WO2022249796A1 - 正極用材料、正極の製造方法、正極板の製造方法、および電池の製造方法 - Google Patents
正極用材料、正極の製造方法、正極板の製造方法、および電池の製造方法 Download PDFInfo
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- WO2022249796A1 WO2022249796A1 PCT/JP2022/018138 JP2022018138W WO2022249796A1 WO 2022249796 A1 WO2022249796 A1 WO 2022249796A1 JP 2022018138 W JP2022018138 W JP 2022018138W WO 2022249796 A1 WO2022249796 A1 WO 2022249796A1
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- positive electrode
- electrode material
- solid electrolyte
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- 229910052737 gold Inorganic materials 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000001989 lithium alloy Substances 0.000 description 1
- 229910001547 lithium hexafluoroantimonate(V) Inorganic materials 0.000 description 1
- 229910001540 lithium hexafluoroarsenate(V) Inorganic materials 0.000 description 1
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 description 1
- QSZMZKBZAYQGRS-UHFFFAOYSA-N lithium;bis(trifluoromethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F QSZMZKBZAYQGRS-UHFFFAOYSA-N 0.000 description 1
- MCVFFRWZNYZUIJ-UHFFFAOYSA-M lithium;trifluoromethanesulfonate Chemical compound [Li+].[O-]S(=O)(=O)C(F)(F)F MCVFFRWZNYZUIJ-UHFFFAOYSA-M 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 125000002950 monocyclic group Chemical group 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 125000003367 polycyclic group Chemical group 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229910052701 rubidium Inorganic materials 0.000 description 1
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 238000000790 scattering method Methods 0.000 description 1
- VSZWPYCFIRKVQL-UHFFFAOYSA-N selanylidenegallium;selenium Chemical compound [Se].[Se]=[Ga].[Se]=[Ga] VSZWPYCFIRKVQL-UHFFFAOYSA-N 0.000 description 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- JBQYATWDVHIOAR-UHFFFAOYSA-N tellanylidenegermanium Chemical compound [Te]=[Ge] JBQYATWDVHIOAR-UHFFFAOYSA-N 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 229910021561 transition metal fluoride Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 125000001889 triflyl group Chemical group FC(F)(F)S(*)(=O)=O 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Images
Classifications
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- 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
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- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G35/00—Compounds of tantalum
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- H01M10/052—Li-accumulators
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—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
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- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/058—Construction or manufacture
- H01M10/0585—Construction or manufacture of accumulators having only flat construction elements, i.e. flat positive electrodes, flat negative electrodes and flat separators
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- H01M4/0404—Methods of deposition of the material by coating on electrode collectors
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- H01M4/00—Electrodes
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- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
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- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
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- H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
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- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
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- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
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- 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
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- C—CHEMISTRY; METALLURGY
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- C01P2004/00—Particle morphology
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- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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- H—ELECTRICITY
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- 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
- H01M2004/028—Positive electrodes
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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
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0065—Solid electrolytes
- H01M2300/0068—Solid electrolytes inorganic
- H01M2300/008—Halides
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- 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 disclosure relates to a positive electrode material, a positive electrode manufacturing method, a positive electrode plate manufacturing method, and a battery manufacturing method.
- a lithium secondary battery includes a positive electrode, a negative electrode, and an electrolyte layer disposed between the positive electrode and the negative electrode.
- an all-solid battery using a solid electrolyte for the electrolyte layer has been proposed.
- the positive electrode is manufactured, for example, by a coating method.
- a coating method for example, a slurry containing a positive electrode active material, a solid electrolyte, and a solvent is applied to a current collector to form a coating film, and the coating film is dried to produce a positive electrode (for example, Patent document 1).
- the present disclosure provides a positive electrode material suitable for manufacturing a positive electrode capable of improving the charging and discharging efficiency of a battery.
- the positive electrode material of the present disclosure is a positive electrode active material; a solid electrolyte; an organic solvent; including the solid electrolyte comprises Li, M, O, and X;
- the M is at least one selected from the group consisting of Ta and Nb, X is at least one selected from the group consisting of F, Cl, Br, and I;
- the organic solvent has a boiling point of 212° C. or less.
- a positive electrode material suitable for manufacturing a positive electrode capable of improving the charging and discharging efficiency of a battery.
- FIG. 1 is a schematic diagram showing a positive electrode material according to Embodiment 1.
- FIG. FIG. 2 is a flow chart showing an example of a method for manufacturing a positive electrode according to Embodiment 2.
- FIG. 3 is a flow chart showing an example of a method for manufacturing a positive electrode plate according to Embodiment 3.
- FIG. 4 is a cross-sectional view showing a schematic configuration of a positive electrode plate obtained by a method for manufacturing a positive electrode plate according to Embodiment 3.
- FIG. FIG. 5 is a schematic diagram showing a schematic configuration of a battery obtained by the method for manufacturing a battery according to Embodiment 4.
- FIG. 6 is a graph showing X-ray diffraction patterns of solid electrolytes according to Examples 1 to 3 and Comparative Example 1.
- sulfide solid electrolytes containing sulfur as a main component As a safer solid electrolyte, an oxyhalide solid electrolyte that does not contain sulfur and can have relatively high ionic conductivity is expected.
- An oxyhalide solid electrolyte means a solid electrolyte containing an oxygen element and a halogen element.
- the positive electrode is produced, for example, by a coating method.
- a coating method for example, a slurry containing a positive electrode active material, a solid electrolyte, and a solvent is applied to a current collector to form a coating film, and the coating film is dried to produce a positive electrode.
- the present inventors have newly found that when a positive electrode is manufactured by a coating method using an oxyhalide solid electrolyte, the resulting positive electrode may have increased resistance. It was also found that a battery using such a positive electrode does not have sufficient charge-discharge efficiency. Therefore, the present inventors have made intensive studies on a positive electrode manufactured by a coating method using an oxyhalide solid electrolyte, and have found a new positive electrode material that enables manufacturing of a positive electrode with suppressed increase in resistance. Found it.
- the positive electrode material according to the first aspect of the present disclosure is a positive electrode active material; a solid electrolyte; an organic solvent; including the solid electrolyte comprises Li, M, O, and X;
- the M is at least one selected from the group consisting of Ta and Nb, X is at least one selected from the group consisting of F, Cl, Br, and I;
- the organic solvent has a boiling point of 212° C. or less.
- the positive electrode material according to the first aspect it is possible to manufacture a positive electrode in which an increase in resistance is suppressed.
- the cause of the increase in the resistance of the resulting positive electrode is not necessarily clear, but for example, the residual solvent reduces the electronic conductivity and ionic conductivity.
- One of the causes is thought to be the increase in resistance.
- the positive electrode material according to the first aspect it is believed that, for example, a positive electrode with a reduced amount of residual solvent can be produced, thereby suppressing an increase in the resistance of the positive electrode.
- the positive electrode material according to the first aspect is suitable for manufacturing a positive electrode capable of improving the charge/discharge efficiency of a battery.
- the organic solvent may have a boiling point of 208°C or lower.
- the positive electrode material according to the second aspect is suitable for manufacturing a positive electrode capable of further improving the charging and discharging efficiency of the battery.
- X may contain Cl.
- the positive electrode material according to the third aspect is suitable for manufacturing positive electrodes capable of further improving the charging and discharging efficiency of batteries.
- the solid electrolyte is obtained by X-ray diffraction measurement using Cu-K ⁇ rays as a radiation source.
- the X-ray diffraction pattern it may contain a crystalline phase having at least one peak in the diffraction angle 2 ⁇ range of 11.05° or more and 13.86° or less.
- the positive electrode material according to the fourth aspect when the solid electrolyte contains the above crystal phase, a path for lithium ions to diffuse in the solid electrolyte is easily formed. Therefore, the positive electrode material according to the fourth aspect includes a solid electrolyte with improved lithium ion conductivity. As a result, the positive electrode manufactured from the positive electrode material according to the fourth aspect can further improve the charging and discharging efficiency of the battery.
- the molar ratio O/X of O to X is 0.16 or more and 0 0.35 or less.
- the positive electrode material according to the fifth aspect when the molar ratio O/X of the solid electrolyte satisfies the above range, a high-conductivity crystalline phase is easily realized in the solid electrolyte. Therefore, the lithium ion conductivity of the solid electrolyte contained in the positive electrode material is further improved. As a result, the positive electrode manufactured from the positive electrode material according to the sixth aspect can further improve the charging and discharging efficiency of the battery.
- the molar ratio Li/M of Li to M is 0.60 or more and 2 .4 or less.
- the positive electrode material according to the sixth aspect when the molar ratio Li/M of the solid electrolyte satisfies the above range, it is possible to optimize the Li concentration serving as a conductive carrier in the solid electrolyte. Therefore, the lithium ion conductivity of the solid electrolyte contained in the positive electrode material is further improved. As a result, the positive electrode manufactured from the positive electrode material according to the sixth aspect can further improve the charging and discharging efficiency of the battery.
- the molar ratio Li/M may be 0.96 or more and 1.20 or less.
- the positive electrode manufactured from the positive electrode material according to the seventh aspect can further improve the charging and discharging efficiency of the battery.
- the organic solvent is at least one selected from the group consisting of a compound having a halogen group and a hydrocarbon. may contain one.
- An organic solvent containing at least one selected from the group consisting of a compound having a halogen group and a hydrocarbon is suitable as a solvent for the positive electrode material. Therefore, the positive electrode material according to the eighth aspect is suitable for producing a positive electrode capable of further improving the charge/discharge efficiency of the battery.
- the compound having a halogen group may have only a halogen group as a functional group.
- a compound having only a halogen group as a functional group can easily disperse an oxyhalide solid electrolyte (that is, a solid electrolyte containing O and X). Therefore, the positive electrode material according to the ninth aspect is suitable for producing a positive electrode capable of further improving the charge/discharge efficiency of the battery.
- the organic solvent may contain an aromatic compound.
- Organic solvents containing aromatic compounds are suitable as solvents for positive electrode materials. Therefore, the positive electrode material according to the tenth aspect is suitable for producing a positive electrode capable of further improving the charge/discharge efficiency of a battery.
- the organic solvent includes tetralin, mesitylene, xylene, cumene, pseudocumene, ethylbenzene, chlorobenzene, 2,4 - from dichlorobenzene, o-chlorotoluene, 1,3-dichlorobenzene, p-chlorotoluene, 1,2-dichlorobenzene, 1,4-dichlorobutane, 2,4-dichlorotoluene and 3,4-dichlorotoluene It may contain at least one selected from the group consisting of:
- the compound that can be used as an organic solvent for the positive electrode material according to the eleventh aspect can easily disperse the oxyhalide solid electrolyte. Therefore, the positive electrode material according to the eleventh aspect is suitable for manufacturing a positive electrode capable of further improving the charge/discharge efficiency of a battery.
- the organic solvent may contain at least one selected from the group consisting of tetralin, mesitylene, and xylene.
- the compound that can be used as an organic solvent for the positive electrode material according to the twelfth aspect can more easily disperse the oxyhalide solid electrolyte. Therefore, the positive electrode material according to the twelfth aspect is suitable for producing a positive electrode capable of further improving the charge/discharge efficiency of the battery.
- the organic solvent has a polar term ⁇ p in the Hansen solubility parameter of 4.3 or less. good.
- the positive electrode material according to the thirteenth aspect of the present disclosure is suitable for manufacturing a positive electrode capable of further improving the charge/discharge efficiency of the battery.
- a method for manufacturing a positive electrode according to a fourteenth aspect of the present disclosure includes: removing the organic solvent from the positive electrode material according to any one of the first to thirteenth aspects; including.
- the manufacturing method according to the fourteenth aspect a positive electrode in which an increase in resistance is suppressed can be obtained. Therefore, the positive electrode obtained by the manufacturing method according to the fourteenth aspect can suppress an increase in the internal resistance of the battery and improve the charge/discharge efficiency. Moreover, according to the manufacturing method according to the fourteenth aspect, it is possible to obtain a positive electrode that is homogeneous and has reduced variations in performance.
- a method for manufacturing a positive electrode plate according to a fifteenth aspect of the present disclosure includes: Applying the positive electrode material according to any one of the first to thirteenth aspects onto a current collector; removing the organic solvent from the positive electrode material applied on the current collector; including.
- the manufacturing method according to the fifteenth aspect a positive electrode plate in which an increase in resistance is suppressed can be obtained. Therefore, the positive electrode plate obtained by the manufacturing method according to the fifteenth aspect can suppress an increase in the internal resistance of the battery and improve the charge/discharge efficiency. Moreover, according to the manufacturing method according to the fifteenth aspect, it is possible to obtain a positive electrode plate that is uniform and has reduced variations in performance.
- a method for manufacturing a battery according to a sixteenth aspect of the present disclosure is a method for manufacturing a battery including a positive electrode, a negative electrode, and a solid electrolyte layer positioned between the positive electrode and the negative electrode, Obtaining the positive electrode by removing the organic solvent from the positive electrode material according to any one of the first to thirteenth aspects; including.
- Embodiment 1 The positive electrode material according to Embodiment 1 will be described below.
- FIG. 1 is a schematic diagram showing a positive electrode material according to Embodiment 1.
- FIG. 1 is a schematic diagram showing a positive electrode material according to Embodiment 1.
- a positive electrode material 1000 according to Embodiment 1 includes a positive electrode active material 110 , a solid electrolyte 100 and an organic solvent 111 .
- the solid electrolyte 100 contains Li, M, O, and X.
- M is at least one selected from the group consisting of Ta and Nb
- X is at least one selected from the group consisting of F, Cl, Br and I. That is, the positive electrode material 1000 contains an oxyhalide solid electrolyte containing an oxygen element and a halogen element.
- the organic solvent 111 has a boiling point of 212° C. or less;
- the positive electrode material 1000 that is suitable for manufacturing a positive electrode capable of improving the charging and discharging efficiency of the battery. Specifically, by using the positive electrode material 1000, a positive electrode in which an increase in resistance is suppressed can be manufactured. Therefore, in a battery including a positive electrode manufactured from the positive electrode material 1000, an increase in internal resistance is suppressed, and charge/discharge efficiency is improved.
- the positive electrode material 1000 may be in the form of a paste or a dispersion liquid.
- the solid electrolyte 100 and the positive electrode active material 110 are particles, for example.
- solid electrolyte 100 and positive electrode active material 110 are mixed with organic solvent 111 .
- the viscosity of the positive electrode material 1000 can be adjusted as appropriate. For example, when coating is performed by a method such as a spray method, the viscosity of the positive electrode material 1000 is relatively low. The viscosity of the positive electrode material 1000 is relatively high when the application is performed by a method such as the doctor blade method.
- the ratio of the combined mass of the solid electrolyte 100 and the positive electrode active material 110 to the combined mass of the solid electrolyte 100, the positive electrode active material 110, and the organic solvent 111 is not particularly limited, and may be, for example, 80% by mass or less. good. With such a configuration, the positive electrode material 1000 can be easily applied to the surface of the current collector.
- the positive electrode active material 110 includes a material that has the property of intercalating and deintercalating metal ions (eg, lithium ions).
- metal ions eg, lithium ions
- the positive electrode active material 110 for example, lithium-containing transition metal oxides, transition metal fluorides, polyanion materials, fluorinated polyanion materials, transition metal sulfides, transition metal oxysulfides, or transition metal oxynitrides can be used.
- lithium-containing transition metal oxides include Li(Ni, Co, Al) O2 , Li(Ni, Co, Mn) O2 , LiCoO2 , and the like.
- the manufacturing cost of the positive electrode can be reduced and the average discharge voltage can be increased.
- the positive electrode active material 110 may contain Ni, Co, and Mn.
- the positive electrode active material 110 may contain lithium nickel cobalt manganate.
- cathode active material 110 may include Li(Ni, Co, Al) O 2 .
- the positive electrode material 1000 can further increase the energy density and charge/discharge efficiency of a battery including a positive electrode manufactured using the positive electrode material 1000.
- At least part of the surface of the positive electrode active material 110 may be covered with a coating material different from that of the positive electrode active material 110 .
- Coating materials include Li—Nb—O compounds such as LiNbO 3 , Li —B—O compounds such as LiBO 2 and Li 3 BO 3 , Li—Al—O compounds such as LiAlO 2 and Li— Si—O compounds, Li—Ti—O compounds such as Li 2 SO 4 and Li 4 Ti 5 O 12 , Li—Zr—O compounds such as Li 2 ZrO 3 , Li—Mo—O compounds such as Li 2 MoO 3 , Li-VO compounds such as LiV 2 O 5 , Li-WO compounds such as Li 2 WO 4 , or Li-P-O compounds such as Li 3 PO 4 .
- Li—Nb—O compounds such as LiNbO 3
- Li —B—O compounds such as LiBO 2 and Li 3 BO 3
- Li—Al—O compounds such as LiAlO 2 and Li— Si—O compounds
- Li—Ti—O compounds such as Li 2 SO 4 and Li 4 Ti 5 O 12
- Li—Zr—O compounds such as Li 2 ZrO 3
- the positive electrode active material 110 By including the positive electrode active material 110 having the above configuration, oxidation of the solid electrolyte 100 can be suppressed in the positive electrode manufactured using the positive electrode material 1000 .
- At least part of the surface of the positive electrode active material 110 may be covered with an oxyhalide solid electrolyte.
- the positive electrode material 1000 can reduce interfacial resistance in a positive electrode manufactured using the positive electrode material 1000 .
- the median diameter of the positive electrode active material 110 may be 0.1 ⁇ m or more and 100 ⁇ m or less.
- the median diameter of the positive electrode active material is 0.1 ⁇ m or more, the positive electrode active material 110 and the solid electrolyte 100 can form a good dispersion state in the positive electrode material 1000 . Therefore, a battery including a positive electrode manufactured from the positive electrode material 1000 can have improved charge/discharge characteristics.
- the median diameter of the positive electrode active material 110 is 100 ⁇ m or less, the diffusion rate of lithium in the positive electrode active material increases. Therefore, a battery having a positive electrode manufactured from the positive electrode material 1000 can operate at high output.
- the median diameter of the positive electrode active material 110 means the particle size (d50) corresponding to 50% of the cumulative volume obtained from the particle size distribution measured on a volume basis by the laser diffraction scattering method.
- the particle size distribution can also be measured, for example, using an image analyzer. The same applies to median diameters of other materials.
- the solid electrolyte 100 contains Li, M, O, and X.
- X is at least one selected from the group consisting of F, Cl, Br and I; That is, the positive electrode material 1000 contains an oxyhalide solid electrolyte.
- Oxyhalide solid electrolytes for example, can have lithium ion conductivity.
- X may contain Cl.
- X1 may be Cl.
- the solid electrolyte 100 can have high ionic conductivity. Therefore, by including a solid electrolyte containing Cl, the positive electrode material 1000 can further increase the charge/discharge efficiency of a battery having a positive electrode manufactured using the positive electrode material 1000 . That is, according to the above configuration, it is possible to obtain the positive electrode material 1000 suitable for manufacturing a positive electrode capable of further improving the charging and discharging efficiency of the battery.
- X may contain Cl and at least one selected from the group consisting of F, Br, and I;
- M is at least one selected from the group consisting of Ta and Nb.
- Solid electrolyte 100 can have high ionic conductivity by containing at least one selected from the group consisting of Ta and Nb. Therefore, by including the solid electrolyte 100 having such a configuration, the positive electrode material 1000 can produce a positive electrode having high lithium ion conductivity. Therefore, according to the above configuration, it is possible to obtain the positive electrode material 1000 suitable for manufacturing a positive electrode capable of further improving the charging and discharging efficiency of the battery.
- the solid electrolyte 100 is a material containing Li, Ta, O, and Cl, a material containing Li, Nb, O, and Cl, and a material containing Li, Ta, Nb, O, and Cl It may contain at least one selected from the group consisting of
- the solid electrolyte 100 may be a material containing Li, Ta, O and Cl, a material containing Li, Nb, O and Cl, or a material containing Li, Ta, Nb, O and Cl. Note that the solid electrolyte 100 may not contain sulfur.
- the molar ratio O/X of O to X may be 0.16 or more and 0.35 or less.
- the molar ratio O/Cl of O to Cl may be 0.16 or more and 0.35 or less.
- the number of moles of X is the total number of moles of the plurality of halogen elements.
- the molar ratio Li/M of Li to M may be 0.60 or more and 2.4 or less. That is, the ratio Li/(Ta+Nb) of the number of moles of Li to the total number of moles of Ta and Nb may be 0.6 or more and 2.4 or less.
- the molar ratio Li/M of the solid electrolyte 100 satisfies the above range, optimization of the Li concentration serving as a conductive carrier in the solid electrolyte 100 can be achieved. Therefore, the lithium ion conductivity of the solid electrolyte 100 contained in the positive electrode material 1000 is further improved. As a result, the positive electrode manufactured from the positive electrode material 1000 can further improve the charging and discharging efficiency of the battery.
- the molar ratio Li/M of Li to M may be 0.96 or more and 1.20 or less. That is, the ratio Li/(Ta+Nb) of the number of moles of Li to the total number of moles of Ta and Nb may be 0.96 or more and 1.20 or less.
- the molar ratio Li/M of the solid electrolyte 100 satisfies the above range, further optimization of the Li concentration serving as a conductive carrier in the solid electrolyte 100 can be achieved. Therefore, the lithium ion conductivity of the solid electrolyte 100 contained in the positive electrode material 1000 is further improved. As a result, the positive electrode manufactured from the positive electrode material 1000 can further improve the charging and discharging efficiency of the battery.
- the solid electrolyte 100 has at least one peak in the diffraction angle 2 ⁇ range of 11.05° or more and 13.86° or less in an X-ray diffraction pattern obtained by X-ray diffraction measurement using a Cu—K ⁇ ray as a radiation source. may contain a crystalline phase in which When solid electrolyte 100 contains such a crystal phase, paths for lithium ions to diffuse in solid electrolyte 100 are easily formed. Therefore, by including the solid electrolyte 100 containing such a crystal phase, the positive electrode material 1000 can produce a positive electrode having high lithium ion conductivity. That is, the positive electrode manufactured from the positive electrode material 1000 can further improve the charging and discharging efficiency of the battery.
- the shape of the solid electrolyte 100 is not particularly limited.
- its shape may be, for example, acicular, spherical, ellipsoidal, or the like.
- the shape of the solid electrolyte 100 may be particulate.
- the median diameter of the solid electrolyte 100 may be 100 ⁇ m or less.
- the solid electrolyte 100 can form a good dispersion state in the positive electrode material 1000 . Therefore, the positive electrode manufactured from the positive electrode material 1000 can further improve the charging and discharging efficiency of the battery.
- the median diameter of the solid electrolyte 100 may be 10 ⁇ m or less. When the median diameter is 10 ⁇ m or less, the solid electrolyte 100 can form a good dispersion state in the positive electrode material 1000 . Therefore, the positive electrode manufactured from the positive electrode material 1000 can further improve the charging and discharging efficiency of the battery.
- the median diameter of the solid electrolyte 100 may be smaller than the median diameter of the positive electrode active material 110 . Thereby, the positive electrode active material 110 and the solid electrolyte 100 can form a good dispersion state in the positive electrode material 1000 .
- the organic solvent 111 has a boiling point of 212° C. or less.
- the positive electrode material 1000 can produce a positive electrode with reduced residual solvent. In the positive electrode thus obtained, an increase in resistance due to residual solvent is suppressed. Therefore, the positive electrode material 1000 is suitable for manufacturing a positive electrode capable of improving the charge/discharge efficiency of a battery.
- the term "boiling point" refers to the temperature at which the saturated vapor pressure of a liquid is equal to 1 atm.
- the organic solvent 111 may have a boiling point of 208°C or lower.
- the positive electrode material 1000 can produce a positive electrode with a further reduced residual solvent. In the positive electrode thus obtained, the increase in resistance caused by the residual solvent is further suppressed. Therefore, the positive electrode material 1000 containing the organic solvent 111 having such a boiling point is suitable for manufacturing a positive electrode capable of further improving the charging/discharging efficiency of the battery.
- the organic solvent 111 may contain at least one selected from the group consisting of compounds having a halogen group and hydrocarbons. These are suitable as solvents for the positive electrode material 1000 . Therefore, the positive electrode material 1000 containing such a solvent is suitable for manufacturing a positive electrode capable of further improving the charging/discharging efficiency of the battery.
- Hydrocarbons are compounds consisting only of carbon and hydrogen.
- the hydrocarbon may be an aliphatic hydrocarbon.
- the hydrocarbons may be saturated hydrocarbons or unsaturated hydrocarbons.
- the hydrocarbon may be linear or branched.
- the number of carbon atoms contained in the hydrocarbon is not particularly limited, and may be 7 or more.
- the hydrocarbon may have a ring structure.
- the ring structure may be an alicyclic hydrocarbon or an aromatic hydrocarbon.
- the ring structure may be monocyclic or polycyclic.
- the solid electrolyte 100 can be easily dispersed in the organic solvent 111 because the hydrocarbon has a ring structure.
- the hydrocarbon may contain an aromatic hydrocarbon.
- the hydrocarbon may be an aromatic hydrocarbon.
- the portion other than the halogen group may consist only of carbon and hydrogen. That is, a compound having a halogen group means a compound in which at least one hydrogen atom contained in a hydrocarbon is substituted with a halogen group.
- Halogen groups include F, Cl, Br, and I.
- the halogen group at least one selected from the group consisting of F, Cl, Br, and I may be used, or a plurality of types may be used.
- Compounds with halogen groups can be highly polar.
- the number of carbon atoms contained in the compound having a halogen group is not particularly limited, and may be 7 or more. As a result, the compound having a halogen group is less likely to volatilize, so that the positive electrode material 1000 can be stably produced.
- Compounds with halogen groups may also have large molecular weights. That is, compounds with halogen groups can have high boiling points.
- a compound having a halogen group may have only a halogen group as a functional group.
- the number of halogens contained in the compound having a halogen group is not particularly limited.
- the halogen at least one selected from the group consisting of F, Cl, Br, and I may be used, or a plurality of types may be used.
- the solid electrolyte can be easily dispersed, so that the positive electrode material 1000 with excellent dispersibility can be obtained.
- the positive electrode material 1000 can form a denser positive electrode.
- the positive electrode material 1000 can easily form a dense positive electrode with few pinholes and irregularities, for example.
- the compound having a halogen group may be a halogenated hydrocarbon.
- a halogenated hydrocarbon means a compound in which all hydrogen atoms contained in a hydrocarbon are substituted with halogen groups.
- the organic solvent 111 may contain, for example, an aromatic compound.
- the organic solvent 111 is, for example, tetralin, mesitylene, xylene, cumene, pseudocumene, ethylbenzene, chlorobenzene, 2,4-dichlorobenzene, o-chlorotoluene, 1,3-dichlorobenzene, p-chlorotoluene, 1,2-dichlorobenzene, It may contain at least one selected from the group consisting of chlorobenzene, 1,4-dichlorobutane, 2,4-dichlorotoluene, and 3,4-dichlorotoluene. These compounds can readily disperse oxyhalide solid electrolytes. Therefore, by using these compounds as the organic solvent 111, the positive electrode material 1000 can form a denser positive electrode. Such a positive electrode can further improve the charge/discharge efficiency of the battery.
- the organic solvent 111 may contain, for example, at least one selected from the group consisting of tetralin, mesitylene, and xylene. These compounds can more easily disperse oxyhalide solid electrolytes. Therefore, by using these compounds as the organic solvent 111, the positive electrode material 1000 can form a denser positive electrode. Such a positive electrode can further improve the charge/discharge efficiency of the battery.
- the number of halogen groups contained in the compound having a halogen group is not particularly limited.
- the number of halogen groups contained in the compound having a halogen group may be, for example, one.
- the lower limit of the boiling point of the organic solvent 111 may be, for example, 100°C or higher.
- the organic solvent 111 may be liquid at normal temperature (25° C.). Such an organic solvent 111 is difficult to volatilize at room temperature, so that the positive electrode material 1000 can be stably produced. Therefore, it is possible to obtain a positive electrode material that can be easily applied to the surface of an electrode or current collector. Also, this allows the organic solvent 111 to be easily removed by drying.
- Organic solvent 111 may be a liquid capable of dispersing the oxyhalide solid electrolyte. The organic solvent 111 does not have to dissolve the oxyhalide solid electrolyte.
- the organic solvent 111 may have a polar term ⁇ p of 4.3 or less in the Hansen solubility parameter.
- the organic solvent 111 satisfying the polar term ⁇ p in the Hansen solubility parameter of 4.3 or less has low reactivity at the interface with other materials, that is, the solid electrolyte 100 and the positive electrode active material 110 . Therefore, in the positive electrode material 1000, the reaction at the interface between the organic solvent 111 and other materials is suppressed, so that the resistance can be lowered. Therefore, the positive electrode material 1000 containing the organic solvent 111 that satisfies the above Hansen solubility parameter is suitable for manufacturing a positive electrode capable of further improving the charge/discharge efficiency of the battery.
- the positive electrode material 1000 may contain a binder for the purpose of improving adhesion between particles.
- a binder is used to improve the binding properties of the material that constitutes the electrode. Binders include polyvinylidene fluoride, polytetrafluoroethylene, polyethylene, polypropylene, aramid resin, polyamide, polyimide, polyamideimide, polyacrylonitrile, polyacrylic acid, polyacrylic acid methyl ester, polyacrylic acid ethyl ester, poly Acrylate hexyl ester, polymethacrylic acid, polymethacrylic acid methyl ester, polymethacrylic acid ethyl ester, polymethacrylic acid hexyl ester, polyvinyl acetate, polyvinylpyrrolidone, polyether, polyethersulfone, hexafluoropolypropylene, styrene-butadiene rubber, and carboxymethyl cellulose, and the like.
- Binders include tetrafluoroethylene, hexafluoroethylene, hexafluoropropylene, perfluoroalkyl vinyl ether, vinylidene fluoride, chlorotrifluoroethylene, ethylene, propylene, pentafluoropropylene, fluoromethyl vinyl ether, acrylic acid, and Copolymers of two or more materials selected from the group consisting of hexadiene can be used. A mixture of two or more selected from these may also be used.
- the positive electrode material 1000 may contain a conductive aid for the purpose of increasing electronic conductivity.
- conductive aids include graphites such as natural graphite and artificial graphite, carbon blacks such as acetylene black and Ketjen black, conductive fibers such as carbon fiber and metal fiber, carbon fluoride, and metal powder such as aluminum.
- conductive whiskers such as zinc oxide and potassium titanate, conductive metal oxides such as titanium oxide, and conductive polymeric compounds such as polyaniline, polypyrrole, and polythiophene. Cost reduction can be achieved when a carbon conductive aid is used as the conductive aid.
- the positive electrode material 1000 may contain a dispersant for the purpose of improving the dispersibility of the solid electrolyte 100 or the positive electrode active material 110 .
- Embodiment 2 A method for manufacturing a positive electrode according to Embodiment 2 will be described below. Contents that overlap with Embodiment 1 are omitted as appropriate.
- FIG. 2 is a flow chart showing an example of a method for manufacturing a positive electrode according to Embodiment 2.
- the manufacturing method of the positive electrode according to the second embodiment includes step S1001 of removing the organic solvent 111 from the positive electrode material 1000 according to the first embodiment. That is, the positive electrode is a member containing solid electrolyte 100 and positive electrode active material 110 .
- the positive electrode material 1000 can be used to manufacture a positive electrode with a reduced amount of residual solvent. Therefore, in the positive electrode manufactured by the manufacturing method according to Embodiment 2, an increase in resistance due to the residual solvent is suppressed. Therefore, in a battery including such a positive electrode, an increase in internal resistance is suppressed, so charging and discharging efficiency is improved. That is, the positive electrode obtained by the manufacturing method according to Embodiment 2 can suppress an increase in the internal resistance of the battery and improve the charge/discharge efficiency.
- step S1001 the organic solvent 111 is removed from the positive electrode material 1000.
- the organic solvent 111 may be removed, for example, by normal pressure drying. Removal of the organic solvent 111 by normal pressure drying means removal of the organic solvent 111 from the positive electrode material 1000 under atmospheric pressure. In normal pressure drying, the positive electrode material 1000 may be heated to, for example, 100° C. or higher and 200° C. or lower.
- the organic solvent 111 may be removed from the positive electrode material 1000 by drying under reduced pressure, for example.
- the positive electrode material 1000 before removing the organic solvent 111 has fluidity. Therefore, the positive electrode material 1000 has excellent moldability and can form a coating film having a uniform thickness, for example. By drying such a coating film, for example, a dense positive electrode with few pinholes and irregularities can be easily obtained.
- Removing the organic solvent 111 by drying under reduced pressure means removing the organic solvent 111 from the positive electrode material 1000 in a pressure atmosphere lower than the atmospheric pressure.
- the pressure atmosphere lower than the atmospheric pressure is, for example, ⁇ 0.01 MPa or less in gauge pressure.
- the positive electrode material 1000 may be heated to, for example, 100° C. or higher and 200° C. or lower.
- the organic solvent 111 may be removed from the positive electrode material 1000 by vacuum drying. Removal of the organic solvent 111 by vacuum drying means removal of the organic solvent 111 from the positive electrode material 1000 at a temperature lower than the boiling point of the organic solvent 111 by 20° C. and below the vapor pressure, for example.
- Removal of the organic solvent 111 is by, for example, Fourier transform infrared spectroscopy (FT-IR), X-ray photoelectron spectroscopy (XPS), gas chromatography (GC), or gas chromatography-mass spectrometry (GC/MS). I can confirm. Note that the positive electrode obtained after drying only needs to have ionic conductivity, and the organic solvent 111 does not have to be completely removed.
- FT-IR Fourier transform infrared spectroscopy
- XPS X-ray photoelectron spectroscopy
- GC gas chromatography
- GC/MS gas chromatography-mass spectrometry
- Embodiment 3 A method for manufacturing a positive electrode plate according to Embodiment 3 will be described below. Contents that overlap with Embodiments 1 and 2 are omitted as appropriate.
- FIG. 3 is a flow chart showing an example of a method for manufacturing a positive electrode plate according to Embodiment 3.
- the method for manufacturing a positive electrode plate according to Embodiment 3 includes a step S2001 of applying the positive electrode material 1000 according to Embodiment 1 onto a current collector, and the positive electrode material 1000 applied onto the current collector. and step S2002 of removing the organic solvent 111 from the.
- FIG. 4 is a cross-sectional view showing a schematic configuration of a positive electrode plate obtained by a method for manufacturing a positive electrode plate according to Embodiment 3.
- the positive electrode plate 2000 comprises a positive electrode 201 and a current collector 202 .
- Positive electrode 201 includes positive electrode active material 110 and solid electrolyte 100 .
- step S2001 for example, the positive electrode material 1000 is applied onto the current collector 202 as a base material to form a positive electrode material 1000 film.
- step S2002 by removing the organic solvent 111 from the film of the positive electrode material 1000, for example, a homogeneous positive electrode 201 can be manufactured.
- the material used for the current collector 202 may have electronic conductivity, and examples thereof include metals, semimetals, and alloys that are mixtures thereof.
- carbon (C), iron (Fe), nickel (Ni), aluminum (Al), or copper (Cu) is desirable. Alloys of the above metals may also be used.
- An aluminum alloy may be used as the material used for the current collector 202 .
- A1050 Al content of 99.50 wt% or more, Fe 0.40 wt% or less, Si 0.25 wt% or less, Cu 0.05 wt% or less), as specified in Japanese Industrial Standards (JIS H4000, etc.)
- pure aluminum such as A1085 (Al content of 99.85 wt% or more, Fe 0.12 wt% or less, Si 0.1 wt% or less, Cu 0.03 wt% or less), A2017 (Al-3.5 to 4.5 wt% Cu alloy), A3003 (Al-1.0 to 1.5 wt% Mn-0.05-0.20 Cu alloy), and A8021 (Al-1.5 wt% Fe-0.05 wt% Cu alloy) and aluminum alloys.
- the current collector 202 contains an aluminum alloy, the current collector 202 is lightweight and has high strength, so a battery that achieves both high weight energy density and high durability can be realized.
- the material used for the current collector 202 may be a polymer material mixed with the above electronically conductive material.
- the current collector 202 may be made of different materials inside and on the surface. That is, the current collector 202 may be configured by coating the surface of the portion constituting the inside with the material having the above-described electron conductivity.
- the shape of the current collector 202 is not limited, but in order to improve the adhesion with the positive electrode 201, for example, a material with a large surface roughness can be used.
- Embodiment 4 A method for manufacturing a battery according to Embodiment 4 will be described below. Contents that overlap with Embodiments 1, 2, and 3 are omitted as appropriate.
- FIG. 5 is a cross-sectional view showing a schematic configuration of a battery obtained by the method for manufacturing a battery according to Embodiment 4.
- a battery 3000 obtained by the manufacturing method according to Embodiment 4 includes a positive electrode 301, a negative electrode 303, and an electrolyte layer 302 positioned between the positive electrode 301 and the negative electrode 303.
- Positive electrode 301 includes positive electrode active material 110 and solid electrolyte 100 .
- the method for manufacturing a battery according to Embodiment 4 includes a step of obtaining positive electrode 301 by removing organic solvent 111 from positive electrode material 1000 according to Embodiment 1 described above.
- the method for manufacturing the positive electrode described in Embodiment 2 above may be performed, or the method for manufacturing the positive electrode described in Embodiment 3 above may be performed.
- a method for manufacturing a positive electrode plate may be implemented.
- the positive electrode material 1000 described in Embodiment 1 is used for manufacturing the positive electrode 301 . Therefore, positive electrode 301 obtained by the manufacturing method according to Embodiment 4 is a positive electrode with reduced residual solvent, and an increase in resistance is suppressed. Therefore, according to the manufacturing method according to Embodiment 4, battery 3000 with improved charge/discharge efficiency can be obtained.
- the positive electrode 301 includes a positive electrode active material 110 and a solid electrolyte 100.
- the volume ratio "v1:100-v1" between the positive electrode active material 110 and the solid electrolyte 100 contained in the positive electrode 301 may satisfy 30 ⁇ v1 ⁇ 98.
- v1 represents the volume ratio of the positive electrode active material 110 when the total volume of the positive electrode active material 110 and the solid electrolyte 100 contained in the positive electrode 301 is 100.
- 30 ⁇ v1 a sufficient energy density of the battery 3000 can be secured.
- v1 ⁇ 95 is satisfied, the battery 3000 can operate at high output.
- the thickness of the positive electrode 301 may be 10 ⁇ m or more and 500 ⁇ m or less. When the thickness of the positive electrode 301 is 10 ⁇ m or more, the energy density of the battery 3000 is sufficiently ensured. When the thickness of the positive electrode 301 is 500 ⁇ m or less, the battery 3000 can operate at high output.
- the electrolyte layer 302 is a layer containing an electrolyte.
- the solid electrolyte contained in the electrolyte layer 302 may be an oxyhalide solid electrolyte.
- an oxyhalide solid electrolyte having the same composition as solid electrolyte 100 contained in positive electrode material 1000 in Embodiment 1, or an oxyhalide solid electrolyte containing the same crystal phase may be used. According to the above configuration, the power density and charge/discharge characteristics of the battery 3000 can be further improved.
- the solid electrolyte contained in the electrolyte layer 302 may be a halide solid electrolyte having a different composition or a different crystal phase from the oxyhalide-based solid electrolyte in the first embodiment.
- the solid electrolyte contained in the electrolyte layer 302 may be a halide solid electrolyte.
- the halide solid electrolyte means a solid electrolyte containing a halogen element and not containing sulfur.
- a solid electrolyte that does not contain sulfur means a solid electrolyte represented by a composition formula that does not contain elemental sulfur. Therefore, solid electrolytes containing a very small amount of sulfur, such as 0.1% by mass or less of sulfur, are included in solid electrolytes that do not contain sulfur.
- the halide solid electrolyte may further contain oxygen as an anion other than the halogen element.
- the solid electrolyte contained in the electrolyte layer 302 may be a sulfide solid electrolyte, an oxide solid electrolyte, a polymer solid electrolyte, or a complex hydride solid electrolyte.
- the sulfide solid electrolyte contained in the electrolyte layer 302 is a sulfide solid electrolyte
- the sulfide solid electrolyte includes Li 2 SP 2 S 5 , Li 2 S—SiS 2 , Li 2 SB 2 S 3 , Li 2 S—GeS 2 , Li 3.25 Ge 0.25 P 0.75 S 4 , Li 10 GeP 2 S 12 and the like can be used.
- LiX, Li2O , MOq , LipMOq , etc. may be added to these.
- Element X in "LiX" is at least one element selected from the group consisting of F, Cl, Br, and I.
- Element M in “MO q " and “Li p MO q” is at least one element selected from the group consisting of P, Si, Ge, B, Al, Ga, In, Fe, and Zn.
- p and q in “MO q “ and “L p MO q " are independent natural numbers.
- the electrolyte layer 302 contains a sulfide solid electrolyte with excellent reduction stability, a low-potential negative electrode material such as graphite or metallic lithium can be used, and the energy density of the battery 3000 can be improved. can be done.
- oxide solid electrolyte examples include NASICON-type solid electrolytes (LaLi), represented by LiTi 2 (PO 4 ) 3 and element-substituted products thereof.
- TiO3 -based perovskite- type solid electrolytes LISICON- type solid electrolytes typified by Li14ZnGe4O16 , Li4SiO4 , LiGeO4 and elemental substitutions thereof , Li7La3Zr2O12 and elemental substitutions thereof
- Garnet - type solid electrolytes represented by Glass or glass-ceramics to which materials such as Li 2 SO 4 and Li 2 CO 3 are added may be used.
- the solid electrolyte contained in the electrolyte layer 302 is a polymer solid electrolyte
- a polymer compound and a lithium salt compound can be used as the polymer solid electrolyte.
- the polymer compound may have an ethylene oxide structure. By having an ethylene oxide structure, the polymer compound can contain a large amount of lithium salt. Therefore, the ionic conductivity can be further increased.
- Lithium salts include LiPF6 , LiBF4 , LiSbF6, LiAsF6 , LiSO3CF3 , LiN ( SO2F )2, LiN(SO2CF3)2 , LiN ( SO2C2F5 ) 2 , LiN( SO2CF3 ) (SO2C4F9 ) , and LiC( SO2CF3 ) 3 , etc. may be used .
- the lithium salt one lithium salt selected from these may be used alone, or a mixture of two or more lithium salts selected from these may be used.
- LiBH 4 --LiI, LiBH 4 --P 2 S 5 or the like can be used as the complex hydride solid electrolyte.
- the electrolyte layer 302 may contain a solid electrolyte as a main component. That is, the electrolyte layer 302 may contain, for example, 50% or more (that is, 50% or more by mass) of the solid electrolyte in terms of mass ratio with respect to the entire electrolyte layer 302 .
- the charge/discharge characteristics of the battery 3000 can be further improved.
- the electrolyte layer 302 may contain 70% or more (that is, 70% or more by mass) of solid electrolyte in terms of mass ratio with respect to the entire electrolyte layer 302 .
- the charge/discharge characteristics of the battery 3000 can be further improved.
- the electrolyte layer 302 contains a solid electrolyte as a main component, and may also contain unavoidable impurities, or starting materials, by-products, decomposition products, etc. used when synthesizing the solid electrolyte.
- the electrolyte layer 302 may contain, for example, 100% (that is, 100% by mass) of solid electrolyte in terms of mass ratio with respect to the entire electrolyte layer 302, excluding impurities that are unavoidably mixed.
- the charge/discharge characteristics of the battery 3000 can be further improved.
- the electrolyte layer 302 may be composed only of the solid electrolyte.
- the electrolyte layer 302 may contain two or more of the above materials exemplified as the solid electrolyte contained in the electrolyte layer 302 .
- electrolyte layer 302 may include a halide solid electrolyte and a sulfide solid electrolyte.
- the thickness of the electrolyte layer 302 may be 1 ⁇ m or more and 300 ⁇ m or less. When the thickness of the electrolyte layer 302 is 1 ⁇ m or more, the short circuit between the positive electrode 301 and the negative electrode 303 is less likely to occur. When the thickness of electrolyte layer 302 is 300 ⁇ m or less, battery 3000 can operate at high output.
- the negative electrode 303 includes a material that has the property of intercalating and deintercalating metal ions (eg, lithium ions).
- the negative electrode 303 contains, for example, a negative electrode active material.
- Metal materials, carbon materials, oxides, nitrides, tin compounds, silicon compounds, and the like can be used as negative electrode active materials.
- the metal material may be a single metal.
- the metal material may be an alloy.
- metallic materials include lithium metal, lithium alloys, and the like.
- carbon materials include natural graphite, coke, ungraphitized carbon, carbon fiber, spherical carbon, artificial graphite, and amorphous carbon.
- Silicon (Si), tin (Sn), silicon compounds, and tin compounds can be used in terms of capacity density.
- the negative electrode 303 may contain a solid electrolyte.
- the solid electrolyte the above-described materials exemplified as the solid electrolyte contained in the electrolyte layer 302 may be used. According to the above configuration, the lithium ion conductivity inside the negative electrode 303 is increased, and the operation of the battery 3000 at high output becomes possible.
- the median diameter of the particles of the negative electrode active material may be 0.1 ⁇ m or more and 100 ⁇ m or less.
- the median diameter of the particles of the negative electrode active material is 0.1 ⁇ m or more, the negative electrode active material and the solid electrolyte can form a good dispersion state in the negative electrode. Thereby, the charge/discharge characteristics of the battery 3000 are improved.
- the median diameter of the particles of the negative electrode active material is 100 ⁇ m or less, diffusion of lithium in the negative electrode active material becomes faster. Therefore, battery 3000 can operate at high output.
- the median diameter of the particles of the negative electrode active material may be larger than the median diameter of the particles of the solid electrolyte contained in the negative electrode 303 . Thereby, the particles of the negative electrode active material and the particles of the solid electrolyte can be well dispersed.
- the volume ratio "v2:100-v2" between the negative electrode active material and the solid electrolyte contained in the negative electrode 303 may satisfy 30 ⁇ v2 ⁇ 95.
- v2 represents the volume ratio of the negative electrode active material when the total volume of the negative electrode active material and the solid electrolyte contained in the negative electrode 303 is taken as 100.
- 30 ⁇ v2 a sufficient energy density of the battery 3000 can be secured.
- v2 ⁇ 95 the battery 3000 can operate at high output.
- the thickness of the negative electrode 303 may be 10 ⁇ m or more and 500 ⁇ m or less. When the thickness of the negative electrode 303 is 10 ⁇ m or more, a sufficient energy density of the battery 3000 can be secured. When the thickness of negative electrode 303 is 500 ⁇ m or less, battery 3000 can operate at high output.
- At least one of the positive electrode 301, the electrolyte layer 302, and the negative electrode 303 may contain a binder for the purpose of improving adhesion between particles.
- a binder is used to improve the binding properties of the material that constitutes the electrode. Binders include polyvinylidene fluoride, polytetrafluoroethylene, polyethylene, polypropylene, aramid resin, polyamide, polyimide, polyamideimide, polyacrylonitrile, polyacrylic acid, polyacrylic acid methyl ester, polyacrylic acid ethyl ester, poly Acrylate hexyl ester, polymethacrylic acid, polymethacrylic acid methyl ester, polymethacrylic acid ethyl ester, polymethacrylic acid hexyl ester, polyvinyl acetate, polyvinylpyrrolidone, polyether, polyethersulfone, hexafluoropolypropylene, styrene-butadiene rubber,
- Binders include tetrafluoroethylene, hexafluoroethylene, hexafluoropropylene, perfluoroalkyl vinyl ether, vinylidene fluoride, chlorotrifluoroethylene, ethylene, propylene, pentafluoropropylene, fluoromethyl vinyl ether, acrylic acid, and Copolymers of two or more materials selected from the group consisting of hexadiene can be used. A mixture of two or more selected from these may also be used.
- At least one of the positive electrode 301 and the negative electrode 303 may contain a conductive aid for the purpose of increasing electronic conductivity.
- conductive aids include graphites such as natural graphite and artificial graphite, carbon blacks such as acetylene black and Ketjen black, conductive fibers such as carbon fiber and metal fiber, carbon fluoride, and metal powder such as aluminum.
- conductive whiskers such as zinc oxide and potassium titanate, conductive metal oxides such as titanium oxide, and conductive polymeric compounds such as polyaniline, polypyrrole, and polythiophene. Cost reduction can be achieved when a carbon conductive aid is used as the conductive aid.
- At least one of the positive electrode 301, the electrolyte layer 302, and the negative electrode 303 may contain a dispersant for the purpose of improving the dispersibility of each constituent member.
- the battery 3000 can be configured as batteries of various shapes such as, for example, coin-shaped, cylindrical, rectangular, sheet-shaped, button-shaped, flat-shaped, and stacked-type.
- the X-ray diffraction pattern was measured by the ⁇ -2 ⁇ method using Cu-K ⁇ rays (wavelengths of 1.5405 ⁇ and 1.5444 ⁇ ) as the X-ray source.
- 6 is a graph showing X-ray diffraction patterns of solid electrolytes according to Examples 1 to 3 and Comparative Example 1.
- a solid electrolyte composed of Li, Ta, O, and Cl is hereinafter referred to as LTOC.
- LTOC was prepared as a solid electrolyte
- NCA lithium nickel-cobalt aluminum oxide
- LTOC, NCA, a conductive aid, and a binder were placed in a commercially available polypropylene container, an organic solvent was further added, and the mixture was stirred with an ultrasonic homogenizer. The amount of the organic solvent was adjusted so that the solid content ratio of the resulting positive electrode material was 76.5%.
- Carbon fiber (VGCF-H) was used as a conductive aid.
- SBR styrene butadiene rubber
- VGCF is a registered trademark of Showa Denko K.K.
- a sulfide solid electrolyte Li 2 SP 2 S 5 equivalent to a thickness of 550 ⁇ m (approximately 80 mg) and a positive electrode plate were laminated in this order in an insulating outer cylinder.
- the positive electrode plate was arranged such that the positive electrode of the positive electrode plate faced the sulfide solid electrolyte.
- dried electrode plates were punched out with a diameter of 9.4 mm and laminated.
- metal Li was laminated on the side of the solid electrolyte layer opposite to the side in contact with the positive electrode.
- a pressure of 80 MPa a laminate composed of a positive electrode, an electrolyte layer, and a negative electrode was produced.
- an insulating ferrule was used to isolate and seal the inside of the insulating outer cylinder from the outside atmosphere.
- Constant current charging was performed at a rate of 0.05C (20 hour rate) for the theoretical capacity of the battery.
- the charge end voltage was set to 4.3 V (vs. Li).
- the discharge termination was set to a voltage of 2.5 V (vs. Li).
- Table 1 shows the initial charge/discharge efficiency of each battery of Examples 1 to 3 and Comparative Example 1.
- the positive electrode material was prepared by the method described above and dried in an argon atmosphere by the method described above. Using this, a battery was produced and a charge/discharge test was carried out.
- Example 2>> Mesitylene with a boiling point of 165° C. was used as organic solvent.
- the polarity term ⁇ p in the Hansen solubility parameter of mesitylene is 0.6.
- the positive electrode material was prepared by the method described above and dried in an argon atmosphere by the method described above. Using this, a battery was produced and a charge/discharge test was carried out.
- Tetralin with a boiling point of 208° C. was used as the organic solvent.
- the polarity term ⁇ p in the Hansen solubility parameter of tetralin is 2.0.
- the positive electrode material was prepared by the method described above and dried in an argon atmosphere by the method described above. Using this, a battery was produced and a charge/discharge test was carried out.
- organic solvent 1,2,4-trichlorobenzene with a boiling point of 213° C. was used.
- the polar term ⁇ p in the Hansen solubility parameter of 1,2,4-trichlorobenzene is 4.2.
- the positive electrode material was prepared by the method described above and dried in an argon atmosphere by the method described above. Using this, a secondary battery was produced and a charge/discharge test was conducted.
- Table 1 shows the charge-discharge efficiency of the batteries of Examples 1 to 3 and Comparative Example 1, in which the positive electrodes were prepared using organic solvents with different boiling points.
- the battery of the present disclosure can be used, for example, as an all-solid lithium ion secondary battery.
- positive electrode material 100 solid electrolyte 110 positive electrode active material 111 organic solvent 2000 positive electrode plate 201 positive electrode 202 current collector 3000 battery 301 positive electrode 302 solid electrolyte layer 303 negative electrode
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Abstract
Description
正極活物質と、
固体電解質と、
有機溶媒と、
を含み、
前記固体電解質は、Li、M、O、およびXを含み、
前記Mは、TaおよびNbからなる群より選択される少なくとも1つであり、
前記Xは、F、Cl、Br、およびIからなる群より選択される少なくとも1つであり、
前記有機溶媒は、212℃以下の沸点を有する。
従来、高エネルギー密度化と大容量化が求められる二次電池の分野では、有機溶媒に電解質塩を溶解させた有機電解液を用いることが主流である。有機電解液を用いる二次電池では、液漏れの懸念があり、短絡などが生じた場合の発熱量が大きくなる可能性も指摘されている。
本開示の第1態様に係る正極用材料は、
正極活物質と、
固体電解質と、
有機溶媒と、
を含み、
前記固体電解質は、Li、M、O、およびXを含み、
前記Mは、TaおよびNbからなる群より選択される少なくとも1つであり、
前記Xは、F、Cl、Br、およびIからなる群より選択される少なくとも1つであり、
前記有機溶媒は、212℃以下の沸点を有する。
第1から第13態様のいずれか1つに係る正極用材料から前記有機溶媒を除去すること、
を含む。
第1から第13態様のいずれか1つに係る正極用材料を集電体上に塗布することと、
前記集電体上に塗布された前記正極用材料から前記有機溶媒を除去することと、
を含む。
第1から第13態様のいずれか1つに係る正極用材料から前記有機溶媒を除去することによって前記正極を得ること、
を含む。
以下、実施の形態1に係る正極用材料が説明される。
正極活物質110は、金属イオン(例えば、リチウムイオン)を吸蔵および放出する特性を有する材料を含む。正極活物質110として、例えば、リチウム含有遷移金属酸化物、遷移金属フッ化物、ポリアニオン材料、フッ素化ポリアニオン材料、遷移金属硫化物、遷移金属オキシ硫化物、または遷移金属オキシ窒化物などが用いられうる。リチウム含有遷移金属酸化物の例としては、Li(Ni,Co,Al)O2、Li(Ni,Co,Mn)O2、LiCoO2などが挙げられる。特に、正極活物質110として、リチウム含有遷移金属酸化物が用いられた場合には、正極の製造コストを安くでき、平均放電電圧を高めることができる。
固体電解質100は、Li、M、O、およびXを含む。Xは、F、Cl、Br、およびIからなる群より選択される少なくとも1つである。すなわち、正極用材料1000は、オキシハライド固体電解質を含む。オキシハライド固体電解質は、例えば、リチウムイオン伝導性を有し得る。
上述のとおり、有機溶媒111は、212℃以下の沸点を有する。このような有機溶媒111を含むことにより、正極用材料1000は、残存溶媒が低減された正極を製造することができる。このようにして得られた正極では、残存溶媒に起因する抵抗の増大が抑制される。したがって、正極用材料1000は、電池の充放電効率を向上させ得る正極の製造に適している。なお、本明細書において、「沸点」は、液体の飽和蒸気圧が1気圧と等しくなる温度を指す。
正極用材料1000には、粒子同士の密着性を向上させる目的で、結着剤が含まれてもよい。結着剤は、電極を構成する材料の結着性を向上させるために用いられる。結着剤としては、ポリフッ化ビニリデン、ポリテトラフルオロエチレン、ポリエチレン、ポリプロピレン、アラミド樹脂、ポリアミド、ポリイミド、ポリアミドイミド、ポリアクリルニトリル、ポリアクリル酸、ポリアクリル酸メチルエステル、ポリアクリル酸エチルエステル、ポリアクリル酸ヘキシルエステル、ポリメタクリル酸、ポリメタクリル酸メチルエステル、ポリメタクリル酸エチルエステル、ポリメタクリル酸ヘキシルエステル、ポリ酢酸ビニル、ポリビニルピロリドン、ポリエーテル、ポリエーテルサルフォン、ヘキサフルオロポリプロピレン、スチレンブタジエンゴム、およびカルボキシメチルセルロース、などが挙げられる。また、結着剤としては、テトラフルオロエチレン、ヘキサフルオロエチレン、ヘキサフルオロプロピレン、パーフルオロアルキルビニルエーテル、フッ化ビニリデン、クロロトリフルオロエチレン、エチレン、プロピレン、ペンタフルオロプロピレン、フルオロメチルビニルエーテル、アクリル酸、およびヘキサジエンからなる群より選択される2種以上の材料の共重合体が用いられうる。また、これらのうちから選択された2種以上の混合物が用いられてもよい。
以下、実施の形態2に係る正極の製造方法が説明される。実施の形態1と重複する内容は、適宜、省略される。
以下、実施の形態3に係る正極板の製造方法が説明される。実施の形態1および実施の形態2と重複する内容は、適宜、省略される。
以下、実施の形態4に係る電池の製造方法が説明される。実施の形態1、実施の形態2、および実施の形態3と重複する内容は、適宜、省略される。
アルゴン雰囲気中で、原料としてLi2O2、TaCl5とを、Li2O2:TaCl5=1:2のモル比となるように秤量した。その後、遊星ボールミル(フリッチュ社製、P-7型)を用い、12時間、600rpmでミリング処理した。さらに、200℃で3時間処理して、Li、Ta、O、およびClからなる結晶相を含有する、実施例1から3および比較例1の固体電解質が得られた。得られた固体電解質について、X線回折装置(Rigaku社、MiniFlex600)を用いて、固体電解質のX線回折パターンが測定された。X線源として、Cu-Kα線(波長1.5405Åおよび1.5444Å)を用い、θ-2θ法によりX線回折パターンが測定された。図6は、実施例1から3および比較例1による固体電解質のX線回折パターンを示すグラフである。図6に示されているように、実施例1から3および比較例1による固体電解質は、回折角2θ=11.08°にピークを有しており、すなわち11.05°以上かつ13.86°以下の回折角2θの範囲に少なくとも1つのピークが存在していた。以下、Li、Ta、O、およびClからなる固体電解質を、LTOCと記す。
固体電解質としてLTOC、正極活物質としてニッケルコバルトアルミニウム酸リチウム(以下、NCAと記す)を準備した。市販のポリプロピレン容器に、LTOC、NCA、導電助剤、および結着剤を入れ、さらにこれに有機溶媒を加え、超音波ホモジナイザーにて攪拌した。得られる正極用材料の固形分比率が76.5%となるように、有機溶媒量を調節した。導電助剤として、カーボンファイバー(VGCF-H)が用いられた。結着剤として、SBR(スチレンブタジエンゴム)が用いられた。なお、VGCFは、昭和電工株式会社の登録商標である。
アルミ箔(厚み15μm)を集電体として用いた。この集電体上に正極用材料を塗工し、ホットプレートに載せてアルゴン雰囲気中で有機溶媒を除去した。乾燥条件は、50℃、30分で仮乾燥した後、110℃、30分本乾燥を実施した。有機溶媒の除去は、目視により確認した。目視にて正極板が得られたと判断した場合「乾燥できた」と判断した。
絶縁性外筒の中で、硫化物固体電解質Li2S-P2S5を厚さ550μm相当分(約80mg)と、正極板を、この順に積層した。正極板は、正極板における正極が硫化物固体電解質に面する向きで配置された。正極板は、乾燥した極板をφ9.4mmで打ち抜き積層した。
電池を25℃の恒温槽に配置した。
有機溶媒として、140℃の沸点を有するキシレンが用いられた。なお、キシレンのハンセンの溶解度パラメーターにおける極性項δpは、1.0である。上述の方法で正極用材料を調整し、上述の方法にてアルゴン雰囲気中で乾燥した。これを用いて電池を作製し充放電試験を実施した。
有機溶媒として、165℃の沸点を有するメシチレンが用いられた。なお、メシチレンのハンセンの溶解度パラメーターにおける極性項δpは、0.6である。上述の方法で正極用材料を調整し、上述の方法にてアルゴン雰囲気中で乾燥した。これを用いて電池を作製し充放電試験を実施した。
有機溶媒として、208℃の沸点を有するテトラリンが用いられた。なお、テトラリンのハンセンの溶解度パラメーターにおける極性項δpは、2.0である。上述の方法で正極用材料を調整し、上述の方法にてアルゴン雰囲気中で乾燥した。これを用いて電池を作製し充放電試験を実施した。
有機溶媒として、213℃の沸点を有する1,2,4-トリクロロベンゼンが用いられた。なお、1,2,4-トリクロロベンゼンのハンセンの溶解度パラメーターにおける極性項δpは、4.2である。上述の方法で正極用材料を調整し、上述の方法にてアルゴン雰囲気中で乾燥した。これを用いて二次電池を作製し充放電試験を実施した。
表1は、沸点の異なる有機溶媒を用いて正極が作製された、実施例1から3および比較例1の電池の充放電効率を示している。沸点が212℃以下である有機溶媒が用いられた実施例1から3の電池は、沸点が212℃を超える有機溶媒が用いられた比較例1の電池と比較して、充放電効率が劇的に向上した。これは、比較例1では乾燥時に溶媒が多く残存してしまい、この残像溶媒により高電位側でオキシハライド固体電解質が劣化したことに起因すると考えられる。
100 固体電解質
110 正極活物質
111 有機溶媒
2000 正極板
201 正極
202 集電体
3000 電池
301 正極
302 固体電解質層
303 負極
Claims (16)
- 正極活物質と、
固体電解質と、
有機溶媒と、
を含み、
前記固体電解質は、Li、M、O、およびXを含み、
前記Mは、TaおよびNbからなる群より選択される少なくとも1つであり、
前記Xは、F、Cl、Br、およびIからなる群より選択される少なくとも1つであり、
前記有機溶媒は、212℃以下の沸点を有する、
正極用材料。 - 前記有機溶媒は、208℃以下の沸点を有する、
請求項1に記載の正極用材料。 - 前記固体電解質において、前記XはClを含む、
請求項1または2に記載の正極用材料。 - 前記固体電解質は、Cu-Kα線を線源として用いたX線回折測定によって得られるX線回折パターンにおいて、11.05°以上かつ13.86°以下の回折角2θの範囲に少なくとも1つのピークが存在する結晶相を含む、
請求項1から3のいずれか一項に記載の正極用材料。 - 前記固体電解質において、
前記Xに対するOのモル比O/Xは、0.16以上0.35以下である、
請求項1から4のいずれか一項に記載の正極用材料。 - 前記固体電解質において、
前記Mに対するLiのモル比Li/Mは、0.60以上2.4以下である、
請求項1から5のいずれか一項に記載の正極用材料。 - 前記モル比Li/Mは、0.96以上1.20以下である、
請求項6に記載の正極用材料。 - 前記有機溶媒は、ハロゲン基を有する化合物および炭化水素からなる群より選択される少なくとも1つを含む、
請求項1から7のいずれか一項に記載の正極用材料。 - 前記ハロゲン基を有する化合物は、官能基として、ハロゲン基のみを有する、
請求項8に記載の正極用材料。 - 前記有機溶媒は、芳香族化合物を含む、
請求項1から9のいずれか一項に記載の正極用材料。 - 前記有機溶媒は、テトラリン、メシチレン、キシレン、クメン、プソイドクメン、エチルベンゼン、クロロベンゼン、2,4-ジクロロベンゼン、o-クロロトルエン、1,3-ジクロロベンゼン、p-クロロトルエン、1,2-ジクロロベンゼン、1,4-ジクロロブタン、2,4-ジクロロトルエン、および3,4-ジクロロトルエンからなる群より選択される少なくとも1つを含む、
請求項1から10のいずれか一項に記載の正極用材料。 - 前記有機溶媒は、テトラリン、メシチレン、およびキシレンからなる群より選択される少なくとも1つを含む、
請求項11に記載の正極用材料。 - 前記有機溶媒は、ハンセンの溶解度パラメーターにおける極性項δpが4.3以下である、
請求項1から12のいずれか一項に記載の正極用材料。 - 請求項1から13のいずれか一項に記載の正極用材料から前記有機溶媒を除去すること、
を含む正極の製造方法。 - 請求項1から13のいずれか一項に記載の正極用材料を集電体上に塗布することと、
前記集電体上に塗布された前記正極用材料から前記有機溶媒を除去することと、
を含む、正極板の製造方法。 - 正極と、負極と、前記正極と前記負極との間に位置する固体電解質層と、を備えた電池の製造方法であって、
請求項1から13のいずれか一項に記載の正極用材料から前記有機溶媒を除去することによって前記正極を得ること、
を含む、電池の製造方法。
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JPWO2022249796A1 (ja) | 2022-12-01 |
EP4349786A1 (en) | 2024-04-10 |
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