WO2023234352A1 - 全固体リチウムイオン二次電池及び全固体リチウムイオン二次電池の製造方法 - Google Patents

全固体リチウムイオン二次電池及び全固体リチウムイオン二次電池の製造方法 Download PDF

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WO2023234352A1
WO2023234352A1 PCT/JP2023/020288 JP2023020288W WO2023234352A1 WO 2023234352 A1 WO2023234352 A1 WO 2023234352A1 JP 2023020288 W JP2023020288 W JP 2023020288W WO 2023234352 A1 WO2023234352 A1 WO 2023234352A1
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solid electrolyte
lithium
solid
layer
active material
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English (en)
French (fr)
Japanese (ja)
Inventor
洋介 白鳥
健太 渡辺
健吾 齋藤
伸太郎 安井
雅俊 東海林
幸洋 奥野
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Fujifilm Corp
Tokyo Institute of Technology NUC
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Fujifilm Corp
Tokyo Institute of Technology NUC
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Priority to EP23816109.5A priority Critical patent/EP4535488A4/en
Priority to CN202380039024.5A priority patent/CN119174026A/zh
Priority to JP2024524911A priority patent/JPWO2023234352A1/ja
Publication of WO2023234352A1 publication Critical patent/WO2023234352A1/ja
Priority to US18/963,552 priority patent/US20250096317A1/en
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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
    • H01M10/056—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
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/058—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
    • H01M4/04—Processes of manufacture in general
    • H01M4/0402—Methods of deposition of the material
    • H01M4/0407—Methods of deposition of the material by coating on an electrolyte layer
    • 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
    • H01M4/04—Processes of manufacture in general
    • H01M4/0471—Processes of manufacture in general involving thermal treatment, e.g. firing, sintering, backing particulate active material, thermal decomposition, pyrolysis
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0065—Solid electrolytes
    • H01M2300/0068—Solid electrolytes inorganic
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • the present invention relates to an all-solid lithium ion secondary battery and a method for manufacturing an all-solid lithium ion secondary battery.
  • the all-solid-state lithium ion secondary battery 10 includes, in this order, a negative electrode current collector 1, a negative electrode active material layer 2, a solid electrolyte layer 3, a positive electrode active material layer 4, and a positive electrode current collector 5 when viewed from the negative electrode side.
  • the layers are in contact with each other and have an adjacent structure.
  • electrons (e ⁇ ) are supplied to the negative electrode side, and lithium ions (Li + ) that have migrated through the solid electrolyte layer 3 are accumulated there.
  • lithium ions (Li + ) accumulated in the negative electrode are returned to the positive electrode side through the solid electrolyte layer 3, and electrons are supplied to the operating region 6.
  • a light bulb is used as a model for the operating portion 6, and the light bulb is lit by discharge.
  • a sulfide-based solid electrolyte or an oxide-based solid electrolyte is mainly used.
  • Sulfide-based solid electrolytes are soft and deform plastically, so the particles are bound together just by pressure molding. Therefore, sulfide-based solid electrolytes have low interparticle interfacial resistance and excellent ionic conductivity.
  • sulfide-based solid electrolytes have the problem of reacting with water and generating toxic hydrogen sulfide.
  • Patent Document 1 discloses a solid electrolyte formed of a lithium-containing oxide with a specific elemental composition, and describes that this solid electrolyte exhibits high ionic conductivity. In order to use it as a solid electrolyte sheet, high-temperature sintering treatment is required.
  • Patent Document 2 describes a lithium compound whose lithium ion conductivity at 25°C is 1.0 ⁇ 10 -6 S/cm or more and a lithium compound obtained from X-ray total scattering measurement.
  • a complex with lithium tetraborate is described whose reduced two-body distribution function G(r) exhibits a particular profile.
  • this composite is composed of a lithium-containing oxide, lithium tetraborate plastically deforms between the lithium compounds and plays the role of connecting the lithium compounds, so this It is said that the composite can form a lithium ion conductor exhibiting good lithium ion conductivity by pressure treatment without being subjected to high temperature sintering treatment.
  • Patent Document 2 Although the composite described in Patent Document 2 is composed of a lithium-containing oxide, it is soft and can be used between particles without being subjected to sintering treatment or without adding a binder such as an organic polymer. It can ensure binding, and has properties that conventional oxide-based solid electrolytes have not been able to achieve.
  • a binder such as an organic polymer.
  • the conductivity of lithium ions is not currently sufficient for practical use as a solid electrolyte layer in all-solid-state lithium-ion secondary batteries, and that It has become clear that there is room for improvement.
  • the lithium ion conductivity of the solid electrolyte used in all-solid-state lithium-ion secondary batteries is an essential property for operating all-solid-state lithium-ion secondary batteries as batteries. Furthermore, since secondary batteries are used by repeatedly charging and discharging, all-solid-state lithium-ion secondary batteries are also required to have characteristics (cycle characteristics) in which battery performance does not deteriorate easily even after repeated charging and discharging. This is an important characteristic.
  • the present invention is an all-solid-state lithium ion secondary battery using a lithium-containing oxide as a solid electrolyte layer, wherein the solid electrolyte layer can be formed using organic polymers, for example, without being subjected to high-temperature sintering treatment.
  • An all-solid lithium ion product that has excellent interparticle binding properties, higher lithium ion conductivity, excellent safety, and excellent cycle characteristics even when no binder is added.
  • An object of the present invention is to provide a secondary battery and a method for manufacturing the same.
  • An all-solid lithium ion secondary battery comprising a positive electrode layer, a solid electrolyte layer, and a negative electrode layer arranged in this order,
  • the solid electrolyte layer includes an amorphous solid electrolyte containing a lithium-containing oxide containing Li, B, and O and a lithium salt, and the content of the lithium-containing oxide in the amorphous solid electrolyte is On the other hand, the ratio value of the content of the lithium salt is 0.001 to 1.5 in molar ratio,
  • the moisture content of the laminate consisting of the positive electrode active material layer, the solid electrolyte layer, and the negative electrode active material layer is 7.0% by mass or less based on Karl Fischer titration at 100°C, and Karl Fischer titration at 100°C and 300°C
  • An all-solid-state lithium ion secondary battery in which the difference in water content based on the method is 0.1 to 5.0% by mass.
  • An all-solid lithium ion secondary battery comprising a positive electrode layer, a solid electrolyte layer, and a negative electrode layer arranged in this order,
  • the solid electrolyte layer includes an amorphous solid electrolyte containing a lithium-containing oxide containing Li, B, and O and a lithium salt, and the content of the lithium-containing oxide in the amorphous solid electrolyte is On the other hand, the ratio value of the content of the lithium salt is 0.001 to 1.5 in molar ratio,
  • An all-solid-state lithium ion secondary battery wherein a laminate including a positive electrode active material layer, the solid electrolyte layer, and a negative electrode active material layer is vacuum-dried.
  • the all-solid-state lithium ion secondary battery according to any one of [1] to [4], wherein the lithium-containing oxide has been subjected to mechanical milling treatment.
  • the all-solid-state lithium ion secondary battery is formed by sealing a laminate in which the positive electrode layer, the solid electrolyte layer, and the negative electrode layer are arranged in this order. All-solid-state lithium-ion secondary battery.
  • the method includes subjecting the laminate to vacuum drying treatment. The method for producing an all-solid lithium ion secondary battery according to any one of [1] to [6].
  • a numerical range expressed using “ ⁇ ” means a range that includes the numerical values written before and after " ⁇ " as lower and upper limits.
  • the all-solid-state lithium ion secondary battery of the present invention uses a lithium-containing oxide in the solid electrolyte layer, and the solid electrolyte layer can be made of, for example, an organic polymer without being subjected to high-temperature sintering treatment. Even when such a binder is not blended, it has excellent binding properties between particles, higher lithium ion conductivity, excellent safety, and excellent cycle characteristics. Further, the method for manufacturing an all-solid lithium ion secondary battery of the present invention is a suitable manufacturing method for obtaining the above-mentioned all-solid lithium ion secondary battery of the present invention.
  • FIG. 1 is a cross-sectional view schematically showing an example of the configuration of an all-solid-state lithium ion secondary battery.
  • FIG. 2 is a diagram showing an example of an X-ray diffraction pattern for explaining the X-ray diffraction characteristics of the solid electrolyte (I) used in the present invention.
  • FIG. 3 is a diagram showing an example of the reduced two-body distribution function G(r) obtained from X-ray total scattering measurement of the solid electrolyte (I) used in the present invention.
  • FIG. 4 is a diagram showing an example of a spectrum obtained when solid state 7 Li-NMR measurement of solid electrolyte (I) used in the present invention is performed at 20°C or 120°C.
  • FIG. 1 is a cross-sectional view schematically showing an example of the configuration of an all-solid-state lithium ion secondary battery.
  • FIG. 2 is a diagram showing an example of an X-ray diffraction pattern for explaining the X-ray diffraction
  • FIG. 5 is a diagram showing an example of a spectrum obtained when solid 7 Li-NMR measurement of lithium tetraborate crystal is performed at 20°C or 120°C.
  • FIG. 6 is a diagram showing an example of a spectrum obtained when solid-state 7 Li-NMR measurement of the solid electrolyte (I) used in the present invention is performed at 20°C.
  • FIG. 7 is a diagram in which the peaks shown in FIG. 6 are separated into waveforms.
  • FIG. 8 is a diagram showing an example of a Raman spectrum of the solid electrolyte (I) used in the present invention.
  • FIG. 9 is a diagram showing a Raman spectrum of a lithium tetraborate crystal.
  • FIG. 10 is a diagram showing the reduced two-body distribution function G(r) obtained by X-ray total scattering measurement of powdered Li 2 B 4 O 7 crystal.
  • FIG. 11 is a diagram showing an X-ray diffraction pattern of powdered Li 2 B 4 O 7 crystal.
  • the all-solid-state lithium ion secondary battery of the present invention (hereinafter also referred to as "the secondary battery of the present invention") includes a positive electrode layer, a solid electrolyte layer, and a negative electrode layer arranged in this order.
  • the solid electrolyte layer is formed using an amorphous solid electrolyte having a specific composition, which will be described later.
  • the secondary battery of the present invention is a laminate (excluding a current collector) consisting of a positive electrode active material layer, the solid electrolyte layer, and a negative electrode active material layer, which constitute a laminated structure of a positive electrode layer, a solid electrolyte layer, and a negative electrode layer.
  • the moisture content (water content determined by Karl Fischer titration at 100°C) of the laminated structure) based on Karl Fischer titration at 100°C is 7.0% by mass or less.
  • the water content based on the Karl Fischer titration method can be determined by the method described in the Examples below.
  • the moisture content of the laminate consisting of the positive electrode active material layer, the solid electrolyte layer, and the negative electrode active material layer based on Karl Fischer titration at 100°C is preferably 6.0% by mass or less, more preferably 5.0% by mass or less. It is preferably 4.0% by mass or less, more preferably 3.0% by mass or less, even more preferably 2.0% by mass or less, even more preferably 1.5% by mass or less, and 1.0% by mass or less.
  • This water content is usually 0.2% by mass or more, preferably 0.4% by mass or more, more preferably 0.6% by mass or more, and even more preferably 0.7% by mass or more. Therefore, the moisture content of the laminate consisting of the positive electrode active material layer, the solid electrolyte layer, and the negative electrode active material layer based on Karl Fischer titration at 100°C is preferably 0.2 to 6.0% by mass, and 0.2% by mass. -5.0% by mass is more preferred, 0.4-4.0% by mass is even more preferred, 0.4-3.0% by mass is even more preferred, 0.4-2.0% by mass is even more preferred, 0. The amount is more preferably .6 to 2.0% by weight, and even more preferably 0.7 to 1.5% by weight.
  • the moisture content of the laminate consisting of the positive electrode active material layer, the solid electrolyte layer, and the negative electrode active material layer is 0.1 to 12.0 mass based on the Karl Fischer titration method at 300°C. %, more preferably 0.5 to 10.0% by mass, even more preferably 1.0 to 8.0% by mass, even more preferably 1.5 to 5.0% by mass, and 1.5 to 3.0% by mass. Mass % is more preferred.
  • the secondary battery of the present invention has a difference in water content based on the Karl Fischer titration method at 100°C and 300°C ([Karl at 300°C Water content based on Fischer titration] - [moisture content based on Karl Fischer titration at 100°C]) is 0.1 to 5.0% by mass.
  • This difference in water content is preferably 0.5 to 5.0% by mass, more preferably 1.0 to 5.0% by mass, even more preferably 2.0 to 5.0% by mass, and even more preferably 3.0 to 5.0% by mass. 0% by weight is more preferable, and 3.0 to 4.0% by weight is also preferable.
  • the difference in water content is preferably 0.1 to 4.0% by mass, preferably 0.5 to 4.0% by mass, and preferably 0.5 to 3.0% by mass. It is also preferably 0.5 to 2.0% by mass, and also preferably 0.5 to 1.5% by mass.
  • the solid electrolyte layer constituting the secondary battery of the present invention contains a solid electrolyte of a specific composition in an amorphous state (synonymous with an amorphous state or an amorphous state), or a mixture of this solid electrolyte and other components.
  • This layer is formed into a layer, and is usually formed through a vacuum drying process.
  • the solid electrolyte with a specific composition in an amorphous state before layer formation includes a lithium-containing oxide containing Li, B, and O (hereinafter also referred to as a "lithium-containing oxide”), a lithium salt, and water.
  • the ratio of the content of lithium salt to the content of lithium-containing oxide is 0.001 to 1.5 in terms of molar ratio. It is. Therefore, also in the secondary battery of the present invention, the ratio of the lithium salt content to the lithium-containing oxide content in the solid electrolyte layer is 0.001 to 1.5 in terms of molar ratio. Further, in the amorphous solid electrolyte before layer formation, the ratio of the water content to the lithium-containing oxide content (water/lithium-containing oxide) is preferably 1 to 12 in terms of molar ratio. .
  • solid electrolyte (I) is usually an inorganic solid electrolyte.
  • the solid electrolyte (I) is in an amorphous state and exhibits elastic properties that allow it to easily undergo plastic deformation.
  • the adhesion between the solid electrolytes (I) and/or the solid electrolyte (I) is improved, the interfacial resistance can be reduced, and better ionic conductivity can be obtained.
  • the water contained in the solid electrolyte (I) includes at least bound water. It is not clear why the solid electrolyte (I) exhibits high lithium ion conductivity, but in the solid electrolyte (I) in an amorphous state, a soft hydration layer is easily formed on the surface of the lithium-containing oxide, and this water It is thought that the sum layer contains a large amount of lithium derived from lithium salt, and as a result, the ionic conductivity is further enhanced.
  • bound water means water other than water existing as free water, or an OH group bonded to a lithium-containing oxide.
  • the solid electrolyte (I) Even if the solid electrolyte (I) contains the above amount of water, it is in the state of solid particles (including a state in which solid particles are bound together). That is, the solid electrolyte (I) contains bound water that is not removed or difficult to remove under normal drying conditions. Note that as long as the solid electrolyte (I) can maintain the state of solid particles, part of the water contained in the solid electrolyte (I) may be free water. When the solid electrolyte (I) contains free water, the solid electrolyte layer (laminated body consisting of a positive electrode active material layer, a solid electrolyte layer, and a negative electrode active material layer) formed using this solid electrolyte (I) will be described later. The drying process removes at least a portion of the free water. In addition, a portion of the bound water may be removed depending on the interaction of the bound water with the lithium-containing oxide or lithium salt, and depending on the level of the drying treatment conditions described above.
  • the solid electrolyte (I) being in an "amorphous state” means that it satisfies the following X-ray diffraction characteristics.
  • the first peak is .65° or less
  • the peak top is located in the range of 25.4 to 25.8° with a diffraction angle 2 ⁇
  • the second peak is with a full width at half maximum of 0.65° or less
  • the diffraction angle 2 ⁇ is 33.4
  • the peak top is located in the range of ⁇ 33.8°
  • the third peak has a full width at half maximum of 0.65° or less
  • the peak top is located in the range of the diffraction angle 2 ⁇ of 34.4 to 34.8°
  • peak X at least one peak (hereinafter referred to as "peak X") among the first peak, second peak, third peak, and fourth peak is present, the peak At least one of the peaks has an intensity ratio of 5.0 or less as calculated by the intensity measurement method described below.
  • the average intensity (Av1) in the range of +0.45° to +0.55° is calculated from the diffraction angle 2 ⁇ of the peak top of peak X, and the average intensity (Av1) is calculated from the diffraction angle 2 ⁇ of the peak X of ⁇ 0.55° to ⁇ 0.
  • the average intensity (Av2) in the range of 45° is calculated, and the additive average value of the above Av1 and Av2 is calculated.
  • the value of the ratio of the peak intensity at the peak top of peak X to this additive average value is defined as the intensity ratio.
  • the X-ray diffraction characteristics will be explained in more detail.
  • the solid electrolyte (I) satisfies the above-mentioned X-ray diffraction characteristics and is in an amorphous state.
  • the full width at half maximum (FWHM) of a peak means the peak width (°) at 1/2 point of the peak intensity at the peak top.
  • FIG. 2 is a diagram showing an example of a peak X appearing in a diffraction pattern obtained from X-ray diffraction measurement using CuK ⁇ rays of solid electrolyte (I).
  • a specific peak whose peak top intensity is 1 is shown.
  • the average intensity (Av1) in the range of +0.45° to +0.55° is calculated from the diffraction angle 2 ⁇ at the peak top of peak
  • the average intensity (Av2) in the range of -0.55° to -0.45° from the top diffraction angle 2 ⁇ is calculated.
  • the average value of Av1 and Av2 is calculated, and the ratio of intensity 1 to the average value is determined as the intensity ratio.
  • the first to fourth peaks above are mainly peaks derived from the crystal structure in the solid electrolyte (for example, the crystal structure of lithium tetraborate), and if these peaks do not exist, it is in an amorphous state. It means something.
  • the fact that the intensity ratio of at least one of the peaks X is 5.0 or less means that the solid electrolyte (I) is This means that there is almost no crystal structure that would impede the effects of the invention.
  • a peak derived from a specific component eg, lithium salt
  • the above X-ray diffraction measurement is performed using CuK ⁇ radiation under measurement conditions of 0.01°/step and 3°/min.
  • the intensity ratio of at least one of the peaks X is 3.0 or less. is preferred. Among them, none of the first peak, second peak, third peak and fourth peak are present, or at least one of the first peak, second peak, third peak and fourth peak is present. Even if two peaks X exist, it is more preferable that the intensity ratio of at least one of the peaks X is 2.0 or less.
  • the diffraction X-ray intensity is the highest.
  • a large peak is selected as the first peak, and the above-mentioned X-ray diffraction characteristics are determined.
  • the peak top is located in the range of 25.4 to 25.8° and there are two or more peaks with a full width at half maximum of 0.65° or less, the diffracted X-ray intensity is the highest.
  • a large peak is selected as the second peak, and the above-mentioned X-ray diffraction characteristics are determined.
  • the peak top is located in the range of 33.4 to 33.8° and there are two or more peaks with a full width at half maximum of 0.65° or less, the diffracted X-ray intensity is the highest.
  • a large peak is selected as the third peak, and the above-mentioned X-ray diffraction characteristics are determined.
  • the peak top is located in the range of 34.4 to 34.8 degrees and there are two or more peaks with a full width at half maximum of 0.65 degrees or less, the diffraction X-ray intensity is the highest.
  • the large peak is selected as the fourth peak, and the above-mentioned X-ray diffraction characteristics are determined.
  • the solid electrolyte (I) preferably satisfies the following requirement A-1 in terms of total X-ray scattering properties. Further, when the solid electrolyte (I) satisfies the above-mentioned X-ray diffraction characteristics, this solid electrolyte (I) usually satisfies the following requirement A-2.
  • G(r) obtained from X-ray total scattering measurement of the solid electrolyte (I)
  • the absolute value of G(r) is less than 1.0 in the range where r is more than 5 ⁇ and less than 10 ⁇ .
  • the oxide solid electrolyte (I) When the solid electrolyte (I) satisfies requirements A-1 and A-2, it has a short-range ordered structure related to the interatomic distances of B-O and B-B, but has almost no long-range ordered structure. Therefore, the oxide solid electrolyte itself exhibits elastic properties that are softer than conventional lithium-containing oxides and easily deform plastically. As a result, in the layer containing the solid electrolyte (I) formed by pressure treatment, the adhesion between the solid electrolytes (I) and/or the bond between the solid electrolyte (I) and other ionic conductors is reduced. It is presumed that adhesion is improved, interfacial resistance can be reduced, and better ion conductivity can be obtained. Requirement A-1 and Requirement A-2 will be explained in more detail with reference to the drawings.
  • FIG. 3 shows an example of the reduced two-body distribution function G(r) obtained by X-ray total scattering measurement of the solid electrolyte (I).
  • the vertical axis in FIG. 3 is a reduced two-body distribution function obtained by Fourier transforming X-ray scattering, and indicates the probability that an atom exists at a position at a distance r.
  • X-ray total scattering measurement can be performed with SPring-8 BL04B2 (acceleration voltage 61.4 keV, wavelength 0.2019 ⁇ ).
  • the reduced two-body distribution function G(r) is obtained by converting the scattering intensity I obtained by experiment according to the following procedure. First, the scattering intensity I obs is expressed by the following formula (1).
  • the structure factor S(Q) is obtained by dividing the coherent scattering I coh by the product of the number N of atoms and the square of the atomic scattering factor f, as expressed by the following formula (2).
  • I obs I coh + I in coh + I fluorescence (1)
  • a structure factor S(Q) is used for PDF (Pair Distribution Function) analysis.
  • the only required intensity is the coherent scattering I coh .
  • Incoherent scattering I incoh and X-ray fluorescence I fluorescence can be subtracted from the scattering intensity I obs by blank measurements, subtraction using theoretical formulas, and detector discriminators.
  • the coherent scattering I coh is expressed by Debye's scattering formula (formula (3) below) (N: total number of atoms, f: atomic scattering factor, r ij : interatomic distance between ij).
  • the two-body distribution function g(r) is expressed by the following formula (7).
  • the two-body distribution function can be obtained by Fourier transformation of the structure factor S(Q).
  • g(r) which oscillates around 0, represents the density difference from the average density at each interatomic distance, and if there is a correlation at a specific interatomic distance, the average density will be higher than 1. Therefore, it reflects the distance and coordination number of elements corresponding to local to intermediate distances.
  • ⁇ (r) approaches the average density, so g(r) approaches 1. Therefore, in an amorphous structure, the larger r becomes, the less order there is, so g(r) becomes 1, that is, G(r) becomes 0.
  • r is 1.43 ⁇ 0.2 ⁇ .
  • G(r) obtained from the X-ray total scattering measurement of the solid electrolyte (I)
  • r is 1.43 ⁇ 0.2 ⁇ .
  • the peak top of the first peak P1 is located at 1.43 ⁇
  • the peak top of the second peak P2 is located at 2.40 ⁇ .
  • the absolute value of G(r) is less than 1.0 in the range of more than 5 ⁇ and less than 10 ⁇ .
  • the fact that the absolute value of G(r) is less than 1.0 in the range where r is more than 5 ⁇ and less than 10 ⁇ means that there is almost no long-range ordered structure in the solid electrolyte (I). .
  • the method for bringing the solid electrolyte (I) into an amorphous state there is no particular restriction on the method for bringing the solid electrolyte (I) into an amorphous state.
  • a method of using a mechanically milled lithium-containing oxide as a raw material This mechanical milling process may be performed in the presence of a lithium salt.
  • -Mechanical milling process is a process in which a sample is ground while applying mechanical energy.
  • the mechanical milling treatment include a ball mill, a vibration mill, a turbo mill, and a disk mill, and a ball mill is preferred from the standpoint of obtaining the solid electrolyte (I) in an amorphous state with good productivity.
  • ball mills include vibrating ball mills, rotary ball mills, and planetary ball mills, with planetary ball mills being more preferred.
  • the conditions for ball milling are adjusted as appropriate depending on the object to be processed.
  • the material of the grinding balls (media) is not particularly limited, and examples thereof include agate, silicon nitride, zirconia, alumina, and iron-based alloys, with stabilized zirconia (YSZ) being preferred.
  • the average particle diameter of the grinding balls is not particularly limited, and is preferably 1 to 10 mm, more preferably 3 to 7 mm, from the standpoint of producing solid electrolyte (I) with good productivity.
  • the above average particle diameter is determined by randomly measuring the diameters of 50 grinding balls and taking the arithmetic average of the diameters. If the crushing ball is not perfectly spherical, the major axis is the diameter.
  • the number of grinding balls is not particularly limited.
  • the material of the grinding pot in ball milling is also not particularly limited. Examples include agate, silicon nitride, zirconia, alumina, and iron-based alloys, with stabilized zirconia (YSZ) being preferred.
  • the rotation speed of the ball milling process is not particularly limited, and can be, for example, 200 to 700 rpm, more preferably 350 to 550 rpm.
  • the processing time of the ball mill is not particularly limited and can be, for example, 10 to 200 hours, more preferably 20 to 140 hours.
  • the atmosphere for the ball milling process may be the atmosphere or an inert gas (eg, argon, helium, nitrogen, etc.) atmosphere.
  • Step 1A Mechanically milling the lithium-containing oxide in the presence of a lithium salt
  • Step 2A Mixing the product obtained in Step 1A with water
  • Step 3A Dispersion obtained in Step 2A Step of obtaining solid electrolyte (I) by removing water from
  • the amount of lithium salt used is not particularly limited, and is appropriately adjusted so as to obtain the solid electrolyte (I) defined in the present invention.
  • the amount of water used is not particularly limited.
  • the amount of water used can be 10 to 200 parts by weight, and more preferably 50 to 150 parts by weight, relative to 100 parts by weight of the product obtained in step 1A.
  • the method of mixing the product obtained in Step 1A and water is not particularly limited, and may be mixed all at once, or may be mixed by adding water stepwise to the product obtained in Step 1A. good.
  • ultrasonic treatment may be performed as necessary.
  • the time for the ultrasonic treatment is not particularly limited, and can be, for example, 10 minutes to 5 hours.
  • Step 3A is a step of removing water from the dispersion obtained in Step 2A to obtain solid electrolyte (I).
  • the method for removing water from the dispersion obtained in step 2A is not particularly limited, and water may be removed by heat treatment or vacuum drying treatment.
  • step 0 may be performed in which the lithium-containing oxide is mechanically milled in an environment where no lithium salt is present.
  • Step 1B Mechanically milling the lithium-containing oxide
  • Step 2B Mixing the product obtained in Step 1B with water and lithium salt
  • Step 3B Remove water from the dispersion obtained in Step 2B Step of obtaining solid electrolyte (I)
  • Step 1B The difference between Step 1B and Step 1A is that in Step 1A, mechanical milling is performed in the presence of lithium salt, whereas in Step 1B, mechanical milling is performed without using lithium salt.
  • Step 2B the product obtained in Step 1B, water, and lithium salt are mixed.
  • the procedure of Step 2B is not particularly limited, and it may be a method (method 1) of mixing the product obtained in Step 1B, water, and lithium salt all at once, or a method of mixing the product obtained in Step 1B with water and lithium salt at once, or and water to prepare a dispersion, and then the resulting dispersion and lithium salt may be mixed (Method 2), or the product obtained in Step 1B and water may be mixed.
  • a method may be used in which dispersion 1 is prepared by mixing, solution 2 is prepared by mixing the lithium salt and water, and dispersion 1 and solution 2 are mixed.
  • a dispersion treatment such as ultrasonication may be appropriately performed.
  • Method 2 when mixing a dispersion of the product obtained in Step 1B and water with a lithium salt, if there is too much lithium salt, the resulting liquid tends to gel, and the mixing of the lithium salt is difficult. Quantity is limited.
  • method 3 even if the product obtained in step 1B and the lithium salt are mixed in equimolar amounts, gelation of the liquid is unlikely to occur, and the amount of lithium salt mixed can be increased. . From this point of view, method 3 is preferred.
  • the procedures of Step 3B and Step 3A are the same.
  • Step 1C A step of mechanically milling the lithium-containing oxide
  • Step 2C A step of mixing the product obtained in Step 1C with water
  • Step 3C A process of removing water from the dispersion obtained in Step 2C.
  • Step 1C and Step 1B are the same.
  • the procedures of Step 2C and Step 2A are the same.
  • Step 3C differs from Steps 3A and 3B in that a product obtained by removing water from the dispersion obtained in Step 2C is mixed with a lithium salt.
  • the amount of lithium salt used is not particularly limited, and is appropriately adjusted so as to obtain the solid electrolyte (I) defined in the present invention.
  • the method of mixing the product obtained by removing water from the dispersion obtained in step 2C with the lithium salt is not particularly limited, and the product is impregnated with a solution of the lithium salt dissolved in water, A method of mixing both may be used.
  • the solid electrolyte (I) used in the present invention is an amorphous solid electrolyte, and the ratio of the content of lithium salt to the content of lithium-containing oxide in this solid electrolyte (I) is The value of the molar ratio is 0.001 to 1.5, and the value of the water content ratio is 1 to 12 in molar ratio.
  • the value of the ratio of the content of lithium salt to the content of lithium-containing oxide in solid electrolyte (I) is preferably 0.001 to 1.2 in molar ratio, more preferably 0.01 to 1.2, More preferably 0.1 to 1.2, particularly preferably 0.5 to 1.2.
  • the molar ratio of the water content to the lithium-containing oxide content in the solid electrolyte (I) is more preferably 2 to 12, and even more preferably 3 to 11. Further, this molar ratio is also preferably 2 to 10, preferably 2 to 8, preferably 2 to 7, and also preferably 3 to 7.
  • the molar amounts of the lithium-containing oxide, lithium salt, and water in the solid electrolyte (I) can be determined based on elemental analysis. Moreover, the molar amount of water can also be determined by the Karl Fischer method.
  • the content of water in the solid electrolyte (I) is preferably 50% by mass or less, more preferably 45% by mass or less, even more preferably 40% by mass or less, and even more preferably 35% by mass or less. Further, the content of water in the solid electrolyte (I) is also preferably 30% by mass or less, and preferably 25% by mass or less. Further, the content of water in the solid electrolyte (I) is usually 5% by mass or more, preferably 10% by mass or more, and preferably 15% by mass or more.
  • the content of water in the solid electrolyte (I) is preferably 5 to 50% by mass, more preferably 5 to 45% by mass, even more preferably 10 to 40% by mass, even more preferably 10 to 35% by mass, It is also preferably 10 to 30% by weight, preferably 15 to 30% by weight, and preferably 15 to 25% by weight.
  • the content of the lithium-containing oxide in the solid electrolyte (I) is preferably 20 to 80% by mass, more preferably 20 to 75% by mass, and even more preferably 25 to 70% by mass.
  • the content of the lithium salt in the solid electrolyte (I) is preferably 0.5 to 60% by mass, more preferably 1.0 to 55% by mass, even more preferably 2.0 to 50% by mass, and 5. It is also preferably 0 to 50% by mass.
  • the lithium-containing oxide constituting the solid electrolyte (I) contains Li, B, and O, as described above.
  • the above lithium-containing oxide is represented by Li 2+x B 4+y O 7+z (-0.3 ⁇ x ⁇ 0.3, -0.3 ⁇ y ⁇ 0.3, -0.3 ⁇ z ⁇ 0.3).
  • Such a lithium-containing oxide typically includes lithium tetraborate (Li 2 B 4 O 7 ). Further, the above lithium-containing oxide has Li 1+x B 3+y O 5+z (-0.3 ⁇ x ⁇ 0.3, -0.3 ⁇ y ⁇ 0.3, -0.3 ⁇ z ⁇ 0.3). Also preferred are the compounds represented. Such a lithium-containing oxide typically includes lithium triborate (LiB 3 O 5 ).
  • the above lithium-containing oxide has Li 3+x B 11+y O 18+z (-0.3 ⁇ x ⁇ 0.3, -0.3 ⁇ y ⁇ 0.3, -0.3 ⁇ z ⁇ 0.3). Also preferred are the compounds represented. A typical example of such a lithium-containing oxide is Li 3 B 11 O 18 . Further, the above lithium-containing oxide has Li 3+x B 7+y O 12+z (-0.3 ⁇ x ⁇ 0.3, -0.3 ⁇ y ⁇ 0.3, -0.3 ⁇ z ⁇ 0.3). Also preferred are the compounds represented. A typical example of such a lithium-containing oxide is Li 3 B 7 O 12 .
  • the lithium-containing oxide is preferably at least one of the above Li 2+x B 4+y O 7+z , the above Li 1+x B 3+y O 5+z , Li 3+x B 11+y O 18+ z , and Li 3+x B 7+y O 12+z .
  • lithium-containing oxides such as LiBO 5 , Li 2 B 7 O 12 , LiB 2 O 3 (OH)H 2 O, and Li 4 B 8 O 13 (OH) 2 (H 2 O) 3 and the like can also be used.
  • the lithium-containing oxide is in an amorphous state.
  • the lithium-containing oxide is also in the desired amorphous state in the solid electrolyte (I) so that the solid electrolyte (I) is in the above-mentioned amorphous state.
  • the lithium-containing oxide is preferably amorphous lithium tetraborate.
  • the lithium salt constituting the solid electrolyte (I) used in the present invention is not particularly limited, and examples include salts composed of Li + and anions, preferably salts composed of Li + and organic anions, and Li More preferred is a salt composed of + and an organic anion having a halogen atom.
  • the lithium salt constituting the solid electrolyte (I) used in the present invention is an element of group 3 of the periodic table, an element of group 4 of the periodic table, an element of group 13 of the periodic table, an element of group 14 of the periodic table, an element of group 14 of the periodic table, or an element of group 14 of the periodic table.
  • LiN(R f1 SO 2 ) (R f2 SO 2 ) R f1 and R f2 each independently represent a halogen atom or a perfluoroalkyl group.
  • R f1 and R f2 are perfluoroalkyl groups, the number of carbon atoms in the perfluoroalkyl group is not particularly limited.
  • R f1 and R f2 are preferably a halogen atom or a perfluoroalkyl group having 1 to 6 carbon atoms, more preferably a halogen atom or a perfluoroalkyl group having 1 to 2 carbon atoms, and are halogen atoms. It is even more preferable.
  • R f1 and R f2 are perfluoroalkyl groups, it is preferable that the number of carbon atoms is small.
  • the lithium salt that can be contained in the solid electrolyte (I) used in the present invention is not limited to the compound represented by the above formula (1). Examples of lithium salts that can be included in the solid electrolyte (I) used in the present invention are shown below.
  • Inorganic lithium salts Inorganic fluoride salts such as LiPF 6 , LiBF 4 , LiAsF 6 and LiSbF 6 ; Perhalates such as LiClO 4 , LiBrO 4 and LiIO 4 ; LiAlCl 4 etc. Inorganic chloride salt.
  • Oxalatoborate salts lithium bis(oxalato)borate and lithium difluorooxalatoborate.
  • LiF, LiCl, LiBr, LiI, Li 2 SO 4 , LiNO 3 , Li 2 CO 3 , CH 3 COOLi, LiAsF 6 , LiSbF 6 , LiAlCl 4 and LiB(C 6 H 5 ) 4 , etc. can be mentioned.
  • LiPF 6 , LiBF 4 , LiAsF 6 , LiSbF 6 , LiClO 4 , Li(R f1 SO 2 ), LiN(R f1 SO 2 ) 2 , LiN(FSO 2 ) 2 , or LiN(R f1 SO 2 )(R f2 SO 2 ) is preferable, and LiPF 6 , LiBF 4 , LiN(R f1 SO 2 ) 2 , LiN(FSO 2 ) 2 or LiN(R f1 SO 2 )(R f2 SO 2 ) is more preferable. .
  • R f1 and R f2 each independently represent a perfluoroalkyl group, and the number of carbon atoms is preferably 1 to 6, more preferably 1 to 4, and even more preferably 1 or 2.
  • the lithium salt are LiNO 3 and lithium 1,1,2,2,3,3-hexafluoropropane-1,3-disulfonimide.
  • solid electrolyte (I) The component composition of the solid electrolyte (I) has been explained based on the compounds constituting the solid electrolyte (I). Next, solid electrolyte (I) will be explained from the viewpoint of preferred elemental composition. That is, in one embodiment of the secondary battery of the present invention, the solid electrolyte (I) does not have "lithium-containing oxide” and "lithium salt” as specific items, but is specified by elemental composition as follows, for example. can do.
  • the solid electrolyte (I) used in the present invention has a Li molar amount of 1.58 to 3.49 (preferably 1.58 ⁇ 3.00, more preferably 1.90 ⁇ 3.00, even more preferably 2.00 ⁇ 3.00).
  • the molar amount of B in the solid electrolyte (I) is 4.00
  • the molar amount of O is 6.23 to 25.00 (preferably 6.50 to 23.00, more preferably 8 .00 to 23.00, more preferably 10.00 to 23.00, even more preferably 10.00 to 18.00).
  • the molar amounts of elements other than B, other than Li, and other than O are each 0.001 to 10.00 (preferably 0.001 ⁇ 6.00, more preferably 0.01 ⁇ 5.00).
  • the content of each element is determined by ordinary elemental analysis.
  • elemental analysis for example, Li and B are analyzed using ICP-OES (inductively coupled plasma optical emission spectrometry), N, etc. are analyzed using an inert gas melting method, and for example, F and S are analyzed using combustion ion analysis. Analyze by chromatography. Regarding O, it can be calculated as a difference from the total amount of powder by adding up the analyzed masses of elements other than O. Note that the method for calculating the content of each element is not limited to the above, and the content of other elements may be estimated from the analysis result of the content of one element, taking into consideration the structure of the compound used. Based on the content of each element calculated by elemental analysis, the molar amounts of Li, O, and other elements are calculated when the molar amount of B is 4.00.
  • the solid electrolyte (I) in addition to Li, B, and O, the solid electrolyte (I) further contains an element of group 4 of the periodic table, an element of group 15 of the periodic table, and an element of group 16 of the periodic table.
  • Group 17 elements of the periodic table Si, C, Sc, and Y.
  • Examples of Group 4 elements of the periodic table include Ti, Zr, Hf, and Rf.
  • Group 15 elements of the periodic table include N, P, As, Sb, Bi, and Mc.
  • Group 16 elements of the periodic table include S, Se, Te, Po, and Lv.
  • Group 17 elements of the periodic table include F, Cl, Br, I, At, and Ts.
  • the solid electrolyte (I) may contain three or more types of element (E), preferably 2 to 5 types, and more preferably 2 to 4 types.
  • the second embodiment of the solid electrolyte (I) preferably contains two or more elements (E) selected from F, S, N, P, and C, and F, S, C, and N It is more preferable to contain two or more elements (E) selected from the following, and it is even more preferable to contain three elements (E), F, S, and N.
  • the molar amount of Li is preferably 1.58 to 3.49. That is, when the molar amount of B is 4.00, the relative value of the molar amount of Li is preferably 1.58 to 3.49.
  • the molar amount of Li is preferably 1.58 to 3.00, and preferably 1.90 to 3.00. 00 is more preferable, and 2.00 to 3.00 is even more preferable.
  • the molar amount of O is expressed with the molar amount of B in the solid electrolyte (I) being 4.00.
  • the molar amount of O is preferably 6.23 to 25.00. That is, when the molar amount of B is 4.00, the relative value of the molar amount of O is preferably 6.23 to 25.00.
  • the molar amount of O in the solid electrolyte (I) is expressed as 4.00, the molar amount of O is preferably 6.50 to 23.00, and preferably 8.00 to 23.00. 00 is more preferable, 10.00 to 23.00 is more preferable, and 10.00 to 18.00 is even more preferable.
  • the molar amount of B in the solid electrolyte (I) is 4.00, and the molar amount of element (E) is When expressed, the molar amount of each element (E) is preferably 0.001 to 10.00. That is, when the molar content of B is 4.00, the relative value of the molar content of each element (E) is preferably 0.001 to 10.00. In particular, when the molar amount of B in solid electrolyte (I) is 4.00 and the molar amount of element (E) is expressed, the molar amount of each element (E) is 0.001 to 6.00. Preferably, 0.01 to 5.00 is more preferable.
  • One preferred embodiment of the elemental composition of the solid electrolyte (I) containing one or more (preferably two or more) of the above elements (E) includes Li, B, O, F, S, and N.
  • the molar amount of B is 4.00
  • the molar amount of Li is 1.58 to 3.49 (preferably 1.58 to 3.00, more preferably 1.90 to 3.00, even more preferably is 2.00 to 3.00)
  • the molar amount of O is 6.23 to 25.00 (preferably 6.50 to 23.00, more preferably 8.00 to 23.00, even more preferably 10.00 to 23.00, more preferably 10.00 to 18.00)
  • the molar amount of F is 0.001 to 10.00 (preferably 0.01 to 10.00)
  • S The molar amount of N is 0.001 to 2.00 (preferably 0.01 to 2.00), and the molar amount of N is 0.001 to 1.00 (preferably 0.005 to 1.00).
  • Examples include solid electrolytes.
  • the solid electrolyte (I) used in the present invention is in the above-mentioned amorphous state, and as a result, this solid electrolyte (I) can exhibit the following properties in addition to the above-mentioned X-ray diffraction properties. preferable.
  • the solid electrolyte (I) shall have a full width at half maximum ratio of 50% or less, which is calculated by the following method from the spectrum obtained by performing solid 7 Li-NMR measurements of the solid electrolyte (I) at 20°C and 120°C. is preferable, more preferably 40% or less, and even more preferably 35% or less.
  • the lower limit is not particularly limited, but is often 10% or more.
  • the above full width at half maximum ratio is determined by performing solid 7 Li-NMR measurements of the solid electrolyte (I) at 20°C and 120°C, respectively, and the chemical shift in the spectrum obtained by measurement at 20°C is in the range of -100 to +100 ppm.
  • FIG. 4 shows an example of a spectrum obtained when solid 7 Li-NMR measurement of solid electrolyte (I) is performed at 20°C or 120°C.
  • the solid line spectrum shown on the lower side of FIG. 4 is the spectrum obtained when solid-state 7 Li-NMR measurement was performed at 20°C
  • the broken line spectrum shown on the upper side of FIG. 4 is the spectrum obtained when solid-state 7 Li-NMR measurement was performed. This is a spectrum obtained when the test was carried out at 120°C.
  • solid-state 7 Li-NMR measurements when the mobility of Li + is high, the peaks obtained are sharper.
  • the spectrum at 20°C and the spectrum at 120°C are compared, the spectrum at 120°C is sharper.
  • the mobility of Li + is high due to the presence of Li defects.
  • Such a solid electrolyte (I) is considered to be easily plastically deformed due to the defect structure as described above, and to have excellent Li + hopping properties.
  • the solid line shown at the bottom of Figure 5 is The spectrum measured at 20° C. and the spectrum measured at 120° C. shown by the broken line shown in the upper part of FIG. 5 tend to have substantially the same shape. That is, the lithium tetraborate crystal has no Li defects, and as a result has a high elastic modulus and is difficult to undergo plastic deformation.
  • the Li-NMR measurement conditions for the above solid 7 are as follows. Using a 4 mm HX CP-MAS probe, single pulse method, 90° pulse width: 3.2 ⁇ s, observation frequency: 155.546 MHz, observation width: 1397.6 ppm, repetition time: 15 sec, integration: 1 time, MAS rotation number: Measure at 0Hz.
  • the solid electrolyte (I) used in the present invention shows that when the waveform of the first peak appearing in the range of -100 to +100 ppm is separated in the spectrum obtained when solid-state 7 Li-NMR measurement is performed at 20°C, the chemical It is preferable that the second peak has a full width at half maximum of 5 ppm or less in a shift range of -3 to 3 ppm, and the ratio of the area intensity of the second peak to the area intensity of the first peak is 0.5% or more.
  • the area strength ratio is more preferably 2% or more, more preferably 5% or more, even more preferably 10% or more, even more preferably 15% or more.
  • the solid state 7 Li-NMR spectral characteristics of the solid electrolyte (I) tend to be as described above.
  • the upper limit of the area strength ratio is not particularly limited, but is often 50% or less.
  • FIG. 6 shows an example of a spectrum obtained when solid 7 Li-NMR measurement of solid electrolyte (I) is performed at 20°C.
  • solid electrolyte (I) has a peak (corresponding to the first peak) observed in the range of -100 to +100 ppm, and in this first peak, the chemical shift is around 0 ppm as shown by the broken line. A small peak is observed.
  • FIG. 7 shows the waveform of the first peak separated. As shown in FIG.
  • the first peak is waveform-separated into a small peak (corresponding to the second peak) represented by a solid line and a large peak represented by a broken line.
  • the second peak appears in a chemical shift range of -3 to 3 ppm, and has a full width at half maximum of 5 ppm or less.
  • the solid electrolyte (I) has a ratio of the area intensity of the second peak shown by the solid line in FIG. 7 to the area intensity of the first peak (the peak before waveform separation) shown in FIG.
  • the area intensity/area intensity of the first peak) ⁇ 100 ⁇ is preferably within the above range.
  • a method for waveform separation a method using known software can be mentioned, and an example of the software is Igor Pro, a graph processing software manufactured by WaveMetrics.
  • the solid electrolyte (I) has a coefficient of determination of 0.9400 or more obtained by linear regression analysis using the least squares method in the wave number region of 600 to 850 cm -1 of the Raman spectrum of the solid electrolyte (I). It is preferably 0.9600 or more, more preferably 0.9800 or more. The upper limit is not particularly limited, but is usually 1.0000 or less.
  • Raman imaging is performed as a method for measuring the Raman spectrum.
  • Raman imaging is a microscopic spectroscopy technique that combines Raman spectroscopy with microscopic technology. Specifically, this is a method in which measurement light including Raman scattered light is detected by scanning excitation light over a sample, and the distribution of components is visualized based on the intensity of the measurement light.
  • the measurement conditions for Raman imaging are as follows: 27°C in the atmosphere, excitation light at 532 nm, objective lens at 100x, mapping method point scanning, 1 ⁇ m steps, exposure time per point for 1 second, and integration once.
  • the measurement range is 70 ⁇ m ⁇ 50 ⁇ m.
  • principal component analysis (PCA) processing is performed on the Raman spectrum data to remove noise. Specifically, in the principal component analysis process, spectra are recombined using components with an autocorrelation coefficient of 0.6 or more.
  • FIG. 8 shows an example of the Raman spectrum of the solid electrolyte (I).
  • the vertical axis shows Raman intensity and the horizontal axis shows Raman shift.
  • a coefficient of determination coefficient of determination R 2
  • a regression line is found by the least squares method, and the coefficient of determination R 2 of the regression line is calculated.
  • the coefficient of determination takes a value between 0 (no linear correlation) and 1 (perfect linear correlation of the measured values) depending on the linear correlation of the measured values.
  • the determination coefficient R2 corresponds to the square of the correlation coefficient (Pearson's product moment correlation coefficient). More specifically, in this specification, the coefficient of determination R2 is calculated by the following formula.
  • x 1 and y 1 represent the wave number in the Raman spectrum and the Raman intensity corresponding to that wave number
  • x 2 is the (additive) average of the wave numbers
  • y 2 is the (additive) Raman intensity. Represents the average.
  • FIG. 9 shows a Raman spectrum of a general lithium tetraborate crystal.
  • peaks are observed in the wave number regions of 716 to 726 cm ⁇ 1 and 771 to 785 cm ⁇ 1 , which are derived from its structure.
  • the coefficient of determination is less than 0.9400 when linear regression analysis is performed using the least squares method in the wave number region of 600 to 850 cm ⁇ 1 to calculate the coefficient of determination. That is, the fact that the coefficient of determination is 0.9400 or more indicates that the solid electrolyte (I) contains almost no crystal structure. Therefore, as a result, it is considered that the solid electrolyte (I) has the property of being easily plastically deformed and the property of having excellent Li + hopping property.
  • the solid electrolyte (I) has a value of the ratio of the maximum absorption intensity in the wavenumber region of 3000 to 3500 cm ⁇ 1 to the maximum absorption intensity in the wavenumber region of 800 to 1600 cm ⁇ 1 (3000 to 3500 cm ⁇ 1
  • the maximum absorption intensity in the wave number region/maximum absorption intensity in the wave number region from 800 to 1600 cm ⁇ 1 is preferably 1/5 or more (0.2 or more).
  • the ratio is preferably 3/10 or more, more preferably 2/5 or more.
  • the upper limit is not particularly limited, but is preferably 1 or less.
  • the above infrared absorption spectrum measurement conditions can be as follows. Objective lens: 32x Cassegrain type (NA 0.65), detector: MCT-A, measurement range: 650 to 4000 cm ⁇ 1 , resolution: 4 cm ⁇ 1 , sample cell: Measurement is performed using a diamond cell. The obtained infrared absorption spectrum is corrected to remove signals derived from atmospheric water and CO 2 , and then offset correction is applied to the background to make the absorption intensity 0. Further, after vacuum drying at 40° C. for 2 hours, measurement is performed in the atmosphere.
  • NA 0.65 32x Cassegrain type
  • detector MCT-A
  • measurement range 650 to 4000 cm ⁇ 1
  • resolution 4 cm ⁇ 1
  • sample cell Measurement is performed using a diamond cell. The obtained infrared absorption spectrum is corrected to remove signals derived from atmospheric water and CO 2 , and then offset correction is applied to the background to make the absorption intensity 0. Further, after vacuum drying at 40° C. for 2 hours, measurement is performed in the atmosphere.
  • the ionic conductivity (27° C.) of the solid electrolyte (I) is not particularly limited, but from the viewpoint of application to various uses, it is preferably 1.0 ⁇ 10 ⁇ 5 S/cm or more, and 1.0 ⁇ 10 ⁇ 4 S /cm or more is more preferable, 1.0 ⁇ 10 ⁇ 3 S/cm or more is even more preferable, and 3.0 ⁇ 10 ⁇ 3 S/cm or more is particularly preferable.
  • the upper limit is not particularly limited, but is often 1.0 ⁇ 10 ⁇ 2 S/cm or less.
  • the solid electrolyte (I) exhibits the following characteristics or physical properties.
  • the mass reduction rate when solid electrolyte (I) is heated to 800° C. is preferably 20 to 40% by mass, more preferably 25 to 35% by mass.
  • the mass reduction caused by the heating is considered to be due to the removal of at least the water contained in the solid electrolyte (I).
  • the conductivity of lithium ions can be further improved.
  • heating is performed at a temperature increase rate of 20°C/sec in the range from 25°C to 800°C.
  • a known thermogravimetric differential thermal analysis (TG-DTA) device can be used to measure the amount of mass loss.
  • the above mass reduction rate is ⁇ (mass at 25°C - mass at 800°C)/mass at 25°C ⁇ x 100 Calculated by In measuring the mass reduction rate, the solid electrolyte (I) was previously subjected to vacuum drying at 40° C. for 2 hours. Furthermore, the mass reduction rate is measured in the atmosphere.
  • the solid electrolyte layer constituting the secondary battery of the present invention may contain other components in addition to the solid electrolyte (I).
  • the solid electrolyte layer can include a binder made of an organic polymer.
  • the organic polymer constituting the binder may be particulate or non-particulate. By including the binder, it becomes possible to more reliably prevent cracks from occurring in the solid electrolyte layer or the electrode layer.
  • the solid electrolyte layer may contain another solid electrolyte other than the solid electrolyte (I).
  • Other solid electrolyte means a solid electrolyte in which lithium ions can be moved.
  • an inorganic solid electrolyte is preferable.
  • solid electrolytes include sulfide-based solid electrolytes, oxide-based solid electrolytes, halide-based solid electrolytes, and hydride-based solid electrolytes.
  • an oxide solid electrolyte is preferred, and an oxide solid electrolyte is more preferred.
  • the content of solid electrolyte (I) is preferably 50% by mass or more, more preferably 60% by mass or more, even more preferably 70% by mass or more, also preferably 80% by mass or more, and 90% by mass. % is also preferable.
  • the thickness of the solid electrolyte layer constituting the secondary battery of the present invention is not particularly limited, and can be, for example, 10 to 1000 ⁇ m, preferably 50 to 400 ⁇ m.
  • the positive electrode layer is generally composed of a positive electrode current collector and a positive electrode active material layer, but when the positive electrode current collector also functions as a positive electrode active material layer (in other words, the positive electrode active material layer is In the case where the positive electrode current collector also functions as a positive electrode current collector), it is not necessary to have a two-layer structure of a positive electrode current collector and a positive electrode active material layer, and a single layer structure may be used. Further, the positive electrode active material layer usually contains a solid electrolyte (preferably an inorganic solid electrolyte) together with the positive electrode active material, but it does not need to contain a solid electrolyte.
  • a solid electrolyte preferably an inorganic solid electrolyte
  • the content of the positive electrode active material in the positive electrode active material layer is preferably 50% by mass or more, more preferably 60% by mass or more, even more preferably 70% by mass or more, also preferably 80% by mass or more, and 90% by mass. It is also preferable that
  • the type of the solid electrolyte is not particularly limited.
  • a sulfide-based solid electrolyte can be used from the viewpoint of placing emphasis on flexibility, and an oxide-based solid electrolyte can be used from the viewpoint of placing importance on higher safety. From the viewpoint of achieving both flexibility and safety at a high level, it is preferable to use the solid electrolyte (I) described above. By doing so, the solid electrolyte (I) also acts like a binder for the solid particles contained in the positive electrode layer, and the positive electrode layer can be made more flexible.
  • positive electrode active material itself used in the positive electrode layer
  • positive electrode active materials that can be used in ordinary lithium ion secondary batteries can be used.
  • a preferred form of the positive electrode active material will be explained below.
  • the positive electrode active material is preferably one that can reversibly insert and/or release lithium ions.
  • the positive electrode active material is not particularly limited, and transition metal oxides are preferred, and transition metal oxides containing the transition metal element Ma (one or more elements selected from Co, Ni, Fe, Mn, Cu, and V) are more preferred. preferable.
  • this transition metal oxide contains element Mb (metal elements of group 1 (Ia) of the periodic table other than lithium, elements of group 2 (IIa) of the periodic table, Al, Ga, In, Ge, Sn, Pb, Sb , Bi, Si, P, and B) may be mixed.
  • the mixing amount is preferably 0 to 30 mol% based on the amount of transition metal element Ma (100 mol%). More preferably, it is synthesized by mixing Li/Ma at a molar ratio of 0.3 to 2.2.
  • Specific examples of transition metal oxides include (MA) transition metal oxides having a layered rock salt structure, (MB) transition metal oxides having a spinel structure, (MC) lithium-containing transition metal phosphate compounds, (MD ) lithium-containing transition metal halide phosphoric acid compounds, and (ME) lithium-containing transition metal silicate compounds.
  • transition metal oxides having a (MA) layered rock salt structure are preferred, and LiCoO 2 or LiNi 1/3 Co 1/3 Mn 1/3 O 2 is more preferred.
  • transition metal oxides having a layered rock salt structure examples include LiCoO 2 (lithium cobalt oxide [LCO]), LiNiO 2 (lithium nickel oxide), LiNi 0.85 Co 0.10 Al 0.05 O 2 (nickel cobalt lithium aluminate [NCA]), LiNi 1/3 Co 1/3 Mn 1/3 O 2 (nickel manganese cobalt lithium [NMC]), and LiNi 0.5 Mn 0.5 O 2 (manganese lithium nickelate).
  • transition metal oxides having a spinel structure examples include LiMn 2 O 4 (LMO), LiNi 0.5 Mn 1.5 O 4 ([LNMO]), LiCoMnO 4 , Li 2 FeMn 3 O 8 , Examples include Li 2 CuMn 3 O 8 , Li 2 CrMn 3 O 8 and Li 2 NiMn 3 O 8 .
  • Lithium-containing transition metal phosphate compounds include, for example, olivine-type iron phosphates such as LiFePO 4 and Li 3 Fe 2 (PO 4 ) 3 , Li 2 CoP 2 O 7 (LCP) and LiFeP 2 O 7 Cobalt phosphate salts such as LiCoPO4, and monoclinic NASICON- type vanadium phosphate salts such as Li3V2 ( PO4 ) 3 (lithium vanadium phosphate) may be mentioned.
  • olivine-type iron phosphates such as LiFePO 4 and Li 3 Fe 2 (PO 4 ) 3
  • Li 2 CoP 2 O 7 (LCP) and LiFeP 2 O 7 Cobalt phosphate salts such as LiCoPO4
  • monoclinic NASICON- type vanadium phosphate salts such as Li3V2 ( PO4 ) 3 (lithium vanadium phosphate) may be mentioned.
  • lithium-containing transition metal halide phosphate compound examples include iron fluorophosphates such as Li 2 FePO 4 F, manganese fluorophosphates such as Li 2 MnPO 4 F, and Li 2 CoPO Examples include cobalt fluoride phosphates such as 4F .
  • lithium-containing transition metal silicate compound examples include Li 2 FeSiO 4 , Li 2 MnSiO 4 , and Li 2 CoSiO 4 .
  • the shape of the positive electrode active material is not particularly limited, and is usually particulate.
  • the volume average particle diameter of the positive electrode active material is not particularly limited, and is preferably, for example, 0.1 to 50 ⁇ m.
  • the volume average particle diameter of the positive electrode active material particles can be determined in the same manner as the volume average particle diameter of the negative electrode active material described below.
  • the positive electrode active material obtained by the calcination method may be used after being washed with water, an acidic aqueous solution, an alkaline aqueous solution, or an organic solvent.
  • the surface of the positive electrode active material may be coated with a surface coating agent described later, sulfur or phosphorus, or even with actinic light.
  • the positive electrode active materials may be used alone or in combination of two or more.
  • the current collector that constitutes the positive electrode layer is an electron conductor. Further, the positive electrode current collector is usually in the form of a film sheet. Examples of the constituent material of the positive electrode current collector include aluminum, aluminum alloy, stainless steel, nickel, and titanium, with aluminum or aluminum alloy being preferred. Note that examples of the positive electrode current collector include aluminum or stainless steel whose surface is treated with carbon, nickel, titanium, or silver (thin film formed thereon).
  • the thickness of the positive electrode active material layer constituting the secondary battery of the present invention is not particularly limited, and can be, for example, 5 to 500 ⁇ m, preferably 20 to 200 ⁇ m. Further, the thickness of the positive electrode current collector constituting the secondary battery of the present invention is not particularly limited, and can be, for example, 10 to 100 ⁇ m, preferably 10 to 50 ⁇ m.
  • the negative electrode layer is generally composed of a negative electrode current collector and a negative electrode active material layer, but when the negative electrode current collector also functions as a negative electrode active material layer (in other words, the negative electrode active material layer is In the case where it also functions as a negative electrode current collector), it is not necessary to have a two-layer structure of a negative electrode current collector and a negative electrode active material layer, and it may be a single-layer structure. Further, the negative electrode active material layer usually contains a solid electrolyte (preferably an inorganic solid electrolyte) together with the negative electrode active material, but it may not contain a solid electrolyte.
  • a solid electrolyte preferably an inorganic solid electrolyte
  • the content of the negative electrode active material in the negative electrode active material layer is preferably 50% by mass or more, more preferably 60% by mass or more, even more preferably 70% by mass or more, also preferably 80% by mass or more, and 90% by mass. It is also preferable that
  • the type of the solid electrolyte is not particularly limited.
  • a sulfide-based solid electrolyte can be used from the viewpoint of placing emphasis on flexibility, and an oxide-based solid electrolyte can be used from the viewpoint of placing importance on higher safety. From the viewpoint of achieving both flexibility and safety at a high level, it is preferable to use the solid electrolyte (I) described above. By doing so, the solid electrolyte (I) also acts like a binder for the solid particles contained in the negative electrode layer, and the negative electrode layer can be made more flexible.
  • negative electrode active material itself used in the negative electrode layer
  • a wide variety of negative electrode active materials that can be used in ordinary lithium ion secondary batteries can be used.
  • a preferred form of the negative electrode active material will be explained below.
  • the negative electrode active material is preferably one that can reversibly insert and release lithium ions.
  • the negative electrode active material is not particularly limited, and includes, for example, a carbonaceous material, an oxide of a metal or metalloid element, lithium alone, a lithium alloy, and a negative electrode active material capable of forming an alloy with lithium.
  • the carbonaceous material used as the negative electrode active material is a material consisting essentially of carbon.
  • carbon black such as acetylene black (AB)
  • graphite natural graphite and artificial graphite such as vapor-grown graphite
  • PAN polyacrylonitrile
  • furfuryl alcohol resin examples include carbonaceous materials made by firing synthetic resins.
  • various carbon fibers such as PAN carbon fiber, cellulose carbon fiber, pitch carbon fiber, vapor grown carbon fiber, dehydrated PVA (polyvinyl alcohol) carbon fiber, lignin carbon fiber, glassy carbon fiber, and activated carbon fiber.
  • graphite mesophase microspheres, graphite whiskers, and tabular graphite.
  • carbonaceous materials can also be divided into non-graphitizable carbonaceous materials (also referred to as hard carbon) and graphite-based carbonaceous materials depending on the degree of graphitization.
  • carbonaceous materials have the lattice spacing, density, or crystallite size described in JP-A-62-022066, JP-A-2-006856, and JP-A-3-045473. It is preferable to have.
  • the carbonaceous material does not need to be a single material, and may include a mixture of natural graphite and artificial graphite described in JP-A-5-090844, and graphite with a coating layer as described in JP-A-6-004516. You can also use As the carbonaceous material, hard carbon or graphite is preferable, and graphite is more preferable.
  • the oxide of a metal element or metalloid element that can be applied as a negative electrode active material is not particularly limited as long as it is an oxide that can absorb and release lithium, and oxides of metal elements (metal oxides) and oxides of metal elements can be used. Examples include composite oxides, composite oxides of metal elements and metalloid elements, and oxides of metalloid elements (metalloid oxides). Note that composite oxides of metal elements and composite oxides of metal elements and metalloid elements are collectively referred to as metal composite oxides. As these oxides, amorphous oxides are preferable, and chalcogenides, which are reaction products of metal elements and elements of group 16 of the periodic table, are also preferable.
  • a metalloid element refers to an element that exhibits intermediate properties between metallic elements and nonmetallic elements, and usually includes six elements: boron, silicon, germanium, arsenic, antimony, and tellurium, and further includes selenium, Contains three elements: polonium and astatine.
  • amorphous means a substance that has a broad scattering band with an apex in the 2 ⁇ value range of 20 to 40 degrees when measured by X-ray diffraction using CuK ⁇ rays, and has a crystalline diffraction line. You may.
  • the strongest intensity among the crystalline diffraction lines seen between 40 and 70 degrees in 2 ⁇ values is less than 100 times the diffraction line intensity at the top of the broad scattering band seen at 20 to 40 degrees in 2 ⁇ values. It is preferably 5 times or less, more preferably 5 times or less, and even more preferably not having any crystalline diffraction lines.
  • amorphous oxides of metalloid elements or the above-mentioned chalcogenides are more preferable, and elements of groups 13 (IIIB) to 15 (VB) of the periodic table (e.g. , Al, Ga, Si, Sn, Ge, Pb, Sb, and Bi) or a (composite) oxide or chalcogenide consisting of one selected from the group consisting of one type or a combination of two or more thereof.
  • Amorphous oxides and chalcogenides include Ga 2 O 3 , GeO, PbO, PbO 2 , Pb 2 O 3 , Pb 2 O 4 , Pb 3 O 4 , Sb 2 O 3 , Sb 2 O 4 , Sb 2 O 8 Bi 2 O 3 , Sb 2 O 8 Si 2 O 3 , Sb 2 O 5 , Bi 2 O 3 , Bi 2 O 4 , GeS, PbS, PbS 2 , Sb 2 S 3 or Sb 2 S 5 are preferred.
  • Examples of negative electrode active materials that can be used in conjunction with amorphous oxide negative electrode active materials mainly containing Sn, Si, or Ge include carbonaceous materials that can absorb and/or release lithium ions or lithium metal, and lithium alone. , a lithium alloy, or a negative electrode active material that can be alloyed with lithium.
  • the oxide of a metal element or metalloid element (particularly a metal (composite) oxide) and the chalcogenide preferably contain at least one of titanium and lithium as a constituent from the viewpoint of high current density charge/discharge characteristics.
  • metal composite oxides containing lithium include composite oxides of lithium oxide and the aforementioned metal oxides, the aforementioned metal composite oxides, or the aforementioned chalcogenides. More specifically, Li 2 SnO 2 is mentioned. It is also preferable that the negative electrode active material (eg, metal oxide) contains a titanium element (titanium oxide).
  • Li 4 Ti 5 O 12 lithium titanate [LTO]
  • Li 4 Ti 5 O 12 has excellent rapid charging and discharging characteristics due to small volume fluctuations when lithium ions are inserted and released, suppresses electrode deterioration, and is an all-solid lithium oxide. This is preferable in that it is possible to improve the life of the ion secondary battery.
  • the lithium alloy as a negative electrode active material is not particularly limited as long as it is an alloy commonly used as a negative electrode active material of all-solid-state lithium ion secondary batteries, and examples thereof include lithium aluminum alloys.
  • the negative electrode active material capable of forming an alloy with lithium is not particularly limited as long as it is commonly used as a negative electrode active material of all-solid-state lithium ion secondary batteries.
  • the negative electrode active material include negative electrode active materials (alloys) containing silicon element or tin element, and various metals such as Al and In. (element-containing active material) is preferable, and a silicon element-containing active material in which the content of silicon element is 50 mol % or more of all constituent elements is more preferable.
  • negative electrodes containing these negative electrode active materials are more expensive than carbon negative electrodes (such as graphite and acetylene black).
  • carbon negative electrodes such as graphite and acetylene black.
  • silicon element-containing active materials include silicon materials such as Si and SiOx (0 ⁇ x ⁇ 1), and silicon-containing alloys containing titanium, vanadium, chromium, manganese, nickel, copper, or lanthanum (e.g. , LaSi 2 , VSi 2 , La-Si, Gd-Si, and Ni-Si), or structured active materials (eg, LaSi 2 /Si).
  • silicon-containing alloys containing titanium, vanadium, chromium, manganese, nickel, copper, or lanthanum e.g. , LaSi 2 , VSi 2 , La-Si, Gd-Si, and Ni-Si
  • structured active materials eg, LaSi 2 /Si
  • Other examples include active materials containing silicon and tin elements, such as SnSiO 3 and SnSiS 3 .
  • SiOx itself can be used as a negative electrode active material (semi-metal oxide), and since SiOx generates Si when an all-solid-state lithium ion secondary battery is operated, it is a negative electrode active material that can be alloyed with lithium. (its precursor substance).
  • the negative electrode active material containing the tin element include Sn, SnO, SnO 2 , SnS, SnS 2 , and active materials containing the silicon element and tin element described above.
  • the negative electrode active material is preferably a negative electrode active material that can be alloyed with lithium, more preferably the silicon material or silicon-containing alloy (alloy containing silicon element), and silicon (Si) or a silicon-containing alloy. More preferred.
  • Titanium niobium composite oxide has a high theoretical volume capacity density, and is expected to have a long life and be capable of rapid charging.
  • examples of the titanium niobium composite oxide include TiNb 2 O 7 and the like.
  • the shape of the negative electrode active material is not particularly limited, a particulate shape is preferable.
  • the volume average particle diameter of the negative electrode active material is not particularly limited, but is preferably 0.1 to 60 ⁇ m, more preferably 0.5 to 20 ⁇ m, and even more preferably 1.0 to 15 ⁇ m.
  • the volume average particle diameter is measured by the following procedure. A 1% by mass dispersion of the negative electrode active material is prepared by diluting it with water (heptane in the case of a substance unstable in water) in a 20 mL sample bottle. The diluted dispersion sample is irradiated with 1 kHz ultrasonic waves for 10 minutes, and immediately thereafter used for the test.
  • the negative electrode active materials may be used alone or in combination of two or more.
  • the surface of the negative electrode active material may be coated with another metal oxide.
  • Surface coating agents include metal oxides containing Ti, Nb, Ta, W, Zr, Al, Si or Li. Specific examples include spinel titanate, tantalum oxides, niobium oxides, and lithium niobate compounds, such as Li 4 Ti 5 O 12 , Li 2 Ti 2 O 5 , LiTaO 3 , LiNbO 3 , LiAlO2 , Li2ZrO3 , Li2WO4 , Li2TiO3 , Li2B4O7 , Li3PO4 , Li2MoO4 , Li3BO3 , LiBO2 , Li2CO3 , Examples include Li 2 SiO 3 , SiO 2 , TiO 2 , ZrO 2 , Al 2 O 3 , B 2 O 3 and Li 3 AlF 6 . Further, the electrode surface containing the negative electrode active material may be surface-treated with sulfur or phosphorus. Furthermore, the particle surface of the negative electrode active
  • the current collector that constitutes the negative electrode layer is an electron conductor. Further, the negative electrode current collector is usually in the form of a film sheet. Examples of the constituent material of the negative electrode current collector include aluminum, copper, copper alloy, stainless steel, nickel, and titanium, with aluminum, copper, copper alloy, or stainless steel being preferred. Note that examples of the negative electrode current collector include aluminum, copper, copper alloy, or stainless steel whose surface is treated with carbon, nickel, titanium, or silver.
  • the thickness of the negative electrode active material layer constituting the secondary battery of the present invention is not particularly limited, and can be, for example, 5 to 500 ⁇ m, preferably 20 to 200 ⁇ m. Further, the thickness of the negative electrode current collector constituting the secondary battery of the present invention is not particularly limited, and may be, for example, 10 to 100 ⁇ m, preferably 10 to 50 ⁇ m.
  • the positive electrode layer and the negative electrode layer may contain components other than the solid electrolyte and other than the active material (other components) in their active material layers.
  • a conductive additive may be included.
  • the conductive aid those known as general conductive aids can be used.
  • conductive aids include electronically conductive materials such as graphites such as natural graphite and artificial graphite, carbon blacks such as acetylene black, Ketjen black, and furnace black, and amorphous materials such as needle coke.
  • Examples include fibrous carbon such as carbon, vapor-grown carbon fiber, and carbon nanotubes, and carbonaceous materials such as graphene and fullerene.
  • conductive polymers such as polyaniline, polypyrrole, polythiophene, polyacetylene, and polyphenylene derivatives may also be used.
  • ordinary conductive aids that do not contain carbon atoms, such as metal powder or metal fibers may be used.
  • a conductive additive is one that does not insert or release Li when a battery is charged or discharged, and does not function as an active material. Therefore, among conductive aids, those that can function as active materials in the active material layer when the battery is charged and discharged are classified as active materials rather than conductive aids. Whether or not it functions as an active material when charging and discharging a battery is not unique, but is determined by the combination with the active material.
  • Other components include the above-mentioned binder and lithium salt.
  • the secondary battery of the present invention can be manufactured with reference to a conventional method for manufacturing an all-solid secondary battery, except for using solid electrolyte (I) at least in the solid electrolyte layer.
  • solid electrolyte (I) at least in the solid electrolyte layer.
  • the production of the secondary battery of the present invention is carried out.
  • the method for manufacturing a secondary battery of the present invention includes obtaining a laminate including a positive electrode layer, a solid electrolyte layer, and a negative electrode layer arranged in this order.
  • the positive electrode active material layer and the negative electrode active material layer are It is preferable to include a step of subjecting the laminate including the solid electrolyte layer and the negative electrode active material layer to a drying treatment. This drying step may be performed at any stage after forming the laminate.
  • the drying treatment it is preferable to subject the drying treatment to a laminate in which at least a positive electrode layer, a solid electrolyte layer, and a negative electrode layer are arranged in this order in a battery cell.
  • the drying method is not particularly limited, and for example, the positive electrode active material layer, the solid electrolyte layer, and the negative electrode active material may be dried using a desiccator, subjected to vacuum drying (preferably freeze-vacuum drying), or subjected to heat treatment.
  • the moisture content of a laminate consisting of layers can be reduced to within the range defined by the present invention.
  • the secondary battery of the present invention is preferably formed by sealing a laminate in which the above-described positive electrode layer, solid electrolyte layer, and negative electrode layer are arranged in this order.
  • sealing it is possible to more reliably prevent moisture from entering the solid electrolyte layer after the drying step, and the cycle characteristics can be further improved.
  • the sealing method is not particularly limited, as long as it can completely block or suppress the ingress of moisture (atmosphere).
  • the laminate is sealed by closing the lid of the casing (battery cell) that houses the laminate in which the above-mentioned positive electrode layer, solid electrolyte layer, and negative electrode layer are arranged in this order through a gasket such as an O-ring. For example, how to stop it.
  • a positive electrode forming composition (slurry) containing a positive electrode active material is applied onto a metal foil that is a positive electrode current collector to form a positive electrode active material layer, and then, on this positive electrode active material layer, A solid electrolyte layer forming dispersion (slurry) containing a solid electrolyte is applied to form a solid electrolyte layer, and a negative electrode forming composition (slurry) containing a negative electrode active material is further applied on the solid electrolyte layer.
  • a negative electrode active material layer is formed, and a negative electrode current collector (metal foil) is placed on the negative electrode active material layer. If necessary, the entire structure is dried and subjected to pressure treatment to obtain an all-solid-state lithium ion secondary battery as shown in FIG. In addition, by reversing the formation method of each layer, a negative electrode active material layer, a solid electrolyte layer, and a positive electrode active material layer are formed on the negative electrode current collector, and if necessary, the whole is subjected to pressure treatment to form an all-solid lithium layer. It is also possible to manufacture ion secondary batteries.
  • Another method is to fabricate a positive electrode active material layer, a solid electrolyte layer, and a negative electrode active material layer separately, laminate them, dry if necessary, and apply pressure to form an all-solid lithium ion secondary layer. Batteries can also be manufactured. In this case, in forming each layer, a support such as a nonwoven fabric may be provided as necessary to make each layer a self-supporting film. Note that the manufacturing method of the secondary battery of the present invention is not limited to that described above as long as the secondary battery defined by the present invention can be obtained.
  • the action of the oxide-based solid electrolyte (I), which can be easily plastically deformed under pressure, can be applied between solid particles or between layers. It is possible to form a layer with reduced interfacial resistance.
  • the solid electrolyte (I) itself is soft and plastically deformable, acts like a binder, and contributes to improving the binding between solid particles or layers, so layer formation is possible without using a binder such as an organic polymer. It is also possible to do so.
  • the secondary battery of the present invention is preferably initialized after manufacture or before use.
  • the method of initialization is not particularly limited, and for example, initial charging and discharging may be carried out under a high press pressure, and then the pressure may be released until the pressure falls within the range of pressure conditions during use of the secondary battery. I can do it.
  • the secondary battery of the present invention can be applied to various uses. There are no particular restrictions on how it can be applied, but for example, when installed in electronic devices, it can be used in notebook computers, pen input computers, mobile computers, e-book players, mobile phones, cordless phone handsets, pagers, handy terminals, mobile fax machines, mobile phones, etc. Examples include photocopiers, portable printers, headphone stereos, video movies, LCD televisions, handy cleaners, portable CDs, mini discs, electric shavers, walkie talkies, electronic organizers, calculators, memory cards, portable tape recorders, radios, and backup power supplies.
  • consumer products include automobiles, electric vehicles, motors, lighting equipment, toys, game equipment, road conditioners, watches, strobes, cameras, and medical equipment (pacemakers, hearing aids, shoulder massagers, etc.). Furthermore, it can be used for various military purposes and space purposes. It can also be combined with solar cells.
  • LiFSI chemical formula: Li(FSO 2 ) 2 N
  • LiFSI lithium salt
  • the obtained powder was added to water so that the powder concentration was 42% by mass, and ultrasonically dispersed for 30 minutes.
  • the obtained dispersion liquid was transferred to a glass Petri dish and dried at 120° C. for 2 hours in the atmosphere to obtain a solid electrolyte film.
  • the obtained film was peeled off to obtain powdered solid electrolyte (I)-1.
  • the powdered solid electrolyte (I)-1 obtained above was compacted at 27° C. (room temperature) and an effective pressure of 220 MPa to obtain a solid electrolyte compact (compact 1).
  • the powder compact 1 has a cylindrical shape with a diameter of 10 mm and a thickness of 0.5 to 1 mm.
  • the ionic conductivity of the compact 1 was 1.5 ⁇ 10 ⁇ 4 S/cm at 27°C and 4.0 ⁇ 10 at 60°C. -4 S/cm.
  • the ionic conductivity of the solid electrolyte (I)-1 was measured at 1 Hz under the conditions of a measurement temperature of 27°C or 60°C and an applied voltage of 50 mV, with two In foil electrodes placed to sandwich the powder compact 1. It was calculated by measuring the AC impedance between both In electrodes in a measurement frequency range of ⁇ 1 MHz and analyzing the arc diameter of the obtained Cole-Cole plot (Nyquist plot).
  • a typical lithium tetraborate crystal has a structure in which BO 4 tetrahedrons and BO 3 triangles exist in a 1:1 ratio (diborate structure), and it is assumed that this structure is maintained in solid electrolyte (I)-1. .
  • the ratio ⁇ (full width at half maximum 2/full width at half maximum 1) ⁇ 100 ⁇ was 33%.
  • the chemical shift was found to be in the range of -3 to 3 ppm, with a full width at half maximum. It had a second peak of 5 ppm or less, and the ratio of the area intensity of the second peak to the area intensity of the first peak was 4%.
  • Solid electrolyte (I)-2 was subjected to various evaluations in the same manner as in Reference Example 1 under atmospheric conditions. The results are summarized in the table below.
  • LiFSI chemical formula: Li(FSO 2 ) 2 N
  • solution 2 3.25 g of LiFSI (chemical formula: Li(FSO 2 ) 2 N) as a lithium salt was added to water at a concentration of 87% by mass, and sonicated for 60 minutes to obtain solution 2. .
  • the obtained dispersion liquid 1 and solution 2 were mixed and stirred and mixed using a magnetic stirrer for 60 minutes.
  • the obtained dispersion was vacuum dried at 40° C. and 10 Pa for 15 hours to obtain a powdery solid electrolyte (I)-3.
  • the obtained powder was allowed to stand in the atmosphere for a certain period of time, and various evaluations were conducted in the atmosphere in the same manner as in Reference Example 1 using solid electrolyte (I)-3.
  • the results are summarized in the table below.
  • Dispersion 3 was obtained in the same manner as in the preparation of Dispersion 1 in Reference Example 3. Next, 2.32 g of LiFSI (chemical formula: Li(FSO 2 ) 2 N) as a lithium salt was added to water at a concentration of 87% by mass, and sonicated for 60 minutes to obtain solution 4. The obtained dispersion liquid 3 and solution 4 were mixed and stirred and mixed using a magnetic stirrer for 60 minutes. Subsequently, the obtained dispersion was vacuum dried at 40° C. and 10 Pa for 15 hours to obtain powdered solid electrolyte (I)-4. The obtained powder was allowed to stand in the atmosphere for a certain period of time, and various evaluations were conducted in the atmosphere in the same manner as in Reference Example 1 using solid electrolyte (I)-4. The results are summarized in the table below.
  • LiFSI chemical formula: Li(FSO 2 ) 2 N
  • Dispersion 5 was obtained in the same manner as in the preparation of Dispersion 1 in Reference Example 3. Next, 4.65 g of LiFSI (chemical formula: Li(FSO 2 ) 2 N) as a lithium salt was added to water at a concentration of 87% by mass, and sonicated for 60 minutes to obtain solution 6. The obtained dispersion liquid 5 and solution 6 were mixed and stirred and mixed using a magnetic stirrer for 60 minutes. Subsequently, the obtained dispersion was vacuum dried at 40° C. and 10 Pa for 15 hours to obtain powdery solid electrolyte (I)-5. The obtained powder was immediately subjected to various evaluations in the same manner as in Reference Example 1 under atmospheric conditions. The results are summarized in the table below.
  • LiFSI chemical formula: Li(FSO 2 ) 2 N
  • Dispersion 7 was obtained in the same manner as in the preparation of Dispersion 1 in Reference Example 3. Next, 7.13 g of LiTFSI (chemical formula: Li(F 3 CSO 2 ) 2 N) as a lithium salt was added to water at a concentration of 87% by mass, and sonicated for 60 minutes to obtain solution 8. The obtained dispersion liquid 7 and solution 8 were mixed and stirred and mixed using a magnetic stirrer for 60 minutes. Subsequently, the obtained dispersion was vacuum dried at 40° C. and 10 Pa for 15 hours to obtain powdered solid electrolyte (I)-6.
  • LiTFSI chemical formula: Li(F 3 CSO 2 ) 2 N
  • the peak top is the first peak located at 1.40 ⁇ (corresponding to the BO proximity), the peak There was a second peak (corresponding to the vicinity of BB) whose top was located at 2.40 ⁇ , and the G(r) at the top of the first and second peaks was 1.0 or more (see FIG. 10).
  • the absolute value of G(r) at the peak top of each peak is 1. It clearly exceeded 0 (see Figure 10).
  • FIG. 11 shows the X-ray diffraction pattern of the LBO powder of Comparative Reference Example 1.
  • a plurality of narrow peaks were observed in the LBO powder used in Comparative Reference Example 1. More specifically, the strongest peak corresponding to the (1,1,2) plane was observed at a 2 ⁇ value of 21.78°.
  • Other main diffraction peaks include a peak corresponding to the (2,0,2) plane at the position of 25.54°, a peak corresponding to the (2,1,3) plane at the position of 33.58°, 34.
  • a peak corresponding to the (3,1,2) plane appeared at the 62° position, and the intensities of these three peaks were almost equal. These peaks are derived from crystalline components.
  • the "Short distance G(r)" column is marked as "A”, and in other cases, it is marked as "B".
  • the "Elemental analysis” column shows the composition of the solid electrolyte (I) obtained in each reference example and the lithium-containing oxide in each comparative reference example relative to the B content of "4.00". The value is expressed as the molar amount of each element.
  • area intensity ratio is the ratio of the area intensity of the second peak to the area intensity of the first peak in the solid-state 7 Li-NMR measurement described above, and the evaluation results based on the following criteria are described.
  • the "maximum absorption intensity ratio" column indicates whether the above-mentioned infrared absorption spectrum characteristics are satisfied, and is [maximum absorption intensity in the wave number region of 3000 to 3500 cm -1 ]/[800 to 1600 cm -1 wave number region] is 0.20 or more is indicated as A, and less than 0.20 is indicated as B.
  • "-" means that no measured value is shown.
  • the drying time was 5 minutes, the pressure was 200 Pa, and the free water was considered to be in a vaporized state, but the ionic conductivity was a high value of 3.8 ⁇ 10 -3 S/cm. Even at a drying time of 1080 minutes and a pressure of 15 Pa, the ionic conductivity was 5.7 ⁇ 10 ⁇ 4 S/cm. This result indicates that bound water other than free water exists and contributes to ionic conductivity.
  • a solid electrolyte (I) was prepared in the same manner as in Reference Example 7, except that LiTFSI was changed to LiFSI, and the contents of water and LiFSI in the obtained solid electrolyte (I) were changed to the amounts listed in the table below.
  • )-9 to (I)-13 were obtained, and various evaluations were conducted in the same manner as in Reference Example 1 under air. The results are summarized in the table below. However, in Reference Example 13, the powder obtained by vacuum drying was immediately evaluated in the atmosphere.
  • the "Lithium-containing oxide fines” column, the “Lithium salt” column, and the “Water” column represent relative molar ratios.
  • the molar ratio of the lithium salt to the fine lithium-containing oxide is 1, and the molar ratio of water to the fine lithium-containing oxide is 11.
  • the said molar ratio was calculated by the following method.
  • lithium and boron were quantitatively analyzed by ICP-OES, fluorine and sulfur were quantitatively analyzed by combustion ion chromatography (combustion IC), and for N, the analytical mass of sulfur was determined by considering the atomic weight of each element in Li salt.
  • the analyzed mass of elements other than O was added up and calculated as the difference from the total amount of solid electrolyte.
  • the carbon content was estimated from the analytical mass of sulfur in consideration of each atomic weight in the lithium salt.
  • the molar ratio between the lithium-containing oxide fines and the lithium salt in the solid electrolyte was calculated from the molar ratio of an element (for example, B) found only in the lithium-containing oxide fines and an element found only in the lithium salt.
  • the molar ratio of lithium-containing oxide fines to water is calculated by subtracting the molar ratio of O contained in lithium-containing oxide fines and lithium salt from the molar ratio of O in the solid electrolyte.
  • the molar amount of derived O was calculated and calculated using the obtained molar amount of O derived from water and the molar amount of fine particles of the lithium-containing oxide.
  • the solid electrolytes of each reference example had desired characteristics or physical properties and exhibited excellent ionic conductivity.
  • the obtained powder was stored in a desiccator (5%) for several days and then analyzed in the atmosphere, it was confirmed that it had the above-mentioned X-ray diffraction characteristics and was in an amorphous state. Further, when the ionic conductivity was measured using the method described above, it was found to be 4.5 ⁇ 10 ⁇ 3 S/cm. Further, the ratio of the LiFSI content to the content of the lithium-containing oxide was 1 in molar ratio, and the ratio of the water content was 9 in molar ratio.
  • CNT carbon nanotubes
  • the multilayer coating film was dried by storing it in a desiccator at a relative humidity of 5% or less for 12 hours, and punched out to a diameter of 10 mm using a hand punch to form the positive electrode side laminate (solid electrolyte layer/positive electrode active material layer/Al current collector). Obtained. Note that the thickness of the solid electrolyte layer was approximately 60 ⁇ m.
  • the multilayer coating film was dried by storing it in a desiccator at a relative humidity of 5% or less for 12 hours, and punched out into a 10 mm diameter piece with a hand punch to obtain a negative electrode side laminate (solid electrolyte layer/negative electrode material layer/Al current collector). Ta. Note that the thickness of the solid electrolyte layer was approximately 60 ⁇ m.
  • Example 1 ⁇ Manufacture of all-solid-state lithium ion secondary battery> (Example 1)
  • the negative electrode side laminate was placed on a 10 mm diameter SUS (stainless steel) stand of an all-solid battery evaluation cell (KP-SolidCell, manufactured by Hosen Co., Ltd.) with the solid electrolyte layer side facing upward.
  • the positive electrode side laminate was placed with the solid electrolyte layer side facing down. In this way, a laminate having a structure of positive electrode side laminate/negative electrode side laminate (this laminate is referred to as a cell) was obtained.
  • a Teflon tube with an inner diameter of 10.2 mm is fitted from the positive electrode current collector side of the cell, and a polished Ti plate with a diameter of 10 mm and a thickness of 2 mm is inserted through the hole at the top of the Teflon tube, and the polished Ti plate is placed on top of the positive electrode stack. Layered. Furthermore, a Ti rod with a diameter of 10 mm and a height of 2 cm was placed on the polished Ti plate. Next, the upper casing of KP-SolidCell was fitted and sealed with a double O-ring, four-point bolts, and wing nuts.
  • the cell was restrained from above and below with a torque of 5 Nm (equivalent to 30 MPa) using a restraining pressure applying mechanism installed on the top of the KP-Solid Cell.
  • the KP-Solid Cell was opened, the cell was taken out, and the excess liquid component that seeped out due to the application of confining pressure was wiped off.
  • the cell was set on the KP-Solid Cell in the same manner as above, and the cell was restrained from above and below.
  • each KP-Solid Cell was subjected to freeze-vacuum drying treatment (10 Pa, 40° C.) for 2 hours to sufficiently remove moisture inside the cell. After taking out the KP-SolidCell from the vacuum dryer, the upper lid was closed and sealed via a double O-ring. After being left for 40 hours, the battery of Example 1 was prepared.
  • Examples 2 to 4, Comparative Example 1 In the production of the battery of Example 1, the amount (number of particles) of silica gel (manufactured by Fujifilm Wako Pure Chemical, medium granule (blue)) placed in the cavity of KP-SolidCell after placing the Ti rod on the polished Ti plate. A battery was obtained in the same manner as in Example 1, except that the vacuum drying time in the freeze-vacuum drying process was as shown in the table below.
  • Cycle characteristic test A confining pressure (30 MPa) was applied to the battery obtained above, and charging and discharging were repeated under the following conditions at a temperature of 27°C using 580-NOHFR manufactured by Toyo Technica. went. Charging is performed at a constant current value I ⁇ until the battery voltage reaches 2.8V, and after reaching 2.8V, the voltage is kept constant (2.8V) until the current value reaches 2.4C rate. went. After charging, the circuit was opened and left for 10 minutes, and then discharged at a constant current value I ⁇ until the battery voltage reached 1.5V. The charging and discharging up to this point was defined as one cycle.
  • the circuit was opened and left for 10 minutes, and then the next charge was started, and charging and discharging were repeated under the same conditions.
  • the current value I ⁇ is set to 0.2C in the first charging and discharging cycle as battery initialization, and is set to 3C in the subsequent charging and discharging. A cycle test was conducted.
  • Example 1 and Comparative Example 1 is the water content (mass%) of the laminate consisting of the positive electrode active material layer, the solid electrolyte layer, and the negative electrode active material layer, and the following: It was decided as follows. The obtained battery was dismantled in an Ar atmosphere, the cell was taken out, and approximately 5 to 10 mg of the laminate portion consisting of the positive electrode active material layer, the solid electrolyte layer, and the negative electrode active material layer was sealed in a special vial as a sample. did. At the same time, only an Ar atmosphere was sealed in a special vial as a blank.

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PCT/JP2023/020288 2022-06-01 2023-05-31 全固体リチウムイオン二次電池及び全固体リチウムイオン二次電池の製造方法 Ceased WO2023234352A1 (ja)

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EP23816109.5A EP4535488A4 (en) 2022-06-01 2023-05-31 ALL-SOLID LITHIUM-ION SECONDARY BATTERY AND METHOD FOR MANUFACTURING ALL-SOLID LITHIUM-ION SECONDARY BATTERIES
CN202380039024.5A CN119174026A (zh) 2022-06-01 2023-05-31 全固态锂离子二次电池及全固态锂离子二次电池的制造方法
JP2024524911A JPWO2023234352A1 (https=) 2022-06-01 2023-05-31
US18/963,552 US20250096317A1 (en) 2022-06-01 2024-11-28 All-solid-state lithium ion secondary battery and manufacturing method of all-solid-state lithium ion secondary battery

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JPS6222066A (ja) 1985-07-23 1987-01-30 Wako Pure Chem Ind Ltd ラテツクス凝集反応測定装置
JPH026856A (ja) 1988-06-27 1990-01-11 Motonobu Shibata 触媒担体およびその製造方法
JPH0345473A (ja) 1989-07-11 1991-02-27 Toyoda Mach Works Ltd 四輪操舵装置
JPH0590844A (ja) 1991-09-26 1993-04-09 Toshiba Corp 歪補償器
JPH064516A (ja) 1992-06-17 1994-01-14 Toshiba Corp 割当て決定支援方式
JP2011054439A (ja) * 2009-09-02 2011-03-17 Nippon Zeon Co Ltd 全固体二次電池
JP2018052755A (ja) 2016-09-26 2018-04-05 公立大学法人首都大学東京 リチウムイオン伝導性材料
JP2021044106A (ja) * 2019-09-09 2021-03-18 トヨタ自動車株式会社 全固体電池
WO2021193204A1 (ja) 2020-03-23 2021-09-30 富士フイルム株式会社 複合体、リチウムイオン伝導体、全固体リチウムイオン二次電池、全固体リチウムイオン二次電池用電極シート、四ホウ酸リチウム
JP2022089965A (ja) 2015-08-17 2022-06-16 フレキシタリック インベストメンツ インコーポレイテッド ガスケット

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JPS6222066A (ja) 1985-07-23 1987-01-30 Wako Pure Chem Ind Ltd ラテツクス凝集反応測定装置
JPH026856A (ja) 1988-06-27 1990-01-11 Motonobu Shibata 触媒担体およびその製造方法
JPH0345473A (ja) 1989-07-11 1991-02-27 Toyoda Mach Works Ltd 四輪操舵装置
JPH0590844A (ja) 1991-09-26 1993-04-09 Toshiba Corp 歪補償器
JPH064516A (ja) 1992-06-17 1994-01-14 Toshiba Corp 割当て決定支援方式
JP2011054439A (ja) * 2009-09-02 2011-03-17 Nippon Zeon Co Ltd 全固体二次電池
JP2022089965A (ja) 2015-08-17 2022-06-16 フレキシタリック インベストメンツ インコーポレイテッド ガスケット
JP2018052755A (ja) 2016-09-26 2018-04-05 公立大学法人首都大学東京 リチウムイオン伝導性材料
JP2021044106A (ja) * 2019-09-09 2021-03-18 トヨタ自動車株式会社 全固体電池
WO2021193204A1 (ja) 2020-03-23 2021-09-30 富士フイルム株式会社 複合体、リチウムイオン伝導体、全固体リチウムイオン二次電池、全固体リチウムイオン二次電池用電極シート、四ホウ酸リチウム

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