WO2022019099A1 - 正極材料および電池 - Google Patents

正極材料および電池 Download PDF

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Publication number
WO2022019099A1
WO2022019099A1 PCT/JP2021/025293 JP2021025293W WO2022019099A1 WO 2022019099 A1 WO2022019099 A1 WO 2022019099A1 JP 2021025293 W JP2021025293 W JP 2021025293W WO 2022019099 A1 WO2022019099 A1 WO 2022019099A1
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Prior art keywords
positive electrode
solid electrolyte
battery
active material
coating material
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PCT/JP2021/025293
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English (en)
French (fr)
Japanese (ja)
Inventor
健太 長嶺
出 佐々木
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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 CN202180061394.XA priority Critical patent/CN116195085A/zh
Priority to JP2022538679A priority patent/JP7766283B2/ja
Priority to EP21845968.3A priority patent/EP4187638A4/en
Publication of WO2022019099A1 publication Critical patent/WO2022019099A1/ja
Priority to US18/153,364 priority patent/US20230163299A1/en
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/582—Halogenides
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0561—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of inorganic materials only
    • H01M10/0562—Solid materials
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/028—Positive electrodes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0065—Solid electrolytes
    • H01M2300/0068—Solid electrolytes inorganic
    • 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
    • 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 for a battery and a battery.
  • Patent Document 1 discloses an all-solid-state lithium battery containing a lithium ion conductive solid electrolyte mainly composed of sulfide and an active material whose surface is coated with a lithium ion conductive oxide.
  • Non-Patent Document 1 describes that in a battery using a sulfide solid electrolyte, an interface layer is formed at the interface between the positive electrode material and the sulfide solid electrolyte after initial charging, and the resistance of the battery increases. ..
  • the present disclosure provides a positive electrode material that can reduce the resistance of the battery.
  • the positive electrode material of the present disclosure is Positive electrode active material and The first solid electrolyte and A coating material that covers at least a part of the surface of the positive electrode active material, and Including The first solid electrolyte is represented by the following composition formula (1).
  • a, b, and c are independent, positive real numbers, respectively.
  • M contains calcium, yttrium, and at least one rare earth element other than yttrium.
  • X comprises at least one selected from the group consisting of F, Cl, Br and I.
  • the present disclosure provides a positive electrode material that can reduce the resistance of the battery.
  • FIG. 1 is a cross-sectional view showing a schematic configuration of the positive electrode material 1000 according to the first embodiment.
  • FIG. 2 is a cross-sectional view showing a schematic configuration of the battery 2000 according to the second embodiment.
  • FIG. 3 is a diagram showing a Nyquist diagram of the battery in Example 1 at 3.7 V.
  • FIG. 4 is a diagram showing an O1s spectrum of the active material used in Example 1 in X-ray photoelectron spectroscopy.
  • Patent Document 1 discloses an all-solid-state lithium battery containing a lithium ion conductive solid electrolyte mainly composed of sulfide and an active material whose surface is coated with a lithium ion conductive oxide.
  • lithium niobate that is, LiNbO 3
  • LiNbO 3 lithium niobate
  • Non-Patent Document 1 the cause of the formation of a high resistance layer between the sulfide solid electrolyte and the surface of the positive electrode active material is the mutual diffusion between the metal elements contained in the positive electrode active material and the elements constituting the solid electrolyte. It is stated that there is.
  • the constituent elements of the solid electrolyte include P and S. That is, the formation of the high resistance layer as described above is derived from the presence of P or S, which is a constituent element of the solid electrolyte.
  • the lithium ion conductive solid electrolyte used as the solid electrolyte of the battery is a halide
  • the potential of the positive electrode becomes high in the charging process of the battery
  • the oxidation of the halogen contained in the solid electrolyte is induced.
  • Such oxidation of halogen causes decomposition of the solid electrolyte.
  • the halogen oxidation reaction occurs, halogen gas is generated, so that a gap is formed at the contact interface between the active material and the solid electrolyte, and the effective reaction area is reduced. This increases the resistance of the battery.
  • the coating material that coats the surface of the active material between the active material and the solid electrolyte By interposing the coating material that coats the surface of the active material between the active material and the solid electrolyte, the contact of the solid electrolyte with the high-potential active material is suppressed, so that the oxidation of halogen can be suppressed. Conceivable. For these reasons, it is considered that the resistance of the battery can be reduced.
  • the halide solid electrolyte is a crystal with strong ionic bonding. Therefore, when the solid electrolyte contains a rare earth element having a relatively large ionic radius, particularly Sc and / or a lanthanoid element, the bond distance between the cation Sc and / or the lanthanoid element and the anion halogen. Is big. A large bond distance means that the bond between the cation and the anion is weak, so that the halogen, which is an anion, is easily released. Therefore, in order to reduce the resistance of the battery, it is more effective to suppress the oxidation of the halogen in the solid electrolyte by coating the active material.
  • the present inventors have reached the following positive electrode materials of the present disclosure capable of reducing the resistance of the battery.
  • the positive electrode material according to the first aspect of the present disclosure is Positive electrode active material and The first solid electrolyte and A coating material that covers at least a part of the surface of the positive electrode active material, and Including
  • the first solid electrolyte is represented by the following composition formula (1).
  • a, b, and c are independent, positive real numbers, respectively.
  • M contains calcium, yttrium, and at least one rare earth element other than yttrium.
  • X comprises at least one selected from the group consisting of F, Cl, Br and I.
  • a coating material is interposed between the positive electrode active material and the first solid electrolyte which is a halide solid electrolyte.
  • This coating material suppresses the transfer of electrons to the halide solid electrolyte even when the potential of the positive electrode is high during the charging process of the battery. Therefore, since the oxidation reaction of halogen in the halide solid electrolyte is suppressed, the decomposition of the first solid electrolyte is suppressed and the generation of halogen gas is also suppressed. As a result, deterioration of the first solid electrolyte is suppressed, and reduction of the effective reaction area between the positive electrode active material and the first solid electrolyte is also suppressed. For these reasons, the positive electrode material according to the first aspect can reduce the resistance of the battery. In addition, the ionic conductivity of the first solid electrolyte can be further improved. This makes it possible to further improve the charge / discharge efficiency of the battery.
  • the coating material may contain O.
  • the positive electrode material according to the second aspect can more effectively reduce the resistance of the battery.
  • the coating material may contain Li.
  • the positive electrode material according to the third aspect can increase the carrier concentration at the interface between the positive electrode active material and the first solid electrolyte, that is, the Li concentration. Therefore, the positive electrode material according to the third aspect can more effectively reduce the resistance of the battery.
  • the coating material is at least one selected from the group consisting of lithium phosphate and lithium niobate. It may be included.
  • Lithium phosphate and lithium niobate can increase the lithium ion conductivity of the coating material. Thereby, the positive electrode material according to the fourth aspect can more effectively reduce the resistance of the battery.
  • the mass ratio of the coating material to the positive electrode active material 110 is 0.5% by mass or more and 2.0. It may be mass% or less.
  • the coating amount is adjusted to the above range, lithium ions are smoothly transferred between the active material and the solid electrolyte, so that the resistance of the battery can be reduced more effectively.
  • the thickness of the coating material may be 2 nm or more and 20 nm or less.
  • the thickness of the covering material is adjusted to the above range, the energy density of the battery can be improved. In addition, the resistance of the battery can be reduced more effectively.
  • the M contains at least one element selected from the group consisting of Gd and Sm. May be good.
  • the positive electrode material according to the seventh aspect can further improve the ionic conductivity of the first solid electrolyte. This makes it possible to further improve the charge / discharge efficiency of the battery.
  • the X contains at least one element selected from the group consisting of F, Cl and Br. You may go out.
  • the X contains at least two elements selected from the group consisting of F, Cl and Br. You may go out.
  • the X may contain Cl and Br.
  • the ionic conductivity of the first solid electrolyte can be further improved.
  • the positive electrode material can further improve the charge / discharge efficiency of the battery.
  • the positive electrode active material may contain a lithium-containing transition metal oxide.
  • the positive electrode material according to the eleventh aspect can improve the energy density of the battery.
  • the battery according to the twelfth aspect of the present disclosure is A positive electrode containing any one of the positive electrode materials according to the first to eleventh embodiments, With the negative electrode An electrolyte layer provided between the positive electrode and the negative electrode, To prepare for.
  • the battery according to the twelfth aspect can reduce the resistance and further improve the charge / discharge efficiency.
  • the electrolyte layer may contain a sulfide solid electrolyte.
  • the resistance can be reduced and the charge / discharge efficiency can be further improved.
  • 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 first solid electrolyte 100, a positive electrode active material 110, and a coating material 111 that covers at least a part of the surface of the positive electrode active material 110.
  • the first solid electrolyte 100 and the positive electrode active material 110 may be in the form of particles.
  • the coating material 111 may cover the entire surface of the positive electrode active material 110, or may partially cover the surface of the positive electrode active material 110. That is, the coating material 111 may cover at least a part of the surface of the positive electrode active material 110.
  • the positive electrode active material 110 and the first solid electrolyte 100 are separated by the coating material 111, and there is a portion that does not touch each other.
  • the positive electrode active material 110 and the first solid electrolyte 100 may have a portion in contact with each other.
  • the first solid electrolyte 100 is represented by the following composition formula (1).
  • a, b, and c are independently positive real numbers.
  • M contains calcium, yttrium, and at least one rare earth element other than yttrium.
  • X comprises at least one selected from the group consisting of F, Cl, Br and I.
  • the coating material 111 is interposed between the positive electrode active material 110 and the first solid electrolyte 100 which is a halide solid electrolyte.
  • the coating material 111 suppresses the transfer of electrons to the halide solid electrolyte even when the potential of the positive electrode is increased during the charging process of the battery. Therefore, since the oxidation reaction of the halogen in the first solid electrolyte 100 is suppressed, the decomposition of the first solid electrolyte 100 is suppressed, and the generation of halogen gas due to the oxidation reaction is also suppressed.
  • the positive electrode material 1000 in the present embodiment can reduce the resistance of the battery. Further, as a result, the positive electrode material 1000 according to the first aspect can improve the charge / discharge efficiency of the battery.
  • the coating material 111 may uniformly cover the entire surface of the positive electrode active material 110.
  • the direct contact between the positive electrode active material 110 and the first solid electrolyte 100 can be suppressed, and the oxidation reaction of the first solid electrolyte 100 can be suppressed more reliably. Therefore, it is possible to further improve the charge / discharge characteristics of the battery and suppress an increase in the reaction overvoltage of the battery.
  • the coating material 111 may cover only a part of the surface of the positive electrode active material 110.
  • the particles of the plurality of positive electrode active materials 110 come into direct contact with each other through the portion not covered with the coating material 111, so that the electron conductivity between the particles of the positive electrode active material 110 is improved. Therefore, it is possible to operate the battery at a high output.
  • a material having low electron conductivity can be used.
  • a material containing O can be used. Examples of materials containing O are oxide materials or oxide solid electrolytes.
  • Oxide materials that can be used for the coating material 111 are, for example, SiO 2 , Al 2 O 3 , TIO 2 , B 2 O 3 , Nb 2 O 5 , WO 3 , or ZrO 2 .
  • the oxide solid electrolyte that can be used for the coating material 111 is, for example, a Li-PO compound such as Li 3 PO 4, a Li-Nb-O compound such as LiNbO 3, or Li- such as LiBO 2 or Li 3 BO 3.
  • the coating material 111 may contain an oxide solid electrolyte.
  • the oxide solid electrolyte has high ionic conductivity and high potential stability. Therefore, by using the oxide solid electrolyte, the charge / discharge efficiency can be further improved.
  • the coating material 111 may contain an oxoacid salt. By including the oxoacid salt in the coating material 111, the resistance of the battery can be reduced more effectively.
  • the oxoacid salt may be a non-metal or metalloid cation oxo acid salt.
  • the "metalloid element” is B, Si, Ge, As, Sb, and Te.
  • Non-metal elements are N, P, S, Cl, Br, and I. That is, these elements are a group of elements that combine with oxygen to produce oxoacids.
  • the coating material 111 may contain at least one selected from the group consisting of B, N, P, S, and Si.
  • the coating material 111 contains at least one selected from the group consisting of B, N, P, S, and Si
  • a coating material having low electron conductivity can be formed on the surface of the positive electrode active material 110. Therefore, the positive electrode material 1000 in the first embodiment can further reduce the oxidation reaction of the first solid electrolyte 100. Also, elements such as B, N, P, S, and Si form strong covalent bonds with oxygen. Therefore, since the electrons in the coating material 111 are delocalized, the electron conductivity of the coating material 111 is low.
  • the thickness of the coating material 111 on the surface of the positive electrode active material 110 is reduced, the transfer of electrons between the positive electrode active material 110 and the first solid electrolyte 100 can be blocked, so that the oxidation reaction of the first solid electrolyte 100 can be blocked. Can be suppressed more effectively. Therefore, by including the coating material 111 selected from the group consisting of B, N, P, S, and Si, the positive electrode material 1000 more effectively reduces the resistance of the battery and further fills it. The discharge efficiency can be improved.
  • the coating material 111 may contain Li. According to this configuration, the carrier concentration at the interface between the positive electrode active material 110 and the first solid electrolyte 100 can be increased, so that the resistance of the battery can be reduced more effectively.
  • the molar ratio Li / (other cations) of lithium and other cations in the coating material 111 may be 0.8 or more and 3.6 or less, and 1.0 or more and 3 It may be 0.0 or less.
  • the molar ratio Li / (other cations) is 0.8 or more and 3.6 or less, the lithium ion conductivity in the coating material 111 can be increased. Thereby, the resistance of the battery can be reduced more effectively.
  • the coating material 111 may contain a glass-forming oxide such as phosphoric acid or silicic acid.
  • the glass-forming oxide means a network-forming oxide that can form glass by itself.
  • Elements that become cations that can form glass-forming oxides, that is, elements called network-forming bodies, are, for example, Si, P, B, Ge, and V. Since the coating material 111 contains a glass-forming oxide, the lithium ion conductivity in the coating material 111 can be increased. Specifically, when the coating material 111 contains a lithium compound of an oxide called a glass-forming oxide such as phosphoric acid or silicic acid, a part of the coating material is amorphized and the ion conduction path is wide. Become. Therefore, the lithium ion conductivity in the coating material 111 can be increased, and the resistance of the battery can be reduced more effectively.
  • the coating material 111 may contain an intermediate oxide such as niobate.
  • the intermediate oxide cannot form glass by itself (that is, cannot form a glass mesh by itself), but may form glass or enter the glass mesh depending on the composition.
  • the elements that become cations that can form intermediate oxides are, for example, Nb, Ti, Zn, Al, and Zr.
  • the coating material 111 contains an intermediate oxide, the lithium ion conductivity in the coating material 111 can be increased.
  • the coating material 111 contains a lithium compound of an oxide called an intermediate oxide such as niobate, a part of the coating material is amorphized and the ion conduction path is widened. Therefore, the lithium ion conductivity in the coating material 111 can be increased, and the resistance of the battery can be reduced more effectively.
  • the coating material 111 may contain at least one selected from the group consisting of lithium phosphate and lithium niobate.
  • Lithium phosphate and lithium niobate can increase the lithium ion conductivity of the coating material 111. Thereby, the positive electrode material 1000 of the present embodiment can more effectively reduce the resistance of the battery.
  • the coating material 111 contains at least one selected from the group consisting of lithium phosphate and lithium niobate as a main component, and further contains unavoidable impurities or a starting material used for forming the coating material 111. And may include by-products and degradation products and the like. That is, the coating material 111 may contain the total of lithium phosphate and lithium niobate in an amount of, for example, 50% or more (50% by mass or more) in terms of mass ratio with respect to the entire coating material 111. The coating material 111 may contain the total of lithium phosphate and lithium niobate in an amount of 100% (100% by mass) with respect to the whole of the coating material 111, for example, excluding impurities inevitably mixed.
  • the coating material 111 may be LiNbO 3.
  • LiNbO 3 has higher ionic conductivity and higher potential stability. Therefore, by using LiNbO 3 , the charge / discharge efficiency of the battery can be further improved.
  • the coating material 111 is interposed between the positive electrode active material 110 and the first solid electrolyte 100.
  • the coating material 111 may also block the electronic contact between the positive electrode active material 110-the conductive auxiliary agent or the positive electrode active materials 110. In that case, the electronic path from the current collector of the battery to the particles of each positive electrode active material 110 may be cut off, and the isolated positive electrode active material 110 may not contribute to the charge / discharge reaction.
  • the coating surface area of the positive electrode active material 110 coated with the coating material 111 with respect to the total surface area of the positive electrode active material 110 may be 18% or more. In order to more effectively reduce the resistance of the battery, the coverage may be 47% or more, 90%, or 100%.
  • the above coverage can be determined by separating the peaks of O1s in X-ray photoelectron spectroscopy (XPS).
  • XPS X-ray photoelectron spectroscopy
  • the elemental amounts of metals such as Ni, Co, and Mn in the positive electrode active material 110 and the cation species in the coating material 111 are measured by XPS measurement.
  • the elemental amount of P or Si may be determined, and the coverage may be determined by the ratio thereof.
  • the coverage may be obtained from the difference in contrast due to the difference in composition between the active material and the coating material.
  • the coverage may be determined by mapping the constituent elements of the active material and the covering material using energy dispersive X-ray analysis (EDX).
  • EDX energy dispersive X-ray analysis
  • the mass ratio of the coating material 111 to the positive electrode active material 110 may be 2.0% by mass or less, or 1.5% by mass or less. According to this configuration, the ratio of the positive electrode active material 110 or the first solid electrolyte 100 in the positive electrode can be increased, so that the energy density of the battery can be increased.
  • the mass ratio of the coating material 111 to the positive electrode active material 110 may be 0.1% by mass or more, or 0.5% by mass or more. According to this configuration, the ratio of the positive electrode active material 110 or the first solid electrolyte 100 in the positive electrode can be increased, so that the energy density of the battery can be increased.
  • the mass ratio of the coating material 111 to the positive electrode active material 110 may be 0.5% by mass or more and 2.0% by mass or less. According to this configuration, the ratio of the positive electrode active material 110 or the first solid electrolyte 100 in the positive electrode can be increased, so that the energy density of the battery can be increased.
  • the mass ratio of the coating material 111 to the positive electrode active material 110 may be 0.5% by mass or more and 1.5% by mass or less.
  • the mass ratio of the coating material 111 to the positive electrode active material 110 is determined by, for example, dissolving the positive electrode with an acid or the like to make an aqueous solution, and then quantifying the contained elements by inductively coupled plasma (ICP) emission spectroscopy and mass. The ratio may be calculated. At this time, it may be obtained from the quantitative values of the elements contained in only one of the positive electrode active material 110 and the coating material 111, assuming a chemical composition. For example, if the LiNiO 2 is coated with Li 3 PO 4, the quantitative value of Ni and P, LiNiO 2 and Li 3 PO 4 is assumed as present in stoichiometric composition, the mass ratio of the coating material 111 May be sought.
  • At least one rare earth element other than yttrium contained in M may contain Sc and a lanthanoid element.
  • Lanthanoid elements are, for example, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu. Since the chemical properties of the rare earth elements are similar to each other, any of them can be used as a constituent element of the halide solid electrolyte of the present embodiment.
  • M may contain calcium, yttrium, and one rare earth element other than yttrium. M may contain at least one rare earth element other than yttrium, and may contain only one rare earth element other than yttrium.
  • M may contain at least one selected from the group consisting of Gd and Sm.
  • M may contain only one selected from the group consisting of Gd and Sm.
  • the ionic conductivity of the first solid electrolyte 100 can be further improved. This makes it possible to further improve the charge / discharge efficiency of the battery.
  • X may contain at least one element selected from the group consisting of F, Cl and Br. In the above composition formula (1), X may contain at least two elements selected from the group consisting of F, Cl and Br. In the above composition formula (1), X may contain Cl and Br. According to this configuration, the ionic conductivity of the first solid electrolyte 100 can be further improved. Thereby, the charge / discharge efficiency of the battery can be further improved.
  • the first solid electrolyte 100 may be represented by the following composition formula (2).
  • composition formula (2) satisfies 0 ⁇ a, 0 ⁇ b ⁇ 1, 0 ⁇ c ⁇ 6, and 0 ⁇ d ⁇ 1.5.
  • the ionic conductivity of the first solid electrolyte 100 can be further improved. This makes it possible to further improve the charge / discharge efficiency of the battery.
  • composition formula (2) may satisfy 0.01 ⁇ a ⁇ 0.3.
  • the ionic conductivity of the first solid electrolyte 100 can be further improved. This makes it possible to further improve the charge / discharge efficiency of the battery.
  • composition formula (2) may satisfy a ⁇ 0.2.
  • the ionic conductivity of the first solid electrolyte 100 can be further improved. This makes it possible to further improve the charge / discharge efficiency of the battery.
  • composition formula (2) may satisfy 0.1 ⁇ b ⁇ 0.9.
  • the ionic conductivity of the first solid electrolyte 100 can be further improved. This makes it possible to further improve the charge / discharge efficiency of the battery.
  • composition formula (2) may satisfy 0.8 ⁇ b ⁇ 1.
  • the ionic conductivity of the first solid electrolyte 100 can be further improved. This makes it possible to further improve the charge / discharge efficiency of the battery.
  • composition formula (2) may satisfy 1.0 ⁇ c ⁇ 1.2.
  • the ionic conductivity of the first solid electrolyte 100 can be further improved. This makes it possible to further improve the charge / discharge efficiency of the battery.
  • the first solid electrolyte 100 and the halide solid electrolyte may not contain sulfur.
  • the positive electrode active material 110 is, for example, a material having a property of occluding and releasing metal ions (for example, lithium ions).
  • positive electrode active materials are lithium-containing transition metal oxides, transition metal fluorides, polyanionic materials, fluorinated polyanionic materials, transition metal sulfides, transition metal oxysulfides, transition metal oxynitrides, and the like.
  • lithium-containing transition metal oxides are Li (NiCoAl) O 2 , Li (NiCoMn) O 2 , LiCoO 2 , and the like.
  • the positive electrode active material 110 may be nickel, cobalt, or lithium manganate.
  • the positive electrode active material 110 may be Li (NiComn) O 2 .
  • the energy density and charge / discharge efficiency of the battery can be further increased.
  • the thickness of the coating material 111 may be 1 nm or more and 100 nm or less.
  • the thickness of the coating material 111 is 1 nm or more, direct contact between the positive electrode active material 110 and the first solid electrolyte 100 can be suppressed, and side reactions of the first solid electrolyte 100 can be suppressed. Therefore, the charge / discharge efficiency can be improved.
  • the thickness of the coating material 111 is 100 nm or less, the thickness of the coating material 111 does not become too thick. Therefore, the internal resistance of the battery can be sufficiently reduced. As a result, the energy density of the battery can be increased.
  • the thickness of the coating material 111 may be 2 nm or more and 20 nm or less.
  • the thickness of the coating material 111 is 2 nm or more, direct contact between the positive electrode active material 110 and the first solid electrolyte 100 can be better suppressed, and side reactions of the first solid electrolyte 100 can be suppressed. Therefore, the charge / discharge efficiency can be improved better.
  • the thickness of the coating material 111 is 40 nm or less, the internal resistance of the battery can be further reduced. As a result, the energy density of the battery can be increased.
  • the thickness of the covering material 111 may be 20 nm or less.
  • the method for measuring the thickness of the coating material 111 is not particularly limited, but it can be obtained by directly observing the thickness of the coating material 111 using, for example, a transmission electron microscope. It can also be obtained from the change in the spectrum derived from the active material by measuring XPS while scraping the coating layer by Ar sputtering.
  • the shape of the first solid electrolyte 100 in the first embodiment is not particularly limited, and may be, for example, needle-shaped, spherical, elliptical spherical, or the like.
  • the shape of the first solid electrolyte 100 may be particles.
  • the median diameter may be 100 ⁇ m or less. If the median diameter is larger than 100 ⁇ m, the positive electrode active material 110 and the first solid electrolyte 100 may not be able to form a good dispersed state in the positive electrode material 1000. Therefore, the charge / discharge characteristics are deteriorated. Further, in the first embodiment, the median diameter may be 10 ⁇ m or less.
  • the positive electrode active material 110 and the first solid electrolyte 100 can form a good dispersed state.
  • the first solid electrolyte 100 may be smaller than the median diameter of the positive electrode active material 110.
  • the first 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 first solid electrolyte 100 can form a good dispersed state in the positive electrode material 1000 in the positive electrode material 1000. As a result, the charge / discharge characteristics of the battery are improved. Further, when 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 ensured. Therefore, the battery can operate at high output.
  • the median diameter of the positive electrode active material 110 may be larger than the median diameter of the first solid electrolyte 100. As a result, the positive electrode active material 110 and the first solid electrolyte 100 can form a good dispersed state.
  • the median 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 first solid electrolyte 100 and the coating material 111 may be in contact with each other as shown in FIG.
  • the positive electrode material 1000 in the first embodiment may include a plurality of particulate first solid electrolytes 100 and a plurality of particulate positive electrode active materials 110.
  • the content of the first 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.
  • the first solid electrolyte in the first embodiment can be produced, for example, by the following method.
  • Raw material powders having a blending ratio of the desired composition are prepared and mixed.
  • Examples of raw material powders are oxides, hydroxides, halides, or acid halides.
  • LiBr and YCl 3 are prepared in a molar ratio of 3: 1.
  • the raw material powder After mixing the raw material powder well, mix, crush, and react the raw material powder with each other using the method of mechanochemical milling.
  • the raw material powder may be mixed well and then sintered in a vacuum.
  • composition of the crystal phase (that is, the crystal structure) in the solid electrolyte can be determined by adjusting the reaction method and reaction conditions between the raw material powders.
  • the positive electrode active material 110 coated with the coating material 111 can be produced by the following method.
  • the powder of the positive electrode active material 110 is produced, for example, by the coprecipitation method.
  • a positive electrode active material 110 can be produced by producing a precursor made of a metal oxide and calcining the precursor together with a lithium source.
  • powders of positive electrode active material 110 having various compositions are commercially available, and they are easily available.
  • the method for forming the covering material 111 is not particularly limited. Examples of the method for forming the coating material 111 include a liquid phase coating method and a vapor phase coating method.
  • the precursor solution of the coating material 111 is applied to the surface of the positive electrode active material 110.
  • the precursor solution can be a mixed solution of solvent, lithium hydroxide and triethyl phosphate.
  • the raw material is not limited as long as it is dissolved or dispersed in a solvent.
  • lithium sources are alkyl lithium such as tert-butyllithium, lithium methoxyd, lithium ethoxydo, lithium isopropoxide, lithium alkoxide such as lithium-tert-butoxide, lithium iodide, lithium bromide, lithium chloride. , Lithium carbonate, lithium nitrate, lithium sulfate, or metallic lithium.
  • Examples of phosphoric acid sources are trimethyl phosphate, tripropyl phosphate, tributyl phosphate, phosphoric acid, monoammonium dihydrogen phosphate, diammonium monohydrogen phosphate, or triammonium phosphate.
  • a raw material containing phosphoric acid and lithium may be used.
  • the solvent is, for example, alcohol such as ethanol.
  • the solvent is not limited as long as the raw material can be dissolved or dispersed, and various solvents can be selected depending on the raw material.
  • solvents are methanol, propanol, isopropanol, butanol, dimethyl carbonate, diethyl carbonate, ethylmethyl carbonate, dimethyl sulfoxide, tetrahydrofuran, hexane, benzene, toluene, methylene chloride, acetone, or acetonitrile.
  • the precursor solution may be acidic or alkaline.
  • FIG. 2 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 includes the positive electrode material 1000 according to the first embodiment.
  • the electrolyte layer 202 is arranged between the positive electrode 201 and the negative electrode 203.
  • the resistance of the battery 2000 can be reduced.
  • 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 first solid electrolyte 100 contained in the positive electrode 201 is 100.
  • v1 ⁇ 30 it is easy to secure a sufficient energy density of the battery 2000.
  • v1 ⁇ 95 the operation of the battery 2000 at a high output becomes easier.
  • 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, sufficient energy density of the battery 2000 can be secured. When the thickness of the positive electrode 201 is 500 ⁇ m or less, the operation of the battery 2000 at high output can be realized.
  • the electrolyte layer 202 is arranged between the positive electrode 201 and the negative electrode 203.
  • the electrolyte layer 202 is a layer containing an electrolyte material.
  • the electrolyte material is, for example, a solid electrolyte (that is, a second solid electrolyte). That is, the electrolyte layer 202 may be a solid electrolyte layer.
  • Examples of the second solid electrolyte contained in the electrolyte layer 202 include the first solid electrolyte according to the first embodiment described above. That is, the electrolyte layer 202 may contain the first solid electrolyte according to the first embodiment described above.
  • the charge / discharge efficiency of the battery 2000 can be further improved.
  • the second solid electrolyte contained in the electrolyte layer 202 may be a halide solid electrolyte different from the first solid electrolyte in the first embodiment described above. That is, the electrolyte layer 202 may contain a halide solid electrolyte different from the first solid electrolyte in the first embodiment described above.
  • the output density and charge / discharge efficiency of the battery 2000 can be improved.
  • the halide solid electrolyte contained in the electrolyte layer 202 may contain Y as a metal element.
  • the output density and charge / discharge efficiency of the battery can be further improved.
  • the material shown as the first solid electrolyte in the above-mentioned first embodiment can be used.
  • a sulfide solid electrolyte may be used as the second solid electrolyte contained in the electrolyte layer 202. That is, the electrolyte layer 202 may contain a sulfide solid electrolyte.
  • a low potential negative electrode material such as graphite or metallic lithium can be used, and the energy density of the battery 2000 can be improved.
  • Examples of the sulfide solid electrolyte include Li 2 SP 2 S 5 , Li 2 S-Si S 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 , etc. may be used.
  • LiX (X: F, Cl, Br, I), Li 2 O, MO q , Li p MO q (M: P, Si, Ge, B, Al, Ga, In, Fe, Zn. Any) (p, q: natural number) and the like may be added.
  • an oxide solid electrolyte, a polymer solid electrolyte, or a complex hydride solid electrolyte may be used as the second solid electrolyte contained in the electrolyte layer 202.
  • oxide solid electrolyte examples include a NASICON type solid electrolyte typified by LiTi 2 (PO 4 ) 3 and its element substituent, a (LaLi) TiO 3 type perovskite type solid electrolyte, Li 14 ZnGe 4 O 16 , Li. 4 SiO 4 , LiGeO 4 and LISON-type solid electrolytes typified by elemental substituents, Li 7 La 3 Zr 2 O 12 and garnet-type solid electrolytes typified by elemental substituents, Li 3 N and its H-substituted products. , Li 3 PO 4 and its N-substituted products, Li-BO compounds such as Li BO 2 , Li 3 BO 3 , and Li 2 SO 4 , Li 2 CO 3, etc. added to glass, glass ceramics, etc. Can be used.
  • NASICON type solid electrolyte typified by LiTi 2 (PO 4 ) 3 and its element substituent
  • a compound of a polymer compound and a lithium salt can be used.
  • the polymer compound may have an ethylene oxide structure. By having an ethylene oxide structure, a large amount of lithium salt can be contained, and the ionic conductivity can be further increased.
  • the lithium salt LiPF 6, LiBF 4, LiSbF 6, LiAsF 6, LiSO 3 CF 3, LiN (SO 2 CF 3) 2, LiN (SO 2 C 2 F 5) 2, LiN (SO 2 CF 3) ( SO 2 C 4 F 9 ), LiC (SO 2 CF 3 ) 3 , etc. can be used.
  • the lithium salt one lithium salt selected from these can be used alone. Alternatively, as the lithium salt, a mixture of two or more kinds of lithium salts selected from these can be used.
  • the complex hydrides solid electrolyte for example, LiBH 4 -LiI, such as LiBH 4 -P 2 S 5, can be used.
  • the electrolyte layer 202 may contain a second solid electrolyte as a main component. That is, the electrolyte layer 202 may contain the second solid electrolyte in an amount of, for example, 50% or more (50% by weight or more) by weight with respect to the entire electrolyte layer 202.
  • the charge / discharge characteristics of the battery 2000 can be further improved.
  • the electrolyte layer 202 may contain the second solid electrolyte in an amount of 70% or more (70% by weight or more) in terms of the weight ratio to the whole of the electrolyte layer 202, for example.
  • the charge / discharge characteristics of the battery 2000 can be further improved.
  • the electrolyte layer 202 contains the second solid electrolyte as a main component, and further contains unavoidable impurities, starting materials, by-products, and decomposition products used in synthesizing the second solid electrolyte. May include.
  • the electrolyte layer 202 may contain the second solid electrolyte in an amount of 100% (100% by weight) based on the total weight of the electrolyte layer 202, for example, excluding impurities inevitably mixed.
  • the charge / discharge characteristics of the battery can be further improved.
  • the electrolyte layer 202 may be composed of only the second solid electrolyte.
  • the electrolyte layer 202 may contain two or more of the materials listed as the second solid electrolyte.
  • 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.
  • the thickness of the electrolyte layer 202 is 1 ⁇ m or more, the possibility that the positive electrode 201 and the negative electrode 203 are short-circuited is low. Further, when the thickness of the electrolyte layer 202 is 300 ⁇ m or less, the operation at high output becomes easy. That is, if the thickness of the electrolyte layer 202 is appropriately adjusted, sufficient safety of the battery 2000 can be ensured, and the battery 2000 can be operated at a high output.
  • 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, or the like can be used.
  • the metal material may be a single metal.
  • the metal material may be an alloy.
  • metal materials include lithium metal or lithium alloy.
  • Examples of carbon materials include natural graphite, coke, developing carbon, carbon fiber, spheroidal 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 third solid electrolyte. According to the above configuration, the lithium ion conductivity inside the negative electrode 203 is enhanced, and operation at high output becomes possible.
  • the third solid electrolyte contained in the negative electrode 203 the material mentioned as an example of the second solid electrolyte of the electrolyte layer 202 can be used.
  • the median diameter of the negative electrode active material particles may be 0.1 ⁇ m or more and 100 ⁇ m or less.
  • the median diameter of the negative electrode active material particles is 0.1 ⁇ m or more, the negative electrode active material particles and the solid electrolyte can form a better dispersed state in the negative electrode. This improves the charge / discharge characteristics of the battery. Further, when the median diameter of the negative electrode active material particles is 100 ⁇ m or less, the diffusion rate of lithium in the negative electrode active material is sufficiently secured. Therefore, the battery can operate at high output.
  • the median diameter of the negative electrode active material particles may be larger than the median diameter of the third solid electrolyte. This makes it possible to form a good dispersed state between the negative electrode active material particles and the solid electrolyte.
  • 30 ⁇ v2 ⁇ 95 may be satisfied with respect to the volume ratio “v2: 100-v2” of the negative electrode active material particles and the solid electrolyte contained in the negative electrode 203.
  • v2 volume ratio
  • v2 ⁇ 95 the operation of the battery 2000 at a high output becomes easier.
  • 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, it becomes easy to secure a sufficient energy density of the battery 2000. When the thickness of the negative electrode 203 is 500 ⁇ m or less, the operation of the battery 2000 at high output becomes easier.
  • 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, Examples include carboxymethyl cellulose and the like.
  • 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 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 such as natural graphite or artificial graphite, carbon blacks such as acetylene black or Ketjen black, conductive fibers such as carbon fibers or metal fibers, and metals such as carbon fluoride and aluminum. Powders, conductive whiskers such as zinc oxide or potassium titanate, conductive metal oxides such as titanium oxide, conductive polymer compounds such as polyaniline, polypyrrole or polythiophene, and the like can be used. When a carbon conductive auxiliary agent is used, the cost can be reduced.
  • the battery 2000 in 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.
  • the positive electrode material 1000, the material for forming the electrolyte layer, and the material for forming the negative electrode in the first embodiment are prepared, and the positive electrode, the electrolyte layer, and the negative electrode are formed by a known method. It may be manufactured by producing the laminated body arranged in this order.
  • Example 1 [Preparation of positive electrode active material whose surface is covered with a coating material]
  • a coating material solution [Preparation of positive electrode active material whose surface is covered with a coating material]
  • 6.3 mg of lithium hydroxide and 16.0 mg of triethyl phosphate were dissolved in an appropriate amount of ultra-dehydrated ethanol (manufactured by Wako Pure Chemical Industries, Ltd.) to prepare a coating material solution.
  • the molar ratio of lithium to phosphorus was 3: 1.
  • NCM Li (NiCoMn) O 2
  • NCM Li (NiCoMn) O 2
  • the powder after drying was placed in an alumina crucible and heat-treated at 400 ° C. for 3 hours in an oxygen atmosphere.
  • the powder after the heat treatment was reground in an agate mortar to obtain a positive electrode active material of Example 1 whose surface was coated with a coating material.
  • the coating material was lithium phosphate (Li 3 PO 4 ).
  • NCM which is a positive electrode active material coated with lithium phosphate, which is a coating material
  • HSE which is a first solid electrolyte
  • vapor-phase growth carbon fiber which is a conductive auxiliary agent (VGCF)
  • the sulfide solid electrolyte Li 6 PS 5 Cl (80 mg), the HSE powder (20 mg), and the above-mentioned positive electrode mixture (18.2 mg) were laminated in order.
  • a pressure of 720 MPa was applied to this to obtain a positive electrode and a solid electrolyte layer.
  • Li foil was laminated on the side of the electrolyte layer opposite to the side in contact with the positive electrode.
  • a pressure of 80 MPa was applied to this to prepare a laminate of a positive electrode, a solid electrolyte layer, and a negative electrode.
  • a negative electrode was formed by the Li foil.
  • Example 1 The battery of Example 1 was placed in a constant temperature bath at 25 ° C. The battery was charged with a constant current at a current value of 0.140 mA, and charging was completed at a voltage of 4.3 V. Next, the battery was discharged at a current value of 0.140 mA, and the discharge was completed at a voltage of 2.5 V.
  • FIG. 3 is a diagram showing a Nyquist diagram of the battery in Example 1 at 3.7 V.
  • the battery of Example 1 was placed in a constant temperature bath at 25 ° C. Then, it was connected to a potentiostat equipped with a frequency response analyzer. After that, the battery was constantly charged with a current value of 0.140 mA, and after reaching a voltage of 3.7 V, constant voltage charging was performed, and the process was completed. After that, the frequency dependence of the resistance component was evaluated by the AC impedance method. In this case, the resistance component appearing in the vicinity of 10 5 -10 2 Hz, separated by curve fitting, the active material - was resistance from the solid electrolyte interface. From this measurement, the resistance of Example 1 was estimated to be 140 ohm.
  • FIG. 4 is a diagram showing an O1s spectrum of the active material used in Example 1 in the XPS method.
  • the O1s spectrum of the surface of the positive electrode active material coated with lithium phosphate was obtained by the XPS method.
  • Al-K ⁇ rays were used as the source of XPS.
  • the peak of 528eV is a peak derived from MO (Ni—O, Mn—O, Co—O) in the positive electrode active material.
  • the 532eV peak is a combination of the peak of CO in lithium carbonate, which is a surface impurity, and the peak of PO in lithium phosphate. Derived from lithium carbonate by subtracting the peak area around 532 eV detected from the peak area of the coated active material near 532 eV, which was obtained by firing the active material not coated with the coating material at 400 ° C. under an oxygen atmosphere. The effect was removed and the peak area from the coating was calculated.
  • Example 1 From these peaks, the ratio of MO and PO in O1s was obtained, and the coverage was estimated. The coverage of lithium phosphate in the active material used in Example 1 was estimated to be 18%.
  • Example 2 [Preparation of positive electrode active material whose surface is covered with a coating material]
  • 14.2 mg of lithium hydroxide and 36.0 mg of triethyl phosphate are dissolved in an appropriate amount of ultra-dehydrated ethanol (manufactured by Wako Pure Chemical Industries, Ltd.) to prepare a coating material solution.
  • ultra-dehydrated ethanol manufactured by Wako Pure Chemical Industries, Ltd.
  • a battery was produced by the same method as in Example 1 except that the coating amount of the active material was changed.
  • Example 3 [Preparation of positive electrode active material whose surface is covered with a coating material]
  • an argon glove box with an argon atmosphere at a dew point of -60 ° C or less 5.95 g of ethoxylithium (manufactured by high-purity chemicals) and 36.43 g of pentaethoxyniobium (manufactured by high-purity chemicals) are mixed with ultra-dehydrated ethanol (manufactured by Wako Pure Chemical Industries, Ltd.). ) Dissolved in 500 mL to prepare a coating material solution.
  • a rolling flow granulation coating device (manufactured by Paulec, FD-MP-01E) was used to form the coating material on the positive electrode active material NCM.
  • the input amount of the positive electrode active material, the stirring rotation speed, and the liquid feeding rate of the coating material solution were 1 kg, 400 rpm, and 6.59 g / min, respectively.
  • the treated powder was placed in an alumina crucible and taken out under an air atmosphere.
  • the powder after the heat treatment was reground in an agate mortar to obtain a positive electrode active material of Example 3 whose surface was coated with a coating material.
  • the coating material was lithium niobate (LiNbO 3 ).
  • Example 4 [Preparation of the first solid electrolyte]
  • a battery was produced in the same manner as in Example 2 except that the solid electrolyte was changed.
  • Comparative Example 1 [Preparation of positive electrode active material]
  • the NCM used as the positive electrode active material in Examples 1 to 4 was used as the positive electrode active material of Comparative Example 1 without covering the surface with the coating material.
  • Table 1 shows the coating material, the thickness of the coating material, the mass ratio, the first solid electrolyte and the resistance of Examples 1 to 4 and Comparative Example 1.
  • the mass ratio means the ratio of the mass of the coating material to the mass of the positive electrode active material.
  • Example 1 In the batteries of Example 1 and Comparative Example 1, the same HSE was used as the first solid electrolyte contained in the positive electrode material. As a result, it was confirmed that even when HSE was used as the first solid electrolyte, the resistance of the battery was reduced by coating the positive electrode active material with the coating material. From this result, it can be seen that the effect of reducing the resistance of the battery can be obtained by coating the surface of the positive electrode active material with the coating material regardless of the difference in the metal type constituting the solid electrolyte.
  • the same HSE was used as the first solid electrolyte contained in the positive electrode material.
  • the same lithium phosphate was used as the coating material for coating the positive electrode active material contained in the positive electrode material.
  • the resistance of the battery was further reduced as the mass ratio of the coating material in the positive electrode active material was increased. It is considered that when the mass ratio of the coating material in the positive electrode active material was increased, the coverage of the positive electrode active material was increased, and the direct contact area between the positive electrode active material and the solid electrolyte could be reduced. That is, it is considered that the resistance of the battery was reduced because the formation of the resistance layer between the active material and the solid electrolyte could be suppressed.
  • Example 3 and Comparative Example 1 show that the resistance of the battery was reduced even when lithium niobate was used as the coating material.
  • an oxide containing lithium, particularly phosphoric acid as a glass-forming oxide, and lithium niobate as an intermediate oxide are used as the coating material, the thickness of the coating material tends to be thin. In this case, firing at a low temperature forms a highly amorphous film. Therefore, it is considered that the formation of the resistance layer between the active material and the solid electrolyte could be suppressed without inhibiting the exchange of lithium between the active material and the solid electrolyte.
  • Example 2 Comparing Example 2 and Example 4, the coating material is the same, but the composition of the first solid electrolyte is different. From this result, it can be seen that the resistance of the battery could be reduced regardless of the ratio of the elements constituting the first solid electrolyte.
  • Example 5 [Preparation of the first solid electrolyte]
  • a battery was produced in the same manner as in Example 2 except that the first solid electrolyte was changed.
  • Table 2 shows the coating material, the thickness of the coating material, the mass ratio, the first solid electrolyte and the resistance of Example 5 and Comparative Example 2.
  • Example 5 a material containing Sm was used as a constituent element of the first solid electrolyte contained in the positive electrode material.
  • the resistance of the battery can be significantly reduced by coating the active material with lithium phosphate.
  • the effect of the present disclosure is not limited to the case where Y and Gd are contained as the constituent elements of the first solid electrolyte, and it can be said that the effect is effective when Y and a rare earth element other than Y are contained.
  • the battery of the present disclosure can be used as, for example, an all-solid-state lithium secondary battery.
  • Positive electrode material 100 1st solid electrolyte 110 Positive electrode active material 111 Coating material 2000 Battery 201 Positive electrode 202 Electrolyte layer 203 Negative electrode

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WO2023032473A1 (ja) * 2021-09-01 2023-03-09 パナソニックＩｐマネジメント株式会社 正極材料および電池
US11735765B2 (en) 2021-01-08 2023-08-22 Samsung Electronics Co., Ltd. Solid ion conductor, solid electrolyte including the solid ion conductor, electrochemical device including the solid electrolyte, and method of preparing the solid ion conductor
JP2023154498A (ja) * 2022-04-07 2023-10-20 トヨタ自動車株式会社 複合粒子、正極および全固体電池
WO2024029216A1 (ja) * 2022-08-02 2024-02-08 パナソニックＩｐマネジメント株式会社 被覆活物質、正極材料、および電池
US11961962B2 (en) 2020-07-02 2024-04-16 Samsung Electronics Co., Ltd. Solid ion conductor compound, solid electrolyte including the same, electrochemical cell including the same, and preparation method thereof
WO2024117673A1 (ko) * 2022-11-29 2024-06-06 삼성에스디아이 주식회사 전고체 전지
EP4401166A3 (en) * 2023-01-11 2024-08-21 Toyota Jidosha Kabushiki Kaisha Composite particle, positive electrode, and all-solid-state battery
WO2024262149A1 (ja) * 2023-06-20 2024-12-26 Ｄｏｗａホールディングス株式会社 全固体電池セル、固体電解質粉末、固体電解質粉末の製造方法、被覆体の製造方法

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Cited By (12)

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Publication number Priority date Publication date Assignee Title
US11961962B2 (en) 2020-07-02 2024-04-16 Samsung Electronics Co., Ltd. Solid ion conductor compound, solid electrolyte including the same, electrochemical cell including the same, and preparation method thereof
EP4001218A1 (en) * 2020-11-12 2022-05-25 Samsung Electronics Co., Ltd. Solid ion conductor compound, solid electrolyte comprising the same, electrochemical cell comprising the same, and method of preparing the same
US12456751B2 (en) 2020-11-12 2025-10-28 Samsung Electronics Co., Ltd. Solid ion conductor compound, solid electrolyte comprising the same, electrochemical cell comprising the same, and method of preparing the same
US11735765B2 (en) 2021-01-08 2023-08-22 Samsung Electronics Co., Ltd. Solid ion conductor, solid electrolyte including the solid ion conductor, electrochemical device including the solid electrolyte, and method of preparing the solid ion conductor
WO2023032473A1 (ja) * 2021-09-01 2023-03-09 パナソニックＩｐマネジメント株式会社 正極材料および電池
JPWO2023032473A1 (https=) * 2021-09-01 2023-03-09
JP2023154498A (ja) * 2022-04-07 2023-10-20 トヨタ自動車株式会社 複合粒子、正極および全固体電池
JP7750165B2 (ja) 2022-04-07 2025-10-07 トヨタ自動車株式会社 複合粒子、正極および全固体電池
WO2024029216A1 (ja) * 2022-08-02 2024-02-08 パナソニックＩｐマネジメント株式会社 被覆活物質、正極材料、および電池
WO2024117673A1 (ko) * 2022-11-29 2024-06-06 삼성에스디아이 주식회사 전고체 전지
EP4401166A3 (en) * 2023-01-11 2024-08-21 Toyota Jidosha Kabushiki Kaisha Composite particle, positive electrode, and all-solid-state battery
WO2024262149A1 (ja) * 2023-06-20 2024-12-26 Ｄｏｗａホールディングス株式会社 全固体電池セル、固体電解質粉末、固体電解質粉末の製造方法、被覆体の製造方法

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