WO2020196040A1 - Batterie secondaire au lithium-ion à l'état solide et procédé de fabrication associé et feuille stratifiée d'électrode négative - Google Patents

Batterie secondaire au lithium-ion à l'état solide et procédé de fabrication associé et feuille stratifiée d'électrode négative Download PDF

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WO2020196040A1
WO2020196040A1 PCT/JP2020/011505 JP2020011505W WO2020196040A1 WO 2020196040 A1 WO2020196040 A1 WO 2020196040A1 JP 2020011505 W JP2020011505 W JP 2020011505W WO 2020196040 A1 WO2020196040 A1 WO 2020196040A1
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conductive layer
ion conductive
negative electrode
electron
secondary battery
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PCT/JP2020/011505
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English (en)
Japanese (ja)
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鈴木　秀幸
真二 今井
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富士フイルム株式会社
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Priority to JP2021509096A priority Critical patent/JP7100196B2/ja
Priority to CN202080022177.5A priority patent/CN113614977A/zh
Priority to KR1020217031329A priority patent/KR102501561B1/ko
Publication of WO2020196040A1 publication Critical patent/WO2020196040A1/fr

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/058—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
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0561—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of inorganic materials only
    • H01M10/0562—Solid materials
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/058—Construction or manufacture
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/04—Processes of manufacture in general
    • H01M4/0438—Processes of manufacture in general by electrochemical processing
    • H01M4/044—Activating, forming or electrochemical attack of the supporting material
    • H01M4/0445—Forming after manufacture of the electrode, e.g. first charge, cycling
    • H01M4/0447—Forming after manufacture of the electrode, e.g. first charge, cycling of complete cells or cells stacks
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/64—Carriers or collectors
    • H01M4/66—Selection of materials
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/021—Physical characteristics, e.g. porosity, surface area
    • 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
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/027—Negative electrodes
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/621—Binders
    • H01M4/622—Binders being polymers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/64—Carriers or collectors
    • H01M4/66—Selection of materials
    • H01M4/661—Metal or alloys, e.g. alloy coatings
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/64—Carriers or collectors
    • H01M4/66—Selection of materials
    • H01M4/669—Steels
    • 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-state lithium ion secondary battery, a method for manufacturing the same, and a laminated sheet for a negative electrode.
  • a lithium ion secondary battery is a storage battery that has a negative electrode, a positive electrode, and an electrolyte sandwiched between the negative electrode and the positive electrode, and can be charged and discharged by reciprocating lithium ions between the two electrodes. ..
  • an organic electrolyte has been used as an electrolyte in a lithium ion secondary battery.
  • the organic electrolytic solution is liable to leak, and there is a possibility that a short circuit may occur inside the battery due to overcharging or overdischarging, and further improvement in reliability and safety is required. Under such circumstances, the development of an all-solid secondary battery using a nonflammable inorganic solid electrolyte instead of the organic electrolyte is underway.
  • the negative electrode, electrolyte, and positive electrode are all made of solid, which can greatly improve the safety or reliability of batteries using organic electrolytes, and can also extend the service life. It is said that it will be.
  • an all-solid-state lithium-ion secondary battery that reciprocates lithium ions between both poles can achieve high energy density while taking advantage of reliability and long life.
  • an all-solid-state lithium-ion secondary battery self-formed Li negative electrode in which the metallic lithium (layer) obtained by reducing and precipitating lithium ions generated in the positive electrode active material layer by charging on the negative electrode side is used as the negative electrode active material layer.
  • the battery can be formed thinner because the negative electrode active material layer is not formed in advance, and a higher energy density can be realized.
  • Examples of the lithium ion secondary battery in which the precipitated metallic lithium (layer) is used as the negative electrode active material layer include the metallic lithium battery of Patent Document 1.
  • This metallic lithium battery includes a positive electrode, a specific negative electrode, a solid electrolyte, and a specific soft electrolyte (non-aqueous electrolyte, polymer electrolyte, or gel electrolyte), and metallic lithium precipitates in the pores of the negative electrode current collector in a charged state.
  • a specific soft electrolyte non-aqueous electrolyte, polymer electrolyte, or gel electrolyte
  • the self-formed Li negative electrode type all-solid-state lithium ion secondary battery has a problem that an internal short circuit is likely to occur and the cycle characteristics are inferior to those of a normal all-solid-state secondary battery. That is, in the self-formed Li negative electrode type all-solid-state lithium ion secondary battery, since the solid electrolyte layer is usually arranged adjacent to the negative electrode current collector, metallic lithium is deposited and dissolved by charging and discharging, and the volume change becomes large. A void is formed. At this time, the dissolution (ionization) of metallic lithium usually proceeds sequentially from the one located on the positive electrode side.
  • the constituent layers of an all-solid-state lithium-ion secondary battery are formed of a solid, the interfacial resistance (internal resistance of the battery) of each layer tends to increase, and the ionic conductivity tends to decrease.
  • the manufacturing method of crimping and laminating each constituent layer is simple and excellent in productivity, it is not possible to secure sufficient contact (area) between adjacent layers, and there is a strong tendency for the resistance of the crimped and laminated interface to increase.
  • the present inventors When the negative electrode sheet is pressure-bonded to the positive electrode active material layer, the present inventors impart lithium ion conductivity and an electron ion conductive layer to which lithium ion conductivity and electron conductivity are imparted, and lithium ion conductivity as the negative electrode sheet.
  • the void ratio of the ion conductive layer is set to 20% or more, and the laminated sheet for the negative electrode laminated on the negative electrode current collector is used to conduct ions without lowering the void ratio of the electron ion conductive layer to less than 15%.
  • pressurizing (compressing) the void ratio of the layer to 10% or less it is possible to suppress the occurrence of internal short circuit while enabling sufficient contact between the ion conductive layer and the positive electrode active material layer, resulting in cycle characteristics.
  • the present inventors have electrons having electron conductivity in addition to lithium ion conductivity as a constituent layer for metal lithium precipitation adjacent to the negative electrode current collector.
  • the formation of isolated lithium is suppressed and the growth of dendrite is promoted.
  • the present invention has been further studied based on these findings and has been completed.
  • a method of manufacturing an all-solid-state lithium ion secondary battery by crimping and laminating a negative electrode sheet having a negative electrode current collector and a positive electrode sheet having a positive electrode active material layer.
  • the negative electrode sheet contains a lithium ion conductive inorganic solid electrolyte and electron conductive particles, and is adjacent to the negative electrode current collector, and has an electron ion conductive layer having a void ratio of 20% or more and a lithium ion conductive inorganic material.
  • a method for manufacturing an all-solid-state lithium-ion secondary battery is
  • ⁇ 2> The method for manufacturing an all-solid-state lithium ion secondary battery according to ⁇ 1>, wherein the electron ion conductive layer of the laminated sheet for the negative electrode contains particles that form voids in the layer.
  • the particles forming the voids include an inorganic solid electrolyte having a particle diameter of 10 ⁇ m or more among the inorganic solid electrolytes.
  • ⁇ 5> The method for producing an all-solid-state lithium ion secondary battery according to any one of ⁇ 1> to ⁇ 4>, wherein the ion conductive layer contains a binder.
  • the electron ion conductive layer and the ion conductive layer contain binder particles,
  • ⁇ 7> The method for manufacturing an all-solid-state lithium ion secondary battery according to any one of ⁇ 1> to ⁇ 6>, wherein the material forming the negative electrode current collector is nickel, stainless steel, or copper.
  • ⁇ 8> After the step of pressurizing, there is a step of charging the all-solid-state lithium ion secondary battery.
  • It contains a lithium ion conductive inorganic solid electrolyte and electron conductive particles, and contains an electron ion conductive layer having a void ratio of 15% or more adjacent to the negative electrode current collector and a lithium ion conductive inorganic solid electrolyte.
  • At least the electron ion conductive layer has a negative electrode active material, and the negative electrode active material is metallic lithium. All-solid-state lithium-ion secondary battery.
  • the electron ion conductive layer contains an inorganic solid electrolyte having lithium ion conductivity and electron conductive particles.
  • the ionic conductive layer contains a lithium ion conductive inorganic solid electrolyte, The porosity of both the electron ion conductive layer and the ion conductive layer is 20% or more.
  • the electron ion conductive layer and the ion conductive layer contain binder particles
  • the all-solid-state lithium-ion secondary battery of the present invention suppresses the occurrence of internal short circuits and has excellent cycle characteristics. Further, the method for manufacturing an all-solid-state lithium-ion secondary battery of the present invention can easily manufacture an all-solid-state lithium-ion secondary battery in which the occurrence of an internal short circuit is suppressed, the cycle characteristics are excellent, and the increase in interfacial resistance is also suppressed. it can. Further, the negative electrode laminated sheet of the present invention can be suitably used in the method for producing an all-solid-state lithium ion secondary battery of the present invention capable of producing an all-solid-state lithium ion secondary battery having the above-mentioned excellent characteristics.
  • FIG. 1 is a vertical cross-sectional view schematically showing a preferred embodiment of the all-solid-state secondary battery of the present invention.
  • FIG. 2 is a vertical cross-sectional view schematically showing a preferred embodiment of the laminated sheet for a negative electrode of the present invention.
  • the numerical range represented by using “-” means a range including the numerical values before and after "-" as the lower limit value and the upper limit value.
  • the all-solid-state lithium-ion secondary battery of the present invention will be described, and then the method for producing the all-solid-state lithium-ion secondary battery of the present invention (sometimes referred to as the production method of the present invention) and the lamination for the negative electrode of the present invention.
  • the sheet will be described.
  • the all-solid-state lithium-ion secondary battery of the present invention has a negative electrode current collector, an electron ion conductive layer having a void ratio of 15% or more, an ion conductive layer having a void ratio of 10% or less, and a positive electrode active material layer in this order. It has a positive electrode current collector on the opposite side of the positive electrode active material layer from the ion conductive layer.
  • the electron ion conductive layer having a porosity of 15% or more is arranged between the negative electrode current collector and the ion conductive layer having a porosity of 10% or less and adjacent to the negative electrode current collector, preferably having a porosity of 10.
  • the ion conductive layer having a porosity of 10% or less and the positive electrode active material layer are arranged adjacent to each other.
  • "adjacent" means that the surfaces are arranged (formed) in a state of being in contact with each other.
  • the porosity of each layer is measured by the following method. That is, the area of the voids in the visual field of 3 ⁇ m ⁇ 2.5 ⁇ m was obtained from the SEM photograph obtained by observing an arbitrary cross section of each layer with a scanning electron microscope (SEM) at a magnification of 30,000, and this area was used as the visual field area.
  • the porosity is the value calculated by the above SEM photography method unless otherwise specified, but the porosity calculated from the true density of the constituent material, the mass of the layer, and the volume of the layer can also be adopted.
  • each layer constituting the all-solid-state lithium ion secondary battery may have a single-layer structure or a multi-layer structure as long as it performs a specific function.
  • the all-solid-state lithium ion secondary battery of the present invention is not particularly limited as long as it has the above configuration, and for example, a known configuration relating to an all-solid-state secondary battery can be adopted.
  • the all-solid-state lithium-ion secondary battery having the above configuration is not a form in which the negative electrode active material layer is formed in advance as a constituent layer, but is a self-formed Li negative electrode type all-solid-state lithium-ion secondary battery. That is, by charging the manufactured all-solid-state lithium-ion secondary battery, the lithium ions generated in the positive electrode active material layer are supplied to the electron ion conductive layer, and at least the metallic lithium deposited by reducing in the electron ion conductive layer.
  • This is a secondary battery in which (layer) is used as a negative electrode active material layer.
  • the metallic lithium may be deposited at least in the electron ion conductive layer (usually in the voids), and further, as appropriate, the surface of the negative electrode current collector (the interface between the electron ion conductive layer and the negative electrode current collector) and electron ions. It may be precipitated at the interface between the conductive layer and the ionic conductive layer, or in the ionic conductive layer.
  • the precipitated metallic lithium has a theoretical capacity 10 times or more that of graphite, which is widely used as a negative electrode active material for ordinary all-solid-state secondary batteries, and the battery is not formed in advance with a negative electrode active material layer. Since it can be formed thin, the self-formed Li negative electrode type all-solid-state lithium ion secondary battery can realize a high energy density.
  • the self-formed Li negative electrode type all-solid-state lithium ion secondary battery has an uncharged mode (a mode in which metallic lithium is not precipitated) and a charged mode (a mode in which metallic lithium is precipitated). Both aspects are included.
  • the self-formed Li negative electrode type all-solid-state lithium ion secondary battery means that the negative electrode active material layer is not formed in the layer forming step in the battery manufacturing, and as described above, the negative electrode active material layer is It is formed by charging.
  • such an all-solid-state lithium-ion secondary battery utilizes metallic lithium precipitated as the negative electrode active material, and therefore is formed as a negative electrode active material layer (formed in battery production) used in a normal all-solid-state secondary battery. Negative electrode active material layer) is not provided.
  • the electron ion conductive layer in the battery has metallic lithium as a negative electrode active material in a charged state, and does not have a negative electrode active material other than metallic lithium (referred to as another negative electrode active material).
  • the fact that the electron ion conductive layer does not have another negative electrode active material includes an embodiment in which the electron ion conductive layer has another negative electrode active material within a range that does not impair the high energy density due to metallic lithium, for example.
  • the charging state means a state in which charging is in progress in addition to the state in which charging is completed
  • the discharging state means a state in which discharging is in progress in addition to the state in which discharging is completed.
  • FIG. 1 is a cross-sectional view schematically showing a laminated state of each constituent layer constituting the battery for one embodiment of an all-solid-state lithium ion secondary battery.
  • the all-solid-state lithium ion secondary battery 10 of the present embodiment has a negative electrode current collector 1, an electron ion conductive layer 2 having a void ratio of 15% or more, and an ion conductive layer 3 having a void ratio of 10% or less when viewed from the negative electrode side. It has a structure in which the positive electrode active material layer 4 and the positive electrode current collector 5 are laminated in this order, and the laminated layers are in direct contact with each other.
  • An all-solid-state lithium ion secondary battery having such a structure during charging, electrons to the negative electrode side (e -) is supplied, the lithium ions generated simultaneously from the positive electrode active material, through the ion-conducting layer 3 (conductive) Then, it moves to the electron ion conductive layer 2 and combines with electrons (reduced) to precipitate metallic lithium.
  • the all-solid-state lithium ion secondary battery of the present invention at least the metallic lithium precipitated in the electron ion conductive layer 2 functions as the negative electrode active material layer. On the other hand, at the time of discharge, the precipitated metallic lithium generates lithium ions and electrons.
  • Lithium ions pass through (conduct) through the ion conductive layer 3 and are returned (moved) to the positive electrode side, electrons are supplied to the operating portion 6 and reach the positive electrode current collector 5.
  • a light bulb is used for the operating portion 6, and the light bulb is turned on by electric discharge.
  • the all-solid-state lithium-ion secondary battery of the present invention having the above configuration is preferably manufactured by the manufacturing method of the present invention.
  • the all-solid-state lithium-ion secondary battery of the present invention suppresses the occurrence of internal short circuits and has excellent cycle characteristics.
  • the increase in interfacial resistance is also suppressed, and high ionic conductivity is exhibited.
  • the all-solid-state lithium-ion secondary battery of the present invention has a porosity of 15% or more between the negative electrode current collector and the ion conductive layer having a porosity of 10% or less adjacent to the negative electrode current collector. It has an electron ion conductive layer of.
  • the porosity of the electron ion conductive layer is set to 15% or more, and the electron ion conductive layer has sufficient voids to accommodate the precipitated metallic lithium.
  • metallic lithium can usually be deposited and accumulated in the electron ion conductive layer (inside the voids).
  • the volume change due to the precipitation and dissolution of metallic lithium can be suppressed, and the formation of unnecessary voids in the electron ion conductive layer (ion conduction layer side) can be suppressed.
  • the electron ion conductive layer is imparted with electron conductivity in addition to ion conductivity. Local precipitation of metallic lithium can be suppressed by suppressing the formation of unnecessary voids and imparting both conductivitys.
  • metallic lithium is preferentially ionized from the ion conductive layer side during discharge, an electron conductive path and an ion conductive path are formed throughout the electron ion conductive layer, and both conductive paths are also formed in the remaining metallic lithium. Is secured.
  • the ionization of metallic lithium and the movement of lithium ions can be realized in the entire electron ion conductive layer, and the precipitated metallic lithium can be sequentially ionized. That is, it is possible to proceed with the ionization of metallic lithium while suppressing the formation of isolated lithium in which the electron conduction path or the ion conduction path is cut off during discharge.
  • the ability to suppress the formation of isolated lithium is unlikely to decrease even after repeated charging and discharging, and the decrease in discharge capacity is particularly suppressed even after repeated charging and discharging.
  • excellent cycle characteristics of the all-solid-state lithium ion secondary battery are obtained. It is considered that (characteristics for maintaining high charge / discharge efficiency) can be imparted.
  • the above-mentioned action of the ionic conduction layer is enhanced by having an electron ionic conduction layer between the negative electrode current collector, and the cycle characteristics are improved while suppressing the occurrence of an internal short circuit by arranging the electron ionic conduction layer and the ionic conduction layer. Then, it can be considered.
  • the ionic conduction layer and the positive electrode active material layer are adjacently laminated in a sufficient contact state (contact area)
  • the interfacial resistance of both layers can be reduced. it can.
  • the electron ion conductive layer can suppress the volume change of the electron ion conductive layer due to charging and discharging, and is in contact with the negative electrode current collector, both conduction paths of the electron ion conductive layer, and The contact state with the ion conductive layer can be maintained. It is considered that this makes it possible to suppress an increase in internal resistance.
  • An electron conductor can be used as the negative electrode current collector 1.
  • the material for forming the negative electrode current collector is not particularly limited, and examples thereof include metal materials such as copper, copper alloy, stainless steel, and nickel, and nickel, stainless steel, or copper is preferable. Further, the surface of these metal materials treated with a material such as bismuth, zinc, gold, or aluminum to be alloyed with lithium (thin film formed) can also be used. Further, a carbon, nickel, titanium or silver-treated surface (thin film formed) can also be used.
  • the shape of the current collector is usually a film sheet, but a net, a punched body, a lath body, a porous body, a foam body, a molded body of a fiber group, or the like can also be used.
  • the thickness of the negative electrode current collector (including the above thin film) is not particularly limited, but is preferably 1 to 500 ⁇ m. It is also preferable that the surface of the negative electrode current collector is made uneven by surface treatment. In the present invention, both the negative electrode current collector and the positive electrode current collector described later may be collectively referred to as a current collector.
  • An electron ion conductive layer having a porosity of 15% or more (sometimes referred to as an electron ion conductive layer in a battery to distinguish it from the electron ion conductive layer of the negative electrode laminated sheet described later) has a porosity of 15% or more. It is a layer capable of containing metallic lithium deposited in the layer (usually voids). When the porosity of the electron ion conductive layer in the battery is 15% or more, it is possible to suppress the volume change of the battery due to the metallic lithium deposited during charging, and it is possible to realize high cycle characteristics and further resistance. It is also possible to suppress the rise of.
  • the porosity of the electron ion conductive layer in the battery is preferably 20% or more, and more preferably 30% or more.
  • the upper limit of the porosity is not particularly limited as long as the layer morphology can be maintained, and is set to a value that does not significantly impair the high energy density exhibited by the self-formed Li negative electrode type all-solid-state lithium ion secondary battery. For example, it is preferably 50% or less, more preferably 40% or less, and even more preferably 35% or less.
  • the porosity of the electron ion conductive layer in the battery is a value calculated as an area ratio by the above method.
  • the electron ion conductive layer in the battery exhibits lithium ion conductivity and electron conductivity.
  • the lithium ion conductivity and electron conductivity exhibited by the electron-ion conductive layer in the battery are not particularly limited, and are within a range that does not impair the ionization of metallic lithium and the conduction of generated lithium ions and electrons (as a constituent layer of a secondary battery). It is set appropriately in the functioning range).
  • Lithium ion conductivity and electron conductivity can be adjusted by the type and content of the contained inorganic solid electrolyte and electron conductive particles.
  • the thickness of the electron ion conductive layer in the battery is not particularly limited, and the amount of metallic lithium precipitated during charging varies depending on the capacity of the positive electrode active material layer. Therefore, it can be arbitrarily set according to the capacity of the positive electrode active material layer. it can. For example, 10 to 500 ⁇ m is preferable.
  • the electron ion conductive layer in the battery contains a lithium ion conductive inorganic solid electrolyte and electron conductive particles (also referred to as an electrolyte electron conductive particle mixed layer), preferably a binder, particles forming voids, and more appropriately. It may contain other components.
  • the inorganic solid electrolyte is not particularly limited as long as it has lithium ion conductivity, and generally does not have electron conductivity.
  • the inorganic solid electrolyte is an inorganic solid electrolyte, and the solid electrolyte is a solid electrolyte capable of transferring lithium ions inside the solid electrolyte. Since it does not contain organic substances as the main lithium ion conductive material, it is represented by organic solid electrolytes (polymer electrolytes such as polyethylene oxide (PEO) and lithium bis (trifluoromethanesulfonyl) imide (LiTFSI)). It is clearly distinguished from organic electrolyte salts).
  • PEO polyethylene oxide
  • LiTFSI lithium bis (trifluoromethanesulfonyl) imide
  • the inorganic solid electrolyte is a solid in a steady state, it is usually not dissociated or liberated into cations and anions. In this respect, it is clearly distinguished from the electrolytic solution or the inorganic electrolyte salt (LiPF 6 , LiBF 4 , LiFSI, LiCl, etc.) in which cations and anions are dissociated or released in the polymer.
  • the inorganic solid electrolyte a solid electrolyte material applicable to this type of product can be appropriately selected and used.
  • the inorganic solid electrolyte include (i) a sulfide-based inorganic solid electrolyte, (ii) an oxide-based inorganic solid electrolyte, (iii) a halide-based inorganic solid electrolyte, and (iV) a hydride-based solid electrolyte.
  • a sulfide-based inorganic solid electrolyte is preferable in terms of high lithium ion conductivity and ease of interparticle interface bonding, and in that the firing step is not essential in the production method of the present invention.
  • the sulfide-based inorganic solid electrolyte is preferably a compound containing a sulfur atom, having lithium ion conductivity, and having electron insulating properties.
  • the sulfide-based inorganic solid electrolyte preferably contains at least Li, S and P as elements and has lithium ion conductivity, but other than Li, S and P may be used depending on the purpose or case. It may contain elements.
  • Examples of the sulfide-based inorganic solid electrolyte include a lithium ion conductive sulfide-based inorganic solid electrolyte satisfying the composition represented by the following formula (1).
  • L represents an element selected from Li, Na and K, with Li being preferred.
  • M represents an element selected from B, Zn, Sn, Si, Cu, Ga, Sb, Al and Ge.
  • A represents an element selected from I, Br, Cl and F.
  • a1 to e1 indicate the composition ratio of each element, and a1: b1: c1: d1: e1 satisfy 1 to 12: 0 to 5: 1: 2 to 12: 0 to 10.
  • a1 is preferably 1 to 9, more preferably 1.5 to 7.5.
  • b1 is preferably 0 to 3, more preferably 0 to 1.
  • the d1 is preferably 2.5 to 10, more preferably 3.0 to 8.5.
  • e1 is preferably 0 to 5, more preferably 0 to 3.
  • composition ratio of each element can be controlled by adjusting the compounding ratio of the raw material compound when producing the sulfide-based inorganic solid electrolyte as described below.
  • the sulfide-based inorganic solid electrolyte may be non-crystal (glass) or crystallized (glass-ceramic), or only a part thereof may be crystallized.
  • Li-PS-based glass containing Li, P and S, or Li-PS-based glass ceramics containing Li, P and S can be used.
  • Sulfide-based inorganic solid electrolytes include, for example, lithium sulfide (Li 2 S), phosphorus sulfide (for example, diphosphorus pentasulfide (P 2 S 5 )), simple phosphorus, simple sulfur, sodium sulfide, hydrogen sulfide, and lithium halide (for example). It can be produced by the reaction of at least two or more raw materials in sulfides of LiI, LiBr, LiCl) and the element represented by M (for example, SiS 2 , SnS, GeS 2 ).
  • the ratio of Li 2 S and P 2 S 5 is, Li 2 S: at a molar ratio of P 2 S 5, preferably 60: 40 ⁇ It is 90:10, more preferably 68:32 to 78:22.
  • the lithium ion conductivity can be made high.
  • the lithium ion conductivity can be preferably 1 ⁇ 10 -4 S / cm or more, and more preferably 1 ⁇ 10 -3 S / cm or more. There is no particular upper limit, but it is practical that it is 1 ⁇ 10 -1 S / cm or less.
  • Li 2 S-P 2 S 5 Li 2 S-P 2 S 5 -LiCl, Li 2 S-P 2 S 5 -H 2 S, Li 2 S-P 2 S 5 -H 2 S-LiCl, Li 2 S-LiI-P 2 S 5 , Li 2 S-LiI-Li 2 O-P 2 S 5 , Li 2 S-LiBr-P 2 S 5 , Li 2 S-Li 2 O-P 2 S 5 , Li 2 S-Li 3 PO 4- P 2 S 5 , Li 2 S-P 2 S 5- P 2 O 5 , Li 2 S-P 2 S 5- SiS 2 , Li 2 S-P 2 S 5- SiS 2- LiCl, Li 2 S-P 2 S 5- SnS, Li 2 S-P 2 S 5- Al 2 S 3 , Li 2 S-GeS 2 , Li 2 S-GeS 2 , Li 2 S-Ge
  • the mixing ratio of each raw material does not matter.
  • an amorphization method can be mentioned.
  • the amorphization method include a mechanical milling method, a solution method and a melt quenching method. This is because processing at room temperature is possible and the manufacturing process can be simplified.
  • the oxide-based inorganic solid electrolyte is preferably a compound containing an oxygen atom, having lithium ion conductivity, and having electron insulating properties.
  • the oxide-based inorganic solid electrolyte preferably has a lithium ion conductivity of 1 ⁇ 10 -6 S / cm or more, more preferably 5 ⁇ 10 -6 S / cm or more, and 1 ⁇ 10 -5. It is particularly preferable that it is S / cm or more.
  • the upper limit is not particularly limited, but it is practical that it is 1 ⁇ 10 -1 S / cm or less.
  • nb (M bb is at least one element of Al, Mg, Ca, Sr, V, Nb, Ta, Ti, Ge, In, Sn, xb satisfies 5 ⁇ xb ⁇ 10, and yb is 1 ⁇ yb.
  • zb satisfies 1 ⁇ zb ⁇ 4, mb satisfies 0 ⁇ mb ⁇ 2, nb satisfies 5 ⁇ nb ⁇ 20), Li xc Byc M cc zc Onc (M cc is). At least one or more elements of C, S, Al, Si, Ga, Ge, In, and Sn, xc satisfies 0 ⁇ xc ⁇ 5, yc satisfies 0 ⁇ yc ⁇ 1, and zc satisfies 0 ⁇ zc ⁇ .
  • Li, P and O Phosphorus compounds containing Li, P and O are also desirable.
  • lithium phosphate Li 3 PO 4
  • LiPON in which a part of oxygen of lithium phosphate is replaced with nitrogen
  • LiPOD 1 Li is Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zr. , Nb, Mo, Ru, Ag, Ta, W, Pt, Au and the like (at least one selected from) and the like.
  • LiA 1 ON A 1 is at least one selected from Si, B, Ge, Al, C, Ga and the like
  • a 1 ON A 1 is at least one selected from Si, B, Ge, Al, C, Ga and the like
  • the halide-based inorganic solid electrolyte is preferably a compound containing a halogen atom, having lithium ion conductivity, and having electron insulating properties.
  • the halide-based inorganic solid electrolyte is not particularly limited, and examples thereof include compounds such as Li 3 YBr 6 and Li 3 YCl 6 described in LiCl, LiBr, LiI, ADVANCED MATERIALS, 2018, 30, 1803075. Of these, Li 3 YBr 6 and Li 3 YCl 6 are preferable.
  • the hydride-based inorganic solid electrolyte is preferably a compound containing a hydrogen atom, having lithium ion conductivity, and having electron insulating properties.
  • the hydride-based inorganic solid electrolyte is not particularly limited, and examples thereof include LiBH 4 , Li 4 (BH 4 ) 3 I, and 3 LiBH 4- LiCl.
  • the inorganic solid electrolyte is preferably particles.
  • the particle size (volume average particle size) of the inorganic solid electrolyte is not particularly limited, but is preferably 0.01 ⁇ m or more, and more preferably 0.1 ⁇ m or more.
  • the upper limit is preferably 100 ⁇ m or less, and more preferably 50 ⁇ m or less.
  • the particle size of the inorganic solid electrolyte is measured by the following procedure. Inorganic solid electrolyte particles are prepared by diluting 1% by mass of a dispersion in a 20 mL sample bottle with water (heptane in the case of a water-unstable substance).
  • the diluted dispersion sample is irradiated with 1 kHz ultrasonic waves for 10 minutes, and immediately after that, it is used for the test.
  • data was captured 50 times using a laser diffraction / scattering particle size distribution measuring device LA-920 (trade name, manufactured by HORIBA) at a temperature of 25 ° C. using a measuring quartz cell. Obtain the volume average particle size.
  • LA-920 trade name, manufactured by HORIBA
  • the inorganic solid electrolyte can be contained (used) as particles forming voids, which will be described later, and is specifically the same as the laminated sheet for negative electrodes described later.
  • the inorganic solid electrolyte may contain one kind or two or more kinds.
  • the content of the inorganic solid electrolyte in the electron ion conduction layer in the battery is not particularly limited, but in terms of the construction of the lithium ion conduction path and the balance with respect to the electron conduction path, the entire uncharged state (discharge completed state). It is preferably 50% by mass or more, more preferably 60% by mass or more, and particularly preferably 70% by mass or more, based on the total mass of the electron ion conductive layer in the battery in the solid-state lithium ion secondary battery.
  • the upper limit is not particularly limited, and is preferably 99% by mass or less, more preferably 97% by mass or less, and particularly preferably 95% by mass or less.
  • the total mass of the electron ion conductive layer in the battery is the total mass of the components excluding metallic lithium constituting the electron ion conductive layer, and the solid content of the composition for forming the electron ion conductive layer is 100% by mass. , Synonymous.
  • the electron conductive particles may be particles that are electron conductive (also simply referred to as conductive particles), and the particles of the conductive auxiliary agent generally used for the electrodes of the all-solid secondary battery are particularly limited. Can be used without.
  • the electron conductive particles are appropriately selected in relation to the precipitated metallic lithium. That is, in the electron ion conductive layer in the battery, a layer that does not insert and release Li during charging and discharging and does not function as an active material is used. Whether or not it functions as an active material during charging and discharging is not unique and is determined by the combination with metallic lithium.
  • the material for forming the electron conductive particles is not particularly limited as long as it is a material exhibiting electron conductivity.
  • graphites such as natural graphite and artificial graphite, and carbon black such as acetylene black, ketjen black and furnace black.
  • Classes amorphous carbon such as needle coke, carbon fibers such as vapor-grown carbon fiber or carbon nanotube, carbonaceous material such as graphene or fullerene, metal such as copper and nickel, and polyaniline, polypyrrole, polythiophene, etc.
  • Conductive polymers such as polyacetylene and polyphenylene derivatives are also mentioned.
  • the electron conductive particles are preferably particles made of the above-mentioned electron conductive material.
  • the shape of the electron conductive particles is not limited to granules, and may be fibrous or indefinite.
  • the particle size of the electron conductive particles is not particularly limited, but is preferably 0.05 to 10 ⁇ m, more preferably 0.1 to 5 ⁇ m.
  • the particle size of the electron conductive particles is a value measured by the same method as the particle size of the inorganic solid electrolyte.
  • the electron-ion conductive layer in the battery may contain one kind or two or more kinds of electron-conducting particles.
  • the content of the electron conductive particles in the electron ion conductive layer in the battery is not particularly limited, but in terms of the construction of the electron conduction path and the balance with respect to the lithium ion conduction path, the uncharged all-solid-state lithium ion II. It is preferably 1 to 20% by mass, more preferably 2 to 15% by mass, based on the total mass of the electron ion conductive layer in the battery in the next battery.
  • the total content of the inorganic solid electrolyte and the electron conductive particles in the battery electron ion conductive layer is not particularly limited as long as each of the above contents is satisfied, but for example, the total mass of the battery electron ion conductive layer. Of the above, 80 to 99.5% by mass is preferable, and 90 to 99% by mass is more preferable.
  • the ratio of the content of the inorganic solid electrolyte to the content of the electron conductive particles in the electron ion conductive layer in the battery is not particularly limited as long as each of the above contents is satisfied, but for example, the content of the inorganic solid electrolyte. Is preferably 5 to 50 times, more preferably 10 to 20 times, the content of the electron conductive particles.
  • the electron ion conductive layer in the battery may contain a binder that binds solid particles such as an inorganic solid electrolyte and electron conductive particles.
  • the binder is not particularly limited, and examples thereof include an organic polymer, and a known organic polymer used for producing an all-solid-state secondary battery can be used without particular limitation. Examples of such organic polymers include fluororesins, hydrocarbon-based thermoplastic resins, acrylic resins, polyurethane resins, polyurea resins, polyamide resins, polyimide resins, polyester resins, polyether resins, polycarbonate resins, cellulose derivative resins and the like. Can be mentioned.
  • a binder made of a polymer having a specific bond described in JP-A-2015-08480 a binder made of an acrylic polymer described in JP-A-2015-88486, International Publication No. 2016/132872.
  • Examples thereof include a binder made of the polymer described in 1.
  • the binder is preferably in the form of particles.
  • it is a particulate binder (also referred to as a binder particle), it functions as a particle that binds solid particles and forms voids, which will be described later.
  • the particle size of the binder particles is not particularly limited, but is preferably 0.01 to 1 ⁇ m, more preferably 0.05 to 0.5 ⁇ m.
  • the particle size of the binder particles is a value measured by the same method as the particle size of the inorganic solid electrolyte.
  • the electron ion conductive layer in the battery may contain one kind of binder or two or more kinds of binders.
  • the content of the binder in the electron ion conductive layer in the battery is not particularly limited, and in the case of the binder particles, the binding strength of the solid particles and, in the case of the binder particles, the adjustment of the void ratio, etc.
  • the total mass of the electron ion conductive layer in the battery in the ion secondary battery for example, 0.1 to 10% by mass is preferable, 1 to 10% by mass is more preferable, and 2 to 6% by mass is further preferable.
  • the electron ion conductive layer in the battery may contain other components.
  • the other components are not particularly limited, and examples thereof include various additives. For example, thickeners, antifoaming agents, leveling agents, dehydrating agents, antioxidants and the like can be mentioned.
  • the content of the other components in the electron ion conductive layer in the battery is not particularly limited and is appropriately set.
  • the electron ion conductive layer in the battery does not have a negative electrode active material (other negative electrode active material) other than metallic lithium.
  • negative electrode active materials include those other than metallic lithium among the negative electrode active materials used in all-solid-state secondary batteries.
  • carbonaceous materials, metal or semi-metallic element oxides (including composite oxides), lithium alone, lithium alloys, or negative electrode active materials capable of alloying with lithium (forming an alloy with lithium). can be mentioned. More specifically, those described in JP-A-2015-88486 can be mentioned.
  • the ion conductive layer having a porosity of 10% or less (sometimes referred to as an ion conductive layer in a battery to distinguish it from the ion conductive layer of the negative electrode laminated sheet described later) is dense with a porosity of 10% or less. It is a layer.
  • the porosity of the ion conductive layer in the battery is 10% or less, the growth of dendrites can be blocked and the occurrence of an internal short circuit can be suppressed. Furthermore, an increase in interface resistance with the positive electrode active material layer can be suppressed.
  • the porosity of the ion conductive layer in the battery is preferably 7% or less in that the occurrence of an internal short circuit can be effectively suppressed.
  • the lower limit of the porosity is not particularly limited, but is actually 0.1% or more, preferably 1% or more, for example.
  • the porosity of the ion conductive layer in the battery is a value calculated as an area ratio by the above method.
  • the difference between the porosity of the ion conductive layer in the battery and the porosity of the electron ion conductive layer in the battery is not particularly limited, but can be, for example, 5% or more, preferably 5 to 30%.
  • the ion conductive layer in the battery exhibits lithium ion conductivity.
  • the lithium ion conductivity exhibited by the ion conductive layer in the battery is not particularly limited, and is appropriately within a range that does not impair the ionization of metallic lithium and the conduction of generated lithium ions (the range that functions as a constituent layer of the secondary battery). Set. Lithium ion conductivity can be adjusted by the type of inorganic solid electrolyte contained.
  • the ion conductive layer in the battery is an electronic insulating layer that does not exhibit electron conductivity (does not contain electron conductive particles) and functions as a separator.
  • the electron insulating layer may be a layer having a conductivity such that electrons are not conducted (moved) between the electron ion conductive layer in the battery and the positive electrode active material layer, and the conductivity is 0 (S). It is not limited to the layer of / m).
  • the thickness of the ion conductive layer in the battery is not particularly limited and is set appropriately. For example, 10 to 1000 ⁇ m is preferable, and 20 to 500 ⁇ m is more preferable, because the growth of dendrite can be blocked.
  • the ion conductive layer in the battery contains a lithium ion conductive inorganic solid electrolyte, preferably a binder, and may further contain other components as appropriate.
  • the ion conductive layer in the battery usually does not contain a positive electrode active material and a negative electrode active material, but metallic lithium may precipitate in a charged state.
  • the ion conductive layer in the battery can be said to be a solid electrolyte layer when focusing on the contained components.
  • the inorganic solid electrolyte contained in the ionic conduction layer in the battery, preferably the binder contained, and other components which may be contained are synonymous with those described in the electron ionic conduction layer in the battery.
  • the particle size is smaller and the content is smaller than that of the inorganic solid electrolyte or binder contained in the electron ion conductive layer in the battery as particles forming voids.
  • This is a preferred embodiment, and specifically, as described in the negative electrode laminated sheet.
  • the content of the inorganic solid electrolyte in the ion conductive layer in the battery is not particularly limited, but in terms of constructing the lithium ion conduction path, all of the ion conductive layer in the battery in the uncharged all-solid-state lithium ion secondary battery.
  • mass it is preferably 80% by mass or more, more preferably 90% by mass or more, and particularly preferably 95% by mass or more.
  • the upper limit is not particularly limited, and is preferably 99.9% by mass or less, more preferably 99.5% by mass or less, and particularly preferably 99% by mass or less.
  • the content of the binder in the ion-conducting layer in the battery is not particularly limited, and the battery in the uncharged all-solid-state lithium-ion secondary battery in terms of the binding strength of solid particles and the adjustment of the void ratio, etc.
  • the total mass of the internal ion conductive layer for example, 0.1 to 10% by mass is preferable, 0.5 to 10% by mass is more preferable, and 1 to 5% by mass is further preferable.
  • the content of the other components in the ion conductive layer in the battery is not particularly limited and is appropriately set.
  • the total mass of the ion conductive layer in the battery is synonymous with the total mass of the components constituting the ion conductive layer and 100% by mass of the solid content of the composition for forming the ion conductive layer.
  • the positive electrode active material layer contains a positive electrode active material and has a function of generating lithium ions by charging and supplying them to the electron ion conductive layer in the battery.
  • the thickness of the positive electrode active material is appropriately determined according to the amount of lithium ions to be supplied and the like, and is preferably 10 to 1000 ⁇ m, more preferably 20 to 500 ⁇ m, for example.
  • the positive electrode active material layer contains a positive electrode active material, preferably an inorganic solid electrolyte having lithium ion conductivity, a conductive additive, a binder, and other components as long as the effects of the present invention are not impaired. ..
  • the inorganic solid electrolyte, binder and other components are synonymous with the inorganic solid electrolyte and other components described in the in-battery electron ion conductive layer.
  • the positive electrode active material is not particularly limited as long as it can reversibly insert and release lithium ions, and can be composited with a transition metal oxide (preferably a transition metal oxide) or Li such as an organic substance or sulfur. Elements and composites of sulfur and metal are preferable.
  • the 1 (Ia) group elements of the transition metal oxide to elemental M b (Table metal periodic other than lithium, the elements of the 2 (IIa) group, Al, Ga, In, Ge , Sn, Pb, Elements such as Sb, Bi, Si, P or B) may be mixed.
  • the mixing amount is preferably 0 ⁇ 30 mol% relative to the amount of the transition metal element M a (100mol%).
  • transition metal oxide examples include (MA) a transition metal oxide having a layered rock salt type structure, (MB) a transition metal oxide having a spinel type structure, (MC) a lithium-containing transition metal phosphoric acid compound, and (MD). ) Lithium-containing transition metal halide phosphoric acid compound, (ME) lithium-containing transition metal silicic acid compound, and the like.
  • transition metal oxide having a layered rock salt structure examples include LiCoO 2 (lithium cobalt oxide [LCO]), LiNi 2 O 2 (lithium nickel oxide), LiNi 0.85 Co 0.10 Al 0. 05 O 2 (Lithium Nickel Cobalt Oxide [NCA]), LiNi 1/3 Co 1/3 Mn 1/3 O 2 (Lithium Nickel Manganese Cobalt Oxide [NMC]) and LiNi 0.5 Mn 0.5 O 2 ( Lithium manganese nickel oxide).
  • LiCoO 2 lithium cobalt oxide [LCO]
  • LiNi 2 O 2 lithium nickel oxide
  • LiNi 0.85 Co 0.10 Al 0. 05 O 2 Lithium Nickel Cobalt Oxide [NCA]
  • LiNi 1/3 Co 1/3 Mn 1/3 O 2 Lithium Nickel Manganese Cobalt Oxide [NMC]
  • LiNi 0.5 Mn 0.5 O 2 Lithium manganese nickel oxide
  • (MB) Specific examples of the transition metal oxide having a spinel structure, LiMn 2 O 4 (LMO) , LiCoMnO 4, Li 2 FeMn 3 O 8, Li 2 CuMn 3 O 8, Li 2 CrMn 3 O 8 and Li 2 Nimn 3 O 8 can be mentioned.
  • Examples of the (MC) lithium-containing transition metal phosphate compound include olivine-type iron phosphate salts such as LiFePO 4 and Li 3 Fe 2 (PO 4 ) 3 , iron pyrophosphates such as LiFeP 2 O 7 , and LiCoPO 4.
  • Examples thereof include cobalt phosphates of the above and monoclinic panocycon-type vanadium phosphate salts such as Li 3 V 2 (PO 4 ) 3 (lithium vanadium phosphate).
  • (MD) as the lithium-containing transition metal halogenated phosphate compound for example, Li 2 FePO 4 F such fluorinated phosphorus iron salt, Li 2 MnPO 4 hexafluorophosphate manganese salts such as F and Li 2 CoPO 4 F
  • cobalt fluoride phosphates such as.
  • Examples of the (ME) lithium-containing transition metal silicic acid compound include Li 2 FeSiO 4 , Li 2 MnSiO 4, and Li 2 CoSiO 4 .
  • a transition metal oxide having a (MA) layered rock salt type structure is preferable, and LCO or NMC is more preferable.
  • the shape of the positive electrode active material is not particularly limited, but it is preferably in the form of particles.
  • the particle size (volume average particle size) of the positive electrode active material is not particularly limited. For example, it can be 0.1 to 50 ⁇ m.
  • a normal crusher or classifier may be used.
  • the positive electrode active material obtained by the firing method may be used after being washed with water, an acidic aqueous solution, an alkaline aqueous solution, or an organic solvent.
  • the average particle size of the positive electrode active material particles can be measured by the same method as the above-mentioned method for measuring the average particle size of the inorganic solid electrolyte.
  • the surface of the positive electrode active material may be surface-coated with another metal oxide.
  • the surface coating agent include metal oxides containing Ti, Nb, Ta, W, Zr, Al, Si or Li. Specific examples thereof include spinel titanate, tantalum oxide, niobate oxide, lithium niobate compound and the like.
  • the surface of the electrode containing the positive electrode active material may be surface-treated with sulfur or phosphorus.
  • the particle surface of the positive electrode active material may be surface-treated with active light rays or an active gas (plasma or the like) before and after the surface coating.
  • the positive electrode active material layer may contain one type of positive electrode active material alone, or may contain two or more types of positive electrode active material.
  • the content of the positive electrode active material in the positive electrode active material layer is not particularly limited, and is preferably 10 to 95% by mass, more preferably 30 to 90% by mass, and 50 to 85% by mass in the total mass of the positive electrode active material layer. Is more preferable, and 55 to 80% by mass is particularly preferable.
  • the content of the inorganic solid electrolyte in the positive electrode active material layer is not particularly limited, but the total content of the positive electrode active material and the inorganic solid electrolyte is preferably 5% by mass or more, preferably 10% by mass or more.
  • the upper limit is not particularly limited, and for example, it is preferably 99.9% by mass or less, more preferably 99.5% by mass or less, and further preferably 99% by mass or less.
  • the conductive auxiliary agent preferably contained in the positive electrode active material layer is not particularly limited, and those known as general conductive auxiliary agents can be used.
  • graphites such as natural graphite and artificial graphite, carbon blacks such as acetylene black, ketjen black and furnace black, amorphous carbon such as needle coke, vapor-grown carbon fibers or carbon nanotubes, which are electron conductive materials.
  • It may be a carbon fiber such as graphene or fullerene, a metal powder such as copper or nickel, or a metal fiber, and a conductive polymer such as polyaniline, polypyrrole, polythiophene, polyacetylene, or polyphenylene derivative. You may use it.
  • the positive electrode active material and the conductive auxiliary agent are used in combination, among the above conductive auxiliary materials, the one that does not insert and release Li ions when the battery is charged and discharged and does not function as the positive electrode active material.
  • the shape of the conductive auxiliary agent is not particularly limited, but is preferably in the form of particles.
  • the particle size is not particularly limited, but is preferably 0.05 to 10 ⁇ m, more preferably 0.1 to 5 ⁇ m.
  • the particle size is a value measured in the same manner as the particle size of the above-mentioned inorganic solid electrolyte.
  • the conductive auxiliary agent one kind may be used, or two or more kinds may be used.
  • the content of the conductive auxiliary agent in the positive electrode active material layer is preferably 0.1 to 20% by mass, preferably 0.5% by mass, based on the total mass of the ion conductive layer in the battery in the uncharged all-solid-state lithium ion secondary battery. -10% by mass is more preferable.
  • the content of the binder in the positive electrode active material layer is not particularly limited, and in terms of the binding strength of solid particles and the like, in the total mass of the positive electrode active material layer in the uncharged all-solid lithium-ion secondary battery, For example, 0.1 to 10% by mass is preferable, 0.5 to 10% by mass is more preferable, and 1 to 5% by mass is further preferable.
  • the content of the other components in the positive electrode active material layer is not particularly limited and is appropriately set.
  • the total mass of the positive electrode active material layer is synonymous with the total mass of the components constituting the positive electrode active material layer and 100% by mass of the solid content of the positive electrode composition for forming the positive electrode active material layer. ..
  • An electron conductor can be used as the positive electrode current collector 5.
  • a material for forming the positive electrode current collector in addition to aluminum, aluminum alloy, stainless steel, nickel and titanium, the surface of aluminum or stainless steel is treated with carbon, nickel, titanium or silver (a thin film is formed). Of these, aluminum and aluminum alloys are more preferable.
  • the shape of the positive electrode current collector is usually a film sheet, but a net, a punched body, a lath body, a porous body, a foam body, a molded body of a fiber group, or the like can also be used.
  • the thickness of the positive electrode current collector (including the above thin film) is not particularly limited, but is preferably 1 to 500 ⁇ m. It is also preferable that the surface of the positive electrode current collector is made uneven by surface treatment.
  • a functional layer may be appropriately interposed between the electron ion conductive layer and the ion conductive layer, and between the positive electrode active material layer and the positive electrode current collector. Further, the laminated body of each of the above constituent layers may appropriately have a member such as a housing on the outside thereof.
  • the all-solid-state lithium-ion secondary battery of the present invention may be used as an all-solid-state lithium-ion secondary battery with the above structure depending on the application. It is also preferable to use it by enclosing it.
  • the housing may be made of metal or resin (plastic). When metallic materials are used, for example, those made of aluminum alloy and stainless steel can be mentioned. It is preferable that the metallic housing is divided into a positive electrode side housing and a negative electrode side housing, and electrically connected to the positive electrode current collector and the negative electrode current collector, respectively. It is preferable that the housing on the positive electrode side and the housing on the negative electrode side are joined and integrated via a gasket for preventing a short circuit.
  • the all-solid-state lithium-ion secondary battery of the present invention can be applied to various applications.
  • the application mode is not particularly limited, but for example, when mounted on an electronic device, a laptop computer, a pen input computer, a mobile computer, an electronic book player, a mobile phone, a cordless phone handset, a pager, a handy terminal, a mobile fax, or a mobile phone. Examples include copying, mobile printers, headphone stereos, video movies, LCD TVs, handy cleaners, portable CDs, mini discs, electric shavers, transceivers, electronic notebooks, calculators, portable tape recorders, radios, backup power supplies, memory cards, etc.
  • Other consumer products include automobiles (electric vehicles, etc.), electric vehicles, motors, lighting equipment, toys, game equipment, road conditioners, watches, strobes, cameras, medical equipment (pacemakers, hearing aids, shoulder massagers, etc.). .. Furthermore, it can be used for various munitions and space. It can also be combined with a solar cell.
  • the manufacturing method of the present invention is a method of manufacturing an all-solid-state lithium ion secondary battery by crimping and laminating a negative electrode sheet having a negative electrode current collector and a positive electrode sheet having a positive electrode active material layer.
  • the negative electrode laminated sheet of the present invention described later is used as the negative electrode sheet, and the negative electrode laminated sheet and the positive electrode sheet are pressurized to form an in-battery electron ion conductive layer and an in-battery ion conductive layer. Is formed (compressed) so as to have the above void ratio.
  • an all-solid-state lithium-ion secondary battery in which the occurrence of internal short circuits is suppressed, the cycle characteristics are excellent, and the increase in interfacial resistance is also suppressed can be manufactured by a simple method of crimp lamination.
  • the laminated sheet for the negative electrode and the sheet for the positive electrode of the present invention are produced.
  • the laminated sheet for a negative electrode used in the production method of the present invention has a negative electrode current collector, an electron ion conductive layer having a porosity of 20% or more, and an ion conductive layer having a porosity of 20% or more in this order, and has a porosity of 20% or more.
  • the electron ion conductive layer having a porosity of 20% or more is arranged adjacent to the negative electrode current collector, and preferably is arranged adjacent to the ion conductive layer having a porosity of 20% or more.
  • the porosity of each layer is measured by the method described above.
  • each layer constituting the negative electrode laminated sheet may have a single-layer structure or a multi-layer structure as long as it fulfills a specific function.
  • the laminated sheet for the negative electrode of the present invention is not particularly limited as long as it has the above configuration, and for example, a known configuration for the negative electrode sheet used in the all-solid secondary battery can be adopted.
  • the laminated sheet for the negative electrode of the present invention is preferably used in combination with the sheet for the positive electrode described later (as a sheet for crimping and laminating the sheet for the positive electrode) in the manufacturing method of the present invention to form an all-solid-state lithium ion secondary battery. To do.
  • FIG. 2 is a cross-sectional view schematically showing a laminated state of each constituent layer constituting the sheet for one embodiment of the negative electrode laminated sheet.
  • the negative electrode laminated sheet 11 of the present embodiment has a structure in which a negative electrode current collector 1, an electron ion conductive layer 8 having a porosity of 20% or more, and an ion conductive layer 9 having a porosity of 20% or more are laminated in this order. The laminated layers are in contact with each other.
  • the negative electrode current collector of the laminated sheet for the negative electrode is as described above (synonymous) with the negative electrode current collector in the all-solid-state lithium ion secondary battery.
  • An electron ion conductive layer having a void ratio of 20% or more provided in a laminated sheet for a negative electrode in order to distinguish it from the in-battery electron ion conductive layer of the above-mentioned all-solid-state lithium ion secondary battery, it is referred to as an in-sheet electron ion conductive layer.
  • (A) is a layer having a void ratio of 20% or more and being incorporated into an all-solid-state lithium ion secondary battery to serve as the electron ion conductive layer in the battery.
  • the porosity of the electron ion conductive layer in the sheet is 20% or more, the porosity of the electron ion conductive layer in the battery is reduced to less than 15% even when pressurized by the crimp lamination method (for example, the manufacturing method of the present invention). This can be suppressed (the electron ion conductive layer in the sheet is excessively compressed).
  • the porosity of the electron ion conductive layer in the sheet varies depending on the pressing force of the pressure bonding lamination method, the porosity of the ion conductive layer having a porosity of 20% or more, and the type or content of particles forming voids, which will be described later. Therefore, it is not uniquely decided. For example, this porosity is preferably 30% or more.
  • the upper limit of the porosity is not particularly limited as long as the layer morphology can be maintained, but for example, it is preferably 70% or less, more preferably 60% or less, and further preferably 50% or less.
  • the porosity of the electron ion conductive layer in the sheet is a value calculated as an area ratio by the above method.
  • the electron-ion conductive layer in the sheet exhibits lithium ion conductivity and electron conductivity, similarly to the electron-ion conductive layer in the battery.
  • the thickness of the electron ion conductive layer in the sheet is not particularly limited, and the compression amount (thickness) varies depending on the pressing force by the pressure bonding method. Therefore, the compression amount is taken into consideration in consideration of the capacity of the positive electrode active material layer to be combined. It can be set arbitrarily according to. For example, 10 to 500 ⁇ m is preferable.
  • the electron-ion conductive layer in the sheet contains a lithium ion-conductive inorganic solid electrolyte and electron-conducting particles, and preferably contains a binder, particles forming voids, and other components as appropriate.
  • the electron ion conductive layer in the sheet does not have a negative electrode active material other than metallic lithium, like the electron ion conductive layer in the battery.
  • the inorganic solid electrolyte and the electron conductive particles contained in the electron ion conductive layer in the sheet, preferably the binder contained, and other components which may be contained are the same as the above-mentioned components in the electron ion conductive layer in the battery. is there.
  • each component is also the same as the content of each component in the electron ion conductive layer in the battery.
  • the standard of the content is the total mass of the electron ion conductive layer in the sheet, and this total mass is the total mass of the components constituting the electron ion conductive layer in the sheet, and further, to form the electron ion conductive layer. It is synonymous with 100% by mass of the solid content of the composition of.
  • the electron ion conductive layer in the sheet may contain particles (sometimes referred to as void forming particles) that form voids in the layer (electron ion conductive layer in the battery) after the pressurizing step described later. It is preferable because it is easy to set both the void ratios of the electron ion conductive layer in the sheet and the electron ion conductive layer in the battery within a predetermined range.
  • the void-forming particles refer to particles that form voids (non-contact gaps between solid particles) together with other solid particles by contacting with other solid particles.
  • the void-forming particles are not particularly limited, but preferably, the above-mentioned inorganic solid electrolyte (particularly those having a particle diameter of 10 ⁇ m or more), the above-mentioned oxide-based inorganic solid electrolyte, the above-mentioned binder particles, and an inorganic compound other than the above-mentioned inorganic solid electrolyte. Particles (inorganic particles) can be mentioned. In the electron ion conductive layer in the sheet, it is more preferable to use an inorganic solid electrolyte or binder particles having a particle diameter of 10 ⁇ m or more. The porosity can be adjusted by selecting the particle size and content of the void-forming particles.
  • the electron ion conductive layer in the sheet may contain the particles of the inorganic solid electrolyte having a particle diameter of 10 ⁇ m or more alone, and the inorganic solid electrolyte as the particles forming the voids. May contain a part of.
  • the void-forming particles contain particles of an inorganic solid electrolyte having a particle diameter of 10 ⁇ m or more and particles of an inorganic solid electrolyte having a particle diameter of less than ⁇ m.
  • the particle size of the inorganic solid electrolyte that functions as the void-forming particles is not particularly limited, and is preferably 10 ⁇ m or more, more preferably 12 ⁇ m or more, and further preferably 14 ⁇ m or more.
  • the particle size of the particles of the inorganic solid electrolyte having a particle size of less than 10 ⁇ m is preferably 5 ⁇ m or less, and more preferably 3 ⁇ m or less.
  • the particles of the inorganic solid electrolyte having a particle diameter of 10 ⁇ m or more and the particles of the inorganic solid electrolyte having a particle diameter of less than 10 ⁇ m are used in combination, the particles of the inorganic solid electrolyte having a particle diameter of 10 ⁇ m or more are contained in the total mass of the electron ion conductive layer in the sheet.
  • the amount is not unique because it varies depending on the void ratio, but can be, for example, 10 to 90% by mass, preferably 20 to 80% by mass.
  • the electron ion conductive layer is formed of a sulfide-based inorganic solid electrolyte
  • the content of the particles of the oxide-based inorganic solid electrolyte can be 5 to 20% by mass based on the total mass of the electron ion conductive layer in the sheet.
  • Particulate particles (binder particles) among the above-mentioned binders can also be used as the void-forming particles.
  • the binder particles contribute to the binding of the negative electrode current collector and the solid particles, and are further arranged at the interface between the inorganic solid electrolyte and the inorganic solid electrolyte (sandwiched between the inorganic solid electrolytes), and a step of pressurizing described later. It is possible to promote the formation of voids in the electron ion conductive layer pressure-compressed by.
  • the particle size of the binder particles that function as the void-forming particles is not unique because it varies depending on the porosity, but for example, it is preferably 0.1 ⁇ m or more, more preferably 0.1 to 1 ⁇ m, and 0.
  • the content of the electron ion conductive layer in the sheet of the binder particles is not unique because it varies depending on the porosity, but it is preferably 0.1 to 10% by mass, for example, in the total mass of the electron ion conductive layer in the sheet. 1 to 10% by mass is more preferable, and 2 to 8% by mass is further preferable. Porosity can be increased by increasing the content and particle size of the binder particles.
  • An ion conductive layer having a void ratio of 20% or more provided in the laminated sheet for the negative electrode in order to distinguish it from the ion conductive layer in the battery of the above-mentioned all-solid-state lithium ion secondary battery, it may be referred to as an ion conductive layer in the sheet).
  • the porosity of the ion conductive layer in the sheet is 20% or more, it is easily compressed and deformed by pressure in the pressure bonding lamination method (for example, the manufacturing method of the present invention), and is bitten into the positive electrode active material layer to be firmly adhered. Thereby, the interfacial resistance between the ion conductive layer in the sheet and the positive electrode active material layer can be reduced.
  • the porosity of the ion conductive layer in the sheet is not uniquely determined because it varies depending on the pressing force of the pressure bonding laminating method, the porosity of the electron ion conductive layer having a porosity of 20% or more, and the like. For example, this porosity is preferably 20% or more, and more preferably 30% or more.
  • the upper limit of the porosity is not particularly limited as long as the layer morphology can be maintained, but for example, it is preferably 70% or less, more preferably 60% or less, and further preferably 55% or less.
  • the porosity of the ion conductive layer in the sheet is a value calculated as an area ratio by the above method.
  • the difference between the porosity of the ion conductive layer in the sheet and the porosity of the electron ion conductive layer in the sheet is not particularly limited.
  • the ion conductive layer in the sheet shows lithium ion conductivity like the ion conductive layer in the battery, and usually does not show electron conductivity.
  • the thickness of the ion conductive layer in the sheet is not particularly limited, and the amount of compression (thickness) varies depending on the pressure applied by the pressure bonding method, so it is appropriately set according to the amount of compression. For example, 10 to 1000 ⁇ m is preferable, and 20 to 500 ⁇ m is more preferable.
  • the ion conductive layer in the sheet contains a lithium ion conductive inorganic solid electrolyte, preferably a binder, and may further contain other components as appropriate.
  • the ion conductive layer in the sheet usually does not contain a positive electrode active material and a negative electrode active material.
  • the inorganic solid electrolyte contained in the ion conductive layer in the sheet, preferably the binder contained, and other components which may be contained are the same as the above-mentioned components in the electron ion conductive layer in the battery.
  • the content of each component is also the same as the content of each component in the electron ion conductive layer in the battery.
  • the standard of the content is the total mass of the ion conductive layer in the sheet, and this total mass is the total mass of the components constituting the ion conductive layer in the sheet, and further, the composition for forming the ion conductive layer. It is synonymous with 100% by mass of the solid content of.
  • the ion conductive layer in the sheet contains a binder.
  • the binder is preferably a particulate binder.
  • the binder particles contained in the ion conductive layer in the sheet preferably have a particle diameter smaller than that of the binder particles contained in the electron ion conductive layer in the sheet.
  • the difference in particle size at this time is not unique because it varies depending on the amount of compression of both layers, but it can be, for example, 0.03 ⁇ m or more, preferably 0.05 to 1 ⁇ m.
  • the content of the binder particles contained in the ion conductive layer in the sheet is preferably smaller than the content of the binder particles contained in the electron ion conductive layer in the sheet.
  • the difference in content at this time is not unique because it varies depending on the amount of compression of both layers, but it can be, for example, 1% by mass or more, and preferably 1 to 5% by mass.
  • the magnitude relationship between the particle size and the content of the binder particles in the in-sheet ion conductive layer and the in-sheet electron ion conductive layer also applies to the inorganic solid electrolyte.
  • the difference in particle diameter can be 0.1 ⁇ m or more, preferably 0.1 to 15 ⁇ m.
  • the difference in content can be 1% by mass or more, preferably 1 to 5% by mass.
  • the laminated sheet for the negative electrode may have other layers such as a protective layer (release sheet) and a coat layer.
  • the laminated sheet for a negative electrode is usually in the form of a sheet, but includes a laminated sheet for a negative electrode cut out into a predetermined shape when used in the production method of the present invention.
  • a plate-shaped or disk-shaped laminated sheet material for a negative electrode may be used depending on the shape of the all-solid-state lithium ion secondary battery.
  • the laminated sheet for the negative electrode is produced by forming an in-sheet electron ion conductive layer on the surface of the negative electrode current collector and then forming an in-sheet ion conductive layer on the in-sheet electron ion conductive layer. Can be done.
  • the electron-ion conducting layer in the sheet and the ion-conducting layer in the sheet may be formed individually, sequentially, or collectively as a laminated body.
  • the electron ion conductive layer composition contains a lithium ion conductive inorganic solid electrolyte and electron conductive particles, preferably containing a binder, particles forming voids, and appropriately containing other components and a dispersion medium. You may.
  • the electron ion conductive layer composition preferably contains (uses) the above-mentioned void-forming particles.
  • the void-forming particles in this composition, their physical properties and their contents are as described above.
  • the ion conductive layer composition may contain a lithium ion conductive inorganic solid electrolyte, preferably a binder, and if appropriate, other components and a dispersion medium.
  • each component other than the dispersion medium contained in the electron ion conductive layer composition and the ion conductive layer composition (sometimes referred to as each composition) is as described above.
  • the standard of the content in each composition is 100 parts by mass of the solid content of each composition.
  • the solid content refers to a component that does not disappear by volatilizing or evaporating when the composition is dried at 130 ° C. for 6 hours under an atmospheric pressure of 1 mmHg and a nitrogen atmosphere. Typically, it refers to components other than the dispersion medium.
  • each composition is a non-aqueous composition.
  • the non-aqueous composition includes not only a water-free aspect but also a form having a water content (also referred to as a water content) of 200 ppm or less.
  • the water content of the composition is preferably 150 ppm or less, more preferably 100 ppm or less, and even more preferably 50 ppm or less.
  • the water content indicates the amount of water contained in the composition (mass ratio to the composition).
  • the water content can be determined by filtering the composition with a 0.45 ⁇ m membrane filter and performing Karl Fischer titration.
  • the dispersion medium may be any one that disperses (dissolves) each of the above components contained in each composition.
  • the dispersion medium is preferably a non-aqueous dispersion medium containing no water, and is usually selected from organic solvents.
  • the term "water-free” includes aspects in which the water content is 0% by mass and 0.1% by mass or less. However, the water content in each composition is preferably within the above range (non-aqueous composition).
  • the organic solvent is not particularly limited, and examples thereof include organic solvents such as alcohol compounds, ether compounds, amide compounds, amine compounds, ketone compounds, aromatic compounds, aliphatic compounds, nitrile compounds, and ester compounds.
  • the dispersion medium contained in each composition may be one kind or two or more kinds.
  • the content of the dispersion medium in each composition is not particularly limited, and is preferably 20 to 80% by mass, more preferably 30 to 70% by mass, and particularly preferably 40 to 60% by mass.
  • Each composition can be prepared, for example, as a solid mixture or slurry by mixing each of the above-mentioned components with, for example, various commonly used mixers.
  • the mixing method is not particularly limited, and can be carried out using a known mixer such as a ball mill, a bead mill, or a disc mill. Further, the mixing conditions are not particularly limited.
  • the mixed atmosphere may be any of air, dry air (dew point ⁇ 20 ° C. or lower), inert gas (for example, argon gas, helium gas, nitrogen gas) and the like. Since the inorganic solid electrolyte reacts with moisture, the mixing is preferably carried out under dry air or in an inert gas.
  • the electron ion conductive layer in the sheet is not particularly limited, but is a coating drying method in which an electron ion conductive layer composition (slurry) containing a dispersion medium is applied on the surface of the negative electrode current collector and then dried, or electron ions. It can be produced by a molding method or the like in which the conductive layer composition is pressure-molded. In either method, the atmosphere during preparation is not particularly limited, and examples thereof include a mixed atmosphere of the above-mentioned quality compositions.
  • the electron ion conductive layer composition for example, various coating methods such as spray coating, spin coating coating, dip coating coating, slit coating, stripe coating, bar coating coating, and coating using a baker type applicator.
  • the drying temperature is not particularly limited, but the lower limit of the drying temperature is preferably 30 ° C. or higher, more preferably 60 ° C. or higher, and even more preferably 80 ° C. or higher.
  • the upper limit of the drying temperature is preferably 300 ° C. or lower, more preferably 250 ° C. or lower, and even more preferably 200 ° C. or lower.
  • the drying time is not particularly limited, and is, for example, 0.3 to 5 hours. It is also possible to pressurize the coating dry layer formed as described above.
  • the pressurizing method is not particularly limited, but press pressurization (for example, press pressurization using a hydraulic cylinder press machine) is preferable.
  • the pressure is not particularly limited, but is set to a pressure at which the porosity after pressurization is 20% or more, and can be, for example, 10 to 200 MPa. It may be heated at the same time as the pressurization of the coating dry layer.
  • the temperature at this time is not particularly limited, but is preferably 10 to 100 ° C., for example.
  • the electron ion conductive layer in the sheet having a predetermined porosity can be formed.
  • the porosity can be appropriately set according to the type, physical properties and content of the above-mentioned void-forming particles, and in the case of pressurization, a pressing force or the like.
  • the ion conductive layer in the sheet is not particularly limited, but a coating drying method in which an ion conductive layer composition (slurry) containing a dispersion medium is applied on the surface, preferably on the surface of the electron ion conductive layer in the sheet, and then dried.
  • the ion conductive layer composition can be produced by a molding method such as pressure molding. In these methods, the formation of the ion conductive layer in the sheet is the same as the formation of the electron ion conductive layer in the sheet, except that the composition used and the surface to be formed are different.
  • the ion conductive layer composition (slurry) is applied on a substrate such as a support, dried, or the ion conductive layer composition is pressure-molded to form an ion conductive layer. Is formed, and is provided on the electron ion conductive layer in the sheet formed on the negative electrode current collector (crimp lamination or sticking).
  • the base material to be used is not particularly limited, and examples thereof include a sheet body (plate-shaped body) such as an organic material and an inorganic material.
  • the organic material include various polymers, and specific examples thereof include polyethylene terephthalate, polypropylene, polyethylene, and cellulose.
  • the inorganic material include glass and ceramics.
  • the method and conditions for applying and drying the ion conductive layer composition (slurry) are the same as the above-mentioned coating and drying method.
  • the conditions for pressure-bonding and laminating may be any condition as long as the ion-conducting layer can be pressure-bonded and laminated on the electron ion-conducting layer in the sheet, and examples thereof include a pressure of 1 to 100 MPa, preferably 10 to 100 ° C.
  • the atmosphere for crimping and laminating is the same as the mixed atmosphere for each of the above compositions.
  • the ion conductive layer in the sheet having a predetermined porosity can be formed on the electron ion conductive layer in the sheet.
  • the porosity can be appropriately set according to the type, physical properties and content of the above-mentioned void-forming particles, and in the case of pressurization, a pressing force or the like.
  • the negative electrode current collector, the electron ion conductive layer in the sheet, and the laminated body of the ion conductive layer in the sheet can be produced and then pressurized as described above.
  • the pressurizing method and pressure are not particularly limited, but are the same as the pressurizing method and pressure of the coating dry layer.
  • the in-sheet electron ion conductive layer and the in-sheet ion conductive layer of the laminated sheet for negative electrode thus produced each contain (remain) the dispersion medium used for the preparation of each composition as long as the effect of the present invention is not impaired. You may be.
  • the residual amount can be, for example, 3% by mass or less in the layer.
  • a laminated sheet for a negative electrode having an in-sheet electron ion conductive layer and an in-sheet ion conductive layer having a predetermined porosity arranged adjacent to each other in this order can be produced in the negative electrode current collector.
  • a positive electrode sheet is used in combination with the negative electrode laminated sheet of the present invention.
  • the positive electrode sheet may be a sheet having a positive electrode active material layer, and examples thereof include a sheet made of a positive electrode active material layer, a sheet having a positive electrode current collector and a positive electrode active material layer, and the like.
  • the positive electrode active material layer and the positive electrode current collector in the positive electrode sheet are the same as those in the above-mentioned all-solid-state lithium ion secondary battery.
  • the positive electrode sheet may have the other layers described in the negative electrode laminated sheet.
  • the positive electrode sheet is usually in the form of a sheet like the negative electrode laminated sheet, but when used in the production method of the present invention, a sheet cut into a predetermined shape (positive electrode sheet material) can also be used.
  • the positive electrode sheet When the positive electrode sheet is produced, it can be produced by forming a positive electrode active material layer on the surface of a base material, preferably a positive electrode current collector.
  • a composition (positive electrode composition) for forming the positive electrode active material layer is prepared.
  • the positive electrode composition may contain a positive electrode active material, preferably an inorganic solid electrolyte having lithium ion conductivity, a conductive auxiliary agent, a binder, and optionally other components and a dispersion medium. ..
  • Each component contained in the positive electrode composition is as described above. The content of each component is the same as the content of each component in the positive electrode active material layer described above, except that the solid content of the positive electrode composition is based on 100 parts by mass.
  • the composition for the positive electrode is preferably a non-aqueous composition.
  • the positive electrode composition can be prepared, for example, as a solid mixture or a slurry by mixing each of the above-mentioned components with, for example, various commonly used mixers.
  • the mixing method, mixing conditions, and the like are the same as the above-mentioned preparation conditions for the electron ion conductive layer composition and the ion conductive layer composition.
  • the positive electrode active material layer is not particularly limited, but is a coating drying method in which a positive electrode composition (slurry) containing a dispersion medium is applied on the surface of a base material, preferably a positive electrode current collector, and then dried, or a positive electrode. It can be produced by a molding method in which the composition for use is pressure-molded. In either method, the atmosphere during preparation is not particularly limited, and examples thereof include a mixed atmosphere of the above-mentioned quality compositions.
  • the method for forming the positive electrode active material layer is the same as that for forming the electron ion conductive layer in the sheet, except that the composition to be used and the surface to be formed are different. However, it is not necessary to positively adjust the porosity when forming the positive electrode active material layer.
  • a positive electrode active material layer may be prepared by using a base material instead of the positive electrode current collector, and this may be provided on the negative electrode current collector (crimp lamination or sticking) to prepare a positive electrode sheet. it can.
  • the base material, pressure-bonding lamination conditions, and the like used in this method are the same as those for another method for producing the ion conductive layer in the sheet of the negative electrode laminated sheet.
  • a positive electrode sheet having a positive electrode active material layer on the positive electrode current collector can be produced.
  • the negative electrode laminated sheet and the positive electrode sheet that have been produced or prepared are pressure-bonded and laminated to each other by sequentially performing the following step of laminating and pressurizing. That is, in the production method of the present invention, a laminated sheet for a negative electrode having an electron ion conductive layer in a sheet and an ion conductive layer in a sheet having a high void ratio of 20% or more is used, and this sheet is pressurized with a positive electrode active material layer.
  • the electron-ion conducting layer in the sheet and the ion-conducting layer in the sheet are compressed to a predetermined void ratio to form the electron-ion conducting layer in the battery and the ion-conducting layer in the battery in which the void ratio is reduced.
  • the method As a result, it is possible to secure a deposition space for metallic lithium and to make the ion conductive layer in the battery dense. Further, the interlayer adhesion between the ion conductive layer in the battery and the positive electrode active material layer can be strengthened.
  • Step of superimposing Step of superimposing the negative electrode laminated sheet and the positive electrode sheet by facing the ion conductive layer in the sheet of the negative electrode laminated sheet as the negative electrode sheet and the positive electrode active material layer of the positive electrode sheet Pressurizing step: A step of pressurizing the laminated negative electrode sheet and the positive electrode sheet in the laminated direction until the void ratio of the electron ion conductive layer is 15% or more and the void ratio of the ion conductive layer is 10% or less.
  • performing steps in order means the time ahead and after performing a certain step and another step, and another step (pause step) is performed between one step and another step. Includes.)
  • the mode in which a certain step and another step are performed in order also includes a mode in which the time, place, or practitioner is appropriately changed.
  • both sheets may be laminated (stacked) by a usual method, and the ion conductive layer in the sheet and the positive electrode active material layer are arranged in contact (adjacent) by this step.
  • the laminated negative electrode sheet and the positive electrode sheet that are superposed are pressurized (compressed) in the superposed direction.
  • the pressing force at this time suppresses the porosity of the electron ion conductive layer after pressurization to 15% or more (while maintaining 15% or more, that is, without reducing it to 15% or less), and after pressurization.
  • the porosity of the ion conductive layer of is set to a pressure of 10% or less (reaching). That is, in the step of pressurizing, both sheets are pressurized to set the porosity of the electron ion conductive layer to 15% or more and the porosity of the ion conductive layer to less than 10%.
  • the porosity of the electron ion conductive layer after pressurization does not have to be less than 15%, and is set to the porosity of the electron ion conductive layer in the battery described above.
  • the amount of reduction of the porosity by pressurization is not particularly limited, but is preferably 5 to 40%, for example, 5 to 30. More preferably.
  • the porosity of the ion conductive layer after pressurization may be less than 10%, and is set to the porosity of the ion conductive layer in the battery described above.
  • the amount of reduction of the porosity by pressurization is not particularly limited, but is preferably 10 to 60%, preferably 20 to 50%, for example. Is more preferable.
  • the pressing force in the pressurizing step may be a pressure such that the porosity of the electron-ion conductive layer and the ion-conducting layer in the sheet after pressurization is within the above range, but the electron-ion-conducting layer in the sheet and the ion-conducting layer in the sheet may be pressed. It is not uniquely determined because it varies depending on the porosity, the porosity after pressurization, and the like.
  • the pressing force can be, for example, 100 to 1000 MPa, preferably 200 to 800 MPa, and more preferably 350 to 800 MPa.
  • the pressurization time can be set appropriately.
  • the pressurizing step can also be heated at the same time as the pressurization.
  • the heating temperature is not particularly limited, but is generally in the range of 30 to 300 ° C.
  • the electron ion conductive layer in the sheet is not compressed until the porosity becomes less than 15%, and the ion conductive layer in the sheet has a porosity. It is compressed to 10% or less.
  • the porosity of the electron ion conductive layer and the ion conductive layer can be set within the above range by the step of pressurizing.
  • the dendrite is densified by compressing the ion conductive layer in the sheet until the porosity of the ion conductive layer in the sheet (electron ion conductive layer in the battery) after pressurization becomes 10% or less. It can prevent the growth reaching the positive electrode active material layer.
  • the ionic conductivity of the ionic conductive layer in the sheet after pressurization is improved, and the ionic conductive layer after pressurization and the positive electrode active material layer are well bonded (strongly adhered (crimped)) at the contact interface. The interfacial resistance between the ionic conduction layer and the positive electrode active material layer after pressurization can be suppressed low.
  • the negative electrode laminated sheet and the positive electrode are obtained by compressing the in-sheet electron ion conductive layer and the in-sheet ion conductive layer having a porosity of 20% or more to 15% or more and 10% or less, respectively. Integrate with the sheet. In this way, the all-solid-state lithium ion secondary battery (discharged state) of the present invention in which the negative electrode active material layer is not formed in advance can be manufactured.
  • the production method of the present invention may include a step of initializing the all-solid-state lithium ion secondary battery (discharged state) obtained above, or may include a step of charging. Initialization is usually performed after the production of the all-solid-state lithium ion secondary battery and before use, and the charging step and the discharging step are performed at least once each.
  • lithium ions are supplied from the positive electrode active material layer to at least the electron ion conductive layer (usually in the voids) in the battery to precipitate metallic lithium as the negative electrode active material layer (all-solid-state lithium ion secondary in a charged state).
  • the charging conditions are not particularly limited, and examples thereof include the following conditions. Current: 0.05 to 30 mA / cm 2 Voltage: 4.0-4.5V Charging time: 0.1-100 hours Temperature: 0-80 ° C
  • the charging step is preferably performed by pressurizing and restraining the all-solid-state lithium ion secondary battery (discharged state) in the superposition direction.
  • the pressure at this time is not particularly limited, but is preferably 0.05 MPa or more, and more preferably 1 MPa.
  • the upper limit is not particularly limited, but is preferably less than 10 MPa, more preferably 5 MPa or less, for example.
  • the metallic lithium precipitated in the electron ion conductive layer in the battery can be ionized and moved to the positive electrode active material layer.
  • the discharge conditions are not particularly limited, and examples thereof include the following conditions. Current: 0.05 to 30 mA / cm 2 Voltage: 4.0-4.5V Charging time: 0.1-100 hours Temperature: 0-80 ° C
  • the discharge step is preferably performed by pressurizing and restraining the all-solid-state lithium ion secondary battery (charged state) in the stacking direction. As a result, the expansion of the all-solid-state lithium ion secondary battery can be suppressed.
  • the pressure at this time is not particularly limited and can be set in the above pressure range in the charging step, and may be the same as or different from the pressure in the charging step.
  • the all-solid-state lithium-ion secondary battery of the present invention is manufactured by performing each step and appropriately initializing. As described above, this all-solid-state lithium-ion secondary battery suppresses the occurrence of internal short circuits and has excellent cycle characteristics. Furthermore, the increase in interfacial resistance is also suppressed.
  • lithium sulfide Li 2 S, Aldrich Corp., purity> 99.98%) 2.42 g, diphosphorus pentasulfide (P 2 S 5, Aldrich Co., purity> 99%) 3.90 g were weighed, charged into an agate mortar, using an agate pestle and mixed for 5 minutes.
  • LPS particle size control> Using the LPS (1) synthesized in Synthesis Example 1 above, wet dispersion was performed under the following conditions to adjust the particle size of LPS. That is, 300 zirconia beads having a diameter of 3 mm were put into a 45 mL container made of zirconia (manufactured by Fritsch), 4.0 g of the synthesized LPS (1) and 6.0 g of diisobutyl ketone as a dispersion medium were added, respectively. This container was set in the planetary ball mill P-7, and wet dispersion was performed for 60 minutes under any of the following conditions 1 to 4. As a result, LPSs (2) to (5) having the particle diameters shown below were obtained.
  • Condition 1 LPS (2) having a rotation speed of 170 rpm and a particle diameter of 7 ⁇ m.
  • Condition 2 LPS (3) having a rotation speed of 200 rpm and a particle diameter of 5 ⁇ m.
  • Condition 3 LPS (4) having a rotation speed of 250 rpm and a particle diameter of 3 ⁇ m.
  • Condition 4 LPS (5) having a rotation speed of 300 rpm and a particle diameter of 2 ⁇ m.
  • a dispersion medium diisobutylketone
  • binder particles B-1 particle size 150 nm
  • acrylic polymer mass average molecular weight 75,000, glass transition temperature ⁇ 5 ° C.
  • the macromonomer AB-6 is a polybutyl acrylate (number average molecular weight 6000) whose terminal functional group is a methacryloyl group.
  • a dispersion liquid of binder particles B-2 (particle size 300 nm) composed of an acrylic polymer (mass average molecular weight 75,000, glass transition temperature ⁇ 5 ° C.) was obtained.
  • the macromonomer AB-6 is a polybutyl acrylate (number average molecular weight 6000) whose terminal functional group is a methacryloyl group.
  • Example 1 Fabrication of Laminated Sheet for Negative Electrode ⁇ Preparation of Laminated Sheet AS-1 for Negative Electrode> (Preparation of electron ion conductive layer composition) LPS (4) whose particle size is adjusted to 3 ⁇ m, acetylene black (particle size 0.1 ⁇ m, manufactured by Denka) as electron conductive particles, and binder particle B-1 dispersion are mixed at 90: 5: 5 (solid content).
  • the mixture was mixed at a mass ratio of (converted), added to a 45 mL container made of zirconia (manufactured by Fritsch), and 20 g of zirconia beads having a diameter of 3 mm and diisobutylketone as a dispersion solvent were added to adjust the solid content concentration to 40% by mass. Then, this container was set in a planetary ball mill P-7 and stirred at a temperature of 25 ° C. and a rotation speed of 100 rpm for 1 hour to prepare an electron ion conductive layer composition (slurry).
  • a baker-type applicator (trade name: SA-201, manufactured by Tester Sangyo Co., Ltd.) on the surface of a 20 ⁇ m-thick stainless steel (SUS) foil (negative electrode current collector) in which the obtained electron ion conductive layer composition is carbon-coated. ), And dried by heating at 100 ° C. for 1 hour to form an electron ion conductive layer having a layer of 80 ⁇ m on the surface of the negative electrode current collector (carbon coat film).
  • LPS (4) whose particle size is adjusted to 3 ⁇ m and binder particle B-1 dispersion are mixed at a mass ratio of 97: 3 (solid content equivalent), and added to a zirconia 45 mL container (Fritsch) to add the diameter. 20 g of 3 mm zirconia beads and diisobutyl ketone as a dispersion solvent were added to adjust the solid content concentration to 40% by mass. Then, this container was set in the planetary ball mill P-7 and stirred at a temperature of 25 ° C. and a rotation speed of 100 rpm for 1 hour to prepare an ion conductive layer composition (slurry).
  • the obtained ion conductive layer composition was applied to the surface of the electron ion conductive layer provided on the negative electrode current collector with a baker type applicator (trade name: SA-201), and dried by heating at 100 ° C. for 1 hour.
  • SA-201 baker type applicator
  • an electron ion conductive layer having a layer of 80 ⁇ m and then an ion conductive layer having a layer of 50 ⁇ m were formed adjacent to each other. In this way, the laminated sheet AS-1 for the negative electrode was produced.
  • the ion conductive layer is directly formed on the surface of the negative electrode current collector (carbon coat film) by changing the coating amount of the ion conductive layer composition without forming the electron ion conductive layer.
  • the negative electrode laminated sheet CAS-2 was produced in the same manner as the negative electrode laminated sheet AS-1 except that it was formed.
  • Example 2 Manufacture of an all-solid-state lithium-ion secondary battery An all-solid-state lithium-ion secondary battery was manufactured as follows, and its characteristics were evaluated. A positive electrode sheet was prepared for the production of an all-solid-state lithium-ion secondary battery. ⁇ Manufacturing of positive electrode sheet> (Preparation of composition for positive electrode) Lithium nickel manganese cobaltate (particle diameter 0.5 ⁇ m, manufactured by Aldrich) as a positive electrode active material, LPS (5) adjusted to a particle diameter of 2 ⁇ m, and acetylene black (particle diameter 0.1 ⁇ m, manufactured by Denka) as a conductive aid.
  • Lithium nickel manganese cobaltate particle diameter 0.5 ⁇ m, manufactured by Aldrich
  • LPS (5) adjusted to a particle diameter of 2 ⁇ m
  • acetylene black particle diameter 0.1 ⁇ m, manufactured by Denka
  • binder particle B-1 dispersion in a mass ratio of 70: 27: 2: 1 solid content equivalent
  • a 45 mL container made of zirconia manufactured by Fritsch
  • 20 g of zirconia beads having a diameter of 3 mm added to a 45 mL container made of zirconia (manufactured by Fritsch)
  • 20 g of zirconia beads having a diameter of 3 mm added to a 45 mL container made of zirconia (manufactured by Fritsch), and add 20 g of zirconia beads having a diameter of 3 mm.
  • diisobutylketone was added as a dispersion solvent to adjust the solid content concentration to 45% by mass.
  • this container was set in the planetary ball mill P-7 and stirred at a temperature of 25 ° C. and a rotation speed of 100 rpm for 1 hour to prepare a positive electrode composition (slurry).
  • the obtained positive electrode composition is applied to the surface of a carbon-coated aluminum foil (positive electrode current collector) having a thickness of 20 ⁇ m with a baker-type applicator (trade name: SA-201) and heated at 100 ° C. for 1 hour. It was dried to prepare a positive electrode sheet having a positive electrode active material layer (coating dry layer) having a thickness of 150 ⁇ m.
  • the prepared positive electrode sheet was punched into a disk shape having a diameter of 1 cm to obtain a positive electrode disk-shaped sheet. Further, the negative electrode laminated sheet shown in Tables 4 and 5 was punched into a disk shape having a diameter of 1.2 cm to obtain a negative electrode laminated disk-shaped sheet (negative electrode laminated sheet material).
  • the positive electrode active material layer of the positive electrode disk-shaped sheet and the ion conductive layer in the sheet of the negative electrode laminated disk-shaped sheet are opposed to each other and superposed so that the positive electrode disk-shaped sheet does not protrude from the negative electrode laminated disk-shaped sheet. It was.
  • the positive electrode disk-shaped sheet and the negative electrode laminated disk-shaped sheet were pressurized at a pressure of 500 MPa for 1 minute in the overlapping direction.
  • the electron-ion conducting layer in the sheet and the ion-conducting layer in the sheet were pressure-compressed to form the electron-ion conducting layer in the battery and the ion-conducting layer in the battery having the porosities shown in Tables 4 and 5.
  • the entire uncharged state having the laminated structure shown in FIG. 1 including the negative electrode current collector, the electron ion conductive layer in the battery, the ion conductive layer in the battery, the positive electrode active material layer, and the positive electrode current collector.
  • Solid-state lithium-ion secondary batteries LIB-1 to LIB13 and CLIB-1 to CLIB-5 were produced, respectively.
  • the thickness of the positive electrode active material layer was 80 ⁇ m after the pressure bonding.
  • Each all-solid-state lithium-ion secondary battery was constrained with a SUS rod having a diameter of 1.5 cm in the stacking direction with a restraining pressure of 5 MPa to obtain a pressure-constrained all-solid-state lithium-ion secondary battery.
  • Tables 4 to 6 show the thickness and porosity (measured values by the above-mentioned measuring method) of the electron-ion conducting layer in the battery and the ion-conducting layer in the battery for each of the manufactured all-solid-state lithium ion secondary batteries.
  • Tables 4 to 6 also show the thickness and porosity of the in-sheet electron ion conductive layer and the in-sheet ion conductive layer in the negative electrode laminated sheet.
  • Table 6 shows the pressing force in the pressurizing step, and also shows the all-solid-state lithium ion secondary batteries LIB-1 and LIB-2.
  • Each all-solid-state lithium-ion secondary battery was pressure restraint was charged to 4.25V at 0.05 mA / cm 2, and discharged at 0.05 mA / cm 2 to 2.5V, initialized.
  • the all-solid-state lithium-ion secondary batteries initialized in this way, LIB-1 to LIB-13, LIB-1-A, LIB-1-B, LIB-2-A, LIB-2-B, and CLIB-1 to CLIB-5. was obtained respectively.
  • Resistance was evaluated as a reference test. Specifically, the resistance was calculated and evaluated by the following formula from the voltage measured immediately after the discharge in the first cycle. The evaluation was performed by obtaining a relative value with respect to the all-solid-state lithium ion secondary battery LIB-1. The resistance value of the all-solid-state lithium-ion secondary battery LIB-1 was sufficiently small for the all-solid-state lithium-ion secondary battery. Resistance calculation formula: (voltage when current is 0mA (opening voltage before voltage discharge start) -1 cycle voltage 10 seconds after discharge start) / discharge current
  • the void ratio of the ion conductive layer in the battery is determined by using the laminated sheets CAS-1 and CAS-2 for the negative electrode which do not have the electron ion conductive layer in the sheet. It is manufactured by setting within the range specified in the present invention. Since these all-solid-state lithium-ion secondary batteries do not have an electron-ion conducting layer in the battery, the occurrence of an internal short circuit cannot be prevented even if the porosity of the ion-conducting layer in the battery is satisfied. It is considered that the metallic lithium was locally precipitated and the solid electrolyte layer was destroyed (cracks were formed).
  • the all-solid-state lithium ion secondary battery CLIB-3 uses a negative electrode laminated sheet CAS-3 having a layer containing no electron conductive particles and an ion conductive layer in the sheet, and the void ratio of the ion conductive layer in the battery. Is manufactured within the range specified in the present invention.
  • this all-solid-state lithium-ion secondary battery since the porosity of the layer containing no electron conductive particles is 35%, it is possible to suppress the destruction of the solid electrolyte layer due to the local precipitation of metallic lithium. However, since it does not have an electron ion conductive layer in the battery, the discharge capacity retention rate is small and the cycle characteristics are inferior.
  • the all-solid-state lithium ion secondary battery CLIB-4 uses the negative electrode laminated sheet CAS-4 having the ion conductive layer in the sheet that does not satisfy the void ratio specified in the present invention, and uses the electron ion conductive layer in the battery and the battery. It is manufactured by setting the void ratio of the internal ion conductive layer within the range specified in the present invention.
  • the ion-conducting layer in the sheet is out of the specified range. It showed significantly higher resistance.
  • the all-solid-state lithium ion secondary battery CLIB-5 is a battery using a negative electrode laminated sheet CAS-5 having an in-sheet electron ion conductive layer and an in-sheet ion conductive layer that do not satisfy the porosity specified in the present invention. It is manufactured by setting the porosity of the internal electron ion conductive layer to a range outside the range specified in the present invention.
  • This all-solid-state lithium-ion secondary battery showed extremely high resistance even if the porosity of the ion-conducting layer in the battery was within the range specified in the present invention because the ion-conducting layer in the sheet was out of the specified range.
  • the electrodes were overloaded during the cycle test, and the cycle characteristics also deteriorated.
  • the porosity of the electron ion conductive layer in the battery is low, it is not possible to prevent the occurrence of an internal short circuit due to repeated charging and discharging.
  • each of CLIB-1-A and CLIB-2-A is a laminated sheet AS-1 or AS for a negative electrode having an in-sheet electron ion conductive layer and an in-sheet ion conductive layer satisfying the porosity specified in the present invention.
  • -2 was used, it was manufactured without being able to compress the porosity of the ion conductive layer in the battery to 10% or less in the pressurizing step. Even if the void ratio of the ion conductive layer in the battery is within the range specified in the present invention, these all-solid-state lithium-ion secondary batteries do not satisfy the void ratio of the ion conductive layer in the battery. The occurrence of a short circuit cannot be prevented.
  • the negative electrode laminated sheet specified in the present invention was produced by pressure-bonding and laminating the positive electrode sheet so that the in-battery electron ion conductive layer and the in-battery ion conductive layer satisfy the void ratio specified in the present invention.
  • the all-solid-state lithium-ion secondary battery can prevent the occurrence of an internal short circuit, has a large discharge capacity retention rate after 50 cycles, and exhibits excellent cycle characteristics. Moreover, an increase in interfacial resistance can be suppressed.
  • the electron-ion conductive layer in the sheet contains void-forming particles having a large particle size
  • the binder particles or the inorganic solid electrolyte having a particle size larger than that of the binder particles or the inorganic solid electrolyte in the ion-conducting layer in the sheet are further contained in the sheet.
  • the electron ion conducting layer can be made dense while increasing the amount of voids in the electron ion conducting layer in the battery, and more excellent cycle characteristics can be exhibited without impairing the suppression of the generation of internal resistance. I understand.
  • Negative electrode current collector 2 Electron ion conductive layer with porosity of 15% or more 3 Ion conductive layer with porosity of 10% or less 4 Positive electrode active material layer 5 Positive electrode current collector 6 Operating part 8 Electrons with porosity of 20% or more Ion conductive layer 9 Ion conductive layer with porosity of 20% or less 10 All-solid-state secondary battery 11 Laminated sheet for negative electrode

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Abstract

La présente invention concerne un procédé de fabrication d'une batterie secondaire au lithium-ion à l'état solide par compression et stratification d'une feuille stratifiée d'électrode négative et d'une feuille d'électrode positive présentant une couche de matériau actif d'électrode positive, la feuille stratifiée d'électrode négative présentant une couche conductrice d'ions d'électrons contenant un électrolyte solide inorganique et des particules conductrices d'électrons et présentant une porosité d'au moins 20 % adjacente à un collecteur de courant d'électrode négative, et présente une couche conductrice d'ions contenant un électrolyte solide inorganique et présentant une porosité d'au moins 20 % sur la couche conductrice d'ions d'électrons. Le procédé de fabrication d'une batterie secondaire au lithium-ion à l'état solide comprend une étape consistant à presser les deux feuilles, dans laquelle la couche conductrice d'ions et la couche de matériau actif d'électrode positive se chevauchent l'une en face de l'autre, jusqu'à ce que la porosité de la couche conductrice d'ions devienne inférieure ou égale à 10 % tout en supprimant la couche conductrice d'ions d'électrons afin de présenter une porosité d'au moins 15 %. La présente invention concerne également une feuille stratifiée d'électrode négative destinée à être utilisée dans le procédé et une batterie secondaire au lithium-ion à l'état solide.
PCT/JP2020/011505 2019-03-22 2020-03-16 Batterie secondaire au lithium-ion à l'état solide et procédé de fabrication associé et feuille stratifiée d'électrode négative WO2020196040A1 (fr)

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CN202080022177.5A CN113614977A (zh) 2019-03-22 2020-03-16 全固态锂离子二次电池及其制造方法、以及负极用层叠片
KR1020217031329A KR102501561B1 (ko) 2019-03-22 2020-03-16 전고체 리튬 이온 이차 전지와 그 제조 방법, 및 부극용 적층 시트

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