WO2022138896A1 - Liant de batterie tout solide utilisant un polymère à base de diène conjugué, couche d'électrode positive, couche d'électrode négative, et couche d'électrolyte utilisant ledit liant, et batterie tout solide comprenant ledit liant et lesdites couches - Google Patents

Liant de batterie tout solide utilisant un polymère à base de diène conjugué, couche d'électrode positive, couche d'électrode négative, et couche d'électrolyte utilisant ledit liant, et batterie tout solide comprenant ledit liant et lesdites couches Download PDF

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WO2022138896A1
WO2022138896A1 PCT/JP2021/048110 JP2021048110W WO2022138896A1 WO 2022138896 A1 WO2022138896 A1 WO 2022138896A1 JP 2021048110 W JP2021048110 W JP 2021048110W WO 2022138896 A1 WO2022138896 A1 WO 2022138896A1
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conjugated diene
polymer
solid
mass
state battery
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PCT/JP2021/048110
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Japanese (ja)
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敬 助川
謙太朗 酒向
知宏 近藤
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旭化成株式会社
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08C—TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
    • C08C19/00—Chemical modification of rubber
    • C08C19/02—Hydrogenation
    • 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
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present invention relates to an all-solid-state battery binder using a conjugated diene-based polymer, a positive electrode layer, a negative electrode layer, an electrolyte layer using the binder, and an all-solid-state battery containing these.
  • Lithium-ion secondary batteries are characterized by their light weight, high energy and long life, and are widely used as power sources for portable electronic devices such as notebook computers, mobile phones, digital cameras and video cameras. There is.
  • power storage for hybrid electric vehicles Hybrid Electric Vehicle: HEV
  • plug-in HEV Plug-in Hybrid Electric Vehicle: PHEV
  • power storage for residential power storage systems etc. It is also attracting attention in the field.
  • an all-solid-state battery in which the positive electrode material, electrolyte, and negative electrode material are all solid has been proposed as a technology that eliminates the need for a flammable electrolyte and dramatically improves safety. ing.
  • PVDF polyvinylidene fluoride
  • NMP N-methylpyrrolidone
  • Electrodes are manufactured by mixing and applying to a current collector, but NMP is not preferable for manufacturing an all-solid-state battery using a sulfide-based solid electrolyte because it has hydrophilicity. Therefore, an electrode fabrication process using a non-polar solvent with low hydrophilicity is desirable, but since PVDF does not dissolve in a non-polar solvent, the development of a new binder that dissolves in a non-polar solvent is required.
  • Patent Document 1 proposes a binder that can be dissolved in a non-polar solvent.
  • Patent Document 2 proposes an all-solid-state battery using a butadiene-based rubber binder as an all-solid-state battery binder.
  • the conjugated diene polymer of the prior art is excellent in removing water from the manufacturing process because it enables the use of a non-polar solvent, but it has the ability to bind the constituents of the electrode active material layer and the solid electrolyte. In terms of binder performance such as the force to adhere to the current collector of the electrode active material layer and the electrode active material layer, it was still insufficient.
  • the present invention has been made in view of the above problems, and is an all-solid-state battery binder having excellent solubility in a non-polar solvent and also having excellent binder performance, and a positive electrode layer and a solid electrolyte layer using the same. , A negative electrode layer, and an all-solid-state battery.
  • the present invention is as follows.
  • It has a polymer block mainly composed of vinyl aromatic monomer units, and contains a conjugated diene-based polymer having a weight average molecular weight of 40 to 2 million. All-solid-state battery binder.
  • the conjugated diene-based polymer has a modifying group, and the modifying group is an acid anhydride group, a hydroxyl group, a carbonyl group, a carboxyl group, an amino group, an epoxy group, an alkoxysilane group, an amide group, a urethane group, or a urea group. , One or more selected from the group consisting of an isocyanate group, and an ionic group.
  • the all-solid-state battery binder according to [1].
  • the weight average molecular weight of the conjugated diene polymer is 200,000 to 800,000.
  • the content of the polymer block is 40% by weight or less with respect to the total amount of the conjugated diene-based polymer.
  • the vinyl bond amount of the conjugated diene monomer unit before hydrogenation is 20 mol% to 60 mol% with respect to the total 100 mol% of the conjugated diene monomer unit.
  • the toluene insoluble content of the conjugated diene polymer is 10 wt% or less.
  • the modifying group is 0.10 mmol or more and 0.50 mmol or less in 100 g of the conjugated diene-based polymer.
  • the modifying group is a primary amino group or a secondary amino group.
  • the terminal or coupling portion of the conjugated diene polymer has the modifying group.
  • the all-solid-state battery binder according to any one of [2] to [8]. [10] It has a polymer block mainly composed of the conjugated diene monomer unit. The all-solid-state battery binder according to any one of [1] to [9]. [11] The conjugated diene polymer is hydrogenated. The all-solid-state battery binder according to any one of [1] to [10]. [12] The amount of butylene and / or the amount of propylene of the conjugated diene monomer unit is 20 mol% to 60 mol% with respect to the total 100 mol% of the conjugated diene monomer unit. The conjugated diene-based polymer has a polymer block mainly composed of a conjugated diene monomer unit.
  • the all-solid-state battery binder according to any one of [1] to [11].
  • the conjugated diene-based polymer has a looseness specific gravity of 0.15 g / cm 3 or more, a degree of compression of less than 30, and is in the form of powder or crumb.
  • the all-solid-state battery binder according to any one of [1] to [12].
  • the total content of the transition metal element and Al, Li, Fe, Zn, and Mg in the conjugated diene polymer is 200 ppm or less with respect to the conjugated diene polymer in terms of atoms.
  • the all-solid-state battery binder according to any one of [1] to [13].
  • [15] It contains the conjugated diene polymer and a phosphorus compound, and is 10 ppm or more with respect to the conjugated diene polymer in terms of phosphorus atom.
  • the all-solid-state battery binder according to any one of [1] to [14].
  • [16] A polymer selected from the group consisting of silica, higher fatty acid metal salts, polyolefins, and fatty acid amides, The all-solid-state battery binder according to any one of [1] to [15].
  • the conjugated diene-based polymer has isoprene as a conjugated diene-based polymer unit.
  • the all-solid-state battery binder according to any one of [1] to [16].
  • Moisture content is 200 ppm or less
  • an all-solid-state battery binder having excellent solubility in a non-polar solvent and excellent binder performance, and a positive electrode layer, a solid electrolyte layer, a negative electrode layer, and an all-solid-state battery using the same are provided. be able to.
  • the present embodiment a mode for carrying out the present invention (hereinafter referred to as “the present embodiment”) will be described in detail.
  • the following embodiments are examples for explaining the present invention, and are not intended to limit the present invention to the following contents.
  • the present invention can be appropriately modified and carried out within the scope of the gist thereof.
  • polymer includes either a polymer composed of a single type of monomer unit or a copolymer having a plurality of types of monomer units.
  • the all-solid-state battery binder of the present embodiment has a polymer block mainly composed of vinyl aromatic monomer units, and contains a conjugated diene-based polymer having a weight average molecular weight of 40 to 2 million.
  • the conjugated diene polymer preferably has a modifying group.
  • the "modifying group” refers to a binder group to a constituent component of the electrode active material layer, a solid electrolyte, and / or an adhesive group to a current collector, and refers to a functional group containing elements other than carbon and hydrogen.
  • the structure of the "modifying group” analyzes conjugated diene polymers and, if necessary, possible modifiers using various analytical chemistry techniques such as NMR, spectroscopic analysis, electrical analysis, separation analysis, mass analysis, titration, etc. It can be confirmed by. Examples of the method for specifying the modifying group include a method of combining NMR, IR, GC-MS and the like.
  • maleic anhydride and succinic anhydride which are acid anhydrides, have an absorption peak near 1750 cm -1 in IR, and therefore can be identified by analyzing a conjugated diene-based polymer. Further, by analyzing the conjugated diene polymer by chromatography using a column having an adsorptive property as a modifying group, it is possible to identify a modifying group such as an amine modifying group. For other functional groups, the chemical shift-modifying group peculiar to the functional group can be identified by analyzing the conjugated diene-based polymer by NMR.
  • the conjugated diene monomer constituting the conjugated diene polymer is a diolefin having a pair of conjugated double bonds.
  • the diolefin is not particularly limited, and is, for example, 1,3-butadiene, 2-methyl-1,3-butadiene (isoprene), 2,3-dimethyl-1,3-butadiene, 1,3-. Examples thereof include pentadiene, 1,3-cyclopentadiene, 2-methyl-1,3-pentadiene, 1,3-hexadiene, 1,3-cyclohexadiene, and farnesene.
  • the conjugated diene-based polymer may be composed of one kind of conjugated diene monomer unit, or may be composed of two or more kinds of conjugated diene monomer units.
  • the conjugated diene-based polymer may contain a polymer block mainly composed of a conjugated diene monomer unit.
  • the content of the conjugated diene monomer unit contained in this polymer block is the electrode active material of the all-solid battery binder.
  • Increase the entanglement of the polymer chains of the block in order to improve the binding property that connects the constituent components such as the electrode active material, conductive auxiliary agent, and solid electrolyte of the layer and electrolyte layer and the adhesiveness (also called adhesion) to the current collector.
  • the "polymer block mainly composed of the conjugated diene monomer unit” means a polymer block in which the content of the conjugated diene monomer unit exceeds 70% by mass with respect to the entire polymer block. do.
  • the upper limit of the content of the conjugated diene monomer unit contained in the polymer block is not particularly limited, and is 100% by mass or less with respect to the total amount of the conjugated diene monomer unit contained in the conjugated diene-based polymer. However, it may be 99% by mass or less.
  • the binding property for connecting the constituent components such as the electrode active material layer of the all-solid-state battery binder, the electrode active material of the electrolyte layer, the conductive auxiliary agent, and the solid electrolyte, and the adhesiveness to the current collector are combined. It is called binder performance.
  • the conjugated diene polymer may be hydrogenated.
  • the solubility of the conjugated diene-based polymer in a solvent having low hydrophilicity, for example, a non-polar solvent, and the binding property of the all-solid battery binder containing the conjugated diene-based polymer and the binding property is preferably 20 mol% or more, more preferably 25 mol% or more, based on the total 100 mol% of the conjugated diene monomer unit. It is more preferably 30 mol% or more, still more preferably 35 mol% or more.
  • the conjugated diene-based polymer may crystallize and the solubility in a non-polar solvent may be significantly reduced.
  • the upper limit of the vinyl bond amount of the conjugated diene monomer unit before hydrogenation may be 100 mol% or less or 99 mol% or less with respect to the total 100 mol% of the conjugated diene monomer unit. It is often preferably 80 mol% or less, more preferably 70 mol% or less, and preferably 60 mol% or less, 50 mol% or less, and 40 mol% or less from the viewpoint of rubber elasticity.
  • the preferable range of the vinyl bond amount before hydrogenation is the same as described above.
  • Amount of vinyl bond before hydrogenation means 1,4-bond (cis and trans) and 1,2-bond due to conjugated diene monomer unit in the conjugated diene-based polymer before hydrogenation.
  • the conjugated diene monomer unit is incorporated into the polymer with 3,4-bonds, 1 for the total amount of 1,4-bonds, 1,2-bonds, and 3,4-bonds. , 2-bond, and 3,4-bond total amount (mol ratio). That is, it is defined using the word "before hydrogenation", but this is because the hydrogenation makes it impossible to call it a "vinyl bond", and even after hydrogenation, it is a 1,4-bond.
  • 1,2-bond or 3,4-bond can be distinguished, so it is an index that can be quantified in the same manner in the polymer after hydrogenation.
  • the amount of butylene and / or propylene of the conjugated diene polymer is preferably 20 mol% or more, more preferably 25 mol% or more, still more preferably 30 mol% or more, still more preferably 35 mol% or more. ..
  • the upper limit of the amount of butylene and / or the amount of propylene of the conjugated diene polymer may be 100 mol% or less, 99 mol% or less, preferably 80 mol% or less, and more preferably 70 mol% or less. From the viewpoint of rubber elasticity, it is preferably 60 mol% or less, 50 mol% or less, and 40 mol% or less.
  • the "amount of butylene and / or the amount of propylene” refers to 1,4-bonds (cis and trans) and 1,2-bonds (cis and trans) due to the conjugated diene monomer unit in the conjugated diene-based polymer after hydrogenation.
  • the conjugated diene monomer unit is incorporated into the polymer with 3,4-bonds, 1 for the total amount of 1,4-bonds, 1,2-bonds, and 3,4-bonds. , 2-bond, and 3,4-bond total amount (mol ratio).
  • the amount of butylene and / or the amount of propylene can be controlled by the amount of vinyl bond and the hydrogenation rate before hydrogenation.
  • the vinyl bond amount and the butylene amount and / or the propylene amount before hydrogenation of the conjugated diene polymer can be measured by using a nuclear magnetic resonance apparatus (NMR) or the like, and specifically, Examples described later. It can be measured by the method described in.
  • NMR nuclear magnetic resonance apparatus
  • ECS400 product name manufactured by JEOL
  • deuterated chloroform is used as a solvent
  • the sample concentration is 50 mg / mL
  • measurement is performed under the following conditions.
  • Measurement condition Observation frequency: 400MHz
  • Chemical shift criteria Chloroform (7.26 ppm) Pulse delay: 3 seconds
  • the amount of vinyl bond before hydrogenation can be determined by using the area value of the signal having a chemical shift in the range of 10.0 ppm to 0.0 ppm in the obtained NMR spectrum. More specifically, it can be obtained by the following equations (1) to (6).
  • (Area value per proton of styrene monomer unit) (X 2 -X 1 ) / 5 (1)
  • (Area value per proton of unhydrogenated 1,2 bonded butadiene monomer unit) X 3/2
  • (Area value per proton of unhydrogenated 1,4-bonded butadiene monomer unit) (X 4- (X 3/2 )) / 2 (3)
  • (Area value per proton of hydrogenated 1,2 bonded butadiene monomer unit) X 5/3 (4)
  • (Area value per proton of hydrogenated 1,4-bonded butadiene monomer unit) (X 6- (1) x 3- (2) x 3- (3) x 4- (4) x 8-X 7 ) / 8 (5)
  • X 1 , X 2 , X 3 , X 4 , X 5 , X 6 and X 7 in the above equations (1) to (5) are defined as follows.
  • X 1 Centered on 7.26 ppm, in each section of 7.26 ppm to 7.25 ppm section and 7.27 ppm to 7.26 ppm section, surrounded by the line connecting the positions with the lowest signal intensity and the NMR spectrum.
  • Area values in the range X 2 Signal positions of 8.0 ppm and 6.0 ppm in the range surrounded by the line connecting the signal positions of 8.0 ppm and 6.0 ppm and the NMR spectrum
  • X 3 Signal positions of 6.0 ppm and 4.0 ppm in the range Of the area values surrounded by the connected line and the NMR spectrum
  • X 4 6.0 ppm
  • Area value of X 5 Of the area value surrounded by the line connecting the signal positions of 4.0 ppm and 0.3 ppm and the NMR spectrum, the valley of the NMR spectrum between 1.05 ppm and 0.85 ppm. Area values in the range of 0.3 ppm from the chemical shift at the position with the lowest signal intensity (however, if there is no valley between 1.05 ppm and 0.85 ppm, the signal positions are 4.0 ppm and 0.3 ppm.
  • the area value is set in the range of 0.3 ppm from the chemical shift at the position where the signal intensity is the lowest between 1.05 ppm and 0.85 ppm.
  • X 6 Area value in the range surrounded by the line connecting the signal positions of 4.0 ppm and 0.3 ppm and the NMR spectrum
  • X 7 1.49 ppm to 1.50 ppm section centered on 1.50 ppm and 1. In each section of the 50ppm to 1.51ppm section, the area value in the range surrounded by the line connecting the positions with the lowest signal intensity and the NMR spectrum (however, the line connecting the positions with the lowest signal intensity is If it exists above the NMR spectrum, it is set to 0.)
  • (1) to (5) in the formulas (5) and (6) are values obtained from the above formulas (1) to (5), respectively.
  • the vinyl bond amount, butylene amount and / or propylene amount refer to a compound such as a Lewis base such as ether and amine as a vinyl bond amount adjusting agent (hereinafter referred to as a vinylizing agent) in the production of a conjugated diene polymer. ), Or by controlling the temperature at the time of manufacture, it can be controlled within the above numerical range. In general, the amount of vinyl bond tends to increase by increasing the amount of the vinyl bond amount adjusting agent or lowering the temperature at the time of production.
  • the present embodiment is carried out from the viewpoint of the solubility of the conjugated diene polymer in a hydrocarbon solvent and the binding property and adhesiveness of the all-solid battery binder containing the conjugated diene polymer.
  • the content of the vinyl aromatic monomer unit is preferably 80% by mass or less with respect to the total amount of the conjugated diene-based polymer. From the same viewpoint and from the viewpoint of further improving the flexibility, the content thereof is more preferably 5% by mass or more and 60% by mass or less.
  • the content thereof is more preferably 10% by mass or more, more preferably 12% by mass or more, and the solid electrolyte due to repeated charging and discharging. From the viewpoint of suppressing the shrinkage of the electrode active material from causing a gap and deteriorating the battery performance, 15% by mass or more is preferable, and 20% by mass or more is preferable. A more preferable upper limit is 40% by mass or less, still more preferably 35% by mass or less, and particularly preferably 30% by mass or less.
  • the content of the vinyl aromatic monomer unit in the conjugated diene polymer can be measured by an ultraviolet spectrophotometer method or a proton nuclear magnetic resonance ( 1 H-NMR) method. Specifically, it can be measured by the method described in Examples.
  • the content of the polymer block mainly composed of the vinyl aromatic monomer unit is preferably 40% by mass or less with respect to the total amount of the conjugated diene-based polymer. From the same viewpoint and from the viewpoint of further improving the flexibility, the content thereof is more preferably 5% by mass or more and 35% by mass or less. From the viewpoint of further improving the low temperature crack resistance of each layer containing the binder, the content thereof is more preferably 10% by mass or more and 33% by mass or less. From the viewpoint of suppressing the deterioration of battery performance due to the shrinkage of the solid electrolyte and the electrode active material due to repeated charging and discharging, 15% by mass or more is preferable, and 20% by mass or more is more preferable.
  • the polymer block mainly composed of the vinyl aromatic monomer unit is preferably present in the main chain of the conjugated diene-based polymer from the viewpoint of heat resistance and strength, and is one counting from the end of the polymer chain. It is preferably present in the eye or the second block.
  • the content of the polymer block mainly composed of vinyl aromatic monomer units in the conjugated diene polymer is such that the copolymer before hydrogenation is oxidized by t-butyl hydroperoxide using osmium tetroxide as a catalyst.
  • the vinyl aromatic simple substance obtained by the decomposition method (method according to IMKOLTHOFF, et al., Polymer. Sci. 1,429 (1946)) (hereinafter, also referred to as "osmium tetroxide decomposition method"). It can be calculated using the mass of the polymer block mainly composed of the polymer unit (however, the vinyl aromatic monomer unit having an average degree of polymerization of about 30 or less is excluded).
  • the content of the polymer block mainly composed of vinyl aromatic monomer unit in the conjugated diene-based polymer after hydrogenation is the conjugated diene-based polymer after hydrogenation (hydrogenated copolymer (b)).
  • the NMR method will be specifically described by taking as an example a case where the vinyl aromatic monomer unit is styrene and the conjugated diene monomer unit is 1,3-butadiene.
  • the content (Ns value) of (is) is obtained from the ratio of the integrated value of the chemical shift of 6.9 ppm to 6.3 ppm to the total integrated value.
  • Polymer block mainly composed of vinyl aromatic monomer unit means a polymer block in which the content of the vinyl aromatic monomer unit exceeds 70% by mass with respect to the entire polymer block. do. From the viewpoint of the binding property and adhesiveness of the all-solid-state battery binder containing the conjugated diene-based polymer, the content of the vinyl aromatic monomer unit of the polymer block mainly composed of the vinyl aromatic monomer unit is preferable. Is 80% by mass or more, more preferably 90% by mass or more, still more preferably 95% by mass or more. In the above range, the polymer block mainly composed of vinyl aromatic monomer units has high cohesive force and serves as a physical cross-linking point. The upper limit of the content of the vinyl aromatic monomer unit of the polymer block mainly composed of the vinyl aromatic monomer unit is not particularly limited, but even if it is 100% by mass or less, it is 99% by mass or less. May be good.
  • the vinyl aromatic monomer is not particularly limited, but for example, styrene, ⁇ -methylstyrene, p-methylstyrene, divinylbenzene, 1,1-diphenylethylene, N, N-dimethyl-p-aminoethylstyrene, And vinyl aromatic compounds such as N, N-diethyl-p-aminoethylstyrene.
  • styrene, ⁇ -methylstyrene, and p-methylstyrene are preferable, and styrene is more preferable, from the viewpoint of availability and productivity.
  • the polymer block mainly composed of a vinyl aromatic compound may be composed of one kind of vinyl aromatic monomer, or may be composed of two or more kinds.
  • the conjugated diene-based polymer has a modifying group
  • it is preferably a binding group to a constituent component of the electrode active material layer or a solid electrolyte and / or an adhesive group to a current collector.
  • a modifying group is not particularly limited, but for example, an acid anhydride group, a hydroxyl group, a carbonyl group, a thiocarbonyl group, an acid halide group, a carboxyl group, a thiocarboxylic acid group, an aldehyde group, a thioaldehyde group, and the like.
  • the conjugated diene-based polymer may have the above-mentioned modifying groups alone or in combination of two or more.
  • Examples of the ionic group include a sulfonic acid group, a sulfonimide group, a sulfate group, a phosphonic acid group, a phosphoric acid group, a carboxylic acid group, and an ammonium group or a salt thereof.
  • the modifying groups of the conjugated diene polymer are acid anhydride group, hydroxyl group, carbonyl group, carboxyl group, amino group, epoxy group, alkoxysilane group, amide group, urethane group, urea group, isocyanate group, and One or more selected from the group consisting of ionic groups is preferred.
  • the modifying groups include acid anhydride groups, carboxyl groups, amino groups, epoxy groups, alkoxysilane groups, and hydroxyl groups from the viewpoint of availability and suppression of hydrogen sulfide generation by reaction with sulfide-based solid electrolytes. Is more preferable. Further, from the viewpoint of suppressing the generation of alcohol, the acid anhydride group, the carboxyl group, the amino group, the epoxy group and the hydroxyl group are more preferable as the modifying group. Further, from the viewpoint of productivity (easiness of adjusting the modification rate and safety), the modifying group is more preferably an amino group, a hydroxyl group, a carboxyl group, or an acid anhydride group.
  • the modifying group includes an amino group, a hydroxyl group and a carboxyl group. preferable.
  • an amino group is preferable as the modifying group from the viewpoint of hydrogen bonding property and bond forming property with a material having a carboxyl group as a surface functional group such as a conductive auxiliary agent.
  • a primary amino group or a secondary amino group is preferable from the viewpoint of bond forming property by chemical reaction and hydrogen bonding property acting as a donor and an acceptor with respect to the functional group on the surface of the current collector and the surface of the battery member.
  • the conjugated diene polymer has a functional group that does not correspond to a constituent component of the electrode active material layer, a binding group to a solid electrolyte, or an adhesive group to a current collector, the functional group and the electrode active material layer
  • the constituents of the above and other compounds that can interact with any of the solid electrolytes or current collectors with the functional groups of the conjugated diene-based polymer, the constituents of the electrode active material layer of the conjugated diene-based polymer and The adhesiveness to the solid electrolyte or the current collector can be further improved.
  • the functional group of the conjugated diene polymer interacts with the other compound by intermolecular force or chemical bond, and the other compound interacting with the functional group constitutes the electrode active material layer.
  • the binding property and adhesiveness of the conjugated diene polymer can be further improved.
  • Examples of such other compounds include, but are not limited to, amide condensing agents such as carbodiimide compounds and diphenylphosphoryl azides, alkoxysilane compounds, amino compounds, hydroxy compounds, isocyanate compounds, and epoxy compounds. .. Other compounds may be used alone or in combination of two or more.
  • the carbodiimide compound is not particularly limited, and examples thereof include N, N'-dicyclohexylcarbodiimide, N, N'-diisopropylcarbodiimide, and 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide.
  • the alkoxysilane compound is not particularly limited, and for example, tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetraisopropoxysilane, tetrabutoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, and the like.
  • Examples include 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, and 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane. Will be.
  • the amine compound is not particularly limited, and examples thereof include diaminobutane, diaminopentane, diaminohexane, diaminoheptane, and diaminooctane.
  • the hydroxy compound is not particularly limited, and examples thereof include dihydroxybutane, dihydroxypentane, dihydroxyhexane, dihydroxyheptane, and dihydroxyoctane.
  • the isocyanate compound is not particularly limited, and examples thereof include hexanemethylene diisocyanate, 1,4-phenylenedi isocyanate, and dicyclohexylmethane 4,4'-diisocyanate.
  • the epoxy compound is not particularly limited, and examples thereof include ethylene glycol diglycidyl ether and 1,4-butanediol diglycidyl ether.
  • These compounds can also be used as a constituent component of the electrode active material layer and a conjugated diene polymer having a binding group to a solid electrolyte or an adhesive group to a current collector.
  • the content of the modifying group contained in the conjugated diene polymer described above is not particularly limited, but is preferably 0.5 pieces / chain or more from the viewpoint of further improving the binding property and the adhesiveness. From the same viewpoint, it is more preferably 0.7 pieces / chain or more, further preferably 1.0 piece / chain or more, and further preferably 2.0 pieces / chain or more.
  • the modifying group can interact more sufficiently with the constituents of the electrode active material layer, the solid electrolyte, or the current collector, and the adhesiveness is further improved. improves.
  • the number is 50 or less, more preferably 20 or less, still more preferably 10 or less, and more preferably 2. It is 0.0 pieces / chain or less, more preferably 1.0 pieces or less.
  • the content of the modifying group is preferably 300 / chain or less from the viewpoint of further preventing problems such as gelation of the all-solid-state battery binder containing the conjugated diene-based polymer.
  • the "chain” here refers to a single molecule of a polymer such as a conjugated diene-based polymer, and when the polymer structure is branched by a chemical bond, one branched chain is counted as a single molecule chain.
  • the conjugated diene-based polymer may have a functional group or a polymer chain that improves ionic conductivity in addition to the above-mentioned modifying group.
  • the functional group and the polymer chain are not particularly limited, but are, for example, an ether group, a crown ether, a polyethylene glycol, a boronic acid group, a boronic acid ester group, and an ionic group containing a lithium ion electrolyte used in a lithium ion battery. , An ionic group containing an ionic liquid and the like.
  • the conjugated diene polymer is preferably hydrogenated.
  • the hydrogenation rate with respect to the total 100 mol% of the conjugated diene monomer unit is preferably 30 mol% or more from the viewpoint of electrochemical stability of the conjugated diene polymer, and more preferably 50 mol from the viewpoint of thermal stability.
  • the hydrogenation rate of the conjugated diene polymer can be measured using a nuclear magnetic resonance apparatus (NMR) or the like, and specifically, it can be measured by the method described in Examples.
  • NMR nuclear magnetic resonance apparatus
  • the hydrogenation rate can be controlled within the above numerical range by, for example, adjusting the amount of hydrogen and the amount of catalyst at the time of hydrogenation.
  • the toluene insoluble content of the conjugated diene polymer is preferably 10 wt% or less, more preferably 5 wt% or less, still more preferably 3 wt% or less, and particularly preferably 1 wt% or less.
  • the lower limit of the amount of toluene insoluble is not particularly limited, but is 0 wt%. When the amount of toluene insoluble is 10 wt% or less, the smoothness of the coating film tends to be further improved.
  • the amount of toluene insoluble can be measured by the method described in Examples.
  • the conjugated diene-based polymer used in the all-solid-state battery binder of the present embodiment may further have a random copolymer block of a conjugated diene monomer unit and a vinyl aromatic monomer unit.
  • the binding property is improved by improving the affinity between the constituent components of the electrode active material layer and the solid electrolyte and the conjugated diene polymer, and the viscoelastic property is controlled to reach the operating temperature range of the battery. By imparting vibration damping properties, the durability of the battery can be improved.
  • Examples of the vinyl aromatic monomer and the conjugated diene monomer that can be contained in the random copolymer block of the conjugated diene compound and the vinyl aromatic compound include the above-mentioned block mainly composed of the vinyl aromatic polymer and the conjugated diene. Examples thereof include those that can be contained in a block mainly composed of a system polymer.
  • the distribution state of the vinyl aromatic monomer unit in the random copolymer block is not particularly limited, and the vinyl aromatic monomer unit may be uniformly distributed or may be distributed in a tapered shape. Further, there may be a plurality of portions in which the vinyl aromatic monomer unit is uniformly distributed and / or a portion in which the vinyl aromatic monomer unit is distributed in a tapered shape, respectively, and the content of the vinyl aromatic monomer unit is high. There may be a plurality of different segments.
  • conjugated diene-based polymer of the present embodiment in addition to the conjugated diene monomer and the vinyl aromatic monomer, another monomer copolymerizable with the conjugated diene monomer and the vinyl aromatic monomer is used. You can also do it.
  • the structure of the conjugated diene-based polymer of the present embodiment is not particularly limited, but for example, it may have a structure represented by the following formula or a structure represented by the following formula. Some are mentioned. In the following formula, the description of the modifying group may be omitted.
  • a is a vinyl aromatic polymer block mainly composed of a vinyl aromatic monomer unit
  • b is a conjugated diene polymer block mainly composed of a conjugated diene monomer unit, b 1 and b 2 .
  • Is a conjugated diene polymer block mainly composed of a conjugated diene monomer unit (however, the vinyl bond amount in b 1 is smaller than the vinyl bond amount in b 2 ), and c is a conjugated diene monomer and a vinyl aromatic single amount.
  • the random copolymer block with the body is shown.
  • the vinyl bond amount of b is not particularly limited.
  • n is an integer of 1 or more, preferably an integer of 1 to 5.
  • m is an integer of 2 or more, preferably an integer of 2 to 11.
  • X indicates a residue of the coupling agent or a residue of the polyfunctional initiator.
  • the conjugated diene-based polymer of the present embodiment mainly contains a structure having b, b 1 or b 2 blocks from the viewpoint of the binding property and the adhesiveness of the all-solid-state battery binder containing the conjugated diene-based polymer. Is preferable. From the viewpoint of improving the mechanical strength, ab, ab-a, a-b-ab, b 1 -b 2 -a, b 1 -b 2 -ab, and b 1 -B 2 -ba-a and a polymer represented by at least one of these couplings having a structural formula are more preferable.
  • the structure has two or more a blocks in the molecular chain. Is preferable.
  • the terminal or the coupling portion of the conjugated diene polymer has a modifying group.
  • the balance between adhesiveness, binding property, and dispersibility of the conductive auxiliary agent tends to be further improved.
  • the weight average molecular weight (Mw) of the conjugated diene polymer (hereinafter referred to as "Mw"). Also referred to as) is preferably 40,000 or more and 2 million or less, more preferably 60,000 or more and 1.5 million or less, further preferably 100,000 or more and 1 million or less, and 200,000 or more and 800,000 or less. Is even more preferable.
  • the lower limit of Mw is more preferably 200,000 or more, and more preferably 250,000 or more.
  • the upper limit is more preferably 500,000 or less, further preferably 450,000 or less. Adjusting the Mw to a preferable range means that the solvent does not volatilize immediately while storing the solution containing the conjugated diene polymer and the solvent used in the slurry preparation, or when the solvent is applied to the current collector. Is important from the viewpoint of storability and coatability, and from the viewpoint of vapor pressure drop due to the polymer solution, the higher the molecular weight of the conjugated diene polymer, the greater the degree of vapor pressure drop and suppress the volatilization of the solvent. It is possible.
  • NMP N-methyl-2-pyrrolidone
  • the solubility of the conjugated diene polymer Due to its low value, it was difficult to use high molecular weight compounds.
  • a non-polar solvent such as a hydrocarbon solvent is preferable as the solvent, and the conjugated diene polymer has excellent solubility in the hydrocarbon solvent, so that a high molecular weight polymer can be used.
  • the weight average molecular weight (Mw) is 30,000 or more, the entanglement of the polymer chains and the cohesive force of the vinyl aromatic polymer block are further improved, and the binding force and the adhesive force tend to be further improved.
  • the weight average molecular weight (Mw) is 2 million or less, the viscosity when dissolved in a non-polar solvent tends to be lower, and the film forming property of each layer tends to be improved during electrode production.
  • the weight average molecular weight (Mw) of the conjugated diene polymer is high from the viewpoint of suppressing the flow.
  • Mw weight average molecular weight
  • the applications that require heat resistance include, for example, power supplies for automobiles installed in engine rooms and power supplies for automobile motors. These include power supplies for motors mounted on large industrial machines, power supplies for medical equipment that requires sterilization and heating, and small power supplies that are mounted directly on home appliances and automobile printed wiring boards. Heat resistance may also be required when undergoing a solder reflow process, such as when mounted directly on a printed wiring board.
  • the weight average molecular weight (Mw) of the conjugated diene polymer is determined by determining the molecular weight of the peak of the chromatogram obtained by measurement by gel permeation chromatography (GPC) based on the calibration curve obtained from the measurement of commercially available standard polystyrene. It is the weight average molecular weight (Mw).
  • the calibration curve may be prepared using the peak molecular weight of standard polystyrene.
  • the molecular weight distribution of the conjugated diene polymer before modification can also be obtained from the measurement by GPC, and the molecular weight distribution can be obtained from the ratio (Mw / Mn) of the weight average molecular weight (Mw) and the number average molecular weight (Mn). Can be done.
  • the molecular weight distribution of a single peak measured by GPC of the conjugated diene polymer is preferably 5.0 or less, more preferably 4.0 or less, still more preferably 3.0 or less, and even more preferably 2. It is less than 5.5.
  • the lower limit of the molecular weight distribution is not particularly limited, but may be 1.0 or more, or 1.1 or more.
  • the all-solid-state battery binder preferably contains no water, and the water content of the all-solid-state battery binder is preferably 200 ppm or less, more preferably 100 ppm or less, still more preferably 50 ppm or less, still more preferably 10 ppm. It is less than or equal to, and particularly preferably 1 ppm or less.
  • Moisture contained in the all-solid-state battery binder may be removed by drying with a dryer under normal pressure or reduced pressure, or may be stored and removed in a dehumidifying environment. At this time, it may be heated or heated and pressurized by a press machine, a roll or the like.
  • the water content of the all-solid-state battery binder before drying or dehumidifying may be 200 ppm or more.
  • the water content of the conjugated diene polymer used in the all-solid-state battery binder is preferably 1 wt% or less, more preferably 0.5 wt% or less, still more preferably 0.1 wt%, from the viewpoint of water removal efficiency. It is less than or equal to, more preferably 0.05 wt% or less, and particularly preferably 0.02 wt% or less.
  • Moisture contained in the conjugated diene polymer may be removed by drying in a dryer under normal pressure or reduced pressure, or may be stored and removed in a dehumidifying environment. At this time, it may be heated or heated and pressurized by a press machine, a roll or the like.
  • the shape of the conjugated diene-based polymer may be pellets, but when reducing the water content of the polymer before preparing the slurry, a shape having a large specific surface area is preferable, and a crumb or powder form is preferable from the viewpoint of water removal efficiency.
  • the slurry containing the conjugated diene polymer preferably has a water content of 1 wt% or less, but since the slurry is diluted with a solvent and other components in addition to the polymer, the water content of the polymer Even if the amount exceeds 1 wt%, it is possible to prepare a slurry having a water content of 1 wt% or less.
  • the water content of the conjugated diene-based polymer may be 1 wt% or more. Since it is desirable that the water content of the binder is 200 ppm or less, it is preferable to use a solvent that azeotropes with water for the slurry to improve the efficiency of water removal by removing the solvent when the water content of the slurry is high. Is.
  • the degree of compression measured by the method described in Examples is preferably less than 30, more preferably 20 or less, still more preferably 15 or less, and even more preferably 10 or less. be.
  • the looseness specific gravity is preferably 0.15 g / cm 3 or more, more preferably 0.20 g / cm 3 or more, from the viewpoint of filling a constant volume supply feeder with a large amount of conjugated diene polymer. More preferably, it is 0.22 g / cm 3 or more.
  • the preferred upper limit is 0.30 g / cm 3 or less, and more preferably 0.25 g / cm 3 or less.
  • the total content of the transition metal element and Al, Li, Zn, and Mg in the conjugated diene polymer is preferably 200 ppm or less with respect to the conjugated diene polymer in terms of atoms.
  • Transition metals include V, Ti, Mn, Fe, Co and Ni.
  • a polymerization initiator when a block copolymer is produced by anion living polymerization a compound containing the metal atom contained in a hydrogenation catalyst in a hydrogenation reaction, and / or moisture in the air in a solvent removal step of polymerization. In some cases, it reacts with the above to form a compound containing the metal, which will be described later, and remains in the conjugated diene-based polymer.
  • the compound containing a transition metal element (for example, Ti, Ni, Co) and / or Li in the conjugated diene-based polymer is not particularly limited, and is, for example, titanium oxide, amorphous titanium oxide, orthotitanic acid or metatitanic acid.
  • Oxides of each atom such as titanium hydroxide, nickel hydroxide, nickel monoxide, lithium oxide, lithium hydroxide, cobalt oxide, cobalt hydroxide, lithium titanate, barium titanate, strontium titanate, nickel titanate, Examples thereof include composite oxides of dissimilar metals and atoms such as nickel and iron oxides.
  • metals such as Al, Li, Zn, Fe and Mg remain in the conjugated diene polymer as metal residuals.
  • the atomic conversion is generally the mass per metal atom calculated from the residual weight and molecular weight of the compound containing the metal atom described above.
  • the compound containing the metal atom can be specified, it may be calculated by the above method, but since such specification is difficult in many cases, the metal with respect to the total amount in the conjugated diene polymer.
  • the total content of the metal atom is measured by the method described in Examples.
  • the conjugated diene polymer By setting the total content of the transition metal element and Al, Li, Zn, Fe and Mg in the conjugated diene polymer to 200 ppm or less with respect to the conjugated diene polymer in terms of atoms, the conjugated diene polymer can be obtained.
  • the thermal stability of the all-solid-state battery using the conjugated diene-based polymer as a binder is suppressed from being lowered.
  • the detailed mechanism of this phenomenon is unknown and, but not limited to, carbon radicals are generally generated when the polymer is exposed to high temperatures, and the reaction with oxygen in the air causes hydro. It is known that peroxides are produced, but in the presence of the above-mentioned metal compounds, decomposition into free radicals by a redox reaction is promoted.
  • the hydrogenated block copolymer itself reacts with the above-mentioned metal compound to generate free radicals.
  • a charge transfer complex and / or active oxygen is generated between the metal ion derived from the above-mentioned metal compound and oxygen in the air, and the active species reacts with the hydrogenated block copolymer to generate a carbon radical. ..
  • the above-mentioned reaction mechanism due to the above-mentioned reaction mechanism, when the above-mentioned amount of metal is large, the amount of free radicals derived from the metal compound tends to be large, and as a result, in the hydrogenated block copolymer.
  • Active species such as carbon radicals and hydroperoxides were generated, and the active species caused deterioration of the polymer due to the bond between radicals and the generation of further radicals, resulting in the bond between hydrogenated block copolymers, and a binder was used.
  • the total content is preferably 200 ppm or less, more preferably 100 ppm or less, further preferably 70 ppm or less, and particularly preferably 50 ppm or less.
  • the lower limit of the total content is not particularly limited, but is 0 ppm.
  • a known method can be applied. If the purpose is only to deactivate or neutralize the hydrogenation catalyst, add water and carbon dioxide after the hydrogenation reaction of the block copolymer to neutralize the hydrogenation catalyst residue, in addition to water and carbon dioxide.
  • a method is used in which an acid is added to neutralize the hydrogenated catalyst residue, but neutralization alone is not sufficient for the purpose of reducing the total metal content, so a decantation or centrifuge is used. It is preferable to use a method for removing metal. More specifically, the method described in Japanese Patent Application No. 2014-557427 can be mentioned.
  • the acid added to the conjugated diene polymer solution is a metal when mixed with water by adding sulfuric acid, hydrochloric acid, nitric acid, etc.
  • P / V value stirring strength
  • the method for producing the conjugated diene-based polymer of the present embodiment is not particularly limited, and may include, for example, the following polymerization step, modification step, and hydrogenation step.
  • the polymerization step is not particularly limited, but for example, by polymerizing a conjugated diene compound and a vinyl aromatic compound in an organic solvent using an organic alkali metal compound as a polymerization initiator, as represented by the above configuration. This is a step of obtaining a random copolymer and / or a block copolymer.
  • the hydrogenation step is not particularly limited, but is, for example, a step of hydrogenating the conjugated diene-based polymer obtained by the polymerization step.
  • the modification step is not particularly limited, but is, for example, a step of reacting a conjugated diene-based polymer with a modifying agent to carry out a modification reaction to obtain a conjugated diene-based polymer.
  • the order of the hydrogenation step and the modification step is not particularly limited. That is, the order may be the polymerization step, the hydrogenation step, and the modification step, or may be the order of the polymerization step, the modification step, and the hydrogenation step. From the viewpoint that the above-mentioned conjugated diene-based polymer can be obtained more easily, the order of the polymerization step, the hydrogenation step, and the modification step is preferable. Further, the modification step may be performed in parallel with the polymerization step as described later.
  • the polymerization step is, for example, a step of obtaining a random copolymer and / or a block copolymer by polymerizing a conjugated diene compound and a vinyl aromatic compound using an organic alkali metal compound as a polymerization initiator in an organic solvent. Is.
  • the polymerization mode may be batch polymerization, continuous polymerization, or a combination thereof. From the viewpoint of keeping the size of the dispersed phase in the all-solid-state battery binder containing the conjugated diene polymer that affects impact resistance and toughness constant, it is preferable to use a batch polymerization method in which the molecular weight distribution is narrowed.
  • the reaction temperature in the polymerization step may be 0 ° C. or higher and 180 ° C. or lower. From the viewpoint that the conjugated diene polymer of the present embodiment can be obtained more easily, the reaction temperature is preferably 20 ° C. or higher and 160 ° C. or lower, and more preferably 30 ° C. or higher and 150 ° C. or lower.
  • the reaction time in the polymerization step varies depending on the target polymer, but may be 48 hours or less. From the viewpoint that the conjugated diene polymer of the present embodiment can be obtained more easily, the reaction time is preferably 0.1 hour or more and 10 hours or less. From the viewpoint of obtaining a conjugated diene-based polymer having a narrow molecular weight distribution and high strength, the reaction time is more preferably 0.5 hours or more and 5 hours or less.
  • the atmosphere of the polymerization system in the polymerization step is not particularly limited as long as it is in a pressure range sufficient to maintain nitrogen and the solvent in the liquid phase. It is preferred that the polymerization system is free of impurities such as water, oxygen and carbon dioxide that inactivate the polymerization initiator and the living polymer.
  • a required amount of a bifunctional or higher functional coupling agent may be added to carry out the coupling reaction.
  • the bifunctional coupling agent conventionally known ones can be applied and are not particularly limited, but for example, trimethoxysilane, triethoxysilane, tetramethoxysilane, tetraethoxysilane, dimethyldimethoxysilane, diethyldimethoxysilane, and dichlorodimethoxysilane.
  • Alkoxysilane compounds such as dichlorodiethoxysilane, trichloromethoxysilane, trichloroethoxysilane, dihalogen compounds such as dichloroethane, dibromoethane, dimethyldichlorosilane, dimethyldibromosilane, methyl benzoate, ethyl benzoate, phenylbenzoate, phthalic acid.
  • alkoxysilane compounds such as dichlorodiethoxysilane, trichloromethoxysilane, trichloroethoxysilane, dihalogen compounds such as dichloroethane, dibromoethane, dimethyldichlorosilane, dimethyldibromosilane, methyl benzoate, ethyl benzoate, phenylbenzoate, phthalic acid.
  • acid esters such as esters.
  • polyfunctional coupling agent having trifunctionality or higher conventionally known ones can be applied and are not particularly limited, but for example, polyalcohols having trivalent or higher valence, epoxidized soybean oil, hydrocarbonidylbisphenol A, 1, 3 -A polyvalent epoxy compound such as bis (N-N'-diglycidylaminomethyl) cyclohexane, general formula R4 -nSiX n (where R is a hydrocarbon group having 1 to 20 carbon atoms, X is a halogen, n is A silicon halide compound represented by (indicating an integer of 3 to 4), for example, methylsilyl trichloride, t-butylsilyl trichloride, silicon tetrachloride and bromide thereof, etc., the general formula R4 -nSnX n (here).
  • R is a hydrocarbon group having 1 to 20 carbon atoms
  • X is a halogen
  • n is an integer of 3 to 4) represented by a halogenated tin compound, for example, methyl tin trichloride, t-butyl tin trichloride, 4. Examples thereof include polyvalent halogen compounds such as tin chloride. Further, dimethyl carbonate, diethyl carbonate or the like may be used.
  • the organic solvent is not particularly limited, and for example, aliphatic hydrocarbons such as n-butane, isobutane, n-pentane, n-hexane, n-heptane, and n-octane; cyclohexane, cycloheptan, and methyl.
  • Alicyclic hydrocarbons such as cyclopentane; and aromatic hydrocarbons such as benzene, xylene, toluene, and ethylbenzene can be mentioned.
  • the organoalkali metal compound that is the polymerization initiator is preferably an organolithium compound.
  • the organic lithium compound is not particularly limited, and examples thereof include an organic monolithium compound, an organic dilithium compound, and an organic polylithium compound.
  • the organic lithium compound is not particularly limited, and is, for example, ethyl lithium, n-propyl lithium, isopropyl lithium, n-butyl lithium, sec-butyl lithium, t-butyl lithium, n-pentyl lithium, n-hexyl lithium, benzyl. Included are lithium, phenyllithium, hexamethylenedilithium, butadienyllithium, isopropenyldilithium, and lithium piperidide.
  • an organolithium compound containing a nitrogen atom is used as a polymerization initiator such as lithium piperidide, a conjugated diene-based polymer having a nitrogen atom can be obtained.
  • polymerization initiators may be used alone or in combination of two or more.
  • n-butyllithium, sec-butyllithium, and lithium piperidide are preferable as the polymerization initiator from the viewpoint of improving the polymerization activity.
  • the amount of the organic alkali metal compound used as the polymerization initiator depends on the molecular weight of the target conjugated diene polymer, but is typically 0.01 fm or more and 1.5 fm or less (where, fm is the monomer 100). The mass portion per part by mass is shown. The same applies hereinafter.), More preferably 0.02 fm or more and 0.3 fm or less, and 0.03 fm or more and 0.2 fm or less. Is even more preferable.
  • the vinyl bond amount of the conjugated diene polymer can be controlled by adding a compound such as a Lewis base, for example, ether and an amine as a vinyl bond amount adjusting agent (hereinafter referred to as "vinyl agent"). ..
  • a vinyl bond amount adjusting agent hereinafter referred to as "vinyl agent”
  • the amount of the vinylizing agent used can be adjusted according to the target amount of vinyl bonding.
  • the vinylizing agent is not particularly limited, and examples thereof include ether compounds and tertiary amine compounds.
  • the ether compound is not particularly limited, and examples thereof include linear ether compounds and cyclic ether compounds.
  • the linear ether compound is not particularly limited, and examples thereof include ethylene glycol dialkyl ether compounds such as dimethyl ether, diethyl ether, diphenyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, and ethylene glycol dibutyl ether, and diethylene glycol dimethyl ether. , Diethylene glycol diethyl ether, and diethylene glycol dialkyl ether compounds such as diethylene glycol dibutyl ether.
  • the cyclic ether compound is not particularly limited, but for example, tetrahydrofuran, dioxane, 2,5-dimethyloxolane, 2,2,5,5-tetramethyloxolane, 2,2-bis (2-oxolanyl).
  • propane and alkyl ethers such as furfuryl alcohol.
  • the tertiary amine-based compound is not particularly limited, and is, for example, trimethylamine, triethylamine, tributylamine, N, N-dimethylaniline, N-ethylpiperidine, N-methylpyrrolidin, N, N, N', N'-.
  • Tetramethylethylenediamine N, N, N', N'-tetraethylethylenediamine, 1,2-dipiperidinoetan, trimethylaminoethylpiperazine, N, N, N', N ", N” -pentamethylethylenetriamine, Examples thereof include N, N'-dioctyl-p-phenylenediamine, pyridine, tetramethylpropanediamine, and bis [2- (N, N-dimethylamino) ethyl] ether.
  • a compound having two amines is preferable. Further, among them, those having a structure showing intramolecular symmetry are more preferable as the tertiary amine-based compound, and N, N, N', N'-tetramethylethylenediamine, bis [2- (N, N-dimethylamino) ethyl] ether, and 1,2-dipiperidinoethane are more preferred. Only one kind of these vinylizing agents may be used alone, or two or more kinds thereof may be used in combination.
  • the conjugated diene monomer alone or the conjugated diene monomer and the vinyl aromatic monomer are used in the presence of an alkali metal alkoxide. It may be polymerized.
  • the alkali metal alkoxide is a compound represented by the general formula MOR (in the formula, M indicates an alkali metal and R indicates an alkyl group).
  • the alkali metal of the alkali metal alkoxide is preferably sodium or potassium from the viewpoint of obtaining a high vinyl bond amount, a narrow molecular weight distribution, a high polymerization reaction rate, and a high blocking rate.
  • the alkali metal alkoxide is not particularly limited, and examples thereof include sodium alkoxide having an alkyl group having 2 to 12 carbon atoms, lithium alkoxide, and potassium alkoxide.
  • the alkali metal alkoxide is preferably sodium alkoxide and potassium alkoxide having an alkyl group having 3 to 6 carbon atoms, and more preferably sodium-t-butoxide, sodium-t-pentoxide, potassium-t-butoxide, and potassium-. It is t-pentoxide. Of these, sodium-t-butoxide and sodium-t-pentoxide are even more preferred.
  • the hydrogenation step is a step of hydrogenating the conjugated diene-based polymer or the conjugated diene-based polymer.
  • the hydrogenation method in the hydrogenation step is not particularly limited, and examples thereof include a method in which hydrogen gas is supplied to the conjugated diene polymer obtained in the above polymerization step in the presence of a hydrogenation catalyst to hydrogenate. Be done.
  • the double bond residue in the conjugated diene monomer unit is hydrogenated, and the hydrogenated conjugated diene weight is more thermally stable. You can get a coalescence.
  • the hydrogenation rate can be controlled, for example, by the amount of catalyst at the time of hydrogenation and the supply of hydrogen gas (hereinafter, also referred to as "feed"). Further, the hydrogenation rate can be controlled by, for example, the amount of catalyst at the time of hydrogenation, the amount of hydrogen gas supplied, the pressure, the temperature, and the like.
  • the hydrogenation step is preferably carried out at the timing after the production reaction of the conjugated diene-based polymer is stopped in the above-mentioned polymerization step.
  • the stabilizer is not particularly limited, and examples thereof include octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate.
  • the solution of the conjugated diene polymer obtained as described above can remove the catalyst residue if necessary and separate the conjugated diene polymer from the solvent.
  • a method for separating the solvent for example, a method of adding a polar solvent which is a poor solvent for the hydrogenated copolymer such as acetone or alcohol to the reaction solution after hydrogenation to precipitate the polymer and recovering the polymer, and stirring the reaction solution.
  • a method of putting the polymer in boiling water and removing the solvent by steam stripping to recover the solvent or a method of directly heating the polymer solution to distill off the solvent.
  • Stabilizers such as various phenol-based stabilizers, phosphorus-based stabilizers, sulfur-based stabilizers, and amine-based stabilizers can be added to the hydrogenated product of the copolymer.
  • the modification step is not particularly limited as long as it is a step of obtaining a conjugated diene polymer having a modifying group, and for example, reacting the conjugated diene polymer and / or the hydrogenated conjugated diene polymer with the modifying agent. This is a step of obtaining a conjugated diene-based polymer. As a result, the obtained conjugated diene-based polymer has a modifying group.
  • the modification step may be performed in parallel with the above-mentioned polymerization step.
  • the modification reaction method is not particularly limited, but for example, in the polymerization reaction in the polymerization step, a polymerization initiator having a binding group to a constituent component of the electrode active material layer or a solid electrolyte or an adhesive group to a current collector.
  • a method using an unsaturated monomer having a constituent component of the electrode active material layer, a binding group to a solid electrolyte, or an adhesive group to a current collector can be mentioned.
  • a binder group for the constituent components of the electrode active material layer, a solid electrolyte, or an adhesive group for the current collector is added to the living end of the conjugated diene polymer obtained by the polymerization reaction in the polymerization step.
  • a method of adding a modifying agent to be formed or contained may be used.
  • the position where the modifying group is introduced is not particularly limited, and may be, for example, the terminal of the conjugated diene polymer, which may be blocked by a part of the main chain of the conjugated diene polymer. It may be arranged randomly or in a tapered shape.
  • the concentration of the modifying group can be controlled according to the amount of the monomer having the modifying group, the amount of the monomer into which the modifying group can be introduced in the subsequent step, or the amount of the modifying agent to react with the polymer terminal. Further, when the polymer terminal is reacted with the modifier, the amount of the modifying group can be reduced by increasing the molecular weight of the polymer and reducing the number of polymer terminals. Introduction to the polymer terminal is suitable for introducing a small amount of modifying group. Further, as the introduction to the polymer terminal, a coupling agent having a modifying group or a modifying group precursor can also be used, and in this case, the coupling portion has a modifying group.
  • the method of reacting the polymer terminal with the modifying agent is suitable, and particularly suitable for a polymer having a molecular weight of 35,000 or more.
  • the modification group weight is 2.9 mmol or less at a molecular weight of 35,000, 1.0 mmol or less at a molecular weight of 100,000, and a molecular weight of 200,000.
  • the amount of the modifying group is not particularly limited as long as there is no problem in practical use, but when the adhesiveness due to the interaction of the modifying group with a different material is expected, the amount of the modifying group is preferably per 100 g of the conjugated diene polymer. It is 0.10 mmol or more, preferably 0.15 mmol or more.
  • the amount of the modifying group is preferably 20 mmol or less, more preferably 5 mmol or less, still more preferably 1.5 mmol or less, more preferably 1.5 mmol or less, per 100 g of the conjugated diene-based polymer from the viewpoint of dispersibility of the conductive auxiliary agent. More preferably, it is 0.10 mmol or more and 0.50 mmol or less.
  • the molecular weight entanglement effect causes the conductive auxiliary agent dispersity and adhesiveness. Can improve the balance of.
  • the "polymerization initiator having a constituent component of the electrode active material layer, a binding group to a solid electrolyte, or an adhesive group to a current collector” is not particularly limited, but is not particularly limited, and is, for example, 3-lithio-1- [N, N.
  • the "unsaturated monomer having a constituent component of the electrode active material layer, a binding group to a solid electrolyte, or an adhesive group to a current collector” is not particularly limited, but is not particularly limited, and is, for example, p- [N, N-bis.
  • the "modifying agent that forms or contains a component of the electrode active material layer, a binding group to a solid electrolyte, or an adhesive group to a current collector” is not particularly limited, and is not particularly limited, and is, for example, tetraglycidylmethylenediamine or tetraglycidyl. -1,3-bisaminomethylcyclohexane, ⁇ -caprolactone, 1,3-dimethyl-2-imidazolidinone, 1,3-diethyl-2-imidazolidinone, N, N'-dimethylpropylene urea, and N- Methylpyrrolidone may be mentioned.
  • a conjugated diene-based polymer is reacted with an organic alkali metal compound such as an organic lithium compound (metallation reaction) to obtain a polymer to which the organic alkali metal is added. Then, a method of adding the above-mentioned modifier to the polymer to which the organic alkali metal is added can be mentioned.
  • an organic alkali metal compound such as an organic lithium compound (metallation reaction)
  • a modifying group for example, an atomic group having a binder group for a constituent component of an electrode active material layer or a solid electrolyte or an adhesive group for a current collector in a conjugated diene polymer.
  • a method of graft-adding There is a method of graft-adding.
  • Such a method may be a method of directly graft-adding to the conjugated diene-based polymer, and the conjugated diene-based polymer into which the primary modifying group has been introduced is bound to the constituent components of the electrode active material layer and the solid electrolyte. It may be a method of reacting with an atomic group having a sex group or an adhesive group to a current collector (secondary modification).
  • the "atomic group having a binding group to a constituent component of the electrode active material layer or a solid electrolyte or an adhesive group to a current collector” is not particularly limited, and is, for example, ⁇ , ⁇ -unsaturated carboxylic acid or a derivative thereof. Included are molecular units including. Examples of ⁇ , ⁇ -unsaturated carboxylic acid or a derivative thereof include maleic acid, halogenated maleic acid, itaconic acid, cis-4-cyclohexene-1,2-dicarboxylic acid, and endo-cis-bicyclo [2,2].
  • Vinyl dimethoxymethyl silane, vinyl diethoxyethyl silane, vinyl dipropoxypropyl silane, vinyl dibutoxybutyl silane, etc. can be mentioned.
  • acrylic acid, anhydride, glycidyl methacrylate, vinyltrimethoxysilane, vinyltriethoxysilane are preferable, and maleic anhydride is more preferable from the viewpoint of further enhancing the adhesiveness.
  • the addition amount of the molecular unit containing ⁇ , ⁇ -unsaturated carboxylic acid or a derivative thereof is preferably 0.1 part by mass or more and 20 parts by mass or less with respect to 100 parts by mass of the conjugated diene polymer, more preferably. Is 0.1 parts by mass or more and 10 parts by mass or less, and more preferably 0.1 parts by mass or more and 5 parts by mass or less. From the viewpoint of the binding property to the constituent components of the electrode active material layer, the solid electrolyte, etc., or the adhesiveness to the current collector, the added amount is preferably 0.1 part by mass or more. On the other hand, from the viewpoint of improving the fluidity of the all-solid-state battery binder containing the conjugated diene-based polymer, the added amount is preferably 20 parts by mass or less.
  • a method of graft addition for example, a method of reacting these in a solution containing a radical initiator, a conjugated diene-based polymer, and a compound containing an ⁇ , ⁇ -unsaturated carboxylic acid or a derivative group thereof; a radical initiator.
  • a compound that reacts with any of the group-containing compounds to form a bond and a conjugated diene-based polymer grafted with an ⁇ , ⁇ -unsaturated carboxylic acid or a compound containing a derivative group thereof are subjected to heat melting or unmelting.
  • graft addition by en addition may be performed without containing a radical initiator.
  • a method of reacting a radical initiator, a conjugated diene polymer, and a compound containing an ⁇ , ⁇ -unsaturated carboxylic acid group or a derivative group thereof under heating and melting, under heating and unmelting, or in a solution is preferable. More preferably, it is a method of reacting under heating and melting.
  • graft addition by en addition may be performed without containing a radical initiator.
  • Examples of a method for reacting a radical initiator, a conjugated diene-based polymer, and a compound containing an ⁇ , ⁇ -unsaturated carboxylic acid group or a derivative group thereof under heating and melting include a Banbury mixer and a single-screw screw extruder. Examples thereof include a method of melt-kneading each component using a general mixer such as a twin-screw extruder, a conider, and a multi-screw screw extruder. From the viewpoint of cost and production stability, a method using a single-screw, twin-screw or multi-screw screw extruder is preferable, and a method using a twin-screw screw extruder is more preferable.
  • the radical initiator, the conjugated diene polymer, and the compound containing an ⁇ , ⁇ -unsaturated carboxylic acid group or a derivative group thereof may be dry-blended and added all at once, or may be fed separately for each raw material. The same raw material may be added in a plurality of times.
  • the rotation speed of the screw is preferably 50 rpm or more and 400 rpm or less, more preferably 50 rpm or less, from the viewpoint of uniformly adding a compound containing an ⁇ , ⁇ -unsaturated carboxylic acid or a derivative group thereof to the conjugated diene-based polymer. , 100 rpm or more and 350 rpm or less. Further, from the viewpoint of suppressing deterioration of the resin due to shearing and uniformly adding a compound containing an ⁇ , ⁇ -unsaturated carboxylic acid or a derivative group thereof to the conjugated diene polymer, the rotation speed is preferably preferable. It is 150 rpm or more and 300 rpm or less.
  • the kneading temperature is not particularly limited as long as it is a temperature at which the conjugated diene polymer melts and a temperature at which radicals are generated from the radical initiator, but is preferably 100 ° C. or higher and 350 ° C. or lower.
  • the kneading temperature is more preferably 120 ° C. or higher and 300 ° C. or lower from the viewpoint of controlling the addition amount of the compound containing ⁇ , ⁇ -unsaturated carboxylic acid or its derivative group and suppressing the deterioration of the resin due to heat. More preferably, it is 150 ° C. or higher and 250 ° C. or lower.
  • melt-kneading may be performed in an atmosphere of an inert gas such as nitrogen.
  • the amount of the modifying group of the conjugated diene polymer is preferably as small as possible from the viewpoint of suppressing moisture absorption in the range where the adhesiveness, the binding property, the volatility and the dispersibility of the conductive auxiliary agent are sufficient, and the amount is 20 mmol or less per 100 g of the polymer. It is preferably 15 mmol or less, more preferably 10 mmol or less, 4 m mmol or less, and 2 m mmol or less. In particular, when the molecular weight is 200,000 or more, it is 15 mmol or less, more preferably 10 mmol or less, 4 m mmol or less, and 2 m mmol or less.
  • the amount of modification is small for functional groups having an affinity for water molecules such as an acid anhydride group, a carboxyl group, an amino group, an epoxy group, an alkoxysilane group and a hydroxyl group.
  • the conductive auxiliary agent is mainly composed of carbon, and since functional groups such as COOH and OH are present on the surface thereof, there is an interaction with the conjugated diene polymer regardless of the type of the conductive auxiliary agent. it is conceivable that.
  • the radical initiator in the graft addition is not particularly limited, and examples thereof include ketone peroxides, peroxyketals, hydroperoxides, dialkyl peroxides, diacyl peroxides, peroxyesters, and peroxydicarbonates.
  • a radical initiator having a 1-minute half-life temperature within the kneading temperature range is preferable. More preferably, it is a radical initiator having a 1-minute half-life temperature of 150 ° C. or higher and 250 ° C. or lower, and examples of such a radical initiator include 1,1-di (t-hexylperoxy) cyclohexane, 1,1.
  • di (2-t-butylperoxyisopropyl) benzene dicumylperoxide, dit-hexylperoxide, 2,5-dimethyl-2,5 -Di (t-butylperoxy) hexane, t-butylcumylperoxide, di-t-butylperoxide, and 2,5-dimethyl-2,5-di (t-butylperoxy) hexin-3 are preferred. .. Of these, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane and 2,5-dimethyl-2,5-di (t-butylperoxy) hexin-3 are more preferable.
  • the moll equivalent of the compound containing ⁇ , ⁇ -unsaturated carboxylic acid or a derivative group thereof is preferably 300 mol equivalent or less, more preferably 200 mol equivalent or less, and more preferably 200 mol equivalent or less with respect to the radical initiator. Is 100 mol equivalent or less.
  • the amount of the compound containing ⁇ , ⁇ -unsaturated carboxylic acid or its derivative group is more than 0 parts by mass and about 10 parts by mass with respect to 100 parts by mass of the conjugated diene polymer. Can be added more easily.
  • the reaction method is particularly limited when the conjugated diene-based polymer into which the primary modifying group is introduced is further subjected to the secondary modification by the constituent components of the electrode active material layer, the solid electrolyte, or the atomic group having adhesiveness to the current collector.
  • a known method can be used instead of the one.
  • common mixers such as Banbury mixers, single-screw screw extruders, twin-screw screw extruders, conidas, and multi-screw screw extruders can be used. Examples thereof include a method of melting and kneading each component using the method, and a method of dissolving or dispersing and mixing each component in a solvent and then heating and removing the solvent.
  • melt-kneading method using an extruder is preferable from the viewpoint of improving productivity and good kneading property.
  • the shape of the conjugated diene polymer of the present embodiment is not particularly limited, and examples thereof include pellets, sheets, strands, chips, powders, and crumbs. Further, after melt-kneading, it may be directly molded, or it may be manufactured in the form of chips, powder, or crumbs. From the viewpoint of water removal efficiency contained in the conjugated diene polymer, a shape having a large specific surface area is preferable, and a crumb or powder form is preferable to pellets.
  • a conjugated diene polymer is extruded into a strand from a uniaxial or biaxial extruder and cut in water by a rotary blade installed on the front surface of the die portion (underwater cut, etc.).
  • a method of molding into a sheet shape by a roll, further cutting the sheet into a strip shape, and then cutting into cubic pellets by a pelletizer can be mentioned.
  • the water can be removed by a post-process such as centrifugal dehydration or air transportation.
  • a post-process such as air blow, suction type draining, and air transportation in an air cooling process.
  • the size and shape of the pellets are not particularly limited, they are more spherical than the columnar pellets obtained by cutting the strands perpendicular to the long axis of the strands from the viewpoint of suppressing adhesion between the pellets. Pellets close to the above are preferable because the adhesive surface between the pellets can be kept small.
  • a general method for producing pellets that are close to a spherical shape for example, underwater cut and center hot cut can be mentioned.
  • the pellet of the conjugated diene polymer may contain a blocking inhibitor for the purpose of suppressing pellet blocking.
  • the conjugated diene polymer may contain a phosphorus compound.
  • the content of the phosphorus compound is preferably 10 ppm or more, more preferably 20 ppm or more, still more preferably 50 ppm or more, relative to the conjugated diene-based copolymer in terms of phosphorus atom.
  • the preferred upper limit is 250 ppm or less, more preferably 120 ppm or less.
  • the blocking inhibitor is not particularly limited, and examples thereof include higher fatty acid metal salts, polyolefins, fatty acid amides, talc, and silica. Specific examples thereof include calcium stearate, magnesium stearate, zinc stearate, polyethylene, polypropylene, ethylene bisstearylamide, talc, and amorphous silica. Calcium stearate, magnesium stearate, zinc stearate, polyethylene, polypropylene, talc, and amorphous silica are preferable from the viewpoint of low bleeding property, and calcium stearate, magnesium stearate, zinc stearate from the viewpoint of slipperiness when hopper is added. , Polyethylene, polypropylene, and amorphous silica are more preferable, polyethylene or amorphous silica is further preferable, and amorphous silica is most preferable from the viewpoint of resistance to dusting.
  • Calcium stearate, polyethylene, polypropylene, and ethylene bisstearylamide are preferable as the blocking inhibitor from the viewpoint of the constituent components of the obtained electrode active material layer and the adhesiveness to the solid electrolyte or the current collector.
  • the preferable amount of the blocking inhibitor to be used is 500 ppm or more and 8000 ppm or less with respect to the conjugated diene-based polymer.
  • the amount is more preferably 1000 ppm or more and 7000 ppm or less with respect to the conjugated diene-based polymer.
  • the blocking inhibitor is preferably blended in a state of being attached to the surface of the pellet, but may be contained inside the pellet.
  • the conjugated dye-based polymer may contain other additives and is not particularly limited, but for example, an oil, a filler, a heat stabilizer, an ultraviolet absorber, a nucleating agent, an antioxidant, a weather resistant agent, and a light stabilizer.
  • Plasticizer Antistatic agent, Flame retardant, Slip agent, Antifogging agent, Lubricating agent, Pigment, Dye, Dispersant, Copper damage inhibitor, Neutralizer, Bubble inhibitor, Weld strength improver, Natural oil, Synthetic oil , Additives such as wax.
  • other elastomers and thermoplastic resins may also be used as additives in arbitrary proportions. Only one of these may be used, or two or more thereof may be used in combination.
  • the all-solid-state battery of the present embodiment includes at least one layer of a positive electrode layer containing the all-solid-state battery binder, a solid electrolyte layer containing the all-solid-state battery binder, and a negative electrode layer containing the all-solid-state battery binder.
  • FIG. 1 is a schematic cross-sectional view showing an example of an all-solid-state battery in this embodiment.
  • the all-solid-state battery (all-solid-state battery) 100 includes a solid electrolyte layer 110, a positive electrode layer 140 and a negative electrode layer 150 sandwiching the solid electrolyte layer 110 from both sides, and a positive electrode current collector 160 (positive electrode) sandwiching a laminate thereof. It is provided with a negative electrode current collector 170 (arranged outside the negative electrode) and a battery exterior 180 for accommodating them.
  • the water content contained in the all-solid-state battery is preferably 200 ppm or less, more preferably 100 ppm or less, still more preferably 50 ppm or less, still more preferably 10 ppm or less, and particularly preferably 1 ppm or less.
  • Moisture may be removed by drying in a dryer under normal pressure or reduced pressure, or may be stored and removed in a dehumidifying environment.
  • the positive electrode has a positive electrode current collector and a positive electrode layer formed on the positive electrode current collector.
  • the positive electrode layer contains a positive electrode active material, and may contain a conductive auxiliary agent, an all-solid-state battery binder, an inorganic solid electrolyte for enhancing ionic conductivity, a polyelectrolyte, a polyelectrolyte, an additive, etc., if necessary. can.
  • a positive electrode active material used in a general lithium ion battery can be used.
  • an oxide active material, a sulfide active material and the like can be mentioned.
  • Li—Co composite oxides such as LiCoO 2 which is a layered rock salt type positive electrode material
  • Li—Ni composite oxides such as LiNiO 2 and nickel-based compounds LiNi (Co, Al) O 2 derived from these.
  • Three-way compound LiNi 1/3 Mn 1/3 Co 1/3 O 2 , LiNi 0.8 Co 0.15 Al 0.05 O 2 , Nickel manganese compound LiNi 0.5 Mn 0.5 O 2 , Lithium excess compound Li 2 MnO 3 -LiMO 2 (M Co, Ni, Mn), Spinel type positive electrode material LiMn 2 O 4 , LiMn 1.5 Ni 0.5 O 4 , Olivin type positive electrode material.
  • a positive electrode material can be used.
  • the positive electrode active material may be used alone or in combination of two or more.
  • the positive electrode is not particularly limited as long as it acts as the positive electrode of the lithium ion secondary battery, and can be obtained, for example, as follows.
  • a positive electrode mixture-containing slurry is prepared by dispersing a positive electrode mixture in which the above positive electrode active material is mixed with other components (for example, a conductive auxiliary agent, a binder, etc.) used as needed in a solvent.
  • the positive electrode mixture-containing slurry is applied to a positive electrode current collector (base material), dried to form a positive electrode layer, and further pressed as necessary to adjust the thickness to produce a positive electrode. ..
  • the solid content concentration in the positive electrode mixture-containing slurry is not particularly limited, but is preferably 30 to 80% by mass, and more preferably 40 to 70% by mass.
  • the positive electrode current collector is composed of, for example, a metal foil such as aluminum, stainless steel, gold, platinum, titanium, tin, copper, and zinc. These materials may be coated with carbon, or these materials may be processed into a mesh shape.
  • a method of filling the particles with a substance having lithium ion conductivity can be used in order to maintain the lithium ion conductivity with the solid electrolyte.
  • a substance having lithium ion conductivity for example, a substance having amorphous lithium ion conductivity can be used, and as the substance having amorphous lithium ion conductivity, a polymer electrolyte or amorphous material can be used. Inorganic compounds having lithium ion conductivity can be used.
  • the amount of water contained in the positive electrode layer is preferably 200 ppm or less, more preferably 100 ppm or less, still more preferably 50 ppm or less, still more preferably 10 ppm or less, and particularly preferably 1 ppm or less.
  • Moisture may be removed by drying in a dryer under normal pressure or reduced pressure, or may be stored and removed in a dehumidifying environment.
  • the negative electrode has a negative electrode current collector and a negative electrode layer formed on the negative electrode current collector.
  • the negative electrode layer may contain a negative electrode active material, and if necessary, a conductive auxiliary agent, an all-solid-state battery binder, an inorganic solid electrolyte for enhancing ionic conductivity, a polyelectrolyte, a polyelectrolyte, an additive, and the like. can.
  • the negative electrode preferably contains one or more materials selected from the group consisting of a material capable of occluding and releasing lithium ions as a negative electrode active material and metallic lithium.
  • materials include metallic lithium, metallic materials such as materials containing elements capable of forming alloys with lithium; for example, amorphous carbon (hard carbon), artificial graphite, natural graphite, graphite, thermal decomposition. Examples thereof include carbon, coke, glassy carbon, calcined bodies of organic polymer compounds, mesocarbon microbeads, carbon fibers, activated carbon, graphite, carbon colloid, and carbon materials typified by carbon black.
  • coke examples include pitch coke, needle coke, petroleum coke, and the like.
  • the calcined body of an organic polymer compound is a polymer material such as a phenol resin or a furan resin that is calcined at an appropriate temperature to be carbonized.
  • the carbon material may contain a heterogeneous compound containing O, B, P, N, S, SiC, B4C and the like in addition to carbon.
  • the content of the dissimilar compound is preferably 0 to 10% by mass with respect to the entire negative electrode active material.
  • the metal material capable of forming an alloy with lithium may be a simple substance of a metal or a semimetal, an alloy, or a compound, and one or more of these phases may be used. It may be something that has at least a part of it. Alternatively, known materials such as oxide active materials such as SiOx, Li 4 Ti 5 O 12 are used. Further, the above-mentioned negative electrode active material may be used alone or in combination of two or more.
  • the number average particle size (primary particle size) of the negative electrode active material is preferably 0.1 ⁇ m to 100 ⁇ m, and more preferably 1 ⁇ m to 10 ⁇ m.
  • the negative electrode is obtained, for example, as follows. First, a negative electrode mixture containing the negative electrode active material mixed with other components (for example, a conductive auxiliary agent, a binder, etc.) used as needed is dispersed in a solvent to prepare a slurry containing the negative electrode mixture. Next, this negative electrode mixture-containing slurry is applied to a negative electrode current collector (base material), dried to form a negative electrode layer, and further pressed as necessary to adjust the thickness to prepare a negative electrode.
  • a negative electrode current collector base material
  • the solid content concentration in the slurry containing the negative electrode mixture is preferably 30 to 80% by mass, more preferably 40 to 70% by mass.
  • the negative electrode current collector is composed of, for example, a metal foil such as copper, nickel, stainless steel, gold, platinum, titanium, tin, and zinc.
  • a method of filling the particles with a substance having lithium ion conductivity can be used.
  • a substance having lithium ion conductivity for example, a substance having amorphous lithium ion conductivity can be used, and as the substance having amorphous lithium ion conductivity, a polymer electrolyte or amorphous material can be used. Inorganic compounds having lithium ion conductivity can be used.
  • the amount of water contained in the negative electrode layer is preferably 200 ppm or less, more preferably 100 ppm or less, still more preferably 50 ppm or less, still more preferably 10 ppm or less, and particularly preferably 1 ppm or less.
  • Moisture may be removed by drying in a dryer under normal pressure or reduced pressure, or may be stored and removed in a dehumidifying environment.
  • the slurry of the present embodiment which can be used as the positive electrode mixture-containing slurry or the negative electrode mixture-containing slurry, contains the all-solid-state battery binder, and if necessary, a conductive auxiliary agent, a solvent, the positive electrode active material, or the above. It may contain a negative electrode active material or the like.
  • the slurry of the present embodiment preferably does not contain water, and the water content of the slurry is preferably 200 ppm or less, more preferably 100 ppm or less, still more preferably 50 ppm or less, still more preferably 10 ppm. It is less than or equal to, and particularly preferably 1 ppm or less. Moisture contained in the all-solid-state battery binder may be removed by drying with a dryer under normal pressure or reduced pressure, or may be stored and removed in a dehumidifying environment.
  • the conductive auxiliary agent of the present embodiment is not particularly limited as long as it has electronic conductivity.
  • graphite carbon black typified by acetylene black and Ketjen black
  • carbon fibers typified by gas phase growth carbon fibers and carbon nanotubes
  • carbon black is preferable.
  • the number average particle size (primary particle size) of the conductive auxiliary agent used for the positive electrode is preferably 10 nm to 10 ⁇ m, more preferably 20 nm to 1 ⁇ m.
  • the number average particle diameter (primary particle diameter) of the conductive auxiliary agent used for the negative electrode is preferably 0.1 ⁇ m to 100 ⁇ m, and more preferably 1 ⁇ m to 10 ⁇ m.
  • the conductive auxiliary agent By using the conductive auxiliary agent, the electron conduction path of each electrode layer can be secured, the internal resistance of the all-solid-state battery can be lowered, and the charge / discharge characteristics of the all-solid-state battery are improved by increasing the amount of current. ..
  • the modifying group of the all-solid-state battery binder according to the functional group on the surface of the conductive auxiliary agent the dispersibility can be controlled by the interaction. Since the surface of the carbon-based conductive auxiliary agent has a carboxyl group, a hydroxyl group, and the like, mutual carboxyl groups, hydroxyl groups, and amino groups are preferable because of the interaction due to hydrogen bonds.
  • Examples of carbon black include oil furnace black and gas furnace black manufactured by the furnace method (incomplete combustion method), acetylene black and thermal black manufactured by the thermal method (pyrolysis method). Of these, oil furnace black and acetylene black are preferable from the viewpoint of electron conductivity.
  • Oil furnace black includes Ketjen Black (a product manufactured by Lion Specialty Chemicals Co., Ltd.), and acetylene black includes Denka Black (registered trademark) (a product manufactured by Denka Co., Ltd.).
  • the binder of this embodiment is a conjugated diene-based polymer.
  • a polymer material other than the conjugated diene polymer in combination.
  • PVDF polyvinylidene fluoride
  • PTFE polytetrafluoroethylene
  • the binder may be used alone or in combination of two or more.
  • the content of the all-solid-state battery binder contained in the positive electrode is not particularly limited, but is preferably when the total weight of the positive electrode (excluding the current collector) is 100 wt% from the viewpoint of ionic conductivity and electron conductivity. Of these, 10 wt% or less is preferable, more preferably 5 wt% or less, still more preferably 3 wt% or less, and particularly preferably 1 wt% or less.
  • the content of the all-solid-state battery binder contained in the negative electrode is not particularly limited, but the total weight of the negative electrode (excluding the current collector) is preferably 100 wt% from the viewpoint of ionic conductivity and electron conductivity. Occasionally, it is preferably 10 wt% or less, more preferably 5 wt% or less, still more preferably 3 wt% or less, and particularly preferably 1 wt% or less.
  • the content of the all-solid-state battery binder contained in the solid electrolyte layer is not particularly limited, but from the viewpoint of ionic conductivity and electron conductivity, it is preferable that the total weight of the solid electrolyte layer is 100 wt%. It is preferably 10 wt% or less, more preferably 5 wt% or less, still more preferably 3 wt% or less, and particularly preferably 1 wt% or less.
  • the all-solid-state battery binder may be uniformly or non-uniformly distributed in each layer, or may be distributed with an inclination. It can also be used for the purpose of adhering the interface of each layer, if necessary.
  • the concentration distribution of the conductive auxiliary agent contained in the positive electrode layer is not particularly limited, but from the viewpoint of electron conductivity, the concentration of the conductive auxiliary agent in the vicinity of the positive electrode current collector is preferable to that in the vicinity of the solid electrolyte layer. Is high.
  • the current of the entire positive electrode layer is concentrated in the vicinity of the positive electrode current collector of the positive electrode layer. Therefore, by increasing the concentration of the conductive auxiliary agent in the vicinity of the positive electrode current collector, the bottleneck of the electron conduction path of the positive electrode layer can be removed, and the charge / discharge load characteristics and the cycle life characteristics of the battery are improved.
  • the concentration of the conductive auxiliary agent contained in the positive electrode layer is higher in the vicinity of the positive electrode current collector than in the vicinity of the solid electrolyte layer, and the concentration of the conductive auxiliary agent is preferably higher.
  • the concentration of the conductive auxiliary agent in the vicinity is 10 times or more the concentration of the conductive auxiliary agent in the vicinity of the solid electrolyte layer.
  • the concentration distribution of the conductive auxiliary agent contained in the negative electrode layer is not particularly limited, but from the viewpoint of electron conductivity, the negative electrode current is preferably collected from the vicinity of the solid electrolyte layer.
  • the concentration of the conductive auxiliary agent near the body is high.
  • the current of the entire negative electrode layer is concentrated in the vicinity of the negative electrode current collector of the negative electrode layer. Therefore, by increasing the concentration of the conductive auxiliary agent in the vicinity of the negative electrode current collector, the bottleneck of the electron conduction path of the negative electrode layer can be removed, and the charge / discharge load characteristics and the cycle life characteristics of the battery are improved.
  • the concentration of the conductive auxiliary agent in the vicinity of the negative electrode current collector may be higher than that in the vicinity of the solid electrolyte layer, and the concentration of the conductive auxiliary agent in the vicinity of the negative electrode current collector is preferably the solid electrolyte layer. It is 8 times or more the concentration of the conductive auxiliary agent in the vicinity.
  • the solvent of the present embodiment is not particularly limited as long as it does not adversely affect the performance of the solid electrolyte, and examples thereof include a non-polar solvent as a solvent having low hydrophilicity.
  • the non-polar solvent include the hydrocarbon solvents heptane, xylene, toluene, hexane and the like, or a combination thereof.
  • a hydrocarbon-based organic solvent which has been dehydrated to reduce the water content is preferably used.
  • a non-polar solvent having a boiling point of 100 ° C. or higher and a melting point of 0 ° C. or lower at normal pressure is preferable, and more preferably, a boiling point at normal pressure of 150 ° C. or higher and a melting point of ⁇ 20 ° C. or lower.
  • Non-polar solvents are preferred.
  • the solid electrolyte layer of the present embodiment contains an ion conductive solid electrolyte and, if necessary, an all-solid-state battery binder.
  • the ionic conductive solid electrolyte is not particularly limited as long as it can be used in an all-solid-state battery, and examples thereof include sulfide-based solid electrolytes and oxide-based solid electrolytes.
  • the sulfide-based solid electrolyte is Li 2 S-SiS 2 , LiI-Li 2 S-SiS 2 , LiI-Li 2 SP 2 S 5 , LiI-Li 2 SP 2 as a sulfide-based amorphous solid electrolyte.
  • Examples include O 5 , LiI-Li 3 PO 4 -P 2 S 5 , Li 2 S-P 2 S 5 , and the like, and examples of the sulfide-based glass-ceramic solid electrolyte include those containing Li 2 S and P 2 S 5 .
  • Examples of the Thi thoroughly-LISION-based solid electrolyte include Li 3.25 Ge 0.25 P 0.75 S 4, Li 10 GeP 2 S 12. and the like.
  • Oxide-based solid electrolytes are ⁇ -LiPO type 4 oxides, reverse fluorite type oxides, and NASICON type oxides Li 1.3 Al 0.3 Ti 0.7 (PO) as oxide-based crystalline solid electrolytes. 4 ) 3 , Perovskite type Li 0.5 La 0.5 TiO 3 , Garnet type Li 7 La 3 Zr 2 O 12 and the like can be mentioned.
  • the oxide-based amorphous solid electrolyte include LiPON, Li 2O-B 2 O 3 -P 2 O 5 , Li 2 O -SiO 2 , and the like. These may be used alone or in combination of two or more.
  • the shape of the solid electrolyte is not particularly limited, and is a particle shape, a thin film shape, or the like.
  • the average particle diameter is preferably 100 ⁇ m or less, more preferably 80 ⁇ m or less, and further preferably 40 ⁇ m or less. As the particles become finer, the packing factor improves and good ionic conductivity is obtained.
  • the particle size is preferably 0.1 ⁇ m or more from the viewpoint of the physical strength of the solid electrolyte layer and the prevention of short circuits.
  • the amount of water contained in the solid electrolyte layer is preferably 200 ppm or less, more preferably 100 ppm or less, still more preferably 50 ppm or less, still more preferably 50 ppm or less. It is 10 ppm or less, and particularly preferably 1 ppm or less. Moisture may be removed by drying in a dryer under normal pressure or reduced pressure, or may be stored and removed in a dehumidifying environment.
  • the method for forming the solid electrolyte layer is not particularly limited, and can be obtained by press-molding a mixture containing, for example, a solid electrolyte or, if necessary, other components such as an all-solid-state battery binder.
  • a slurry containing a solid electrolyte or, if necessary, a mixture containing other components such as an all-solid-state battery binder is applied to the substrate, dried, and further pressed as necessary to adjust the thickness, and then peeled off from the substrate. By doing so, a solid electrolyte layer can be obtained.
  • the all-solid-state battery in the present embodiment is manufactured by a known method using the above-mentioned positive electrode, negative electrode, and solid electrolyte layer.
  • a positive electrode, a negative electrode, and a solid electrolyte layer are interposed, or a multilayer structure in which an electron conductor is interposed between a plurality of positive electrodes and a negative electrode in which the laminates are alternately laminated.
  • the electrode laminate is configured according to the configuration mode and the like.
  • the all-solid-state battery of the present embodiment can be manufactured by accommodating the electrode laminate in a battery case (exterior) and sealing it.
  • a pressure of 0.1 to 4000 kgf / cm 2 to the facing surfaces of the positive electrode and the negative electrode, and more preferably a pressure of 0.1 to 100 kgf / cm 2 . It is most preferable to pressurize at a pressure of 0.5 to 15 kgf / cm 2 .
  • the pressure By setting the pressure to 0.1 kgf / cm 2 or more, the contact state between the electrode active material and the solid electrolyte is improved and the battery characteristics are improved.
  • the pressure By setting the pressure to 4000 kgf / cm 2 or less, a short circuit due to internal damage to the battery can be prevented.
  • the battery can be operated while maintaining the pressurized state at the time of manufacturing the battery, but can also be operated without pressurization if there is no problem in the charge / discharge characteristics.
  • the shape of the all-solid-state battery of the present embodiment is not particularly limited, and for example, a cylindrical shape, an elliptical shape, a square cylinder type, a button shape, a coin shape, a flat shape, a laminated shape, or the like is preferably adopted. Further, the solid electrolyte of the present embodiment can be applied not only to the all-solid-state battery as described above but also to other batteries.
  • the temperature conditions for the measurement by gas chromatography were that the polymerization rate of butadiene was constant at 90 ° C. and the polymerization rate of styrene was 90 ° C. (hold for 10 minutes) to 150 ° C. (10 ° C./min). ..
  • Amount of vinyl bond before hydrogenation of conjugated diene polymer The amount of vinyl bond before hydrogenation of the conjugated diene polymer is determined by using a polymer solution sampled at each step of the polymerization process of the conjugated diene polymer. , Proton nuclear magnetic resonance ( 1 H-NMR) method.
  • ECS400 manufactured by JEOL
  • deuterated chloroform was used as a solvent
  • the sample concentration was 50 mg / mL
  • the amount of vinyl bond was determined by determining the integrated value of the signals attributed to 1,4-bond and 1,2-bond in the conjugated diene monomer unit, and then the 1,4-bond and 1,2-bond. Calculated from the signal ratio.
  • Measurement condition Observation frequency: 400MHz Chemical shift standard: Tetramethylsilane Pulse delay: 2.904 seconds
  • Hydrogenation rate of conjugated diene-based polymer The hydrogenation rate of unsaturated bonds based on the conjugated diene monomer unit of the conjugated diene-based polymer is determined by using the conjugated diene-based polymer before and after hydrogenation. It was measured by magnetic resonance ( 1 H-NMR). The measurement conditions and the method for processing the measurement data were the same as in (2) above.
  • the hydrogenation rate was calculated from the integrated value of the signal derived from the double bond of 4.5 to 5.5 ppm and the signal derived from the hydrogenated conjugated diene, and the signal ratio thereof.
  • the total amount of butylene and propylene is the total amount of conjugated diene after hydrogenation with respect to the total of 100 mol% of the conjugated diene monomer units in the conjugated diene-based polymer. It was measured by proton nuclear magnetic resonance ( 1 H-NMR) using a system polymer. The measurement conditions and the method for processing the measurement data were the same as in (2) and (3) above.
  • the amount of butylene is the signal derived from all the conjugated diene monomer units in the conjugated diene polymer after hydrogenation, and the butylene portion (hydrogenated 1, 2) at 0 to 2.0 ppm of the spectrum. -The integrated value of the signal derived from (binding) was obtained and calculated from the signal ratio.
  • Styrene content of conjugated diene-based polymer It was calculated from the absorption intensity at 262 nm using an ultraviolet spectrophotometer (UV-2450, manufactured by Shimadzu Corporation) using the copolymer before hydrogenation. Since the content of the total vinyl aromatic compound monomer unit does not change significantly before and after hydrogenation, the total vinyl aromatic compound monomer unit (styrene monomer unit) obtained for the copolymer before hydrogenation The content of the hydrogenated copolymer was defined as the content of the total vinyl aromatic compound monomer unit (total styrene content).
  • a 0.1 g / 125 mL tertiary butanol solution of osmic acid was used for the decomposition of the undenatured conjugated diene polymer before hydrogenation.
  • Weight average molecular weight and molecular weight distribution of the conjugated diene polymer and the conjugated diene polymer are determined by GPC [GPC apparatus: HLC8220 (manufactured by Toso). Product name), column: 4.6 mm ⁇ 30 cm TSKgelSUPER-HZM-N (product name manufactured by Sigma-Polymer)] was used for measurement. Tetrahydrofuran was used as the solvent.
  • the weight average molecular weight was determined from the peak of the chromatogram based on the calibration curve obtained using commercially available standard polystyrene. For the molecular weight when there are a plurality of peaks in the chromatogram, the weight average molecular weight was obtained from the molecular weight of each peak and the composition ratio of each peak (determined by the area ratio of each peak in the chromatogram).
  • the conjugated diene-based polymer may be adsorbed on the column due to the interaction between the modifying group and the column, in which case the molecular weight of the non-adsorbed portion or the copolymer before modification is measured.
  • the molecular weight distribution was calculated from the ratio (Mw / Mn) of the obtained weight average molecular weight (Mw) to the number average molecular weight (Mn).
  • the conjugated diene-based polymer may be adsorbed on the column due to the interaction between the modifying group and the column, in which case the molecular weight of the non-adsorbed portion is measured.
  • the ratio of the conjugated diene polymer to the standard polystyrene in the measured chromatogram was compared, and the amount adsorbed on the silica gel column was measured from the difference between them, and this ratio was taken as the modification rate. It was calculated by the following formula.
  • a Area (%) of the total polymer measured with a polystyrene-based gel (PLgel).
  • b Area (%) of low molecular weight internal standard PS measured with polystyrene gel.
  • c Area (%) of the total polymer measured on a silica-based column (Zorbox).
  • d Area (%) of low molecular weight internal standard PS measured with a silica-based column (Zorbox).
  • Interface peel strength (adhesiveness) between the conjugated diene polymer and the aluminum sheet
  • the interfacial peel strength between the conjugated diene-based polymer and the aluminum sheet was measured by a 180-degree peeling test using a multilayer body obtained by heat-welding the conjugated diene-based polymer to the aluminum sheet. Specifically, a 1 mm thick aluminum sheet and a 2 mm thick conjugated diene polymer sheet are stacked and fixed in a 2 mm thick mold, preheated at 200 ° C. for 5 minutes without applying pressure, and then at 200 ° C.
  • a multilayer body composed of a 1 mm thick aluminum sheet and a 1 mm thick conjugated diene polymer was prepared by heating and pressing at 10 MPa for 2 minutes and then cooling and pressing at 10 MPa for 3 minutes at 20 ° C.
  • a 10 mm wide notch was made in the surface of the obtained multilayer on the side of the conjugated diene polymer, and the end of the layer made of the conjugated diene polymer was peeled off by several cm.
  • the peeled portion of the layer made of the conjugated diene polymer and the aluminum sheet were separately fixed to the chucks of a tensile tester [MinebeaMitsumi Co., Ltd., TGE-500N (product name)].
  • the two layers were peeled off by pulling the peeled portion of the layer made of the conjugated diene polymer and the aluminum sheet at 300 mm / min in the 180 ° C. direction.
  • the tensile force applied at the time of peeling was defined as the interfacial peel strength (N / cm) of the multilayer of the conjugated diene polymer and the aluminum sheet, and was evaluated according to the following evaluation criteria. (Evaluation criteria) ⁇ : 10 N / cm or more ⁇ : 3 N / cm or more and less than 10 N / cm ⁇ : less than 3 N / cm
  • Binding property of conjugated diene polymer binder 0.15 g of conjugated diene polymer, 0.35 g of acetylene black and 4.5 g of toluene are stirred at 2000 rpm for 2 minutes with a stirrer, and toluene is further adjusted for viscosity. Was added in an appropriate amount to obtain a slurry. This slurry is applied on aluminum foil with an applicator, allowed to stand on a hot plate, dried at 50 ° C. for 5 minutes, and further dried at 70 ° C. for 10 hours to form an electrode in which an electrode layer and a current collector are integrated. Obtained.
  • the electrode was wound around a SUS rod having a diameter of 10 mm, and the state of the curved electrode layer was visually observed to evaluate the binding property of the binder. (Evaluation criteria) ⁇ : There was no crack in the electrode layer and strong adhesion was shown. ⁇ : A part of the electrode layer was cracked and showed moderate adhesion. ⁇ : The entire electrode layer was cracked and weak adhesion was obtained. Indicated
  • composition change is small during storage as a binder solution or slurry
  • composition change is moderate at 3 g or more and less than 5 g
  • composition change is moderate during storage as a binder solution or slurry ⁇ : 5 g or more and less than 7 g
  • binder solution Large change in composition during storage as a binder solution or slurry ⁇ : 7 g or more, large change in composition during storage as a binder solution or slurry
  • Electrochemical stability of the electrode layer containing the conjugated diene polymer binder 0.15 g of the conjugated diene polymer, 0.35 g of acetylene black and 4.5 g of toluene are stirred at 2000 rpm for 2 minutes with a stirrer, and further. An appropriate amount of toluene was added to adjust the viscosity, and the mixture was stirred at 2000 rpm for 2 minutes to obtain a slurry. This slurry is applied on a platinum foil with an applicator, allowed to stand on a hot plate, dried at 50 ° C. for 5 minutes, and further dried at 70 ° C. for 10 hours. An evaluation electrode was obtained.
  • an electrode layer containing a conjugated diene polymer binder and an electrode for evaluation on the oxidation side or an electrode for evaluation on the reduction side (each) integrated with a current collector. (14 mm x 20 mm square) with a platinum lead piece connected to draw current as the working electrode, a nickel lead piece connected to the lithium metal sheet as the counter electrode, and a current to the lithium metal sheet. Refer to the one to which a lead piece made of nickel is connected to take out the electrode.
  • a laminated sheet of micropore membrane separator and glass non-woven fabric is used as a separator between each electrode, and these are housed in the exterior of the aluminum laminated sheet and 1M LiPF 6 /.
  • After injecting (ethylene carbonate / methyl ethyl carbonate ( 30 wt% / 70 wt%)) into the outer body as an electrolytic solution, the outer body was sealed to prepare a laminated cell for measurement. The measurement was performed using this cell under the following conditions. (conditions) Measurement method: Linear sweep voltammetry Sweep speed; 2 mV / sec Voltage range; (oxidation side) 3.0V (initial voltage) -5.4V (final voltage) vs.
  • the electrochemical stability of the electrode layer containing the conjugated diene polymer binder is such that the oxidation side has a current value of 0.0005 A / mg or more at 3.0 V (vs. Li / Li + / V) or more. If the voltage is 4.6 V (vs. Li / Li + / V) or more, the result is acceptable ( ⁇ ), and on the reduction side, the current value is ⁇ 0 . If the voltage of 0.0005 A / mg or less is less than 0.1 V (vs. Li / Li + / V), it is judged as acceptable ( ⁇ ).
  • the hydrogenation catalyst used for the hydrogenation reaction of the conjugated diene polymer was prepared by the following method. In a nitrogen-substituted reaction vessel, 1 L of dried and purified cyclohexane is placed, 100 mmol of bis ( ⁇ 5-cyclopentadienyl) titanium dichloride is added, and an n-hexane solution containing 200 mmol of trimethylaluminum is added with sufficient stirring. , The reaction was carried out at room temperature for about 3 days to obtain a hydrogenated catalyst.
  • a cyclohexane solution (styrene concentration: 20% by mass) containing 16 parts by mass of styrene (relative to 100 parts by mass of all monomers; the same shall apply hereinafter in this paragraph) was added to the reactor and polymerized at 70 ° C. for 45 minutes. ..
  • a cyclohexane solution containing 68 parts by mass of butadiene (butadiene concentration: 20% by mass) was added, and the mixture was polymerized at 70 ° C. for 1.5 hours.
  • a cyclohexane solution containing 16 parts by mass of styrene (styrene concentration: 20% by mass) was added, and the mixture was polymerized at 70 ° C. for 45 minutes.
  • methanol was added to obtain a conjugated diene-based block copolymer as Step 1.
  • the obtained conjugated diene-based block copolymer had a styrene content of 32% by mass, a polystyrene block content of 32% by mass, and a vinyl bond content of the butadiene portion of 36 mol%.
  • Step 2> The hydrogenation catalyst described above is added to the obtained conjugated diene-based block copolymer so that the titanium-equivalent concentration is 100 ppm with respect to the conjugated diene-based block copolymer, and the hydrogen pressure is 0.7 MPa and the temperature is 70 ° C. A hydrogenation reaction was carried out.
  • octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate was then added as a stabilizer at 0.3 with respect to 100 parts by mass of the conjugated diene-based block copolymer.
  • a conjugated diene-based block copolymer was added by mass and hydrogenated to produce a hydrogenated conjugated diene-based block copolymer.
  • the obtained hydrogenated conjugated diene block copolymer (a-1) has a styrene content of 32% by mass, a butylene content of 36 mol%, a weight average molecular weight of 69,000, a molecular weight distribution of 1.2, and a hydrogenation rate. It was 99 mol%.
  • a cyclohexane solution (styrene concentration: 20% by mass) containing 9.5 parts by mass of styrene (relative to 100 parts by mass of all monomers; the same shall apply hereinafter in this paragraph) was added to the reactor, and the mixture was added to the reactor at 70 ° C. for 45 minutes. Polymerized.
  • a cyclohexane solution containing 81 parts by mass of butadiene (butadiene concentration: 20% by mass) was added, and the mixture was polymerized at 70 ° C. for 1.5 hours.
  • the obtained conjugated diene-based block copolymer had a styrene content of 19% by mass, a polystyrene block content of 19% by mass, and a vinyl bond content of the butadiene portion of 36 mol%.
  • Step 2> The hydrogenation catalyst described above is added to the obtained conjugated diene-based block copolymer so that the titanium-equivalent concentration is 100 ppm with respect to the conjugated diene-based block copolymer, and the hydrogen pressure is 0.7 MPa and the temperature is 70 ° C. A hydrogenation reaction was performed.
  • octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate was then added as a stabilizer at 0.3 with respect to 100 parts by mass of the conjugated diene-based block copolymer.
  • a conjugated diene-based block copolymer was added by mass and hydrogenated to produce a hydrogenated conjugated diene-based block copolymer.
  • the obtained hydrogenated conjugated diene block copolymer (a-2) has a styrene content of 19% by mass, a butylene content of 36 mol%, a weight average molecular weight of 85,000, a molecular weight distribution of 1.2, and a hydrogenation rate. It was 99 mol%.
  • a cyclohexane solution (styrene concentration: 20% by mass) containing 6.5 parts by mass of styrene (relative to 100 parts by mass of all monomers; the same shall apply hereinafter in this paragraph) was added to the reactor and at 70 ° C. for 45 minutes. Polymerized. Next, a cyclohexane solution containing 87 parts by mass of butadiene (butadiene concentration: 20% by mass) was added, and the mixture was polymerized at 50 ° C. for 80 minutes. Next, a cyclohexane solution containing 6.5 parts by mass of styrene (styrene concentration: 20% by mass) was added, and the mixture was polymerized at 70 ° C. for 45 minutes. After completion of the reaction, methanol was added to obtain a conjugated diene-based block copolymer.
  • the obtained conjugated diene-based block copolymer had a styrene content of 13% by mass, a polystyrene block content of 13% by mass, and a vinyl bond content of the butadiene portion of 45 mol%.
  • Step 2> The hydrogenation catalyst described above is added to the obtained conjugated diene-based block copolymer so that the titanium-equivalent concentration is 100 ppm with respect to the conjugated diene-based block copolymer, and the hydrogen pressure is 0.7 MPa and the temperature is 70 ° C. A hydrogenation reaction was performed.
  • octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate was then added as a stabilizer at 0.3 with respect to 100 parts by mass of the conjugated diene-based block copolymer.
  • a conjugated diene-based block copolymer was added by mass and hydrogenated to produce a hydrogenated conjugated diene-based block copolymer.
  • the obtained hydrogenated conjugated diene block copolymer (a-3) has a styrene content of 13% by mass, a butylene content of 45 mol%, a weight average molecular weight of 80,000, a molecular weight distribution of 1.2, and a hydrogenation rate. It was 99 mol%.
  • a cyclohexane solution (butadiene concentration: 20% by mass) containing 5 parts by mass of butadiene (relative to 100 parts by mass of all monomers; the same shall apply hereinafter in this paragraph) was added and polymerized at 70 ° C. for 20 minutes.
  • a cyclohexane solution containing 9 parts by mass of styrene (styrene concentration: 20% by mass) was added, and the mixture was polymerized at 70 ° C. for 45 minutes.
  • a cyclohexane solution containing 77 parts by mass of butadiene (butadiene concentration: 20% by mass) was added, and the mixture was polymerized at 50 ° C. for 80 minutes.
  • the obtained conjugated diene-based block copolymer had a styrene content of 18% by mass, a polystyrene block content of 18% by mass, and a vinyl bond content of the butadiene portion of 73 mol%.
  • Step 2> The hydrogenation catalyst described above is added to the obtained conjugated diene-based block copolymer so that the titanium-equivalent concentration is 100 ppm with respect to the conjugated diene-based block copolymer, and the hydrogen pressure is 0.7 MPa and the temperature is 70 ° C.
  • a hydrogenation reaction was performed. After completion of the hydrogenation reaction, octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate was then added as a stabilizer at 0.3 with respect to 100 parts by mass of the conjugated diene-based block copolymer.
  • An unmodified hydrogenated conjugated diene block copolymer (a-4) was produced by adding parts by mass.
  • the obtained hydrogenated conjugated diene block copolymer (a-4) has a styrene content of 18% by mass, a butylene content of 73 mol%, a weight average molecular weight of 107,000, a molecular weight distribution of 1.2, and a hydrogenation rate. It was 99 mol%.
  • a cyclohexane solution (butadiene concentration: 20% by mass) containing 5 parts by mass of butadiene (relative to 100 parts by mass of all monomers; the same shall apply hereinafter in this paragraph) was added and polymerized at 70 ° C. for 20 minutes.
  • a cyclohexane solution containing 7 parts by mass of styrene (styrene concentration: 20% by mass) was added, and the mixture was polymerized at 70 ° C. for 45 minutes.
  • a cyclohexane solution containing 82 parts by mass of butadiene (butadiene concentration: 20% by mass) was added, and the mixture was polymerized at 50 ° C. for 80 minutes.
  • the obtained conjugated diene-based block copolymer had a styrene content of 13% by mass, a polystyrene block content of 13% by mass, and a vinyl bond amount of 78 mol% in the butadiene portion.
  • Step 2> The above-mentioned hydrogenation catalyst is added to the obtained conjugated diene-based block copolymer so that the titanium equivalent concentration is 100 ppm with respect to the block copolymer, and the hydrogenation reaction is carried out at a hydrogen pressure of 0.7 MPa and a temperature of 70 ° C. Was done.
  • a conjugated diene-based block copolymer (a-5) was produced by adding parts by mass and hydrogenating.
  • the obtained hydrogenated conjugated diene block copolymer (a-5) has a styrene content of 13% by mass, a butylene content of 78 mol%, a weight average molecular weight of 160,000, a molecular weight distribution of 1.2, and a hydrogenation rate. It was 99 mol%.
  • a cyclohexane solution (styrene concentration: 20% by mass) containing 6.5 parts by mass of styrene (relative to 100 parts by mass of all monomers; the same shall apply hereinafter in this paragraph) was added, and the mixture was polymerized at 70 ° C. for 45 minutes.
  • a cyclohexane solution containing 87 parts by mass of butadiene (butadiene concentration: 20% by mass) was added, and the mixture was polymerized at 50 ° C. for 80 minutes.
  • a cyclohexane solution containing 6.5 parts by mass of styrene (styrene concentration: 20% by mass) was added, and the mixture was polymerized at 70 ° C. for 45 minutes.
  • methanol was added to obtain a conjugated diene-based block copolymer.
  • the obtained conjugated diene-based block copolymer had a styrene content of 13% by mass, a polystyrene block content of 13% by mass, and a vinyl bond amount of 78 mol% in the butadiene portion.
  • Step 2> The above-mentioned hydrogenation catalyst is added to the obtained conjugated diene-based block copolymer so that the titanium-equivalent concentration is 100 ppm with respect to the block copolymer, and the hydrogenation reaction is carried out at a hydrogen pressure of 0.7 MPa and a temperature of 70 ° C. Was done.
  • a conjugated diene-based block copolymer (a-6) was produced by adding parts by mass and hydrogenating.
  • the obtained hydrogenated conjugated diene block copolymer (a-6) has a styrene content of 13% by mass, a butylene content of 78 mol%, a weight average molecular weight of 160,000, a molecular weight distribution of 1.2, and a hydrogenation rate. It was 99 mol%.
  • a cyclohexane solution (butadiene concentration: 20% by mass) containing 10 parts by mass of butadiene (relative to 100 parts by mass of all monomers; the same shall apply hereinafter in this paragraph) was added and polymerized at 65 ° C. for 20 minutes.
  • 1.50 mol of TMEDA was added to 1 mol of n-butyllithium, and 0.05 mol of sodium-t-pentoxide was added to 1 mol of n-butyllithium, and then a cyclohexane solution containing 85 parts by mass of butadiene (butadiene concentration). : 20% by mass) was added and polymerized at 60 ° C. for 70 minutes.
  • the obtained conjugated diene-based block copolymer has a styrene content of 5% by mass, a polystyrene block content of 5% by mass, and a polymer block mainly composed of a conjugated diene monomer unit (hereinafter, also referred to as "butadiene portion").
  • the vinyl bond amount was 78 mol%.
  • Step 2> The above-mentioned hydrogenation catalyst is added to the obtained conjugated diene-based block copolymer so that the titanium equivalent concentration is 100 ppm with respect to the block copolymer, and the hydrogenation reaction is carried out at a hydrogen pressure of 0.7 MPa and a temperature of 70 ° C. Was done.
  • a conjugated diene-based block copolymer (a-7) was produced by adding parts by mass and hydrogenating.
  • the obtained hydrogenated conjugated diene block copolymer (a-7) has a styrene content of 5% by mass, a butylene content of 78 mol%, a weight average molecular weight of 249000, a molecular weight distribution of 1.2, and a hydrogenation rate. It was 99 mol%.
  • a cyclohexane solution (butadiene concentration: 20% by mass) containing 5 parts by mass of butadiene (relative to 100 parts by mass of all monomers; the same applies hereinafter in this paragraph) was added and polymerized at 70 ° C. for 20 minutes.
  • a cyclohexane solution containing 21.5 parts by mass of styrene (styrene concentration: 20% by mass) was added, and the mixture was polymerized at 70 ° C. for 45 minutes.
  • a cyclohexane solution containing 52 parts by mass of butadiene (butadiene concentration: 20% by mass) was added, and the mixture was polymerized at 50 ° C. for 80 minutes.
  • the obtained conjugated diene-based block copolymer had a styrene content of 43% by mass, a polystyrene block content of 43% by mass, and a vinyl bond content of the butadiene portion of 78 mol%.
  • Step 2> The above-mentioned hydrogenation catalyst was added to the obtained block copolymer so that the titanium equivalent concentration was 100 ppm with respect to the block copolymer, and the hydrogenation reaction was carried out at a hydrogen pressure of 0.7 MPa and a temperature of 70 ° C. ..
  • a conjugated diene-based block copolymer (a-8) was produced by adding parts by mass and hydrogenating.
  • the obtained hydrogenated conjugated diene block copolymer (a-8) has a styrene content of 43% by mass, a butylene content of 78 mol%, a weight average molecular weight of 103,000, a molecular weight distribution of 1.2, and hydrogenation. The rate was 99 mol%.
  • a cyclohexane solution (styrene concentration: 20% by mass) containing 16 parts by mass of styrene (relative to 100 parts by mass of all monomers; the same shall apply hereinafter in this paragraph) was added to the reactor and polymerized at 70 ° C. for 45 minutes. ..
  • a cyclohexane solution containing 68 parts by mass of butadiene (butadiene concentration: 20% by mass) was added, and the mixture was polymerized at 70 ° C. for 1.5 hours.
  • a cyclohexane solution containing 16 parts by mass of styrene (styrene concentration: 20% by mass) was added, and the mixture was polymerized at 70 ° C. for 45 minutes.
  • methanol was added to obtain a conjugated diene-based block copolymer as Step 1.
  • the obtained conjugated diene-based block copolymer had a styrene content of 32% by mass, a polystyrene block content of 32% by mass, and a vinyl bond content of the butadiene portion of 36 mol%.
  • Step 2> The hydrogenation catalyst described above is added to the obtained conjugated diene-based block copolymer so that the titanium-equivalent concentration is 100 ppm with respect to the conjugated diene-based block copolymer, and the hydrogen pressure is 0.7 MPa and the temperature is 70 ° C. A hydrogenation reaction was carried out.
  • octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate was then added as a stabilizer at 0.3 with respect to 100 parts by mass of the conjugated diene-based block copolymer.
  • a conjugated diene-based block copolymer was added by mass and hydrogenated to produce a hydrogenated conjugated diene-based block copolymer.
  • the obtained hydrogenated conjugated diene block copolymer (a-9-1) has a styrene content of 32% by mass, a butylene content of 36 mol%, a weight average molecular weight of 285,000, a molecular weight distribution of 1.2, and hydrogen.
  • the addition rate was 99 mol%.
  • Tris (2,4-di-tert-butylphenoxy) phosphine was added to (a-9-1) so as to be 10 ppm, 50 ppm, and 100 ppm in terms of phosphorus atoms, and (a-9-2), ( A-9-3) and (a-9-4) were obtained, respectively.
  • the obtained hydrogenated block copolymer solution was decalcified as shown below to reduce the amount of metal caused by the initiator and hydrogenated catalyst. That is, after the completion of watering, 30 parts by mass of a mixed solution of water / sulfuric acid was added to 100 parts by mass of the hydrogenated block copolymer. The amount of sulfuric acid added was adjusted so that the pH of the water removed by the decanter in the subsequent step was 7.0. Most of the water was removed from the solution by decanter until the amount of water reached 3 parts by mass, and 0.4 mol of carbon dioxide gas was added to 1 mol of the metal as an initiator and mixed.
  • octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate was added as a stabilizer.
  • the solution is subjected to the steam stripping method described in Japanese Patent Publication No. 05-54845 (after removing most of the solvent in water at 90 to 98 ° C., an aqueous dispersion slurry having a crumb concentration of about 5% by weight is subjected to a twin-screw extruder.
  • the hydrogenated block copolymers (a-9-5) and (a-9-6) were obtained by a method of removing the solvent by throwing them into the water.
  • the obtained hydrogenated conjugated diene-based block copolymer (a-9-1) is freeze-ground, and the looseness specific gravity and the dispersity become the values shown in the table (a-9-7) to (a). -9-11) were obtained respectively.
  • the obtained hydrogenated conjugated diene-based block copolymer (a-9-1) was freeze-crushed, and the looseness specific gravity and dispersity were set to the values shown in the table, and the conjugated diene-based block copolymer was made amorphous.
  • (A-9-12) and (a-9-13) coated with 1000 ppm of silica and calcium stearate were obtained, respectively.
  • a cyclohexane solution (styrene concentration: 20% by mass) containing 16 parts by mass of styrene (relative to 100 parts by mass of all monomers; the same shall apply hereinafter in this paragraph) was added to the reactor and polymerized at 70 ° C. for 45 minutes. ..
  • a cyclohexane solution containing 68 parts by mass of butadiene (butadiene concentration: 20% by mass) was added, and the mixture was polymerized at 70 ° C. for 1.5 hours.
  • a cyclohexane solution containing 16 parts by mass of styrene (styrene concentration: 20% by mass) was added, and the mixture was polymerized at 70 ° C.
  • DMI 1,3-dimethyl-2-imidazolidinone
  • methanol was added to obtain a modified conjugated diene-based block copolymer as Step 1.
  • the obtained conjugated diene-based block copolymer had a styrene content of 32% by mass, a polystyrene block content of 32% by mass, and a vinyl bond content of the butadiene portion of 36 mol%.
  • Step 2> The hydrogenation catalyst described above was added to the obtained modified conjugated diene-based block copolymer so that the titanium-equivalent concentration was 100 ppm with respect to the modified conjugated diene-based block copolymer, and the hydrogen pressure was 0.7 MPa and the temperature was 70. The hydrogenation reaction was carried out at ° C.
  • octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate was then added as a stabilizer to 100 parts by mass of the modified conjugated diene-based block copolymer. 3 parts by mass was added to produce a hydrogenated modified conjugated diene-based block copolymer.
  • the obtained hydrogenated conjugated diene block copolymer (a-10) has a styrene content of 32% by mass, a butylene content of 36 mol%, a weight average molecular weight of 75,000, a molecular weight distribution of 1.2, and a hydrogenation rate.
  • the modification rate was 72 mol% and the modification rate was 65% (the number of modifying groups per polymer chain was 0.65).
  • a conjugated diene-based polymer was produced using the following materials.
  • Maleic anhydride manufactured by Fuso Chemical Industry Co., Ltd.
  • Radical initiator Perhexa 25B (manufactured by NOF CORPORATION)
  • a cyclohexane solution (styrene concentration: 20% by mass) containing 16 parts by mass of styrene (relative to 100 parts by mass of all monomers; the same shall apply hereinafter in this paragraph) was added to the reactor and polymerized at 70 ° C. for 45 minutes. ..
  • a cyclohexane solution containing 68 parts by mass of butadiene (butadiene concentration: 20% by mass) was added, and the mixture was polymerized at 70 ° C. for 1.5 hours.
  • a cyclohexane solution containing 16 parts by mass of styrene (styrene concentration: 20% by mass) was added, and the mixture was polymerized at 70 ° C. for 45 minutes.
  • methanol was added to obtain a conjugated diene-based block copolymer as Step 1.
  • the obtained conjugated diene-based block copolymer had a styrene content of 32% by mass, a polystyrene block content of 32% by mass, and a vinyl bond content of the butadiene portion of 36 mol%.
  • Step 2> The hydrogenation catalyst described above is added to the obtained conjugated diene-based block copolymer so that the titanium-equivalent concentration is 100 ppm with respect to the conjugated diene-based block copolymer, and the hydrogen pressure is 0.7 MPa and the temperature is 70 ° C. A hydrogenation reaction was carried out.
  • octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate was then added as a stabilizer at 0.3 with respect to 100 parts by mass of the conjugated diene-based block copolymer.
  • a conjugated diene-based block copolymer was added by mass and hydrogenated to produce a hydrogenated conjugated diene-based block copolymer.
  • the obtained hydrogenated conjugated diene block copolymer (a-11) has a styrene content of 32% by mass, a butylene content of 36 mol%, a weight average molecular weight of 287,000, a molecular weight distribution of 1.2, and a hydrogenation rate. It was 75 mol%.
  • the obtained hydrogenated conjugated diene block copolymer (a-12) has a styrene content of 32% by mass, a butylene content of 36 mol%, a weight average molecular weight of 190,000, a molecular weight distribution of 1.2, and a hydrogenation rate. It was 99 mol%.
  • (A-13-1) had a styrene content of 32% by mass, a butylene content of 36 mol%, a weight average molecular weight of 351,000, a molecular weight distribution of 1.2, and a hydrogenation rate of 99 mol%.
  • the styrene content was 32% by mass, the butylene content was 58 mol%, the weight average molecular weight was 351,000, the molecular weight distribution was 1.2, and the hydrogenation rate was 99 mol%.
  • A-15-1) had a styrene content of 32% by mass, a butylene content of 36 mol%, a weight average molecular weight of 451,000, a molecular weight distribution of 1.2, and a hydrogenation rate of 99 mol%.
  • Tris (2,4-di-tert-butylphenoxy) phosphine was added to (a-13-1) so as to be 10 ppm, 50 ppm, and 100 ppm in terms of phosphorus atoms, and (a-13-2), ( A-13-3) and (a-13-4) were obtained, respectively.
  • the obtained hydrogenated block copolymer solution was decalcified as shown below to reduce the amount of metal caused by the initiator and hydrogenated catalyst. That is, after the completion of watering, 30 parts by mass of a mixed solution of water / sulfuric acid was added to 100 parts by mass of the hydrogenated block copolymer. The amount of sulfuric acid added was adjusted so that the pH of the water removed by the decanter in the subsequent step was 7.0. Most of the water was removed from the solution by decanter until the amount of water reached 3 parts by mass, and 0.4 mol of carbon dioxide gas was added to 1 mol of the metal as an initiator and mixed.
  • octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate was added as a stabilizer.
  • the solution is subjected to the steam stripping method described in Japanese Patent Publication No. 05-54845 (after removing most of the solvent in water at 90 to 98 ° C., an aqueous dispersion slurry having a crumb concentration of about 5% by weight is subjected to a twin-screw extruder.
  • the hydrogenated block copolymers (a-13-5) and (a-13-6) were obtained by a method of removing the solvent by throwing them into the water.
  • the obtained hydrogenated conjugated diene-based block copolymer (a-13-1) is freeze-ground, and the looseness specific gravity and the dispersity become the values shown in the table (a-13-7) to (a). -13-11) were obtained respectively.
  • the obtained hydrogenated conjugated diene block copolymer (a-13-1) was freeze-crushed, and the loose bulk specific gravity and the dispersity were set to the values shown in the table, and the conjugated diene block copolymer was made amorphous.
  • Tris (2,4-di-tert-butylphenoxy) phosphine was added to (a-15-1) so as to be 10 ppm, 50 ppm, and 100 ppm in terms of phosphorus atoms, and (a-15-2), ( A-15-3) and (a-15-4) were obtained, respectively.
  • the obtained hydrogenated block copolymer solution was decalcified as shown below to reduce the amount of metal caused by the initiator and hydrogenated catalyst. That is, after the completion of watering, 30 parts by mass of a mixed solution of water / sulfuric acid was added to 100 parts by mass of the hydrogenated block copolymer. The amount of sulfuric acid added was adjusted so that the pH of the water removed by the decanter in the subsequent step was 7.0. Most of the water was removed from the solution by decanter until the amount of water reached 3 parts by mass, and 0.4 mol of carbon dioxide gas was added to 1 mol of the metal as an initiator and mixed.
  • octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate was added as a stabilizer.
  • the solution is subjected to the steam stripping method described in Japanese Patent Publication No. 05-54845 (after removing most of the solvent in water at 90 to 98 ° C., an aqueous dispersion slurry having a crumb concentration of about 5% by weight is subjected to a twin-screw extruder.
  • the hydrogenated block copolymers (a-15-5) and (a-15-6) were obtained by a method of removing the solvent by throwing them into the water.
  • the obtained hydrogenated conjugated diene-based block copolymer (a-15-1) is freeze-ground, and the looseness specific gravity and the dispersity become the values shown in the table (a-15-7) to (a). -15-11) were obtained respectively.
  • the obtained hydrogenated conjugated diene block copolymer (a-15-1) was freeze-crushed, and the loose bulk specific gravity and the dispersity were set to the values shown in the table, and the conjugated diene block copolymer was made amorphous.
  • (A-15-12) and (a-15-13) coated with 1000 ppm of silica and calcium stearate were obtained, respectively.
  • the obtained hydrogenated conjugated diene block copolymer (a-16) has a styrene content of 19% by mass, a butylene content of 36 mol%, a weight average molecular weight of 352,000, a molecular weight distribution of 1.2, and a hydrogenation rate. It was 99 mol%.
  • a cyclohexane solution (styrene concentration: 20% by mass) containing 15 parts by mass of styrene (relative to 100 parts by mass of all monomers; the same shall apply hereinafter in this paragraph) was added to the reactor and polymerized at 70 ° C. for 45 minutes. ..
  • a cyclohexane solution containing 35 parts by mass of butadiene / 35 parts by mass of isoprene concentration of butadiene and total isoprene: 20% by mass was added, and the mixture was polymerized at 70 ° C. for 1.5 hours.
  • the obtained conjugated diene-based block copolymer had a styrene content of 30% by mass, a polystyrene block content of 30% by mass, and a vinyl bond content of the butadiene / isoprene portion of 36 mol%.
  • Step 2> The hydrogenation catalyst described above is added to the obtained conjugated diene-based block copolymer so that the titanium-equivalent concentration is 100 ppm with respect to the conjugated diene-based block copolymer, and the hydrogen pressure is 0.7 MPa and the temperature is 70 ° C. A hydrogenation reaction was carried out.
  • octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate was then added as a stabilizer at 0.3 with respect to 100 parts by mass of the conjugated diene-based block copolymer.
  • a conjugated diene-based block copolymer was added by mass and hydrogenated to produce a hydrogenated conjugated diene-based block copolymer.
  • the obtained hydrogenated conjugated diene block copolymer (a-17) has a styrene content of 30% by mass, a butylene content of 36 mol%, a weight average molecular weight of 450,000, a molecular weight distribution of 1.2, and a hydrogenation rate. It was 99 mol%.
  • a cyclohexane solution (styrene concentration: 20% by mass) containing 20 parts by mass of styrene (relative to 100 parts by mass of all monomers; the same shall apply hereinafter in this paragraph) was added to the reactor and polymerized at 45 ° C. for 30 minutes. ..
  • a cyclohexane solution containing 80 parts by mass of butadiene (butadiene concentration: 20% by mass) was added, and the mixture was polymerized at 80 ° C. for 1.0 hour.
  • 0.27 mol of tetramethoxysilane was added to 1 mol of n-butyllithium to carry out a coupling reaction. After completion of the reaction, methanol was added to obtain a conjugated diene-based block copolymer as Step 1.
  • the obtained conjugated diene-based block copolymer had a styrene content of 20% by mass, a polystyrene block content of 20% by mass, and a vinyl bond content of the butadiene portion of 63 mol%.
  • Step 2> The hydrogenation catalyst described above was added to the obtained conjugated diene block copolymer so that the titanium equivalent concentration was 100 ppm per 100 parts by mass of the conjugated diene block copolymer, and the hydrogen pressure was 0.7 MPa and the temperature was increased. The hydrogenation reaction was carried out at 70 ° C.
  • octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate was then added as a stabilizer at 0.3 with respect to 100 parts by mass of the conjugated diene-based block copolymer.
  • a conjugated diene-based block copolymer was added by mass and hydrogenated to produce a hydrogenated conjugated diene-based block copolymer.
  • the obtained hydrogenated conjugated diene block copolymer (a-18) has a styrene content of 20% by mass, a butylene content of 62 mol%, a weight average molecular weight of 434,000, a molecular weight distribution of 2.3, and a hydrogenation rate. It was 99 mol%.
  • the obtained hydrogenated conjugated diene block copolymer (a-19) has a styrene content of 32% by mass, a butylene content of 30 mol%, a weight average molecular weight of 180,000, a molecular weight distribution of 1.1, and a hydrogenation rate.
  • the modification rate was 87 mol% and the modification rate was 71% (the number of modifying groups per polymer chain was 0.71).
  • the obtained hydrogenated conjugated diene block copolymer (a-20) has a styrene content of 32% by mass, a butylene content of 21 mol%, a weight average molecular weight of 203,000, a molecular weight distribution of 1.1, and a hydrogenation rate.
  • the modification rate was 87 mol% and the modification rate was 71% (the number of modifying groups per polymer chain was 0.71).
  • the obtained hydrogenated conjugated diene block copolymer (a-21) has a styrene content of 32% by mass, a butylene content of 30 mol%, a weight average molecular weight of 203,000, a molecular weight distribution of 1.1, and a hydrogenation rate.
  • the modification rate was 87 mol% and the modification rate was 70% (the number of modifying groups per polymer chain was 0.70).
  • (A-22) has a styrene content of 32% by mass, a butylene content of 36 mol%, a weight average molecular weight of 252,000, a molecular weight distribution of 1.1, a hydrogenation rate of 84 mol%, and a modification rate of 71% (per polymerized chain).
  • the number of modifying groups was 0.71).
  • (A-23) has a styrene content of 32% by mass, a butylene content of 36 mol%, a weight average molecular weight of 251,000, a molecular weight distribution of 1.1, a hydrogenation rate of 84 mol%, and a modification rate of 25% (per polymerized chain). The number of modifying groups was 0.25).
  • (A-24) has a styrene content of 32% by mass, a butylene content of 36 mol%, a weight average molecular weight of 351,000, a molecular weight distribution of 1.1, a hydrogenation rate of 84 mol%, and a modification rate of 71% (per polymerized chain). The number of modifying groups was 0.71).
  • (A-25) has a styrene content of 32% by mass, a butylene content of 36 mol%, a weight average molecular weight of 450,000, a molecular weight distribution of 1.1, a hydrogenation rate of 84 mol%, and a modification rate of 71% (modifying groups per polymerized chain). The number was 0.71).
  • the obtained hydrogenated conjugated diene block copolymer (a-26) has a styrene content of 38% by mass, a butylene content of 36 mol%, a weight average molecular weight of 252,000, a molecular weight distribution of 1.1, and a hydrogenation rate.
  • the modification rate was 83 mol% and the modification rate was 70% (the number of modifying groups per polymer chain was 0.70).
  • the obtained hydrogenated conjugated diene block copolymer (a-27) has a styrene content of 42% by mass, a butylene content of 36 mol%, a weight average molecular weight of 252,000, a molecular weight distribution of 1.1, and a hydrogenation rate.
  • the modification rate was 84 mol% and the modification rate was 75% (the number of modifying groups per polymer chain was 0.75).
  • the obtained hydrogenated conjugated diene block copolymer (a-28) has a styrene content of 13% by mass, a butylene content of 36 mol%, a weight average molecular weight of 250,000, a molecular weight distribution of 1.1, and a hydrogenation rate.
  • the modification rate was 83 mol% and the modification rate was 75% (the number of modifying groups per polymer chain was 0.75).
  • the obtained hydrogenated conjugated diene block copolymer (a-29) has a styrene content of 32% by mass, a butylene content of 59 mol%, a weight average molecular weight of 250,000, a molecular weight distribution of 1.1, and a hydrogenation rate.
  • the modification rate was 83 mol% and the modification rate was 75% (the number of modifying groups per polymer chain was 0.75).
  • the obtained hydrogenated conjugated diene block copolymer (a-30) has a styrene content of 32% by mass, a butylene content of 36 mol%, a weight average molecular weight of 351,000, a molecular weight distribution of 1.1, and a hydrogenation rate.
  • the modification rate was 90 mol% (the number of modifying groups per polymer chain was 0.9).
  • the obtained hydrogenated conjugated diene block copolymer (a-31) has a styrene content of 32% by mass, a butylene content of 36 mol%, a weight average molecular weight of 351,000, a molecular weight distribution of 1.1, and a hydrogenation rate.
  • the modification rate was 90 mol% (the number of modifying groups per polymer chain was 0.9).
  • the obtained hydrogenated conjugated diene block copolymer (a-32) has a styrene content of 13% by mass, a butylene content of 36 mol%, a weight average molecular weight of 151,000, a molecular weight distribution of 1.2, and a hydrogenation rate.
  • the modification rate was 87 mol% and the modification rate was 80% (the number of modifying groups per polymer chain was 0.80).
  • the obtained hydrogenated conjugated diene block copolymer (a-33) has a styrene content of 32% by mass, a butylene content of 38 mol%, a weight average molecular weight of 60,000, a molecular weight distribution of 1.2, and a hydrogenation rate.
  • the modification rate was 87 mol% and the modification rate was 72% (the number of modifying groups per polymer chain was 0.72).
  • the obtained hydrogenated conjugated diene block copolymer (a-34) has a styrene content of 25% by mass, a butylene content of 54 mol%, a weight average molecular weight of 90,000, a molecular weight distribution of 1.2, and a hydrogenation rate.
  • the modification rate was 98 mol% and the modification rate was 90% (the number of modifying groups per polymer chain was 0.9).
  • Manufacturing Example 45 Manufacturing of Modified Conjugated Diene Block Copolymer (aa-10) 100 parts by mass of a hydrogenated conjugated diene polymer (a-13) in pellet form, 1.5 parts by mass of maleic anhydride, and 0.10 parts by mass of perhexa 25B, each component in the dry blend.
  • a maleic anhydride-conjugated diene polymer (aa-10) was produced in the same manner as in Production Example 11 except that the cylinder set temperature was changed to 240 ° C.
  • PVDF Polyvinylidene fluoride (polyvinylidene fluoride, manufactured by Kureha Corporation, KF-1100) was used as the binder (a-36).
  • Examples 1 to 85 are conjugated diene-based polymers having excellent adhesiveness and electrochemical stability, and have a low water content, and are suitable as an all-solid-state battery binder. I understood it. Among them, a binder having a high molecular weight having a modifying group has an excellent balance of adhesiveness, binding property and volatility, and even a binder having a small modifying group equivalent and having a high molecular weight as in Examples 65 to 80 has high binding property. It turned out to show. It was also found that the binder having few modifying groups has excellent dispersibility of the conductive auxiliary agent even if it is polymerized.
  • the modified conjugated diene block copolymer of the present invention has industrial applicability as a binder for batteries such as all-solid-state batteries.

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Abstract

L'invention concerne un liant de batterie tout solide qui contient un polymère à base de diène conjugué qui comprend un bloc polymère ayant une unité monomère aromatique vinylique en tant que composant principal, et qui a un poids moléculaire moyen en poids de 40 000 à 2 000 000.
PCT/JP2021/048110 2020-12-25 2021-12-24 Liant de batterie tout solide utilisant un polymère à base de diène conjugué, couche d'électrode positive, couche d'électrode négative, et couche d'électrolyte utilisant ledit liant, et batterie tout solide comprenant ledit liant et lesdites couches WO2022138896A1 (fr)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2024111212A1 (fr) * 2022-11-24 2024-05-30 パナソニックホールディングス株式会社 Plaque d'électrode, et batterie
WO2024111213A1 (fr) * 2022-11-24 2024-05-30 パナソニックホールディングス株式会社 Plaque d'électrode, et batterie
WO2024111211A1 (fr) * 2022-11-24 2024-05-30 パナソニックホールディングス株式会社 Collecteur, plaque d'électrode, et batterie

Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH103943A (ja) * 1996-06-14 1998-01-06 Matsushita Electric Ind Co Ltd 全固体リチウム電池
JP2010186682A (ja) * 2009-02-13 2010-08-26 Toyota Motor Corp 固体電解質層の製造方法
JP2011134675A (ja) * 2009-12-25 2011-07-07 Toyota Motor Corp 電極層、固体電解質層および全固体二次電池
JP2012178256A (ja) * 2011-02-25 2012-09-13 Toyota Motor Corp イオン伝導体材料、固体電解質層、電極活物質層および全固体電池
JP2012243476A (ja) * 2011-05-17 2012-12-10 Nippon Zeon Co Ltd 全固体二次電池の製造方法
WO2013065738A2 (fr) * 2011-10-31 2013-05-10 日本ゼオン株式会社 Batterie secondaire entièrement solide
WO2013146896A1 (fr) * 2012-03-28 2013-10-03 日本ゼオン株式会社 Batterie secondaire entièrement à l'état solide
WO2016194705A1 (fr) * 2015-05-29 2016-12-08 富士フイルム株式会社 Composition d'électrolyte solide, feuille d'électrode pour batterie secondaire entièrement solide, batterie secondaire entièrement solide, et procédé de fabrication de feuille d'électrode pour batterie secondaire entièrement solide et de batterie secondaire entièrement solide
WO2021039949A1 (fr) * 2019-08-30 2021-03-04 富士フイルム株式会社 Composition contenant un électrolyte solide inorganique, feuille pour batterie secondaire tout à l'état solide, batterie secondaire tout à l'état solide, et procédés de fabrication de feuille pour batterie secondaire tout à l'état solide et batterie secondaire tout à l'état solide
WO2021187273A1 (fr) * 2020-03-17 2021-09-23 Jsr株式会社 Composition de liant pour batteries secondaires entièrement solides, boue pour batteries secondaires entièrement solides, feuille d'électrolyte solide pour batteries secondaires entièrement solides, procédé de fabrication de ladite feuille d'électrolyte solide pour batteries secondaires entièrement solides, batterie secondaire entièrement solide et procédé de fabrication de ladite batterie secondaire entièrement solide

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2008087966A1 (fr) * 2007-01-16 2008-07-24 Zeon Corporation Composition de liant, laitier pour électrode, électrode et batterie secondaire électrolytique non aqueuse
JPWO2011086983A1 (ja) * 2010-01-15 2013-05-20 Jsr株式会社 全固体型電池用バインダー組成物および全固体型電池電極用スラリー
WO2017018456A1 (fr) * 2015-07-30 2017-02-02 富士フイルム株式会社 Composition d'électrolyte solide, feuille d'électrode pour batterie secondaire tout solide, batterie secondaire tout solide, et procédés de fabrication de feuille d'électrode pour batterie secondaire tout solide et batterie secondaire tout solide

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH103943A (ja) * 1996-06-14 1998-01-06 Matsushita Electric Ind Co Ltd 全固体リチウム電池
JP2010186682A (ja) * 2009-02-13 2010-08-26 Toyota Motor Corp 固体電解質層の製造方法
JP2011134675A (ja) * 2009-12-25 2011-07-07 Toyota Motor Corp 電極層、固体電解質層および全固体二次電池
JP2012178256A (ja) * 2011-02-25 2012-09-13 Toyota Motor Corp イオン伝導体材料、固体電解質層、電極活物質層および全固体電池
JP2012243476A (ja) * 2011-05-17 2012-12-10 Nippon Zeon Co Ltd 全固体二次電池の製造方法
WO2013065738A2 (fr) * 2011-10-31 2013-05-10 日本ゼオン株式会社 Batterie secondaire entièrement solide
WO2013146896A1 (fr) * 2012-03-28 2013-10-03 日本ゼオン株式会社 Batterie secondaire entièrement à l'état solide
WO2016194705A1 (fr) * 2015-05-29 2016-12-08 富士フイルム株式会社 Composition d'électrolyte solide, feuille d'électrode pour batterie secondaire entièrement solide, batterie secondaire entièrement solide, et procédé de fabrication de feuille d'électrode pour batterie secondaire entièrement solide et de batterie secondaire entièrement solide
WO2021039949A1 (fr) * 2019-08-30 2021-03-04 富士フイルム株式会社 Composition contenant un électrolyte solide inorganique, feuille pour batterie secondaire tout à l'état solide, batterie secondaire tout à l'état solide, et procédés de fabrication de feuille pour batterie secondaire tout à l'état solide et batterie secondaire tout à l'état solide
WO2021187273A1 (fr) * 2020-03-17 2021-09-23 Jsr株式会社 Composition de liant pour batteries secondaires entièrement solides, boue pour batteries secondaires entièrement solides, feuille d'électrolyte solide pour batteries secondaires entièrement solides, procédé de fabrication de ladite feuille d'électrolyte solide pour batteries secondaires entièrement solides, batterie secondaire entièrement solide et procédé de fabrication de ladite batterie secondaire entièrement solide

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2024111212A1 (fr) * 2022-11-24 2024-05-30 パナソニックホールディングス株式会社 Plaque d'électrode, et batterie
WO2024111213A1 (fr) * 2022-11-24 2024-05-30 パナソニックホールディングス株式会社 Plaque d'électrode, et batterie
WO2024111211A1 (fr) * 2022-11-24 2024-05-30 パナソニックホールディングス株式会社 Collecteur, plaque d'électrode, et batterie

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