a high utilization rate and a high utilization rate. It can be expressed reversibly.
- the fluoride ion secondary battery using the negative electrode active material proposed in Patent Document 5 has an electrochemical 1st cycle electrification efficiency of about 50%, and further improvement has been required.
- the fluoride ion secondary battery using the negative electrode active material proposed in Patent Document 5 is a discharge start battery because a compound having a fluoride ion in the positive electrode as the opposite electrode is selected.
- the present invention has been made in view of the above background technology, and an object of the present invention is to realize a fluoride ion secondary battery having high initial charge / discharge efficiency and starting charging in a fluoride ion secondary battery. It is an object of the present invention to provide a negative electrode mixture composite for a fluoride ion secondary battery, a negative electrode and a secondary battery for a fluoride ion secondary battery using the composite, and a method for producing the composite.
- the present inventors have diligently investigated the cause of the low electrification efficiency of the negative electrode active material proposed in Patent Document 5. Then, it was considered that aluminum fluoride formed by the refluorination reaction after defluorination coats the surface of the negative electrode active material to form an insulating layer, and thus the reactivity is lowered.
- the negative electrode active material is nanoparticles, the particles agglomerate during the initial charge and discharge, and as a result, it is considered that the electron conduction path and the ion conduction path are not sufficiently formed.
- a compound capable of releasing fluoride ions which are ion carriers, can be present as a negative electrode active material, it may be possible to construct a battery using a compound having no fluoride ions as a positive electrode. ..
- the present inventors use nanoparticle-sized aluminum and metal fluoride as the negative electrode active material to form a complex together with other components of the negative electrode mixture, the refluoridation reaction after depolarization It is possible to suppress the coating with aluminum fluoride formed by the above, and also to suppress the aggregation of the particles of the negative electrode active material with each other. As a result, it has high initial charge / discharge efficiency and can start charging. We have found that a fluoride ion secondary battery can be realized, and have completed the present invention.
- the present invention is a negative electrode mixture composite for a fluoride ion secondary battery containing a negative electrode active material and a fluoride ion conductive fluoride, and the negative electrode active material is aluminum and metal fluoride. It is a negative electrode mixture composite for a fluoride ion secondary battery containing.
- the metal fluoride may be a metal that releases fluorine ions under battery reaction conditions and is composed of a metal of 0 V or higher according to the SHE standard.
- the metal fluoride may be silver fluoride.
- the aluminum may have an average particle size of 10 to 200 nm.
- the negative electrode mixture composite for a fluoride ion secondary battery may further contain carbon black.
- Another invention of the present invention is a negative electrode for a fluoride ion secondary battery, which comprises the above-mentioned negative electrode mixture composite for a fluoride ion secondary battery.
- Another invention is a fluoride ion secondary battery including the above-mentioned negative electrode for a fluoride ion secondary battery, a solid electrolyte, and a positive electrode.
- Another invention is a method for producing a negative electrode mixture composite for a fluoride ion secondary battery, in which a negative electrode active material, a fluoride ion conductive fluoride, and carbon black are mixed to produce a negative electrode.
- a mixing step of obtaining a mixture and pulverizing and mixing the negative electrode mixture, the negative electrode active material, the fluoride ion conductive fluoride, and the carbon black are combined to form a composite.
- the negative electrode active material is a method for producing a negative electrode mixture composite for a fluoride ion secondary battery, which comprises an aluminum and a metal fluoride.
- the metal fluoride releases fluorine ions under battery reaction conditions and is composed of a metal having a SHE standard of 0 V or higher. May be good.
- the metal fluoride may be silver fluoride.
- the aluminum may have an average particle size of 10 to 200 nm.
- the pulverization and mixing treatment may be dry pulverization.
- the pulverization and mixing treatment may be performed by a ball mill.
- the negative electrode mixture composite for a fluoride ion secondary battery of the present invention it is possible to realize a fluoride ion secondary battery having high initial charge / discharge efficiency and starting charging.
- 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 mixture composite for a fluoride ion secondary battery of the present invention contains a negative electrode active material and a fluoride ion conductive fluoride, and is a composite containing aluminum and metal fluoride as a negative electrode active material.
- the body contains a negative electrode active material and a fluoride ion conductive fluoride, and is a composite containing aluminum and metal fluoride as a negative electrode active material.
- the negative electrode mixture composite for a fluoride ion secondary battery of the present invention may contain aluminum and metal fluoride as a negative electrode active material as constituent components, and may further contain fluoride ion conductive fluoride. It may be a complex containing any other component.
- aluminum which is a negative electrode active material, is an alloy with other constituents of the composite and exists as a simple substance of aluminum.
- the shape of the negative electrode mixture composite for a fluoride ion secondary battery of the present invention is not particularly limited. Among them, it is preferable that the granules are granulated and have a spherical shape. Then, it is preferable that aluminum and metal fluoride as a negative electrode active material, fluoride ion conductive fluoride, and any other components are present in each particle.
- the particles When the particles are granulated into a spherical shape, it is possible to create an electrode filled with no gaps at the time of electrode pressing, and it is possible to improve the volumetric energy density of the battery.
- the presence of the constituent components of the complex in each complex particle provides an electron conduction path for the fluorination / defluorination reaction required for the electrochemical reaction and an electron conduction path.
- Ion conduction paths can be formed in nano size.
- the negative electrode for a fluoride ion secondary battery which is an aggregate of objects, has a structure having a high surface area. As a result, the contact area with the solid electrolyte contained in the adjacent solid electrolyte layer can be increased.
- the average particle size thereof is preferably in the range of 0.5 to 10 ⁇ m. It is particularly preferably in the range of 1 to 5 ⁇ m.
- the average particle size of the negative electrode mixture composite for a fluoride ion secondary battery is within the above range, the particles collide with each other during the pulverization and mixing process to obtain the composite particles, resulting in micro-size particles.
- An electron conduction path and an ion conduction path for the fluoride / defluoride reaction are firmly adhered and formed in the particles. Since the particle structure having an electron conduction path and an ion conduction path can follow the volume change accompanying the reaction of aluminum, which is the negative electrode active material, it is possible to suppress the structural collapse of the negative electrode layer and reversible the electrochemical reaction. The sex can be further improved.
- the negative electrode active material of the negative electrode mixture composite for a fluoride ion secondary battery of the present invention contains aluminum and metal fluoride.
- AlF 3 which is a fluoride of aluminum
- the charge / discharge reaction (defluorination / refluorination reaction) exists within the constraint of -2.41V, which is Pb / PbF 2 and is the potential window of LBF which is a fluoride ion solid electrolyte.
- An oxide film may be present on the surface of aluminum.
- the shape of aluminum as the negative electrode active material is preferably spherical. Due to the spherical shape, it is possible to create an electrode filled with no gap at the time of electrode pressing, and it is possible to improve the volumetric energy density of the battery.
- the average particle size of aluminum is preferably in the range of 10 to 200 nm, and particularly preferably in the range of 40 to 100 nm.
- the obtained negative electrode mixture composite for a fluoride ion secondary battery becomes a granule that is close to a spherical shape.
- the metal fluoride which is the second component of the negative electrode active material preferably releases fluorine ions under battery reaction conditions and is composed of a metal having a voltage of 0 V or higher according to the SHE standard.
- the metal fluoride is a metal fluoride composed of a metal of 0 V or more according to the SHE standard, when it is used as a negative electrode active material, the metal fluoride is reduced to a metal during the reduction reaction of the negative electrode and fluorine ions can be released.
- Examples of the metal fluoride composed of a metal having a SHE standard of 0 V or higher, which is preferable in the present invention, include BiF 3 , CuF 2 , MnF 3 , SnF 4 , and AgF 2 .
- the metal fluoride which is the second component of the negative electrode active material has electron conductivity and fluoride ion conductivity after releasing fluoride ions by the reduction reaction. If it becomes insulating or has low fluoride ion conductivity after releasing fluoride ions, it will hinder the reactivity of the battery.
- silver fluoride (AgF 2 ) is most preferable because it satisfies the above requirements and has a high SHE standard.
- the fluoride ion conductive fluoride which is an essential component of the negative electrode mixture composite for a fluoride ion secondary battery of the present invention, is not particularly limited as long as it is a fluoride having fluoride ion conductivity. ..
- Ce 0.95 Ba 0.05 F 2.95 , Ba 0.6 La 0.4 F 2.4 and the like can be mentioned.
- the average particle size of fluoride is preferably in the range of 0.1 to 100 ⁇ m, and particularly preferably in the range of 0.1 to 10 ⁇ m.
- Fluoride ionic conductivity When the average particle size of fluoride is in the range of 0.1 to 100 ⁇ m, a thin-layer electrode can be formed while having relatively high ionic conductivity.
- the type of carbon black is not particularly limited, and examples thereof include furnace black, ketjen black, and acetylene black.
- the average particle size of carbon black is also not particularly limited, but is preferably in the range of 20 to 50 nm.
- the average particle size of carbon black is in the range of 20 to 50 nm, it is possible to form an electrode having high electron conductivity with a small weight.
- composition (aluminum)
- the ratio of aluminum in the negative electrode mixture composite for a fluoride ion secondary battery of the present invention is preferably 1 to 25% by mass with respect to the entire negative electrode mixture composite for a fluoride ion secondary battery. It is more preferably in the range of ⁇ 13% by mass.
- the ratio of aluminum is within the above range, the capacity per weight of the obtained fluoride ion secondary battery increases.
- the ratio of metal fluoride in the negative electrode mixture composite for a fluoride ion secondary battery of the present invention shall be 0.4 to 25% by mass with respect to the entire negative electrode mixture composite for a fluoride ion secondary battery. Is preferable, and the range is more preferably in the range of 0.4 to 13% by mass.
- the ratio of metal fluoride is within the above range, the capacity per weight of the obtained fluoride ion secondary battery increases.
- the mass ratio of aluminum as a negative electrode active material to metal fluoride is preferably in the range of 7: 3 to 4: 6. More preferably, it is in the range of 7: 3 to 5: 5.
- the ratio of fluoride ion conductive fluoride in the negative electrode mixture composite for a fluoride ion secondary battery of the present invention is 70 to 90% by mass with respect to the entire negative electrode mixture composite for a fluoride ion secondary battery. It is preferable that the amount is in the range of 80 to 90% by mass, and more preferably.
- the ratio of fluoride ion conductive fluoride is within the above range, an electrode having high ion conductivity can be formed.
- the ratio of the conductive auxiliary agent is 5 with respect to the entire negative electrode mixture composite for a fluoride ion secondary battery. It is preferably in the range of ⁇ 25% by mass, and more preferably in the range of 5 to 10% by mass.
- the ratio of the conductive auxiliary agent is within the above range, an electrode having high electron conductivity can be formed.
- the mass ratios of aluminum, metal fluoride, fluoride ion conductive fluoride, and conductive auxiliary agent are 1 to 25: 0.4 to 25:
- the range is preferably 70 to 90: 5 to 25. More preferably, it is in the range of 1 to 13: 0.4 to 13: 80 to 90: 5 to 10.
- the fluoride ion secondary battery negative electrode mixture composite of the present invention if the mass ratios of aluminum, metal fluoride, fluoride ion conductive fluoride, and conductive auxiliary agent are within the above range, the fluoride ions obtained can be obtained. The capacity per weight of the secondary battery increases.
- the negative electrode for a fluoride ion secondary battery of the present invention is characterized by containing the negative electrode mixture composite for a fluoride ion secondary battery of the present invention.
- Other configurations are not particularly limited as long as the negative electrode mixture composite for a fluoride ion secondary battery of the present invention is included.
- the fluoride ion secondary battery of the present invention includes a negative electrode for a fluoride ion secondary battery containing the negative electrode mixture composite for a fluoride ion secondary battery of the present invention, a solid electrolyte, and a positive electrode.
- the fluoride ion secondary battery of the present invention is not particularly limited in other configurations as long as it uses a negative electrode containing the negative electrode mixture composite for the fluoride ion secondary battery of the present invention.
- 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 containing the negative electrode mixture composite for the fluoride ion secondary battery of the present invention is provided.
- the characteristics as a fluoride ion secondary battery are high, and a desired battery voltage can be realized.
- a battery that starts charging can be realized. That is, it is possible to manufacture the battery in a discharged state with a low energy state, and it is possible to improve the stability of the active material in the electrode.
- Preferred positive electrodes for the fluoride ion secondary battery of the present invention include, for example, Cu, Bi, Ag, etc.
- Cu is particularly preferable because it is an inexpensive material.
- the method for producing a negative electrode mixture composite for a fluoride ion secondary battery of the present invention includes a mixing step and a compounding step.
- a negative electrode active material In the mixing step in the method for producing a negative electrode mixture composite for a fluoride ion secondary battery of the present invention, a negative electrode active material, a fluoride ion conductive fluoride, and carbon black are mixed to obtain a negative electrode mixture mixture. This is a step of obtaining, and in the present invention, the negative electrode active material contains aluminum and metal fluoride.
- Aluminum and metal fluoride as the negative electrode active material, fluoride ion conductive fluoride, and carbon black as the conductive auxiliary agent are the same as those described above. Further, aluminum, metal fluoride, fluoride ion conductive fluoride, and carbon black may be contained as essential components, and other substances may be optionally blended.
- the mixing method is not particularly limited, and a desired mass may be weighed for each component, and the components may be simultaneously or sequentially charged into the same space for mixing. In addition, in the case of sequentially inputting, the order thereof is not particularly limited.
- the negative electrode mixture obtained in the above mixing step is pulverized and mixed to combine the negative electrode active material, the fluoride ion conductive fluoride, and carbon black to form a composite. Is the process of obtaining.
- the negative electrode active material, the fluoride ion conductive fluoride, and carbon black constituting the negative electrode mixture mixture are alloyed.
- the complex Since aluminum, which is the negative electrode active material, is a relatively soft material, it is supported on fluoride ion conductive fluoride, which is a hard substance, due to the impact during crushing and mixing treatment. It is considered that the nanoparticles can be thermally diffused inside the complex by the heat during the pulverization and mixing treatment, and as a result, the complex is alloyed.
- the pulverization and mixing treatment for alloying and granulating the negative electrode mixture mixture is not particularly limited as long as the negative electrode mixture mixture can be mixed while being pulverized in an inert atmosphere.
- the pulverization and mixing treatment may be either dry pulverization or wet pulverization, but since the oxide film on the particle surface is peeled off and an active surface appears during the pulverization and mixing treatment, the dry type under an inert atmosphere It is preferably pulverized.
- the ball mill is a closed type, the mixing ratio does not fluctuate during pulverization and dispersion, and stable pulverization and mixing treatment can be performed.
- a planetary ball mill is preferable because it has a large crushing power and enables fine crushing and shortening of crushing time.
- the pulverizing and mixing conditions when using a ball mill are also not particularly limited, but are set to, for example, 400 rpm for 10 hours.
- Example 1 In Example 1, aluminum and silver fluoride (AgF 2 ) are used as the negative electrode active materials, CeBaF 2.95 is used as the fluoride ion conductive fluoride, and acetylene black is used as the conductive auxiliary agent for the fluoride ion secondary battery. A negative electrode mixture composite was prepared.
- Al and silver fluoride Al and silver fluoride (AgF 2 ) are used as the negative electrode active materials
- CeBaF 2.95 is used as the fluoride ion conductive fluoride
- acetylene black is used as the conductive auxiliary agent for the fluoride ion secondary battery.
- a negative electrode mixture composite was prepared.
- Table 1 shows the recovery rate of the obtained negative electrode mixture for a fluoride ion secondary battery.
- Modified Aluminum Fluoride Aluminum fluoride (AlF 3 ) was converted to modified aluminum fluoride using a lithium (Li) metal.
- Example 2 A negative electrode mixture composite for a fluoride ion secondary battery was obtained in the same manner as in Example 1 except that aluminum was used as the negative electrode active material without using silver fluoride (AgF 2).
- a fluoride ion secondary battery was prepared by the following method using the following materials.
- La 0.95 Ba 0.05 F 2.95 (LBF), which is a tysonite-based solid electrolyte, was used.
- LBF is a known compound (see Non-Patent Documents 5 to 7) and was prepared by the method described in Document 5.
- Non-Patent Document 5 ACS Appl. Mater. Interfaces 2014, 6, 2103-1110
- Non-Patent Document 6 J. Phys. Chem. C 2013, 117,4943-4950
- Non-Patent Document 7 J. Mol. Phys. Chem. C 2014, 118, 7117-7129
- Electrode mixture powder [Positive electrode mixture powder] Lead fluoride powder (manufactured by High Purity Chemical Co., Ltd.) 63.7% by mass, tin fluoride (manufactured by High Purity Chemical Co., Ltd.) 29.6% by mass, and acetylene black (manufactured by Denka Co., Ltd.) 6. 7% by mass was mixed with a ball mill and then fired at 400 ° C. for 1 hour in an argon atmosphere to obtain a positive electrode mixture powder.
- FIG. 3 shows a method for manufacturing a fluoride ion secondary battery.
- the battery material 3 is sequentially charged into the ceramic pipe 2 and pressed from above and below at a pressure of 40 MPa to form a pellet.
- a mold cell was prepared.
- gold foil manufactured by Nirako Co., Ltd., 99.9 +%, thickness: 10 ⁇ m
- the above negative electrode mixture powder was 10 mg
- the solid electrolyte was 200 mg
- the positive electrode mixture powder 30 mg
- a lead foil manufactured by Niraco Co., Ltd., purity: 99.99%, thickness: 200 ⁇ m
- FIG. 4 shows a cross-sectional view of the produced fluoride ion secondary battery.
- the positive electrode mixture layer 4, the solid electrolyte layer 5, and the negative electrode mixture layer 6 are laminated while being sandwiched between the tablet molding machines. ing.
- the fluoride ion secondary battery produced in Example 1 and Comparative Example 1 is applied from the charging current, and the fluoride ion secondary battery produced in Comparative Example 2 is applied from the discharge current to charge and discharge a constant current.
- the test was carried out. The charge / discharge curve is shown in FIG.
- the fluoride ion secondary battery using the negative electrode mixture composite for the fluoride ion secondary battery of the present invention is charged during charging even when charging / discharging is performed by starting charging. It can be seen that the difference between the capacity of the battery and the capacity at the time of discharge is small, and the reversibility of the electrochemical reaction is improved.
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Abstract
Description
フッ化物イオン二次電池の負極は、放電時にフッ化物イオン(F-)を収容し、充電時にフッ化物イオン(F-)を放出可能なものである必要がある。
本発明のフッ化物イオン二次電池用負極合材複合体の形状は、特に限定されるものではない。なかでは、造粒化されて球状となっていることが好ましい。そして、それぞれの粒子内に、負極活物質としてのアルミニウムおよび金属フッ化物、フッ化物イオン伝導性フッ化物、さらに任意の他の成分が存在していることが好ましい。
本発明のフッ化物イオン二次電池用負極合材複合体の形状が球状である場合には、その平均粒径は、0.5~10μmの範囲であることが好ましい。1~5μmの範囲であることが特に好ましい。
本発明のフッ化物イオン二次電池用負極合材複合体の負極活物質は、アルミニウムと、金属フッ化物とを含む。
アルミニウムのフッ化物であるフッ化アルミニウムAlF3の電位は、図1に示されるように、-1.78V vs.Pb/PbF2であり、フッ化物イオン固体電解質であるLBFの電位窓である-2.41Vの制約内に充放電反応(脱フッ化/再フッ化反応)が存在する。
負極活物質となるアルミニウムの形状は、球状であることが好ましい。球状であることで、電極プレス時に、より隙間なく充填された電極を作成することができ、電池の体積エネルギー密度を向上させることができる。
アルミニウムの平均粒径は、10~200nmの範囲であることが好ましく、40~100nmの範囲であることが特に好ましい。
負極活物質の第2成分となる金属フッ化物は、電池反応条件下でフッ素イオンを放出し、SHE基準で0V以上の金属で構成されたものであることが好ましい。
Ag2++e-→Ag+ (1.98VSHE)
Bi3++3e-→Bi (0.32VSHE)
Cu2++2e-→Cu (0.34VSHE)
Mn3++e-→Mn2+ (1.5VSHE)
Pb2++2e-→Pb (-0.13VSHE)
Sn2++2e-→Sn (-0.14VSHE)
Sn4++2e-→Sn2+(0.15VSHE))
本発明のフッ化物イオン二次電池用負極合材複合体の必須構成成分であるフッ化物イオン伝導性フッ化物は、フッ化物イオン伝導性を有するフッ化物であれば、特に限定されるものではない。例えば、Ce0.95Ba0.05F2.95、Ba0.6La0.4F2.4等が挙げられる。
フッ化物イオン伝導性フッ化物の平均粒径は、0.1~100μmの範囲であることが好ましく、0.1~10μmの範囲であることが特に好ましい。
本発明のフッ化物イオン二次電池用負極合材複合体は、必須構成成分である、負極活物質としてのアルミニウムおよび金属フッ化物と、フッ化物イオン伝導性フッ化物以外に、その他の成分を任意に含んでいてもよい。その他の成分としては、例えば、導電助剤やバインダー等が挙げられる。
本発明のフッ化物イオン二次電池用負極合材複合体においては、特に、導電助剤としてカーボンブラックを含むことが好ましい。カーボンブラックが複合体内に存在することで、電気化学反応に必要なフッ化/脱フッ化反応のための電子伝導パスおよびイオン伝導パスを、容易に形成することができる。
(アルミニウム)
本発明のフッ化物イオン二次電池用負極合材複合体におけるアルミニウムの比率は、フッ化物イオン二次電池用負極合材複合体全体に対して、1~25質量%とすることが好ましく、1~13質量%の範囲であることがさらに好ましい。
本発明のフッ化物イオン二次電池用負極合材複合体における金属フッ化物の比率は、フッ化物イオン二次電池用負極合材複合体全体に対して、0.4~25質量%とすることが好ましく、0.4~13質量%の範囲であることがさらに好ましい。
本発明のフッ化物イオン二次電池用負極合材複合体において、負極活物質となるアルミニウムと金属フッ化物との質量割合は、7:3~4:6の範囲とすることが好ましい。さらに好ましくは、7:3~5:5の範囲である。
本発明のフッ化物イオン二次電池用負極合材複合体におけるフッ化物イオン伝導性フッ化物の比率は、フッ化物イオン二次電池用負極合材複合体全体に対して、70~90質量%とすることが好ましく、80~90質量%の範囲であることがさらに好ましい。
本発明のフッ化物イオン二次電池用負極合材複合体が導電助剤を含む場合には、導電助剤の比率は、フッ化物イオン二次電池用負極合材複合体全体に対して、5~25質量%とすることが好ましく、5~10質量%の範囲であることがさらに好ましい。
本発明のフッ化物イオン二次電池用負極合材複合体において、アルミニウム、金属フッ化物、フッ化物イオン伝導性フッ化物、および導電助剤の質量割合は、1~25:0.4~25:70~90:5~25の範囲とすることが好ましい。さらに好ましくは1~13:0.4~13:80~90:5~10の範囲である。
本発明のフッ化物イオン二次電池用負極は、本発明のフッ化物イオン二次電池用負極合材複合体を含むことを特徴とする。本発明のフッ化物イオン二次電池用負極合材複合体を含んでいれば、その他の構成は特に限定されるものではない。
本発明のフッ化物イオン二次電池は、本発明のフッ化物イオン二次電池用負極合材複合体を含むフッ化物イオン二次電池用負極と、固体電解質と、正極と、を備える。本発明のフッ化物イオン二次電池は、本発明のフッ化物イオン二次電池用負極合材複合体を含む負極を用いていれば、その他の構成は特に限定されるものではない。
本発明のフッ化物イオン二次電池用負極合材複合体の製造方法は、混合工程と、複合化工程と、を含む。
本発明のフッ化物イオン二次電池用負極合材複合体の製造方法における混合工程は、負極活物質と、フッ化物イオン伝導性フッ化物と、カーボンブラックと、を混合して負極合材混合物を得る工程であり、本発明において負極活物質は、アルミニウムと金属フッ化物とを含む。
複合化工程は、上記の混合工程で得られた負極合材混合物を粉砕混合処理することにより、負極活物質と、フッ化物イオン伝導性フッ化物と、カーボンブラックと、を複合化させて複合体を得る工程である。
実施例1においては、負極活物質としてアルミニウムとフッ化銀(AgF2)、フッ化物イオン伝導性フッ化物としてCeBaF2.95、導電助剤としてアセチレンブラックを用いて、フッ化物イオン二次電池用負極合材複合体を作製した。
アルミニウム、フッ化銀(AgF2)、Ce0.95Ba0.05F2.95、およびアセチレンブラックを、表1に示すように秤量した。秤量の後、Ce0.95Ba0.05F2.95およびアセチレンブラックを、窒化ケイ素製ボールミル容器(独フリッチュ社製、内容積:80cc、PL-7専用容器)に投入し、続いて、アルミニウムとフッ化銀(AgF2)とを投入した。さらに、直径2mmの窒化ケイ素製ボールを40グラム投入し、ボールミル容器を密封した。
密封したボールミル容器を、回転数400rpmで10時間回転させて粉砕混合処理を実施し、フッ化物イオン二次電池用負極合材複合体を得た。粉砕混合処理の後、処理された粉末を回収した。回収率を、表1に示す。
アルミニウムとフッ化銀(AgF2)に代えて、特願2018-059703号に記載された改質フッ化アルミニウムを負極活物質とした以外は、実施例1と同様にして、フッ化物イオン二次電池用負極合材を得た。
リチウム(Li)金属を用いて、フッ化アルミニウム(AlF3)を改質フッ化アルミニウムとした。
フッ化アルミニウム(AlF3)、およびリチウム(Li)金属を、フッ化アルミニウム:リチウム(モル比率)が90:10であり、全量が6.0グラムになるよう秤量した。メノウ製の乳鉢と乳棒を用いて、約1時間、予備混合し、原料混合粉末を得た。
フッ化銀(AgF2)を用いることなく、アルミニウムのみを負極活物質とした以外は、実施例1と同様にして、フッ化物イオン二次電池用負極合材複合体を得た。
実施例および比較例で作製したフッ化物イオン二次電池用負極合材複合体およびフッ化物イオン二次電池用負極合材につき、各種の観察および評価を行った。
XRD(リガク社製、SmartLaB、Cu-Kα線源、λ=1.5418Å)を用いて、実施例1で作製したフッ化物イオン二次電池用負極合材複合体、アルミニウム(Al)、フッ化銀(AgF2)、CeBaF2.95(CeBaFXと表示)、比較例1で得られた改質フッ化アルミニウム(AlF3)の結晶構造を解析した。XRDチャートを、図2に示す。
以下の材料を用いて、以下の方法で、フッ化物イオン二次電池を作製した。
実施例および比較例で作製したフッ化物イオン二次電池用負極合材複合体、またはフッ化物イオン二次電池用負極合材を用いた。
タイソナイト系の固体電解質であるLa0.95Ba0.05F2.95(LBF)を用いた。LBFは公知の化合物(非特許文献5~7参照)であり、文献5に記載された方法にて作製した。
非特許文献5:ACS Appl.Mater.Interfaces 2014,6,2103-2110
非特許文献6:J.Phys.Chem.C 2013,117,4943-4950
非特許文献7:J.Phys.Chem.C 2014,118,7117-7129
フッ化鉛粉末((株)高純度化学製)63.7質量%と、フッ化スズ((株)高純度化学製)29.6質量%と、アセチレンブラック(デンカ(株)製)6.7質量%とを、ボールミルで混合後、アルゴン雰囲気下にて400℃で1時間焼成し、正極合材粉末とした。
図3に、フッ化物イオン二次電池の作製方法を示す。図3に示されるように、錠剤成形器(1aおよび1b)を用いて、セラミックスパイプ2の中に、電池材料3を順次投入し、上下から圧力40MPaでプレスすることにより、圧粉成型したペレット型セルを作製した。電池材料3としては、順次、負極集電体として金箔((株)ニラコ製、99.9+%、厚さ:10μm)、上記の負極合材粉末を10mg、固体電解質を200mg、正極合材粉末を30mg、正極集電体として鉛箔((株)ニラコ製、純度:99.99%、厚さ:200μm)を、投入した。
[定電流充放電試験]
上記で得られたペレット型のフッ化物イオン二次電池を、真空環境下で140℃に加熱し、電気化学反応(充放電反応)を実施した。具体的には、ポテンショガルバノスタット装置(ソーラトロン社、SI1287/1255B)を用いて、充電0.02mA、放電0.01mAの電流にて、下限電圧-2.35V、上限電圧-0.1Vにて、実施例1および比較例1で作製したフッ化物イオン二次電池については充電電流より印加し、比較例2で作製したフッ化物イオン二次電池については放電電流より印加して、定電流充放電試験を実施した。充放電曲線を、図5に示す。
2 セラミックスパイプ
3 電池材料
4 正極合材層
5 固体電解質層
6 負極合材層
Claims (13)
- 負極活物質と、フッ化物イオン伝導性フッ化物と、を含むフッ化物イオン二次電池用負極合材複合体であって、
前記負極活物質は、アルミニウムと、金属フッ化物とを含む、フッ化物イオン二次電池用負極合材複合体。 - 前記金属フッ化物は、電池反応条件下でフッ素イオンを放出し、SHE基準で0V以上の金属で構成されたものである、請求項1に記載のフッ化物イオン二次電池用負極合材複合体。
- 前記金属フッ化物は、フッ化銀である、請求項1または2に記載のフッ化物イオン二次電池用負極合材複合体。
- 前記アルミニウムは、平均粒径が10~200nmである、請求項1~3いずれかに記載のフッ化物イオン二次電池用負極合材複合体。
- さらにカーボンブラックを含む、請求項1~4いずれかに記載のフッ化物イオン二次電池用負極合材複合体。
- 請求項1~5いずれかに記載のフッ化物イオン二次電池用負極合材複合体を含む、フッ化物イオン二次電池用負極。
- 請求項6に記載のフッ化物イオン二次電池用負極と、固体電解質と、正極と、を備えるフッ化物イオン二次電池。
- フッ化物イオン二次電池用負極合材複合体を製造する方法であって、
負極活物質と、フッ化物イオン伝導性フッ化物と、カーボンブラックと、を混合して負極合材混合物を得る混合工程と、
前記負極合材混合物を粉砕混合処理することにより、前記負極活物質と、前記フッ化物イオン伝導性フッ化物と、前記カーボンブラックと、を複合化させて複合体を得る複合化工程と、を含み、
前記負極活物質は、アルミニウムと、金属フッ化物とを含む、フッ化物イオン二次電池用負極合材複合体の製造方法。 - 前記金属フッ化物は、電池反応条件下でフッ素イオンを放出し、SHE基準で0V以上の金属で構成されたものである、請求項8に記載のフッ化物イオン二次電池用負極合材複合体の製造方法。
- 前記金属フッ化物は、フッ化銀である、請求項8または9に記載のフッ化物イオン二次電池用負極合材複合体。
- 前記アルミニウムは、平均粒径が10~200nmである、請求項8~10いずれかに記載のフッ化物イオン二次電池用負極合材複合体の製造方法。
- 前記粉砕混合処理は、乾式粉砕である、請求項8~11いずれかに記載のフッ化物イオン二次電池用負極合材複合体の製造方法。
- 前記粉砕混合処理は、ボールミルによるものである、請求項8~11いずれかに記載のフッ化物イオン二次電池用負極合材複合体の製造方法。
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
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US17/767,442 US20240079586A1 (en) | 2019-10-09 | 2019-10-09 | Fluoride ion secondary battery negative electrode mixture composite, fluoride ion secondary battery negative electrode and secondary battery using fluoride ion secondary battery negative electrode mixture composite, and production method for fluoride ion secondary battery negative electrode mixture composite |
PCT/JP2019/039885 WO2021070299A1 (ja) | 2019-10-09 | 2019-10-09 | フッ化物イオン二次電池用負極合材複合体、当該複合体を用いたフッ化物イオン二次電池用負極および二次電池、ならびに当該複合体の製造方法 |
CN201980101227.6A CN114556632A (zh) | 2019-10-09 | 2019-10-09 | 氟化物离子二次电池用负极复合材料复合体、使用了该复合体的氟化物离子二次电池用负极及二次电池、以及该复合体的制造方法 |
JP2021551017A JP7324856B2 (ja) | 2019-10-09 | 2019-10-09 | フッ化物イオン二次電池用負極合材複合体、当該複合体を用いたフッ化物イオン二次電池用負極および二次電池、ならびに当該複合体の製造方法 |
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WO2019070414A1 (en) * | 2017-10-04 | 2019-04-11 | Honda Motor Co., Ltd. | ANODE FOR FLUORIDE ION BATTERY |
JP2019087403A (ja) * | 2017-11-07 | 2019-06-06 | トヨタ自動車株式会社 | 正極活物質およびフッ化物イオン電池 |
JP2019121596A (ja) * | 2017-12-28 | 2019-07-22 | パナソニック株式会社 | フッ化物イオン伝導体およびフッ化物イオン二次電池 |
WO2019187943A1 (ja) * | 2018-03-27 | 2019-10-03 | 本田技研工業株式会社 | フッ化物イオン二次電池用負極活物質、当該活物質を用いた負極、およびフッ化物イオン二次電池、並びに当該活物質の製造方法 |
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WO2019070414A1 (en) * | 2017-10-04 | 2019-04-11 | Honda Motor Co., Ltd. | ANODE FOR FLUORIDE ION BATTERY |
JP2019087403A (ja) * | 2017-11-07 | 2019-06-06 | トヨタ自動車株式会社 | 正極活物質およびフッ化物イオン電池 |
JP2019121596A (ja) * | 2017-12-28 | 2019-07-22 | パナソニック株式会社 | フッ化物イオン伝導体およびフッ化物イオン二次電池 |
WO2019187943A1 (ja) * | 2018-03-27 | 2019-10-03 | 本田技研工業株式会社 | フッ化物イオン二次電池用負極活物質、当該活物質を用いた負極、およびフッ化物イオン二次電池、並びに当該活物質の製造方法 |
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