WO2024089460A1 - 全固体電池 - Google Patents

全固体電池 Download PDF

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Publication number
WO2024089460A1
WO2024089460A1 PCT/IB2023/000564 IB2023000564W WO2024089460A1 WO 2024089460 A1 WO2024089460 A1 WO 2024089460A1 IB 2023000564 W IB2023000564 W IB 2023000564W WO 2024089460 A1 WO2024089460 A1 WO 2024089460A1
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Prior art keywords
negative electrode
intermediate layer
solid
lithium
solid electrolyte
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Ceased
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PCT/IB2023/000564
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English (en)
French (fr)
Japanese (ja)
Inventor
雄介 大塚
祐輝 山本
高志 久保田
卓也 三科
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Renault SAS
Nissan Motor Co Ltd
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Renault SAS
Nissan Motor Co Ltd
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Priority to EP23880897.6A priority Critical patent/EP4611089A4/en
Priority to JP2024552513A priority patent/JP7810281B2/ja
Priority to CN202380074947.4A priority patent/CN120113078A/zh
Publication of WO2024089460A1 publication Critical patent/WO2024089460A1/ja
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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
    • 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
    • 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
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
    • H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
    • 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
    • H01M4/04—Processes of manufacture in general
    • H01M4/0438—Processes of manufacture in general by electrochemical processing
    • H01M4/044—Activating, forming or electrochemical attack of the supporting material
    • H01M4/0445—Forming after manufacture of the electrode, e.g. first charge, cycling
    • 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
    • H01M4/134—Electrodes based on metals, Si or alloys
    • 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
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/381—Alkaline or alkaline earth metals elements
    • H01M4/382—Lithium
    • 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
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/40—Alloys based on alkali metals
    • H01M4/405—Alloys based on lithium
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • 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
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0065—Solid electrolytes
    • 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 an all-solid-state battery.
  • Solid electrolytes are materials that are primarily composed of ion conductors that are capable of ion conduction in a solid state. For this reason, all-solid-state batteries have the advantage that, in principle, they do not suffer from the various problems that arise from flammable organic electrolytes, as occurs with conventional liquid batteries that use non-aqueous electrolytes.
  • lithium precipitation type in which lithium metal is precipitated on the negative electrode current collector during the charging process.
  • the lithium metal precipitated during the charging process is ionized during the discharging process, causing voids in the lithium metal, which can cause a decrease in discharge capacity. Therefore, in order to suppress the occurrence of such voids, a restraining pressure is generally applied in the stacking direction of the battery in lithium precipitation type all-solid-state secondary batteries.
  • JP 2020-191202 A discloses a technology in which an anode active material layer (anode intermediate layer) containing Ag is provided between the anode current collector and the solid electrolyte layer.
  • anode active material layer anode intermediate layer
  • Li precipitates as a Li(Ag) alloy with Ag in solid solution during the charging process.
  • only Li dissolves from the Li(Ag) alloy during the discharging process, and the Ag that was in solid solution remains, which is said to suppress the occurrence of voids.
  • the present invention aims to provide a lithium precipitation type all-solid-state battery that has excellent resistance during charging, cycle characteristics, and short circuit rate during charging.
  • the present inventors conducted intensive research to solve the above problems. As a result, they discovered that in an all-solid-state battery equipped with a lithium deposition-type power generating element, the above problems can be solved by providing a negative electrode intermediate layer containing a metal material capable of alloying with lithium or a carbon material capable of absorbing lithium ions and a binder between the negative electrode current collector and the solid electrolyte layer, and by controlling the porosity of the negative electrode intermediate layer within a specific range, thereby completing the present invention.
  • one embodiment of the present invention is an all-solid-state battery that includes a power generating element having a positive electrode having a positive electrode active material layer containing a positive electrode active material, a negative electrode having a negative electrode current collector on which lithium metal is deposited during charging, a solid electrolyte layer that is interposed between the positive electrode and the negative electrode and contains a solid electrolyte, and a negative electrode intermediate layer that is adjacent to the surface of the solid electrolyte layer facing the negative electrode current collector and contains at least one material selected from the group consisting of a metal material that can be alloyed with lithium and a carbon material that can occlude lithium ions, and a binder, and the porosity of the negative electrode intermediate layer is 10% or more and 70% or less.
  • FIG. 1 is a cross-sectional view showing a schematic overall structure of a stacked type (internal parallel connection type) all-solid-state lithium secondary battery (stacked type secondary battery) according to one embodiment of the present invention.
  • One embodiment of the present invention is an all-solid-state battery comprising a power generating element including a positive electrode having a positive electrode active material layer containing a positive electrode active material, a negative electrode having a negative electrode current collector on which lithium metal is deposited during charging, a solid electrolyte layer interposed between the positive electrode and the negative electrode and containing a solid electrolyte, and a negative electrode intermediate layer adjacent to the surface of the solid electrolyte layer facing the negative electrode current collector and containing at least one selected from the group consisting of a metal material capable of alloying with lithium and a carbon material capable of absorbing lithium ions, and a binder, wherein the porosity of the negative electrode intermediate layer is 10% or more and 70% or less.
  • a power generating element including a positive electrode having a positive electrode active material layer containing a positive electrode active material, a negative electrode having a negative electrode current collector on which lithium metal is deposited during charging, a solid electrolyte layer interposed between the positive electrode and the negative electrode and containing
  • FIG. 1 is a cross-sectional view showing a schematic overall structure of a stacked type (internal parallel connection type) all-solid-state lithium secondary battery (hereinafter, also simply referred to as a "stacked type secondary battery") according to one embodiment of the present invention.
  • FIG. 1 shows a cross section of the stacked type secondary battery during charging.
  • the stacked type secondary battery 10a shown in FIG. 1 has a structure in which a substantially rectangular power generation element 21, in which the actual charge/discharge reaction proceeds, is sealed inside a laminate film 29, which is the battery exterior body.
  • the power generation element 21 has a structure in which a negative electrode, a solid electrolyte layer 17, and a positive electrode are stacked.
  • the negative electrode has a structure in which a negative electrode current collector 11' and a negative electrode active material layer 13 made of lithium metal precipitated on the surface of the negative electrode current collector 11' are stacked.
  • a negative electrode intermediate layer 14 is arranged adjacent to the surface of the negative electrode active material layer 13 facing the solid electrolyte layer 17.
  • the positive electrode has a structure in which a positive electrode active material layer 15 is disposed on the surface of a positive electrode collector 11".
  • the negative electrode, solid electrolyte layer, and positive electrode are laminated in this order, with the negative electrode intermediate layer 14 and the positive electrode active material layer 15 facing each other via the solid electrolyte layer 17.
  • adjacent negative electrodes, solid electrolyte layers, and positive electrodes constitute one unit cell layer 19.
  • the stacked secondary battery 10a shown in FIG. 1 can be said to have a structure in which a plurality of unit cell layers 19 are laminated and electrically connected in parallel.
  • a negative electrode current collector 25 and a positive electrode current collector 27 that are conductive with each electrode (negative electrode and positive electrode) are attached to the negative electrode current collector 11' and the positive electrode current collector 11", respectively, and are structured to be sandwiched between the ends of the laminate film 29 and led out of the laminate film 29.
  • a restraining pressure is applied to the stacked secondary battery 10a in the stacking direction of the power generating element 21 by a pressure member (not shown). Therefore, the volume of the power generating element 21 is kept constant.
  • the current collector (negative electrode current collector, positive electrode current collector) has a function of mediating the movement of electrons from the electrode active material layer (negative electrode active material layer, positive electrode active material layer).
  • the material constituting the current collector There is no particular limitation on the material constituting the current collector.
  • metals such as aluminum, nickel, iron, stainless steel, titanium, and copper, and conductive resins can be used as the material constituting the current collector.
  • the thickness of the current collector but an example is 10 to 100 ⁇ m.
  • the all-solid-state battery according to the present embodiment is a so-called lithium precipitation type battery in which lithium metal is precipitated on the negative electrode current collector during the charging process.
  • the layer made of lithium metal precipitated on the negative electrode current collector during this charging process is the negative electrode active material layer of the all-solid-state battery according to the present embodiment. Therefore, the thickness of the negative electrode active material layer increases with the progress of the charging process, and the thickness of the negative electrode active material layer decreases with the progress of the discharging process.
  • the negative electrode active material layer may not be present during full discharge, but in some cases, a negative electrode active material layer made of a certain amount of lithium metal may be placed during full discharge.
  • the thickness of the negative electrode active material layer (lithium metal layer) during full charge is not particularly limited, but is usually 0.1 to 1000 ⁇ m.
  • the negative electrode intermediate layer is a layer adjacent to the surface of the solid electrolyte layer facing the negative electrode current collector, and contains at least one selected from the group consisting of a metal material capable of alloying with lithium and a carbon material capable of absorbing lithium ions, and a binder. It is preferable that the negative electrode intermediate layer has electrical conductivity as a whole.
  • the volume resistivity of the negative electrode intermediate layer is not particularly limited, but is preferably 10 2 ⁇ cm or less, and more preferably 10 ⁇ cm or less. In this specification, the volume resistivity of the negative electrode intermediate layer is a value measured using an electrode resistance measurement system (manufactured by Hioki E.E. Corporation, product name: RM2610).
  • the negative electrode intermediate layer preferably contains at least one selected from the group consisting of metal materials that can be alloyed with lithium.
  • metal materials that can be alloyed with lithium include indium (In), aluminum (Al), silicon (Si), tin (Sn), magnesium (Mg), gold (Au), silver (Ag), zinc (Zn), and alloys containing at least one of these.
  • the metal material preferably contains at least one selected from the group consisting of In, Al, Si, Sn, Mg, Au, Ag, and Zn, more preferably contains at least one selected from the group consisting of Ag, Mg, Zn, and Al, even more preferably contains at least one selected from the group consisting of Ag, Mg, and Zn, and particularly preferably contains Ag.
  • the negative electrode intermediate layer preferably contains at least one selected from the group consisting of carbon materials that can occlude lithium ions.
  • the negative electrode intermediate layer preferably contains at least one selected from the group consisting of carbon materials that can occlude lithium ions.
  • carbon black specifically, acetylene black, Ketjen Black (registered trademark), furnace black, channel black, thermal lamp black, etc.
  • carbon nanotubes (CNT) graphite, hard carbon, etc.
  • the carbon material preferably contains at least one selected from the group consisting of carbon black, and more preferably contains at least one selected from the group consisting of acetylene black, Ketjen Black (registered trademark), furnace black, channel black, and thermal lamp black.
  • the negative electrode intermediate layer may further contain a metal material other than the metal material capable of alloying with lithium (a metal material that does not alloy with lithium) in addition to at least one selected from the group consisting of a metal material capable of alloying with lithium and a carbon material capable of absorbing lithium ions.
  • metal materials that do not alloy with lithium include nickel (Ni) and copper (Cu).
  • the negative electrode intermediate layer contains at least one selected from the group consisting of a carbon material capable of absorbing lithium ions and a metal material that does not alloy with lithium.
  • the negative electrode intermediate layer contains at least one type of metal particles containing the above-mentioned metal material capable of alloying with lithium and/or at least one type of carbon particles containing the above-mentioned carbon material capable of absorbing lithium ions.
  • the negative electrode intermediate layer contains at least one type of metal particles containing the above-mentioned metal material capable of alloying with lithium and at least one type of carbon particles containing the above-mentioned carbon material capable of absorbing lithium ions.
  • the average primary particle diameter of the metal particles is, for example, 500 nm or less, preferably 300 nm or less, more preferably 200 nm or less, even more preferably 100 nm or less, and particularly preferably 80 nm or less.
  • the lower limit of the average primary particle diameter of the metal particles is not particularly limited, but is, for example, 10 nm or more, preferably 20 nm or more, even more preferably 30 nm or more, and even more preferably 40 nm or more.
  • the average primary particle diameter of the carbon particles is, for example, 200 nm or less, preferably 150 nm or less, more preferably 100 nm or less, even more preferably 80 nm or less, even more preferably 60 nm or less, even more preferably 50 nm or less, and especially preferably 45 nm or less.
  • the lower limit of the average primary particle diameter of the carbon particles is not particularly limited, but is preferably 10 nm or more, more preferably 20 nm or more, and even more preferably 25 nm or more.
  • the average primary particle diameter of a particle refers to the 50% cumulative diameter (D50) of the particle diameter of the particle observed in several to several tens of fields of view when the cross section of a layer containing the particles is observed with a scanning electron microscope (SEM) (the maximum distance between any two points on the contour line of the observed particle).
  • D50 50% cumulative diameter
  • SEM scanning electron microscope
  • the mass ratio of carbon particles to metal particles is preferably 10:1 to 1:1, more preferably 5:1 to 2:1, and even more preferably 4:1 to 2.5:1.
  • the volume ratio of carbon particles to metal particles is preferably 99:1 to 70:30, and more preferably 95:5 to 75:25.
  • the blending ratio (mass ratio or volume ratio) of carbon particles to metal particles is within the above range, an all-solid-state battery with better charging resistance, cycle characteristics, and short circuit rate during charging can be obtained.
  • the volume of metal particles may change significantly (expand) when alloyed with lithium.
  • the ratio of the mass of carbon particles to the mass of metal particles contained in the negative electrode intermediate layer exceeds 1. This makes it easier to maintain a predetermined porosity, and an all-solid-state battery with better cycle characteristics and short circuit rate during charging can be obtained.
  • the average primary particle diameter of the carbon particles is smaller than the average primary particle diameter of the metal particles.
  • the ratio of the average primary particle diameter of the carbon atoms to the average primary particle diameter of the metal particles is preferably less than 1, more preferably 0.9 or less, even more preferably 0.8 or less, and even more preferably 0.7 or less. This makes it easier to maintain a predetermined porosity, and an all-solid-state battery with even better cycle characteristics and short circuit rate during charging can be obtained.
  • the ratio of the primary particle diameter of the carbon particles to the average primary particle diameter of the metal particles is, for example, 0.3 or more, more preferably 0.4 or more, and even more preferably 0.5 or more.
  • the ratio of the mass of carbon particles to the mass of metal particles contained in the negative electrode intermediate layer exceeds 1, and the ratio of the average primary particle diameter of carbon atoms to the average primary particle diameter of metal particles (average primary particle diameter of carbon particles/average primary particle diameter of metal particles) is less than 1. This makes it easier to maintain a predetermined porosity, and an all-solid-state battery with even better cycle characteristics and short circuit rate during charging can be obtained.
  • the negative electrode intermediate layer further contains a binder.
  • binder There are no particular limitations on the type of binder, and binders known in the art can be used as appropriate. Examples of binders include polyvinylidene fluoride (PVDF), compounds in which hydrogen atoms in PVDF are replaced with other halogen elements, polytetrafluoroethylene (PTFE), styrene-butadiene rubber (SBR), and carboxymethyl cellulose (CMC).
  • PVDF polyvinylidene fluoride
  • PTFE polytetrafluoroethylene
  • SBR styrene-butadiene rubber
  • CMC carboxymethyl cellulose
  • the binder contains polyvinylidene fluoride (PVDF), and it is more preferable that the binder is polyvinylidene fluoride (PVDF).
  • PVDF polyvinylidene fluoride
  • the content of the binder in the negative electrode intermediate layer is, for example, 8% by mass or more, preferably 10% by mass or more, and more preferably 12% by mass or more, relative to 100% by mass, which is the total mass of the metal material (e.g., metal particles), carbon material (e.g., carbon particles), and binder. If the content of the binder is within the above range, it becomes easy to control the porosity of the negative electrode intermediate layer described below within a predetermined range. There is no particular upper limit to the content of the binder, but from the viewpoint of suppressing an increase in resistance, it is preferably 20% by mass or less, more preferably 18% by mass or less, and even more preferably 16% by mass or less.
  • the ratio of the total surface area of at least one kind of metal particles containing a metal material capable of alloying with lithium and at least one kind of carbon particles containing a carbon material capable of absorbing lithium ions to the mass of the binder contained in the negative electrode intermediate layer is preferably 800 m 2 /g or less.
  • total surface area of metal particles and carbon particles/mass of binder is 800 m 2 /g or less, a sufficient amount of binder is present on the surfaces of the metal particles and the carbon particles, so that the adhesive strength between these particles is increased.
  • the value of (total surface area of metal particles and carbon particles/mass of binder) is more preferably 700 m 2 /g or less, even more preferably 600 m 2 /g or less, even more preferably 500 m 2 /g or less, and particularly preferably 450 m 2 /g or less.
  • the value of (total surface area of metal particles and carbon particles/mass of binder) is, for example, 10 m 2 /g or more, preferably 100 m 2 /g or more, more preferably 200 m 2 /g or more, and even more preferably 300 m 2 /g or more.
  • the above range can improve the energy density of the all-solid-state battery.
  • the value of (total surface area of metal particles and carbon particles/mass of binder) is calculated as follows: For each type of particle, the volume per particle is calculated as a spherical particle having a radius of its average primary particle diameter/2.
  • the number of particles contained in the negative electrode intermediate layer per unit mass is calculated based on the blending ratio of each component contained in the negative electrode intermediate layer, and the surface area per particle of the spherical particles is calculated and multiplied to obtain the total surface area for each type of particle.
  • the total surface areas of each type of particle are then added together to obtain the total surface area, which is then divided by the mass of the binder contained in the negative electrode intermediate layer per unit mass to obtain the (total surface area of metal particles and carbon particles/mass of binder). Specifically, it can be determined by the method described in the Examples below.
  • the average primary particle size of the metal particles or carbon particles contained in the negative electrode intermediate layer is 30 nm or more, and the binder content can be 10 parts by mass or more per 100 parts by mass of the total of the metal particles, carbon particles, and binder.
  • the above (total surface area of metal particles and carbon particles/mass of binder) means (total surface area of metal particles/mass of binder).
  • the above (total surface area of metal particles and carbon particles/mass of binder) means (total surface area of carbon particles/mass of binder).
  • the ratio of the total mass of the metal material, carbon material, and binder to the total mass of the negative electrode intermediate layer is preferably 90 mass% or more, more preferably 95 mass% or more, even more preferably 98 mass% or more, particularly preferably 99 mass% or more, and most preferably 100 mass%.
  • the all-solid-state battery according to this embodiment is characterized in that the porosity of the negative electrode intermediate layer is 10% or more and 70% or less.
  • lithium ions are supplied from the positive electrode side during charging, and lithium metal is precipitated between the negative electrode current collector and the negative electrode intermediate layer to form a negative electrode active material layer, but the lithium metal may also precipitate in the voids of the negative electrode intermediate layer and partially contact the solid electrolyte layer.
  • the porosity of the negative electrode intermediate layer exceeds 70%, lithium metal is more likely to precipitate in the voids of the negative electrode intermediate layer, and the lithium metal precipitated in the voids of the negative electrode active material layer and the solid electrolyte layer are more likely to come into contact with each other.
  • the precipitated lithium metal may grow through the pores in the solid electrolyte layer and come into contact with the positive electrode active material layer, which may lead to a short circuit in the battery.
  • the porosity of the negative electrode intermediate layer exceeds 70%, the solid electrolyte contained in the solid electrolyte layer may penetrate close to the negative electrode active material layer (lithium metal deposited on the negative electrode current collector), and the deposited lithium metal may cause the solid electrolyte to be reduced and decomposed, resulting in degradation.
  • the porosity of the negative electrode intermediate layer exceeds 70%, the strength of the negative electrode intermediate layer may decrease. As a result, repeated deposition and disappearance of lithium metal occurs with the charge/discharge cycle of the battery, and the structure of the negative electrode intermediate layer may be destroyed by the stress caused by the lithium metal during deposition, resulting in the destruction of the conductive path.
  • the strength may further decrease with the charge/discharge cycle of the battery, causing cracks in the negative electrode intermediate layer. For these reasons, even if no short circuit occurs, the cycle durability of the battery may decrease. In addition, since the contact area between the negative electrode intermediate layer and the solid electrolyte layer is small, the resistance during charging may increase.
  • the porosity of the negative electrode intermediate layer is less than 10%, the current density will be high during charging, which will promote the generation of lithium dendrites and may cause a short circuit. Even if no short circuit occurs, the current density will be high during charging, which may increase the cell resistance during charging.
  • the porosity of the negative electrode intermediate layer is preferably 65% or less, more preferably 60% or less, and even more preferably 55% or less.
  • the porosity of the negative electrode intermediate layer is preferably 15% or more, more preferably 20% or more, and even more preferably 25% or more.
  • the porosity of the negative electrode intermediate layer is 10% or more and 60% or less. This can further improve the resistance during charging and the cycle durability.
  • the porosity of the negative electrode intermediate layer is 20% or more and 60% or less. This can further improve the resistance during charging and the cycle durability.
  • the porosity of the negative electrode intermediate layer is a value measured by the method described in the Examples below.
  • the method of controlling the porosity of the negative electrode intermediate layer within a predetermined range is not particularly limited, but a two-stage pressing method may be adopted in which, in the production of an all-solid-state battery, a solid electrolyte layer is pressed at a predetermined pressure, and then the solid electrolyte layer and the negative electrode intermediate layer are laminated and pressed at a predetermined pressure. More specifically, a solid electrolyte slurry containing a solid electrolyte is applied to the surface of a support (e.g., a metal foil), and the coating is dried to obtain a solid electrolyte layer formed on the surface of the support.
  • a support e.g., a metal foil
  • first pressing step the solid electrolyte layer formed on the surface of the support is pressed at a predetermined pressure.
  • first pressing step This improves the arrangement of the solid electrolyte particles on the surface of the solid electrolyte layer adjacent to the support, thereby reducing unevenness.
  • pressing may be performed using another metal foil or the like.
  • the exposed surface of a separately prepared positive electrode active material layer may be placed on the exposed surface of the solid electrolyte layer, and the first pressing step may be performed in a state in which the solid electrolyte layer and the positive electrode active material layer are stacked.
  • the exposed surface of the positive electrode active material layer prepared separately is placed on the exposed surface of the solid electrolyte layer, and the first pressing step is performed in a state in which the solid electrolyte layer and the positive electrode active material layer are overlapped.
  • a negative electrode intermediate layer slurry containing materials contained in the negative electrode intermediate layer is applied to the surface of a negative electrode current collector (e.g., stainless steel foil), and the coating is dried to obtain a negative electrode intermediate layer formed on the surface of the negative electrode current collector.
  • the support (metal foil) used in the first pressing step is peeled off to expose the solid electrolyte layer, and the exposed surface of the solid electrolyte layer and the exposed surface of the negative electrode intermediate layer are overlapped so that they face each other, and pressed at a predetermined pressure (second pressing step).
  • the porosity of the negative electrode intermediate layer can be adjusted by adjusting the pressing pressure, pressing temperature, and pressing time of the second pressing step.
  • the porosity of the negative electrode intermediate layer can be more appropriately adjusted by further adjusting the amount of metal particles and/or carbon particles contained in the negative electrode intermediate layer, the average primary particle diameter thereof, and the amount of binder.
  • the porosity can be easily controlled within a predetermined range. Furthermore, this is preferable because the porosity achieved by the pressing process can be maintained even after the pressing pressure is released.
  • cold isostatic pressing CIP is suitable for the pressing in the first pressing step and the second pressing step, but is not limited thereto.
  • the pressing pressure in the first pressing step varies depending on the material contained in the solid electrolyte layer, and when the first pressing step is performed in a state where the solid electrolyte layer and the positive electrode active material layer are stacked, it varies depending on the materials contained in the solid electrolyte layer and the positive electrode active material layer, and can be appropriately set by a person skilled in the art.
  • the pressing pressure in the first pressing step is preferably 300 MPa or more and 1000 MPa or less, more preferably 300 MPa or more and 800 MPa or less, and even more preferably 500 MPa or more and 700 MPa or less.
  • the pressing temperature in the first pressing step is also not particularly limited, but is, for example, 20 to 80°C, preferably 20 to 40°C.
  • the pressing time in the first pressing step is also not particularly limited, but is, for example, 10 seconds to 30 minutes, preferably 10 seconds to 10 minutes.
  • the pressing pressure in the second pressing step varies depending on the material contained in the negative electrode intermediate layer and the desired porosity, and can be set appropriately by a person skilled in the art.
  • the pressing pressure in the second pressing step is preferably 100 MPa or more and 700 MPa or less, more preferably 300 MPa or more and 700 MPa or less, and even more preferably 500 MPa or more and 700 MPa or less.
  • the porosity of the negative electrode intermediate layer can be easily controlled to a predetermined value.
  • the pressing temperature in the second pressing step varies depending on the material contained in the negative electrode intermediate layer and the desired porosity, and can be set appropriately by a person skilled in the art.
  • the pressing temperature in the second pressing step is preferably 20 to 90°C, and more preferably 25 to 80°C. Within the above range, the porosity of the negative electrode intermediate layer can be easily controlled to a predetermined value.
  • the pressing time of the second pressing step varies depending on the material contained in the negative electrode intermediate layer and the desired porosity, and can be set appropriately by a person skilled in the art.
  • the pressing time of the second pressing step is preferably 10 seconds to 30 minutes, and more preferably 1 to 10 minutes. Within the above range, the porosity of the negative electrode intermediate layer can be easily controlled to a predetermined value.
  • the thickness of the negative electrode intermediate layer is not particularly limited, but is preferably 10 ⁇ m or less, more preferably 7 ⁇ m or less, and even more preferably 6 ⁇ m or less.
  • the thickness of the negative electrode intermediate layer is 10 ⁇ m or less, the path of the lithium ions moving through the negative electrode intermediate layer during charging is not too long, so that the resistance during charging can be kept low.
  • the energy density of the all-solid-state battery can be improved.
  • the lower limit of the thickness of the negative electrode intermediate layer is not particularly limited, but from the viewpoint of ensuring the strength of the negative electrode intermediate layer, it is, for example, 1 ⁇ m or more, preferably 1.5 ⁇ m or more, and more preferably 2 ⁇ m or more. In this specification, the thickness of the negative electrode intermediate layer is measured by the method described in the Examples below.
  • Solid electrolyte layer The solid electrolyte layer is interposed between the negative electrode and the positive electrode and contains a solid electrolyte (usually as a main component).
  • the solid electrolyte contained in the solid electrolyte layer is not particularly limited, and can be appropriately adopted from those known in the art, for example, sulfide solid electrolytes and oxide solid electrolytes.
  • this solid electrolyte exhibits excellent lithium ion conductivity, it is preferably a sulfide solid electrolyte containing an S element, more preferably a sulfide solid electrolyte containing an Li element, an M element, and an S element, the M element being a sulfide solid electrolyte containing at least one element selected from the group consisting of P, Si, Ge, Sn, Ti, Zr, Nb, Al, Sb, Br, Cl, and I, and more preferably a sulfide solid electrolyte containing an S element, an Li element, and an P element.
  • Examples include sulfide solid electrolytes such as LPS ( Li2S - P2S5 ), Li6PS5X (wherein X is Cl, Br or I), Li7P3S11 , Li3.2P0.96S and Li3PS4 . These sulfide solid electrolytes are preferably used because they have excellent lithium ion conductivity.
  • the ionic conductivity (e.g., Li ion conductivity) of the solid electrolyte (e.g., sulfide solid electrolyte) at room temperature (25° C.) is preferably, for example, 1 ⁇ 10 ⁇ 5 S/cm or more, and more preferably 1 ⁇ 10 ⁇ 4 S/cm or more.
  • the ionic conductivity value of the solid electrolyte can be measured by an AC impedance method.
  • the shape of the solid electrolyte may be, for example, particulate, such as spherical or elliptical, or thin film.
  • its average particle size (D50) is not particularly limited, but is preferably 0.01 ⁇ m or more and 40 ⁇ m or less, more preferably 0.1 ⁇ m or more and 20 ⁇ m or less, and even more preferably 0.5 ⁇ m or more and 10 ⁇ m or less.
  • the solid electrolyte content in the solid electrolyte layer is preferably 50 to 100% by mass, and more preferably 90 to 100% by mass.
  • the solid electrolyte layer may further contain a binder in addition to the solid electrolyte.
  • a binder there are no particular limitations on the binder, and any known binder may be used as appropriate.
  • the binder described above for the negative electrode intermediate layer may be similarly employed.
  • the content of the binder in the solid electrolyte layer is, for example, 1 to 10 mass %.
  • the thickness of the solid electrolyte layer varies depending on the configuration of the intended all-solid-state battery, but is usually 0.1 to 1000 ⁇ m, and preferably 10 to 100 ⁇ m.
  • the positive electrode active material layer essentially contains a positive electrode active material, and may contain a solid electrolyte, a binder, and a conductive assistant as necessary.
  • the type of positive electrode active material contained in the positive electrode active material layer is not particularly limited, and examples thereof include layered rock salt type active materials such as LiCoO2 , LiMnO2 , LiNiO2 , LiVO2 , and Li(Ni-Mn - Co ) O2 , spinel type active materials such as LiMn2O4 and LiNi0.5Mn1.5O4 , olivine type active materials such as LiFePO4 and LiMnPO4 , and Si-containing active materials such as Li2FeSiO4 and Li2MnSiO4 .
  • oxide active materials other than those mentioned above include Li4Ti5O12 .
  • Li(Ni-Mn-Co) O2 and those in which part of the transition metal is replaced by another element hereinafter, also simply referred to as "NMC composite oxide" are preferably used as the positive electrode active material.
  • one preferred embodiment is to use a sulfur-based positive electrode active material.
  • sulfur-based positive electrode active materials include particles or thin films of organic sulfur compounds or inorganic sulfur compounds, and any material can be used as long as it is capable of releasing lithium ions during charging and absorbing lithium ions during discharging by utilizing the oxidation-reduction reaction of sulfur.
  • the content of the positive electrode active material in the positive electrode active material layer is not particularly limited, but is preferably 30 to 99 mass%, more preferably 40 to 90 mass%, and even more preferably 45 to 80 mass%.
  • the positive electrode active material layer preferably further contains a solid electrolyte.
  • the specific form of the solid electrolyte contained in the positive electrode active material layer may be the same as that described in the solid electrolyte layer section.
  • a sulfide solid electrolyte is preferably used because it has excellent lithium ion conductivity and a low bulk modulus, allowing it to follow the volume change of the positive electrode active material associated with charging and discharging.
  • There is no particular restriction on the content of the solid electrolyte in the positive electrode active material layer but it is, for example, 1 to 70 mass%, preferably 10 to 60 mass%, and more preferably 20 to 55 mass%.
  • the binder used in the positive electrode active material layer is not particularly limited, and any known binder may be used as appropriate.
  • the binder described above for the negative electrode intermediate layer may be used.
  • the content of the binder in the positive electrode active material layer is not particularly limited, and is, for example, 1 to 10 mass %.
  • the conductive assistant used in the positive electrode active material layer is not particularly limited, and for example, carbon such as carbon black (specifically, acetylene black, Ketjen Black (registered trademark), furnace black, channel black, thermal lamp black, etc.) can be used.
  • the content of the conductive assistant in the positive electrode active material layer is not particularly limited, and is, for example, 10 to 30 mass%.
  • the thickness of the positive electrode active material layer varies depending on the configuration of the intended all-solid-state battery, but is usually 0.1 to 1000 ⁇ m, and preferably 10 to 300 ⁇ m.
  • the negative electrode intermediate layer contains at least one kind of metal particles containing a metal material capable of alloying with lithium and at least one kind of carbon particles containing a carbon material capable of absorbing lithium ions; 7.
  • the all-solid-state battery according to 5. or 6. wherein the ratio of the total surface area of the at least one kind of metal particles containing a metal material capable of alloying with lithium and the at least one kind of carbon particles containing a carbon material capable of absorbing lithium ions to the mass of the binder contained in the negative electrode intermediate layer is 800 m 2 /g or less.
  • Example 1 Preparation of Positive Electrode
  • an NMC composite oxide composition: LiNi0.8Mn0.1Co0.1O2
  • an argyrodite-type sulfide solid electrolyte Li6PS5Cl
  • acetylene black as a conductive additive
  • SBR styrene-butadiene rubber
  • the NMC composite oxide, solid electrolyte, and acetylene black were weighed out to a mass ratio of 50:30:20, mixed in an agate mortar in a glove box, and then further mixed and stirred in a planetary ball mill.
  • 2 parts by mass of styrene-butadiene rubber (SBR) were added to 100 parts by mass of the resulting mixed powder, and xylene was added as a solvent to prepare a positive electrode active material slurry.
  • SBR styrene-butadiene rubber
  • xylene was added as a solvent to prepare a positive electrode active material slurry.
  • the positive electrode active material slurry prepared above was applied to the surface of a carbon-coated aluminum foil serving as a positive electrode current collector, and dried to form a positive electrode active material layer (thickness 200 ⁇ m), thereby producing a positive electrode.
  • the positive electrode active material layer formed on the aluminum foil (positive electrode current collector) surface and the solid electrolyte layer formed on the stainless steel foil surface were stacked so that the exposed surface of the positive electrode active material layer and the exposed surface of the solid electrolyte layer faced each other, and pressed by cold isostatic pressing (CIP) at 700 MPa and 25 ° C. for 1 minute (first pressing step).
  • CIP cold isostatic pressing
  • the solid electrolyte layer and the negative electrode intermediate layer formed on the stainless steel foil (negative electrode current collector) surface were stacked so that the exposed surface of the solid electrolyte layer and the exposed surface of the negative electrode intermediate layer faced each other, and pressed by cold isostatic pressing (CIP) at 500 MPa and 80 ° C. for 1 minute (second pressing step).
  • CIP cold isostatic pressing
  • an aluminum positive electrode tab and a nickel negative electrode tab were bonded to the aluminum foil (positive electrode current collector) and the stainless steel foil (negative electrode current collector), respectively, using an ultrasonic welding machine, and the resulting laminate was placed inside an aluminum laminate film and vacuum sealed to obtain an evaluation cell, which is the lithium precipitation-type all-solid-state battery of this example.
  • Example 2 The evaluation cell of this example was produced in the same manner as in Example 1, except that in the above (production of evaluation cell), the pressing temperature in the second pressing step was changed to 25°C.
  • Example 3 In the above (Preparation of Evaluation Cell), the evaluation cell of this example was prepared in the same manner as in Example 1, except that the pressing pressure in the second pressing step was changed to 700 MPa and the pressing temperature was changed to 25°C.
  • Example 4 In the above (Preparation of Evaluation Cell), the evaluation cell of this example was prepared in the same manner as in Example 1, except that the pressing pressure in the second pressing step was changed to 700 MPa and the pressing time was changed to 10 minutes.
  • Example 5 In the above (Preparation of Evaluation Cell), the evaluation cell of this example was prepared in the same manner as in Example 1, except that the pressing pressure in the second pressing step was changed to 100 MPa and the pressing temperature was changed to 25°C.
  • the porosity of the negative electrode intermediate layer is a value calculated from the negative electrode intermediate layer in a post-discharge state, which is calculated after the all-solid-state battery is completely discharged, the cell is released from restraints, and the exterior body is removed, and can be calculated using "3D-SEM.”
  • the power generating element was removed from the evaluation cell after full discharge, and a cross section perpendicular to the surface direction (laminated cross section) was exposed by ion milling.
  • a cross section perpendicular to the surface direction (laminated cross section) was exposed by ion milling.
  • FIB-SEM Hitachi High-Tech Science focused ion beam processing-scanning electron microscope
  • a SEM photograph of the laminated cross section of the power generating element viewed from the front was taken of a photograph of the surface part of the negative electrode intermediate layer (5 ⁇ m x 5 ⁇ m size photograph).
  • an ion beam was irradiated onto the surface of the negative electrode intermediate layer, the surface of the negative electrode intermediate layer was excavated, and a photograph of the surface of the negative electrode intermediate layer was taken again.
  • the lithium metal in the negative electrode intermediate layer is considered to be voids. Specifically, if lithium metal remains in the voids in the evaluation cell after discharge, the lithium metal is considered to be voids and its area is calculated.
  • the lithium metal is identified by high-sensitivity EDS and is also identified by the contrast of the identified lithium metal, and its area is calculated.
  • the cross section was also observed using a SEM, and the thickness was measured at several to several dozen different points in the negative electrode intermediate layer, and the arithmetic mean value was taken as the thickness of the negative electrode intermediate layer.
  • the evaluation cells after the charge/discharge test described below were fully discharged and the porosity and thickness of the negative electrode intermediate layer were measured.
  • the evaluation cells before the first charge also had similar values for the porosity and thickness of the negative electrode intermediate layer.
  • the total surface area of the acetylene black particles and the total surface area of the silver nanoparticles are calculated and added together using the formula 4 ⁇ r2 ⁇ number of particles (r is the average primary particle size of the acetylene black particles or silver nanoparticles/2), and the result is divided by the mass of the binder per unit mass of the negative electrode intermediate layer.
  • a positive electrode lead and a negative electrode lead were connected to the positive electrode current collector and the negative electrode current collector of the evaluation cell (before the first charge) prepared above, respectively, and a restraining pressure of 3 MPa was applied in the stacking direction of the evaluation cell using a pressure member, while charging from SOC 0% at a charge rate of 0.5C in a thermostatic chamber at 60°C, and the presence or absence of a short circuit in the evaluation cell within 30 minutes was examined. It was determined that a short circuit had occurred when the voltage of the evaluation cell dropped during the charging process. In addition, the evaluation cells determined to have a short circuit were disassembled and the inside of the cells were observed, and the occurrence of dendrites due to lithium metal was confirmed in all of them. The results are shown in Table 1 below.
  • ⁇ Cycle test> A positive electrode lead and a negative electrode lead were connected to the positive electrode current collector and the negative electrode current collector of the evaluation cell (before the first charge) prepared above, respectively, and a cycle test was performed while applying a restraining pressure of 3 MPa in the stacking direction of the evaluation cell using a pressure member.
  • the cycle test was performed by repeating charge and discharge (charge CCCV mode (0.01C cutoff), discharge CC mode) at a charge and discharge rate of 0.5C 200 times at 60 ° C. and in a cell voltage range of 3.0V to 4.3V. Then, the ratio of the 200th discharge capacity to the first discharge capacity was calculated, and the discharge capacity retention rate (capacity retention rate) (%) was obtained.
  • Table 1 shows that the discharge capacity retention rate could not be measured for the evaluation cells of Comparative Examples 1 and 2 due to short circuit.
  • Table 1 show that the evaluation cells of Examples 1 to 5, which contain a specified metal material (metal particles), carbon material (carbon particles), and binder and have a negative electrode intermediate layer with a porosity of 10 to 70%, all had good resistance during charging, cycle characteristics, and short circuit rate during charging.
  • the evaluation cells of Comparative Examples 1 and 2 in which the porosity of the negative electrode intermediate layer is outside the above range, caused a short circuit during charging.
  • the evaluation cells of Comparative Examples 3 to 5, in which the porosity of the negative electrode intermediate layer is outside the above range did not cause a short circuit, but had low cycle durability, and it was not possible to obtain a battery that showed good performance in any of the resistance during charging, cycle characteristics, and short circuit rate during charging.
  • 10a stacked secondary battery; 11' negative electrode current collector, 11" positive electrode current collector, 13 negative electrode active material layer, 14 negative electrode intermediate layer, 15 positive electrode active material layer, 17 solid electrolyte layer, 19 cell layer, 21 power generating element, 25 negative electrode current collector, 27 positive electrode current collector, 29 Laminating film.

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Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2019033053A (ja) * 2017-08-10 2019-02-28 トヨタ自動車株式会社 リチウム固体電池、およびリチウム固体電池の製造方法
JP2019036537A (ja) * 2017-08-10 2019-03-07 トヨタ自動車株式会社 リチウム固体電池
WO2020196040A1 (ja) * 2019-03-22 2020-10-01 富士フイルム株式会社 全固体リチウムイオン二次電池とその製造方法、及び負極用積層シート
JP2020191202A (ja) 2019-05-21 2020-11-26 三星電子株式会社Ｓａｍｓｕｎｇ Ｅｌｅｃｔｒｏｎｉｃｓ Ｃｏ．，Ｌｔｄ． 全固体リチウム二次電池
JP2021089814A (ja) * 2019-12-03 2021-06-10 トヨタ自動車株式会社 全固体電池
US20220052343A1 (en) * 2020-08-12 2022-02-17 Hyundai Motor Company All-solid-state battery including lithium precipitate
WO2022038670A1 (ja) * 2020-08-18 2022-02-24 ＴｅｒａＷａｔｔ Ｔｅｃｈｎｏｌｏｇｙ株式会社 リチウム２次電池
US20220200002A1 (en) * 2020-12-21 2022-06-23 Hyundai Motor Company All-solid-state battery comprising lithium storage layer having multilayer structure and method of manufacturing same
US20220320483A1 (en) * 2021-03-31 2022-10-06 Hyundai Motor Company Anode for all-solid-state battery containing no active material and all-solid-state battery including the same
JP2022172093A (ja) 2015-04-23 2022-11-15 株式会社半導体エネルギー研究所 電子機器

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2016115681A (ja) * 2014-12-16 2016-06-23 日本碍子株式会社 リチウム電池用負極層、リチウム電池
JP6944773B2 (ja) * 2016-09-26 2021-10-06 日産自動車株式会社 非水電解質二次電池用負極
US11069897B2 (en) * 2019-05-16 2021-07-20 TeraWatt Technology Inc. Volume-expansion accommodable anode-free solid-state battery
FR3112031B1 (fr) * 2020-06-26 2025-03-07 Accumulateurs Fixes Electrode negative poreuse
WO2022098151A1 (ko) * 2020-11-05 2022-05-12 주식회사 엘지에너지솔루션 코팅층과 이온 전달층을 포함하는 전고체전지용 음극 및 이를 포함하는 리튬 이차전지.
JP7632352B2 (ja) * 2022-03-10 2025-02-19 トヨタ自動車株式会社 固体電池および固体電池システム

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2022172093A (ja) 2015-04-23 2022-11-15 株式会社半導体エネルギー研究所 電子機器
JP2019033053A (ja) * 2017-08-10 2019-02-28 トヨタ自動車株式会社 リチウム固体電池、およびリチウム固体電池の製造方法
JP2019036537A (ja) * 2017-08-10 2019-03-07 トヨタ自動車株式会社 リチウム固体電池
WO2020196040A1 (ja) * 2019-03-22 2020-10-01 富士フイルム株式会社 全固体リチウムイオン二次電池とその製造方法、及び負極用積層シート
JP2020191202A (ja) 2019-05-21 2020-11-26 三星電子株式会社Ｓａｍｓｕｎｇ Ｅｌｅｃｔｒｏｎｉｃｓ Ｃｏ．，Ｌｔｄ． 全固体リチウム二次電池
JP2021089814A (ja) * 2019-12-03 2021-06-10 トヨタ自動車株式会社 全固体電池
US20220052343A1 (en) * 2020-08-12 2022-02-17 Hyundai Motor Company All-solid-state battery including lithium precipitate
WO2022038670A1 (ja) * 2020-08-18 2022-02-24 ＴｅｒａＷａｔｔ Ｔｅｃｈｎｏｌｏｇｙ株式会社 リチウム２次電池
US20220200002A1 (en) * 2020-12-21 2022-06-23 Hyundai Motor Company All-solid-state battery comprising lithium storage layer having multilayer structure and method of manufacturing same
US20220320483A1 (en) * 2021-03-31 2022-10-06 Hyundai Motor Company Anode for all-solid-state battery containing no active material and all-solid-state battery including the same

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of EP4611089A4

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