Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
  • C08G73/02—Polyamines
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
  • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
  • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
  • H01G11/04—Hybrid capacitors
  • H01G11/06—Hybrid capacitors with one of the electrodes allowing ions to be reversibly doped thereinto, e.g. lithium ion capacitors [LIC]
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
  • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
  • H01G11/22—Electrodes
  • H01G11/30—Electrodes characterised by their material
  • H01G11/48—Conductive polymers
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M4/00—Electrodes
  • H01M4/02—Electrodes composed of, or comprising, active material
  • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
  • H01M4/137—Electrodes based on electro-active polymers
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M4/00—Electrodes
  • H01M4/02—Electrodes composed of, or comprising, active material
  • H01M4/36—Selection of substances as active materials, active masses, active liquids
  • H01M4/60—Selection of substances as active materials, active masses, active liquids of organic compounds
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
  • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
  • Y02E60/10—Energy storage using batteries

Definitions

• the present invention relates to a polymer, an electrode, an electricity storage device, and a method for producing the polymer.
• Aromatic amine polymers such as polyaniline are known as conductive polymers, and they can be used as hole transport materials used in organic EL, organic transistors, solar cells, and electrode materials such as lithium ion secondary batteries. Expected.
• an aromatic amine polymer for example, a linear polyarylene amine proposed in Patent Document 1 is known in addition to polyaniline.
• aromatic diamine compounds such as N, N, N ′, N′-tetramethyl-benzidine are useful as electrode active materials for power storage devices (see Patent Document 2).
• one embodiment of the present invention provides a novel aromatic amine polymer excellent in solubility in an organic solvent and a method for producing the same.
• another embodiment of the present invention provides a novel aromatic amine polymer that provides satisfactory characteristics when used as an electrode active material of an electricity storage device, and a method for producing the same.
• a configuration example of the present invention is as follows.
• a polymer having at least one of the structures represented by the following formulas (1) and (2) (hereinafter also referred to as “the present polymer 1”); A polymer having a structure represented by the following formulas (3) and (R ′) and having a polystyrene-equivalent weight average molecular weight measured by gel permeation chromatography of 2,000 or more (hereinafter “present polymer 2”) Or) A polymer having a structure represented by the following formulas (1) and (6) (hereinafter also referred to as “present polymer 3”) is provided. These polymers 1 to 3 are also collectively referred to as this polymer A.
• one embodiment of the present invention provides an electrode containing the present polymer A, and further provides an electricity storage device comprising the electrode as a positive electrode.
• an embodiment of the present invention In the presence of a base, a method for producing a polymer comprising a step of reacting a compound represented by the following formula (7) with a compound represented by the following formula (8) (hereinafter also referred to as “the present method I”). Or a method for producing a polymer comprising a step of reacting a compound represented by the following formula (9) with a compound represented by the following formula (10) in the presence of a base (hereinafter also referred to as “the present method II”) .)I will provide a.
• an aromatic amine polymer having excellent solubility in an organic solvent can be obtained. Therefore, the polymer is extremely useful as a positive electrode transport material applied to a liquid phase process. Further, by using the polymer, an electricity storage device satisfying satisfactory characteristics, specifically, high discharge capacity, high cycle characteristics, and high rate characteristics can be easily obtained. Therefore, the polymer is extremely useful as an electrode material for an electricity storage device.
• the present polymer A is any one of the following present polymers 1 to 3.
• the present polymer 1 is represented by the structure represented by the following formula (1) (hereinafter also referred to as “structure (1)”. Other structures may be expressed in the same manner) and the following formula (2).
• the present polymer 1 having the structure (1) (hereinafter also referred to as “the present polymer 1a”) is particularly excellent in solubility in an organic solvent, and is extremely useful as a positive electrode transport material or the like applied to a liquid phase process. Moreover, when this polymer 1a is used as an electrode material, particularly as an active material, an electricity storage device having excellent cycle characteristics can be easily obtained.
• Ar 1 is an independently substituted or unsubstituted aromatic hydrocarbon group, and a bond bonded to Ar 1 is bonded to N.
• aromatic ring constituting the aromatic hydrocarbon group include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a biphenyl ring, and the like, and a benzene ring is preferable.
• the substituent include a hydrocarbon group having 1 to 12 carbon atoms, preferably 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms, a fluoro group, and a carboxy group.
• Ar 1 is preferably an unsubstituted aromatic hydrocarbon group, more preferably a p-phenylene group.
• Y independently represents a single bond, a divalent linking group, or two hydrogen atoms or substituents bonded to each of two Ar 1 groups.
• the linking group include —O—, —NR— (R is a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms), —S—, —CO—, an alkylene group having 1 to 4 carbon atoms, and the like.
• the substituent include the same groups as the substituent for Ar 1 .
• Y is preferably a single bond, two hydrogen atoms bonded to each of —S— or Ar 1 .
• Several Y in Formula (1) may be the same respectively, and may differ. The same description in this specification shows the same meaning.
• N represents an integer of 4 or more, and is preferably an integer such that the weight average molecular weight of the obtained polymer falls within the following range, and more preferably 10 to 100.
• polymer 1a examples include the following polymers.
• N in the following polymer has the same meaning as n in the formula (1).
• the present polymer 1a is the present polymer 3 having a structure represented by the above formula (1) and the following formula (6) from the viewpoint that a polymer excellent in solubility in an organic solvent is obtained. preferable.
• “*” in the following formula (6) represents a bond that bonds to Ar 1 in the formula (1).
• Ar 4 represents a substituted or unsubstituted aromatic hydrocarbon group independently of each other.
• aromatic rings and substituents constituting the aromatic hydrocarbon group in Ar 4 and preferred groups are the same as those for Ar 1 .
• R 2 independently represents a hydrogen atom, a halo group, a nitro group, a hydroxyl group, a sulfo group, an amino group, or an organic group.
• the organic group include a hydrocarbon group having 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms, and an alkoxy group having 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms.
• the halo group is preferably a fluoro group or a bromo group, and more preferably a fluoro group.
• R 2 is a polar group such as a halo group, a nitro group, a hydroxyl group, a sulfo group, an amino group, or an alkoxy group
• a polymer that can swell in a general electrolyte solution can be obtained.
• an electricity storage device exhibiting high rate characteristics and excellent cycle characteristics can be easily obtained.
• this polymer 3 in which R 2 is a hydrogen atom or an alkoxy group having 1 to 4 carbon atoms, particularly a hydrogen atom or a methoxy group is used as an electrode material, particularly an active material, an electricity storage device having excellent cycle characteristics can be easily obtained. Obtainable.
• R 2 is a hydrogen atom, a fluoro group or a hydrocarbon group, particularly a fluoro group or a methyl group
• an electricity storage device having a high discharge capacity can be easily obtained.
• R 2 is preferably a hydrogen atom, a fluoro group, a bromo group, a methyl group, or a methoxy group.
• Z represents a single bond, a divalent linking group, or two hydrogen atoms or substituents bonded to each of two Ar 4 groups.
• Examples of the linking group and substituent in Z, and preferred groups are the same as those for Y.
• R in the following structure has the same meaning as R 2 in formula (6), and is preferably a hydrogen atom, a methyl group, a methoxy group, a fluoro group, or a bromo group.
• Formula (6) shows that R ⁇ 1 > couple
• R 1 represents a hydrogen atom, a halo group, a nitro group, a hydroxyl group, a sulfo group, an amino group or an organic group.
• Examples of the organic group for R 1 include the same groups as the organic group for R 2 , and substituted or unsubstituted aromatic hydrocarbon groups.
• the organic group includes “ ⁇ N—Ar — **”. [Ar represents a substituted or unsubstituted aromatic hydrocarbon group, and ** represents a bond bonded to N in the structure (1). It is preferably a group other than a group including a structure represented by R 1 is preferably a hydrogen atom or a substituted or unsubstituted aromatic hydrocarbon group, and particularly preferably a hydrogen atom.
• present polymer 1a and / or the present polymer 3 include polymers of the following groups (a1) to (a4).
• N in the following polymer has the same meaning as n in the formula (1).
• the present polymer 1 may be a polymer having a structure represented by the following formula (2) (hereinafter also referred to as “present polymer 1b”).
• present polymer 1b When the polymer 1b is used as an electrode material, particularly as an active material, an electricity storage device that is excellent in balance between discharge capacity and rate characteristics can be easily obtained.
• Ar 2 represents a group containing an aromatic ring independently of each other (provided that all of Ar 2 are all biphenyl-4,4′-diyl), and Ar 3 represents a mutual group. Independently represents a group containing an aromatic ring.
• Examples of the group containing an aromatic ring in Ar 2 and Ar 3 include a group in which a plurality of the aromatic hydrocarbon groups are linked by a divalent linking group in addition to the aromatic hydrocarbon group exemplified for Ar 1. .
• Examples of the divalent linking group include —O—, —S—, —SO 2 —, —NH—, —NHCO—, —COO—, a substituted or unsubstituted divalent hydrocarbon group, —N (C 6 H 5 ) — and the like.
• Examples of the substituent include the same groups as the substituent for Ar 1 .
• Ar 2 and Ar 3 a group containing an unsubstituted benzene ring is preferable, and a group containing 1 to 5 unsubstituted benzene rings is particularly preferable. Note that a group bonded to N in —Ar 3 — (N) b ⁇ may be bonded to Ar 2 to form a ring.
• a represents an integer of 1 to 10.
• b shows 1 or 2 mutually independently.
• the present polymer 1b has a structure represented by the following formula (2 ′) from the viewpoint that a discharge capacity and rate characteristics are excellent in balance and an electric storage device having a particularly large discharge capacity can be easily obtained. Polymers are preferred.
• polymer 1b examples include the following polymers.
• This polymer 2 has a structure represented by the following formulas (3) and (R ′), and has a polystyrene-equivalent weight average molecular weight (Mw) measured by gel permeation chromatography (GPC) of 2,000 or more. It is.
• Mw polystyrene-equivalent weight average molecular weight measured by gel permeation chromatography
• GPC gel permeation chromatography
• Such a polymer 2 is particularly excellent in solubility in an organic solvent, and is extremely useful as a positive electrode transport material or the like applied to a liquid phase process. Further, the polymer 2 is used as an electrode material, particularly an active material. When used as a substance, an electricity storage device having excellent cycle characteristics can be easily obtained.
• Ar 1 and Y are independently of one another have the same meanings as defined above Ar 1 and Y.
• m represents an integer of 2 or more.
• the organic group in R 1 include the same groups as the organic group in R 2 , and substituted or unsubstituted aromatic hydrocarbon groups.
• R 1 is preferably a hydrogen atom or a substituted or unsubstituted group.
• An aromatic hydrocarbon group particularly preferably a hydrogen atom.
• This polymer 2 has a repeating unit represented by the following formula (3-1) and a structure represented by the above formula (6) from the viewpoint of obtaining a polymer excellent in solubility in an organic solvent. Is preferred.
• “*” represents a bond that bonds to Ar 1 in the following formula (3-1).
• the repeating unit represented by the following formula (3-1) is between the core of the polymer 2 represented by R 1 — and the terminal of the polymer 2 represented by the formula (6). It means a repeating unit derived from a monomer.
• the present polymer 2 preferably has one or more structural units represented by the following formula (3-2) between repeating units represented by the following formula (3-1).
• Ar 1, Ar 4, R 2, Y and Z are independently of one another have the same meanings as defined above Ar 1, Ar 4, R 2 , Y and Z.
• * 1 represents a bond that is bonded to N in the repeating unit represented by Formula (3-1) or N in Structure (3-2).
• * 2 indicates a bond that binds to an Ar 1 in the formula at least one or the structure of Ar 1 in the repeating unit represented by (3-1) (3-2).
• the present polymer 2 preferably contains 10 to 100 repeating units represented by the formula (3-1).
• Specific examples of the present polymer 2 include, for example, the polymers represented by the groups (a1) to (a3), and those represented by the groups (a1) to (a3) in addition to the polymers having n of 2 or more.
• a polymer having one or a plurality of structural units represented by the above formula (3-2) between a repeating unit (structural unit enclosed in parentheses) and the repeating unit is given. It is done.
• the Mw of the present polymer A is preferably 2, from the viewpoint that, when the polymer A is used as an electrode material, particularly an active material, an electricity storage device having excellent rate characteristics and cycle characteristics can be easily obtained.
• Mw is measured by the method described in the following examples.
• the production method of the present polymer A is not particularly limited, but from the viewpoint that a polymer having a desired structure can be easily produced, the present polymer A is produced by the following method I or this method. It is preferable to manufacture by II.
• a compound represented by the following formula (7) (hereinafter also referred to as “compound (7)”.
• Other compounds may be expressed in the same manner) and the following formula (8).
• the method of reacting with the compound represented by this According to this method, a polymer having a branched chain structure such as the present polymer 1a, the present polymer 2 and the present polymer 3, particularly a hyperbranched polymer can be easily produced.
• Ar 1 and Y have the same meanings as Ar 1 and Y in the formulas independently of one another (1).
• X represents a chloro group, a bromo group, or an iodo group independently of each other, and a bromo group is preferable from the viewpoint that the reaction proceeds more easily.
• Compound (7) used in Method I may be one type or two or more types.
• Compound (7) may be a commercially available product or may be synthesized by a conventionally known method. As the compound (7), the following compounds are preferable.
• Ar 4, R 2 and Z are as defined Ar 4, R 2 and Z in formula independently of one another (6).
• Compound (8) used in Method I may be one type or two or more types.
• the following compounds are preferable.
• Compound (8) may be a commercially available product, or may be synthesized by a conventionally known method.
• Examples of the conventionally known method for example, a compound represented by R 2 -Ar 4 -NH 2 (wherein R 2 and Ar 4 has the same meaning as R 2 and Ar 4 in the formula (8).), R 2 -Ar 4 -X (wherein R 2 and Ar 4 has the same meaning as R 2 and Ar 4 in the formula (8), X is a halo group.) and a compound represented by the following Pd (P (t -Bu) 3 ) A method of reacting in the presence of a catalyst such as 2, and the like.
• a precursor thereof is a compound represented by the R 2 —Ar 4 —NH 2
• a compound represented by the R 2 —Ar 4 —X May be used.
• the base is not particularly limited, and a conventionally known base can be used, but is preferably a strong base, more preferably a base with low nucleophilicity, specifically, a metal alkoxide, Examples thereof include metal amides, preferably sodium t-butoxide, potassium t-butoxide and the like.
• the base used in Method I may be one type or two or more types.
• a catalyst In the reaction in the present method I, it is preferable to use a catalyst.
• the catalyst conventionally known catalysts can be used, and specific examples include the following compounds. Of these, a catalyst comprising a trialkylphosphine and a palladium compound is preferable.
• the catalyst may be one type or two or more types.
• Ms represents a mesylate group
• Cy represents a cyclohexyl group
• L represents a ligand
• iprO represents an isopropoxy group
• the reaction in Method I is usually performed in the presence of a solvent.
• a solvent a conventionally known solvent can be used, and is not particularly limited, but a solvent capable of dissolving the compounds (7) and (8) is preferable, and specifically, an ether solvent such as THF (tetrahydrofuran). And aromatic hydrocarbon solvents such as benzene, toluene and xylene.
• the solvent may be one type or two or more types.
• reaction conditions in Method I are not particularly limited, but the reaction temperature is preferably 25 to 150 ° C., and the reaction time is preferably 0.5 to 10 hours.
• the ratio of compound (7) to compound (8) used is preferably in the range of 100: 100 to 90: 100 in terms of molar ratio. .
• NH in the polymer obtained by the above method is reacted with the compound containing R 1 such as R 1 X (X is a halo group) to thereby form the structure.
• R 1 X is a halo group
• a polymer in which R 1 is bonded to N in (1) and (3) can be obtained.
• the compound represented by R 1 X include chlorobenzene, bromonaphthalene, bromoanthracene, bromobenzoic acid, and the like.
• This method II is a method including a step of reacting a compound represented by the following formula (9) and a compound represented by the following formula (10) in the presence of a base. According to this method, a network polymer such as the present polymer 1b can be easily produced.
• Ar 5 represents a group containing an aromatic ring.
• groups containing an aromatic ring in Ar 5 and preferred groups are the same as those for Ar 2 and Ar 3 .
• the aromatic ring is excellent in that the discharge capacity and rate characteristics are excellent in balance and an electric storage device having a particularly large discharge capacity can be easily obtained.
• a compound in which an amino group is bonded to the para-position is preferred.
• Compound (9) used in Method II may be one type or two or more types.
• Compound (9) may be a commercially available product or may be synthesized by a conventionally known method.
• Ar 6 has the same meaning as Ar 5 in the formula (9), and X represents a halo group independently of each other.
• the aromatic ring is excellent in that the discharge capacity and rate characteristics are excellent in balance and in particular, an electricity storage device having a large discharge capacity can be easily obtained.
• a compound in which a halo group is bonded to the para-position is preferred.
• the compound (10) used in Method II may be one kind or two or more kinds.
• Compound (10) may be a commercially available product, or may be obtained by synthesis by a conventionally known method.
• the compound (10) the following compounds are preferable.
• the base used in Method II is not particularly limited, and a conventionally known base can be used, but the same bases as those used in Method I can be mentioned.
• the base used in Method II may be one kind or two or more kinds.
• reaction in Method II it is preferable to use the same catalyst and solvent as in Method I.
• Each of these catalysts and solvents may be one kind or two or more kinds.
• the reaction conditions in this method II also include the same conditions as in this method I.
• the ratio of compound (9) to compound (10) used is preferably in the range of 50:90 to 50: 110 in terms of molar ratio. .
• the present polymer A can be suitably used as a hole transport material for an electricity storage device, an organic EL, an organic transistor, a solar cell, etc. It is preferably used as a device, more preferably used as an electrode material, and particularly preferably used as a positive electrode material, specifically as a positive electrode active material.
• Electrode The electrode according to one embodiment of the present invention (hereinafter, also referred to as “main electrode”) is not particularly limited as long as it contains one or two or more main polymers A, but the main polymer on the current collector is not limited.
• An electrode having an active material layer containing A and a binder is preferred.
• the present polymer A used for the present electrode can be used as an electrode material as it is, but can also be used as an electrode material after being combined with activated carbon or an inorganic substance.
• this polymer A can also be used as an electrode material with well-known positive electrode active materials, such as lithium cobalt oxide, lithium nickel oxide, lithium manganese oxide, and lithium iron phosphate.
• the present polymer A, a composite of the present polymer A and activated carbon, or a mixture of the present polymer A and a known positive electrode active material is also referred to as a present active material.
• the active material layer may be manufactured, for example, by preparing a slurry containing the active material and a binder, applying the slurry onto a current collector, and drying the active material layer. You may manufacture by forming a film from the mixture which contains beforehand, and arrange
• the present electrode is preferably a positive electrode of a non-aqueous electrolyte secondary battery that includes the active material as a positive electrode active material, and includes a positive electrode active material in which the present polymer A is combined with activated carbon. It is also preferable that it is a positive electrode of a double layer capacitor.
• the content of the active material in the electrode is not particularly limited, but is preferably 10 to 90% by mass with respect to 100% by mass of the obtained active material layer.
• the active material contained in the electrode of one embodiment of the present invention may be one kind or two or more kinds.
• Examples of the material for the current collector include aluminum, stainless steel, copper, and nickel.
• the electrode according to an embodiment of the present invention is a positive electrode, aluminum, stainless steel, and the like are preferable.
• the thickness of the current collector is usually 10 to 50 ⁇ m.
• binder examples include rubber binders such as styrene-butadiene rubber (SBR) and acrylonitrile-butadiene rubber (NBR); fluorine resins such as polytetrafluoroethylene (PTFE) and polyvinylidene fluoride; polypropylene, polyethylene
• SBR styrene-butadiene rubber
• NBR acrylonitrile-butadiene rubber
• fluorine resins such as polytetrafluoroethylene (PTFE) and polyvinylidene fluoride
• polypropylene polyethylene
• Other examples include fluorine-modified (meth) acrylic binders disclosed in JP-A-2009-246137.
• the binder may be one type or two or more types.
• the content of the binder is not particularly limited, but is preferably 1 to 50% by mass, more preferably 5 to 30% by mass with respect to 100% by mass of the active material layer obtained.
• carbon black acetylene black, ketjen black, etc.
• graphite graphite
• vapor-grown carbon fiber VGCF
• MAXSORB high surface area activated carbon
• Conductive agent such as nanotube (SWNT, MWNT, etc.), metal powder, etc .; increase of carboxyl methyl cellulose, its Na salt or ammonium salt, methyl cellulose, hydroxymethyl cellulose, ethyl cellulose, hydroxypropyl cellulose, polyvinyl alcohol, oxidized starch, phosphorylated starch or casein
• You may contain arbitrary components, such as a sticking agent. Each of the optional components may be one kind or two or more kinds.
• the thickness of the active material layer is not particularly limited, but is usually 5 to 500 ⁇ m, preferably 10 to 200 ⁇ m, particularly preferably 10 to 100 ⁇ m.
• An electricity storage device includes the electrode as a positive electrode.
• Examples of the electricity storage device include a nonaqueous electrolyte secondary battery, an electric double layer capacitor, and a lithium ion capacitor.
• the power storage device usually includes at least a negative electrode and an electrolyte in addition to the main electrode used as a positive electrode.
• the configuration and manufacturing method of the electrode according to an embodiment of the present invention used as the positive electrode are as described in the above “electrode”.
• the basic configuration and manufacturing method of the negative electrode may be any conventionally known configuration and manufacturing method, and may be the same as described in the “electrode” except for the type of active material.
• the negative electrode active material used include metallic lithium, a carbon-based material doped with lithium (such as graphite and activated carbon), and a lithium alloy. These negative electrode active materials can use 1 type (s) or 2 or more types.
• the electrolyte is usually used in the state of an electrolytic solution dissolved in a solvent.
• the electrolyte is not particularly limited, but is preferably one that can generate lithium ions.
• LiClO 4 , LiAsF 6 , LiBF 4 , LiPF 6 , LiN (C 2 F 5 SO 2 ) 2 examples thereof include LiN (CF 3 SO 2 ) 2 and LiN (FSO 2 ) 2 .
• These electrolytes can use 1 type (s) or 2 or more types.
• the solvent for dissolving the electrolyte is preferably an aprotic organic solvent, and specifically, ethylene carbonate, propylene carbonate, butylene carbonate, 1-fluoroethylene carbonate, 1- (trifluoromethyl) ethylene carbonate, dimethyl Examples thereof include carbonate, diethyl carbonate, methyl ethyl carbonate, ⁇ -butyrolactone, acetonitrile, dimethoxyethane, diglyme, tetraglyme, dioxolane, methylene chloride, sulfolane and the like. These solvents can be used alone or in combination of two or more.
• the electrolyte is usually prepared and used in a liquid state as described above, but a gel or a solid may be used for the purpose of preventing leakage or elution of the active material.
• a separator is usually provided between the positive electrode and the negative electrode so that the positive electrode and the negative electrode are not in physical contact.
• a conventionally known separator may be used as the separator, and examples thereof include a nonwoven fabric or a porous film made of cellulose rayon, polyethylene, polypropylene, polyamide, polyester, polyimide and the like, paper, glass filter, and the like.
• Example 1 In a 100 ml eggplant flask, 3.27 g of bis (4-bromophenyl) amine (BPA), 1.69 g of diphenylamine (DPA), 2.88 g of sodium t-butoxide (NaOtBu), and bis (tri-tBuphosphine as a catalyst) ) 5 mg of palladium (0) and 10 ml of toluene were added, and the mixture was heated at 100 ° C. for 6 hours. The contents were put into methanol, and the resulting white powder was washed with methanol and acetone to obtain 3.3 g of polymer A-1.
• BPA bis (4-bromophenyl) amine
• DPA diphenylamine
• NaOtBu sodium t-butoxide
• tri-tBuphosphine as a catalyst bis (tri-tBuphosphine as a catalyst)
• Example 2 In a 100 ml eggplant flask, 3.27 g of BPA, 1.97 g of p, p'-ditolylamine (MPA), 2.88 g of NaOtBu, 51 mg of bis (tri-tBuphosphine) palladium (0) as a catalyst and 10 ml of toluene In addition, the mixture was heated at 100 ° C. for 6 hours. The contents were put into methanol, and the resulting white powder was washed with methanol and acetone to obtain 3.6 g of polymer A-2. In 1 H-NMR (CDCl 3 ), peaks were present at 6.9 ppm (aromatic) and 2.5 ppm (methyl group).
• the Mw in terms of polystyrene measured under the same conditions as described above was 9,000. Further, as a result of analysis by MALDI-TOFMS, a mass spectrum indicating the presence of a structure in which R 2 is a methyl group in the formulas (A) to (D) was obtained, and the formulas (1), (3), It was confirmed to have a structure represented by (3-1) to (3-2) and (6).
• Example 3 In a 100 ml eggplant flask, 3.27 g of BPA, 2.29 g of bis (methoxyphenyl) amine (MOPA), 2.88 g of NaOtBu, 51 mg of bis (tri-tBuphosphine) palladium (0) as a catalyst and 10 ml of THF In addition, the mixture was heated at 70 ° C. for 6 hours. The contents were put into methanol, and the resulting white powder was washed with methanol and acetone to obtain 3.7 g of polymer A-3. In 1 H-NMR (CDCl 3 ), peaks were present at 6.7 ppm, 6.9 ppm (aromatic) and 3.8 ppm (methoxy group).
• the Mw in terms of polystyrene measured under the same conditions as described above was 11,000. Further, as a result of analysis by MALDI-TOFMS, a mass spectrum indicating the presence of a structure in which R 2 is a methoxy group in the formulas (A) to (D) was obtained, and the formulas (1), (3), It was confirmed to have a structure represented by (3-1) to (3-2) and (6).
• Example 4 In a 100 ml eggplant flask, 3.27 g of BPA, 2.05 g of bis (4-fluorophenyl) amine (FPA), 2.88 g of NaOtBu, 51 mg of bis (tri-tBuphosphine) palladium (0) as a catalyst and THF was added and heated at 70 ° C. for 6 hours. The contents were put into methanol, and the resulting white powder was washed with methanol and acetone to obtain 3.7 g of polymer A-4. In 1 H-NMR (CDCl 3 ), peaks were present at 6.7 ppm and 6.9 ppm (aromatic).
• the polystyrene-equivalent Mw measured under the same conditions as described above was 8,000. Further, as a result of analysis by MALDI-TOFMS, a mass spectrum showing the presence of a structure in which R 2 is a fluoro group in the formulas (A) to (D) was obtained, and the formulas (1), (3), It was confirmed to have a structure represented by (3-1) to (3-2) and (6).
• Example 5 (Production of polymer having structure (2)) In a 100 ml eggplant flask, 0.54 g of paraphenylenediamine (PDA), 2.35 g of 1,4-dibromobenzene, 2.88 g of NaOtBu, 51 mg of bis (tri-tBuphosphine) palladium (0) as a catalyst and toluene was added and heated at 100 ° C. for 6 hours. The contents were put into methanol, and the resulting white powder was washed with methanol and acetone to obtain 1.3 g of polymer B-1. It was confirmed by FT-IR that there was no vibration derived from the bond of NH and C—Br.
• Example 6 (Production of polymer having structure (2)) In a 100 ml eggplant flask, 0.54 g of metaphenylenediamine (MDA), 2.35 g of 1,3-dibromobenzene, 2.88 g of NaOtBu, 51 mg of bis (tri-tBuphosphine) palladium (0) as a catalyst and toluene was added and heated at 100 ° C. for 6 hours. The contents were put into methanol, and the resulting white powder was washed with methanol and acetone to obtain 1.3 g of polymer B-2. It was confirmed by FT-IR that there was no vibration derived from the bond of NH and C—Br.
• Example 7 (Production of polymer having structure (2)) In a 100 ml eggplant flask, 0.54 g of PDA, 1.56 g of 4,4′-dibromobiphenyl, 1.2 g of 1,4-dibromobenzene, 2.88 g of NaOtBu, bis (tri-tBuphosphine) palladium as a catalyst 51 mg of (0) and 10 ml of toluene were added, and the mixture was heated at 100 ° C. for 6 hours. The contents were put into methanol, and the resulting white powder was washed with methanol and acetone to obtain 1.8 g of polymer B-3. It was confirmed by FT-IR that there was no vibration derived from the bond of NH and C—Br.
• Example 8 (Production of polymer having structure (2)) To a 100 ml eggplant flask, 2.48 g of 2,4-dibromoaniline, 2.88 g of NaOtBu, 51 mg of bis (tri-tBuphosphine) palladium (0) and 10 ml of toluene were added and heated at 100 ° C. for 6 hours. did. The contents were put into methanol, and the resulting white powder was washed with methanol and acetone to obtain 0.88 g of polymer B-4. It was confirmed by FT-IR that there was no vibration derived from the bond of NH and C—Br.
• the obtained electrode sheet was cut into a circle and used as the positive electrode of the battery.
• the produced coin cell was subjected to a charge / discharge test using a Toyo System Co., Ltd. TOSCAT-3100 as a charge / discharge tester at a current value of 0.1 C at room temperature and a cut-off potential shown in Table 1.
• Table 1 shows the capacity retention ratio (the ratio of the discharge capacity at the 50th cycle to the discharge capacity at the 1st cycle) after 50 cycles of charge and discharge.
• Example 9 A coin cell was prepared in the same manner as in the above ⁇ cycle characteristics> except that 0.08 g of polymer A-3 and 0.32 g of lithium iron phosphate (LiFePO 4 ) were used instead of polymers A-1 to A-4. Produced. About the produced coin cell, the cycle characteristics and the discharge capacity were evaluated in the same manner as in the above ⁇ cycle characteristics> and ⁇ discharge capacity and rate characteristics>. At this time, the cut-off potential was set to 3.8 to 2.8V. As a result, the capacity retention rate after 50 cycles was 99%, the capacity retention rate after 5000 cycles was 84%, and the discharge capacity was 150 mAh / g.
• LiFePO 4 lithium iron phosphate
• the present polymer is considered to be extremely useful as a hole transport material used in organic EL, organic transistors, solar cells, etc., in addition to electrode materials for power storage devices such as electrode active materials and electrode binders.

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