WO2024048235A1 - アルカリ水電解用隔膜、アルカリ水電解セル、及び、アルカリ水電解方法 - Google Patents

アルカリ水電解用隔膜、アルカリ水電解セル、及び、アルカリ水電解方法 Download PDF

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Publication number
WO2024048235A1
WO2024048235A1 PCT/JP2023/029162 JP2023029162W WO2024048235A1 WO 2024048235 A1 WO2024048235 A1 WO 2024048235A1 JP 2023029162 W JP2023029162 W JP 2023029162W WO 2024048235 A1 WO2024048235 A1 WO 2024048235A1
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Prior art keywords
water electrolysis
diaphragm
alkaline water
impregnated
porous support
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PCT/JP2023/029162
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English (en)
French (fr)
Japanese (ja)
Inventor
信也 中山
寛信 芥川
裕二 三佐和
重徳 光島
兼作 長澤
義之 黒田
アシュラフ アブドルハリム
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Nippon Shokubai Co Ltd
Yokohama National University NUC
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Nippon Shokubai Co Ltd
Yokohama National University NUC
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Application filed by Nippon Shokubai Co Ltd, Yokohama National University NUC filed Critical Nippon Shokubai Co Ltd
Priority to CN202380063070.9A priority Critical patent/CN119790191A/zh
Priority to JP2024544087A priority patent/JPWO2024048235A1/ja
Priority to EP23860001.9A priority patent/EP4582595A1/en
Publication of WO2024048235A1 publication Critical patent/WO2024048235A1/ja
Anticipated expiration legal-status Critical
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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
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • C25B1/01—Products
    • C25B1/02—Hydrogen or oxygen
    • C25B1/04—Hydrogen or oxygen by electrolysis of water
    • 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
    • C25B13/02—Diaphragms; Spacing elements characterised by shape or form
    • 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
    • C25B13/05—Diaphragms; Spacing elements characterised by the material based on inorganic materials
    • C25B13/07—Diaphragms; Spacing elements characterised by the material based on inorganic materials based on ceramics
    • 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
    • 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
    • C25B15/00—Operating or servicing cells
    • C25B15/02—Process control or regulation
    • 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
    • C25B15/00—Operating or servicing cells
    • C25B15/02—Process control or regulation
    • C25B15/023—Measuring, analysing or testing during electrolytic production
    • 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
    • C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
    • C25B9/17—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof
    • C25B9/19—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof with diaphragms
    • 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 a diaphragm for alkaline water electrolysis, an alkaline water electrolysis cell, and an alkaline water electrolysis method.
  • a common method for obtaining hydrogen gas by electrolysis of water is to apply a direct current to water to which sodium hydroxide, potassium hydroxide, or the like has been added. This method is also called alkaline water electrolysis.
  • an alkaline water electrolysis cell which has an anode chamber and a cathode chamber, which are separated by a diaphragm (diaphragm for alkaline water electrolysis). Since electrolysis is performed by the movement of electrons (or ions), the diaphragm needs to have high ion permeability in order to perform electrolysis efficiently. Gas barrier properties are also required to block oxygen gas generated in the anode chamber and hydrogen gas generated in the cathode chamber. Furthermore, since alkaline water electrolysis uses an alkaline aqueous solution with a high concentration of about 30% and is carried out at a temperature of about 80 to 90°C, the diaphragm must also be resistant to high temperatures and alkalis.
  • Patent Documents 1 to 3 various diaphragms for alkaline water electrolysis have been proposed (for example, Patent Documents 1 to 3).
  • oxygen gas is generated in the anode chamber (anode) and hydrogen gas is generated in the cathode chamber (cathode).
  • cathode cathode
  • these two types of gases are separated by a diaphragm arranged between the electrodes, but since the diaphragm has a porous structure, a considerable amount of each gas passes through the gas and mixes with the gases. From the viewpoint of resource utilization and safety, it is desired that these two types of gas be recovered with high purity. Furthermore, it is desirable to increase the purity of a desired gas among the generated gases depending on the use or operating conditions after recovery.
  • the present invention has been made in view of the above-mentioned current situation, and an object of the present invention is to provide a diaphragm for alkaline water electrolysis that can improve the purity of the target generated gas in alkaline water electrolysis.
  • the present inventor conducted various studies on a diaphragm for alkaline water electrolysis, and found that it comprises a porous membrane containing an organic polymer resin and inorganic particles, and a porous support, and the porous membrane is impregnated into the porous support.
  • the diaphragm for alkaline water electrolysis includes an impregnated part, and the impregnated part has a gap of a specific size between the porous membrane and the porous support, and the impregnated part has a gas permeability from one of the pair of main surfaces to the other. It has been found that the gas permeability from the other of the pair of main surfaces to the one of the pair of main surfaces has different gas permeation anisotropy.
  • the present invention utilizes this gas permeation anisotropy to set the direction of the diaphragm in alkaline water electrolysis, thereby improving the recovery rate of the target product gas and producing the desired product gas with high purity.
  • the present inventors have discovered that the present invention can be obtained, and have completed the present invention.
  • An alkali comprising a porous membrane containing an organic polymer resin and inorganic particles and a porous support, the porous membrane including an impregnated part formed by impregnating the porous support, and having a pair of main surfaces.
  • a diaphragm for water electrolysis wherein the impregnated portion has a void having a size of 0.5 to 10 ⁇ m between the porous membrane and the porous support, and the impregnated portion has a void having a size of 0.5 to 10 ⁇ m from one of the pair of main surfaces to the other.
  • a diaphragm for alkaline water electrolysis wherein the diaphragm has gas permeation anisotropy in which the gas permeability between the main surfaces and the gas permeability from the other of the pair of main surfaces to the one of the pair of main surfaces are different.
  • a diaphragm for alkaline water electrolysis including a non-impregnated part that is not impregnated into the body and having a pair of main surfaces, the impregnated part forming one of the pair of main faces, and the non-impregnated part
  • the impregnated portion forms the other main surface of the pair of main surfaces, and on the one main surface, the impregnated portion has a void having a size of 0.5 to 10 ⁇ m between the porous membrane and the porous support.
  • the porous membrane includes a non-impregnated part that is not impregnated into the porous support, and the ratio of the thickness of the non-impregnated part to the impregnated part [(thickness of the non-impregnated part)/(impregnated part)]
  • the diaphragm for alkaline water electrolysis according to any one of [1] to [3] above, wherein the diaphragm has a thickness of 0.1 to 1.0.
  • the diaphragm for alkaline water electrolysis of the present invention can improve the purity of the target generated gas. Further, it is possible to suitably provide an alkaline water electrolysis cell and an alkaline water electrolysis method that can efficiently improve the purity of the target generated gas.
  • FIG. 1 is a schematic diagram of a cross section of an example of a diaphragm for alkaline water electrolysis of the present invention in a direction perpendicular to its main surface.
  • An example of a state in which line segments are drawn in an observation image of an impregnated part of a diaphragm obtained by SEM (1000x magnification) is shown when measuring the size of a void between a porous membrane and a porous support.
  • An example of an observation image of the impregnated portion of the diaphragm obtained by SEM (200x magnification) is shown when determining the ratio of the amount of voids between the porous membrane and the porous support.
  • X to Y means from X to Y, inclusive.
  • 0.5 to 10 ⁇ m means 0.5 ⁇ m or more and 10 ⁇ m or less.
  • Diaphragm for alkaline water electrolysis of the present invention comprises a porous membrane containing an organic polymer resin and inorganic particles, and a porous support, and the porous membrane is impregnated into the porous support.
  • a diaphragm for alkaline water electrolysis including an impregnated part and having a pair of main surfaces, wherein the impregnated part has a void having a size of 0.5 to 10 ⁇ m between the porous membrane and the porous support. characterized in that the gas permeability from one of the pair of main surfaces to the other and the gas permeability from the other of the pair of main surfaces to the one have different gas permeation anisotropy. .
  • the purity can be improved by setting the orientation of the diaphragm for alkaline water electrolysis of the present invention depending on the gas whose purity is to be increased. A highly targeted product gas can be obtained.
  • the diaphragm for alkaline water electrolysis of the present invention has gas permeation anisotropy.
  • the gas permeation anisotropy refers to a property in which the gas permeability from one of the pair of main surfaces of the diaphragm to the other is different from the gas permeability from the other of the pair of main surfaces to the one. More specifically, it is also a characteristic that the amount of hydrogen gas that permeates through the diaphragm for alkaline water electrolysis per unit time changes depending on the orientation of the diaphragm for alkaline water electrolysis, and the amount of oxygen gas that permeates through the diaphragm for alkaline water electrolysis per unit time.
  • the amount changes depending on the orientation of the diaphragm for alkaline water electrolysis.
  • the gas permeability of the diaphragm for alkaline water electrolysis changes depending on the orientation in which it is installed, so by changing the orientation of the diaphragm depending on the generated gas to be recovered, it is possible to increase the purity of the gas to be recovered. Can be done.
  • the diaphragm for alkaline water electrolysis of the present invention comprises a porous membrane containing an organic polymer resin and inorganic particles, and a porous support, and includes an impregnated portion in which the porous membrane is impregnated into the porous support, It has a pair of main surfaces.
  • the porous membrane is impregnated throughout the porous support, and is laminated as a portion consisting only of the porous membrane on one side of the pair of main surfaces of the porous support. On the other side of the pair of main surfaces of the porous support, the porous membrane and the porous support are approximately flush with each other.
  • the diaphragm for alkaline water electrolysis of the present invention has an impregnated part in which the porous membrane is impregnated into the porous support, and a porous membrane in which the porous support does not contain the porous membrane.
  • the impregnated portion constitutes one of the pair of principal surfaces, and the non-impregnated portion constitutes the other of the pair of principal surfaces.
  • the impregnated portion has a void having a size of 0.5 to 10 ⁇ m between the porous membrane and the porous support.
  • the impregnated portion can exhibit gas permeation anisotropy by having voids having a size within the above-mentioned range between the porous membrane and the porous support.
  • the size of the voids is preferably 1 to 8 ⁇ m, more preferably 2 to 7 ⁇ m, from the viewpoint of further improving gas permeation anisotropy.
  • the diaphragm for alkaline water electrolysis of the present invention comprises a porous membrane containing an organic polymer resin and inorganic particles, and a porous support, and an impregnated portion formed by impregnating the porous support with the porous membrane.
  • a diaphragm for alkaline water electrolysis having a pair of main surfaces
  • the porous membrane includes a non-impregnated part that is not impregnated into the porous support, the impregnated part is a non-impregnated part that is not impregnated into the porous support; the non-impregnated portion forms the other of the pair of main surfaces, and on the one main surface, the impregnated portion has a size between the porous membrane and the porous support.
  • the diaphragm for alkaline water electrolysis of the present invention has a gas permeability from one of the pair of main surfaces to the other, and a gas permeation rate from the other of the pair of main surfaces to the one. It has gas permeation anisotropy with different degrees.
  • FIG. 1 shows a schematic cross-sectional view of an example of the diaphragm for alkaline water electrolysis of the present invention in a direction perpendicular to its main surface.
  • the diaphragm 1 for alkaline water electrolysis includes a porous membrane 2 and a porous support 3, and the porous membrane 2 includes an impregnated portion 4 formed by impregnating the porous support 3, and only the porous membrane.
  • the observation area is selected.
  • an observation image with a magnification of 1000 is obtained using a SEM.
  • the size of the void is measured using image analysis software (Image-Pro Premier, Media Cybernetics).
  • image analysis software Image-Pro Premier, Media Cybernetics.
  • line segments are drawn at 10 ⁇ m intervals along the longitudinal direction of the fibrous-looking porous support. This line segment is drawn perpendicularly to the surface of the porous support from the surface of the porous support to the surface of the porous membrane.
  • FIG. 2 shows a diagram in which the above line segments are drawn in a SEM observation image of one field of view.
  • the proportion of voids between the porous membrane and the porous support on the surface of the alkaline water electrolysis diaphragm is preferably 1 to 8%.
  • the proportion of the voids is preferably 2 to 7%, and even more preferably 2.5 to 6.5%, from the standpoint of further improving ion permeability and gas permeation anisotropy.
  • the ratio of the amount of voids between the porous membrane and the porous support in the diaphragm for alkaline water electrolysis can be determined by the following method. That is, on the main surface of the diaphragm for alkaline water electrolysis consisting of the impregnated portion (the main surface on which the non-impregnated portion is not formed), arbitrary 10 points are set as observation areas. In the observation area, an observation image at a magnification of 200 is obtained using a SEM. In each of the obtained 10 observed images (10 fields of view), the proportion of voids is measured using image analysis software (Image-Pro Premier, Media Cybernetics). Specifically, first, 1) in the above observation image, a void portion and a non-void portion are visually recognized (see FIG.
  • the ratio of the thickness of the non-impregnated part to the impregnated part is 0.1 to 1.0. It is preferable that there be.
  • the thickness ratio of the non-impregnated portion to the impregnated portion is within the above range, gas permeation anisotropy is excellent.
  • the thickness ratio between the non-impregnated part and the impregnated part is more preferably 0.2 to 0.9, and more preferably 0.3 to 0.8, from the viewpoint of further improving gas permeation anisotropy. It is more preferably 0.4 to 0.7, and even more preferably 0.4 to 0.7.
  • the thickness ratio between the non-impregnated part and the impregnated part is such that, for example, the diaphragm for alkaline water electrolysis has an impregnated part in which the porous membrane is impregnated throughout the porous support, and a non-impregnated part consisting only of the porous membrane.
  • an impregnated part use a digimatic micrometer (product name: Coolant Proof Micrometer MDC-PXT, manufactured by Mitutoyo) to measure any 10 points on each of the porous support and the diaphragm for alkaline water electrolysis. It can be determined by measuring and calculating the average value.
  • the thickness of the diaphragm for alkaline water electrolysis and the thickness of the porous support are determined, and the thickness of the impregnated part is determined. is the same as the thickness of the porous support, and the thickness of the non-impregnated portion can be calculated by subtracting the thickness of the impregnated portion from the thickness of the diaphragm for alkaline water electrolysis.
  • the thickness of the diaphragm for alkaline water electrolysis is not particularly limited, and may be selected appropriately depending on the size of the equipment used, ease of handling, etc., but from the viewpoint of gas barrier properties, ion permeability, and strength of the diaphragm,
  • the thickness is preferably 1000 ⁇ m, more preferably 100 to 500 ⁇ m, even more preferably 200 to 400 ⁇ m.
  • the porosity of the diaphragm for alkaline water electrolysis is preferably 20 to 80% by volume, more preferably 25 to 75% by volume, and even more preferably 30 to 70% by volume. When the porosity is within the above range, the pores in the membrane are continuously filled with the electrolyte, resulting in a membrane with excellent ion permeability and gas barrier properties.
  • porous membrane The porous membrane includes an organic polymer resin and inorganic particles.
  • organic polymer resin examples include fluororesins, olefin resins, aromatic hydrocarbon resins, and the like.
  • fluororesin examples include ethylene-tetrafluoroethylene copolymer, polyvinylidene fluoride, polyvinyl fluoride, vinylidene fluoride-hexafluoropropylene copolymer, tetrafluoroethylene-hexafluoropropylene copolymer, and polytetrafluoroethylene copolymer.
  • olefin resin examples include polyethylene, polypropylene, polybutene, polymethylpentene, and the like.
  • aromatic hydrocarbon resin examples include polyethylene terephthalate, polybutylene terephthalate, polybutylene naphthalate, polystyrene, polysulfone, polyether sulfone, polyphenylene sulfide, polyphenylsulfone, polyarylate, polyetherimide, polyimide, and polyamideimide. etc.
  • the above-mentioned organic polymer resin is preferably an aromatic hydrocarbon resin because it has excellent heat resistance, alkali resistance, and solubility in the solvent described below, and is selected from the group consisting of polysulfone, polyether sulfone, and polyphenylsulfone. It is more preferable to contain at least one kind of polysulfone, and even more preferably to contain polysulfone.
  • the above-mentioned organic polymer resins may contain only one type, or may contain two or more types.
  • the content of the organic polymer resin is preferably 10 to 40% by mass, more preferably 15 to 35% by mass, and even more preferably 20 to 30% by mass based on 100% by mass of the porous membrane. preferable.
  • the inorganic particles include metal hydroxides or metal oxides such as magnesium, zirconium, titanium, zinc, aluminum, and tantalum; sulfates such as calcium, barium, lead, and strontium; and nitrides such as titanium, zirconium, and hafnium.
  • metal hydroxides or metal oxides are preferred from the viewpoint of further improving ion permeability, and contain at least one selected from the group consisting of zirconium oxide, titanium oxide, magnesium hydroxide, and barium sulfate. is more preferable, and it is even more preferable that at least one selected from the group consisting of zirconium oxide and magnesium hydroxide is included.
  • the above-mentioned inorganic particles may contain only one type, or may contain two or more types.
  • the surface of the inorganic particles may be untreated or surface-treated.
  • Examples of the above-mentioned surface treatment include known surface treatments using a silane coupling agent, stearic acid, oleic acid, phosphoric acid ester, and the like.
  • the shape of the above-mentioned inorganic particles is not particularly limited, and may be any shape such as amorphous; granular; granular; plate-like, such as flaky or hexagonal plate; or fibrous; From the viewpoint of easy dispersion and preparation of a coating solution, granular, plate-like, and fibrous shapes are preferable; from the viewpoint of adhesion with resin and ion permeability, granular and plate-like forms are more preferable; It is more preferable that it is, and it is particularly preferable that it is flaky.
  • the average particle diameter of the inorganic particles is preferably 0.01 to 1.5 ⁇ m. When the average particle diameter of the inorganic particles is within the above range, ion permeability and gas barrier properties are excellent.
  • the average particle diameter of the inorganic particles is preferably 0.1 to 1.0 ⁇ m, and even more preferably 0.2 to 0.5 ⁇ m, from the viewpoint of further improving ion permeability and gas barrier properties. .
  • the above average particle diameter is the volume average particle diameter (D50) determined from particle size distribution measurement using a laser diffraction method. Specifically, the average particle diameter is determined by measuring the particle size distribution using a laser diffraction/scattering particle size distribution analyzer (model number LA-950, manufactured by Horiba, Ltd.), and calculating the median diameter (D50) in the volume-based particle size distribution. is the average particle diameter.
  • the measurement sample is prepared by mixing inorganic particles in a 0.2% by mass aqueous sodium hexametaphosphate solution and dispersing the mixture by irradiating it with ultrasonic waves. Specifically, it can be determined by the method described in Examples described later.
  • the aspect ratio of the inorganic particles is preferably 1.0 to 8.0. When the aspect ratio of the inorganic particles is within the above range, ion permeability and gas barrier properties are excellent.
  • the aspect ratio of the inorganic particles is more preferably 2.0 to 8.0, and even more preferably 2.5 to 7.0, in terms of further improving ion permeability and gas barrier properties. It is even more preferably 3.0 to 6.0.
  • the aspect ratio means the ratio [(a)/(b)] between the longest diameter (a) and the shortest diameter (b).
  • the inorganic particles are observed with a SEM, and the ratio [(a)/(b)] is measured for each of ten arbitrary inorganic particles in the obtained image using analysis software.
  • the shortest diameter among the diameters orthogonal to the longest diameter is defined as the shortest diameter (b).
  • the specific surface area of the inorganic particles is preferably 5 to 35 m 2 /g. When the specific surface area of the inorganic particles is within the above range, ion permeability is excellent.
  • the specific surface area of the inorganic particles is more preferably 5.5 to 25 m 2 /g, and even more preferably 6 to 20 m 2 /g.
  • the above-mentioned specific surface area can be determined by measuring using a BET specific surface area meter, and specifically, can be determined by the method described in the Examples described later.
  • the content of the inorganic particles is preferably 60 to 95% by mass, more preferably 65 to 92% by mass, and even more preferably 75 to 90% by mass based on 100% by mass of the porous membrane.
  • the porous film preferably contains 10 to 60 parts by mass, more preferably 15 to 55 parts by mass, and preferably 20 to 50 parts by mass of the organic polymer resin based on 100 parts by mass of the inorganic particles. More preferred.
  • the diaphragm for alkaline water electrolysis has excellent ion permeability, gas barrier properties, heat resistance, and alkali resistance.
  • the thickness of the porous membrane is preferably 50 to 1000 ⁇ m, more preferably 100 to 500 ⁇ m, and preferably 200 to 400 ⁇ m in order to further improve ion permeability, gas barrier properties, and strength. More preferred.
  • the porous support is a member that is porous and serves as a support for a diaphragm for alkaline water electrolysis.
  • the porous support is preferably a sheet-like member.
  • the material for the porous support examples include resins such as polyethylene, polypropylene, polysulfone, polyethersulfone, polyphenylsulfone, polyphenylene sulfide, polyketone, polyimide, polyetherimide, and fluororesin. These may be used alone or in combination of two or more. Among these, it is preferable to contain at least one resin selected from the group consisting of polypropylene, polyethylene and polyphenylene sulfide, from the viewpoint of exhibiting excellent heat resistance and alkali resistance. It is more preferable that at least one type of resin is included.
  • resins such as polyethylene, polypropylene, polysulfone, polyethersulfone, polyphenylsulfone, polyphenylene sulfide, polyketone, polyimide, polyetherimide, and fluororesin. These may be used alone or in combination of two or more. Among these, it is preferable to contain at least one resin selected from the group consisting of poly
  • porous support examples include a nonwoven fabric, a woven fabric, a mesh, a porous membrane, a mixed fabric of a nonwoven fabric and a woven fabric, and preferably a nonwoven fabric, a woven fabric, or a mesh. More preferably, nonwoven fabrics and meshes are mentioned, and still more preferably nonwoven fabrics are mentioned.
  • porous supports used in the present invention nonwoven fabrics, woven fabrics, or meshes containing at least one resin selected from the group consisting of polypropylene, polyethylene, and polyphenylene sulfide are preferred.
  • the porous support is preferably a nonwoven fabric or mesh containing polyphenylene sulfide.
  • the thickness of the porous support is not particularly limited as long as the diaphragm for alkaline water electrolysis of the present invention can exhibit the effects of the present invention, but is preferably 30 to 2000 ⁇ m, More preferably 50 to 1000 ⁇ m, still more preferably 80 to 250 ⁇ m.
  • the mass per unit is preferably 20 to 200 g/m 2 .
  • the mass per unit is within the above range, ion permeability and gas barrier properties are excellent.
  • the mass per unit of the porous support is more preferably 40 to 150 g/m 2 , even more preferably 60 to 100 g/m 2 .
  • the alkaline water electrolysis diaphragm of the present invention can be manufactured, for example, by a nonsolvent-induced phase separation method including the following steps (1) to (4).
  • a nonsolvent-induced phase separation method including the following steps (1) to (4).
  • Step of preparing a composition for forming a porous membrane (2) Step of applying the above-mentioned composition for forming a porous membrane to a porous support (3) Step of bringing the coated porous support into contact with a non-solvent (4) Step of drying the porous support after the above-mentioned contact
  • steps (1) to (4) (1) Step of preparing a composition for forming a porous membrane (2) Step of applying the above-mentioned composition for forming a porous membrane to a porous support (3) Step of bringing the coated porous support into contact with a non-solvent (4) Step of drying the porous support after the above-mentioned contact.
  • Step (1) is a step of preparing a composition for forming a porous membrane.
  • the composition for forming a porous film is prepared by mixing the above-mentioned organic polymer resin, inorganic particles, solvent, and nonionic surfactant.
  • the mixing method is not particularly limited; for example, a resin solution in which an organic polymer resin is dissolved in a solvent and a dispersion liquid (slurry) in which inorganic particles are dispersed in a solvent are prepared, and then a nonionic interface between them is prepared. It may also be mixed with an activator.
  • the above-mentioned solvent is not particularly limited as long as it has the property of dissolving the above-mentioned organic polymer resin, and examples thereof include N-methyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, Examples include dimethyl sulfoxide. These solvents may be used alone or in combination of two or more.
  • the content of the organic polymer resin in the resin solution is not particularly limited, but is preferably 10 to 50% by mass, more preferably 15 to 45% by mass, and 20 to 40% by mass. is even more preferable.
  • the content of inorganic particles in the dispersion is not particularly limited, but is preferably 20 to 80% by mass, more preferably 30 to 70% by mass, and even more preferably 40 to 60% by mass. preferable.
  • the dispersion liquid may further contain a dispersant in order to improve the dispersibility of the inorganic particles.
  • a dispersant include known dispersants such as phosphoric acid polyester, polyvinylpyrrolidone, and polyacrylic acid.
  • the resin solution and the dispersion preferably contain 10 to 60 parts by mass of organic polymer resin, more preferably 15 to 55 parts by mass, still more preferably 20 to 50 parts by mass, based on 100 parts by mass of inorganic particles. It is preferable to mix so that
  • nonionic surfactants examples include glycerin fatty acid esters, sorbitan acid fatty acid esters, polyoxyethylene alkyl ethers, polyoxyalkylene derivatives, and the like. These solvents may be used alone or in combination of two or more.
  • the composition for forming a porous membrane facilitates the diffusion of water into the impregnated portion in step (3). This facilitates the formation of voids with a size of 0.5 to 10 ⁇ m between the porous membrane and the porous support in the impregnated portion.
  • Step (2) is a step of applying the porous film-forming composition obtained in step (1) above to a porous support.
  • the coating method is not particularly limited, and known apparatuses such as die coating, spin coating, gravure coating, curtain coating, spraying, methods using applicators, coaters, etc. can be used.
  • the amount of the composition for forming a porous membrane to be applied is not particularly limited, but it may be sufficient as long as the composition for forming a porous membrane is impregnated into the entire porous support.
  • the porous film forming composition is applied onto one surface of the porous support until it permeates the other surface of the porous support. Impregnation is preferred.
  • Step (3) is a step of bringing the porous support coated with the porous film-forming composition in step (2) into contact with a non-solvent.
  • the non-solvent diffuses into the coated porous film-forming composition, and the organic polymer resin that is insoluble in the non-solvent solidifies.
  • the solvent in the porous membrane-forming composition that can be dissolved in the non-solvent is eluted. As such phase separation occurs, the organic polymer resin solidifies, and a membrane containing inorganic particles and having pores (porous membrane) is formed.
  • Examples of the method of bringing the porous support into contact with the nonsolvent include a method of immersing the porous support in the nonsolvent (coagulation bath).
  • the non-solvent is not particularly limited as long as it has the property of not substantially dissolving the organic polymer resin; for example, water (ion-exchanged water); lower alcohols such as methanol, ethanol, and propyl alcohol; or , and mixed solvents thereof, among which water is preferred from the viewpoint of economy and drainage treatment.
  • the non-solvent may also contain a small amount of the same solvent as the solvent contained in the coating film.
  • the porous support is preferably brought into contact with a non-solvent as soon as possible after the coating, since voids of the above-mentioned size are likely to be formed between the porous membrane and the porous support. If the time between application and contact with the non-solvent is long, the coated surface will solidify before contact with the non-solvent, making it difficult for the non-solvent to penetrate and forming a porous membrane with the desired structure. may become difficult. It is preferable that the time after the above-mentioned application is 20 seconds or less before contacting with the non-solvent. This facilitates the formation of voids with a size of 0.5 to 10 ⁇ m between the porous membrane and the porous support in the impregnated portion.
  • Step (4) is a step of drying the porous support after being brought into contact with the non-solvent in step (3) above.
  • a porous film can be formed by drying the coating film solidified in step (3) above to remove the non-solvent.
  • the above-mentioned drying is not particularly limited, and can be performed by a known method.
  • the drying temperature is preferably 60 to 150°C, more preferably 70 to 140°C.
  • the drying time is preferably 0.5 to 120 minutes, more preferably 1 to 60 minutes, and even more preferably 1 to 30 minutes.
  • the diaphragm for alkaline water electrolysis of the present invention can be easily produced by the steps (1) to (4) described above.
  • An alkaline water electrolysis cell comprising an anode (anode), a cathode (cathode), and the diaphragm for alkaline water electrolysis disposed between the anode and the cathode is also part of the present invention.
  • the side separated by the alkaline water electrolysis diaphragm and where the anode is present is an anode chamber
  • the side where the cathode is present is a cathode chamber.
  • Examples of the anode and cathode include known electrodes including a conductive substrate containing nickel or a nickel alloy.
  • the diaphragm for alkaline water electrolysis of the present invention has gas permeation anisotropy, the orientation of the diaphragm for alkaline water electrolysis is changed depending on the target gas to be produced and water splitting is carried out to achieve the desired result.
  • the purity of the generated gas can be increased.
  • one main surface of the diaphragm for alkaline water electrolysis consists of an impregnated part formed by impregnating the porous support with the porous membrane, and the other main surface consists of a non-impregnated part, the impregnated part If water electrolysis is performed by installing a diaphragm so that the main surface of the diaphragm is oriented toward the anode side, the permeation of oxygen gas from the anode side to the cathode side is suppressed, thereby increasing the purity of the hydrogen gas generated at the cathode. be able to.
  • Alkaline water electrolysis method using an alkaline water electrolysis cell equipped with the diaphragm for alkaline water electrolysis of the present invention is also one of the present invention.
  • the alkaline water electrolysis cell includes an anode, a cathode, and a diaphragm for alkaline water electrolysis disposed between the anode and the cathode.
  • the diaphragm for alkaline water electrolysis includes a porous membrane containing an organic polymer resin and inorganic particles, and a porous support, the porous membrane includes an impregnated part in which the porous support is impregnated, and a pair of main It has a surface.
  • the impregnated portion has a void having a size of 0.5 to 10 ⁇ m between the porous membrane and the porous support.
  • the diaphragm for alkaline water electrolysis has gas permeation anisotropy in which the gas permeability from one of the pair of main surfaces to the other is different from the gas permeability from the other of the pair of main surfaces to the one. .
  • alkaline water electrolysis is performed by changing the direction of the alkaline water electrolysis diaphragm depending on the target generated gas among the generated gases on the anode side and the cathode side. conduct.
  • the alkaline water electrolysis method of the present invention is not particularly limited, and any known method can be used. For example, this can be carried out by filling the above-mentioned alkaline water electrolysis cell with an electrolytic solution and applying a current in the electrolytic solution.
  • an alkaline aqueous solution in which an electrolyte such as potassium hydroxide or sodium hydroxide is dissolved is used.
  • concentration of the electrolyte in the electrolytic solution is not particularly limited, but is preferably 20 to 40% by mass, since the electrolytic efficiency can be further improved.
  • temperature at which electrolysis is performed is preferably 50 to 120°C, more preferably 80 to 90°C, since the ionic conductivity of the electrolytic solution can be further improved and the electrolytic efficiency can be further improved.
  • the current can be applied under known conditions and methods, and is usually 0.2 A/cm 2 or more, preferably 0.3 A/cm 2 or more.
  • the higher the current density applied the more hydrogen and oxygen can be obtained in a short period of time, and therefore hydrogen can be produced more efficiently.
  • the current density is too high, the generated hydrogen and oxygen may adhere to the ion-permeable membrane and electrodes and inhibit the reaction, and the electrode reaction resistance will increase the overvoltage, which will increase the electrolytic voltage and prevent electrolysis.
  • the amount of electricity required to do this increases, and the electrolytic efficiency deteriorates. For this reason, it is preferable to adjust the current density to be high so that the electrolysis voltage is about 2V, for example within a range not exceeding 1.5 to 2.5V.
  • the measurement conditions for various physical properties, etc. are as follows.
  • ⁇ Average particle diameter of inorganic particles> A laser diffraction/scattering particle size distribution measuring device (product The particle size distribution was measured by adjusting the transmittance of the red laser to 90 to 98% and the transmittance of the blue laser to 85 to 92% using an LA-950 (manufactured by Horiba, Ltd.).
  • the median diameter (d50) in the standard particle size distribution was defined as the average particle diameter ( ⁇ m) of the inorganic particles.
  • the specific surface area of the inorganic particles was measured using a BET specific surface area meter (trade name: Macsorb HM model-1210, manufactured by Mountech Co., Ltd.). Specifically, 1 g of inorganic particles (powder) was placed in a cell as a measurement sample, and degassing was performed at 200° C. while nitrogen gas was flowing through the cell. After the degassing treatment, the cell was immersed in liquid nitrogen while nitrogen gas was flowing through the cell to adsorb nitrogen onto the measurement sample at a temperature of -196°C. Next, the specific surface area was measured by the BET method by keeping the cell at room temperature and measuring the amount of nitrogen desorbed. The measurement was performed three times for each sample, and the average value was taken as the specific surface area (m 2 /g) of the inorganic particles.
  • ⁇ Film thickness> The thickness of the porous support and the obtained diaphragm for alkaline water electrolysis was measured using a Digimatic micrometer (trade name: Coolant Proof Micrometer MDC-PXT, manufactured by Mitutoyo Corporation). Measurements were made at 10 arbitrary points, and the average value was taken as the film thickness.
  • the thickness of the impregnated part of the diaphragm for alkaline water electrolysis was the same as the thickness of the porous support, and the thickness of the non-impregnated part was calculated by subtracting the thickness of the impregnated part from the thickness of the diaphragm after impregnation. .
  • FE-SEM product name: JSM-7600F, manufactured by JEOL Ltd.
  • An observation image magnification: 1,000 times
  • the porous membrane, porous support, and voids were identified from the obtained observation image using analysis software (trade name: Image-Pro Premier, Media Cybernetics).
  • line segments perpendicular to the surface of the porous support were drawn from the porous support to the surface of the porous membrane at intervals of 10 ⁇ m along the surface of the porous support observed in the form of fibers.
  • the lengths of all line segments were measured, and their average value was taken as the pore size between the porous support and the porous membrane in one field of view. Similar treatment was performed on the remaining 9 fields of view, and the average value of the 10 fields of view was taken as the void size between the porous support and the porous membrane.
  • FE-SEM product name: JSM-7600F, manufactured by JEOL Ltd.
  • An observation image magnification: 200 times
  • the obtained surface observation image was analyzed using analysis software (trade name: Image-Pro Premier, manufactured by Media Cybernetics). First, five brightness points were designated for each of the portions that were determined to be voids and the portions that were determined to be porous membranes according to the analyst's recognition.
  • Cell elements include an anode (Ni mesh base material coated with Ni-Co oxide) and a cathode (Ni mesh base material coated with Ru-Ln oxide) with an electrode area of 27.8 cm 2 ; It consists of a current collector, an end plate, a chamber block, and a joint.
  • the anode and cathode have a zero-gap structure in which they are pressed against the diaphragm for alkaline water electrolysis using the spring structure of the current collector.
  • a 30% by mass potassium hydroxide aqueous solution was circulated through both the anode and cathode at a rate of 20 mL/min.
  • the anolyte and catholyte are circulated and supplied in completely separate systems, and the two solutions are not mixed in the reservoir or piping system.
  • the temperature was 80° C. for both the anode and cathode, and the outlet of the pipe was opened to atmospheric pressure.
  • a water bridge was installed between the anode and cathode piping to create a structure in which both the anode and cathode had the same pressure.
  • the electrolytic conditions were such that a constant current density was applied from 1.0 to 0.2 A cm -2 in 0.2 A cm -2 increments.
  • the waiting time at each constant current density is 1.0 Acm -2 for 2 hours, 0.8 Acm -2 for 3 hours, 0.6 Acm -2 for 4 hours, 0.4 Acm -2 for 5 hours, 0.2 Acm -2
  • gas purity was measured by gas chromatography and repeated 4 to 5 times until the gas purity value stabilized.
  • the purity of oxygen gas at the anode and the purity of hydrogen gas at the cathode as gas produced during alkaline water electrolysis were measured.
  • the gas is passed through a water removal piping system that cools the gas at 0 to 1°C, and then subjected to gas chromatography (product name: The purity of oxygen gas and hydrogen gas was measured using GC-2014A (manufactured by Shimadzu Corporation).
  • Example 1 ⁇ Preparation of inorganic particle dispersion> 100 parts by mass of magnesium hydroxide particles (plate-shaped, average particle diameter 0.36 ⁇ m, specific surface area: 10 m 2 /g, aspect ratio 4.7) and 60 parts by mass of N-methyl-2-pyrrolidone (manufactured by Mitsubishi Chemical Corporation) and 3 parts by mass of phosphoric acid polyester were mixed, and a dispersion treatment was performed for 30 minutes using a bead mill using zirconia beads. Thereafter, the zirconia beads were removed to obtain a magnesium hydroxide particle dispersion.
  • composition for forming porous film 200 parts by mass of the obtained magnesium hydroxide particle dispersion and polysulfone resin (trade name: Ultrason S3010, manufactured by BASF) were dissolved in N-methyl-2-pyrrolidone (manufactured by Mitsubishi Chemical Corporation) at a concentration of 35% by mass. 100 parts by mass of the polysulfone resin solution and 1 part by mass of sorbitan monooleate were mixed at room temperature using an autorotation-revolution mixer (trade name: Awatori Rentaro ARE-500, manufactured by Shinky Co., Ltd.) at room temperature. Mixing was performed for 10 minutes at 1000 min ⁇ 1 . Thereafter, filtration was performed through a SUS mesh to obtain a composition for forming a porous membrane.
  • autorotation-revolution mixer trade name: Awatori Rentaro ARE-500, manufactured by Shinky Co., Ltd.
  • the composition for forming a porous film was applied with an applicator onto one surface of a nonwoven fabric (fabric weight: 100 g/m 2 , film thickness: 190 ⁇ m) made of polyphenylene sulfide fibers (coating amount: 28 mg/cm 2 ), and the composition was applied to the other surface.
  • the nonwoven fabric was impregnated with the composition for forming a porous membrane until it penetrated the surface.
  • the nonwoven fabric impregnated with the composition for forming a porous membrane was immersed in a water tank and bathed in water for 3 minutes at room temperature to obtain a water-containing membrane consisting of magnesium hydroxide particles, polysulfone resin, and nonwoven fabric.
  • the obtained membrane was dried in a dryer at 80° C. for 30 minutes to obtain a diaphragm for alkaline water electrolysis.
  • the thickness of the obtained diaphragm for alkaline water electrolysis was 260 ⁇ m
  • the thickness of the non-impregnated portion was 70 ⁇ m
  • the thickness of the impregnated portion was 190 ⁇ m.
  • the void size between the porous membrane of the diaphragm and the nonwoven fabric was 2.6 ⁇ m, and the void amount ratio was 2%.
  • Example 2 ⁇ Preparation of inorganic particle dispersion> 200 parts by mass of barium sulfate particles (plate-like, average particle diameter 0.90 ⁇ m, specific surface area: 5 m 2 /g, aspect ratio 5.2), 150 parts by mass of N,N-dimethylacetamide (manufactured by Mitsubishi Gas Chemical Co., Ltd.) , and 5 parts by mass of polyvinylpyrrolidone were mixed, and a dispersion treatment was performed for 30 minutes using a bead mill using zirconia beads. Thereafter, the zirconia beads were removed to obtain a barium sulfate particle dispersion.
  • barium sulfate particles plate-like, average particle diameter 0.90 ⁇ m, specific surface area: 5 m 2 /g, aspect ratio 5.2
  • N,N-dimethylacetamide manufactured by Mitsubishi Gas Chemical Co., Ltd.
  • polyvinylpyrrolidone 5 parts by mass of polyvinylpyrrolidone
  • composition for forming porous film 200 parts by mass of the obtained barium sulfate particle dispersion and polyether sulfone resin (trade name: Ultrason E3010, manufactured by BASF) were mixed into N,N-dimethylacetamide (manufactured by Mitsubishi Gas Chemical) at a concentration of 35% by mass. 100 parts by mass of the dissolved polyether sulfone resin solution and 2 parts by mass of sorbitan monooleate were mixed at room temperature using a rotation-revolution mixer (trade name: Awatori Rentaro ARE-500, manufactured by Shinky Co., Ltd.). The mixture was mixed for about 10 minutes at a rotational speed of 1000 min -1 . Thereafter, filtration was performed through a SUS mesh to obtain a composition for forming a porous membrane.
  • a rotation-revolution mixer trade name: Awatori Rentaro ARE-500, manufactured by Shinky Co., Ltd.
  • the composition for forming a porous film was applied with an applicator onto one surface of a nonwoven fabric (fabric weight: 60 g/m 2 , film thickness: 130 ⁇ m) made of polyphenylene sulfide fibers (coating amount: 20 mg/cm 2 ), and the other surface was
  • the nonwoven fabric was impregnated with the composition for forming a porous membrane until it penetrated the surface.
  • the nonwoven fabric impregnated with the composition for forming a porous membrane was immersed in a water tank and bathed in water for 3 minutes at room temperature to obtain a water-containing membrane consisting of barium sulfate particles, polyether sulfone resin, and nonwoven fabric.
  • the obtained membrane was dried in a dryer at 80° C. for 30 minutes to obtain a diaphragm for alkaline water electrolysis.
  • the membrane thickness of the obtained diaphragm for alkaline water electrolysis was 145 ⁇ m
  • the thickness of the non-impregnated part was 15 ⁇ m
  • the thickness of the impregnated part was 130 ⁇ m
  • the void size between the porous membrane and the nonwoven fabric of the diaphragm was 0.
  • the diameter was 6 ⁇ m
  • the percentage of voids was 1%.
  • Example 3 ⁇ Preparation of inorganic particle dispersion> 200 parts by mass of zirconium oxide particles (spherical, average particle diameter 0.02 ⁇ m, specific surface area: 25 m 2 /g, aspect ratio 1.1), 150 parts by mass of N-methyl-2-pyrrolidone (manufactured by Mitsubishi Chemical Corporation), The mixture was mixed with 5 parts by mass of polyacrylic acid and subjected to a dispersion treatment for 30 minutes using a bead mill using zirconia beads. Thereafter, the zirconia beads were removed to obtain a zirconium oxide particle dispersion.
  • composition for forming porous film 200 parts by mass of the obtained zirconium oxide particle dispersion and polyphenylsulfone resin (trade name: Ultrason P3010, manufactured by BASF) were mixed into N-methyl-2-pyrrolidone (manufactured by Mitsubishi Chemical Corporation) at a concentration of 35% by mass. 100 parts by mass of the dissolved polyphenylsulfone resin solution and 5 parts by mass of sorbitan monolaurate were mixed at room temperature using a rotation-revolution mixer (trade name: Awatori Rentaro ARE-500, manufactured by Shinky Co., Ltd.). The mixture was mixed for about 10 minutes at a rotational speed of 1000 min -1 . Thereafter, filtration was performed through a SUS mesh to obtain a composition for forming a porous membrane.
  • a rotation-revolution mixer trade name: Awatori Rentaro ARE-500, manufactured by Shinky Co., Ltd.
  • the composition for forming a porous film was applied with an applicator onto one surface of a nonwoven fabric made of polypropylene fibers (fabric weight: 80 g/m 2 , film thickness: 160 ⁇ m) (coating amount: 76 mg/cm 2 ), and then applied to the other surface.
  • the composition for forming a porous membrane was impregnated into the nonwoven fabric until it penetrated into the composition. After 20 seconds of application, the nonwoven fabric impregnated with the composition for forming a porous film was immersed in a water bath and bathed at room temperature for 3 minutes to solidify the coated film to obtain a water-containing film. The obtained membrane was dried in a dryer at 80° C.
  • the membrane thickness of the obtained diaphragm for alkaline water electrolysis was 310 ⁇ m
  • the thickness of the non-impregnated part was 150 ⁇ m
  • the thickness of the impregnated part was 160 ⁇ m
  • the void size between the porous membrane and the nonwoven fabric of the diaphragm was 9.
  • the diameter was 5 ⁇ m
  • the percentage of voids was 8%.
  • Example 4 ⁇ Preparation of inorganic particle dispersion> 200 parts by mass of zirconium oxide particles (spherical, average particle diameter 0.36 ⁇ m, specific surface area: 10 m 2 /g, aspect ratio 1.1), 150 parts by mass of N-methyl-2-pyrrolidone (manufactured by Mitsubishi Chemical Corporation), The mixture was mixed with 6 parts by mass of phosphoric acid polyester and subjected to a dispersion treatment for 30 minutes using a bead mill using zirconia beads. Thereafter, the zirconia beads were removed to obtain a zirconium oxide particle dispersion.
  • composition for forming porous film 200 parts by mass of the obtained zirconium oxide particle dispersion and polysulfone resin (trade name: Ultrason S3010, manufactured by BASF) were dissolved in N-methyl-2-pyrrolidone (manufactured by Mitsubishi Chemical Corporation) at a concentration of 35% by mass. 100 parts by mass of the polysulfone resin solution and 5 parts by mass of sorbitan monolaurate were mixed at room temperature at a rotational speed of 1000 min using a rotation-revolution mixer (trade name: Awatori Rentaro ARE-500, manufactured by Shinky Co., Ltd.). -1 for about 10 minutes. Thereafter, filtration was performed through a SUS mesh to obtain a composition for forming a porous membrane.
  • polysulfone resin trade name: Ultrason S3010, manufactured by BASF
  • the composition for forming a porous film was applied with an applicator onto one surface of a nonwoven fabric (fabric weight: 100 g/m 2 , film thickness: 190 ⁇ m) made of polyphenylene sulfide fibers (coating amount: 45 mg/cm 2 ), and the composition was applied to the other surface.
  • the nonwoven fabric was impregnated with the composition for forming a porous membrane until it penetrated the surface. After 20 seconds of application, the nonwoven fabric impregnated with the composition for forming a porous film was immersed in a water bath and bathed at room temperature for 3 minutes to solidify the coated film to obtain a water-containing film.
  • the obtained membrane was dried in a dryer at 80° C. for 30 minutes to obtain a diaphragm for alkaline water electrolysis.
  • the membrane thickness of the obtained diaphragm for alkaline water electrolysis was 260 ⁇ m
  • the thickness of the non-impregnated part was 70 ⁇ m
  • the thickness of the impregnated part was 190 ⁇ m
  • the void size between the porous membrane and the nonwoven fabric of the diaphragm was 2.
  • the diameter was 4 ⁇ m, and the percentage of voids was 2%.
  • inorganic particle dispersion > 200 parts by mass of zirconium oxide particles (spherical, average particle diameter 0.02 ⁇ m, specific surface area: 25 m 2 /g, aspect ratio 1.1), 100 parts by mass of N-methyl-2-pyrrolidone (manufactured by Mitsubishi Chemical Corporation), 2 parts by mass of polyvinylpyrrolidone were mixed, and a dispersion treatment was performed for 30 minutes using a bead mill using zirconia beads. Thereafter, the zirconia beads were removed to obtain a zirconium oxide particle dispersion.
  • composition for forming porous film > 200 parts by mass of the obtained zirconium oxide particle dispersion and polysulfone resin (trade name: Ultrason S3010, manufactured by BASF) were dissolved in N-methyl-2-pyrrolidone (manufactured by Mitsubishi Chemical Corporation) at a concentration of 35% by mass. and 100 parts by mass of the polysulfone resin solution were mixed at room temperature for about 10 minutes at a rotational speed of 1000 min -1 using a rotation-revolution mixer (trade name: Awatori Rentaro ARE-500, manufactured by Shinky Co., Ltd.). Thereafter, filtration was performed through a SUS mesh to obtain a composition for forming a porous membrane.
  • polysulfone resin trade name: Ultrason S3010, manufactured by BASF
  • the composition for forming a porous film was applied with an applicator onto one surface of a nonwoven fabric (fabric weight: 100 g/m 2 , film thickness: 90 ⁇ m) made of polyphenylene sulfide fibers (coating amount: 59 mg/cm 2 ), and the other surface was
  • the nonwoven fabric was impregnated with the composition for forming a porous membrane until it penetrated the surface. After 60 seconds of application, the nonwoven fabric impregnated with the composition for forming a porous film was immersed in a water bath and bathed at room temperature for 3 minutes to solidify the coated film to obtain a water-containing film.
  • the obtained membrane was dried in a dryer at 80° C.
  • the membrane thickness of the obtained diaphragm for alkaline water electrolysis was 240 ⁇ m
  • the thickness of the non-impregnated part was 150 ⁇ m
  • the thickness of the impregnated part was 90 ⁇ m
  • the void size between the porous membrane and the nonwoven fabric of the diaphragm was 0.
  • the diameter was 2 ⁇ m
  • the percentage of voids was 0.5%.

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PCT/JP2023/029162 2022-09-01 2023-08-09 アルカリ水電解用隔膜、アルカリ水電解セル、及び、アルカリ水電解方法 Ceased WO2024048235A1 (ja)

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WO2025040149A1 (zh) * 2023-08-23 2025-02-27 东丽纤维研究所（中国）有限公司 水电解槽用复合隔膜

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JP2014129563A (ja) 2012-12-28 2014-07-10 Asahi Kasei Corp アルカリ水電解用隔膜及びその製造方法
WO2016148302A1 (ja) * 2015-03-18 2016-09-22 旭化成株式会社 アルカリ水電解用隔膜、アルカリ水電解装置、水素の製造方法及びアルカリ水電解用隔膜の製造方法
JP2017002389A (ja) 2015-06-16 2017-01-05 川崎重工業株式会社 アルカリ水電解用隔膜及びその製造方法
JP2020527193A (ja) 2017-07-10 2020-09-03 アグフア−ゲヴエルト，ナームローゼ・フエンノートシヤツプ アルカリ加水分解に強化されたセパレーター
JP2021090909A (ja) * 2019-12-10 2021-06-17 株式会社日本触媒 アルカリ水電解用隔膜の製造方法
WO2022002904A1 (en) * 2020-07-03 2022-01-06 Agfa-Gevaert Nv A separator for alkaline water electrolysis

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JP2014129563A (ja) 2012-12-28 2014-07-10 Asahi Kasei Corp アルカリ水電解用隔膜及びその製造方法
WO2016148302A1 (ja) * 2015-03-18 2016-09-22 旭化成株式会社 アルカリ水電解用隔膜、アルカリ水電解装置、水素の製造方法及びアルカリ水電解用隔膜の製造方法
JP2017002389A (ja) 2015-06-16 2017-01-05 川崎重工業株式会社 アルカリ水電解用隔膜及びその製造方法
JP2020527193A (ja) 2017-07-10 2020-09-03 アグフア−ゲヴエルト，ナームローゼ・フエンノートシヤツプ アルカリ加水分解に強化されたセパレーター
JP2021090909A (ja) * 2019-12-10 2021-06-17 株式会社日本触媒 アルカリ水電解用隔膜の製造方法
WO2022002904A1 (en) * 2020-07-03 2022-01-06 Agfa-Gevaert Nv A separator for alkaline water electrolysis

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2025040149A1 (zh) * 2023-08-23 2025-02-27 东丽纤维研究所（中国）有限公司 水电解槽用复合隔膜

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