WO2024202358A1 - 固体電池 - Google Patents

固体電池 Download PDF

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Publication number
WO2024202358A1
WO2024202358A1 PCT/JP2023/047055 JP2023047055W WO2024202358A1 WO 2024202358 A1 WO2024202358 A1 WO 2024202358A1 JP 2023047055 W JP2023047055 W JP 2023047055W WO 2024202358 A1 WO2024202358 A1 WO 2024202358A1
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Prior art keywords
negative electrode
solid electrolyte
solid
active material
electrode active
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PCT/JP2023/047055
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English (en)
French (fr)
Japanese (ja)
Inventor
健斗 本田
裕佑 船田
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Murata Manufacturing Co Ltd
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Murata Manufacturing Co Ltd
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Priority to CN202380096574.0A priority Critical patent/CN120883382A/zh
Priority to JP2025509760A priority patent/JPWO2024202358A1/ja
Publication of WO2024202358A1 publication Critical patent/WO2024202358A1/ja
Priority to US19/339,670 priority patent/US20260024768A1/en
Anticipated expiration legal-status Critical
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—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
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0561—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of inorganic materials only
    • H01M10/0562—Solid materials
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
    • 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
    • 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
    • H01M2300/0068—Solid electrolytes inorganic
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0065—Solid electrolytes
    • H01M2300/0068—Solid electrolytes inorganic
    • H01M2300/0071—Oxides
    • 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 a solid-state battery.
  • Secondary batteries which can be repeatedly charged and discharged, have been used for a variety of purposes.
  • secondary batteries are used as power sources for electronic devices such as smartphones and laptops.
  • a liquid electrolyte is generally used as a medium for the ion movement that contributes to charging and discharging.
  • electrolytic solution is used in secondary batteries.
  • safety is generally required to prevent leakage of the electrolytic solution.
  • organic solvents used in the electrolytic solution are flammable, so safety is also required in that respect. Therefore, research is being conducted on solid-state batteries that use solid electrolytes instead of electrolytic solutions.
  • a solid-state battery comprises a battery element including a positive electrode layer, a negative electrode layer, and a solid electrolyte interposed between the electrode layers of the positive electrode layer and the negative electrode layer.
  • the positive electrode layer includes a positive electrode active material and a solid electrolyte
  • the negative electrode layer includes a negative electrode active material and a solid electrolyte.
  • the electrode layer which is a component thereof, and in particular the negative electrode layer, may be made of a combination of a negative electrode active material containing a Li composite oxide and a garnet-type oxide-based solid electrolyte.
  • a garnet-type oxide-based solid electrolyte it is difficult for a garnet-type oxide-based solid electrolyte to form a dense interface with the particles of the negative electrode active material, making it difficult to reduce the porosity within the electrode. This can result in increased interfacial resistance between the active material and the solid electrolyte within the negative electrode, making it difficult for lithium ions to move across this interface. As a result, there is a risk that the volumetric energy density of the solid-state battery cannot be increased.
  • the object of the present invention is to provide a solid-state battery equipped with a negative electrode layer that can reduce the interfacial resistance between the active material and the solid electrolyte.
  • the negative electrode layer includes a negative electrode active material including a Li composite oxide and an oxide glass-based solid electrolyte, a content of the solid electrolyte in the negative electrode layer relative to a total amount of the negative electrode active material and the solid electrolyte is 20 mass% or more and 60 mass% or less, A ratio (B/A) of an actual density B of the negative electrode active material to a true density A of the negative electrode active material is 0.3 or more and 0.6 or less.
  • the solid-state battery according to one embodiment of the present invention can provide a negative electrode layer that can reduce the interfacial resistance between the active material and the solid electrolyte.
  • FIG. 1 is a schematic external perspective view of a solid-state battery according to one embodiment of the present invention.
  • FIG. 2 is a schematic cross-sectional view of the solid-state battery of FIG. 1 taken along line AA as viewed in the direction of the arrows.
  • cross-sectional view refers to the shape of the solid-state battery when viewed from a direction approximately perpendicular to the stacking direction in the stacked structure (in simple terms, the shape when cut along a plane parallel to the thickness direction of the layers).
  • planar view and planar shape used in this specification are based on a sketch of the object when viewed from above or below along the thickness direction of the layers (i.e., the stacking direction described above).
  • the vertical downward direction i.e., the direction in which gravity acts
  • the opposite direction to that corresponds to the "upward direction” can be considered to correspond to the vertical downward direction
  • solid-state battery refers in a broad sense to a battery whose components are made of solids, and in a narrow sense to an all-solid-state battery whose components (particularly preferably all components) are made of solids.
  • the solid-state battery of the present invention is a laminated solid-state battery in which the layers constituting the battery building blocks are laminated on top of each other, and preferably each such layer is made of a sintered body.
  • a "solid-state battery” is a so-called “secondary battery” that can be repeatedly charged and discharged.
  • the term “secondary battery” should not be overly limited to its name, and can also include, for example, a power storage device.
  • the feature of the present invention relates to the positive electrode layer contained in the solid-state battery.
  • the basic configuration of the solid-state battery of the present invention in order to understand the overall structure of the solid-state battery.
  • the configuration of the solid-state battery explained here is merely an example for understanding the invention and does not limit the invention.
  • Fig. 1 is a perspective view showing a schematic external appearance of a solid-state battery according to an embodiment of the present invention.
  • Fig. 2 is a schematic cross-sectional view of the A-A cross section of the solid-state battery in Fig. 1 as viewed in the direction of the arrows.
  • the solid-state battery has at least positive and negative electrode layers and a solid electrolyte.
  • the solid-state battery 200 includes a solid-state battery stack 100 including battery constituent units consisting of a positive electrode layer 10A, a negative electrode layer 10B, and at least a solid electrolyte 20 interposed therebetween.
  • a solid-state battery 200 comprises: a solid-state battery stack 100 including at least one battery constituent unit, arranged along a stacking direction L, the battery constituent unit being composed of a positive electrode layer 10A, a negative electrode layer 10B, and a solid electrolyte layer 20 interposed therebetween; and a positive electrode terminal 40A and a negative electrode terminal 40B provided on opposing side surfaces of the solid-state battery stack 100, respectively.
  • the positive electrode layers 10A and the negative electrode layers 10B are stacked alternately with the solid electrolyte layer 20 interposed therebetween.
  • each of the constituent layers may be formed by firing, and the positive electrode layer, negative electrode layer, solid electrolyte layer, etc. may form a fired layer.
  • the positive electrode layer, negative electrode layer, and solid electrolyte layer are each fired integrally with each other, and the solid-state battery laminate forms an integrally fired body.
  • the positive electrode layer is an electrode layer that includes at least a positive electrode active material.
  • the positive electrode layer may further include a solid electrolyte.
  • the positive electrode layer is composed of a sintered body that includes at least positive electrode active material particles and solid electrolyte particles.
  • the negative electrode layer is an electrode layer that includes at least a negative electrode active material.
  • the negative electrode layer may further include a solid electrolyte.
  • the negative electrode layer is composed of a sintered body that includes at least negative electrode active material particles and solid electrolyte particles.
  • a positive electrode layer having such a configuration is called a "composite positive electrode body," and similarly, a negative electrode layer can be called a "composite negative electrode body.”
  • the positive electrode active material and the negative electrode active material are materials involved in the transfer of electrons in solid-state batteries. Charging and discharging are performed by the transfer of electrons as ions move (conduct) between the positive electrode layer and the negative electrode layer via the solid electrolyte. It is preferable that each electrode layer of the positive electrode layer and the negative electrode layer is a layer capable of absorbing and releasing lithium ions or sodium ions in particular. In other words, it is preferable that the solid-state battery is an all-solid-state secondary battery in which lithium ions or sodium ions move between the positive electrode layer and the negative electrode layer via the solid electrolyte to charge and discharge the battery.
  • the positive electrode active material contained in the positive electrode layer may be selected from, for example, lithium-containing layered oxides, lithium-containing oxides having a spinel structure, etc.
  • lithium-containing layered oxides include LiCoO 2 , LiCo 1/3 Ni 1/3 Mn 1/3 O 2 , etc.
  • lithium-containing oxides having a spinel structure include LiMn 2 O 4 , LiNi 0.5 Mn 1.5 O 4 , etc.
  • the positive electrode active material capable of absorbing and releasing sodium ions can be selected from sodium-containing layered oxides, sodium-containing oxides having a spinel structure, etc.
  • the positive electrode layer and/or the negative electrode layer may contain a conductive material.
  • the conductive material contained in the positive electrode layer and the negative electrode layer include at least one of metal materials such as silver, palladium, gold, platinum, aluminum, copper, and nickel, and carbon.
  • the positive electrode layer and/or the negative electrode layer may contain a sintering aid.
  • the sintering aid may be at least one selected from the group consisting of lithium oxide, sodium oxide, potassium oxide, boron oxide, silicon oxide, bismuth oxide, and phosphorus oxide.
  • the thickness of the positive electrode layer and the negative electrode layer is not particularly limited, but may be, for example, independently 2 ⁇ m or more and 50 ⁇ m or less, particularly 5 ⁇ m or more and 30 ⁇ m or less.
  • the positive electrode layer and the negative electrode layer may each include a positive electrode current collector layer 11A and a negative electrode current collector layer 11B.
  • the positive electrode current collector layer and the negative electrode current collector layer may each have the form of a foil.
  • the positive electrode current collector layer and the negative electrode current collector layer may each have the form of a sintered body.
  • the positive electrode current collector constituting the positive electrode current collector layer and the negative electrode current collector constituting the negative electrode current collector it is preferable to use a material with high electrical conductivity, and for example, silver, palladium, gold, platinum, aluminum, copper, and/or nickel may be used.
  • the positive electrode current collector and the negative electrode current collector may each have an electrical connection part for electrical connection to the outside, and may be configured to be electrically connectable to a terminal.
  • the positive electrode current collecting layer and the negative electrode current collecting layer may be composed of a sintered body containing a conductive material and a sintering aid.
  • the conductive material contained in the positive electrode current collecting layer and the negative electrode current collecting layer may be selected from, for example, materials similar to the conductive materials that may be contained in the positive electrode layer and the negative electrode layer.
  • the sintering aid contained in the positive electrode current collecting layer and the negative electrode current collecting layer may be selected from, for example, materials similar to the sintering aids that may be contained in the positive electrode layer and the negative electrode layer.
  • the solid electrolyte is a material capable of conducting lithium ions or sodium ions.
  • the solid electrolyte may form a layer capable of conducting lithium ions between the positive electrode layer and the negative electrode layer.
  • the solid electrolyte may also be included in the positive electrode layer and the negative electrode layer.
  • the solid electrolyte layer may contain a sintering aid.
  • the sintering aid contained in the solid electrolyte layer may be selected from materials similar to the sintering aids that may be contained in the positive electrode layer and the negative electrode layer, for example.
  • the thickness of the solid electrolyte layer is not particularly limited.
  • the thickness of the solid electrolyte layer located between the positive electrode layer and the negative electrode layer may be, for example, 1 ⁇ m or more and 15 ⁇ m or less, particularly 1 ⁇ m or more and 5 ⁇ m or less.
  • the solid-state battery 200 of the present invention may further have an electrode separator (also called a "blank layer” or “blank portion”) 30 (30A, 30B).
  • an electrode separator also called a "blank layer” or “blank portion” 30 (30A, 30B).
  • the electrode separator 30A (positive electrode separator) is disposed around the positive electrode layer 10A, thereby separating the positive electrode layer 10A from the negative electrode terminal 40B.
  • the electrode separator 30B (negative electrode separator) is disposed around the negative electrode layer 10B, thereby separating the negative electrode layer 10B from the positive electrode terminal 40A.
  • the electrode separator 30 may be composed of one or more materials selected from the group consisting of, for example, solid electrolytes, insulating materials, and mixtures thereof.
  • the solid electrolyte that can form the electrode separator 30 can be made of the same material as the solid electrolyte that can form the solid electrolyte layer.
  • the insulating material that may constitute the electrode separator 30 may be a material that does not conduct electricity, i.e., a non-conductive material.
  • the insulating material may be, for example, a glass material, a ceramic material, or the like.
  • a glass material may be selected.
  • the glass material may be at least one selected from the group consisting of soda-lime glass, potash glass, borate-based glass, borosilicate-based glass, barium borosilicate-based glass, zinc borate-based glass, barium borate-based glass, bismuth borosilicate-based glass, bismuth zinc borate-based glass, bismuth silicate-based glass, phosphate-based glass, aluminophosphate-based glass, and zinc phosphate-based glass.
  • the ceramic material may be at least one selected from the group consisting of aluminum oxide ( Al2O3 ), boron nitride (BN), silicon dioxide ( SiO2 ), silicon nitride ( Si3N4 ), zirconium oxide ( ZrO2 ), aluminum nitride (AlN), silicon carbide (SiC), and barium titanate ( BaTiO3 ).
  • the solid-state battery 200 of the present invention is generally provided with terminals (external terminals) 40 (40A, 40B).
  • positive and negative terminals 40A, 40B are provided on the side of the solid-state battery in a pair. More specifically, a positive terminal 40A connected to the positive electrode layer 10A and a negative terminal 40B connected to the negative electrode layer 10B are provided in a pair.
  • the terminals 40A, 40B may be also referred to as "end electrodes" since they may be provided to cover at least one side of the solid-state battery.
  • Such terminals 40 (40A, 40B) may be made of a material having a high electrical conductivity.
  • the material of the terminal 40 is not particularly limited, but may be at least one conductive material selected from the group consisting of silver, gold, platinum, aluminum, copper, tin, and nickel.
  • the terminal 40 (40A, 40B) may further contain a sintering aid.
  • the sintering aid include materials similar to the sintering aid that may be contained in the positive electrode layer 10A.
  • the terminal 40 (40A, 40B) is composed of a sintered body that contains at least a conductive material and a sintering aid.
  • the solid-state battery 200 of the present invention usually further has an outer layer material 60.
  • the outer layer material 60 can generally be formed on the outermost surface of the solid-state battery, and serves to provide electrical, physical, and/or chemical protection. It is preferable that the material constituting the outer layer material 60 is excellent in insulation, durability, and/or moisture resistance, and is environmentally safe. For example, glass, ceramics, thermosetting resin, photosetting resin, and mixtures thereof can be used.
  • the same material as the glass material that can form the electrode separator can be used.
  • the ceramic material that can form the outer layer material the same material as the ceramic material that can form the electrode separator can be used.
  • the present inventors have intensively studied solutions for reducing the interface resistance between the active material and the solid electrolyte in the negative electrode layer of a solid-state battery, and as a result, have newly devised the present invention having technical features relating to a specific combination of the negative electrode active material and the solid electrolyte in the negative electrode layer, as well as specific ranges of the density of the negative electrode active material and the content of the solid electrolyte.
  • the technical features of the present invention are that the negative electrode layer contains a negative electrode active material containing a Li composite oxide and an oxide glass-based solid electrolyte, the content of the solid electrolyte is 20% by mass or more and 60% by mass or less with respect to the total amount of the negative electrode active material and the solid electrolyte in the negative electrode layer, and the ratio (B/A) of the actual density B of the negative electrode active material to the true density A of the negative electrode active material is 0.3 or more and 0.6 or less.
  • negative electrode active material and solid electrolyte in the negative electrode layer refers to the negative electrode active material and solid electrolyte located in the area other than the void that may be formed in the negative electrode layer of the final solid-state battery (corresponding to the finished product).
  • the content of the solid electrolyte in the negative electrode layer is 20% by mass or more and 60% by mass or less
  • a predetermined ratio (0.3 or more and 0.6 or less) of the actual density B of the negative electrode active material in the battery after production to the true density A of the negative electrode active material can be ensured.
  • the true density A of the negative electrode active material can be 3.0 g/cm 3 or more and 4.0 g/cm 3 or less, and can be 3.5 g/cm 3 as an example.
  • a predetermined amount of solid electrolyte is ensured compared to when the content is less than 20% by mass.
  • the contact interface between the negative electrode active material and the solid electrolyte in the negative electrode layer can be made dense, and a conductive path for lithium ions can be suitably formed.
  • the interfacial resistance between the negative electrode active material and the solid electrolyte in the negative electrode layer can be reduced, making it easier for lithium ions to move across this interface.
  • the internal resistance in the battery can be reduced, and the volumetric energy density can be improved.
  • the ratio (B/A) of the actual density B of the negative electrode active material to the true density A of the negative electrode active material can be ensured to be 0.3 or more, compared to when the content exceeds 60 mass%.
  • the "true density of the negative electrode active material” in this specification refers to the density specific to a specific type of negative electrode active material
  • the "true density of the solid electrolyte” in this specification refers to the density specific to a specific type of solid electrolyte.
  • the true densities of the negative electrode active material and the solid electrolyte can be calculated by a gas-phase substitution method using helium gas, and the true density can be calculated by changing the pressure and volume to determine the volume of the object to be measured, and then measuring the weight.
  • the "real density of the negative electrode active material” in this specification refers to the volume density of the negative electrode active material in the negative electrode layer of the solid-state battery after fabrication.
  • the actual density B of the negative electrode active material after the battery is fabricated can be calculated using the true density A of the negative electrode active material, the true density C of the solid electrolyte, the porosity E in the negative electrode, the content F of the negative electrode active material in the negative electrode layer, and the content G of the solid electrolyte.
  • the porosity within the electrode can be calculated by forming a smooth cross section by ion milling the obtained solid-state battery and observing it at 5000x magnification using an SEM; software called Image J can be used for this calculation.
  • the negative electrode active material content F and solid electrolyte content G can also be calculated in a similar manner.
  • the content of the solid electrolyte is 30% by mass or more and 50% by mass or less with respect to the total amount of the negative electrode active material and the solid electrolyte.
  • the content of the solid electrolyte in the negative electrode layer is increased by 10% by mass, so that the contact interface between the negative electrode active material and the solid electrolyte in the negative electrode layer can be made denser, and the conduction path of the lithium ions can be more suitably formed.
  • the amount of negative electrode active material increases by 10 mass% compared to when the solid electrolyte content is 60 mass%, and the distance between particles of the negative electrode active material in the negative electrode layer can be kept at a distance that allows for more optimal formation of an electronic path.
  • a discharge capacity that can achieve a charge/discharge efficiency above a predetermined standard value (95% or more), and it is possible to more optimally improve the battery characteristics of the solid-state battery.
  • the ratio (C/A) of the true density C of the solid electrolyte to the true density A of the negative electrode active material can be 0.55 to 0.9.
  • the true density C of the solid electrolyte can be 2.0 g/ cm3 to 3.0 g/cm3, preferably 2.0 g/ cm3 to 2.5 g/ cm3 .
  • the ratio C/A is within this range, the actual density B of the negative electrode active material in the battery after manufacture can be ensured to be a specified ratio (0.3 or more and 0.6 or less) to the true density A of the negative electrode active material.
  • the ratio C/A is outside this range (specifically, 0.51), the actual density B of the negative electrode active material in the battery after manufacture cannot be ensured to be a specified ratio (0.3 or more and 0.6 or less) to the true density A of the negative electrode active material.
  • the ratio B/A can be 0.35 or more and 0.5 or less.
  • the ratio B/A can be made higher than when the ratio C/A is less than 0.6.
  • a predetermined amount of the negative electrode active material (and solid electrolyte) is more preferably secured in the negative electrode layer in the fabricated battery, so that the contact interface between the negative electrode active material and the solid electrolyte in the negative electrode layer can be made denser, and a conduction path for lithium ions can be more preferably formed.
  • the Li complex oxide contained in the above-mentioned negative electrode active material can be an oxide containing Li and a transition metal element, and as an example, can be an oxide containing Li and at least one metal element selected from the group consisting of titanium (Ti), silicon (Si), tin (Sn), chromium (Cr), iron (Fe), niobium (Nb) and molybdenum (Mo).
  • the Li complex oxide contained in the above-mentioned negative electrode active material can be an oxide containing Li and Ti. When an oxide containing Li and Ti is used, a high energy density can be obtained while suppressing the expansion and contraction of the negative electrode layer during charging and discharging.
  • the oxide glass-based solid electrolyte of the negative electrode layer is advantageous in that it can contribute to reducing the porosity in the negative electrode, and can be, for example, lithium borosilicate glass.
  • the lithium borosilicate glass is an oxide glass material that contains at least lithium (Li), silicon (Si) and boron (B) as constituent elements, and can be, for example, 50Li 4 SiO 4 ⁇ 50Li 3 BO 3.
  • the lithium borosilicate glass can be advantageous in that it has a low glass transition temperature and can form a dense negative electrode layer.
  • the solid electrolyte may further include a solid electrolyte used in other known solid-state batteries in addition to the lithium borosilicate glass as a glass-based solid electrolyte.
  • a solid electrolyte may be, for example, one or more of a crystalline solid electrolyte, a glass-based solid electrolyte other than lithium borosilicate glass, and a glass ceramic-based solid electrolyte.
  • the crystalline solid electrolyte is, for example, an oxide-based crystal material.
  • oxide-based crystal material examples include a lithium-containing phosphate compound having a Nasicon structure, an oxide having a perovskite structure, an oxide having a garnet-type or garnet-like structure, and an oxide glass ceramic-based lithium ion conductor.
  • An example of a lithium-containing phosphate compound having a Nasicon structure is Li x M y (PO 4 ) 3 (1 ⁇ x ⁇ 2, 1 ⁇ y ⁇ 2, M is at least one selected from the group consisting of titanium (Ti), germanium (Ge), aluminum (Al), gallium (Ga) and zirconium (Zr).
  • An example of a lithium-containing phosphate compound having a Nasicon structure is Li 1.2 Al 0.2 Ti 1.8 (PO 4 ) 3.
  • An example of an oxide having a perovskite structure is La 0.55 Li 0.35 TiO 3.
  • An example of an oxide having a garnet type or a garnet type-like structure is Li 7 La 3 Zr 2 O 12.
  • the crystalline solid electrolyte may contain a polymer material (e.g., polyethylene oxide (PEO)).
  • Other possible glass - based solid electrolytes besides lithium borosilicate glass include 30Li2S.26B2S3.44LiI , 63Li2S.36SiS2.1Li3PO4 , 57Li2S.38SiS2.5Li4SiO4 , 70Li2S.30P2S5 , and 50Li2S.50GeS2 .
  • the glass ceramic solid electrolyte may be, for example, an oxide-based glass ceramic material.
  • a phosphate compound containing lithium, aluminum, and titanium as constituent elements (LATP) or a phosphate compound containing lithium, aluminum, and germanium as constituent elements (LAGP) may be used as the oxide - based glass ceramic material.
  • LATP is Li1.07Al0.69Ti1.46 ( PO4 ) 3 .
  • LAGP is Li1.5Al0.5Ge1.5 ( PO4 ).
  • the solid electrolyte may further contain an oxide having a garnet-type or garnet-like structure in order to improve ionic conductivity.
  • the solid-state battery of the present invention can be manufactured by a printing method such as a screen printing method, a green sheet method using a green sheet, or a combination of these methods.
  • a printing method such as a screen printing method, a green sheet method using a green sheet, or a combination of these methods.
  • the solid-state battery may be manufactured in accordance with a conventional method for manufacturing solid-state batteries.
  • the chronological matters such as the order of description below are merely for the convenience of explanation and are not necessarily bound by them.
  • pastes are used as inks, such as a paste for a positive electrode layer, a paste for a negative electrode layer, a paste for a solid electrolyte layer, a paste for a positive electrode current collector layer, a paste for a negative electrode current collector layer, a paste for an electrode separator, and a paste for an outer layer material, etc.
  • the pastes are applied by a printing method and dried to form a solid-state battery laminate precursor having a predetermined structure on a support base.
  • a solid-state battery laminate precursor that corresponds to a specified solid-state battery structure can be formed on a substrate by sequentially stacking printed layers with a specified thickness and pattern shape.
  • the type of pattern formation method is not particularly limited as long as it is a method capable of forming a specified pattern, but may be, for example, one or more of the following: screen printing and gravure printing.
  • the paste can be prepared by wet mixing the specific constituent materials for each layer appropriately selected from the group consisting of positive electrode active material particles, negative electrode active material particles, conductive material, solid electrolyte material, current collector layer material, insulating material, sintering aid, and other materials mentioned above, with an organic vehicle in which an organic material is dissolved in a solvent.
  • the paste for the positive electrode layer contains, for example, positive electrode active material particles, a solid electrolyte material, an organic material and a solvent, and optionally a sintering aid.
  • the paste for the negative electrode layer contains, for example, negative electrode active material particles, a solid electrolyte material, an organic material and a solvent, and optionally a sintering aid.
  • the paste for the solid electrolyte layer contains, for example, a solid electrolyte material, an organic material, and a solvent, and optionally a sintering aid.
  • the paste for the positive electrode current collecting layer contains a conductive material, an organic material, a solvent, and optionally a sintering aid.
  • the paste for the negative electrode current collecting layer contains a conductive material, an organic material, a solvent, and optionally a sintering aid.
  • the paste for the electrode separator contains, for example, a solid electrolyte material, an insulating material, an organic material, a solvent, and optionally a sintering aid.
  • the paste for the outer layer material contains, for example, an insulating material, an organic material, a solvent, and optionally a sintering aid.
  • the organic material contained in the paste is not particularly limited, but at least one polymeric material selected from the group consisting of polyvinyl acetal resin, cellulose resin, polyacrylic resin, polyurethane resin, polyvinyl acetate resin, polyvinyl alcohol resin, etc. can be used.
  • the type of solvent is not particularly limited, but may be, for example, one or more of organic solvents such as butyl acetate, N-methyl-pyrrolidone, toluene, terpineol, and N-methyl-pyrrolidone.
  • media can be used, specifically, the ball mill method or the viscomill method, etc. can be used.
  • wet mixing methods that do not use media can also be used, such as the sand mill method, the high-pressure homogenizer method, or the kneader dispersion method.
  • the supporting substrate is not particularly limited as long as it is capable of supporting each paste layer, but for example, it may be a release film with one surface treated for release.
  • a substrate made of a polymeric material such as polyethylene terephthalate may be used.
  • a substrate that is heat resistant to the firing temperature may be used.
  • green sheets can be formed from each paste and the resulting green sheets can be stacked to produce a solid-state battery laminate precursor.
  • the support base coated with each paste is dried on a hot plate heated to 30°C or higher and 90°C or lower, to form a positive electrode layer green sheet, a negative electrode layer green sheet, a solid electrolyte layer green sheet, a positive electrode current collector layer green sheet, a negative electrode current collector layer green sheet, an electrode separator green sheet, and/or an outer layer green sheet, each having a predetermined shape and thickness, on each support base (e.g., a PET film).
  • each green sheet is peeled off from the substrate. After peeling, the green sheets of each component are stacked in order along the stacking direction to form a solid-state battery stack precursor. After stacking, a solid electrolyte layer, an insulating layer, and/or a protective layer may be provided on the side regions of the electrode green sheets by screen printing.
  • the solid battery laminate precursor is subjected to firing.
  • firing is performed by heating in an oxygen-containing nitrogen gas atmosphere or in the air, for example at 200° C. or higher to remove organic materials, and then heating in a nitrogen gas atmosphere or in the air, for example at 300° C. or higher and 500° C. or lower.
  • the firing can be performed while applying pressure of 20 to 100 MPa to the solid battery laminate precursor in the stacking direction (and in some cases in the stacking direction and in a direction perpendicular to the stacking direction).
  • a positive terminal is attached to the solid-state battery stack using a conductive adhesive
  • a negative terminal is attached to the solid-state battery stack using a conductive adhesive, thereby attaching the positive terminal and the negative terminal to the solid-state battery stack, and finally, a desired solid-state battery can be obtained.
  • Example 1 Provides for Producing Green Sheet for Solid Electrolyte Layer
  • a halogen-containing lithium borosilicate glass 60Li2O - 10SiO2-30B2O3 in which 10% of O was replaced with Cl
  • an acrylic binder 60Li2O - 10SiO2-30B2O3 in which 10% of O was replaced with Cl
  • the true density of the solid electrolyte used in Example 1 was 2.5 g/ cm3 .
  • the obtained mixture was mixed with butyl acetate as a solvent so that the solid content was 30% by mass, and then this was stirred for 4 hours with zirconia balls having a diameter of 5 mm to obtain a paste for the solid electrolyte layer.
  • this paste was applied onto a release film and dried at 80°C for 20 minutes to produce a green sheet for the solid electrolyte layer as a precursor for the solid electrolyte layer.
  • lithium cobalt oxide LiCoO 2
  • LiCoO 2 as a positive electrode active material LiCoO 2
  • the obtained mixture was mixed with terpineol so that the solid content was 60 mass%.
  • the obtained mixture was stirred with a zirconia ball having a diameter of 5 mm for 1 hour to obtain a paste for a positive electrode layer.
  • this paste was applied on a release film and dried at 80 ° C for 20 minutes to prepare a green sheet for a positive electrode layer as a positive electrode layer precursor.
  • Li4Ti5O12 (Merck, product number 915939) as a negative electrode active material
  • the negative electrode active material used had a true density of 3.5 g/cm 3 .
  • the obtained mixture was mixed with terpineol so that the solid content was 60% by mass.
  • the obtained mixture was then stirred for 1 hour with zirconia balls having a diameter of 5 mm to obtain a paste for the negative electrode layer.
  • this paste was applied onto a release film and dried at 80°C for 20 minutes to produce a green sheet for the negative electrode layer as a precursor for the negative electrode layer.
  • a green sheet for a negative electrode current collecting layer was prepared in the same manner as in the above-mentioned process for preparing the green sheet for a positive electrode current collecting layer.
  • alumina particle powder manufactured by Kojundo Chemical Research Co., Ltd., product number ⁇ -Al 2 O 3 alumina
  • alumina particle powder manufactured by Kojundo Chemical Research Co., Ltd., product number ⁇ -Al 2 O 3 alumina
  • the obtained mixture was mixed with terpineol so that the solid content was 60 mass%.
  • the obtained mixture was stirred for 1 hour together with zirconia balls having a diameter of 5 mm to obtain a paste for the main surface exterior material.
  • this paste was applied to a release film and dried to prepare a green sheet for the exterior layer material as an exterior layer material precursor.
  • a laminate having the configuration shown in Figures 1 and 2 was produced as follows. Specifically, first, each green sheet was processed into the shape shown in Figures 1 and 2, and then released from the release film. Next, each green sheet was laminated in order so as to correspond to the configuration of the battery element shown in Figures 1 and 2, and then heat-pressed by heating to 100°C while applying pressure in the thickness direction. As a result, a laminate was obtained as a battery element precursor.
  • a silver plate was attached using a conductive adhesive (thermosetting silver paste) to the first and second end faces (or side faces) of the laminate where the positive electrode current collecting layer and the negative electrode current collecting layer were exposed, respectively, to form positive and negative electrode terminals, thereby producing a solid-state battery.
  • a conductive adhesive thermosetting silver paste
  • the degreased sample was heated at 350°C for 10 minutes in a pressure sintering machine P-5058-00 (NPA Systems Co., Ltd.) while applying pressure in the thickness direction under conditions of 20 to 100 MPa, and then cooled in air for 30 minutes to sinter and obtain a cell element.
  • a 100 ⁇ m thick Li foil was then punched out to a diameter of ⁇ 10 mm and attached to the cell element to produce the half cell used in this evaluation.
  • the mass ratio of the negative electrode active material to the solid electrolyte was 80:20 after the acrylic binder was removed.
  • Example 6 In Example 6, as in Example 3, in the process of preparing the green sheet for the negative electrode layer, Li 4 Ti 5 O 12 : solid electrolyte: binder was mixed at a mass ratio of 54:36:10. That is, in the prepared cell, the mass-based content ratio of the negative electrode active material and the solid electrolyte became 60:40 due to the removal of the acrylic binder. Meanwhile, in Example 6, unlike Example 3, the composition ratio of Li, B, and Si components, which are the main components of the solid electrolyte, was adjusted. For example, a solid electrolyte with a true density of 2.2 g/cm 3 was used by reducing the content ratio of Si.
  • Example 7 In Example 7, in the process of preparing the green sheet for the negative electrode material layer, Li 4 Ti 5 O 12 : solid electrolyte: binder was mixed at a mass ratio of 54:36:10, as in Example 3. That is, in the prepared cell, the mass-based content ratio of the negative electrode active material and the solid electrolyte was 60:40 due to the removal of the acrylic binder.
  • the composition ratio of the Li, B, and Si components, which are the main components of the solid electrolyte was adjusted to, for example, further reduce the Si content ratio, thereby using a solid electrolyte with a true density of 2.0 g/cm 3 .
  • Comparative Example 3 In Comparative Example 3, in the process of preparing the green sheet for the negative electrode material layer, Li 4 Ti 5 O 12 : solid electrolyte: binder was mixed at a mass ratio of 54:36:10, as in Example 3. That is, in the prepared cell, the mass-based content ratio of the negative electrode active material and the solid electrolyte was 60:40 due to the removal of the acrylic binder. On the other hand, in Comparative Example 3, unlike Example 3, the composition ratio of the Li, B, and Si components, which are the main components of the solid electrolyte, was adjusted to, for example, further reduce the Si content ratio, thereby using a solid electrolyte with a true density of 1.8 g/cm 3 .
  • the cell was also discharged to a predetermined potential at a constant current of 0.05C, and after reaching the predetermined potential, the cell was discharged in constant voltage mode until the current was reduced to 0.005C (cut-off voltage 1.0V).
  • the charge/discharge capacity of the half cell was confirmed by this charge/discharge test.
  • Table 1 shows the measurement results for Examples 1 to 5 and Comparative Examples 1 and 2.
  • the charge capacity was about 170 mAh/g.
  • the charge/discharge efficiency was calculated from the ratio of the discharge capacity to the charge capacity. Charge/discharge efficiency of 85% or more was judged as ⁇ , charge/discharge efficiency of 95% or more was judged as ⁇ , and charge/discharge efficiency of less than 85% or discharge capacity measurement was not possible was judged as ⁇ .
  • the charge/discharge efficiency was 85% or more when the content ratio (by mass) of the negative electrode active material and the solid electrolyte was 80:20 to 40:60, i.e., the content of the solid electrolyte relative to the total amount of the negative electrode active material and the solid electrolyte was 20% by mass or more and 60% by mass or less, and the ratio (B/A) of the actual density B of the negative electrode active material to the true density A of the negative electrode active material was 0.3 to 0.6.
  • the content ratio of the negative electrode active material to the solid electrolyte was 70:30 to 50:50, i.e., when the content of the solid electrolyte was 30% by mass or more and 50% by mass or less with respect to the total amount of the negative electrode active material and the solid electrolyte, it was found that the charge/discharge efficiency was 95% or more.
  • the density of the negative electrode active material B after preparation in this case was 0.3 g/ cm3 or more and 0.5 g/cm3 or less.
  • Comparative Example 1 when the mass content ratio of the negative electrode active material to the solid electrolyte is 90:10, i.e., the content of the solid electrolyte is 10 mass% relative to the total amount of the negative electrode active material and the solid electrolyte, and the porosity in the negative electrode layer is 20.0 volume% or less, a battery can be fabricated, but the discharge capacity cannot be measured. From the above, it was found that because the content of the negative electrode active material is high and the content of the solid electrolyte is low, the contact interface between the negative electrode active material and the solid electrolyte cannot be made dense, and a conduction path for lithium ions cannot be formed.
  • Comparative Example 2 it was found that when the mass content ratio of the negative electrode active material to the solid electrolyte is 30:70, that is, the content of the solid electrolyte relative to the total amount of the negative electrode active material and the solid electrolyte is 70 mass%, and the ratio (B/A) of the actual density B of the negative electrode active material to the true density A of the negative electrode active material is less than 0.3, the charge/discharge efficiency is less than 85%. From the above, it was found that when the content of the solid electrolyte in the negative electrode layer exceeds 60 mass% and the ratio (B/A) is less than 0.3, the interparticle distance of the negative electrode active material cannot be made large enough to form an electron path.
  • the contact interface between the negative electrode active material and the solid electrolyte can be made dense, a conductive path for lithium ions can be suitably formed, and the distance between particles of the negative electrode active material in the negative electrode layer can be made to be a distance that allows the formation of a suitable electronic path.
  • Example 2 shows the measurement results for Example 3, Example 6, Example 7, and Comparative Example 3.
  • the charge capacity was about 170 mAh/g, as in Example 1, and the charge/discharge efficiency was calculated from the ratio of the discharge capacity to the charge capacity based on this value.
  • the charge/discharge efficiency of 85% or more was judged as ⁇
  • the charge/discharge efficiency of 95% or more was judged as ⁇
  • the charge/discharge efficiency of less than 85% or the discharge capacity could not be measured was judged as ⁇ .
  • the ratio C/A when the ratio C/A is 0.6 or more and 0.75 or less, the ratio B/A is 0.35 or more and 0.5 or less, and a charge/discharge efficiency of 95% or more is ensured.
  • the ratio (C/A) when the ratio (C/A) is less than 0.55, the ratio B/A is less than 0.3, and a charge/discharge efficiency is less than 85%.
  • the ratio (C/A) of the true density C of the solid electrolyte to the true density A of the negative electrode active material is also related to the charge/discharge efficiency, i.e., the battery characteristics.
  • the present invention can take the following forms.
  • the negative electrode layer includes a negative electrode active material including a Li composite oxide and an oxide glass-based solid electrolyte, a content of the solid electrolyte in the negative electrode layer relative to a total amount of the negative electrode active material and the solid electrolyte is 20 mass% or more and 60 mass% or less, A solid-state battery, wherein a ratio (B/A) of an actual density B of the negative electrode active material to a true density A of the negative electrode active material is 0.3 or more and 0.6 or less.
  • ⁇ 2> The solid-state battery according to ⁇ 1>, wherein a content of the solid electrolyte is 30% by mass or more and 50% by mass or less with respect to a total amount of the negative electrode active material and the solid electrolyte.
  • ⁇ 3> The solid-state battery according to ⁇ 1> or ⁇ 2>, wherein a ratio (C/A) of a true density C of the solid electrolyte to a true density A of the negative electrode active material is 0.55 or more and 0.9 or less.
  • ⁇ 4> The solid-state battery according to ⁇ 3>, wherein when the C/A is 0.6 or more and 0.75 or less, the B/A is 0.35 or more and 0.5 or less.
  • ⁇ 5> The solid-state battery according to any one of ⁇ 1> to ⁇ 4>, wherein the negative electrode active material has a true density A of 3.0 g/cm 3 or more and 4.0 g/cm 3 or less.
  • ⁇ 6> The solid-state battery according to ⁇ 3> or ⁇ 4>, wherein the solid electrolyte has a true density C of 2.0 g/cm 3 or more and 3.0 g/cm 3 or less.
  • ⁇ 7> The solid-state battery according to any one of ⁇ 1> to ⁇ 6>, wherein the Li composite oxide is an oxide containing Li and a transition metal element.
  • ⁇ 8> The solid-state battery according to ⁇ 7>, wherein the Li composite oxide is an oxide containing Li and Ti.
  • the Li composite oxide of the positive electrode active material is an oxide containing Li and Co.
  • the solid-state battery of the present invention can be used in various fields where electricity storage is expected.
  • the solid-state battery of the present invention can be used in the electrical, information, and communication fields where mobile devices are used (for example, the electrical and electronic devices fields or mobile device fields including small electronic devices such as mobile phones, smartphones, notebook computers, digital cameras, activity meters, arm computers, electronic paper, RFID tags, card-type electronic money, and smart watches), household and small industrial applications (for example, power tools, golf carts, household, nursing care, and industrial robots), large industrial applications (for example, forklifts, elevators, and port cranes), transportation systems (for example, hybrid cars, electric cars, buses, trains, electrically assisted bicycles, and electric motorcycles), power system applications (for example, various power generation, road conditioners, smart grids, and general household installation-type electricity storage systems), medical applications (medical equipment fields such as earphone hearing aids), pharmaceutical applications (fields such as medication management systems), as well as the IoT field, and space and deep sea applications (for example, fields
  • Electrode layer 10A Positive electrode layer 10B: Negative electrode layer 11: Electrode current collector layer 11A: Positive electrode current collector layer 11B: Negative electrode current collector layer 20: Solid electrolyte layer 30: Electrode separator 30A: Positive electrode separator 30B: Negative electrode separator 40: Terminal 40A: Positive electrode terminal 40B: Negative electrode terminal 60: Outer layer material 100: Solid-state battery laminate 200: Solid-state battery

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001126757A (ja) * 1999-10-25 2001-05-11 Kyocera Corp リチウム電池
WO2018123479A1 (ja) * 2016-12-27 2018-07-05 日本碍子株式会社 リチウムイオン電池及びその製造方法
WO2018131337A1 (ja) * 2017-01-13 2018-07-19 株式会社日立製作所 全固体電池、およびその製造方法
WO2020250981A1 (ja) * 2019-06-13 2020-12-17 株式会社村田製作所 固体電池
WO2022186087A1 (ja) * 2021-03-01 2022-09-09 株式会社村田製作所 固体電池

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001126757A (ja) * 1999-10-25 2001-05-11 Kyocera Corp リチウム電池
WO2018123479A1 (ja) * 2016-12-27 2018-07-05 日本碍子株式会社 リチウムイオン電池及びその製造方法
WO2018131337A1 (ja) * 2017-01-13 2018-07-19 株式会社日立製作所 全固体電池、およびその製造方法
WO2020250981A1 (ja) * 2019-06-13 2020-12-17 株式会社村田製作所 固体電池
WO2022186087A1 (ja) * 2021-03-01 2022-09-09 株式会社村田製作所 固体電池

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