WO2013183584A1 - Membrane perméable aux ions - Google Patents

Membrane perméable aux ions Download PDF

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Publication number
WO2013183584A1
WO2013183584A1 PCT/JP2013/065342 JP2013065342W WO2013183584A1 WO 2013183584 A1 WO2013183584 A1 WO 2013183584A1 JP 2013065342 W JP2013065342 W JP 2013065342W WO 2013183584 A1 WO2013183584 A1 WO 2013183584A1
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ion
microporous membrane
membrane
metal oxide
porous
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PCT/JP2013/065342
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English (en)
Japanese (ja)
Inventor
樋口　浩之
隆史 熊野
健郎 井上
網野　一郎
正也 西川原
島谷　俊一
敦 大門
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日東電工株式会社
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Publication of WO2013183584A1 publication Critical patent/WO2013183584A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B13/00—Diaphragms; Spacing elements
    • C25B13/04—Diaphragms; Spacing elements characterised by the material
    • C25B13/08—Diaphragms; Spacing elements characterised by the material based on organic materials
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/12—Layered products comprising a layer of synthetic resin next to a fibrous or filamentary layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
    • B32B27/286—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42 comprising polysulphones; polysulfides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • B32B27/322—Layered products comprising a layer of synthetic resin comprising polyolefins comprising halogenated polyolefins, e.g. PTFE
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/02—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/54—Yield strength; Tensile strength
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/714—Inert, i.e. inert to chemical degradation, corrosion
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2457/00—Electrical equipment
    • B32B2457/10—Batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis

Definitions

  • the present invention relates to an ion permeable diaphragm.
  • This ion-permeable diaphragm shows wettability to water based on the wettability of a large amount of hydrophilic inorganic material added, and has ion permeability because it is porous. Since it is essentially hydrophobic, there is a problem that the wettability with respect to alkaline water is insufficient, and in electrolysis using alkaline water as an electrolytic solution, there is a problem that electrical resistance characteristics and electrolytic performance are insufficient. Moreover, the voltage rise by the gas produced
  • the present invention has been made in order to solve the above-described conventional problems.
  • the object of the present invention is to provide characteristics (i.e., (1) ions required for ion-permeable membranes generally used for alkaline water electrolysis). (2) Mechanical strength and chemical stability against alkaline water, (3) No gas passage through the diaphragm, and (4) Short circuit prevention between electrodes It is an object to provide an ion-permeable diaphragm that is excellent in that the gas generated by the electrode during electrolysis adheres to the surface of the diaphragm (particularly the outermost surface).
  • the ion-permeable diaphragm of the present invention includes a microporous membrane, and at least one metal oxide selected from titanium oxide and zirconium oxide is attached to the microporous membrane.
  • the ion permeable membrane of the present invention further comprises a porous reinforcement.
  • at least one metal oxide selected from titanium oxide and zirconium oxide is attached to the porous reinforcing body.
  • the microporous membrane is composed of polytetrafluoroethylene, polyvinylidene fluoride, polypropylene, ultrahigh molecular weight polyethylene, high density polyethylene, polypropylene, poly-4-methylpentene-1, polysulfone, or polyethersulfone.
  • the porous reinforcing body is composed of polytetrafluoroethylene, polyvinylidene fluoride, polypropylene, polyethylene, ultrahigh molecular weight polyethylene, poly-4-methylpentene-1, polysulfone, polyethersulfone, or polyphenylene sulfide.
  • the manufacturing method of the said ion permeable diaphragm is provided.
  • the microporous membrane or the laminate of the microporous membrane and the porous reinforcing body is immersed in a solution containing a metal fluoride complex and a fluorine ion scavenger, and the microporous membrane or the laminate is laminated. It includes immersing in alkaline water after depositing a metal oxide on the body. In a preferred embodiment, a heat treatment is performed after depositing a metal oxide on the microporous film or laminate.
  • the present invention by providing a microporous film to which at least one metal oxide selected from titanium oxide and zirconium oxide is attached, excellent wettability with respect to alkaline water is exhibited.
  • the ion permeability is excellent in ion permeability (that can contribute to lowering the electrolysis voltage), and can prevent the gas generated during electrolysis from adhering to the outermost surface of the diaphragm and suppress the increase in electrolysis voltage.
  • a diaphragm can be obtained.
  • the ion-permeable membrane of the present invention is excellent in durability over time even in high-concentration alkaline water, and can suppress an increase in electrical resistance (an increase in electrolysis voltage) without losing wettability with respect to alkaline water. .
  • the ion-permeable diaphragm of the present invention is excellent in durability, it is a salt electrolysis battery, a battery using a strong alkaline to strongly acidic aqueous electrolyte, an organic solvent battery such as a lithium battery, an alkaline fuel cell, etc. It is also useful as a diaphragm for electrochemical cells.
  • (A) is a schematic sectional drawing of the ion permeable diaphragm by preferable embodiment of this invention.
  • (B) is a schematic sectional view of an ion permeable membrane according to another preferred embodiment of the present invention.
  • (C) is a schematic sectional view of an ion permeable membrane according to still another preferred embodiment of the present invention.
  • 1 is a schematic cross-sectional view of an ion permeable diaphragm according to a preferred embodiment of the present invention.
  • FIG. 1A is a schematic cross-sectional view of an ion permeable diaphragm according to a preferred embodiment of the present invention.
  • An ion permeable diaphragm 100 shown in FIG. 1A includes a microporous membrane 10. At least one metal oxide 20 selected from titanium oxide and zirconium oxide is attached to the microporous film 10.
  • FIG. 1 (b) is a schematic cross-sectional view of an ion-permeable diaphragm according to another preferred embodiment of the present invention.
  • FIG. 1 (c) is a schematic cross-sectional view of an ion permeable membrane according to still another preferred embodiment of the present invention.
  • An ion permeable diaphragm 300 shown in FIG. 1C further includes porous reinforcing bodies 30 on both sides of the microporous membrane 10.
  • the porous reinforcing body 30 may be disposed on one side of the microporous membrane 10 as shown in FIG. 1 (b), and on both sides of the microporous membrane 10 as shown in FIG. 1 (c). It may be arranged.
  • the ion permeable diaphragm 200 of the present invention may be used with the microporous membrane 10 disposed on the anode electrode side. You may arrange
  • the ion-permeable diaphragm of the present invention includes a porous reinforcing body, the metal oxide 20 is preferably attached to the microporous membrane 10 and the porous reinforcing body 30.
  • FIG. 2 is a schematic view of an ion permeable membrane according to another preferred embodiment of the present invention.
  • An ion permeable diaphragm 400 shown in FIG. 2 includes microporous membranes 10 and 10 on both sides of the porous reinforcing body 30.
  • the ion-permeable diaphragm of the present invention has excellent wettability with respect to alkaline water due to the adhesion of at least one metal oxide selected from titanium oxide and zirconium oxide as described above, and The wettability is not easily lost for a long time.
  • the gas generated during electrolysis can be prevented from adhering to the outermost surface of the diaphragm, so that the electrolysis voltage can be lowered and the voltage rise can be suppressed. can do.
  • the ion-permeable membrane of the present invention exhibits good wettability (specifically, wettability such that the aqueous solution can penetrate in the thickness direction) with respect to an aqueous solution of potassium hydroxide having a concentration of 30% by weight.
  • wettability is not easily lost for a long time in the aqueous solution.
  • the fact that wettability is not easily lost for a long time is also referred to as excellent wet durability.
  • “showing wet durability with respect to an aqueous potassium hydroxide solution” means that the ion-permeable diaphragm is immersed in an aqueous potassium hydroxide solution at a temperature of 80 ° C./concentration of 30% by weight for 100 hours. It also means that wettability is not lost.
  • the ion-permeable membrane is referred to as an ion-permeable membrane that “shows wet durability against an aqueous potassium hydroxide solution”.
  • the thickness of the ion-permeable membrane of the present invention is preferably 15 ⁇ m to 1500 ⁇ m, more preferably 35 ⁇ m to 1000 ⁇ m, still more preferably 55 ⁇ m to 600 ⁇ m, and particularly preferably 80 ⁇ m to 400 ⁇ m.
  • microporous membrane The material constituting the microporous membrane is sufficient as an ion permeable membrane (specifically, for example, a membrane for alkaline water electrolysis) under a condition where a high potential is applied in a high-temperature strongly alkaline aqueous solution.
  • a material having chemical stability and capable of maintaining sufficient mechanical strength is preferably used. More specifically, the diaphragm for alkaline water electrolysis under the condition that a potential of 1.5 V to 3 V is applied in a potassium hydroxide aqueous solution or sodium hydroxide having a concentration of 10 wt% to 40 wt% / temperature of 60 ° C. to 100 ° C.
  • a material having sufficient chemical stability and capable of maintaining sufficient mechanical strength is preferably used. Examples of such a material include a fluorine polymer, an olefin polymer, and an aromatic hydrocarbon polymer.
  • fluorine-based polymer examples include polyvinylidene fluoride, ethylene-tetrafluoroethylene copolymer, tetrafluoroethylene-hexafluoropropylene copolymer, polytetrafluoroethylene, tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer. And polychlorotrifluoroethylene, tetrafluoroethylene-hexafluoropropylene-vinylidene fluoride copolymer, and the like. Of these, polytetrafluoroethylene and polyvinylidene fluoride are preferable. It is because it is excellent in chemical stability.
  • the olefin polymer examples include low density polyethylene, high density polyethylene, ultrahigh molecular weight polyethylene, polypropylene, polybutene, poly-4-methylpentene-1, and a copolymer having a repeating unit constituting these compounds. Etc. Among these, polypropylene, ultrahigh molecular weight polyethylene, high density polyethylene, polypropylene, and poly-4-methylpentene-1 are preferable. It is because it is excellent in chemical stability.
  • the viscosity average molecular weight of the ultra high molecular weight polyethylene is preferably 500,000 to 10,000,000, more preferably 1,000,000 to 7,000,000. In addition, the said viscosity average molecular weight can be measured by the viscosity method prescribed
  • aromatic hydrocarbon polymer examples include polyether ether ketone, polyether ketone, polysulfone, polyether sulfone, polyphenylene sulfide, polyarylate, polyether imide, polyimide, thermoplastic polyimide, and compounds thereof.
  • examples thereof include a copolymer having a constituting repeating unit. Of these, polysulfone and polyethersulfone are preferable. It is because it is excellent in chemical stability.
  • the microporous membrane can be obtained by making the material porous by any appropriate method.
  • the method for making porous include a phase conversion method (microphase separation method), an extraction method, a stretching method, a wet gel stretching method, and the like.
  • the phase inversion method is a method of forming a film with a solution obtained by dissolving a polymer material in a good solvent and coagulating it in a poor solvent.
  • the extraction method is a method in which an inorganic powder such as calcium carbonate is kneaded into a polymer material to form a film, and after the film formation, the inorganic powder is dissolved and extracted, and further stretched as necessary.
  • the stretching method is a method in which a film is formed from a polymer material having a predetermined crystal structure and then stretched under predetermined conditions.
  • the wet gel stretching method is a method in which a mixture of ultra high molecular weight polyethylene and high density polyethylene is thermally swollen with liquid paraffin to form a gel-like sheet, which is biaxially stretched, and then liquid paraffin is extracted and removed.
  • the microporous membrane preferably has hydrophilicity. If the microporous membrane has hydrophilicity, a necessary and sufficient metal oxide can be uniformly attached to the microporous membrane. Hydrophilization of the microporous membrane can be performed by any appropriate hydrophilic treatment, but hydrophilic treatment that can impart hydrophilic durability that does not impair the hydrophilicity in the operation of depositing metal oxide (described later). Is preferred. By performing such a hydrophilic treatment on the microporous film before adhering the metal oxide, the metal oxide precipitation reaction first occurs in the form of dots, and then the microporous film with the point as a nucleus. Spread to cover the entire surface.
  • a microporous film having hydrophilicity it is possible to prevent the attached metal oxide from falling off.
  • gas phase treatment such as UV ozone treatment, corona treatment, sputter etching treatment, plasma treatment; potassium dichromate / concentrated sulfuric acid treatment, metallic sodium / naphthalene / tetrahydrofuran treatment, hydrophilicity And chemical treatments such as graft polymerization treatment of hydrophilic monomers, crosslinking or coating treatment of hydrophilic polymers, and the like.
  • potassium dichromate / concentrated sulfuric acid treatment metallic sodium / naphthalene / tetrahydrofuran treatment, hydrophilic monomer graft polymerization treatment, hydrophilic polymer Chemical treatment such as crosslinking or coating treatment.
  • hydrophilic monomer graft polymerization treatment hydrophilic polymer Chemical treatment such as crosslinking or coating treatment.
  • the microporous film excellent in hydrophilic durability can be obtained.
  • any appropriate method can be adopted as the graft polymerization treatment method.
  • the hydrophilic monomer used in the graft polymerization treatment include acrylic acid, methacrylic acid, 2-hydroxymethyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 3-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, 2 -Hydroxymethyl methacrylate, 2-hydroxyethyl methacrylate, vinyl acetate, allylamine, acrylamide, methacrylamide, N, N-dimethylacrylamide, N, N-diethylacrylamide, N, N-dimethylaminopropylacrylamide, N, N-dimethylamino Ethyl acrylate 2- (dimethylamino) ethyl acrylate, N- (2-hydroxyethyl) acrylamide, acryloylmorpholine, N-isopropyla Rilamide, acrylonitrile, methacrylonitrile, 1-vin
  • acrylic acid, methacrylic acid, 2-hydroxymethyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxymethyl methacrylate, 2-hydroxyethyl methacrylate, acrylamide or methacrylamide are preferable.
  • These monomers may be used alone or in combination of two or more.
  • hydrophilic polymer used for the crosslinking or coating treatment of the hydrophilic polymer examples include polyvinyl alcohol, polyacrylic acid, polymethacrylic acid, polyvinyl acetate, polyacrylamide, polymethacrylamide, poly (N, N-dimethylacrylamide), Examples include polyvinyl pyrrolidone, styrene sulfonic acid, vinyl sulfonic acid, and polyethylene glycol.
  • the coating of the hydrophilic polymer can be performed, for example, by immersing a microporous membrane wetted with alcohol in an aqueous hydrophilic polymer solution.
  • the thickness of the microporous membrane is preferably 10 ⁇ m to 200 ⁇ m, more preferably 20 ⁇ m to 150 ⁇ m. Within such a range, when used as a diaphragm for electrolysis, it is possible to obtain an ion permeable diaphragm having excellent product gas separation performance and excellent ion permeability.
  • the pore diameter of the microporous membrane is preferably 0.001 ⁇ m to 10 ⁇ m, more preferably 0.01 ⁇ m to 2 ⁇ m, and still more preferably 0.02 ⁇ m to 1.0 ⁇ m. Within such a range, when used as a diaphragm for electrolysis, it is possible to obtain an ion permeable diaphragm having excellent product gas separation performance and excellent ion permeability.
  • the porosity of the microporous membrane is preferably 10% to 90%, more preferably 30% to 85%, and further preferably 50% to 85%.
  • the porosity is lower than 10%, the ion permeation resistance may be increased.
  • the porosity is higher than 90%, the strength of the membrane is insufficient, the membrane may be crushed, and the ion permeation resistance may be increased.
  • a higher porosity within the range allowed by the film strength is preferable because the ion permeation resistance can be lowered.
  • the porosity of the microporous membrane refers to a value calculated by the formula ⁇ 1- (apparent density of microporous membrane / true specific gravity of the material constituting the microporous membrane) ⁇ ⁇ 100. .
  • metal oxide At least one metal oxide selected from titanium oxide and zirconium oxide is attached to the microporous film. More specifically, the metal oxide is attached to the surface of the microporous film.
  • the surface of the microporous membrane refers to the interface (pore surface) between the material constituting the microporous membrane and air when no metal oxide is attached. That is, the metal oxide can exist not only near the outside of the microporous membrane (near the outer surface) but also inside the microporous membrane.
  • the metal oxide may be attached so as to cover the entire surface of the microporous film, or may be attached so as to cover a part of the surface.
  • the metal oxide can be adhered over a wide range by previously hydrophilizing the microporous membrane.
  • the metal oxide is preferably attached so as to form a coating on at least a part of the surface of the microporous membrane, and more preferably attached so as to form a coating on the entire surface of the microporous membrane.
  • the adhesion rate of the metal oxide is preferably 10% to 200%, more preferably 15% to 100%, still more preferably 20% to 100%, and particularly preferably 20% to 70%. is there. If the adhesion rate is less than 10%, the wettability with respect to alkaline water and the wet durability may be insufficient. When the adhesion rate is higher than 200%, the metal oxide may block the pores of the microporous membrane and the ion permeability may be reduced. In the present specification, the adhesion rate is the weight of the metal oxide relative to the weight of the microporous membrane (the total weight of the microporous membrane and the porous reinforcing body in the case of having a porous reinforcing body as described later).
  • Examples of the method for attaching the metal oxide to the microporous film include a liquid phase precipitation method described in JP-A-2008-44826.
  • the liquid phase precipitation method is a method utilizing a hydrolysis equilibrium reaction of a metal fluoride complex.
  • F ⁇ Fluorine ion scavenger for example, H 3 BO 3 as shown in the following reaction formula (2)
  • the equilibrium reaction of the chemical formula (1) is moved to the oxide production side, and a method of depositing a metal oxide is used. More specifically, the metal oxide can be deposited on the microporous film by immersing the microporous film in a solution containing the metal fluoride complex and the fluorine ion scavenger.
  • the metal fluoride complexes for example, (NH 4) 2 TiF 6 , include (NH 4) 2 ZrF 6 and the like.
  • fluorine ion scavenger a compound capable of forming a stable complex with fluorine ions can be used.
  • fluorine ion scavenger include H 3 BO 3 , sodium hydroxide, potassium hydroxide, aluminum chloride, aluminum hydroxide, and metal aluminum.
  • the concentration of the metal fluoride complex in the solution containing the metal fluoride complex and the fluorine ion scavenger is preferably 0.01 mol / L to 2 mol / L, more preferably 0.05 mol / L to 0.5 mol. / L. If the concentration of the metal fluoride complex is too low, the amount of metal oxide attached may be insufficient. On the other hand, if the concentration is too high, it may be difficult to dissolve the metal oxide, and / or metal There is a possibility that oxides are generated excessively and clog the pores of the microporous membrane.
  • the concentration of the fluorine ion scavenger in the solution containing the metal fluoride complex and the fluorine ion scavenger is preferably 0.05 mol / L to 2 mol / L, more preferably 0.1 mol / L to 0.5 mol. / L. If the concentration of the fluorine ion scavenger is too low, the amount of metal oxide attached may be insufficient. On the other hand, when the concentration is too high, the deposition reaction rate of the metal oxide is increased, and there is a possibility that the precipitation in the solution is larger than the precipitation in the microporous film.
  • any appropriate solvent can be used as the solvent of the solution containing the metal fluoride complex and the fluorine ion scavenger as long as the solvent can dissolve the metal fluoride complex and the fluorine ion scavenger.
  • Specific examples of the solvent include water, acetonitrile and the like.
  • reaction temperature reaction temperature
  • immersion time reaction time
  • heat treatment may be further performed in a gas phase such as an inert gas.
  • the inert gas include air, nitrogen, and the like.
  • the heat treatment can be performed when the composition and / or crystal structure of the metal oxide is incomplete.
  • the reaction represented by the above reaction formula (1) is promoted, and a metal oxide having a desired composition and / or crystal structure can be obtained.
  • the temperature of the heat treatment is, for example, 100 ° C. to 400 ° C.
  • the heat treatment time is, for example, 1 minute to 24 hours.
  • the heating temperature is preferably set in a range that does not adversely affect the structure of the microporous membrane. Moreover, if it is such a range, the time of heat processing can be shortened, so that temperature is high.
  • the microporous film is immersed in alkaline water.
  • alkaline water for example, a sodium hydroxide aqueous solution or a potassium hydroxide aqueous solution having a concentration of 10 to 40% by weight can be used.
  • the temperature of the alkaline water is preferably 60 ° C. to 120 ° C., more preferably 70 ° C. to 90 ° C.
  • the immersion time is preferably 1 hour to 200 hours, more preferably 2 hours to 100 hours.
  • an ion-permeable diaphragm that is remarkably excellent in wettability and wettability with respect to alkaline water (for example, potassium hydroxide aqueous solution) can be obtained.
  • alkaline water for example, potassium hydroxide aqueous solution
  • the mechanism by which such an ion permeable membrane is obtained is not clear, but by soaking in alkaline water, the hydrophilic functional groups of the polymer or metal oxide constituting the microporous membrane are increased, resulting in wettability and wettability. It is thought that durability is improved.
  • the ion-permeable diaphragm of the present invention may include a porous reinforcement.
  • the strength as the diaphragm for electrolysis can be improved, and the short-circuit preventing property between the electrodes can be improved.
  • the diaphragm is generally easily damaged and short-circuited by the unevenness of the electrode.
  • the porous reinforcing body is porous, the above effects can be exhibited without impairing ion permeability. Furthermore, the strength is improved by providing the porous reinforcing body, and an ion-permeable diaphragm having sufficient strength can be obtained even if the thickness is reduced.
  • the microporous membrane and the porous reinforcing body are preferably integrated by, for example, thermal lamination.
  • thermal lamination is performed by applying a predetermined pressure to a material constituting the microporous membrane and the porous reinforcing body at a temperature equal to or higher than the melting point of at least one of the materials by a pair of heating rolls, a hot press, or the like. be able to.
  • the microporous membrane and the porous reinforcing body may be integrated through an adhesive layer. Any appropriate adhesive can be used as the adhesive constituting the adhesive layer as long as the effects of the present invention can be obtained. Examples of the adhesive layer include an adhesive layer obtained by applying a polyolefin-based hot melt material in a mesh shape.
  • the material constituting the porous reinforcing body a polymer having excellent strength and having mechanical durability and chemical durability against alkaline water is preferably used.
  • the material constituting the porous reinforcing body include polytetrafluoroethylene, polyvinylidene fluoride, polypropylene, polyethylene, ultrahigh molecular weight polyethylene, poly-4-methylpentene-1, polysulfone, polyethersulfone, and polyphenylene sulfide. It is done.
  • the porous reinforcing body is porous.
  • Examples of the form of the porous reinforcing body include a woven fabric, a nonwoven fabric, a net, a mesh, and a sintered porous membrane.
  • a nonwoven fabric, a mesh or a sintered porous membrane is preferred, and a sintered porous membrane is more preferred.
  • a sintered porous membrane is excellent in strength and ion permeability. Examples of a method for obtaining a sintered porous film include a sintering method described in JP-A-2-214647.
  • the thickness of the porous reinforcing body is preferably 30 ⁇ m to 800 ⁇ m, more preferably 50 ⁇ m to 500 ⁇ m. If it is a porous reinforcement body which has the thickness of such a range, it has sufficient intensity
  • the porosity of the porous reinforcing body is preferably 10% to 80%, more preferably 20% to 60%. When the porosity is lower than 10%, the ion permeation resistance may be increased. If the porosity is higher than 80%, the strength may be insufficient.
  • the porous reinforcing body preferably has hydrophilicity. If the porous reinforcing body has hydrophilicity, a necessary and sufficient metal oxide can be uniformly attached to the porous reinforcing body. Hydrophilization of the porous reinforcing body can be performed, for example, by the method described in the above section B.
  • the hydrophilic treatment of the porous reinforcement may be performed separately from the hydrophilic treatment of the microporous membrane.
  • the microporous membrane and the porous reinforcement Hydrophilic treatment may be performed on the laminate.
  • At least one metal oxide selected from titanium oxide and zirconium oxide is attached to the porous reinforcing body. More specifically, the metal oxide is attached to the surfaces of the microporous membrane and the porous reinforcing body.
  • the surface of the microporous membrane is as described in the above section C.
  • the surface of the porous reinforcing body refers to the interface between the material constituting the porous reinforcing body and air when no metal oxide is attached. That is, the metal oxide can be present not only near the outside (near the outer surface) of the microporous membrane and / or porous reinforcing body but also inside the microporous membrane and / or porous reinforcing body.
  • the metal oxide may be attached so as to cover the entire surface of the porous reinforcing body, or may be attached so as to cover a part of the surface.
  • the metal oxide can be adhered over a wide range by hydrophilizing the porous reinforcing body in advance.
  • the metal oxide is preferably attached so as to form a film on at least a part of the surface of the porous reinforcing body, and more preferably attached so as to form a film on the entire surface of the porous reinforcing body.
  • Examples of the method for attaching the metal oxide to the porous reinforcing body include the method described in the above section C. It is preferable that a microporous membrane and a porous reinforcing body are laminated, and a metal oxide is attached to the obtained laminated body by the liquid phase precipitation method described in the above section C.
  • the heat treatment as described in the above section C may be performed.
  • a microporous membrane and a porous reinforcing body are laminated, and a heat treatment is performed on the obtained laminated body.
  • a laminate of the microporous membrane and the porous reinforcing body is formed.
  • the alkaline water for example, a sodium hydroxide aqueous solution or a potassium hydroxide aqueous solution having a concentration of 10 to 40% by weight can be used.
  • the temperature of the alkaline water is preferably 60 ° C. to 120 ° C., more preferably 70 ° C. to 90 ° C.
  • the immersion time is preferably 1 hour to 200 hours, more preferably 2 hours to 100 hours.
  • Adhesion rate (%) (total weight of microporous membrane and porous reinforcing body after metal oxide deposition ⁇ total weight of microporous membrane and porous reinforcing body before metal oxide deposition) / (before metal oxide deposition) Total weight of microporous membrane and porous reinforcing body) (3) Wettability with respect to aqueous potassium hydroxide solution An ion-permeable membrane was immersed in an aqueous 30 wt% potassium hydroxide solution maintained at 80 ° C. for 100 hours. Thereafter, the porous reinforcing body was pulled up, and the remaining potassium hydroxide aqueous solution was sufficiently washed and removed, and then dried.
  • a pH test paper (manufactured by ASONE, product number “1-1745-01”) is applied to one surface (back surface) of the porous reinforcing body, and hydroxylation at a concentration of 30% by weight from the other surface (front surface).
  • One drop (about 50 mg) of an aqueous potassium solution was added dropwise. After 10 minutes from dropping, when the potassium hydroxide aqueous solution reached the back surface and the pH test paper was discolored, it was judged that there was wettability.
  • Alkaline water electrolysis evaluation Alkaline water electrolysis evaluation of the ion-permeable diaphragms obtained in Examples and Comparative Examples was performed using an H-cell made of acrylic resin.
  • the electrolyte used was an aqueous solution of potassium hydroxide having a concentration of 30% by weight, and the electrode used was an electrode (effective electrode diameter of ⁇ 30 mm, aperture ratio of 40%) having 90 holes of ⁇ 2 mm in a 1 mm thick Ni plate. .
  • the liquid temperature at the time of measurement was set to 25 ° C.
  • the current density was 0.2 A / cm 2 , the voltage when a constant current was applied continuously for 1 hour was measured, and alkaline water electrolysis was evaluated based on the average value of the measured values 55 minutes to 1 hour after the start of measurement. Went.
  • the measurement was performed after the ion-permeable diaphragm was immersed in the electrolyte for 10 minutes. In the case where the ion-permeable diaphragm has a two-layer structure (Examples 1 to 9 and Comparative Example 6), the measurement was performed with the microporous membrane placed on the anode side.
  • Example 1 A polytetrafluoroethylene (PTFE) porous membrane (trade name “TEMISH NTF-1122” manufactured by Nitto Denko Corporation, pore size 0.2 ⁇ m, thickness 85 ⁇ m) is dipped in 2-propanol and wetted, and then the membrane is not dried. And then immersed in an aqueous solution of polyvinyl alcohol (PVA, degree of polymerization 2000) (concentration: 1.2% by weight) and allowed to stand at 25 ° C. for 30 minutes for replacement.
  • PVA polyvinyl alcohol
  • this porous PTFE membrane was immersed in a crosslinking liquid (liquid temperature: 35 ° C.) prepared by mixing 90 g of a glutaraldehyde aqueous solution (concentration 25 wt%), 15 g of 6 molar hydrochloric acid and 795 g of pure water for 1 hour. And a crosslinking reaction was carried out.
  • a crosslinking reaction was carried out.
  • the PTFE porous membrane is fixed to the stainless steel frame with a clip in a wet state, and a hot air circulating dryer at 80 ° C. And dried for 30 minutes to obtain a hydrophilic microporous membrane.
  • the “total weight of the microporous membrane and the porous reinforcing body before the metal oxide adhesion” refers to the weight of the microporous membrane subjected to the hydrophilic treatment.
  • the hydrophilic microporous membrane (80 ⁇ 120 mm) is immersed in 100 g of this solution, heated at 60 ° C. for 9 hours, and further at 80 ° C. for 3 hours, and TiO 2 is added to the microporous membrane. Precipitated. Thereafter, the microporous membrane is taken out from the solution, fixed with a clip to a stainless steel frame in a wet state, and heat-treated for 30 minutes with a hot air circulating dryer at 80 ° C. to obtain an ion-permeable membrane (thickness: 84 ⁇ m).
  • the total weight of the microporous membrane and the porous reinforcing body after the metal oxide is deposited refers to the weight of the ion-permeable diaphragm.
  • the obtained ion-permeable diaphragm was subjected to the above evaluations (1) to (4). The results are shown in Table 1.
  • Example 2 Polytetrafluoroethylene (PTFE) porous membrane (trade name “Temisch NTF-1131” manufactured by Nitto Denko Corporation, pore size 1.0 ⁇ m, thickness 85 ⁇ m) as a microporous membrane, and spun pond non-woven fabric (Unitika) as a porous reinforcement
  • Product name “T0303 / WD0” core: polyester / sheath: polyethylene, weight per unit area 30 g / m 2 , thickness 170 ⁇ m) are thermally bonded with a heating roll at 135 ° C. to obtain a laminate (microporous membrane / porous) Strength reinforcement).
  • This laminate was dipped in 2-propanol and wetted, and then dipped in an aqueous solution of polyvinyl alcohol (PVA, polymerization degree 2000) (concentration: 1.2% by weight) so that the laminate was not dried, at 25 ° C. Replaced by standing for 30 minutes. Thereafter, this laminate was immersed in a crosslinking liquid (liquid temperature: 35 ° C.) prepared by mixing 90 g of a glutaraldehyde aqueous solution (concentration 25% by weight), 15 g of 6 molar hydrochloric acid and 795 g of pure water, and crosslinked for 1 hour. Reacted.
  • PVA polyvinyl alcohol
  • the laminate is taken out of the cross-linking solution, washed 5 times with pure water, then fixed with a clip on a stainless steel frame in a wet state, and dried for 30 minutes with a hot air circulating dryer at 80 ° C.
  • a laminate subjected to hydrophilic treatment was obtained.
  • the total weight of the microporous membrane and the porous reinforcing body before the metal oxide is adhered refers to the weight of the hydrophilically treated laminate.
  • the laminate is taken out of the solution, fixed in a stainless steel frame with a clip in a wet state, and heat-treated for 30 minutes with a hot air circulating dryer at 80 ° C. to obtain an ion-permeable diaphragm (thickness: 146 ⁇ m).
  • ion-permeable diaphragm thickness: 146 ⁇ m.
  • the total weight of the microporous membrane and the porous reinforcing body after the metal oxide is deposited refers to the weight of the ion-permeable diaphragm.
  • the obtained ion-permeable diaphragm was subjected to the above evaluations (1) to (4). The results are shown in Table 1.
  • Example 3 Polytetrafluoroethylene (PTFE) porous membrane (manufactured by Nitto Denko Corporation, trade name “Temish NTF-1131”, pore diameter 1.0 ⁇ m, thickness 85 ⁇ m), polytetrafluoroethylene (PTFE) porous membrane (Nitto Denko Corporation) An ion-permeable membrane (thickness: 120 ⁇ m) was obtained in the same manner as in Example 2 except that the product name “Temisch NTF-1026”, pore diameter 0.6 ⁇ m, thickness 25 ⁇ m) was used. The obtained ion-permeable diaphragm was subjected to the above evaluations (1) to (4). The results are shown in Table 1.
  • Example 4 As the microporous membrane, a hydrophilic polyvinylidene fluoride (PVdF) porous membrane (trade name “Durapore membrane filter GVWP14250”, pore size 0.22 ⁇ m, manufactured by Millipore) was used.
  • PVdF polyvinylidene fluoride
  • the “total weight of the microporous membrane and the porous reinforcing body before the metal oxide adhesion” refers to the hydrophilic polyvinylidene fluoride (PVdF) porous membrane. Refers to weight.
  • the microporous membrane is taken out from the solution, fixed in a wet state with a clip to a stainless steel frame, and heat-treated for 30 minutes with a hot air circulating dryer at 80 ° C. to obtain an ion-permeable membrane (thickness: 123 ⁇ m).
  • the total weight of the microporous membrane and the porous reinforcing body after the metal oxide is deposited refers to the weight of the ion-permeable diaphragm.
  • the obtained ion-permeable diaphragm was subjected to the above evaluations (1) to (4). The results are shown in Table 1.
  • Example 5 Hydrophilic polyvinylidene fluoride (PVdF) porous membrane (Millipore's product name “Durapore membrane filter GVWP14250”, pore size 0.22 ⁇ m), instead of hydrophilic polyvinylidene fluoride (PVdF) porous membrane (Millipore product)
  • An ion permeable membrane (thickness: 111 ⁇ m) was obtained in the same manner as in Example 4 except that the name “Durapore membrane filter HVLP14250” (pore diameter 0.45 ⁇ m) was used.
  • the obtained ion-permeable diaphragm was subjected to the above evaluations (1) to (4). The results are shown in Table 1.
  • PTFE polytetrafluoroethylene
  • HEP-60HCF core: polypropylene / sheath: polyethylene, basis weight 60 g / m 2 , thickness 160 ⁇ m) and heat bonded with a heating roll at 145 ° C. to laminate (microporous membrane / porous) Reinforcing body) was obtained.
  • PTFE polytetrafluoroethylene
  • HEP-60HCF core: polypropylene / sheath: polyethylene, basis weight 60 g / m 2 , thickness 160 ⁇ m) and heat bonded with a heating roll at 145 ° C. to laminate (microporous membrane / porous) Reinforcing body) was obtained.
  • the laminate was subjected to a hydrophilic treatment in the same manner as in Example 2 to obtain a hydrophilic treated laminate.
  • An aluminum plate (A1050, thickness 0.2 mm ⁇ 100 mm ⁇ 100 mm) and the hydrophilically treated laminate (80 ⁇ 120 mm) are immersed in 95.0 g of this solution, and left at 25 ° C. for 150 hours. Then, ZrO 2 was deposited on the laminate (that is, the microporous film and the porous reinforcing body). Thereafter, the laminate is taken out of the solution, fixed with a clip to a stainless steel frame in a wet state, and heat-treated for 30 minutes with a hot air circulation dryer at 80 ° C. to obtain an ion-permeable diaphragm (thickness: 240 ⁇ m). Got.
  • the total weight of the microporous membrane and the porous reinforcing body after the metal oxide is deposited refers to the weight of the ion-permeable diaphragm.
  • the obtained ion-permeable diaphragm was subjected to the above evaluations (1) to (4). The results are shown in Table 1.
  • Example 8 In the same manner as in Example 1, a microporous membrane subjected to hydrophilic treatment was obtained. Separately, a solution obtained by dissolving 7.77 g of zircon hydrofluoric acid (Morita Chemical Co., Ltd.) in 67.2 g of pure water; A solution obtained by dissolving 0.62 g of boric acid (manufactured by Wako Pure Chemical Industries, Ltd.) in 19.4 g of pure water was mixed to prepare a solution for precipitation of zirconium oxide.
  • zircon hydrofluoric acid Morita Chemical Co., Ltd.
  • boric acid manufactured by Wako Pure Chemical Industries, Ltd.
  • An aluminum plate (A1050, thickness 0.2 mm ⁇ 100 mm ⁇ 100 mm) and the above-mentioned hydrophilic microporous film (80 ⁇ 120 mm) were immersed in 95.0 g of this solution, and the plate was allowed to stand at 25 ° C. for 150 hours. And ZrO 2 was deposited on the microporous membrane. Thereafter, the microporous membrane is taken out from the solution, fixed in a stainless steel frame with a clip in a wet state, and heat-treated for 30 minutes with a hot air circulating dryer at 150 ° C. to obtain an ion-permeable membrane (thickness: 73 ⁇ m).
  • the total weight of the microporous membrane and the porous reinforcing body after the metal oxide is deposited refers to the weight of the ion-permeable diaphragm.
  • the obtained ion-permeable diaphragm was subjected to the above evaluations (1) to (4). The results are shown in Table 1.
  • Example 9 An ion permeable membrane (thickness: 85 ⁇ m) was obtained in the same manner as in Example 1 except that the temperature of the heat treatment after depositing TiO 2 on the microporous membrane was 200 ° C. The obtained ion-permeable diaphragm was subjected to the above evaluations (1) to (4). The results are shown in Table 1.
  • a 200-mesh, 190- ⁇ m thick polyethylene net (nip (polyethylene) strong net, manufactured by NBC Co., Ltd.) was stretched and 10 ml of the suspension was poured onto a 10 cm ⁇ 10 cm glass frame placed on the bottom. . Thereafter, the frame into which the suspension was poured was immersed in pure water at 25 ° C. and left at room temperature for 10 minutes to extract 1-methyl-2-pyrrolidone. Thereafter, the solidified sheet-like material is peeled off from the frame, further washed in pure water at 25 ° C. for 30 minutes, air-dried at 25 ° C., and then dried in a dryer at 80 ° C.
  • the ion permeable membrane obtained in Comparative Example 1 has many irregularities on the surface, the film thickness varies from 570 ⁇ m to 1170 ⁇ m, and electrolyte leakage due to poor sealing is generated, so alkaline water electrolysis evaluation is not possible. There wasn't.
  • the obtained ion permeable diaphragm had a smooth surface and a uniform film thickness of around 340 ⁇ m.
  • the obtained ion-permeable diaphragm was used for the evaluations (1), (3) and (4). The results are shown in Table 1.
  • Example 3 The hydrophilic microporous membrane obtained in Example 1, that is, a microporous membrane (thickness: 77 ⁇ m) to which no metal oxide was adhered was subjected to the above evaluations (1) to (4). The results are shown in Table 1.
  • the ion-permeable diaphragm of this invention is excellent in durability in alkaline water, can maintain the wettability with respect to alkaline water over a long period of time, and can suppress an increase in electrolytic voltage.
  • the ion-permeable diaphragm shown in the comparative example cannot maintain wettability in high-temperature and high-concentration alkaline water. In such an ion-permeable diaphragm, the electrolysis voltage increases with time.
  • the ion-permeable membrane of the present invention can be suitably used as a membrane used in alkaline water electrolysis and a membrane for batteries.

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Abstract

La présente invention concerne une membrane perméable aux ions présentant d'excellentes caractéristiques généralement requises pour les membranes perméables aux ions à utiliser dans l'électrolyse d'une solution aqueuse alcaline [à savoir, (1) être perméable aux ions, (2) avoir une résistance mécanique et une stabilité chimique suffisantes vis-à-vis de la solution aqueuse alcaline, (3) être imperméable aux gaz à travers la membrane, et (4) pouvoir prévenir tout court-circuit entre les électrodes] et, parallèlement, pouvant empêcher toute augmentation de tension provoquée par l'adhérence du gaz à la surface de la membrane, ledit gaz étant généré à partir des électrodes pendant l'électrolyse. La membrane perméable aux ions selon la présente invention est dotée d'un film microporeux et d'au moins un type d'oxyde métallique choisi parmi l'oxyde de titane et l'oxyde de zirconium qui adhère au dit film microporeux.
PCT/JP2013/065342 2012-06-08 2013-06-03 Membrane perméable aux ions WO2013183584A1 (fr)

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WO2016148302A1 (fr) * 2015-03-18 2016-09-22 旭化成株式会社 Membrane pour électrolyse d'eau alcaline, appareil d'électrolyse d'eau alcaline, procédé pour produire de l'hydrogène, et procédé pour produire une membrane pour électrolyse d'eau alcaline
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EP4060088A2 (fr) 2021-03-18 2022-09-21 Kabushiki Kaisha Toshiba Dispositif électrolytique de dioxyde de carbone
EP4060087A1 (fr) 2021-03-18 2022-09-21 Kabushiki Kaisha Toshiba Dispositif d'électrolyse de dioxyde de carbone
EP4234763A2 (fr) 2021-03-18 2023-08-30 Kabushiki Kaisha Toshiba Dispositif d'électrolyse de dioxyde de carbone
WO2023085400A1 (fr) * 2021-11-12 2023-05-19 国立大学法人東京工業大学 Membrane, membrane composite, ensemble membrane-électrode et dispositif d'électrolyse de l'eau
CN114561654A (zh) * 2022-03-25 2022-05-31 中山市刻沃刻科技有限公司 一种涂层式碱性电解水制氢气隔膜

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