WO2013100079A1 - レドックスフロー二次電池及びレドックスフロー二次電池用電解質膜 - Google Patents
レドックスフロー二次電池及びレドックスフロー二次電池用電解質膜 Download PDFInfo
- Publication number
- WO2013100079A1 WO2013100079A1 PCT/JP2012/083944 JP2012083944W WO2013100079A1 WO 2013100079 A1 WO2013100079 A1 WO 2013100079A1 JP 2012083944 W JP2012083944 W JP 2012083944W WO 2013100079 A1 WO2013100079 A1 WO 2013100079A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- redox flow
- electrolyte
- secondary battery
- compound
- polymer
- Prior art date
Links
Images
Classifications
-
- 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
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
- H01M8/102—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F14/00—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 a halogen
- C08F14/18—Monomers containing fluorine
-
- 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
- H01M8/18—Regenerative fuel cells, e.g. redox flow batteries or secondary fuel cells
- H01M8/184—Regeneration by electrochemical means
- H01M8/188—Regeneration by electrochemical means by recharging of redox couples containing fluids; Redox flow type batteries
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F214/00—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 a halogen
- C08F214/18—Monomers containing fluorine
-
- 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
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/002—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from unsaturated compounds
- C08G65/005—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from unsaturated compounds containing halogens
- C08G65/007—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from unsaturated compounds containing halogens containing fluorine
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/20—Manufacture of shaped structures of ion-exchange resins
- C08J5/22—Films, membranes or diaphragms
- C08J5/2206—Films, membranes or diaphragms based on organic and/or inorganic macromolecular compounds
- C08J5/2218—Synthetic macromolecular compounds
- C08J5/2231—Synthetic macromolecular compounds based on macromolecular compounds obtained by reactions involving unsaturated carbon-to-carbon bonds
- C08J5/2237—Synthetic macromolecular compounds based on macromolecular compounds obtained by reactions involving unsaturated carbon-to-carbon bonds containing fluorine
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
- C08L71/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
- C08L71/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
- C08L71/12—Polyphenylene oxides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L81/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur with or without nitrogen, oxygen or carbon only; Compositions of polysulfones; Compositions of derivatives of such polymers
- C08L81/02—Polythioethers; Polythioether-ethers
-
- 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
- H01M8/02—Details
-
- 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
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
-
- 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
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
- H01M8/102—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer
- H01M8/1025—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer having only carbon and oxygen, e.g. polyethers, sulfonated polyetheretherketones [S-PEEK], sulfonated polysaccharides, sulfonated celluloses or sulfonated polyesters
-
- 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
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
- H01M8/102—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer
- H01M8/1032—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer having sulfur, e.g. sulfonated-polyethersulfones [S-PES]
-
- 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
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
- H01M8/1039—Polymeric electrolyte materials halogenated, e.g. sulfonated polyvinylidene fluorides
-
- 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
- H01M8/18—Regenerative fuel cells, e.g. redox flow batteries or secondary fuel cells
-
- 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
- H01M8/20—Indirect fuel cells, e.g. fuel cells with redox couple being irreversible
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2327/00—Characterised by the use of homopolymers or 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 a halogen; Derivatives of such polymers
- C08J2327/02—Characterised by the use of homopolymers or 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 a halogen; Derivatives of such polymers not modified by chemical after-treatment
- C08J2327/12—Characterised by the use of homopolymers or 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 a halogen; Derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- 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
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Definitions
- the present invention relates to a redox flow secondary battery and an electrolyte membrane for a redox flow secondary battery.
- a redox flow secondary battery stores and discharges electricity, and belongs to a large stationary battery used for leveling electricity usage.
- a redox flow secondary battery is composed of an electrolyte containing a positive electrode and a positive electrode active material (positive electrode cell), and a negative electrode electrolyte containing a negative electrode and a negative electrode active material (negative electrode cell) separated by a diaphragm, and oxidizing both active materials. Charging and discharging is performed using a reduction reaction, and an electrolytic solution containing both the active materials is circulated from a storage tank to an electrolytic cell to be used.
- an iron-chromium system for example, an iron-chromium system, a chromium-bromine system, a zinc-bromine system, or a vanadium system utilizing a difference in charge is used.
- vanadium-based secondary batteries have the advantages of high electromotive force, fast electrode reaction of vanadium ions, small amount of hydrogen generation as a side reaction, high output, and so on. .
- the diaphragm is devised so as not to mix the electrolyte containing the active material of both electrodes.
- the conventional diaphragm has a problem that it is easily oxidized and the electric resistance must be sufficiently low. While transmission of each of the active material ions contained in the cell electrolyte bipolar (contamination of the electrolyte bipolar electrolytic solution) is required to prevent as much as possible in order to increase the current efficiency of the cell, a proton carrying charge (H + ) Is sufficiently permeable, and an ion exchange membrane excellent in ion selective permeability is required.
- vanadium divalent (V 2+ ) / 3 valent (V 3+ ) in the negative electrode cell and vanadium tetravalent (V 4+ ) / 5 valent (V 5+ ) oxidation-reduction in the positive electrode cell Utilizing the reaction. Therefore, since the electrolyte solution of the positive electrode cell and the negative electrode cell is the same kind of metal ion species, even if the electrolyte solution is mixed through the diaphragm, it is regenerated normally by charging, so compared to other types of metal species Hard to be a big problem. However, since active materials that are wasted increase and current efficiency decreases, active material ions should not permeate freely as much as possible.
- Patent Document 1 discloses a polytetrafluoroethylene (hereinafter also referred to as “PTFE”) porous membrane, a polyolefin (hereinafter also referred to as “PO”) porous membrane, a PO nonwoven fabric, and the like as a redox battery diaphragm. Is disclosed.
- PTFE polytetrafluoroethylene
- PO polyolefin
- Patent Document 2 discloses a composite membrane combining a porous membrane and a hydrous polymer for the purpose of improving the charge / discharge energy efficiency of a redox flow secondary battery and improving the mechanical strength of the diaphragm.
- Patent Document 3 for the purpose of improving the charge / discharge energy efficiency of a redox flow secondary battery, a non-porous hydrophilic polymer film having a hydrophilic hydroxyl group excellent in ion permeability is used as a cellulose or ethylene-vinyl alcohol copolymer.
- the use of polymeric membranes is disclosed.
- Patent Document 4 discloses that by using a polysulfone membrane (anion exchange membrane) as a hydrocarbon ion exchange resin, the current efficiency of a vanadium redox secondary battery is 80% to 88.5%, and resistance to radical oxidation. It is also described that it is excellent.
- Patent Document 5 discloses a method of increasing the reaction efficiency by supporting expensive platinum on porous carbon of the positive electrode in order to increase the current efficiency of the redox flow secondary battery.
- Nafion manufactured by DuPont is disclosed.
- N117 and polysulfone-based ion exchange membrane are described as the diaphragm.
- Patent Document 6 discloses an iron-chromium redox flow battery in which a hydrophilic resin is applied to pores of a porous film such as polypropylene (hereinafter also referred to as “PP”).
- a hydrophilic resin is applied to pores of a porous film such as polypropylene (hereinafter also referred to as “PP”).
- PP polypropylene
- Nafion includes a repeating unit represented by — (CF 2 —CF 2 ) — and — (CF 2 —CF (—O— (CF 2 CFXO) n — (CF 2 ) m —SO 3 H).
- Patent Document 7 discloses a vanadium-based redox flow secondary battery in which cell electrical resistance is reduced as much as possible by improving the electrode, such as using a two-layer liquid-permeable porous carbon electrode having a specific surface lattice. An example is disclosed.
- Patent Document 8 discloses a vanadium-based redox flow battery using an anion exchange type diaphragm made of a crosslinked polymer having a low membrane resistance, excellent proton permeability, etc., and having a pyridinium group (using cation N + ). Examples are disclosed.
- a crosslinked polymer a polymer obtained by copolymerizing a pyridinium group-containing vinyl polymerizable monomer, a styrene monomer, and a crosslinking agent such as divinylbenzene is disclosed.
- Patent Document 9 a cation exchange membrane (fluorine polymer or other hydrocarbon polymer) and an anion exchange membrane (polysulfone type) are used as a diaphragm for the purpose of reducing cell resistance and improving power efficiency.
- a redox flow secondary battery using a film formed by alternately laminating a polymer or the like, and having a cation exchange membrane on the side of the film in contact with the positive electrode electrolyte.
- Patent Document 10 discloses that a vinyl heterocyclic compound having two or more hydrophilic groups on a porous substrate made of a porous PTFE resin as a membrane having excellent chemical resistance, low resistance and excellent ion selective permeability.
- a secondary battery using an anion exchange membrane formed by combining a crosslinked polymer having a repeating unit (such as vinylpyrrolidone having an amino group) as a diaphragm is disclosed.
- a potential difference when a potential difference is applied, metal cations having a large ionic diameter and charge amount are electrically repelled by cations on the surface layer of the diaphragm, and the metal cation permeates through the membrane. It is described that protons (H + ) which are small and monovalent can easily diffuse and permeate a diaphragm having a cation, and thus have a low electric resistance.
- the battery disclosed in Patent Document 1 does not have sufficient electrical resistance and ion selective permeability of the diaphragm, and has insufficient current efficiency and durability.
- the composite membrane disclosed in Patent Document 2 has high electric resistance, and each ion is not as large as the porous membrane, but has a problem that it diffuses freely, and the current efficiency of the battery is not high.
- the film disclosed in Patent Document 3 also has the same problem as described above and is inferior in oxidation resistance.
- the battery disclosed in Patent Document 4 still has insufficient current efficiency, is inferior in oxidation resistance deterioration in a sulfuric acid electrolyte over a long period of time, and has insufficient durability.
- the battery disclosed in Patent Document 7 uses a polysulfone-based diaphragm, the ion selective permeability and oxidation degradation resistance of the diaphragm are not sufficient, and the electric resistance, current efficiency, and durability of the battery are not sufficient.
- the battery disclosed in Patent Document 8 has insufficient current efficiency and also has problems with long-term use because of oxidative degradation.
- the film disclosed in Patent Document 9 has a problem that electric resistance is increased. According to the results shown in the examples of Patent Document 10, it cannot be said that the internal resistance (electrical resistance) of the film is sufficiently low, and oxidation resistance deterioration becomes a problem in long-term use.
- Conventional electrolyte membranes for vanadium redox flow batteries consist of a cell (negative electrode side) with a large majority of vanadium ion ions as the active material of the electrolyte solution of both electrodes, and a high charge.
- the active material ions are prevented from being diffused and transferred to the counter electrode (cell), and the proton (H + ) Is selectively transmitted.
- the performance is not sufficient.
- a membrane base material mainly composed of a hydrocarbon resin a porous membrane having only ion-selective permeability that simply isolates the electrolyte containing the electrolyte that plays a leading role in both cells, or ion-selective (non-porous)
- a hydrophilic membrane substrate, a porous membrane in which a hydrophilic membrane substrate is embedded or coated is used.
- a so-called cation exchange membrane having various anion groups or a composite membrane in which a cation exchange resin is coated or embedded in pores of a porous membrane substrate, similarly, an anion exchange membrane in which the membrane itself has a cation group, Similarly, a composite membrane in which an anion exchange resin is coated or embedded on a porous membrane base material, a laminated type of the two, and the like are used as a diaphragm, and researches that make use of the respective characteristics are being conducted.
- An ion-exchange resin membrane that fully satisfies the two contradicting properties of electrical resistance (mainly dependent on proton permeability) as a membrane and metal ion (polyvalent cation) permeability blocking, which is the main active material. Furthermore, an ion exchange resin membrane that satisfies the above-mentioned two performances in addition to long-term oxidation deterioration resistance (hydroxy radical resistance) has not been developed so far. Fluorine ion exchange resins are also excellent in proton (H + ) permeability and have not been fully studied for contradictory properties such as suppressing the permeation of active material ions, resulting in low electrical resistance and high current. A redox flow battery and an electrolyte membrane therefor have not been developed that sufficiently satisfy the efficiency and the long-term oxidation degradation resistance (hydroxy radical resistance).
- the present invention provides a redox flow secondary battery having low electrical resistance, excellent current efficiency, and durability, and without degrading proton (H + ) permeability.
- An object of the present invention is to provide an electrolyte membrane for a redox flow secondary battery having excellent ion selective permeability capable of suppressing substance ion permeability, and further having oxidation deterioration resistance (hydroxy radical resistance).
- the present inventors include a fluorine-based polymer electrolyte polymer having a specific structure, and further, by adjusting the ion cluster diameter of the membrane to a specific range, It has been found that an electrolyte membrane having excellent ion selective permeability and excellent oxidation resistance (hydroxy radical resistance) can be provided, and by using the electrolyte membrane as a diaphragm, electric resistance is low and current efficiency is improved. In addition, the present inventors have found that a redox flow secondary battery having excellent durability and durability can be provided.
- a positive electrode cell chamber including a positive electrode made of a carbon electrode;
- a negative electrode cell chamber including a negative electrode made of a carbon electrode;
- An electrolyte membrane as a diaphragm for separating and separating the positive electrode cell chamber and the negative electrode cell chamber; Having an electrolytic cell containing
- the positive electrode cell chamber contains a positive electrode electrolyte containing a positive electrode active material, and the negative electrode cell chamber contains a negative electrode electrolyte containing a negative electrode active material,
- a redox flow secondary battery that charges and discharges based on a valence change of the positive electrode active material and the negative electrode active material in the electrolyte solution,
- the electrolyte membrane includes an ion exchange resin composition containing a fluorine-based polymer electrolyte polymer having a structure represented by the following formula (1):
- a redox flow secondary battery in which the electrolyte membrane has an ion cluster diameter of 1.00 to 2.95 nm as measured by a small-
- X 1 , X 2 and X 3 each independently represents one or more selected from the group consisting of a halogen atom and a perfluoroalkyl group having 1 to 3 carbon atoms.
- X 4 Represents COOZ, SO 3 Z, PO 3 Z 2 or PO 3 HZ, where Z is a hydrogen atom, an alkali metal atom, an alkaline earth metal atom, or an amine (NH 4 , NH 3 R 1 , NH 2 R 1 R 2 , NHR 1 R 2 R 3 , NR 1 R 2 R 3 R 4 ), R 1 , R 2 , R 3 and R 4 are each independently selected from the group consisting of an alkyl group and an arene group.
- R 1 and R 2 are each independently a halogen atom
- a perfluoroalkyl group having 1 to 10 carbon atoms and 1 or more selected from the group consisting of trifluorochloroalkyl groups, a and g are numbers satisfying 0 ⁇ a ⁇ 1, 0 ⁇ g ⁇ 1, a + g 1, b is 0-8 C represents 0 or 1.
- d, e and f each independently represent an integer of 0 to 6 (provided that d, e and f are not 0 at the same time).
- the ion exchange resin composition according to any one of [1] to [4], wherein the ion exchange resin composition includes 0.1 to 200 parts by mass of a polyazole compound with respect to 100 parts by mass of the fluoropolymer electrolyte polymer.
- the redox flow secondary battery as described.
- the polyazole compound comprises a polymer of a heterocyclic compound containing one or more nitrogen atoms in the ring, and a polymer of a heterocyclic compound containing one or more nitrogen atoms and oxygen and / or sulfur in the ring.
- the polyazole compound is selected from the group consisting of a polyimidazole compound, a polybenzimidazole compound, a polybenzobisimidazole compound, a polybenzoxazole compound, a polyoxazole compound, a polythiazole compound, and a polybenzothiazole compound.
- the redox flow secondary battery according to [6] which is one or more selected.
- X 1 , X 2 and X 3 each independently represents one or more selected from the group consisting of a halogen atom and a perfluoroalkyl group having 1 to 3 carbon atoms.
- X 4 Represents COOZ, SO 3 Z, PO 3 Z 2 or PO 3 HZ, where Z is a hydrogen atom, an alkali metal atom, an alkaline earth metal atom, or an amine (NH 4 , NH 3 R 1 , NH 2 R 1 R 2 , NHR 1 R 2 R 3 , NR 1 R 2 R 3 R 4 ), R 1 , R 2 , R 3 and R 4 are each independently selected from the group consisting of an alkyl group and an arene group.
- R 1 and R 2 are each independently a halogen atom
- a perfluoroalkyl group having 1 to 10 carbon atoms and 1 or more selected from the group consisting of fluorochloroalkyl groups, a and g are numbers satisfying 0 ⁇ a ⁇ 1, 0 ⁇ g ⁇ 1, and a + g 1, b is an integer of 0 to 8 C represents 0 or 1.
- d, e and f each independently represent an integer of 0 to 6 (provided that d, e and f are not 0 at the same time).
- the ion exchange resin composition includes 0.1 to 200 parts by mass of a polyazole compound with respect to 100 parts by mass of the fluorine-based polymer electrolyte polymer.
- the electrolyte membrane for redox flow secondary batteries as described.
- the polyazole compound is composed of a polymer of a heterocyclic compound containing one or more nitrogen atoms in the ring, and a polymer of a heterocyclic compound containing one or more nitrogen atoms and oxygen and / or sulfur in the ring.
- the polyazole compound is selected from the group consisting of a polyimidazole compound, a polybenzimidazole compound, a polybenzobisimidazole compound, a polybenzoxazole compound, a polyoxazole compound, a polythiazole compound, and a polybenzothiazole compound.
- Electrolyte membrane for redox flow secondary battery [19] The electrolyte membrane for a redox flow secondary battery according to any one of [11] to [18], wherein the electrolyte membrane is heat-treated at 130 to 200 ° C. for 1 to 60 minutes. [20] The electrolyte membrane for a redox flow secondary battery according to any one of [11] to [19], wherein the electrolyte membrane further includes a reinforcing material.
- the redox flow secondary battery of the present invention has low electrical resistance and high current efficiency. Furthermore, compared with a redox flow secondary battery using a hydrocarbon-based electrolyte as a diaphragm, desorption of ionic groups and polymer electrolyte It is possible to suppress the collapse phenomenon, etc., and has excellent durability.
- the electrolyte membrane for a redox flow secondary battery of the present invention has excellent ion selective permeability, is excellent in high proton (H + ) permeability and permeation-preventing ability of active material ions in the electrolytic solution, and Is excellent in oxidation deterioration resistance (hydroxy radical resistance) over a long period of time.
- a redox flow secondary battery By using it as a diaphragm of a redox flow secondary battery, it is possible to provide a redox flow secondary battery with low cell electrical resistance and high current efficiency. In addition, since it exhibits a high oxidative degradation prevention effect for a long time against hydroxy radicals generated in the electrolyte cell in the system, ionic group desorption that occurs when using ordinary hydrocarbon electrolytes, The collapse phenomenon of molecular electrolytes can be suppressed.
- the present embodiment a mode for carrying out the present invention (hereinafter referred to as “the present embodiment”) will be described in detail.
- this invention is not limited to the following this embodiment.
- the redox flow secondary battery in this embodiment is A positive electrode cell chamber including a positive electrode made of a carbon electrode; A negative electrode cell chamber including a negative electrode made of a carbon electrode; An electrolyte membrane as a diaphragm for separating and separating the positive electrode cell chamber and the negative electrode cell chamber; Having an electrolytic cell containing
- the positive electrode cell chamber contains a positive electrode electrolyte containing a positive electrode active material
- the negative electrode cell chamber contains a negative electrode electrolyte containing a negative electrode active material
- a redox flow secondary battery that charges and discharges based on a valence change of the positive electrode active material and the negative electrode active material in the electrolyte solution
- the electrolyte membrane includes an ion exchange resin composition containing a fluorine-based polymer electrolyte polymer having a structure represented by the following formula (1):
- the redox flow secondary battery having an ion cluster diameter of 1.00 to 2.95 nm as measured by a small angle X-
- X 1 , X 2 and X 3 each independently represents one or more selected from the group consisting of a halogen atom and a perfluoroalkyl group having 1 to 3 carbon atoms.
- X 4 Represents COOZ, SO 3 Z, PO 3 Z 2 or PO 3 HZ, where Z is a hydrogen atom, an alkali metal atom, an alkaline earth metal atom, or an amine (NH 4 , NH 3 R 1 , NH 2 R 1 R 2 , NHR 1 R 2 R 3 , NR 1 R 2 R 3 R 4 ), R 1 , R 2 , R 3 and R 4 are each independently selected from the group consisting of an alkyl group and an arene group.
- R 1 and R 2 are each independently a halogen atom
- a perfluoroalkyl group having 1 to 10 carbon atoms and 1 or more selected from the group consisting of trifluorochloroalkyl groups, a and g are numbers satisfying 0 ⁇ a ⁇ 1, 0 ⁇ g ⁇ 1, a + g 1, b is 0-8 C represents 0 or 1.
- d, e and f each independently represent an integer of 0 to 6 (provided that d, e and f are not 0 at the same time).
- FIG. 1 shows an example of a schematic diagram of a redox flow secondary battery in the present embodiment.
- the redox flow secondary battery 10 in this embodiment includes a positive electrode cell chamber 2 including a positive electrode 1 made of a carbon electrode, a negative electrode cell chamber 4 including a negative electrode 3 made of a carbon electrode, the positive electrode cell chamber 2, and the negative electrode cell.
- An electrolytic cell 6 including an electrolyte membrane 5 as a diaphragm that separates and separates the chamber 4 from the chamber 4, wherein the positive electrode cell chamber 2 contains a positive electrode electrolyte containing a positive electrode active material, and the negative electrode cell chamber 4 contains a negative electrode active material.
- a negative electrode electrolyte containing The positive electrode electrolyte and the negative electrode electrolyte containing the active material are stored, for example, by the positive electrode electrolyte tank 7 and the negative electrode electrolyte tank 8, and are supplied to each cell chamber by a pump or the like (arrows A and B).
- the current generated by the Redox flow secondary battery may be converted from direct current to alternating current via the AC / DC converter 9.
- the redox flow secondary battery according to the present embodiment has a liquid-permeable porous collector electrode (for negative electrode and positive electrode) arranged on both sides of the diaphragm, sandwiched by pressing, and partitioned by the diaphragm. Is a positive electrode cell chamber and the other is a negative electrode cell chamber, and the thickness of both cell chambers is secured by a spacer.
- a positive electrode electrolyte composed of a sulfuric acid electrolyte containing vanadium tetravalent (V 4+ ) and vanadium pentavalent (V 5+ ) is provided in the positive electrode cell chamber, and vanadium is provided in the negative electrode cell chamber.
- the battery is charged and discharged by circulating a negative electrode electrolyte containing trivalent (V 3+ ) and vanadium divalent (V 2+ ).
- V 4+ is oxidized to V 5+ in the positive electrode cell chamber because the vanadium ions emit electrons, and in the negative cell chamber, V 3+ is reduced to V 2+ by the electrons returning through the outer path.
- protons (H + ) are excessive in the positive electrode cell chamber, while protons (H + ) are insufficient in the negative electrode cell chamber.
- the diaphragm selectively moves excess protons in the positive electrode cell chamber to the negative electrode chamber, thereby maintaining electrical neutrality.
- the reverse reaction proceeds during discharge.
- the battery efficiency (%) at this time is expressed as a ratio (%) obtained by dividing the discharge power amount by the charge power amount. Both power amounts depend on the internal resistance of the battery cell, the ion selectivity of the diaphragm, and other current losses. To do. A reduction in internal resistance improves voltage efficiency, and an improvement in ion selective permeability and other reductions in current loss improve current efficiency, and thus are important indicators for redox flow secondary batteries.
- the electrolyte membrane for a redox flow secondary battery of this embodiment includes an ion exchange resin composition containing a fluorine-based polymer electrolyte polymer having a specific structure and has a specific ion cluster diameter. Thereby, the ion selective permeability is excellent.
- the ion exchange resin composition contains a fluorine-based polymer electrolyte polymer having a structure represented by the above formula (1).
- the fluorine-based polymer electrolyte polymer has a structure represented by the following formula (1).
- the fluorine-based polymer electrolyte polymer in the present embodiment is not particularly limited as long as it has a structure represented by the following formula (1), and may include other structures.
- X 1 , X 2 and X 3 each independently represents one or more selected from the group consisting of a halogen atom and a perfluoroalkyl group having 1 to 3 carbon atoms.
- X 4 Represents COOZ, SO 3 Z, PO 3 Z 2 or PO 3 HZ, where Z is a hydrogen atom, an alkali metal atom, an alkaline earth metal atom, or an amine (NH 4 , NH 3 R 1 , NH 2 R 1 R 2 , NHR 1 R 2 R 3 , NR 1 R 2 R 3 R 4 ), R 1 , R 2 , R 3 and R 4 are each independently selected from the group consisting of an alkyl group and an arene group.
- R 1 and R 2 are each independently a halogen atom
- a perfluoroalkyl group having 1 to 10 carbon atoms and 1 or more selected from the group consisting of trifluorochloroalkyl groups, a and g are numbers satisfying 0 ⁇ a ⁇ 1, 0 ⁇ g ⁇ 1, a + g 1, b is 0-8 C represents 0 or 1.
- d, e and f each independently represent an integer of 0 to 6 (provided that d, e and f are not 0 at the same time).
- X 1 , X 2 and X 3 each independently represent one or more selected from the group consisting of a halogen atom and a perfluoroalkyl group having 1 to 3 carbon atoms.
- the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
- X 1 , X 2 and X 3 are preferably a fluorine atom or a perfluoroalkyl group having 1 to 3 carbon atoms from the viewpoint of chemical stability such as oxidation resistance of the polymer.
- X 4 represents COOZ, SO 3 Z, PO 3 Z 2 or PO 3 HZ.
- X 4 is also referred to as an “ion exchange group”.
- Z is a hydrogen atom, an alkali metal atom, an alkaline earth metal atom, or an amine (NH 4 , NH 3 R 1 , NH 2 R 1 R 2 , NHR 1 R 2 R 3 , NR 1 R 2 R 3 R 4 ).
- NH 4 , NH 3 R 1 , NH 2 R 1 R 2 , NHR 1 R 2 R 3 , NR 1 R 2 R 3 R 4 .
- it does not specifically limit as an alkali metal atom, A lithium atom, a sodium atom, a potassium atom, etc. are mentioned.
- alkaline-earth metal atom A calcium atom, a magnesium atom, etc. are mentioned.
- R 1 , R 2 , R 3 and R 4 each independently represent one or more selected from the group consisting of an alkyl group and an arene group.
- X 4 is PO 3 Z 2
- Z may be the same or different.
- X 4 is preferably SO 3 Z from the viewpoint of chemical stability such as oxidation resistance of the polymer.
- R 1 and R 2 each independently represents one or more selected from the group consisting of a halogen atom, a perfluoroalkyl group having 1 to 10 carbon atoms and a fluorochloroalkyl group.
- a halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
- b represents an integer of 0 to 8.
- c represents 0 or 1;
- d, e and f each independently represent an integer of 0 to 6. However, d, e, and f are not 0 at the same time.
- the fluorine-based polymer electrolyte polymer in the present embodiment is preferably a perfluorocarbon sulfonic acid resin (hereinafter also referred to as “PFSA resin”) because the effects of the present invention tend to become more prominent.
- the PFSA resin in this embodiment has a main chain composed of a PTFE skeleton chain, a perfluorocarbon as a side chain, and one to two or more sulfonic acid groups in each side chain (some of which are in a salt form). Which may be bonded).
- the PFSA resin is It preferably contains a repeating unit represented by — (CF 2 —CF 2 ) — and a repeating unit derived from a compound represented by the following formula (3) or (4), and — (CF 2 It is preferably composed of a repeating unit represented by —CF 2 ) — and a repeating unit derived from the compound represented by the formula (3) or the formula (4).
- [A] represents (CF 2 ) m —SO 3 H (m represents an integer of 0 to 6. However, n and m are not 0 at the same time), Or Formula (4): CF 2 ⁇ CF—O— (CF 2 ) P —CFX (—O— (CF 2 ) K —SO 3 H) or CF 2 ⁇ CF—O— (CF 2 ) P —CFX ( — (CF 2 ) L —O— (CF 2 ) m —SO 3 H) (wherein X represents a perfluoroalkyl group having 1 to 3 carbon atoms, P represents an integer of 0 to 12, Represents an integer of 1 to 5, L represents an integer of 1 to 5, and m represents an integer of 0 to 6. However, K and L may be the same or different, and P, K and L are It is not 0 at the same time.)
- the PFSA resin includes a repeating unit represented by — (CF 2 —CF 2 ) — and — (CF 2 —CF (—O— (CF 2 CFXO) n — (CF 2 ) m —SO 3 H.
- X represents F or CF 3 , n represents an integer of 0 to 5 and m represents an integer of 0 to 12, provided that BR> An and m Are not simultaneously 0), and is represented by — (CF 2 —CF (—O— (CF 2 CFXO) n — (CF 2 ) m —SO 3 H)) —
- a co-polymer containing a repeating unit (wherein X represents CF 3 , n represents 0 or 1, m represents an integer of 0 to 12, provided that n and m are not 0 at the same time). More preferably, it is a coalescence.
- the PFSA resin is a copolymer having the above structure and has a predetermined equivalent mass EW, the obtained electrolyte membrane has sufficient hydrophilicity and has high resistance to radical species generated by oxidative degradation. There is a tendency.
- n in the repeating unit represented by — (CF 2 —CF (—O— (CF 2 CFXO) n — (CF 2 ) m —SO 3 H)) — in the PFSA resin is 0, Is an integer of 1 to 6, or —CF 2 —CFX (—O— (CF 2 ) P —CFX (—O— (CF 2 ) K —SO 3 H) — And —CF 2 —CFX (—O— (CF 2 ) P —CFX (— (CF 2 ) L —O— (CF 2 ) m —SO 3 H) — And the hydrophilicity of the resulting electrolyte membrane tends to increase.
- the fluorine-based polymer electrolyte polymer represented by the formula (1) in the present embodiment is a PFSA resin having a structure represented by the following formula (2) because the effects of the present invention tend to become more prominent. It is preferable.
- the fluorinated polymer electrolyte polymer represented by the above formula (1) and the PFSA resin having the structure represented by the above formula (2) are represented by the above formula (1) and the above formula (2), respectively.
- the fluorine-based polymer electrolyte polymer represented by the above formula (1) and the PFSA resin having the structure represented by the above formula (2) are directly or partially between the molecules of the ion exchange group. Indirect partial cross-linking reaction may be used.
- the partial crosslinking is preferable from the viewpoint of controlling solubility and excessive swelling. For example, even if the EW of the fluorine-based polymer electrolyte polymer is about 280, the water solubility of the fluorine-based polymer electrolyte polymer can be reduced (water resistance is improved) by performing the partial crosslinking.
- a fluorine-type polymer electrolyte polymer is a low melt flow area
- the intermolecular entanglement can be increased by the said partial bridge
- Examples of the partial crosslinking reaction include a reaction between an ion exchange group and a functional group or main chain of another molecule, a reaction between ion exchange groups, an oxidation-resistant low molecular compound, an oligomer, or a high molecular substance. In some cases, it may be a reaction with a salt (including an ionic bond with a SO 3 H group) forming substance.
- Examples of the oxidation-resistant low molecular weight compound, oligomer or polymer substance include polyhydric alcohols and organic diamines.
- the molecular weight of the fluorine-based polymer electrolyte polymer in the present embodiment is not particularly limited, but is 0 as a melt flow index (MFI) value measured according to ASTM: D1238 (measurement conditions: temperature 270 ° C., load 2160 g). 0.05 to 50 (g / 10 minutes) is preferable, 0.1 to 30 (g / 10 minutes) is more preferable, and 0.5 to 20 (g / 10 minutes) is even more preferable. preferable.
- MFI melt flow index
- the equivalent mass EW of the fluoropolymer electrolyte polymer in this embodiment is preferably 300 to 1300 (g / eq), More preferred is 350 to 1000 (g / eq), still more preferred is 400 to 900 (g / eq), and particularly preferred is 450 to 750 (g / eq).
- the ion exchange resin composition containing it is excellent in combination with the chemical structure.
- the electrolyte membrane obtained by using the resin composition can impart hydrophilicity, has lower electrical resistance, higher hydrophilicity, and smaller clusters (the ion exchange groups coordinate water molecules and / or Or a large number of adsorbed minute portions), and oxidation resistance (hydroxy radical resistance) and ion selective permeability tend to be further improved.
- the equivalent mass EW of the fluorine-based polymer electrolyte polymer is preferably 300 or more from the viewpoint of hydrophilicity and water resistance of the film, and is preferably 1300 or less from the viewpoint of hydrophilicity and electric resistance of the film.
- the equivalent mass EW of the fluorine-based polymer electrolyte polymer can be measured by salt-substituting the fluorine-based polymer electrolyte polymer and back titrating the solution with an alkaline solution.
- the equivalent mass EW can be adjusted by the copolymerization ratio of the fluorine-based monomer that is a raw material of the fluorine-based polymer electrolyte polymer, the selection of the monomer type, and the like.
- the fluorine-based polymer electrolyte polymer in the present embodiment can be obtained, for example, by producing a precursor of a polymer electrolyte polymer (hereinafter also referred to as “resin precursor”) and then hydrolyzing it. .
- a PFSA resin for example, a PFSA resin comprising a copolymer of a fluorinated vinyl ether compound represented by the following general formula (5) or (6) and a fluorinated olefin monomer represented by the following general formula (7) It is obtained by hydrolyzing the precursor.
- Formula (5) CF 2 ⁇ CF—O— (CF 2 CFXO) n —A
- X represents F or a perfluoroalkyl group having 1 to 3 carbon atoms
- n represents an integer of 0 to 5
- A represents (CF 2 ) m -W
- m represents 0.
- Formula (6) CF 2 ⁇ CF—O— (CF 2 ) P —CFX (—O— (CF 2 ) K —W) or CF 2 ⁇ CF—O— (CF 2 ) P —CFX (— (CF 2) L -O- (CF 2) m -W)
- X represents a perfluoroalkyl group having 1 to 3 carbon atoms
- P represents an integer of 0 to 12
- K represents an integer of 1 to 5
- L represents an integer of 1 to 5
- m represents an integer of 0 to 6
- W represents a functional group that can be converted to SO 3 H by hydrolysis.
- Formula (7): CF 2 CFZ (In Formula (7), Z represents H, Cl, F, a perfluoroalkyl group having 1 to 3 carbon atoms, or a cyclic perfluoroalkyl group that may contain oxygen.)
- the W shown a functional group capable of conversion to SO 3 H by hydrolysis in the above formula (5) is not particularly limited, SO 2 F, SO 2 Cl , SO 2 Br are preferred.
- X CF 3
- W SO 2 F
- Z F.
- the resin precursor in this embodiment can be synthesized by a known means.
- a radical generator such as peroxide.
- fluorinated olefins such as tetrafluoroethylene (TFE).
- the polymerization method is not particularly limited, and a method of polymerizing by dissolving the vinyl fluoride compound or the like and a gas of fluorinated olefin in a polymerization solvent such as fluorine-containing hydrocarbon (reaction polymerization), fluorine-containing A method in which a vinyl fluoride compound itself is polymerized as a polymerization solvent without using a solvent such as hydrocarbon (bulk polymerization), an aqueous solution of a surfactant is used as a medium, and a vinyl fluoride compound and a fluorinated olefin gas are charged.
- a polymerization solvent such as fluorine-containing hydrocarbon
- reaction polymerization reaction polymerization
- fluorine-containing fluorine-containing
- an aqueous solution of a surfactant is used as a
- Polymerization method by reacting (emulsion polymerization), Polymerization method by emulsifying and reacting an aqueous solution of co-emulsifier such as surfactant and alcohol with a vinyl fluoride compound and a fluorinated olefin gas. Polymerization), and by suspending and reacting an aqueous suspension stabilizer solution with a vinyl fluoride compound and a fluorinated olefin gas. How to (suspension polymerization), or the like can be used.
- any of those prepared by any of the polymerization methods described above can be used. Moreover, it is good also considering the polymer of a block shape or a taper shape obtained by adjusting superposition
- the resin precursor is obtained by treating an impurity terminal generated in a resin molecular structure during a polymerization reaction or a structurally oxidizable portion (CO group, H bond portion, etc.) under a fluorine gas by a known method,
- the part may be fluorinated.
- a part of an ion exchange group precursor group (for example, SO 2 F group) may be partially imidized (including intermolecular) (such as alkyl imidization).
- the molecular weight of the resin precursor is not particularly limited, but the precursor was measured to have a melt flow index (MFI) value of 0.00 based on ASTM: D1238 (measurement conditions: temperature 270 ° C., load 2160 g). It is preferably 05 to 50 (g / 10 minutes), more preferably 0.1 to 30 (g / 10 minutes), and still more preferably 0.5 to 20 (g / 10 minutes). .
- MFI melt flow index
- the shape of the resin precursor is not particularly limited. From the viewpoint of increasing the treatment speed in the hydrolysis treatment and acid treatment described later, the resin precursor is in the form of pellets of 0.5 cm 3 or less, dispersed liquid, powder particles In particular, it is preferable to use a powdered product after polymerization. From the viewpoint of cost, an extruded film-like resin precursor may be used.
- the method for producing the fluorinated polymer electrolyte polymer of the present embodiment from the resin precursor is not particularly limited. For example, the resin precursor is extruded using a nozzle or a die using an extruder and then hydrolyzed. There is a method in which a hydrolysis treatment is performed after the treatment is performed or the product obtained by polymerization is used in the form of a dispersed liquid or a powder that is precipitated and filtered.
- the method for producing the fluorinated polymer electrolyte polymer of the present embodiment from the resin precursor is not particularly limited.
- the resin precursor is extruded using a nozzle or a die using an extruder and then hydrolyzed.
- a hydrolysis treatment is performed after the treatment is performed or the product obtained by polymerization is used in the form of a dispersed liquid or a powder that is precipitated and filtered.
- the resin precursor obtained as described above and molded as necessary is subsequently immersed in a basic reaction liquid and hydrolyzed.
- the basic reaction solution used for the hydrolysis treatment is not particularly limited, but is an aqueous solution of an amine compound such as dimethylamine, diethylamine, monomethylamine and monoethylamine, or hydroxide of an alkali metal or alkaline earth metal.
- An aqueous solution of the product is preferable, and an aqueous solution of sodium hydroxide and potassium hydroxide is particularly preferable.
- an alkali metal or alkaline earth metal hydroxide is used, its content is not particularly limited, but it is preferably 10 to 30% by mass with respect to the entire reaction solution.
- the reaction solution further preferably contains a swellable organic compound such as methyl alcohol, ethyl alcohol, acetone, and dimethyl sulfoxide (DMSO). The content of the swellable organic compound is preferably 1 to 30% by mass with respect to the entire reaction solution.
- the resin precursor is hydrolyzed in the basic reaction liquid, sufficiently washed with warm water, and then acid-treated.
- the acid used for the acid treatment is not particularly limited, but preferred are mineral acids such as hydrochloric acid, sulfuric acid and nitric acid, and organic acids such as oxalic acid, acetic acid, formic acid and trifluoroacetic acid, and a mixture of these acids and water. Is more preferable.
- the said acids may be used independently or may use 2 or more types together.
- the basic reaction solution used in the hydrolysis treatment may be removed in advance before the acid treatment, for example, by treatment with a cation exchange resin.
- the ion exchange group precursor group of the resin precursor is protonated to generate an ion exchange group.
- W in the formula (5) is protonated by acid treatment to become SO 3 H.
- the fluorine-based polymer electrolyte polymer obtained by the hydrolysis and acid treatment can be dispersed or dissolved in a protic organic solvent, water, or a mixed solvent of both.
- the content of the fluorine-based polymer electrolyte polymer having the structure represented by the formula (1) contained in the ion exchange resin composition forming the electrolyte membrane in the present embodiment is not particularly limited, but ion selective permeability
- the ion exchange resin composition is preferably mainly composed of a fluorine-based polymer electrolyte polymer having the specific structure.
- “mainly” means that the lower limit of the content in the resin composition is about 33.3 mass%, preferably 40 mass%, more preferably 50 mass%, still more preferably 50 mass%, more More preferably, it means 80% by mass, particularly preferably 90% by mass.
- the upper limit value is not particularly limited, but is preferably 99.5% by mass or less.
- the fluorine-based polyelectrolyte polymer is a partial salt (0.01 to 5 of total ion exchange group equivalent) with an alkali metal, an alkaline earth metal, and other radical-degradable transition metals (Ce compound, Mn compound, etc.). It may be contained alone or in a form used in combination with a basic polymer described later.
- the ion exchange resin composition in the present embodiment contains a polyazole compound in addition to or in addition to the above-described fluorine-based polymer electrolyte polymer, and a basic polymer (low molecular weight substance such as an oligomer is added). Containing) is preferred because the chemical stability (mainly oxidation resistance and the like) of the resin composition tends to increase. These compounds partially form an ion complex in the resin composition in a form close to fine particles or molecular dispersion to form an ion cross-linked structure.
- the EW of the fluorine-based polymer electrolyte polymer is low (for example, 300 to 500), the water resistance and electrical resistance, or the water-containing cluster diameter tends to decrease, so that the ion exchange resin composition is polyazole-based. It is preferable from the viewpoint of balance, such as ion selective permeability, to contain a compound, or in place of / in addition to it, a basic polymer (including a low molecular weight substance such as an oligomer).
- the polymer of the heterocyclic compound which contains one or more nitrogen atoms in a ring the polymer of the heterocyclic compound which contains one or more nitrogen atoms in a ring
- the structure of the heterocyclic ring is not particularly limited, but a 5-membered ring is preferable.
- polyazole type compound a polyimidazole type compound, a polybenzimidazole type compound, a polybenzobisimidazole type compound, a polybenzoxazole type compound, a polyoxazole type compound, a polythiazole type compound, and a polybenzothiazole 1 or more types selected from the group which consists of a system compound are mentioned.
- polybenzimidazole compounds are preferred from the viewpoints of ease of ionic bond formation and film strength.
- the polyazole compound may be activated by including or reacting a phosphoric acid compound (single substance or polyphosphoric acid) and binding a part thereof to the polyazole compound.
- a phosphoric acid compound single substance or polyphosphoric acid
- the polyazole compound is preferably in a dispersed state so as not to decrease the strength of the electrolyte membrane, and more preferably dispersed in a sea island-like mosaic state.
- the polyazole compound may be present in a state of being ionized with various acids so that a partial surface of the membrane forms an ionic bond and the inside of the membrane is in an ionic (cation) state. It is preferable from the viewpoint of the strength and durability of the electrolyte membrane that the fluorine-based polymer electrolyte polymer and the polyazole-based compound form an ionic bond in at least a part thereof.
- a state in which at least a part of the ion exchange group of the fluorine-based polyelectrolyte polymer and at least a part of the polyazole compound are reacted in a form close to molecular dispersion (for example, ion-bonded, acid-base ion complex) More preferably, it is in a state of chemical bonding such as a state of forming s. Whether or not the ionic bond exists can be confirmed using a Fourier-Transform Infrared Spectrometer (hereinafter referred to as FT-IR).
- FT-IR Fourier-Transform Infrared Spectrometer
- the fluoropolymer electrolyte polymer is a PFSA resin
- examples of ionic bonds are not particularly limited.
- the sulfonic acid group of the PFSA resin may be an imidazole group, an oxazole group, a thiazole group, or the like in a polyazole compound.
- the state etc. which are ion-bonded to the nitrogen atom in each reactive group are mentioned. By controlling this state, it is possible to control the cluster diameter, which is an ion channel formed with the sulfonic acid group of the PFSA resin, centering on water molecules.
- an electrolyte membrane having an excellent balance of ion selective permeability, water resistance, and oxidation resistance without significantly sacrificing any contradictory performance without increasing the electrical resistance of the membrane. Therefore, the performance can be greatly improved as compared with the conventional one.
- the content of the polyazole-based compound is preferably 0.1 to 200 parts by mass, more preferably 0.1 to 200 parts by mass with respect to 100 parts by mass of the fluorine-based polymer electrolyte polymer having the structure represented by the formula (1). It is 5 to 150 parts by mass, more preferably 1 to 100 parts by mass, and particularly preferably 1 to 50 parts by mass.
- the ion exchange resin composition in the present embodiment preferably further contains a polyphenylene sulfide (PPS) resin from the viewpoint of the oxidation resistance of the electrolyte membrane and the cluster diameter.
- PPS resin can be mixed with a resin composition containing a fluoropolymer electrolyte polymer by an extrusion method, or an aqueous solvent dispersion of a PPS resin can be mixed with a stock solution dispersion of a resin composition containing a fluoropolymer electrolyte polymer. It can be added by the method to do.
- the amount of PPS resin added is preferably 0.1 to 20 parts by mass with respect to 100 parts by mass of the fluorine-based polymer electrolyte polymer having the structure represented by the formula (1), and 0.5 to It is more preferable that it is 10 mass parts.
- the content of the PPS resin is 0.1 part by mass or more, the oxidation resistance and ion selective permeability of the electrolyte membrane tend to be further improved, and when it is 20 parts by mass or less, sufficient membrane strength is obtained. There is a tendency.
- the ion exchange resin composition in the present embodiment preferably further contains a polyphenylene ether resin.
- the content of the polyphenylene ether resin is preferably 0.1 to 20 parts by mass, more preferably 0.1 to 20 parts by mass with respect to 100 parts by mass of the fluorine-based polymer electrolyte polymer having the structure represented by the formula (1). 1 to 10 parts by mass.
- chemical durability such as oxidation resistance tends to be further improved.
- the ion exchange resin composition in the present embodiment contains a fluorine resin other than the fluorine polymer electrolyte polymer represented by the formula (1) (resin containing carboxylic acid, phosphoric acid, etc. and other known fluorine resins). May be.
- the fluororesin is preferably contained in an amount of 30 to 50 parts by mass, preferably 10 to 30 parts by mass with respect to 100 parts by mass of the fluoropolymer electrolyte polymer represented by the formula (1) used in the present embodiment. More preferably, it is more preferably 0 to 10 parts by mass.
- the mixing method is not particularly limited, and may be mixed in a solvent or dispersed in a medium, or resin precursors may be extruded and mixed.
- the ion clusters existing in the electrolyte membrane in the present embodiment are moderate molecules that are a hydrophobic portion that forms a fluorinated hydrocarbon portion that forms the main chain of the polymer electrolyte polymer molecule, and a side chain that is bonded to the main chain.
- a plurality of large-sized channels (so-called ion clusters) and small-sized ion channels that connect the channels are formed, and as a result, the ion channels continuously communicate in the thickness direction of the membrane.
- the electrolyte membrane of the present embodiment has an ion cluster diameter measured by a small angle X-ray method in water at 25 ° C. of 1.00 to 2.95 nm, preferably 1.50 to 2.95 nm, more preferably 1.70. It is ⁇ 2.95 nm, particularly preferably 2.00 to 2.75 nm. Since the electrolyte membrane of this embodiment has an ion cluster diameter of 2.95 nm or less, it is difficult to transmit large ions, ion selective permeability is improved, and the strength of the membrane tends to be improved. A redox flow secondary battery using a membrane as a diaphragm improves current efficiency. On the other hand, when the ion cluster diameter is 1.00 nm or more, protons (H + ) coordinated with water molecules can easily pass, and the electrical resistance decreases.
- the number of ion clusters (units / nm 3 ) per unit volume of the electrolyte membrane is preferably 0.06 to 0.25, more preferably 0.09 to 0.22, and still more preferably 0.12 to 0.00. 20.
- the film strength tends to be improved, and when it is 0.06 or more, the electric conductivity is further improved (the film electric resistance is further reduced). )There is a tendency.
- a specific calculation method of the ion cluster diameter and the number of clusters is as follows. Small-angle X-ray scattering measurement is performed in a state where the electrolyte membrane is impregnated with water at 25 ° C., and empty cell scattering correction and absolute intensity correction are performed on the obtained scattering profile. When measurement is performed using a two-dimensional detector, the data is made one-dimensional by a rational method such as an annular average, and the scattering angle dependence of the scattering intensity is obtained.
- a cluster was constructed according to the method described in Yasuhiro Hashimoto, Naoki Sakamoto, Hideki Iijima Polymer Sciences Vol.63 No.3 pp.166 2006
- the diameter can be determined.
- the theoretical scattering formula based on this model is used to fit the region where scattering from clusters in the measured scattering profile is dominant.
- the average cluster diameter (cluster diameter) and the cluster number density can be obtained.
- the core portion corresponds to a cluster
- the core diameter is the cluster diameter.
- Equation 1 The theoretical scattering equation of the model used for fitting is shown in Equation 1.
- C is a device constant
- N is a cluster number density
- ⁇ is a core, that is, a volume fraction of a cluster part and a virtual shell around it, assuming that it is a hard sphere
- ⁇ is a Bragg angle
- ⁇ is X used
- t is the shell layer thickness
- a 0 is the average cluster radius (half of the cluster diameter)
- ⁇ the standard deviation of the core diameter (cluster diameter).
- I b (q) represents background scattering including thermal diffuse scattering, and is assumed to be a constant here.
- N, ⁇ , a 0 , ⁇ , and I b (q) are set as variable parameters.
- the ion cluster diameter and the number of ion clusters of the electrolyte membrane can be adjusted by the polymer structure, polymer composition, film forming conditions, and the like.
- the ion cluster diameter tends to be improved by lowering the EW of the polymer or adjusting the heat treatment conditions of the electrolyte membrane.
- the equilibrium moisture content of the electrolyte membrane in the present embodiment is preferably 5% by mass or more, more preferably 10% by mass or more, and further preferably 15% by mass or more.
- the equilibrium water content of the electrolyte membrane in the present embodiment is preferably 80% by mass or less, more preferably 50% by mass or less, and further preferably 40% by mass or less.
- the equilibrium water content of the electrolyte membrane is 5% by mass or more, the electric resistance, current efficiency, oxidation resistance, and ion selective permeability of the membrane tend to be good.
- the equilibrium moisture content is 50% by mass or less, the dimensional stability and strength of the membrane are improved, and the increase in water-soluble components tends to be suppressed.
- the equilibrium moisture content of the electrolyte membrane is based on a membrane obtained by forming a resin composition from a dispersion of water and an alcohol-based solvent and drying at 160 ° C. or lower, and the equilibrium is 23 ° C. and 50% relative humidity (RH). It is expressed as saturated water absorption (Wc).
- the membrane maximum water content of the electrolyte membrane in the present embodiment is not particularly limited, but is preferably 10% by mass or more, more preferably 15% by mass from the viewpoint of electrical resistance, current efficiency, oxidation resistance, and ion selective permeability of the membrane. % Or more, more preferably 20% by mass or more.
- the membrane maximum moisture content refers to the maximum value of the moisture content measured during the equilibrium moisture content measurement.
- the equilibrium moisture content of the electrolyte membrane can be adjusted by the same method as that for EW described above.
- the electrolyte membrane in the present embodiment preferably has a reinforcing material from the viewpoint of membrane strength.
- the reinforcing material is not particularly limited, and examples thereof include a general nonwoven fabric, a woven fabric, and a porous film made of various materials.
- the porous membrane is not particularly limited, but preferably has a good affinity with a fluorine-based polymer electrolyte polymer. Among them, a stretched and porous PTFE-based membrane is used, and this is used in this embodiment.
- a reinforcing membrane in which an ion exchange resin composition containing a fluorine-based polymer electrolyte polymer is embedded substantially without gaps is more preferable from the viewpoint of the strength of the thin film and the suppression of dimensional changes in the plane (longitudinal and lateral) directions.
- the reinforcing membrane is prepared by immersing an appropriate amount of a dispersion of an appropriate concentration of a solute having the above-described components in an organic solvent or alcohol-water containing the above-described ion exchange resin composition in a porous membrane, It can be obtained by drying.
- the solvent used for preparing the reinforcing membrane is not particularly limited, but a solvent having a boiling point of 250 ° C. or lower is preferable, a solvent having a boiling point of 200 ° C. or lower is more preferable, and a boiling point of 120 ° C. or lower is more preferable. It is a solvent. Of these, water and aliphatic alcohols are preferable, and specific examples include water, methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, isobutyl alcohol, and tert-butyl alcohol.
- the said solvent may be used by a single solvent, or may use 2 or more types together.
- the method for producing an electrolyte membrane (film formation method) in the present embodiment is not particularly limited, and a known extrusion method or cast film formation can be used.
- the electrolyte membrane may be a single layer or a multilayer (2 to 5 layers). In the case of a multilayer, it is possible to improve the performance of the electrolyte membrane by laminating films having different properties (for example, EW and resins having different functional groups). it can. In the case of a multilayer, it may be laminated at the time of extrusion film formation or casting, or the obtained respective films may be laminated.
- the electrolyte membrane formed by the above method is thoroughly washed with water (or treated with a dilute aqueous acidic solution such as hydrochloric acid, nitric acid, sulfuric acid or the like before washing with water if necessary) to remove impurities.
- the film is heat-treated in air or in an inert gas (preferably in an inert gas), preferably at 130 to 200 ° C., more preferably at 140 to 180 ° C., and even more preferably at 150 to 170 ° C. for 1 to 30 minutes. It is preferable.
- the heat treatment time is more preferably 2 to 20 minutes, further preferably 3 to 15 minutes, and particularly preferably about 5 to 10 minutes.
- the heat treatment is not sufficiently entangled between the particles derived from the raw material (between the primary particles and the secondary particles) and between the molecules, so that the particles and the molecules are entangled with each other.
- it is useful for water resistance (especially lowering the hot water-dissolved component ratio), stabilizing the saturated water absorption rate of water, and generating stable clusters.
- It is also useful from the viewpoint of improving the film strength. This is particularly useful when the cast film forming method is used.
- the heat treatment contributes to water resistance and stable cluster formation by generating minute intermolecular cross-links between molecules of the fluorine-based polymer electrolyte polymer, and also has the effect of making the cluster diameter uniform and small. Presumed to be.
- the ion-exchange group of the fluorine-based polymer electrolyte polymer in the ion-exchange resin composition becomes active reaction sites (such as aromatic rings) of other additives (including resin) and at least a part thereof. It is presumed that through the reaction, minute cross-links are generated and stabilized (particularly due to the reaction of ion exchange groups existing in the vicinity of other resin components which are dispersed additives).
- the degree of this crosslinking is preferably 0.001 to 5%, more preferably 0.1 to 3%, and still more preferably 0.2 to 0.2% in terms of EW (degree of EW reduction before and after heat treatment). About 2%.
- Performing the above heat treatment under the above suitable conditions can be caused by the viewpoint of exerting the effect of the above heat treatment and the generation and increase of defluorination, dehydrofluorination, desulfonic acid, thermal oxidation sites, etc. It is preferable from the viewpoint of suppressing the deterioration of the oxidation deterioration resistance during the actual use as an electrolytic membrane, starting from the defects in the structure.
- the electrolyte membrane in the present embodiment has excellent ion selective permeability, low electrical resistance, excellent durability (mainly hydroxyl radical oxidation resistance), and excellent performance as a diaphragm for redox flow secondary batteries. To demonstrate. In addition, each physical property in this specification can be measured according to the method described in the following Examples, unless otherwise specified.
- Charging / discharging test Redox flow secondary batteries have liquid-permeable porous collector electrodes (for negative electrode and positive electrode) arranged on both sides of the diaphragm on both sides of the diaphragm. One was sandwiched and separated by a diaphragm, the positive electrode cell chamber, the other was the negative electrode cell chamber, and the thickness of both cell chambers was secured with a spacer.
- the positive electrode cell chamber is composed of a sulfuric acid electrolyte containing vanadium tetravalent (V 4+ ) and pentavalent (V 5+ ), and the negative electrode cell chamber is composed of vanadium trivalent (V 3+ ) and divalent (
- the negative electrode electrolyte containing V 2+ ) was circulated to charge and discharge the battery. At this time, in charging, V 4+ is oxidized to V 5+ in the positive electrode cell chamber because the vanadium ions emit electrons, and in the negative cell chamber, V 3+ is reduced to V 2+ by the electrons returning through the outer path. It was.
- protons (H + ) are excessive in the positive electrode cell chamber, while protons (H + ) are insufficient in the negative electrode cell chamber.
- the diaphragm selectively moved the excess protons in the positive electrode cell chamber to the negative electrode chamber to maintain electrical neutrality.
- the reverse reaction progressed during the discharge.
- the battery efficiency (energy efficiency) (%) at this time is expressed as a ratio (%) obtained by dividing the discharge power amount by the charge power amount, and both the power amounts are the ion resistance of the battery cell and the ion selective permeability of the diaphragm. Others depend on current loss.
- the current efficiency (%) is expressed as a ratio (%) obtained by dividing the amount of discharged electricity by the amount of charged electricity, and both the amounts of electricity depend on the ion selective permeability of the diaphragm and other current losses.
- Battery efficiency is expressed as the product of current efficiency and voltage efficiency. Reduction of internal resistance, that is, cell electrical resistivity improves voltage efficiency (battery efficiency (energy efficiency)), and improvement of ion selective permeability and other reduction of current loss improve current efficiency, so a redox flow secondary battery. Is an important indicator. The charge / discharge experiment was performed using the battery obtained as described above.
- aqueous electrolyte with a total vanadium concentration of 2 M / L and a total sulfate radical concentration of 4 M / L, and the thickness of the installed positive and negative electrode cell chambers is 5 mm, respectively, between the porous electrode and the diaphragm.
- a porous felt made of carbon fiber having a thickness of 5 mm and a bulk density of about 0.1 g / cm 3 .
- the charge / discharge experiment was conducted at a current density of 80 mA / cm 2 .
- the cell electrical resistivity ( ⁇ ⁇ cm 2 ) was determined by measuring a DC resistance value at an AC voltage of 10 mV and a frequency of 20 kHz at the start of discharge using the AC impedance method, and multiplying it by the electrode area.
- the cell internal resistance was determined by dividing the difference between the charging intermediate voltage and the discharging intermediate voltage at constant current charging / discharging by 2, and multiplying the value (resistance) divided by the current value by the electrode area.
- Durability Durability was evaluated by current efficiency (%) and cell electrical resistivity ( ⁇ ⁇ cm 2 ) after 200 cycles of charge / discharge of (6) above.
- CF 2 ⁇ CFO (CF 2 ) 2 —SO 2 F An amount of CF 2 ⁇ CFO (CF 2 ) 2 —SO 2 F is continuously supplied to perform polymerization, and the polymerization conditions are adjusted to an optimum range to obtain various perfluorocarbon sulfonic acid resin precursor powders. It was.
- the MFI of the obtained PFSA resin precursor powder is 0.5 (g / 10 min) for A1, 1.5 (g / 10 min) for A2, 0.8 (g / 10 min) for A3, A4 was 2.0 (g / 10min).
- PFSA resin precursor powder was dissolved in potassium hydroxide (15% by mass) and methyl alcohol (50% by mass) at 80 ° C. for 20 hours. It was made to contact and the hydrolysis process was performed. Then, it was immersed in 60 degreeC water for 5 hours. Next, the treatment of immersing in a 2N aqueous hydrochloric acid solution at 60 ° C. for 1 hour was repeated 5 times by updating the aqueous hydrochloric acid solution every time, and then washed with ion-exchanged water and dried.
- the EW of the obtained PFSA resin was A1 of 450 (g / eq), A2 of 650 (g / eq), A3 of 750 (g / eq), and A4 of 850 (g / eq), respectively.
- ASF1 dispersion
- ASF2 dispersion
- ASF3 dispersion
- ASF4 dispersion
- the polybenzimidazole (PBI) powder is dissolved in an alkaline aqueous solution (10% aqueous KOH solution) and stirred in each of the PFSA resin dispersions while being uniformly mixed and dispersed.
- the dispersion was uniformly mixed so as to be 6 parts by mass, 4 parts by mass, 3 parts by mass, and 1 part by mass, respectively (in the order of ASF1 to ASF4).
- these are passed through a column packed with particulate cation exchange resin particles, and the alkali ion component is almost completely removed, and ionic bonds between at least some of the functional groups (sulfonic acid groups and alkaline nitrogen atoms) are formed.
- the resulting mixed dispersion (ASBF) was ASBF1, ASBF2, ASBF3, and ASBF4, respectively.
- the equilibrium water content of the obtained electrolyte membrane is the group (I) ⁇ ASF> not containing PBI in the above order; ASF1 (19 mass%), ASF2 (12 mass%), ASF3 (9 mass%), It was ASF4 (6 mass%).
- the maximum water content of each electrolyte membrane in 25 ° C. water for 3 hours was ASF1 (27 mass%), ASF2 (23 mass%), ASF3 (18 mass%), and ASF4 (15 mass%), respectively.
- the maximum moisture content indicates the maximum value observed when measuring the equilibrium moisture content.
- the electrolyte membrane after the predetermined conditioning treatment has a cluster diameter (nm) / number of clusters (pieces / nm 3 ) of PSF-free group (I) ⁇ ASF> is ASF1 (2.00 / 0. 25), ASF2 (2.50 / 0.15), ASF3 (2.92 / 0.10), and ASF4 (3.00 / 0.08).
- group (II) ⁇ ASBF> containing PBI ASBF1 (1.70 / 0.35), ASBF2 (2.25 / 0.25), ASBF3 (2.75 / 0.13), respectively.
- ASBF4 (2.95 / 0.10). From the above results, the group containing PBI had a tendency to be preferred, since the cluster diameter decreased and the number of clusters per unit volume increased. These effects are presumed to be due to the ionic bond between the added PBI and the PFSA resin.
- Example 1 An electrolyte in the same manner as in Example 1 except that Nafion DE2021 (registered trademark, manufactured by DuPont, 20% solution, EW1050) was used instead of the 20% PFSA resin dispersion (AS1 to AS4) used in Example 1. A membrane was obtained. The equilibrium water content of this membrane was 4% by mass. Using the obtained electrolyte membrane, the cluster diameter (nm) / number of clusters (pieces / nm 3 ) was measured by the same method as in the example, and found to be 3.20 / 0.04. The number of clusters per unit volume was small, which was inferior to the film of the example.
- Nafion DE2021 registered trademark, manufactured by DuPont, 20% solution, EW1050
- AS1 to AS4 20% PFSA resin dispersion
- Table 1 shows the results of Examples 1 to 8 and Comparative Example 1 described above.
- the redox flow secondary battery of the present invention has low electrical resistance, high current efficiency, and excellent durability.
- the electrolyte membrane for redox flow secondary battery of the present invention has excellent ion selective permeability, low electrical resistance, and excellent durability (mainly hydroxyl radical oxidation resistance), and is used for redox flow secondary batteries. Industrial applicability as a diaphragm.
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Sustainable Development (AREA)
- General Chemical & Material Sciences (AREA)
- Electrochemistry (AREA)
- Sustainable Energy (AREA)
- Life Sciences & Earth Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Polymers & Plastics (AREA)
- Medicinal Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Fuel Cell (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Conductive Materials (AREA)
Abstract
Description
特許文献2に開示された複合膜は、電気抵抗が高く、また、各イオンは多孔膜ほどではないが、自由に拡散してしまうという問題があり、電池の電流効率は高くない。特許文献3に開示された膜についても、上記と同様の問題があり、耐酸化耐久性にも劣る。
特許文献4に開示された電池は、電流効率が未だ不十分であり、長期にわたる硫酸電解液中での耐酸化劣化性にも劣り、耐久性も不十分である。同文献には、比較例として、PTFE系イオン交換膜を使用する電池が開示されているが、その電流効率は64.8~78.6%であり、不十分であることが記載されている。
特許文献5に開示された電池も、上記と同様の問題点を解決できておらず、また、大型設備では、価格的にも高価となってしまうという問題がある。
特許文献6に開示された膜は、塗布膜の厚みを極薄(数μm)にしないと、内部抵抗が増加すると記載されている。また、イオン選択透過性を向上させる工夫については一切記載されていない。
特許文献7に開示された電池は、ポリスルホン系隔膜を使用するため、隔膜のイオン選択透過性や耐酸化劣化性が十分ではなく、電池の電気抵抗、電流効率、耐久性が十分ではない。
特許文献8に開示された電池は、電流効率が不十分であり、また、酸化劣化するため長期使用に関しても問題点を有している。
特許文献9に開示された膜は、電気抵抗が高くなるという問題点を有している。
特許文献10の実施例に示された結果では、膜の内部抵抗(電気抵抗)が十分低いとは言えず、また、長期使用では耐酸化劣化が問題となる。
炭化水素系樹脂を主とした膜基材としては、両セルの主役の電解質を含む電解液を単に隔離するだけの単なるイオン選択透過性のない多孔膜や、イオン選択性のない(無孔の)親水性膜基材、多孔膜に親水性膜基材を埋め込むか又は被覆したもの等が用いられている。また、膜自身が各種アニオン基を有する所謂カチオン交換膜、又は多孔質膜基材の孔に、カチオン交換性樹脂を被覆又は埋め込んだ複合膜、同様に膜自身がカチオン基を有するアニオン交換膜、同様に多孔膜基材に、アニオン交換性樹脂を被覆又は埋め込んだ複合膜、両者の積層型等が隔膜として用いられており、それぞれの特徴を生かした研究が行われている。
隔膜としての、電気抵抗(プロトン透過性に主に依存)と、主役の活物質である、金属イオン(多価カチオン)透過性阻止という、相反する2つの性能を十分に満足するイオン交換樹脂隔膜、更には前記2つの性能に加えて長期にわたる耐酸化劣化性(耐ヒドロキシラジカル性)を満足するイオン交換樹脂隔膜は、これまで開発されていない。フッ素系イオン交換樹脂に関しても、プロトン(H+)透過性に優れ、且つ、活物質イオンの透過を抑制するという相矛盾する性質に対する工夫が十分に検討されておらず、低電気抵抗、高電流効率、及び長期にわたる耐酸化劣化性(耐ヒドロキシラジカル性)などを充分に満足するレドックスフロー電池やそのための電解質膜は開発されていない。
[1]
炭素電極からなる正極を含む正極セル室と、
炭素電極からなる負極を含む負極セル室と、
前記正極セル室と、前記負極セル室とを隔離分離させる、隔膜としての電解質膜と、
を含む電解槽を有し、
前記正極セル室は正極活物質を含む正極電解液を、前記負極セル室は負極活物質を含む負極電解液を含み、
前記電解液中の正極活物質及び前記負極活物質の価数変化に基づき充放電するレドックスフロー二次電池であって、
前記電解質膜が下記式(1)で表される構造を有するフッ素系高分子電解質ポリマーを含有するイオン交換樹脂組成物を含み、
前記電解質膜の、25℃水中における小角X線法により測定されるイオンクラスター径が1.00~2.95nmであるレドックスフロー二次電池。
-[CF2-CX1X2]a-[CF2-CF((-O-CF2-CF(CF2X3))b-Oc-(CFR1)d-(CFR2)e-(CF2)f-X4)]g- (1)
(式(1)中、X1、X2及びX3は、それぞれ独立して、ハロゲン原子及び炭素数1~3のパーフルオロアルキル基からなる群から選択される1種以上を示す。X4は、COOZ、SO3Z、PO3Z2又はPO3HZを示す。Zは、水素原子、アルカリ金属原子、アルカリ土類金属原子、又はアミン類(NH4、NH3R1、NH2R1R2、NHR1R2R3、NR1R2R3R4)を示す。R1、R2、R3及びR4は、それぞれ独立して、アルキル基及びアレーン基からなる群から選択されるいずれか1種以上を示す。ここで、X4がPO3Z2である場合、Zは同じでも異なっていてもよい。R1及びR2は、それぞれ独立して、ハロゲン原子、炭素数1~10のパーフルオロアルキル基及びフルオロクロロアルキル基からなる群から選択される1種以上を示す。a及びgは、0≦a<1、0<g≦1、a+g=1を満たす数を示す。bは0~8の整数を示す。cは0又は1を示す。d、e及びfは、それぞれ独立して、0~6の整数を示す(ただし、d、e及びfは同時に0ではない。)。)
[2]
前記正極電解液及び負極電解液として、バナジウムを含む硫酸電解液を用いる、前記[1]に記載のレドックスフロー二次電池。
[3]
前記フッ素系高分子電解質ポリマーが、下記式(2)で表される構造を有するパーフルオロカーボンスルホン酸樹脂(PFSA)である、前記[1]又は[2]に記載のレドックスフロー二次電池。
-[CF2-CF2]a-[CF2-CF(-O-(CF2)m-SO3H)]g- (2)(式(2)中、a及びgは、0≦a<1、0<g≦1、a+g=1を満たす数を示し、mは1~6の整数を示す。)
[4]
前記フッ素系高分子電解質ポリマーの当量質量EW(イオン交換基1当量あたりの乾燥質量グラム数)が300~1300g/eqであり、前記電解質膜の平衡含水率が5~80質量%である、前記[1]~[3]のいずれか1項に記載のレドックスフロー二次電池。
[5]
前記イオン交換樹脂組成物が、前記フッ素系高分子電解質ポリマー100質量部に対して、0.1~200質量部のポリアゾール系化合物を含む、前記[1]~[4]のいずれか1項に記載のレドックスフロー二次電池。
[6]
前記ポリアゾール系化合物が、環内に窒素原子を1個以上含む複素環化合物の重合体、及び環内に窒素原子を1個以上と酸素及び/又は硫黄を含む複素環化合物の重合体からなる群から選択される1種以上である、前記[5]に記載のレドックスフロー二次電池。
[7]
前記ポリアゾール系化合物が、ポリイミダゾール系化合物、ポリベンズイミダゾール系化合物、ポリベンゾビスイミダゾール系化合物、ポリベンゾオキサゾール系化合物、ポリオキサゾール系化合物、ポリチアゾール系化合物、及びポリベンゾチアゾール系化合物からなる群から選択される1種以上である、前記[6]に記載のレドックスフロー二次電池。
[8]
前記フッ素系高分子電解質ポリマーと前記ポリアゾール系化合物とが、少なくともその一部においてイオン結合を形成している、前記[5]~[7]のいずれか1項に記載のレドックスフロー二次電池。
[9]
前記フッ素系高分子電解質ポリマー100質量部に対して0.1~20質量部のポリフェニレンエーテル樹脂及び/又はポリフェニレンスルフィド樹脂を更に含む、前記[1]~[8]のいずれか1項に記載のレドックスフロー二次電池。
[10]
前記フッ素系高分子電解質ポリマーを、前記イオン交換樹脂組成物100質量部に対して、50~100質量部含有する、前記[1]~[9]のいずれか1項に記載のレドックスフロー二次電池。
[11]
下記式(1)で表される構造を有するフッ素系高分子電解質ポリマーを含有するイオン交換樹脂組成物を含み、25℃水中における小角X線法により測定したイオンクラスター径が1.00~2.95nmであるレドックスフロ-二次電池用電解質膜。
-[CF2-CX1X2]a-[CF2-CF((-O-CF2-CF(CF2X3))b-Oc-(CFR1)d-(CFR2)e-(CF2)f-X4)]g- (1)
(式(1)中、X1、X2及びX3は、それぞれ独立して、ハロゲン原子及び炭素数1~3のパーフルオロアルキル基からなる群から選択される1種以上を示す。X4は、COOZ、SO3Z、PO3Z2又はPO3HZを示す。Zは、水素原子、アルカリ金属原子、アルカリ土類金属原子、又はアミン類(NH4、NH3R1、NH2R1R2、NHR1R2R3、NR1R2R3R4)を示す。R1、R2、R3及びR4は、それぞれ独立して、アルキル基及びアレーン基からなる群から選択されるいずれか1種以上を示す。ここで、X4がPO3Z2である場合、Zは同じでも異なっていてもよい。R1及びR2は、それぞれ独立して、ハロゲン原子、炭素数1~10のパーフルオロアルキル基及びフルオロクロロアルキル基からなる群から選択される1種以上を示す。a及びgは、0≦a<1、0<g≦1、a+g=1を満たす数を示す。bは0~8の整数を示す。cは0又は1を示す。d、e及びfは、それぞれ独立して、0~6の整数を示す(ただし、d、e及びfは同時に0ではない。)。)
[12]
前記フッ素系高分子電解質ポリマーが、下記式(2)で表される構造を有するパーフルオロカーボンスルホン酸樹脂である、前記[11]に記載のレドックスフロー二次電池用電解質膜。
-[CF2-CF2]a-[CF2-CF(-O-(CF2)m-SO3H)]g- (2)(式(2)中、a及びgは、0≦a<1、0<g≦1、a+g=1を満たす数を示し、mは1~6の整数を示す。)
[13]
前記フッ素系高分子電解質ポリマーの当量質量EW(イオン交換基1当量あたりの乾燥質量グラム数)が300~1300であり、前記電解質膜の平衡含水率が5~80質量%である、前記[11]又は[12]に記載のレドックスフロー二次電池用電解質膜。
[14]
前記イオン交換樹脂組成物が、前記フッ素系高分子電解質ポリマー100質量部に対して、0.1~200質量部のポリアゾール系化合物を含む、前記[11]~[13]のいずれか1項に記載のレドックスフロー二次電池用電解質膜。
[15]
ポリアゾール系化合物が、環内に窒素原子を1個以上含む複素環化合物の重合体、及び環内に窒素原子を1個以上と酸素及び/又は硫黄を含む複素環化合物の重合体からなる群から選択される1種以上である、前記[14]に記載のレドックスフロー二次電池用電解質膜。
[16]
前記ポリアゾール系化合物が、ポリイミダゾール系化合物、ポリベンズイミダゾール系化合物、ポリベンゾビスイミダゾール系化合物、ポリベンゾオキサゾール系化合物、ポリオキサゾール系化合物、ポリチアゾール系化合物、及びポリベンゾチアゾール系化合物からなる群から選択される1種以上である、前記[15]に記載のレドックスフロー二次電池用電解質膜。
[17]
前記フッ素系高分子電解質ポリマーと前記ポリアゾール系化合物とが、少なくともその一部においてイオン結合を形成している、前記[14]~[16]のいずれか1項に記載のレドックスフロー二次電池用電解質膜。
[18]
前記フッ素系高分子電解質ポリマー100質量部に対して0.1~20質量部のポリフェニレンエーテル樹脂及び/又はポリフェニレンスルフィド樹脂を更に含む、前記[11]~[17]のいずれか1項に記載のレドックスフロー二次電池用電解質膜。
[19]
前記電解質膜が、130~200℃にて1~60分間加熱処理されたものである、前記[11]~[18]のいずれか1項に記載のレドックスフロー二次電池用電解質膜。
[20]
前記電解質膜が補強材を更に有する、前記[11]~[19]のいずれか1項に記載のレドックスフロー二次電池用電解質膜。
[21]
前記フッ素系高分子電解質ポリマーを、前記イオン交換樹脂組成物100質量部に対して、50~100質量部含有する、前記[11]~[20]のいずれか1項に記載のレドックスフロー二次電池用電解質膜。
本発明のレドックスフロー二次電池用電解質膜は、優れたイオン選択透過性を有しており、高いプロトン(H+)透過性と電解液中の活物質イオンの透過阻止性とに優れ、更には、長期にわたる耐酸化劣化性(耐ヒドロキシラジカル性)に優れるため、レドックスフロー二次電池の隔膜として使用することにより、セル電気抵抗が低く、電流効率が高いレドックスフロー二次電池を提供でき、また、系内の電解液セル内で発生するヒドロキシラジカルに対して長期に渡り、高い酸化劣化防止効果を発揮するため、通常の炭化水素系電解質を用いる場合に生じるイオン基の脱離や、高分子電解質の崩壊現象などを抑えることができる。
本実施形態におけるレドックスフロー二次電池は、
炭素電極からなる正極を含む正極セル室と、
炭素電極からなる負極を含む負極セル室と、
前記正極セル室と、前記負極セル室とを隔離分離させる、隔膜としての電解質膜と、
を含む電解槽を有し、
前記正極セル室は正極活物質を含む正極電解液を、前記負極セル室は負極活物質を含む負極電解液を含み、
前記電解液中の正極活物質及び前記負極活物質の価数変化に基づき充放電するレドックスフロー二次電池であって、
前記電解質膜が下記式(1)で表される構造を有するフッ素系高分子電解質ポリマーを含有するイオン交換樹脂組成物を含み、
前記電解質膜の、25℃水中における小角X線法により測定したイオンクラスター径が1.00~2.95nmであるレドックスフロー二次電池である。
-[CF2-CX1X2]a-[CF2-CF((-O-CF2-CF(CF2X3))b-Oc-(CFR1)d-(CFR2)e-(CF2)f-X4)]g- (1)
(式(1)中、X1、X2及びX3は、それぞれ独立して、ハロゲン原子及び炭素数1~3のパーフルオロアルキル基からなる群から選択される1種以上を示す。X4は、COOZ、SO3Z、PO3Z2又はPO3HZを示す。Zは、水素原子、アルカリ金属原子、アルカリ土類金属原子、又はアミン類(NH4、NH3R1、NH2R1R2、NHR1R2R3、NR1R2R3R4)を示す。R1、R2、R3及びR4は、それぞれ独立して、アルキル基及びアレーン基からなる群から選択されるいずれか1種以上を示す。ここで、X4がPO3Z2である場合、Zは同じでも異なっていてもよい。R1及びR2は、それぞれ独立して、ハロゲン原子、炭素数1~10のパーフルオロアルキル基及びフルオロクロロアルキル基からなる群から選択される1種以上を示す。a及びgは、0≦a<1、0<g≦1、a+g=1を満たす数を示す。bは0~8の整数を示す。cは0又は1を示す。d、e及びfは、それぞれ独立して、0~6の整数を示す(ただし、d、e及びfは同時に0ではない。)。)
バナジウム系レドックスフロー二次電池の場合、正極セル室には、バナジウム4価(V4+)及びバナジウム5価(V5+)を含む硫酸電解液からなる正極電解液を、負極セル室には、バナジウム3価(V3+)及びバナジウム2価(V2+)を含む負極電解液を流通させることにより、電池の充電及び放電が行われる。このとき、充電時には、正極セル室においては、バナジウムイオンが電子を放出するためV4+がV5+に酸化され、負極セル室では外路を通じて戻って来た電子によりV3+がV2+に還元される。この酸化還元反応では、正極セル室ではプロトン(H+)が過剰になり、一方負極セル室では、プロトン(H+)が不足する。隔膜は正極セル室の過剰なプロトンを選択的に負極室に移動させ電気的中性が保たれる。放電時には、この逆の反応が進む。この時の電池効率(%)は、放電電力量を充電電力量で除した比率(%)で表され、両電力量は、電池セルの内部抵抗と隔膜のイオン選択性及びその他電流損失に依存する。内部抵抗の減少は電圧効率を向上させ、イオン選択透過性の向上及びその他電流損失の低減は、電流効率を向上させるので、レドックスフロー二次電池においては、重要な指標となる。
本実施形態のレドックスフロー二次電池用電解質膜は、特定の構造を有するフッ素系高分子電解質ポリマーを含有するイオン交換樹脂組成物を含み、且つ、特定のイオンクラスター径を有する。これによって、イオン選択透過性に優れる。
本実施形態において、イオン交換樹脂組成物は、上記式(1)で表される構造を有するフッ素系高分子電解質ポリマーを含有する。
本実施形態において、フッ素系高分子電解質ポリマーは、下記式(1)で表される構造を有する。
本実施形態におけるフッ素系高分子電解質ポリマーは、下記式(1)で表される構造を有するものであれば、特に限定されず、他の構造を含むものであってもよい。
-[CF2-CX1X2]a-[CF2-CF((-O-CF2-CF(CF2X3))b-Oc-(CFR1)d-(CFR2)e-(CF2)f-X4)]g- (1)
(式(1)中、X1、X2及びX3は、それぞれ独立して、ハロゲン原子及び炭素数1~3のパーフルオロアルキル基からなる群から選択される1種以上を示す。X4は、COOZ、SO3Z、PO3Z2又はPO3HZを示す。Zは、水素原子、アルカリ金属原子、アルカリ土類金属原子、又はアミン類(NH4、NH3R1、NH2R1R2、NHR1R2R3、NR1R2R3R4)を示す。R1、R2、R3及びR4は、それぞれ独立して、アルキル基及びアレーン基からなる群から選択されるいずれか1種以上を示す。ここで、X4がPO3Z2である場合、Zは同じでも異なっていてもよい。R1及びR2は、それぞれ独立して、ハロゲン原子、炭素数1~10のパーフルオロアルキル基及びフルオロクロロアルキル基からなる群から選択される1種以上を示す。a及びgは、0≦a<1、0<g≦1、a+g=1を満たす数を示す。bは0~8の整数を示す。cは0又は1を示す。d、e及びfは、それぞれ独立して、0~6の整数を示す(ただし、d、e及びfは同時に0ではない。)。)
-(CF2-CF2)-で表される繰り返し単位と、下記式(3)又は(4)で表される化合物から誘導される繰り返し単位を含有することが好ましく、さらに、-(CF2-CF2)-で表される繰り返し単位と、前記式(3)又は前記式(4)で表される化合物から誘導される繰り返し単位とからなることが好ましい。
式(3):CF2=CF(-O-(CF2CFXO)n-[A])(式中、Xは、F又は炭素数1~3のパーフルオロアルキル基を示し、nは0~5の整数を示す。[A]は(CF2)m-SO3H(mは0~6の整数を示す。ただし、nとmは同時に0にならない。)、
又は式(4):CF2=CF-O-(CF2)P-CFX(-O-(CF2)K-SO3H)若しくはCF2=CF-O-(CF2)P-CFX(-(CF2)L-O-(CF2)m-SO3H)(式中、Xは、炭素数1~3のパーフルオロアルキル基を示し、Pは0~12の整数を示し、Kは1~5の整数を示し、Lは1~5の整数を示し、mは0~6の整数を示す。ただし、KとLは同じでも、異なっていてもよく、P、K、Lは同時に0とはならない。)。
本発明者らが検討したところ、レドックスフロー二次電池用電解質膜として使用する場合には、前記ナフィオンに比べて、前記-(CF2-CF(-O-(CF2CFXO)n-(CF2)m-SO3H))-で表される繰り返し単位中のnが0であり、mが1~6の整数であるもの、又は式(4)で表される-CF2-CF(-O-(CF2)P-CFX(-O-(CF2)K-SO3H)-及び-CF2-CF(-O-(CF2)P-CFX(-(CF2)L-O-(CF2)m-SO3H)-の両方の繰り返し単位を含むPFSA樹脂の方が、親水性やイオン選択透過性が優れており、得られるレドックスフロー二次電池の電気抵抗が低く、電流効率も向上する傾向にあることがわかった。
-[CF2CF2]a-[CF2-CF(-O-(CF2)m-SO3H)]g- (2)(式(2)中、a及びgは、0≦a<1、0<g≦1、a+g=1を満たす数を示し、mは1~6の整数を示す。)
例えば、フッ素系高分子電解質ポリマーのEWが280程度であっても、前記部分架橋を行うことにより、フッ素系高分子電解質ポリマーの水溶解性を低下(耐水性が向上)させることができる。
また、フッ素系高分子電解質ポリマーが低メルトフロー領域(高分子領域)である場合にも、前記部分架橋により、分子間絡みを増加し、溶解性や過剰膨潤性を低下できる。
本実施形態におけるフッ素系高分子電解質ポリマーの当量質量EW(イオン交換基1当量あたりのフッ素系高分子電解質ポリマーの乾燥質量グラム数)は、300~1300(g/eq)であることが好ましく、より好ましくは350~1000(g/eq)、更に好ましくは400~900(g/eq)、特に好ましくは450~750(g/eq)である。
本実施形態におけるフッ素系高分子電解質ポリマーは、例えば、高分子電解質ポリマーの前駆体(以下、「樹脂前駆体」ともいう。)を製造した後、それを加水分解処理することにより得ることができる。
PFSA樹脂の場合、例えば、下記一般式(5)又は(6)で表されるフッ化ビニルエーテル化合物と、下記一般式(7)で表されるフッ化オレフィンモノマーとの共重合体からなるPFSA樹脂前駆体を加水分解することにより得られる。
(式(5)中、Xは、F又は炭素数1~3のパーフルオロアルキル基を示し、nは0~5の整数を示し、Aは(CF2)m-Wを示し、mは0~6の整数を示し、nとmは同時に0にならず、Wは加水分解によりSO3Hに転換し得る官能基を示す。)、
式(6): CF2=CF-O-(CF2)P-CFX(-O-(CF2)K-W)又はCF2=CF-O-(CF2)P-CFX(-(CF2)L-O-(CF2)m-W)
(式(6)中、Xは、炭素数1~3のパーフルオロアルキル基を示し、Pは0~12の整数を示し、Kは1~5の整数を示し、Lは1~5の整数を示し(ただし、L、K、mは同時に0とならない。)、mは0~6の整数を示し、Wは加水分解によりSO3Hに転換し得る官能基を示す。)
式(7): CF2=CFZ
(式(7)中、Zは、H、Cl、F、炭素数1~3のパーフルオロアルキル基、又は酸素を含んでいてもよい環状パーフルオロアルキル基を示す。)
前記樹脂前駆体から本実施形態のフッ素系高分子電解質ポリマーを製造する方法は、特に限定されず、例えば、前記樹脂前駆体を押し出し機を用いてノズル又はダイ等で押し出し成型した後、加水分解処理を行うか、重合した時の産出物のまま、即ち分散液状、又は沈殿、ろ過させた粉末状の物とした後、加水分解処理を行う方法がある。
より具体的には、上記のようにして得られ、必要に応じて成型された樹脂前駆体は、引き続き塩基性反応液体中に浸漬し、加水分解処理される。加水分解処理に使用する塩基性反応液としては、特に限定されるものではないが、ジメチルアミン、ジエチルアミン、モノメチルアミン及びモノエチルアミン等のアミン化合物の水溶液や、アルカリ金属又はアルカリ土類金属の水酸化物の水溶液が好ましく、水酸化ナトリウム及び水酸化カリウムの水溶液が特に好ましい。アルカリ金属又はアルカリ土類金属の水酸化物を用いる場合、その含有量は特に限定されないが、反応液全体に対して10~30質量%であることが好ましい。上記反応液は、さらにメチルアルコール、エチルアルコール、アセトン及びジメチルスルホキシド(DMSO)等の膨潤性有機化合物を含有することがより好ましい。膨潤性の有機化合物の含有量は、反応液全体に対して1~30質量%であることが好ましい。
本実施形態における電解質膜を形成するイオン交換樹脂組成物中に含まれる前記式(1)で表される構造を有するフッ素系高分子電解質ポリマーの含有量は、特に限定されないが、イオン選択透過性及び耐酸化劣化性の観点から、イオン交換樹脂組成物が前記特定の構造を有するフッ素系高分子電解質ポリマーを主体とすることが好ましい。ここで、「主体とする」とは、樹脂組成物中の含有量の下限値が約33.3質量%、好ましくは40質量%、より好ましくは50質量%、更に好ましくは50質量%、より更に好ましくは80質量%、特に好ましくは90質量%含まれることをいう。上限値は特に制限はないが、99.5質量%以下であることが好ましい。
本実施形態におけるイオン交換樹脂組成物は、上述したフッ素系高分子電解質ポリマーの他に、ポリアゾール系化合物を含有するか、それに代えて/加えて、塩基性重合体(オリゴマーなどの低分子量物質を含む)を含有すると、樹脂組成物としての化学的安定性(主に耐酸化性等)が増加する傾向にあり、好ましい。これらの化合物は、樹脂組成物中で微細粒子状又は分子分散に近い形でイオンコンプレックスを部分的に作り、イオン架橋構造を形成する。特に、フッ素系高分子電解質ポリマーのEWが低い場合(例えば300~500の場合)には、耐水性と電気抵抗、又は含水クラスター径が小さくなる傾向にあるため、イオン交換樹脂組成物がポリアゾール系化合物を含有するか、それに代えて/加えて、塩基性重合体(オリゴマーなどの低分子量物質を含む)を含有することが、イオン選択透過性等のバランス面の観点から好ましい。
膜の一部表面がイオン結合を形成し、膜の内部がイオン(カチオン)状態となるように、ポリアゾール系化合物は、各種酸で電離させた状態で存在してもよい。
フッ素系高分子電解質ポリマーとポリアゾール系化合物とが、少なくともその一部においてイオン結合を形成していることは、電解質膜の強度、耐久性の観点から好ましい。特に、フッ素系高分子電解質ポリマーのイオン交換基の少なくとも一部とポリアゾール系化合物の少なくとも一部が、分子分散に近い形で反応している状態(例えば、イオン結合して、酸塩基のイオンコンプレックスを形成している状態等の化学結合している状態)がより好ましい。
なお、上記イオン結合が存在するか否かについては、フーリエ変換赤外分光計(Fourier-Transform Infrared Spectrometer)(以下、FT-IRとする)を用いて確認することができる。例えば、高分子電解質としてパーフルオロカーボンスルホン酸樹脂、ポリアゾール化合物としてポリ[2,2'(m-フェニレン)-5,5'-ベンゾイミダゾール](以下、「PBI」という。)を用いた場合、FT-IRによる測定を行うと、上記高分子電解質中のスルホン酸基とPBI中のイミダゾール基との化学結合に由来するシフトした吸収ピークが、1458cm-1付近、1567cm-1付近、1634cm-1付近に認められる。
本実施形態におけるイオン交換樹脂組成物は、電解質膜の耐酸化性やクラスター径の観点から、ポリフェニレンスルフィド(PPS)樹脂を更に含有することが好ましい。
PPS樹脂は、押し出し法によりフッ素系高分子電解質ポリマーを含有する樹脂組成物に混合する方法やPPS樹脂の水性溶媒分散体をフッ素系高分子電解質ポリマーを含有する樹脂組成物の原液分散体に混合する方法により、添加できる。
PPS樹脂の含有添加量は、前記式(1)で表される構造を有するフッ素系高分子電解質ポリマー100質量部に対して、0.1~20質量部であることが好ましく、0.5~10質量部であることがより好ましい。PPS樹脂の含有量が0.1質量部以上である場合、電解質膜の耐酸化性やイオン選択透過性が一層向上する傾向にあり、20質量部以下である場合、十分な膜強度が得られる傾向にある。
本実施形態におけるイオン交換樹脂組成物は、ポリフェニレンエーテル樹脂を更に含有することが好ましい。ポリフェニレンエーテル樹脂の含有量は、前記式(1)で表される構造を有するフッ素系高分子電解質ポリマー100質量部に対して、好ましくは0.1~20質量部であり、より好ましくは0.1~10質量部である。ポリフェニレンエーテル樹脂を上記範囲で含有する場合、耐酸化性等の化学的耐久性が一層向上する傾向にある。
これらの樹脂を2種以上用いる場合、混合方法は特に限定されず、溶媒に溶解又は媒体に分散させて混合してもよく、樹脂前駆体同士を押し出し混合してもよい。
(イオンクラスター)
本実施形態における電解質膜にはイオンクラスターが存在する。
本実施形態における電解質膜に存在するイオンクラスターは、高分子電解質ポリマー分子の主鎖をなすフッ素化炭化水素部分を形成する疎水部分と、該主鎖に結合している側鎖である適度な分子構造及び該長さ部分を形成していて先端に位置するイオン交換基である親水基が(分子を介して)複数集まった部分と、その周辺に配位している水分子及び水素結合その他の親和力で近辺に集められている自由水(遊離水とも言う)とからなる。
本実施形態における電解質膜では、複数個の、大きいサイズのチャンネル(所謂イオンクラスター)と、その間を繋ぐ小さなサイズのイオンチャンネルが形成され、結果として、膜の厚み方向に連続してイオンチャンネルが通じ、これがイオン(特にプロトンH+の)伝導通路(チャンネル)として機能する。
電解質膜を25℃の水に含浸した状態で小角X線散乱測定を実施し、得られた散乱プロフィールに対して空セル散乱補正、絶対強度補正を行う。2次元検出器を用いて測定を行った場合は円環平均等合理的な手法によりデータを1次元化し、散乱強度の散乱角依存性を求める。こうして得られた散乱強度の散乱角依存性(散乱プロフィール)を用いて、橋本康博、坂本直紀、飯嶋秀樹 高分子論文集 vol.63 No.3 pp.166 2006に記載された手法に準じてクラスター径を求めることができる。すなわち、クラスター構造が粒径分布を持つコアーシェル型の剛体球で表されると仮定し、このモデルに基づく理論散乱式をもちいて実測の散乱プロフィールのクラスター由来の散乱が支配的な領域をフィッティングすることで平均クラスター直径(クラスター径)、クラスター個数密度を得ることができる。このモデルにおいて、コアの部分がクラスターに相当し、コアの直径がクラスター径となる。なお、シェル層は仮想的なものでシェル層の電子密度はマトリックス部分と同じとする。またシェル層厚みは0.25nmとする。フィッティングに用いるモデルの理論散乱式を式1に示す。ただし、Cは装置定数、Nはクラスター個数密度、ηはコア、つまりクラスター部分とその周りの仮想的なシェルを剛体球と仮定した場合のその体積分率、θはブッラグ角、λは用いるX線波長、tはシェル層厚み、a0は平均クラスター半径(クラスター径の半分)、σはコア径(クラスター径)の標準偏差を示している。Ib(q)は熱散漫散乱を含むバックグラウンド散乱を表しており,ここでは定数と仮定する。フィッティングの際には上記パラメータのうち、N、η、a0、σ、Ib(q)を可変パラメータとする。
本実施形態における電解質膜の平衡含水率は、好ましくは5質量%以上であり、より好ましくは10質量%以上、さらに好ましくは15質量%以上である。また、本実施形態における電解質膜の平衡含水率は、好ましくは80質量%以下、より好ましくは50質量%以下、さらに好ましくは40質量%以下である。電解質膜の平衡含水率が5質量%以上であると、膜の電気抵抗や電流効率、耐酸化性、イオン選択透過性が良好となる傾向にある。一方、平衡含水率が50質量%以下であると、膜の寸法安定性や強度が良好となり、また水溶解性成分の増加を抑制できる傾向にある。電解質膜の平衡含水率は、樹脂組成物を水とアルコール系溶媒での分散液から成膜し、160℃以下で乾燥した膜を基準とし、23℃、50%関係湿度(RH)での平衡(24Hr放置)飽和吸水率(Wc)で表す。
本実施形態における電解質膜の膜最大含水率は、特に限定されないが、膜の電気抵抗や電流効率、耐酸化性、イオン選択透過性の点から、10質量%以上が好ましく、より好ましくは15質量%以上、さらに好ましくは20質量%以上である。また、膜の寸法安定性や強度の点から、80質量%以下が好ましく、より好ましくは50質量%以下、さらに好ましくは40質量%以下である。ここで、膜最大含水率は、前記平衡含水率測定の際に測定される含水率のうち最大値をいう。
本実施形態における電解質膜は、膜強度の観点から、補強材を有することが好ましい。補強材としては、特に限定されず、一般的な不織布や織布、各種素材からなる多孔膜が挙げられる。
前記多孔膜としては、特に限定されないが、フッ素系高分子電解質ポリマーとの親和性が良好なものが好ましく、中でも、延伸されて多孔化したPTFE系膜を利用して、これに本実施形態におけるフッ素系高分子電解質ポリマーを含有するイオン交換樹脂組成物を実質的に隙間無く埋め込んだ補強膜が、薄膜の強度の観点、及び面(縦横)方向の寸法変化を抑える観点から、より好ましい。
前記補強膜は、前述のイオン交換樹脂組成物を含む有機溶媒又はアルコール-水を溶媒とした、適度な該成分を有する溶質の適度な濃度の分散液を、適量多孔膜に含浸漬させて、乾燥させることにより得ることができる。
本実施形態における電解質膜の製造方法(成膜法)としては、特に限定されず、公知の、押し出し方法、キャスト成膜を用いることができる。電解質膜は単層でも多層(2~5層)でもよく、多層の場合は性質の異なる膜(例えば、EWや官能基の異なる樹脂)を積層することにより、電解質膜の性能を改善することができる。多層の場合は、押し出し製膜時、キャスト時に積層させるか、又は得られたそれぞれの膜を積層させればよい。
(1)PFSA樹脂前駆体のメルトフローインデックス
ASTM:D1238に準拠して、測定条件:温度270℃、荷重2160gで測定を行った。
PFSA樹脂0.3gを、25℃、飽和NaCl水溶液30mLに浸漬し、攪拌しながら30分間放置した。次いで、飽和NaCl水溶液中の遊離プロトンを、フェノールフタレインを指示薬として0.01N水酸化ナトリウム水溶液を用いて中和滴定した。中和滴定の終点をpH7とし、中和滴定後に得られた、イオン交換基の対イオンがナトリウムイオンの状態となっているPFSA樹脂分を純水ですすぎ、さらに上皿乾燥機により160℃で乾燥し、秤量した。中和に要した水酸化ナトリウムの物質量をM(mmol)、イオン交換基の対イオンがナトリウムイオンの状態となっているPFSA樹脂の質量をW(mg)とし、下記式より当量質量EW(g/eq)を求めた。
EW=(W/M)-22
以上の操作を5回繰り返した後、算出された5つのEW値の最大値および最小値を除き、3つの値を相加平均して測定結果とした。
PFSA樹脂の分散液を清澄なガラス板上に塗布し、150℃で約10分間乾燥し、剥離して約30μmの膜を形成させ、これを23℃の水中に約3時間放置し、その後23℃、関係湿度(RH)50%の部屋に24時間放置した時の平衡含水率を測定した。基準の乾燥膜としては、80℃真空乾燥膜を用いた。平衡含水率は、膜の質量変化から算出した。
最大含水率は、平衡含水率測定時に観測される最大値を示す。
電解質膜を25℃水中で24hr浸漬し、水に浸漬した状態で膜法線方向からポイントフォーカスのX線を入射して透過散乱光を検出した。測定には株式会社リガク社製小角X線散乱測定装置Nano Viewerを使用し、入射X線波長は0.154nm、カメラ長は850mm、測定時間は15分とした。検出器にはPILATUS100Kを用いた。透過散乱光から得られる散乱プロファイルからクラスター径及びクラスター数を算出した。
レドックスフロー二次電池は、隔膜の両側にて、液透過性で多孔質の集電体電極(負極用、正極用)を隔膜の両側にそれぞれ配置し、押圧でそれらを挟み、隔膜で仕切られた一方を正極セル室、他方を負極セル室とし、スペーサーで両セル室の厚みを確保した。正極セル室には、バナジウム4価(V4+)及び同5価(V5+)を含む硫酸電解液からなる正極電解液を、負極セル室にはバナジウム3価(V3+)及び同2価(V2+)を含む負極電解液を流通させ、電池の充電及び放電を行った。このとき、充電時には、正極セル室においては、バナジウムイオンが電子を放出するためV4+がV5+に酸化され、負極セル室では外路を通じて戻って来た電子によりV3+がV2+に還元された。この酸化還元反応では、正極セル室ではプロトン(H+)が過剰になり、一方負極セル室では、プロトン(H+)が不足する。隔膜は正極セル室の過剰なプロトンを選択的に負極室に移動させ電気的中性が保たれた。放電時には、この逆の反応が進んだ。この時の電池効率(エネルギー効率)(%)は、放電電力量を充電電力量で除した比率(%)で表され、両電力量は、電池セルの内部抵抗と隔膜のイオン選択透過性及びその他電流損失に依存する。
また、電流効率(%)は、放電電気量を充電電気量で除した比率(%)で表され、両電気量は、隔膜のイオン選択透過性及びその他電流損失に依存する。電池効率は、電流効率と電圧効率の積で表される。内部抵抗すなわちセル電気抵抗率の減少は電圧効率(電池効率(エネルギー効率))を向上させ、イオン選択透過性の向上及びその他電流損失の低減は、電流効率を向上させるので、レドックスフロー二次電池において、重要な指標となる。
充放電実験は、上述のようにして得られた電池を用いて行った。全バナジウム濃度が2M/Lで、全硫酸根濃度が4M/Lでの水系電解液を使用し、また、設置した正極及び負極セル室の厚みがそれぞれ5mmで、両多孔質電極と隔膜の間には炭素繊維からなる厚み5mmで嵩密度が約0.1g/cm3の多孔質状のフエルトを挟んで用いた。充放電実験は電流密度80mA/cm2で実施した。
セル電気抵抗率(Ω・cm2)は、ACインピーダンス法を用いて、放電開始時においてAC電圧10mV,周波数20kHzでの直流抵抗値を測定し、それに電極面積を掛けることによって求めた。
セル内部抵抗は、定電流充放電時の充電の中間電圧と放電の中間電圧の差を2で割り、さらに電流値で割った値(抵抗)に電極面積を掛けることによって求めた。
耐久性は、前記(6)の充放電を200サイクル実施した後の電流効率(%)及びセル電気抵抗率(Ω・cm2)により評価した。
(1)PFSA樹脂前駆体の作製
ステンレス製攪拌式オートクレーブに、C7F15COONH4の10%水溶液と純水とを仕込み、十分に真空、窒素置換を行った後、テトラフルオロエチレン(CF2=CF2、TFE)ガスを導入してケージ圧力で0.7MPaまで昇圧した。引き続いて、過硫酸アンモニウム水溶液を注入して重合を開始した。重合により消費されたTFEを補給するため、連続的にTFEガスを供給してオートクレーブの圧力を0.7MPaに保つようにして、供給したTFEに対して、質量比で0.70倍に相当する量のCF2=CFO(CF2)2-SO2Fを連続的に供給して重合を行い、それぞれ重合条件を最適な範囲に調整して、各種のパーフルオロカーボンスルホン酸樹脂前駆体粉末を得た。得られたPFSA樹脂前駆体粉末のMFIは、それぞれ、A1が0.5(g/10分)、A2が1.5(g/10分)、A3が0.8(g/10分)、A4が2.0(g/10分)であった。
得られたPFSA樹脂前駆体粉末を、水酸化カリウム(15質量%)とメチルアルコール(50質量%)を溶解した水溶液中に、80℃で20時間接触させて、加水分解処理を行った。その後、60℃水中に5時間浸漬した。次に、60℃の2N塩酸水溶液に1時間浸漬させる処理を、毎回塩酸水溶液を更新して5回繰り返した後、イオン交換水で水洗、乾燥した。これにより、スルホン酸基(SO3H)を有し、式(2)(m=2)で表される構造を有するPFSA樹脂を得た。得られたPFSA樹脂のEWは、それぞれ、A1が450(g/eq)、A2が650(g/eq)、A3が750(g/eq)、A4が850(g/eq)であった。
得られたPFSA樹脂分散液を、上記同様の順に、分散液(ASF1)、分散液(ASF2)、分散液(ASF3)、分散液(ASF4)とした。
得られた分散液(ASF1~ASF4)及び混合分散液(ASBF1~ASBF4)を、公知の通常の方法にて、担体シートであるポリイミド製フィルム上にキャストし、120℃(20分)の熱風を当てて、溶媒をほぼ完全に飛ばし、乾燥させることにより膜を得た。これを更に、160℃10分の条件下における熱風空気雰囲気下で、熱処理することにより膜厚50μmの電解質膜を得た。得られた電解質膜の上記熱処理前後のEWは、その変化率が0.2~0.3%程度であつた。
得られた電解質膜の平衡含水率は、それぞれ上記の順に、PBIを含まない群(I)<ASF>は;ASF1(19質量%)、ASF2(12質量%)、ASF3(9質量%)、ASF4(6質量%)であった。
25℃水中3時間におけるそれぞれの電解質膜の最大含水率は、それぞれ、ASF1(27質量%)、ASF2(23質量%)、ASF3(18質量%)、ASF4(15質量%)であつた。ここで、最大含水率は、平衡含水率測定時に観測される最大値を示す。
PBIを含む群(II)<ASBF>の電解質膜の平衡含水率については;ASBF1(18質量%)、ASBF2(11質量%)、ASBF3(8質量%)、ASBF4(6質量%)であった。
25℃水中3時間におけるそれぞれの電解質膜の最大含水率は、それぞれ、ASBF1(21質量%)、ASBF2(21質量%)、ASBF3(17質量%)、ASBF4(14質量%)であった。
上記結果から、PBIを含む群の方が、より良好な耐水性が見られる傾向にあった。
上記結果から、PBIを含む群の方が、クラスター径の減少や単位体積あたりのクラスター数の個数が増加している傾向が見られ、好ましい傾向があった。これらの効果は、添加したPBIとPFSA樹脂とのイオン結合によるものと推測される。
次に、同様の方法によりPBIを含む群(II)<ASBF>についてセル電気抵抗率/電流効率を測定したところ、ASBF1(98.9/0.80)、ASBF2(98.3/0.95)、ASBF3(97.8/1.05)、ASBF4(97.2/1.10)であり、より優れた傾向が見られた。
実施例1で用いた20%PFSA樹脂分散液(AS1~AS4)の代わりにナフィオンDE2021(登録商標、デュポン社製、20%溶液、EW1050)を用いたこと以外は実施例1と同様にして電解質膜を得た。この膜の平衡含水率は4質量%であった。
得られた電解質膜を用いて、実施例と同様の方法によりクラスター径(nm)/クラスター数(個/nm3)を測定したところ3.20/0.04であり、クラスター径が大きく、また単位体積あたりのクラスター個数も少なく、実施例の膜よりも劣っていた。また、実施例と同様の方法により充放電試験を行った結果、電流効率(%)/セル電気抵抗率(Ω・cm2)は94.5/1.20であり、電流効率についても、実施例よりもかなり低いレベルであった。これは、比較例1の電解質膜は、イオン選択透過性が低いためと推測される。また、耐久試験として、充放電を200サイクル実施した結果においても、電流効率が86%、電気抵抗が1.30であり、耐久性にも劣っていた。
本発明のレドックスフロー二次電池用電解質膜は、イオンの選択透過性に優れ、電気抵抗も低く、耐久性(主に、ヒドロキシラジカル耐酸化性)にも優れており、レドックスフロー二次電池用の隔膜としての産業上利用可能性を有する。
2 正極セル室
3 負極
4 負極セル室
5 電解質膜
6 電解槽
7 正極電解液タンク
8 負極電解液タンク
9 交直変換装置
10 レドックスフロー二次電池
Claims (21)
- 炭素電極からなる正極を含む正極セル室と、
炭素電極からなる負極を含む負極セル室と、
前記正極セル室と、前記負極セル室とを隔離分離させる、隔膜としての電解質膜と、
を含む電解槽を有し、
前記正極セル室は正極活物質を含む正極電解液を、前記負極セル室は負極活物質を含む負極電解液を含み、
前記電解液中の正極活物質及び前記負極活物質の価数変化に基づき充放電するレドックスフロー二次電池であって、
前記電解質膜が下記式(1)で表される構造を有するフッ素系高分子電解質ポリマーを含有するイオン交換樹脂組成物を含み、
前記電解質膜の、25℃水中における小角X線法により測定されるイオンクラスター径が1.00~2.95nmであるレドックスフロー二次電池。
-[CF2-CX1X2]a-[CF2-CF((-O-CF2-CF(CF2X3))b-Oc-(CFR1)d-(CFR2)e-(CF2)f-X4)]g- (1)
(式(1)中、X1、X2及びX3は、それぞれ独立して、ハロゲン原子及び炭素数1~3のパーフルオロアルキル基からなる群から選択される1種以上を示す。X4は、COOZ、SO3Z、PO3Z2又はPO3HZを示す。Zは、水素原子、アルカリ金属原子、アルカリ土類金属原子、又はアミン類(NH4、NH3R1、NH2R1R2、NHR1R2R3、NR1R2R3R4)を示す。R1、R2、R3及びR4は、それぞれ独立して、アルキル基及びアレーン基からなる群から選択されるいずれか1種以上を示す。ここで、X4がPO3Z2である場合、Zは同じでも異なっていてもよい。R1及びR2は、それぞれ独立して、ハロゲン原子、炭素数1~10のパーフルオロアルキル基及びフルオロクロロアルキル基からなる群から選択される1種以上を示す。a及びgは、0≦a<1、0<g≦1、a+g=1を満たす数を示す。bは0~8の整数を示す。cは0又は1を示す。d、e及びfは、それぞれ独立して、0~6の整数を示す(ただし、d、e及びfは同時に0ではない。)。) - 前記正極電解液及び負極電解液として、バナジウムを含む硫酸電解液を用いる、請求項1に記載のレドックスフロー二次電池。
- 前記フッ素系高分子電解質ポリマーが、下記式(2)で表される構造を有するパーフルオロカーボンスルホン酸樹脂である、請求項1又は2に記載のレドックスフロー二次電池。
-[CF2-CF2]a-[CF2-CF(-O-(CF2)m-SO3H)]g- (2)(式(2)中、a及びgは、0≦a<1、0<g≦1、a+g=1を満たす数を示し、mは1~6の整数を示す。) - 前記フッ素系高分子電解質ポリマーの当量質量EW(イオン交換基1当量あたりの乾燥質量グラム数)が300~1300g/eqであり、前記電解質膜の平衡含水率が5~80質量%である、請求項1~3のいずれか1項に記載のレドックスフロー二次電池。
- 前記イオン交換樹脂組成物が、前記フッ素系高分子電解質ポリマー100質量部に対して、0.1~200質量部のポリアゾール系化合物を含む、請求項1~4のいずれか1項に記載のレドックスフロー二次電池。
- 前記ポリアゾール系化合物が、環内に窒素原子を1個以上含む複素環化合物の重合体、及び環内に窒素原子を1個以上と酸素及び/又は硫黄を含む複素環化合物の重合体からなる群から選択される1種以上である、請求項5に記載のレドックスフロー二次電池。
- 前記ポリアゾール系化合物が、ポリイミダゾール系化合物、ポリベンズイミダゾール系化合物、ポリベンゾビスイミダゾール系化合物、ポリベンゾオキサゾール系化合物、ポリオキサゾール系化合物、ポリチアゾール系化合物、及びポリベンゾチアゾール系化合物からなる群から選択される1種以上である、請求項6に記載のレドックスフロー二次電池。
- 前記フッ素系高分子電解質ポリマーと前記ポリアゾール系化合物とが、少なくともその一部においてイオン結合を形成している、請求項5~7のいずれか1項に記載のレドックスフロー二次電池。
- 前記フッ素系高分子電解質ポリマー100質量部に対して0.1~20質量部のポリフェニレンエーテル樹脂及び/又はポリフェニレンスルフィド樹脂を更に含む、請求項1~8のいずれか1項に記載のレドックスフロー二次電池。
- 前記フッ素系高分子電解質ポリマーを、前記イオン交換樹脂組成物100質量部に対して、50~100質量部含有する、請求項1~9のいずれか1項に記載のレドックスフロー二次電池。
- 下記式(1)で表される構造を有するフッ素系高分子電解質ポリマーを含有するイオン交換樹脂組成物を含み、25℃水中における小角X線法により測定したイオンクラスター径が1.00~2.95nmであるレドックスフロ-二次電池用電解質膜。
-[CF2-CX1X2]a-[CF2-CF((-O-CF2-CF(CF2X3))b-Oc-(CFR1)d-(CFR2)e-(CF2)f-X4)]g- (1)
(式(1)中、X1、X2及びX3は、それぞれ独立して、ハロゲン原子及び炭素数1~3のパーフルオロアルキル基からなる群から選択される1種以上を示す。X4は、COOZ、SO3Z、PO3Z2又はPO3HZを示す。Zは、水素原子、アルカリ金属原子、アルカリ土類金属原子、又はアミン類(NH4、NH3R1、NH2R1R2、NHR1R2R3、NR1R2R3R4)を示す。R1、R2、R3及びR4は、それぞれ独立して、アルキル基及びアレーン基からなる群から選択されるいずれか1種以上を示す。ここで、X4がPO3Z2である場合、Zは同じでも異なっていてもよい。R1及びR2は、それぞれ独立して、ハロゲン原子、炭素数1~10のパーフルオロアルキル基及びフルオロクロロアルキル基からなる群から選択される1種以上を示す。a及びgは、0≦a<1、0<g≦1、a+g=1を満たす数を示す。bは0~8の整数を示す。cは0又は1を示す。d、e及びfは、それぞれ独立して、0~6の整数を示す(ただし、d、e及びfは同時に0ではない。)。) - 前記フッ素系高分子電解質ポリマーが、下記式(2)で表される構造を有するパーフルオロカーボンスルホン酸樹脂である、請求項11に記載のレドックスフロー二次電池用電解質膜。
-[CF2-CF2]a-[CF2-CF(-O-(CF2)m-SO3H)]g- (2)(式(2)中、a及びgは、0≦a<1、0<g≦1、a+g=1を満たす数を示し、mは1~6の整数を示す。) - 前記フッ素系高分子電解質ポリマーの当量質量EW(イオン交換基1当量あたりの乾燥質量グラム数)が300~1300であり、前記電解質膜の平衡含水率が5~80質量%である、請求項11又は12に記載のレドックスフロー二次電池用電解質膜。
- 前記イオン交換樹脂組成物が、前記フッ素系高分子電解質ポリマー100質量部に対して、0.1~200質量部のポリアゾール系化合物を含む、請求項11~13のいずれか1項に記載のレドックスフロー二次電池用電解質膜。
- ポリアゾール系化合物が、環内に窒素原子を1個以上含む複素環化合物の重合体、及び環内に窒素原子を1個以上と酸素及び/又は硫黄を含む複素環化合物の重合体からなる群から選択される1種以上である、請求項14に記載のレドックスフロー二次電池用電解質膜。
- 前記ポリアゾール系化合物が、ポリイミダゾール系化合物、ポリベンズイミダゾール系化合物、ポリベンゾビスイミダゾール系化合物、ポリベンゾオキサゾール系化合物、ポリオキサゾール系化合物、ポリチアゾール系化合物、及びポリベンゾチアゾール系化合物からなる群から選択される1種以上である、請求項15に記載のレドックスフロー二次電池用電解質膜。
- 前記フッ素系高分子電解質ポリマーと前記ポリアゾール系化合物とが、少なくともその一部においてイオン結合を形成している、請求項14~16のいずれか1項に記載のレドックスフロー二次電池用電解質膜。
- 前記フッ素系高分子電解質ポリマー100質量部に対して0.1~20質量部のポリフェニレンエーテル樹脂及び/又はポリフェニレンスルフィド樹脂を更に含む、請求項11~17のいずれか1項に記載のレドックスフロー二次電池用電解質膜。
- 前記電解質膜が、130~200℃にて1~60分間加熱処理されたものである、請求項11~18のいずれか1項に記載のレドックスフロー二次電池用電解質膜。
- 前記電解質膜が補強材を更に有する、請求項11~19のいずれか1項に記載のレドックスフロー二次電池用電解質膜。
- 前記フッ素系高分子電解質ポリマーを、前記イオン交換樹脂組成物100質量部に対して、50~100質量部含有する、請求項11~20のいずれか1項に記載のレドックスフロー二次電池用電解質膜。
Priority Applications (7)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201280064267.6A CN104115322B (zh) | 2011-12-28 | 2012-12-27 | 氧化还原液流二次电池和氧化还原液流二次电池用电解质膜 |
AU2012361558A AU2012361558B2 (en) | 2011-12-28 | 2012-12-27 | Redox flow secondary battery and electrolyte membrane for redox flow secondary batteries |
JP2013551826A JP6005065B2 (ja) | 2011-12-28 | 2012-12-27 | レドックスフロー二次電池及びレドックスフロー二次電池用電解質膜 |
EP12861957.4A EP2800191B8 (en) | 2011-12-28 | 2012-12-27 | Redox flow secondary battery and electrolyte membrane for redox flow secondary batteries |
US14/367,059 US9799906B2 (en) | 2011-12-28 | 2012-12-27 | Redox flow secondary battery and electrolyte membrane for redox flow secondary battery |
IN1284MUN2014 IN2014MN01284A (ja) | 2011-12-28 | 2012-12-27 | |
KR1020147017289A KR101684036B1 (ko) | 2011-12-28 | 2012-12-27 | 레독스 플로우 2차 전지 및 레독스 플로우 2차 전지용 전해질막 |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2011290035 | 2011-12-28 | ||
JP2011-290035 | 2011-12-28 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2013100079A1 true WO2013100079A1 (ja) | 2013-07-04 |
Family
ID=48697558
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2012/083944 WO2013100079A1 (ja) | 2011-12-28 | 2012-12-27 | レドックスフロー二次電池及びレドックスフロー二次電池用電解質膜 |
Country Status (9)
Country | Link |
---|---|
US (1) | US9799906B2 (ja) |
EP (1) | EP2800191B8 (ja) |
JP (1) | JP6005065B2 (ja) |
KR (1) | KR101684036B1 (ja) |
CN (2) | CN105845958B (ja) |
AU (1) | AU2012361558B2 (ja) |
IN (1) | IN2014MN01284A (ja) |
TW (1) | TWI499108B (ja) |
WO (1) | WO2013100079A1 (ja) |
Cited By (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2013168364A (ja) * | 2012-01-20 | 2013-08-29 | Asahi Kasei E-Materials Corp | レドックスフロー二次電池用電解質膜 |
CN104377371A (zh) * | 2013-08-13 | 2015-02-25 | 旭化成电子材料株式会社 | 氧化还原液流二次电池用电解质膜 |
JP2015081320A (ja) * | 2013-10-24 | 2015-04-27 | 独立行政法人物質・材料研究機構 | パーフルオロスルホン酸ポリマー−アゾールブレンド膜及びその製造方法、並びに固体高分子型燃料電池 |
JP2016524280A (ja) * | 2013-05-16 | 2016-08-12 | ユナイテッド テクノロジーズ コーポレイションUnited Technologies Corporation | 最大水ドメインクラスターサイズを有する水和イオン交換膜を備えるフローバッテリ |
JP2017184586A (ja) * | 2016-03-31 | 2017-10-05 | 旭化成株式会社 | イオン交換型高分子アクチュエータ |
JP2019503418A (ja) * | 2016-03-31 | 2019-02-07 | エルジー・ケム・リミテッド | イオン交換分離膜、これを含む電気化学電池、フロー電池および燃料電池、およびその製造方法 |
WO2019088298A1 (ja) * | 2017-11-06 | 2019-05-09 | Agc株式会社 | レドックスフロー電池に好適なイオン交換膜 |
WO2020080427A1 (ja) * | 2018-10-19 | 2020-04-23 | Agc株式会社 | イオン交換膜、レドックスフロー電池 |
JP2020076149A (ja) * | 2018-11-05 | 2020-05-21 | 旭化成株式会社 | イオン交換膜及び電解槽 |
US11539064B2 (en) | 2016-09-08 | 2022-12-27 | Asahi Kasei Kabushiki Kaisha | Polymer electrolyte membrane and method for producing the same |
Families Citing this family (19)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP6410380B2 (ja) * | 2015-05-18 | 2018-10-24 | 旭化成株式会社 | イオン交換膜 |
KR102101688B1 (ko) * | 2015-12-24 | 2020-04-17 | 도레이 카부시키가이샤 | 폴리올레핀 미다공막, 전지용 세퍼레이터 및 그것들의 제조 방법 |
CA3013441C (en) * | 2016-02-18 | 2022-09-20 | Toray Industries, Inc. | Composite polymer electrolyte membrane, and membrane electrode assembly and solid polymer fuel cell using same |
KR101952923B1 (ko) * | 2017-08-29 | 2019-02-27 | 한국화학연구원 | 비율이 조절된 측쇄를 포함하는 폴리벤즈이미다졸 전해질막, 제조방법, 이를 이용한 전기화학소자 |
KR20190026530A (ko) * | 2017-09-05 | 2019-03-13 | 롯데케미칼 주식회사 | 레독스 흐름 전지용 분리막, 레독스 흐름 전지용 제조방법, 및 레독스 흐름 전지 |
KR102066239B1 (ko) | 2017-09-18 | 2020-01-14 | 롯데케미칼 주식회사 | 분리막 복합체 및 레독스 흐름 전지 |
US11056698B2 (en) | 2018-08-02 | 2021-07-06 | Raytheon Technologies Corporation | Redox flow battery with electrolyte balancing and compatibility enabling features |
KR20210057114A (ko) | 2018-09-14 | 2021-05-20 | 유니버시티 오브 싸우스 캐롤라이나 | 산화환원 유동 배터리용 저투과도 폴리벤즈이미다졸 (pbi) 멤브레인 |
CN112823182B (zh) | 2018-09-14 | 2022-08-30 | 南卡罗莱纳大学 | 无有机溶剂生产pbi膜的新方法 |
CN112955498B (zh) | 2018-09-14 | 2024-05-10 | 南卡罗来纳大学 | 用于氧化还原液流电池的聚苯并咪唑(pbi)膜 |
CN111139498B (zh) * | 2018-11-05 | 2022-06-03 | 旭化成株式会社 | 离子交换膜和电解槽 |
KR20200065695A (ko) * | 2018-11-30 | 2020-06-09 | 롯데케미칼 주식회사 | 레독스 흐름 전지용 분리막 및 이의 제조방법 |
CN109440491B (zh) * | 2018-12-04 | 2022-01-04 | 太仓宝霓实业有限公司 | 一种牛仔布电还原染色方法 |
EP3937282A4 (en) * | 2019-03-08 | 2022-06-08 | Asahi Kasei Kabushiki Kaisha | ELECTROLYTE MEMBRANE FOR REDOX FLOW BATTERIES, REDOXIZED FLOW BATTERY, AND METHOD FOR PRODUCING ELECTROLYTE MEMBRANE |
KR102485668B1 (ko) * | 2019-05-17 | 2023-01-05 | 주식회사 엘지에너지솔루션 | 전기화학소자용 분리막 및 이를 포함하는 전기화학소자 |
US11777124B2 (en) | 2020-03-06 | 2023-10-03 | University Of South Carolina | Proton-conducting PBI membrane processing with enhanced performance and durability |
US11271226B1 (en) | 2020-12-11 | 2022-03-08 | Raytheon Technologies Corporation | Redox flow battery with improved efficiency |
WO2023167545A1 (ko) * | 2022-03-04 | 2023-09-07 | 한국화학연구원 | 보호기가 도입된 폴리벤즈이미다졸, 이를 이용한 막의 제조방법 및 이의 용도 |
CN115353579B (zh) * | 2022-10-20 | 2023-04-18 | 国家电投集团氢能科技发展有限公司 | 抗溶胀两性离子交换树脂及制备方法和离子交换膜及应用 |
Citations (15)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS62226580A (ja) | 1986-03-26 | 1987-10-05 | Sumitomo Electric Ind Ltd | レドツクスフロ−電池 |
JPH05242905A (ja) | 1991-06-06 | 1993-09-21 | Agency Of Ind Science & Technol | レドックス電池 |
JPH05275108A (ja) * | 1992-03-13 | 1993-10-22 | Hitachi Ltd | 電 池 |
JPH06188005A (ja) | 1992-01-13 | 1994-07-08 | Kashimakita Kyodo Hatsuden Kk | レドックス電池 |
JPH06260183A (ja) | 1993-03-04 | 1994-09-16 | Sumitomo Electric Ind Ltd | 水溶媒系電気化学装置用隔膜およびそれを用いた水溶媒系電池 |
JPH06105615B2 (ja) | 1986-03-25 | 1994-12-21 | 住友電気工業株式会社 | レドツクスフロ−電池 |
JPH0992321A (ja) | 1995-09-27 | 1997-04-04 | Kashimakita Kyodo Hatsuden Kk | レドックス電池 |
JPH10208767A (ja) | 1996-11-22 | 1998-08-07 | Tokuyama Corp | バナジウム系レドックスフロー電池用隔膜及びその製造方法 |
JPH11260390A (ja) | 1998-03-05 | 1999-09-24 | Kashimakita Kyodo Hatsuden Kk | レドックスフロー電池 |
JP2000235849A (ja) | 1998-12-14 | 2000-08-29 | Sumitomo Electric Ind Ltd | 電池用隔膜 |
JP2005158383A (ja) | 2003-11-25 | 2005-06-16 | Sumitomo Electric Ind Ltd | レドックス電池 |
JP2005294171A (ja) * | 2004-04-02 | 2005-10-20 | Toyota Motor Corp | 固体高分子電解質、その製造方法、及び固体高分子電解質膜 |
WO2006046620A1 (ja) * | 2004-10-27 | 2006-05-04 | Asahi Glass Company, Limited | 電解質材料、電解質膜、及び固体高分子形燃料電池用膜電極接合体 |
WO2010143634A1 (ja) * | 2009-06-09 | 2010-12-16 | シャープ株式会社 | レドックスフロー電池 |
WO2011034179A1 (ja) * | 2009-09-18 | 2011-03-24 | 旭化成イーマテリアルズ株式会社 | 電解質エマルション及びその製造方法 |
Family Cites Families (19)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS6031862B2 (ja) | 1977-05-16 | 1985-07-24 | 株式会社トクヤマ | 陽イオン交換膜の製造方法 |
US4421579A (en) | 1981-06-26 | 1983-12-20 | Diamond Shamrock Corporation | Method of making solid polymer electrolytes and electrode bonded with hydrophyllic fluorocopolymers |
JP3487869B2 (ja) | 1992-09-25 | 2004-01-19 | 株式会社タカキタ | ロールベーラ |
ATE236460T1 (de) * | 1993-11-17 | 2003-04-15 | Pinnacle Vrb | Stabilisierte elektrolytlösungen, verfahren und deren herstellung und redoxzellen und batterien, die diese lösungen enthalten |
JPH09223513A (ja) | 1996-02-19 | 1997-08-26 | Kashimakita Kyodo Hatsuden Kk | 液循環式電池 |
WO2002026883A1 (fr) | 2000-09-27 | 2002-04-04 | Asahi Kasei Kabushiki Kaisha | Composition en dispersion de copolymere a base de perfluorocarbone |
US20030170521A1 (en) * | 2001-11-16 | 2003-09-11 | Zhengming Zhang | Proton exchange membrane (PEM) for a fuel cell |
JP4649094B2 (ja) | 2003-03-07 | 2011-03-09 | 旭化成イーマテリアルズ株式会社 | 燃料電池用膜電極接合体の製造方法 |
EP2916377B1 (en) | 2003-05-13 | 2016-07-20 | Asahi Glass Company, Limited | Process for the production of a membrane-electrode assembly |
JP4447007B2 (ja) | 2004-04-23 | 2010-04-07 | 旭化成イーマテリアルズ株式会社 | 芳香族炭化水素系樹脂を含有する高分子電解質組成物 |
JP4578174B2 (ja) | 2004-08-17 | 2010-11-10 | 旭化成イーマテリアルズ株式会社 | 高分子電解質組成物、プロトン交換膜、膜電極接合体及び固体高分子型燃料電池 |
US7662498B2 (en) * | 2004-04-23 | 2010-02-16 | Asahi Kasei Chemicals Corporation | Polymer electrolyte composition containing aromatic hydrocarbon-based resin |
JP2006147374A (ja) * | 2004-11-19 | 2006-06-08 | Kansai Electric Power Co Inc:The | バナジウムレドックスフロー電池システムの運転方法 |
CN101213700B (zh) | 2005-06-20 | 2012-11-21 | 新南创新私人有限公司 | 用于氧化还原电池和电池组的改进的全氟化膜和改进的电解液 |
JP5548445B2 (ja) | 2007-02-21 | 2014-07-16 | 旭化成イーマテリアルズ株式会社 | 高分子電解質組成物、高分子電解質膜、膜電極接合体、及び固体高分子電解質型燃料電池 |
KR101049179B1 (ko) | 2007-11-05 | 2011-07-14 | 한국에너지기술연구원 | 격리막을 포함하는 레독스 플로우 전지 |
JP5454015B2 (ja) | 2009-08-31 | 2014-03-26 | 東洋紡株式会社 | 高分子電解質膜とその製造方法、及び高分子電解質膜積層体とその製造方法 |
WO2011111717A1 (ja) | 2010-03-12 | 2011-09-15 | 住友電気工業株式会社 | レドックスフロー電池 |
KR101118448B1 (ko) | 2010-03-12 | 2012-03-06 | 스미토모덴키고교가부시키가이샤 | 레독스 흐름 전지 |
-
2012
- 2012-12-27 JP JP2013551826A patent/JP6005065B2/ja active Active
- 2012-12-27 EP EP12861957.4A patent/EP2800191B8/en active Active
- 2012-12-27 AU AU2012361558A patent/AU2012361558B2/en active Active
- 2012-12-27 IN IN1284MUN2014 patent/IN2014MN01284A/en unknown
- 2012-12-27 US US14/367,059 patent/US9799906B2/en active Active
- 2012-12-27 CN CN201610146371.XA patent/CN105845958B/zh active Active
- 2012-12-27 KR KR1020147017289A patent/KR101684036B1/ko active IP Right Grant
- 2012-12-27 WO PCT/JP2012/083944 patent/WO2013100079A1/ja active Application Filing
- 2012-12-27 CN CN201280064267.6A patent/CN104115322B/zh active Active
- 2012-12-28 TW TW101150910A patent/TWI499108B/zh active
Patent Citations (15)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH06105615B2 (ja) | 1986-03-25 | 1994-12-21 | 住友電気工業株式会社 | レドツクスフロ−電池 |
JPS62226580A (ja) | 1986-03-26 | 1987-10-05 | Sumitomo Electric Ind Ltd | レドツクスフロ−電池 |
JPH05242905A (ja) | 1991-06-06 | 1993-09-21 | Agency Of Ind Science & Technol | レドックス電池 |
JPH06188005A (ja) | 1992-01-13 | 1994-07-08 | Kashimakita Kyodo Hatsuden Kk | レドックス電池 |
JPH05275108A (ja) * | 1992-03-13 | 1993-10-22 | Hitachi Ltd | 電 池 |
JPH06260183A (ja) | 1993-03-04 | 1994-09-16 | Sumitomo Electric Ind Ltd | 水溶媒系電気化学装置用隔膜およびそれを用いた水溶媒系電池 |
JPH0992321A (ja) | 1995-09-27 | 1997-04-04 | Kashimakita Kyodo Hatsuden Kk | レドックス電池 |
JPH10208767A (ja) | 1996-11-22 | 1998-08-07 | Tokuyama Corp | バナジウム系レドックスフロー電池用隔膜及びその製造方法 |
JPH11260390A (ja) | 1998-03-05 | 1999-09-24 | Kashimakita Kyodo Hatsuden Kk | レドックスフロー電池 |
JP2000235849A (ja) | 1998-12-14 | 2000-08-29 | Sumitomo Electric Ind Ltd | 電池用隔膜 |
JP2005158383A (ja) | 2003-11-25 | 2005-06-16 | Sumitomo Electric Ind Ltd | レドックス電池 |
JP2005294171A (ja) * | 2004-04-02 | 2005-10-20 | Toyota Motor Corp | 固体高分子電解質、その製造方法、及び固体高分子電解質膜 |
WO2006046620A1 (ja) * | 2004-10-27 | 2006-05-04 | Asahi Glass Company, Limited | 電解質材料、電解質膜、及び固体高分子形燃料電池用膜電極接合体 |
WO2010143634A1 (ja) * | 2009-06-09 | 2010-12-16 | シャープ株式会社 | レドックスフロー電池 |
WO2011034179A1 (ja) * | 2009-09-18 | 2011-03-24 | 旭化成イーマテリアルズ株式会社 | 電解質エマルション及びその製造方法 |
Non-Patent Citations (1)
Title |
---|
YASUHIRO HASHIMOTO; NAOKI SAKAMOTO; HIDEKI IIJIMA; KOBUNSHI RONBUNSHU, JAPANESE JOURNAL OF POLYMER SCIENCE AND TECHNOLOGY, vol. 63, no. 3, 2006, pages 166 |
Cited By (15)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2013168364A (ja) * | 2012-01-20 | 2013-08-29 | Asahi Kasei E-Materials Corp | レドックスフロー二次電池用電解質膜 |
JP2016524280A (ja) * | 2013-05-16 | 2016-08-12 | ユナイテッド テクノロジーズ コーポレイションUnited Technologies Corporation | 最大水ドメインクラスターサイズを有する水和イオン交換膜を備えるフローバッテリ |
CN104377371A (zh) * | 2013-08-13 | 2015-02-25 | 旭化成电子材料株式会社 | 氧化还原液流二次电池用电解质膜 |
JP2015081320A (ja) * | 2013-10-24 | 2015-04-27 | 独立行政法人物質・材料研究機構 | パーフルオロスルホン酸ポリマー−アゾールブレンド膜及びその製造方法、並びに固体高分子型燃料電池 |
JP2017184586A (ja) * | 2016-03-31 | 2017-10-05 | 旭化成株式会社 | イオン交換型高分子アクチュエータ |
JP2019503418A (ja) * | 2016-03-31 | 2019-02-07 | エルジー・ケム・リミテッド | イオン交換分離膜、これを含む電気化学電池、フロー電池および燃料電池、およびその製造方法 |
US11539064B2 (en) | 2016-09-08 | 2022-12-27 | Asahi Kasei Kabushiki Kaisha | Polymer electrolyte membrane and method for producing the same |
WO2019088298A1 (ja) * | 2017-11-06 | 2019-05-09 | Agc株式会社 | レドックスフロー電池に好適なイオン交換膜 |
JPWO2019088298A1 (ja) * | 2017-11-06 | 2020-11-19 | Agc株式会社 | レドックスフロー電池に好適なイオン交換膜 |
JP7188395B2 (ja) | 2017-11-06 | 2022-12-13 | Agc株式会社 | レドックスフロー電池に好適なイオン交換膜 |
JPWO2020080427A1 (ja) * | 2018-10-19 | 2021-09-24 | Agc株式会社 | イオン交換膜、レドックスフロー電池 |
WO2020080427A1 (ja) * | 2018-10-19 | 2020-04-23 | Agc株式会社 | イオン交換膜、レドックスフロー電池 |
JP7393601B2 (ja) | 2018-10-19 | 2023-12-07 | Agc株式会社 | イオン交換膜、レドックスフロー電池 |
JP2020076149A (ja) * | 2018-11-05 | 2020-05-21 | 旭化成株式会社 | イオン交換膜及び電解槽 |
JP7421898B2 (ja) | 2018-11-05 | 2024-01-25 | 旭化成株式会社 | イオン交換膜及び電解槽 |
Also Published As
Publication number | Publication date |
---|---|
EP2800191B8 (en) | 2018-12-19 |
EP2800191B1 (en) | 2018-10-10 |
CN105845958A (zh) | 2016-08-10 |
CN105845958B (zh) | 2018-04-06 |
KR20140098189A (ko) | 2014-08-07 |
CN104115322A (zh) | 2014-10-22 |
TW201338240A (zh) | 2013-09-16 |
EP2800191A4 (en) | 2015-08-26 |
AU2012361558A1 (en) | 2014-07-17 |
JPWO2013100079A1 (ja) | 2015-05-11 |
IN2014MN01284A (ja) | 2015-07-03 |
KR101684036B1 (ko) | 2016-12-07 |
TWI499108B (zh) | 2015-09-01 |
CN104115322B (zh) | 2016-09-07 |
US9799906B2 (en) | 2017-10-24 |
AU2012361558B2 (en) | 2016-03-17 |
EP2800191A1 (en) | 2014-11-05 |
US20140377687A1 (en) | 2014-12-25 |
JP6005065B2 (ja) | 2016-10-12 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP6005065B2 (ja) | レドックスフロー二次電池及びレドックスフロー二次電池用電解質膜 | |
JP6002685B2 (ja) | レドックスフロー二次電池及びレドックスフロー二次電池用電解質膜 | |
JP6034200B2 (ja) | レドックスフロー二次電池 | |
JP5823601B2 (ja) | 高分子電解質膜 | |
JP5942210B2 (ja) | レドックスフロー二次電池用隔膜及びそれを用いたレドックスフロー二次電池 | |
KR101494289B1 (ko) | 고분자전해질 다공성복합막, 상기 다공성복합막 제조방법 및 상기 다공성복합막을 포함하는 에너지저장장치 | |
WO2013100083A1 (ja) | レドックスフロー二次電池及びレドックスフロー二次電池用電解質膜 | |
US10211474B2 (en) | Redox flow secondary battery and electrolyte membrane for redox flow secondary battery | |
JP6131051B2 (ja) | レドックスフロー二次電池用電解質膜及びそれを用いたレドックスフロー二次電池 | |
KR102218941B1 (ko) | 고체 고분자 전해질막 및 그 제조 방법 | |
KR20150060510A (ko) | 이온 교환막 및 그 제조방법 | |
JP2014099415A (ja) | 燃料電池用電極触媒層、膜電極接合体及び固体高分子型燃料電池。 | |
JP6338896B2 (ja) | 樹脂付電極層、樹脂付電極複合体及びレドックスフロー二次電池 | |
WO2021215126A1 (ja) | レドックスフロー電池用隔膜、レドックスフロー電池用隔膜の製造方法、レドックスフロー電池用隔膜電極接合体、レドックスフロー電池用セル、及びレドックスフロー電池 | |
JP6101494B2 (ja) | レドックスフロー二次電池用電解質膜 | |
JP2014110232A (ja) | フッ素系高分子電解質膜 | |
WO2023085206A1 (ja) | 固体高分子型水電解用膜電極接合体および水電解装置 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 12861957 Country of ref document: EP Kind code of ref document: A1 |
|
ENP | Entry into the national phase |
Ref document number: 2013551826 Country of ref document: JP Kind code of ref document: A |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2012861957 Country of ref document: EP Ref document number: 14367059 Country of ref document: US |
|
ENP | Entry into the national phase |
Ref document number: 20147017289 Country of ref document: KR Kind code of ref document: A |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
ENP | Entry into the national phase |
Ref document number: 2012361558 Country of ref document: AU Date of ref document: 20121227 Kind code of ref document: A |