WO2025005120A1 - 非水二次電池用分散剤ポリマー、非水二次電池用組成物、全固体二次電池用シート及び全固体二次電池、並びに、全固体二次電池用シート及び全固体二次電池の製造方法 - Google Patents

非水二次電池用分散剤ポリマー、非水二次電池用組成物、全固体二次電池用シート及び全固体二次電池、並びに、全固体二次電池用シート及び全固体二次電池の製造方法 Download PDF

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WO2025005120A1
WO2025005120A1 PCT/JP2024/023136 JP2024023136W WO2025005120A1 WO 2025005120 A1 WO2025005120 A1 WO 2025005120A1 JP 2024023136 W JP2024023136 W JP 2024023136W WO 2025005120 A1 WO2025005120 A1 WO 2025005120A1
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group
secondary battery
polymer
solid
present
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French (fr)
Japanese (ja)
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浩司 安田
裕三 永田
郁雄 木下
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Fujifilm Corp
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Fujifilm Corp
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Priority to JP2025530161A priority patent/JPWO2025005120A1/ja
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • the present invention relates to a dispersant polymer for non-aqueous secondary batteries, a composition for non-aqueous secondary batteries, a sheet for all-solid-state secondary batteries and an all-solid-state secondary battery, and a method for manufacturing the sheet for all-solid-state secondary batteries and the all-solid-state secondary battery.
  • a non-aqueous electrolyte secondary battery (also called a non-aqueous secondary battery) is a storage battery that has a negative electrode, a positive electrode, and a non-aqueous electrolyte between the negative electrode and the positive electrode, and is capable of charging and discharging by moving specific metal ions such as lithium ions back and forth between the two electrodes.
  • non-aqueous secondary batteries non-aqueous electrolyte secondary batteries using organic electrolytes and all-solid-state secondary batteries using solid electrolyte layers are used for a wide range of applications.
  • all-solid-state secondary batteries are made of solid negative electrodes, electrolytes, and positive electrodes, and can greatly improve the safety and reliability that are issues with non-aqueous electrolyte secondary batteries. It is also said that they can be made to have a long life. Furthermore, all-solid-state secondary batteries can be structured so that the electrodes and solid electrolyte are directly arranged in series. Therefore, all-solid-state secondary batteries can achieve higher energy density than non-aqueous electrolyte secondary batteries, and are expected to be used in electric vehicles or large storage batteries.
  • Constituent layers in nonaqueous electrolyte secondary batteries are usually formed using compositions (constituent layer forming materials) containing raw material compounds constituting each layer such as active material and inorganic solid electrolyte, as well as a dispersant for dispersing the raw material compounds, a binder for binding the raw material compounds, etc., in consideration of improving productivity, etc. Therefore, the dispersant, binder, and constituent layer forming material have been studied.
  • this (meth)acrylic polymer include 2-hydroxyethyl methacrylate, Blenmer PME-200, and (meth)acrylic polymer-10 obtained by copolymerizing ethylhexyl acrylate and acrylic acid.
  • ⁇ 3> The dispersant polymer for a non-aqueous secondary battery according to ⁇ 1> or ⁇ 2>, in which the SP value of the polymer chain in the dispersant polymer for a non-aqueous secondary battery is 15.0 to 25.0 MPa 1/2 .
  • ⁇ 4> The dispersant polymer for a non-aqueous secondary battery according to any one of ⁇ 1> to ⁇ 3>, which has a multi-branched structure having a core portion and at least three polymeric arm portions.
  • ⁇ 5> The dispersant polymer for a nonaqueous secondary battery according to any one of ⁇ 1> to ⁇ 4>, which is a hyperbranched polymer represented by the following formula (1):
  • L represents an n-valent linking group.
  • the expression of a compound is used to mean not only the compound itself, but also its salts and ions. It also means to include derivatives that are partially modified by introducing a substituent or the like within the scope that does not impair the effects of the present invention.
  • the term "(meth)acrylic” refers to either or both of acrylic and methacrylic. The same applies to (meth)acrylate.
  • the substituents, linking groups, etc. hereinafter referred to as substituents, etc.) that are not specified as substituted or unsubstituted may have an appropriate substituent.
  • this YYY group includes an embodiment that has a substituent in addition to an embodiment that has no substituent.
  • a preferred substituent is, for example, the substituent Z described below.
  • the respective substituents etc. may be the same or different from each other.
  • multiple substituents etc. may be linked to each other or condensed to form a ring.
  • a polymer means a polymeric material.
  • the main chain of a polymer refers to a linear molecular chain in which all other molecular chains constituting the polymer can be regarded as branched chains or pendant groups relative to the main chain.
  • the longest chain among the molecular chains constituting the polymer becomes the main chain, although this depends on the weight average molecular weight of the branched chains considered as branched chains or pendant groups.
  • the terminal groups at the polymer ends are not included in the main chain.
  • the side chain of a polymer refers to branched chains other than the main chain, including short chains and long chains (graft chains).
  • the terminal group of a polymer is not particularly limited, and may have an appropriate group depending on the polymerization method, etc.
  • Examples of the terminal group include a hydrogen atom, an alkyl group, an aryl group, a hydroxyl group, and even a residue of a polymerization initiator.
  • the dispersant polymer for a non-aqueous secondary battery of the present invention contains a polymer chain and a constituent component (X) having a molecular weight of 400 or more, and has a viscosity of 0.10 to 10,000 Pa s at a temperature of 25° C. and a shear rate of 1 s -1 .
  • the polymer of the present invention can disperse solid particles in a dispersion medium in a short time even if the solid content of the non-aqueous secondary battery composition (constituent layer forming material) to be prepared is increased, and can reduce the dispersion energy and load acting on the solid particles during dispersion, thereby suppressing damage such as deterioration and decomposition of the solid particles.
  • the polymer of the present invention can realize a non-aqueous secondary battery composition that has excellent solid particle dispersion characteristics, and preferably has a moderate viscosity, high fluidity, and excellent characteristics (handling properties) for forming a good coating film.
  • this excellent non-aqueous secondary battery composition as a constituent layer forming material, a non-aqueous secondary battery sheet having a constituent layer with low resistance (high conductivity), and more preferably a flat and good surface property, and a non-aqueous secondary battery that has low resistance and excellent cycle characteristics can be realized.
  • the polymer of the present invention functions as a dispersant that disperses solid particles in a dispersion medium while shortening the dispersion time and reducing the load acting on the solid particles, etc. That is, the dispersant polymer for a non-aqueous secondary battery of the present invention can be said to be a dispersant containing a polymer that contains a polymer chain, has a constituent component (X) with a molecular weight of 400 or more, and has a viscosity of 0.10 to 10,000 Pa s at a temperature of 25° C. and a shear rate of 1 s ⁇ 1 .
  • the polymer of the present invention can function as a binder that adsorbs to solid particles in a constituent layer formed from the composition for a non-aqueous secondary battery to bind the solid particles and further binds the current collector and the solid particles.
  • the polymer of the present invention may or may not have a function of binding the solid particles.
  • the adsorption of the polymer of the present invention to the solid particles includes not only physical adsorption but also chemical adsorption (adsorption by chemical bond formation, adsorption by electron transfer, etc.).
  • the polymer of the present invention which exhibits the above-mentioned excellent effects, can be preferably used as a sheet for a non-aqueous secondary battery (including an electrode sheet for a non-aqueous secondary battery) or a material for forming a constituent layer of a non-aqueous secondary battery.
  • the polymer of the present invention has a component (X) which contains a polymer chain and has a molecular weight of 400 or more.
  • the component (X) of the polymer of the present invention is a component containing a polymer chain and has a molecular weight of 400 or more.
  • this component is called the component (X).
  • This component (X) is preferably a component that does not have a polar functional group, and is one of the preferred embodiments in which it is a component that does not have a polar functional group in a partial structure other than the polymer chain.
  • the polymer chain may be present in a partial structure that will be the main chain of the polymer of the present invention, but it is preferable that the polymer chain is present in a molecular chain that will be a side chain of the polymer of the present invention, and more preferably, the polymer chain is incorporated, for example, into the inside or end of the molecular chain that will be the side chain of the polymer of the present invention.
  • a component (X) can incorporate a graft structure into the chemical structure of the polymer of the present invention, thereby enhancing the excluded volume effect.
  • the molecular chain that serves as a side chain of the polymer of the present invention refers to a molecular chain that constitutes a side chain of the polymer of the present invention into which the constituent component (X) is incorporated, and is a molecular chain other than the molecular chain that constitutes the main chain of the polymer of the present invention, usually a molecular chain bonded to a molecular chain (atomic group) that constitutes the main chain.
  • the type of polymer chain contained in one component (X) may be at least one type, and is preferably one or two types.
  • the number of polymer chains contained in one component (X) is not particularly limited, but is usually one.
  • this component (X) examples include components derived from a polycondensable compound having a polycondensable group and a polymer chain.
  • the polycondensable group is appropriately determined according to the main chain structure of the polymer of the present invention. For example, when the polymer of the present invention is a step-polymerized polymer, a condensable functional group is selected, and when the polymer of the present invention is a chain-polymerized polymer, a polymerizable group (ethylenically unsaturated group) is selected.
  • examples of the polycondensable group include, in addition to the above, a group reactive to a sulfanyl group, such as an ethylenically unsaturated group capable of ene-thiol reaction or radical polymerization, a carboxyl group capable of condensation reaction, or a halogenated alkyl group capable of thioetherification.
  • examples of the ethylenically unsaturated group include a vinyl group.
  • examples of the step-growth polymerized polymer include polymers obtained by polycondensation, polyaddition, or addition condensation of raw material compounds, such as polyurethane, polyurea, polyamide, polyimide, polyester, polysiloxane, or copolymers thereof.
  • examples of the chain-polymerized polymer include polymers having a polymer chain of carbon-carbon double bonds as the main chain, such as hydrocarbon polymers, vinyl polymers, (meth)acrylic polymers, or copolymers thereof, with (meth)acrylic polymers being preferred.
  • examples of the (meth)acrylic polymer include polymers made of (co)polymers containing 50% by mass or more of a component derived from a (meth)acrylic compound (M1) described later.
  • examples of the vinyl polymer include polymers made of copolymers containing 50% by mass or more of a component derived from a vinyl-based compound (M2) described later (however, the content of the component derived from the (meth)acrylic compound (M1) is less than 50% by mass).
  • the polymer chain of a carbon-carbon double bond refers to a polymer chain formed by polymerization of a carbon-carbon double bond (ethylenically unsaturated group), and specifically refers to a polymer chain formed by polymerization (homopolymerization or copolymerization) of a monomer having a carbon-carbon unsaturated bond.
  • the polymer chain is a molecular chain in which one or more types of repeating units are bonded together.
  • Such a polymer chain is not particularly limited, and a chain made of a normal polymer, for example, the above-mentioned step-polymerized polymer or chain-polymerized polymer, can be applied without any particular limitation.
  • a polymer chain having a repeating unit represented by the following formula (L P ) is preferred, and a polymer chain made of polyester, a polymer chain made of polyether, a polymer chain made of polysiloxane, or a polymer chain made of (meth)acrylic polymer is more preferred, and a polymer chain made of polysiloxane is even more preferred.
  • X represents a divalent substituent
  • L represents a single bond or a linking group
  • n represents the (average) degree of polymerization.
  • the substituent that can be taken as X is not particularly limited, and examples thereof include a group obtained by further removing one hydrogen atom from a group appropriately selected from the substituent Z described below, and preferably indicates a hydrocarbon group or an alkylsilylene group in terms of dispersion characteristics.
  • the hydrocarbon group that can be taken as X is not particularly limited, and examples thereof include an alkylene group, an alkenyl group, an arylene group, and the like, and an alkylene group is preferable.
  • the alkylene group that can be taken as X includes a group obtained by further removing one hydrogen atom from each corresponding group of the substituent Z described below.
  • the number of carbon atoms of the alkylene group is more preferably 1 to 8.
  • the repeating unit represented by the above formula (L P ) is an alkyleneoxy group
  • the number of carbon atoms of the alkylene group is more preferably 1 to 6.
  • the alkylsilylene group that can be taken as X is not particularly limited, and examples thereof include a -Si(R S 2 )- group in a polymer chain made of a polysiloxane described below.
  • X may have a substituent.
  • L is selected according to the type of polymer chain, for example, in the case of a chain made of a chain-polymerized polymer, it is a single bond, and in the case of a chain made of a step-growth polymer, it is a linking group.
  • the linking group that can be taken as L is not particularly limited as long as it is a group that can be bonded to another repeating unit, and is appropriately selected according to the type of polymer chain.
  • This linking group is usually a linking group having a hetero atom, and examples thereof include an ester bond (-CO-O-), an ether bond (-O-), a carbonate bond (-O-CO-), an amide bond (-CO-N(R N )-), a urethane bond (-N(R N )-CO-), a urea bond (-N(R N )-CO-N(R N )-), and an imide bond (-CO-N(R N )-CO-).
  • R N represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an aryl group having 6 to 10 carbon atoms. Any of the bonding portions of the above linking group may be bonded to the above X.
  • the linking group is more preferably an ester bond, an ether bond, a carbonate bond, or the like.
  • n indicates the (average) degree of polymerization, and may be 2 or more, and is appropriately determined taking into consideration factors such as the number average molecular weight of the polymer chain, which will be described later.
  • the degree of polymerization n is as described later.
  • two or more repeating units may be the same or different.
  • the bonding pattern is not particularly limited and may be random, alternating, or block.
  • Examples of the polymer chain having a repeating unit represented by the above formula (L P ) include a chain made of a chain-polymerized polymer and a polymer chain made of a step-growth polymer. More specifically, preferred examples include a polymer chain made of a (meth)acrylic polymer, a polymer chain made of polystyrene, a polymer chain made of polyether, a polymer chain made of polyester, a polymer chain made of polycarbonate, and a polymer chain made of polysiloxane. From the viewpoints of shortening the dispersion time and improving the dispersion characteristics, a polymer chain made of polysiloxane is more preferred.
  • the group bonded to the end of the polymer chain is not particularly limited and may be an appropriate group depending on the polymerization method, etc. Examples include a hydrogen atom, an alkyl group, an aryl group, and a hydroxyl group, and also includes the substituent that can be taken as R 16A in formula 4 described below.
  • the group bonded to the end of the polymer chain is preferably an alkyl group (having preferably 1 to 20 carbon atoms, more preferably 4 to 20 carbon atoms, and even more preferably 4 to 12 carbon atoms). This group may further have a substituent, but is preferably unsubstituted.
  • Examples of the polymer chain made of polyether include polyalkyleneoxy chains and polyaryleneoxy chains, and examples of the alkylene and arylene groups include groups in which one hydrogen atom has been further removed from an alkyl or aryl group appropriately selected from the substituent Z described below, and preferably the alkylene and arylene groups that can be taken as X above.
  • the polymer chain made of polysiloxane is preferably a polymer chain having a structure represented by -(Si(R S 2 )-O)ns-, where R S represents a hydrogen atom or a substituent, and a substituent is preferable.
  • the substituent is not particularly limited, and examples thereof include those selected from the substituent Z described below, such as a hydroxy group, an alkyl group (preferably having 1 to 12 carbon atoms, more preferably having 1 to 6 carbon atoms, and particularly preferably having 1 to 3 carbon atoms), an alkenyl group (preferably having 2 to 12 carbon atoms, more preferably having 2 to 6 carbon atoms, and particularly preferably having 2 or 3 carbon atoms), an alkoxy group (preferably having 1 to 24 carbon atoms, more preferably having 1 to 12 carbon atoms, even more preferably having 1 to 6 carbon atoms, and particularly preferably having 1 to 3 carbon atoms), an aryl group (preferably having 6 to 22 carbon atoms, more preferably having 6 to 14 carbon atoms, and particularly preferably having 6 to 10 carbon atoms), an aryloxy group (preferably having 6 to 22 carbon atoms, more preferably having 6 to 14 carbon atoms, and particularly preferably having 6 to 10 carbon atoms), an aral
  • ns indicates the degree of polymerization (average number of repetitions) of the siloxane structure, and is appropriately determined in consideration of the number average molecular weight of the polymer chain and the molecular weight of the constituent (X), which will be described later, and is preferably as described later.
  • the polysiloxane structure has a terminal group bonded to its end.
  • the terminal group is not particularly limited, and may be a hydrogen atom or a substituent.
  • the substituent that may be used as the terminal group is as described above, and may be, for example, a substituent that may be used as R 5 S.
  • the polysiloxane structure is preferably a polysiloxane structure having a chemical structure represented by the following formula 4A.
  • R 15 and R 16 represent an alkyl group or an aryl group, and Z represents a group represented by formula (Z) described later.
  • R 15 , R 16 and Z in formula 4A are the same as R 15 , R 16 and Z in formula 4 described later, respectively.
  • x1, x2, and x3 are integers of 0 or more
  • y1 is an integer of 1 to 30.
  • x1, x2, x3, and y1 in formula 4A are the same as x1, x2, x3, and y1, respectively, in formula 4 described below.
  • Polyester polymer chains include chains made of known polyesters. For example, polyester polymer chains obtained by reacting a polyol such as alkylene glycol with a polybasic acid such as an aromatic dicarboxylic acid or an aliphatic dicarboxylic acid, and polyester polymer chains obtained by ring-opening polymerization of a cyclic ester compound such as a caprolactone monomer are included.
  • a polyol such as alkylene glycol
  • a polybasic acid such as an aromatic dicarboxylic acid or an aliphatic dicarboxylic acid
  • polyester polymer chains obtained by ring-opening polymerization of a cyclic ester compound such as a caprolactone monomer are included.
  • Preferred examples of the chain made of a chain-polymerized polymer include a polymer chain made of a (meth)acrylic polymer and a polymer chain made of polystyrene.
  • the polymer chain made of (meth)acrylic polymer preferably has a component derived from (meth)acrylic compound (M1) such as (meth)acrylic acid compound, (meth)acrylic acid ester compound, (meth)acrylamide compound, (meth)acrylonitrile compound, etc., described later, and a component derived from vinyl compound (M2) described later.
  • the content of the component derived from the (meth)acrylic acid long-chain alkyl ester compound is preferably 20 to 100% by mass, and more preferably 50 to 100% by mass
  • the content of the component derived from the (meth)acrylic acid short-chain alkyl ester compound is preferably 5 to 80% by mass, and more preferably 5 to 40% by mass.
  • linking group L A1 examples include linking groups containing a structural part derived from a chain transfer agent (e.g., 3-mercaptopropionic acid) or a polymerization initiator used in the synthesis of the polymer chain, and further, linking groups in which this structural part is bonded to a structural part derived from a (meth)acrylic compound (M1) that reacts with the chain transfer agent.
  • a chain transfer agent e.g., 3-mercaptopropionic acid
  • M1 (meth)acrylic compound
  • R 11 represents a hydrogen atom or methyl.
  • B2 represents a linking group.
  • the linking group that can be taken as B2 is not particularly limited, and examples thereof include those listed as the linking groups that can be taken as the linking group L A1 above.
  • the linking group as B2 is preferably an alkylene group, an alkenylene group, an arylene group, an oxygen atom, a sulfur atom, a carbonyl group, or a group related to a combination thereof, more preferably a group containing a -CO-O- group, and particularly preferably a -CO-O- group or a -CO-O-alkylene group.
  • R 15 represents an alkyl group or an aryl group, and is preferably an alkyl group.
  • the alkyl group and aryl group that can be taken as R 15 are the same as the alkyl group and aryl group that can be taken as R S in the above polysiloxane structure, and the preferred ones are also the same.
  • R 15 is particularly preferably methyl.
  • the two R 15s bonded to the same silicon atom may be the same or different, but are preferably both methyl.
  • R 16 represents an alkyl group or an aryl group, and is preferably an alkyl group. Two R 16s bonded to the same silicon atom may be the same or different.
  • R 16 The alkyl group and aryl group that can be taken as R 16 are the same as the alkyl group and aryl group that can be taken as R S in the polysiloxane structure, and the preferred groups are also the same. However, R 16 is particularly preferably methyl.
  • R 16A represents a hydrogen atom or a substituent.
  • the substituent that can be taken by R 16A is not particularly limited, and includes the substituent Z described below, and is preferably the substituent that can be taken by the above-mentioned R S.
  • Z represents a group represented by the following formula (Z).
  • R 17 and R 18 each represent an alkyl group or an aryl group.
  • the alkyl group and aryl group that can be taken as R 17 and R 18 are the same as the alkyl group and aryl group that can be taken as R S in the polysiloxane structure, respectively, and the preferred ones are also the same.
  • R 17 and R 18 may be the same or different.
  • R 19 represents an unsubstituted alkyl group having 1 to 4 carbon atoms.
  • y2 represents an integer of 1 to 100, preferably an integer of 1 to 50, and more preferably an integer of 1 to 20.
  • x2 is preferably an integer of 0 to 50, and more preferably an integer of 0 to 20.
  • x3 is preferably an integer of 1 to 100, and more preferably an integer of 1 to 30.
  • x1, x2 and x3 in total are an integer of 1 to 100, preferably an integer of 2 to 70, and more preferably an integer of 2 to 50.
  • x1 and x3 each take an integer of 2 or more, in formula 4, two Z or R 15 bonded to the same silicon atom may be the same or different.
  • y1 is an integer of 1 to 30, preferably an integer of 1 to 20, and more preferably an integer of 1 to 10. It is preferable that x1, x2, x3, y1 and y2 are 0, x3 is an integer of 1 to 100, and y1 is an integer of 1 to 30.
  • the component (X) is not particularly limited, but is preferably a component derived from a compound obtained by introducing (substituting) a polymer chain into the polycondensable compound described below.
  • the polycondensation compound is not particularly limited as long as it is a condensation-polymerizable compound having an ethylenically unsaturated bond, and examples thereof include (meth)acrylic compounds (M1) such as (meth)acrylic acid compounds, (meth)acrylic acid ester compounds, (meth)acrylamide compounds, and (meth)acrylonitrile compounds; vinyl compounds (M2) such as vinyl aromatic compounds such as styrene compounds, vinyl naphthalene compounds, and vinyl carbazole compounds, allyl compounds, vinyl ether compounds, vinyl ester compounds, cyclic olefin compounds, diene compounds, and vinyl carboxylate compounds; and further, compounds such as dialkyl itaconate compounds and unsaturated carboxylic acid anhydrides.
  • M1 such as (me
  • styrene compounds (meth)acrylic acid compounds, (meth)acrylic acid ester compounds, and (meth)acrylamide compounds are preferred.
  • the (meth)acrylic acid ester compound include (meth)acrylic acid alkyl ester compounds and (meth)acrylic acid aryl ester compounds, with (meth)acrylic acid alkyl ester compounds being preferred.
  • the number of carbon atoms in the alkyl group constituting the (meth)acrylic acid alkyl ester compound is not particularly limited, but can be, for example, 1 to 24, preferably 1 to 12, more preferably 1 to 6, and even more preferably 1 to 4.
  • the number of carbon atoms in the aryl group constituting the aryl ester is not particularly limited, but can be, for example, 6 to 24, preferably 6 to 10, and more preferably 6.
  • this polar functional group functions as a linking group and is not a polar functional group selected from the functional group group (a).
  • the constituent (X) is derived from a compound having the above polycondensable group and the above polymer chain, even if the above linking group L A1 connecting the above polycondensable group and the above polymer chain has a polar functional group included in the functional group group (a) described below, this polar functional group does not fully exhibit the function of adsorbing or adhering to solid particles, and therefore the constituent (X) is included in an embodiment not having a polar functional group (a constituent not corresponding to the constituent (A)).
  • component (X) examples include those shown below, but the present invention is not limited thereto.
  • R 1 Y and R 1 Z represent linking groups or substituents.
  • the polymerization degree of the repeating unit is specifically shown, but can be appropriately changed in the present invention.
  • Specific examples of the component (X) represented by the above formula 4 include, for example, terminal (meth)acrylic-modified silicone compounds, specifically, those shown in each polymer synthesized in the examples described below, but the present invention is not limited thereto.
  • the constituent (X) may be a constituent derived from a macromonomer having a polymer chain, and has a molecular weight of at least 400, as long as the repeating unit has a degree of polymerization of 2 or more.
  • the constituent (X) contains a polymer chain and has a molecular weight of at least 400, the dispersibility of the solid particles is improved, making it possible to shorten the dispersion time and improve the dispersion characteristics.
  • the molecular weight of the constituent (X) is appropriately determined in consideration of the molecular weight of the polymer of the present invention, the content of the constituent (X), etc., and for example, from the viewpoint of achieving both a shortened dispersion time and an improved dispersion characteristic, it is preferably 600 or more, more preferably 800 or more, even more preferably 2000 or more, and particularly preferably 3000 or more. There is no particular restriction on the upper limit, and from the viewpoint of achieving both a shortened dispersion time and an improved dispersion characteristic, it is preferably 200,000 or less, more preferably 50,000 or less, even more preferably 20,000 or less, particularly preferably 7,000 or less, and most preferably 5,000 or less.
  • the molecular weight of the component (X) means the total molecular weight of the number average molecular weight of the polymer chain and the molecular weight of other partial structures.
  • the number average molecular weight of the polymer chain can be measured as a number average molecular weight converted into standard polystyrene in the same manner as the weight average molecular weight of the polymer of the present invention.
  • the number average molecular weight of the polymer chain and the degree of polymerization of all structural units forming the polymer chain are not particularly limited, and are appropriately determined in consideration of the molecular weight of the constituent component (X), the molecular weight of the polymer of the present invention, etc.
  • the degree of polymerization of all structural units forming the polymer chain is, for example, preferably 2 to 1,000, more preferably 2 to 200, and further preferably 6 to 80.
  • the SP value of the constituent component (X) is not particularly limited and is appropriately determined taking into consideration the SP value of the polymer of the present invention described below.
  • the polymer of the present invention preferably contains a component (A) having at least one polar functional group selected from the following functional group group (a), in that the adsorptivity or adhesion to solid particles is strengthened and the dispersion characteristics of solid particles can be improved without impairing the effect of shortening the dispersion time.
  • a functional group group
  • the component (A) is a component that does not have a polymer chain defined by the component (X) in its molecular structure, and more preferably a component that does not have a polymer chain defined by the component (X) in its molecular structure regardless of the molecular weight.
  • the polar functional group is preferably present in the molecular chain that will become the side chain of the polymer of the present invention, and more preferably incorporated, for example, inside or at the end of the molecular chain that will become the side chain of the polymer of the present invention.
  • the molecular chain serving as a side chain of the polymer of the present invention refers to a molecular chain that constitutes a side chain of the polymer of the present invention incorporating the component (A), and is a molecular chain other than the molecular chain that constitutes the main chain of the polymer of the present invention, usually a molecular chain bonded to the molecular chain (atomic group) that constitutes the main chain.
  • the polycondensable compound from which the component (A) is derived is acrylamide, it refers to a molecular chain (-CONH 2 ) that is bonded to the ethylenic double bond that is a polymerizable group.
  • Component (A) may have at least one polar functional group, and typically preferably has one to three polar functional groups.
  • the number of polar functional groups possessed by the polymer of the present invention is not particularly limited, and is appropriately determined depending on the number of polar functional groups possessed by component (A) itself, the content of component (A), the molecular weight of the polymer of the present invention, etc.
  • This component (A) may have a polar functional group, and may be, for example, a component derived from a polycondensable compound having at least one polar functional group selected from the following functional group group (a).
  • the polycondensable compound is preferably, for example, a compound having a polycondensable group, a polar functional group or a substituent having a polar functional group, and a linking group L A2 that appropriately links the polycondensable group and the substituent, and is more preferably a low molecular weight compound.
  • the molecular weight of the component (A) is not particularly limited, but is one of the preferred embodiments in which it is less than 400.
  • the component (A) may have a repeating structure in a partial structure other than the polycondensable group, or may not have a repeating structure.
  • the component (A) is preferably a compound that does not have a repeating structure in a partial structure other than the polycondensable group.
  • the polycondensable group has the same meaning as the polycondensable group in the above-mentioned component (X).
  • the substituent forming the substituent having a polar functional group is not particularly limited, but for example, a group selected from the substituent Z described below, and a polymer chain are included.
  • a polymer chain that can be taken as the substituent a polymer chain having a number average molecular weight that makes the molecular weight of the component (X) less than 400 is preferably included.
  • a polymer chain As such a polymer chain (however, the number average molecular weight is limited to that of the component (A) less than 400), although it is not particularly limited, a polymer chain having a repeating unit represented by the above-mentioned formula (L P ) in the above-mentioned component (X) is included, and a polymer chain made of polyether is preferable, and a polyalkyleneoxy chain is more preferable.
  • the substituent is preferably an alkyl group or a polyalkyleneoxy chain.
  • a substituent forming a substituent having a polar functional group can also correspond to a linking group L A2 , this substituent is interpreted as a substituent forming a substituent having a polar functional group.
  • the linking group L A2 the above-mentioned linking group L A1 which links the polycondensable group and the polymer chain in the above-mentioned constituent (X) can be used without any particular limitation.
  • the sulfonic acid group, phosphoric acid group, phosphonic acid group, and the like included in the functional group group (a) are not particularly limited, but each has the same meaning as the corresponding group of the substituent Z described later.
  • the dicarboxylic acid group is not particularly limited, but includes a group obtained by removing one or more hydrogen atoms from a dicarboxylic anhydride, and a constituent component itself formed by copolymerization of a polymerizable dicarboxylic anhydride as a polymerizable compound, and further includes a group obtained by reacting a dicarboxylic anhydride with an active hydrogen compound to cleave an anhydride group.
  • a group obtained by removing one or more hydrogen atoms from a dicarboxylic anhydride a group obtained by removing one or more hydrogen atoms from a cyclic dicarboxylic anhydride is preferable.
  • the dicarboxylic anhydride include non-cyclic dicarboxylic anhydrides such as acetic anhydride, propionic anhydride, and benzoic anhydride, and cyclic dicarboxylic anhydrides such as maleic anhydride, phthalic anhydride, fumaric anhydride, succinic anhydride, and itaconic anhydride.
  • polymerizable dicarboxylic anhydride examples include, but are not particularly limited to, dicarboxylic anhydrides having an unsaturated bond in the molecule, and preferably polymerizable cyclic dicarboxylic anhydrides. Specific examples include maleic anhydride and itaconic anhydride.
  • the active hydrogen compound is not particularly limited as long as it is a compound that reacts with a dicarboxylic anhydride group, and examples thereof include alcohol compounds, amine compounds, and thiol compounds.
  • An ether group (-O-), a thioether group (-S-), and a thioester group (*-CO-S-**, *-CS-O-**, *-CS-S-**) each mean a bond shown in parentheses.
  • An ester group (*-CO-O-**), an amide group (*-CONR NA1 -**), a urethane group (*-NR NA1 -CO-O-**), a urea group (-NR NA1 -CO-NR NA1 -), and an imide group (*-CO-NR NA2 -CO-**) each mean a bond shown in parentheses.
  • R NA1 represents a hydrogen atom or a substituent
  • R NA2 represents a bond, a hydrogen atom, or a substituent.
  • the substituents that can be taken by R NA1 and R NA2 are not particularly limited, and examples thereof include a group selected from the substituent Z described below, and an alkyl group (including a cycloalkyl group), an aryl group, a heterocyclic group, and the like are preferable.
  • the number of carbon atoms in the alkyl group is preferably 1 to 20, more preferably 1 to 12, and even more preferably 1 to 6.
  • the number of carbon atoms in the aryl group is preferably 6 to 26, more preferably 6 to 20, and even more preferably 6 to 12.
  • RNA1 is preferably a hydrogen atom
  • RNA2 is preferably a bond or a hydrogen atom.
  • either of the two bonding sites * and ** may be bonded to the main chain side of the polymer of the present invention, but it is preferable that the bonding site * is bonded to the main chain side of the polymer of the present invention.
  • the ester group does not include a partial structure that forms the main chain of the polymer of the present invention when the constituent component (A) is incorporated into the polymer of the present invention, such as an ester group that is directly bonded to the polymer chain of the carbon-carbon double bond.
  • the terminal group bonded to each of these groups is not particularly limited and represents a hydrogen atom or a substituent.
  • substituent that can be taken as the terminal group include groups selected from the substituent Z described below. Among them, an alkyl group (including a cycloalkyl group), an aryl group, and a heterocyclic group are preferable, and an alkyl group or an aryl group is more preferable.
  • the number of carbon atoms of the alkyl group is preferably 1 to 20, more preferably 2 to 12, and even more preferably 3 to 8.
  • the number of carbon atoms of the aryl group is the same as the number of carbon atoms of the aryl group that can be taken as RNA1 . In the present invention, when either the above RNA1 or the terminal group has a hydrogen atom, this hydrogen atom is interpreted as the above RNA1 .
  • ether groups are included in carboxy groups, hydroxy groups, oxetane groups, epoxy groups, dicarboxylic anhydride groups, ester groups, etc., but the -O- groups contained in these are not considered to be ether groups.
  • thioether groups Ester groups are included in urethane groups, but the -CO-O- groups contained therein are not considered to be ester groups.
  • amide groups are included in urethane groups, urea groups, imide groups, etc., but the -CO-N RN - groups contained therein are not considered to be amide groups.
  • the polar functional group may form a cyclic structure.
  • the imide group may form a cyclic imide group, specifically, a cyclic imide group derived from maleimide or phthalimide.
  • the fluoroalkyl group is a fluoroalkyl group in which at least one hydrogen atom in the alkyl group is substituted with a fluorine atom, and the molecular structure may be any of linear, branched, or cyclic, and linear or branched is preferred.
  • the number of carbon atoms in the fluoroalkyl group is not particularly limited, but is preferably 1 to 20, more preferably 1 to 12, even more preferably 2 to 8, and particularly preferably 2 to 7. It is also a preferred embodiment that the lower limit of the number of carbon atoms is 3 or more, and when the fluoroalkyl group is linear, it is also a preferred embodiment that the lower limit is 4 or more.
  • the fluoroalkyl group may have some of the hydrogen atoms substituted with fluorine atoms, or may have all of the hydrogen atoms substituted with fluorine atoms.
  • a fluoroalkyl group in which some of the hydrogen atoms are substituted with fluorine atoms is preferred
  • a fluoroalkyl group containing a methylene group (-CH 2 -) in which the carbon atom bonded to the main chain side of the polymer of the present invention is not substituted with a fluorine atom is more preferred
  • a fluoroalkyl group containing an ethylene group (-CH 2 -CH 2 -) or a propylene group (-CH 2 -CH 2 -CH 2 -) in which none of two or three consecutive carbon atoms, including the carbon atom bonded to the main chain side of the polymer of the present invention, is substituted with a fluorine atom is even more preferred.
  • the remaining alkyl group bonded to the carbon atom not substituted with a fluorine atom is preferably a perfluoroalkyl group in which all of the hydrogen atoms are substituted with fluorine atoms.
  • the fluoroalkyl group may have a substituent other than a fluorine atom, for example, a substituent that can be taken as Rf described later (excluding a fluorine atom).
  • Groups that can form salts such as sulfonic acid groups (sulfo groups), phosphoric acid groups, phosphonic acid groups, hydroxy groups, carboxy groups, and dicarboxylic acid groups, may form salts with cations.
  • sulfonic acid groups sulfo groups
  • phosphoric acid groups phosphoric acid groups
  • phosphonic acid groups hydroxy groups
  • carboxy groups and dicarboxylic acid groups
  • cations include various metal salts, and ammonium or amine salts.
  • amide groups, urethane groups, urea groups, and imide groups may form salts with anions.
  • anions include various inorganic or organic acid anions.
  • the polar substituent of component (A) is preferably a sulfonic acid group, a phosphoric acid group, a phosphonic acid group, a hydroxy group, a carboxy group, an oxetane group, an epoxy group, a dicarboxylic acid group, an ether group, an amide group, or a salt thereof, and from the viewpoint of shortening the dispersion time and improving the dispersion characteristics, an amide group, a hydroxy group, etc. are more preferable.
  • the component (A) has two or more polar functional groups
  • the combination of the polar functional groups is not particularly limited and can be appropriately determined.
  • a combination containing an amide group is preferable, and specifically, a combination of an amide group and a dicarboxylic acid group can be mentioned.
  • Component (A) usually has one polar substituent, but two or more polar functional groups may be linked to form a repeating structure as long as the molecular weight is less than 400. In the present invention, as described above, it is preferable that component (A) has one polar substituent.
  • Component (A) is not particularly limited, but is preferably a component derived from the polycondensable compound described above, a component derived from a compound obtained by introducing (substituting) the polar functional group into the polycondensable compound described above, a component derived from a compound having the polar functional group introduced into the polymer chain (provided that the molecular weight is less than 400), or a component derived from a maleimide compound, an N-vinyl substituted imide compound, or a vinyl succinimide compound, more preferably a component derived from a (meth)acrylic acid compound, a component derived from a compound having the polar functional group introduced into a (meth)acrylic acid ester compound, or a component derived from a (meth)acrylamide compound, and even more preferably a compound having the polar functional group introduced into a (meth)acrylic acid alkyl ester, or a component derived from a (meth)acrylamide compound.
  • Examples of the (meth)acrylamide compound include (meth)acrylamide compounds such as N-unsubstituted (meth)acrylamide compounds and N-mono- or di-substituted (meth)acrylamide compounds, and more specifically, N-unsubstituted (meth)acrylamide compounds, N-alkyl (meth)acrylamide compounds, N,N-dialkyl (meth)acrylamide compounds, N-aryl (meth)acrylamide compounds, and N,N-diaryl (meth)acrylamide compounds are preferred.
  • examples of the substituent substituting the nitrogen atom include RNA1 or a terminal group bonded to the end of the amide bond, and an alkyl group or an aryl group is preferred.
  • the (meth)acrylamide compound a compound leading to a group having a chemical structure represented by formula (A1) described later is also preferred.
  • the compound that leads to the component (A) containing an amide group include, in addition to (meth)acrylamide compounds, vinyl compounds containing an amide group, (meth)acrylate compounds containing an amide group, and (meth)acrylamide compounds containing an amide group.
  • the amide group of the component (A) may be a sulfonamide group.
  • Examples of compounds that lead to the component (A) containing a sulfonamide group include vinyl aromatic sulfonamide compounds, (meth)acrylic compounds (M1) containing a sulfonamide group, etc., and preferably include compounds in which a sulfonamide group is introduced into a vinyl aromatic compound such as a styrene compound or a vinyl naphthalene compound, etc., and more preferably include vinylbenzenesulfonamide, etc.
  • the compound that leads to the component (A) containing a sulfonamide group may be an N-mono- or di-substituted sulfonamide compound, and examples of the substituent that replaces the nitrogen atom of the sulfonamide group include RNA1 or a terminal group that is bonded to the end of the amide bond, and an alkyl group is preferred.
  • Examples of the (meth)acrylic acid ester compound from which the component (A) is derived include (meth)acrylic acid alkyl ester compounds and (meth)acrylic acid aryl ester compounds, with (meth)acrylic acid alkyl ester compounds being preferred.
  • the number of carbon atoms in the alkyl group constituting the (meth)acrylic acid alkyl ester compound is not particularly limited, but can be, for example, 1 to 24.
  • the number of carbon atoms in the alkyl group is usually preferably 1 to 12, more preferably 1 to 6, and even more preferably 1 to 4. From the viewpoint of solubility in the dispersion medium, the number of carbon atoms in the alkyl group is preferably 3 to 16, and more preferably 6 to 14.
  • the number of carbon atoms in the aryl group constituting the aryl ester is not particularly limited, but can be, for example, 6 to 24, preferably 6 to 10, and more preferably 6.
  • the compound having the above-mentioned polar functional group introduced into the polymer chain include compounds having a molecular weight of less than 400 when used as a constituent component, such as a compound having the above-mentioned polymer chain, preferably a polyalkyleneoxy chain, introduced into the above-mentioned polycondensable compound, and further having the above-mentioned polar functional group introduced into this polymer chain.
  • ком ⁇ онент (A) a component represented by the following formula (A1) is particularly preferred from the viewpoints of shortening the dispersion time and improving the dispersion characteristics.
  • X1 represents a hydrogen atom or a substituent.
  • the substituent that can be taken as X1 is not particularly limited, and may be a group selected from the substituent Z described below, among which an alkyl group is preferable.
  • X1 is preferably a hydrogen atom or a methyl group.
  • L1 represents a single bond or a linking group, and a single bond is preferred.
  • the linking group that can be taken as L1 is not particularly limited, and the above-mentioned linking group L A2 can be applied without any particular limitation.
  • the linking group that can be taken as L1 does not form a urethane group, a urea group, or an imide group together with the amide group in formula (A1).
  • Y1 and Y2 each represent a hydrogen atom or a substituent.
  • the substituents that can be taken as Y1 and Y2 are not particularly limited and have the same meaning as the above-mentioned RNA1 or the terminal group bonded to the end of the amide bond, and Y1 is preferably a hydrogen atom and Y2 is preferably an alkyl group. However, the substituents that can be taken as Y1 and Y2 do not form an imide group together with the amide group in formula (A1). Y1 and Y2 may be the same or different from each other.
  • the alkyl groups that can be taken as Y1 and Y2 are preferably the same as the alkyl groups that can be taken as the terminal group bonded to the end of the RNA1 or the amide bond, and examples thereof include methyl, ethyl, normal propyl, isopropyl, normal butyl, tertiary butyl, linear or branched octyl group, linear or branched dodecyl group, etc.
  • the alkyl groups that can be taken as Y1 and Y2 may have a substituent, but preferably do not have a hydroxy group, and more preferably do not have the polar functional group.
  • the combination of alkyl groups that can be taken as Y1 and Y2 is not particularly limited, and the alkyl groups listed above can be appropriately combined.
  • the constituent represented by formula (A1) may have a substituent.
  • the carbon atom bonded to the carbon atom having X1 is represented as an unsubstituted carbon atom (methylene group: -CH2- ), but may have a substituent.
  • Such a substituent is not particularly limited, and examples thereof include the above-mentioned substituents that can be adopted as X1 .
  • component (A) include the components contained in the polymers synthesized in the examples, as well as components derived from acrylamide compounds, but the present invention is not limited to these.
  • the molecular weight of the component (A) is appropriately determined taking into consideration the molecular weight of the polymer of the present invention, the content of the component (A), etc., and is not particularly limited.
  • the SP value of the component (A) is not particularly limited and is appropriately determined taking into consideration the SP value of the polymer of the present invention described below.
  • the polymer of the present invention may have other components in addition to the above-mentioned components (X) and (A).
  • the other components may be any components that do not fall under the above-mentioned components, and may include components that do not have a polymer chain and a polar functional group.
  • a component derived from a low molecular weight polycondensable compound having an ethylenically unsaturated group and not having a polar functional group may be mentioned. More specifically, the above-mentioned (meth)acrylic acid compound (M1) or vinyl compound (M2) may be mentioned.
  • a component derived from a styrene compound, a (meth)acrylic acid ester compound, or a (meth)acrylonitrile compound is preferred, and a component derived from a (meth)acrylic acid unsubstituted alkyl ester compound or a component derived from an aryl group-substituted alkyl ester compound of (meth)acrylic acid is preferred.
  • a component derived from an acrylic acid ester compound of a long-chain unsubstituted alkyl group is one of the more preferred aspects.
  • the number of carbon atoms of the long-chain unsubstituted alkyl group can be, for example, 4 to 20, preferably 4 to 16, and more preferably 6 to 14.
  • a component derived from an acrylate compound of a short-chain unsubstituted alkyl group and a component derived from an acrylate compound of a short-chain alkyl group substituted with an aryl group are also preferred in another embodiment.
  • the number of carbon atoms in the short-chain alkyl group is preferably 1 to 3, for example.
  • the polymer of the present invention preferably does not contain any other constituents.
  • the polymer of the present invention may contain one or more of the above-mentioned components.
  • the content of each of the constituent components in the polymer of the present invention is not particularly limited and is determined taking into consideration the physical properties of the entire polymer of the present invention, and is set, for example, within the following ranges.
  • the content of each component in the polymer of the present invention is set, for example, within the following range so that the total content of all components is 100 mass %.
  • the polymer contains two or more components corresponding to a specific component, the total content of these components is used.
  • the total content of the component (X) in the polymer of the present invention is not particularly limited and can be appropriately determined in consideration of shortening the dispersion time, improving the dispersion characteristics, etc.
  • the total content of the component (X) is, for example, preferably 50 to 99 mass% relative to the total content of all the components, and from the viewpoint of shortening the dispersion time and improving the dispersion characteristics, more preferably 55 to 95 mass%, even more preferably 60 to 90 mass%, and particularly preferably 65 to 80 mass%.
  • the total content of the component (A) in the polymer of the present invention is not particularly limited and can be appropriately determined in consideration of shortening the dispersion time and improving the dispersion characteristics.
  • the total content of the component (A) is, for example, preferably 0 to 50 mass% relative to the total content of all the components, from the viewpoint of easily setting the viscosity of the nonaqueous secondary battery composition in the range described below, and more preferably 1 to 50 mass%, further preferably 5 to 45 mass%, particularly preferably 10 to 40 mass%, and most preferably 20 to 35 mass%, from the viewpoint of shortening the dispersion time and improving the dispersion characteristics.
  • the ratio of the total content of the component (X) to the total content of the component (A) [total content of the component (X)/total content of the component (A)] is not particularly limited and can be, for example, 1.0 to 99. From the viewpoint of shortening the dispersion time and improving the dispersion characteristics, it is preferably 1.2 to 19, more preferably 1.5 to 9.0, and even more preferably 1.9 to 4.0.
  • the total content of the other components is not particularly limited, but is preferably 0 to 50 mass%, more preferably 0 to 30 mass%, and even more preferably 0 to 10 mass%, based on the combined content of all the components.
  • the polymer of the present invention may have a substituent other than the polar functional group included in the above-mentioned substituent group (a).
  • substituents that the polymer of the present invention may have include the substituent Z (excluding polar functional groups) described below.
  • the polymer of the present invention does not have a hydroxy group among polar functional groups and substituents.
  • the molecular structure of the polymer of the present invention is not particularly limited as long as it has the above-mentioned component (X), but it usually has a branched structure or a multi-branched structure in which the polymer chain of the component (X) is a branched chain (side chain).
  • the branched structure refers to a polymer in which the polymer chain has a branched structure, for example, a structure in which one or more other polymer chains (side chains) are bonded to the main chain.
  • examples of the branched structure include a graft structure, a star structure (also called a star-shaped structure), and a dendritic structure.
  • the graft structure usually refers to a polymer that does not have a core part and has a large number of polymer chains (as side chains) bonded to one main chain in a branched form
  • the star structure refers to a polymer having a multi-branched structure in which multiple, usually three or more, polymeric arm parts are bonded to the core part.
  • the polymeric arm part constituting the star structure may be a straight chain structure or a graft structure.
  • the polymeric arm part refers to a partial structure containing a polymer chain, and a partial structure that forms an arm part of a multi-branched polymer by bonding to the core part.
  • the primary structures of the main chain and the graft chain in the graft structure (bonding pattern of the components) and the primary structure of the polymeric arm portion in the star structure (bonding pattern of the components) are not particularly limited and may be any bonding pattern such as a random structure, a block structure, an alternating structure, etc.
  • the polymer of the present invention preferably has a graft structure or a star structure.
  • the polymer of the present invention has a graft structure
  • it can be synthesized by homopolymerizing or copolymerizing the compound that leads to the above-mentioned component (X).
  • the polymer of the present invention is preferably a hyperbranched polymer represented by the following formula (1).
  • L represents an n-valent linking group.
  • P1 represents a polymer chain as a polymeric arm portion, and n P1 's may be the same or different.
  • n is an integer of 3 or more.
  • L is an n-valent linking group, and is usually a linking group (organic linking group) made of an organic group containing a skeleton in which carbon atoms are bonded by covalent bonds, and preferably a linking group further containing an oxygen atom.
  • the molecular weight of this linking group is not particularly limited, and for example, it is preferably 200 or more, and more preferably a molecular weight of 300 or more.
  • the upper limit of the molecular weight is preferably 5000 or less, more preferably 4000 or less, and particularly preferably 3000 or less. It is preferable that this linking group does not have only one tetravalent carbon atom.
  • the valence of this linking group is 3 to 10 and is the same as n described below, and the preferred range is also the same.
  • the linking group preferably has a group represented by the following formula 1a.
  • the number of groups represented by formula 1a in the linking group L is preferably the same as the n valence, which is the valence of L. When the linking group has a plurality of such groups, they may be the same or different.
  • n is an integer of 0 to 10, preferably an integer of 1 to 6, and more preferably 1 or 2.
  • R f represents a hydrogen atom or a substituent, and a hydrogen atom is preferred.
  • the substituent that can be taken as R f is not particularly limited, and examples thereof include the substituent Z described below. Specific examples thereof include halogen atoms (e.g., fluorine atoms, chlorine atoms, iodine atoms, and bromine atoms), alkyl groups (preferably having 1 to 12 carbon atoms, more preferably having 1 to 6 carbon atoms, and particularly preferably having 1 to 3 carbon atoms), alkoxy groups (preferably having 1 to 12 carbon atoms, more preferably having 1 to 6 carbon atoms, and particularly preferably having 1 to 3 carbon atoms), acyl groups (preferably having 2 to 12 carbon atoms, more preferably having 2 to 6 carbon atoms, and particularly preferably having 2 to 3 carbon atoms), aryl groups (preferably having 6 to 22 carbon atoms, more preferably having 6 to 10 carbon atoms), alkenyl groups (preferably having 2 to 12 carbon atoms, and more preferably having 2 to 5 carbon atoms), hydroxy groups, nitro groups
  • the linking group L is preferably a linking group represented by the following formula 1A or 1B.
  • R f and n are the same as R f and n in the above formula 1a, and the preferred ones are also the same.
  • * indicates a bond to the sulfur atom in formula 1.
  • R 1A indicates a hydrogen atom or a substituent.
  • the substituent that can be taken as R 1A is not particularly limited, and examples thereof include each of the above substituents that can be taken as R f , and further includes a group represented by the above formula 1a. Among them, an alkyl group or a group represented by the above formula 1a is preferred.
  • the number of carbon atoms in the alkyl group is preferably 1 to 12, more preferably 1 to 6, and particularly preferably 1 to 3.
  • the substituent that can be taken as R 1A may further have one or more substituents, and the further substituent that may be further taken is not particularly limited, and examples thereof include each of the above substituents that can be taken as R f . Among them, a hydroxy group is preferred. Examples of the substituent that may further have one or more substituents include a hydroxyalkyl group (the number of carbon atoms is as described above), and specifically, hydroxymethyl is preferred. In formula 1B, R 1C represents a linking group.
  • the linking group that can be taken as R 1C is not particularly limited, and is preferably, for example, an alkylene group having 1 to 30 carbon atoms, a cycloalkylene group having 3 to 12 carbon atoms, an arylene group having 6 to 24 carbon atoms, a heteroarylene group having 3 to 12 carbon atoms, an ether group (-O-), a sulfide group (-S-), a phosphinidene group (-PR-: R is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms), a silylene group (-SiR S1 R S2 -: R S1 , R S2 are a hydrogen atom or an alkyl group having 1 to 6 carbon atoms), a carbonyl group, an imino group (-NR N -: R N is a bonding site, a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an aryl group having 6 to 10 carbon atoms
  • R 1B represents a hydrogen atom or a substituent, and a hydrogen atom is preferred.
  • the substituent that can be taken as R 1B is not particularly limited, and examples thereof include the above-mentioned substituents that can be taken as R f .
  • groups represented by the same symbol may be the same or different.
  • linking group L in addition to the above-mentioned linking groups, for example, in the above formula 1B, a linking group in which one or more of the groups represented by the above formula 1a are substituted with each of the above-mentioned substituents which can be taken as Rf , particularly hydroxymethyl, is also a preferred embodiment.
  • the linking group R 1 is also preferably a linking group represented by any one of the following formulas 1C to 1H: In each formula, * indicates the bond to S in formula 1.
  • T is a linking group, preferably a group represented by any one of formulae T1 to T6 below, or a linking group obtained by combining two or more of these (preferably two or three).
  • An example of the combined linking group is a linking group (-OCO-alkylene group) obtained by combining a linking group represented by formula T6 with a linking group represented by formula T1.
  • Any of the groups represented by formulae T1 to T6 may have a bond that bonds to the sulfur atom in formula 1 above, but when T is an oxyalkylene group (groups represented by formulae T2 to T5) or an -OCO-alkylene group, it is preferable that the terminal carbon atom (bond) bonds to the sulfur atom in formula 1 above.
  • n is an integer, preferably an integer of 0 to 14, more preferably an integer of 0 to 5, and particularly preferably an integer of 1 to 3.
  • ZD is a linking group, and is preferably a group represented by Z1 or Z2 below.
  • m is an integer of 1 to 8, more preferably an integer of 1 to 5, and particularly preferably an integer of 1 to 3.
  • Z3 is a linking group, which is preferably an alkylene group having 1 to 12 carbon atoms, and more preferably an alkylene group having 1 to 6 carbon atoms, and particularly preferably a 2,2-propanediyl group.
  • linking group L is given below, but the present invention is not limited to these.
  • * indicates the bond to the sulfur atom in formula 1.
  • P1 in formula (1) is a polymer chain that forms a polymeric arm portion of a star structure.
  • the polymer chain P1 as a whole contains the above-mentioned component (X), preferably contains the above-mentioned component (A), and may contain the above-mentioned other components as appropriate, but preferably does not contain any other components.
  • the n polymer chains P1 each contain the above-mentioned component (X), preferably contain the above-mentioned component (A), and may appropriately contain the other components described above, or may contain the component (X) or the component (A), and appropriately contain other components.
  • polymer chains P 1 may be the same or different, and in terms of shortening the dispersion time and dispersion characteristics, it is preferable that at least one polymer chain P 1 is a polymer chain containing the above-mentioned component (X) (hereinafter, sometimes referred to as “polymer chain P 1X "), and at least one other polymer chain P 1 is a polymer chain containing the above-mentioned component (A) (hereinafter, sometimes referred to as "polymer chain P 1A ").
  • X above-mentioned component
  • A a polymer chain containing the above-mentioned component
  • the polymer chain P 1X does not contain the above-mentioned component (A), and may contain other components, but it is more preferable that it does not contain any other components, that is, it is a homopolymer chain of the component (X), and it is even more preferable that it is a homopolymer chain of a component having a polymer chain made of polysiloxane, and it is particularly preferable that it is a homopolymer chain of a (meth)acrylic compound (M1) having a polymer chain made of polysiloxane.
  • the polymer chain P1A does not contain the above-mentioned component (X). It may contain other components, but it is more preferable that it does not contain any other components, that is, it is a homopolymer chain of the component (A), and it is particularly preferable that it is a homopolymer chain of a (meth)acrylamide compound.
  • the numbers of the polymer chains P 1X and P 1A are appropriately determined within the range represented by n in the above formula (1), and can be, for example, the same as nA and mX in the formula (2) described below.
  • the primary structure of the polymer chain P1 is not particularly limited and may have any bonding pattern such as a random structure, a block structure, an alternating structure, etc., but a random structure or a block structure is preferred.
  • the group bonded to the end of the polymer chain P1 is not particularly limited, and as described above, an appropriate group can be chosen depending on the polymerization method or the like.
  • the content of the constituent component (X) in the polymer chain P1X is not particularly limited, but from the viewpoints of shortening the dispersion time and dispersion characteristics, it is preferably 50% by mass or more, more preferably 75% by mass or more, more preferably 90% by mass or more, and even more preferably 95% by mass or more, and 100% by mass is also one of the preferred embodiments.
  • the content of the constituent component (A) in the polymer chain P 1X is not particularly limited, but from the viewpoints of shortening the dispersion time and dispersion characteristics, it is preferably 50 mass % or less, more preferably 10 mass % or less, and more preferably 5 mass % or less, and 0 mass % is also one of the preferred embodiments.
  • the content of other components in the polymer chain P1X is not particularly limited, but from the viewpoints of shortening the dispersion time and dispersion characteristics, it is preferably 50 mass % or less, more preferably 30 mass % or less, and more preferably 10 mass % or less, and 0 mass % is also one of the preferred embodiments.
  • the content of the constituent component (A) in the polymer chain P1A is not particularly limited, but from the viewpoints of shortening the dispersion time and dispersion characteristics, it is preferably 50% by mass or more, more preferably 75% by mass or more, more preferably 90% by mass or more, and even more preferably 95% by mass or more, and 100% by mass is also one of the preferred embodiments.
  • the content of the constituent component (X) in the polymer chain P1A is not particularly limited, but from the viewpoints of shortening the dispersion time and dispersion characteristics, it is preferably 50 mass % or less, more preferably 10 mass % or less, and more preferably 5 mass % or less, and 0 mass % is also one of the preferred embodiments.
  • the content of other components in the polymer chain P1A is not particularly limited, but from the viewpoints of shortening the dispersion time and dispersion characteristics, it is preferably 50% by mass or less, more preferably 30% by mass or less, and more preferably 10% by mass or less, and 0% by mass is also one of the preferred embodiments.
  • the weight average molecular weight Mw P1 of the polymer chain P1 (the average value of the weight average molecular weight of n polymer chains P1 ) is not particularly limited and is appropriately set in consideration of the weight average molecular weight of polymer (1), which is an example of the polymer of the present invention, and is, for example, preferably 500 to 20,000, more preferably 1,000 to 10,000.
  • the degree of polymerization of all components in the polymer chain P1 (the average value of the degree of polymerization of n polymer chains P1 ) is not particularly limited, but is preferably 5 to 300, more preferably 8 to 150.
  • the weight average molecular weight Mw P1X of the polymer chain P 1X (the average value of the weight average molecular weights of all the polymer chains P 1X ) is not particularly limited and is appropriately set in consideration of the weight average molecular weight of the polymer (1) described below, which is an example of the polymer of the present invention, and is, for example, preferably 400 to 50,000, more preferably 1,000 to 20,000.
  • the degree of polymerization of all the constituent components in the polymer chain P 1X (the average value of the degrees of polymerization of all the polymer chains P 1X ) is not particularly limited, but is preferably 1 to 10, more preferably 1 to 3.
  • the weight average molecular weight Mw P1A of the polymer chain P 1A (the average value of the weight average molecular weights of all the polymer chains P 1A ) is not particularly limited and is appropriately set in consideration of the weight average molecular weight of the polymer (1) described below, which is an example of the polymer of the present invention, and is, for example, preferably 100 to 10,000, more preferably 200 to 3,000.
  • the degree of polymerization of all the constituent components in the polymer chain P 1A (the average value of the degrees of polymerization of all the polymer chains P 1A ) is not particularly limited, but is preferably 1 to 100, more preferably 2 to 30.
  • the combination of the polymer chain A 1X and the polymer chain A 1A is not particularly limited, and the constituent (X ) constituting the polymer chain A 1X and the constituent (A) constituting the polymer chain A 1X can be appropriately combined.
  • the combination of the polymer chain A 1X and the polymer chain A 1A a combination of a suitable constituent that can be taken as the constituent (X) and a suitable constituent that can be taken as the constituent (A) is preferable, and for example, the combination in the polymer shown in the examples can be mentioned.
  • n is an integer of 3 or more, preferably an integer of 3 to 10, more preferably an integer of 3 to 8, even more preferably an integer of 3 to 6, and particularly preferably an integer of 4 to 6.
  • the content of the core part L in the polymer (1) is not particularly limited, but can be 1 to 40 mass% in total with "S" in the polymer (1). From the viewpoint of shortening the dispersion time and improving the dispersion characteristics, the content is preferably 2 to 30 mass%, more preferably 2 to 20 mass%, and further preferably 3 to 10 mass%.
  • the total content of the polymer chains P1 in the polymer (1) is not particularly limited, but can be 60 to 99% by mass. From the viewpoints of shortening the dispersion time and improving the dispersion characteristics, it is preferably 70 to 98% by mass, more preferably 80 to 98% by mass, and even more preferably 90 to 97% by mass.
  • the total content of the polymer chains P1X in the polymer (1) can be appropriately determined taking into consideration the total content of the polymer chains P1 .
  • the total content in the total content of the polymer chains P1 is preferably the same as the total content of the constituent component (X) in the polymer of the present invention.
  • the total content of the polymer chains P 1A in the polymer (1) can be appropriately determined in consideration of the total content of the polymer chains P 1 , and for example, it is preferable that the total content in the total content of the polymer chains P 1 is the same as the total content of the component (A) in the polymer of the present invention.
  • the ratio of the total content of the polymer chains P 1X to the total content of the polymer chains P 1A [total content of the polymer chains P 1X /total content of the polymer chains P 1A ] is not particularly limited, and is preferably the same as the ratio of the total content in the polymer of the present invention [total content of the component (X)/total content of the component (A)].
  • the hyperbranched polymer represented by the above formula (1) is preferably represented by the following formula (2).
  • L represents a (nA+mX)-valent linking group and is the same as L in formula (1) above.
  • P 1A represents the polymer chain P 1A containing the above-mentioned component (A), and nA P 1A 's may be the same or different.
  • P 1X represents the polymer chain P 1X containing the above-mentioned component (X), and nX P 1X may be the same or different.
  • nA is an integer of 1 to 8, preferably an integer of 1 to 4, more preferably an integer of 1 to 3, and even more preferably 1 or 2.
  • mX is an integer of 2 to 9, preferably an integer of 2 to 5, and more preferably an integer of 3 to 5.
  • nA+mX is an integer of 3 to 10, preferably an integer of 3 to 8, more preferably an integer of 3 to 6, and further preferably an integer of 4 to 6.
  • L, P 1A and P 1X in the polymer (1) are the same as the contents of L, P 1A and P 1X in the above formula (1).
  • polymer represented by formula (1) or formula (2) include the polymers synthesized in the examples described below, but the present invention is not limited to these.
  • the polymer of the present invention may be a commercially available product or a synthetic product.
  • the polymer (1) may be synthesized by selecting a raw material compound by a known method.
  • the polymer may be synthesized by condensation, homopolymerization, or copolymerization using a surfactant, an emulsifier or a dispersant, a polycondensable compound that derives the component (X), a polycondensable compound that derives the component (A), and a polycondensable compound that derives other components, by a normal synthesis method.
  • the multi-branched polymer represented by formula (1) or formula (2) may be synthesized, for example, by addition reaction of the above raw material compound with a polyvalent thiol compound corresponding to the core portion L. Specifically, the polymer may be synthesized by a method described in the examples described later.
  • the method of incorporating a polar functional group into the polymer of the present invention is not particularly limited, and examples thereof include a method of copolymerizing a compound having a functional group, a method using a polymerization initiator or chain transfer agent having (generating) the functional group, a method utilizing a polymer reaction, an ene reaction to a double bond, an ene-thiol reaction, or an ATRP (Atom Transfer Radical Polymerization) polymerization method using a copper catalyst.
  • a functional group can be introduced by using a functional group present in the main chain, side chain, or end of the polymer as a reaction point.
  • a functional group can be introduced by various reactions with a dicarboxylic anhydride group in a polymer chain using a compound having a functional group.
  • Substituent Z - alkyl groups (preferably alkyl groups having 1 to 20 carbon atoms, for example, methyl, ethyl, isopropyl, t-butyl, pentyl, heptyl, 1-ethylpentyl, benzyl, 2-ethoxyethyl, 1-carboxymethyl, etc.), alkenyl groups (preferably alkenyl groups having 2 to 20 carbon atoms, for example, vinyl, allyl, oleyl, etc.), alkynyl groups (preferably alkynyl groups having 2 to 20 carbon atoms, for example, ethynyl, butadiynyl, phenylethynyl, etc.), cycloalkyl groups (preferably cycloalkyl groups having 3 to 20 carbon atoms, for example, cyclopropyl, cyclopentyl, cyclohexyl, 4-methylcyclohexyl, etc.), In
  • Heterocyclic groups include aromatic heterocyclic groups and aliphatic heterocyclic groups. Examples of such groups include a tetrahydropyran ring group, a tetrahydrofuran ring group, 2-pyridyl, 4-pyridyl, 2-imidazolyl, 2-benzimidazolyl, 2-thiazolyl, 2-oxazolyl, and pyrrolidone groups, alkoxy groups (preferably alkoxy groups having 1 to 20 carbon atoms, such as methoxy, ethoxy, isopropyloxy, and benzyloxy), aryloxy groups (preferably aryloxy groups having 6 to 26 carbon atoms, such as phenoxy, 1-naphthyloxy, 3-methylphenoxy, and 4-methoxyphenoxy), heterocyclic oxy groups (groups in which the above-mentioned heterocyclic groups are bonded to an -O- group), and alkoxycarbonyl groups ( Preferably, the alkoxycarbonyl group
  • acylamino groups such as acetylamino and benzoylamino
  • alkylthio groups preferably alkylthio groups having 1 to 20 carbon atoms, such as methylthio, ethylthio, isopropylthio and benzylthio
  • arylthio groups preferably arylthio groups having 6 to 26 carbon atoms, such as phenylthio, 1-naphthylthio, 3-methylphenylthio and 4-methoxyphenylthio
  • heterocyclic thio groups groups in which the above-mentioned heterocyclic groups are bonded to an -S- group
  • alkylsulfonyl groups preferably alkylsulfonyl groups having 1 to 20 carbon atoms, such as methylsulfonyl and ethylsulfonyl
  • arylsulfonyl groups preferably arylsulfonyl groups having 6 to
  • R P is a hydrogen atom or a substituent (preferably a group selected from the substituent Z). Each of the groups given as the substituent Z may be further substituted with the above-mentioned substituent Z.
  • the above alkyl group, alkylene group, alkenyl group, alkenylene group, alkynyl group and/or alkynylene group may be cyclic or chain-like, and may be straight-chain or branched.
  • the polymer of the present invention has a viscosity of 0.10 to 10,000 Pa ⁇ s at a temperature of 25° C. and a shear rate of 1 s ⁇ 1 .
  • the viscosity of the polymer of the present invention is within the above range, it becomes liquid at 25° C., so that the solid particles can be easily dispersed in the dispersion medium, and the dispersion time of the solid particles can be shortened. Furthermore, even if the dispersion time of the solid particles is shortened, the solid particles can be dispersed in the dispersion medium, and excellent dispersion properties can be achieved.
  • the viscosity of the polymer of the present invention is preferably 0.50 to 9000 Pa ⁇ s in terms of shortening the dispersion time and improving the dispersion characteristics.
  • the viscosity is more preferably 10 to 8000 Pa ⁇ s, and even more preferably 105 to 6000 Pa ⁇ s, within the above range.
  • the viscosity is more preferably 10 to 9000 Pa ⁇ s, and even more preferably 100 to 8000 Pa ⁇ s, and particularly preferably 1500 to 7500 Pa ⁇ s, and most preferably 2000 to 6300 Pa ⁇ s, within the above range.
  • the viscosity of the polymer of the present invention can be measured using a rheometer at a temperature of 25° C. and a shear rate of 1 s ⁇ 1 .
  • the viscosity is measured using a RheoStress RS6000 (trade name, manufactured by HAAKE Corporation) as the rheometer.
  • the viscosity of the polymer of the present invention can be appropriately adjusted by changing the molecular structure of the polymer, the type and content of the polycondensable compound, the weight average molecular weight, and the like.
  • the polymer of the present invention preferably has the following physical properties or characteristics. From the viewpoint of shortening the dispersion time and improving the dispersion characteristics, the polymer of the present invention preferably has an SP value of the polymer chain of 15.0 to 25.0 MPa 1/2 , more preferably 17.0 to 22.0 MPa 1/2 , and even more preferably 17.5 to 20.0 MPa 1/2 .
  • the SP value of a polymer chain refers to an SP value calculated from all components derived from the polycondensable compound constituting the polymer of the present invention, without taking into consideration compounds that lead to partial structures other than the polymerizable compound, for example, a value calculated without including the terminal groups of the polymer chain, and further the core portion of a hyperbranched polymer, etc.
  • the SP values of the constituents and the polymer of the present invention are calculated by the Okitsu method.
  • the Okitsu method is described in detail, for example, in Journal of the Adhesion Society of Japan, 1993, Vol. 29, No. 6, pp. 249-259, and Journal of Sen-i-gakkaishi, 1994, Vol. 50, No. 6, pp. 273-277.
  • the SP value of the constituents is calculated based on the structure in which the constituents are incorporated in the polymer of the present invention.
  • the SP value of the polymer of the present invention is calculated from the SP value of each constituent and the mass fraction of the constituent.
  • the SP value of the polymer of the present invention can be appropriately adjusted by changing the type and content of the polycondensable compound.
  • the weight average molecular weight of the polymer of the present invention is not particularly limited, and is, for example, preferably at least 3000, more preferably at least 5000, and even more preferably at least 7000.
  • the upper limit of the weight average molecular weight is substantially at most 100000, but is preferably at most 50000, and from the viewpoint of shortening the dispersion time and improving the dispersion characteristics, is more preferably at most 30000, even more preferably at most 20000, and particularly preferably at most 15000.
  • the weight average molecular weight may be any suitable weight average molecular weight within the above range, but in a preferred embodiment, it is preferably from 3,000 to 30,000, and more preferably from 4,000 to 15,000.
  • the weight average molecular weight may be any suitable weight average molecular weight within the above range, but in a preferred embodiment, it is preferably from 5,000 to 70,000, and more preferably from 10,000 to 30,000.
  • the weight average molecular weight of the polymer of the present invention can be appropriately adjusted by changing the type and content of the polymerization initiator, polymerization time, polymerization temperature, and the like.
  • the molecular weight of a polymer or polymer chain refers to a weight average molecular weight or number average molecular weight measured by gel permeation chromatography (GPC) in terms of standard polystyrene.
  • the measurement method basically includes a method set under the following condition 1 or condition 2 (preferential). However, depending on the type of polymer or polymer chain, an appropriate eluent may be selected and used. (Condition 1) Column: Two TOSOH TSKgel Super AWM-H (product name, manufactured by Tosoh Corporation) connected together Carrier: 10 mM LiBr/N-methylpyrrolidone Measurement temperature: 40° C.
  • Carrier flow rate 1.0 ml/min Sample concentration: 0.1% by mass Detector: RI (refractive index) detector (condition 2) Column: A column connected with TOSOH TSKgel Super HZM-H, TOSOH TSKgel Super HZ4000, and TOSOH TSKgel Super HZ2000 (all trade names, manufactured by Tosoh Corporation) is used.
  • Carrier Tetrahydrofuran Measurement temperature: 40°C
  • Carrier flow rate 1.0 ml/min Sample concentration: 0.1% by mass Detector: RI (refractive index) detector
  • the polymer of the present invention preferably has no flash point. Since the polymer of the present invention has no flash point, a high dispersing effect can be obtained, although the detailed mechanism is unclear.
  • the polymer of the present invention having no flash point means that the polymer has a flash point of 250° C. or higher. In other words, the polymer of the present invention preferably has a flash point of 250° C. or higher.
  • the absence of a flash point for the polymer of the present invention can be confirmed by measuring the flash point according to Japanese Industrial Standards (JIS) K 2265-1, ASTM D3278, JIS K 2265-3, etc., usually JIS K 2265-1.
  • JIS Japanese Industrial Standards
  • the polymer of the present invention has the constituent component (A) having the polar functional group, and preferably has a small acid value, for example, more preferably 3 mgKOH/g or less. It is considered that the acid value of 3 mgKOH/g or less can suppress excessive aggregation and precipitation of the polymer of the present invention and solid particles.
  • the acid value of the polymer of the present invention is more preferably 2 mgKOH/g or less, particularly preferably 1 mgKOH/g or less, and more preferably 0.5 mgKOH/g or less.
  • the lower limit of the acid value of the polymer of the present invention is preferably 0 mgKOH/g.
  • the acid value of the polymer of the present invention indicates the number of milligrams of potassium hydroxide required to neutralize the acidic groups present in 1 g of the polymer of the present invention, and can be measured by the following method.
  • the acidic group is not particularly limited as long as it is neutralized with potassium hydroxide, and examples thereof include a carboxylic acid group (carboxy group), a sulfonic acid group (sulfo group), a phosphoric acid group (phospho group), a phosphonic acid group, a phosphinic acid group, or salts thereof.
  • the polymer of the present invention has the constituent component (A) having the polar functional group, but the base number is preferably small, for example, preferably 2 mgKOH/g or less. It is considered that the base number is 2 mgKOH/g or less, and excessive aggregation and precipitation of the polymer of the present invention and solid particles can be suppressed.
  • the base number of the polymer of the present invention is more preferably 1 mgKOH/g or less, and even more preferably 0.5 mgKOH/g or less.
  • the lower limit of the base number of the polymer of the present invention is preferably 0 mgKOH/g.
  • the base number of the polymer of the present invention is expressed as the number of milligrams of potassium hydroxide equivalent to the number of moles of acid required to neutralize the basic groups present in 1 g of the polymer of the present invention, and can be measured by the following method.
  • the basic group is not particularly limited as long as it is neutralized with HCl, and examples thereof include groups having a basic nitrogen atom, preferably groups having a basic nitrogen atom bonded to a hydrogen atom. Specific examples thereof include an amino group, a pyridyl group, an imino group, an amidine group, and further the above-mentioned urea group or urethane group having a hydrogen atom bonded to a nitrogen atom.
  • the number of moles of HCl required for neutralization can be calculated by dissolving 1 g of the polymer of the present invention in 25 g of tetrahydrofuran and titrating the solution with 1N-HCl solution using a potentiometric titrator, and converting the number of moles of HCl into milligrams of potassium hydroxide.
  • the acid value and base value of the polymer of the present invention may be within the above ranges, but it is more preferable that the acid value is 0.5 mg KOH/g or less and the base value is 0.5 mg KOH/g or less.
  • the polymer of the present invention may be a non-crosslinked polymer or a crosslinked polymer. Furthermore, when crosslinking of the polymer of the present invention progresses due to heating or application of voltage, the molecular weight may be larger than the above-mentioned molecular weight. Preferably, the polymer of the present invention has a weight average molecular weight in the above-mentioned range when the all-solid-state secondary battery is first used.
  • the polymer of the present invention is preferably amorphous.
  • amorphous means that a polymer typically does not show an endothermic peak due to crystalline melting when measured at the glass transition temperature.
  • the water concentration of the polymer of the present invention is preferably 100 ppm (mass basis) or less.
  • the polymer of the present invention may be crystallized and dried, or the polymer dispersion may be used as it is.
  • the polymer of the present invention usually comprises the above-mentioned polymer of the present invention, but may contain components used during polymerization, such as a polymerization initiator, or decomposition products thereof, etc.
  • the polymer of the present invention may also be used as a polymer liquid of the present invention, dissolved or dispersed in a dispersion medium, etc., which will be described later.
  • the non-aqueous secondary battery composition of the present invention is a composition containing the polymer of the present invention.
  • the non-aqueous secondary battery composition when used as a material for forming a constituent layer of an all-solid-state secondary battery, it is called an inorganic solid electrolyte-containing composition, and is used as an electrode layer of a non-aqueous electrolyte secondary battery.
  • the composition When used as a material for forming a non-aqueous electrolyte secondary battery electrode composition, the composition is sometimes called a non-aqueous electrolyte secondary battery electrode composition.
  • the non-aqueous secondary battery composition of the present invention preferably contains, in addition to the polymer of the present invention, appropriate components depending on the intended use.
  • a non-aqueous electrolyte secondary battery electrode composition In the case of an inorganic solid electrolyte-containing composition, the composition contains the polymer of the present invention and an active material, and optionally contains a conductive assistant, other components described below, a dispersion medium, etc.
  • the polymer of the present invention and an inorganic solid electrolyte having ion conductivity of a metal belonging to Group 1 or Group 2 of the periodic table are contained, and an active material, a conductive assistant, and a dispersion medium are appropriately added. and other ingredients described below.
  • each component contained in the polymer of the present invention does not need to be present integrally as the polymer of the present invention, and each component may be present independently (separately). May be present.
  • the solid particles such as the inorganic solid electrolyte are dispersed with excellent dispersion properties without being damaged.
  • the solid content concentration is not uniquely determined depending on the temperature of the composition, the type of solid particles, etc., but can be, for example, 40 mass % or more at 25° C., and can also be 50 mass % or more.
  • composition for a nonaqueous secondary battery of the present invention exhibiting the above-mentioned properties can be used as a material for forming a constituent layer of a nonaqueous secondary battery to realize a sheet for a nonaqueous secondary battery having a constituent layer with low resistance, and a nonaqueous secondary battery with low resistance (high conductivity) and excellent cycle characteristics. Therefore, the composition for a non-aqueous secondary battery of the present invention can be preferably used as a material for forming a constituent layer of a non-aqueous secondary battery sheet (including an electrode sheet for a non-aqueous secondary battery) or a non-aqueous secondary battery.
  • the polymer of the present invention may be dispersed in a particulate form without showing solubility in the dispersion medium contained in the non-aqueous secondary battery composition, but it is preferable that the polymer of the present invention is soluble. That is, depending on the content, the polymer of the present invention in the non-aqueous secondary battery composition is preferably present in a state dissolved in the dispersion medium in the non-aqueous secondary battery composition. When the polymer of the present invention is dissolved, it stably exhibits the function of dispersing solid particles in the dispersion medium, and the dispersion characteristics of the solid particles in the non-aqueous secondary battery composition can be further improved.
  • the polymer of the present invention being dissolved in a dispersion medium is not limited to an embodiment in which the entire polymer of the present invention is dissolved in the dispersion medium.
  • the polymer of the present invention may be partially insoluble in the nonaqueous secondary battery composition as long as the solubility in the dispersion medium is 80% or more as described below.
  • the method for measuring the solubility is as follows.
  • a specified amount of the polymer of the present invention to be measured is weighed into a glass bottle, 100 g of the same type of dispersion medium as the dispersion medium contained in the nonaqueous secondary battery composition is added thereto, and the mixture is stirred for 24 hours at a rotation speed of 80 rpm on a mix rotor at a temperature of 25° C.
  • the transmittance of the mixture thus obtained after stirring for 24 hours is measured under the following conditions.
  • the polymer of the present invention is particulate (does not dissolve in the dispersion medium contained in the non-aqueous secondary battery composition), its shape is not particularly limited and may be flat, amorphous, etc., but is preferably spherical or granular.
  • the average particle diameter of the particulate polymer of the present invention in the non-aqueous secondary battery composition is not particularly limited, but is preferably 1 nm or more, more preferably 10 nm or more, and even more preferably 30 nm or more.
  • the upper limit is preferably 5 ⁇ m or less, and more preferably 1 ⁇ m or less.
  • the average particle diameter of the polymer of the present invention can be measured in the same manner as the particle diameter of the inorganic solid electrolyte.
  • the average particle diameter of the polymer of the present invention can be adjusted, for example, by the type of dispersion medium, the composition of the polymer, etc.
  • the solubility of the polymer of the present invention in the dispersion medium can be appropriately imparted by the structure, composition (type and content of constituent components), weight average molecular weight, and further combination with the dispersion medium of the polymer of the present invention.
  • the nonaqueous secondary battery composition of the present invention is preferably a slurry in which solid particles such as an inorganic solid electrolyte are dispersed in a dispersion medium.
  • the non-aqueous secondary battery composition of the present invention is preferably a non-aqueous composition.
  • the non-aqueous composition includes, in addition to an embodiment that does not contain water, a form in which the water content (also referred to as water content) is preferably 500 ppm or less.
  • the water content is more preferably 200 ppm or less, further preferably 100 ppm or less, and particularly preferably 50 ppm or less.
  • the non-aqueous secondary battery composition is a non-aqueous composition
  • the polymer of the present invention can be dissolved and the deterioration of solid particles, particularly inorganic solid electrolytes, can be suppressed.
  • the water content indicates the amount of water contained in the non-aqueous secondary battery composition (mass ratio to the non-aqueous secondary battery composition), and specifically, it is a value measured by filtering with a 0.02 ⁇ m membrane filter and using Karl Fischer titration.
  • the nonaqueous secondary battery composition of the present invention also includes an embodiment that contains an active material and further a conductive assistant, etc., in addition to the inorganic solid electrolyte (the composition in this embodiment is referred to as an electrode composition).
  • the composition in this embodiment is referred to as an electrode composition.
  • the non-aqueous secondary battery composition of the present invention contains the above-mentioned polymer of the present invention.
  • the non-aqueous secondary battery composition may contain one type or two or more types of the polymer of the present invention.
  • the content (solids content equivalent) of the polymer of the present invention in the composition for a non-aqueous secondary battery can be appropriately determined, and is preferably 0.1 to 5.0 mass%, more preferably 0.2 to 4.0 mass%, and even more preferably 0.3 to 2.0 mass% from the viewpoints of suppressing damage to solid particles and dispersing properties of solid particles.
  • the content (solids content equivalent) of the polymer of the present invention in 100 mass% solids of the composition for a non-aqueous secondary battery is preferably 0.1 to 6.0 mass%, more preferably 0.2 to 5.0 mass%, and even more preferably 0.3 to 2.5 mass%.
  • the mass ratio of the total mass (total amount) of the inorganic solid electrolyte and the active material to the mass of the polymer of the present invention is preferably in the range of 2,000 to 1. This ratio is more preferably 1,000 to 10, and even more preferably 500 to 20.
  • the nonaqueous secondary battery composition of the present invention contains an inorganic solid electrolyte.
  • the inorganic solid electrolyte refers to an inorganic solid electrolyte
  • the solid electrolyte refers to a solid electrolyte in which ions can move inside.
  • the inorganic solid electrolyte does not contain an organic substance as the main ion conductive material, it is clearly distinguished from organic solid electrolytes (polymer electrolytes represented by polyethylene oxide (PEO) and the like, and organic electrolyte salts represented by lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) and the like).
  • organic solid electrolytes polymer electrolytes represented by polyethylene oxide (PEO) and the like
  • LiTFSI lithium bis(trifluoromethanesulfonyl)imide
  • an electrolytic solution or an inorganic electrolyte salt LiPF 6 , LiBF 4 , lithium bis(fluorosulfonyl)imide (LiFSI), LiCl, etc.
  • the inorganic solid electrolyte is not particularly limited as long as it has ionic conductivity of a metal belonging to Group 1 or Group 2 of the periodic table, and generally does not have electronic conductivity.
  • the inorganic solid electrolyte preferably has ionic conductivity for lithium ions.
  • the inorganic solid electrolyte can be selected from solid electrolyte materials that are normally used in all-solid-state secondary batteries.
  • the inorganic solid electrolyte can be (i) a sulfide-based inorganic solid electrolyte, (ii) an oxide-based inorganic solid electrolyte, (iii) a halide-based inorganic solid electrolyte, and (iv) a hydride-based inorganic solid electrolyte.
  • the polymer of the present invention can reduce the load acting on the inorganic solid electrolyte during preparation of the non-aqueous secondary battery composition, thereby suppressing deterioration and decomposition, so that a sulfide-based inorganic solid electrolyte that is generally prone to deterioration and decomposition can be used, and a better interface can be formed between the active material and the inorganic solid electrolyte to effectively suppress an increase in interface resistance.
  • Sulfide-based inorganic solid electrolyte preferably contains sulfur atoms, has the ionic conductivity of a metal belonging to Group 1 or 2 of the periodic table, and has electronic insulation.
  • the sulfide-based inorganic solid electrolyte preferably contains at least Li, S, and P as elements and has lithium ion conductivity, but may contain other elements other than Li, S, and P as appropriate.
  • sulfide-based inorganic solid electrolyte is a lithium ion conductive inorganic solid electrolyte having a composition represented by the following formula (S1).
  • L a1 M b1 P c1 S d1 A e1
  • L represents an element selected from Li, Na, and K, and Li is preferred.
  • M represents an element selected from B, Zn, Sn, Si, Cu, Ga, Sb, Al, and Ge.
  • A represents an element selected from I, Br, Cl, and F.
  • a1 to e1 represent the composition ratio of each element, and a1:b1:c1:d1:e1 satisfies 1-12:0-5:1:2-12:0-10.
  • a1 is preferably 1-9, and more preferably 1.5-7.5.
  • b1 is preferably 0-3, and more preferably 0-1.
  • d1 is preferably 2.5-10, and more preferably 3.0-8.5.
  • e1 is preferably 0-5, and more preferably 0-3.
  • composition ratio of each element can be controlled by adjusting the amounts of raw material compounds used when producing a sulfide-based inorganic solid electrolyte, as shown below.
  • the sulfide-based inorganic solid electrolyte may be amorphous (glass) or crystallized (glass ceramic), or may be only partially crystallized.
  • glass glass
  • glass ceramic glass ceramic
  • Li-P-S glass containing Li, P, and S, or Li-P-S glass ceramic containing Li, P, and S can be used.
  • the sulfide-based inorganic solid electrolyte can be produced by reacting at least two or more raw materials selected from the group consisting of lithium sulfide (Li 2 S), phosphorus sulfide (e.g., diphosphorus pentasulfide (P 2 S 5 )), elemental phosphorus, elemental sulfur, sodium sulfide, hydrogen sulfide, lithium halides (e.g., LiI, LiBr, LiCl), and sulfides of elements represented by M above (e.g., SiS 2 , SnS, GeS 2 ).
  • Li 2 S lithium sulfide
  • P 2 S 5 diphosphorus pentasulfide
  • elemental phosphorus elemental sulfur
  • sodium sulfide sodium sulfide
  • hydrogen sulfide hydrogen sulfide
  • lithium halides e.g., LiI, LiBr, LiCl
  • the ratio of Li 2 S to P 2 S 5 is preferably 60:40 to 90:10, more preferably 68:32 to 78:22, in terms of the molar ratio of Li 2 S :P 2 S 5.
  • the lithium ion conductivity can be made high.
  • the lithium ion conductivity can be made preferably 1 ⁇ 10 ⁇ 4 S/cm or more, more preferably 1 ⁇ 10 ⁇ 3 S/cm or more. There is no particular upper limit, but it is practical to set it to 1 ⁇ 10 ⁇ 1 S/cm or less.
  • Li 2 S-P 2 S 5 Li 2 S-P 2 S 5 -LiCl, Li 2 S-P 2 S 5 -H 2 S, Li 2 S-P 2 S 5 -H 2 S-LiCl, Li 2 S-LiI-P 2 S 5 , Li 2 S-LiI-Li 2 O-P 2 S 5 , Li 2 S-LiBr-P 2 S 5 , Li 2 S-Li 2 OP 2 S 5 , Li 2 S-Li 3 PO 4 -P 2 S 5 , Li 2 S-P 2 S 5 -P 2 O 5 , Li 2 SP 2 S 5 -SiS 2 , Li 2 S-P 2 S 5 -SiS 2 -LiCl, Li 2 S-P 2 S 5 -SnS, Li 2 S-P 2 S 5 -Al 2 S 3 , Li 2 S-
  • the mixing ratio of each raw material does not matter.
  • an amorphization method can be mentioned.
  • the amorphization method for example, a mechanical milling method, a solution method, and a melt quenching method can be mentioned. This is because it is possible to perform processing at room temperature, and the manufacturing process can be simplified.
  • the oxide-based inorganic solid electrolyte preferably contains oxygen atoms, has the ionic conductivity of a metal belonging to Group 1 or 2 of the periodic table, and has electronic insulation properties.
  • the oxide-based inorganic solid electrolyte preferably has an ionic conductivity of 1 ⁇ 10 ⁇ 6 S/cm or more, more preferably 5 ⁇ 10 ⁇ 6 S/cm or more, and particularly preferably 1 ⁇ 10 ⁇ 5 S/cm or more. There is no particular upper limit, but it is practical to have an ionic conductivity of 1 ⁇ 10 ⁇ 1 S/cm or less.
  • the compound examples include Li xa La ya TiO 3 (xa satisfies 0.3 ⁇ xa ⁇ 0.7, and ya satisfies 0.3 ⁇ ya ⁇ 0.7) (LLT); Li xb La yb Zr zb M bb mb O nb (M bb is one or more elements selected from Al, Mg, Ca, Sr, V, Nb, Ta, Ti, Ge, In, and Sn.
  • xb satisfies 5 ⁇ xb ⁇ 10, yb satisfies 1 ⁇ yb ⁇ 4, zb satisfies 1 ⁇ zb ⁇ 4, mb satisfies 0 ⁇ mb ⁇ 2, and nb satisfies 5 ⁇ nb ⁇ 20); Li xc B yc M cc zc O nc (M cc is one or more elements selected from C, S, Al, Si, Ga, Ge, In, and Sn.
  • xc satisfies 0 ⁇ xc ⁇ 5, yc satisfies 0 ⁇ yc ⁇ 1, zc satisfies 0 ⁇ zc ⁇ 1, and nc satisfies 0 ⁇ nc ⁇ 6.); Li xd (Al, Ga) yd (Ti, Ge) zd Si ad P md O nd (xd satisfies 1 ⁇ xd ⁇ 3, yd satisfies 0 ⁇ yd ⁇ 1, zd satisfies 0 ⁇ zd ⁇ 2, ad satisfies 0 ⁇ ad ⁇ 1, md satisfies 1 ⁇ md ⁇ 7, and nd satisfies 3 ⁇ nd ⁇ 13.); Li (3-2xe) M ee xe D ee O (xe represents a number from 0 to 0.1, M ee represents a divalent metal atom.
  • D ee represents a halogen atom or a combination of two or more halogen atoms.
  • Li xf Si yf O zf (xf satisfies 1 ⁇ xf ⁇ 5, yf satisfies 0 ⁇ yf ⁇ 3, and zf satisfies 1 ⁇ zf ⁇ 10)
  • Li xg S yg O zg (xg satisfies 1 ⁇ xg ⁇ 3, yg satisfies 0 ⁇ yg ⁇ 2, and zg satisfies 1 ⁇ zg ⁇ 10)
  • Li 7 La 3 Zr 2 O 12 (LLZ); and the like.
  • phosphorus compounds containing Li, P and O examples include lithium phosphate (Li 3 PO 4 ); LiPON in which part of the oxygen element of lithium phosphate is replaced with nitrogen element; LiPOD 1 (D 1 is preferably one or more elements selected from Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zr, Nb, Mo, Ru, Ag, Ta, W, Pt and Au).
  • LiA 1 ON (A 1 is one or more elements selected from Si, B, Ge, Al, C and Ga) can also be preferably used.
  • the halide-based inorganic solid electrolyte is preferably a compound that contains a halogen atom, has ionic conductivity of a metal belonging to Group 1 or 2 of the periodic table, and has electronic insulation.
  • the halide-based inorganic solid electrolyte is not particularly limited, and examples thereof include compounds such as LiCl, LiBr, LiI, and Li 3 YBr 6 and Li 3 YCl 6 described in ADVANCED MATERIALS, 2018, 30, 1803075. Among these, Li 3 YBr 6 and Li 3 YCl 6 are preferred.
  • the hydride-based inorganic solid electrolyte is preferably a compound that contains hydrogen atoms, has the ionic conductivity of a metal belonging to Group 1 or 2 of the periodic table, and has electronic insulation properties.
  • the hydride-based inorganic solid electrolyte is not particularly limited, but examples thereof include LiBH 4 , Li 4 (BH 4 ) 3 I, and 3LiBH 4 --LiCl.
  • the inorganic solid electrolyte is preferably in the form of particles in the non-aqueous secondary battery composition.
  • the particle size (volume average particle size) of the inorganic solid electrolyte is not particularly limited, but is preferably 0.01 ⁇ m or more, more preferably 0.1 ⁇ m or more.
  • the upper limit is preferably 100 ⁇ m or less, more preferably 50 ⁇ m or less.
  • the particle size of the inorganic solid electrolyte is measured by the following procedure. A 1% by mass dispersion of inorganic solid electrolyte particles is prepared by diluting the particles in water (heptane in the case of a substance unstable in water) in a 20 mL sample bottle.
  • the diluted dispersion sample is irradiated with 1 kHz ultrasonic waves for 10 minutes and used for testing immediately thereafter.
  • data is taken 50 times using a quartz cell for measurement at a temperature of 25°C using a laser diffraction/scattering type particle size distribution measuring device LA-920 (trade name, manufactured by HORIBA Co., Ltd.) to obtain the volume average particle size.
  • LA-920 trade name, manufactured by HORIBA Co., Ltd.
  • JIS Japanese Industrial Standards
  • Z 8828 2013
  • the method for adjusting the particle size is not particularly limited, and known methods can be applied, such as a method using a normal grinder or classifier.
  • a grinder or classifier for example, a mortar, ball mill, sand mill, vibration ball mill, satellite ball mill, planetary ball mill, swirling airflow type jet mill, or sieve is preferably used.
  • wet grinding can be performed in the presence of a dispersion medium such as water or methanol.
  • a dispersion medium such as water or methanol.
  • it is preferable to perform classification There is no particular limit to the classification, and it can be performed using a sieve, air classifier, etc. Both dry and wet classification can be used.
  • the composition for a nonaqueous secondary battery may contain one type or two or more types of inorganic solid electrolytes.
  • the content of the inorganic solid electrolyte in the non-aqueous secondary battery composition is not particularly limited, but in terms of the dispersion state and resistance of the solid particles, it is preferably 50% by mass or more, more preferably 70% by mass or more, and particularly preferably 90% by mass or more, based on 100% by mass of the solid content. From the same viewpoint, the upper limit is preferably 99.9% by mass or less, more preferably 99.5% by mass or less, and particularly preferably 99% by mass or less.
  • the content of the inorganic solid electrolyte in the non-aqueous secondary battery composition is preferably such that the total content of the active material and the inorganic solid electrolyte falls within the above range.
  • the solid content refers to components that do not volatilize or vaporize when the nonaqueous secondary battery composition is dried at 150° C. for 6 hours under an atmospheric pressure of 1 mmHg in a nitrogen atmosphere, and typically refers to components other than the dispersion medium described below.
  • the dispersion medium contained in the nonaqueous secondary battery composition of the present invention may be any organic compound that is liquid in the usage environment, and examples of the dispersion medium include various organic solvents. Specific examples of the dispersion medium include alcohol compounds, ether compounds, amide compounds, amine compounds, ketone compounds, aromatic hydrocarbon compounds, aliphatic hydrocarbon compounds, nitrile compounds, and ester compounds.
  • the dispersion medium may be either a non-polar dispersion medium (hydrophobic dispersion medium) or a polar dispersion medium (hydrophilic dispersion medium), but a non-polar dispersion medium is preferred in terms of exhibiting excellent dispersibility.
  • a non-polar dispersion medium generally refers to a medium having a low affinity for water, and in the present invention, examples of the non-polar dispersion medium include ester compounds, ketone compounds, ether compounds, aromatic hydrocarbon compounds, and aliphatic hydrocarbon compounds.
  • alcohol compounds include methyl alcohol, ethyl alcohol, 1-propyl alcohol, 2-propyl alcohol, 2-butanol, ethylene glycol, propylene glycol, glycerin, 1,6-hexanediol, cyclohexanediol, sorbitol, xylitol, 2-methyl-2,4-pentanediol, 1,3-butanediol, and 1,4-butanediol.
  • ether compounds include alkylene glycols (diethylene glycol, triethylene glycol, polyethylene glycol, dipropylene glycol, etc.), alkylene glycol monoalkyl ethers (ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, tripropylene glycol monomethyl ether, diethylene glycol monobutyl ether, etc.), alkylene glycol dialkyl ethers (ethylene glycol dimethyl ether, etc.), dialkyl ethers (dimethyl ether, diethyl ether, diisopropyl ether, dibutyl ether, etc.), and cyclic ethers (tetrahydrofuran, dioxane (including the 1,2-, 1,3-, and 1,4-isomers), etc.).
  • alkylene glycols diethylene glycol, triethylene glycol, polyethylene glycol, dipropy
  • amide compounds include N,N-dimethylformamide, N-methyl-2-pyrrolidone, 2-pyrrolidinone, 1,3-dimethyl-2-imidazolidinone, ⁇ -caprolactam, formamide, N-methylformamide, acetamide, N-methylacetamide, N,N-dimethylacetamide, N-methylpropanamide, and hexamethylphosphoric triamide.
  • Examples of the amine compound include triethylamine, diisopropylethylamine, and tributylamine.
  • Examples of the ketone compound include acetone, methyl ethyl ketone, methyl isobutyl ketone (MIBK), cyclopentanone, cyclohexanone, cycloheptanone, dipropyl ketone, dibutyl ketone, diisopropyl ketone, diisobutyl ketone (DIBK), isobutyl propyl ketone, sec-butyl propyl ketone, pentyl propyl ketone, and butyl propyl ketone.
  • MIBK methyl isobutyl ketone
  • DIBK diisopropyl ketone
  • DIBK diisobutyl ketone
  • aromatic hydrocarbon compounds examples include benzene, toluene, xylene, and perfluorotoluene.
  • aliphatic hydrocarbon compounds examples include hexane, heptane, octane, nonane, decane, dodecane, cyclohexane, methylcyclohexane, ethylcyclohexane, cycloheptane, cyclooctane, decalin, paraffin, gasoline, naphtha, kerosene, and diesel.
  • nitrile compound examples include acetonitrile, propionitrile, and isobutyronitrile.
  • ester compound examples include ethyl acetate, propyl acetate, butyl acetate, ethyl butyrate, propyl butyrate, isopropyl butyrate, butyl butyrate, isobutyl butyrate, butyl pentanoate, pentyl pentanoate, ethyl isobutyrate, propyl isobutyrate, isopropyl isobutyrate, isobutyl isobutyrate, propyl pivalate, isopropyl pivalate, butyl pivalate, and isobutyl pivalate.
  • ether compounds, ketone compounds, aromatic hydrocarbon compounds, aliphatic hydrocarbon compounds, and ester compounds are preferred, and ester compounds, ketone compounds, aromatic hydrocarbon compounds, and ether compounds are more preferred.
  • the number of carbon atoms in the compound that constitutes the dispersion medium is not particularly limited, but is preferably 2 to 30, more preferably 4 to 20, even more preferably 6 to 15, and particularly preferably 7 to 12.
  • the boiling point of the dispersion medium at normal pressure (1 atm: 101,325 Pa) is preferably 50°C or higher, and more preferably 70°C or higher.
  • the upper limit is preferably 250°C or lower, and even more preferably 220°C or lower.
  • the nonaqueous secondary battery composition may contain one or more types of dispersion medium.
  • the content of the dispersion medium in the non-aqueous secondary battery composition is not particularly limited and can be appropriately set.
  • the content is preferably 20 to 80 mass%, more preferably 30 to 70 mass%, and particularly preferably 40 to 60 mass%.
  • the content of the dispersion medium can be set to 60 mass% or less, or can be set to 50 mass% or less.
  • the nonaqueous secondary battery composition of the present invention contains an active material capable of inserting and releasing ions of a metal belonging to Group 1 or Group 2 of the periodic table.
  • the active material include a positive electrode active material and a negative electrode active material, which will be described below.
  • a non-aqueous secondary battery composition containing an active material positive electrode active material or negative electrode active material
  • an electrode composition positive electrode composition or negative electrode composition
  • the positive electrode active material is an active material capable of inserting and releasing ions of a metal belonging to Group 1 or Group 2 of the periodic table, and is preferably capable of inserting and releasing lithium ions reversibly.
  • the material is not particularly limited as long as it has the above characteristics, and may be a transition metal oxide, or an organic substance, or an element such as sulfur that can be composited with Li. Among them, it is preferable to use a transition metal oxide as the positive electrode active material, and a transition metal oxide having a transition metal element M a (one or more elements selected from Co, Ni, Fe, Mn, Cu and V) is more preferable.
  • this transition metal oxide may be mixed with an element M b (an element of the first (Ia) group of the periodic table of metals other than lithium, an element of the second (IIa) group, Al, Ga, In, Ge, Sn, Pb, Sb, Bi, Si, P and B, etc.).
  • the amount of the mixture is preferably 0 to 30 mol% with respect to the amount of the transition metal element M a (100 mol%). It is more preferable to mix and synthesize the transition metal element M a so that the molar ratio of Li/M a is 0.3 to 2.2.
  • transition metal oxides include (MA) transition metal oxides having a layered rock salt structure, (MB) transition metal oxides having a spinel structure, (MC) lithium-containing transition metal phosphate compounds, (MD) lithium-containing transition metal halide phosphate compounds, and (ME) lithium-containing transition metal silicate compounds.
  • transition metal oxides having a (MA) layered rock salt structure include LiCoO2 (lithium cobalt oxide [LCO]), LiNi2O2 (lithium nickel oxide ) , LiNi0.85Co0.10Al0.05O2 (lithium nickel cobalt aluminate [NCA]), LiNi1 /3Co1 / 3Mn1 / 3O2 ( lithium nickel manganese cobalt oxide [ NMC]) and LiNi0.5Mn0.5O2 (lithium manganese nickel oxide ) .
  • LiCoO2 lithium cobalt oxide [LCO]
  • LiNi2O2 lithium nickel oxide
  • LiNi0.85Co0.10Al0.05O2 lithium nickel cobalt aluminate [NCA]
  • LiNi1 /3Co1 / 3Mn1 / 3O2 lithium nickel manganese cobalt oxide [ NMC]
  • LiNi0.5Mn0.5O2 lithium manganese nickel oxide
  • transition metal oxides having a spinel structure include LiMn2O4 ( LMO ) , LiCoMnO4 , Li2FeMn3O8 , Li2CuMn3O8 , Li2CrMn3O8 , and Li2NiMn3O8 .
  • lithium-containing transition metal phosphate compounds include olivine-type iron phosphates such as LiFePO4 and Li3Fe2 ( PO4 ) 3 , iron pyrophosphates such as LiFeP2O7 , cobalt phosphates such as LiCoPO4 , and monoclinic Nasicon-type vanadium phosphates such as Li3V2 ( PO4 ) 3 (lithium vanadium phosphate).
  • the lithium-containing transition metal halophosphate compound include iron fluorophosphates such as Li 2 FePO 4 F, manganese fluorophosphates such as Li 2 MnPO 4 F, and cobalt fluorophosphates such as Li 2 CoPO 4 F.
  • lithium - containing transition metal silicate compounds examples include Li2FeSiO4 , Li2MnSiO4 , and Li2CoSiO4 .
  • transition metal oxides having a layered rock-salt structure (MA) are preferred, and LCO or NMC are more preferred.
  • the shape of the positive electrode active material is not particularly limited, but it is preferably particulate in the nonaqueous secondary battery composition.
  • the particle size (volume average particle size) of the positive electrode active material is not particularly limited. For example, it can be 0.1 to 50 ⁇ m.
  • the particle size of the positive electrode active material particles can be measured in the same manner as the particle size of the inorganic solid electrolyte. To obtain a predetermined particle size, a normal grinder or classifier is used, as in the case of the inorganic solid electrolyte.
  • the positive electrode active material obtained by the baking method may be used after being washed with water, an acidic aqueous solution, an alkaline aqueous solution, or an organic solvent.
  • the positive electrode active material contained in the nonaqueous secondary battery composition may be one type or two or more types.
  • the content of the positive electrode active material in the nonaqueous secondary battery composition is not particularly limited, and is preferably 10 to 97 mass%, more preferably 30 to 95 mass%, still more preferably 40 to 93 mass%, and particularly preferably 50 to 90 mass%, based on 100 mass% of the solid content.
  • the negative electrode active material is an active material capable of inserting and releasing ions of a metal belonging to Group 1 or Group 2 of the periodic table, and is preferably capable of inserting and releasing lithium ions reversibly.
  • the material is not particularly limited as long as it has the above characteristics, and examples thereof include carbonaceous materials, metal oxides, metal composite oxides, lithium alone, lithium alloys, and negative electrode active materials capable of forming an alloy with lithium (alloyable).
  • carbonaceous materials, metal composite oxides, and lithium alone are preferably used from the viewpoint of reliability. In terms of enabling the capacity of the all-solid-state secondary battery to be increased, active materials capable of alloying with lithium are preferred.
  • the carbonaceous material used as the negative electrode active material is a material that is substantially made of carbon.
  • carbon black such as petroleum pitch and acetylene black (AB)
  • graphite natural graphite, artificial graphite such as vapor-grown graphite, etc.
  • carbonaceous materials obtained by firing various synthetic resins such as PAN (polyacrylonitrile)-based resins or furfuryl alcohol resins can be mentioned.
  • various carbon fibers such as PAN-based carbon fibers, cellulose-based carbon fibers, pitch-based carbon fibers, vapor-grown carbon fibers, dehydrated PVA (polyvinyl alcohol)-based carbon fibers, lignin carbon fibers, glassy carbon fibers, and activated carbon fibers, mesophase microspheres, graphite whiskers, and plate-like graphite can also be mentioned.
  • These carbonaceous materials can be divided into non-graphitizable carbonaceous materials (also called hard carbon) and graphite-based carbonaceous materials depending on the degree of graphitization.
  • the carbonaceous material preferably has the interplanar spacing or density and crystallite size described in JP-A-62-22066, JP-A-2-6856, and JP-A-3-45473.
  • the carbonaceous material does not need to be a single material, and a mixture of natural graphite and artificial graphite described in JP-A-5-90844, graphite having a coating layer described in JP-A-6-4516, and the like can also be used.
  • As the carbonaceous material hard carbon or graphite is preferably used, and graphite is more preferably used.
  • Oxides of metals or metalloid elements used as negative electrode active materials are not particularly limited as long as they are oxides capable of absorbing and releasing lithium, and examples of such oxides include oxides of metal elements (metal oxides), composite oxides of metal elements or composite oxides of metal elements and metalloid elements (collectively referred to as metal composite oxides), and oxides of metalloid elements (metalloid oxides). As these oxides, amorphous oxides are preferred, and chalcogenides, which are reaction products of metal elements and elements of group 16 of the periodic table, are also preferred.
  • metalloid elements refer to elements that exhibit intermediate properties between metal elements and non-metalloid elements, and generally include six elements, boron, silicon, germanium, arsenic, antimony, and tellurium, and further include three elements, selenium, polonium, and astatine.
  • amorphous means that the material has a broad scattering band with a peak in the 2 ⁇ value range of 20° to 40° in an X-ray diffraction method using CuK ⁇ rays, and may have crystalline diffraction lines.
  • the strongest intensity of the crystalline diffraction lines seen at 2 ⁇ values of 40° to 70° is preferably 100 times or less, more preferably 5 times or less, the diffraction line intensity of the apex of the broad scattering band seen at 2 ⁇ values of 20° to 40°, and it is particularly preferable that there are no crystalline diffraction lines.
  • amorphous oxides or the above-mentioned chalcogenides of metalloid elements are more preferable, and (composite) oxides or chalcogenides consisting of one element selected from elements of Groups 13 (IIIB) to 15 (VB) of the periodic table (e.g., Al, Ga, Si, Sn, Ge, Pb, Sb, and Bi) or a combination of two or more elements thereof are particularly preferable.
  • elements of Groups 13 (IIIB) to 15 (VB) of the periodic table e.g., Al, Ga, Si, Sn, Ge, Pb, Sb, and Bi
  • preferred amorphous oxides and chalcogenides include Ga2O3 , GeO , PbO , PbO2 , Pb2O3 , Pb2O4 , Pb3O4 , Sb2O3 , Sb2O4 , Sb2O8Bi2O3 , Sb2O8Si2O3 , Sb2O5 , Bi2O3 , Bi2O4 , GeS , PbS , PbS2 , Sb2S3 or Sb2S5 .
  • Suitable examples of negative electrode active materials that can be used in combination with the amorphous oxide mainly composed of Sn, Si, or Ge include carbonaceous materials that can occlude and/or release lithium ions or lithium metal, lithium alone, lithium alloys, and negative electrode active materials that can be alloyed with lithium.
  • the oxide of a metal or metalloid element contains at least one of titanium and lithium as a constituent.
  • the metal composite oxide (lithium composite metal oxide) containing lithium include a composite oxide of lithium oxide and the above metal (composite) oxide or the above chalcogenide, more specifically Li 2 SnO 2 .
  • the negative electrode active material for example, a metal oxide, is preferably one containing titanium element (titanium oxide).
  • Li 4 Ti 5 O 12 lithium titanate [LTO]
  • Li 4 Ti 5 O 12 lithium titanate [LTO]
  • LTO lithium titanate
  • the lithium alloy used as the negative electrode active material is not particularly limited as long as it is an alloy that is normally used as a negative electrode active material in secondary batteries, and examples thereof include lithium aluminum alloys, specifically lithium aluminum alloys in which lithium is the base metal and 10 mass % aluminum is added.
  • the negative electrode active material capable of forming an alloy with lithium is not particularly limited as long as it is normally used as the negative electrode active material of secondary batteries.As such active material, (negative electrode) active material (alloy, etc.) having silicon element or tin element, metals such as Al and In can be mentioned, and the negative electrode active material having silicon element (silicon element-containing active material) that enables higher battery capacity is preferable, and the silicon element-containing active material whose silicon element content is 50 mol% or more of all constituent elements is more preferable.
  • negative electrodes containing these negative electrode active materials can absorb more Li ions than carbon negative electrodes (e.g., graphite and acetylene black). That is, the amount of Li ions absorbed per unit mass increases. Therefore, the battery capacity (energy density) can be increased. As a result, there is an advantage that the battery driving time can be extended.
  • silicon-containing active materials include silicon materials such as Si and SiO x (0 ⁇ x ⁇ 1), silicon-containing alloys containing titanium, vanadium, chromium, manganese, nickel, copper, lanthanum, etc.
  • SiO x itself can be used as a negative electrode active material (semi-metal oxide), and can be used as a negative electrode active material (precursor material) that can be alloyed with lithium because it produces Si by the operation of the all-solid-state secondary battery.
  • Examples of the negative electrode active material containing tin include Sn, SnO, SnO2 , SnS, SnS2 , and the above-mentioned active materials containing silicon and tin.
  • composite oxides with lithium oxide, such as Li2SnO2 can also be mentioned.
  • the above-mentioned negative electrode active materials can be used without any particular restrictions, but in terms of battery capacity, a negative electrode active material that can be alloyed with lithium is a preferred embodiment, and among these, the above-mentioned silicon material or silicon-containing alloy (alloy containing silicon element) is more preferred, and it is even more preferred that the material contains silicon (Si) or a silicon-containing alloy.
  • the negative electrode active material contained in the nonaqueous secondary battery composition may be one type or two or more types.
  • the content of the negative electrode active material in the nonaqueous secondary battery composition is not particularly limited, and is preferably 10 to 90 mass %, more preferably 20 to 85 mass %, still more preferably 30 to 80 mass %, and even more preferably 40 to 75 mass %, based on 100 mass % of the solid content.
  • the surfaces of the positive electrode active material and the negative electrode active material may be coated with another metal oxide.
  • the surface coating agent include metal oxides containing Ti, Nb, Ta, W, Zr, Al, Si, or Li.
  • Specific examples of the oxides include titanate spinel, tantalum-based oxides, niobium -based oxides, and lithium niobate -based compounds, and specific examples of the oxides include Li4Ti5O12 , Li2Ti2O5 , LiTaO3 , LiNbO3 , LiAlO2 , Li2ZrO3 , Li2WO4 , Li2TiO3 , Li2B4O7, Li3PO4 , Li2MoO4 , Li3BO3 , LiBO2 , Li2CO3 , Li2SiO3 , SiO2 , TiO2 , ZrO2 , Al2O3 , and B2O3 .
  • the electrode surface containing the positive electrode active material or the negative electrode active material may be surface-treated with sulfur or phosphorus. Furthermore, the particle surfaces of the positive electrode active material or the negative electrode active material may be subjected to a surface treatment with active light or active gas (plasma, etc.) before or after the above-mentioned surface coating.
  • active light or active gas plasma, etc.
  • a conductive assistant is contained. It is preferable to use an active material in combination with a conductive assistant. For example, it is preferable to use a silicon atom-containing active material as a negative electrode active material in combination with a conductive assistant.
  • the conductive assistant is not particularly limited, and may be any known conductive assistant.
  • it may be an electron conductive material, such as graphites such as natural graphite and artificial graphite, carbon blacks such as acetylene black, ketjen black, and furnace black, amorphous carbon such as needle coke, carbon fibers such as vapor-grown carbon fibers or carbon nanotubes, carbonaceous materials such as graphene or fullerene, metal powders or metal fibers such as copper and nickel, or conductive polymers such as polyaniline, polypyrrole, polythiophene, polyacetylene, and polyphenylene derivatives.
  • graphites such as natural graphite and artificial graphite
  • carbon blacks such as acetylene black, ketjen black, and furnace black
  • amorphous carbon such as needle coke
  • carbon fibers such as vapor-grown carbon fibers or carbon nanotubes
  • carbonaceous materials such as graphene or fullerene
  • metal powders or metal fibers such as copper and nickel
  • conductive polymers such as polyaniline, polypyrrol
  • an active material and a conductive assistant when used in combination, among the above conductive assistants, those that do not insert or release ions (preferably Li ions) of metals belonging to Group 1 or Group 2 of the periodic table when the battery is charged and discharged and do not function as active materials are considered to be conductive assistants. Therefore, among the conductive assistants, those that can function as active materials in the active material layer when the battery is charged and discharged are classified as active materials rather than conductive assistants. Whether or not they function as active materials when the battery is charged and discharged is not unique, but is determined by the combination with the active material.
  • ions preferably Li ions
  • the conductive assistant is preferably in a particulate form in the non-aqueous secondary battery composition.
  • the particle size (volume average particle size) of the conductive assistant is not particularly limited, but is preferably, for example, 0.02 to 1.0 ⁇ m.
  • the particle size of the conductive assistant can be measured in the same manner as the particle size of the inorganic solid electrolyte.
  • the conductive assistant contained in the nonaqueous secondary battery composition may be one type or two types.
  • the content of the conductive assistant in the non-aqueous secondary battery composition is preferably 0 to 10 mass % relative to 100 mass % of the solid content.
  • the non-aqueous secondary battery composition of the present invention also preferably contains a lithium salt (supporting electrolyte).
  • the lithium salt is preferably a lithium salt that is usually used in this type of product, and is not particularly limited.
  • the lithium salt described in paragraphs 0082 to 0085 of JP 2015-088486 A is preferable.
  • the content of the lithium salt is preferably 0.1 parts by mass or more, more preferably 5 parts by mass or more, relative to 100 parts by mass of the inorganic solid electrolyte.
  • the upper limit is preferably 50 parts by mass or less, more preferably 20 parts by mass or less.
  • the non-aqueous secondary battery composition of the present invention does not need to contain any dispersant other than the polymer of the present invention because the above-mentioned polymer of the present invention functions as a dispersant, but may contain a dispersant other than the polymer of the present invention (referred to as other dispersant) to reinforce the dispersing function of the polymer of the present invention.
  • a dispersant other than the polymer of the present invention referred to as other dispersant
  • the other dispersant one that is normally used in non-aqueous secondary batteries can be appropriately selected and used.
  • a compound intended for particle adsorption and steric repulsion and/or electrostatic repulsion is preferably used.
  • the nonaqueous secondary battery composition of the present invention does not need to contain any binder other than the polymer of the present invention because the above-mentioned polymer of the present invention can also function as a binder in the constituent layer, but may contain a binder other than the polymer of the present invention to reinforce the binder function of the polymer of the present invention.
  • a binder one that is normally used in nonaqueous secondary batteries can be appropriately selected and used.
  • the binder other than the polymer of the present invention contained in the nonaqueous secondary battery composition of the present invention may be one type or two or more types.
  • the content of the binder is appropriately determined.
  • the content of the binder in the non-aqueous secondary battery composition is not particularly limited, but is preferably 0.1 to 4.0 mass%, more preferably 0.2 to 2.0 mass%, and even more preferably 0.5 to 1.5 mass% in terms of the binding property of the solid particles.
  • the content of the binder in 100 mass% solid content of the non-aqueous secondary battery composition is preferably 0.1 to 5.0 mass%, more preferably 0.3 to 3.0 mass%, and even more preferably 0.5 to 1.5 mass%.
  • the mass ratio of the combined mass (total amount) of the inorganic solid electrolyte and the active material to the mass of the binder other than the polymer of the present invention is preferably in the range of 1,000 to 1. This ratio is more preferably 500 to 2, and even more preferably 100 to 10.
  • the nonaqueous secondary battery composition of the present invention may appropriately contain, as components other than the above-mentioned components, an ionic liquid, a thickener, a crosslinking agent (such as one that undergoes a crosslinking reaction by radical polymerization, condensation polymerization, or ring-opening polymerization), a polymerization initiator (such as one that generates an acid or radical by heat or light), a defoaming agent, a leveling agent, a dehydrating agent, an antioxidant, etc.
  • the ionic liquid is contained in order to further improve ion conductivity, and any known ionic liquid can be used without any particular limitation.
  • the non-aqueous secondary battery composition of the present invention can be prepared as a mixture, preferably as a slurry, by mixing the polymer of the present invention and the above-mentioned components according to the intended use, for example, in a commonly used mixer.
  • an active material is further mixed.
  • the mixing method is not particularly limited, and can be performed using a known mixer such as a ball mill, a bead mill, a planetary mixer, a blade mixer, a roll mill, a kneader, a disk mill, a self-rotating mixer, or a narrow gap disperser.
  • the components may be mixed all at once or sequentially.
  • the mixing environment is not particularly limited, and examples thereof include dry air (dew point -20°C or lower) or in an inert gas (e.g., in argon gas, helium gas, or nitrogen gas).
  • the mixing conditions are also not particularly limited and are appropriately set, and for example, the mixing temperature can be 15 to 40°C.
  • the rotation speed of the self-rotating mixer or the like can be 200 to 3,000 rpm.
  • the mixing time is not particularly limited and can be appropriately determined depending on the dispersibility of the solid particles, and can be, for example, 1 to 180 minutes. Since the polymer of the present invention can disperse the solid particles in the dispersion medium to a desired dispersion state in a short time, the mixing time (dispersion time) can be set short, for example, 30 minutes or less, and preferably 5 to 25 minutes.
  • the mixing time shortened by the polymer of the present invention refers to the mixing time when mixing the solid particles, the polymer of the present invention, and the dispersion medium, and when mixing each component is performed in multiple stages, the mixing time at each stage can be shortened.
  • the nonaqueous secondary battery composition of the present invention has excellent dispersion characteristics of solid particles, it can be stored after preparation and does not need to be prepared each time it is used.
  • a sheet for a non-aqueous secondary battery can be produced using the composition for a non-aqueous secondary battery of the present invention.
  • the sheet for a non-aqueous secondary battery is a sheet-like molded article capable of forming a constituent layer of a non-aqueous secondary battery, and includes various embodiments depending on the application.
  • the constituent layer formed from the composition for a non-aqueous secondary battery has a low resistance and preferably has a flat surface.
  • a sheet for an all-solid-state secondary battery which is a preferred embodiment of the sheet for a non-aqueous secondary battery, will be described below, but the following description of the sheet for an all-solid-state secondary battery can also be applied to the sheet for a non-aqueous secondary battery.
  • the sheet for an all-solid-state secondary battery of the present invention is a sheet-like molded product capable of forming a constituent layer of an all-solid-state secondary battery, and includes various aspects depending on its application.
  • a sheet preferably used for a solid electrolyte layer also referred to as a solid electrolyte sheet for an all-solid-state secondary battery
  • a sheet preferably used for an electrode or a laminate of an electrode and a solid electrolyte layer (electrode sheet for an all-solid-state secondary battery), etc.
  • these various sheets are collectively referred to as a sheet for an all-solid-state secondary battery.
  • each layer constituting the sheet for an all-solid-state secondary battery may have a single-layer structure or a multi-layer structure.
  • the solid electrolyte layer or the active material layer on the substrate is formed from the composition for non-aqueous secondary batteries of the present invention. Therefore, the layer formed from the composition for non-aqueous secondary batteries of the present invention is formed from components derived from the composition for non-aqueous secondary batteries (excluding the dispersion medium), and usually, solid particles (inorganic solid electrolyte and conductive assistant, and further active material) and the polymer of the present invention are in close contact (bonded) in a mixed state.
  • the sheet for all-solid-state secondary batteries can be incorporated into an all-solid-state secondary battery as is, or after appropriately peeling off the substrate, to achieve low resistance (improved conductivity) and excellent cycle characteristics of the all-solid-state secondary battery.
  • the solid electrolyte sheet for an all-solid-state secondary battery of the present invention may be a sheet having a solid electrolyte layer, and may be a sheet in which the solid electrolyte layer is formed on a substrate, or a sheet formed from the solid electrolyte layer without a substrate (a sheet from which the substrate is peeled off).
  • the solid electrolyte sheet for an all-solid-state secondary battery may have other layers in addition to the solid electrolyte layer. Examples of the other layers include a protective layer (peeling sheet), a current collector, and a coating layer.
  • the solid electrolyte layer of the solid electrolyte sheet for an all-solid-state secondary battery is preferably formed from the non-aqueous secondary battery composition (inorganic solid electrolyte-containing composition) of the present invention.
  • the content of each component in this solid electrolyte layer is not particularly limited, but is preferably the same as the content of each component in the solid content of the non-aqueous secondary battery composition of the present invention.
  • the layer thickness of each layer constituting the solid electrolyte sheet for an all-solid-state secondary battery is the same as the layer thickness of each layer described in the all-solid-state secondary battery described below.
  • the solid electrolyte sheet for an all-solid-state secondary battery of the present invention may be, for example, a sheet having, on a substrate, a layer constituted of the composition for a nonaqueous secondary battery of the present invention, a normal solid electrolyte layer, and a protective layer, in this order.
  • the substrate is not particularly limited as long as it can support the solid electrolyte layer, and examples include sheets (plates) of the materials described below for the current collector, organic materials, inorganic materials, etc.
  • Organic materials include various polymers, and specific examples include polyethylene terephthalate, polypropylene, polyethylene, cellulose, etc.
  • Inorganic materials include, for example, glass, ceramics, etc.
  • the electrode sheet for an all-solid-state secondary battery of the present invention may be an electrode sheet having an active material layer, and may be a sheet in which the active material layer is formed on a substrate (current collector), or a sheet formed from an active material layer without a substrate (a sheet from which the substrate is peeled off).
  • This electrode sheet is usually a sheet having a current collector and an active material layer, but it also includes an embodiment having a current collector, an active material layer, and a solid electrolyte layer in this order, as well as an embodiment having a current collector, an active material layer, a solid electrolyte layer, and an active material layer in this order.
  • the solid electrolyte layer and active material layer of the electrode sheet are preferably formed from the non-aqueous secondary battery composition of the present invention (inorganic solid electrolyte-containing composition or electrode composition).
  • the content of each component in the solid electrolyte layer or active material layer is not particularly limited, but is preferably synonymous with the content of each component in the solid content of the non-aqueous secondary battery composition of the present invention.
  • the layer thickness of each layer constituting the electrode sheet of the present invention is the same as the layer thickness of each layer described in the all-solid-state secondary battery described later.
  • the electrode sheet may have other layers as described above. When the solid electrolyte layer or the active material layer is not formed from the nonaqueous secondary battery composition of the present invention, it is formed from a typical constituent layer forming material.
  • the sheet for an all-solid-state secondary battery of the present invention at least one of the solid electrolyte layer and the active material layer is formed from the composition for a non-aqueous secondary battery of the present invention. Therefore, the sheet for an all-solid-state secondary battery of the present invention has a constituent layer with a flat surface and low resistance to which solid particles containing an inorganic solid electrolyte are bonded. By using this constituent layer as a constituent layer of an all-solid-state secondary battery, it is possible to realize an all-solid-state secondary battery with low resistance (high conductivity) and excellent cycle characteristics.
  • the method of manufacturing the sheet for all-solid-state secondary batteries of the present invention is not particularly limited, and the sheet can be manufactured by forming each of the above layers using the composition for non-aqueous secondary batteries of the present invention.
  • a method of forming a layer (coated and dried layer) of the composition for non-aqueous secondary batteries on a substrate or a current collector (which may be provided with other layers) by film formation (coating and drying) can be mentioned. This makes it possible to manufacture a sheet for all-solid-state secondary batteries having a substrate or a current collector and a coated and dried layer.
  • the adhesion between the current collector and the active material layer can be strengthened.
  • the coated and dried layer refers to a layer formed by coating the composition for non-aqueous secondary batteries of the present invention and drying the dispersion medium (i.e., a layer formed by using the composition for non-aqueous secondary batteries of the present invention and having a composition obtained by removing the dispersion medium from the composition for non-aqueous secondary batteries of the present invention).
  • the active material layer and the coated and dried layer may contain residual dispersion medium as long as the effect of the present invention is not impaired, and the residual amount can be, for example, 3 mass % or less in each layer.
  • each step such as coating and drying will be described in the method for producing an all-solid-state secondary battery below.
  • the coated and dried layer obtained as described above can also be pressed.
  • the pressing conditions and the like will be described later in the method for producing an all-solid-state secondary battery.
  • the substrate, protective layer (particularly the release sheet), etc. can also be peeled off.
  • the nonaqueous secondary battery of the present invention has a positive electrode active material layer, a negative electrode active material layer facing the positive electrode active material layer, and an electrolyte layer disposed between the positive electrode active material layer and the negative electrode active material layer.
  • the nonaqueous secondary battery of the present invention is not particularly limited in configuration other than that, so long as it has an electrolyte layer between the positive electrode active material layer and the negative electrode active material layer, and can employ, for example, a known configuration related to nonaqueous secondary batteries.
  • the all-solid-state secondary battery of the present invention has a positive electrode active material layer, a negative electrode active material layer facing the positive electrode active material layer, and a solid electrolyte layer disposed between the positive electrode active material layer and the negative electrode active material layer.
  • the all-solid-state secondary battery of the present invention is not particularly limited in its configuration as long as it has a solid electrolyte layer between the positive electrode active material layer and the negative electrode active material layer, and can adopt, for example, a known configuration related to all-solid-state secondary batteries.
  • the positive electrode active material layer is preferably formed on a positive electrode current collector and constitutes a positive electrode.
  • the negative electrode active material layer is preferably formed on a negative electrode current collector and constitutes a negative electrode.
  • each constituent layer (including a current collector, etc.) constituting the all-solid-state secondary battery may have a single-layer structure or a multi-layer structure.
  • At least one of the negative electrode active material layer, the positive electrode active material layer, and the solid electrolyte layer is preferably formed from the non-aqueous secondary battery composition of the present invention.
  • at least one of the negative electrode active material layer and the positive electrode active material layer is also formed from the non-aqueous secondary battery composition of the present invention.
  • all layers are also formed from the non-aqueous secondary battery composition of the present invention.
  • forming the constituent layers of the all-solid-state secondary battery from the non-aqueous secondary battery composition of the present invention includes an embodiment in which the constituent layers are formed from the all-solid-state secondary battery sheet of the present invention (however, in the case where a layer other than the layer formed from the non-aqueous secondary battery composition of the present invention is present, the sheet from which this layer has been removed).
  • the all-solid-state secondary battery of the present invention in which at least one of the constituent layers is formed from the non-aqueous secondary battery composition of the present invention, exhibits low resistance (high conductivity) and excellent cycle characteristics.
  • the all-solid-state secondary battery of the present invention exhibits low resistance and high ionic conductivity, and therefore can also extract a large current.
  • each of the constituent layers (including the current collector and the like) constituting the all-solid-state secondary battery may have a single-layer structure or a multi-layer structure.
  • the active material layer or solid electrolyte layer formed from the non-aqueous secondary battery composition of the present invention is preferably the same as or similar to the solid electrolyte layer of the non-aqueous secondary battery composition of the present invention in terms of the types and contents of the components contained therein. The same as in minutes.
  • the thickness of the negative electrode active material layer, the solid electrolyte layer, and the positive electrode active material layer is not particularly limited.
  • the thickness of each layer is preferably 10 to 1,000 ⁇ m, which is within the dimensions of a typical all-solid-state secondary battery.
  • the thickness of at least one of the positive electrode active material layer and the negative electrode active material layer is preferably 50 ⁇ m or more and less than 500 ⁇ m. preferable.
  • the positive electrode active material layer and the negative electrode active material layer may each have a current collector on the side opposite to the solid electrolyte layer.
  • the positive electrode current collector and the negative electrode current collector are preferably made of an electronic conductor. In the present invention, either the positive electrode current collector or the negative electrode current collector, or both of them together, may be simply referred to as current collectors.
  • As the material for forming the positive electrode current collector in addition to aluminum, aluminum alloys, stainless steel, nickel, titanium, etc., aluminum or stainless steel surfaces treated with carbon, nickel, titanium or silver (thin film formed) are preferable, and among these, aluminum and aluminum alloys are more preferable.
  • the material for forming the negative electrode current collector in addition to aluminum, copper, a copper alloy, stainless steel, nickel, and titanium, etc., aluminum, copper, a copper alloy, or stainless steel whose surface is treated with carbon, nickel, titanium, or silver is preferable, and aluminum, copper, a copper alloy, and stainless steel are more preferable.
  • the current collector is usually in the form of a film sheet, but it is also possible to use a net, a punched material, a lath, a porous material, a foam, a molded material of a fiber group, or the like.
  • the thickness of the current collector is not particularly limited, but is preferably 1 to 500 ⁇ m. It is also preferable that the surface of the current collector is made uneven by surface treatment.
  • functional layers or members may be appropriately interposed or disposed between or on the outside of the negative electrode current collector, the negative electrode active material layer, the solid electrolyte layer, the positive electrode active material layer, and the positive electrode current collector.
  • the all-solid-state secondary battery of the present invention may be used as an all-solid-state secondary battery with the above structure, but in order to make it into a dry cell, it is preferable to further encapsulate it in a suitable case.
  • the case may be made of metal or resin (plastic).
  • a metal case for example, an aluminum alloy or stainless steel case can be mentioned.
  • the metal case is divided into a positive electrode case and a negative electrode case, and is electrically connected to the positive electrode current collector and the negative electrode current collector, respectively. It is preferable that the positive electrode case and the negative electrode case are joined and integrated via a gasket for preventing short circuit.
  • FIG. 1 is a cross-sectional view showing a schematic diagram of an all-solid-state secondary battery (lithium ion secondary battery) according to a preferred embodiment of the present invention.
  • the all-solid-state secondary battery 10 according to this embodiment has, as viewed from the negative electrode side, a negative electrode current collector 1, a negative electrode active material layer 2, a solid electrolyte layer 3, a positive electrode active material layer 4, and a positive electrode current collector 5, in this order.
  • Each layer is in contact with each other and has an adjacent structure.
  • a light bulb is used as a model for the operating part 6, and it is configured to be lit by discharging.
  • this all-solid-state secondary battery When an all-solid-state secondary battery having the layer structure shown in FIG. 1 is placed in a 2032-type coin case 11 (see, for example, FIG. 2), this all-solid-state secondary battery is called a laminate 12 for an all-solid-state secondary battery, and a battery produced by placing this laminate 12 for an all-solid-state secondary battery in a 2032-type coin case 11 is sometimes called a (coin-type) all-solid-state secondary battery 13.
  • the positive electrode active material layer 4, the solid electrolyte layer 3, and the negative electrode active material layer 2 are all formed of the nonaqueous secondary battery composition of the present invention.
  • the inorganic solid electrolyte and the polymer of the present invention contained in the solid electrolyte layer 3 and the negative electrode active material layer 2 may be the same or different from each other.
  • the conductive assistants contained in the layers 2 may be the same or different.
  • either the positive electrode active material layer or the negative electrode active material layer, or both of them may be simply referred to as an active material layer or an electrode active material layer. Either one or both together may be simply referred to as an active material or an electrode active material.
  • the solid electrolyte layer contains an inorganic solid electrolyte having ion conductivity of a metal belonging to Group 1 or 2 of the periodic table, the polymer of the present invention, and the optional components described above within a range that does not impair the effects of the present invention, and usually does not contain a positive electrode active material and/or a negative electrode active material.
  • the positive electrode active material layer contains an inorganic solid electrolyte having ion conductivity of a metal belonging to Group 1 or 2 of the periodic table, a positive electrode active material, the polymer of the present invention, and the above-mentioned optional components and the like within the scope not impairing the effects of the present invention.
  • the constituent layers are formed from the nonaqueous secondary battery composition of the present invention, it is possible to realize an all-solid-state secondary battery that has low resistance and exhibits excellent cycle characteristics.
  • the positive electrode current collector 5 and the negative electrode current collector 1 are as described above.
  • a layer formed from a known constituent layer forming material can also be applied.
  • each layer may be composed of a single layer or multiple layers.
  • the nonaqueous secondary battery can be produced by a conventional method using the composition for a nonaqueous secondary battery of the present invention.
  • the all-solid-state secondary battery can be manufactured by forming each of the above layers using the non-aqueous secondary battery composition of the present invention, etc.
  • the all-solid-state secondary battery of the present invention can be manufactured by carrying out a method (the method for manufacturing the sheet for all-solid-state secondary batteries of the present invention) that includes (intervenes) a step of applying the non-aqueous secondary battery composition of the present invention onto a suitable substrate (e.g., a metal foil that serves as a current collector) and forming (forming) a coating film.
  • a suitable substrate e.g., a metal foil that serves as a current collector
  • a non-aqueous secondary battery composition containing a positive electrode active material as a positive electrode material (positive electrode composition) is applied and dried on a metal foil that is a positive electrode current collector to form a positive electrode active material layer, thereby preparing a positive electrode sheet for an all-solid-state secondary battery.
  • a non-aqueous secondary battery composition composition containing an inorganic solid electrolyte for forming a solid electrolyte layer is applied and dried on the positive electrode active material layer to form a solid electrolyte layer.
  • a non-aqueous secondary battery composition containing a negative electrode active material as a negative electrode material (negative electrode composition) is applied and dried on the solid electrolyte layer to form a negative electrode active material layer.
  • an all-solid-state secondary battery having a structure in which a solid electrolyte layer is sandwiched between a positive electrode active material layer and a negative electrode active material layer can be obtained. This can also be enclosed in a case to form a desired all-solid-state secondary battery. Furthermore, the method for forming each layer can be reversed, and an anode active material layer, a solid electrolyte layer, and a cathode active material layer can be formed on an anode current collector, and then a cathode current collector can be stacked on top of the anode active material layer to produce an all-solid-state secondary battery.
  • Another method is the following method. That is, a positive electrode sheet for an all-solid-state secondary battery is prepared as described above. A non-aqueous secondary battery composition containing a negative electrode active material is applied and dried as a negative electrode material (negative electrode composition) on a metal foil that is a negative electrode current collector to form a negative electrode active material layer, thereby preparing a negative electrode sheet for an all-solid-state secondary battery. Next, a solid electrolyte layer is formed on one of the active material layers of these sheets as described above.
  • the other of the positive electrode sheet for an all-solid-state secondary battery and the negative electrode sheet for an all-solid-state secondary battery is laminated on the solid electrolyte layer so that the solid electrolyte layer and the active material layer are in contact with each other.
  • an all-solid-state secondary battery can be manufactured.
  • Another method is the following method. That is, as described above, a positive electrode sheet for an all-solid-state secondary battery and a negative electrode sheet for an all-solid-state secondary battery are prepared. Separately from this, a nonaqueous secondary battery composition is applied to a substrate and dried to prepare a solid electrolyte sheet for an all-solid-state secondary battery consisting of a solid electrolyte layer.
  • the positive electrode sheet for an all-solid-state secondary battery and the negative electrode sheet for an all-solid-state secondary battery are laminated so as to sandwich the solid electrolyte layer peeled off from the substrate. In this way, an all-solid-state secondary battery can be manufactured.
  • a positive electrode sheet for an all-solid-state secondary battery or a negative electrode sheet for an all-solid-state secondary battery, and a solid electrolyte sheet for an all-solid-state secondary battery are prepared.
  • the positive electrode sheet for an all-solid-state secondary battery or the negative electrode sheet for an all-solid-state secondary battery and the solid electrolyte sheet for an all-solid-state secondary battery are stacked and pressed in a state in which the positive electrode active material layer or the negative electrode active material layer is in contact with the solid electrolyte layer. In this way, the solid electrolyte layer is transferred to the positive electrode sheet for an all-solid-state secondary battery or the negative electrode sheet for an all-solid-state secondary battery.
  • the solid electrolyte layer from which the base material of the solid electrolyte sheet for an all-solid-state secondary battery has been peeled off and the negative electrode sheet for an all-solid-state secondary battery or the positive electrode sheet for an all-solid-state secondary battery are stacked (in a state in which the negative electrode active material layer or the positive electrode active material layer is in contact with the solid electrolyte layer) and pressed. In this way, an all-solid-state secondary battery can be manufactured.
  • the pressurizing method and pressurizing conditions in this method are not particularly limited, and the method and pressurizing conditions described in the pressurizing step described later can be applied.
  • the solid electrolyte layer or the like can also be formed, for example, by pressure molding a nonaqueous secondary battery composition or the like on a substrate or an active material layer under pressure conditions described below.
  • a nonaqueous secondary battery of the present invention it is sufficient to use the composition for a non-aqueous secondary battery of the present invention for any one of the positive electrode composition, the inorganic solid electrolyte-containing composition, and the negative electrode composition.
  • the composition for a non-aqueous secondary battery of the present invention can be used for any of the compositions.
  • a solid electrolyte layer or an active material layer is formed using a composition other than the composition for a nonaqueous secondary battery of the present invention
  • examples of the material include compositions that are commonly used, etc.
  • a negative electrode active material layer instead of forming a negative electrode active material layer during the production of an all-solid-state secondary battery, a negative electrode active material layer can be formed by bonding ions of a metal belonging to Group 1 or Group 2 of the periodic table, which has accumulated in the negative electrode current collector during initialization or charging during use, as described below, with electrons and depositing the metal on the negative electrode current collector, etc.
  • the method of applying the non-aqueous secondary battery composition is not particularly limited and can be appropriately selected. For example, it can be applied by coating (preferably wet coating), spray coating, spin coating, dip coating, slit coating, stripe coating, or bar coating.
  • the coating temperature is not particularly limited and can be, for example, applied without heating, usually in the temperature range of about room temperature (for example, 15 to 30°C).
  • the applied nonaqueous secondary battery composition is dried (heated). The drying may be performed after each composition is applied, or after multiple compositions are applied in layers.
  • the drying temperature is not particularly limited. The lower limit is preferably 30° C. or higher, more preferably 60° C. or higher, and even more preferably 80° C. or higher.
  • the upper limit is preferably 300° C. or lower, more preferably 250° C. or lower, and even more preferably 200° C. or lower.
  • the dispersion medium can be removed and the solid state (coated dry layer) can be obtained.
  • the temperature is not too high and each component of the all-solid-state secondary battery is not damaged. As a result, the all-solid-state secondary battery can exhibit excellent overall performance, and can obtain good binding properties and good ionic conductivity.
  • a pressing method include a hydraulic cylinder press.
  • the pressing force is not particularly limited, and is generally preferably in the range of 5 to 1500 MPa.
  • the applied nonaqueous secondary battery composition may be heated at the same time as being pressed.
  • the heating temperature is not particularly limited, and is generally in the range of 30 to 300° C. Pressing may also be performed at a temperature higher than the glass transition temperature of the inorganic solid electrolyte.
  • pressing may also be performed at a temperature higher than the glass transition temperature of the polymer of the present invention.
  • the temperature is generally not higher than the melting point of the polymer of the present invention.
  • the pressurization may be carried out in a state where the coating solvent or dispersion medium has been dried in advance, or in a state where the solvent or dispersion medium still remains.
  • the compositions may be applied simultaneously, or the coating, drying and pressing may be performed simultaneously and/or successively. After being applied to separate substrates, the compositions may be laminated by transfer.
  • the atmosphere in the film-forming method is not particularly limited, and may be any of the atmosphere, dry air (dew point -20°C or lower), and inert gas (for example, argon gas, helium gas, and nitrogen gas).
  • the pressing time may be short (e.g., within a few hours) and high pressure may be applied, or long (one day or more) and moderate pressure may be applied.
  • a restraining device for the all-solid-state secondary battery (such as a screw tightening pressure) may be used to continue applying moderate pressure.
  • the pressing pressure may be uniform or different for the pressed part such as the sheet surface.
  • the pressing pressure may be changed according to the area or film thickness of the pressed part. The same part may also be changed in stages with different pressures.
  • the pressing surface may be smooth or roughened.
  • the nonaqueous secondary battery produced as described above is preferably initialized after production or before use.
  • the initialization is not particularly limited, and can be performed, for example, by performing initial charging and discharging under an elevated pressure and then releasing the pressure until the pressure becomes the general pressure for use in nonaqueous secondary batteries.
  • the nonaqueous secondary battery of the present invention can be applied to various applications.
  • examples include notebook computers, pen-input personal computers, mobile personal computers, electronic book players, mobile phones, cordless phone sub-units, pagers, handheld terminals, mobile fax machines, mobile copiers, mobile printers, headphone stereos, video movie machines, liquid crystal televisions, handheld cleaners, portable CDs, mini-discs, electric shavers, transceivers, electronic organizers, calculators, memory cards, portable tape recorders, radios, and backup power sources.
  • Other consumer applications include automobiles (electric vehicles, etc.), electric vehicles, motors, lighting equipment, toys, game equipment, road conditioners, watches, strobes, cameras, and medical equipment (pacemakers, hearing aids, shoulder massagers, etc.). Furthermore, it can be used for various military applications and space applications. It can also be combined with solar cells.
  • a hyperbranched polymer B-07 having, as polymer arm portions, a polymer chain P 1X consisting of a homopolymer of X-22-174ASX and a polymer chain P 1A consisting of a homopolymer of tBuAAm was synthesized, and a polymer solution B-07 (concentration 10% by mass) consisting of this polymer was obtained.
  • polymer B-21 was synthesized using macromonomer M-7 as follows.
  • 120.0 g of Blenmar AE-400 NOF Corporation
  • 2.40 g of a polymerization initiator V-601 trade name, Fujifilm Wako Pure Chemical Industries, Ltd.
  • M2 monomer solution
  • 300 g of the macromonomer M-7 solution (120.0 g solid) and 225.0 g of butyl butyrate were added and stirred at 80° C., and the monomer solution (M2) was added dropwise over 2 hours.
  • the acid value and base value of each of the synthesized polymers were measured by the above-mentioned methods.
  • the acid value of polymer B-06 was 13 mgKOH/g
  • the acid value of polymer B-19 was 6 mgKOH/g
  • the acid value of polymer B-20 was 20 mgKOH/g
  • the acid value of polymer T-5 was 8 mgKOH/g
  • the acid values of the other polymers were 0 mgKOH/g.
  • the base numbers of the polymers B-01 to B-21 and T-1 to T-7 were all 0 mgKOH/g.
  • the viscosity and weight average molecular weight of each synthesized polymer are shown in Table 1.
  • the viscosity and weight average molecular weight were measured by the above-mentioned method.
  • the viscosity was measured by thoroughly drying the solvent under reduced pressure and preparing a sample of the polymer alone.
  • the "State” column in Table 1 shows the state of the polymer in each composition described below, as determined by measuring the solubility in the dispersion medium by the above-mentioned method, and judging it as "dissolved” or "particles” (not dissolved but dispersed in particle form). None of the synthesized polymers had a flash point (the flash point was 250°C or higher).
  • the “content (mass %)" shown in Table 1 is a value calculated from the charge ratio of each compound during preparation.
  • M-1 X-22-174ASX (product number, molecular weight 900, manufactured by Shin-Etsu Chemical Co., Ltd., SP value 16.7 M-2: X-22-174BX: (product number, molecular weight 2300, manufactured by Shin-Etsu Chemical Co., Ltd., SP value 16.4 M-3: KF-2012 (product number, molecular weight 4600, manufactured by Shin-Etsu Chemical Co., Ltd., SP value 16.3 M-4: X-22-2404 (product number, molecular weight 400, manufactured by Shin-Etsu Chemical Co., Ltd., SP value 16.8 M-5: Methoxypolyethylene glycol monomethacrylate (Blenmer PME-200, NOF Corp.), molecular weight 300, SP value 20.3 M-6: Polyethylene glycol monomethacrylate (Blenmer AE-400, NOF Corp.), molecular weight 500, SP value 21.5 M-7: Macromonomer synthesized in Synthesis Example B-21, number average mole
  • Component (A) in Table 1 shows the following compounds from which the above-mentioned component (A) is derived.
  • tBuAAm N-tert-butylacrylamide (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., SP value 24.1)
  • iPrAAm N-iso-propylacrylamide (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., SP value 25.8)
  • MeAAm N-methylacrylamide (Sigma-Aldrich, SP value 31.4)
  • PhAAm N-phenylacrylamide (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., SP value 27.9)
  • HEA 2-hydroxyethyl acrylate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., SP value 23.5)
  • GMA glycidyl methacrylate (Tokyo Chemical Industry Co., Ltd., SP value 23.7)
  • MEA Methoxyethyl acryl
  • the "Core portion” column in Table 1 shows the following compounds which lead to "L-(S-)n” in the above formula (1).
  • DPMP dipentaerythritol hexakis(3-mercaptopropionate), manufactured by SC Organic Chemicals
  • PEMP pentaerythritol tetra(3-mercaptopropionate), manufactured by SC Organic Chemicals
  • MUT4 pentaerythritol tetrapropanethiol (trade name: Multiol (registered trademark) Y-4, manufactured by SC Organic Chemicals TMMP: trimethylolpropane tris(3-mercaptopropionate), manufactured by SC Organic Chemicals
  • Example 2 Synthesis of sulfide-based inorganic solid electrolyte ⁇ Synthesis Example A> The sulfide-based inorganic solid electrolyte was synthesized with reference to non-patent literatures T. Ohtomo, A. Hayashi, M. Tatsumisago, Y. Tsuchida, S. Hama, K. Kawamoto, Journal of Power Sources, 233, (2013), pp. 231-235, and A. Hayashi, S. Hama, H. Morimoto, M. Tatsumisago, T. Minami, Chem. Lett. , (2001), pp. 872-873.
  • Li2S lithium sulfide
  • P2S5 diphosphorus pentasulfide
  • Table 2 Each of the compositions shown in Tables 2-1 to 2-4 (collectively referred to as Table 2) was prepared as follows.
  • ⁇ Preparation of Inorganic Solid Electrolyte-Containing Composition> In a 45 mL zirconia container (manufactured by Fritsch), 60 g of zirconia beads having a diameter of 5 mm were added, and 9.85 g of LPS synthesized in the above Synthesis Example A, 0.15 g (solid content mass) of the polymer solution or dispersion shown in Table 2-1 or Table 2-4, and 10 g (total amount) of butyl butyrate as a dispersion medium were added. Then, this container was set in a planetary ball mill P-7 (trade name). The mixture was mixed for 5 minutes at a temperature of 25°C and a rotation speed of 150 rpm to prepare inorganic solid electrolyte-containing compositions (slurries) K-1 to K-21 and Kc11 to Kc17, respectively.
  • NMC manufactured by Aldrich Corporation
  • AB acetylene black
  • 0.10 g (solid content mass) of the polymer solution or dispersion shown in Table 2-2 or Table 2-4 were added to the container, and the container was set in a planetary ball mill P-7 (product name) and mixing was continued for 15 minutes at a temperature of 25° C. and a rotation speed of 200 rpm to prepare positive electrode compositions (slurries) PK-1 to PK-21 and PKc21 to PKc27, respectively.
  • ⁇ Preparation of negative electrode composition> In a 45 mL zirconia container (manufactured by Fritsch), 60 g of zirconia beads having a diameter of 5 mm were added, 4.53 g of LPS synthesized in Synthesis Example A, 0.08 g (solid content mass) of the polymer solution or dispersion shown in Table 2-3 or Table 2-4, and 10 g (total amount) of butyl butyrate were added.
  • This container was set in a planetary ball mill P-7 (trade name) and mixed for 30 minutes at a temperature of 25 ° C. and a rotation speed of 300 rpm.
  • the composition content is the content (mass %) relative to the total mass of the composition
  • the solid content is the content (mass %) relative to 100% by mass of the solid content of the composition, and units are omitted in the table.
  • ⁇ Evaluation 1 Dispersion Time Test>
  • the LPS, polymer solution, dispersion medium, active material and conductive assistant were mixed in the same ratio as the composition content and solid content ratio shown in Table 2 under the same preparation conditions as each composition to prepare a composition for evaluating dispersibility (slurry).
  • Each prepared composition was checked for the occurrence of solid particle aggregates using a grind meter (manufactured by Asahi Research Institute Co., Ltd.). In this test, the particle size at which linear and granular marks were generated was observed with a grind meter, and a case of 5 ⁇ m or less was defined as the absence of aggregates.
  • each composition was evaluated for whether it could be applied uniformly (at a constant coating thickness without liquid cutting) using a Baker-type applicator (trade name: SA-201) at 25 ° C.
  • the dispersion time under the preparation conditions of each composition was determined as the type condition (Tp) for this evaluation (presence or absence of aggregates and applicability), and the dispersion time was extended to determine which of the following evaluation criteria for the type condition the shortest dispersion time (T) at which the composition could be uniformly applied without generating aggregates was included in.
  • Tp type condition
  • T shortest dispersion time
  • each of the compositions prepared the occurrence (presence or absence) of aggregates of solid particles was confirmed using a grind meter (manufactured by Asahi Research Institute Co., Ltd.). The size of the aggregates at this time was taken as X ( ⁇ m) and was used as an index of initial dispersibility.
  • each of the prepared compositions was left at 25°C for 24 hours, and then mixed again at a temperature of 25°C using a planetary ball mill P-7 (trade name). The rotation speed and time during remixing were the same as those for the preparation of the inorganic solid electrolyte composition, the positive electrode composition, and the negative electrode composition. The remixed composition was checked for the occurrence (presence) of aggregates of solid particles using the grind meter.
  • the size of the aggregates at this time was taken as Y ( ⁇ m) and was used as an index of redispersibility after storage.
  • the size of the aggregates was determined by the point at which noticeable spots appeared on the applied material on the grind meter (see JIS K-5600-2-5 6.6).
  • the tendency of agglomerates to form (aggregation or sedimentation) was evaluated as the storage stability (redispersibility of solid particles) of the solid electrolyte composition depending on which of the following evaluation criteria the aggregate sizes X and Y were included in. In this test, the smaller the aggregate size X, the better the initial dispersibility, and the smaller the aggregate size Y, the better the storage stability.
  • LPS LPS synthesized in Synthesis Example A
  • NMC LiNi 1/3 Co 1/3 Mn 1/3 O 2 Si: Silicon (APS 1-5 ⁇ m, manufactured by Alfa Aesar)
  • AB Acetylene black
  • VGCF Carbon nanofiber
  • the dried inorganic solid electrolyte-containing composition was heated and pressed at a temperature of 120° C. and a pressure of 40 MPa for 10 seconds to prepare solid electrolyte sheets for all-solid secondary batteries (referred to as solid electrolyte sheets in Tables 3-1 and 3-4) 101 to 121 and c11 to c17, respectively.
  • the film thickness of the solid electrolyte layer was 40 ⁇ m.
  • negative electrode sheets for all-solid-state secondary batteries referred to as negative electrode sheets in Tables 3-3 and 3-4 301 to 321 and c31 to c37 having a negative electrode active material layer with a thickness of 60 ⁇ m, respectively.
  • An all-solid-state secondary battery No. 401 having the layer structure shown in FIG. 1 was produced as follows.
  • the positive electrode sheet for all-solid-state secondary batteries No. 201 (the aluminum foil of the solid electrolyte-containing sheet had been peeled off) with the solid electrolyte layer obtained above was cut into a disk shape with a diameter of 14.5 mm, and placed in a stainless steel 2032-type coin case 11 incorporating a spacer and a washer (not shown in FIG. 2) as shown in FIG. 2.
  • a lithium foil cut into a disk shape with a diameter of 15 mm was placed on the solid electrolyte layer.
  • the all-solid-state secondary battery thus produced has the layer structure shown in FIG. 1 (wherein the lithium foil corresponds to the negative electrode active material layer 2 and the negative electrode current collector 1).
  • All-solid-state secondary batteries Nos. 402 to 421 and c101 to c107 were produced as follows. In the production of the all-solid-state secondary battery No. 401, except that the positive electrode sheet for an all-solid-state secondary battery having a solid electrolyte layer represented by the No. shown in the "Electrode active material layer (sheet No.)" column in Tables 4-1 and 4-3 was used instead of the positive electrode sheet for an all-solid-state secondary battery having a solid electrolyte layer in the production of the all-solid-state secondary battery No. 401, all-solid-state secondary batteries No. 402 to 421 and c101 to c107 were produced in the same manner as in the production of the all-solid-state secondary battery No. 401.
  • An all-solid-state secondary battery No. 501 having the layer structure shown in FIG. 1 was produced as follows.
  • the solid electrolyte-containing negative electrode sheet No. 301 for all-solid-state secondary batteries obtained above (the aluminum foil of the solid electrolyte-containing sheet had already been peeled off) was cut into a disk shape with a diameter of 14.5 mm, and placed in a stainless steel 2032-type coin case 11 incorporating a spacer and a washer (not shown in FIG. 2) as shown in FIG. 2.
  • a positive electrode sheet (positive electrode active material layer) punched out to a diameter of 14.0 mm from the positive electrode sheet for all-solid-state secondary batteries prepared below was laminated on the solid electrolyte layer.
  • a stainless steel foil (positive electrode current collector) was further laminated on top of the positive electrode sheet to form a laminate 12 for all-solid-state secondary batteries (a laminate consisting of stainless steel foil-aluminum foil-positive electrode active material layer-solid electrolyte layer-negative electrode active material layer-copper foil). Then, the 2032-type coin case 11 was crimped to produce the all-solid-state secondary battery No. 501 shown in FIG. 2.
  • the dried positive electrode composition was pressed (10 MPa, 1 minute) at 25° C. using a heat press machine to produce a positive electrode sheet for an all-solid-state secondary battery having a positive electrode active material layer having a thickness of 80 ⁇ m.
  • All-solid-state secondary batteries Nos. 502 to 521 and c201 to c207 were produced as follows. In the production of the all-solid-state secondary battery No. 501, except that the negative electrode sheet for an all-solid-state secondary battery having a solid electrolyte layer represented by the No. shown in the "Electrode active material layer (sheet No.)" column in Tables 4-2 and 4-3 was used in place of the negative electrode sheet for an all-solid-state secondary battery having a solid electrolyte layer in the production of the all-solid-state secondary battery No. 501, all-solid-state secondary batteries Nos. 502 to 521 and c201 to c207 were produced in the same manner as in the production of the all-solid-state secondary battery No. 501.
  • the polymer of the present invention having a viscosity of 0.10 to 10,000 Pa ⁇ s at a temperature of 25° C. and a shear rate of 1 s ⁇ 1 , and a constituent (X) containing a polymer chain and a molecular weight of 400 or more is used in combination with solid particles
  • the solid particles can be dispersed in the dispersion medium as desired, despite the fact that the dispersion time of the solid particles can be shortened, and an inorganic solid electrolyte-containing composition having excellent dispersion stability and handleability can be prepared.
  • an all-solid-state secondary battery produced using an inorganic solid electrolyte-containing composition exhibiting such excellent dispersion characteristics has low battery resistance (conductivity) and excellent cycle characteristics.

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WO2020067106A1 (ja) * 2018-09-27 2020-04-02 富士フイルム株式会社 固体電解質組成物、全固体二次電池用シート、全固体二次電池用電極シート及び全固体二次電池、並びに、全固体二次電池用シート及び全固体二次電池の製造方法
WO2021193826A1 (ja) * 2020-03-27 2021-09-30 富士フイルム株式会社 無機固体電解質含有組成物、全固体二次電池用シート及び全固体二次電池並びに、全固体二次電池用シート及び全固体二次電池の製造方法
WO2022085637A1 (ja) * 2020-10-23 2022-04-28 富士フイルム株式会社 無機固体電解質含有組成物、全固体二次電池用シート及び全固体二次電池、並びに、全固体二次電池用シート及び全固体二次電池の製造方法

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* Cited by examiner, † Cited by third party
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WO2020067106A1 (ja) * 2018-09-27 2020-04-02 富士フイルム株式会社 固体電解質組成物、全固体二次電池用シート、全固体二次電池用電極シート及び全固体二次電池、並びに、全固体二次電池用シート及び全固体二次電池の製造方法
WO2021193826A1 (ja) * 2020-03-27 2021-09-30 富士フイルム株式会社 無機固体電解質含有組成物、全固体二次電池用シート及び全固体二次電池並びに、全固体二次電池用シート及び全固体二次電池の製造方法
WO2022085637A1 (ja) * 2020-10-23 2022-04-28 富士フイルム株式会社 無機固体電解質含有組成物、全固体二次電池用シート及び全固体二次電池、並びに、全固体二次電池用シート及び全固体二次電池の製造方法

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