WO2025022870A1 - 電池 - Google Patents

電池 Download PDF

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Publication number
WO2025022870A1
WO2025022870A1 PCT/JP2024/021943 JP2024021943W WO2025022870A1 WO 2025022870 A1 WO2025022870 A1 WO 2025022870A1 JP 2024021943 W JP2024021943 W JP 2024021943W WO 2025022870 A1 WO2025022870 A1 WO 2025022870A1
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Prior art keywords
solid electrolyte
battery
titanium
layer
containing material
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PCT/JP2024/021943
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English (en)
French (fr)
Japanese (ja)
Inventor
英一 古賀
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Panasonic Intellectual Property Management Co Ltd
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Panasonic Intellectual Property Management Co Ltd
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Priority to CN202480044383.4A priority Critical patent/CN121444232A/zh
Priority to JP2025535635A priority patent/JPWO2025022870A1/ja
Publication of WO2025022870A1 publication Critical patent/WO2025022870A1/ja
Anticipated expiration legal-status Critical
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • 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
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid 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
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • 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

  • This disclosure relates to batteries.
  • Patent Document 1 discloses a battery that uses a solid electrolyte that contains Li, Ti, M, and F and that coats the active material.
  • M is at least one selected from the group consisting of Ca, Mg, Al, Y, and Zr.
  • the solid electrolyte is contained in a coating layer that coats the active material.
  • this disclosure provides a battery with improved reliability by increasing mechanical strength.
  • the battery of the present disclosure comprises: A first electrode layer, a second electrode layer; and an electrolyte layer disposed between the first electrode layer and the second electrode layer.
  • a battery comprising: The battery satisfies at least one configuration selected from the group consisting of (I) and (II) below: (I) At least one selected from the group consisting of the first electrode layer, the second electrode layer, and the electrolyte layer contains at least one titanium-containing material selected from the group consisting of halogenated titanium oxides and titanium oxides.
  • the battery further comprises a side layer comprising at least one titanium-containing material selected from the group consisting of halogenated titanium oxides and titanium oxides, disposed on at least one side selected from the group consisting of the first electrode layer, the second electrode layer, and the electrolyte layer.
  • the halogenated titanium oxide is represented by the following composition formula (1): TiO ⁇ 1 X1 ⁇ 1 ...Formula (1)
  • the X1 is at least one selected from the group consisting of F, Cl, Br, and I, the ⁇ 1 satisfies 0.95 ⁇ 1.05, and the ⁇ 1 satisfies 1.95 ⁇ 2.05;
  • the titanium oxide is represented by the following composition formula (2): TiO ⁇ 2 ...Formula (2) In the composition formula (2), the ⁇ 2 satisfies 1.95 ⁇ 2.05.
  • This disclosure can provide a battery with improved reliability.
  • FIG. 1 is a cross-sectional view and a plan view showing a schematic configuration of a battery 1000 according to a first embodiment.
  • FIG. 2 is a cross-sectional view and a plan view showing a schematic configuration of a battery 1100 according to the second embodiment.
  • FIG. 3 is a cross-sectional view and a plan view showing a schematic configuration of a battery 1200 according to the third embodiment.
  • FIG. 4 is a cross-sectional view and a plan view showing a schematic configuration of a battery 1300 according to the fourth embodiment.
  • FIG. 5 is a cross-sectional view and a plan view showing a schematic configuration of a battery 1400 according to the fifth embodiment.
  • FIG. 6 is a cross-sectional view and a plan view showing a schematic configuration of a battery 1500 according to a sixth embodiment.
  • the x-axis, y-axis, and z-axis represent the three axes of a three-dimensional Cartesian coordinate system.
  • the z-axis direction is the thickness direction of the battery.
  • the "thickness direction” refers to the direction perpendicular to the plane on which each layer of the battery is stacked.
  • planar view refers to the battery viewed along the stacking direction of each layer in the battery.
  • Thiickness in this specification refers to the length of the battery and each layer in the stacking direction.
  • the “side surface” refers to the surface along the stacking direction of each layer in the battery, and the “main surface” refers to a surface other than the side surface.
  • the terms “inside” and “outside” refer to the center side of the battery, as seen in the stacking direction of the layers in the battery, and the peripheral side of the battery, as seen in the stacking direction of the layers in the battery.
  • the terms “above” and “below” in the battery configuration do not refer to the upward (vertically upward) and downward (vertically downward) directions in absolute spatial recognition, but are used as terms defined by the relative positional relationship based on the stacking order in the stacking configuration. Furthermore, the terms “above” and “below” are applied not only to cases where two components are arranged with a gap between them and another component exists between the two components, but also to cases where two components are arranged in close contact with each other and the two components are in contact.
  • the battery according to the first embodiment includes a first electrode layer, a second electrode layer, and an electrolyte layer.
  • the electrolyte layer is disposed between the first electrode layer and the second electrode layer.
  • the battery according to the first embodiment satisfies at least one configuration selected from the group consisting of the following (I) and (II): (I) At least one selected from the group consisting of the first electrode layer, the second electrode layer, and the electrolyte layer contains at least one titanium-containing material selected from the group consisting of titanium oxide halides and titanium oxide. (II) The battery according to the first embodiment further comprises a side layer comprising at least one titanium-containing material selected from the group consisting of halogenated titanium oxides and titanium oxides, disposed on at least one side selected from the group consisting of the first electrode layer, the second electrode layer, and the electrolyte layer.
  • the above-mentioned halogenated titanium oxide is represented by the following composition formula (1).
  • X1 is at least one selected from the group consisting of F, Cl, Br, and I, ⁇ 1 satisfies 0.95 ⁇ 1 ⁇ 1.05, and ⁇ 1 satisfies 1.95 ⁇ 1 ⁇ 2.05.
  • the titanium oxide is represented by the following composition formula (2). TiO ⁇ 2 ...Formula (2) In the above composition formula (2), ⁇ 2 satisfies 1.95 ⁇ 2 ⁇ 2.05.
  • ⁇ 1 may be 1. In the composition formula (1), ⁇ 1 may be 2.
  • the halogenated titanium oxide may be represented by TiOX1-2 .
  • ⁇ 2 may be 2. That is, the above titanium oxide may be represented by TiO2 .
  • the titanium-containing material is relatively hard, for example harder than the solid electrolyte contained in the battery. Therefore, the battery according to the first embodiment containing the titanium-containing material has increased mechanical strength, and improved flexural strength and impact resistance. Therefore, the battery according to the first embodiment can have increased mechanical strength and improved reliability.
  • the titanium-containing material may be adjusted in any content and at any location depending on the purpose. This allows the battery according to the first embodiment to obtain the desired reliability.
  • the above effects can be achieved when the battery according to the first embodiment satisfies either the configuration (I) or (II) above.
  • the configuration (I) above when the configuration (I) above is satisfied, the strength of the electrode layer and/or electrolyte layer, which are the power generating elements of the battery, can be improved, improving the reliability of the battery.
  • structural defects i.e., cracks or peeling from the side
  • structural defects i.e., cracks or peeling from the side
  • the side layer containing the titanium-containing material improving the reliability of the battery.
  • titanium-containing material refers to at least one selected from the group consisting of titanium oxide halide represented by the above composition formula (1) and titanium oxide represented by the above composition formula (2).
  • the configuration example described below is an example in which the battery according to the first embodiment satisfies the above configuration (I) and the electrolyte layer is a solid electrolyte layer.
  • the battery of the configuration example described below is, for example, an all-solid-state battery.
  • FIG. 1 is a cross-sectional view and a plan view showing the general configuration of a battery 1000 according to a first embodiment.
  • FIG. 1(a) shows a cross-sectional view of a battery 1000 according to the first embodiment.
  • FIG. 1(b) shows a plan view of the battery 1000 according to the first embodiment as viewed from below in the z-axis direction.
  • FIG. 1(a) shows a cross-section at the position indicated by line I-I in FIG. 1(b).
  • the battery 1000 includes a first electrode layer 100, a second electrode layer 200 arranged parallel to and facing the first electrode layer 100, and a solid electrolyte layer 300 located between the first electrode layer 100 and the second electrode layer 200.
  • the battery 1000 is a battery including the first electrode layer 100, the solid electrolyte layer 300, and the second electrode layer 200 in this order in the stacking direction.
  • the first electrode layer 100 and the solid electrolyte layer 300 include a titanium-containing material.
  • the included titanium-containing material may be particulate titanium-containing material (hereinafter referred to as "titanium-containing material particles" 400.
  • the battery 1000 is, for example, an all-solid-state battery.
  • the first electrode layer 100 includes a first current collector 110 and a first active material layer 120.
  • the first active material layer 120 includes titanium-containing material particles 400.
  • the second electrode layer 200 includes a second current collector 210 and a second active material layer 220.
  • the solid electrolyte layer 300 includes titanium-containing material particles 400, is located between the first active material layer 120 and the second active material layer 220, and is in contact with each of the first active material layer 120 and the second active material layer 220.
  • the first electrode layer 100 and the solid electrolyte layer 300 include titanium-containing material particles 400, but the second electrode layer 200 may also include titanium-containing material particles 400.
  • the first current collector 110, the first active material layer 120, the solid electrolyte layer 300, the second active material layer 220, and the second current collector 210 each have a schematic rectangular shape in a plan view.
  • the shapes of these components are not limited to a rectangular shape.
  • the current collector 110, the first active material layer 120, the solid electrolyte layer 300, the second active material layer 220, and the second current collector 210 are the same size and have the same outline in a plan view, but this is not limited to this.
  • the first active material layer 120 may be smaller than the second active material layer 220.
  • the first active material layer 120 and the second active material layer 220 may be smaller than the solid electrolyte layer 300.
  • a portion of the solid electrolyte layer 300 may be in contact with at least one of the first current collector 110 and the second current collector 210.
  • the first electrode layer 100 is a positive electrode layer
  • the second electrode layer 200 is a negative electrode layer.
  • the first current collector 110 is a positive electrode current collector
  • the first active material layer 120 is a positive electrode active material layer
  • the second current collector 210 is a negative electrode current collector
  • the second active material layer 220 is a negative electrode active material layer.
  • the first electrode layer 100 may be a negative electrode, and the second electrode layer 200 may be a positive electrode.
  • the first current collector 110 may be a negative electrode current collector
  • the first active material layer 120 may be a negative electrode active material layer.
  • the second current collector 210 may be a positive electrode current collector
  • the second active material layer 220 may be a positive electrode active material layer.
  • the positive electrode active material layer and the negative electrode active material layer may be collectively referred to simply as “active material layer.”
  • the positive electrode current collector and the negative electrode current collector may be collectively referred to simply as “current collector.”
  • the current collector is formed of a material having electrical conductivity.
  • Examples of the material of the current collector include stainless steel, nickel (Ni), aluminum (Al), iron (Fe), titanium (Ti), copper (Cu), palladium (Pd), gold (Au), platinum (Pt), or an alloy of two or more of these.
  • a foil, plate, or mesh made of these materials can be used as the current collector.
  • the material of the current collector may be selected taking into consideration the manufacturing process, the temperature of use, the pressure of use, the operating potential of the battery applied to the current collector, or electrical conductivity.
  • the material of the current collector may also be selected according to the tensile strength or heat resistance required for the battery.
  • the current collector may be a high-strength electrolytic copper foil or a clad material made by laminating foils of different metals.
  • the thickness of the current collector is, for example, 10 ⁇ m or more and 100 ⁇ m or less.
  • the surface of the current collector may be roughened to improve adhesion to the active material layer.
  • the surface of the current collector may be coated with an adhesive component such as an organic binder.
  • an adhesive component such as an organic binder.
  • insulating particles, conductive particles, or semiconducting particles may be attached to the surface of the current collector. This strengthens the bonding at the interface between the current collector and other layers (e.g., active material layers), and can improve the mechanical and thermal reliability, as well as the cycle characteristics, of the battery 1000.
  • the first active material layer 120 is, for example, a positive electrode active material layer.
  • the first active material layer 120 is sandwiched between the first current collector 110 and the solid electrolyte layer 300.
  • the first active material layer 120 may be in contact with a main surface of the first current collector 110.
  • the first active material layer 120 may be in contact with a main surface of the solid electrolyte layer 300.
  • the second active material layer 220 is, for example, a negative electrode active material layer.
  • the second active material layer 220 is sandwiched between the second current collector 210 and the solid electrolyte layer 300.
  • the second active material layer 220 may be in contact with the main surface of the second current collector 210.
  • the second active material layer 220 may be in contact with the main surface of the solid electrolyte layer 300.
  • the positive electrode active material layer contains a positive electrode active material.
  • the positive electrode active material is a material in which metal ions such as lithium (Li) ions or magnesium (Mg) ions are inserted or removed from the crystal structure at a higher potential than the negative electrode, resulting in oxidation or reduction.
  • the type of positive electrode active material can be appropriately selected depending on the type of battery, and known positive electrode active materials can be used.
  • the positive electrode active material is, for example, a compound containing lithium and a transition metal element.
  • the compound is, for example, an oxide containing lithium and a transition metal element, or a phosphate compound containing lithium and a transition metal element.
  • oxides containing lithium and a transition metal element include lithium nickel composite oxides such as LiNi x M 1-x O 2 (wherein M is at least one selected from the group consisting of Co, Al, Mn, V, Cr, Mg, Ca, Ti, Zr, Nb, Mo, and W, and 0 ⁇ x ⁇ 1 is satisfied), layered oxides such as lithium cobalt oxide (LiCoO 2 ) and lithium nickel oxide (LiNiO 2 ), or lithium manganate having a spinel structure (e.g., LiMn 2 O 4 , Li 2 MnO 3 , or LiMnO 2 ).
  • lithium nickel composite oxides such as LiNi x M 1-x O 2 (wherein M is at least one selected from the group consisting of Co, Al, Mn, V, Cr, Mg, Ca, Ti, Zr, Nb, Mo, and W, and 0 ⁇ x ⁇ 1 is satisfied
  • layered oxides such as lithium cobalt oxide (LiCoO 2 ) and lithium nickel oxide (
  • a phosphate compound containing lithium and a transition metal element is lithium iron phosphate (LiFePO 4 ) having an olivine structure.
  • the positive electrode active material sulfur (S) and sulfides such as lithium sulfide (Li 2 S) may be used.
  • the positive electrode active material particles may be coated with or may have lithium niobate (LiNbO 3 ) or the like added thereto.
  • the positive electrode active material may be made of only one of these materials, or may be made of a combination of two or more of these materials.
  • the positive electrode active material layer may contain a titanium-containing material. This allows the titanium-containing material to absorb external stress and stress caused by expansion and contraction of the positive electrode active material due to charging and discharging, and stress caused by expansion and contraction of the positive electrode active material due to thermal cycles, thereby improving the mechanical strength of the positive electrode active material layer and suppressing the occurrence of defects.
  • the compatibility of the positive electrode active material layer with the solid electrolyte layer 300 e.g., expansion and contraction due to charging and discharging, or expansion and contraction due to thermal cycles
  • the titanium-containing material may be titanium-containing material particles 400.
  • the positive electrode active material layer may contain, in addition to the positive electrode active material, a material other than the positive electrode active material and the titanium-containing material. That is, the positive electrode active material layer may be a mixture layer. Examples of such materials are solid electrolytes such as inorganic solid electrolytes and sulfide solid electrolytes, conductive assistants such as acetylene black, or binding binders such as polyethylene oxide and polyvinylidene fluoride.
  • the solid electrolyte may be, for example, a halide solid electrolyte. Examples of the halide solid electrolyte contained in the positive electrode active material layer are the same as the examples of the halide solid electrolyte contained in the solid electrolyte layer 300 described below.
  • the positive electrode active material layer can improve the ionic conductivity within the positive electrode active material layer and can also improve the electronic conductivity.
  • the positive electrode active material layer may have a thickness of, for example, 5 ⁇ m or more and 300 ⁇ m or less.
  • the negative electrode active material layer contains a negative electrode active material.
  • the negative electrode active material layer is a layer that is mainly composed of negative electrode materials such as negative electrode active materials.
  • a negative electrode active material is a material in which metal ions such as lithium (Li) ions or magnesium (Mg) ions are inserted or removed from the crystal structure at a lower potential than the positive electrode, and oxidation or reduction occurs accordingly.
  • the type of negative electrode active material can be appropriately selected depending on the type of battery, and known negative electrode active materials can be used.
  • Examples of the negative electrode active material are carbon materials such as natural graphite, artificial graphite, graphite carbon fiber, and resin-sintered carbon, or alloy-based materials mixed with a solid electrolyte.
  • Examples of the alloy-based materials are lithium alloys such as LiAl, LiZn, Li 3 Bi, Li 3 Cd, Li 3 Sb, Li 4 Si, Li 4.4 Pb, Li 4.4 Sn, Li 0.17 C, and LiC 6, oxides of lithium and transition metal elements such as lithium titanate (Li 4 Ti 5 O 12 ), zinc oxide (ZnO), or metal oxides such as silicon oxide (SiO x ).
  • negative electrode active material only one of these materials may be used, or two or more of these materials may be used in combination.
  • the negative electrode active material layer may contain, in addition to the negative electrode active material, a material other than the negative electrode active material.
  • a material other than the negative electrode active material examples include solid electrolytes such as inorganic solid electrolytes and sulfide solid electrolytes, conductive assistants such as acetylene black, or binding binders such as polyethylene oxide and polyvinylidene fluoride.
  • the solid electrolyte may be, for example, a halide solid electrolyte. Examples of halide solid electrolytes contained in the negative electrode active material layer are the same as the examples of halide solid electrolytes contained in the solid electrolyte layer 300 described below.
  • the negative electrode active material layer may have a thickness of, for example, 5 ⁇ m or more and 300 ⁇ m or less.
  • the negative electrode active material layer may contain a titanium-containing material, similar to the positive electrode active material layer described above.
  • the solid electrolyte layer 300 includes a solid electrolyte.
  • the solid electrolyte layer 300 contains, for example, a solid electrolyte as a main component.
  • the main component refers to the component that is contained most abundantly in the solid electrolyte layer 300 in terms of mass percentage.
  • the solid electrolyte layer 300 contains, for example, a titanium-containing material.
  • the titanium-containing material is, for example, titanium-containing material particles 400.
  • the solid electrolyte may be any known solid electrolyte for batteries that has ionic conductivity.
  • the solid electrolyte contained in the solid electrolyte layer 300 may be, for example, a solid electrolyte that conducts metal ions such as lithium ions or magnesium ions.
  • solid electrolyte a sulfide solid electrolyte, an oxide solid electrolyte, or a halide solid electrolyte can be used.
  • Examples of sulfide-based solid electrolytes include Li2S - P2S5 - based, Li2S - SiS2- based, Li2S - B2S3 - based, Li2S - GeS2- based, Li2S -SiS2 - LiI-based, Li2S - SiS2 - Li3PO4 - based, Li2S - Ge2S2 -based, Li2S - GeS2 - P2S5 - based, and Li2S -GeS2 - ZnS -based.
  • the oxide-based solid electrolyte is, for example, a lithium-containing metal oxide, a lithium-containing metal nitride, lithium phosphate (Li 3 PO 4 ), or a lithium-containing transition metal oxide.
  • a lithium-containing metal oxide is Li 2 O—SiO 2 or Li 2 O—SiO 2 —P 2 O 5.
  • An example of a lithium-containing metal nitride is Li x P y O 1-z N z (0 ⁇ z ⁇ 1).
  • An example of a lithium-containing transition metal oxide is lithium titanium oxide.
  • the halogenated solid electrolyte is, for example, a solid electrolyte that contains Li, at least one element selected from the group consisting of metal elements and metalloid elements other than Li, and a halogen element.
  • Metalloid elements are B, Si, Ge, As, Sb, and Te.
  • Metal elements are all elements in groups 1 to 12 of the periodic table (except hydrogen) and all elements in groups 13 to 16 of the periodic table (except B, Si, Ge, As, Sb, Te, C, N, P, O, S, and Se).
  • the halide solid electrolyte is substantially free of sulfur.
  • a halide solid electrolyte is substantially free of sulfur means that the halide solid electrolyte does not contain sulfur as a constituent element, except for sulfur that is inevitably mixed in as an impurity. In this case, the amount of sulfur mixed in as an impurity in the halide solid electrolyte is, for example, 1 mol % or less. It is more desirable that the halide solid electrolyte is free of sulfur.
  • a solid electrolyte that does not contain sulfur is safe because it does not generate hydrogen sulfide even when exposed to the atmosphere.
  • the solid electrolyte layer 300 includes, for example, a halide solid electrolyte.
  • a halide solid electrolyte when the titanium-containing material particles 400 include a halide titanium oxide, the thermal expansion characteristics of the halide solid electrolyte included in the solid electrolyte layer 300 and the titanium-containing material particles 400 are easily matched because they are both halides. Therefore, the bonding interface between the titanium-containing material particles 400 and the halide solid electrolyte is strengthened. This suppresses the occurrence of structural defects caused by peeling at the bonding interface between the titanium-containing material particles 400 and the halide solid electrolyte due to thermal shock or thermal cycles. In other words, according to this configuration, the action and effect of the titanium-containing material against thermal shock and thermal cycles is further improved. As a result, the reliability of the battery 1000 according to the first embodiment is further improved.
  • the halide solid electrolyte may contain Ti. According to this configuration, a solid electrolyte layer 300 containing a solid electrolyte having high ionic conductivity of, for example, 1 ⁇ S/cm or more can be obtained. In addition, due to the presence of Ti commonly contained in the titanium-containing material and the halide solid electrolyte, the titanium-containing material and the solid electrolyte are firmly bonded to each other, and it becomes easier to form an integrated bonded interface. As a result, when the titanium-containing material is contained in the solid electrolyte layer, the titanium-containing material can coexist stably with the solid electrolyte in the solid electrolyte layer (for example, without forming fine defects around it).
  • the halide solid electrolyte containing Ti has excellent atmospheric stability and excellent heat resistance from about 650 ° C to 700 ° C, even if TiFO 2 with a high melting point is contained as the titanium-containing material, the effect of containing TiFO 2 can be obtained up to high temperatures.
  • the halide solid electrolyte may include a first halide solid electrolyte including a crystal phase represented by the following composition formula (3).
  • X2 is at least one selected from the group consisting of F, Cl, Br, and I.
  • the first halide solid electrolyte has high ionic conductivity, for example, 1 ⁇ S/cm or more, and atmospheric stability. Therefore, the inclusion of the first halide solid electrolyte improves the ionic conductivity of the solid electrolyte layer 300.
  • the crystalline phase represented by Li 2 TiX2 6 can be confirmed by the diffraction pattern of the micro-area X-ray diffraction (XRD) described above, or by powder XRD using a powder sample obtained by cutting out the solid electrolyte.
  • the composition of the solid electrolyte can also be evaluated by elemental analysis using, for example, an electron probe microanalyzer (EPMA) or energy dispersive X-ray spectroscopy (EDS).
  • EPMA electron probe microanalyzer
  • EDS energy dispersive X-ray spectroscopy
  • the first halide solid electrolyte may include a crystal phase represented by the following composition formula (4). Li 2 TiF 6 ...Formula (4)
  • the first halide solid electrolyte has improved atmospheric stability. This makes it possible to suppress fluctuations in the properties of the solid electrolyte caused by changes in the environment during the manufacturing process, and therefore makes it possible to reproducibly obtain a solid electrolyte layer 300 having the desired properties.
  • strict dew point environment control, temperature control, and humidity control are no longer necessary, there are also manufacturing benefits, such as reduced manufacturing costs.
  • the halide solid electrolyte may further include a second halide solid electrolyte having a different composition from the first halide solid electrolyte. This configuration further improves the adhesion of the solid electrolyte in the solid electrolyte layer 300, making the solid electrolyte layer 300 denser, increasing its strength, and improving its ionic conductivity.
  • the second halide solid electrolyte may have a higher melting point than the first halide solid electrolyte. Since the second halide solid electrolyte has a higher melting point than the first halide solid electrolyte, it can maintain a harder state than the first halide solid electrolyte at high temperatures. As a result, when the solid electrolyte layer 300 containing the first halide solid electrolyte further contains the second halide solid electrolyte, the hardness of the solid electrolyte layer 300 increases. Therefore, the solid electrolyte layer 300 becomes stronger, and the flexural strength and impact resistance are improved, and the reliability of the solid electrolyte layer 300 is improved. Therefore, a battery 1000 with improved reliability can be realized.
  • the second halide solid electrolyte may be harder than the first halide solid electrolyte.
  • the hardness of the solid electrolyte layer 300 increases.
  • the solid electrolyte layer 300 becomes stronger, and the flexural strength and impact resistance are improved, and the reliability of the solid electrolyte layer 300 is improved.
  • the softness of the second halide solid electrolyte and the first halide solid electrolyte can be compared by evaluation using a method such as micro-Vickers.
  • the second halide solid electrolyte may include a crystal phase represented by the following composition formula (5).
  • M is at least one element selected from the group consisting of metal elements and semi-metal elements having a valence of three.
  • the second halide solid electrolyte containing the crystalline phase represented by composition formula (5) is harder than the first halide solid electrolyte. Therefore, when the second halide solid electrolyte is further contained in the solid electrolyte layer containing the first halide solid electrolyte, the hardness of the solid electrolyte layer 300 increases. As a result, the solid electrolyte layer 300 becomes stronger, and the flexural strength and impact resistance are improved, and the reliability of the solid electrolyte layer 300 is improved. Therefore, a battery 1000 with improved reliability can be realized.
  • M may contain Al, or M may be Al. This increases the ionic conductivity of the second halide solid electrolyte to the same level as that of the first halide solid electrolyte (for example, 1 ⁇ S/cm or more). Thus, a solid electrolyte layer 300 having high ionic conductivity and high reliability can be obtained. Thus, a battery 1000 having excellent performance and reliability can be obtained. Furthermore, when M is Al, that is, when the second halide solid electrolyte has a composition of Li 3 AlF 6 , it can have stable and soft properties up to a relatively high temperature.
  • the solid electrolyte layer 300 can be densified and the ionic conductivity of the solid electrolyte layer 300 can be further improved. Furthermore, since Li 3 AlF 6 has excellent heat resistance up to about 700° C. to 800° C., even if TiFO 2 , which has a high melting point, is included as the titanium-containing material, the effect of including TiFO 2 can be obtained up to high temperatures.
  • the solid electrolyte layer 300 may contain, in addition to the solid electrolyte, a bonding binder such as polyethylene oxide or polyvinylidene fluoride.
  • the thickness of the solid electrolyte layer 300 may be 5 ⁇ m or more and 500 ⁇ m or less, 10 ⁇ m or more and 500 ⁇ m or less, or 5 ⁇ m or more and 150 ⁇ m or less.
  • the solid electrolyte material may be composed of an agglomerate of particles.
  • the solid electrolyte material may be composed of a sintered structure.
  • the titanium-containing material contained in the battery 1000 according to the first embodiment may be in the form of particles, such as the titanium-containing material particles 400.
  • the titanium-containing material can be contained in the coating layers of the solid electrolyte particles and the active material particles, or can be contained inside the solid electrolyte particles. That is, when the titanium-containing material is contained in the electrode layer and the solid electrolyte layer, the options for the form of the titanium-containing material are expanded.
  • finely pulverized particles of the titanium-containing material can make the solid electrolyte layer 300 thinner, or the coating layer of the active material particles, etc. thinner, thereby improving the capacity of the battery.
  • the titanium-containing material particles 400 are, for example, uniformly dispersed within the first electrode layer 100 and the solid electrolyte layer 300.
  • the titanium-containing material particles 400 may have an average particle size of, for example, 0.3 ⁇ m or more and 20 ⁇ m or less.
  • the titanium-containing material particles 400 are shown to have a spherical particle shape, but may have a particle shape other than spherical, such as a scale shape.
  • the particle diameter of the titanium-containing material particles 400 is preferably small. This allows the titanium-containing material particles 400 to be uniformly dispersed throughout the first electrode layer 100 and the solid electrolyte layer 300, thereby increasing the surface area of the titanium-containing material particles 400 and, as a result, increasing the bonding area between the titanium-containing material particles 400 and the active material or solid electrolyte present therearound. Therefore, the mechanical reliability (flexural strength) of the first electrode layer 100 and the solid electrolyte layer 300 is further improved by miniaturizing the titanium-containing material particles 400 (for example, miniaturizing the particle diameter to 1 ⁇ m or less).
  • the titanium-containing material includes, for example, TiOF 2.
  • the titanium-containing material may be TiOF 2.
  • the mechanical bonding between solid electrolyte particles and active material particles i.e., the anchor effect
  • the solid electrolyte particles can be made harder.
  • TiOF 2 when TiOF 2 is included in the coating layer of the solid electrolyte particles and/or the active material particles, TiOF 2 also serves as an anchor that strengthens the bonding between the particles. Therefore, a battery with excellent bending resistance and impact resistance is obtained.
  • TiOF 2 has excellent heat resistance (for example, about 1000 ° C.). Therefore, when TiOF 2 is included, the battery 1000 can have excellent reliability even at high temperatures.
  • TiOF2 may have a cubic crystal structure. Such a crystal structure can be obtained by heat treatment conditions.
  • TiOF 2 having a cubic crystal structure is stable at room temperature and has excellent heat resistance, for example, stable at high temperatures of about 400 ° C. Furthermore, since TiOF 2 having a cubic crystal structure is hard, it also contributes to improving the mechanical strength of the battery 1000. Therefore, by including TiOF 2 having a cubic crystal structure in the electrode layer and/or solid electrolyte layer 300, both the heat resistance and mechanical strength of the battery 1000 can be improved. TiOF 2 having a cubic crystal structure transitions to a hexagonal system at about 400 ° C. or higher, but since the melting point of TiOF 2 is 1000 ° C. or higher, the effect of improving the mechanical strength is maintained up to high temperatures.
  • the organic binder included in the all-solid-state battery rapidly softens at a glass transition point of, for example, 100 ° C. or higher and 250 ° C. or lower. Therefore, by including TiOF 2 having a cubic crystal structure in the electrode layer and/or the solid electrolyte layer 300, the decrease in mechanical strength of the battery 1000 at high temperatures, for example, exceeding 100° C., can be suppressed.
  • the crystal structure of TiO2 used as the titanium-containing material may be rutile or anatase.
  • Rutile has the highest high-temperature stability because the phase transition point from anatase to rutile is about 900°C. Therefore, the crystal structure of TiO2 is preferably rutile.
  • the titanium-containing material When the titanium-containing material is particulate, at least a portion of the surface of the titanium-containing material particles may be coated with a coating layer containing a solid electrolyte.
  • the solid electrolyte coating the titanium-containing material particles acts as a binder. This improves the bonding between the titanium-containing material particles, or between the titanium-containing material particles and other particles (e.g., solid electrolyte particles and active material particles), further improving the reliability of the battery.
  • the ionic conductivity of the solid electrolyte layer is also improved.
  • the titanium-containing material may contain both TiOF 2 and TiO 2 having a cubic crystal structure. This allows the titanium-containing material to have excellent bonding between TiOF 2 and TiO 2 due to the common element Ti, while also having improved hardness.
  • a titanium-containing material containing TiO 2 having high heat resistance stability together with TiOF 2 in a battery, the binding property of the solid electrolyte particles and the active material particles at high temperatures can be improved.
  • a battery with excellent mechanical strength and heat resistance can be obtained.
  • Such an improvement in strength can suppress deformation of the electrode layer and/or the solid electrolyte layer 300 due to external impact, thereby suppressing the occurrence of structural defects (peel-off and cracks between layers or within layers).
  • the crystal systems of TiO2 and TiOF2 can be identified, for example, by a diffraction pattern obtained by micro X-ray diffraction (micro XRD) of the side surface of the electrode layer and the solid electrolyte layer 300 exposed on the side surface of the battery 1000. Alternatively, they can be confirmed by a lattice image of a high-resolution transmission electron microscope (TEM).
  • micro XRD micro X-ray diffraction
  • the titanium-containing material may be particulate, and the surface region of the titanium-containing material particle may have a higher content of TiOF 2 than the content of TiO 2 , and the inner region of the titanium-containing material particle may have a higher content of TiO 2 than the content of TiOF 2.
  • the titanium-containing material particle contains a large amount of hard and heat-resistant TiO 2 inside the particle, and a large amount of heat-resistant TiOF 2 in the surface layer portion.
  • the titanium-containing material particle can have high bonding with the halide solid electrolyte particle because they both contain a halogen element. Therefore, according to this configuration, a power generating element having high mechanical strength and heat resistance can be obtained. Therefore, a highly reliable battery can be obtained.
  • the morphology of the composite particles described above can be evaluated, for example, by SEM observation of the cross section of an ion-polished battery.
  • the titanium-containing material is a composite particle as described above
  • at least a portion of the surface of the titanium-containing material particle may be coated with a coating layer containing a solid electrolyte. This improves the bonding between the titanium-containing material and the solid electrolyte contained in the electrolyte layer or electrode layer. This increases the reliability of the solid electrolyte layer or electrode layer against thermal shock and external stress.
  • the titanium-containing material may be particulate, and the particles of the titanium-containing material may include first particles composed of TiOF2 having a cubic crystal structure, and second particles containing TiOF2 and TiO2 having a cubic crystal structure. This allows the heat resistance and mechanical strength of the titanium-containing material to be adjusted according to the application by controlling the mixture ratio of the first particles and the second particles.
  • the average particle diameter of the second particles may be larger than the average particle diameter of the first particles. This allows the effect of improving hardness by the second particles to be obtained, while the first particles, which are softer and more deformable than the second particles, can reduce voids or unevenness that tend to form around the second particles. Therefore, by reducing voids and unevenness, the electrolyte layer and electrode layer have a homogenized structure, improving mechanical strength and impact resistance. This results in a highly reliable battery.
  • the content of the titanium-containing material in the solid electrolyte layer 300 may be, for example, 0.01 vol. % or more and 5 vol. % or less, and in the first electrode layer 100, may be, for example, 0.01 vol. % or more and 3 vol. % or less.
  • the content of such titanium-containing material can be confirmed by elemental analysis using a high-resolution composition map such as EPMA of a cross section processed by ion polishing or the like.
  • the titanium-containing material may be dispersed in the solid electrolyte layer 300 and/or the electrode layer, and may be present between the solid electrolyte particles and/or the active material particles or in the voids, or may be contained in the solid electrolyte layer 300 and/or the electrode layer in another form.
  • a titanium-containing material may be included in the coating layer that covers at least a portion of the surface of the solid electrolyte material particles and/or the active material particles. This enhances the mechanical bonding (i.e., anchor effect) between the solid electrolyte particles and/or between the active material particles, improving the reliability of the battery 1000 against external stresses and thermal cycles of the solid electrolyte layer 300 and/or the electrode layer.
  • the coating layer may include a titanium-containing material.
  • This configuration can enhance the adhesion and mechanical bonding between the active material particles (i.e., the anchor effect). This improves the strength of the electrode layer against external stress and thermal cycles, and can suppress the occurrence of structural defects such as cracks in the electrode layer. This can further improve the reliability of the battery 1000.
  • the coating layer may include a titanium-containing material.
  • This configuration can enhance the adhesion and mechanical bonding (i.e., anchor effect) between the solid electrolyte particles included in the electrode layer and/or solid electrolyte layer 300, which are the power generating elements of the battery 1000. This improves the strength of the power generating elements against external stress and thermal cycles, and can further improve the reliability of the battery 1000.
  • At least one selected from the group consisting of the first electrode layer 100, the second electrode layer 200, and the solid electrolyte layer 300 may contain solid electrolyte particles, and the inside of this solid electrolyte particle may contain a titanium-containing material.
  • the titanium-containing material may be contained inside the solid electrolyte particle.
  • at least a part of the surface of the particle of the titanium-containing material may be covered with a coating layer containing a solid electrolyte.
  • the surface layer part of the solid electrolyte particle can be made softer than the inside of the particle, the surface layer part of the particle can have bondability and deformability. Therefore, the bondability between the particles can be improved.
  • the hardness of the solid electrolyte particles can be adjusted, for example, by selecting a halogen element in the halogenated titanium oxide contained as the titanium-containing material, or by including a combination of multiple halogen elements.
  • the titanium-containing material is contained inside the solid electrolyte particles, the decrease in ionic conductivity between the solid electrolyte particles caused by the titanium-containing material is reduced.
  • the solid electrolyte particles containing the titanium-containing material can be produced, for example, by using a raw material containing a titanium-containing material or a substance that produces a titanium-containing material as an intermediate product as a starting raw material for synthesizing the solid electrolyte particles, and controlling the synthesis conditions of the solid electrolyte (for example, heat treatment conditions or conditions of mechanical energy applied during mechanochemical treatment, etc.).
  • solid electrolyte particles containing the titanium-containing material can be produced by using synthesis conditions under which the titanium-containing material exists inside the particles and the synthesized solid electrolyte exists on the particle surface.
  • the heat treatment temperature is set lower than usual and/or the heat treatment time is set shorter than usual, which makes it easier to produce the solid electrolyte particles containing the titanium-containing material.
  • the mixing time is set shorter than usual and/or the dispersion time is set shorter than usual, which also makes it easier to produce the solid electrolyte particles containing the titanium-containing material.
  • a titanium-containing material may be included at the bonding interface between the solid electrolyte layer 300 and the electrode layer. This configuration improves the bonding between the solid electrolyte layer 300 and the electrode layer, suppressing delamination that is likely to occur due to external impacts and thermal cycles.
  • the presence of titanium-containing materials in the battery 1000 can be determined by EPMA, EDS, and X-ray fluorescence spectrometry (XRF).
  • the form and composition can be analyzed by composition analysis (point analysis or area analysis) using EPMA and EDS, etc., of a polished cross section processed with an ion polisher, etc.
  • a titanium-containing material into the solid electrolyte layer 300 and/or the electrode layer, which are susceptible to structural defects caused by external impacts, charge/discharge cycles, and thermal cycles, it is possible to suppress structural defects and deterioration of material properties. Therefore, it is possible to reduce deterioration of the properties of the solid electrolyte layer 300 and/or the electrode layer, and a highly reliable battery 1000 can be realized.
  • the softness of the titanium-containing material may be adjusted depending on the purpose. For example, multiple types of titanium-containing materials may be used in combination. This improves the mechanical strength of the battery 1000 and suppresses the occurrence of structural defects associated with external impacts, charge/discharge cycles, and thermal cycles.
  • Patent Document 1 describes that the bonding state with respect to Ti in a solid electrolyte containing Li, Ti, M, and F includes TiO bonds and TiOF bonds.
  • Patent Document 1 does not describe that a titanium-containing material is included as a component in the solid electrolyte layer or electrode layer.
  • the technology described in Patent Document 1 is different from the technology of the battery according to the first embodiment of the present disclosure that improves the reliability (e.g., mechanical strength and thermal shock resistance) of the solid electrolyte layer and/or electrode layer.
  • Patent Document 1 does not disclose or suggest that the mechanical strength can be improved and the reliability of the battery can be improved by including a titanium-containing material in the electrode layer and solid electrolyte layer.
  • the battery 1000 according to the first embodiment includes a titanium-containing material, thereby improving the mechanical strength and the reliability of the battery.
  • FIG. 2 is a cross-sectional view and a plan view showing the general configuration of the battery 1100 of the second embodiment.
  • FIG. 2(a) is a cross-sectional view of the battery 1100 of the second embodiment.
  • FIG. 2(b) is a plan view of the battery 1100 of the second embodiment as viewed from below in the z-axis direction.
  • FIG. 2(a) shows a cross-sectional view taken along dotted line II-II in FIG. 2(b).
  • the battery 1100 according to the second embodiment has a different solid electrolyte layer configuration from the battery 1000 according to the first embodiment.
  • the solid electrolyte layer 301 in the battery 1100 according to the second embodiment differs in that the titanium-containing material particles 400 contained as the titanium-containing material are unevenly distributed in the region of the solid electrolyte layer 301 that contacts the first active material layer 120, and are not contained in the region that contacts the second active material layer 220.
  • This configuration makes it possible to selectively include the titanium-containing material in the electrode layer where structural defects are likely to occur, for example, in the region on the electrode layer side that contains an active material that expands and contracts greatly during charging and discharging, or has a large thermal expansion coefficient. This makes it possible to efficiently improve the reliability of the battery 1100.
  • the concentration of the titanium-containing material particles 400 in the region of the solid electrolyte layer 301 that contacts the first active material layer 120 is higher than the concentration of the titanium-containing material particles 400 in the region of the solid electrolyte layer 301 that contacts the second active material layer 220.
  • This configuration can also efficiently improve the reliability of the battery 1100.
  • FIG. 3 is a cross-sectional view and a plan view showing the general configuration of a battery 1200 according to a third embodiment.
  • FIG. 3(a) is a cross-sectional view of the battery 1200 of the third embodiment.
  • FIG. 3(b) is a plan view of the battery 1200 of the third embodiment as viewed from below in the z-axis direction.
  • FIG. 3(a) shows a cross section taken along the line III-III in FIG. 3(b).
  • the battery 1200 according to the third embodiment has a different solid electrolyte layer configuration from the battery 1000 according to the first embodiment.
  • the solid electrolyte layer 302 in the battery 1100 according to the second embodiment includes a first layer 302a in contact with the first electrode layer 100 and a second layer 302b in contact with the second electrode layer 200.
  • the first layer 302a and the second layer 302b include solid electrolytes having different compositions.
  • the first layer 302a includes titanium-containing material particles 400 as a titanium-containing material.
  • the second layer 302b does not include a titanium-containing material.
  • the solid electrolyte material in contact with the first electrode layer 100 and the solid electrolyte material in contact with the second electrode layer 200 may be made of different materials.
  • a configuration may be used in which a halide solid electrolyte is used as the solid electrolyte material on the positive electrode layer side and a sulfide solid electrolyte is used as the solid electrolyte material on the negative electrode layer side.
  • the solid electrolyte layer is formed of two or more layers made of different materials, selectively including a titanium-containing material in the layer in which a material that is prone to structural defects is used can selectively suppress defects. Therefore, the reliability of the battery 1200 can be efficiently improved.
  • both the first layer 302a and the second layer 302b contain titanium-containing material particles 400, and the concentration of the titanium-containing material particles 400 in the first layer 302a is higher than the concentration of the titanium-containing material particles 400 in the second layer 302b.
  • This configuration can also efficiently improve the reliability of the battery 1200.
  • FIG. 4 is a cross-sectional view and a plan view showing the general configuration of a battery 1300 according to a fourth embodiment.
  • FIG. 4(a) is a cross-sectional view of the battery 1300 of the fourth embodiment.
  • FIG. 4(b) is a plan view of the battery 1300 of the fourth embodiment as viewed from below in the z-axis direction.
  • FIG. 4(a) shows a cross section taken along the line IV-IV in FIG. 4(b).
  • the battery 1300 according to the fourth embodiment differs from the battery 1000 according to the first embodiment in that it further includes a side layer 500 containing a titanium-containing material arranged on at least one side surface selected from the group consisting of the first electrode layer 100, the second electrode layer 200, and the electrolyte layer 300.
  • the battery 1300 according to the fourth embodiment satisfies the above configuration (II).
  • the battery 1300 according to the fourth embodiment can suppress external stress from the side and suppress the occurrence of structural defects in the side portion. As a result, the reliability of the battery 1200 is further improved.
  • the side layer 500 contains a titanium-containing material.
  • the description of the titanium-containing material contained in the side layer 500 is the same as that of the titanium-containing material described in the first embodiment, and therefore a detailed description is omitted here.
  • the side layer 500 may contain, for example, titanium-containing material particles and an organic binder for bonding.
  • the side layer 500 can be formed, for example, by applying a paste containing titanium-containing material particles and an organic binder onto at least one side surface selected from the group consisting of the first electrode layer 100, the second electrode layer 200, and the electrolyte layer 300, and drying the coating.
  • the thickness of the side layer 500 may be, for example, 1 ⁇ m or more and 30 ⁇ m or less.
  • the battery 1300 according to the fourth embodiment has a configuration in which the titanium-containing material is also contained in the power generating element, i.e., it also satisfies the above configuration (I), but it does not have to satisfy the above configuration (I). In other words, the titanium-containing material does not have to be contained in the power generating element.
  • FIG. 5 is a cross-sectional view and a plan view showing the general configuration of a battery 1400 according to a fifth embodiment.
  • FIG. 5(a) is a cross-sectional view of the battery 1400 of the fifth embodiment.
  • FIG. 5(b) is a plan view of the battery 1400 of the fifth embodiment as viewed from below in the z-axis direction.
  • FIG. 5(a) shows a cross section taken at the position indicated by the line V-V in FIG. 5(b).
  • the battery 1400 according to the fifth embodiment differs from the battery 1000 according to the first embodiment in that only the first electrode layer 100 contains titanium-containing material particles 400 as the titanium-containing material.
  • This configuration can suppress the problem of structural defects occurring easily in layers (e.g., electrode layers) that expand and contract significantly during charge/discharge cycles and thermal cycles. As a result, the reliability of the battery 1400 is improved.
  • FIG. 6 is a cross-sectional view and a plan view showing the general configuration of a battery 1500 according to a sixth embodiment.
  • FIG. 6(a) is a cross-sectional view of a battery 1500 according to a sixth embodiment.
  • FIG. 6(b) is a plan view of the battery 1500 according to the sixth embodiment as viewed from below in the z-axis direction.
  • FIG. 6(a) shows a cross section taken along the line VI-VI in FIG. 6(b).
  • the battery 1500 according to the sixth embodiment differs from the battery 1000 according to the first embodiment in that the concentrations of the titanium-containing material contained in the first electrode layer and the solid electrolyte layer are different in each layer.
  • the concentration of the titanium-containing material particles 400 is higher on the outer periphery (side surface).
  • the concentration of the titanium-containing material particles 400 changes gradually and continuously toward the outer periphery, but it may also change in a stepwise manner.
  • the outer periphery of the first electrode layer 101 e.g., the first active material layer 121 and the solid electrolyte layer 303, which are easily damaged by external impact (or easily peeled off (interlayer, intralayer) during charge/discharge or thermal cycles), can be surrounded by a high concentration of titanium-containing material particles 400.
  • the region with high concentration of titanium-containing material particles 400 may be, for example, rectangular, circular, polygonal, or other shapes in plan view, and high reliability can be achieved by surrounding the outer periphery and making it a shape that can protect the inside of the battery.
  • an all-solid-state battery has been described as an example, but the battery of the present disclosure is not limited to an all-solid-state battery and may be a liquid battery. That is, in the battery of the present disclosure, the electrolyte layer may be composed of, for example, an electrolyte solution and a separator impregnated with the electrolyte solution. Even in the case of a liquid battery, a highly reliable battery can be realized by including a titanium-containing material, as in the all-solid-state batteries described in the first to sixth embodiments.
  • At least one selected from the group consisting of the first electrolyte layer and the second electrode layer contains a titanium-containing material.
  • the titanium-containing material is, for example, contained in a coating layer that covers at least a portion of the surface of the active material particles contained in the electrolyte layer.
  • This coating layer may contain, for example, a solid electrolyte and a titanium-containing material.
  • the first electrode layer 100 is a positive electrode layer and the second electrode layer 200 is a negative electrode layer. That is, in the following description, the first active material layer 120 is a positive electrode active material layer, the first current collector 110 is a positive electrode current collector, the second active material layer 220 is a negative electrode active material layer, and the second current collector 210 is a negative electrode current collector.
  • pastes for printing the positive and negative active material layers are prepared.
  • the solid electrolyte for the positive and negative active material layers for example, a powder of a solid electrolyte (Li 3 AlF 6 -Li 2 TiF 6 ) having an average particle size of about 3 ⁇ m and containing a halide as a main component is prepared.
  • this powder for example, one having high ionic conductivity (for example, 1 ⁇ 10 -3 S/cm to 3 ⁇ 10 -3 S/cm) is used.
  • the positive electrode active material for example, a powder of LiNiCoAl composite oxide ( LiNi0.8Co0.15Al0.05O2 ) having a layered structure and an average particle size of about 5 ⁇ m is used. Also, as the titanium-containing material, TiOF2 powder having an average particle size of about 1 ⁇ m is prepared.
  • a paste for a positive electrode active material layer is prepared by dispersing a mixture containing the above-mentioned positive electrode active material, the above-mentioned solid electrolyte powder, and TiOF2 powder in an organic solvent or the like using a triple roll roller.
  • the negative electrode active material for example, a powder of natural graphite with an average particle size of about 10 ⁇ m is used.
  • a paste for the negative electrode active material layer is prepared in the same manner as the paste for the positive electrode active material layer, by dispersing a mixture containing the above-mentioned negative electrode active material and the above-mentioned powder of the solid electrolyte in an organic solvent or the like.
  • copper foil with a thickness of about 30 ⁇ m is prepared as a material used as a positive electrode collector and a negative electrode collector.
  • the paste for the positive electrode active material layer and the paste for the negative electrode active material layer are printed on one surface of each copper foil by screen printing, respectively, in a predetermined shape and with a thickness of about 50 ⁇ m to 100 ⁇ m.
  • the paste for the positive electrode active material layer and the paste for the negative electrode active material layer are dried at 80 ° C to 130 ° C to become a thickness of 30 ⁇ m to 60 ⁇ m.
  • the paste for the positive electrode active material layer contains TiOF2 powder. This results in a collector (copper foil) on which the positive electrode active material layer and the negative electrode active material layer are formed, respectively.
  • a paste for a solid electrolyte layer dispersed in an organic solvent or the like is prepared by including TiOF2 powder.
  • the above-mentioned paste for a solid electrolyte layer containing TiOF2 powder is printed, for example, to a thickness of about 100 ⁇ m on the main surface of the positive electrode active material layer formed on the positive electrode current collector using a metal mask.
  • the above-mentioned paste for a solid electrolyte layer containing TiOF2 powder is printed, for example, to a thickness of about 100 ⁇ m on the main surface of the negative electrode active material layer formed on the negative electrode current collector using a metal mask.
  • the positive electrode active material layer and the negative electrode active material layer on whose main surfaces the paste for a solid electrolyte layer is printed are dried at 80 ° C. to 130 ° C.
  • the solid electrolyte printed on the positive electrode active material layer formed on the positive electrode current collector and the solid electrolyte printed on the negative electrode active material layer formed on the negative electrode current collector are laminated so that they are in contact with each other and face each other, and the resulting laminate is placed in a die mold with a rectangular outer shape.
  • an elastic sheet having a thickness of, for example, about 50 ⁇ m to 100 ⁇ m and an elastic modulus of about 5 ⁇ 10 6 Pa is inserted between the pressing die and the laminate.
  • pressure is applied to the laminate via the elastic sheet.
  • the pressing die is pressed for, for example, about 90 seconds while being heated to 50° C. to 80° C. at a pressure of 300 MPa to 350 MPa.
  • a battery including a positive electrode layer, a negative electrode layer, and an electrolyte layer disposed between the positive electrode layer and the negative electrode layer.
  • the battery manufacturing method is not limited to the above example.
  • Printing methods that may be used include, for example, a doctor blade method, a calendar method, a spin coating method, a dip coating method, an inkjet method, an offset method, a die coating method, and a spray method.
  • a battery comprising: The battery satisfies at least one configuration selected from the group consisting of (I) and (II) below: (I) At least one selected from the group consisting of the first electrode layer, the second electrode layer, and the electrolyte layer contains at least one titanium-containing material selected from the group consisting of halogenated titanium oxides and titanium oxides.
  • the battery further comprises a side layer comprising at least one titanium-containing material selected from the group consisting of halogenated titanium oxides and titanium oxides, disposed on at least one side selected from the group consisting of the first electrode layer, the second electrode layer, and the electrolyte layer.
  • the halogenated titanium oxide is represented by the following composition formula (1): TiO ⁇ 1 X1 ⁇ 1 ...Formula (1)
  • X1 is at least one selected from the group consisting of F, Cl, Br, and I
  • ⁇ 1 satisfies 0.95 ⁇ 1 ⁇ 1.05, and ⁇ 1 satisfies 1.95 ⁇ 1 ⁇ 2.05
  • the titanium oxide is represented by the following composition formula (2): TiO ⁇ 2 ...Formula (2) In the composition formula (2), the ⁇ 2 satisfies 1.95 ⁇ 2 ⁇ 2.05. battery.
  • the titanium-containing material is relatively hard, for example harder than the solid electrolyte contained in the battery. Therefore, the battery of Technology 1 containing the titanium-containing material has increased mechanical strength, and improved flexural strength and impact resistance. Thus, the battery of Technology 1 can have increased mechanical strength and improved reliability.
  • the titanium-containing material may be adjusted in any content and at any location according to the purpose. This allows the battery of Technology 1 to obtain the desired reliability.
  • the above effects can be achieved with either the configuration (I) or (II).
  • the strength of the electrode layer and/or electrolyte layer, which are the power generating elements of the battery can be improved, improving the reliability of the battery.
  • structural defects i.e., cracks or peeling from the side
  • structural defects i.e., cracks or peeling from the side
  • the side layer containing the titanium-containing material improving the reliability of the battery.
  • the electrolyte layer is a solid electrolyte layer.
  • This configuration makes it possible to provide an all-solid-state battery with improved reliability.
  • the solid electrolyte layer includes a halide solid electrolyte.
  • This configuration makes it possible to obtain a more reliable battery.
  • titanium oxide halide when titanium oxide halide is included as the titanium-containing material, the thermal expansion characteristics of the halide solid electrolyte contained in the solid electrolyte layer and the halide oxide halide are more likely to match because they are both halides. This strengthens the bonding interface between the halide oxide halide and the halide solid electrolyte. This suppresses the occurrence of structural defects caused by peeling at the bonding interface between the halide oxide halide and the halide solid electrolyte due to thermal shock or thermal cycles. In other words, when titanium oxide halide is included as the titanium-containing material, for example, the action and effect of the titanium-containing material against thermal shock and thermal cycles is further improved. This makes it possible to obtain a more reliable battery.
  • the electrolyte layer is composed of an electrolytic solution and a separator impregnated with the electrolytic solution.
  • This configuration makes it possible to provide a liquid battery with improved reliability.
  • the battery satisfies (I), at least one selected from the group consisting of the first electrode layer, the second electrode layer, and the electrolyte layer includes solid electrolyte particles and a coating layer that coats at least a portion of a surface of the solid electrolyte particles;
  • the coating layer includes the titanium-containing material.
  • This configuration can improve the adhesion and mechanical bonding (i.e., anchor effect) between the solid electrolyte particles contained in the electrode layer and/or electrolyte layer, which are the power generation elements of the battery. This improves the strength of the power generation elements against external stress and thermal cycles, thereby further improving the reliability of the battery.
  • the battery satisfies (I), at least one selected from the group consisting of the first electrode layer, the second electrode layer, and the electrolyte layer contains solid electrolyte particles; the titanium-containing material is contained inside the solid electrolyte particles; The battery according to any one of claims 1 to 4.
  • the solid electrolyte particles contained in the electrode layer and/or electrolyte layer which are the power generating elements of the battery, can have their strength improved by making the inside harder, so that the hardness of the solid electrolyte particles can be adjusted according to the purpose.
  • the surface layer of the solid electrolyte particles can be made softer than the inside of the particles, so that the surface layer of the particles can have bonding and deformability. Therefore, the bonding between the particles can be improved.
  • the reliability of the power generating element against external stress and thermal cycles is improved, so that the reliability of the battery can be further improved.
  • the hardness of the solid electrolyte particles can be adjusted, for example, by selecting a halogen element in the halogenated titanium oxide contained as the titanium-containing material, or by including a combination of multiple halogen elements.
  • a halogen element in the halogenated titanium oxide contained as the titanium-containing material or by including a combination of multiple halogen elements.
  • the titanium-containing material is included in the inside of the solid electrolyte particles, the decrease in ionic conductivity between the solid electrolyte particles caused by the titanium-containing material is reduced.
  • the battery satisfies (I), At least one selected from the group consisting of the first electrode layer and the second electrode layer includes active material particles and a coating layer that coats at least a portion of a surface of the active material particles, The coating layer includes the titanium-containing material.
  • the battery according to any one of claims 1 to 6.
  • This configuration can improve the mechanical bonding between the active material particles (i.e., the anchor effect). This improves the strength of the electrode layer against external stress and thermal cycles, and can suppress the occurrence of structural defects such as cracks in the electrode layer. This can further improve the reliability of the battery.
  • This configuration makes it easier to incorporate the titanium-containing material into the coating layers of the solid electrolyte particles and active material particles, or into the interior of the solid electrolyte particles.
  • finely pulverized particles of titanium-containing material can make the electrolyte layer thinner and the coating layers of the active material particles, etc. thinner, thereby improving the capacity of the battery.
  • the titanium-containing material includes TiOF2 ;
  • the mechanical bonding between solid electrolyte particles and between active material particles is improved by the presence of hard particles of TiOF 2.
  • TiOF 2 which is harder than the solid electrolyte
  • the solid electrolyte particles can be made harder.
  • TiOF 2 when TiOF 2 is contained in the coating layer of the solid electrolyte particles and/or the active material particles, TiOF 2 also becomes an anchor that strengthens the bonding between the particles. Therefore, a battery with excellent bending resistance and impact resistance is obtained.
  • TiOF 2 has excellent heat resistance (for example, about 1000 ° C.). Therefore, excellent reliability can be obtained even at high temperatures.
  • TiOF2 that is stable even at high temperatures, for example, around 400°C. Therefore, TiOF2 with excellent mechanical strength and heat resistance can be contained in the battery, resulting in a more reliable battery.
  • the crystal system of TiOF2 can be identified, for example, by the diffraction pattern obtained by micro-XRD of the surface exposed on the side surface of the battery. Alternatively, it can be confirmed by the lattice image of a high-resolution TEM.
  • the titanium-containing material is in particulate form; At least a portion of the surface of the particles of the titanium-containing material is coated with a coating layer containing a solid electrolyte.
  • the solid electrolyte coating the titanium-containing material particles acts as a binder. This improves the bonding between the titanium-containing material particles and between the titanium-containing material particles and other particles (e.g., solid electrolyte particles and active material particles), further improving the reliability of the battery.
  • the titanium-containing material includes TiOF2 having a cubic crystal structure and TiO2 ; 12.
  • the titanium-containing material can have excellent bonding between TiOF2 and TiO2 due to the common element Ti, while also having improved hardness.
  • a titanium-containing material containing TiO2 which has high heat resistance stability, together with TiOF2 into a battery, the binding property of the solid electrolyte particles and the active material particles at high temperatures can be improved. Therefore, a battery with excellent mechanical strength and heat resistance can be obtained.
  • the titanium-containing material is in particulate form; In the surface region of the particles of the titanium-containing material, the content of TiOF2 is greater than the content of TiO2 ; In the inner region of the particle of the titanium-containing material, the content of TiO2 is greater than the content of TiOF2 ; 13.
  • the particles of the titanium-containing material contain a large amount of TiO2, which is hard and heat-resistant, inside the particles, and a large amount of TiOF2 , which is heat-resistant, in the surface layer portion.
  • the particles of the titanium-containing material can have high bonding with the halide solid electrolyte particles because they both contain a halogen element. Therefore, according to this configuration, a power generating element with high mechanical strength and heat resistance can be obtained. Therefore, a highly reliable battery can be obtained.
  • the titanium-containing material is in particulate form;
  • the particles of titanium-containing material are A first particle composed of TiOF2 having a cubic crystal structure; second particles including TiOF2 and TiO2 having a cubic crystal structure; Including, The battery according to claim 9.
  • the heat resistance and mechanical strength of the titanium-containing material can be adjusted according to the application by controlling the mixing ratio of the first particles and the second particles.
  • a solid electrolyte layer containing a solid electrolyte with high ionic conductivity for example, 1 ⁇ S/cm or more
  • Ti which is commonly contained in the titanium-containing material and the halide solid electrolyte
  • the titanium-containing material and the solid electrolyte are firmly bonded together, making it easier to form an integrated bonded interface.
  • the titanium-containing material when a titanium-containing material is contained in the solid electrolyte layer, the titanium-containing material can coexist stably with the solid electrolyte within the solid electrolyte layer (for example, without forming fine defects around it). This results in a battery with improved reliability.
  • the halide solid electrolyte includes a first halide solid electrolyte including a crystal phase represented by the following composition formula (3): Li 2 TiX2 6 ...Formula (3)
  • X2 is at least one selected from the group consisting of F, Cl, Br, and I. 18.
  • the solid electrolyte layer contains a solid electrolyte having a high ionic conductivity of, for example, 1 ⁇ S/ cm or more, so that the ionic conductivity of the solid electrolyte layer is improved.
  • the crystal phase represented by Li2TiX26 can be confirmed by the diffraction pattern of the micro-area XRD described above, or by powder XRD using a powder sample obtained by cutting out the solid electrolyte.
  • the composition of the solid electrolyte can also be evaluated by elemental analysis using, for example, EPMA or EDS.
  • the first halide solid electrolyte includes a crystalline phase represented by the following composition formula (4): Li 2 TiF 6 ...Formula (4) 19.
  • the first halide solid electrolyte has improved atmospheric stability. This makes it possible to suppress fluctuations in the properties of the solid electrolyte caused by changes in the environment during the manufacturing process, and therefore makes it possible to reproducibly obtain a solid electrolyte layer with the desired properties.
  • manufacturing benefits such as reduced manufacturing costs, because strict dew point environment control, temperature control, and humidity control are no longer necessary.
  • the halide solid electrolyte further includes a second halide solid electrolyte having a composition different from that of the first halide solid electrolyte.
  • This configuration further improves the adhesion of the solid electrolyte in the solid electrolyte layer, making the solid electrolyte layer denser, increasing its strength, and improving its ionic conductivity.
  • the second halide solid electrolyte has a higher melting point than the first halide solid electrolyte. 21.
  • the second halide solid electrolyte has a higher melting point than the first halide solid electrolyte, and therefore can maintain a harder state than the first halide solid electrolyte at high temperatures.
  • a solid electrolyte layer containing a first halide solid electrolyte further contains a second halide solid electrolyte
  • the hardness of the solid electrolyte layer increases. This makes the solid electrolyte layer stronger, improving its flexural strength and impact resistance, and improving the reliability of the solid electrolyte layer. This makes it possible to realize a battery with improved reliability.
  • the second halide solid electrolyte is harder than the first halide solid electrolyte. 22.
  • the second halide solid electrolyte includes a crystalline phase represented by the following composition formula (5): Li 3 MF 6 ...(5)
  • the M is at least one element selected from the group consisting of metal elements and semi-metal elements having a valence of three. 23.
  • the M includes Al. 24.
  • the ionic conductivity of the second halide solid electrolyte is increased to the same level as that of the first halide solid electrolyte (e.g., 1 ⁇ S/cm or more). This makes it possible to obtain a solid electrolyte layer with high ionic conductivity and high reliability. This makes it possible to obtain a battery with excellent performance and reliability.
  • the battery disclosed herein can be used, for example, as a secondary battery such as an all-solid-state battery or liquid battery for use in various electronic devices or automobiles.

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