Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C317/00—Sulfones; Sulfoxides
  • C07C317/16—Sulfones; Sulfoxides having sulfone or sulfoxide groups and singly-bound oxygen atoms bound to the same carbon skeleton
  • C07C317/22—Sulfones; Sulfoxides having sulfone or sulfoxide groups and singly-bound oxygen atoms bound to the same carbon skeleton with sulfone or sulfoxide groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
  • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
  • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
  • C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
  • C07D213/62—Oxygen or sulfur atoms
  • C07D213/63—One oxygen atom
  • C07D213/64—One oxygen atom attached in position 2 or 6
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
  • C09K3/00—Materials not provided for elsewhere
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M10/00—Secondary cells; Manufacture thereof
  • H01M10/05—Accumulators with non-aqueous electrolyte
  • H01M10/052—Li-accumulators
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M10/00—Secondary cells; Manufacture thereof
  • H01M10/05—Accumulators with non-aqueous electrolyte
  • H01M10/056—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
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M14/00—Electrochemical current or voltage generators not provided for in groups H01M6/00 - H01M12/00; Manufacture thereof
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M14/00—Electrochemical current or voltage generators not provided for in groups H01M6/00 - H01M12/00; Manufacture thereof
  • H01M14/005—Photoelectrochemical storage cells
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M4/00—Electrodes
  • H01M4/02—Electrodes composed of, or comprising, active material
  • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M4/00—Electrodes
  • H01M4/02—Electrodes composed of, or comprising, active material
  • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
  • H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
• • 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
  • H01M8/00—Fuel cells; Manufacture thereof
  • H01M8/06—Combination of fuel cells with means for production of reactants or for treatment of residues
  • H01M8/0662—Treatment of gaseous reactants or gaseous residues, e.g. cleaning
  • H01M8/0668—Removal of carbon monoxide or carbon dioxide
• • 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
  • H01G11/50—Electrodes characterised by their material specially adapted for lithium-ion capacitors, e.g. for lithium-doping or for intercalation
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
  • H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
  • H01G9/20—Light-sensitive devices
  • H01G9/2004—Light-sensitive devices characterised by the electrolyte, e.g. comprising an organic electrolyte
  • H01G9/2013—Light-sensitive devices characterised by the electrolyte, e.g. comprising an organic electrolyte the electrolyte comprising ionic liquids, e.g. alkyl imidazolium iodide
• • 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
  • Y02E10/00—Energy generation through renewable energy sources
  • Y02E10/50—Photovoltaic [PV] energy
  • Y02E10/542—Dye sensitized solar cells
• • 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
  • 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
  • Y02E60/30—Hydrogen technology
  • Y02E60/50—Fuel cells

Definitions

• the present invention relates to a fluoroalkane derivative, a gelling agent, a gel-like composition, an electrode for an electrochemical device, an electrolyte solution for a dye-sensitized solar cell, and a carbon dioxide-absorbing composition.
• liquid substances are solidified, that is, solidified into a jelly or thickened.
• a gelling agent is used for the purpose. These gelling agents include those that gel (solidify) water, and those that gel (solidify) non-aqueous solvents and solutions mainly containing them.
• the structure of the gelling agent can be roughly classified into a high molecular weight type and a low molecular weight type.
• the high molecular weight type gelling agent is mainly used for gelation of non-aqueous solvents, and it is characterized by keeping oil solid while taking in oils in the entangled molecule of lipophilic polymer.
• low molecular weight type gelling agents contain hydrogen-bonding functional groups (for example, amino groups, amide groups, and urea groups) in the molecule, and water and non-aqueous solvents are gelated by hydrogen bonds.
• the low molecular weight type gelling agent is generally used as a water gelling agent, but its development as a nonaqueous solvent gelling agent has been relatively delayed.
• the present invention has been made in view of the above circumstances, and a novel fluoroalkane derivative capable of gelling or solidifying various nonaqueous solvents with a small amount of addition, a gelling agent comprising the compound, and a gelling agent thereof are provided. It is an object of the present invention to provide a gel composition containing an electrode, an electrode containing a novel fluoroalkane derivative, an electrolyte solution for a dye-sensitized solar cell, and a carbon dioxide absorbing composition.
• a fluoroalkane derivative represented by the following general formula (1) R—SO 2 —Ar—O—R 1 (1)
• Ar represents a substituted or unsubstituted divalent aromatic group having 8 to 30 nuclear atoms
• R 1 represents a saturated or unsaturated monovalent hydrocarbon group having 1 to 20 carbon atoms
• R represents a saturated or unsaturated monovalent hydrocarbon group having 2 to 22 carbon atoms having a perfluoroalkyl group.
• R represents a group represented by the following general formula (2).
• Ar is a condensed ring having one or more aromatic hydrocarbon rings, or a group in which a plurality of aromatic rings are bonded by a single bond, and one or more of the aromatic rings are aromatic carbonized
• a gelling agent comprising the fluoroalkane derivative according to any one of [1] to [4].
• a gel composition containing the gelling agent according to [5] and an organic solvent.
• An electrode for an electrochemical device comprising the fluoroalkane derivative according to any one of [1] to [4].
• An electrolyte solution for a dye-sensitized solar cell comprising the fluoroalkane derivative according to any one of [1] to [4].
• a carbon dioxide-absorbing composition comprising the fluoroalkane derivative according to any one of [1] to [4] and an ionic liquid.
• a novel fluoroalkane derivative capable of gelling or solidifying various nonaqueous solvents with a small amount of addition, a gelling agent comprising the compound, a gel composition containing the gelling agent, and a novel fluoro
• a gelling agent comprising the compound, a gel composition containing the gelling agent, and a novel fluoro
• An electrode containing an alkane derivative, an electrolyte solution for a dye-sensitized solar cell, and a carbon dioxide-absorbing composition can be provided.
• the fluoroalkane derivative of the present embodiment has an alkylsulfonyl group having a perfluoroalkyl group and a hydrocarbon oxy group, and is a compound represented by the above general formula (1) (hereinafter referred to as “compound (1)”).
• compound (1) a compound represented by the above general formula (1)
• compound (2) a compound represented by the above general formula (2)
• Ar represents a substituted or unsubstituted divalent aromatic group having 8 to 30 nuclear atoms.
• the divalent aromatic group is a cyclic divalent group exhibiting so-called “aromaticity”.
• the divalent aromatic group may be a carbocyclic group or a heterocyclic group. These divalent aromatic groups may be substituted with a substituent or may be an unsubstituted one that is not substituted.
• the substituent of the divalent aromatic group is preferably selected from the viewpoint of easily allowing the introduction of a perfluoroalkyl (oligomethylene) thio group and a hydrocarbon oxy group described later.
• the carbocyclic group has 10 to 30 nuclear atoms, may be substituted with a substituent, or may be unsubstituted or unsubstituted. Specific examples thereof include a divalent group having a nucleus represented by a biphenylene group, a terphenylene group, a naphthylene group, an anthranylene group, a phenanthrylene group, a pyrenylene group, a chrysenylene group, and a fluoranthenylene group. Further, the carbocyclic group may have two or more of the above divalent groups (which may be the same or different from each other) within the range of 10 to 30 nuclear atoms. Good.
• the heterocyclic group has 8 to 30 nuclear atoms.
• a nucleus represented by a furylene group, a thiophenylene group, a triazolen group, an oxadiazolene group, a pyridylene group, or a pyrimidylene group is substituted with a nucleus atom.
• examples thereof include a divalent group having two or more (which may be the same or different from each other) within the range of the number 8 to 30.
• Ar may be a group having both the carbocyclic group and the heterocyclic group within the range of 8 to 30 nuclear atoms.
• Ar has a high gelling ability when the number of nuclear atoms is 8 or more, and the degree of freedom in selecting the structure of R and R 1 and the number of carbon atoms is increased. Moreover, the raw material of the compound (1) in which the number of atomic atoms of Ar is 30 or less is easy to obtain and can be easily synthesized.
• a condensed ring having one or more substituted or unsubstituted aromatic hydrocarbon rings (more preferably a benzene ring) as a divalent aromatic group from the viewpoint of gelation ability and ease of synthesis
• a group in which a plurality of aromatic rings are bonded by a single bond, and one or more of the aromatic rings is an aromatic hydrocarbon ring (more preferably a benzene ring) is preferable.
• the divalent aromatic group is more preferably a substituted or unsubstituted biphenylene group, terphenylene group, naphthylene group, anthranylene group and phenylenepyridylene group (-Ph-Py-; Ph is a benzene ring, Py is a pyridine ring. And a biphenylene group is most preferred.
• the alkyl group represented by the methyl group and the ethyl group, and a halogen atom are mentioned.
• the “aromatic ring” may be carbocyclic or heterocyclic.
• R 1 represents a saturated or unsaturated monovalent hydrocarbon group having 1 to 20 carbon atoms, may be an aliphatic hydrocarbon group, and may further have an aromatic hydrocarbon group.
• this hydrocarbon group is a monovalent aliphatic hydrocarbon group, it may be branched or unbranched. Further, when the monovalent hydrocarbon group has an aromatic hydrocarbon group, the aromatic hydrocarbon group may or may not further have a substituent.
• the monovalent hydrocarbon group includes a compound (1) such as an arylalkyl group typified by a benzyl group in order for the compound (1) to be dissolved in a non-aqueous solvent and to gel the non-aqueous solvent.
• the monovalent hydrocarbon group represented by R 1 is preferably an alkyl group having 1 to 14 carbon atoms from the viewpoints of gelling ability, ease of synthesis, and handling.
• R represents a saturated or unsaturated monovalent hydrocarbon group having 2 to 22 carbon atoms having a perfluoroalkyl group, which may be an aliphatic hydrocarbon group, and further has an aromatic hydrocarbon group. Also good. When this hydrocarbon group is a monovalent aliphatic hydrocarbon group, it may be branched or unbranched. Further, when the monovalent hydrocarbon group has an aromatic hydrocarbon group, the aromatic hydrocarbon group may or may not further have a substituent.
• the monovalent hydrocarbon group may have a perfluoroalkyl group on the main chain of the molecule or a side chain. Further, the monovalent hydrocarbon group may have one perfluoroalkyl group or two or more perfluoroalkyl groups.
• the perfluoroalkyl group may be linear or branched.
• the carbon number of the perfluoroalkyl group is preferably 2 to 12, and more preferably 2 to 6.
• the perfluoroalkyl group is preferably linear. The longer the perfluoroalkyl group, the higher the gelling ability, and the shorter the perfluoroalkyl group, the easier the raw material acquisition and synthesis.
• Ar represents a substituted or unsubstituted divalent aromatic group having 8 to 30 nuclear atoms.
• the divalent aromatic group is a cyclic divalent group exhibiting so-called “aromaticity”.
• the divalent aromatic group may be a carbocyclic group or a heterocyclic group. These divalent aromatic groups may be substituted with a substituent or may be an unsubstituted one that is not substituted.
• the substituent of the divalent aromatic group is preferably selected from the viewpoint of easily allowing introduction of a perfluoroalkyl (oligomethylene) thio group and introduction of a hydrocarbon oxy group described later.
• the carbocyclic group has 10 to 30 nuclear atoms, may be substituted with a substituent, or may be unsubstituted or unsubstituted. Specific examples thereof include a divalent group having a nucleus represented by a biphenylene group, a terphenylene group, a naphthylene group, an anthranylene group, a phenanthrylene group, a pyrenylene group, a chrysenylene group, and a fluoranthenylene group. Further, the carbocyclic group may have two or more of the above divalent groups (which may be the same or different from each other) within the range of 10 to 30 nuclear atoms. Good.
• the heterocyclic group has 8 to 30 nuclear atoms.
• a nucleus represented by a furylene group, a thiophenylene group, a triazolen group, an oxadiazolene group, a pyridylene group, or a pyrimidylene group is substituted with a nucleus atom.
• examples thereof include a divalent group having two or more (which may be the same or different from each other) within the range of the number 8 to 30.
• Ar may be a group having both the carbocyclic group and the heterocyclic group within the range of 8 to 30 nuclear atoms.
• Ar exhibits a high gelling ability when the number of nuclear atoms is 8 or more, and the degree of freedom in the selection range is high with respect to the structure of R and the range of m values. Moreover, the raw material of the compound (2) in which the number of atomic atoms of Ar is 30 or less is easy to obtain and is easy to synthesize.
• the divalent aromatic group is more preferably a substituted or unsubstituted biphenylene group, terphenylene group, naphthylene group, anthranylene group and phenylenepyridylene group (-Ph-Py-; Ph is a benzene ring, Py is a pyridine ring. And a biphenylene group is most preferred.
• the alkyl group represented by the methyl group and the ethyl group, and a halogen atom are mentioned.
• R 1 represents a saturated or unsaturated monovalent hydrocarbon group having 1 to 20 carbon atoms, may be an aliphatic hydrocarbon group, and may further have an aromatic hydrocarbon group.
• this hydrocarbon group is a monovalent aliphatic hydrocarbon group, it may be branched or unbranched. Further, when the monovalent hydrocarbon group has an aromatic hydrocarbon group, the aromatic hydrocarbon group may or may not further have a substituent.
• the monovalent hydrocarbon group includes a compound (2) such as an arylalkyl group typified by a benzyl group so that the compound (2) is dissolved in a non-aqueous solvent and gels the non-aqueous solvent.
• the monovalent hydrocarbon group represented by R 1 is preferably an alkyl group having 1 to 14 carbon atoms from the viewpoints of gelling ability, ease of synthesis, and handling.
• M represents a natural number of 2 to 16, preferably a natural number of 2 to 12, more preferably a natural number of 2 to 6.
• p represents an integer of 0 to 6, and is preferably a natural number of 2 to 4.
• the sum of the value of m and the number of carbons in R 1 is 7 Is preferably -20, more preferably 8-16, and even more preferably 10-14.
• the synthesis method of the compound (1) and the compound (2) is not particularly limited, and the compound (1) and the compound (2) can be synthesized by any method. For example, after preparing the skeleton of the aromatic group first, it can be synthesized by reacting alkyl chains etc. at both ends, or by first preparing the chains at both ends and finally synthesizing a predetermined aromatic group. it can.
• the compounds (1) and (2) can be obtained by the following synthesis method.
• a thiol compound represented by the following general formula (1a) is sulfided with a compound represented by the following general formula (1b) in the presence of a base such as triethylamine in a solvent such as dry THF.
• the compound represented by (1c) is obtained.
• Ar, m and p have the same meanings as in the formulas (1) and (2)
• X 1 represents a halogen atom such as an iodine atom. Show.
• HS-Ar-OH (1a) C m F 2m + 1 C p H 2p X 1
• the compound represented by the general formula (1c) is etherified with a compound represented by the following general formula (1d) in the presence of an alkali metal compound such as K 2 CO 3 in a solvent such as 3-pentanone.
• the compound represented by the following general formula (1e) is obtained.
• Ar, R 1 , m and p are as defined in the formulas (1) and (2), and X 2 represents a halogen atom such as a bromine atom, for example. .
• R 1 X 2 (1d) C m F 2m + 1 C p H 2p —S—Ar—O—R 1 (1e)
• the compound represented by the general formula (1e) is oxidized with an oxidizing agent such as hydrogen peroxide in the presence of a catalyst such as acetic acid to obtain the compound (1) and the compound (2).
• the compound (1) and the compound (2) are obtained by the following synthesis method, for example. be able to.
• a thiol compound represented by the following general formula (1f) is sulfided with a compound represented by the above general formula (1b) in the presence of a base such as triethylamine in a solvent such as dry THF.
• a compound represented by (1 g) is obtained.
• the compound (1) and the compound (2) of this embodiment can be used as a gelling agent that gels a non-aqueous solvent.
• such compounds are advantageous in that various non-aqueous solvents can be gelled or solidified by addition of a small amount.
• the gel composition of this embodiment contains 1 type, or 2 or more types of compounds (1) or a compound (2), and a nonaqueous solvent.
• the non-aqueous solvent contained in the gel composition of the present embodiment is not particularly limited, but a non-aqueous solvent that is liquid at room temperature is generally used.
• non-aqueous solvents include alcohols such as methanol, ethanol, isopropanol, butanol and octanol, methyl acetate, ethyl acetate, propyl acetate, butyl acetate and ⁇ -butyrolactone, ⁇ -valerolactone, ⁇ -caprolactone, etc.
• Acid esters dimethyl ketone, diethyl ketone, methyl ethyl ketone, ketones such as 3-pentanone and acetone, hydrocarbons such as pentane, hexane, octane, cyclohexane, benzene, toluene, xylene, fluorobenzene and hexafluorobenzene, diethyl Ethers, 1,2-dimethoxyethane, 1,4-dioxane, crown ethers, glymes, ethers such as tetrahydrofuran and fluoroalkyl ether, N, N-dimethylacetoa Amides such as N, N-dimethylformamide, ethylenediamine and pyridine, carbonates such as propylene carbonate, ethylene carbonate, vinylene carbonate, fluoroethylene carbonate, diethyl carbonate and ethyl methyl carbonate, acetonitrile,
• an ionic liquid can also be used as a non-aqueous solvent.
• An ionic liquid is a room temperature molten salt composed of ions obtained by combining an organic cation and an anion. Ionic liquids are flame retardant, have low explosive properties, and have almost no vapor pressure. In addition, ionic liquids have high heat and ion conductivity, physical property control design is possible by selecting ionic species, and selective and high gas absorption capability, so that they can be used in various applications. Is expected.
• Examples of the organic cation include imidazolium ions such as a dialkylimidazolium cation and a trialkylimidazolium cation, a tetraalkylammonium ion, an alkylpyridinium ion, a dialkylpyrrolidinium ion, and a dialkylpiperidinium ion.
• Examples of the anion serving as a counter for these organic cations include PF 6 anion, PF 3 (C 2 F 5 ) 3 anion, PF 3 (CF 3 ) 3 anion, BF 4 anion, and BF 2 (CF 3 ) 2 anion.
• nonaqueous solvents may be used alone or in combination of two or more.
• the gel composition of the present embodiment preferably contains 0.05 to 10.0% by mass, more preferably 0.1 to 5.0% by mass of the compound (1) or the compound (2) with respect to the total amount.
• the content is preferably 0.3 to 3.0% by mass.
• compound (1) or compound (2) tends to function more satisfactorily as a gelling agent.
• the gel composition of the present embodiment preferably contains 80 to 99.95% by mass of the nonaqueous solvent, more preferably 90 to 99.9% by mass, and more preferably 90 to 99.7% by mass with respect to the total amount of the gel composition. It is more preferable.
• the content When the content is not less than the above lower limit value, the performance of the nonaqueous solvent tends to be further prevented from being lowered.
• the compound (1) or the compound (2) Tends to function more fully as a gelling agent.
• the gel-like composition of the present embodiment is not limited to other compounds as long as it does not inhibit the function of the compound (1) or compound (2) as a gelling agent. You may contain a component. Examples of such components include gelling agents other than compound (1) or compound (2), coagulants, thickeners, stabilizers, antioxidants, emulsifiers, lubricants, and safety improving additives. Can be mentioned.
• the method for preparing the gel composition of the present embodiment is not particularly limited.
• a nonaqueous solvent, a gelling agent (that is, compound (1) or compound (2)) and other additives are mixed while heating. It can be prepared by lowering the temperature of the mixed solution after making it into a uniform mixed solution.
• the order of mixing the components is not particularly limited, but it is preferable to prepare a solution composed of a nonaqueous solvent and an additive in advance and then mix the gelling agent, so that a uniform mixed solution can be obtained more easily.
• the electrode of this embodiment is an electrode for an electrochemical device containing one or more compounds (1) or compounds (2).
• the method of incorporating the compound (1) or the compound (2) into the electrode may be introduced at the same time when the electrode active material mixture is prepared, or may be applied / coated later on the prepared electrode. Good.
• the method for applying and applying the compound (1) or the compound (2) on the electrode is not particularly limited.
• the compound (1) or the compound (2) is dissolved or dispersed in a solvent (preferably a non-aqueous solvent).
• a solution or slurry is prepared, and the solution or slurry may be applied / coated on the electrode by a bar coating method, or may be applied / coated by a casting method. Alternatively, the solution or slurry may be applied by spraying or brushing.
• the safety, reliability, and durability of the electrode and the electrochemical device including the electrode are improved.
• the content of the compound (1) or the compound (2) in the electrode of the present embodiment is not particularly limited as long as it does not inhibit the function as an electrode.
• the content is preferably 0.1 to 20.0 parts by mass, more preferably 1.0 to 10.0 from 100 parts by mass of the electrode active material, from the viewpoint of maintaining adhesiveness and improving safety. Part by mass.
• a secondary battery and a storage battery represented by a lithium ion secondary battery, a capacitor and a capacitor represented by a lithium ion capacitor and an electric double layer capacitor, a fuel cell and a solar battery are representative.
• the electrode of this embodiment is suitably used in a lithium ion secondary battery and a lithium ion capacitor.
• the electrochemical device of the present embodiment may have a conventionally known structure except that the electrode is used.
• the electrolyte solution for dye-sensitized solar cells of this embodiment contains 1 type, or 2 or more types of compound (1) or compound (2), Preferably, it contains a nonaqueous solvent and electrolyte further.
• the nonaqueous solvent used in the dye-sensitized solar cell electrolyte is not particularly limited, and various solvents can be used, but a solvent having a nitrile group, such as acetonitrile, propionitrile, methoxyacetonitrile, is preferable, More preferred is acetonitrile.
• an ionic liquid can also be used as a nonaqueous solvent of the electrolyte solution for dye-sensitized solar cells.
• ionic liquids can be selected, and ionic liquids having cations containing imidazolium groups have attracted attention (for example, “Functional creation and application of ionic liquids”, NTS Corporation, 2004)), which is preferable.
• electrolyte The electrolyte solution contained in the electrolyte solution of the conventional dye-sensitized solar cell may be sufficient.
• the content of the compound (1) or the compound (2) in the dye-sensitized solar cell electrolyte solution of the present embodiment is not particularly limited as long as it does not hinder the function as the dye-sensitized solar cell.
• the content thereof is preferably 0.1 to 7.0% by mass, more preferably 0.5 to 5.0% by mass, from the viewpoint of gelling ability and performance as an electrolytic solution.
• the carbon dioxide-absorbing composition of the present embodiment is a composition containing one or more compounds (1) or compounds (2) and an ionic liquid.
• Carbon dioxide separation / recovery technology using ionic liquid is attracting attention as an environmental technology (for example, “CO 2 separation / recovery and storage / sequestration technology”, NTS Corporation, issued in 2009).
• the carbon dioxide-absorbing composition is characterized in that it can selectively physically absorb CO 2 at around room temperature and can separate and recover CO 2 by a simple operation.
• Various ionic liquids can be used and are not particularly limited, but ions having an imidazolium moiety or an ammonium moiety as a cation are preferred.
• the carbon dioxide-absorbing composition can be prepared by gelling an ionic liquid having the property of absorbing carbon dioxide with a gelling agent of compound (1) or compound (2).
• the content of the compound (1) or the compound (2) in the carbon dioxide-absorbing composition of the present embodiment is not particularly limited as long as it does not hinder the function as the carbon dioxide absorbent.
• the content thereof is preferably 0.1 to 10.0% by mass, more preferably 1.0 to 5.0% by mass, from the viewpoints of gelling ability, carbon dioxide absorption ability and handling property.
• the fluoroalkane derivative of the present embodiment can be gelled or solidified with only a small amount of, for example, 10% or less with respect to relatively various non-aqueous solvents.
• the gel composition using this can hardly be transferred to the sol even at a relatively high temperature, and can exist stably as a gel for a long period of time.
• the function of the gelling agent is ensured even in a non-aqueous solvent and in a system where hydrogen bonding cannot exist stably.
• gel composition Evaluated as a “gel composition” as a gelled material that has lost its fluidity, and is necessary to change the mixing ratio of the non-aqueous solvent and the gelling agent into a gel composition.
• concentration of the gelling agent concentration of the gelling agent based on the total amount of the gel composition
• the results are shown in Tables 1 to 3 and 5. In Tables 1 to 3 and 5, “%” means mass%.
• (Iii) Lithium Deposition Test of Lithium Ion Secondary Battery The lithium deposition test was performed by producing a lithium ion battery that is a single-layer laminated battery equipped with an electrode described later. The battery charged to 4.2 V at a constant current of 9.0 mA was discharged to 3.0 V at 9.0 mA, and further charged for 1.5 hours at a constant current of 45 mA. The rechargeable battery was disassembled in an atmosphere having a dew point of ⁇ 60 ° C. or lower and a water concentration of 10 ppm or lower. The negative electrode surface of the disassembled battery was observed with an optical microscope having a magnification of 2000 times, and the behavior of lithium deposition was evaluated according to the following criteria. A: No precipitation of lithium is observed.
• Carbon dioxide absorption capacity test was measured at each carbon dioxide pressure by a gravimetric method using a magnetic floating balance (manufactured by Nippon Bell Co., Ltd., trade name “MSB-AD”). The carbon dioxide absorption capacity was evaluated by the amount of carbon dioxide absorption capacity per unit weight converted to 25 ° C. and 1 atmosphere.
• compound (a) was obtained according to the following scheme. Specifically, in a 200 mL eggplant flask, 15.04 g (3.17 ⁇ 10 ⁇ 2 mol) 2- (perfluorohexyl) ethyl iodide and 5.97 g (3.16 ⁇ 10 5) p-bromothiophenol were used. in dry tetrahydrofuran (dryTHF) 100mL solution of -2 mol), was added triethylamine 4.88g (4.82 ⁇ 10 -2 mol) , it was refluxed for 20 hours in an oil bath at 84 ° C.. After returning it to room temperature, a solid was confirmed in the solution, and thus the solid was removed by suction filtration.
• dry tetrahydrofuran dry tetrahydrofuran
• the compound (b) was obtained according to the following scheme. Specifically, in a 300 mL eggplant flask, 5.01 g (9.36 ⁇ 10 ⁇ 3 mol) of the above compound (a) in 50 mL of glacial acetic acid was added 2.75 g (2.83 ⁇ 10 5) of 35% hydrogen peroxide. -2 mol), and the mixture was stirred in an oil bath at 70 ° C. for 89 hours. After returning to room temperature, 5 mL of 20% aqueous sodium hydrogen sulfite solution was added to reduce unreacted hydrogen peroxide. At this time, a solid had already precipitated in the solution, but when 90 mL of water was added, a solid further precipitated.
• the compound (f), ie, a compound (3) was obtained like the following scheme. More specifically, in the recovery flask 100 mL, 4-methoxyphenylboronic acid 0.60g (3.95 ⁇ 10 -3 mol) , compound (b) 2.24g (3.95 ⁇ 10 -3 mol) 30 mL of a 2M aqueous sodium carbonate solution and 40 mL of 1,4-dioxane (amount added until the solid dissolved) were added.
• compound (4) The compound represented by the above formula (4) (referred to as compound (4), hereinafter the same) was synthesized as follows.
• Compound (5), compound (6), compound (7), compound (8) and compound (9) were also synthesized according to the synthesis method of compound (4).
• compound (a) was obtained according to the following scheme. Specifically, 11.34 g (60 mmol) of p-bromothiophenol was charged into a 200 mL eggplant flask under a nitrogen atmosphere, and 70 mL of DME was added thereto. Further, 29.86 g (63 mmol) of 2- (perfluorohexyl) ethyl iodide and 12.42 g (90 mmol) of K 2 CO 3 were added, and the mixture was heated to 50 ° C. and stirred for 3 hours. After returning it to room temperature, the solid remaining in the solution was removed by suction filtration. The filtrate after removing the solid was concentrated under reduced pressure.
• the compound (b) was obtained according to the following scheme. Specifically, in a 200 mL eggplant flask under a nitrogen atmosphere, 26 mL (300 mmol) of 35% hydrogen peroxide solution was added to 100 mL of a glacial acetic acid solution of 32.82 g of the above compound (a), and 2 in a 70 ° C. oil bath. Stir for hours. Water was added thereto, and the resulting white solid was filtered by suction filtration. Water was added to the solid to wash twice, and hexane was further added to wash once. Furthermore, it dried at 90 degreeC under pressure reduction, and 26.34g of compounds (b) were obtained (yield 75%). The structure of the compound (b) was confirmed by 1 H-NMR (CDCl 3 ).
• compound (j) was obtained according to the following scheme. Specifically, 4.4 g (20 mmol) of the following compound (i) and 70 mL of 3-pentanone were charged into a 200 mL eggplant flask under a nitrogen atmosphere, and stirred at room temperature, and then C 6 H 13 Br4. 13 g (25 mmol) and 4.14 g (30 mmol) of K 2 CO 3 were added and refluxed in an oil bath at 120 ° C. for 11 hours. After returning it to room temperature, the remaining solid was removed by suction filtration. The filtrate after removing the solid was concentrated under reduced pressure to obtain a brown oily substance, which was then vacuum-dried (80 ° C.) to quantitatively obtain 6.87 g of a solid compound (j). . The structure of the compound (j) was confirmed by 1 H-NMR (CDCl 3 ).
• the compound (k), ie, a compound (4) was obtained like the following scheme. Specifically, in a 200 mL eggplant flask, 2.0 g (6.58 mmol) of compound (j), 3.7 g (6.58 mmol) of compound (b), 60 mL of 1,4-dioxane, palladium diacetate 0 .295 g (1.31 mmol), 1.18 g (4.5 mmol) of triphenylphosphine and 2M aqueous sodium carbonate solution (7 g of sodium carbonate dissolved in 30 mL of water) were added. Next, a Dimroth tube was attached to the eggplant flask, heated to 95 ° C. under a nitrogen atmosphere, and held for 120 minutes.
• Triphenylphosphine (0.34 g, 0.0013 mol) and palladium acetate (0.0754 g, 0.00034 mol) were further added thereto, and the mixture was vigorously stirred at 95 ° C. for 2.5 hours. After returning to the air atmosphere, 50 mL of water was added thereto at room temperature and stirred for 30 minutes to cool the inside. After completion of the reaction, solids were confirmed in the flask, and dissolved by adding ethyl acetate. After the contents were transferred to a separatory funnel and the aqueous layer was removed, the organic layer was washed 3 times with 1M hydrochloric acid, and the organic layer was further washed once with water and brine.
• Example 12 ⁇ Preparation of positive electrode for lithium ion battery> Lithium cobalt acid (LiCoO 2 ) as a positive electrode active material, acetylene black as a conductive additive, and polyvinylidene fluoride (PVdF) as a binder were mixed at a mass ratio of 89.5: 4.5: 6.0. N-methyl-2-pyrrolidone was further mixed with the obtained mixture to prepare a slurry solution. This slurry solution was applied to an aluminum foil having a thickness of 20 ⁇ m and a width of 200 nm, and the solvent was removed by drying, followed by rolling with a roll press and further vacuum drying at 150 ° C.
• Lithium cobalt acid (LiCoO 2 ) as a positive electrode active material, acetylene black as a conductive additive, and polyvinylidene fluoride (PVdF) as a binder were mixed at a mass ratio of 89.5: 4.5: 6.0. N-methyl-2-
• a positive electrode was obtained by punching.
• the amount per unit area is 24.8 g / cm 2 ⁇ 3%
• the thickness on one side is 82.6 ⁇ m ⁇ 3%
• the density is 3.0 g ⁇
• the slurry-like solution was prepared while adjusting the amount of the solvent so that cm 3 ⁇ 3% and the coating width was 150 nm with respect to the aluminum foil width of 200 nm.
• Graphite carbon powder (trade name “MCMB25-28”, manufactured by Osaka Gas Chemical Co., Ltd.) as a negative electrode active material, acetylene black as a conductive additive, and polyvinylidene fluoride (PVdF) as a binder, 93.0: 2 Mixed at a mass ratio of 0.0: 5.0.
• N-methyl-2-pyrrolidone was further mixed with the obtained mixture to prepare a slurry solution.
• This slurry-like solution was applied to an aluminum foil having a thickness of 14 ⁇ m and a width of 200 nm, and the solvent was removed by drying, followed by rolling with a roll press, followed by vacuum drying at 150 ° C.
• the amount per unit area is 11.8 g / cm 2 ⁇ 3%
• the thickness on one side is 84.6 ⁇ m ⁇ 3%
• the density is 1.4 g ⁇
• the slurry-like solution was prepared while adjusting the amount of the solvent so that cm 3 ⁇ 3% and the coating width was 150 nm with respect to the aluminum foil width of 200 nm.
• the solution ( ⁇ ) was applied on the positive electrode in a heated state so that the positive electrode active material and the compound (4) were in a mass ratio of 4: 1.
• dimethyl carbonate was distilled off by continuing heating from the back surface of the electrode, and the compound (4) was cast coated on the positive electrode.
• the solution ( ⁇ ) applying the solution ( ⁇ ) on the negative electrode in a heated state so that the negative electrode material and the compound (4) are in a mass ratio of 2: 1, and further heating is continued.
• Dimethyl carbonate was distilled off, and the compound (4) was cast on the negative electrode.
• ⁇ Battery assembly> Two laminated films (no drawing, thickness 120 ⁇ m, 68 mm ⁇ 48 mm) laminated with an aluminum layer and a resin layer were stacked with the aluminum layer side facing out, and three sides were sealed to produce a laminate cell exterior. . Subsequently, a polyethylene microporous membrane (film thickness 20 ⁇ m, 53 mm ⁇ 33 mm) was prepared as a separator, and a plurality of positive electrodes and negative electrodes coated with the compound (4) were alternately stacked via the separator as described above. The laminate was placed in the laminate cell exterior. Next, an electrolytic solution was injected into the cell exterior, and the laminate was immersed in the electrolytic solution.
• the electrolyte volume ratio of ethylene carbonate and methyl ethyl carbonate 1 for two of the mixed solution, a LiPF 6 was used was 1M dissolved.
• the electrolytic solution was injected while repeating atmospheric pressure and reduced pressure of 100 mmHg until no bubbles were generated. In an environment where the pressure was reduced to 100 mmHg, the remaining one side of the laminate cell exterior was sealed to obtain a lithium ion secondary battery.
• “(Iii) Lithium deposition test of lithium ion secondary battery” was performed on the obtained lithium ion secondary battery. The results are shown in Table 6.
• Example 12 Comparative Example 4
• a battery was assembled in the same manner as in Example 12 except that whether or not the compound (4) was applied to each electrode was changed, and "(iii) Lithium deposition test of lithium ion secondary battery” was performed.
• the evaluation results are shown in Table 6.
• Example 15 The compound (13) was added in an amount of 5.3 parts by mass with respect to 100 parts by mass of P13 TFSI, which is an ionic liquid, heated to 80 ° C. and dissolved, and then cooled to room temperature to prepare an evaluation sample. “(Iv) Carbon dioxide absorption ability test” was performed using the sample. Table 7 shows the evaluation results.
• the fluoroalkane derivative, gelling agent and gel composition of the present invention solidify liquid substances in various industrial fields (for example, paints, cosmetics, pharmaceutical medicine, petroleum spill treatment, electronic / optical material applications, environmental fields, etc.). Can be used to let

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