WO2024128127A1 - 酸化物及びその製造方法、固体電解質並びに蓄電デバイス - Google Patents

酸化物及びその製造方法、固体電解質並びに蓄電デバイス Download PDF

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WO2024128127A1
WO2024128127A1 PCT/JP2023/043839 JP2023043839W WO2024128127A1 WO 2024128127 A1 WO2024128127 A1 WO 2024128127A1 JP 2023043839 W JP2023043839 W JP 2023043839W WO 2024128127 A1 WO2024128127 A1 WO 2024128127A1
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oxide
solid electrolyte
solid
formula
ion conductivity
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French (fr)
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孝章 名取
朋子 仲野
直彦 斎藤
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Toagosei Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B25/00—Phosphorus; Compounds thereof
    • C01B25/16—Oxyacids of phosphorus; Salts thereof
    • C01B25/26—Phosphates
    • C01B25/45—Phosphates containing plural metal, or metal and ammonium
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B33/00—Silicon; Compounds thereof
    • C01B33/20—Silicates
    • C01B33/32—Alkali metal silicates
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
    • C04B35/16—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on silicates other than clay
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
    • C04B35/447—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on phosphates, e.g. hydroxyapatite
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
    • H01B1/08—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances oxides
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0561—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of inorganic materials only
    • H01M10/0562—Solid materials
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present invention relates to oxides and their manufacturing methods, solid electrolytes, and electricity storage devices.
  • LIB is a secondary battery that has a negative electrode, a positive electrode, and an electrolyte, and charges and discharges by transferring lithium ions between the two electrodes via the electrolyte.
  • the electrolyte usually uses an organic electrolyte solution in which an electrolyte salt such as LiPF6 is dissolved in a carbonate-based solvent, and since the organic solvent used is flammable, there is a concern that the battery may catch fire in the event of a short circuit.
  • Known solid electrolytes having sodium ion conductivity include sulfide-based solid electrolytes and oxide-based solid electrolytes. Of these, sulfide-based solid electrolytes are unstable in the atmosphere and have the risk of generating hydrogen sulfide, posing safety issues, whereas oxide-based solid electrolytes are more stable in the atmosphere than sulfide-based solid electrolytes and therefore safer.
  • Non-Patent Document 1 Ce (cerium) is doped.
  • the present invention was made in consideration of the above-mentioned circumstances, and aims to provide a new NASICON-based oxide that exhibits high Na ion conductivity and a method for producing the same. It also aims to provide a solid electrolyte and an electricity storage device that use this oxide.
  • the present invention is as follows.
  • M1 contains an element that becomes a divalent cation
  • M2 contains an element that becomes a trivalent cation
  • M3 contains an element that becomes a tetravalent cation containing Ti (excluding Zr and Si)
  • x, y, z, and ⁇ satisfy x ⁇ 0, y ⁇ 0, z>0, and ⁇ >0.
  • the method for producing an oxide according to any one of [9] to [11], wherein the calcination step includes a step of calcining at 900° C. or higher.
  • high Na ion conductivity can be obtained in a NASICON-based oxide.
  • high Na ion conductivity can be obtained in a NASICON-based oxide.
  • a NASICON-based oxide can be used as the solid electrolyte.
  • a NASICON-based oxide having high Na ion conductivity can be obtained.
  • FIG. 1A is an explanatory diagram illustrating an example of an all-solid-state battery as an electricity storage device
  • % means “% by mass”
  • parts means “parts by mass”
  • ppm means “ppm by mass”
  • numeric value X to numeric value Y means “numeric value X or more and numeric value Y or less”.
  • each embodiment described later can be an embodiment in which two or more of each are combined.
  • Oxide The oxide of the present invention is characterized by satisfying the following formula (1).
  • An oxide satisfying the following formula (1). Na 3 + 2x + y + ⁇ M1 x M2 y M3 z Zr 2-x-y-z Si 2 + ⁇ P 1- ⁇ O 12 ...
  • M1 includes an element that can be a divalent cation
  • M2 includes an element that can be a trivalent cation
  • M3 includes an element that can be a tetravalent cation containing Ti (excluding Zr and Si)
  • x, y, z, and ⁇ satisfy x ⁇ 0, y ⁇ 0, z>0, and ⁇ >0.
  • this oxide has Na 3 Zr 2 Si 2 PO 12 as its base (parent structure), and it is essential that a part of Zr is replaced by M3 (including Ti), and may be further replaced by M1 or M2, and it can be said to be an oxide in which the amount of Si in the composition is increased compared to the parent structure.
  • M1 is an element that becomes a divalent cation.
  • examples of such elements include elements that become divalent cations among Group 2 elements, Group 12 elements, and transition elements (Groups 3 to 11 elements), as well as Sn and Pd.
  • M2 is an element that becomes a trivalent cation. Examples of such elements include elements that become trivalent cations among Group 3 elements, Group 13 elements, and transition elements (Groups 3 to 11 elements), as well as Sb and Bi.
  • B boron
  • M3 contains an element (excluding Zr and Si) that becomes a tetravalent cation containing Ti. That is, M3 may contain an element that becomes a tetravalent cation other than Ti, Zr, and Si. Examples of such elements include elements (Te, Ce, Th) that become tetravalent cations among Group 14 elements and transition elements (Groups 3 to 11 elements).
  • x, y, z, and ⁇ may satisfy x ⁇ 0, y ⁇ 0, z>0, and ⁇ >0. However, it is preferable that x ⁇ 0.3 is further satisfied, and better Na ion conductivity can be obtained compared to the case where x>0.3. This is believed to be because the segregation of M1 can be suppressed by satisfying x ⁇ 0.3. As the content of M1 increases, the solid solubility limit in the Zr site is approached, and an impurity phase containing a large amount of M1 begins to form, which inhibits Na ion conduction.
  • the condition of x ⁇ 0.3 is believed to contribute.
  • the presence or absence of segregation of M1 can be detected by measuring the distribution of M1 using energy dispersive X-ray spectroscopy. From the above viewpoint, it is considered that the condition x ⁇ 0.3 contributes to this.
  • the upper limit of x is preferably x ⁇ 0.2, and more preferably x ⁇ 0.1
  • the lower limit of x is preferably 0.01 ⁇ x, and more preferably 0.03 ⁇ x, and even more preferably 0.05 ⁇ x.
  • M1 has a smaller valence than Zr, the electrostatic repulsion force between M1 and a Na ion, which is a monovalent cation, is smaller than that between M1 and Zr. Therefore, it is considered that the substitution of Zr with M1 facilitates the diffusion of Na ions in the vicinity of M1.
  • y ⁇ 0.3 be satisfied, and better Na ion conductivity can be obtained as compared with the case where y>0.3.
  • the content of M2 increases, the solid solubility limit in the Zr site is approached, and an impurity phase containing a large amount of M2 begins to form, which inhibits Na ion conduction. For this reason, a composition in which the impurity phase is unlikely to form is preferable, and from this perspective, the condition y ⁇ 0.3 is believed to contribute.
  • the presence or absence of segregation of M2 can be detected by measuring the distribution of M2 using energy dispersive X-ray spectroscopy.
  • the condition y ⁇ 0.3 contributes.
  • the upper limit of y is preferably y ⁇ 0.2, more preferably y ⁇ 0.1
  • the lower limit of y is preferably 0.01 ⁇ y, more preferably 0.03 ⁇ y, and even more preferably 0.05 ⁇ y.
  • M2 has a smaller valence than Zr
  • z ⁇ 0.3 be satisfied, and better Na ion conductivity can be obtained as compared with the case where z>0.3.
  • the content of M3 increases, the solid solubility limit in the Zr site is approached, and an impurity phase containing a large amount of M3 begins to form, which inhibits Na ion conduction. For this reason, a composition in which the impurity phase is unlikely to form is preferable, and from this perspective, the condition z ⁇ 0.3 is believed to contribute.
  • the presence or absence of segregation of M3 can be detected by measuring the distribution of M3 using energy dispersive X-ray spectroscopy.
  • the condition z ⁇ 0.3 contributes to this.
  • the upper limit of z is preferably z ⁇ 0.2, more preferably z ⁇ 0.15, and even more preferably z ⁇ 0.1.
  • the lower limit of z is preferably z ⁇ 0.01, more preferably z ⁇ 0.02, even more preferably z ⁇ 0.03, even more preferably z ⁇ 0.04, and even more preferably z ⁇ 0.05.
  • the ionic radius of Ti is smaller than that of Zr, and it is considered that the substitution of Ti for Zr sites reduces the activation energy at the bottleneck in the migration path of Na, making it easier for Na ions to diffuse.
  • Si has a smaller valence than P, the electrostatic repulsion with Na ions, which are monovalent cations, is smaller than that of P. Therefore, it is considered that by substituting Si for P, diffusion of Na ions in the vicinity of Si is likely to occur.
  • the amount of Si substitution increases, the effect of inhibiting Na ion conduction due to the capture of Na ions in the vicinity of Si becomes significant. For this reason, it is considered that the ion conductivity deteriorates when the amount of Si substitution is large. From this viewpoint, it is considered that the condition ⁇ 1.0 contributes.
  • the upper limit of ⁇ is preferably ⁇ 0.9, more preferably ⁇ 0.8, even more preferably ⁇ 0.7, even more preferably ⁇ 0.6, and even more preferably ⁇ 0.5.
  • the lower limit of ⁇ is preferably ⁇ 0.1, more preferably ⁇ 0.15, even more preferably ⁇ 0.2, even more preferably ⁇ 0.25, and even more preferably ⁇ 0.3.
  • the oxide represented by formula (1) is described as having a stoichiometric ratio of O of 12. However, in reality, it is sufficient to maintain the charge neutrality of the oxide as a whole, and the value may be less than 12 or more than 12.
  • formula (1) when formula (1) is expressed as formula (2) as shown below (M1, M2, M3, x, y, z, and ⁇ are the same as formula (1)), Na 3 + 2x + y + ⁇ M1 x M2 y M3 z Zr 2-x-y-z Si 2 + ⁇ P 1- ⁇ O 12 + ⁇ ... (2) ⁇ can be set to, for example, 0 ⁇ 1.
  • the oxide of the present invention is not limited to a phase structure, and as a result, it is preferable that the oxide has high Na ion conductivity. Among them, it is preferable that the oxide exhibits a NASICON (Na Super Ionic Conductor) type. This is because the NASICON type is advantageous in use as a solid electrolyte. That is, unlike a layered structure, the NASICON type has a three-dimensionally expanded space for Na ion movement, and zirconium is stable even under high voltage, so it is useful as a solid electrolyte with a high operating voltage. Whether or not the oxide of the present invention exhibits a NASICON type can be determined from a diffraction profile obtained by powder X-ray diffraction measurement.
  • the relative density of the oxide of the present invention is preferably 80% or more, more preferably 85% or more, even more preferably 90% or more, and even more preferably 95% or more, in terms of obtaining better Na ion conductivity.
  • the relative density can be obtained by measuring the diameter, thickness, and mass of the solid electrolyte, calculating the actual density from the actual measured values of the volume and mass, and then calculating the ratio (%) of the actual density to the theoretical density.
  • the use of the oxide of the present invention is not particularly limited, but it can be used, for example, as a material for an electricity storage device (material for an all-solid-state battery, various secondary battery materials), a CO 2 sensor, etc.
  • the material include solid electrolytes (solid electrolyte materials) of all-solid-state batteries, electrodes (electrode materials) of all-solid-state batteries, and separators.
  • the oxide described above may be produced in any manner, and may be produced using a solid-phase method or a liquid-phase method, but in the present invention, it can be produced using a solid-phase method. More specifically, it can be produced by including a mixing step and a firing step.
  • the mixing step is a step of mixing a plurality of supply components containing one or more elements selected from Na, the M1, the M2, the M3, Zr, Si, and P so as to satisfy the formula (1) to obtain a mixture of the supply components.
  • the firing step is a step of firing the mixture to obtain an oxide.
  • the supply components for supplying each of the elements Na, M1, M2, M3, Zr, Si and P may be inorganic compounds or organic compounds.
  • carbonates, hydrogen carbonates, sulfates, sulfites, nitrates, nitrites, phosphates, acetates, citrates, ammonium salts, oxides, hydroxides, chlorides, sulfides, etc. of these metal elements can be used.
  • one of these feed components may be a compound containing two or more elements selected from Na, M1, M2, M3, Zr, Si, and P.
  • a plurality of supply components including one or more elements selected from Na, M1, M2, M3, Zr, Si, and P are weighed so as to satisfy formula (1), i.e., so as to satisfy the stoichiometric ratio of the composition expressed by formula (1), and the weighed amounts are then mixed.
  • Mixing may be performed by dry mixing, but it is preferable to use a liquid for wet mixing. By performing wet mixing, the density of the sintered body after firing can be increased compared to the case of performing dry mixing, and the Na ion conductivity can also be relatively improved.
  • the liquid used for wet mixing water, various organic solvents, mixtures thereof, etc. can be appropriately used.
  • the mixture obtained in the mixing step may be fired without being molded, or may be molded and then fired.
  • the firing temperature is not limited, but may be, for example, 900° C. or higher, preferably 1,000° C. or higher, more preferably 1,100° C. or higher, even more preferably 1,150° C. or higher, even more preferably 1,200° C. or higher, and even more preferably 1,250° C. or higher.
  • the firing temperature may be 1,600° C. or lower, preferably 1,500° C. or lower, more preferably 1,400° C. or lower, even more preferably 1,350° C. or lower, and even more preferably 1,300° C. or lower.
  • the firing may be performed in one step, or in multiple steps via pre-firing. That is, the temperature can be increased stepwise from a temperature lower than the firing temperature, and the temperature required for firing can be finally imposed.
  • each pre-firing step can be followed by a grinding step in which the obtained pre-firing product is ground.
  • the firing may be performed in two stages, such as performing the first pre-firing at 1,000° C. or higher and lower than 1,150° C., and performing the main firing at 1,150° C. or higher; the firing may be performed in three stages, such as performing the first pre-firing in a temperature range of 400° C.
  • the firing time is not limited, but for example, the pre-firing can be performed for 1 hour or more and 40 hours or less, and the main firing can be performed for 1 hour or more and 40 hours or less.
  • the solid electrolyte of the present invention is characterized by containing the above-mentioned oxide.
  • the amount of the oxide contained in this solid electrolyte is not limited, and for example, when the content of the oxide is X mass % when the entire solid electrolyte is 100 mass %, it can be 0 ⁇ X (mass %) ⁇ 100. Also, for example, it can be 50 ⁇ X (mass %) ⁇ 100, or 75 ⁇ X (mass %) ⁇ 100.
  • the solid electrolyte of the present invention may contain other oxides that have Na ion conductivity but are not represented by formula (1).
  • examples of other solid electrolytes include oxides having Na ion conductivity that satisfy the following formula (3), oxides having Na ion conductivity that satisfy the following formula (4), oxides having Na ion conductivity that satisfy the following formula (5), oxides having Na ion conductivity that satisfy the following formula (6), oxides having Na ion conductivity that satisfy the following formula (7), and oxides having Na ion conductivity that satisfy the following formula (8). These may be used alone or in combination of two or more.
  • M1 is a divalent element
  • M2 is a trivalent element
  • M4 is a tetravalent element other than Ti
  • x, y, and ⁇ satisfy x ⁇ 0, y ⁇ 0, ⁇ >0, and x+y>0.
  • M1 is a divalent element
  • M2 is a trivalent element
  • M3 is a tetravalent element
  • x, y, and z satisfy x ⁇ 0, y ⁇ 0, and z>0.
  • M1 is a divalent element
  • M2 is a trivalent element
  • M3 is a tetravalent element
  • x, y, z, and ⁇ satisfy x ⁇ 0, y ⁇ 0, z>0, and ⁇ >0.
  • M1 is a divalent element
  • M2 is a trivalent element
  • M3 is a tetravalent element
  • M5 is a pentavalent element
  • x, y, z, ⁇ , and ⁇ satisfy x ⁇ 0, y ⁇ 0, z>0, ⁇ 0, and ⁇ >0.
  • divalent nonmetallic elements and divalent metallic elements can be applied to M1 in the above formulas (3), (5), (6), (7) and (8).
  • Trivalent nonmetallic elements and trivalent metallic elements can be applied to M2.
  • tetravalent nonmetallic elements and tetravalent metallic elements can be applied to M4 in the above formula (5).
  • tetravalent nonmetallic elements and tetravalent metallic elements can be applied to M3 in the above formulas (6), (7) and (8).
  • pentavalent nonmetallic elements and pentavalent metallic elements can be applied to M5 in the above formula (8).
  • the all-solid-state battery 1 of the present invention is an all-solid-state battery comprising the above-described solid electrolyte 23 (solid electrolyte layer) (see FIG. 1).
  • the all-solid-state battery 1 includes a positive electrode 22 (positive electrode layer) and a negative electrode 24 (negative electrode layer) in addition to a solid electrolyte 23.
  • the all-solid-state battery may be of a bulk type (see FIG. 1(a)) or a thin-film type (see FIG. 1(b)).
  • the positive electrode 22 and the negative electrode 24 can be arranged to face each other with the solid electrolyte 23 interposed therebetween.
  • the positive electrode 22 and the negative electrode 24 are also arranged in contact with the solid electrolyte 23.
  • the all-solid-state battery 1 can include the solid electrolyte 23, the positive electrode 22, and the negative electrode 24 as an integrated sintered body.
  • the battery when the solid electrolyte 23 (solid electrolyte layer) has two main surfaces, i.e., when it is a plate, membrane, sheet, or film, the battery can be configured to include the positive electrode 22 on one main surface and the negative electrode 24 on the other main surface with the solid electrolyte 23 interposed therebetween.
  • the positive electrode usually contains a positive electrode active material, and may also contain, for example, one or more of a conductive material, a solid electrolyte, a binder, and the like.
  • the negative electrode also usually contains a negative electrode active material, and may also contain, for example, one or more of a conductive material, a solid electrolyte, a binder, and the like.
  • Each electrode may have a current collector. That is, the positive electrode 22 may have a positive electrode current collector 21 on the surface not in contact with the solid electrolyte 23. Similarly, the negative electrode 24 may have a negative electrode current collector 25 on the surface not in contact with the solid electrolyte 23.
  • the positive electrode 22 and the negative electrode 24 can be disposed apart from each other so that a portion of each of them is in contact with the solid electrolyte 23.
  • the all-solid-state battery 1 can be provided as an integrated sintered body in which the negative electrode 24, the solid electrolyte 23, and the positive electrode 22 are laminated in this order.
  • the positive electrode usually contains a positive electrode active material and may contain one or more of, for example, a conductive material, a solid electrolyte, a binder, etc.
  • the negative electrode usually contains a negative electrode active material and may contain one or more of, for example, a conductive material, a solid electrolyte, a binder, etc.
  • Each electrode may be provided with a current collector.
  • the resulting mixture was dried at 100° C. for 3 hours, transferred to an alumina crucible (capacity 30 mL), heated to 1,100° C. over 5.5 hours, and held at that temperature for 5 hours to perform first pre-firing. Thereafter, the mixture was allowed to cool to room temperature to obtain a first pre-firing product.
  • the first calcined product was ground in an ethanol dispersion medium for 1 hour using a planetary ball mill with ⁇ 5 mm ZrO2 balls, then passed through a 330 mesh sieve, and the resulting dispersion was dried at 80°C.
  • 0.3 g of the pulverized product of the first calcined product obtained was placed in a metal mold having a diameter of 1.2 cm, and molded into a coin shape by applying a load of 1 ton using a hydraulic press.
  • the molded product obtained was placed on a platinum plate, and the temperature was raised to 800°C over 30 minutes, and then the temperature was further raised to the main calcination temperature (1,200°C) described in Example 1 in Table 1 over 2 hours and maintained at that temperature for 4 hours to perform main calcination.
  • the product was then allowed to cool to room temperature, and the oxide of Example 1 was obtained.
  • Example 2 to 18 and Comparative Examples 1 to 3 In the same manner as in Example 1, the respective samples were weighed so as to obtain the molar ratios shown in Examples 2 to 18 and Comparative Examples 1 to 3 in Table 1, and each sample was placed in a mortar, and 20 g of pure water was added thereto to perform wet mixing to obtain a mixture. The obtained mixture was pre-fired and fired under the same conditions as in Example 1 to obtain the oxides of Examples 2 to 18 and Comparative Examples 1 to 3.
  • the first calcined product was molded into a coin shape in the same manner as in Example 1, and the resulting molded product was placed on a platinum plate and heated to 800° C.
  • Examples 10 to 13 in Table 1 the main calcination temperature shown in Examples 10 to 13 in Table 1 over 2 hours and held for 4 hours to perform main calcination. Thereafter, the product was allowed to cool to room temperature to obtain each oxide of Examples 10 to 13.
  • aluminum oxide manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.
  • magnesium oxide manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. was used as the Mg raw material.

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PCT/JP2023/043839 2022-12-15 2023-12-07 酸化物及びその製造方法、固体電解質並びに蓄電デバイス Ceased WO2024128127A1 (ja)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000126556A (ja) * 1998-10-23 2000-05-09 Agency Of Ind Science & Technol リチウム同位体分離剤
JP2018538653A (ja) * 2015-10-09 2018-12-27 フォルシュングスツェントルム・ユーリッヒ・ゲゼルシャフト・ミット・ベシュレンクテル・ハフツング 固体ナトリウムイオン電池用のｎａｓｉｃｏｎ構造を有する電解質材料およびその製造方法
CN113675463A (zh) * 2021-08-21 2021-11-19 西南石油大学 一种nasicon型无机固态电解质材料及其制备方法和应用

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000126556A (ja) * 1998-10-23 2000-05-09 Agency Of Ind Science & Technol リチウム同位体分離剤
JP2018538653A (ja) * 2015-10-09 2018-12-27 フォルシュングスツェントルム・ユーリッヒ・ゲゼルシャフト・ミット・ベシュレンクテル・ハフツング 固体ナトリウムイオン電池用のｎａｓｉｃｏｎ構造を有する電解質材料およびその製造方法
CN113675463A (zh) * 2021-08-21 2021-11-19 西南石油大学 一种nasicon型无机固态电解质材料及其制备方法和应用

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
CHEN DAN, LUO FA, ZHOU WANCHENG, ZHU DONGMEI: "Influence of Nb5+, Ti4+, Y3+ and Zn2+ doped Na3Zr2Si2PO12 solid electrolyte on its conductivity", JOURNAL OF ALLOYS AND COMPOUNDS, ELSEVIER SEQUOIA, LAUSANNE., CH, vol. 757, 1 August 2018 (2018-08-01), CH , pages 348 - 355, XP093182701, ISSN: 0925-8388, DOI: 10.1016/j.jallcom.2018.05.116 *
SAMIEE MOJTABA, RADHAKRISHNAN BALACHANDRAN, RICE ZANE, DENG ZHI, MENG YING SHIRLEY, ONG SHYUE PING, LUO JIAN: "Divalent-doped Na3Zr2Si2PO12 natrium superionic conductor: Improving the ionic conductivity via simultaneously optimizing the phase and chemistry of the primary and secondary phases", JOURNAL OF POWER SOURCES, ELSEVIER, AMSTERDAM, NL, vol. 347, 1 April 2017 (2017-04-01), AMSTERDAM, NL, pages 229 - 237, XP093182703, ISSN: 0378-7753, DOI: 10.1016/j.jpowsour.2017.02.042 *

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