WO2022080404A1 - Batterie à semi-conducteur - Google Patents

Batterie à semi-conducteur Download PDF

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Publication number
WO2022080404A1
WO2022080404A1 PCT/JP2021/037860 JP2021037860W WO2022080404A1 WO 2022080404 A1 WO2022080404 A1 WO 2022080404A1 JP 2021037860 W JP2021037860 W JP 2021037860W WO 2022080404 A1 WO2022080404 A1 WO 2022080404A1
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Prior art keywords
electrode layer
solid
state battery
layer
external electrode
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PCT/JP2021/037860
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English (en)
Japanese (ja)
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修 近川
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株式会社村田製作所
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Publication of WO2022080404A1 publication Critical patent/WO2022080404A1/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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0561—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of inorganic materials only
    • H01M10/0562—Solid materials
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/058—Construction or manufacture
    • H01M10/0585—Construction or manufacture of accumulators having only flat construction elements, i.e. flat positive electrodes, flat negative electrodes and flat separators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/50—Current conducting connections for cells or batteries
    • H01M50/531—Electrode connections inside a battery casing
    • H01M50/54—Connection of several leads or tabs of plate-like electrode stacks, e.g. electrode pole straps or bridges
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/50—Current conducting connections for cells or batteries
    • H01M50/543—Terminals
    • H01M50/547—Terminals characterised by the disposition of the terminals on the cells
    • H01M50/548—Terminals characterised by the disposition of the terminals on the cells on opposite sides of the cell
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/50—Current conducting connections for cells or batteries
    • H01M50/572—Means for preventing undesired use or discharge
    • H01M50/584—Means for preventing undesired use or discharge for preventing incorrect connections inside or outside the batteries
    • H01M50/586—Means for preventing undesired use or discharge for preventing incorrect connections inside or outside the batteries inside the batteries, e.g. incorrect connections of electrodes
    • 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
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • the present invention relates to a solid-state battery.
  • Secondary batteries that can be repeatedly charged and discharged have been used for various purposes.
  • a secondary battery is used as a power source for electronic devices such as smartphones and notebook computers.
  • the conventional solid-state battery 500' has a battery element 100'with a positive electrode layer 10A' facing each other, a negative electrode layer 10B', and a solid electrolyte layer 20' intervening between the positive electrode layer 10A'and the negative electrode layer 10B'. And an external electrode 200'provided on the surface of the battery element 100'(see FIGS. 8 and 9).
  • the inventor of the present application has newly found that the conventional solid-state battery 500'may have the following technical problems.
  • the interface region 300'between the battery element 100'and the external electrode 200' has a substantially planar shape in a cross-sectional view of the battery. That is, the substantially planar end faces of the battery element 100'and the substantially planar end faces of the external electrode 200' are merely in opposite contact with each other.
  • the electrode layer 10'of the positive electrode layer 10A'and the negative electrode layer 10B' has at least an electrode material layer of a non-metal material such as an oxide material as a main constituent member.
  • the external electrode 200'provided on the surface of the battery element 100' is made of a metal material.
  • the constituent material of the electrode material layer as the main constituent member of the electrode layer 10'and the constituent material of the external electrode 200' can be different from each other. Due to the difference in the materials, the degree of integral sintering of the electrode layer 10'and the external electrode 200' is not sufficient.
  • the substantially planar end faces of the battery element 100'and the substantially planar end faces of the external electrode 200' are in facing contact with each other, and (ii) the degree of integral sintering of the electrode layer 10'and the external electrode 200'.
  • the degree of interconnection between the electrode layer 10'and the external electrode 200' is not strong, and it may be difficult to maintain the interconnection.
  • stress is applied to the interconnected portion due to the expansion and contraction of the electrode layer 10'during charging and discharging, so that the interconnection between the two may not be maintained. ..
  • a main object of the present invention is to provide a solid-state battery capable of suitably maintaining the interconnection between the electrode layer and the external electrode.
  • a battery element having a positive electrode layer, a negative electrode layer, and a solid electrolyte layer interposed between the positive electrode layer and the negative electrode layer, and a battery element. Equipped with an external electrode provided on the surface of the battery element, A solid-state battery is provided in which a fitting portion in which at least one of the positive electrode layer and the negative electrode layer and the external electrode are fitted to each other is formed in an interface region between the battery element and the external electrode.
  • the interconnection between the electrode layer and the external electrode can be suitably maintained.
  • FIG. 1 is a sectional view schematically showing a solid-state battery according to an embodiment of the present invention.
  • FIG. 2 is an enlarged cross-sectional view schematically showing a solid-state battery according to an embodiment of the present invention.
  • FIG. 3 is a sectional view schematically showing a solid-state battery according to another embodiment of the present invention.
  • FIG. 4 is an enlarged cross-sectional view schematically showing a solid-state battery according to another embodiment of the present invention.
  • FIG. 5 is a sectional view schematically showing a solid-state battery according to another embodiment of the present invention.
  • FIG. 6 is an enlarged cross-sectional view schematically showing a solid-state battery according to another embodiment of the present invention.
  • FIG. 1 is a sectional view schematically showing a solid-state battery according to an embodiment of the present invention.
  • FIG. 2 is an enlarged cross-sectional view schematically showing a solid-state battery according to an embodiment of the present invention.
  • FIG. 3 is a sectional view schematic
  • FIG. 7 is an enlarged cross-sectional view schematically showing a solid-state battery according to another embodiment of the present invention.
  • FIG. 8 is a cross-sectional view schematically showing a conventional solid-state battery.
  • FIG. 9 is an enlarged cross-sectional view schematically showing a conventional solid-state battery.
  • solid-state battery refers to a battery whose constituent elements are composed of solids in a broad sense, and in a narrow sense, all the constituent elements (particularly all constituent elements) are composed of solids.
  • the solid-state battery of 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” as used herein can include not only a secondary battery that can be repeatedly charged and discharged, but also a primary battery that can only be discharged.
  • the solid-state battery is a secondary battery.
  • the "secondary battery” is not overly bound by its name and may include, for example, a power storage device.
  • the "cross-sectional view” as used herein is a state when the solid-state battery is viewed from a direction substantially perpendicular to the thickness direction based on the stacking direction of the material layers constituting the solid-state battery.
  • 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 figure, respectively. Unless otherwise specified, the same sign or symbol shall indicate the same member / part or the same meaning. 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 has at least an electrode layer of a positive electrode / a negative electrode and a solid electrolyte.
  • the solid-state battery includes a battery element (corresponding to a solid-state battery laminate) including a battery constituent unit composed of a positive electrode layer, a negative electrode layer, and a solid electrolyte interposed therein at least.
  • each layer constituting the solid-state battery may be formed by firing, and the positive electrode layer, the negative electrode layer, the solid electrolyte, and the like may form the firing layer.
  • the positive electrode layer, the negative electrode layer and the solid electrolyte are integrally fired with each other, and therefore the battery elements (corresponding to the solid-state battery laminate) form an integrally fired body.
  • the positive electrode layer is an electrode layer containing at least a positive electrode active material.
  • the positive electrode layer may further contain a solid electrolyte.
  • the positive electrode layer is composed of a calcined body containing at least positive electrode active material particles and solid electrolyte particles.
  • the negative electrode layer is an electrode layer containing at least a negative electrode active material.
  • the negative electrode layer may further contain a solid electrolyte.
  • the negative electrode layer is composed of a sintered body containing at least negative electrode active material particles and solid electrolyte particles.
  • the positive electrode active material and the negative electrode active material are substances involved in the transfer of electrons in a solid-state battery. Ions move (conduct) between the positive electrode layer and the negative electrode layer via the solid electrolyte, and electrons are transferred to charge and discharge. It is particularly preferable that each of the electrode layers of the positive electrode layer and the negative electrode layer is a layer capable of occluding and releasing lithium ions or sodium ions. That is, the solid-state battery 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 the solid electrolyte to charge and discharge the battery.
  • Examples of the positive electrode active material contained in the positive electrode layer include a lithium-containing phosphoric acid compound having a pearcon-type structure, a lithium-containing phosphoric acid compound having an olivine-type structure, a lithium-containing layered oxide, and lithium having a spinel-type structure. At least one selected from the group consisting of oxides and the like can be mentioned.
  • Examples of lithium-containing phosphoric acid compounds having a pear-con type structure include Li 3 V 2 (PO 4 ) 3 .
  • Examples of lithium-containing phosphoric acid compounds having an olivine-type structure include Li 3 Fe 2 (PO 4 ) 3 , LiFePO 4 , and / or LiMnPO 4 .
  • lithium-containing layered oxides examples include LiCoO 2 and / or LiCo 1/3 Ni 1/3 Mn 1/3 O 2 and the like.
  • lithium-containing oxides having a spinel-type structure examples include LiMn 2 O 4 and / or LiNi 0.5 Mn 1.5 O 4 and the like.
  • the type of the lithium compound is not particularly limited, and may be, for example, a lithium transition metal composite oxide and a lithium transition metal phosphoric acid compound.
  • the lithium transition metal composite oxide is a general term for oxides containing lithium and one or more kinds of transition metal elements as constituent elements, and the lithium transition metal phosphoric acid compound is one or more kinds with lithium. It is a general term for phosphoric acid compounds containing the transition metal element of.
  • the type of the transition metal element is not particularly limited, and is, for example, cobalt (Co), nickel (Ni), manganese (Mn), iron (Fe), and the like.
  • a sodium-containing phosphoric acid compound having a nacicon-type structure a sodium-containing phosphoric acid compound having an olivine-type structure, a sodium-containing layered oxide, and sodium having a spinel-type structure are contained.
  • At least one selected from the group consisting of oxides and the like can be mentioned.
  • sodium-containing phosphoric acid compounds Na 3 V 2 (PO 4 ) 3 , NaCoFe 2 (PO 4 ) 3 , Na 2 Ni 2 Fe (PO 4 ) 3 , Na 3 Fe 2 (PO 4 ) 3 , Na. 2 FeP 2 O 7 , Na 4 Fe 3 (PO 4 ) 2 (P 2 O 7 ), and at least one selected from the group consisting of NaFeO 2 as a sodium-containing layered oxide.
  • the positive electrode active material may be, for example, an oxide, a disulfide, a chalcogenide, a conductive polymer, or the like.
  • the oxide may be, for example, titanium oxide, vanadium oxide, manganese dioxide, or the like.
  • the disulfide is, for example, titanium disulfide or molybdenum sulfide.
  • the chalcogenide may be, for example, niobium selenate or the like.
  • the conductive polymer may be, for example, disulfide, polypyrrole, polyaniline, polythiophene, polyparastyrene, polyacetylene, polyacene and the like.
  • Examples of the negative electrode active material contained in the negative electrode layer include oxides containing at least one element selected from the group consisting of Ti, Si, Sn, Cr, Fe, Nb and Mo, carbon materials such as graphite, and graphite-lithium. At least one selected from the group consisting of compounds, lithium alloys, lithium-containing phosphoric acid compounds having a pearcon-type structure, lithium-containing phosphoric acid compounds having an olivine-type structure, lithium-containing oxides having a spinel-type structure, and the like. Be done. Examples of lithium alloys include Li-Al and the like.
  • lithium-containing phosphoric acid compounds having a pear-con type structure examples include Li 3 V 2 (PO 4 ) 3 and / or LiTi 2 (PO 4 ) 3 .
  • lithium-containing phosphoric acid compounds having an olivine-type structure examples include Li 3 Fe 2 (PO 4 ) 3 and / or LiCuPO 4 .
  • lithium-containing oxides having a spinel-type structure include Li 4 Ti 5 O 12 .
  • the negative electrode active material capable of absorbing and releasing sodium ions includes a sodium-containing phosphoric acid compound having a nacicon-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. There is at least one selected from the group consisting of.
  • the positive electrode layer and the negative electrode layer may be made of the same material.
  • 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 metal material 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.
  • 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 thicknesses of the positive electrode layer and the negative electrode layer are not particularly limited, but may be, for example, 2 ⁇ m or more and 50 ⁇ m or less, particularly 5 ⁇ m or more and 30 ⁇ m or less, respectively.
  • the positive electrode layer and the negative electrode layer may include a positive electrode current collector layer and a negative electrode current collector layer, respectively.
  • 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 are in the form of a fired body, respectively. May have.
  • 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 having a high conductivity, for example, silver, palladium, gold, platinum, aluminum, copper. , And / or nickel and the like may be used.
  • Each of the positive electrode current collector and the negative electrode current collector may have an electrical connection portion for electrically connecting to the outside, and may be configured to be electrically connectable to the external electrode.
  • the positive electrode current collector layer and the negative electrode current collector layer have the form of a fired body, they may be composed of a fired body containing a conductive material and a sintering aid.
  • the conductive material contained in the positive electrode current collector layer and the negative electrode current collector layer may be selected from, for example, the same materials as the conductive material that can be contained in the positive electrode layer and the negative electrode layer.
  • the sintering aid contained in the positive electrode current collector layer and the negative 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 and the negative electrode layer.
  • the positive electrode collector layer and the negative electrode current collector layer are not essential in the solid-state battery, and a solid-state battery in which such a positive electrode current collector layer and the negative electrode current collector layer are not provided is also conceivable. That is, the solid-state battery included in the package of the present invention may be a solid-state battery without a current collector layer.
  • the solid electrolyte is a material capable of conducting lithium ions or sodium ions.
  • the solid electrolyte that forms a battery constituent unit in a solid-state battery may form a layer in which lithium ions can be conducted between the positive electrode layer and the negative electrode layer.
  • Specific examples of the solid electrolyte include a lithium-containing phosphoric acid compound having a pearcon structure, an oxide having a perovskite structure, an oxide having a garnet type or a garnet type similar structure, and an oxide glass ceramics-based lithium ion conductor. Can be mentioned.
  • Li x My (PO 4 ) 3 (1 ⁇ x ⁇ 2, 1 ⁇ y ⁇ 2, M is from the group consisting of Ti, Ge, Al, Ga and Zr. At least one selected).
  • Examples of the lithium-containing phosphoric acid compound having a pear-con structure include Li 1.2 Al 0.2 Ti 1.8 (PO 4 ) 3 .
  • Examples of oxides having a perovskite structure include La 0.55 Li 0.35 TiO 3 and the like.
  • Li 7 La 3 Zr 2 O 12 and the like can be mentioned.
  • oxide glass ceramics-based lithium ion conductor for example, a phosphoric acid compound (LATP) containing lithium, aluminum and titanium as a constituent element, and a phosphoric acid compound (LAGP) containing lithium, aluminum and germanium as constituent elements are used. Can be done.
  • LATP phosphoric acid compound
  • LAGP phosphoric acid compound
  • Examples of the solid electrolyte in which sodium ions can be conducted include sodium-containing phosphoric acid compounds having a nacicon structure, oxides having a perovskite structure, oxides having a garnet type or a garnet type similar structure, and the like.
  • sodium-containing phosphoric acid compound having a pearcon structure Na x My (PO 4 ) 3 (1 ⁇ x ⁇ 2, 1 ⁇ y ⁇ 2, M is from the group consisting of Ti, Ge, Al, Ga and Zr. At least one selected).
  • the solid electrolyte may contain a sintering aid.
  • the sintering aid contained in the solid electrolyte may be selected from, for example, the same materials as the sintering aid that can be contained in the positive electrode layer and the negative electrode layer.
  • the thickness of the solid electrolyte 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 is generally provided with an external electrode.
  • an external electrode is provided on the side of the solid-state battery.
  • an external electrode on the positive electrode side connected to the positive electrode layer and an external electrode on the negative electrode side connected to the negative electrode layer are provided on the side portion of the solid-state battery.
  • the external electrode on the positive electrode layer side is joined to an end portion of the positive electrode layer, specifically, a drawer portion formed at the end portion of the positive electrode layer.
  • the external electrode on the negative electrode layer side is joined to an end portion of the negative electrode layer, specifically, a drawer portion formed at the end portion of the negative electrode layer.
  • the external electrode preferably comprises glass or glass ceramics from the viewpoint of joining to the extraction portion of the electrode layer.
  • the external electrode preferably contains a material having a high conductivity.
  • the specific material of the external electrode is not particularly limited, but may include at least one selected from the group consisting of silver, gold, platinum, aluminum, copper, tin and nickel.
  • the exterior can generally be formed on the outermost side of the solid state battery and is intended for electrical, physical and / or chemical protection.
  • the material constituting the exterior is preferably excellent in insulation, durability and / or moisture resistance, and is environmentally safe.
  • the exterior is a layer that covers the surface of the battery element so that the drawer portion of each electrode layer and each external electrode can be joined. Specifically, the exterior covers the surface of the battery element so that the drawer portion of the positive electrode layer and the external electrode on the positive electrode side can be bonded, and the extraction portion of the negative electrode layer and the external electrode on the negative electrode side can be bonded to the battery element. Cover the surface of the. That is, the exterior does not cover the entire surface of the battery element without gaps, but the drawer portion of the electrode layer (the end portion of the electrode layer) is exposed in order to join the drawer portion of the electrode layer of the battery element and the external electrode. Cover the battery elements as such.
  • the inventor of the present application has diligently studied a solution for making it possible to suitably maintain the interconnection between the electrode layer and the external electrode.
  • the inventor of the present application has come up with the present invention based on the following technical idea.
  • the electrode layer and the external electrode are brought into contact with each other, instead of bringing the electrode layer, which is a component of the battery element, and the external electrode provided on the surface of the battery element into end face contact as in the conventional case. It is based on the technical idea of fitting.
  • the “interface region between the battery element and the external electrode” as used herein refers to a boundary region where the battery element and the external electrode are in contact with each other.
  • the “fitting portion” as used herein refers to a portion in which the electrode layer and the external electrode are fitted to each other in a broad sense, and in a narrow sense, an end portion of the electrode layer, that is, one side of a drawer portion and an external electrode. Refers to the part where the main surface of the is fitted to each other. It should be noted that the “fitting portion” is not limited to a mode in which one of the electrode layer and the external electrode have a convex shape and the other has a concave shape as long as the electrode layer and the external electrode fit each other. I will add it.
  • the term “electrode layer” as used herein is a general term for a positive electrode layer and a negative electrode layer, and is used when the positive electrode layer and the negative electrode layer are not particularly distinguished.
  • FIG. 1 is a sectional view schematically showing a solid-state battery according to an embodiment of the present invention.
  • FIG. 2 is an enlarged cross-sectional view schematically showing a solid-state battery according to an embodiment of the present invention.
  • the solid-state battery 500 includes a positive electrode layer 10A, a negative electrode layer 10B, and a battery element 20 having a solid electrolyte layer 20 interposed between the positive electrode layer 10A and the negative electrode layer 10B. Consists of having 100.
  • the battery element 100 includes at least one battery building unit including the positive electrode layer 10A, the negative electrode layer 10B, and the solid electrolyte layer 20 along the stacking direction.
  • the positive electrode layer 10A includes at least a positive electrode material layer (which may also be referred to as a positive electrode active material layer or a positive electrode mixture layer), and the negative electrode layer 10B includes at least a negative electrode material layer (which may also be referred to as a negative electrode active material layer or a negative electrode mixture layer).
  • the electrode layer 10 does not necessarily have to have a current collector layer.
  • the electrode layer 10 includes a body portion extending in a direction different from the stacking direction, for example, a substantially vertical direction, and an end portion extending in the stacking direction.
  • the end portion includes an end portion (corresponding to a drawer portion) 10a on the external electrode connection side and an end portion on the external electrode non-connection side.
  • the electrode material layer contained in the electrode layer 10 contains a non-metal material such as an oxide material.
  • the external electrode 200 is made of a metal material. That is, the constituent material of the electrode material layer included in the electrode layer 10 and the constituent material of the external electrode 200 may be different from each other.
  • one embodiment of the present invention is based on the technical idea of fitting the electrode layer 10 and the external electrode 200, which are the constituent elements of the battery element 100, to each other.
  • a fitting portion in which the electrode layer 10 and the external electrode 200 are fitted to each other is formed in the interface region 300 between the battery element 100 and the external electrode 200.
  • the fact that the fitting portion is formed means that one of the electrode layer 10 and the external electrode 200 is provided so as to be partially inserted into the other of the electrode layer 10 and the external electrode 200.
  • the fact that the fitting portion is formed means that one of the electrode layer 10 and the external electrode 200 is partially surrounded by the other of the electrode layer 10 and the external electrode 200 in the interface region 300. It means that it is.
  • the substantially planar end face of the battery element including the electrode layer and the substantially planar end face of the external electrode are in opposite contact with each other. Focusing on the electrode layer, the electrode layer also has a substantially planar end face. Therefore, between the electrode layer and the external electrode, the end faces having a substantially planar shape are merely in opposition contact with each other. Further, the difference between the constituent material of the electrode material layer contained in the electrode layer 10 and the constituent material of the external electrode 200 may lead to the difficulty of integral sintering of the electrode layer 10 and the external electrode 200.
  • the end faces having a substantially planar shape of both face each other as before.
  • the end faces of the electrode layer and the external electrode having a substantially planar shape are merely opposed to each other. Therefore, for example, the electrode layer (specifically, the drawer portion of the electrode layer) and the external electrode are fitted to each other.
  • the electrode layer specifically, the drawer portion of the electrode layer
  • the external electrode are fitted to each other.
  • a fitting portion in which the two are fitted together is formed in the “part where integral sintering is not easy between the electrode layer 10 and the external electrode 200”, such fitting results in the fitting.
  • the contact area between the end portion 10a (corresponding to the drawer portion) of the electrode layer 10 and the external electrode 200 can be relatively increased.
  • This provides a so-called “anchor effect”, which can improve the degree of interconnection between the electrode layer 10 and the external electrode 200. That is, this combined portion can function as an anchor effect providing portion.
  • a thermal shock is applied to the fitting portion or the solid-state battery 500 is repeatedly charged and discharged, it is possible to suitably maintain the interconnection between the two.
  • the contact resistance can be made smaller than that of the conventional solid-state battery, thereby increasing the internal resistance of the solid-state battery 500. Can be made smaller. From the above, it is possible to suitably charge and discharge the solid-state battery 500 as a whole. That is, improvement in the characteristics of the solid-state battery according to the embodiment of the present invention can be expected.
  • the electrode layer 10 can have a convex end (corresponding to a drawer), and the external electrode 200 can locally have a concave portion.
  • the electrode layer 10 can have a convex end (corresponding to a drawer), and the external electrode 200 can locally have a concave portion.
  • FIGS. 1 and 2 such a form will be described as an example (see FIGS. 1 and 2).
  • the end portion 10a (corresponding to the drawer portion) of the electrode layer 10 has a convex portion shape.
  • the end surface of the external electrode 200 locally has a concave shape into which the end portion 10a of the electrode layer 10 having the convex shape can be fitted.
  • the end portion 10a of the convex portion-shaped electrode layer 10 is configured to be inserted into the concave portion-shaped portion of the external electrode 200 at the fitting portion.
  • the concave portion of the external electrode 200 mateably receives the end portion 10a of the convex electrode layer 10.
  • the end portion 10a of the convex portion-shaped electrode layer 10 can be inserted into the concave portion-shaped portion of the external electrode 200.
  • the end portion 10a of the electrode layer 10 has an outer curved surface in a cross-sectional view of the battery.
  • the fitting surface itself between the end portion 10a of the electrode layer 10 and the recess of the external electrode 200 has a fine uneven shape (corresponding to a jagged shape).
  • the present invention is not limited to this, and from the viewpoint of realizing fitting, at least a part of the convex portion-shaped end portion of the electrode layer 10 may be positioned in the concave portion portion of the external electrode 200.
  • the degree of insertion of the convex end portion of the electrode layer 10 into the external electrode 200 is fitted from the viewpoint of both suitable fitting of the two and prevention of protrusion of the electrode layer 10 from the outer surface of the external electrode 200. It is preferably 5% or more and 70% or less, 10% or more and 60% or less, and 20% or more and 50% or less, for example, about 50% of the thickness of the external electrode 200 in the portion where the joint portion is not formed.
  • the cross-sectional shape of the interface region between the battery element and the external electrode is a substantially planar shape as a whole.
  • the interface region 300 is composed of a substantially planar main interface region 301 and a non-planar sub-interface region continuous with the main portion 301. It will be configured. That is, it can be said that the shape of the interface region 300 is a combination of a substantially planar shape and a non-planar shape as compared with the conventional solid-state battery.
  • the interface region 300 composed of a combination of a substantially planar shape and a non-planar shape
  • the following aspects can be adopted.
  • an embodiment in which the non-planar sub-interface region itself is composed of only the region 302 forming the fitting portion can be adopted.
  • the region 302 is positioned outside the main interface region 301 having a substantially planar shape.
  • FIG. 3 is a sectional view schematically showing a solid-state battery according to another embodiment of the present invention.
  • FIG. 4 is an enlarged cross-sectional view schematically showing a solid-state battery according to another embodiment of the present invention.
  • the non-planar sub-interface region is a region 302I having an outwardly curved shape forming a fitting portion, and a region 302I continuous with the region 302I and opposite to the region 302I. It is possible to take an embodiment composed of the region 303I having a shape curved in the direction. In this case, the outer curved region 302I is positioned inside the substantially planar main interface region 301I.
  • the region 303I having a shape curved in the opposite direction is not itself an interface region forming a fitting portion between the electrode layer 10I and the external electrode 200I.
  • the region 303I is an interface region forming a portion where the convex external electrode 200I locally and the concave portion of the corresponding solid electrolyte 20I are fitted.
  • FIG. 5 is a sectional view schematically showing a solid-state battery according to another embodiment of the present invention.
  • FIG. 6 is an enlarged cross-sectional view schematically showing a solid-state battery according to another embodiment of the present invention.
  • the interface region 300II between the battery element 100II and the external electrode 200II can have a slope morphology.
  • the interface region 300II is composed of a main interface region 301II having a slope and a substantially planar shape and a sub-interface region having a non-planar shape continuous with the main portion 301II.
  • the non-planar sub-interface region itself is composed of only the region 302II forming the fitting portion, and the region 302II is positioned outside the sloped and substantially planar main interface region 301.
  • the embodiments shown in FIGS. 5 and 6 are more preferable than the embodiments shown in FIG. 1 in the following points.
  • the main interface region 301 extends in the substantially vertical direction and has a substantially planar shape.
  • the main interface region 301II has a slope and a substantially planar shape.
  • an increase in the area size of the fitting portion means an increase in the contact area between the end portion 10aII of the electrode layer 10II and the external electrode 200II.
  • the contact resistance can be made smaller as compared with the embodiment shown in FIG. 1, and the internal resistance of the solid-state battery 500II can also be made smaller. From the above, it is possible to suitably charge and discharge the solid-state battery 500II as a whole.
  • the fitting portion where the end portion (corresponding to the drawer portion) of the electrode layer and the external electrode are fitted to each other is at a predetermined interval. It is preferable that two or more of them are formed (see FIGS. 1, 3 and 5). It was
  • the single fitting portion has been focused on according to the embodiments shown in FIGS. 1, 3 and 5.
  • the technical effect that can be achieved by the fitting portions is more preferable. Can be played.
  • the contact resistance can be made smaller by increasing the number of portions where the contact area between the end of the electrode layer and the external electrode increases, so that the internal resistance of the solid-state battery can also be made smaller. Therefore, it becomes possible to more preferably charge and discharge the solid-state battery as a whole.
  • FIG. 7 is an enlarged cross-sectional view schematically showing a solid-state battery according to another embodiment of the present invention.
  • the electrode layer and the external electrode are fitted to each other in the "fitting portion" formed by the end portion (corresponding to the drawer portion) of the electrode layer and the external electrode.
  • the relationship is not limited to a mode in which one of the two has a convex shape and the other has a concave shape.
  • the embodiment shown in FIGS. 1 to 6 is based on an embodiment in which the electrode layer has a convex shape and the external electrode has a concave shape.
  • the embodiment shown in FIGS. 1 to 6 is only an example for forming the fitting portion, and as shown in FIG. 7, the external electrode has a convex shape and the electrode layer has a concave shape. It can also be based on aspects.
  • the electrode layer 10III may have a concave end portion 10aIII (corresponding to a drawer portion), and the external electrode 200III may locally have a convex end surface.
  • the convex portion-shaped portion of the external electrode 200III is locally inserted into the end portion 10aIII of the concave-shaped electrode layer 10III.
  • the concave electrode layer 10III mateably accepts the convex portion of the external electrode 20033.
  • a fitting portion in which both are fitted is formed in the "part where integral sintering is not easy between the electrode layer 10III and the external electrode 200III". Therefore, such fitting can relatively increase the contact area between the end portion 10aIII (corresponding to the drawer portion) of the electrode layer 10III and the external electrode 200III as compared with the conventional solid-state battery. This provides a so-called “anchor effect” and can improve the degree of interconnection between the electrode layer 10III and the external electrode 200III.
  • the solid-state battery according to the embodiment 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 composite method thereof.
  • Step of forming unfired laminate First, on each base material (for example, PET film), a paste for a solid electrolyte layer, a paste for a positive electrode material layer, a paste for a positive electrode current collector layer, a paste for a negative electrode material layer, a paste for a negative electrode current collector layer, and a paste for an insulating portion. , And the protective layer paste is applied.
  • base material for example, PET film
  • Each paste uses a predetermined constituent material of each layer appropriately selected from the group consisting of a positive electrode active material, a negative electrode active material, a conductive material, a solid electrolyte material, an insulating material, and a sintering aid, and an organic material as a solvent. It can be produced by wet mixing with a dissolved organic vehicle.
  • the paste for the positive electrode material layer includes, for example, a positive electrode active material, a conductive material, a solid electrolyte material, an organic material and a solvent.
  • the paste for the negative electrode material layer includes, for example, a negative electrode active material, a conductive material, a solid electrolyte material, an organic material and a solvent.
  • the paste for the positive electrode current collector layer / the paste for the negative electrode current collector layer at least one may be selected from the group consisting of, for example, silver, palladium, gold, platinum, aluminum, copper, and nickel.
  • the paste for the solid electrolyte layer includes, for example, a solid electrolyte material, a sintering aid, an organic material and a solvent.
  • Protective layer pastes include, for example, insulating material materials, organic materials and solvents. Insulating pastes include, for example, insulating material materials, organic materials and solvents.
  • Media can be used in wet mixing, and specifically, a ball mill method, a viscomill method, or the like can be used. On the other hand, a wet mixing method that does not use a medium may be used, and a sand mill method, a high-pressure homogenizer method, a kneader dispersion method, or the like can be used.
  • a paste for a predetermined solid electrolyte layer can be prepared by wet-mixing a predetermined solid electrolyte material, a sintering aid, and an organic vehicle in which an organic material is dissolved in a solvent.
  • the solid electrolyte material include a lithium-containing phosphoric acid compound having a pearcon structure, an oxide having a perovskite structure, an oxide having a garnet type or a garnet type similar structure, and the like.
  • the lithium-containing phosphoric acid compound having a pear-con structure Li x My (PO 4 ) 3 (1 ⁇ x ⁇ 2, 1 ⁇ y ⁇ 2, M is from the group consisting of Ti, Ge, Al, Ga and Zr. At least one selected).
  • Examples of the lithium-containing phosphoric acid compound having a pear-con structure include Li 1.2 Al 0.2 Ti 1.8 (PO 4 ) 3 .
  • Examples of oxides having a perovskite structure include La 0.55 Li 0.35 TiO 3 and the like.
  • As an example of an oxide having a garnet type or a garnet type-like structure Li 7 La 3 Zr 2 O 12 and the like can be mentioned.
  • Examples of the positive electrode active material contained in the positive electrode material layer paste include a lithium-containing phosphoric acid compound having a pearcon-type structure, a lithium-containing phosphoric acid compound having an olivine-type structure, a lithium-containing layered oxide, and a spinel-type structure. At least one is selected from the group consisting of lithium-containing oxides and the like.
  • the insulating material contained in the paste for the insulating portion may be composed of, for example, a glass material, a ceramic material, or the like.
  • the insulating material material contained in the protective layer paste for example, it is preferable to use at least one selected from the group consisting of glass materials, ceramic materials, thermosetting resin materials, photocurable resin materials and the like.
  • 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 solvent is not particularly limited as long as it can dissolve the organic material, and for example, toluene and / or ethanol can be used.
  • Examples of the negative electrode active material contained in the paste for the negative electrode material layer include an oxide containing at least one element selected from the group consisting of Ti, Si, Sn, Cr, Fe, Nb, and Mo, and graphite-lithium. It is selected from at least one group consisting of a compound, a lithium alloy, a lithium-containing phosphoric acid compound having a pearcon-type structure, a lithium-containing phosphoric acid compound having an olivine-type structure, a lithium-containing oxide having a spinel-type structure, and the like.
  • the sintering aid may be at least one selected from the group consisting of lithium oxide, sodium oxide, potassium oxide, boron oxide, and silicon oxide.
  • the coated paste is dried on a hot plate heated to 30 to 50 ° C. to form a solid electrolyte layer sheet, a positive electrode layer sheet, and a negative electrode layer sheet having a predetermined thickness on a substrate (for example, PET film), respectively.
  • a substrate for example, PET film
  • a solid electrolyte sheet or an insulating sheet is provided in the side region of the electrode sheet by screen printing.
  • a solid electrolyte portion sheet or an insulating portion sheet is provided so as to surround the external electrode non-connecting portion excluding the portion of the side portion of the electrode sheet to which the external electrode is connected later.
  • thermocompression bonding at a predetermined pressure (for example, about 50 to about 100 MPa) and subsequent isotropic pressure pressing at a predetermined pressure (for example, about 150 to about 300 MPa). From the above, a predetermined laminated body can be formed.
  • the end face of the laminated body is pressed against a predetermined mold.
  • the end portion (specifically, the end portion on the external electrode connection side) of the portion to be the electrode layer can be exposed from the end surface (corresponding to the side surface) of the laminated body.
  • a predetermined laminate in which the end of the portion to be the electrode layer is exposed is subjected to firing.
  • the firing is carried out by heating at, for example, 600 ° C. to 1000 ° C. in a nitrogen gas atmosphere.
  • the laminated body may be further subjected to an individualization step if necessary.
  • the exposure of the end of the electrode layer is not limited to the method of pressing the end face of the laminated body against a predetermined mold.
  • an external electrode is attached to the side surface of the laminate having the electrode layer with the exposed end.
  • an external electrode is attached to the side surface of the laminate (corresponding to a battery element) so as to cover the end of the exposed electrode layer.
  • External electrodes are provided so as to be electrically connectable to the positive electrode layer and the negative electrode layer, respectively.
  • the external electrode is preferably composed of at least one selected from silver, gold, platinum, aluminum, copper, tin, and nickel. Further, it is preferable to provide a protective layer to the extent that the external electrode is not covered by sputtering, spray coating or the like.
  • the solid-state battery 500 according to the embodiment of the present invention can be suitably manufactured (see FIG. 1).
  • a fitting portion in which both are fitted is formed at "a portion where integral sintering is not easy between the electrode layer 10 and the external electrode 200".
  • the contact area between the end portion 10a (corresponding to the drawer portion) of the electrode layer 10 and the external electrode 200 can be relatively increased as compared with the conventional solid-state battery.
  • This provides a so-called “anchor effect”, which can improve the degree of interconnection between the electrode layer 10 and the external electrode 200.
  • anchor effect which can improve the degree of interconnection between the electrode layer 10 and the external electrode 200.
  • the solid-state battery according to the embodiment of the present invention can be used in various fields where storage is expected. Although only an example, the solid-state battery according to the embodiment of the present invention is used in the fields of electricity, information, and communication (for example, mobile phones, smartphones, smart watches, laptop computers, digital cameras, activities, etc.) in which mobile devices and the like are used.
  • the solid-state battery according to the embodiment of the present invention is used in the fields of electricity, information, and communication (for example, mobile phones, smartphones, smart watches, laptop computers, digital cameras, activities, etc.) in which mobile devices and the like are used.
  • Mobile device fields such as scales, arm computers, and electronic paper), home / small industrial applications (eg, power tools, golf carts, home / nursing / industrial robot fields), large industrial applications (eg, forklifts, etc.) Elevators, Gulf Cranes), Transportation Systems (eg, Hybrid Vehicles, Electric Vehicles, Buses, Trains, Electric Assisted Bicycles, Electric motorcycles, etc.), Power Systems Applications (eg, Power Generation, Road Conditioners, Smart Grids) , General household installation type power storage system, etc.), medical use (medical equipment field such as earphone hearing aid), pharmaceutical use (dose management system, etc.), IoT field, space / deep sea use (for example, space exploration) It can be used in fields such as aircraft and submersible research vessels).
  • home / small industrial applications eg, power tools, golf carts, home / nursing / industrial robot fields
  • large industrial applications eg, forklifts, etc.
  • Elevators Gulf Cranes
  • Transportation Systems eg,

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Abstract

Dans un mode de réalisation de la présente invention, une batterie à semi-conducteur est fournie. La batterie à semi-conducteur est caractérisée en ce qu'elle comprend : un élément de batterie pourvu d'une couche d'électrode positive, d'une couche d'électrode négative et d'une couche d'électrolyte solide interposée entre la couche d'électrode positive et la couche d'électrode négative ; et une électrode externe située sur la surface de l'élément de batterie, une partie d'ajustement dans laquelle la couche d'électrode positive et/ou la couche d'électrode négative est ajustée à l'électrode externe étant formée dans la région d'interface entre l'élément de batterie et l'électrode externe.
PCT/JP2021/037860 2020-10-16 2021-10-13 Batterie à semi-conducteur WO2022080404A1 (fr)

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JP2020-174968 2020-10-16
JP2020174968 2020-10-16

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2020100682A1 (fr) * 2018-11-16 2020-05-22 株式会社村田製作所 Batterie à semi-conducteur
WO2020100683A1 (fr) * 2018-11-16 2020-05-22 株式会社村田製作所 Batterie solide

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2020100682A1 (fr) * 2018-11-16 2020-05-22 株式会社村田製作所 Batterie à semi-conducteur
WO2020100683A1 (fr) * 2018-11-16 2020-05-22 株式会社村田製作所 Batterie solide

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