WO2024157812A1 - 全固体電池用電極、その製造方法、および全固体電池 - Google Patents

全固体電池用電極、その製造方法、および全固体電池 Download PDF

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WO2024157812A1
WO2024157812A1 PCT/JP2024/000724 JP2024000724W WO2024157812A1 WO 2024157812 A1 WO2024157812 A1 WO 2024157812A1 JP 2024000724 W JP2024000724 W JP 2024000724W WO 2024157812 A1 WO2024157812 A1 WO 2024157812A1
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solid
electrode
state battery
solid electrolyte
mixture
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French (fr)
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春樹 上剃
政嗣 石澤
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Maxell Ltd
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Maxell Ltd
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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
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—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

Definitions

  • the present invention relates to an electrode that can be used to construct an all-solid-state battery with low internal resistance, a method for manufacturing the electrode, and an all-solid-state battery with low internal resistance.
  • lithium batteries particularly lithium ion batteries, that can meet this demand use lithium-containing composite oxides such as lithium cobalt oxide ( LiCoO2 ) and lithium nickel oxide ( LiNiO2 ) as the positive electrode active material, graphite or the like as the negative electrode active material, and an organic electrolyte solution containing an organic solvent and a lithium salt as the non-aqueous electrolyte.
  • lithium-containing composite oxides such as lithium cobalt oxide ( LiCoO2 ) and lithium nickel oxide ( LiNiO2 ) as the positive electrode active material, graphite or the like as the negative electrode active material, and an organic electrolyte solution containing an organic solvent and a lithium salt as the non-aqueous electrolyte.
  • lithium-ion batteries As devices that use lithium-ion batteries continue to develop, there is a demand for longer life, higher capacity, and higher energy density for lithium-ion batteries, as well as a high demand for the reliability of lithium-ion secondary batteries with longer life, higher capacity, and higher energy density.
  • the organic electrolyte used in lithium-ion batteries contains organic solvents, which are flammable substances, and so there is a possibility that the organic electrolyte may generate abnormal heat if an abnormality such as a short circuit occurs in the battery. Furthermore, with the recent trend toward higher energy density in lithium-ion batteries and an increasing amount of organic solvent in organic electrolytes, there is an even greater demand for the reliability of lithium-ion batteries.
  • All-solid-state lithium batteries that do not use organic solvents (all-solid-state batteries) are also being considered.
  • All-solid-state lithium batteries use a molded solid electrolyte that does not use organic solvents instead of the conventional organic solvent-based electrolyte, and are highly reliable with no risk of abnormal heat generation from the solid electrolyte. For this reason, there are high expectations for them, especially in product areas that require high-capacity secondary batteries.
  • Solid-state batteries are also highly reliable and environmentally resistant, and have a long lifespan, making them promising maintenance-free batteries that can contribute to social development while also continuing to contribute to safety and security.
  • Providing solid-state batteries to society can contribute to the achievement of Goal 3 (Ensure healthy lives and promote well-being for all at all ages), Goal 7 (Ensure access to affordable, reliable, sustainable and modern energy for all), Goal 11 (Make cities and human settlements inclusive, safe, resilient and sustainable), and Goal 12 (Ensure sustainable consumption and production patterns) out of the 17 Sustainable Development Goals (SDGs) established by the United Nations.
  • SDGs Sustainable Development Goals
  • all-solid-state batteries use electrodes that have compacts formed by pressing a powdered electrode mixture that contains an active material (positive electrode active material or negative electrode active material) and a solid electrolyte.
  • an active material positive electrode active material or negative electrode active material
  • a solid electrolyte In order to increase the capacity of such all-solid-state batteries, it is possible to increase the area of the electrodes and to increase the density of the electrode mixture compact, but in this case, it is necessary to pressurize the electrode mixture compact with a higher pressure than before.
  • the area of the electrode mixture molded body in plan view is about 1.8 cm 2 or less, it is relatively easy to obtain a high density by molding at a pressure of about 800 to 2000 MPa (Patent Document 1, etc.).
  • Patent Document 1 Patent Document 1
  • the density of the electrode mixture molded body becomes small, there is a problem that the internal resistance of the electrode and further the internal resistance of the all-solid-state battery using it increases.
  • Patent Document 2 proposes a method in which a powder of a sulfide-based inorganic solid electrolyte and a powder of an electrode active material are pressure-molded, pulverized to produce a granulated powder with an average particle size of 10 to 50 ⁇ m, and this granulated powder is then pressure-molded again as is to obtain an electrode mixture compact.
  • the particle shape of the sulfide-based inorganic solid electrolyte disappears to form a sea-island structure, which bonds the sulfide-based inorganic solid electrolyte and the electrode active material and improves the ion conduction path at the interface between the two materials, and it is therefore thought that the density of the electrode mixture compact may also be improved.
  • JP 2021-163582 A paragraphs [0078], [0079], etc.
  • JP 2014-192061 A claims, paragraph [0010], etc.
  • the present invention was made in consideration of the above circumstances, and its purpose is to provide an electrode that can be used to construct an all-solid-state battery with low internal resistance, a method for manufacturing the electrode, and an all-solid-state battery with low internal resistance.
  • the electrode for an all-solid-state battery of the present invention comprises a composite obtained by pressure molding a mixture containing an active material and a solid electrolyte (A), and a molded body of an electrode mixture containing a solid electrolyte (B) that is the same as or different from the solid electrolyte (A), and the molded body of the electrode mixture is characterized in that it has a porosity of 10% or less and an area of more than 1.8 cm2 .
  • the method for producing an electrode for an all-solid-state battery of the present invention is characterized by comprising: a step (a) of pressing a mixture 1 containing an active material and a solid electrolyte (A) at a pressure of 800 MPa or more to form a composite; a step (b) of mixing the composite with a solid electrolyte (B) that is the same as or different from the solid electrolyte (A) to prepare a mixture 2; and a step (c) of forming a layer of the mixture 2 having a predetermined thickness and an area greater than 1.8 cm2 , and pressing the layer at a predetermined pressure of less than 800 MPa to form a molded body of the electrode mixture.
  • the all-solid-state battery of the present invention is characterized in that a power generating element in which a positive electrode having a molded body of a positive electrode mixture, a solid electrolyte layer, and a negative electrode having a molded body of a negative electrode mixture are laminated is enclosed in an exterior body, and at least one of the positive electrode and the negative electrode is an electrode for the all-solid-state battery of the present invention.
  • the present invention provides an electrode that can be used to construct an all-solid-state battery with low internal resistance, a method for manufacturing the electrode, and an all-solid-state battery with low internal resistance.
  • FIG. 1 is a cross-sectional view illustrating a schematic example of an all-solid-state battery of the present invention.
  • FIG. 2 is a cross-sectional view illustrating a schematic diagram of another example of the all-solid-state battery of the present invention.
  • the electrode for an all-solid-state battery of the present invention has a molded body of an electrode mixture containing an active material and a solid electrolyte, and is used for the positive electrode or negative electrode of an all-solid-state battery.
  • Examples of the form of the electrode include an electrode mixture molded body alone, and an electrode mixture layer (electrode mixture layer) formed on a current collector.
  • the molded body of the electrode mixture contains a composite obtained by pressure molding a mixture containing an active material and a solid electrolyte (A) [a composite which is a molded body (pressure molded body) of the mixture] and a solid electrolyte (B) which is present between the composite (e.g., a granular material thereof) and is the same as or different from the solid electrolyte (A) separately from the solid electrolyte (A), and has a porosity of 10% or less and an area of greater than 1.8 cm2 .
  • the method for producing an electrode for an all-solid-state battery of the present invention includes a step (a) of pressing a mixture 1 containing an active material and a solid electrolyte (A) at a pressure of 800 MPa or more to form a composite, a step (b) of mixing the composite with a solid electrolyte (B) that is the same as or different from the solid electrolyte (A) to prepare a mixture 2, and a step (c) of forming a layer of the mixture 2 having a predetermined thickness and an area greater than 1.8 cm2 , and pressing the layer at a predetermined pressure of less than 800 MPa to form a molded body of the electrode mixture.
  • the electrode for an all-solid-state battery of the present invention can be produced by this production method.
  • step (a) the mixture 1 containing the active material and solid electrolyte constituting the electrode mixture compact is pressed at a pressure of 800 MPa or more to form a composite.
  • the mixture 1 is pressed and molded to a size smaller than the final electrode mixture compact, for example, an area of 1.8 cm2 or less, to form a composite (molded body), so that the mixture 1 can be made into a high-density molded body (for example, a molded body with a porosity of 8% or less) by applying a pressure of 800 MPa or more by a pressure molding method using a normal device.
  • step (b) the mixture 1 obtained as a composite through step (a) [or the granular material obtained by pulverizing the mixture 1 obtained as a composite through step (a) in the pulverization step described below] is mixed with a solid electrolyte (B) that is the same as or different from the solid electrolyte (A) of the mixture 1 to obtain a mixture 2, which is then made into a layered material having a predetermined thickness and an area greater than 1.8 cm 2 in step (c), and then pressed at a predetermined pressure of less than 800 MPa to form a molded body of the electrode mixture.
  • a solid electrolyte (B) that is the same as or different from the solid electrolyte (A) of the mixture 1 to obtain a mixture 2, which is then made into a layered material having a predetermined thickness and an area greater than 1.8 cm 2 in step (c), and then pressed at a predetermined pressure of less than 800 MPa to form a molded body of the electrode mixture.
  • the action of the solid electrolyte (B) used together with the mixture 1 obtained in step (a) can increase the density of the molded body of the electrode mixture, improve ion conductivity, and reduce internal resistance. Therefore, in the manufacturing method of the electrode for an all-solid-state battery of the present invention, a molded body of an electrode mixture having an area in a plan view of more than 1.8 cm2 can be formed at a high density (for example, the porosity of the molded body calculated from the true density and composition ratio of each material constituting the molded body of the electrode mixture and the mass and volume of the molded body is 10% or less) without using a special device. Therefore, according to the manufacturing method of the present invention, it is possible to manufacture the electrode for an all-solid-state battery of the present invention having a low internal resistance while increasing the area in a plan view of the molded body of the electrode mixture as described above.
  • active materials used in electrodes for solid-state batteries include the following:
  • the active material can be the same as the positive electrode active material used in a conventionally known non-aqueous electrolyte primary battery.
  • the active material include manganese dioxide, lithium-containing manganese oxides (e.g., LiMn 3 O 6 , and composite oxides having the same crystal structure as manganese dioxide ( ⁇ -type, ⁇ -type, or a structure in which ⁇ -type and ⁇ -type are mixed, etc.) and a Li content of 3.5 mass% or less, preferably 2 mass% or less, more preferably 1.5 mass% or less, and particularly preferably 1 mass% or less), lithium-containing composite oxides such as Li a Ti 5/3 O 4 (4/3 ⁇ a ⁇ 7/3); vanadium oxide; niobium oxide; titanium oxide; sulfides such as iron disulfide; graphite fluoride; silver sulfides such as Ag
  • the active material may be the same as the positive electrode active material used in conventionally known non-aqueous electrolyte secondary batteries, that is, the active material capable of absorbing and releasing Li (lithium) ions.
  • a spinel-type lithium manganese composite oxide represented by Li 1-x M r Mn 2-r O 4 (wherein M is at least one element selected from the group consisting of Li, Na, K, B, Mg, Ca, Sr, Ba, Ti, V, Cr, Zr, Fe, Co, Ni, Cu, Zn, Al, Sn, Sb, In, Nb, Ta, Mo, W, Y, Ru, and Rh, and 0 ⁇ x ⁇ 1, 0 ⁇ r ⁇ 1), Li r Mn (1-s-t) Ni s M t O (2-u) F v (wherein M is at least one element selected from the group consisting of Co, Mg, Al, B, Ti, V, Cr, Fe, Cu, Zn, Zr, Mo, Sn, Ca, Sr, and W, and 0 ⁇ r ⁇ 1.2, 0 ⁇ s ⁇ 0.5, 0 ⁇ t ⁇ 0.5, u+v ⁇ 1, -0.1 ⁇ u ⁇ 0.2, 0 ⁇ v ⁇ 0.1), a layered compound represented by Li 1-x M
  • the average particle diameter of the positive electrode active material contained therein is preferably 1 ⁇ m or more, more preferably 2 ⁇ m or more, and preferably 10 ⁇ m or less, more preferably 8 ⁇ m or less.
  • the positive electrode active material may be either primary particles or secondary particles formed by agglomeration of primary particles.
  • the average particle diameter of various particles means the 50% diameter value ( D50 ) in the volume-based integrated fraction when the integrated volume is calculated from particles with small particle sizes using a particle size distribution measurement device (such as the Microtrack particle size distribution measurement device "HRA9320" manufactured by Nikkiso Co., Ltd.).
  • examples of the active material (negative electrode active material) used in an all-solid-state primary battery include metallic lithium and lithium alloys (lithium-aluminum alloy, lithium-indium alloy, etc.).
  • the active material is not particularly limited as long as it is an active material capable of absorbing and releasing Li ions that is used in conventionally known lithium secondary batteries.
  • the negative electrode active material one or a mixture of two or more carbon-based materials capable of absorbing and releasing lithium, such as graphite, pyrolytic carbons, cokes, glassy carbons, baked bodies of organic polymer compounds, mesocarbon microbeads (MCMB), and carbon fibers, is used.
  • the negative electrode active material may be an oxide, for example, a composite oxide having a monoclinic crystal structure represented by Li x Nb y TiM 6 a O ⁇ 5y+4/2 ⁇ + ⁇ (wherein M 6 is at least one selected from the group consisting of V, Cr, Mo, Ta, Zr, Mn, Fe, Mg, B, Al, Cu, and Si, and 0 ⁇ x ⁇ 49, 0.5 ⁇ y ⁇ 24, ⁇ 5 ⁇ 5, 0 ⁇ a ⁇ 0.3), titanium dioxide having an anatase structure, lithium titanate having a ramsdellite structure represented by Li 2 Ti 3 O 7 , and a spinel-type lithium titanium composite oxide represented by Li 4 Ti 5 O 12 , and the like, and one or more of these may be used.
  • M 6 is at least one selected from the group consisting of V, Cr, Mo, Ta, Zr, Mn, Fe, Mg, B, Al, Cu, and Si, and 0 ⁇ x ⁇ 49, 0.5 ⁇ y ⁇ 24, ⁇ 5 ⁇ 5,
  • the negative electrode active material there can be used simple substances, compounds and alloys thereof containing elements such as Si, Sn, Ge, Bi, Sb, and In; compounds that can be charged and discharged at a low voltage close to that of lithium metal, such as nitrides or lithium-containing oxides containing lithium and transition metals such as Co, Ni, Mn, Fe, Cr, Ti, and W; or metallic lithium and lithium alloys (lithium-aluminum alloy, lithium-indium alloy, and the like).
  • lithium metal such as nitrides or lithium-containing oxides containing lithium and transition metals such as Co, Ni, Mn, Fe, Cr, Ti, and W
  • metallic lithium and lithium alloys lithium-aluminum alloy, lithium-indium alloy, and the like.
  • the active material may have a reaction suppression layer on its surface to suppress reaction between the active material and the solid electrolyte.
  • a reaction suppression layer is provided on the surface of the active material (positive electrode active material).
  • the reaction suppression layer may be made of a material that has ion conductivity and can suppress the reaction between the active material and the solid electrolyte.
  • materials that can form the reaction suppression layer include oxides containing Li and at least one element selected from the group consisting of Nb, P, B, Si, Ge, Ti, Zr, Ta and W, more specifically, Nb-containing oxides such as LiNbO 3 , Li 3 PO 4 , Li 3 BO 3 , Li 4 SiO 4 , Li 4 GeO 4 , LiTiO 3 , LiZrO 3 , Li 2 WO 4 and the like.
  • the reaction suppression layer may contain only one of these oxides, or may contain two or more of them, and further, a plurality of these oxides may form a composite compound. Among these oxides, it is preferable to use an Nb-containing oxide, and it is more preferable to use LiNbO 3 .
  • the reaction suppression layer is preferably present on the surface in an amount of 0.1 to 1.0 parts by mass per 100 parts by mass of active material (base material particles that form the reaction suppression layer). This range allows for good suppression of the reaction between the active material and the solid electrolyte.
  • Methods for forming a reaction inhibitor layer on the surface of an active material include the sol-gel method, mechanofusion method, CVD method, PVD method, and ALD method.
  • the content of the active material in the electrode mixture molded body is preferably 60 to 98 mass % from the viewpoint of increasing the energy density of the all-solid-state battery.
  • the content of the active material in the electrode mixture molded body is preferably 40 to 99 mass % from the viewpoint of increasing the energy density of the all-solid-state battery.
  • the solid electrolyte in the electrode for the all-solid-state battery is not particularly limited as long as it has lithium ion conductivity, and for example, a sulfide-based solid electrolyte, a hydride-based solid electrolyte, a halide-based solid electrolyte, an oxide-based solid electrolyte, etc. can be used.
  • Examples of sulfide-based solid electrolytes include particles of Li 2 S-P 2 S 5 , Li 2 S-SiS 2 , Li 2 S-P 2 S 5 -GeS 2 , and Li 2 S-B 2 S 3 based glass.
  • thio-LISICON type electrolytes which have been attracting attention in recent years for their high Li ion conductivity, are Li 12-12a-b+c+6d-e M 1 3 + a-b-c-d M 2 b M 3 c M 4 d M 5 12-e X e (wherein M 1 is Si, Ge , or Sn, and M M2 is P or V, M3 is Al, Ga, Y or Sb, M4 is Zn, Ca, or Ba, M5 is S or either S and O, and X is F, Cl, Br or I, 0 ⁇ a ⁇ 3, 0 ⁇ b+c+d ⁇ 3, 0 ⁇ e ⁇ 3] or one having an argyrodite-type crystal structure can also be used.
  • Examples of hydride-based solid electrolytes include LiBH 4 , solid solutions of LiBH 4 and the following alkali metal compounds (for example, those in which the molar ratio of LiBH 4 to the alkali metal compound is 1:1 to 20:1), etc.
  • Examples of the alkali metal compounds in the solid solutions include at least one selected from the group consisting of lithium halides (LiI, LiBr, LiF, LiCl, etc.), rubidium halides (RbI, RbBr, RbF, RbCl, etc.), cesium halides (CsI, CsBr, CsF, CsCl, etc.), lithium amide, rubidium amide, and cesium amide.
  • lithium halides LiI, LiBr, LiF, LiCl, etc.
  • rubidium halides RbI, RbBr, RbF, RbCl, etc.
  • cesium halides CsI, CsBr, CsF, Cs
  • Other known solid electrolytes that can be used include those described in, for example, WO 2020/070958 and WO 2020/070955.
  • oxide-based solid electrolytes examples include garnet-type Li 7 La 3 Zr 2 O 12 , NASICON-type Li 1+O Al 1+O Ti 2-O (PO 4 ) 3 and Li 1+p Al 1+p Ge 2-p (PO 4 ) 3 , and perovskite-type Li 3q La 2/3-q TiO 3 .
  • sulfide-based solid electrolytes are preferred due to their high lithium ion conductivity, sulfide-based solid electrolytes containing Li and P are more preferred, and sulfide-based solid electrolytes having an argyrodite crystal structure are even more preferred due to their higher lithium ion conductivity and high chemical stability.
  • the electrode for an all-solid-state battery contains, in the electrode mixture compact, a solid electrolyte (A) that forms a complex with the active material, and a solid electrolyte (B) that exists between the complexes separately from this solid electrolyte (A).
  • the solid electrolyte (B) which contributes to the moldability of the electrode mixture compact, is preferably a sulfide-based solid electrolyte that has excellent moldability, and it is more preferable that both the solid electrolyte (A) and the solid electrolyte (B) are sulfide-based solid electrolytes.
  • sulfide-based solid electrolyte having an argyrodite-type crystal structure those represented by the following general composition formula (1), the following general composition formula (2), or the following general composition formula (3), such as Li 6 PS 5 Cl, are particularly preferred.
  • X represents one or more halogen elements, and 0.2 ⁇ k ⁇ 2.0 or 0.2 ⁇ k ⁇ 1.8.
  • the average particle size of the solid electrolyte is preferably 0.1 ⁇ m or more, and more preferably 0.2 ⁇ m or more, from the viewpoint of reducing grain boundary resistance, while it is preferably 10 ⁇ m or less, and more preferably 5 ⁇ m or less, from the viewpoint of forming a sufficient contact interface between the active material and the solid electrolyte.
  • the content of the solid electrolyte in the molded body of the electrode mixture is preferably 10 parts by mass or more, more preferably 30 parts by mass or more, and particularly preferably 50 parts by mass or more, when the content of the positive electrode active material is 100 parts by mass, from the viewpoint of further increasing the ion conductivity in the positive electrode and further improving the output characteristics of the all-solid-state battery.
  • the amount of solid electrolyte in the molded body of the electrode mixture is too large, the amount of other components may be reduced, and the effects of these components may be reduced.
  • the content of the solid electrolyte in the molded body of the electrode mixture is preferably 90 parts by mass or less, more preferably 80 parts by mass or less, and particularly preferably 70 parts by mass or less, when the content of the positive electrode active material is 100 parts by mass.
  • the content of the solid electrolyte in the electrode mixture molded body is preferably 30 parts by mass or more, and more preferably 35 parts by mass or more, when the content of the negative electrode active material is 100 parts by mass, from the viewpoint of further increasing the ionic conductivity in the negative electrode and further improving the output characteristics of the all-solid-state battery.
  • the content of solid electrolyte in the electrode mixture molded body is preferably 130 parts by mass or less, and more preferably 110 parts by mass or less, when the content of the negative electrode active material is 100 parts by mass.
  • the electrode mixture molded body of the electrode for the all-solid-state battery can contain a conductive assistant.
  • conductive assistants include highly crystalline carbon materials such as graphite (natural graphite, artificial graphite), graphene (single-layer graphene, multi-layer graphene), and carbon nanotubes; and low-crystalline carbon materials such as carbon black; and one or more of these can be used.
  • the content of the conductive assistant in the electrode mixture molded body is preferably 1 to 10 mass%. Also, when the all-solid-state battery electrode is used as the negative electrode of an all-solid-state battery, the content of the conductive assistant in the electrode mixture molded body is preferably 5 to 15 mass%.
  • the electrode mixture compact of the all-solid-state battery electrode can contain a binder.
  • a binder include fluororesins such as polyvinylidene fluoride (PVDF).
  • PVDF polyvinylidene fluoride
  • the electrode mixture molded body requires a binder, its content is preferably 15% by mass or less, and preferably 0.5% by mass or more. On the other hand, if the electrode mixture molded body can obtain moldability without requiring a binder, its content is preferably 0.5% by mass or less, more preferably 0.3% by mass or less, and even more preferably 0% by mass (i.e., no binder is contained).
  • the thickness of the electrode mixture molded body is preferably 500 to 3000 ⁇ m.
  • the shape of the electrode mixture compact can be in the form of a pellet (flat plate) that is circular or polygonal in plan view.
  • a current collector can be used for the electrode for the all-solid-state battery.
  • examples of the current collector include foils of metals such as aluminum and stainless steel, punched metals, mesh, expanded metals, foamed metals, carbon sheets, etc.
  • examples of the current collector include foils of copper or nickel, punched metals, mesh, expanded metals, foamed metals, carbon sheets, etc.
  • the thickness of the current collector is preferably 30 to 100 ⁇ m.
  • step (a) of the method for producing an electrode for an all-solid-state battery a mixture 1 containing an active material and a solid electrolyte (A) is pressurized to form the mixture 1 into a composite.
  • the electrode mixture forming body contains a conductive assistant or binder, these can be added when preparing mixture 1. Also, as described below, if after step (a), the composite mixture 1 is pulverized to form granules of adjusted size, and then mixture 2 is prepared in step (b), the conductive assistant or binder may be added when preparing mixture 2.
  • the means of pressure molding when compound 1 is made into a composite there are no particular limitations on the means of pressure molding when compound 1 is made into a composite, and any known device capable of pressure molding powders may be used, but the pressure applied is 800 MPa or more, preferably 1000 MPa or more, and more preferably 1200 MPa or more. This increases the density of the compound 1, and the effect of this, combined with the effect of the solid electrolyte used in the subsequent process, increases the density of the final electrode compound molded body and reduces internal resistance.
  • the upper limit of the pressure applied when compound 1 is made into a composite is usually around 2000 MPa.
  • the shape of the composite of the mixture 1 obtained by pressing can be a circular or polygonal pellet (flat plate) or a sphere in plan view.
  • the size of the composite of the mixture 1 is preferably 1.8 cm 2 or less in plan view, more preferably 1.5 cm 2 or less, and particularly preferably 1 cm 2 or less, so that the total pressure during pressing is within the range that can be applied by a general molding device (for example, up to about 200 kN).
  • the area of the composite in plan view is preferably 0.1 cm 2 or more, more preferably 0.2 cm 2 or more, and particularly preferably 0.5 cm 2 or more.
  • the thickness of the composite is not particularly limited if it is crushed and the size is adjusted before use, but if it is used to form the mixture 2 in the shape obtained at the time of pressure molding, it should be adjusted taking into account the thickness of the molded electrode mixture to be produced.
  • step (b) of the method for producing an electrode for an all-solid-state battery the composite of mixture 1 obtained in step (a) is mixed with solid electrolyte (B) to prepare mixture 2.
  • the mixture 1 When preparing the mixture 2, the mixture 1 may be used as it is in the form of the complex obtained in step (a), or the mixture 1 may be used in the form of granules obtained in a step of pulverizing the complex of the mixture 1 prior to step (b).
  • the mixture 2 prepared after pulverizing the complex of the mixture 1 into granules the uniformity of the distribution of each component in the resulting molded body of the electrode mixture is improved, and the characteristics of the electrode for an all-solid-state battery and the all-solid-state battery obtained using this electrode are improved.
  • the size is preferably, for example, an average particle size larger than 50 ⁇ m, more preferably larger than 100 ⁇ m, in order to make it easier to mold the electrode mixture compact at a higher density.
  • the average particle size of the granules is 1 mm or less.
  • the average particle size of the granules referred to here is D50 , which is obtained by the same method as the method for measuring the average particle size of the positive electrode active material, etc.
  • step (a) When preparing mixture 2, it is preferable to use 20 to 60 parts by mass of solid electrolyte (B) per 100 parts by mass of the composite obtained in step (a). Therefore, the amount of solid electrolyte (A) used to prepare mixture 1 in step (a) can be determined taking into account the amount to be used in step (b).
  • a conductive additive or binder may be added to the composite 2.
  • combination 2 there are no particular limitations on the method for preparing combination 2, and the various components to be contained in combination 2 may be mixed by any known method.
  • step (c) of the method for producing an electrode for an all-solid-state battery the mixture 2 is made into a layer having a predetermined thickness and an area greater than 1.8 cm2 , and then pressed to form a molded body of the electrode mixture.
  • the means of pressure molding there is no particular limitation on the means of pressure molding, and a known device capable of pressure molding a strip-shaped film, powder, or pellet-shaped material may be used, but the pressure to be applied may be adjusted according to the area of the layered material of the mixture 2 so that the total pressure is within a range that can be applied by a general molding device (for example, up to about 200 kN), and for example, when the area of the layered material of the mixture 2 is 5 cm 2 , the maximum pressure can be about 400 MPa. This makes it possible to easily increase the density of the molded body of the electrode mixture, thereby reducing the internal resistance of the electrode for an all-solid-state battery.
  • a general molding device for example, up to about 200 kN
  • the maximum pressure can be about 400 MPa.
  • the pressure applied to the layered material is preferably 200 MPa or more, and more preferably 300 MPa or more.
  • the molded body of the electrode mixture can be used as it is to form an electrode for an all-solid-state battery, but when it is used to form an electrode for an all-solid-state battery that also has a current collector, for example, in step (c), the mixture 2 can be pressed on the current collector to form a molded body of the electrode mixture.
  • a solid electrolyte layer can be prepared in advance, and a molded body of an electrode mixture can be formed on the solid electrolyte layer by step (c), thereby bonding the solid electrolyte layer and the electrodes for an all-solid-state battery.
  • a power generating element in which electrodes for an all-solid-state battery are formed on both sides of a solid electrolyte layer can be obtained by forming a molded body of a positive electrode mixture (or a molded body of a negative electrode mixture) on one side of the solid electrolyte layer by step (c), and further forming a molded body of a negative electrode mixture (or a molded body of a positive electrode mixture) on the other side of the solid electrolyte layer by step (c).
  • the area in plan view is not particularly limited as long as it is a value greater than 1.8 cm2 .
  • a general hydraulic press or mold it can be formed to have an area similar to that of electrodes conventionally used (for example, in the case of a coin-shaped battery, about 3 cm2).
  • pressure molding using a roll press or the like it is possible to increase the area to 10 cm2 or more, and it is also possible to correspond to batteries requiring a larger electrode area. Even in such a case, it is possible to obtain an electrode for an all-solid-state battery having low internal resistance and good characteristics.
  • the all-solid-state battery of the present invention includes a power generating element that is laminated with a positive electrode having a molded body of a positive electrode mixture, a solid electrolyte layer, and a negative electrode having a molded body of a negative electrode mixture, and is enclosed in an exterior body, and at least one of the positive electrode and the negative electrode is an electrode for the all-solid-state battery of the present invention.
  • the all-solid-state battery of the present invention has a low internal resistance all-solid-state battery electrode in at least one of the positive electrode and the negative electrode, and therefore has reduced internal resistance.
  • the all-solid-state battery of the present invention it is sufficient if only one of the positive electrode and the negative electrode is an electrode for the all-solid-state battery of the present invention, but it is preferable that both the positive electrode and the negative electrode are electrodes for the all-solid-state battery of the present invention.
  • the negative electrode can be, for example, a negative electrode having a molded body of a negative electrode mixture obtained by molding a negative electrode mixture, which is a mixture of constituent materials such as a negative electrode active material and a solid electrolyte, in a manner similar to that of step (c) without going through steps (a) and (b); a negative electrode consisting only of a foil of various alloys (lithium alloys such as lithium-aluminum alloys and lithium-indium alloys) or metallic lithium that function as a negative electrode active material, or a negative electrode in which the foil is laminated as an active material layer on a current collector; etc.
  • a negative electrode having a molded body of a negative electrode mixture obtained by molding a negative electrode mixture, which is a mixture of constituent materials such as a negative electrode active material and a solid electrolyte, in a manner similar to that of step (c) without going through steps (a) and (b); a negative electrode consisting only of a foil of various alloys (lithium alloys such
  • the positive electrode when only the negative electrode is an electrode for an all-solid-state battery of the present invention, can be a positive electrode having a molded body of a positive electrode mixture obtained by molding a positive electrode mixture, which is a mixture of constituent materials such as a positive electrode active material and a solid electrolyte, in a manner similar to that of step (c), without going through steps (a) and (b).
  • solid electrolytes constituting the solid electrolyte layer in the power generation element for the all-solid-state battery include the same solid electrolytes as those exemplified above as those usable in the electrodes for the all-solid-state battery.
  • solid electrolytes it is preferable to use a sulfide-based solid electrolyte because it has high lithium ion conductivity and also has the function of improving formability, and it is more preferable to use a sulfide-based solid electrolyte having an argyrodite-type crystal structure, and it is even more preferable to use one represented by the general composition formula (1), the general composition formula (2), or the general composition formula (3).
  • the solid electrolyte layer may have a porous body such as a resin nonwoven fabric as a support.
  • the thickness of the solid electrolyte layer is preferably 10 to 200 ⁇ m.
  • All-solid-state batteries are manufactured by producing at least one of the positive electrode and the negative electrode using the method of manufacturing electrodes for all-solid-state batteries of the present invention to form a power generating element, which is then enclosed in an exterior body.
  • FIG. 1 shows a schematic longitudinal cross-sectional view of an example of an all-solid-state battery of the present invention.
  • the all-solid-state battery 10 shown in FIG. 1 has a power generating element 20 having a positive electrode 21, a negative electrode 22, and a solid electrolyte layer 23 interposed between them, and this power generating element 20 is enclosed in an exterior body formed by an exterior container 60 and a lid 70.
  • External terminals 80, 90 are provided on the underside of the outer container 60 in the figure for electrically connecting to a device to which the all-solid-state battery 10 is applied.
  • the external terminal 80 is also electrically connected to the positive electrode 21 of the power generation element 20 through a conductive path 81.
  • the external terminal 90 is also electrically connected to the negative electrode 22 of the power generation element 20 through a lead 40 and a conductive path 91.
  • the positive electrode 21 constituting the power generating element 20 has a positive electrode mixture layer (a molded body of a positive electrode mixture) 211 and a current collector 212.
  • the negative electrode 22 constituting the power generating element 20 has a negative electrode mixture layer (a molded body of a negative electrode mixture) 221 and a current collector 222.
  • a conductive sheet (metal foil, foamed metal porous body, etc.) 30 is disposed on the surface of the current collector 212 of the positive electrode 21 (the surface opposite the positive electrode mixture layer 211), and the positive electrode 21 is electrically connected to the conductive sheet 30 by contacting the current collector 212, and this conductive sheet 30 is electrically connected to the conductive path 81.
  • a spacer 50 is disposed between the lead 40 and the lid 70, and has the effect of pressing the power generating element 20 toward the conductive sheet 30.
  • the effect of this spacer 50 improves the electrical connection between the lead 40 and the negative electrode 22 and the conductive path 91, the electrical connection between the positive electrode 21 and the conductive sheet 30, and the electrical connection between the conductive sheet 30 and the conductive path 81.
  • FIG. 2 is a vertical cross-sectional view showing a schematic representation of another example of the all-solid-state battery of the present invention.
  • the all-solid-state battery 11 shown in FIG. 2 has an exterior body formed of an exterior can 100, a sealing can 110, and a resin gasket 120 interposed between them, and a power generating element 20 in which a positive electrode 21, a solid electrolyte layer 23, and a negative electrode 22 are laminated is enclosed.
  • the sealing can 110 fits into the opening of the exterior can 100 via a gasket 120, and the open end of the exterior can 100 is tightened inward, causing the gasket 120 to come into contact with the sealing can 110, sealing the opening of the exterior can 100 and creating an airtight structure inside the battery.
  • a current collector 130 is interposed between the positive electrode 21 and the exterior can 100, and the exterior can 100 also serves as a positive electrode terminal by electrically connecting to the positive electrode 21 on its inner surface via the current collector 130.
  • a current collector 131 is interposed between the negative electrode 22 and the sealing can 110, and the sealing can 110 also serves as a negative electrode terminal by electrically connecting to the negative electrode 22 on its inner surface via the current collector 131.
  • the exterior can also serves as a negative electrode terminal
  • the sealing can also serves as a positive electrode terminal.
  • all-solid-state batteries can use a current collector for the positive electrode that is separate from the positive electrode, or a current collector for the negative electrode that is separate from the negative electrode.
  • the positive electrode and the negative electrode can be in direct contact with the inner surface of the outer can or the inner surface of the sealing can without the current collector between them.
  • the power generating element can be manufactured, for example, by bonding a positive electrode, a solid electrolyte layer, and a negative electrode.
  • a solid electrolyte is first pressure-molded to form a solid electrolyte layer, and an electrode for the all-solid-state battery of the present invention (positive electrode or negative electrode) is provided on one side of the solid electrolyte layer, and an electrode for the all-solid-state battery of the present invention (negative electrode or positive electrode) is provided on the other side of the solid electrolyte layer, or an electrode (negative electrode or positive electrode) other than the electrode for the all-solid-state battery of the present invention is bonded to the solid electrolyte layer.
  • the electrode for the all-solid-state battery of the present invention When providing the electrode for the all-solid-state battery of the present invention on the solid electrolyte layer, a method of bonding a separately manufactured electrode for the all-solid-state battery to the solid electrolyte layer can be used, but as described above, the electrode for the all-solid-state battery can also be directly manufactured on the solid electrolyte layer.
  • an all-solid-state battery examples include a battery container having an exterior container and a lid as shown in Figure 1; a flat battery container (coin-shaped, button-shaped, etc.) having an exterior can and a sealing can as shown in Figure 2; and a sheet-shaped battery container made of a resin film or a resin-metal laminate film.
  • the outer container can be made of ceramics or resin.
  • the lid can be made of ceramics, resin, or metal (iron-nickel alloy, iron-based alloy such as iron-nickel-cobalt alloy, etc.).
  • the external terminal and the conductive path connecting the electrodes of the electrode stack and the external terminal can be made of metals such as manganese, cobalt, nickel, copper, molybdenum, silver, palladium, tungsten, platinum, gold, etc., or alloys containing these metals.
  • the outer container and the lid can be sealed by bonding them together with an adhesive, or, if a metal lid is used, the lid side of the side wall of the recess in the outer container can be made of metal (such as an iron-nickel alloy or an iron-based alloy such as an iron-nickel-cobalt alloy) and then welded to the lid to seal.
  • metal such as an iron-nickel alloy or an iron-based alloy such as an iron-nickel-cobalt alloy
  • the exterior can and the sealing can can be made of stainless steel or the like.
  • the exterior can and the sealing can can be sealed using a resin adhesive or a method of crimping with a gasket in between.
  • the gasket can be made of polypropylene, nylon, or the like.
  • fluororesins such as tetrafluoroethylene-perfluoroalkoxyethylene copolymer (PFA), polyphenylene ether (PPE), polysulfone (PSF), polyarylate (PAR), polyethersulfone (PES), polyphenylene sulfide (PPS), polyetheretherketone (PEEK), and other heat-resistant resins with melting points exceeding 240°C can also be used.
  • PFA tetrafluoroethylene-perfluoroalkoxyethylene copolymer
  • PPE polyphenylene ether
  • PSF polysulfone
  • PAR polyarylate
  • PES polyethersulfone
  • PPS polyphenylene sulfide
  • PEEK polyetheretherketone
  • Example 1 ⁇ Preparation of Positive Electrode> Mixture 1 was obtained by mixing 83 parts by mass of LiCo0.98Al0.01Mg0.01O2 (positive electrode active material) having an average particle size of 5 ⁇ m and a coating layer of LiNbO3 formed on the surface , 14 parts by mass of a sulfide-based solid electrolyte ( Li5.8PS4.4Cl1.2 ) having an average particle size of 0.7 ⁇ m , and 3 parts by mass of graphene (conductive assistant) having an average particle size: 8 ⁇ m, a thickness: 10 to 20 nm, and a BET specific surface area: 24 m2/g.
  • LiCo0.98Al0.01Mg0.01O2 positive electrode active material
  • LiNbO3 a coating layer of LiNbO3 formed on the surface
  • Li5.8PS4.4Cl1.2 sulfide-based solid electrolyte
  • graphene conductive assistant
  • the mixture 1 was placed in a powder molding die and pressure-molded using a press at a surface pressure of 1,400 MPa (total pressure was 110 kN, the upper limit of the press used) to produce a composite that was circular in plan view (diameter: 1 cm, area: 0.79 cm2 , porosity: 4%).
  • the composite was pulverized to obtain granules having an average particle size of approximately 300 ⁇ m, and then 65 parts by mass of the granules were mixed with 32 parts by mass of the same sulfide-based solid electrolyte as above, and 3 parts by mass of the same graphene as above to obtain mixture 2.
  • This mixture 2 was placed in a powder molding die and pressure-molded using the same press as above at a surface pressure of 350 MPa (total pressure was 110 kN, the upper limit of the press used), to produce a positive electrode consisting of a positive electrode mixture compact (diameter: 2 cm, area: 3.14 cm2 , thickness: 0.96 mm, porosity: 7%) that was circular in plan view.
  • the ratio of the positive electrode active material, solid electrolyte, and conductive assistant contained in the entire positive electrode mixture was 54:41:5 (mass ratio).
  • a negative electrode mixture was prepared by mixing lithium titanate (Li 4 Ti 5 O 12 ) having an average particle size of 2 ⁇ m, the same sulfide-based solid electrolyte as that used in the positive electrode, and the same graphene (conductive additive) as that used in the positive electrode in a mass ratio of 50:41:9.
  • the same sulfide-based solid electrolyte used for the positive electrode was placed on top of the molded body that would become the positive electrode in the powder molding die, and a press was used to perform pressure molding at a surface pressure of 70 MPa to form a provisional molded layer for the solid electrolyte layer.
  • the negative electrode mixture was then placed on the upper surface of the provisional molded layer for the solid electrolyte layer and pressure molding was performed at a surface pressure of 50 MPa, and a provisional molded layer for the negative electrode was further formed on top of the provisional molded layer for the solid electrolyte layer.
  • the whole was then pressure molded at a surface pressure of 350 MPa (total pressure was 110 kN, the upper limit of the press used), to produce a power generation element in which the positive electrode, a solid electrolyte layer with a thickness of 0.1 mm, and a negative electrode made of a molded body with a thickness of 1.4 mm were stacked.
  • Example 2 A mixture 2 was prepared in the same manner as in Example 1, except that the composite of mixture 1 was pulverized to form granules having an average particle size of about 30 ⁇ m. Further, a positive electrode consisting of a positive electrode mixture compact (diameter: 2 cm, area: 3.14 cm2 , thickness: 0.98 mm, porosity: 9%) was prepared using the mixture 2. A coin-type all-solid-state secondary battery was prepared in the same manner as in Example 1, except that the composite of mixture 1 was pulverized to form granules having an average particle size of about 30 ⁇ m.
  • Comparative Example 1 A positive electrode mixture was prepared by mixing the same positive electrode active material, solid electrolyte, and conductive assistant as those used in Example 1 in a ratio (mass ratio) of 54:41:5. Next, the positive electrode mixture was placed in a powder molding die and pressure-molded using a press at a surface pressure of 350 MPa (total pressure was 110 kN, which was the upper limit of the press used), to prepare a positive electrode consisting of a positive electrode mixture compact (diameter: 2 cm, area: 3.14 cm 2 , thickness: 0.96 mm, porosity: 17%) that was circular in plan view.
  • a coin-type all-solid-state secondary battery was fabricated in the same manner as in Example 1, except that the power generating element was fabricated using the positive electrode.
  • Comparative Example 2 The same positive electrode active material, solid electrolyte, and conductive assistant as those used in Example 1 were mixed in a ratio (mass ratio) of 54:41:5 to prepare a mixture 1.
  • the mixture 1 was placed in a powder molding die and pressure-molded using a press at a surface pressure of 1400 MPa (total pressure was 110 kN, the upper limit of the press used), producing a composite that was circular in plan view (diameter: 1 cm, porosity: 5%).
  • the composite was pulverized to obtain granules having an average particle size of about 30 ⁇ m, and the granules were then placed in a powder molding die and pressure-molded using a press at a surface pressure of 350 MPa (total pressure was 110 kN, which was the upper limit of the press used), to produce a positive electrode consisting of a positive electrode mixture compact (diameter: 2 cm, area: 3.14 cm2 , thickness: 0.96 mm, porosity: 12%) that was circular in plan view.
  • a coin-type all-solid-state secondary battery was fabricated in the same manner as in Example 1, except that the power generating element was fabricated using the positive electrode.
  • the negative electrode and solid electrolyte layer are common to the batteries in the examples and comparative examples, it is believed that the difference in the internal resistance of the batteries directly reflects the difference in the internal resistance of the positive electrode. Therefore, the internal resistance of the positive electrode can be evaluated from the internal resistance of the battery obtained by this measurement.
  • the all-solid-state battery of the present invention can be used for the same purposes as conventionally known all-solid-state batteries (all-solid-state primary batteries or all-solid-state secondary batteries).
  • the electrodes for the all-solid-state battery of the present invention can constitute the all-solid-state battery of the present invention.

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WO2013121642A1 (ja) * 2012-02-17 2013-08-22 ソニー株式会社 二次電池、二次電池の製造方法、二次電池用電極および電子機器
JP2017111954A (ja) * 2015-12-16 2017-06-22 セイコーエプソン株式会社 金属酸化物成膜用組成物、正極複合体、正極複合体の製造方法、電池、および電池の製造方法
JP2018163736A (ja) * 2017-03-24 2018-10-18 セイコーエプソン株式会社 複合体の製造方法、電池の製造方法
JP2023145413A (ja) * 2022-03-28 2023-10-11 Tdk株式会社 全固体電池用電極及び全固体電池

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2013121642A1 (ja) * 2012-02-17 2013-08-22 ソニー株式会社 二次電池、二次電池の製造方法、二次電池用電極および電子機器
JP2017111954A (ja) * 2015-12-16 2017-06-22 セイコーエプソン株式会社 金属酸化物成膜用組成物、正極複合体、正極複合体の製造方法、電池、および電池の製造方法
JP2018163736A (ja) * 2017-03-24 2018-10-18 セイコーエプソン株式会社 複合体の製造方法、電池の製造方法
JP2023145413A (ja) * 2022-03-28 2023-10-11 Tdk株式会社 全固体電池用電極及び全固体電池

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