WO2021132500A1 - Batterie à semi-conducteur - Google Patents

Batterie à semi-conducteur Download PDF

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Publication number
WO2021132500A1
WO2021132500A1 PCT/JP2020/048532 JP2020048532W WO2021132500A1 WO 2021132500 A1 WO2021132500 A1 WO 2021132500A1 JP 2020048532 W JP2020048532 W JP 2020048532W WO 2021132500 A1 WO2021132500 A1 WO 2021132500A1
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Prior art keywords
positive electrode
solid
electrode layer
layer
state battery
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PCT/JP2020/048532
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English (en)
Japanese (ja)
Inventor
克明 東
馬場　彰
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株式会社村田製作所
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Publication of WO2021132500A1 publication Critical patent/WO2021132500A1/fr

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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
    • H01M10/052—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
    • H01M4/06—Electrodes for primary cells
    • 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
    • H01M4/06—Electrodes for primary cells
    • H01M4/08—Processes of manufacture
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • 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
    • H01M4/64—Carriers or collectors
    • H01M4/66—Selection of materials
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M6/00—Primary cells; Manufacture thereof
    • H01M6/14—Cells with non-aqueous electrolyte
    • H01M6/18—Cells with non-aqueous electrolyte with solid electrolyte
    • 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.
  • a secondary battery may be used as a power source for electronic devices such as smartphones and notebook computers.
  • a liquid electrolyte is generally used as a medium for ion transfer that contributes to charging and discharging. That is, a so-called electrolytic solution is used in the secondary battery.
  • electrolytic solution is used in the secondary battery.
  • safety is generally required in terms of preventing leakage of the electrolytic solution.
  • organic solvent and the like used in the electrolytic solution are flammable substances, safety is also required in that respect as well.
  • Patent Document 1 Japanese Patent Document 1
  • the inventors of the present invention have found a new problem that short-circuit defects and / or charging defects occur when charging and discharging are repeated under a high charging voltage (for example, 4.2 V) using a conventional solid-state battery. .. It is considered that such a problem occurs because the electric field is excessively concentrated on the unevenness (particularly the convex portion) of the positive electrode layer in the conventional solid-state battery.
  • An object of the present invention is to provide a solid-state battery that is sufficiently suppressed.
  • the present invention A solid-state battery including a positive electrode layer, a negative electrode layer, and a solid electrolyte layer interposed between the positive electrode layer and the negative electrode layer.
  • the present invention relates to a solid-state battery in which the unevenness of the surface of the positive electrode layer in contact with the solid electrolyte layer is 1.0 ⁇ m or less in a cross-sectional view of the solid-state battery.
  • a preferred embodiment of the present invention is A positive electrode layer, a negative electrode layer, a solid electrolyte layer interposed between the positive electrode layer and the negative electrode layer, and a positive electrode current collector layer arranged on a surface of the positive electrode layer opposite to the surface in contact with the solid electrolyte layer.
  • a solid-state battery containing The positive electrode layer contains at least a lithium transition metal composite oxide and contains.
  • the negative electrode layer and the positive electrode current collector layer contain at least a carbon material and contain at least a carbon material.
  • the present invention relates to a solid-state battery in which the unevenness of the surface of the positive electrode layer in contact with the solid electrolyte layer is 1.0 ⁇ m or less in a cross-sectional view of the solid-state battery.
  • the solid-state battery according to the present invention more sufficiently suppresses short-circuit defects and charging defects even when charging and discharging are repeated under a high charging voltage (for example, 4.2 V).
  • FIG. 1 is an external perspective view schematically showing a solid-state battery according to an embodiment of the present invention.
  • FIG. 2 is a schematic cross-sectional view of the solid-state battery of FIG. 1 when viewed in the direction of an arrow.
  • FIG. 3 is a photomicrograph of a solid-state battery according to an embodiment of the present invention, which is a plane parallel to the stacking direction L and the width direction W and passes through a central point in the plan view shape of the solid-state battery.
  • FIG. 4 is a photomicrograph of a cross section of a solid-state battery for explaining the “distance from the reference line to the positive electrode active material particles of the positive electrode layer” measured due to the “unevenness of the surface of the positive electrode layer” defined in the present invention.
  • FIG. 5 is a photomicrograph of a cross section of a solid-state battery for explaining the “distance from the reference line to the positive electrode active material particles of the positive electrode layer” measured due to the “unevenness of the surface of the positive electrode layer” defined in the present invention.
  • it is a photomicrograph for explaining the end point of the distance.
  • Solid-state battery Solid-state battery
  • the contents shown are merely schematic and exemplary for the purpose of understanding the present invention, and the appearance, dimensional ratio, and the like may differ from the actual product.
  • the “solid-state battery” as used in the present invention refers to a battery whose components are composed of solids in a broad sense, and in a narrow sense, its components (particularly preferably all components) are composed of solids. Refers to an all-solid-state battery.
  • the solid-state battery in the present invention is a laminated solid-state battery in which the layers forming the battery building unit are laminated to each other, and preferably such layers are made of a sintered body.
  • the "solid-state battery” includes not only a so-called “secondary battery” capable of repeating charging and discharging, but also a "primary battery” capable of only discharging.
  • the "solid-state battery” is a secondary battery.
  • the “secondary battery” is not overly bound by its name and may also include an electrochemical device such as a "storage device”.
  • the "plan view” referred to in the present specification is based on a form in which an object is viewed from above or below along a thickness direction based on a stacking direction of each layer constituting a solid-state battery, and is a plan view (top view). ( Figure and bottom view).
  • the “cross-sectional view” referred to in the present specification is a form when viewed from a direction substantially perpendicular to the thickness direction based on the stacking direction of each layer constituting the solid-state battery (in short, parallel to the thickness direction). It is based on the form when cut out on a flat surface) and includes a cross-sectional view.
  • the "cross-sectional view” may be based on a surface parallel to the thickness direction based on the stacking direction of each layer constituting the solid-state battery, and may be based on a form cut off at a surface passing through the positive electrode terminal and the negative electrode terminal.
  • the "vertical direction” and “horizontal direction” used directly or indirectly in the present specification correspond to the vertical direction and the horizontal direction in the drawings, respectively. Unless otherwise specified, the same reference numerals or symbols shall indicate the same members / parts or the same meanings. In one preferred embodiment, it can be considered that the vertical downward direction (that is, the direction in which gravity acts) corresponds to the "downward direction” and the opposite direction corresponds to the "upward direction”.
  • the solid-state battery 200 according to the present invention includes, for example, a positive electrode layer 10A, a negative electrode layer 10B, and a solid electrolyte layer 20 interposed between them, as shown in FIGS. 1, 2 and 3, for example.
  • the solid-state battery 200 according to the present invention is usually A solid-state battery laminate 100 including at least one battery structural unit including a positive electrode layer 10A, a negative electrode layer 10B, and a solid electrolyte layer 20 interposed between them along the stacking direction L; Positive electrode terminals 40A and negative electrode terminals 40B provided on opposite side surfaces of the solid-state battery laminate 100, respectively. Consists of having.
  • FIG. 1 is an external perspective view schematically showing a solid-state battery according to an embodiment of the present invention.
  • FIG. 2 is a schematic cross-sectional view of the solid-state battery of FIG. 1 when viewed in the direction of an arrow.
  • FIG. 3 is a photomicrograph of a solid-state battery according to an embodiment of the present invention, which is a plane parallel to the stacking direction L and the width direction W and passes through a central point in the plan view shape of the solid-state battery.
  • the positive electrode layer 10A, the negative electrode layer 10B, the solid electrolyte layer 20, and the like form a sintered layer.
  • the positive electrode layer 10A, the negative electrode layer 10B, and the solid electrolyte layer 20 are integrally fired with each other, and therefore the battery constituent units form an integrally sintered body.
  • the positive electrode layer 10A is an electrode layer 10 including at least a positive electrode active material.
  • the positive electrode layer 10A may further contain a solid electrolyte and / or a conductive material.
  • the positive electrode layer is composed of a sintered body containing at least a positive electrode active material and a solid electrolyte. As shown in FIGS. 2 and 3, the positive electrode layer 10A may or may not have the positive electrode current collecting layer 11.
  • the unevenness of the surface of the positive electrode layer 10A in contact with the solid electrolyte layer 20 is 1.0 ⁇ m or less in the cross-sectional view of the solid-state battery.
  • the unevenness exceeds 1.0 ⁇ m, the electric field concentration on the unevenness (particularly the convex portion) of the positive electrode layer at the boundary between the positive electrode layer and the solid electrolyte layer cannot be sufficiently suppressed, and the operating rate of the solid-state battery decreases. To do.
  • the lower limit of the unevenness on the surface of the positive electrode layer in contact with the solid electrolyte layer 20 is not particularly limited, and the unevenness is usually 0.1 ⁇ m or more, particularly 0.5 ⁇ m or more.
  • the unevenness of the surface of the positive electrode layer in contact with the solid electrolyte layer 20 is preferably 0.65 ⁇ m or more and 0.95 ⁇ m or less, more preferably 0.70 ⁇ m or more, from the viewpoint of more sufficiently suppressing the concentration of the electric field on the unevenness of the positive electrode layer. It is 0.82 ⁇ m or less.
  • the unevenness of the surface of the positive electrode layer in contact with the solid electrolyte layer is usually larger than the unevenness of the surface of the negative electrode layer in contact with the solid electrolyte layer, and smaller than the unevenness of the surface of the positive electrode layer in contact with the positive electrode current collector layer.
  • the unevenness of the surface of the positive electrode layer 10A in contact with the solid electrolyte layer 20 is such that the negative electrode layer 10B and the solid electrolyte are formed in the solid electrolyte layer 20 arranged between the positive electrode layer 10A and the negative electrode layer 10B.
  • the interface with the layer 20 is set as the reference line 15, and the distances (arrows in FIG. 4) from the reference line 15 to the positive electrode active material particles of the positive electrode layer 10A are measured at 1 ⁇ m intervals. It is a value expressed by the standard deviation. That is, the standard deviation (that is, variation) with respect to a plurality of measured values of the distance from the reference line 15 to the positive electrode active material particles (arrows in FIG.
  • the reference line 15 is a line that defines the interface between the negative electrode layer 10B and the solid electrolyte layer 20 in a cross-sectional view, and is usually shown in a linear shape.
  • FIG. 4 is a photomicrograph of a cross section of a solid-state battery for explaining the “distance from the reference line to the positive electrode active material particles of the positive electrode layer” measured due to the “unevenness of the surface of the positive electrode layer” defined in the present invention. In particular, it is a micrograph for explaining the reference line (starting point) of the distance.
  • FIG. 5 is a photomicrograph of a cross section of a solid-state battery for explaining the “distance from the reference line to the positive electrode active material particles of the positive electrode layer” measured due to the “unevenness of the surface of the positive electrode layer” defined in the present invention. In particular, it is a photomicrograph for explaining the end point of the distance.
  • the distance from the reference line 15 to the positive electrode active material particles of the positive electrode layer 10A is determined by drawing a vertical line starting from the reference line 15 toward the positive electrode layer 10A and first contacting the positive electrode active material.
  • the distance to the particles (positive electrode layer 10A) (end point).
  • such distances are measured at 1 ⁇ m intervals, and the standard deviations of those measured values are obtained.
  • some distances are measured relatively long as shown by arrow 16B, and some distances are measured relatively short as shown by arrow 16A.
  • the perpendicular line starting from the reference line 15 is a line perpendicular to the surface where the positive electrode layer 10A and the solid electrolyte layer 20 are in contact with each other, and is usually perpendicular to the surface where the negative electrode layer 10B and the solid electrolyte layer 20 are in contact with each other. It may be a line and / or a line parallel to the stacking direction L.
  • the distance from the reference line 15 to the positive electrode active material particles of the positive electrode layer 10A (hereinafter, may be referred to as “distance A”) is measured in the central portion of the obtained solid-state battery 200.
  • the central portion means a central portion in a plan view, and is a central portion in the width direction W and the depth direction P.
  • the width direction W is a direction that defines the shortest distance between the positive electrode terminal 40A and the negative electrode terminal 40B, and particularly in a direction that defines the shortest distance between the positive electrode terminal 40A and the negative electrode terminal 40B when the solid-state battery 200 has a rectangular shape. It is a parallel direction and is a direction perpendicular to the stacking direction L.
  • the rectangular parallelepiped shape includes a so-called cubic shape.
  • the depth direction P is a direction parallel to the positive electrode terminal 40A and the negative electrode terminal 40B, and particularly when the solid-state battery 200 has a rectangular parallelepiped shape, it is a direction perpendicular to both the stacking direction L and the width direction W. Is.
  • a cross-sectional photograph for example, FIG.
  • the center point means the center of gravity of the solid-state battery in the plan view shape when the solid-state battery is viewed in a two-dimensional plane from the stacking direction L.
  • the center of gravity is the point when a homogeneous material (for example, paper) is cut out by the contour of the plan view shape of the solid-state battery and supported by points in a balanced manner.
  • the vicinity of the central portion of the solid electrolyte layer 20 arranged between the positive electrode layer 10A and the negative electrode layer 10B is enlarged so as to have a magnification of 3000 times.
  • the distance A described above was measured at 1 ⁇ m intervals of 20 ⁇ m width from the center line to the right and left to obtain a total of 41 measured values, and the standard deviation of these values was calculated.
  • the center line is the axis of the solid-state battery, more specifically, a line parallel to the stacking direction L and a line passing through the above-mentioned center point in the plan view shape of the solid-state battery.
  • the unevenness of the surface of the positive electrode layer in contact with the solid electrolyte layer described above is arranged in the center in the stacking direction L among all the solid electrolyte layers 20 arranged between the positive electrode layer 10A and the negative electrode layer 10B. It suffices if it is filled between one solid electrolyte layer 20 and the positive electrode layer 10A in contact with the solid electrolyte layer.
  • the one solid electrolyte layer 20 arranged in the center in the stacking direction L is the k + 1th solid from the bottom. It is an electrolyte layer.
  • the total number of the solid electrolyte layers 20 included in the solid battery is 1, one solid electrolyte layer 20 arranged at the center in the stacking direction L is the one solid electrolyte layer.
  • the irregularities on the surface of the positive electrode layer in contact with the solid electrolyte layer described above are all arranged between the positive electrode layer 10A and the negative electrode layer 10B in the solid-state battery from the viewpoint of more sufficiently suppressing the electric field concentration on the irregularities of the positive electrode layer. It is preferable that the solid electrolyte layer 20 is filled between the solid electrolyte layer 20 and the positive electrode layer 10A in contact with the solid electrolyte layer.
  • the unevenness of the surface of the positive electrode layer in contact with the solid electrolyte layer can be controlled during the production of the positive electrode layer by adjusting the mixing conditions and the like when preparing the paste for producing the positive electrode layer, as will be described in detail later. it can.
  • the average primary particle size of the positive electrode active material is not particularly limited, and is usually 1.0 ⁇ m or more and 20 ⁇ m or less, and is preferably 1 from the viewpoint of achieving the unevenness of the surface of the positive electrode layer in contact with the solid electrolyte layer described above. It is 5.5 ⁇ m or more and 6 ⁇ m or less.
  • the average primary particle size of the positive electrode active material in the positive electrode layer 10A the average value calculated from the measured values of any 100 positive electrode active material particles is used in the cross-sectional photograph.
  • the positive electrode active material contained in the positive electrode layer 10A is a substance involved in the transfer of electrons in a solid-state battery. Charging and discharging are performed by the movement (conduction) of ions between the positive electrode layer and the negative electrode layer via the solid electrolyte and the transfer of electrons between the positive electrode layer and the negative electrode layer via an external circuit.
  • the positive electrode layer is particularly preferably a layer capable of occluding and releasing lithium ions or sodium ions. That is, the solid-state battery of the present invention is preferably 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 a solid electrolyte to charge and discharge the battery. ..
  • the constituent material of the positive electrode active material is not particularly limited, and is, for example, a lithium-containing compound.
  • the type of the lithium-containing compound is not particularly limited, and is, for example, a lithium transition metal composite oxide and a lithium transition metal phosphoric acid compound.
  • Lithium transition metal composite oxide is a general term for oxides containing lithium and one or more types of transition metal elements as constituent elements.
  • Lithium transition metal phosphoric acid compound is a general term for phosphoric acid compounds containing lithium and one or more kinds of transition metal elements as constituent elements.
  • the type of transition metal element is not particularly limited, and is, for example, cobalt (Co), nickel (Ni), manganese (Mn), iron (Fe), and the like.
  • the lithium transition metal composite oxide is, for example, a compound represented by Li x M1O 2 and Li y M2O 4, respectively.
  • Lithium transition metal phosphate compound for example, a compound represented by Li z M3PO 4, and the like.
  • each of M1, M2 and M3 is one kind or two or more kinds of transition metal elements.
  • the respective values of x, y and z are arbitrary.
  • the lithium transition metal composite oxide is, for example, LiCoO 2 (that is, lithium cobalt oxide), LiNiO 2 , LiVO 2 , LiCrO 2 , LiMn 2 O 4 (that is, lithium manganate), LiCo 1/3 Ni 1 / 3 Mn 1/3 O 2 and LiNi 0.5 Mn 1.5 O 4 and the like.
  • the lithium transition metal phosphoric acid compound is, for example, LiFePO 4 , LiCoPO 4, LiMnPO 4, or the like.
  • the positive electrode active material capable of occluding and releasing sodium ions a sodium-containing phosphoric acid compound having a pearcon-type structure, a sodium-containing phosphoric acid compound having an olivine-type structure, a sodium-containing layered oxide, and a sodium-containing material having a spinel-type structure are contained. At least one selected from the group consisting of oxides and the like can be mentioned.
  • the positive electrode active material is preferably a lithium transition metal composite oxide (particularly lithium cobalt oxide or lithium manganate), and more preferably lithium cobalt oxide, from the viewpoint of more sufficiently suppressing electric field concentration on the unevenness of the positive electrode layer.
  • the content of the positive electrode active material in the positive electrode layer 10A is usually 50% by mass or more (that is, 50% by mass or more and 99% by mass or less) with respect to the total amount of the positive electrode layer, which is more sufficient for the electric field concentration on the unevenness of the positive electrode layer. From the viewpoint of sufficient suppression, it is preferably 60% by mass or more and 90% by mass or less, and more preferably 60% by mass or more and 80% by mass or less.
  • the positive electrode layer may contain two or more kinds of positive electrode active materials, and in that case, the total content thereof may be within the above range.
  • the solid electrolyte that may be contained in the positive electrode layer 10A may be selected from, for example, the same materials as the solid electrolyte that can be contained in the solid electrolyte layer described later.
  • the positive electrode layer 10A may contain a glass-ceramic solid electrolyte as the solid electrolyte.
  • the content of the solid electrolyte in the positive electrode layer 10A is not particularly limited, and is usually 1 to 50% by mass, particularly 10 to 40% by mass, based on the total amount of the positive electrode layer.
  • the positive electrode layer may contain two or more kinds of solid electrolytes, in which case the total content thereof may be within the above range.
  • the positive electrode layer 10A may further contain a sintering aid.
  • a sintering aid at least one selected from the group consisting of lithium oxide, sodium oxide, potassium oxide, boron oxide, silicon oxide, bismuth oxide and phosphorus oxide can be mentioned.
  • the thickness of the positive electrode layer 10A is not particularly limited, and may be, for example, 1 ⁇ m or more and 100 ⁇ m or less, particularly 5 ⁇ m or more and 50 ⁇ m or less.
  • the thickness of the positive electrode layer 10A is per one side of the positive electrode current collecting layer 11. The thickness.
  • the positive electrode layer 10A may or may not have the positive electrode current collector layer 11. From the viewpoint of the current collecting efficiency of the positive electrode layer, the positive electrode layer preferably has a positive electrode current collecting layer.
  • the positive electrode layer 10A may be formed on both sides of the positive electrode current collecting layer 11 or may be formed on one side as shown in FIG. In this case, the positive electrode layer 10A is preferably formed on both sides of the positive electrode current collector layer 11 as shown in FIG. 2 from the viewpoint of improving the battery capacity.
  • the positive electrode current collector layer 11 is usually arranged on the surface of the positive electrode layer opposite to the surface in contact with the solid electrolyte layer.
  • the positive electrode current collecting layer 11 is a connecting layer that achieves an electrical connection between the positive electrode layer 10A and the positive electrode terminal 40A, and includes at least a conductive material.
  • the positive electrode current collector layer 11 may further contain a solid electrolyte.
  • the positive electrode current collector layer is composed of a sintered body containing at least a conductive material and a solid electrolyte.
  • the conductive material that may be contained in the positive electrode current collector layer 11 is usually a material having a relatively high conductivity, and is composed of, for example, a carbon material, silver, palladium, gold, platinum, aluminum, copper and nickel. At least one selected may be used.
  • the positive electrode current collecting layer 11 preferably contains a carbon material (particularly graphite) from the viewpoint of more sufficiently suppressing the concentration of the electric field on the unevenness of the positive electrode layer. Examples of the carbon material include graphite, graphitizable carbon, non-graphitizable carbon, mesocarbon microbeads (MCMB) and highly oriented graphite (HOPG).
  • the positive electrode current collector layer 11 contains a carbon material (particularly graphite) and is solid.
  • the unevenness of the surface of the positive electrode layer in contact with the electrolyte layer 20 can be absorbed on the positive electrode current collecting layer side. Therefore, the unevenness of the surface of the positive electrode layer in contact with the solid electrolyte layer 20 can be controlled more easily within the above range.
  • the content of the conductive material (particularly carbon material) in the positive electrode current collector layer 11 is usually 50% by mass or more (for example, 50 to 99% by mass), particularly 60 to 90% by mass, based on the total amount of the positive electrode current collector layer. is there.
  • the positive electrode current collector layer may contain two or more kinds of conductive materials, and in that case, the total content thereof may be within the above range.
  • the solid electrolyte that may be contained in the positive electrode current collector layer 11 may be selected from, for example, the same materials as the solid electrolyte that can be contained in the solid electrolyte layer described later.
  • the positive electrode current collector layer 11 may contain a glass-ceramic solid electrolyte as the solid electrolyte.
  • the content of the solid electrolyte in the positive electrode current collector layer 11 is not particularly limited, and is usually 1 to 50% by mass, particularly 10 to 40% by mass, based on the total amount of the positive electrode current collector layer.
  • the positive electrode current collector layer may contain two or more kinds of solid electrolytes, in which case the total content thereof may be within the above range.
  • the positive electrode current collector layer 11 may further contain a sintering aid.
  • the sintering agent contained in the positive electrode current collector layer may be selected from, for example, the same materials as the sintering aid that can be contained in the positive electrode layer.
  • the thickness of the positive electrode current collector layer 11 is not particularly limited, and may be, for example, 1 ⁇ m or more and 100 ⁇ m or less, particularly 3 ⁇ m or more and 20 ⁇ m or less.
  • the negative electrode layer 10B is an electrode layer including at least a negative electrode active material.
  • the negative electrode layer 10B may further contain a solid electrolyte.
  • the negative electrode layer is composed of a sintered body containing at least a negative electrode active material and a solid electrolyte.
  • the negative electrode active material contained in the negative electrode layer 10B is a substance involved in the transfer of electrons in a solid-state battery. Charging and discharging are performed by the movement (conduction) of ions between the positive electrode layer and the negative electrode layer via the solid electrolyte and the transfer of electrons between the positive electrode layer and the negative electrode layer via an external circuit.
  • the negative electrode layer is particularly preferably a layer capable of occluding and releasing lithium ions.
  • Examples of the negative electrode active material include carbon materials, metal-based materials, lithium alloys, and lithium-containing compounds.
  • the negative electrode active material preferably contains a carbon material from the viewpoint of more sufficiently suppressing the concentration of the electric field on the unevenness of the positive electrode layer.
  • the carbon material is, for example, graphite, graphitizable carbon, non-graphitizable carbon, mesocarbon microbeads (MCMB), highly oriented graphite (HOPG), and the like.
  • Metallic material is a general term for materials containing one or more of metal elements and metalloid elements capable of forming alloys with lithium as constituent elements.
  • This metallic material may be a simple substance, an alloy, or a compound. Since the purity of the simple substance described here is not necessarily limited to 100%, the simple substance may contain a trace amount of impurities.
  • Metal elements and semi-metal elements include, for example, silicon (Si), tin (Sn), aluminum (Al), indium (In), magnesium (Mg), boron (B), gallium (Ga), germanium (Ge). , Lead (Pb), Bismus (Bi), Cadmium (Cd), Titanium (Ti), Chromium (Cr), Iron (Fe), Niobium (Nb), Molybdenum (Mo), Silver (Ag), Zinc (Zn) , Hafnium (Hf), zirconium (Zr), ittrium (Y), palladium (Pd) and platinum (Pt).
  • the metal-based materials include, for example, Si, Sn, SiB 4 , TiSi 2 , SiC, Si 3 N 4 , SiO v (0 ⁇ v ⁇ 2), LiSiO, SnO w (0 ⁇ w ⁇ 2). , SnSiO 3 , LiSnO, Mg 2 Sn, and the like.
  • the lithium-containing compound is, for example, a lithium transition metal composite oxide.
  • the definition of the lithium transition metal composite oxide is as described above.
  • the lithium transition metal double oxides are, for example, Li 3 V 2 (PO 4 ) 3 , Li 3 Fe 2 (PO 4 ) 3 , Li 4 Ti 5 O 12 , LiTi 2 (PO 4 ) 3 , And LiCuPO 4 and the like.
  • the negative electrode active material capable of occluding and releasing sodium ions is a group consisting of a sodium-containing phosphoric acid compound having a pearcon-type structure, a sodium-containing phosphoric acid compound having an olivine-type structure, a sodium-containing oxide having a spinel-type structure, and the like. At least one selected from is mentioned.
  • the interface between the negative electrode layer 10B and the solid electrolyte layer 20 can usually be represented in a sufficiently linear shape in a cross-sectional photograph (cross-sectional view) at a magnification of 1000 times. ..
  • the interface between the negative electrode layer 10B and the solid electrolyte layer 20 can be further represented in a sufficiently linear shape. If it is difficult to represent the interface between the negative electrode layer 10B and the solid electrolyte layer 20 in a linear shape, the reference line 15 is the center line on the most solid electrolyte layer 20 side of the negative electrode layer 10B in cross-sectional view.
  • It may be a line passing through a point in contact with (or intersecting with) the negative electrode active material and defining a surface perpendicular to the stacking direction L. If the interface between the negative electrode layer and the solid electrolyte layer is smooth, it becomes easier to accept ions (for example, lithium ions), and by using soft graphite powder for the current collecting layer, the unevenness of the positive electrode active material (for example, LCO) is collected. It can be absorbed on the layer side to improve the operating rate.
  • ions for example, lithium ions
  • the content of the negative electrode active material (particularly carbon material) in the negative electrode layer 10B is usually 50 to 99% by mass, particularly 60 to 90% by mass, based on the total amount of the negative electrode layer.
  • the negative electrode layer may contain two or more kinds of negative electrode active materials, and in that case, the total content thereof may be within the above range.
  • the solid electrolyte that may be contained in the negative electrode layer 10B may be selected from, for example, the same materials as the solid electrolyte that can be contained in the solid electrolyte layer described later.
  • the negative electrode layer 10B may contain a glass-ceramic solid electrolyte as the solid electrolyte.
  • the content of the solid electrolyte in the negative electrode layer 10B is not particularly limited, and is usually 1 to 50% by mass, particularly 10 to 40% by mass, based on the total amount of the negative electrode layer.
  • the negative electrode layer may contain two or more kinds of solid electrolytes, in which case the total content thereof may be within the above range.
  • the negative electrode layer 10B may further contain a sintering aid.
  • a sintering aid include materials similar to those of the sintering aid that may be contained in the positive electrode layer 10A.
  • the thickness of the negative electrode layer 10B is not particularly limited, and may be, for example, 1 ⁇ m or more and 100 ⁇ m or less.
  • the negative electrode layer 10B may not have the negative electrode current collector layer as shown in FIG. 2, or may have the negative electrode current collector layer (not shown). From the viewpoint of the current collecting efficiency of the negative electrode layer, it is preferable that the negative electrode layer does not have the negative electrode current collecting layer.
  • the negative electrode layer 10B may be formed on both sides of the negative electrode current collecting layer or may be formed on one side.
  • the negative electrode current collector layer is a connecting layer that achieves electrical connection between the negative electrode layer 10B and the negative electrode terminal 40B, and includes at least a conductive material.
  • the negative electrode current collector layer may further contain a solid electrolyte.
  • the negative electrode current collector layer is composed of a sintered body containing at least a conductive material and a solid electrolyte.
  • the negative electrode current collector layer may be composed of the same constituent materials as the above-mentioned positive electrode current collector layer 11 in the same ratio.
  • the solid electrolyte layer 20 is a layer containing at least a solid electrolyte.
  • the solid electrolyte layer is composed of a sintered body containing at least the solid electrolyte.
  • the solid electrolyte constituting the solid electrolyte layer 20 is a material capable of conducting lithium ions or sodium ions.
  • the solid electrolyte forms a layer in which lithium ions or sodium ions can be conducted, particularly between the positive electrode layer and the negative electrode layer.
  • the solid electrolyte may be provided at least between the positive electrode layer and the negative electrode layer. That is, the solid electrolyte may also be present around the positive electrode layer and / or the negative electrode layer so as to protrude from between the positive electrode layer and the negative electrode layer.
  • Specific solid electrolytes include, for example, any one or more of crystalline solid electrolytes and glass-ceramic solid electrolytes.
  • the solid electrolyte layer 20 may contain a glass-ceramic solid electrolyte as the solid electrolyte.
  • the crystalline solid electrolyte is a crystalline electrolyte.
  • the crystalline solid electrolyte capable of conducting lithium ions is, for example, an inorganic material and a polymer material
  • the inorganic material is, for example, a sulfide and an oxide.
  • Sulfides include, for example, Li 2 SP 2 S 5 , Li 2 S-SiS 2 -Li 3 PO 4 , Li 7 P 3 S 11 , Li 3.25 Ge 0.25 P 0.75 S and Li 10 GeP 2 S 12 and the like.
  • Oxides for example, Li x M y (PO 4 ) 3 (1 ⁇ x ⁇ 2,1 ⁇ y ⁇ 2, M is at least one selected from the group consisting of Ti, Ge, Al, Ga and Zr) , Li 7 La 3 Zr 2 O 12 , Li 6.75 La 3 Zr 1.75 Nb 0.25 O 12 , Li 6 BaLa 2 Ta 2 O 12 , Li 1 + x Al x Ti 2-x (PO 4 ) 3 , La 2 / 3- x Li 3x TiO 3 , Li 1.2 Al 0.2 Ti 1.8 (PO 4 ) 3, La 0.55 Li 0.35 TiO 3 and Li 7 La 3 Zr 2 O 12 etc. is there.
  • the polymeric material is, for example, polyethylene oxide (PEO).
  • the glass-ceramic solid electrolyte is an electrolyte in which amorphous and crystalline are mixed.
  • This glass-ceramic solid electrolyte is, for example, an oxide containing lithium (Li), silicon (Si) and boron (B) as constituent elements, and more specifically, lithium oxide (Li 2 O) and oxidation. It contains silicon (SiO 2 ), boron oxide (B 2 O 3 ) and the like.
  • the ratio of the content of lithium oxide to the total content of lithium oxide, silicon oxide and boron oxide is not particularly limited, but is, for example, 40 mol% or more and 73 mol% or less.
  • the ratio of the content of silicon oxide to the total content of lithium oxide, silicon oxide and boron oxide is not particularly limited, but is, for example, 8 mol% or more and 40 mol% or less.
  • the ratio of the content of boron oxide to the total content of lithium oxide, silicon oxide and boron oxide is not particularly limited, but is, for example, 10 mol% or more and 50 mol% or less.
  • ICP-AES inductively coupled plasma emission spectrometry
  • ICP-AES inductively coupled plasma emission spectrometry
  • Examples of the solid electrolyte in which sodium ions can be conducted include sodium-containing phosphoric acid compounds having a pearcon structure, oxides having a perovskite structure, oxides having a garnet type or a garnet type similar structure, and the like.
  • the sodium-containing phosphate compound having a NASICON structure, Na x M y (PO 4 ) 3 (1 ⁇ x ⁇ 2,1 ⁇ y ⁇ 2, M is, Ti, Ge, Al, from the group consisting of Ga and Zr At least one selected).
  • the solid electrolyte layer 20 may further contain a sintering aid.
  • a sintering aid include materials similar to those of the sintering aid that may be contained in the positive electrode layer 10A.
  • the thickness of the solid electrolyte layer is not particularly limited, and may be, for example, 1 ⁇ m or more and 50 ⁇ m or less, particularly 1 ⁇ m or more and 5 ⁇ m or less.
  • the solid-state battery 200 of the present invention usually further has an electrode separation portion (also referred to as a "margin layer” or “margin portion”) 30 (30A, 30B).
  • an electrode separation portion also referred to as a "margin layer” or “margin portion” 30 (30A, 30B).
  • the electrode separating portion 30A (positive electrode separating portion) is arranged around the positive electrode layer 10A to separate the positive electrode layer 10A from the negative electrode terminal 40B.
  • the electrode separating portion 30B (negative electrode separating portion) is also arranged around the negative electrode layer 10B to separate the negative electrode layer 10B from the positive electrode terminal 40A.
  • the electrode separating portion 30 may be composed of one or more materials selected from the group consisting of, for example, a solid electrolyte, an insulating material, a mixture thereof, and the like.
  • the insulating material that can form the electrode separating portion 30 may be a material that does not conduct electricity, that is, 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 is not particularly limited, but the glass material is soda lime glass, potash glass, borate glass, borosilicate glass, barium borate glass, subhydrate borate glass, barium borate glass, etc.
  • the ceramic material includes aluminum oxide (Al 2 O 3 ), boron nitride (BN), silicon dioxide (SiO 2 ), silicon nitride (Si 3 N 4 ), and zirconium oxide (ZrO). 2 )
  • At least one selected from the group consisting of aluminum nitride (AlN), silicon carbide (SiC) and barium titanate (BaTIO 3) can be mentioned.
  • the solid-state battery 200 of the present invention is generally provided with terminals (external terminals) 40 (40A, 40B).
  • positive and negative electrode terminals 40A and 40B are provided on the side surface of the solid-state battery so as to form a pair.
  • the positive electrode side terminal 40A connected to the positive electrode layer 10A and the negative electrode side terminal 40B connected to the negative electrode layer 10B are provided so as to form a pair.
  • the material of the terminal 40 is not particularly limited, and examples thereof include at least one conductive material selected from the group consisting of silver, gold, platinum, aluminum, copper, tin, and nickel.
  • Terminal 40 may further contain a sintering aid.
  • the sintering aid include materials similar to those of the sintering aid that may be contained in the positive electrode layer 10A.
  • Terminal 40 (40A, 40B) is, in one preferred embodiment, composed of a sintered body containing at least a conductive material and a sintering aid.
  • the solid-state battery 200 of the present invention usually further includes an outer layer material 60.
  • the outer layer material 60 can generally be formed on the outermost side of the solid-state battery and is for electrical, physical and / or chemical protection.
  • the material constituting the outer layer material 60 is preferably excellent in insulation, durability and / or moisture resistance, and is environmentally safe.
  • glass, ceramics, thermosetting resins, photocurable resins, and mixtures thereof may be used.
  • the same material as the glass material that can form the electrode separation portion 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 separation portion can be used.
  • the solid-state battery of the present invention can be produced by a printing method such as a screen printing method, a green sheet method using a green sheet, or a composite method thereof.
  • a printing method such as a screen printing method, a green sheet method using a green sheet, or a composite method thereof.
  • the printing method and the green sheet method are adopted for understanding the present invention will be described in detail, but the present invention is not limited to this method.
  • Forming process of solid-state battery laminated precursor there are several types of pastes such as positive electrode layer paste, negative electrode layer paste, solid electrolyte layer paste, positive electrode current collector layer paste, negative electrode current collector layer paste, electrode separation part paste, and outer layer material paste.
  • Use paste as ink That is, a solid-state battery laminated precursor having a predetermined structure is formed on the support substrate by applying and drying the paste by a printing method.
  • a solid-state battery lamination precursor corresponding to a predetermined solid-state battery structure can be formed on a substrate by sequentially laminating print layers having a predetermined thickness and pattern shape.
  • the type of the pattern forming method is not particularly limited as long as it is a method capable of forming a predetermined pattern, and is, for example, any one or more of the screen printing method and the gravure printing method.
  • the paste is an appropriately selected layer 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, and sintering aid, and other materials described above. It can be produced by wet-mixing a predetermined constituent material and an organic vehicle in which an organic material is dissolved in a solvent.
  • the positive electrode layer paste contains, for example, positive electrode active material particles, solid electrolyte materials, organic materials and solvents, and optionally a sintering aid.
  • the negative electrode layer paste contains, for example, negative electrode active material particles, solid electrolyte materials, organic materials and solvents, and optionally a sintering aid.
  • the solid electrolyte layer paste contains, for example, solid electrolyte materials, organic materials and solvents, and optionally sintering aids.
  • the paste for the positive electrode current collector contains, for example, a conductive material, an organic material and a solvent, and optionally a sintering aid.
  • the paste for the negative electrode current collector contains, for example, a conductive material, an organic material and a solvent, and optionally a sintering aid.
  • the electrode separation paste contains, for example, a solid electrolyte material, an insulating material, an organic material and a solvent, and optionally a sintering aid.
  • the outer layer paste contains, for example, an insulating material, an organic material and a solvent, and optionally a sintering aid.
  • the organic material contained in the paste is not particularly limited, but at least one polymer material selected from the group consisting of polyvinyl acetal resin, cellulose resin, polyacrylic resin, polyurethane resin, polyvinyl acetate resin, polyvinyl alcohol resin and the like can be used. Can be used.
  • the type of solvent is not particularly limited as long as it dissolves the organic material, and for example, one or two of organic solvents such as butyl acetate, N-methyl-pyrrolidone, toluene, terpineol and N-methyl-pyrrolidone. That is all.
  • any mixed dispersion method may be adopted for the preparation of the paste for the negative electrode layer, the paste for the solid electrolyte layer, the paste for the positive electrode current collector layer, the paste for the negative electrode current collector layer, the paste for the electrode separation portion, and the paste for the outer layer material. .. Specifically, a mixture containing a predetermined material is wet-mixed. For example, in wet mixing, a medium can be used, and specifically, a bead mill method, a ball mill method, a sand mill method, a visco mill method, or the like can be used. Further, for example, a wet mixing method that does not use media may be used, and a three-roll mill sand mill method, a high-pressure homogenizer method, a kneader dispersion method, or the like can be used.
  • the paste for the positive electrode layer is, for example, a combination of at least a "wet mixing method using media", preferably a "wet mixing method using media” and a “wet mixing method using media” (particularly, a planetary mixer dispersion method).
  • a mixture containing a predetermined material is mixed by a wet mixing method that does not use media, and then a paste for a positive electrode layer obtained by mixing by a wet mixing method that uses media is used.
  • the wet mixing method without using a medium is a mixing method in which a shearing force is applied to a mixture (for example, an object to be crushed), for example, a planetary stirring mixer such as a planetary mixer or a rotation / revolution mixer, and a three-roll mill.
  • a shearing force is applied to a mixture (for example, an object to be crushed), for example, a planetary stirring mixer such as a planetary mixer or a rotation / revolution mixer, and a three-roll mill.
  • a disperser that does not use media such as a high-pressure homogenizer and kneader.
  • the planetary mixer exerts a strong shearing force mainly by the precise spacing between the blades and between the blades and the inner surface of the tank by the planetary motion (eg planetary motion) of a plurality of (for example, two) frame-shaped blades. It is a mixing device.
  • the wet mixing method using media is a mixing method in which an impact force is applied to a mixture to be mixed (for example, an object to be crushed), and for example, a disperser using media such as a bead mill, a ball mill, a sand mill, or a visco mill is used.
  • a bead mill is a mixing device in which an impact force is mainly applied by beads energized by centrifugal force generated by high-speed rotation of a stirring mechanism (disk).
  • the constituent material of the beads is not particularly limited, and examples thereof include zirconia, alumina, steel, and glass.
  • the particle size of the beads is as described below.
  • the mixture containing a predetermined material is mixed with a planetary mixer and then dispersed by a bead mill, and the paste for producing a positive electrode layer is used to bring the mixture into contact with the above-mentioned solid electrolyte layer.
  • the unevenness of the surface of the positive electrode layer can be achieved.
  • the unevenness of the surface of the positive electrode layer can be controlled by, for example, adjusting the dispersion time and rotation speed of the bead mill and the diameter of the beads used in the bead mill. For example, the longer the dispersion time by the bead mill, the smaller the unevenness on the surface of the positive electrode layer.
  • the shorter the dispersion time the larger the unevenness on the surface of the positive electrode layer.
  • the higher the rotation speed of the bead mill the smaller the unevenness on the surface of the positive electrode layer.
  • the lower the rotation speed the larger the unevenness on the surface of the positive electrode layer.
  • the smaller the diameter of the beads used in the bead mill the smaller the unevenness on the surface of the positive electrode layer.
  • the larger the diameter the larger the unevenness on the surface of the positive electrode layer.
  • the support substrate is not particularly limited as long as it is a support capable of supporting each paste layer, but is, for example, a release film having a release treatment on one surface.
  • a substrate made of a polymer material such as polyethylene terephthalate can be used.
  • a substrate that exhibits heat resistance to the firing temperature may be used.
  • each green sheet can be formed from each of the above-mentioned pastes, and the obtained green sheets can be laminated to prepare a solid-state battery laminated precursor.
  • a positive electrode layer green sheet having a predetermined shape and thickness on each support substrate (for example, PET film) by heating the green sheet of each paste formed on the support substrate to 80 ° C. or higher and 150 ° C. or lower.
  • 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 separation portion green sheet and / or an outer layer material green sheet are formed, respectively.
  • each green sheet is peeled off from the substrate.
  • the green sheet of each component is laminated in order along the lamination direction to form a solid-state battery lamination precursor.
  • a solid electrolyte layer, an insulating layer and / or a protective layer and the like may be provided on the side region of the electrode green sheet by screen printing.
  • the solid-state battery laminated precursor is subjected to firing.
  • the firing is carried out after removing the organic material by heating in a nitrogen gas atmosphere containing oxygen gas or in the atmosphere, for example, at 200 ° C. or higher and 600 ° C. or lower for 3 hours or more and 48 hours or less. It is carried out by heating in a nitrogen gas atmosphere or in the atmosphere, for example, at 300 ° C. or higher and 500 ° C. or lower for 10 to 120 minutes.
  • the firing may be performed while pressurizing the solid-state battery laminated precursor in the laminating direction and the direction perpendicular to the laminating direction.
  • Forming process of positive electrode terminal and negative electrode terminal For example, a conductive adhesive is used to bond the positive electrode terminals to the solid-state battery laminate, and a conductive adhesive is used to bond the negative electrode terminals to the solid-state battery laminate. As a result, each of the positive electrode terminal and the negative electrode terminal is attached to the solid-state battery laminate, so that the solid-state battery is completed.
  • the positive electrode terminal and the negative electrode terminal can be formed by adhering or applying the positive electrode terminal paste and the negative electrode terminal paste to the side surfaces of the solid-state battery laminate and sintering them.
  • the side surface of the solid-state battery laminate to which the paste for the positive electrode terminal is attached or applied is, for example, the side surface where the positive electrode current collector layer is exposed.
  • the side surface of the solid-state battery laminate to which the paste for the negative electrode terminal is attached or applied is, for example, the side surface where the negative electrode current collector layer is exposed.
  • Sintering can be carried out by heating in a nitrogen gas atmosphere or in the air, for example, at 150 ° C. or higher and 300 ° C. or lower for 10 minutes or longer and 120 minutes or shorter.
  • the positive electrode terminal paste and the negative electrode terminal paste contain a conductive material, an organic material and a solvent, and optionally a sintering aid.
  • the obtained mixture was dispersed in a bead mill using zirconia beads having a diameter of 5 mm for 30 minutes to obtain a paste for preparing a positive electrode layer. Subsequently, this paste was printed on a green sheet for producing a solid electrolyte layer and dried at 150 ° C. for 10 minutes to prepare a green sheet for producing a positive electrode layer as a precursor of the positive electrode layer.
  • terpineol was mixed so that the solid content became 30% by mass.
  • the obtained mixture was dispersed by a three-roll mill to obtain a paste for producing a main surface exterior material.
  • this paste was printed on a green sheet for producing a solid electrolyte layer and dried at 150 ° C. for 10 minutes to prepare a green sheet for producing an outer layer material as a precursor of the main surface outer layer material.
  • each green sheet was processed into the shapes shown in FIGS. 1 and 2, and then released from the release film. Subsequently, the green sheets were sequentially laminated so as to correspond to the configurations of the battery elements shown in FIGS. 1 and 2, and then thermocompression bonded at 100 ° C. for 10 minutes. As a result, a laminated body as a battery element precursor was obtained.
  • the center point means the center of gravity of the solid-state battery in the plan view shape when the solid-state battery is viewed in a two-dimensional plane from the stacking direction L.
  • the center of gravity is the point when a homogeneous material (for example, paper) is cut out by the contour of the plan view shape of the solid-state battery and supported by points in a balanced manner.
  • a homogeneous material for example, paper
  • the distance A is the distance from the reference line 15 to the positive electrode active material particles of the positive electrode layer 10A.
  • the center line is the axis of the solid-state battery, more specifically, a line parallel to the stacking direction L and a line passing through the above-mentioned center point in the plan view shape of the solid-state battery.
  • a charge / discharge test was performed on 18 solid-state batteries, and the ratio of solid-state batteries (non-defective products) in which short-circuit defects and charging defects did not occur was determined as the operating rate.
  • the charge / discharge test was performed in a temperature environment of 23 ° C. Specifically, the rated capacity of the battery is set to 1C, and the battery is charged with a constant current of 0.1C until it reaches 4.2V, and after reaching 4.2V, it is charged in the constant voltage mode until the current is reduced to 0.01C. (Constant current constant voltage charging). Then, the discharge was carried out at a constant current of 0.1 C until it reached 3.0 V (constant current discharge).
  • Short-circuit failure and charge failure were judged by the shape of the charge / discharge curve in the above charge / discharge test. More specifically, a short circuit failure is when the voltage hardly rises even after the start of the charge / discharge test, and a charge failure is when the voltage drops when the voltage exceeds a certain voltage and does not rise to 4.2V. Certified. ⁇ ; Operation rate was 90% or more (best); ⁇ ; The operation rate was 80% or more and less than 90% (good); ⁇ ; The operating rate was 70% or more and less than 80% (no problem in practical use); X; The operating rate was less than 70%.
  • the cross section of the positive electrode layer is observed with an optical microscope or an electron microscope, the cross section of 100 randomly selected particles is measured, and the average primary particle size is calculated. A line is drawn from one end of the cross section to the other, and the distance between two points, which is the maximum length, is defined as the particle size.
  • Example 2 In the step of producing the green sheet for producing the positive electrode layer, the solid-state battery was produced and evaluated by the same method as in Example 1 except that the dispersion time by the bead mill was doubled.
  • Example 3 In the step of producing the green sheet for producing the positive electrode layer, the solid-state battery was produced and evaluated by the same method as in Example 1 except that the dispersion time by the bead mill was quadrupled.
  • Example 4 A solid-state battery was produced and evaluated by the same method as in Example 1 except that lithium manganate (LiMnO4) (average particle size 5 ⁇ m) was used as the positive electrode active material in the process of producing the green sheet for producing the positive electrode layer. It was.
  • lithium manganate LiMnO4 (average particle size 5 ⁇ m)
  • LiMnO4 lithium manganate (average particle size 5 ⁇ m) was used as the positive electrode active material, and instead of the dispersion by the bead mill, the dispersion was performed twice by the three-roll ceramics roll mill. Except for the above, the solid-state battery was manufactured and evaluated by the same method as in Example 1.
  • Each solid-state battery of Examples 1 to 4 had the following relationship in cross-sectional view: The unevenness of the surface of the positive electrode layer in contact with the solid electrolyte layer is larger than the unevenness of the surface of the negative electrode layer in contact with the solid electrolyte layer; It is smaller than the unevenness of.
  • the solid-state battery of the present invention can be used in various fields where battery use or storage is expected. Although merely an example, the solid-state battery of the present invention can be used in the field of electronics mounting.
  • the solid-state battery of the present invention also includes electric / information / communication fields (for example, mobile phones, smartphones, laptop computers and digital cameras, activity meters, arm computers, electronic papers, wearable devices, RFID tags) in which mobile devices and the like are used.
  • Card-type electronic money, electrical / electronic equipment field including small electronic devices such as smart watches or mobile equipment field), household / small industrial applications (for example, electric tools, golf carts, household / nursing / industrial robots) Fields), large industrial applications (eg, forklifts, elevators, bay port cranes), transportation systems (eg, hybrid vehicles, electric vehicles, buses, trains, electrically assisted bicycles, electric motorcycles, etc.), power systems Applications (for example, various power generation, road conditioners, smart grids, general household installation type power storage systems, etc.), medical applications (medical equipment fields such as earphone hearing aids), pharmaceutical applications (fields such as dose management systems), and It can be used in the IoT field, space / deep sea applications (for example, fields such as space explorers and submersible research vessels).
  • household / small industrial applications for example, electric tools, golf carts, household / nursing / industrial robots) Fields
  • large industrial applications eg, forklifts, elevators, bay port cranes
  • transportation systems e

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Abstract

La présente invention concerne une batterie à semi-conducteur dans laquelle la concentration de champ électrique sur des pics et des vallées (en particulier, des pics) d'une couche d'électrode positive est supprimée, et par conséquent, des défauts de court-circuit et des défauts de charge sont en outre supprimés même si la charge et la décharge sont répétées sous une tension de charge élevée (par exemple, 4,2 V). La présente invention concerne une batterie à semi-conducteur comprenant une couche d'électrode positive, une couche d'électrode négative, et une couche d'électrolyte solide interposée entre la couche d'électrode positive et la couche d'électrode négative, dans une vue en coupe transversale de la batterie solide, une irrégularité sur la surface de l'électrode positive en contact avec la couche d'électrolyte solide est inférieure ou égale à 1,0 µm, l'irrégularité étant une valeur représentée par un écart-type d'une pluralité de valeurs mesurées obtenues par mesure de la distance d'une ligne de référence à une particule de matériau actif d'électrode positive de la couche d'électrode positive, la ligne de référence étant l'interface entre la couche d'électrode négative et la couche d'électrolyte solide.
PCT/JP2020/048532 2019-12-27 2020-12-24 Batterie à semi-conducteur WO2021132500A1 (fr)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2024070051A1 (fr) * 2022-09-29 2024-04-04 Fdk株式会社 Batterie à électrolyte solide et son procédé de production

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