WO2023119876A1 - 全固体電池 - Google Patents

全固体電池 Download PDF

Info

Publication number
WO2023119876A1
WO2023119876A1 PCT/JP2022/040469 JP2022040469W WO2023119876A1 WO 2023119876 A1 WO2023119876 A1 WO 2023119876A1 JP 2022040469 W JP2022040469 W JP 2022040469W WO 2023119876 A1 WO2023119876 A1 WO 2023119876A1
Authority
WO
WIPO (PCT)
Prior art keywords
solid electrolyte
electrode layer
positive electrode
average particle
negative electrode
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2022/040469
Other languages
English (en)
French (fr)
Japanese (ja)
Inventor
関口正史
伊藤大悟
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Taiyo Yuden Co Ltd
Original Assignee
Taiyo Yuden Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Taiyo Yuden Co Ltd filed Critical Taiyo Yuden Co Ltd
Priority to JP2023569125A priority Critical patent/JPWO2023119876A1/ja
Priority to US18/714,724 priority patent/US20250030044A1/en
Publication of WO2023119876A1 publication Critical patent/WO2023119876A1/ja
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Images

Classifications

    • 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
    • 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
    • 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
    • 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
    • H01M10/058—Construction or manufacture
    • H01M10/0585—Construction or manufacture of accumulators having only flat construction elements, i.e. flat positive electrodes, flat negative electrodes and flat separators
    • 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
    • H01M4/36—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
    • 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
    • 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
    • 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
    • H01M2004/021—Physical characteristics, e.g. porosity, surface area
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/027—Negative electrodes
    • 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
    • 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 all-solid-state batteries.
  • lithium-ion secondary batteries are used in various fields such as consumer equipment, industrial machinery, and automobiles.
  • existing lithium-ion secondary batteries contain an electrolytic solution, so there is a risk of leakage of the electrolytic solution, smoke, or fire. Therefore, in particular, all-solid-state lithium-ion secondary batteries employing an oxide-based solid electrolyte that is stable in the atmosphere have been actively developed (see, for example, Patent Document 1).
  • JP 2018-73554 A Japanese Patent Application Laid-Open No. 2021-108258
  • the electrode active material and the solid electrolyte in the electrode layer must be packed as densely as possible so that they have many contacts with each other, and then sintered to make them more effective. It is desirable to form mutual contacts at However, it is difficult to improve interdispersibility and fillability. For example, in a multi-layered all-solid-state battery manufactured according to the manufacturing flow described in Patent Document 2, it is difficult to efficiently improve interdispersibility and filling properties when manufacturing an electrode mixture.
  • the present invention has been made in view of the above problems, and an object thereof is to provide an all-solid-state battery capable of realizing a high-density electrode layer.
  • An all-solid-state battery includes a solid electrolyte layer containing a first solid electrolyte, a positive electrode layer provided on a first main surface of the solid electrolyte layer and containing a positive electrode active material and a second solid electrolyte, a negative electrode layer provided on the second main surface of the solid electrolyte layer and containing a negative electrode active material and a third solid electrolyte, wherein at least one of the positive electrode layer and the negative electrode layer,
  • the average particle size of the second solid electrolyte or the third solid electrolyte is 2.5 ⁇ m or less, and the ratio of the average particle size of the positive electrode active material to the average particle size of the second solid electrolyte or the third solid electrolyte
  • the ratio of the average particle size of the negative electrode active material to the average particle size of the solid electrolyte is 0.4 or more and 10 or less.
  • the second solid electrolyte or the third solid electrolyte in a cross section viewed from a direction perpendicular to the direction in which the positive electrode layer and the negative electrode layer face each other may be 25% or more and 75% or less.
  • the average particle size of the second solid electrolyte or the third solid electrolyte of the all-solid-state battery may be 0.05 ⁇ m or more.
  • At least one of the electrode layers of the all-solid-state battery may have a porosity of 10% or less.
  • the second solid electrolyte or the third solid electrolyte of the all-solid-state battery may be a phosphate-based solid electrolyte.
  • the second solid electrolyte or the third solid electrolyte of the all-solid-state battery may have a NASICON crystal structure.
  • the positive electrode active material may contain Co and P.
  • the second solid electrolyte or the third solid electrolyte may contain Co.
  • the positive electrode active material may contain at least one of LiCoPO 4 , LiCo 2 P 3 O 10 , Li 2 CoP 2 O 7 , and Li 6 Co 5 (P 2 O 7 ) 4 . good.
  • FIG. 1 is a schematic cross-sectional view showing the basic structure of an all-solid-state battery
  • FIG. 2 is a schematic cross-sectional view showing details of a positive electrode layer and a negative electrode layer
  • (a) is a diagram plotting the relationship between the porosity and its overall conductivity
  • (b) is a diagram plotting the relationship between the porosity and the capacity retention rate.
  • 1 is a schematic cross-sectional view of a stacked all-solid-state battery
  • FIG. 3 is a schematic cross-sectional view of another stacked all-solid-state battery. It is a figure which illustrates the flow of the manufacturing method of an all-solid-state battery.
  • (a) and (b) are figures which illustrate a lamination process.
  • FIG. 1 is a schematic cross-sectional view showing the basic structure of an all-solid-state battery 100 according to an embodiment.
  • the all-solid battery 100 has a structure in which a solid electrolyte layer 30 is sandwiched between a positive electrode layer 10 and a negative electrode layer 20 .
  • the positive electrode layer 10 is formed on the first main surface of the solid electrolyte layer 30 and the negative electrode layer 20 is formed on the second main surface of the solid electrolyte layer 30 .
  • the solid electrolyte layer 30 is mainly composed of an ionically conductive solid electrolyte (first solid electrolyte).
  • the solid electrolyte of the solid electrolyte layer 30 is, for example, an oxide-based solid electrolyte having lithium ion conductivity.
  • the solid electrolyte is, for example, a phosphate-based solid electrolyte having a NASICON structure. Phosphate-based solid electrolytes having the NASICON structure have properties of high electrical conductivity and stability in the air.
  • a phosphate-based solid electrolyte is, for example, a phosphate containing lithium.
  • the phosphate is not particularly limited, but examples thereof include a composite lithium phosphate with Ti (eg, LiTi 2 (PO 4 ) 3 ).
  • Ti can be partially or wholly substituted with tetravalent transition metals such as Ge, Sn, Hf, and Zr.
  • tetravalent transition metals such as Ge, Sn, Hf, and Zr.
  • trivalent transition metals such as Al, Ga, In, Y and La. More specifically, for example, Li 1+x Al x Ge 2-x (PO 4 ) 3 , Li 1+x Al x Zr 2-x (PO 4 ) 3 , Li 1+x Al x Ti 2-x (PO 4 ) 3 etc.
  • a Li--Al--Ge-- PO.sub.4 -based material to which the same transition metal as the transition metal contained in the phosphate having an olivine crystal structure contained in the positive electrode layer 10 and the negative electrode layer 20 is previously added is preferable.
  • the positive electrode layer 10 and the negative electrode layer 20 contain a phosphate containing Co and Li
  • the solid electrolyte layer 30 contains a Li—Al—Ge—PO 4 -based material to which Co has been added in advance. is preferred. In this case, the effect of suppressing the elution of the transition metal contained in the electrode active material into the electrolyte can be obtained.
  • the solid electrolyte layer 30 is made of a Li—Al—Ge—PO 4 -based material to which the transition metal has been previously added. is preferably included in
  • the positive electrode layer 10 has a structure in which particles of the positive electrode active material 11, particles of the solid electrolyte 12 (second solid electrolyte), etc. are dispersed.
  • the positive electrode layer 10 may include a conductive aid or the like in addition to the positive electrode active material 11 and the solid electrolyte 12 .
  • the negative electrode layer 20 has a structure in which particles of the negative electrode active material 21, particles of the solid electrolyte 22 (third solid electrolyte), and the like are dispersed.
  • the negative electrode layer 20 may include a conductive aid or the like in addition to the negative electrode active material 21 and the solid electrolyte 22 .
  • the all-solid battery 100 can be used as a secondary battery.
  • the positive electrode layer 10 with the solid electrolyte 12 and the negative electrode layer 20 with the solid electrolyte 22 have ion conductivity. Electroconductivity is obtained in the positive electrode layer 10 and the negative electrode layer 20 by providing the positive electrode layer 10 and the negative electrode layer 20 with the conductive aid.
  • the positive electrode active material 11 is, for example, an electrode active material having an olivine crystal structure.
  • the electrode active material having an olivine-type crystal structure may also be contained in the negative electrode layer 20 .
  • Examples of such electrode active materials include phosphates containing transition metals and lithium.
  • the olivine type crystal structure is a crystal of natural olivine and can be identified by X-ray diffraction.
  • LiCoPO4 containing Co and P can be used as a typical example of an electrode active material having an olivine crystal structure.
  • a phosphate or the like in which the transition metal Co is replaced in this chemical formula can also be used.
  • the ratio of Li and PO4 can vary depending on the valence.
  • Co, Mn, Fe, Ni, etc. are preferably used as transition metals.
  • LiCo 2 P 3 O 10 , Li 2 CoP 2 O 7 , Li 6 Co 5 (P 2 O 7 ) 4 or the like can also be used as the positive electrode active material containing Co and P.
  • the electrode active material acts as a positive electrode active material.
  • the negative electrode layer 20 also contains an electrode active material having an olivine-type crystal structure, although the mechanism of action is not completely clear, it is based on the formation of a partial solid solution state with the negative electrode active material. The effect of increasing the discharge capacity and increasing the operating potential accompanying the discharge, which is presumed to be, is exerted.
  • each electrode active material preferably contains a transition metal that may be the same or different from each other. included. “They may be the same or different” means that the electrode active materials contained in the positive electrode layer 10 and the negative electrode layer 20 may contain the same type of transition metal, or may contain different types of transition metals. It means that it may be included.
  • the positive electrode layer 10 and the negative electrode layer 20 may contain only one kind of transition metal, or may contain two or more kinds of transition metals.
  • the positive electrode layer 10 and the negative electrode layer 20 contain the same type of transition metal. More preferably, both electrodes contain the same electrode active material in chemical composition.
  • the compositional similarity of both internal electrode layers increases. Even if the positive and negative terminals are attached in reverse, depending on the application, malfunction does not occur and the device can endure actual use.
  • the negative electrode layer 20 functions as a negative electrode layer by containing the negative electrode active material 21 .
  • the negative electrode active material 21 By including the negative electrode active material in only one electrode, it becomes clear that the one electrode acts as a negative electrode and the other electrode acts as a positive electrode. However, both electrodes may contain what is known as a negative electrode active material.
  • the negative electrode active material of the electrode prior art in secondary batteries can be appropriately referred to, for example, titanium oxide, lithium titanium composite oxide, lithium titanium composite phosphate, carbon, compounds such as vanadium lithium phosphate is mentioned.
  • Solid electrolyte 12 and solid electrolyte 22 are not particularly limited as long as they are oxide-based solid electrolytes having ion conductivity.
  • the solid electrolyte 12 and the solid electrolyte 22 are, for example, oxide-based solid electrolytes having lithium ion conductivity.
  • the solid electrolyte is, for example, a phosphate-based solid electrolyte having a NASICON structure.
  • a phosphate-based solid electrolyte is, for example, a phosphate containing lithium.
  • the phosphate is not particularly limited, but examples thereof include a composite lithium phosphate with Ti (eg, LiTi 2 (PO 4 ) 3 ).
  • Ti can be partially or wholly substituted with tetravalent transition metals such as Ge, Sn, Hf, and Zr. Moreover, in order to increase the Li content, it may be partially substituted with trivalent transition metals such as Al, Ga, In, Y and La. More specifically, for example, Li 1+x Al x Ge 2-x (PO 4 ) 3 , Li 1+x Al x Zr 2-x (PO 4 ) 3 , Li 1+x Al x Ti 2-x (PO 4 ) 3 etc.
  • the solid electrolyte 12 and the solid electrolyte 22 can be the same as the main component solid electrolyte of the solid electrolyte layer 30, for example.
  • the solid electrolytes 12 and 22 preferably contain Co.
  • the inclusion of Co during co-firing facilitates improvement in the oxidation resistance stability of the solid electrolyte, thereby facilitating cycle stability.
  • a carbon material or the like may be contained as a conductive aid contained in the positive electrode layer 10 and the negative electrode layer 20 .
  • a metal may be contained as a conductive aid. Examples of the metal of the conductive aid include Pd, Ni, Cu, Fe, alloys containing these, and the like.
  • the solid electrolyte layer 30 is obtained by firing a solid electrolyte green sheet obtained by applying a slurry containing solid electrolyte powder. During the firing process, the solid electrolyte powder is sintered to obtain desired properties.
  • the positive electrode layer 10 and the negative electrode layer 20 are obtained by printing a paste containing an electrode active material, a solid electrolyte, and a conductive aid and simultaneously firing the solid electrolyte green sheet.
  • FIG. 3(a) is a diagram plotting the relationship between the porosity in the single plate and the total conductivity thereof by producing fired single plates (electrode layers) with different mixing ratios of the electrode active material and the solid electrolyte. is.
  • the electrode active material with the same composition and average particle size is used, and the solid electrolyte with the same composition and average particle size is used.
  • Au is sputtered on both sides of the sample to form an electrode layer, and the measurement is performed under the conditions of a voltage amplitude of 30 mV and a frequency of 0.1 Hz to 500 kHz at 25 ° C. From the obtained Nyquist plot, the bulk resistance and It is evaluated by reading the grain boundary resistance.
  • the porosity tends to decrease by increasing the amount of solid electrolyte. It is believed that this is because the sinterability improves as the amount of the solid electrolyte increases.
  • the overall electrical conductivity increases as the porosity decreases. Therefore, from the viewpoint of improving the sinterability and increasing the overall electrical conductivity, it is preferable that the proportion of the solid electrolyte in the electrode layer is high.
  • FIG. 3(b) shows a layered all-solid-state battery chip using the sintered single plate produced in FIG. 3(a) as an electrode layer.
  • FIG. 4 is a diagram plotting the relationship between the porosity in the electrode layer and the capacity retention rate after 100 cycles with respect to the area occupancy.
  • the porosity tends to decrease as the area occupation ratio of the solid electrolyte increases. It is believed that this is because the sinterability improves as the amount of the solid electrolyte increases. As the porosity decreased, the capacity retention rate decreased. Therefore, from the viewpoint of improving the sinterability and increasing the capacity retention rate, it is preferable that the solid electrolyte has a high area ratio in the electrode layer.
  • the sinterability can be improved without increasing the content of the solid electrolyte, and the electrode active material and the solid electrolyte in the electrode layer are made as dense as possible so that they have many contacts with each other. Filling is desired.
  • At least one of the positive electrode layer 10 and the negative electrode layer 20 according to this embodiment has a configuration that enables high-density filling. As an example, the details will be described by focusing on the positive electrode layer 10 .
  • the average particle size of the solid electrolyte 12 in the positive electrode layer 10 is 2.5 ⁇ m or less, preferably 1.5 ⁇ m or less, and more preferably 1.0 ⁇ m or less.
  • the average particle size of the solid electrolyte 12 in the positive electrode layer 10 is preferably 0.05 ⁇ m or more, more preferably 0.1 ⁇ m or more, and even more preferably 0.3 ⁇ m or more.
  • the average particle size ratio in the positive electrode layer 10 is set for the average particle size ratio in the positive electrode layer 10 .
  • the average particle diameter ratio in the positive electrode layer 10 is 0.4 or more, preferably 0.7 or more, and more preferably 1.0 or more.
  • the average particle size ratio in the positive electrode layer 10 is (average particle size of the positive electrode active material)/(average particle size of the solid electrolyte 12).
  • the average particle size ratio in the positive electrode layer 10 is 10 or less, preferably 5.0 or less, and more preferably 3.0 or less.
  • the average particle diameter of the solid electrolyte 12 is 2.5 ⁇ m or less, and the average particle diameter ratio is 0.4 or more and 10 or less.
  • the porosity of the positive electrode layer 10 is preferably 10% or less, more preferably 7% or less, and even more preferably 5% or less.
  • the porosity of the electrode layer can be determined, for example, by performing cross-section processing with a cross-section polisher (CP), using a scanning electron microscope (manufactured by Hitachi High-Tech Co., Ltd., model: S-4800), accelerating voltage 5 kV, It can be calculated by acquiring 10 secondary electron images at the same magnification and measuring the average occupancy of the hole area by image analysis.
  • CP cross-section processing
  • S-4800 scanning electron microscope
  • the area occupation ratio of the solid electrolyte 12 is preferably 25% or more, more preferably 30% or more, and even more preferably 40% or more.
  • the area occupation ratio of the solid electrolyte 12 in the cross section in the thickness direction of the positive electrode layer 10 is preferably 75% or less, more preferably 65% or less, and preferably 60% or less. More preferred.
  • the average particle size of the electrode active material and solid electrolyte in the electrode layer can be measured by the following method. First, a cross-section polisher (CP) or the like is used to expose the electrode layer from a direction substantially perpendicular to the stacking thickness direction of the all-solid-state battery. Next, for example, observation is performed using a scanning electron microscope (manufactured by Hitachi High-Tech Co., Ltd., model: SU-7000) at an acceleration voltage of 5 kV. The region of the active material particles in the positive electrode or the negative electrode, and the solid electrolyte particles in the inside are discriminated.
  • At least 10 locations are observed, and among the positive or negative electrode active material particles and the solid electrolyte particles that have been identified, particles existing in isolation from other particles are selected and at least 10 particle sizes are obtained.
  • the particle area of each selected particle is measured, the circle equivalent diameter (Heywood diameter) is measured from the particle area, and the x-axis is the particle size and the y-axis is plotted with the frequency.
  • the median diameter (D50 value) of each particle can be calculated and defined as the average particle diameter of each particle.
  • each area occupation ratio of the electrode active material and the solid electrolyte in the electrode layer can be measured by the following method.
  • a cross-section polisher (CP) or the like is used to expose the electrode layer from a direction substantially perpendicular to the stacking thickness direction of the all-solid-state battery.
  • observation is performed using a scanning electron microscope (manufactured by Hitachi High-Tech Co., Ltd., model: SU-7000) at an acceleration voltage of 5 kV. Get 10 analyzes.
  • image analysis software the areas of the active material and the solid electrolyte occupying the acquired image can be discriminated, and the arithmetic mean value of each occupied area ratio can be calculated.
  • the positive electrode layer 10 as an example. It may have a numerical range.
  • the thickness of the solid electrolyte layer 30 is, for example, 0.5 ⁇ m or more and 100 ⁇ m or less, 1 ⁇ m or more and 50 ⁇ m or less, and 2 ⁇ m or more and 20 ⁇ m or less.
  • the thickness of the positive electrode layer 10 is, for example, 1 ⁇ m or more and 500 ⁇ m or less, 2 ⁇ m or more and 400 ⁇ m or less, or 5 ⁇ m or more and 300 ⁇ m or less.
  • the thickness of the negative electrode layer 20 is, for example, 1 ⁇ m or more and 500 ⁇ m or less, 2 ⁇ m or more and 400 ⁇ m or less, or 5 ⁇ m or more and 300 ⁇ m or less.
  • the thickness of each layer is obtained by cross-section processing from a direction substantially perpendicular to the stacking thickness direction of the all-solid-state battery using a cross-section polisher (CP) or the like.
  • FIG. 4 is a schematic cross-sectional view of a stacked all-solid-state battery 100a in which a plurality of battery units are stacked.
  • the all-solid-state battery 100a includes a laminated chip 60 having a substantially rectangular parallelepiped shape.
  • the first external electrode 40a and the second external electrode 40b are provided so as to be in contact with two side surfaces of the four surfaces other than the top surface and the bottom surface of the stacking direction end.
  • the two side surfaces may be two adjacent side surfaces or two side surfaces facing each other.
  • the first external electrode 40a and the second external electrode 40b are provided so as to be in contact with two side surfaces (hereinafter referred to as two end surfaces) facing each other.
  • the all-solid-state battery 100a a plurality of positive electrode layers 10 and a plurality of negative electrode layers 20 are alternately laminated with solid electrolyte layers 30 interposed therebetween. Edges of the plurality of positive electrode layers 10 are exposed on the first end surface of the laminated chip 60 and are not exposed on the second end surface. Edges of the plurality of negative electrode layers 20 are exposed on the second end surface of the laminated chip 60 and are not exposed on the first end surface. Thereby, the positive electrode layer 10 and the negative electrode layer 20 are alternately connected to the first external electrode 40a and the second external electrode 40b.
  • the solid electrolyte layer 30 extends from the first external electrode 40a to the second external electrode 40b.
  • the all-solid-state battery 100a has a structure in which a plurality of battery units are stacked.
  • a cover layer 50 is laminated on the upper surface of the laminated structure of the positive electrode layer 10, the solid electrolyte layer 30, and the negative electrode layer 20 (in the example of FIG. 4, the upper surface of the uppermost positive electrode layer 10).
  • a cover layer 50 is also laminated on the lower surface of the laminated structure (in the example of FIG. 4, the lower surface of the lowermost positive electrode layer 10).
  • the cover layer 50 is mainly composed of, for example, an inorganic material containing Al, Zr, Ti, etc. (eg, Al 2 O 3 , ZrO 2 , TiO 2 , etc.).
  • the cover layer 50 may contain the main component of the solid electrolyte layer 30 as a main component.
  • the positive electrode layer 10 and the negative electrode layer 20 may have collector layers.
  • the first current collector layer 13 may be provided within the positive electrode layer 10 .
  • a second current collector layer 23 may be provided in the negative electrode layer 20 .
  • the first current collector layer 13 and the second current collector layer 23 are mainly composed of a conductive material.
  • metal, carbon, or the like can be used as the conductive material of the first collector layer 13 and the second collector layer 23 .
  • FIG. 6 is a diagram illustrating the flow of the method for manufacturing the all-solid-state battery 100a.
  • raw material powder for the solid electrolyte layer that constitutes the solid electrolyte layer 30 described above is prepared.
  • raw material powder of an oxide-based solid electrolyte can be produced by mixing raw materials, additives, and the like and using a solid-phase synthesis method or the like.
  • a desired average particle size For example, a planetary ball mill using 5 mm ⁇ ZrO 2 balls is used to adjust the desired average particle size.
  • raw material powder of ceramics that constitutes the cover layer 50 is prepared.
  • raw material powder for the cover layer can be produced by mixing raw materials, additives, and the like and using a solid-phase synthesis method or the like.
  • a desired average particle size For example, a planetary ball mill using 5 mm ⁇ ZrO 2 balls is used to adjust the desired average particle size.
  • raw material powder for the solid electrolyte layer can be substituted.
  • an internal electrode paste for producing the above-described positive electrode layer 10 and negative electrode layer 20 are individually produced.
  • an internal electrode paste can be obtained by uniformly dispersing a conductive aid, an electrode active material, a solid electrolyte material, a sintering aid, a binder, a plasticizer, and the like in water or an organic solvent.
  • the solid electrolyte material the solid electrolyte paste described above may be used.
  • a carbon material or the like is used as the conductive aid.
  • a metal may be used as the conductive aid. Examples of the metal of the conductive aid include Pd, Ni, Cu, Fe, alloys containing these, and the like. Pd, Ni, Cu, Fe, alloys containing these, and various carbon materials may also be used.
  • Examples of sintering aids for internal electrode paste include Li—B—O compounds, Li—Si—O compounds, Li—C—O compounds, Li—S—O compounds, Li—P—O
  • a glass component such as any one or more of the glass components such as base compounds is included.
  • the average particle size of the solid electrolyte material is preferably 2.5 ⁇ m or less. Also, the ratio of the average particle size of the electrode active material to the average particle size of the solid electrolyte material is preferably in the range of 0.4 or more and 10 or less.
  • an external electrode paste for producing the first external electrode 40a and the second external electrode 40b is prepared.
  • an external electrode paste can be obtained by uniformly dispersing a conductive material, a glass frit, a binder, a plasticizer, and the like in water or an organic solvent.
  • a solid electrolyte slurry having a desired average particle size is prepared by uniformly dispersing the raw material powder for the solid electrolyte layer in an aqueous solvent or an organic solvent together with a binder, a dispersant, a plasticizer, etc., followed by wet pulverization. get At this time, a bead mill, a wet jet mill, various kneaders, a high-pressure homogenizer, or the like can be used, and it is preferable to use a bead mill from the viewpoint of being able to simultaneously adjust the particle size distribution and disperse.
  • a binder is added to the obtained solid electrolyte slurry to obtain a solid electrolyte paste.
  • the solid electrolyte green sheet 51 can be produced.
  • the coating method is not particularly limited, and a slot die method, a reverse coating method, a gravure coating method, a bar coating method, a doctor blade method, or the like can be used.
  • the particle size distribution after wet pulverization can be measured, for example, using a laser diffraction measurement device using a laser diffraction scattering method.
  • an internal electrode paste 52 is printed on one surface of a solid electrolyte green sheet 51 .
  • a reverse pattern 53 is printed on a region of the solid electrolyte green sheet 51 where the internal electrode paste 52 is not printed.
  • the reverse pattern 53 the same one as the solid electrolyte green sheet 51 can be used.
  • a plurality of solid electrolyte green sheets 51 after printing are alternately shifted and laminated.
  • the laminate is obtained by crimping the cover sheets 54 from above and below in the lamination direction. In this case, in the laminate, the internal electrode paste 52 for the positive electrode layer 10 is exposed on one end surface, and the internal electrode paste 52 for the negative electrode layer 20 is exposed on the other end surface.
  • the cover sheet 54 can be formed by coating the raw material powder for the cover layer in the same manner as in the solid electrolyte green sheet production process.
  • the cover sheet 54 is formed thicker than the solid electrolyte green sheet 51 . The thickness may be increased during coating, or may be increased by stacking a plurality of coated sheets.
  • the external electrode paste 55 is applied to each of the two end faces by a dipping method or the like and dried. Thereby, a molding for forming the all-solid-state battery 100a is obtained.
  • the firing conditions are oxidizing atmosphere or non-oxidizing atmosphere, and the maximum temperature is preferably 400° C. to 1000° C., more preferably 500° C. to 900° C., without any particular limitation.
  • a step of holding below the maximum temperature in an oxidizing atmosphere may be provided to sufficiently remove the binder until the maximum temperature is reached. In order to reduce process costs, it is desirable to bake at as low a temperature as possible. After firing, reoxidation treatment may be performed. Through the above steps, the all-solid-state battery 100a is produced.
  • current collector layers can be formed in the positive electrode layer 10 and the negative electrode layer 20 by sequentially laminating the internal electrode paste, the current collector paste containing a conductive material, and the internal electrode paste. can.
  • LiCoPO 4 was used as a positive electrode active material
  • LAGP was used as a solid electrolyte
  • Co 3 O 4 was used as a Co source added to the solid electrolyte.
  • a positive electrode active material, an electron conduction aid, a solid electrolyte, and Co 3 O 4 were weighed in a mass ratio of 35:10:54.5:0.5, and mixed with a dispersant, a plasticizer, an organic solvent, and an organic binder. was added and kneaded to prepare an internal electrode paste for the positive electrode layer.
  • TiO2 was used as the negative electrode active material
  • LAGP was used as the solid electrolyte.
  • a negative electrode active material, an electron conduction aid, and a solid electrolyte were weighed so that the mass ratio was 35:10:55.
  • An internal electrode paste was prepared.
  • a solid electrolyte green sheet was produced using a slurry composed of an organic binder, a dispersant, a plasticizer, and an organic solvent.
  • the internal electrode paste for the positive electrode layer was applied by screen printing.
  • An internal electrode paste for a negative electrode layer was applied onto the second solid electrolyte green sheet by screen printing.
  • the internal electrode paste for the positive electrode layer and the internal electrode paste for the negative electrode layer were made to have the same thickness.
  • a plurality of first solid electrolyte green sheets and a plurality of second solid electrolyte green sheets were laminated such that the positive electrode layer and the negative electrode layer were alternately pulled out to the left and right to obtain a green chip of a laminated all-solid-state battery. .
  • the green chip was sintered by degreasing and firing, and an external electrode paste was applied and cured to form an external electrode, thereby obtaining a stacked all-solid-state battery.
  • the average particle size of the electrode active material (positive electrode active material) in the positive electrode layer and the electrode active material (negative electrode active material) in the negative electrode layer was measured. Also, the average particle size of the solid electrolyte in the positive electrode layer and the average particle size of the solid electrolyte in the negative electrode layer were measured. In each of the positive electrode layer and the negative electrode layer, the ratio of the average particle size of the electrode active material to the average particle size of the solid electrolyte (average particle size ratio) was measured.
  • Example 1 the average particle size of the positive electrode active material in the positive electrode layer and the average particle size of the negative electrode active material in the negative electrode layer were 0.98 ⁇ m.
  • the average particle size of the solid electrolyte in the positive electrode layer and the average particle size of the solid electrolyte in the negative electrode layer were 0.79 ⁇ m.
  • the average particle size ratio in each of the positive electrode layer and the negative electrode layer was 1.24.
  • Example 2 the average particle size of the positive electrode active material in the positive electrode layer and the average particle size of the negative electrode active material in the negative electrode layer were 3.02 ⁇ m.
  • the average particle size of the solid electrolyte in the positive electrode layer and the average particle size of the solid electrolyte in the negative electrode layer were 0.79 ⁇ m.
  • the average particle size ratio in each of the positive electrode layer and the negative electrode layer was 3.82.
  • Example 3 the average particle size of the positive electrode active material in the positive electrode layer and the average particle size of the negative electrode active material in the negative electrode layer were 0.98 ⁇ m.
  • the average particle size of the solid electrolyte in the positive electrode layer and the average particle size of the solid electrolyte in the negative electrode layer were 1.05 ⁇ m.
  • the average particle size ratio in each of the positive electrode layer and the negative electrode layer was 0.93.
  • Example 4 the average particle size of the positive electrode active material in the positive electrode layer and the average particle size of the negative electrode active material in the negative electrode layer were 0.98 ⁇ m.
  • the average particle size of the solid electrolyte in the positive electrode layer and the average particle size of the solid electrolyte in the negative electrode layer were 2.21 ⁇ m.
  • the average particle size ratio in each of the positive electrode layer and the negative electrode layer was 0.44.
  • Example 5 the average particle size of the positive electrode active material in the positive electrode layer and the average particle size of the negative electrode active material in the negative electrode layer were 6.99 ⁇ m.
  • the average particle size of the solid electrolyte in the positive electrode layer and the average particle size of the solid electrolyte in the negative electrode layer were 0.79 ⁇ m.
  • the average particle size ratio in each of the positive electrode layer and the negative electrode layer was 8.85.
  • Example 6 the average particle size of the positive electrode active material in the positive electrode layer and the average particle size of the negative electrode active material in the negative electrode layer were 0.49 ⁇ m.
  • the average particle size of the solid electrolyte in the positive electrode layer and the average particle size of the solid electrolyte in the negative electrode layer were 0.79 ⁇ m.
  • the average particle size ratio in each of the positive electrode layer and the negative electrode layer was 0.62.
  • the average particle size of the positive electrode active material in the positive electrode layer and the average particle size of the negative electrode active material in the negative electrode layer were 0.98 ⁇ m.
  • the average particle size of the solid electrolyte in the positive electrode layer and the average particle size of the solid electrolyte in the negative electrode layer were 2.66 ⁇ m.
  • the average particle size ratio in each of the positive electrode layer and the negative electrode layer was 0.37.
  • the average particle size of the positive electrode active material in the positive electrode layer and the average particle size of the negative electrode active material in the negative electrode layer were 8.13 ⁇ m.
  • the average particle size of the solid electrolyte in the positive electrode layer and the average particle size of the solid electrolyte in the negative electrode layer were 0.79 ⁇ m.
  • the average particle size ratio in each of the positive electrode layer and the negative electrode layer was 10.29.
  • the average particle size of the positive electrode active material in the positive electrode layer and the average particle size of the negative electrode active material in the negative electrode layer were 0.30 ⁇ m.
  • the average particle size of the solid electrolyte in the positive electrode layer and the average particle size of the solid electrolyte in the negative electrode layer were 0.79 ⁇ m.
  • the average particle size ratio in each of the positive electrode layer and the negative electrode layer was 0.38.
  • Example 1 the porosity of the positive electrode layer and the negative electrode layer was 4.9%.
  • Example 2 the porosity of the positive electrode layer and the negative electrode layer was 5.6%.
  • Example 3 the porosity of the positive electrode layer and the negative electrode layer was 6.2%.
  • Example 4 the porosity of the positive electrode layer and the negative electrode layer was 8.0%.
  • Example 5 the porosity of the positive electrode layer and the negative electrode layer was 8.4%.
  • Example 6 the porosity of the positive electrode layer and the negative electrode layer was 9.3%.
  • Comparative Example 1 the porosity of the positive electrode layer and the negative electrode layer was 11.0%.
  • Comparative Example 2 the porosity of the positive electrode layer and the negative electrode layer was 10.3%.
  • Comparative Example 3 the porosity of the positive electrode layer and the negative electrode layer was 12.2%.
  • the porosity was determined to be "poor”.
  • the average particle size of the solid electrolyte was larger than 2.5 ⁇ m, and the average particle size ratio was smaller than 0.4.
  • Comparative Example 2 it is considered that the average particle size ratio exceeded 10 and increased.
  • Comparative Example 3 it is considered that the average particle size ratio was less than 0.4 and became small.
  • the area occupation ratio of the solid electrolyte in the positive electrode layer and the area occupation ratio of the solid electrolyte in the negative electrode layer were measured for each of Examples 1 to 6 and Comparative Examples 1 to 3.
  • Example 1 the area occupation ratio of the solid electrolyte in the positive electrode layer and the area occupation ratio of the solid electrolyte in the negative electrode layer were 45%.
  • Example 2 the area occupation ratio of the solid electrolyte in the positive electrode layer and the area occupation ratio of the solid electrolyte in the negative electrode layer were 42%.
  • the area occupancy of the solid electrolyte in the positive electrode layer and the area occupancy of the solid electrolyte in the negative electrode layer were 41%.
  • Example 4 the area occupation ratio of the solid electrolyte in the positive electrode layer and the area occupation ratio of the solid electrolyte in the negative electrode layer were 39%. In Example 5, the area occupation ratio of the solid electrolyte in the positive electrode layer and the area occupation ratio of the solid electrolyte in the negative electrode layer were 36%. In Example 6, the area occupation ratio of the solid electrolyte in the positive electrode layer and the area occupation ratio of the solid electrolyte in the negative electrode layer were 36%. In Comparative Example 1, the area occupation ratio of the solid electrolyte in the positive electrode layer and the area occupation ratio of the solid electrolyte in the negative electrode layer were 34%.
  • Reference Example 1 is an example in which the initial discharge capacity per unit cell was 18 ⁇ Ah when the area occupation ratio of the solid electrolyte was 50%, and was judged as " ⁇ ".
  • Reference Example 2 is an example in which the initial discharge capacity per unit cell was 16 ⁇ Ah when the area occupation ratio of the solid electrolyte was 43%, and was judged to be "good”.
  • Reference Example 3 is an example in which the initial discharge capacity per unit cell was 13 ⁇ Ah when the area occupation ratio of the solid electrolyte was 64%, and was judged to be "good”.
  • Reference Example 4 is an example in which the initial discharge capacity per unit cell was 9 ⁇ Ah when the area occupation ratio of the solid electrolyte was 32%, and was judged to be "good”.
  • Reference Example 5 is an example in which the initial discharge capacity per unit cell was 4 ⁇ Ah when the area occupation ratio of the solid electrolyte was 81%, and was judged as " ⁇ ".
  • Reference Example 6 is an example in which the initial discharge capacity per unit cell was 3 ⁇ Ah when the area occupation ratio of the solid electrolyte was 24%, and was judged as " ⁇ ”.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Secondary Cells (AREA)
PCT/JP2022/040469 2021-12-20 2022-10-28 全固体電池 Ceased WO2023119876A1 (ja)

Priority Applications (2)

Application Number Priority Date Filing Date Title
JP2023569125A JPWO2023119876A1 (https=) 2021-12-20 2022-10-28
US18/714,724 US20250030044A1 (en) 2021-12-20 2022-10-28 All solid battery

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2021-205768 2021-12-20
JP2021205768 2021-12-20

Publications (1)

Publication Number Publication Date
WO2023119876A1 true WO2023119876A1 (ja) 2023-06-29

Family

ID=86902012

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2022/040469 Ceased WO2023119876A1 (ja) 2021-12-20 2022-10-28 全固体電池

Country Status (3)

Country Link
US (1) US20250030044A1 (https=)
JP (1) JPWO2023119876A1 (https=)
WO (1) WO2023119876A1 (https=)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2024048102A1 (ja) * 2022-08-31 2024-03-07 パナソニックＩｐマネジメント株式会社 電極、それを用いた電池及び電極の製造方法
CN118738267A (zh) * 2024-06-11 2024-10-01 高能时代(深圳)新能源科技有限公司 一种复合正极极片和固态电池

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2016001598A (ja) * 2014-05-19 2016-01-07 Tdk株式会社 リチウムイオン二次電池
JP2017157305A (ja) * 2016-02-29 2017-09-07 Fdk株式会社 全固体電池の製造方法および全固体電池
JP2020047462A (ja) * 2018-09-19 2020-03-26 太陽誘電株式会社 全固体電池
JP2021051825A (ja) * 2019-09-20 2021-04-01 Fdk株式会社 全固体電池、正極および全固体電池製造方法
JP2021140973A (ja) * 2020-03-06 2021-09-16 Fdk株式会社 固体電池及び固体電池の製造方法

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2016001598A (ja) * 2014-05-19 2016-01-07 Tdk株式会社 リチウムイオン二次電池
JP2017157305A (ja) * 2016-02-29 2017-09-07 Fdk株式会社 全固体電池の製造方法および全固体電池
JP2020047462A (ja) * 2018-09-19 2020-03-26 太陽誘電株式会社 全固体電池
JP2021051825A (ja) * 2019-09-20 2021-04-01 Fdk株式会社 全固体電池、正極および全固体電池製造方法
JP2021140973A (ja) * 2020-03-06 2021-09-16 Fdk株式会社 固体電池及び固体電池の製造方法

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2024048102A1 (ja) * 2022-08-31 2024-03-07 パナソニックＩｐマネジメント株式会社 電極、それを用いた電池及び電極の製造方法
CN118738267A (zh) * 2024-06-11 2024-10-01 高能时代(深圳)新能源科技有限公司 一种复合正极极片和固态电池

Also Published As

Publication number Publication date
US20250030044A1 (en) 2025-01-23
JPWO2023119876A1 (https=) 2023-06-29

Similar Documents

Publication Publication Date Title
JP7027125B2 (ja) 全固体電池およびその製造方法
WO2023119876A1 (ja) 全固体電池
WO2023053748A1 (ja) 全固体電池およびその評価方法
WO2022185710A1 (ja) 全固体電池及びその製造方法
JP7393203B2 (ja) 全固体電池
JP7594866B2 (ja) 全固体電池
US20240356066A1 (en) All solid battery
JP7299105B2 (ja) 全固体電池およびその製造方法
JP2023161894A (ja) 全固体電池およびその製造方法
JP7830027B2 (ja) 全固体電池およびその製造方法
US20250140852A1 (en) All solid battery
JP7748163B2 (ja) 全固体電池
US20260045497A1 (en) Positive electrode active material and all solid battery
JP7594865B2 (ja) 全固体電池
JP7519825B2 (ja) 全固体電池
JP2021072195A (ja) 全固体電池
JP7402040B2 (ja) 全固体電池およびその製造方法
JP2024174497A (ja) 全固体電池
JP2025000289A (ja) 全固体電池
JP2024142141A (ja) 全固体電池
JP2024072940A (ja) 全固体電池、回路基板、および全固体電池の製造方法
WO2023127283A1 (ja) 全固体電池およびその製造方法
JP2024050182A (ja) 負極活物質および全固体電池
JP2023165328A (ja) 全固体電池およびその製造方法
JP2024151622A (ja) 電極活物質および全固体電池

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 22910597

Country of ref document: EP

Kind code of ref document: A1

WWE Wipo information: entry into national phase

Ref document number: 18714724

Country of ref document: US

WWE Wipo information: entry into national phase

Ref document number: 2023569125

Country of ref document: JP

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 22910597

Country of ref document: EP

Kind code of ref document: A1