WO2021241418A1 - 正極活物質、正極材料、電池、および正極活物質の製造方法 - Google Patents

正極活物質、正極材料、電池、および正極活物質の製造方法 Download PDF

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WO2021241418A1
WO2021241418A1 PCT/JP2021/019287 JP2021019287W WO2021241418A1 WO 2021241418 A1 WO2021241418 A1 WO 2021241418A1 JP 2021019287 W JP2021019287 W JP 2021019287W WO 2021241418 A1 WO2021241418 A1 WO 2021241418A1
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positive electrode
active material
electrode active
solid electrolyte
battery
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English (en)
French (fr)
Japanese (ja)
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勇祐 西尾
好政 名嘉真
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Panasonic Intellectual Property Management Co Ltd
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Panasonic Intellectual Property Management Co Ltd
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Priority to EP21814544.9A priority Critical patent/EP4160742A4/en
Priority to CN202180036610.5A priority patent/CN115699364A/zh
Priority to JP2022526970A priority patent/JP7756341B2/ja
Publication of WO2021241418A1 publication Critical patent/WO2021241418A1/ja
Priority to US18/051,871 priority patent/US20230084392A1/en
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    • H—ELECTRICITY
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    • H01M4/02—Electrodes composed of, or comprising, active material
    • 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
    • C—CHEMISTRY; METALLURGY
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    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
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    • C01B17/22—Alkali metal sulfides or polysulfides
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    • C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
    • C01D15/00—Lithium compounds
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    • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F17/00—Compounds of rare earth metals
    • C01F17/30—Compounds containing rare earth metals and at least one element other than a rare earth metal, oxygen or hydrogen, e.g. La4S3Br6
    • C01F17/36—Compounds containing rare earth metals and at least one element other than a rare earth metal, oxygen or hydrogen, e.g. La4S3Br6 halogen being the only anion, e.g. NaYF4
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    • C01G53/42—Complex oxides containing nickel and at least one other metal element containing alkali metals, e.g. LiNiO2
    • C01G53/44—Complex oxides containing nickel and at least one other metal element containing alkali metals, e.g. LiNiO2 containing manganese
    • C01G53/50—Complex oxides containing nickel and at least one other metal element containing alkali metals, e.g. LiNiO2 containing manganese of the type (MnO2)n-, e.g. Li(NixMn1-x)O2 or Li(MyNixMn1-x-y)O2
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    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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    • 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
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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
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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
    • H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • H—ELECTRICITY
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    • H01M4/36—Selection of substances as active materials, active masses, active liquids
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    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
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    • H01M4/02—Electrodes composed of, or comprising, active material
    • 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
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • H—ELECTRICITY
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    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H—ELECTRICITY
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    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
    • C01P2004/82—Particles consisting of a mixture of two or more inorganic phases two phases having the same anion, e.g. both oxidic phases
    • C01P2004/84—Particles consisting of a mixture of two or more inorganic phases two phases having the same anion, e.g. both oxidic phases one phase coated with the other
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
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    • C01P2006/80—Compositional purity
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    • 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
    • H—ELECTRICITY
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    • 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
    • H—ELECTRICITY
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    • 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
    • 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 active material, a positive electrode material, a battery, and a method for manufacturing a positive electrode active material.
  • Patent Document 1 discloses an all-solid-state battery having a coating layer containing a coating material on the surface and using a positive electrode active material and a sulfide solid electrolyte dried in the range of 120 ° C to 300 ° C.
  • the present disclosure provides a battery having a high capacity retention rate at high temperature storage.
  • the positive electrode active material of the present disclosure contains a composite oxide represented by the following formula (1) as a main component, and has a hydrogen element content of 238.8 mass ppm or less.
  • x satisfies 0.5 ⁇ x ⁇ 1
  • Me is at least one element selected from the group consisting of Mn, Co, and Al.
  • FIG. 1 is a cross-sectional view showing a schematic configuration of the positive electrode material 1000 and the battery 2000 in the first and second embodiments.
  • the present inventor has diligently studied the factors that deteriorate the capacity when the battery is stored at high temperature. As a result, the present inventor has found that the elemental hydrogen contained in the active material reacts with the solid electrolyte to deteriorate the capacity. Based on this finding, the present inventor considered that measures for reducing water content, hydrated water, hydroxyl groups, hydrogen ions in the crystal structure, etc. in the active material were necessary, and proceeded with further research. As a result, it was found that the amount of hydrogen contained in the active material can be significantly reduced by drying under predetermined conditions. When a battery was manufactured using the active material thus manufactured, deterioration of the capacity could be reduced by high-temperature storage in a charged state.
  • the positive electrode active material according to the first aspect of the present disclosure is The main component is the composite oxide represented by the following formula (1), and the hydrogen element content is 238.8 mass ppm or less.
  • x satisfies 0.5 ⁇ x ⁇ 1
  • Me is at least one element selected from the group consisting of Mn, Co, and Al.
  • the positive electrode active material according to the first aspect contains a small amount of hydrogen. Therefore, it is possible to suppress the deterioration of the capacity of the battery using the positive electrode active material according to the first aspect in high temperature storage.
  • the hydrogen element content may be 114.3 mass ppm or less.
  • the positive electrode active material according to the second aspect can suppress the deterioration of the capacity of the battery during high temperature storage.
  • the positive electrode active material according to the first or second aspect further comprises a coating material for coating the surface of the positive electrode active material, and the coating material is composed of lithium element (Li). It may contain at least one element selected from the group consisting of an oxygen element (O), a fluorine element (F), and a chlorine element (Cl).
  • the positive electrode active material according to the third aspect can suppress the deterioration of the capacity of the battery during high temperature storage.
  • the coating material is lithium niobate, lithium phosphate, lithium titanate, lithium tungstate, lithium fluoride zirconate, aluminum fluoride. It may contain at least one selected from the group consisting of lithium acid, lithium titanate fluoride, and lithium magnesium fluoride.
  • the positive electrode active material according to the fourth aspect can suppress the deterioration of the capacity of the battery during high temperature storage.
  • the positive electrode material according to the fifth aspect of the present disclosure is The positive electrode active material and the solid electrolyte according to any one of the first to fourth aspects are included.
  • the positive electrode material according to the fifth aspect can suppress deterioration of the capacity of the battery due to high temperature storage.
  • the solid electrolyte is represented by the following formula (2).
  • ⁇ , ⁇ , and ⁇ are independently greater than 0, respectively.
  • M comprises at least one selected from the group consisting of metallic elements other than Li and metalloid elements.
  • X comprises at least one selected from the group consisting of F, Cl, Br, and I.
  • the positive electrode material according to the sixth aspect can suppress the deterioration of the capacity of the battery due to high temperature storage.
  • the M may contain yttrium.
  • the positive electrode material according to the eighth aspect can suppress the deterioration of the capacity of the battery due to high temperature storage.
  • the X may contain at least one selected from the group consisting of Cl and Br.
  • the battery according to the tenth aspect of the present disclosure is A positive electrode containing a positive electrode material according to any one of the fifth to ninth aspects, and a positive electrode. With the negative electrode An electrolyte layer arranged between the positive electrode and the negative electrode, To prepare for.
  • the battery according to the tenth aspect can suppress the deterioration of the capacity due to high temperature storage.
  • the electrolyte layer may contain the solid electrolyte.
  • the battery according to the eleventh aspect can suppress the deterioration of the capacity due to high temperature storage.
  • the electrolyte layer may contain a halide solid electrolyte different from the solid electrolyte.
  • the battery according to the twelfth aspect can suppress the deterioration of the capacity due to high temperature storage.
  • the electrolyte layer may contain a sulfide solid electrolyte.
  • the battery according to the thirteenth aspect can suppress the deterioration of the capacity due to high temperature storage.
  • the method for producing a positive electrode active material according to the 14th aspect of the present disclosure is as follows.
  • a method for producing a positive electrode active material according to any one of the first to fourth aspects. At least one selected from the group consisting of the production method of drying at a temperature of 70 ° C. or higher and lower than 400 ° C. for 1 hour or longer, and drying at a temperature of 500 ° C. or higher and 850 ° C. or lower for 0.5 hours or longer. including.
  • a positive electrode active material having a small amount of hydrogen can be produced. As a result, deterioration of the capacity of the battery due to high temperature storage can be suppressed.
  • FIG. 1 is a cross-sectional view showing a schematic configuration of the positive electrode material 1000 according to the first embodiment.
  • the positive electrode material 1000 in the first embodiment includes a solid electrolyte 100 and a positive electrode active material 110. As shown in FIG. 1, the positive electrode active material 110 and the solid electrolyte 100 are, for example, in the form of particles.
  • the positive electrode active material 110 contains a composite oxide represented by the following formula (1) as a main component, and has a hydrogen element content of 238.8 mass ppm or less.
  • x satisfies 0.5 ⁇ x ⁇ 1
  • Me is at least one element selected from the group consisting of Mn, Co, and Al.
  • the capacity retention rate of the battery at high temperature storage can be improved.
  • the “main component” is the component contained most in the mass ratio.
  • the hydrogen element content of the positive electrode active material 110 is measured by a non-dispersive infrared absorption method (NDIR), for example, an inert gas melting-non-dispersion infrared absorption method.
  • NDIR non-dispersive infrared absorption method
  • the hydrogen element content of the positive electrode active material 110 may be 114.3 mass ppm or less.
  • the hydrogen element content of the positive electrode active material 110 may be 61.6 mass ppm or more.
  • the positive electrode active material 110 has a low hydrogen element content of 238.8 mass ppm or less. As a result, the reaction between the hydrogen element contained in the positive electrode active material 110 and the solid electrolyte is suppressed, so that the positive electrode active material 110 can improve the capacity retention rate in the high temperature storage of the battery.
  • the positive electrode active material 110 may contain a material that can be used as an active material for an all-solid-state lithium-ion battery, in addition to the composite oxide represented by the formula (1).
  • LiCoO 2 LiNi x Co 1-x O 2 (0 ⁇ x ⁇ 0.5), LiNi 1/3 Co 1/3 Mn 1/3 O 2 , LiMnO 2 , dissimilar element substituted Li-Mn spinel (eg LiMn 1.5) Ni 0.5 O 4 , LiMn 1.5 Al 0.5 O 4 , LiMn 1.5 Mg 0.5 O 4 , LiMn 1.5 Co 0.5 O 4 , LiMn 1.5 Fe 0.5 O 4 or LiMn 1.5 Zn 0.5 O 4 ), Lithium titanate (eg Li 4 Ti) 5 O 12 ), lithium metal phosphate (eg LiFePO 4 , LiMnPO 4 , LiCoPO 4 , or LiNiPO 4 ), transition metal oxides (eg V 2 O 5 , MoO 3 ).
  • LiMn 1.5 Ni 0.5 O 4
  • LiMn 1.5 Al 0.5 O 4 LiMn 1.5 Mg 0.5 O 4
  • LiMn 1.5 Co 0.5 O 4 LiMn 1.5 Fe 0.5 O 4 or LiMn 1.5 Zn
  • LiCoO 2 LiNi x Co 1-x O 2 (0 ⁇ x ⁇ 0.5), LiNi 1/3 Co 1/3 Mn 1/3 O 2 , LiMnO 2 , dissimilar element substitution Li- Lithium-containing composite oxides selected from Mn spinel, lithium metal phosphate, and the like are preferred.
  • the positive electrode active material 110 has a hydrogen element content of 238.8 mass ppm or less. By suppressing the hydrogen element content in the positive electrode active material 110 to 238.8 mass ppm or less, when applied to an all-solid-state lithium-ion battery, the solid electrolyte 100 and the positive electrode active material 110 described later at high temperature and high potential are used. Side reaction with hydrogen contained in can be suppressed. Therefore, by using the positive electrode active material 110, a battery having a high capacity retention rate in high temperature storage can be obtained.
  • the positive electrode active material 110 is preheated at a temperature of 70 ° C. or higher and lower than 400 ° C. for 1 hour or longer and / or at a temperature of 500 ° C. or higher and 850 ° C. or lower for 0.5 hours or longer before forming the positive electrode material.
  • the atmosphere at the time of drying may be an atmosphere with a dew point of ⁇ 60 ° C. or lower under vacuum or normal pressure. As long as the dew point is ⁇ 60 ° C. or lower, it may be in nitrogen gas or oxygen gas.
  • the hydrogen element content of the dried positive electrode active material 110 is measured by NDIR.
  • the positive electrode active material 110 may be dried in advance by heating at 70 ° C. or higher and lower than 150 ° C. for 12 hours or more before forming the positive electrode material, and the positive electrode active material 110 may be dried in advance before forming the positive electrode material. Select from the group consisting of heating for 12 hours or more in the range of 70 ° C or higher and lower than 150 ° C, 0.5 hours or longer in the range of 150 ° C or higher and lower than 400 ° C, and 0.5 hours or longer in the range of 500 ° C or higher and 850 ° C or lower. It may be dried by at least one heating.
  • Heating in the range of 70 ° C or higher and lower than 150 ° C may be 500 hours or less. That is, heating in the range of 70 ° C. or higher and lower than 150 ° C. may be 12 hours or longer and 500 hours or shorter. Heating in the range of 70 ° C. or higher and lower than 150 ° C. may be 24 hours or longer and 350 hours or shorter.
  • At least one selected from the group consisting of heating in the range of 150 ° C. or higher and lower than 400 ° C. and heating in the range of 500 ° C. or higher and 850 ° C. or lower may be 24 hours or less. That is, at least one selected from the group consisting of heating in the range of 150 ° C. or higher and lower than 400 ° C. and heating in the range of 500 ° C. or higher and 850 ° C. or lower may be 0.5 hours or longer and 24 hours or shorter. .. At least one selected from the group consisting of heating in the range of 150 ° C. or higher and lower than 400 ° C. and heating in the range of 500 ° C. or higher and 850 ° C. or lower may be 1 hour or more and 12 hours or less.
  • the positive electrode active material 110 may be provided with a coating material 120 on the surface.
  • the covering material 120 may cover the entire surface of the positive electrode active material 110, or may partially cover the surface.
  • the coating material 120 may contain Li and at least one element selected from the group consisting of O, F, and Cl.
  • the coating material 120 is selected from the group consisting of lithium niobate, lithium phosphate, lithium titanate, lithium tungstate, lithium zirconium fluoride, lithium aluminium fluoride, lithium titanium fluoride, and lithium magnesium fluoride. It may contain at least one that is to be.
  • FIG. 1 schematically shows the configuration of the positive electrode material 1000.
  • the positive electrode material 1000 includes a positive electrode active material 110 and a solid electrolyte 100.
  • a halide solid electrolyte may be used as the solid electrolyte material contained in the solid electrolyte 100.
  • the solid electrolyte 100 may be a compound represented by the following composition formula (2).
  • ⁇ , ⁇ , and ⁇ are values larger than 0.
  • M comprises at least one selected from the group consisting of metallic elements other than Li and metalloid elements.
  • X is at least one selected from the group consisting of F, Cl, Br, and I.
  • the metalloid element is B, Si, Ge, As, Sb, or Te.
  • Metallic elements are all elements contained in groups 1 to 12 of the periodic table except hydrogen, and groups 13 to 12 excluding the above-mentioned metalloid elements C, N, P, O, S, and Se. All elements contained in Group 16. That is, a metal element is a group of elements that can become a cation when a halogen compound and an inorganic compound are formed.
  • Li 3 YX 6 Li 2 MgX 4 , Li 2 FeX 4 , Li (Al, Ga, In) X 4 , Li 3 (Al, Ga, In) X 6 and the like can be used. ..
  • X is at least one selected from the group consisting of F, Cl, Br, and I.
  • (A, B, C) means "at least one selected from the group consisting of A, B, and C”.
  • the initial charge / discharge efficiency of the battery can be improved.
  • X may contain at least one selected from the group consisting of Cl and Br.
  • M may include yttrium (Y).
  • the solid electrolyte containing Y may be, for example, a compound represented by the composition formula of Li a M'b Y c X 6.
  • M' is at least one selected from the group consisting of metal elements and metalloid elements other than Li and Y.
  • m indicates the valence of M'.
  • X is at least one selected from the group consisting of F, Cl, Br, and I.
  • M' at least one selected from the group consisting of Mg, Ca, Sr, Ba, Zn, Sc, Al, Ga, Bi, Zr, Hf, Ti, Sn, Ta, and Nb may be used.
  • solid electrolytes containing Y Li 3 YF 6 , Li 3 YCl 6 , Li 3 YBr 6 , Li 3 YI 6 , Li 3 YBrCl 5 , Li 3 YBr 3 Cl 3 , Li 3 YBr 5 Cl, Li.
  • the resistance of the battery can be further reduced.
  • the halide solid electrolyte does not have to contain sulfur.
  • the shapes of the solid electrolyte 100 and the positive electrode active material 110 in the first embodiment are not particularly limited, and may be, for example, needle-shaped, spherical, elliptical spherical, or the like.
  • the shapes of the solid electrolyte 100 and the positive electrode active material 110 may be in the form of particles.
  • the median diameter may be 100 ⁇ m or less.
  • the positive electrode active material 110 and the solid electrolyte 100 can form a good dispersed state in the positive electrode material 1000. This improves the charge / discharge characteristics of the battery.
  • the median diameter of the solid electrolyte 100 may be 10 ⁇ m or less.
  • the positive electrode active material 110 and the solid electrolyte 100 can form a good dispersed state.
  • the solid electrolyte 100 may be smaller than the median diameter of the positive electrode active material 110.
  • the solid electrolyte 100 and the positive electrode active material 110 can form a better dispersed state in the electrode.
  • the median diameter of the positive electrode active material 110 may be 0.1 ⁇ m or more and 100 ⁇ m or less.
  • the positive electrode active material 110 When the median diameter of the positive electrode active material 110 is 0.1 ⁇ m or more, the positive electrode active material 110 and the solid electrolyte 100 can form a good dispersed state in the positive electrode material 1000. As a result, the charge / discharge characteristics of the battery are improved.
  • 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 110 is sufficiently secured. Therefore, it is possible to operate the battery at a high output.
  • volume diameter means the particle size when the cumulative volume in the volume-based particle size distribution is equal to 50%.
  • the volume-based particle size distribution is measured, for example, by a laser diffraction measuring device or an image analysis device.
  • the particles of the solid electrolyte 100 and the particles of the positive electrode active material 110 may be in contact with each other as shown in FIG. At this time, the coating material 120 and the positive electrode active material 110 are in contact with each other.
  • the positive electrode material 1000 in the first embodiment may include particles of a plurality of solid electrolytes 100 and particles of a plurality of positive electrode active materials 110.
  • the content of the solid electrolyte 100 and the content of the positive electrode active material 110 in the positive electrode material 1000 in the first embodiment may be the same or different from each other.
  • FIG. 1 is a cross-sectional view showing a schematic configuration of the battery 2000 according to the second embodiment.
  • the battery 2000 in the second embodiment includes a positive electrode 201, an electrolyte layer 202, and a negative electrode 203.
  • the positive electrode 201 contains the positive electrode material 1000.
  • the electrolyte layer 202 is arranged between the positive electrode 201 and the negative electrode 203.
  • 30 ⁇ v1 ⁇ 95 may be satisfied with respect to the volume ratio “v1: 100 ⁇ v1” of the positive electrode active material 110 and the solid electrolyte 100 contained in the positive electrode 201.
  • the energy density of the battery 2000 is sufficiently secured.
  • v1 ⁇ 95 is satisfied, operation at high output becomes possible.
  • the thickness of the positive electrode 201 may be 10 ⁇ m or more and 500 ⁇ m or less. When the thickness of the positive electrode 201 is 10 ⁇ m or more, the energy density of the battery 2000 is sufficiently secured. When the thickness of the positive electrode 201 is 500 ⁇ m or less, operation at high output is possible.
  • the electrolyte layer 202 is a layer containing an electrolyte material.
  • the electrolyte material is, for example, a solid electrolyte material. That is, the electrolyte layer 202 may be a solid electrolyte layer.
  • the material exemplified as the material of the solid electrolyte 100 in the first embodiment may be used. That is, the electrolyte layer 202 may contain a solid electrolyte having the same composition as that of the solid electrolyte contained in the positive electrode material 1000.
  • the charge / discharge efficiency of the battery 2000 can be further improved.
  • the electrolyte layer 202 may contain a halide solid electrolyte having a composition different from that of the solid electrolyte contained in the positive electrode material 1000.
  • the electrolyte layer 202 may contain a sulfide solid electrolyte.
  • the electrolyte layer 202 may contain only one type of solid electrolyte selected from the above-mentioned group of solid electrolytes, or may contain two or more types of solid electrolytes selected from the above-mentioned group of solid electrolytes. .. Multiple solid electrolytes have different compositions from each other.
  • the electrolyte layer 202 may contain a halide solid electrolyte and a sulfide solid electrolyte.
  • the thickness of the electrolyte layer 202 may be 1 ⁇ m or more and 300 ⁇ m or less. When the thickness of the electrolyte layer 202 is 1 ⁇ m or more, the positive electrode 201 and the negative electrode 203 are unlikely to be short-circuited. When the thickness of the electrolyte layer 202 is 300 ⁇ m or less, operation at high output is possible.
  • the negative electrode 203 contains a material having the property of occluding and releasing metal ions (for example, lithium ions).
  • the negative electrode 203 contains, for example, a negative electrode active material.
  • a metal material, a carbon material, an oxide, a nitride, a tin compound, a silicon compound, etc. can be used as the negative electrode active material.
  • the metal material may be a single metal.
  • the metal material may be an alloy.
  • metal materials include lithium metals, lithium alloys, and the like.
  • carbon materials include natural graphite, coke, developing carbon, carbon fiber, spherical carbon, artificial graphite, amorphous carbon, and the like. From the viewpoint of capacitance density, silicon (Si), tin (Sn), a silicon compound, or a tin compound can be preferably used.
  • the negative electrode 203 may contain a solid electrolyte material. According to the above configuration, the lithium ion conductivity inside the negative electrode 203 is enhanced, and operation at high output becomes possible.
  • the solid electrolyte the material exemplified in the first embodiment may be used. That is, the negative electrode 203 may contain a solid electrolyte having the same composition as that of the solid electrolyte contained in the positive electrode material 1000.
  • the median diameter of the negative electrode active material may be 0.1 ⁇ m or more and 100 ⁇ m or less.
  • the median diameter of the negative electrode active material is 0.1 ⁇ m or more, the negative electrode active material and the solid electrolyte material can form a good dispersed state. As a result, the charge / discharge characteristics of the battery are improved.
  • the median diameter of the negative electrode active material is 100 ⁇ m or less, the diffusion rate of lithium in the negative electrode active material is sufficiently secured. Therefore, it is possible to operate the battery at a high output.
  • the median diameter of the negative electrode active material may be larger than the median diameter of the solid electrolyte material. This makes it possible to form a good dispersed state between the negative electrode active material and the solid electrolyte material.
  • 30 ⁇ v2 ⁇ 95 may be satisfied with respect to the volume ratio “v2: 100-v2” of the negative electrode active material and the solid electrolyte material contained in the negative electrode 203.
  • the energy density of the battery 2000 is sufficiently secured.
  • v2 ⁇ 95 is satisfied, operation at high output becomes possible.
  • the thickness of the negative electrode 203 may be 10 ⁇ m or more and 500 ⁇ m or less. When the thickness of the negative electrode 203 is 10 ⁇ m or more, the energy density of the battery 2000 is sufficiently secured. When the thickness of the negative electrode 203 is 500 ⁇ m or less, operation at high output is possible.
  • At least one selected from the group consisting of the positive electrode 201, the electrolyte layer 202, and the negative electrode 203 may contain a binder for the purpose of improving the adhesion between the particles.
  • the binder is used to improve the binding property of the material constituting the electrode.
  • polyvinylidene fluoride polytetrafluoroethylene, polyethylene, polypropylene, aramid resin, polyamide, polyimide, polyamideimide, polyacrylic nitrile, polyacrylic acid, polyacrylic acid methyl ester, polyacrylic acid ethyl ester, poly Acrylic acid hexyl ester, polymethacrylic acid, polymethacrylic acid methyl ester, polymethacrylic acid ethyl ester, polymethacrylic acid hexyl ester, polyvinylidene acetate, polyvinylpyrrolidone, polyether, polyether sulfone, hexafluoropolypropylene, styrene butadiene rubber, Carboxymethyl cellulose, etc.
  • the binders include tetrafluoroethylene, hexafluoroethylene, hexafluoropropylene, perfluoroalkyl vinyl ether, vinylidene fluoride, chlorotrifluoroethylene, ethylene, propylene, pentafluoropropylene, fluoromethyl vinyl ether, acrylic acid, and hexadiene. Copolymers of two or more materials selected from the above can be used. Further, two or more kinds selected from these may be mixed and used as a binder.
  • At least one selected from the group consisting of the positive electrode 201 and the negative electrode 203 may contain a conductive auxiliary agent for the purpose of enhancing electronic conductivity.
  • the conductive auxiliary agent include graphites of natural graphite or artificial graphite, carbon blacks such as acetylene black and ketjen black, conductive fibers such as carbon fibers or metal fibers, and metal powders such as carbon fluoride and aluminum.
  • conductive whiskers such as zinc oxide or potassium titanate, conductive metal oxides such as titanium oxide, conductive polymer compounds such as polyaniline, polypyrrole, polythiophene, and the like can be used.
  • the cost can be reduced.
  • the battery according to the second embodiment can be configured as a battery having various shapes such as a coin type, a cylindrical type, a square type, a sheet type, a button type, a flat type, and a laminated type.
  • Example 1 [Preparation of positive electrode active material]
  • the positive electrode active material LiNi 0.8 (Co, Mn) 0.2 O 2 was vacuum dried at 100 ° C. for 2 weeks and then taken out in a dry atmosphere with a dew point of ⁇ 20 ° C. or lower.
  • LiNi 0.8 (Co, Mn) 0.2 O 2 is referred to as NCM. In this way, the positive electrode active material of Example 1 was obtained.
  • the amount of the hydrogen element contained in the prepared positive electrode active material of Example 1 was measured by a hydrogen analyzer (manufactured by Horiba, EMGA-930) using an inert gas melting-non-dispersive infrared absorption method. ..
  • the output of the gas extraction furnace was 3.5 kW, and the amount of hydrogen element was measured by the integrated value for 10 seconds from the start of detection.
  • the hydrogen element content of the positive electrode active material of Example 1 was 64.4 mass ppm.
  • metal Li thickness 200 ⁇ m
  • metal Li thickness 200 ⁇ m
  • Example 1 was produced by sealing the inside of the insulating outer cylinder from the outside air atmosphere by sealing the insulating outer cylinder using an insulating ferrule.
  • the battery was placed in a constant temperature bath at 25 ° C and connected to a potentiostat (manufactured by Solartron) equipped with a frequency response analyzer.
  • the second discharge capacity of the battery of Example 1 was 1767.4 ⁇ Ah, the discharge capacity after storage was 1485.5 ⁇ Ah, and the capacity retention rate after storage was 84.1%.
  • Example 3 After vacuum drying the NCM at 100 ° C. for 2 weeks, it was calcined at 500 ° C. for 1 hour in a nitrogen gas atmosphere. Then, it was taken out in a dry atmosphere with a dew point of ⁇ 20 ° C. or lower. In this way, the positive electrode active material of Example 3 was obtained.
  • Example 4 After vacuum drying the NCM at 100 ° C. for 2 weeks, it was calcined at 600 ° C. for 1 hour in a nitrogen gas atmosphere. Then, it was taken out in a dry atmosphere with a dew point of ⁇ 20 ° C. or lower. In this way, the positive electrode active material of Example 4 was obtained.
  • Example 5 After vacuum drying the NCM at 100 ° C. for 2 weeks, it was calcined at 800 ° C. for 1 hour in a nitrogen gas atmosphere. Then, it was taken out in a dry atmosphere with a dew point of ⁇ 20 ° C. or lower. In this way, the positive electrode active material of Example 5 was obtained.
  • the elemental hydrogen content may be more preferably 114.3 mass ppm or less.
  • the hydrogen element content may be 61.6 mass ppm or more.
  • the battery of the present disclosure can be used as, for example, an all-solid-state battery.
  • Positive electrode material 100 Solid electrolyte 110 Positive electrode active material 120 Coating material 2000 Battery 201 Positive electrode 202 Electrolyte layer 203 Negative electrode

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PCT/JP2021/019287 2020-05-27 2021-05-21 正極活物質、正極材料、電池、および正極活物質の製造方法 Ceased WO2021241418A1 (ja)

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