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  • C08F12/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
  • C08F12/02—Monomers containing only one unsaturated aliphatic radical
  • C08F12/04—Monomers containing only one unsaturated aliphatic radical containing one ring
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  • C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
  • C08F212/02—Monomers containing only one unsaturated aliphatic radical
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  • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
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  • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
  • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
  • C08F220/52—Amides or imides
  • C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
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  • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
  • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
  • C08F220/52—Amides or imides
  • C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
  • C08F220/60—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide containing nitrogen in addition to the carbonamido nitrogen
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  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
  • C08L33/02—Homopolymers or copolymers of acids; Metal or ammonium salts thereof
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M10/00—Secondary cells; Manufacture thereof
  • H01M10/05—Accumulators with non-aqueous electrolyte
  • H01M10/052—Li-accumulators
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  • H01M10/00—Secondary cells; Manufacture thereof
  • H01M10/05—Accumulators with non-aqueous electrolyte
  • H01M10/052—Li-accumulators
  • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M10/00—Secondary cells; Manufacture thereof
  • H01M10/05—Accumulators with non-aqueous electrolyte
  • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
  • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
  • H01M10/0565—Polymeric materials, e.g. gel-type or solid-type
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  • H01M10/00—Secondary cells; Manufacture thereof
  • H01M10/05—Accumulators with non-aqueous electrolyte
  • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
  • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
  • H01M10/0566—Liquid materials
  • H01M10/0567—Liquid materials characterised by the additives
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  • H01M10/00—Secondary cells; Manufacture thereof
  • H01M10/05—Accumulators with non-aqueous electrolyte
  • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
  • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
  • H01M10/0566—Liquid materials
  • H01M10/0569—Liquid materials characterised by the solvents
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  • H01M2300/00—Electrolytes
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  • H01M2300/0025—Organic electrolyte
  • H01M2300/0028—Organic electrolyte characterised by the solvent
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  • H01M2300/0034—Fluorinated solvents
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  • H01M2300/00—Electrolytes
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  • H01M2300/0065—Solid electrolytes
  • H01M2300/0082—Organic polymers
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
  • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
  • Y02E60/10—Energy storage using batteries

Definitions

• the present disclosure relates to polymers, electrolyte compositions, and batteries.
• Known electrolytes for lithium ion batteries and the like include solutions of lithium salts containing organic solvents or ionic liquids.
• Patent Document 1 In addition to lithium ion batteries, research is also being conducted on batteries that use other alkaline ions, such as sodium and potassium, which are more abundant than lithium.
• the present disclosure has been made in consideration of the above circumstances, and aims to provide a polymer with high ionic conductivity, an electrolyte composition, and a battery using the same.
• R 1 is a -COOA group or a monovalent organic group having a -COOA group
• R 2 to R 4 are each independently a hydrogen atom or a monovalent substituent, or one of R 2 and R 3 is a hydrogen atom or a monovalent substituent and the other forms a ring together with R 4.
• R5 is a hydrogen atom or a monovalent substituent
• R6 to R8 are each independently a hydrogen atom or a monovalent substituent
• one of R6 and R7 is a hydrogen atom or a monovalent substituent and the other forms a ring together with R8 .
• * denotes a bonding site of the structural unit (B) to another structural unit.
• the plasticizer comprises at least one selected from the group consisting of carbonate-based solvents, ether-based solvents, fluorine-based solvents, and phosphate-based solvents.
• a battery comprising the electrolyte composition according to any one of [3] to [6].
• the present disclosure provides a polymer with high ionic conductivity, an electrolyte composition, and a battery using the same.
• the polymer of the present embodiment has a -COOA group (A is an alkali metal element).
• the polymer includes a structural unit (A) represented by the following formula (A) and a structural unit (B) represented by the following formula (B).
• the polymer may be one in which the structural unit (A) and the structural unit (B) tend to be arranged alternately, and may be an alternating copolymer.
• the structural unit constituting the polymer does not need to have a structural unit having a carbonyl group other than the structural unit (A), and may be composed of the structural unit (A) and the structural unit (B).
• R 1 is a -COOA group or a monovalent organic group having a -COOA group
• R 2 to R 4 are each independently a hydrogen atom or a monovalent substituent, or one of R 2 and R 3 is a hydrogen atom or a monovalent substituent and the other forms a ring together with R 4.
• * denotes a bonding site of the structural unit (A) to another structural unit.
• R5 is a hydrogen atom or a monovalent substituent
• R6 to R8 are each independently a hydrogen atom or a monovalent substituent, or one of R6 and R7 is a hydrogen atom or a monovalent substituent and the other forms a ring together with R8 .
• * denotes a bonding site of the structural unit (B) to another structural unit.
• each structural unit is relatively uniformly dispersed and introduced into the molecular chain of the polymer, and the environment in which each structural unit (A) is placed in the polymer is particularly uniform. For this reason, in the NMR spectrum of the above polymer measured under predetermined conditions, the half-width of the peak derived from carbonyl carbon is narrow. In this way, the presence of the structural unit (A) dispersed in a similar environment in the molecular chain of the above polymer facilitates the movement of the cation of the alkali metal element between the structural units (A), and excellent ionic conductivity can be exhibited.
• each structural unit (A) when the environment in which each structural unit (A) is placed differs for each structural unit, such as when the structural unit (A) and the structural unit (B) are randomly arranged in the molecular chain of the polymer, the distance between the structural units (A) is also considered to vary, such as when a portion in which the structural unit (A) does not exist is generated in the molecular chain of the polymer, and once the cation of the alkali metal element strongly interacts with the -COO - group of the polymer, energy is required for the subsequent movement, and the ionic conductivity as a whole is not exhibited as much as expected from the structure.
• the resonance frequency of the carbonyl carbon of each structural unit (A) is different, and the width of the peak becomes wider.
• the immobilized anions are non-uniform, a portion where no -COO - group exists on the polymer chain is generated, and it becomes difficult for Li + to move to that portion. Therefore, when considering Li + movement along the polymer chain, it is considered important that the anions are uniformly dispersed.
• the immobilized anions are generally present at a close distance from each other.
• the ionic interaction acts strongly, and it becomes difficult for the cation of the alkali metal element to move with the counter cation.
• the polymer of this embodiment may have a region in which the structural unit (A) and the structural unit (B) are arranged alternately.
• the polymer has a narrow half-width of a peak derived from carbonyl carbon in an NMR spectrum measured under specified conditions, and satisfies at least one of the following (1) to (3):
• the present disclosure is based on the idea that the half-width of a peak derived from carbonyl carbon in an NMR spectrum is useful as an index for grasping the intramolecular distribution of structural units (A) in the polymer.
• the half-value width of the peak derived from the carbonyl carbon of the —COOA group is 1,380 Hz or less.
• the half-value width of the peak derived from the carbonyl carbon of the —COOA group is 80 Hz or less.
• the ratio of the peak height to the half width of the peak derived from the carbonyl carbon of the —COOA group is 0.4 ⁇ 10 ⁇ 4 abn/Hz or more.
• the half-width of the peak derived from carbonyl carbon in the solid-state 13 C-NMR spectrum may be 1350 Hz or less, 1330 Hz or less, 1300 Hz or less, 1280 Hz or less, or 1250 Hz or less.
• the half-width of the peak derived from carbonyl carbon in the solid-state 13 C-NMR spectrum may be 500 Hz or more, 600 Hz or more, 700 Hz or more, 750 Hz or more, or 800 Hz or more. It may be 1000 Hz or more, 1050 Hz or less, 1100 Hz or more, 1150 Hz or more, or 1200 Hz or less.
• the half-width is the full width at half maximum (FWHM) unless otherwise specified. When multiple peaks derived from carbonyl carbon are observed, the half-width of the peak with the greatest intensity may be in the above range.
• the half-width of the peak derived from the carbonyl carbon of the -COOA group of the polymer measured in deuterated methanol may be 70 Hz or less, 60 Hz or less, 50 Hz or less, or 40 Hz or less.
• the half-width of the peak derived from the carbonyl carbon of the -COOA group of the polymer measured in deuterated methanol (CD 3 OD) may be 5 Hz or more, 7 Hz or more, or 10 Hz or more.
• the ratio of the peak height to the half width of the peak may be 0.5 ⁇ 10 ⁇ 4 abn/Hz or more, 0.75 ⁇ 10 ⁇ 4 abn/Hz or more, 1.0 ⁇ 10 ⁇ 4 abn/Hz or more, or 1.2 ⁇ 10 ⁇ 4 abn/Hz or more.
• the ratio of the peak height to the half width of the peak may be 5.0 ⁇ 10 ⁇ 4 abn/Hz or less, or 3.0 ⁇ 10 ⁇ 4 abn/Hz or less.
• the polymer of this embodiment is an alkali metal-containing polymer having an alkali metal-modified carboxyl group.
• an alkali metal-modified carboxyl group refers to a group in which the H of a -COOH group is replaced with an alkali metal element.
• a in the -COOA group may contain at least one selected from the group consisting of potassium, sodium, and lithium, may contain at least one of sodium and lithium, and may contain lithium.
• the content of one type of alkali metal element among the alkali metal elements contained in the polymer may be 80 mol% or more, may be 85 mol%, or may be 90 mol%.
• the one type of alkali metal element may be potassium, sodium, or lithium, may be sodium or lithium, or may be lithium.
• R 1 may be a -COOA group itself, but may also be a monovalent organic group having a -COOA group.
• the number of carbon atoms in the monovalent organic group may be 1 to 20, 1 to 15, 1 to 10, 1 to 5, or 1 to 3.
• the monovalent organic group may have one or more -COOA groups, or may have one -COOA group.
• the -COOA group is bonded to a carbon atom in another part of R 1.
• the monovalent group may also have a substituent that replaces a hydrogen atom bonded to the carbon atom.
• Examples of the substituent include electron-withdrawing groups such as halogen atoms.
• the hydrocarbon group is not particularly limited, and may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group.
• the aliphatic hydrocarbon group may be any of a linear hydrocarbon group, a branched hydrocarbon group, and a cyclic hydrocarbon group.
• the hydrocarbon group may be any of a saturated hydrocarbon group and an unsaturated hydrocarbon group.
• the aromatic hydrocarbon group is a hydrocarbon group having an aromatic portion such as a benzene ring, and may have an aliphatic portion.
• the cyclic hydrocarbon group is a hydrocarbon group having an aliphatic carbon ring portion, and may have a linear or branched aliphatic portion.
• R 1 may be a group represented by -R 9 -COOA.
• R 9 is a divalent organic group.
• the number of carbon atoms in the divalent organic group may be 1 to 19, 1 to 14, 1 to 9, 1 to 4, or 1 or 2.
• the divalent group may have a substituent that replaces a hydrogen atom bonded to the carbon atom.
• the substituent examples include an electron-withdrawing group such as a halogen atom.
• the hydrocarbon group is not particularly limited, and may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group.
• the aliphatic hydrocarbon group may be any of a linear hydrocarbon group, a branched hydrocarbon group, and a cyclic hydrocarbon group.
• the hydrocarbon group may be either a saturated hydrocarbon group or an unsaturated hydrocarbon group.
• examples of the electron-withdrawing group that R 1 may contain include a halogen atom, a sulfonic acid group or a salt thereof, a sulfonic acid ester, a nitro group, a nitrile group, a carboxyl group or a salt thereof, etc.
• the halogen atom may be at least one of Cl and F, and may be F.
• R 4 when R 4 is a monovalent substituent, the substituent may be a monovalent organic group.
• the number of carbon atoms in the monovalent organic group may be 1 to 20, 1 to 15, 1 to 10, 1 to 5, or 1 to 3.
• R 4 in the above formula (A) may be a hydrogen atom or a methyl group.
• R 2 or R 3 when R 4 is a monovalent organic group, R 2 or R 3 may be a group having a -COOA group, or may be a -COOA group.
• R2 or R3 when R2 or R3 is a monovalent substituent, the substituent may be a monovalent organic group.
• the monovalent organic group include those exemplified as R4 above. At least one of R2 and R3 may be a hydrogen atom, and both R2 and R3 may be hydrogen atoms.
• R4 when R2 or R3 is a monovalent organic group, R4 may be a group having a -COOA group, or may be a -COOA group.
• the ring when one of R2 and R3 forms a ring together with R4 , the ring may have 4 to 10 ring members, 5 to 8 ring members, or 5 or 6 ring members.
• a substituent may be bonded to the carbon atom that is a ring member. Examples of the substituent include a halogen atom such as a fluorine atom.
• Structural unit (B) is a structural unit other than structural unit (A) and does not contain a -COOA group.
• R 5 when R 5 is a monovalent substituent, it may be a monovalent organic group.
• the number of carbon atoms in the monovalent organic group may be 1 to 20, 2 to 15, or 4 to 10.
• the aromatic ring may have at least one of a carbocycle and a heterocycle, and may be a carbocycle.
• An atom that is a member of the aromatic ring in R 5 in the above formula (B) may be bonded to a carbon atom of the ethylene group in formula (B) (the carbon atom to which R 5 is directly bonded in formula (B)), and a carbon atom that is a member of the aromatic ring in R 5 may be bonded to a carbon atom of the ethylene group in formula (B).
• the group having an aromatic ring may be either a monocyclic or condensed ring, or may be a group having a benzene ring.
• the group having an aromatic ring may have a monovalent substituent, and the monovalent substituent may be bonded to a carbon atom that is a member of the aromatic ring.
• R 5 is a group having an aromatic ring
• the group having an aromatic ring has a monovalent substituent bonded to the aromatic ring
• examples of the monovalent substituent bonded to the aromatic ring include monovalent organic groups, electron-withdrawing groups such as halogen atoms (excluding those which are monovalent organic groups), and electron-donating groups such as amino groups (-NH 2 ) (excluding those which are monovalent organic groups).
• Examples of the monovalent substituent bonded to the aromatic ring include monovalent organic groups such as substituted or unsubstituted hydrocarbon groups and groups represented by the formula: -R 41 -(W 1 -R 42 ) n -W 2 R 43.
• R 41 is a covalent bond or a divalent organic group.
• the divalent organic group may be a divalent hydrocarbon group.
• the number of carbon atoms in the divalent hydrocarbon group may be 1 to 8, 1 to 5, or 1 to 3.
• the hydrogen atom bonded to the divalent hydrocarbon group may be substituted with a substituent such as a monovalent substituent (i.e., the divalent hydrocarbon group may be a substituted hydrocarbon group).
• the substituent include a halogen atom such as a fluorine atom.
• the divalent hydrocarbon group may be either an aromatic hydrocarbon group or an aliphatic hydrocarbon group, or may be an aliphatic hydrocarbon group.
• the aliphatic hydrocarbon group may be a saturated aliphatic hydrocarbon group, or may be a straight-chain or branched-chain aliphatic hydrocarbon group.
• Specific examples of the divalent hydrocarbon group include a methylene group, an ethylene group, a 1,2-propylene group, a 1,3-propylene group, or a group in which some or all of the hydrogen atoms in these groups have been substituted with halogen atoms such as fluorine atoms, or may be a methylene group.
• R 42 is a divalent organic group, and may be a divalent hydrocarbon group.
• the number of carbon atoms in the divalent hydrocarbon group may be 1 to 8, 1 to 5, or 1 to 3.
• the hydrogen atom bonded to the divalent hydrocarbon group may be substituted with a substituent such as a monovalent substituent (i.e., the divalent hydrocarbon group may be a substituted hydrocarbon group). Examples of the substituent include a halogen atom such as a fluorine atom.
• the divalent hydrocarbon group may be either an aromatic hydrocarbon group or an aliphatic hydrocarbon group, and may be an aliphatic hydrocarbon group.
• the aliphatic hydrocarbon group may be a saturated aliphatic hydrocarbon group, and may be a straight-chain or branched-chain aliphatic hydrocarbon group.
• Specific examples of the divalent hydrocarbon group include a methylene group, an ethylene group, a 1,2-propylene group, a 1,3-propylene group, or a group in which some or all of the hydrogen atoms of these groups have been substituted with halogen atoms such as fluorine atoms, and may be an ethylene group.
• n may be 1 to 10, 1 to 5, or 1 to 3.
• the n may be an integer or a rational number (for example, n is an average value across the structural units (B) in the polymer). When there are multiple R 42 in one structural unit, they may be different or the same.
• R 43 may be a hydrogen atom or a divalent hydrocarbon group.
• the number of carbon atoms in the monovalent hydrocarbon group may be 1 to 8, 1 to 5, or 1 to 3.
• the hydrogen atom bonded to the monovalent hydrocarbon group may be substituted with a substituent such as a monovalent substituent (i.e., the monovalent hydrocarbon group may be a substituted hydrocarbon group). Examples of the substituent include a halogen atom such as a fluorine atom.
• the monovalent hydrocarbon group may be either an aromatic hydrocarbon group or an aliphatic hydrocarbon group, and may be an aliphatic hydrocarbon group.
• the aliphatic hydrocarbon group may be a saturated aliphatic hydrocarbon group, and may be a linear or branched aliphatic hydrocarbon group.
• Specific examples of the divalent hydrocarbon group include a methyl group, an ethyl group, an isopropyl group, an n-propyl group, or a group in which some or all of the hydrogen atoms in these groups are substituted with halogen atoms such as fluorine atoms, and may be a methyl group.
• the structural unit (B) may contain at least one structural unit derived from a monomer represented by the following formula (B1). (In the formula, m is 0 to 4, and n is 0 to 10.
• R 20 may be a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. The alkyl group may be a methyl group or an ethyl group, or may be a methyl group.)
• m may be 1 to 3, 1 to 2, or 1.
• the above m may be an integer or an average value across all structural units derived from the monomer represented by formula (B1) contained in the polymer (in this case, m is a rational number).
• n may be 1 to 4, or 1 to 3.
• the above n may be an integer or an average value across all structural units derived from the monomer represented by formula (B1) contained in the polymer (in this case, n is a rational number).
• R 6 to R 8 when at least one of R 6 to R 8 is a monovalent substituent, the substituent can be a monovalent organic group.
• the monovalent organic group include those exemplified above as R 4.
• at least one of R 6 to R 8 can be a hydrogen atom, or all of R 6 to R 8 can be hydrogen atoms.
• the polymer according to the present disclosure contains multiple structural units (A), and the multiple structural units (A) may be the same or different from each other, and may contain multiple types of structural units (A) with different chemical structures.
• the polymer according to the present disclosure may also contain multiple structural units (B), and when multiple structural units (B) are contained, the multiple structural units (B) may be the same or different from each other, and may contain multiple types of structural units (B) with different chemical structures.
• the number average molecular weight (Mn) of the polymer according to the present disclosure may be 5,000 to 400,000, 8,000 to 200,000, 10,000 to 150,000, 10,000 to 100,000, or 10,000 to 50,000.
• the number average molecular weight of the polymer can be measured by gel permeation chromatography.
• the gel permeation chromatography is performed under the following conditions.
• a standard sample of polymethyl methacrylate manufactured by Polymer Laboratories, Mn 800 to 2,200,000
• ⁇ GPC measurement conditions Equipment: GPC-104 (Shodex) DU-H2000 precision pump 74S-RI refractive-index detector 41-UV UV/vis detector
• the method for producing the polymer of this embodiment includes a method of radically polymerizing a monomer composition containing monomers having a monomer reactivity ratio of 0.5 or less.
• the monomer reactivity ratio can be calculated by the Fineman-Ross method or the Kelen-Tuedos method.
• Specific examples of the method for producing the polymer include the following two production methods (production method (I) and production method (II)).
• a method comprising the steps of: obtaining a raw material polymer by polymerizing a monomer mixture containing a monomer (A') having a functional group capable of inducing a -COOA group, and a monomer (B) other than the monomer in which the functional group of the monomer (A') has been converted to a -COOA group, and converting the functional group in the raw material polymer to a -COOA group.
• the monomers (A') and (B) can be selected such that the reactivity ratio r1' of the monomer (A') and the reactivity ratio r2' of the monomer (B) in the polymerization reaction between the monomer (A') and the monomer (B) are both 0.5 or less.
• a method comprising a step of polymerizing a monomer mixture containing a monomer (A) having a -COOA group and a monomer (B) other than the monomer (A), wherein the reactivity ratio r1 of the monomer (A) and the reactivity ratio r2 of the monomer (B) in the polymerization reaction between the monomer (A) and the monomer (B) are both 0.5 or less.
• the structural unit derived from the monomer (A') becomes the above structural unit (A) by converting the functional group capable of inducing a -COOA group into a -COOA group after it is incorporated as a structural unit into the raw polymer.
• the structural unit derived from the monomer means, in the case of radical polymerization, a structural unit having a chemical structure obtained directly by radical polymerization of the monomer.
• R 1 ' to R 4 ' may correspond to R 1 to R 4 in formula (A), respectively.
• R 1 ' is a functional group capable of inducing a -COOA group
• R 2 to R 4 are each independently a hydrogen atom or a monovalent substituent
• one of R 2 and R 3 is a hydrogen atom or a monovalent substituent and the other forms a ring together with R 4.
• A is an alkali metal element.
• Examples of the functional group capable of inducing a -COOA group contained in the monomer (A') include a group that is hydrolyzed to a -COOH group.
• Examples of the group that is hydrolyzed to a -COOH group include a -COOR group (R is a monovalent organic group, which may be a substituted or unsubstituted hydrocarbon group or a substituted or unsubstituted alkyl group), and examples of the functional groups include the following: (In the formula, * represents a bonding site for the functional group, and the hydrogen atom of the benzene ring may be substituted with a substituent.)
• the reactivity ratio r1' of monomer (A') in the polymerization reaction between monomer (A') and monomer (B) may be 0.4 or less, 0.3 or less, 0.2 or less, or 0.05 or less.
• the reactivity ratio r2' of monomer (B) in the polymerization reaction between monomer (A') and monomer (B) may be 0.4 or less, 0.3 or less, 0.2 or less, or 0.05 or less.
• the reactivity ratio r1 of monomer (A) in the polymerization reaction between monomer (A) and monomer (B) may be 0.4 or less, 0.3 or less, 0.2 or less, or 0.05 or less.
• the reactivity ratio r2 of monomer (B) in the polymerization reaction between monomer (A) and monomer (B) may be 0.4 or less, 0.3 or less, 0.2 or less, or 0.05 or less.
• the half-width of the above NMR spectrum of the obtained polymer can be set within a predetermined range by selecting, from among monomers (A') that can derive the same structural unit as the structural unit derived from monomer (A), one that has a low reactivity ratio in a polymerization reaction with monomer (B).
• the monomer reactivity ratio of the monomers is less than 1, which increases the alternating copolymerizability.
• a monomer X having an ethylenically unsaturated group with an electron deficiency is polymerized with a monomer Y having an ethylenically unsaturated group with an electron richness, it is easy to obtain a copolymer in which monomer X and monomer Y are arranged alternately.
• the ethylenically unsaturated group in the monomer (A') is electron deficient and the ethylenically unsaturated group in the monomer (B) is electron rich, a polymer in which structural units derived from the monomer (A') and structural units derived from the monomer (B) are arranged alternately is easily obtained.
• a monomer having an electron-withdrawing group may be used as the monomer (A').
• a monomer having an aromatic ring directly bonded to the ethylenically unsaturated group may be used as the monomer (B).
• the monomer (B) may further have an electron-donating group.
• the ethylenically unsaturated group in the monomer (A) is electron deficient and the ethylenically unsaturated group in the monomer (B) is electron rich, a polymer in which structural units derived from the monomer (A) and structural units derived from the monomer (B) are arranged alternately is easily obtained.
• a monomer having an electron-withdrawing group may be used as the monomer (A).
• a monomer having an aromatic ring directly bonded to the ethylenically unsaturated group may be used as the monomer (B).
• the monomer (B) may further have an electron-donating group.
• the polymer obtained by the manufacturing method of this embodiment can be used as a component of an electrolyte composition.
• One embodiment of the electrolyte composition may contain the above-mentioned polymer and, if necessary, components other than the above-mentioned polymer.
• Such components include anion receptors, plasticizers, alkali metal salts, other resins such as fluorine-based resins (binder resins, etc.), fabrics such as nonwoven fabrics, porous materials, viscosity adjusters, etc.
• the electrolyte composition may contain an anion receptor.
• the anion receptor is a chemical species that captures anions by forming electrostatic interactions, hydrogen bonds, acid-base complexes, etc. with the anions.
• the anion receptor captures the counter anion of the alkali metal ion and promotes dissociation between the counter anion and the alkali metal ion. This increases the mobility of the metal ion. This also tends to improve the conductivity and transport number of the alkali metal ion in the electrolyte composition.
• the anion receptor may have a formula weight (molecular weight) of, for example, 1,000 or less, 800 or less, or 500 or less.
• the anion receptor may have Lewis acidity.
• the anion receptor can capture the anion by accepting the unshared electron pair of the anion and forming an acid-base complex.
• Examples of such compounds include compounds having an electron-deficient atom.
• An electron-deficient atom is an atom that is covalently bonded to another atom but has fewer than eight electrons in its outermost shell.
• Examples of the electron-deficient atom include atoms belonging to Group 13 of the periodic table, and more specifically, it may be at least one of an aluminum atom and a boron atom, or it may be a boron atom.
• Anion receptors having a boron atom include boron compounds that function as Lewis acids, such as diborane and compounds represented by the following chemical formulas IA to IE.
• R 31 is a halogen atom or a monovalent organic group.
• the halogen atom may be a fluorine atom or a chlorine atom, or may be a fluorine atom.
• the number of carbon atoms in the monovalent organic group may be 1 to 20, 1 to 15, 2 to 10, or 2 to 6.
• the hydrogen atom bonded to the hydrocarbon portion in the monovalent organic group may be substituted with a substituent.
• the monovalent organic group is bonded to the boron atom (B) in formula IA through a carbon atom in the monovalent organic group.
• the substituent may be a monovalent substituent such as a halogen atom, a monovalent electron-withdrawing group, or a fluorine atom.
• the monovalent organic group may be a hydrocarbon group or a halogen-substituted hydrocarbon group, and the halogen-substituted hydrocarbon group may be a partially or fully fluorinated hydrocarbon group.
• the multiple R 31 may be different from each other or all be the same.
• R 32 is a hydrogen atom or a monovalent organic group.
• the number of carbon atoms in the monovalent organic group may be 1 to 20, 1 to 15, 2 to 10, or 2 to 6.
• the monovalent organic group is bonded to the oxygen atom (O) in formula IB via a carbon atom in the monovalent organic group.
• the hydrogen atom bonded to the hydrocarbon portion in the monovalent organic group may be substituted with a substituent.
• the substituent may be a monovalent substituent such as a halogen atom, a monovalent electron-withdrawing group, or a fluorine atom.
• the monovalent organic group may be a hydrocarbon group or a halogen-substituted hydrocarbon group, and the halogen-substituted hydrocarbon group may be a partially or fully fluorinated hydrocarbon group.
• the multiple R 32 may be different from each other or all be the same.
• R 35 is a divalent organic group
• Z 2 is a covalent bond or an oxygen atom.
• the number of carbon atoms in the divalent organic group may be 1 to 15, may be 2 to 10, or may be 3 to 8.
• R 35 , two Z 2 , and the boron atom (B) form a ring, and the ring may have 4 to 8 ring members, or may have 5 or 6 ring members.
• Z2 is an oxygen atom
• the divalent organic group is bonded to Z2 in formula IC through a carbon atom contained in the divalent organic group
• Z2 is a covalent bond
• the divalent organic group is bonded to the boron atom (B) in formula IC through a carbon atom contained in the divalent organic group.
• the hydrogen atom bonded to the hydrocarbon portion of the divalent organic group may be substituted with a substituent.
• the substituent may be a monovalent substituent such as a halogen atom, a monovalent electron-attracting group, or a fluorine atom.
• the divalent organic group may be a hydrocarbon group or a halogen-substituted hydrocarbon group, and the halogen-substituted hydrocarbon group may be a partially or fully fluorinated hydrocarbon group.
• the multiple Z2 may be different from each other or all the same.
• R 36 is a hydrogen atom or a monovalent organic group.
• the monovalent organic group may be a group that bonds to the boron atom (B) in formula IC through a carbon atom contained in the monovalent organic group, but may also be a group represented by -OR 37.
• R 37 in the group represented by -OR 37 is a hydrogen atom or a monovalent organic group.
• the monovalent organic group represented by R 37 is bonded to the oxygen atom of -OR 37 through a carbon atom contained in the monovalent organic group.
• the number of carbon atoms contained in the organic group may be 1 to 20, may be 1 to 15, may be 2 to 10, or may be 2 to 6.
• the number of carbon atoms contained in the monovalent organic group represented by R 37 may be 1 to 20, may be 1 to 15, may be 2 to 10, or may be 2 to 6.
• the hydrogen atom bonded to the hydrocarbon portion of the monovalent organic group may be substituted with a substituent.
• the monovalent organic group is bonded to the boron atom (B) in formula IA through a carbon atom possessed by the monovalent organic group.
• the substituent may be a monovalent substituent such as a halogen atom, a monovalent electron-withdrawing group, or a fluorine atom.
• the monovalent organic group may be a hydrocarbon group or a halogen-substituted hydrocarbon group, and the halogen-substituted hydrocarbon group may be a partially or fully fluorinated hydrocarbon group.
• R 33 is a hydrogen atom, a halogen atom, or a monovalent organic group.
• the halogen atom may be a fluorine atom or a chlorine atom, or may be a fluorine atom.
• the number of carbon atoms in the monovalent organic group may be 1 to 20, 1 to 15, 2 to 10, or 2 to 6.
• the hydrogen atom bonded to the hydrocarbon portion of the monovalent organic group may be substituted with a substituent.
• the monovalent organic group is bonded to the boron atom (B) in formula ID through a carbon atom in the monovalent organic group.
• the substituent may be a monovalent substituent such as a halogen atom, a monovalent electron-withdrawing group, or a fluorine atom.
• the monovalent organic group may be a hydrocarbon group or a halogen-substituted hydrocarbon group, and the halogen-substituted hydrocarbon group may be a partially or fully fluorinated hydrocarbon group.
• the multiple R 33 may be different from each other or all be the same.
• R 34 is a hydrogen atom or a monovalent organic group.
• the number of carbon atoms in the monovalent organic group may be 1 to 20, 1 to 15, 2 to 10, or 2 to 6.
• the hydrogen atom bonded to the hydrocarbon portion in the monovalent organic group may be substituted with a substituent.
• the monovalent organic group is bonded to the oxygen atom (O) in formula IE via a carbon atom in the monovalent organic group.
• the substituent may be a monovalent substituent such as a halogen atom, a monovalent electron-withdrawing group, or a fluorine atom.
• the monovalent organic group may be a hydrocarbon group or a halogen-substituted hydrocarbon group, and the halogen-substituted hydrocarbon group may be a partially or fully fluorinated hydrocarbon group.
• the multiple R 34s may be different from each other or all be the same.
• boron compounds include diborane, boron trifluoride, boric acid, boroxine, trimethylborane, triethylborane, tri-n-propylborane, triisopropylborane, triphenylborane, trimethylborate, triethylborate, triphenylborate, tri-n-propylborate, triisopropylborate, 2-methoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane, 2-ethoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane, These include organic boron compounds such as loran, 2,4,6-trimethylboroxine, 2,4,6-triethylboroxine, 2,4,6-trivinylboroxine, 2,4,6-trimethoxyboroxine, 2,4,6-trimethoxyboroxine, and triphenylboroxine, and halogen-substitute
• anion receptors having an aluminum atom include aluminum compounds that function as Lewis acids, such as compounds represented by the formula AlX 1 3 (X 1 in this formula is a halogen atom and may be a fluorine atom) and compounds represented by the formula Al(OR 35 ) 3 (R 35 in this formula is a hydrocarbon group and may be an alkyl group).
• the anion receptor may also be an azaether.
• An azaether is a compound in which -O- of an ether compound is replaced with -NR E - (wherein R E is a hydrogen atom or an organic group).
• the azaether may be either a chain azaether or a cyclic azaether.
• the azaether may have an electron-withdrawing group, for example, in the hydrocarbon portion.
• the content of the anion receptor in the electrolyte composition may be 10 to 200 parts by mass, 30 to 180 parts by mass, 50 to 150 parts by mass, or 80 to 130 parts by mass relative to 100 parts by mass of the polymer of this embodiment.
• the plasticizer may be an organic solvent.
• the organic solvent may be an aprotic solvent.
• the organic solvent may contain one or more organic solvents selected from the group consisting of carbonate solvents, ether solvents, fluorine solvents, nitrile solvents, and phosphate solvents, and may contain a phosphate ester.
• Carbonate solvents include chain carbonates such as dimethyl carbonate, diethyl carbonate, and ethyl methyl carbonate; and cyclic carbonates such as ethylene carbonate, propylene carbonate, butylene carbonate, and vinylene carbonate.
• Ether solvents include cyclic ethers such as tetrahydrofuran, 2-methyltetrahydrofuran, tetrahydropyran, and 1,3-dioxolane; and chain ethers such as 1,2-diethoxyethane and ethoxymethoxyethane.
• fluorine-based solvents examples include hydrofluorocarbons such as perfluorooctane; hydrofluoroethers such as methyl nonafluorobutyl ether and ethyl nonafluorobutyl ether; and hydrofluoroolefins such as 1,3,3,3-tetrafluoropropene.
• hydrofluorocarbons such as perfluorooctane
• hydrofluoroethers such as methyl nonafluorobutyl ether and ethyl nonafluorobutyl ether
• hydrofluoroolefins such as 1,3,3,3-tetrafluoropropene.
• phosphate esters examples include trimethyl phosphate (TMP), triethyl phosphate (TEP), and tris(2,2,2-trifluoroethyl) phosphate (TFEP).
• TMP trimethyl phosphate
• TEP triethyl phosphate
• TFEP tris(2,2,2-trifluoroethyl) phosphate
• DMSO dimethyl sulfoxide
• amide-based solvents such as dimethylformamide (DMF) and dimethylacetamide (DMA)
• organic solvents having a carbonyl group such as acetone (referring to carbonyl compounds other than
• the content of the organic solvent in the electrolyte composition may be 100 to 500 parts by mass, 150 to 450 parts by mass, 200 to 400 parts by mass, or 250 to 350 parts by mass relative to 100 parts by mass of the polymer of this embodiment.
• the content of the organic solvent in the electrolyte composition may be 30 to 90 mass%, 35 to 85 mass%, 40 to 80 mass%, 45 to 75 mass%, 50 to 70 mass%, or 60 to 70 mass%, based on the total amount of the electrolyte composition.
• the electrolyte composition may further contain other resins such as fluororesins (e.g., binder resins), fabrics such as nonwoven fabrics, porous materials, viscosity adjusters, etc.
• the electrolyte composition may contain a resin having a carbon chain as the main chain as the fluororesin.
• the carbon chain may be formed by radical polymerization of an ethylenically unsaturated group.
• fluororesins include poly(vinylidene fluoride-co-hexafluoropropylene) (PVDF-HFP), polyvinylidene fluoride (PVDF), etc.
• the content of the other resin in the electrolyte composition may be 10 to 100 parts by mass, 20 to 80 parts by mass, 30 to 70 parts by mass, or 40 to 60 parts by mass relative to 100 parts by mass of the polymer of this embodiment.
• the electrolyte composition may contain an alkali metal salt.
• the alkali metal salt include MF, MCl, MBr, MI, MClO 4 , MPF 6 , MBF 4 , M 2 SO 4 , M[(C h F 2h+1 )SO 3 ] (h is 0 to 3), M[(C h F 2h+1 )SO 2 ] 2 N (h is 0 to 3), M ⁇ [(C h F 2h+1 )SO 2 ]N[(C i F 2i+1 )SO 2 ] ⁇ (h, i is 0 to 3), and the like, where M is an alkali metal.
• One or more types of alkali metal salts may be used.
• the alkali metal contained in the alkali metal salt may be the same alkali metal element as the alkali metal element contained in the structural unit (A) described in the description of the polymer of the present disclosure.
• the content of the alkali metal salt in the electrolyte composition may be 10 to 200 parts by mass, 20 to 150 parts by mass, 30 to 100 parts by mass, or 40 to 75 parts by mass relative to 100 parts by mass of the polymer of this embodiment.
• the method for producing the electrolyte composition is not particularly limited, but examples include a method in which a dry film of the polymer of this embodiment or a dry film is produced by mixing the polymer of this embodiment with a binder resin, and then the dry film is impregnated with an organic solvent.
• an organic solvent may be added after a dry film is produced by mixing the polymer and, optionally, a binder resin and an alkali metal salt or anion receptor, or the alkali metal salt or anion receptor may be dissolved in an organic solvent and added to the dry film.
• the electrolyte composition of this embodiment can be used as a composition for forming an electrolyte for batteries, capacitors, etc. That is, the electrolyte of this embodiment includes the electrolyte composition.
• the battery include batteries that perform charging and discharging by the movement of alkali metal ions, such as lithium ion batteries and sodium ion batteries.
• the battery may be a primary battery, a secondary battery, or a solid-state battery.
• the battery of this embodiment includes a positive electrode, a negative electrode, and an electrolyte disposed between the positive electrode and the negative electrode.
• the positive electrode may be a layer containing a positive electrode material formed on a current collector.
• the negative electrode may be a layer containing a negative electrode material formed on a current collector.
• the negative electrode of the lithium ion battery is not particularly limited, and may contain a negative electrode active material and, if necessary, a conductive agent, a binder, etc.
• the negative electrode active material include simple elements such as Li, Si, P, Sn, Si-Mn, Si-Co, Si-Ni, In, and Au, as well as alloys or composites containing these elements, carbon materials such as graphite, substances in which lithium ions are inserted between the layers of the carbon material, and oxides containing titanium.
• the positive electrode of the lithium ion battery is not particularly limited, and may contain a positive electrode active material and, if necessary, a conductive assistant, a binder, etc.
• the positive electrode active material include lithium composite metal oxides containing lithium and a transition metal element.
• the transition metal element may be at least one selected from the group consisting of V, Cr, Mn, Fe, Co, Ni, Cu, and Al, and may contain Ni.
• lithium composite metal oxide examples include LiCoO2 , LiNiO2, LiMn2O4 , LiNi0.5Mn1.5O4 , Li2MnO3 , LiNi x Mn y Co1 -x-y O2 [0 ⁇ x+y ⁇ 1 ] ) , LiNi x Co y Al1 -x-y O2 [ 0 ⁇ x +y ⁇ 1]), LiCr0.5Mn0.5O2 , LiFePO4 , Li2FeP2O7 , LiMnPO4 , LiFeBO3, Li3V2 ( PO4 ) 3 , Li2CuO2 , Li2
• the positive electrode active material include FeSiO 4 and Li 2 MnSiO 4. When the positive electrode active material contains an alkali metal element other than Li, specific examples thereof include those in which Li in the above specific examples is replaced with another alkali metal.
• the negative electrode (negative electrode material) and positive electrode (positive electrode material) of this embodiment may further contain a solid electrolyte material, a binding resin (binder), a conductive assistant, etc.
• the battery may have a separator.
• the separator may be a porous material, or may be a porous material made of resin. Specific examples include a porous polyolefin membrane and a porous ceramic membrane.
• Example 1 The lithiated carboxyl group-containing copolymer of Example 1 was produced by the following method.
• the raw copolymer was alcoholyzed with methanol instead of water to synthesize a copolymer of MMA and St, and the molecular weight of the copolymer was measured by gel permeation chromatography.
• the number average molecular weight of the copolymer was 18,200.
• Example 2 The lithiated carboxyl group-containing copolymer of Example 2 was produced by the following method.
• the -COO - group which is the counter anion of the lithium ion, was fixed on the copolymer, so that it was not transferred even when a voltage was applied, and the transport number of the lithium ion was sufficiently high.
• the raw copolymer was alcoholyzed with methanol instead of water to synthesize a copolymer of MMA and St, and the molecular weight of the copolymer was measured by gel permeation chromatography.
• the number average molecular weight of the copolymer was 30,100.
• Comparative Example 1 A lithiated carboxyl group-containing copolymer of Comparative Example 1 was produced by the following method.
• tert-Butyl methacrylate (tBMA) (1.22 mL, 7.5 mmol
• styrene (St) (0.86 mL, 7.5 mmol
• azobisisobutyronitrile (20.0 mg, 0.12 mmol) were dissolved in toluene (13.0 mL) and stirred at 60° C. for 24 hours to obtain a copolymer of tert-butyl methacrylate and styrene (raw copolymer) (0.59 g).
• the -COOH group-containing copolymer (0.36 g) was dissolved in dimethylformamide (3.0 mL) to obtain a solution. 2.5 equivalents of LiOH were added to the solution relative to the amount of tBMA initially charged when producing the raw material copolymer, and the mixture was stirred at room temperature (25°C) for 3 days. As a result, a copolymer (lithiated carboxyl group-containing copolymer) in which the -COOH group of the -COOH group-containing copolymer was converted to -COOLi was obtained (0.26 g).
• TMP Trimethyl phosphate
• TEP Triethyl phosphate
• EC Ethylene carbonate
• PC Propylene carbonate
• PVDF-HFP Vinylidene fluoride-co-hexafluoropropylene
• ⁇ Measurement of ionic conductivity> The ionic conductivity of the electrolyte composition was measured by the method described below. Table 2 shows the ionic conductivity ( ⁇ 25 ) at 25° C.
• an evaluation cell of the coin-type battery CR2032 was assembled in a glove box under a dry argon atmosphere. Specifically, a test laminate was prepared by stacking each layer in the evaluation cell in the following order: stainless steel plate/electrolyte composition/stainless steel plate.
• Measurements are performed using an impedance measuring device under the conditions of 25°C, a frequency range of 0.1 Hz to 1 MHz, and an applied voltage of 10 mV (vs. open circuit voltage).
• Each component was mixed according to the composition shown in Tables 3 and 4 to prepare each electrolyte composition containing an anion receptor, and the ionic conductivity and activation energy at 25° C. were determined by the above-mentioned method.
• LiTFSI lithium (bistrifluoromethanesulfonyl)imide
• MTD 2-methoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane
• TEB tris(2,2,2-trifluoroethyl)borate
• TFB 2,4,6-tris(4-fluorophenyl)boroxine
• PVDF-HFP vinylidene fluoride-co-hexafluoropropylene
• the electrolyte compositions of Examples A8 and A9 were produced by mixing the polymer and PVDF-HFP to produce a dry film, and then impregnating the dry film with an organic solvent in which a lithium salt and an anion receptor were dissolved.
• the electrolyte composition of Example A10 was produced by mixing a polymer, PVDF-HFP, a lithium salt, and an anion receptor to produce a dry film, and then impregnating the dry film with an organic solvent.
• Each component was mixed according to the composition shown in Table 5 to prepare each electrolyte composition containing an anion receptor, and the ionic conductivity and activation energy at 25° C. were determined by the above-mentioned method.
• an evaluation cell of the coin-type lithium battery CR2032 was assembled in a glove box under a dry argon atmosphere. Specifically, each layer was stacked in the evaluation cell in the order of lithium/electrolyte composition/lithium to create a test laminate.

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