WO2023054455A1 - 電極用シート及び全固体二次電池、並びに、電極用シート、電極シート及び全固体二次電池の製造方法 - Google Patents

電極用シート及び全固体二次電池、並びに、電極用シート、電極シート及び全固体二次電池の製造方法 Download PDF

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WO2023054455A1
WO2023054455A1 PCT/JP2022/036128 JP2022036128W WO2023054455A1 WO 2023054455 A1 WO2023054455 A1 WO 2023054455A1 JP 2022036128 W JP2022036128 W JP 2022036128W WO 2023054455 A1 WO2023054455 A1 WO 2023054455A1
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active material
material layer
group
layer
electrode sheet
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French (fr)
Japanese (ja)
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秀幸 鈴木
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Fujifilm Corp
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Fujifilm Corp
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Priority to JP2023551591A priority Critical patent/JPWO2023054455A1/ja
Priority to CN202280049834.4A priority patent/CN117716524A/zh
Publication of WO2023054455A1 publication Critical patent/WO2023054455A1/ja
Priority to US18/406,190 priority patent/US20240162483A1/en
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0561—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of inorganic materials only
    • H01M10/0562—Solid materials
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • 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
    • H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/058—Construction or manufacture
    • H01M10/0585—Construction or manufacture of accumulators having only flat construction elements, i.e. flat positive electrodes, flat negative electrodes and flat separators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/04—Processes of manufacture in general
    • H01M4/0402—Methods of deposition of the material
    • H01M4/0407—Methods of deposition of the material by coating on an electrolyte layer
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/04—Processes of manufacture in general
    • H01M4/043—Processes of manufacture in general involving compressing or compaction
    • 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
    • H01M4/62—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
    • 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
    • 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
    • H01M2004/028—Positive 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
    • 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 electrode sheet, an all-solid secondary battery, and a method for manufacturing an electrode sheet, an electrode sheet, and an all-solid secondary battery.
  • the negative electrode, electrolyte, and positive electrode are all solid, and can greatly improve safety and reliability, which are problems of batteries using organic electrolytes. In addition, it is said that it will be possible to extend the service life. Furthermore, the all-solid secondary battery can have a structure in which the electrodes and the electrolyte are directly arranged in series. Therefore, it is possible to achieve a higher energy density than a secondary battery using an organic electrolyte, and it is expected to be applied to electric vehicles, large storage batteries, and the like.
  • inorganic solid electrolytes, active materials, and the like are examples of materials that form an active material layer (also referred to as an electrode layer).
  • active material layer of the all-solid secondary battery is usually a material (active material layer forming material, electrode composition ) is formed (coated and dried) on a substrate to form an electrode sheet.
  • Patent Document 1 A method for manufacturing an electrode laminate having an active material layer and a solid electrolyte layer on the surface of the active material layer, wherein the active material layer is formed by and a solid electrolyte layer forming step of forming the solid electrolyte layer on the active material layer by applying slurry for a solid electrolyte layer on the active material layer and drying the active material layer. and the volume ratio of the active material in the active material layer is 0.33 or more and 0.41 or less.
  • Patent Document 2 describes a method of forming an active material layer by applying a slurry or paste containing an active material, a solid electrolyte, and various additives onto a current collector, drying it, and then rolling it. It is
  • the active material layer formed of the solid particles (inorganic solid electrolyte, active material, conductive aid, etc.) described above the state of interfacial contact between the solid particles and the state of interfacial contact between the solid particles and the current collector are restricted. As a result, the interfacial resistance tends to increase, and the binding strength between the solid particles and between the solid particles and the substrate (current collector) is insufficient.
  • An all-solid secondary battery having such an active material layer causes an increase in battery resistance and a deterioration in battery performance such as cycle characteristics. For this reason, when an active material layer is made from solid particles, it has been conventional to use a relatively large amount of binder together, press the active material layer, etc.
  • Patent Document 1 (Example) includes a step of pressing an active material layer formed using a 5% by mass binder, and sets the filling rate of the active material layer to 51 to 77%.
  • Patent Document 2 in order to increase the density ratio of the active material layer, the active material layer is made to contain 5% by mass of a binder in the active material layer production process, and then the active material layer is pressed by roll pressing or the like. It is said that the process can be carried out.
  • the binder exhibits electronic and ionic insulation, so even if the interfacial contact state of the solid particles can be improved, the resistance will increase as a result.
  • the present invention provides an electrode sheet that can suppress the occurrence of defects in the active material layer precursor layer even when it is applied to an industrial manufacturing method by realizing high transportability while suppressing an increase in resistance, and a method for manufacturing the same.
  • the task is to provide Another object of the present invention is to provide an all-solid secondary battery using this electrode sheet, and a method for manufacturing the electrode sheet and the all-solid secondary battery.
  • the present inventors have made intensive studies on the filling state of the active material layer in the electrode sheet, the resistance reduction, and the transportability. Contrary to the methods or techniques that have been generally adopted, a layer formed by adding a small amount of polymer binder and adhering solid particles at a low filling rate (sparse state) is applied to industrial manufacturing methods. It has been found that high transportability is exhibited even if Moreover, by pressing the layer formed by bonding the solid particles at a low filling rate in the manufacturing process of the all-solid secondary battery, it can be converted into an active material layer in which the solid particles are bound at a high filling rate. As a result, the inventors have found that a low-resistance all-solid-state secondary battery can be manufactured. The present invention has been completed through further studies based on these findings.
  • An electrode sheet comprising an active material layer precursor layer containing an inorganic solid electrolyte having ion conductivity of a metal belonging to Group 1 or Group 2 of the periodic table, an active material, and a polymer binder.
  • An electrode sheet wherein an active material layer precursor layer contains a polymer binder in a content of 3% by mass or less and exhibits a filling rate of 35 to 50%.
  • ⁇ 3> The electrode sheet according to ⁇ 1> or ⁇ 2>, wherein the inorganic solid electrolyte is a sulfide-based inorganic solid electrolyte.
  • the inorganic solid electrolyte has a particle size of 0.1 to 2.5 ⁇ m.
  • the active material layer precursor layer is a positive electrode active material layer precursor layer having a film density of 1.4 to 2.0 g/cm 3 . electrode sheet.
  • the active material layer precursor layer is a negative electrode active material layer precursor layer having a film density of 0.8 to 1.0 g/cm 3 . electrode sheet.
  • An electrode composition containing an inorganic solid electrolyte having ion conductivity of a metal belonging to Group 1 or Group 2 of the periodic table, an active material, a polymer binder and a dispersion medium is coated on a substrate and dried.
  • a method for producing an electrode sheet having an active material layer on a substrate A method for producing an electrode sheet, comprising pressing the active material layer precursor layer of the electrode sheet obtained by the method for producing an electrode sheet according to ⁇ 7> above to form an active material layer.
  • a method for manufacturing an all-solid secondary battery comprising a positive electrode active material layer, a solid electrolyte layer, and a negative electrode active material layer in this order, At least one of the positive electrode active material layer and the negative electrode active material layer is pressed in a state in which the electrode sheet obtained by the electrode sheet manufacturing method described in ⁇ 7> and the solid electrolyte layer or the solid electrolyte layer forming material are stacked.
  • a method for manufacturing an all-solid secondary battery comprising: ⁇ 10> An all-solid secondary battery manufactured by the method for manufacturing an all-solid secondary battery according to ⁇ 9> above.
  • the present invention can provide an electrode sheet that can suppress the occurrence of defects in an active material layer even when it is applied to an industrial manufacturing method by realizing high transportability while suppressing an increase in resistance, and a method for manufacturing the same.
  • Another object of the present invention is to provide an all-solid secondary battery using this electrode sheet, and a method for manufacturing the electrode sheet and the all-solid secondary battery.
  • FIG. 1 is a vertical cross-sectional view schematically showing an electrode sheet according to a preferred embodiment of the present invention.
  • FIG. 2 is a vertical cross-sectional view schematically showing an all-solid secondary battery according to a preferred embodiment of the present invention.
  • a numerical range represented by "to” means a range including the numerical values before and after “to” as lower and upper limits.
  • the upper limit and lower limit forming the numerical range are described before and after "-" as a specific numerical range. It is not limited to a specific combination, and can be a numerical range in which the upper limit value and the lower limit value of each numerical range are appropriately combined.
  • the expression of a compound (for example, when it is called with a compound at the end) is used to mean the compound itself, its salt, and its ion.
  • (meth)acryl means one or both of acryl and methacryl.
  • substituents, linking groups, etc. for which substitution or non-substitution is not specified are intended to mean that the group may have an appropriate substituent. Therefore, in the present invention, even when the YYY group is simply described, this YYY group includes not only the embodiment having no substituent but also the embodiment having a substituent.
  • substituents include, for example, substituent Z described later.
  • the respective substituents, etc. may be the same or different from each other. means that Further, even if not otherwise specified, when a plurality of substituents and the like are adjacent to each other, they may be connected to each other or condensed to form a ring.
  • a polymer means a polymer and is synonymous with a so-called high molecular compound.
  • a polymer binder also referred to simply as a binder means a binder composed of a polymer, and includes the polymer itself and a binder composed (formed) of a polymer.
  • the electrode sheet includes a positive electrode sheet having a positive electrode active material layer precursor layer whose active material layer precursor layer is converted to a positive electrode active material layer of an all-solid secondary battery, and an all-solid secondary battery. and a negative electrode sheet provided with a negative electrode active material layer precursor layer to be converted into a negative electrode active material layer of a battery.
  • the electrode sheet also includes a positive electrode sheet provided with a positive electrode active material layer and a negative electrode sheet provided with a negative electrode active material layer.
  • a composition containing an inorganic solid electrolyte, an active material and a dispersion medium and used as a material for forming an active material layer of an all-solid secondary battery is used as an electrode for an all-solid secondary battery.
  • Composition, or simply electrode composition a composition containing an inorganic solid electrolyte and used as a material for forming a solid electrolyte layer of an all-solid secondary battery is called an inorganic solid electrolyte-containing composition, and this composition usually does not contain an active material.
  • the electrode composition includes a positive electrode composition containing a positive electrode active material and a negative electrode composition containing a negative electrode active material.
  • one or both of the positive electrode composition and the negative electrode composition may be simply referred to as an electrode composition, and one or both of the positive electrode active material layer and the negative electrode active material layer may be collectively referred to as an electrode composition. Therefore, it may simply be referred to as an active material layer or an electrode active material layer. Furthermore, either or both of the positive electrode active material and the negative electrode active material may be simply referred to as an active material or an electrode active material.
  • the electrode sheet of the present invention comprises an active material layer precursor layer containing an inorganic solid electrolyte having ion conductivity of a metal belonging to Group 1 or Group 2 of the periodic table, an active material, and a polymer binder. It is an electrode sheet, and is suitably used as an electrode sheet, an active material layer of an all-solid secondary battery, or a material sheet for manufacturing a laminate (electrode) of a current collector and an active material layer.
  • the active material layer precursor layer contains a polymer binder in a content of 3% by mass or less and exhibits a low filling rate of 35 to 50%.
  • An electrode sheet provided with such an active material layer precursor layer suppresses an increase in resistance and achieves high transportability.
  • the generation can be suppressed, and when a substrate is provided, peeling between the substrate and the active material layer precursor layer can also be suppressed. As a result, the electrode sheet can suppress an increase in resistance of the all-solid secondary battery by being converted into an active material layer.
  • the active material layer precursor layer of the electrode sheet has a polymer binder content of 3% by mass or less and a filling rate described later of 35 to 50%, which suppresses an increase in resistance due to the inclusion of the polymer binder.
  • a filling rate described later of 35 to 50%, which suppresses an increase in resistance due to the inclusion of the polymer binder.
  • it can maintain the adhesion force of the solid particles, and exhibits flexibility.
  • the stress e.g., compressive stress, elongation stress acting during transport, winding, etc. in an industrial manufacturing method is relieved and follows bending well, maintaining low resistance while preventing adhesion collapse of solid particles. can be suppressed.
  • the electrode sheet of the present invention can suppress the occurrence of defects in the active material layer precursor layer even when applied to an industrial manufacturing method, and the active material layer required for an all-solid secondary battery by pressing. , and it is thought that the suppression of resistance increase required for all-solid-state secondary batteries can be realized.
  • An all-solid-state secondary battery with a suppressed increase in resistance can prevent deterioration of solid particles by preventing overcurrent from occurring during charging and discharging, and has excellent cycle characteristics without causing a significant deterioration in battery characteristics even after repeated charging and discharging. It becomes a thing.
  • an all-solid secondary battery manufactured using an electrode sheet having excellent transportability is less susceptible to defects in the active material layer, and can suppress the occurrence of short circuits.
  • the electrode sheet preferably includes a substrate, particularly a substrate that functions as a current collector for an all-solid secondary battery. can also suppress the occurrence of peeling.
  • the active material layer precursor layer is arranged on the substrate directly or via another layer.
  • the active material layer precursor layer, base material and other layers constituting the electrode sheet may each have a single layer structure or a multilayer structure as long as they exhibit specific functions.
  • Other configurations of the electrode sheet of the present invention are not particularly limited as long as they have the above configuration.
  • the electrode sheet may have other layers in addition to the layers described above. Other layers include, for example, a protective layer (release sheet) and a coat layer.
  • the electrode sheet of the present invention may be a single sheet, but is preferably a long sheet because of its excellent transportability.
  • the electrode sheet includes those cut into a predetermined shape (sheet material) when used for manufacturing an all-solid secondary battery, for example, depending on the shape of the all-solid secondary battery. and the like.
  • FIG. 1 schematically shows a preferred embodiment of the electrode sheet of the present invention.
  • the electrode sheet 11 has a structure in which a substrate 8 and an active material layer precursor layer 9 are laminated in this order, and each of the substrate 8 and the active material layer precursor layer 9 has a single layer structure. , are in contact with each other.
  • the base material of the electrode sheet is not particularly limited as long as it can support the active material layer precursor layer. ), etc., and the materials described in the current collector are preferable.
  • Examples of organic materials include various polymers, and specific examples include polyethylene terephthalate, polypropylene, polyethylene, cellulose, and the like.
  • Examples of inorganic materials include glass and ceramics.
  • the active material layer precursor layer is a precursor layer that is converted into an electrode sheet and an active material layer of an all-solid-state secondary battery by pressing. It contains an inorganic solid electrolyte having properties, an active material, and a polymer binder. Details of each component contained in the active material layer precursor layer will be described later.
  • This active material layer precursor layer exhibits a filling rate of 35% or more and 50% or less. When the filling rate of the active material layer precursor layer is 50% or less, it is possible to realize high transportability of the electrode sheet while maintaining battery characteristics (suppression of increase in resistance).
  • the filling rate of the active material layer precursor layer can be converted to an active material layer with low resistance and high filling rate in which solid particles are firmly bound, and both transportability and battery characteristics can be achieved at a higher level. , preferably 35 to 48%, more preferably 38 to 46%.
  • the filling rate of the active material layer precursor layer is calculated by the following formula from the film density (g/cm 3 ) of the active material layer precursor layer and the true density (g/cm 3 ) of the active material layer precursor layer.
  • the value calculated by Filling rate (%) (film density/true density) x 100
  • the film density (g/cm 3 ) of the active material layer precursor layer is a value obtained by dividing the mass of the active material layer precursor layer by the volume of the active material layer precursor layer. It can be calculated by the method and conditions described.
  • the true density (g/cm 3 ) of the active material layer precursor layer means the density without taking into account the volume of interstices generated between the solid particles forming the active material layer precursor layer.
  • the true density is a value obtained by dividing the mass of the solid particles constituting the active material layer precursor layer by the true volume of the solid particles.
  • the true density of solid particles can be measured, for example, by a gas replacement method at 25° C. using a density measuring device: BELPYCNO (trade name, manufactured by Microtrac-Bell).
  • the true volume means a volume in which only the volume of solid particles is taken into consideration, and the volume in which gaps generated between solid particles are not taken into account.
  • a method for setting the filling rate of the active material layer precursor layer within the above range will be described in the method for manufacturing the electrode sheet described later.
  • the active material layer precursor layer includes, in addition to the applied dried layer itself obtained by applying and drying the electrode composition described later, a layer subjected to a treatment usually performed on this applied dried layer, for example, within a range where the filling rate does not deviate. It includes a precursor layer obtained by applying pressure (such as roll pressing) to the coated dry layer.
  • the film density of the active material layer precursor layer is not particularly limited, and is appropriately set in consideration of the filling rate, layer thickness, and the like. For example, it can be 0.8 to 2.2 g/cm 3 , and can also be 0.8 to 2.0 g/cm 3 .
  • the electrode sheet of the present invention is a positive electrode sheet, it is preferably 1.4 to 2.2 g/cm 3 , more preferably 1.4 to 2.0 g/cm 3 .
  • the film density of the negative electrode active material layer precursor layer is preferably 0.8 to 1.0 g/cm 3 .
  • the layer thickness (film thickness) of the active material layer precursor layer is appropriately determined in consideration of the layer thickness of the active material layer of the all-solid secondary battery, the amount of compression by pressing, and the like. It is preferably 50 to 500 ⁇ m, more preferably 100 to 300 ⁇ m. Since the electrode sheet of the present invention exhibits high transportability (bending resistance), the layer thickness can be increased. For example, it can be 100 ⁇ m or more, preferably 150 ⁇ m or more, and more preferably 200 ⁇ m or more. The upper limit is not particularly limited, and may be, for example, 1000 ⁇ m or less, preferably 500 ⁇ m or less, and more preferably 300 ⁇ m or less.
  • the physical properties of the solid particles contained in the active material layer precursor layer are the same as those of the solid particles used to form the active material layer precursor layer, and the physical properties of the solid particles used can be adjusted to activate the active material layer.
  • the physical properties of the solid particles in the material layer precursor layer can be appropriately set.
  • the electrode composition of the present invention contains an inorganic solid electrolyte.
  • an inorganic solid electrolyte means an inorganic solid electrolyte
  • a solid electrolyte means a solid electrolyte in which ions can move. Since the main ion-conducting materials do not contain organic substances, organic solid electrolytes (polymer electrolytes typified by polyethylene oxide (PEO), etc., organic electrolytes typified by lithium bis(trifluoromethanesulfonyl)imide (LiTFSI), etc.) electrolyte salt).
  • PEO polyethylene oxide
  • LiTFSI lithium bis(trifluoromethanesulfonyl)imide
  • the inorganic solid electrolyte is solid in a steady state, it is not usually dissociated or released into cations and anions. In this respect, it is clearly distinguished from electrolytes or inorganic electrolyte salts that are dissociated or released into cations and anions in polymers (LiPF 6 , LiBF 4 , lithium bis(fluorosulfonyl)imide (LiFSI), LiCl, etc.). be done.
  • the inorganic solid electrolyte is not particularly limited as long as it has ion conductivity of a metal belonging to Group 1 or Group 2 of the periodic table, and generally does not have electronic conductivity.
  • the inorganic solid electrolyte contained in the electrode composition of the present invention solid electrolyte materials that are commonly used in all-solid secondary batteries can be appropriately selected and used.
  • the inorganic solid electrolyte includes (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 inorganic solid electrolyte. mentioned.
  • the inorganic solid electrolyte preferably has ion conductivity of lithium ions.
  • Sulfide-based inorganic solid electrolyte contains sulfur atoms, has the ion conductivity of a metal belonging to Group 1 or Group 2 of the periodic table, and is electronically insulating. It is preferable to use a material having properties.
  • the sulfide-based inorganic solid electrolyte preferably contains at least Li, S and P as elements and has lithium ion conductivity, but may contain elements other than Li, S and P as appropriate. .
  • Examples of sulfide-based inorganic solid electrolytes include lithium ion conductive inorganic solid electrolytes that satisfy the composition represented by the following formula (S1).
  • L represents an element selected from Li, Na and K, preferably Li.
  • 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 satisfies 1-12:0-5:1:2-12:0-10.
  • a1 is preferably 1 to 9, more preferably 1.5 to 7.5.
  • b1 is preferably 0-3, more preferably 0-1.
  • 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 amount of the raw material compound when producing the sulfide-based inorganic solid electrolyte as described below.
  • the sulfide-based inorganic solid electrolyte may be amorphous (glass), crystallized (glass-ceramics), or only partially crystallized.
  • glass glass
  • glass-ceramics glass-ceramics
  • Li--P--S type glass containing Li, P and S, or Li--P--S type 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 (e.g., diphosphorus pentasulfide (P 2 S 5 )), elemental phosphorus, elemental sulfur, sodium sulfide, hydrogen sulfide, and lithium halides (e.g., LiI, LiBr, LiCl) and sulfides of the element represented by M (eg, SiS 2 , SnS, GeS 2 ) are reacted with at least two raw materials.
  • Li 2 S lithium sulfide
  • phosphorus sulfide e.g., diphosphorus pentasulfide (P 2 S 5 )
  • elemental phosphorus e.g., elemental sulfur, sodium sulfide, hydrogen sulfide
  • lithium halides e.g., LiI, LiBr, LiCl
  • the ratio of Li 2 S and P 2 S 5 in the Li—P—S type glass and Li—P—S type glass ceramics is Li 2 S:P 2 S 5 molar ratio, preferably 60:40 to 90:10, more preferably 68:32 to 78:22.
  • the lithium ion conductivity can be increased.
  • the lithium ion conductivity can be preferably 1 ⁇ 10 ⁇ 4 S/cm or higher, more preferably 1 ⁇ 10 ⁇ 3 S/cm or higher. Although there is no particular upper limit, it is practical to be 1 ⁇ 10 ⁇ 1 S/cm or less.
  • Li 2 SP 2 S 5 Li 2 SP 2 S 5 , Li 2 SP 2 S 5 -LiCl, Li 2 SP 2 S 5 -H 2 S, Li 2 SP 2 S 5 -H 2 S-LiCl, Li 2 S—LiI—P 2 S 5 , Li 2 S—LiI—Li 2 OP 2 S 5 , Li 2 S—LiBr—P 2 S 5 , Li 2 S—Li 2 OP 2 S 5 , Li 2 S—Li 3 PO 4 —P 2 S 5 , Li 2 SP 2 S 5 —P 2 O 5 , Li 2 SP 2 S 5 —SiS 2 , Li 2 SP 2 S 5 —SiS 2- LiCl , Li2SP2S5 - SnS , Li2SP2S5 - Al2S3 , Li2S - GeS2 , Li2S - GeS2 - ZnS,
  • Amorphization method include, for example, a mechanical milling method, a solution method, and a melt quenching method. This is because the process can be performed at room temperature, and the manufacturing process can be simplified.
  • the oxide-based inorganic solid electrolyte contains oxygen atoms, has the ion conductivity of a metal belonging to Group 1 or Group 2 of the periodic table, and is electronically insulating. It is preferable to use a material having properties.
  • the ion conductivity of the oxide-based inorganic solid electrolyte is preferably 1 ⁇ 10 ⁇ 6 S/cm or more, more preferably 5 ⁇ 10 ⁇ 6 S/cm or more, and 1 ⁇ 10 ⁇ 5 S/cm or more. /cm or more is particularly preferable. Although the upper limit is not particularly limited, it is practically 1 ⁇ 10 ⁇ 1 S/cm or less.
  • a specific example of the compound is Li xa La ya TiO 3 [xa satisfies 0.3 ⁇ xa ⁇ 0.7, and ya satisfies 0.3 ⁇ ya ⁇ 0.7. ] ( LLT ) ; _ _ xb satisfies 5 ⁇ xb ⁇ 10, yb satisfies 1 ⁇ yb ⁇ 4, zb satisfies 1 ⁇ zb ⁇ 4, mb satisfies 0 ⁇ mb ⁇ 2, and nb satisfies 5 ⁇ nb ⁇ 20. satisfy .
  • Li 7 La 3 Zr 2 O 12 having a garnet-type crystal structure.
  • Phosphorus compounds containing Li, P and O are also desirable.
  • lithium phosphate Li 3 PO 4
  • LiPON in which part of the oxygen element of lithium phosphate is replaced with nitrogen element
  • LiPOD 1 LiPON in which part of the oxygen element of lithium phosphate is replaced with nitrogen element
  • LiPOD 1 LiPON in which part of the oxygen element of lithium phosphate is replaced with nitrogen element
  • LiPOD 1 (D 1 is preferably Ti, V, Cr, Mn, Fe, Co, It is one or more elements selected from Ni, Cu, Zr, Nb, Mo, Ru, Ag, Ta, W, Pt and Au.) and the like.
  • LiA 1 ON A 1 is one or more elements selected from Si, B, Ge, Al, C and Ga
  • the halide-based inorganic solid electrolyte contains a halogen atom and has ion conductivity of a metal belonging to Group 1 or Group 2 of the periodic table, and electron Compounds having insulating properties are preferred.
  • the halide-based inorganic solid electrolyte include, but are not limited to, compounds such as LiCl, LiBr, LiI, and Li 3 YBr 6 and Li 3 YCl 6 described in ADVANCED MATERIALS, 2018, 30, 1803075. Among them, Li 3 YBr 6 and Li 3 YCl 6 are preferred.
  • the hydride-based inorganic solid electrolyte contains hydrogen atoms, has the ion conductivity of a metal belonging to Group 1 or Group 2 of the periodic table, and is electronically insulating. compounds having the properties are preferred.
  • the hydride-based inorganic solid electrolyte is not particularly limited, but examples include LiBH 4 , Li 4 (BH 4 ) 3 I, 3LiBH 4 --LiCl, and the like.
  • the inorganic solid electrolyte contained in the active material layer precursor layer of the electrode sheet of the present invention is preferably particulate in the active material layer precursor layer.
  • the shape of the particles is not particularly limited, and may be flat, amorphous, or the like, but is preferably spherical or granular.
  • the particle size (volume average particle size) of the inorganic solid electrolyte is not particularly limited, but is preferably 0.01 ⁇ m or more, more preferably 0.1 ⁇ m or more. It is more preferably 0.5 ⁇ m or more.
  • the upper limit is preferably 100 ⁇ m or less, more preferably 50 ⁇ m or less, more preferably 10 ⁇ m or less, still more preferably 5.0 ⁇ m or less, and particularly preferably 2.5 ⁇ m or less. preferable.
  • the particle size of the inorganic solid electrolyte is measured by the following procedure. A 1% by mass dispersion of inorganic solid electrolyte particles is prepared by diluting it in a 20 mL sample bottle with water (heptane for water-labile substances).
  • the diluted dispersion sample is irradiated with ultrasonic waves of 1 kHz for 10 minutes and immediately used for the test.
  • a laser diffraction/scattering particle size distribution analyzer LA-920 (trade name, manufactured by HORIBA)
  • data was taken 50 times using a quartz cell for measurement at a temperature of 25 ° C.
  • JIS Japanese Industrial Standard
  • Z 8828 2013
  • a method for adjusting the particle size of the inorganic solid electrolyte used for forming the active material layer precursor layer is not particularly limited, and a known method can be applied, for example, a method using an ordinary pulverizer or classifier.
  • the pulverizer or classifier for example, a mortar, ball mill, sand mill, vibrating ball mill, satellite ball mill, planetary ball mill, whirling jet mill, sieve, or the like is preferably used.
  • wet pulverization can be performed in which a dispersion medium such as water or methanol is allowed to coexist.
  • Classification is preferably carried out in order to obtain a desired particle size. Classification is not particularly limited, and can be performed using a sieve, an air classifier, or the like. Both dry and wet classification can be used.
  • the true density (g/cm 3 ) of the inorganic solid electrolyte contained in the active material layer precursor layer is not particularly limited and is appropriately set.
  • the true density of the inorganic solid electrolyte is preferably 1 to 3 g/cm 3 and more preferably 1.5 to 2.5 g/cm 3 in that the filling rate can be easily set within the above range.
  • the true volume (cm 3 ) of the inorganic solid electrolyte is not particularly limited and is appropriately set.
  • One or two or more inorganic solid electrolytes may be contained in the active material layer precursor layer.
  • the content of the inorganic solid electrolyte in the active material layer precursor layer is not particularly limited and is appropriately determined.
  • the active material layer precursor layer (100% by mass) it is preferably 50% by mass or more, more preferably 70% by mass or more, and 90% by mass or more in total with the active material described later. is particularly preferred.
  • the upper limit 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 active material layer precursor layer contains two or more components such as an inorganic solid electrolyte, the content of each component is the total content.
  • the active material layer precursor layer contains an active material capable of inserting and releasing ions of a metal belonging to Group 1 or Group 2 of the periodic table.
  • the active material include a positive electrode active material and a negative electrode active material, which will be described below.
  • An active material layer precursor layer containing a positive electrode active material is sometimes referred to as a positive electrode active material layer precursor layer, and an active material layer precursor layer containing a negative electrode active material is sometimes referred to as a negative electrode active material layer precursor layer.
  • the positive electrode active material is an active material capable of inserting and releasing metal ions belonging to Group 1 or Group 2 of the periodic table, and preferably capable of reversibly inserting and releasing lithium ions.
  • the material is not particularly limited as long as it has the above characteristics, and may be a transition metal oxide or an element such as sulfur that can be combined with Li by decomposing the battery. Among them, it is preferable to use a transition metal oxide as the positive electrode active material. objects are more preferred.
  • the transition metal oxide may contain an element M b (an element of group 1 (Ia) of the periodic table of metals other than lithium, an element of group 2 (IIa) of the periodic table, Al, Ga, In, Ge, Sn, Pb, elements such as Sb, Bi, Si, P and B) may be mixed.
  • the mixing amount is preferably 0 to 30 mol % with respect to the amount (100 mol %) of the transition metal element Ma . More preferred is one synthesized by mixing so that the Li/M a molar ratio is 0.3 to 2.2.
  • transition metal oxide examples include (MA) a transition metal oxide having a layered rock salt structure, (MB) a transition metal oxide having a spinel structure, (MC) a lithium-containing transition metal phosphate compound, (MD ) lithium-containing transition metal halide phosphate compounds and (ME) lithium-containing transition metal silicate compounds.
  • transition metal oxides having a layered rocksalt structure include LiCoO 2 (lithium cobaltate [LCO]), LiNi 2 O 2 (lithium nickelate), LiNi 0.85 Co 0.10 Al 0.85 .
  • 05O2 lithium nickel cobalt aluminum oxide [NCA]
  • LiNi1 /3Co1/ 3Mn1 / 3O2 lithium nickel manganese cobaltate [NMC]
  • LiNi0.5Mn0.5O2 lithium manganese nickelate
  • transition metal oxides having a spinel structure include 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 2NiMn3O8 .
  • Examples of (MC) lithium-containing transition metal phosphate compounds include olivine-type iron phosphates such as LiFePO 4 and Li 3 Fe 2 (PO 4 ) 3 , iron pyrophosphates such as LiFeP 2 O 7 , and LiCoPO 4 . and monoclinic Nasicon-type vanadium phosphates such as Li 3 V 2 (PO 4 ) 3 (lithium vanadium phosphate).
  • lithium-containing transition metal halogenated phosphate compounds include iron fluorophosphates such as Li 2 FePO 4 F, manganese fluorophosphates such as Li 2 MnPO 4 F, and Li 2 CoPO 4 F. and cobalt fluoride phosphates.
  • Lithium-containing transition metal silicate compounds include, for example, Li 2 FeSiO 4 , Li 2 MnSiO 4 , Li 2 CoSiO 4 and the like. In the present invention, transition metal oxides having a (MA) layered rocksalt structure are preferred, and LCO or NMC is more preferred.
  • the positive electrode active material obtained by the sintering method may be used after washing with water, an acidic aqueous solution, an alkaline aqueous solution, or an organic solvent.
  • the positive electrode active material contained in the active material layer precursor layer is preferably particulate in the active material layer precursor layer.
  • the shape of the particles is not particularly limited, and may be flat, amorphous, or the like, but is preferably spherical or granular.
  • the particle size (volume average particle size) of the positive electrode active material is not particularly limited, but is preferably 0.1 to 50 ⁇ m, more preferably 0.5 to 10 ⁇ m.
  • the particle size of the positive electrode active material particles can be adjusted in the same manner as the particle size of the inorganic solid electrolyte, and can be measured in the same manner as the particle size of the inorganic solid electrolyte.
  • the true density (g/cm 3 ) of the positive electrode active material contained in the active material layer precursor layer is not particularly limited and is appropriately set.
  • the true density of the positive electrode active material is preferably 3 to 7 g/cm 3 and more preferably 4 to 6 g/cm 3 in that the filling rate can be easily set within the above range.
  • the true volume (cm 3 ) of the positive electrode active material is not particularly limited and is set appropriately.
  • One kind or two or more kinds of positive electrode active materials may be contained in the active material layer precursor layer.
  • the content of the positive electrode active material in the active material layer precursor layer is not particularly limited and is determined as appropriate. For example, it is preferably 10 to 97% by mass, more preferably 30 to 95% by mass, even more preferably 40 to 93% by mass, and particularly preferably 50 to 90% by mass in the active material layer precursor layer.
  • the negative electrode active material is an active material capable of inserting and releasing metal ions belonging to Group 1 or Group 2 of the periodic table, and preferably capable of reversibly inserting and releasing lithium ions.
  • the material is not particularly limited as long as it has the above properties, and carbonaceous materials, metal oxides, metal composite oxides, elemental lithium, lithium alloys, negative electrode active materials that can be alloyed with lithium (alloyable). substances and the like.
  • a carbonaceous material, a metal composite oxide, or lithium simple substance is preferably used from the viewpoint of reliability.
  • An active material that can be alloyed with lithium is preferable from the viewpoint that the capacity of an all-solid secondary battery can be increased.
  • a carbonaceous material used as a negative electrode active material is a material substantially composed of carbon.
  • petroleum pitch carbon black such as acetylene black (AB), graphite (natural graphite, artificial graphite such as vapor-grown graphite, etc.), and various synthetics such as PAN (polyacrylonitrile)-based resin or furfuryl alcohol resin
  • PAN polyacrylonitrile
  • various carbon fibers such as PAN-based carbon fiber, cellulose-based carbon fiber, pitch-based carbon fiber, vapor growth carbon fiber, dehydrated PVA (polyvinyl alcohol)-based carbon fiber, lignin carbon fiber, vitreous carbon fiber and activated carbon fiber.
  • carbonaceous materials can be classified into non-graphitizable carbonaceous materials (also referred to as hard carbon) and graphitic carbonaceous materials according to the degree of graphitization.
  • the carbonaceous material preferably has the interplanar spacing or density and crystallite size described in JP-A-62-22066, JP-A-2-6856 and JP-A-3-45473.
  • the carbonaceous material does not have to be a single material, and a mixture of natural graphite and artificial graphite described in JP-A-5-90844, graphite having a coating layer described in JP-A-6-4516, etc. can be used.
  • hard carbon or graphite is preferably used, and graphite is more preferably used.
  • the oxide of a metal or metalloid element that is applied as a negative electrode active material is not particularly limited as long as it is an oxide that can occlude and release lithium.
  • examples include oxides, composite oxides of metal elements and metalloid elements (collectively referred to as metal composite oxides), and oxides of metalloid elements (semimetal oxides).
  • metal composite oxides composite oxides of metal elements and metalloid elements
  • oxides of metalloid elements oxides of metalloid elements (semimetal oxides).
  • amorphous oxides are preferred, and chalcogenides, which are reaction products of metal elements and Group 16 elements of the periodic table, are also preferred.
  • the metalloid element refers to an element that exhibits intermediate properties between metal elements and non-metalloid elements, and usually includes the six elements boron, silicon, germanium, arsenic, antimony and tellurium, and further selenium.
  • amorphous means a broad scattering band having an apex in the region of 20° to 40° in terms of 2 ⁇ value in an X-ray diffraction method using CuK ⁇ rays, and a crystalline diffraction line. may have.
  • the strongest intensity among the crystalline diffraction lines seen at 2 ⁇ values of 40° to 70° is 100 times or less than the diffraction line intensity at the top of the broad scattering band seen at 2 ⁇ values of 20° to 40°. is preferable, more preferably 5 times or less, and it is particularly preferable not to have a crystalline diffraction line.
  • amorphous oxides of metalloid elements or chalcogenides are more preferable, and elements of groups 13 (IIIB) to 15 (VB) of the periodic table (for example, , Al, Ga, Si, Sn, Ge, Pb, Sb and Bi) are particularly preferable.
  • elements of groups 13 (IIIB) to 15 (VB) of the periodic table for example, , Al, Ga, Si, Sn, Ge, Pb, Sb and Bi
  • preferred amorphous oxides and chalcogenides include Ga 2 O 3 , GeO, PbO, PbO 2 , Pb 2 O 3 , Pb 2 O 4 , Pb 3 O 4 , Sb 2 O 3 and Sb 2 .
  • Examples of negative electrode active materials that can be used together with amorphous oxides mainly composed of Sn, Si, and Ge include carbonaceous materials capable of absorbing and/or releasing lithium ions or lithium metal, elemental lithium, lithium alloys, and lithium. and a negative electrode active material that can be alloyed with.
  • the oxides of metals or semimetals especially metal (composite) oxides and chalcogenides, preferably contain at least one of titanium and lithium as a constituent component.
  • lithium-containing metal composite oxides include composite oxides of lithium oxide and the above metal (composite) oxides or chalcogenides, more specifically Li 2 SnO 2 . mentioned.
  • the negative electrode active material such as a metal oxide, contain a titanium element (titanium oxide).
  • Li 4 Ti 5 O 12 (lithium titanate [LTO]) exhibits excellent rapid charge-discharge characteristics due to its small volume fluctuation during lithium ion occlusion and desorption, suppressing electrode deterioration and promoting lithium ion secondary This is preferable in that the life of the battery can be improved.
  • the lithium alloy as the negative electrode active material is not particularly limited as long as it is an alloy normally used as a negative electrode active material for secondary batteries. Lithium-aluminum alloys added by mass % can be mentioned.
  • the negative electrode active material capable of forming an alloy with lithium is not particularly limited as long as it is commonly used as a negative electrode active material for secondary batteries.
  • active materials include (negative electrode) active materials (alloys, etc.) containing silicon element or tin element, metals such as Al and In, and negative electrode active materials containing silicon element that enable higher battery capacity.
  • (Silicon element-containing active material) is preferable, and a silicon element-containing active material having a silicon element content of 50 mol % or more of all constituent elements is more preferable.
  • negative electrodes containing these negative electrode active materials are carbon negative electrodes (graphite, acetylene black, etc. ), more Li ions can be occluded. That is, the amount of Li ions stored per unit mass increases. Therefore, the battery capacity (energy density) can be increased. As a result, there is an advantage that the battery driving time can be lengthened.
  • Silicon element-containing active materials include, for example, silicon materials such as Si and SiOx (0 ⁇ x ⁇ 1), and silicon-containing alloys containing titanium, vanadium, chromium, manganese, nickel, copper, lanthanum, etc.
  • SiOx itself can be used as a negative electrode active material (semimetal oxide), and since Si is generated by the operation of the all-solid secondary battery, the negative electrode active material that can be alloyed with lithium (the can be used as a precursor substance).
  • negative electrode active materials containing tin examples include Sn, SnO, SnO 2 , SnS, SnS 2 , active materials containing silicon and tin, and the like.
  • composite oxides with lithium oxide, such as Li 2 SnO 2 can also be mentioned.
  • the above-described negative electrode active material can be used without any particular limitation.
  • the above silicon materials or silicon-containing alloys are more preferred, and silicon (Si) or silicon-containing alloys are even more preferred.
  • the negative electrode active material contained in the active material layer precursor layer is preferably particulate in the active material layer precursor layer.
  • the shape of the particles is not particularly limited, and may be flat, amorphous, or the like, but is preferably spherical or granular.
  • the particle size (volume average particle size) of the negative electrode active material is not particularly limited, but is preferably 0.1 to 60 ⁇ m, more preferably 0.5 to 10 ⁇ m.
  • the particle size of the negative electrode active material particles can be adjusted in the same manner as the particle size of the inorganic solid electrolyte, and can be measured in the same manner as the particle size of the inorganic solid electrolyte.
  • the true density (g/cm 3 ) of the negative electrode active material contained in the active material layer precursor layer is not particularly limited and is appropriately set.
  • the true density of the negative electrode active material is preferably from 1 to 3 g/cm 3 , more preferably from 1.5 to 2.5 g/cm 3 in that the filling rate can be easily set within the above range.
  • the true density of the negative electrode active material is the value measured by the gas replacement method described above. Note that the true volume (cm 3 ) of the negative electrode active material is not particularly limited, and is set appropriately.
  • One or two or more negative electrode active materials may be contained in the active material layer precursor layer.
  • the content of the negative electrode active material in the active material layer precursor layer is not particularly limited and is appropriately determined.
  • the % in the active material layer precursor layer is preferably 10 to 90% by mass, more preferably 20 to 85% by mass, more preferably 30 to 80% by mass, and 40 to 75% by mass. It is even more preferable to have
  • the negative electrode active material layer can also be formed by charging the secondary battery.
  • ions of a metal belonging to Group 1 or Group 2 of the periodic table generated in the all-solid secondary battery can be used instead of the negative electrode active material.
  • a negative electrode active material layer can be formed by combining this ion with an electron and depositing it as a metal.
  • the chemical formula of the compound obtained by the above firing method can be calculated by inductively coupled plasma (ICP) emission spectrometry as a measurement method and from the difference in mass of the powder before and after firing as a simple method.
  • ICP inductively coupled plasma
  • the surfaces of the positive electrode active material and the negative electrode active material may be surface-coated with another metal oxide.
  • surface coating agents include metal oxides containing Ti, Nb, Ta, W, Zr, Al, Si or Li.
  • Specific examples include spinel titanate, tantalum-based oxides , niobium -based oxides, and lithium niobate -based compounds.
  • Specific examples include Li4Ti5O12 , Li2Ti2O5 , and LiTaO3 .
  • the surface of the electrode containing the positive electrode active material or the negative electrode active material may be surface-treated with sulfur or phosphorus.
  • the surface of the particles of the positive electrode active material or the negative electrode active material may be surface-treated with actinic rays or an active gas (such as plasma) before and after the surface coating.
  • the polymer binder contained in the electrode composition of the present invention contains one or more of the following polymer binders.
  • the polymer binder is dissolved or dispersed in a dispersion medium in the form of particles, adsorbed to the active material or the inorganic solid electrolyte, or interposed between the solid particles to disperse the active material or the inorganic solid electrolyte. It is thought that it shows the function of dispersing in the medium.
  • the polymer binder in the active material layer precursor layer and the active material layer, is considered to function as an adhesion agent or a binder that adsorbs to the active material or the inorganic solid electrolyte and adheres or binds them to each other.
  • the adsorption of the polymer binder to the active material or inorganic solid electrolyte is not particularly limited, but includes not only physical adsorption but also chemical adsorption (adsorption due to chemical bond formation, adsorption due to electron transfer, etc.).
  • the polymer binder may also function as a binder that binds the current collector and the solid particles.
  • the polymer binder contained in the active material layer precursor layer may exist in any form in the active material layer precursor layer. It may be particulate derived from dispersed particles in the electrode composition.
  • Polymers forming polymer binder are not particularly limited, and various polymers can be used. Among them, preferred are polymers having at least one bond selected from a urethane bond, a urea bond, an amide bond, an imide bond and an ester bond, or a polymer chain of a carbon-carbon double bond in the main chain.
  • the polymer chain of carbon-carbon double bonds refers to a polymer chain formed by polymerizing carbon-carbon double bonds (ethylenically unsaturated groups).
  • the main chain of a polymer refers to a linear molecular chain in which all other molecular chains constituting the polymer can be regarded as branched chains or pendant groups with respect to the main chain.
  • the longest chain among the molecular chains constituting the polymer is typically the main chain.
  • the main chain does not include terminal groups possessed by polymer terminals.
  • the side chains of a polymer refer to molecular chains other than the main chain, and include short molecular chains and long molecular chains.
  • the above bond is not particularly limited as long as it is contained in the main chain of the polymer, and may be contained in a structural unit (repeating unit) and/or contained as a bond connecting different structural units. .
  • the number of the bonds contained in the main chain is not limited to 1, but may be 2 or more, preferably 1 to 6, more preferably 1 to 4.
  • the binding mode of the main chain is not particularly limited, and may have two or more types of bonds at random. It can be a chain.
  • the main chain having the bond is not particularly limited, but a main chain having at least one segment of the above bond is preferable, and a main chain made of polyamide, polyurea, polyurethane, (meth)acrylic polymer is more preferable, and polyurethane. or a main chain made of (meth)acrylic polymer is more preferable.
  • Examples of the polymer having a urethane bond, urea bond, amide bond, imide bond or ester bond in the main chain among the above bonds include successive polymerization (polycondensation, polyaddition or addition) of polyurethane, polyurea, polyamide, polyimide, polyester, etc. condensation) polymers, or copolymers thereof.
  • the copolymer may be a block copolymer having each of the above polymers as a segment, or a random copolymer in which two or more constituent components of each of the above polymers are randomly bonded.
  • Polymers having a polymer chain of carbon-carbon double bonds in the main chain include chain polymerized polymers such as fluoropolymers (fluoropolymers), hydrocarbon polymers, vinyl polymers, and (meth)acrylic polymers.
  • the polymerization mode of these chain-polymerized polymers is not particularly limited, and may be block copolymers, alternating copolymers or random copolymers.
  • the polymers forming the binder may be of one type or two or more types.
  • the polymer forming the binder preferably has a component represented by any one of the following formulas (1-1) to (1-5), and the following formula (1-1) or formula (1-2) It is more preferable to have a component represented by
  • R 1 represents a hydrogen atom or an alkyl group (having preferably 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, and still more preferably 1 to 3 carbon atoms).
  • the alkyl group that can be used as R 1 may have a substituent.
  • the substituent is not particularly limited, but includes the substituent Z described later and the like, and is preferably a group other than the functional group selected from the functional group (a), such as a halogen atom.
  • R 2 represents a group having a hydrocarbon group with 4 or more carbon atoms.
  • a group having a hydrocarbon group is a group consisting of a hydrocarbon group itself (the hydrocarbon group is directly bonded to the carbon atom in the above formula to which R 1 is bonded) and the above-mentioned group to which R 2 is bonded. and a group consisting of a linking group linking a carbon atom in the formula and a hydrocarbon group (the hydrocarbon group is linked via a linking group to the carbon atom in the above formula to which R 1 is linked).
  • a hydrocarbon group is a group composed of carbon and hydrogen atoms and is usually introduced at the end of R2 .
  • the hydrocarbon group is not particularly limited, but is preferably an aliphatic hydrocarbon group, more preferably an aliphatic saturated hydrocarbon group (alkyl group), and still more preferably a linear or branched alkyl group.
  • the number of carbon atoms in the hydrocarbon group may be 4 or more, preferably 6 or more, more preferably 8 or more, and may be 10 or more.
  • the upper limit is not particularly limited, preferably 20 or less, more preferably 18 or less, and even more preferably 14 or less.
  • the linking group is not particularly limited, but includes, for example, an alkylene group (having preferably 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, and still more preferably 1 to 3 carbon atoms), an alkenylene group (having 2 to 6 carbon atoms, preferably 2 to 3), an arylene group (having preferably 6 to 24 carbon atoms, more preferably 6 to 10 carbon atoms), an oxygen atom, a sulfur atom, an imino group (-NR N -: R N is a hydrogen atom, An alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 10 carbon atoms.), carbonyl group, phosphoric acid linking group (-O-P(OH)(O)-O-), phosphonic acid linking group ( —P(OH)(O)—O—), or a group related to a combination thereof.
  • an alkylene group having preferably 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms
  • Alkylene groups and oxygen atoms can also be combined to form a polyalkyleneoxy chain.
  • the linking group is preferably a group formed by combining an alkylene group, an arylene group, a carbonyl group, an oxygen atom, a sulfur atom and an imino group, and a group formed by combining an alkylene group, an arylene group, a carbonyl group, an oxygen atom and an imino group. More preferably, a group containing a -CO-O- group, a -CO-N(R N )- group (R N is as described above), and a -CO-O- group or a -CO-N ( R N )--groups, where R N is as defined above, are particularly preferred.
  • the number of atoms constituting the linking group and the number of linking atoms are as described later.
  • the polyalkyleneoxy chain constituting the linking group is not limited to the above.
  • the number of atoms constituting the linking group is preferably 1 to 36, more preferably 1 to 24, even more preferably 1 to 12, and 1 to 6.
  • the number of connecting atoms in the connecting group is preferably 10 or less, more preferably 8 or less.
  • the lower limit is 1 or more.
  • Each of the hydrocarbon group and the linking group may or may not have a substituent.
  • substituents which may be present include a substituent Z, preferably a group other than a functional group selected from the functional group (a), and preferably a halogen atom.
  • the carbon atom adjacent to the carbon atom to which R 1 is bonded has two hydrogen atoms, but in the present invention it may have one or two substituents.
  • the substituent is not particularly limited, but includes the substituent Z described later, and is preferably a group other than the functional group selected from the functional group (a).
  • the compound that leads to the component represented by formula (1-1) is not particularly limited, but for example, a (meth)acrylic acid linear alkyl ester compound (linear alkyl means an alkyl group having 4 or more carbon atoms) are mentioned.
  • R 3 represents a linking group containing a polybutadiene chain or a polyisoprene chain and having a weight average molecular weight of 500 or more and 200,000 or less.
  • the end of the above chain that can be used as R 3 can be appropriately changed to a general chemical structure that can be incorporated into the constituents represented by the above formulas as R 3 .
  • R 3 is a divalent molecular chain, but at least one hydrogen atom is replaced with -NH-CO-, -CO-, -O-, -NH- or -N ⁇ , and 3 It may be a chain with more than the valency.
  • Polybutadiene chains and polyisoprene chains that can be used as R 3 include known polybutadiene and polyisoprene chains as long as they satisfy the weight average molecular weight. Both the polybutadiene chain and the polyisoprene chain are diene-based polymers having double bonds in the main chain. non-diene polymers having no double bonds in the chain). In the present invention, hydrides of polybutadiene chains or polyisoprene chains are preferred.
  • the polybutadiene chain and the polyisoprene chain, as raw material compounds preferably have a reactive group at their terminal, and more preferably have a polymerizable terminal reactive group.
  • the polymerizable terminal reactive group is polymerized to form a group that bonds to R3 in each of the above formulas.
  • a terminal reactive group include a hydroxy group, a carboxy group, an amino group, etc. Among them, a hydroxy group is preferred.
  • polybutadiene and polyisoprene having terminal reactive groups include, for example, NISSO-PB series (manufactured by Nippon Soda Co., Ltd.), Claysol series (manufactured by Tomoe Kogyo Co., Ltd.), PolyVEST-HT series (manufactured by Evonik), all of which are trade names.
  • poly-bd series manufactured by Idemitsu Kosan Co., Ltd.
  • poly-ip series manufactured by Idemitsu Kosan Co., Ltd.
  • EPOL manufactured by Idemitsu Kosan Co., Ltd.
  • the chain that can be used as R 3 preferably has a mass average molecular weight (converted to polystyrene) of 500 to 200,000.
  • the lower limit is preferably 500 or more, more preferably 700 or more, and even more preferably 1,000 or more.
  • the upper limit is preferably 100,000 or less, more preferably 10,000 or less.
  • the mass-average molecular weight is measured by the method described below for the raw material compound before it is incorporated into the main chain of the polymer.
  • the content of the component represented by any of the above formulas (1-1) to (1-5) in the polymer is not particularly limited, but is preferably 10 to 100 mol%.
  • the content of the component represented by the above formula (1-1) is more preferably 30 to 98 mol%, more preferably 50 to 95 mol%, in terms of dispersion stability, binding properties, etc. is more preferred.
  • the content of the component represented by any of the above formulas (1-2) to (1-5) is more preferably 30 to 98 mol%, more preferably 50 to 95 mol%, from the viewpoint of dispersion stability and the like. More preferably, it is mol %.
  • the content is preferably 0 to 90 mol%, more preferably 10 to 80 mol%, and even more preferably 20 to 70 mol%.
  • the polymer forming the polymer binder preferably contains a constituent component having, for example, a functional group selected from the following functional group group (a) as a substituent.
  • the component having a functional group may be any component that functions to improve the adsorption of the binder to the solid particles and forms a polymer.
  • Functional groups may be incorporated into the backbone of the polymer or into side chains. When incorporated into a side chain, the functional group may be directly attached to the main chain or via the linking group described above.
  • the linking group is not particularly limited, but includes the linking groups described below.
  • ⁇ Functional Group (a)> Hydroxy group, amino group, carboxy group, sulfo group, phosphate group, phosphonic acid group, sulfanyl group, ether bond (-O-), imino group ( NR, -NR-), ester bond (-CO-O- ), amide bond (-CO-NR-), urethane bond (-NR-CO-O-), urea bond (-NR-CO-NR-), heterocyclic group, aryl group, carboxylic anhydride group
  • the amino group, sulfo group, phosphate group (phosphoryl group), heterocyclic group, and aryl group contained in (a) are not particularly limited, but are synonymous with the groups corresponding to the substituent Z described later.
  • the number of carbon atoms in the amino group is more preferably 0 to 12, still more preferably 0 to 6, and particularly preferably 0 to 2.
  • the phosphonic acid group is not particularly limited, and includes, for example, a phosphonic acid group having 0 to 20 carbon atoms.
  • the ring structure contains an amino group, an ether bond, an imino group (--NR--), an ester bond, an amide bond, a urethane bond, a urea bond, etc., it is classified as a heterocycle.
  • a hydroxy group, an amino group, a carboxy group, a sulfo group, a phosphate group, a phosphonic acid group, and a sulfanyl group may form a salt.
  • R in each bond represents a hydrogen atom or a substituent, preferably a hydrogen atom.
  • the substituent is not particularly limited, is selected from substituents Z described later, and is preferably an alkyl group.
  • the carboxylic anhydride group is not particularly limited, but may be a group obtained by removing one or more hydrogen atoms from a carboxylic anhydride (for example, a group represented by the following formula (2a)), or a copolymerizable compound.
  • the component itself (for example, the component represented by the following formula (2b)) obtained by copolymerizing the polymerizable carboxylic anhydride as is included.
  • the group obtained by removing one or more hydrogen atoms from a carboxylic anhydride is preferably a group obtained by removing one or more hydrogen atoms from a cyclic carboxylic anhydride.
  • a carboxylic anhydride group derived from a cyclic carboxylic anhydride corresponds to a heterocyclic group, but is classified as a carboxylic anhydride group in the present invention.
  • Examples include non-cyclic carboxylic anhydrides such as acetic anhydride, propionic anhydride and benzoic anhydride, and cyclic carboxylic anhydrides such as maleic anhydride, phthalic anhydride, fumaric anhydride and succinic anhydride.
  • the polymerizable carboxylic acid anhydride is not particularly limited, but includes a carboxylic acid anhydride having an unsaturated bond in the molecule, preferably a polymerizable cyclic carboxylic acid anhydride. Specifically, maleic anhydride etc. are mentioned.
  • An example of the carboxylic anhydride group includes a group represented by the following formula (2a) or a constituent represented by the formula (2b), but the present invention is not limited thereto. In each formula, * indicates a bond
  • ester bonds (-CO-O-), amide bonds (-CO-NR-), urethane bonds (-NR-CO-O-) and urea bonds (-NR-CO-NR-) are
  • the chemical structure of the polymer is represented by constituents derived from the raw material compound, respectively, -CO- group and -O- group, -CO group and -NR- group, -NR-CO- group and -O- group, - It is represented by dividing into an NR--CO-- group and a --NR-- group.
  • constituents having these bonds are defined as constituents derived from carboxylic acid compounds or constituents derived from isocyanate compounds, regardless of the notation of polymers, and do not include constituents derived from polyols or polyamine compounds.
  • the component having an ester bond (excluding an ester bond forming a carboxyl group) or an amide bond is incorporated as a branched chain or a pendant chain in the main chain of the chain polymerization polymer, or in the chain polymerization polymer.
  • a component in which an ester bond or an amide bond is not directly bonded to an atom constituting the main chain of a polymer chain for example, a polymer chain possessed by a macromonomer
  • a component derived from a (meth)acrylic acid alkyl ester does not include
  • the amino group, ether bond, imino group, ester bond, amide bond, urethane bond, urea bond, heterocyclic group and aryl group are preferably incorporated into the branched chain of the polymer.
  • One component may have one or two or more functional groups, and when two or more functional groups are present, they may or may not be bonded to each other. Also, the number of functional groups possessed by one component is not particularly limited as long as it is 1 or more, and can be 1 to 4.
  • the linking group that bonds the functional group and the main chain is not particularly limited, but a hydrocarbon group having 4 or more carbon atoms, which can be taken as R 2 in the above formula (1-1), is not particularly limited except for the following linking groups that are particularly preferable. is synonymous with the linking group in the group having.
  • a particularly preferable linking group is a -CO-O- group or a -CO-N(R N )- group (R N is as described above) and an alkylene group. or a group formed by combining with a polyalkyleneoxy chain.
  • the component having the functional group is not particularly limited as long as it has the functional group. is introduced, a component represented by formula (I-1) or formula (I-2) described later, a component derived from a compound represented by formula (I-5) described later, and a formula ( I-3) or a component represented by the formula (I-4) or a component obtained by introducing the functional group into a component derived from the compound represented by the formula (I-6), and a (meth) acrylic described later.
  • Examples include the compound (M1) or other polymerizable compound (M2), a component obtained by introducing the functional group into a component represented by any of the formulas (b-1) to (b-3) described later, and the like. be done.
  • the compound leading to the component having the functional group is not particularly limited. are introduced into the compound.
  • the content of the component having the functional group in the polymer is not particularly limited.
  • the content is preferably 0.01 to 50 mol%, more preferably 0.1 to 50 mol%, more preferably 0.3, from the viewpoint of solid particle dispersion characteristics, binding properties, etc. More preferably ⁇ 50 mol%.
  • the content is preferably 0.01 to 80 mol%, more preferably 0.01 to 70 mol%, more preferably 0.1 in terms of solid particle dispersion characteristics, binding properties, etc. ⁇ 50 mol% is more preferred, 0.3 to 50 mol% is particularly preferred, and 3 to 20 mol% is most preferred.
  • the lower limit of the content may be 5 mol % or more or 20 mol % or more.
  • the successively polymerized polymer as the polymer forming the binder is the above-mentioned component having a functional group selected from the functional group (a) or any of the above formulas (1-2) to (1-5) It is preferable to have constituents represented by and may further have constituents different from these constituents.
  • constituents represented by formula (I-1) or formula (I-2), constituents derived from compounds represented by formula (I-5) are functional group groups (a) It also corresponds to a component having a functional group selected from but will be described with another component.
  • Constituents obtained by successively polymerizing a diamine compound that leads to the constituents can be mentioned.
  • the combination of each constituent component is appropriately selected according to the polymer species.
  • One component used in combination of components means a component represented by any one of the following formulas, even if it contains two components represented by one of the following formulas: , is not to be construed as two components.
  • R P1 and R P2 each represent a molecular chain having a (mass average) molecular weight of 20 or more and 200,000 or less.
  • the molecular weight of this molecular chain depends on its type and cannot be unambiguously determined.
  • the upper limit is preferably 100,000 or less, more preferably 10,000 or less.
  • the molecular weight of the molecular chain is measured on the starting compound before it is incorporated into the backbone of the polymer.
  • the molecular chains that can be used as R P1 and R P2 are not particularly limited, but are preferably hydrocarbon chains, polyalkylene oxide chains, polycarbonate chains or polyester chains, more preferably hydrocarbon chains or polyalkylene oxide chains, and hydrocarbon chains. , polyethylene oxide chains or polypropylene oxide chains are more preferred.
  • Hydrocarbon chains that can be used as R P1 and R P2 mean hydrocarbon chains composed of carbon and hydrogen atoms, more specifically, at least two of compounds composed of carbon and hydrogen atoms. It means a structure in which an atom (eg, hydrogen atom) or group (eg, methyl group) is eliminated.
  • the hydrocarbon chain also includes a chain having a group containing an oxygen atom, a sulfur atom or a nitrogen atom, such as a hydrocarbon group represented by the following formula (M2). Any terminal group that may be present at the end of the hydrocarbon chain shall not be included in the hydrocarbon chain.
  • the hydrocarbon chain may have carbon-carbon unsaturated bonds and may have an aliphatic and/or aromatic ring structure. That is, the hydrocarbon chain may be a hydrocarbon chain composed of hydrocarbons selected from aliphatic hydrocarbons and aromatic hydrocarbons.
  • Such a hydrocarbon chain may be one that satisfies the above molecular weight.
  • a low-molecular-weight hydrocarbon chain is a chain composed of ordinary (non-polymeric) hydrocarbon groups, such as aliphatic or aromatic hydrocarbon groups, specifically is an alkylene group (preferably 1 to 12 carbon atoms, more preferably 1 to 6, more preferably 1 to 3), an arylene group (preferably 6 to 22 carbon atoms, preferably 6 to 14, 6 to 10 is more preferred), or a group consisting of a combination thereof.
  • the hydrocarbon group forming a low-molecular-weight hydrocarbon chain that can be used as R P2 is more preferably an alkylene group, more preferably an alkylene group having 2 to 6 carbon atoms, and particularly preferably an alkylene group having 2 or 3 carbon atoms.
  • This hydrocarbon chain may have a polymer chain (for example, (meth)acrylic polymer) as a substituent.
  • the aliphatic hydrocarbon group is not particularly limited. group) and the like.
  • the aromatic hydrocarbon group includes, for example, a hydrocarbon group possessed by each component illustrated below, and an arylene group (for example, one or more hydrogen atoms from the aryl group listed for the substituent Z described below).
  • a removed group specifically a phenylene group, a tolylene group or a xylylene group
  • a hydrocarbon group represented by the following formula (M2) is preferable.
  • X represents a single bond, —CH 2 —, —C(CH 3 ) 2 —, —SO 2 —, —S—, —CO— or —O—, from the viewpoint of binding and -CH 2 - or -O- is preferred, and -CH 2 - is more preferred.
  • the alkylene group and methyl group exemplified here may be substituted with a substituent Z, preferably a halogen atom (more preferably a fluorine atom).
  • R M2 to R M5 each represent a hydrogen atom or a substituent, preferably a hydrogen atom.
  • Substituents that can be taken as R M2 to R M5 are not particularly limited, and examples thereof include an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 1 to 20 carbon atoms, —OR M6 , —N(R M6 ) 2 , —SR M6 (R M6 represents a substituent, preferably an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 10 carbon atoms.), halogen atom (e.g., fluorine atom, chlorine atom, bromine atom) are mentioned.
  • halogen atom e.g., fluorine atom, chlorine atom, bromine atom
  • —N(R M6 ) 2 is an alkylamino group (having preferably 1 to 20 carbon atoms, more preferably 1 to 6 carbon atoms) or an arylamino group (having preferably 6 to 40 carbon atoms, more preferably 6 to 20 carbon atoms). is more preferable).
  • a hydrocarbon polymer chain is a polymer chain formed by polymerizing (at least two) polymerizable hydrocarbons, provided that the chain comprises a hydrocarbon polymer having a higher number of carbon atoms than the low molecular weight hydrocarbon chains described above.
  • it is preferably a chain composed of a hydrocarbon polymer composed of 30 or more carbon atoms, more preferably 50 or more carbon atoms.
  • the upper limit of the number of carbon atoms constituting the hydrocarbon polymer is not particularly limited, and can be, for example, 3,000.
  • This hydrocarbon polymer chain is preferably a chain composed of a hydrocarbon polymer composed of an aliphatic hydrocarbon having a main chain satisfying the above number of carbon atoms, and composed of an aliphatic saturated hydrocarbon or an aliphatic unsaturated hydrocarbon. It is more preferred that the chain consists of a polymer (preferably an elastomer) that Specific examples of the polymer include a diene polymer having a double bond in its main chain and a non-diene polymer having no double bond in its main chain.
  • diene polymers examples include styrene-butadiene copolymers, styrene-ethylene-butadiene copolymers, copolymers of isobutylene and isoprene (preferably butyl rubber (IIR)), ethylene-propylene-diene copolymers, and the like. is mentioned.
  • non-diene polymers include olefin polymers such as ethylene-propylene copolymers and styrene-ethylene-butylene copolymers, and hydrogen reduction products of the above diene polymers.
  • the hydrocarbon that forms the hydrocarbon chain preferably has a reactive group at its terminal, and more preferably has a reactive terminal group capable of polycondensation.
  • a terminal reactive group capable of condensation polymerization or polyaddition forms a group attached to R P1 or R P2 in each of the above formulas by condensation polymerization or polyaddition.
  • Examples of such terminal reactive groups include an isocyanate group, a hydroxy group, a carboxy group, an amino group, an acid anhydride, etc. Among them, a hydroxy group is preferred.
  • Hydrocarbon polymers having terminal reactive groups include, for example, the NISSO-PB series (manufactured by Nippon Soda Co., Ltd.), the Claysole series (manufactured by Tomoe Kogyo Co., Ltd.), and the PolyVEST-HT series (manufactured by Evonik), all of which are trade names.
  • poly-bd series manufactured by Idemitsu Kosan Co., Ltd.
  • poly-ip series manufactured by Idemitsu Kosan Co., Ltd.
  • EPOL manufactured by Idemitsu Kosan Co., Ltd.
  • Polytail series manufactured by Mitsubishi Chemical Co., Ltd.
  • polyalkylene oxide chains examples include known chains composed of polyalkyleneoxy groups.
  • the number of carbon atoms in the alkyleneoxy group in the polyalkyleneoxy chain is preferably 1 to 10, more preferably 1 to 6, and more preferably 2 or 3 (polyethyleneoxy chain or polypropyleneoxy chain).
  • the polyalkyleneoxy chain may be a chain consisting of one type of alkyleneoxy group, or a chain consisting of two or more types of alkyleneoxy groups (for example, a chain consisting of an ethyleneoxy group and a propyleneoxy group).
  • Polycarbonate or polyester chains include known polycarbonate or polyester chains.
  • the polyalkyleneoxy chain, polycarbonate chain or polyester chain each preferably has an alkyl group (having preferably 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms) at its terminal.
  • the ends of the polyalkyleneoxy chains, polycarbonate chains and polyester chains that can be used as R P1 and R P2 are appropriately changed to ordinary chemical structures that can be incorporated into the constituents represented by the above formulas as R P1 and R P2 . be able to.
  • a polyalkyleneoxy chain may be stripped of the terminal oxygen atoms and incorporated as R P1 or R P2 in the above components.
  • R P1 and R P2 are divalent molecular chains, but at least one hydrogen atom is substituted with -NH-CO-, -CO-, -O-, -NH- or -N ⁇ . , it may be a trivalent or higher molecular chain.
  • R P1 is preferably a hydrocarbon chain, more preferably a low-molecular-weight hydrocarbon chain, more preferably a hydrocarbon chain composed of an aliphatic or aromatic hydrocarbon group, Hydrocarbon chains consisting of aliphatic hydrocarbon groups are particularly preferred.
  • R P2 is preferably a low molecular weight hydrocarbon chain (more preferably an aliphatic hydrocarbon group) or a molecular chain other than a low molecular weight hydrocarbon chain (more preferably a polyalkylene oxide chain). .
  • the component represented by the above formula (I-1) are shown below and in the exemplary polymers described later.
  • the constituent represented by formula (I-1) and the raw material compounds leading to it are not limited to the following specific examples and those described in the above literature.
  • the raw material compound (carboxylic acid or acid chloride thereof, etc.) leading to the constituent represented by the above formula (I-2) is not particularly limited, and is described in, for example, paragraph [0074] of WO 2018/020827. , carboxylic acid or acid chloride compounds and specific examples thereof (eg, adipic acid or esters thereof).
  • the constituent represented by formula (I-3) or formula (I-4) are shown below and in Examples. Further, the raw material compound (diol compound or diamine compound) leading to the component represented by the above formula (I-3) or formula (I-4) is not particularly limited. 020827 and specific examples thereof, and also dihydroxyoxamide. In the present invention, the constituents represented by formula (I-3) or formula (I-4) and the raw material compounds leading to them are not limited to the following specific examples, exemplary polymers described later, and those described in the above literature. .
  • the number of repetitions is an integer of 1 or more, and is appropriately set within a range that satisfies the molecular weight or the number of carbon atoms of the molecular chain.
  • R 3 P3 represents an aromatic or aliphatic linking group (tetravalent), preferably a linking group represented by any one of the following formulas (i) to (iix).
  • X 1 represents a single bond or a divalent linking group.
  • divalent linking group an alkylene group having 1 to 6 carbon atoms (eg, methylene, ethylene, propylene) is preferred. Propylene is preferably 1,3-hexafluoro-2,2-propanediyl.
  • R X and R Y each represent a hydrogen atom or a substituent.
  • * indicates the bonding site with the carbonyl group in formula (I-5).
  • Substituents that can be taken as R X and R Y are not particularly limited, and include the substituent Z described later, and an alkyl group (having preferably 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, more preferably 1 to 3 carbon atoms, more preferred) or an aryl group (having preferably 6 to 22 carbon atoms, more preferably 6 to 14 carbon atoms, and still more preferably 6 to 10 carbon atoms).
  • the carboxylic acid dianhydride represented by the above formula (I-5) and the raw material compound (diamine compound) leading to the constituent component represented by the above formula (I-6) are not particularly limited, for example, Each compound described in International Publication No. 2018/020827 and International Publication No. 2015/046313 and specific examples thereof can be mentioned.
  • R P1 , R P2 and R P3 may each have a substituent.
  • the substituent is not particularly limited, and examples thereof include the substituent Z described later and each group contained in the above functional group group (a), and the above substituents that can be taken as R M2 are suitable.
  • the constituent represented by any one of the above formulas (1-1) to (1-5), preferably selected from the functional group group (a) (including a component represented by the following formula (I-1)) having a functional group, and further the above formula (I-3), formula (I-4) or formula (I-5 ) may have a component represented by Examples of the component represented by formula (I-3) include components represented by at least one of the following formulas (I-3A) to (I-3C).
  • the component represented by formula (I-4) is the same as the component represented by formula (I-3), but in each of formulas (I-3A) to (I-3C) below, Replace oxygen atoms with nitrogen atoms.
  • R P1 is as described above.
  • R P2A represents a chain of low molecular weight hydrocarbon groups (preferably aliphatic hydrocarbon groups).
  • R P2B represents a polyalkyleneoxy chain.
  • R P2C represents a hydrocarbon polymer chain.
  • a chain composed of a low-molecular-weight hydrocarbon group that can be taken as R P2A , a polyalkyleneoxy chain that can be taken as R P2B , and a hydrocarbon polymer chain that can be taken as R P2C are each taken as R P2 in the above formula (I-3). are synonymous with an aliphatic hydrocarbon group, a polyalkyleneoxy chain, and a hydrocarbon polymer chain, and preferred ones are also the same.
  • the polymer (successively polymerized polymer) forming the binder may have constituents other than the constituents represented by the above formulas. Such constituents are not particularly limited as long as they are sequentially polymerizable with the raw material compound leading to the constituents represented by the above formulas.
  • the (total) content of the constituent components represented by the formulas (I-1) to (I-6) in the polymer forming the binder is not particularly limited, but is 5 to 100 mol%. is preferred, 5 to 80 mol% is more preferred, and 10 to 60 mol% is even more preferred.
  • the upper limit of this content can be, for example, 100 mol % or less, regardless of the above 60 mol %.
  • the content of constituent components other than the constituent components represented by the above formulas in the polymer forming the binder is not particularly limited, but is preferably 50 mol % or less.
  • the content thereof is not particularly limited and is appropriately selected. , can be set in the following range. That is, in the polymer forming the binder, the constituent represented by formula (I-1) or formula (I-2), or the structure derived from the carboxylic acid dianhydride represented by formula (I-5)
  • the content of the component is not particularly limited, but is preferably the same as the content of the component having a functional group described above.
  • the content of the component represented by formula (I-3), formula (I-4) or formula (I-6) in the polymer forming the binder is not particularly limited, and is 10 to 85 mol%.
  • each component represented by any one of formulas (I-3A) to (I-3C) above takes into consideration the content of the component represented by formula (I-3) above. is set appropriately.
  • the content of the component represented by the above formula (I-3A) is preferably 0 to 85 mol%, more preferably 10 to 30 mol%.
  • the content of the component represented by the above formula (I-3B) is preferably 0 to 85 mol%, more preferably 10 to 45 mol%.
  • the content of the component represented by the above formula (I-3C) is preferably 0 to 85 mol%, more preferably 30 to 60 mol%.
  • the content of each constituent component is the total content.
  • the polymer (each component and raw material compound) forming the binder may have a substituent.
  • the substituent is not particularly limited, but preferably includes a group selected from the following substituents Z.
  • the polymer forming the binder can be synthesized by selecting raw material compounds by a known method according to the type of bond possessed by the main chain, and subjecting the raw material compounds to polyaddition or polycondensation.
  • a known method for example, International Publication No. 2018/151118 can be referred to.
  • the method for incorporating a functional group is not particularly limited, and examples thereof include a method of copolymerizing a compound having a functional group selected from the functional group (a), and a method of using a polymerization initiator having (generates) the functional group. , a method utilizing a polymer reaction, and the like.
  • Polyurethane, polyurea, polyamide, and polyimide polymers that can be used as polymers that form the binder include, for example, WO 2018/020827 and WO 2015/046313, and JP 2015-088480. Each polymer described in can be mentioned.
  • Substituent Z - alkyl groups preferably alkyl groups having 1 to 20 carbon atoms, such as methyl, ethyl, isopropyl, t-butyl, pentyl, heptyl, 1-ethylpentyl, benzyl, 2-ethoxyethyl, 1-carboxymethyl, etc.
  • alkenyl groups preferably alkenyl groups having 2 to 20 carbon atoms, such as vinyl, allyl, oleyl, etc.
  • alkynyl groups preferably alkynyl groups having 2 to 20 carbon atoms, such as ethynyl, butadiynyl, phenylethynyl, etc.
  • cycloalkyl groups Preferably a cycloalkyl group having 3 to 20 carbon atoms, for example, cyclopropyl, cyclopentyl, cyclohexyl, 4-methylcyclohexyl, etc.
  • alkyl group usually means including a cycloalkyl group, but here it is separately described ), an aryl group (preferably an aryl group having 6 to 26 carbon atoms, such as phenyl, 1-naphthyl, 4-methoxyphenyl, 2-chlorophenyl, 3-methylphenyl, etc.), an aralkyl group (preferably having 7 to 23 aralkyl groups such as benzyl, phenethyl, etc.), heterocyclic groups (preferably heterocyclic groups having 2 to 20 carbon atoms, more preferably 5 or 6 having at least one oxygen, sulfur or nitrogen atom It is a membered heterocyclic group, including aromatic heterocyclic groups and aliphatic heterocyclic groups, such as tetrahydropyran ring group, tetrahydrofuran ring group, 2-pyridyl, 4-pyridyl, and 2-imidazolyl.
  • an aryl group preferably an aryl group having 6 to 26 carbon
  • alkoxy groups preferably alkoxy groups having 1 to 20 carbon atoms, such as methoxy, ethoxy, isopropyloxy, benzyloxy, etc.
  • aryloxy groups Preferably, an aryloxy group having 6 to 26 carbon atoms, such as phenoxy, 1-naphthyloxy, 3-methylphenoxy, 4-methoxyphenoxy, etc.
  • a heterocyclic oxy group bonded to the above heterocyclic group
  • alkoxycarbonyl group preferably an alkoxycarbonyl group having 2 to 20 carbon atoms, such as ethoxycarbonyl, 2-ethylhexyloxycarbonyl, dodecyloxycarbonyl, etc.
  • aryloxycarbonyl group preferably aryl having 6 to 26 carbon atoms Oxycarbonyl group, e.g
  • R P is a hydrogen atom or a substituent (preferably a group selected from substituent Z). Further, each of the groups exemplified for the substituent Z may be further substituted with the substituent Z described above.
  • the alkyl group, alkylene group, alkenyl group, alkenylene group, alkynyl group and/or alkynylene group, etc. may be cyclic or chain, and may be linear or branched.
  • the chain polymerization polymer preferably has a component having a functional group selected from the functional group group (a) or a component represented by the above formula (1-1), and has the functional group It is more preferable to have a constituent component and a constituent component represented by formula (1-1), and may further contain a constituent component other than these constituent components.
  • the chain-polymerized polymer is a polymer that does not have a component having a functional group selected from the functional group (a) or a component represented by the above formula (1-1) and is composed of another component.
  • fluorine-containing polymers examples include polytetrafluoroethylene (PTFE), polyvinylidene difluoride (PVdF), a copolymer of polyvinylidene difluoride and hexafluoropropylene (PVdF-HFP), polyvinylidene difluoride and hexafluoropropylene.
  • PTFE polytetrafluoroethylene
  • PVdF polyvinylidene difluoride
  • PVdF-HFP a copolymer of polyvinylidene difluoride and hexafluoropropylene
  • PVdF-HFP-TFE a copolymer of propylene and tetrafluoroethylene
  • the copolymerization ratio [PVdF:HFP] (mass ratio) of PVdF and HFP is not particularly limited, but is preferably 9:1 to 5:5, and 9:1 to 7:3 is adhesive. It is more preferable from the point of view.
  • the copolymerization ratio [PVdF:HFP:TFE] (mass ratio) of PVdF, HFP and TFE is not particularly limited, but is preferably 20 to 60:10 to 40:5 to 30. More preferably, it is 25-50:10-35:10-25.
  • Hydrocarbon polymers include, for example, polyethylene, polypropylene, natural rubber, polybutadiene, polyisoprene, polystyrene, polystyrene-butadiene copolymer, styrenic thermoplastic elastomer, polybutylene, acrylonitrile-butadiene copolymer, or hydrogenated (hydrogenated ) polymers.
  • Styrene-based thermoplastic elastomers or hydrogenated products thereof are not particularly limited, but examples include styrene-ethylene-butylene-styrene block copolymer (SEBS), styrene-isoprene-styrene block copolymer (SIS), and hydrogenated SIS.
  • styrene-butadiene-styrene block copolymer SBS
  • hydrogenated SBS styrene-ethylene-ethylene-propylene-styrene block copolymer
  • SEEPS styrene-ethylene-propylene-styrene block copolymer
  • SEPS styrene-ethylene-propylene-styrene block copolymer
  • examples include styrene-butadiene rubber (SBR), hydrogenated styrene-butadiene rubber (HSBR), and random copolymers corresponding to the block copolymers such as SEBS.
  • the hydrocarbon polymer preferably does not have an unsaturated group (eg, 1,2-butadiene component) bonded to the main chain because it can suppress the formation of chemical crosslinks.
  • vinyl polymers include polymers containing, for example, 50 mol % or more of vinyl monomers other than the (meth)acrylic compound (M1).
  • vinyl monomers include vinyl compounds described later.
  • Specific examples of vinyl polymers include polyvinyl alcohol, polyvinyl acetal, polyvinyl acetate, and copolymers containing these.
  • This vinyl polymer preferably has a component derived from a (meth)acrylic compound (M1) forming a (meth)acrylic polymer to be described later, in addition to the component derived from the vinyl monomer.
  • the content of the component derived from the vinyl monomer is preferably the same as the content of the component derived from the (meth)acrylic compound (M1) in the (meth)acrylic polymer.
  • the content of the component derived from the (meth)acrylic compound (M1) is not particularly limited as long as it is less than 50 mol% in the polymer, but is preferably 0 to 30 mol%.
  • a (meth)acrylic polymer at least one ( A polymer obtained by copolymerizing a meth)acrylic compound (M1) is preferred.
  • a (meth)acrylic polymer having a component derived from a macromonomer is also preferred.
  • the macromonomer is not particularly limited as long as it is a monomer that can be copolymerized with the (meth)acrylic compound (M1).
  • a (meth)acrylic polymer is preferable as a chain polymerization polymer that can be used as a polymer chain.
  • the number average molecular weight of the macromonomer is not particularly limited, it is preferably 500 to 100,000, more preferably 2,000 to 20,000.
  • Other polymerizable compounds (M2) are not particularly limited, and include styrene compounds, vinylnaphthalene compounds, vinylcarbazole compounds, allyl compounds, vinyl ether compounds, vinyl ester compounds, dialkyl itaconate compounds, unsaturated carboxylic acid anhydrides, and the like. vinyl compounds and fluorinated compounds thereof; Examples of the vinyl compound include "vinyl-based monomers" described in JP-A-2015-88486.
  • the (meth)acrylic compound (M1) and other polymerizable compound (M2) may have a substituent.
  • the substituent is not particularly limited as long as it is a group other than the functional group included in the functional group (a) described above, and preferably includes a group selected from the substituent Z described above.
  • the content of the component derived from the macromonomer in the (meth)acrylic polymer is not particularly limited, but can be, for example, 10 mol % or less.
  • the content of the component derived from the other polymerizable compound (M2) in the (meth)acrylic polymer is not particularly limited, but can be, for example, 50 mol % or less.
  • (meth)acrylic compound (M1) and vinyl compound (M2) leading to the constituent components of the (meth)acrylic polymer and vinyl polymer compounds represented by the following formula (b-1) are preferable.
  • This compound is different from the compound that leads to the component having a functional group included in the above functional group (a) and the component represented by the above formula (1-1).
  • R 1 is a hydrogen atom, a hydroxy group, a cyano group, a halogen atom, an alkyl group (preferably 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, particularly preferably 1 to 6 carbon atoms), an alkenyl group (2 carbon atoms to 24 are preferred, 2 to 12 are more preferred, and 2 to 6 are particularly preferred), an alkynyl group (having preferably 2 to 24 carbon atoms, more preferably 2 to 12, and particularly preferably 2 to 6), or an aryl group ( preferably 6 to 22 carbon atoms, more preferably 6 to 14 carbon atoms).
  • a hydrogen atom or an alkyl group is preferable, and a hydrogen atom or a methyl group is more preferable.
  • R2 represents a hydrogen atom or a substituent.
  • Substituents that can be taken as R 2 are not particularly limited. particularly preferred), aryl groups (preferably 6 to 22 carbon atoms, more preferably 6 to 14 carbon atoms), aralkyl groups (preferably 7 to 23 carbon atoms, more preferably 7 to 15 carbon atoms), and cyano groups.
  • Alkyl groups preferably have 1 to 3 carbon atoms.
  • the alkyl group may have, for example, a group other than the functional groups included in the functional group (a) among the substituents Z described above.
  • L 1 is a linking group, which is not particularly limited and includes, for example, an alkylene group having 1 to 6 carbon atoms (preferably 1 to 3), an alkenylene group having 2 to 6 carbon atoms (preferably 2 to 3 carbon atoms), 6 to 24 (preferably 6 to 10) arylene groups, oxygen atoms, sulfur atoms, imino groups (-NR N -: R N are as described above.), carbonyl groups, phosphoric acid linking groups (-OP ( OH) (O) -O-), a phosphonic acid linking group (-P (OH) (O) -O-), or a group related to a combination thereof, and the like, -CO-O- group, -CO- N(R N )—groups, where R N is as described above, are preferred.
  • the linking group may have any substituent. The number of atoms constituting the linking group and the number of linking atoms are as described later. Examples of optional substituents include the substituent Z described above, such as an al
  • n is 0 or 1, preferably 1; However, when —(L 1 ) n —R 2 represents one type of substituent (for example, an alkyl group), n is 0 and R 2 is a substituent (alkyl group).
  • (meth)acrylic compound (M1) compounds represented by the following formula (b-2) or (b-3) are also preferred. These compounds are different from the compounds leading to the component having a functional group included in the above functional group (a) and the component represented by the above formula (1-1).
  • R 1 and n have the same definitions as in formula (b-1) above.
  • R3 has the same definition as R2 .
  • L 2 is a linking group and has the same definition as L 1 above.
  • L 3 is a linking group, which has the same definition as L 1 above, but is preferably an alkylene group having 1 to 6 carbon atoms (preferably 1 to 3 carbon atoms).
  • m is an integer of 1-200, preferably an integer of 1-100, more preferably an integer of 1-50.
  • the substituent is not particularly limited, and includes, for example, the above groups that can be taken as R 1 .
  • substituents are used within a range that does not impair the effects of the present invention.
  • the substituent may be any substituent other than a functional group selected from the functional group (a), and examples thereof include groups selected from the substituent Z described later, and specific examples include a halogen atom and the like. be done.
  • the (meth)acrylic polymer preferably has a component having a functional group selected from the functional group group (a) or a component represented by the above formula (1-1), (meth ) It can have a constituent component derived from the acrylic compound (M1), a constituent component derived from the vinyl compound (M2), and other constituent components copolymerizable with the compound leading to these constituent components. Having a component represented by the above formula (1-1) and a component having a functional group selected from the functional group group (a) among the (meth) acrylic compounds (M1) disperses It is preferable in terms of stability and binding properties.
  • the chain polymerization polymer (each component and raw material compound) may have a substituent.
  • the substituent is not particularly limited, and preferably includes a group selected from the substituent Z described above, and is preferably a group other than the functional groups included in the functional group group (a) described above.
  • the content of the constituent components in the (meth)acrylic polymer is not particularly limited and is appropriately selected, and can be set, for example, within the following ranges.
  • the contents of the component represented by formula (1-1) and the component having a functional group selected from the functional group group (a) are as described above.
  • the content of the component derived from the (meth)acrylic compound (M1) in the (meth)acrylic polymer is not particularly limited and may be 100 mol%, but is preferably 1 to 90 mol%. It is preferably 10 to 80 mol %, and particularly preferably 20 to 70 mol %.
  • the content of the component derived from the vinyl compound (M2) in the (meth)acrylic polymer is not particularly limited, but is preferably 1 to 50 mol%, more preferably 10 to 50 mol%. , more preferably 20 to 50 mol %, more preferably 23 to 35 mol %.
  • the chain polymerization polymer (each component and raw material compound) may have a substituent.
  • the substituent is not particularly limited as long as it is a group other than the functional group included in the functional group (a) described above, and preferably includes a group selected from the substituent Z described above.
  • a chain polymerized polymer can be synthesized by selecting raw material compounds and polymerizing the raw material compounds by a known method.
  • the method for incorporating the functional group is not particularly limited, and for example, a method of copolymerizing a compound having a functional group selected from the functional group group (a), a polymerization initiator having (generates) the functional group, or chain transfer a method using an agent, a method using a polymer reaction, an ene reaction to a double bond (for example, in the case of a fluoropolymer, it is formed by a dehydrofluorination reaction of VDF constituents, etc.), an ene-thiol reaction, or An ATRP (Atom Transfer Radical Polymerization) polymerization method using a copper catalyst and the like can be mentioned.
  • ATRP Atom Transfer Radical Polymerization
  • a functional group can be introduced using a functional group present in the main chain, side chain or end of the polymer as a reaction point.
  • a compound having a functional group can be used to introduce a functional group selected from the functional group (a) through various reactions with carboxylic acid anhydride groups in the polymer chain.
  • polymer forming the polymer binder examples include those shown below in addition to those synthesized in Examples, but the present invention is not limited to these.
  • the number attached to the lower right of the constituent component indicates the content in the polymer, and the unit is mol %.
  • an appropriate polymer can be selected.
  • a chain polymerization polymer is preferable, and a hydrocarbon polymer or (meth)acrylic polymer is more preferable.
  • the true density (g/cm 3 ) of the polymer binder contained in the active material layer precursor layer is not particularly limited and is set appropriately.
  • the true density of the polymer binder is preferably 0.5 to 2.5 g/cm 3 and more preferably 0.8 to 2.2 g/cm 3 in that the filling rate can be easily set within the above range. preferable.
  • the true density of the polymer binder is the value measured by the gas replacement method described above.
  • the true volume (cm 3 ) of the polymer binder is not particularly limited and is appropriately set.
  • the polymer binder may be one that dissolves in the dispersion medium described later (also referred to as a soluble binder) or one that does not dissolve and exists in the form of particles (also referred to as a particulate binder).
  • a soluble binder is preferred, and the soluble binder usually exists in a state dissolved in a dispersion medium in the electrode composition described later, although it depends on the content, solubility, content of the dispersion medium, etc. do.
  • the fact that the polymer binder dissolves in the dispersion medium means that the solubility is 10% by mass or more in the solubility measurement, for example.
  • the polymer binder is not dissolved in the dispersion medium (insoluble) means that the solubility is less than 10% by mass in the solubility measurement.
  • the particle size of the particulate binder is not particularly limited, it is preferably 0.01 to 10 ⁇ 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 for the particle size of the inorganic solid electrolyte. The method for measuring solubility is as follows.
  • the mass average molecular weight of the polymer forming the polymer binder is not particularly limited, but is preferably 15,000 or more, more preferably 30,000 or more, and still more preferably 50,000 or more.
  • the upper limit is substantially 5,000,000 or less, preferably 4,000,000 or less, more preferably 3,000,000 or less, even more preferably 700,000 or less, and particularly 500,000 or less. Preferably, 200,000 or less is most preferred.
  • the weight average molecular weight of the polymer can be appropriately adjusted by changing the type and content of the polymerization initiator, polymerization time, polymerization temperature, and the like.
  • the molecular weights of polymers, polymer chains, polymer chains and macromonomers refer to mass average molecular weights or number average molecular weights in terms of standard polystyrene by gel permeation chromatography (GPC) unless otherwise specified.
  • GPC gel permeation chromatography
  • the measuring method basically, the method set to the following condition 1 or condition 2 (priority) can be mentioned. However, depending on the type of polymer, polymer chain, or macromonomer, an appropriate eluent may be selected and used.
  • the water concentration of the polymer is preferably 100 ppm (by mass) or less.
  • the polymer binder may be obtained by crystallizing and drying a polymer, or a polymer solution may be used as it is.
  • the polymer forming the polymeric binder is preferably amorphous.
  • a polymer being "amorphous" typically means that no endothermic peak due to crystalline melting is observed when measured at the glass transition temperature.
  • the polymer that forms the polymeric binder may be a non-crosslinked polymer or a crosslinked polymer.
  • the molecular weight may be larger than the above molecular weight.
  • the weight-average molecular weight of the polymer is within the above range at the start of use of the all-solid secondary battery.
  • the content of the polymer binder in the active material layer precursor layer is 3% by mass or less. As a result, it is possible to achieve low resistance of the all-solid secondary battery while maintaining the adhesion and binding of the solid particles, and it is also excellent in transportability.
  • the content of the polymer binder is preferably 0.5 to 2.5% by mass, more preferably 0.7 to 2.0% by mass, in terms of achieving both transportability and battery characteristics at a higher level. is more preferable, and 0.8 to 1.5% by mass is even more preferable.
  • the mass ratio of the total mass of the inorganic solid electrolyte and the active material to the total mass of the polymer binder in 100% by mass of the active material layer precursor layer [(mass of inorganic solid electrolyte + mass of active material) / ( The total mass of the polymer binder)] is preferably in the range of 1,000-1. This ratio is more preferably 500-2, even more preferably 100-10.
  • the active material layer precursor layer preferably contains a conductive aid.
  • a conductive aid there are no particular restrictions on the conductive aid, and any commonly known conductive aid can be used.
  • electronic conductive materials 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 fiber or carbon nanotube.
  • carbon fibers such as carbon fibers such as graphene or fullerene, metal powders such as copper and nickel, metal fibers, and conductive polymers such as polyaniline, polypyrrole, polythiophene, polyacetylene, and polyphenylene derivatives. may be used.
  • ions of metals belonging to Group 1 or Group 2 of the periodic table preferably Li A material that does not insert or release ions
  • a conductive aid those that can function as an active material in the active material layer during charging and discharging of the battery are classified as active materials rather than conductive aids. Whether or not it functions as an active material when the battery is charged/discharged is not univocally determined by the combination with the active material.
  • the conductive aid contained in the active material layer precursor layer is preferably particulate in the electrode composition.
  • the shape of the particles is not particularly limited, and may be flat, amorphous, or the like, but is preferably spherical or granular.
  • the particle size (volume average particle size) of the conductive aid is not particularly limited, but is preferably 0.02 to 1.0 ⁇ m, more preferably 0.03 to 0.5 ⁇ m. preferable.
  • the particle size of the conductive aid can be adjusted in the same manner as the particle size of the inorganic solid electrolyte, and can be measured in the same manner as the particle size of the inorganic solid electrolyte.
  • the true density (g/cm 3 ) of the conductive aid contained in the active material layer precursor layer is not particularly limited and is appropriately set.
  • the true density of the conductive aid is preferably 1 to 3 g/cm 3 , more preferably 1.5 to 2.0 g/cm 3 , since the filling rate can be easily set within the above range. It is more preferably g/cm 3 .
  • the true density of the conductive aid is the value measured by the gas replacement method described above.
  • the true volume (cm 3 ) of the conductive aid is not particularly limited and is appropriately set.
  • One or more conductive aids may be contained in the active material layer precursor layer.
  • the content of the conductive aid in the active material layer precursor layer is not particularly limited and is appropriately determined. For example, it is preferably 10% by mass or less, more preferably 1.0 to 5.0% by mass, in the active material layer precursor layer.
  • the active material layer precursor layer can also contain a lithium salt (supporting electrolyte).
  • the lithium salt is preferably a lithium salt that is usually used in this type of product, and is not particularly limited.
  • the content of the lithium salt is preferably 0.1 parts by mass or more, more preferably 5 parts by mass or more, relative to 100 parts by mass of the inorganic solid electrolyte.
  • the upper limit is preferably 50 parts by mass or less, more preferably 20 parts by mass or less.
  • the active material layer precursor layer does not need to contain any dispersant other than the polymer binder, since the polymer binder described above also functions as a dispersant.
  • the active material layer precursor layer contains a dispersing agent other than the polymer binder, as the dispersing agent, those commonly used in all-solid secondary batteries can be appropriately selected and used. Generally compounds intended for particle adsorption and steric and/or electrostatic repulsion are preferably used.
  • the active material layer precursor layer contains, as other components other than the components described above, an ionic liquid, a thickening agent, a cross-linking agent (such as one that undergoes a cross-linking reaction by radical polymerization, condensation polymerization, or ring-opening polymerization, etc.), and a polymerization initiator.
  • Agents such as those that generate acid or radicals by heat or light
  • antifoaming agents leveling agents, dehydrating agents, antioxidants, and the like can be contained.
  • the ionic liquid is contained in order to further improve the ionic conductivity, and known liquids can be used without particular limitation. Further, it may contain a polymer other than the polymer forming the polymer binder described above, a commonly used binder, and the like.
  • the electrode sheet (also referred to as an all-solid secondary battery electrode sheet) is a sheet produced by pressing the active material layer precursor layer of the electrode sheet of the present invention, and is used for the all-solid secondary battery. It is suitably used as a material sheet for manufacturing an active material layer or a laminate of a current collector and an active material layer. Therefore, the electrode sheet includes various aspects according to its use. For example, it may be a sheet in which an active material layer is formed on a substrate (current collector), or a sheet in which an active material layer is formed without a substrate.
  • the electrode sheet is usually a sheet having a substrate (current collector) and an active material layer.
  • a current collector an active material layer, a solid electrolyte layer and an active material layer in this order are also included.
  • the electrode sheet may have other layers in addition to the above layers. Other layers include, for example, a protective layer (release sheet) and a coat layer.
  • each layer constituting the electrode sheet may have a single-layer structure or a multi-layer structure.
  • the electrode sheet may be a long sheet or a single sheet.
  • the active material layer formed by pressing the active material layer precursor layer is not particularly limited, but has a filling rate of 60% or more, which is normally required for the active material layer of all-solid secondary batteries.
  • the filling rate of the active material layer is preferably 70% or more, more preferably 80% or more, and even more preferably 90% or more, from the viewpoint of battery characteristics (reduction of resistance increase).
  • the upper limit of the filling rate is ideally 100%, but in practice it can be 97% or less.
  • the filling rate of the active material layer is a value calculated in the same manner as the filling rate of the active material layer precursor layer.
  • the film density of the active material layer is not particularly limited, and is appropriately determined according to the filling rate of the active material layer precursor layer, the compressibility by pressing, etc., and is, for example, 1.5 to 4.6 g/cm 3 . It is preferably 3.0 to 4.0 g/cm 3 , more preferably 3.5 to 4.0 g/cm 3 .
  • the film density of the positive electrode active material layer is preferably 2.5 to 4.6 g/cm 3 .
  • the film density is preferably 1.2-2.2 g/cm 3 .
  • At least one of the active material layers of the electrode sheet is preferably formed of the active material layer precursor layer of the electrode sheet of the present invention.
  • the content of each component in the active material layer formed of the active material layer precursor layer of the electrode sheet of the present invention is not particularly limited, but is preferably the content of each component in the active material layer precursor layer. Synonymous.
  • the layer thickness of each layer constituting the electrode sheet is appropriately determined, and is the same as the layer thickness of each layer described in the all-solid secondary battery described later. Note that the active material layer that is not formed of the solid electrolyte layer or the active material layer precursor layer is formed of a normal constituent layer-forming material.
  • the electrode sheet has at least one active material layer formed of the electrode sheet of the present invention, and by using it as an active material layer of an all-solid secondary battery, an all-solid secondary battery that exhibits low resistance and excellent battery characteristics. Batteries can also be manufactured in industrial manufacturing methods. In particular, when an electrode sheet in which an active material layer precursor layer is formed on a current collector is used, the active material layer precursor layer and the current collector exhibit strong binding properties, thereby realizing further improvement in battery characteristics. In addition, an electrode consisting of a current collector and an active material layer can be formed at once, improving productivity.
  • the electrode sheet of the present invention is suitably used as a sheet-like member forming an active material layer, preferably an electrode (incorporated as an active material layer or an electrode) of an all-solid secondary battery.
  • the all-solid secondary battery of the present invention includes a positive electrode active material layer, a negative electrode active material layer facing the positive electrode active material layer, and a solid electrolyte layer disposed between the positive electrode active material layer and the negative electrode active material layer. have.
  • the all-solid secondary battery of the present invention is not particularly limited as long as it has a solid electrolyte layer between the positive electrode active material layer and the negative electrode active material layer. configuration can be adopted.
  • the positive electrode active material layer forms a positive electrode by laminating a positive electrode current collector on the surface opposite to the solid electrolyte layer, and the negative electrode active material layer forms a negative electrode on the surface opposite to the solid electrolyte layer.
  • a current collector is laminated to form a negative electrode.
  • each constituent layer (including a current collector and the like) that constitutes the all-solid secondary battery may have a single-layer structure or a multi-layer structure.
  • the all-solid secondary battery of the present invention is preferably an all-solid secondary battery manufactured by a method for manufacturing an all-solid secondary battery, which will be described later.
  • the all-solid secondary battery of the present invention at least one of the positive electrode active material layer and the negative electrode active material layer, preferably the positive electrode active material layer, accounts for 60% or more of the active material layer precursor layer in the electrode sheet of the present invention. It is preferable that the active material layer (electrode sheet produced by pressing the electrode sheet of the present invention) is compressed (pressed) to a filling rate of (formed).
  • both the negative electrode active material layer and the positive electrode active material layer are composed of active material layers obtained by compressing the electrode sheet of the present invention.
  • the negative electrode laminate of a negative electrode current collector and a negative electrode current collector
  • the positive electrode laminate of a positive electrode current collector and a positive electrode current collector
  • the active material layer is preferably formed by compressing the active material layer precursor layer of the electrode sheet, and both are formed by compressing the active material layer precursor layer of the electrode sheet of the present invention. is also one of the preferred aspects.
  • constructing the active material layer of the all-solid secondary battery from the active material layer obtained by compressing the active material layer precursor layer of the electrode sheet of the present invention means that only the active material layer is composed of the active material layer precursor layer.
  • a laminate of the active material layer and the solid electrolyte layer is used as an active material layer. It includes an embodiment in which an active material layer obtained by compressing a material layer precursor layer and a solid electrolyte layer are laminated.
  • the active material layer formed by compressing the active material layer precursor layer of the electrode sheet of the present invention preferably contains component species and their contents in the active material layer precursor layer. same as quantity.
  • the active material layer can be produced using a known material.
  • each constituent layer (including a current collector and the like) that constitutes the all-solid secondary battery may have a single-layer structure or a multi-layer structure.
  • each of the negative electrode active material layer and the positive electrode active material layer is not particularly limited.
  • the thickness of each layer is preferably 10 to 1,000 ⁇ m, more preferably 20 ⁇ m or more and less than 500 ⁇ m, considering the dimensions of a general all-solid secondary battery.
  • the thickness of at least one of the positive electrode active material layer and the negative electrode active material layer is more preferably 50 ⁇ m or more and less than 500 ⁇ m, and particularly preferably 50 ⁇ m or more and 250 ⁇ m or less. .
  • the active material layer is composed of an active material layer obtained by compressing the active material layer precursor layer of the electrode sheet of the present invention
  • a low-resistance all-solid secondary battery can be manufactured even in an industrial manufacturing method. be able to.
  • the solid electrolyte layer is formed using a known material capable of forming a solid electrolyte layer of an all-solid secondary battery.
  • the thickness is not particularly limited, it is preferably 10 to 1,000 ⁇ m, more preferably 20 ⁇ m or more and less than 500 ⁇ m.
  • Each of the positive electrode active material layer and the negative electrode active material layer preferably has a current collector on the side opposite to the solid electrolyte layer. Electron conductors are preferable as such a positive electrode current collector and a negative electrode current collector. In the present invention, either one of the positive electrode current collector and the negative electrode current collector, or both of them may simply be referred to as the current collector.
  • Examples of materials for forming the positive electrode current collector include aluminum, aluminum alloys, stainless steel, nickel and titanium, as well as materials obtained by treating the surface of aluminum or stainless steel with carbon, nickel, titanium or silver (thin films are formed). ) are preferred, and among them, aluminum and aluminum alloys are more preferred.
  • Materials for forming the negative electrode current collector include aluminum, copper, copper alloys, stainless steel, nickel and titanium, and the surface of aluminum, copper, copper alloys or stainless steel is treated with carbon, nickel, titanium or silver. and more preferably aluminum, copper, copper alloys and stainless steel.
  • a film sheet is usually used, but a net, a punched one, a lath, a porous body, a foam, a molded body of fibers, and the like can also be used.
  • the thickness of the current collector is not particularly limited, it is preferably 1 to 500 ⁇ m. It is also preferable that the surface of the current collector is roughened by surface treatment.
  • a functional layer or member is appropriately interposed or disposed between or outside each layer of the negative electrode current collector, the negative electrode active material layer, the solid electrolyte layer, the positive electrode active material layer, and the positive electrode current collector.
  • the all-solid secondary battery of the present invention may be used as an all-solid secondary battery with the above structure.
  • the housing may be made of metal or resin (plastic). When using a metallic one, for example, an aluminum alloy or a stainless steel one can be used. It is preferable that the metal casing be divided into a positive electrode side casing and a negative electrode side casing 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 short-circuit prevention.
  • FIG. 2 is a cross-sectional view schematically showing an all-solid secondary battery (lithium ion secondary battery) according to a preferred embodiment of the present invention.
  • the all-solid secondary battery 10 of the present embodiment has a negative electrode current collector 1, a negative electrode active material layer 2, a solid electrolyte layer 3, a positive electrode active material layer 4, and a positive electrode current collector 5 in this order when viewed from the negative electrode side. .
  • Each layer is in contact with each other and has an adjacent structure. By adopting such a structure, electrons (e ⁇ ) are supplied to the negative electrode during charging, and lithium ions (Li + ) are accumulated there.
  • the lithium ions (Li + ) accumulated in the negative electrode are returned to the positive electrode side, and electrons are supplied to the operating portion 6 .
  • a light bulb is used as a model for the operating portion 6, and is lit by discharge.
  • a battery fabricated in a 2032-type coin case is sometimes called a (coin-type) all-solid-state secondary battery.
  • both the positive electrode active material layer and the negative electrode active material layer are formed by compressing the active material layer precursor layer of the electrode sheet of the present invention.
  • the positive electrode in which the positive electrode active material layer and the positive electrode current collector are laminated, and the negative electrode in which the negative electrode active material layer and the negative electrode current collector are laminated are applied to the current collector as the base material of the electrode sheet of the present invention.
  • the active material layer is formed by compressing the active material layer precursor layer.
  • the positive electrode active material layer is synonymous with the positive electrode active material layer of the electrode sheet, and includes an inorganic solid electrolyte having ion conductivity of a metal belonging to Group 1 or Group 2 of the periodic table, a positive electrode active material, and a polymer. It contains a binder and any of the above-described optional components within a range that does not impair the effects of the present invention.
  • the negative electrode active material layer is synonymous with the negative electrode active material layer of the electrode sheet, and includes an inorganic solid electrolyte having ion conductivity of a metal belonging to Group 1 or Group 2 of the periodic table, a negative electrode active material, and a polymer binder.
  • the negative electrode active material layer can be a lithium metal layer.
  • the lithium metal layer include a layer formed by depositing or molding lithium metal powder, a lithium foil, a lithium deposition film, and the like.
  • the thickness of the lithium metal layer can be, for example, 1 to 500 ⁇ m regardless of the thickness of the negative electrode active material layer.
  • Solid electrolyte layer As the solid electrolyte layer, those applied to conventional all-solid secondary batteries can be used without particular limitation.
  • the solid electrolyte layer contains an inorganic solid electrolyte having ion conductivity of a metal belonging to Group 1 or Group 2 of the periodic table and any of the above-mentioned optional components as appropriate, and usually contains an active material. does not contain
  • the components contained in the positive electrode active material layer 4, the solid electrolyte layer 3, and the negative electrode active material layer 2, particularly the inorganic solid electrolyte, the conductive aid, and the polymer binder, may be of the same type or different types.
  • the positive electrode current collector 5 and the negative electrode current collector 1 are respectively as described above.
  • the all-solid secondary battery of the present invention can be applied to various uses. There are no particular restrictions on the mode of application, but for example, when installed in electronic equipment, notebook computers, pen-input computers, mobile computers, e-book players, mobile phones, cordless phone slaves, pagers, handy terminals, mobile faxes, mobile phones, etc. Copiers, portable printers, headphone stereos, video movies, liquid crystal televisions, handy cleaners, portable CDs, minidiscs, electric shavers, transceivers, electronic notebooks, calculators, memory cards, portable tape recorders, radios, backup power sources, etc.
  • Other consumer products include automobiles (electric vehicles, etc.), electric vehicles, motors, lighting equipment, toys, game devices, road conditioners, clocks, strobes, cameras, and medical devices (pacemakers, hearing aids, shoulder massagers, etc.). . Furthermore, it can be used for various military applications and space applications. It can also be combined with a solar cell.
  • the method for producing the electrode sheet of the present invention is not particularly limited as long as the method can form the active material layer precursor layer by setting the content of the polymer binder and the filling rate of the active material layer precursor layer within the above ranges. .
  • the solid content of the polymer binder is set to 3% by mass or less to prepare an electrode composition, and a step (operation) of setting the filling rate of the active material layer precursor layer to 35 to 50% (hereinafter referred to as the electrode for the present invention It may be called a sheet manufacturing method.).
  • the electrode sheet manufacturing method of the present invention can be applied to the active material layer precursor layer.
  • an electrode composition is prepared.
  • This electrode composition contains an inorganic solid electrolyte, an active material, a polymer binder and a dispersion medium, preferably a conductive aid, and further contains the above-described lithium salt, dispersant and other additives as appropriate.
  • the electrode composition is preferably a slurry in which an inorganic solid electrolyte, an active material, etc. are dispersed in a dispersion medium.
  • This electrode composition is preferably a non-aqueous composition.
  • the non-aqueous composition includes not only a form containing no water but also a form having a water content (also referred to as water content) of preferably 500 ppm or less.
  • the water content is more preferably 200 ppm or less, still more preferably 100 ppm or less, and particularly preferably 50 ppm or less. If the electrode composition is a non-aqueous composition, deterioration of the inorganic solid electrolyte can be suppressed.
  • the water content indicates the amount of water contained in the electrode composition (mass ratio with respect to the electrode composition), and specifically, it is measured using Karl Fischer titration after filtration through a 0.02 ⁇ m membrane filter. value.
  • each component other than the dispersion medium contained in the electrode composition is as described above, and the content of each component in 100% by mass of the solid content of the electrode composition is the content in the active material layer precursor layer. is the same as In particular, the content of the polymer binder is set to 3% by mass or less based on 100% by mass of the solid content of the electrode composition.
  • the solid content refers to a component that does not disappear by volatilization or evaporation when the electrode composition is dried at 150° C. for 6 hours under a pressure of 1 mmHg under a nitrogen atmosphere. Typically, it refers to components other than the dispersion medium, which will be described later.
  • content in a total solid content shows content in 100 mass % of total mass of solid content.
  • the dispersion medium contained in the electrode composition may be any organic compound that exhibits a liquid state in the environment of use, and examples thereof include various organic solvents. Specific examples include alcohol compounds, ether compounds, amide compounds, amine compounds, Ketone compounds, aromatic compounds, aliphatic compounds, nitrile compounds, ester compounds, and the like.
  • the dispersion medium may be either a non-polar dispersion medium (hydrophobic dispersion medium) or a polar dispersion medium (hydrophilic dispersion medium), but a non-polar dispersion medium is preferable in that excellent dispersion characteristics can be exhibited.
  • a non-polar dispersion medium generally means a property with low affinity for water, and in the present invention, examples thereof include ester compounds, ketone compounds, ether compounds, aromatic compounds, and aliphatic compounds.
  • alcohol compounds include methyl alcohol, ethyl alcohol, 1-propyl alcohol, 2-propyl alcohol, 2-butanol, ethylene glycol, propylene glycol, glycerin, 1,6-hexanediol, cyclohexanediol, sorbitol, xylitol, 2 -methyl-2,4-pentanediol, 1,3-butanediol, 1,4-butanediol.
  • ether compounds include alkylene glycol (diethylene glycol, triethylene glycol, polyethylene glycol, dipropylene glycol, etc.), alkylene glycol monoalkyl ether (ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, diethylene glycol monomethyl ether, dipropylene glycol monomethyl ether, tripropylene glycol monomethyl ether, diethylene glycol monobutyl ether, etc.), alkylene glycol dialkyl ethers (ethylene glycol dimethyl ether, etc.), dialkyl ethers (dimethyl ether, diethyl ether, diisopropyl ether, dibutyl ether, etc.), cyclic ethers (tetrahydrofuran, dioxane (including 1,2-, 1,3- and 1,4-isomers), etc.).
  • alkylene glycol diethylene glycol, triethylene glycol, polyethylene glycol, dipropylene glycol, etc.
  • amide compounds include N,N-dimethylformamide, N-methyl-2-pyrrolidone, 2-pyrrolidinone, 1,3-dimethyl-2-imidazolidinone, ⁇ -caprolactam, formamide, N-methylformamide, and acetamide. , N-methylacetamide, N,N-dimethylacetamide, N-methylpropanamide, hexamethylphosphoric triamide and the like.
  • amine compounds include triethylamine, diisopropylethylamine, and tributylamine.
  • Ketone compounds include, for example, acetone, methyl ethyl ketone, methyl isobutyl ketone (MIBK), cyclopentanone, cyclohexanone, cycloheptanone, dipropyl ketone, dibutyl ketone, diisopropyl ketone, diisobutyl ketone (DIBK), isobutyl propyl ketone, sec- Butyl propyl ketone, pentyl propyl ketone, butyl propyl ketone and the like.
  • aromatic compounds include benzene, toluene, xylene, perfluorotoluene, and the like.
  • aliphatic compounds include hexane, heptane, octane, nonane, decane, dodecane, cyclohexane, methylcyclohexane, ethylcyclohexane, cycloheptane, cyclooctane, decalin, paraffin, gasoline, naphtha, kerosene, and light oil.
  • Nitrile compounds include, for example, acetonitrile, propionitrile, isobutyronitrile, and the like.
  • Ester compounds include, for example, ethyl acetate, propyl acetate, butyl acetate, ethyl butyrate, propyl butyrate, isopropyl butyrate, butyl butyrate, isobutyl butyrate, butyl pentanoate, pentyl pentanoate, ethyl isobutyrate, propyl isobutyrate, and isopropyl isobutyrate.
  • ether compounds, ketone compounds, aromatic compounds, aliphatic compounds, and ester compounds are preferred, and ester compounds, ketone compounds, and ether compounds are more preferred.
  • the number of carbon atoms in the compound constituting the dispersion medium is not particularly limited, preferably 2 to 30, more preferably 4 to 20, even more preferably 6 to 15, and particularly preferably 7 to 12.
  • the boiling point of the dispersion medium at normal pressure (1 atm) is not particularly limited, it is preferably 90°C or higher, more preferably 120°C or higher.
  • the upper limit is preferably 230°C or lower, more preferably 200°C or lower.
  • the dispersion medium contained in the electrode composition of the present invention may be of one type or two or more types.
  • Mixed xylene a mixture of o-xylene, p-xylene, m-xylene, and ethylbenzene
  • the content of the dispersion medium in the electrode composition is not particularly limited and can be set as appropriate. For example, it is preferably 20 to 80% by mass, more preferably 30 to 70% by mass, particularly preferably 40 to 60% by mass in the electrode composition.
  • An electrode composition can be prepared by a conventional method. For example, an inorganic solid electrolyte, an active material, a polymer binder and a dispersion medium, preferably a conductive aid, and optionally, a lithium salt, a dispersant, and other components are mixed, for example, with various commonly used mixers, It can be prepared as a mixture, preferably as a slurry. At this time, the content of the polymer binder is set to 3% by mass or less in 100% by mass of the solid content of the electrode composition.
  • the method of mixing the above components is not particularly limited, and the above components may be mixed together or sequentially.
  • an electrode composition can be prepared by mixing an active material, preferably a conductive aid, and a dispersion medium with a solid electrolyte composition prepared by mixing an inorganic solid electrolyte, a polymer binder, and a dispersion medium. preferable.
  • the amount of each component used is appropriately set in consideration of the content of each component in the target electrode composition. It is set in the same range as the amount.
  • the dispersion medium used for preparing each composition is appropriately set in consideration of the content of the dispersion medium in the electrode composition. When lithium salts, dispersants and other additives are used in this preparation method, these ingredients may be mixed in any step.
  • the mixing method and mixing conditions in preparation of each composition are not particularly limited and can be set as appropriate.
  • the components may be mixed together or sequentially.
  • the mixing method can be carried out using known mixers such as ball mills, bead mills, planetary mixers, blade mixers, roll mills, kneaders, disc mills, rotation-revolution mixers and narrow-gap dispersers.
  • the mixing conditions are, for example, a mixing temperature of 10 to 60° C., a rotation speed of a rotation/revolution mixer or the like of 10 to 700 rpm (rotation per minute), and a mixing time of 5 minutes to 5 hours. can.
  • the mixer When a ball mill is used as the mixer, it is preferable to set the number of revolutions to 50 to 700 rpm, the mixing time to 5 minutes to 24 hours, preferably 5 to 60 minutes, at the above mixing temperature. In addition, the mixing in this step can also be performed in multiple steps.
  • the prepared electrode composition is preferably applied on the surface of the substrate (which may be via another layer) and dried (film formation) to form an electrode composition. to form a dry coating layer.
  • the coated dry layer is a layer formed by applying the electrode composition and drying the dispersion medium (that is, the electrode composition is used and the dispersion medium is removed from the electrode composition. ).
  • a dispersion medium may remain in the coated dry layer as long as it does not impair the effects of the present invention, and the residual amount can be, for example, 3% by mass or less in the coated dry layer.
  • the dried coated film of the electrode composition may be used as the active material layer precursor layer as it is, and the dried coated layer may be subjected to a treatment that is usually performed, for example, the filling rate may deviate.
  • the applied dried film may be pressurized to the extent that it does not become the active material layer precursor layer.
  • the method of applying the electrode composition is not particularly limited and can be selected as appropriate. Examples thereof include wet coating methods such as coating (preferably wet coating), spray coating, spin coating, dip coating, slit coating, stripe coating and bar coating.
  • the applied electrode composition is dried (heated).
  • the drying temperature is not particularly limited as long as the dispersion medium can be removed, and is appropriately set according to the boiling point of the dispersion medium and the like.
  • 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 is preferably 300°C or lower, more preferably 250°C or lower, and even more preferably 200°C or lower.
  • the dispersion medium By heating in such a temperature range, the dispersion medium can be removed and a solid state (coated dry layer) can be obtained. Moreover, it is preferable because the temperature is not too high and each member of the electrode sheet is not damaged.
  • the drying time is appropriately determined according to the drying temperature and the like, and is not particularly limited. For example, it can be 0.1 to 5 hours, preferably 0.2 to 1 hour.
  • the applied pressure is not particularly limited, and can be set to an appropriate applied pressure in consideration of the filling rate of the active material layer precursor layer.
  • the pressurization time high pressure may be applied for a short period of time (for example, within several hours), or for a long period of time (one day or more).
  • the press pressure may be uniform or different with respect to the pressed portion of the coated dry layer.
  • the press pressure can also be changed according to the area or film thickness of the portion to be pressed. Also, the same part can be changed step by step with different pressures.
  • the pressing surface may be smooth or roughened. The pressing may be performed under heating, but is preferably performed without heating, for example, at an ambient temperature of 0 to 50°C.
  • the applied electrode composition may be heated at the same time as being pressurized.
  • the heating temperature is not particularly limited, and generally ranges from 30 to 300.degree. It is also possible to press at a temperature higher than the glass transition temperature of the inorganic solid electrolyte. It should be noted that pressing can also be performed at a temperature higher than the glass transition temperature of the polymer that constitutes the polymer binder. However, generally the temperature does not exceed the melting point of the polymer. Pressurization may be performed after drying the coating solvent or dispersion medium in advance, or may be performed while the solvent or dispersion medium remains. Note that the electrode composition may be coated, dried and pressed simultaneously and/or sequentially.
  • the atmosphere in which the electrode sheet is produced is not particularly limited, and includes atmospheric air, dry air (dew point of ⁇ 20° C. or less), inert gas (eg, argon gas, helium gas, nitrogen gas), and the like. Either is fine. Since the inorganic solid electrolyte readily reacts with moisture, it is preferably under dry air or in an inert gas.
  • Step (operation) of setting the filling rate to 35 to 50% In the electrode sheet manufacturing method of the present invention, a step (operation) of setting the filling rate of the formed active material layer precursor layer to 35 to 50% is performed. However, when the active material layer precursor layer formed by coating and drying the electrode composition has a filling rate of 35 to 50%, the following step of setting the filling rate of the active material layer precursor layer (operation ) is not required.
  • the step of setting the filling rate is the step of adjusting the film density or true density, for example, the type, particle size or content of each component, particularly solid particles, the solid content concentration or drying conditions of the electrode composition, etc.
  • the filling rate increases, and the true density of each solid particle can be set within the range described above. preferable.
  • the particle diameter of the solid particles is reduced, the filling rate tends to decrease.
  • the filling rate tends to decrease.
  • the filling rate tends to decrease. For example, if the content of the solid concentration is within the above range, for example, 60% by mass or more, preferably 65% by mass or more, the filling rate can be set to 50% or less.
  • the filling rate tends to decrease.
  • the filling rate can be reduced by shortening the drying time.
  • the drying time is preferably 2 hours or less, preferably 1 hour or less.
  • the filling rate can be reduced. °C or higher, the filling rate can be reduced within the above range, and high transportability can be achieved while maintaining low resistance.
  • the filling rate can also be set by changing the type or properties of the polymer binder. For example, when the type of polymer forming the polymer binder is changed from one that dissolves in the dispersion medium to a particulate form that disperses, the filling rate tends to increase. In addition, when the particle size of the particulate polymer binder is reduced, the filling rate tends to increase. Furthermore, when the interaction (adsorptivity) of the polymer binder to the solid particles is weakened, for example, when the content of the component having the above-described functional group contained in the polymer forming the polymer binder is decreased, the filling rate tends to decrease. . Specifically, if the content of the constituent component having a functional group is 3 to 20 mol % within the above range, it becomes easier to set the filling rate to 35 to 50% or less, especially for the chain polymer.
  • a step of setting the film density of the active material layer precursor layer can be performed.
  • the step (operation) of setting the film density is performed. No need.
  • the step of setting the film density includes the same step as the above-described step of adjusting the film density.
  • each component, particularly the type, particle size or content of solid particles, the solid content concentration or drying conditions of the electrode composition, the step of changing the layer thickness of the coated dry layer, etc. For example, a process of mixing a material that decomposes and volatilizes by spraying, drying to remove the dispersion medium, and then decomposing and volatilizing the material.
  • the film density increases, and the true density of each solid particle can be set within the ranges described above. preferable.
  • the particle diameter of the solid particles is reduced, the film density tends to decrease.
  • the solid content concentration of the electrode composition is increased (the content of the dispersion medium is decreased), the film density tends to decrease.
  • the film density is 0.8 to 2.2 g/cm 3 or less, preferably 1 .4 to 2.0 g/cm 3 or less.
  • the film density can be reduced by shortening the drying time. Specifically, the drying time is preferably 2 hours or less, preferably 1 hour or less.
  • the drying temperature is increased, the film density can be reduced. °C or more, the film density can be reduced within the above range, and high transportability can be achieved while maintaining low resistance.
  • Film density can also be set by changing the type or properties of the polymeric binder. For example, when the type of polymer forming the polymer binder is changed from one that dissolves in the dispersion medium to a particulate form that disperses, the film density tends to increase. In addition, when the particle size of the particulate polymer binder is reduced, the film density tends to increase. Furthermore, when the interaction (adsorptivity) of the polymer binder with respect to the solid particles is weakened, for example, when the content of the component having the above functional group contained in the polymer forming the polymer binder is decreased, the film density tends to decrease. .
  • the film density is 0.8 to 2.2 g/cm 3 or less, preferably 1.4 to 2.0 g/cm 3 . 0 g/cm 3 or less.
  • an electrode sheet having an active material layer precursor layer that satisfies the filling rate and film density can be manufactured.
  • the electrode sheet can be manufactured by a method of forming an active material layer by pressing the active material layer precursor layer of the electrode sheet of the present invention (hereinafter sometimes referred to as the electrode sheet manufacturing method of the present invention). can.
  • the active material layer precursor layer is pressed in the thickness direction of the active material layer precursor layer.
  • a normal pressing method can be applied without particular limitation, and examples thereof include a method using a hydraulic cylinder press.
  • the applied pressure is not particularly limited as long as it is a pressure that can increase the filling rate of the active material layer to 60% or more.
  • the electrode sheet manufacturing method of the present invention is set to an appropriate pressure in consideration of the damage of For example, it is preferably 5 to 1500 MPa, more preferably 50 to 1000 MPa, even more preferably 100 to 600 MPa.
  • heating may be performed at the same time as the pressing.
  • the heating method and conditions are not particularly limited, and the above-described heating method and conditions performed simultaneously with pressurization of the applied electrode composition can be applied.
  • the atmosphere in which the electrode sheet manufacturing method is carried out is not particularly limited, and may be the same atmosphere as the atmosphere in which the electrode sheet is manufactured.
  • the electrode sheet When the electrode sheet has a solid electrolyte layer, it can be produced by pressing a solid electrolyte layer or a solid electrolyte layer-forming material overlaid on the electrode sheet of the present invention.
  • an electrode sheet manufacturing method of the present invention described above an electrode sheet having an active material layer which is a pressure layer of the active material layer precursor layer and has a filling rate of 60% or more can be manufactured.
  • An all-solid secondary battery can be produced by forming an active material layer or an electrode using the electrode sheet of the present invention or the electrode sheet.
  • a solid electrolyte layer, a solid electrolyte sheet, or a solid electrolyte layer-forming material is prepared for manufacturing an all-solid secondary battery.
  • a solid electrolyte layer or a solid electrolyte sheet can be produced by forming an inorganic solid electrolyte-containing composition into a film on a substrate. Any commonly used inorganic solid electrolyte-containing composition can be used without particular limitation.
  • a composition containing the above-mentioned inorganic solid electrolyte, polymer binder and dispersion medium, and appropriately containing a conductive aid, a lithium salt, a dispersant, other additives and the like may be mentioned.
  • Appropriate methods and conditions can be applied without any particular limitation on the film-forming method and conditions.
  • the solid electrolyte layer or solid electrolyte sheet can also be produced by pressure-molding a powder mixture containing no dispersion medium by a normal method.
  • the solid electrolyte layer-forming material may be any material as long as it can form a solid electrolyte layer, and includes, for example, the inorganic solid electrolytes described above, as appropriate, polymer binders, conductive aids, lithium salts, dispersants, other additives, and the like. materials (usually solid compositions) that
  • the method for manufacturing an all-solid secondary battery using the electrode sheet of the present invention comprises the electrode sheet of the present invention and a solid electrolyte layer or a solid electrolyte layer forming material
  • the electrode sheet of the present invention and the solid electrolyte layer or the solid electrolyte layer-forming material are stacked.
  • the electrode sheet of the present invention when forming both active material layers with the electrode sheet of the present invention, the electrode sheet of the present invention, the solid electrolyte layer or the solid electrolyte layer-forming material and the electrode sheet of the present invention are stacked to form the electrode sheet of the present invention.
  • a solid electrolyte layer or a solid electrolyte layer-forming material is placed between two sheets of active material layer precursor layers.
  • the active material layer precursor layer of the electrode sheet of the present invention is pressed in the superimposed state until the filling rate is usually 60% or more.
  • This pressing is performed by stacking the active material layer precursor layer together with the solid electrolyte layer or the solid electrolyte layer-forming material in a state in which the solid electrolyte layer is laminated on the active material layer precursor layer or the solid electrolyte layer-forming material is placed. It is collectively (integrally) carried out in the combined direction (thickness direction of the active material layer precursor layer).
  • the method and conditions for pressing are not particularly limited, but for example, the method and conditions described in the method and conditions for pressing the active material layer precursor layer in the electrode sheet manufacturing method of the present invention can be applied.
  • an appropriate material for forming the active material layer is placed on the pressed body of the electrode sheet of the present invention and the solid electrolyte layer or solid electrolyte layer-forming material. Then, pressurize as appropriate, or stack the electrode sheet of the present invention with a solid electrolyte layer or a solid electrolyte layer-forming material and an appropriate material, and pressurize as appropriate to produce an all-solid secondary battery.
  • a method of pressing the active material layer precursor layer can be applied as a pressurizing method at this time, and the pressurizing force is not particularly limited, but can be, for example, 5 to 1500 MPa.
  • a method for manufacturing an all-solid-state secondary battery using an electrode sheet includes stacking an electrode sheet and a solid electrolyte layer, or stacking an electrode sheet and a solid electrolyte layer-forming material and pressing them to form an active material layer or an electrode. It is a method of forming (a laminate of a current collector and an active material layer). Here, when forming one of the active material layers with the electrode sheet, the electrode sheet and the solid electrolyte layer or solid electrolyte layer-forming material are stacked.
  • the electrode sheet and the solid electrolyte layer or the solid electrolyte layer-forming material and the electrode sheet are stacked, and the solid electrolyte layer or the solid electrolyte is placed between the active material layers of the two electrode sheets. Laying down the layering material.
  • the method of pressing the active material layer precursor layer can be applied, and the pressing force is not particularly limited, but can be, for example, 5 to 1500 MPa.
  • an appropriate material for forming the active material layer is placed on the solid electrolyte layer or the solid electrolyte layer-forming material superimposed on the electrode sheet, and pressurized appropriately to completely A solid secondary battery can be manufactured.
  • a method of pressing the active material layer precursor layer can be applied as a pressurizing method at this time, and the pressurizing force is not particularly limited, but can be, for example, 5 to 1500 MPa.
  • the atmosphere in which the battery manufacturing method is carried out is not particularly limited, and can be the same atmosphere as the atmosphere in which the electrode sheet is manufactured.
  • the all-solid secondary battery manufactured as described above is preferably initialized after manufacturing or before use. Initialization is not particularly limited, and can be performed, for example, by performing initial charge/discharge while press pressure is increased, and then releasing the pressure to the general working pressure of all-solid secondary batteries.
  • Neostan U-600 (trade name, manufactured by Nitto Kasei Co., Ltd.) was added and stirred at 80° C. for 12 hours to synthesize polymer B3 (polyurethane) to synthesize a polymer comprising polymer B3.
  • a binder solution B3 (concentration 35% by weight) was obtained.
  • a liquid prepared in a separate container ethyl acrylate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) 177 g, acrylic acid (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) 13 g, macromonomer AB-6 (trade name, Toagosei Co., Ltd.) (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) and 2.0 g of polymerization initiator V-601 (manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.) was added dropwise over 2 hours, followed by stirring at 80° C. for 2 hours. An additional 1.0 g of V-601 was added to the resulting mixture and stirred at 90° C.
  • each synthesized polymer is shown below.
  • the numbers on the bottom right of each component indicate the content (% by mol).
  • the weight average molecular weights of polymers B1 to B5 were 100,000, 150,000, 50,000, 100,000, 530,000 in order. Met.
  • the form (dissolved or insoluble) of the polymer binders B1 to B5 in the electrode composition described later was determined by measuring the solubility in the dispersion medium (butyl butyrate) used in the electrode composition by the method described above. .
  • polymer binders B1 to B3 were dissolved in the dispersion medium in the electrode composition, and polymer binders B4 and B5 were dispersed in the dispersion medium in the electrode composition in the form of particles.
  • Li 2 S lithium sulfide
  • P 2 S 5 diphosphorus pentasulfide
  • Particle size preparation The obtained LPS was subjected to wet dispersion under the following conditions to adjust the particle size of LPS.
  • Particle size preparation example A1 160 zirconia beads with a diameter of 5 mm were put into a zirconia 45 mL container (manufactured by Fritsch), and after adding 4.0 g of the synthesized LPS and 6.0 g of diisobuketone as an organic solvent, the mixture was placed in a planetary ball mill P-7. A container was set and wet dispersion was performed at 250 rpm for 30 minutes to obtain LPS1 having a particle size (volume average particle size) of 2.5 ⁇ m.
  • Example 1 ⁇ Preparation of positive electrode composition (slurry) S-1> 70 parts by mass of NMC (lithium nickel manganese cobaltate, particle size 5 ⁇ m, manufactured by Aldrich) as a positive electrode active material, 27 parts by mass of LPS1 (particle size 2.5 ⁇ m) obtained in the above particle size preparation example A1 as an inorganic solid electrolyte, 2 parts by mass of acetylene black (particle size 0.1 ⁇ m, manufactured by Denka) as a conductive aid, 1 part by mass of polymer binder solution B1 (in terms of solid content) as a polymer binder, and a dispersion medium, in the order of steps 1 and 2 below. to prepare a positive electrode composition S-1 having a solid content concentration of 65% by mass.
  • NMC lithium nickel manganese cobaltate, particle size 5 ⁇ m, manufactured by Aldrich
  • LPS1 particle size 2.5 ⁇ m
  • acetylene black particle size 0.1 ⁇ m, manufactured by Denka
  • Step 1 20 g of zirconia beads with a diameter of 3 mm were added to a zirconia 45 mL container (manufactured by Fritsch), 27 parts by mass of an inorganic solid electrolyte, 1 part by mass of polymer binder solution B1 (in terms of solid content), and butyl butyrate as a dispersion medium. was added to adjust the solid content concentration to 60% by mass.
  • this container was set in a planetary ball mill P-7 (trade name, manufactured by Fritsch) and stirred at a temperature of 25° C. and a rotation speed of 100 rpm for 30 minutes to obtain a solid electrolyte composition S1-1 having a solid content concentration of 60% by mass.
  • Step 2 70 parts by mass of the positive electrode active material, 2 parts by mass of acetylene black, and butyl butyrate as a dispersion medium were added to the total amount of the solid electrolyte composition S1-1 in the container obtained in step (1). It was adjusted to the solid content concentration shown in . After that, 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 30 minutes to obtain a positive electrode composition S-1.
  • Each of the positive electrode compositions S-1 to S-12 and cS-1 to cS-9 obtained above is placed on an aluminum foil having a thickness of 20 ⁇ m with a Baker-type applicator (trade name: SA-201, manufactured by Tester Sangyo Co., Ltd.). and set to the "coating and drying conditions" shown in Table 1, and dried by heating (removing the dispersion medium).
  • a positive electrode active material layer precursor layer was formed on the aluminum foil to prepare positive electrode sheets S-1 to S-12 and cS-1 to cS-9 for all-solid secondary batteries.
  • the positive electrode sheet S-12 is the same as the positive electrode sheet S-3.
  • the units for the particle size ( ⁇ m), solid content concentration (mass%), drying temperature (°C), drying time (hour), and filling rate (%) of the inorganic solid electrolyte are omitted.
  • the content of the polymer binder indicates the content (% by mass) with respect to 100% by mass of the solid content of each positive electrode composition, but the unit is omitted in the table.
  • a pressure of 350 MPa was applied to the current collector side of each positive electrode sheet and LPS with a SUS rod to collectively pressurize the positive electrode active material layer precursor layer and LPS.
  • a positive electrode sheet having a positive electrode active material layer and a solid electrolyte layer in this order on an aluminum foil as a substrate was produced.
  • the positive electrode sheet S-12 was pressurized together with LPS by setting the pressure to 150 MPa.
  • the true density of the positive electrode active material layer precursor layer was calculated as described above. Specifically, first, for each of the active material, the inorganic solid electrolyte, the conductive aid, and the polymer binders B1 to B5, a density measuring device: BELPYCNO (trade name, manufactured by Microtrack Bell) was used at 25 ° C. A true density was measured by a gas replacement method. As a result, the true density (g/cm 3 ) of the active material was 5.3, LPS1 was 2.0, LPS2 was 2.0, LPS3 was 2.0, and the conductive aid was 2.0, polymer binders B1 to 4 were all 1.1, and polymer binder B5 was 1.8.
  • BELPYCNO trade name, manufactured by Microtrack Bell
  • the true density of the positive electrode active material layer precursor layer (g / cm 3 ) was calculated.
  • True density of positive electrode active material layer precursor layer (g/cm 3 ) [true density of active material x content ratio] + [true density of inorganic solid electrolyte x content ratio] + [true density of conductive aid x content ratio ] + [(true density of polymer binder x content ratio)
  • the filling rate (%) of the positive electrode active material layer precursor layer was calculated by the method described above. (Measurement of film thickness) The film thickness of the positive electrode active material layer precursor layer was the film thickness ( ⁇ m) measured in the above calculation of the film density.
  • the inorganic solid electrolyte was recovered from the active material layer precursor layer of each positive electrode sheet, and the particle size was measured by the above-described measurement method.
  • each electrode sheet and each all-solid secondary battery manufactured were evaluated as follows. No other evaluation was performed on the all-solid secondary batteries that did not pass the bending resistance test (except for the all-solid secondary battery cS-8). Also, in Table 2, the units of filling rate (%) and film density (g/cm 3 ) are omitted.
  • ⁇ Evaluation 1-1 Calculation of filling rate of positive electrode active material layer> Each all-solid secondary battery was cut, the cross section was observed with a scanning electron microscope (SEM), and the film thickness (average film thickness) of the positive electrode active material layer was measured. Using the obtained film thickness, the filling rate was calculated in the same manner as the filling rate of the positive electrode active material layer precursor layer.
  • ⁇ Evaluation 1-2 Calculation of film density of positive electrode active material layer> The film density of the positive electrode active material layer taken out from each all-solid secondary battery was measured in the same manner as the film density of the positive electrode active material layer precursor layer. The filling rate and film density of the positive electrode active material layer in each positive electrode sheet are the same as the filling rate and film density of the positive electrode active material layer in the all-solid secondary battery shown in Table 2.
  • the sheet test piece was set with the positive electrode active material layer precursor layer on the opposite side of the mandrel (with the base material or current collector on the mandrel side) and the width direction parallel to the axis of the mandrel. The test was conducted by gradually reducing the diameter of the mandrel from 32 mm.
  • the evaluation is based on the occurrence of defects (cracks, cracks, chips, etc.) due to adhesion collapse of solid particles in the positive electrode active material layer precursor layer in a state wound around a mandrel and a state in which the winding is canceled and the sheet is restored.
  • the minimum diameter at which peeling between the active material layer precursor layer and the current collector could not be confirmed was measured, and evaluation was performed based on which of the following evaluation criteria this minimum diameter corresponds to. In this test, it means that the smaller the minimum diameter, the more flexible the solid particles constituting the positive electrode active material layer precursor layer are while maintaining the adhesion force, and the more flexible the solid particles are, the more suitable the roll conveying step in the industrial manufacturing method is.
  • the passing level of the test of the present invention is the evaluation standard "B" or higher. All-solid secondary battery No. The smallest diameters of c101, c102, c105, c106, c108 and c109 were all 32 mm. - Evaluation criteria - A: Minimum diameter ⁇ 14mm B: 14 mm ⁇ minimum diameter ⁇ 25 mm C: 25mm ⁇ minimum diameter
  • ⁇ Evaluation 3 resistance test> The battery resistance of each of the manufactured all-solid secondary batteries was evaluated by the following method. The results are shown in the "battery resistance" column of the "all-solid secondary battery” column in Table 2. Specifically, using each of the manufactured all-solid-state secondary batteries (half cells), the batteries were charged in an environment of 25° C. with a charging current value of 0.1 mA until the battery voltage reached 3.6 V. Thereafter, each all-solid secondary battery was initialized by discharging until the battery voltage reached 1.9 V under the condition of a discharge current value of 0.1 mA.
  • the discharge capacity was measured using a charge/discharge evaluation device TOSCAT-3000 (trade name, manufactured by Toyo System Co., Ltd.). Using the measured discharge capacity, the maintenance rate (%) of the discharge capacity was calculated from the following formula, and applied to the following evaluation criteria to evaluate the rate characteristics of the all-solid secondary battery. In this test, the higher the maintenance rate (%), the lower the battery resistance (resistance of the positive electrode active material layer) of the all-solid secondary battery. . All-solid secondary battery No. The maintenance ratios (%) of c103, c104 and c107 are 65%, 65% and 68%, respectively, and all-solid secondary battery No.
  • the retention rates (%) of c108 and c109 were 62% and 64%, respectively.
  • Maintenance rate (%) [discharge capacity in charge/discharge step (2)/discharge capacity in charge/discharge step (1)] x 100 - Evaluation criteria - A: 90% ⁇ retention rate B: 80% ⁇ retention rate ⁇ 90% C: Retention rate ⁇ 80%
  • the results shown in Tables 1 and 2 show the following.
  • the positive electrode sheet of the comparative example which does not satisfy the content or filling rate of the polymer binder, is inferior in transportability, or cannot suppress an increase in resistance of the all-solid secondary battery.
  • the electrode sheets of Examples satisfying the content and filling rate of the polymer binder are excellent in transportability, and can form an active material layer with a high filling rate by pressing in the manufacturing process of the all-solid secondary battery. It is possible to effectively suppress an increase in resistance of an all-solid secondary battery.

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PCT/JP2022/036128 2021-09-29 2022-09-28 電極用シート及び全固体二次電池、並びに、電極用シート、電極シート及び全固体二次電池の製造方法 Ceased WO2023054455A1 (ja)

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