WO2023248992A1 - Film composite - Google Patents

Film composite Download PDF

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Publication number
WO2023248992A1
WO2023248992A1 PCT/JP2023/022670 JP2023022670W WO2023248992A1 WO 2023248992 A1 WO2023248992 A1 WO 2023248992A1 JP 2023022670 W JP2023022670 W JP 2023022670W WO 2023248992 A1 WO2023248992 A1 WO 2023248992A1
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WIPO (PCT)
Prior art keywords
composite membrane
base material
mass
porous base
inorganic compound
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PCT/JP2023/022670
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English (en)
Japanese (ja)
Inventor
優 長尾
敬也 小川
太陽 谷内
将基 吉田
敏樹 中薗
Original Assignee
帝人株式会社
国立大学法人京都大学
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Application filed by 帝人株式会社, 国立大学法人京都大学 filed Critical 帝人株式会社
Publication of WO2023248992A1 publication Critical patent/WO2023248992A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/26—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by elimination of a solid phase from a macromolecular composition or article, e.g. leaching out

Definitions

  • the present disclosure relates to composite membranes.
  • a composite membrane in which the pores of a porous base material are filled with proton-conducting inorganic nanoparticles and a proton-conducting polymer (for example, see Patent Document 1).
  • Perfluorosulfonic acid polymers such as Nafion (registered trademark, hereinafter the same) are known as proton conductive polymers. Although perfluorosulfonic acid polymers have excellent proton conductivity, they easily absorb water, and conventional composite membranes filled with proton conductive polymers were unable to block the permeation of water itself.
  • ⁇ 4> The composite membrane according to any one of ⁇ 1> to ⁇ 3>, which is water impermeable.
  • ⁇ 5> The composite membrane according to any one of ⁇ 1> to ⁇ 4>, which has a water contact angle of 68° or more.
  • ⁇ 6> The composite membrane according to any one of ⁇ 1> to ⁇ 5>, wherein the mass filling rate of the zirconium phosphonate inorganic compound calculated from the following formula 1 is 40% by mass or more.
  • Mass filling rate (mass%) (composite membrane basis weight - base material basis weight) / composite membrane basis weight x 100...
  • the zirconium phosphonate inorganic compound is Zr(HPO 4 ) 2 , Zr(HPO 4 ) 2 ⁇ nH 2 O, Zr(O 3 PR 1 -SO 3 H) 2 , Zr(O 3 P -R 1 -SO 3 H) 2.nH 2 O , Zr(O 3 PR 2 -SO 3 H) 2-x (O 3 PR 3 -COOH) x , Zr(O 3 PR 2 -SO 3 H) 2-x (O 3 PR 3 -COOH) x ⁇ nH 2 O, Zr(O 3 PR 4 -NH 2 ) 2 , Zr(O 3 PR 5 -(PO 3 H 2 ) a ) 2 (wherein R 1 - R 4 each independently represent a divalent organic group.
  • R 5 represents a 1+a-valent organic group.
  • a is bonded to R 5 (PO 3 H 2 ) is an integer of 1 or 2 or more indicating the number of groups.
  • n is a real number greater than 0 indicating the number of hydration water.
  • x is a real number greater than 0 and less than 2.
  • ⁇ 9> The composite membrane according to any one of ⁇ 1> to ⁇ 8>, wherein the porous base material has an average pore diameter of 40 nm or less.
  • step includes not only a step that is independent from other steps, but also a step that cannot be clearly distinguished from other steps, as long as the purpose of the step is achieved.
  • numerical ranges indicated using “ ⁇ ” include the numerical values written before and after " ⁇ " as minimum and maximum values, respectively.
  • the upper limit or lower limit described in one numerical range may be replaced with the upper limit or lower limit of another numerical range described step by step.
  • the upper limit or lower limit of the numerical range may be replaced with the values shown in the Examples.
  • each component may contain multiple types of applicable substances.
  • the content rate or content of each component is the total content rate or content of the multiple types of substances present in the composition, unless otherwise specified. means quantity.
  • the term “layer” or “film” refers to the case where the layer or film is formed only in a part of the region, in addition to the case where the layer or film is formed in the entire region when observing the region where the layer or film is present. This also includes cases where it is formed.
  • the term “laminate” refers to stacking layers, and two or more layers may be bonded, or two or more layers may be removable.
  • the composite membrane of the present disclosure includes: a porous base material containing a hydrophobic resin; a zirconium phosphonate-based inorganic compound that is filled in the pores of the porous base material as a continuous body and adheres to the porous base material; has.
  • the phrase "filled with a zirconium phosphonate inorganic compound as a continuum" refers to a state in which the zirconium phosphonate inorganic compound is adhered to the pores of a porous base material without using a binder or the like. . That is, it means that the particles of the zirconium phosphonate inorganic compound are not bound to each other by a binder or the like.
  • the shape of the particles of the zirconium phosphonate-based inorganic compound is spherical, elliptical, plate-like, acicular, or amorphous. Whether the zirconium phosphonate inorganic compound is "filled as a continuum" can be confirmed by observing the cross section of the composite membrane with a transmission electron microscope (TEM) or a scanning electron microscope (SEM). .
  • TEM transmission electron microscope
  • SEM scanning electron microscope
  • a zirconium phosphonate-based inorganic compound is attached as a proton conductive component in a state in which the pores of a porous base material are filled. Therefore, the composite membrane of the present disclosure can have proton conductivity. Furthermore, in the composite membrane of the present disclosure, the pores of the porous base material are filled with the zirconium phosphonate inorganic compound, which is a proton conductive component, in the form of a continuum.
  • the zirconium phosphonate inorganic compound is a porous substrate
  • a binder resin such as a proton-conducting polymer
  • the composite membrane of the present disclosure has excellent water barrier properties.
  • the water barrier properties of the zirconium phosphonate-based inorganic compound are higher than that of Nafion, which is an example of a proton-conducting polymer, as shown by the "water contact angle" evaluation in the Examples of the present application.
  • porous base material the zirconium phosphonate-based inorganic compound, and other elements such as the proton conductive polymer used as necessary will be explained, which constitute the composite membrane of the present disclosure.
  • the composite membrane of the present disclosure has a porous base material containing a hydrophobic resin.
  • the hydrophobic resin contained in the porous base material is not particularly limited, and is appropriately selected depending on the physical properties required of the composite membrane.
  • a fluororesin or a hydrocarbon resin that has excellent mechanical strength, chemical stability, heat resistance, etc. can be used.
  • fluororesins examples include polytetrafluoroethylene (PTFE), polychlorotrifluoroethylene (CTFE), polyvinylidene fluoride (PVDF), tetrafluoroethylene-hexafluoropropylene copolymer (FEP), and tetrafluoroethylene-perfluoroethylene.
  • PTFE polytetrafluoroethylene
  • CFE polychlorotrifluoroethylene
  • PVDF polyvinylidene fluoride
  • FEP tetrafluoroethylene-hexafluoropropylene copolymer
  • ECTFE chlorotrifluoroethylene-ethylene copolymer
  • Hydrocarbon resins include polyolefins such as polyethylene, polypropylene, polybutylene, polymethylpentene, copolymers of polypropylene and polyethylene, heat-resistant crosslinked polyethylene, polycarbonates, polyimides, polyesters, polyethersulfones, polyetherketones, Examples include polyetheretherketone, polysulfone, polysulfide, polyamide, polyamideimide, polyphenylene, polyether, polyetherimide, polyetheramide, and the like.
  • the porous base material may be a microporous membrane or a fibrous base material (nonwoven fabric, woven fabric, etc.), but a microporous membrane is preferred.
  • a microporous polyolefin membrane is preferable from the viewpoints of chemical stability, mechanical strength, and hydrophobicity.
  • a microporous membrane containing polyolefin is referred to as a "microporous polyolefin membrane.”
  • a microporous membrane refers to a membrane that has a structure in which a large number of fine pores are connected to each other, and allows gas or liquid to pass from one surface to the other. do.
  • the microporous polyolefin membrane preferably has a three-dimensional network structure made of polyolefin fibrils.
  • polystyrene resin examples include polyethylene, polypropylene, polybutylene, polymethylpentene, and a copolymer of polypropylene and polyethylene.
  • polyethylene is preferred, and high-density polyethylene, a mixture of high-density polyethylene and ultra-high molecular weight polyethylene, etc. are preferred.
  • polyolefin microporous membrane is a polyethylene microporous membrane in which the polyolefin contained is only polyethylene.
  • polyolefin microporous membrane is a microporous membrane containing polypropylene from the viewpoint of having heat resistance that does not easily rupture when exposed to high temperatures.
  • microporous polyolefin membrane is a microporous polyolefin membrane containing a mixture of at least polyethylene and polypropylene.
  • microporous polyolefin membrane is a microporous polyolefin membrane having a laminated structure of two or more layers, at least one layer containing polyethylene, and at least one layer containing polypropylene.
  • the weight average molecular weight (Mw) of the polyolefin contained in the polyolefin microporous membrane is preferably 500,000 to 5,000,000. When the Mw of the polyolefin is 500,000 or more, sufficient mechanical properties can be imparted to the microporous membrane. When the Mw of the polyolefin is 5 million or less, it is easy to form a microporous membrane.
  • the weight average molecular weight (Mw) of the polyethylene contained in the microporous polyolefin membrane is preferably 800,000 or more, more preferably 1,000,000 or more, and even more preferably 1,100,000 or more, from the viewpoint of densifying the porous structure of the microporous membrane. . From the viewpoint of increasing the porosity of the microporous polyolefin membrane, the weight average molecular weight (Mw) of the polyethylene contained in the microporous polyolefin membrane is preferably 4 million or less, more preferably 3.5 million or less, and even more preferably 3 million or less.
  • the weight average molecular weight of the polyolefin and polyethylene constituting the polyolefin microporous membrane was determined by heating and dissolving the polyolefin microporous membrane in o-dichlorobenzene and performing gel permeation chromatography (system: Waters Alliance GPC 2000 model, column: GMH6- HT and GMH6-HTL) under conditions of a column temperature of 140°C and a flow rate of 1.0 mL/min. Monodisperse polystyrene (manufactured by Tosoh Corporation) is used for molecular weight calibration.
  • a polyolefin composition in the present disclosure, means a mixture of polyolefins containing two or more types of polyolefins, and when the polyolefin contained is only polyethylene, it is referred to as a polyethylene composition).
  • a polyethylene composition examples include microporous membranes containing The polyolefin composition forms a network structure as it fibrillates during stretching, and has the effect of increasing the porosity of the microporous polyolefin membrane.
  • the polyolefin composition is preferably a polyolefin composition containing 5% by mass to 90% by mass of ultra-high molecular weight polyethylene having a weight average molecular weight of 9 ⁇ 10 5 or more based on the total amount of polyolefin, and preferably 10% by mass to 88% by mass. %, more preferably a polyolefin composition containing 15% to 85% by mass.
  • the polyolefin composition consists of ultra-high molecular weight polyethylene having a weight average molecular weight of 9 ⁇ 10 5 or more and high molecular weight polyethylene having a weight average molecular weight of 2 ⁇ 10 5 to 8 ⁇ 10 5 and a density of 920 kg/m 3 to 960 kg/m 3 . It is preferable to use a polyolefin composition in which density polyethylene is mixed at a mass ratio of 5:95 to 95:5 (more preferably 10:90 to 90:10, still more preferably 15:85 to 85:15).
  • microporous polyolefin membrane is a microporous polyolefin membrane that has been subjected to a hydrophilic treatment.
  • Hydrophilized microporous polyolefin membranes include, for example, microporous polyolefin membranes whose surface is coated with a hydrophilic compound (e.g., ethylene-vinyl alcohol copolymer); Microporous polyolefin membranes subjected to plasma treatment or corona treatment; and the like.
  • the method for producing the polyolefin microporous membrane in the present disclosure is not particularly limited, and, for example, a method of producing it through the following steps (1) to (5) is preferable.
  • the polyolefin used as the raw material is as described above.
  • a polyolefin solution is prepared by dissolving polyolefin in a solvent.
  • the solvent include paraffin, liquid paraffin, paraffin oil, mineral oil, castor oil, tetralin, ethylene glycol, glycerin, decalin, toluene, xylene, diethyltriamine, ethyldiamine, dimethylsulfoxide, hexane, and the like.
  • the solvents may be used alone or in combination of two or more.
  • examples of volatile solvents include those having a boiling point of less than 300°C under atmospheric pressure, such as decalin, toluene, xylene, diethyltriamine, ethyldiamine, dimethyl sulfoxide, hexane, tetralin, ethylene glycol, and glycerin. It will be done.
  • examples of the nonvolatile solvent include solvents having a boiling point of 300° C. or higher at atmospheric pressure, such as paraffin, liquid paraffin, paraffin oil, mineral oil, and castor oil.
  • the mixed solvent a combination of decalin and liquid paraffin is preferred.
  • the polyolefin concentration of the polyolefin solution is preferably 1% by mass to 45% by mass, more preferably 10% by mass to 40% by mass.
  • the polyolefin concentration is 1% by mass or more, the gel composition obtained by cooling and gelling can be maintained so as not to be highly swollen by the solvent, so that it is difficult to deform and has good handling properties.
  • the polyolefin concentration is 45% by mass or less, the pressure during extrusion is suppressed, making it possible to maintain the discharge amount and resulting in excellent productivity.
  • solvent removal treatment Next, the solvent is removed from the gel composition.
  • a volatile solvent used in preparing the polyolefin solution
  • the solvent can be removed from the gel composition by evaporating it by heating or the like, which also serves as a preheating step.
  • a nonvolatile solvent used in preparing the polyolefin solution
  • the solvent can be removed by squeezing out under pressure. It is not necessary to completely remove the solvent.
  • the gel composition is stretched.
  • a relaxation treatment may be performed before the stretching treatment.
  • the gel-like composition is heated and uniaxially or biaxially stretched at a predetermined magnification by a conventional tenter method, roll method, rolling method, or a combination of these methods. Biaxial stretching may be done simultaneously or sequentially. Further, vertical multi-stage stretching or 3- or 4-stage stretching can also be performed.
  • the stretching temperature is preferably 80°C or higher and lower than the melting point of the polyolefin used for production, more preferably 90°C to 130°C. When the heating temperature is lower than the melting point, the gel-like composition is difficult to dissolve, so that stretching can be performed well.
  • the gel-like composition when the heating temperature is 80° C. or higher, the gel-like composition is sufficiently softened and can be stretched at a high magnification without rupturing the membrane during stretching.
  • the stretching ratio varies depending on the thickness of the original fabric, but it is preferably at least 2 times or more, preferably 4 times to 20 times, in the uniaxial direction. After stretching, heat setting is performed as necessary to provide thermal dimensional stability.
  • Extraction/Removal of Solvent The stretched gel composition is immersed in an extraction solvent to extract the solvent, particularly the nonvolatile solvent.
  • extraction solvents include hydrocarbons such as pentane, hexane, heptane, cyclohexane, decalin, and tetralin, chlorinated hydrocarbons such as methylene chloride, carbon tetrachloride, and methylene chloride, fluorinated hydrocarbons such as trifluoroethane, and diethyl. Easily volatile ethers such as ether and dioxane can be used.
  • solvents can be appropriately selected depending on the solvent used for preparing the polyolefin solution, particularly the nonvolatile solvent, and can be used alone or in combination.
  • the solvent extraction removes the solvent in the polyolefin microporous membrane to less than 1% by mass.
  • the average thickness of the porous base material is preferably 0.01 ⁇ m or more, more preferably 3 ⁇ m or more, and even more preferably 4 ⁇ m or more. From the viewpoint of reducing initial pressure loss, the average thickness of the porous base material is preferably 300 ⁇ m or less, more preferably 100 ⁇ m or less, and even more preferably 50 ⁇ m or less. The average thickness of the porous base material is preferably 0.01 ⁇ m to 300 ⁇ m, more preferably 3 ⁇ m to 100 ⁇ m, and even more preferably 4 ⁇ m to 50 ⁇ m.
  • the average film thickness of the porous base material is determined by measuring at 20 points using a contact type film thickness meter and averaging the results.
  • the porosity of the porous base material is preferably 10% or more, more preferably 30% or more, and even more preferably 40% or more from the viewpoint of the filling rate of the proton-conducting inorganic compound. From the viewpoint of the mechanical strength of the membrane, the porosity of the porous base material is preferably 95% or less, more preferably 90% or less, and even more preferably 80% or less. The porosity of the porous base material is preferably 10% to 95%, more preferably 30% to 90%, even more preferably 40% to 80%.
  • the porosity of the porous base material is determined by the following calculation method. That is, regarding constituent material 1, constituent material 2, constituent material 3, ..., constituent material n of the porous base material, the mass of each constituent material is W 1 , W 2 , W 3 , ..., W n (g/cm 2 ), the true density of each constituent material is d 1 , d 2 , d 3 , ..., d n (g/cm 3 ), and the film thickness is t (cm), then the porosity ⁇ (% ) is determined by the following formula.
  • the Gurley value of the porous base material is preferably 2 seconds/100 mL or more, more preferably 3 seconds/100 mL or more, and even more preferably 5 seconds/100 mL or more from the viewpoint of mechanical strength. From the viewpoint of reducing initial pressure loss, the Gurley value of the porous base material is preferably 100 seconds/100 mL or less, more preferably 90 seconds/100 mL or less, and even more preferably 70 seconds/100 mL or less.
  • the Gurley value of the porous base material is a value measured according to JIS P8117:2009.
  • the breaking strength of the porous base material is preferably 50 MPa to 400 MPa, more preferably 80 MPa to 300 MPa, from the viewpoint of mechanical strength.
  • the breaking strength of a porous substrate is measured as follows. First, a porous base material is cut to have a width of 25 mm and a length of 100 mm to obtain a test piece. Breaking strength is measured by using a tensile tester in accordance with JIS L1015:2010. In addition, in measuring the breaking strength, the distance between chucks is 100 mm, and the tensile speed is 50 mm/min. Furthermore, as the tensile tester, EZ-LX manufactured by Shimadzu Corporation or an equivalent device can be used.
  • the average pore diameter of the porous base material is preferably from 0.001 ⁇ m to 100 ⁇ m, more preferably from 0.005 ⁇ m to 3 ⁇ m, from the viewpoint of mechanical strength.
  • the average pore diameter of the porous base material is preferably 40 nm or less, more preferably 35 nm or less, and even more preferably 32 nm or less, from the viewpoint of filling the pores of the porous base material with the zirconium phosphonate-based inorganic compound.
  • the average pore diameter of the porous base material is preferably 1 nm or more, more preferably 5 nm or more, and even more preferably 10 nm or more.
  • the average pore diameter of the porous base material is preferably 1 nm to 40 nm, more preferably 5 nm to 35 nm, even more preferably 10 nm to 32 nm.
  • the average pore diameter of the porous substrate can be measured using a palm porometer in accordance with ASTM E1294-89.
  • a fluorine-based inert liquid is used for the immersion liquid.
  • the composite membrane of the present disclosure includes a zirconium phosphonate-based inorganic compound.
  • zirconium phosphonate-based inorganic compounds include Zr(HPO 4 ) 2 , Zr(HPO 4 ) 2 ⁇ nH 2 O, Zr(O 3 PR 1 -SO 3 H) 2 , Zr(O 3 PR 1 -SO 3 H) 2 ⁇ nH 2 O, Zr(O 3 PR 2 -SO 3 H) 2-x (O 3 PR 3 -COOH) x , Zr(O 3 PR 2 -SO 3 H) 2-x (O 3 PR 3 -COOH) x ⁇ nH 2 O, Zr(O 3 PR 4 -NH 2 ) 2 , Zr(O 3 PR 5 -(PO 3 H 2 ) a ) 2 (wherein R 1 - R 4 each independently represent a divalent organic group.
  • R 5 represents a 1+a-valent organic group.
  • a is bonded to R 5 (PO 3 H 2 ) is an integer of 1 or 2 or more indicating the number of groups.
  • n is a real number greater than 0 indicating the number of hydration water, and may be an integer of 1 or 2 or greater.
  • x is an integer greater than 0 (a real number less than 2).
  • Examples of the divalent organic group represented by R 1 to R 4 include alkylene groups such as methylene group, ethylene group, and propylene group, and phenylene group.
  • Examples of the 1+a-valent organic group represented by R 5 include alkylene groups such as a methylene group, ethylene group, and propylene group, and a phenylene group when R 5 is a divalent organic group.
  • R 5 is an organic group having a valence of 3 or more, examples include a group obtained by removing the number of hydrogen atoms obtained by subtracting 2 from the valence of R 5 from the above specific examples.
  • the organic group represented by R 1 to R 5 may contain a halogen atom, a hydroxyl group, or the like.
  • the organic group represented by R 1 to R 5 may contain one or more heteroatoms such as nitrogen atoms and oxygen atoms. More specific examples include zirconium phosphate, zirconium 1-hydroxyethane-1,1-diphosphonate, and zirconium nitrilotris(methylenephosphonate).
  • the method of filling the pores of the porous base material with the zirconium phosphonate inorganic compound as a continuous body and adhering it to the porous base material is not particularly limited.
  • it may be done as follows.
  • a zirconium phosphonate-based inorganic compound is produced by reacting a zirconium alkoxide, a chelating agent (surface modifier), and a catalyst in a solvent, resulting in a hydrolysis and polycondensation reaction of a metal alkoxide, generally called the sol-gel method.
  • a precursor is impregnated into the pores of the porous substrate.
  • the precursor is converted into a zirconium phosphonate inorganic compound, and the zirconium phosphonate inorganic compound is generated in the pores of the porous base material.
  • the pores of the porous base material can be filled with the zirconium phosphonate-based inorganic compound as a continuous body, and the zirconium phosphonate inorganic compound can be attached to the porous base material.
  • the zirconium phosphonate inorganic compound used in the present disclosure is produced by impregnating a precursor of the zirconium phosphonate inorganic compound into the pores of a porous base material, and then applying phosphonic acid to the zirconium phosphonate inorganic compound precursor. It may be obtained by adding .
  • the alkoxide of zirconium alkoxide has a linear or branched alkyl group, and the alkyl group preferably has 1 to 24 carbon atoms, more preferably 1 to 10 carbon atoms.
  • the alkyl group include methyl group, ethyl group, n-propyl group, n-butyl group, i-propyl group, i-butyl group, pentyl group, hexyl group, n-octyl group, 2-ethylhexyl group, t -octyl group, decyl group, dodecyl group, tetradecyl group, 2-hexyldecyl group, n-hexadecyl group, octadecyl group, cyclohexylmethyl group, octylcyclohexyl group, and the like.
  • Zirconium alkoxides may be used alone or in combination of
  • the organic solvent used in the sol-gel reaction is not particularly limited as long as it dissolves the zirconium alkoxide.
  • carbonate compounds ethylene carbonate, propylene carbonate, etc.
  • heterocyclic compounds (3-methyl-2-oxazolidinone, N-methylpyrrolidone, etc.)
  • cyclic ethers dioxane, tetrahydrofuran, etc.
  • chain ethers diethyl ether, etc.
  • alcohols methanol, ethanol, 2-propanol, ethylene glycol monoalkyl ether, propylene glycol monoalkyl ether, polyethylene glycol monoalkyl ether) , polypropylene glycol monoalkyl ether, etc.
  • polyhydric alcohols ethylene glycol, propylene glycol, polyethylene glycol, polypropylene glycol, glycerin, etc.
  • nitrile compounds acetonitrile, glutaronitrile, methoxyacetonitrile, propionitrile, benzonitrile, etc.
  • esters carbboxylic esters, phosphoric esters, phosphonic esters, etc.
  • aprotic polar substances dimethyl sulfoxide, sulfolane, dimethyl formamide, dimethyl acetamide, etc.
  • alcohols such as ethanol and 2-propanol
  • nitrile compounds such as acetonitrile, glutaronitrile, methoxyacetonitrile, propionitrile, and benzonitrile
  • cyclic ethers such as dioxane and tetrahydrofuran are preferred.
  • the organic solvents may be used alone or in combination of two or more.
  • a chemical modifier that can chelate zirconium atoms may be used.
  • chemical modifiers include acetoacetic esters (ethyl acetoacetate, etc.), 1,3-diketones (acetylacetone, etc.), acetoacetamides (N,N-dimethylaminoacetoacetamide, etc.), and the like.
  • Chemical modifiers may be used alone or in combination of two or more.
  • An acid or alkali is preferably used as a catalyst for hydrolysis and dehydration condensation in the sol-gel reaction. Common alkalis include alkali metal hydroxides such as sodium hydroxide, ammonia, and the like. Inorganic or organic protonic acids can be used as acid catalysts.
  • inorganic protonic acids examples include hydrochloric acid, nitric acid, sulfuric acid, boric acid, perchloric acid, tetrafluoroboric acid, hexafluoroarsenic acid, and hydrobromic acid.
  • organic protonic acids include acetic acid, oxalic acid, and methanesulfonic acid.
  • the catalysts may be used alone or in combination of two or more.
  • Examples of the phosphonic acid added to the precursor of the zirconium phosphonate-based inorganic compound include phosphoric acid, H 2 O 3 PR 1 -SO 3 H, H 2 O 3 PR 2 -SO 3 H, H 2 O 3 PR 3 -COOH, H 2 O 3 PR 4 -NH 2 , H 2 O 3 PR 5 -(PO 3 H 2 ) a , and the like.
  • R 1 to R 4 each independently represent a divalent organic group.
  • R 5 represents a 1+a-valent organic group.
  • a is an integer of 1 or 2 or more indicating the number of (PO 3 H 2 ) groups bonded to R 5 .
  • Specific examples of R 1 to R 5 are as described above.
  • Specific examples of phosphonic acids include phosphoric acid, 1-hydroxyethane-1,1-diphosphonic acid, nitrilotris (methylenephosphonic acid), and the like. Phosphonic acids may be used alone or in combination of two or more.
  • the concentration of zirconium alkoxide contained in the solvent is preferably 0.01 mol/L to 0.5 mol/L, more preferably 0.03 mol/L to 0.3 mol/L, and 0.01 mol/L to 0.5 mol/L, more preferably 0.03 mol/L to 0.3 mol/L, in terms of zirconium atoms. More preferably .05 mol/L to 0.1 mol/L.
  • the molar ratio of the chemical modifier to the zirconium alkoxide (chemical modifier/zirconium alkoxide) is preferably 1.0 to 3.0, more preferably 1.2 to 2.5, and 1.5 to 2. 2 is more preferred.
  • the molar ratio of protons to zirconium alkoxide (H + /zirconium alkoxide) in the acid catalyst is preferably 0.1 to 0.7, and preferably 0.2 to 0.6. More preferably, 0.3 to 0.5 is even more preferable.
  • a precursor of a zirconium phosphonate-based inorganic compound can be obtained by adding a chemical modifier to a solution of zirconium alkoxide, then adding a catalyst, and volatilizing the solvent while heating.
  • the obtained precursor of the zirconium phosphonate inorganic compound is dissolved in a solvent again, the obtained solution is impregnated into a porous base material, and the porous base material is then dried to dissolve the zirconium phosphonate inorganic compound.
  • a precursor is filled into the pores of the porous substrate.
  • a mixed solution of phosphonic acid, an organic solvent, and an acid is applied to the precursor of the zirconium phosphonate inorganic compound filled in the pores of the porous base material, and then dried to form the precursor of the zirconium phosphonate inorganic compound. It can be a zirconium phosphonate-based inorganic compound.
  • the same organic solvent as used in the sol-gel reaction may be used.
  • the concentration of the precursor of the zirconium phosphonate inorganic compound is preferably 0.5% to 50% by weight, more preferably 0.7% to 40% by weight, and even more preferably 1% to 30% by weight.
  • the phosphonic acid/organic solvent/acid mixed solution is preferably a solution containing phosphonic acid, water, an organic solvent, and an acid.
  • Examples of organic solvents used in the phosphonic acid/organic solvent/acid mixed solution include halogenated organic compounds such as chloroform and carbon tetrachloride, water-soluble aprotic organic solvents such as acrylonitrile, acetone, and methyl ethyl ketone, methanol, ethanol, n- Examples include alcohols such as propanol and isopropanol.
  • Examples of acids used in the phosphonic acid/organic solvent/acid mixed solution include nitric acid, sulfuric acid, and hydrochloric acid.
  • the phosphonic acid/organic solvent/acid mixed solution can be prepared by adding an acid to a phosphonic acid/organic solvent mixed solution obtained by adding water and an organic solvent to phosphonic acid.
  • the concentration of phosphonic acid in the phosphonic acid/organic solvent mixed solution is preferably 1 x 10 -4 mol/g to 2 x 10 -3 mol/g as the amount of phosphorus (P) per unit solution mass. , more preferably from 2 ⁇ 10 ⁇ 4 mol/g to 1 ⁇ 10 ⁇ 3 mol/g, and still more preferably from 3 ⁇ 10 ⁇ 4 mol/g to 8 ⁇ 10 ⁇ 4 mol/g.
  • the mass ratio of water to organic solvent (water:organic solvent) in the phosphonic acid/organic solvent mixed solution is preferably 1:90 to 10:90, more preferably 2:90 to 8:90.
  • the mixing ratio of the phosphonic acid/organic solvent mixed solution and the acid is, for example, when a 1M nitric acid aqueous solution is used as the acid, the mass ratio of the phosphonic acid/organic solvent mixed solution and the 1M nitric acid aqueous solution (phosphonic acid/organic solvent mixed solution: 1M nitric acid aqueous solution) is preferably 95:0.1 to 95:50, more preferably 95:0.5 to 95:30, even more preferably 95:1 to 95:10.
  • the mass content of the zirconium phosphonate inorganic compound calculated from the following formula 1 is preferably 40% by mass or more, and 42% by mass or more, from the viewpoint of maximizing the physical properties of the zirconium phosphonate inorganic compound. is more preferable, and still more preferably 45% by mass or more.
  • the mass content of the zirconium phosphonate inorganic compound is preferably 90% by mass or less, more preferably 80% by mass or less, and even more preferably 70% by mass or less.
  • the mass content of the zirconium phosphonate inorganic compound is preferably 40% to 90% by mass, more preferably 42% to 80% by mass, and even more preferably 45% to 70% by mass.
  • Mass filling rate (mass%) (composite membrane basis weight - base material basis weight) / composite membrane basis weight x 100...
  • the composite film basis weight means the mass per unit area of the composite membrane
  • the base material basis weight means the mass per unit area of the porous base material.
  • the basis weight of the composite membrane and the base material are each calculated from the following formula 2 based on the mass of the composite membrane or base material and the area of the composite membrane or base material.
  • Fabric weight (mg/cm 2 ) mass of composite membrane or base material/area of composite membrane or base material...
  • the mass of the composite membrane or base material is the value measured using an electronic balance.
  • the area of the composite membrane or base material is calculated by analyzing a photograph of the composite membrane or base material using image analysis software.
  • the composite membrane of the present disclosure may optionally include a proton-conducting polymer.
  • the proton conductive polymer is filled into the pores of the porous base material.
  • Proton conductive polymers include polymers having protonic acid groups such as sulfonic acid groups, carboxylic acid groups, phosphonic acid groups, alkylsulfonic acid groups, alkylcarboxylic acid groups, alkylphosphonic acid groups, phosphoric acid groups, and phenolic hydroxyl groups. means.
  • Examples of the proton conductive polymer include sulfonated polymers, and specific examples include perfluorosulfonic acid polymers.
  • the proportion of the proton conductive polymer in the total amount of the zirconium phosphonate inorganic compound and the proton conductive polymer is determined from the viewpoint of ensuring water barrier properties of the composite membrane. , is preferably 40% by mass or less, more preferably 30% by mass or less, even more preferably 20% by mass or less.
  • the proportion of the proton conductive polymer in the total amount of the zirconium phosphonate inorganic compound and the proton conductive polymer may be 10% by mass or more.
  • the pores do not need to be filled with a proton-conducting polymer.
  • the proportion of the proton conductive polymer in the total amount of the zirconium phosphonate inorganic compound and the proton conductive polymer is 0% by mass.
  • the composite membrane of the present disclosure is preferably water-impermeable. Whether or not the composite membrane of the present disclosure is water-impermeable can be determined by the value of the water contact angle of the composite membrane.
  • the water contact angle of the composite membrane of the present disclosure is preferably 68° or more, more preferably 69° or more, and even more preferably 70° or more. In the present disclosure, if the water contact angle of the composite membrane of the present disclosure is 68° or more, the composite membrane can be determined to be water impermeable.
  • the water contact angle of the composite membrane of the present disclosure is preferably 90° or less, more preferably 88° or less, and even more preferably 87° or less.
  • the water contact angle of the composite membrane of the present disclosure is preferably 68° to 90°, more preferably 69° to 88°, and even more preferably 70° to 87°.
  • Water contact angle refers to a value measured by the following method using a contact angle meter. At 25° C., a drop of 1 ⁇ L to 2 ⁇ L of distilled water is dropped onto the composite membrane, and the contact angle of the water drop with the composite membrane is measured within 20 seconds after dropping. The contact angle is calculated by the 2 ⁇ method.
  • the contact angle meter for example, DMs401FE (manufactured by Kyowa Interface Science Co., Ltd.) can be used. Further, as the contact angle meter dispenser, for example, MD-100 (22G) can be used.
  • the composite membrane of the present disclosure has improved water barrier properties because proton conductivity can be ensured due to the presence of the zirconium phosphonate inorganic compound even if the pores of the porous base material are not filled with a proton conductive polymer. It becomes possible to do so. Therefore, the composite membrane of the present disclosure is useful as an electrolyte membrane that requires water barrier properties.
  • the composite membrane of the present disclosure is suitably used as an electrolyte membrane for a hydrogen addition reaction using water as a hydrogen source. Examples of hydrogen addition reactions using water as a hydrogen source include electrolytic synthesis of ammonia, reduction reaction of carbon dioxide, and reduction reaction of nitroarene.
  • the composite membrane of the present disclosure is also useful as a membrane reactor because a catalytic function can be imparted to the composite membrane by modifying the hydroxyl group contained in the zirconium phosphonate-based inorganic compound.
  • the composite membrane of the present disclosure will be explained in more detail by giving examples below.
  • the materials, amounts used, proportions, processing procedures, etc. shown in the following examples can be changed as appropriate without departing from the spirit of the present disclosure. Therefore, the scope of the composite membrane of the present disclosure should not be construed as being limited by the specific examples shown below.
  • the film thickness of the polyolefin microporous membrane which is a porous base material, was measured at 20 points using a contact type film thickness meter (manufactured by Mitutoyo Corporation), and the average film thickness of the porous base material was determined by averaging these values.
  • a cylindrical contact terminal with a bottom surface having a diameter of 0.5 cm was used.
  • the measurement pressure was 0.1N.
  • the average flow rate pore diameter measured by the following method was defined as the average pore diameter of the porous substrate.
  • the average flow pore size due to gas/liquid phase exchange was determined using a pore size distribution measurement test method [half-dry method (ASTM E1294-89) using a PMI automatic pore size distribution measuring system [Capillary Flow Porometer] for porous materials. )].
  • the test solution used was a fluorine-based inert liquid (trade name: Fluorinert) (interfacial tension value: 16.0 dyne/cm), and the measurement temperature was 25°C.
  • the measurement pressure was in the range of 0 psi to 500 psi, and the measurement was carried out under the following conditions.
  • the uniform electrode area was A [cm 2 ], the distance between the electrodes was L [cm], the read resistance was R [ ⁇ ], and the conductivity was ⁇ [Scm ⁇ 1 ].
  • ⁇ 1/R ⁇ L/A
  • the film thickness of the composite film was measured using a digital macrometer (manufactured by Mitutoyo Co., Ltd., model: MDC-25M).
  • the water barrier property (water contact angle) of the composite membrane obtained by the method described below was measured as follows.
  • the contact angle meter used was DMs401FE (manufactured by Kyowa Interface Science Co., Ltd.).
  • One drop of 1 ⁇ L to 2 ⁇ L of distilled water (manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.) was dropped onto the composite membrane, and the contact angle of the water droplet with respect to the composite film was measured within 20 seconds after dropping.
  • the contact angle meter dispenser used was MD-100 (22G). Further, the contact angle was calculated by the 2 ⁇ method.
  • a polyethylene composition was used in which 12 parts by mass of high molecular weight polyethylene (PE1) having a weight average molecular weight of 4 million and 5 parts by mass of low molecular weight polyethylene (PE2) having a weight average molecular weight of 300,000 were mixed.
  • a polyethylene solution was prepared by mixing a mixed solvent of 51 parts by mass of liquid paraffin and 32 parts by mass of decalin (decahydronaphthalene) prepared in advance so that the concentration of the total amount of polyethylene resin was 17% by mass.
  • This polyethylene solution is extruded into a sheet form from a die at a temperature higher than the melting point of polyethylene, and then the extrudate is cooled at 20°C in a water bath, and a water stream is provided on the surface layer of the water bath, so that the inside of the gelled sheet in the water bath is cooled.
  • a gel-like sheet (base tape) was prepared while preventing the mixed solvent released from the water and floating on the water surface from adhering to the sheet again. After drying the base tape at 60°C for 7 minutes and then at 95°C for 7 minutes to remove decalin from within the base tape, it was subsequently conveyed on a roller heated to 90°C while applying a pressure of 0.05 MPa.
  • a portion of the liquid paraffin was removed from within the base tape. Thereafter, the base tape was stretched in the longitudinal direction at a magnification of 6 times at a temperature higher than the softening temperature of polyethylene (longitudinal stretching), and subsequently stretched in the width direction at a magnification of 10 times at a temperature higher than the softening temperature of polyethylene (longitudinal stretching). Lateral stretching), and then heat treatment (heat setting) at the crystallization temperature of polyethylene. Next, liquid paraffin was extracted while continuously immersing the base tape in two separate methylene chloride baths for 30 seconds each.
  • a polyethylene composition was used in which 17 parts by mass of high molecular weight polyethylene (PE1) having a weight average molecular weight of 4 million and 4 parts by mass of low molecular weight polyethylene (PE2) having a weight average molecular weight of 300,000 were mixed.
  • a polyethylene solution was prepared by mixing a mixed solvent of 78 parts by mass of liquid paraffin and 1 part by mass of decalin (decahydronaphthalene) prepared in advance so that the concentration of the total amount of polyethylene resin was 21% by mass.
  • This polyethylene solution is extruded into a sheet form from a die at a temperature higher than the melting point of polyethylene, and then the extrudate is cooled at 20°C in a water bath, and a water stream is provided on the surface layer of the water bath, so that the inside of the gelled sheet in the water bath is cooled.
  • a gel-like sheet (base tape) was prepared while preventing the mixed solvent released from the water and floating on the water surface from adhering to the sheet again. After drying the base tape at 60°C for 7 minutes and then at 95°C for 7 minutes to remove decalin from within the base tape, it was subsequently conveyed on a roller heated to 90°C while applying a pressure of 0.05 MPa.
  • a portion of the liquid paraffin was removed from within the base tape. Thereafter, the base tape was stretched in the longitudinal direction at a magnification of 6 times at a temperature higher than the softening temperature of polyethylene (longitudinal stretching), and subsequently stretched in the width direction at a magnification of 10 times at a temperature higher than the softening temperature of polyethylene (longitudinal stretching). Lateral stretching), and then heat treatment (heat setting) at the crystallization temperature of polyethylene. Next, liquid paraffin was extracted while continuously immersing the base tape in two separate methylene chloride baths for 30 seconds each.
  • the purity of the cleaning solvent when the side where immersion starts is set as the first tank and the side where immersion ends is set as the second tank is (low) first layer ⁇ second tank (high).
  • methylene chloride was removed by drying at 40° C., and annealing treatment was performed while conveying it on a roller heated to 100° C., thereby obtaining a porous base material 2 which is a microporous polyolefin membrane.
  • Table 1 shows the physical properties of the porous base material 2 obtained.
  • a polyethylene composition was used in which 6 parts by mass of high molecular weight polyethylene (PE1) having a weight average molecular weight of 4 million and 24 parts by mass of low molecular weight polyethylene (PE2) having a weight average molecular weight of 300,000 were mixed.
  • a polyethylene solution was prepared by mixing a mixed solvent of 68 parts by mass of liquid paraffin and 2 parts by mass of decalin (decahydronaphthalene) prepared in advance so that the concentration of the total amount of polyethylene resin was 30% by mass.
  • This polyethylene solution is extruded into a sheet form from a die at a temperature higher than the melting point of polyethylene, and then the extrudate is cooled at 20°C in a water bath, and a water stream is provided on the surface layer of the water bath, so that the inside of the gelled sheet in the water bath is cooled.
  • a gel-like sheet (base tape) was prepared while preventing the mixed solvent released from the water and floating on the water surface from adhering to the sheet again. After drying the base tape at 60°C for 7 minutes and then at 95°C for 7 minutes to remove decalin from within the base tape, it was subsequently conveyed on a roller heated to 90°C while applying a pressure of 0.05 MPa.
  • a portion of the liquid paraffin was removed from within the base tape. Thereafter, the base tape was stretched in the longitudinal direction at a magnification of 6 times at a temperature higher than the softening temperature of polyethylene (longitudinal stretching), and subsequently stretched in the width direction at a magnification of 10 times at a temperature higher than the softening temperature of polyethylene (longitudinal stretching). Lateral stretching), and then heat treatment (heat setting) at the crystallization temperature of polyethylene. Next, liquid paraffin was extracted while continuously immersing the base tape in two separate methylene chloride baths for 30 seconds each.
  • the purity of the cleaning solvent when the side where immersion starts is set as the first tank and the side where immersion ends is set as the second tank is (low) first layer ⁇ second tank (high).
  • methylene chloride was removed by drying at 40° C., and annealing treatment was performed while conveying on rollers heated to 120° C., thereby obtaining a porous base material 3 which is a microporous polyolefin membrane.
  • Table 1 shows the physical properties of the porous base material 3 obtained.
  • Example preparation 85% Zirconium(IV) Butoxide (Zr-butoxide), 1-Butanol Solution and 2-Propanol, Super Dehydrated were purchased from Fujifilm Wako Pure Chemical Industries, Ltd. 99.8% Methanol, Acetylacetone, 1 mol/L (1M) nitric acid and phosphoric acid were purchased from Nacalai Tesque Co., Ltd. 1-Hydroxyethane-1,1-diphosphonic Acid (ca. 60% in Water, ca. 4.2 mol/L) (HEDPA)] and Nitrilotris (methylenephosphonic acid) [ Nitrilotris (methylenephosphonic acid) (ca. 50% in Water, ca.
  • Nafion stock solution Nafion perfluorinated resin solution (5% by weight in lower aliphatic alcohols and water, contains 15%-20% by weight) was purchased from Sigma-Aldrich.
  • the solution was heated to 80° C. using a hot stirrer in a draft chamber to completely evaporate the solution to obtain Acac-Zr powder.
  • (Preparation of Acac-Zr membrane) The Acac-Zr powder obtained in the above procedure was dissolved in methanol to obtain a 3% by mass Acac-Zr methanol solution. The procedure of dropping the solution onto the porous substrate 1 and drying it at room temperature was repeated about 5 times until the film became visually transparent. However, after the first drop, the vacuum state was kept at room temperature for about 1 minute.
  • a transparent Acac-Zr film was obtained by washing the transparent film twice with ultrapure water and drying it in a vacuum at 80°C for 30 minutes or more.
  • a sufficient amount of the phosphoric acid/alcohol/nitric acid mixed solution obtained in the above procedure was dropped onto the previously prepared Acac-Zr film, and the film was dried in an open system at 80°C on a hot stirrer for about 10 minutes. Furthermore, the membrane was turned over, and a mixed solution of phosphoric acid, alcohol, and nitric acid was added dropwise and dried again. The obtained membrane was washed twice in ultrapure water and dried in a vacuum at 80° C. for more than half a day.
  • a composite membrane 1 having zirconium phosphate which is a type of zirconium phosphonate, was filled as a continuous body into the pores of the porous base material 1 and adhered to the porous base material.
  • the proton conductivity, water contact angle, and mass filling rate were determined by the above-mentioned methods. The results obtained are shown in Table 2. Further, a TEM photograph was taken of the composite film 1 by the method described above. The obtained results are shown in FIGS. 1 and 2. Note that the proportion of the proton conductive polymer in the total amount of the zirconium phosphonate-based inorganic compound and the proton conductive polymer in the composite membrane 1 is 0% by mass.
  • Example 2 A composite membrane 2 was obtained in the same manner as in Example 1 except that porous base material 2 was used instead of porous base material 1. The mass filling rate of the obtained composite membrane 2 was determined by the method described above. The results obtained are shown in Table 2. Note that the proportion of the proton conductive polymer in the total amount of the zirconium phosphonate-based inorganic compound and the proton conductive polymer in the composite membrane 2 is 0% by mass.
  • Example 3 A composite membrane 3 was obtained in the same manner as in Example 1 except that porous base material 3 was used instead of porous base material 1.
  • the mass filling rate of the obtained composite membrane 3 was determined by the method described above. The results obtained are shown in Table 2. Note that the proportion of the proton conductive polymer in the total amount of the zirconium phosphonate-based inorganic compound and the proton conductive polymer in the composite membrane 3 is 0% by mass.
  • Example 4 Composite membrane 4 was obtained in the same manner as in Example 1, except that 1-Hydroxyethane-1,1-diphosphonic acid (HEDPA) was used instead of phosphoric acid. Regarding the obtained composite membrane 4, the proton conductivity, water contact angle, and mass filling rate were determined by the above-mentioned methods. The results obtained are shown in Table 2. In the composite membrane 4, zirconium 1-hydroxyethane-1,1-diphosphonate is filled in the pores as a continuum. Note that the proportion of the proton conductive polymer in the total amount of the zirconium phosphonate-based inorganic compound and the proton conductive polymer in the composite membrane 4 is 0% by mass.
  • HEDPA 1-Hydroxyethane-1,1-diphosphonic acid
  • Example 5 A composite membrane 5 was obtained in the same manner as in Example 1 except that Nitrilotris (methylenephosphonic acid) (ATMPA) was used instead of phosphoric acid. Regarding the obtained composite membrane 5, the proton conductivity, water contact angle, and mass filling rate were determined by the above-mentioned methods. The results obtained are shown in Table 2. In the composite membrane 5, nitrilotris (methylenephosphonic acid) zirconium is filled in the pores as a continuum. Note that the proportion of the proton conductive polymer in the total amount of the zirconium phosphonate-based inorganic compound and the proton conductive polymer in the composite membrane 5 is 0% by mass.
  • ATMPA Nitrilotris (methylenephosphonic acid)
  • the composite membranes 1 and 4-5 of Examples 1 and 4-5 have excellent water barrier properties compared to the comparative composite membrane of Comparative Example 1. Further, it can be seen that the composite membranes 1 and 4-5 of Examples 1 and 4-5 exhibit proton conductivity. It is known that the proton conductivity of Nafion's cast membrane is 0.01 S/cm - 0.1 S/cm at 80°C and 95% RH (Yoshitsugu Sone, Per Ekdunge, and Daniel Simonsson). , Proton Conductivity of Nafion 117 as Measured by a Four-Electrode AC Impedance Method, J. Electrochem. Soc., 143, 1254 (1996)).
  • PI-SPES polyimide-sulfonated polyether sulfone

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Abstract

Le film composite de la présente invention possède : un substrat poreux contenant une résine hydrophobe ; et un composé inorganique à base de zirconium d'acide phosphonique avec lequel l'intérieur des trous dudit substrat poreux est rempli en tant que corps continu, et qui se trouve en adhésion sur ledit substrat poreux.
PCT/JP2023/022670 2022-06-20 2023-06-19 Film composite WO2023248992A1 (fr)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2007029346A1 (fr) * 2005-08-19 2007-03-15 The University Of Tokyo Matériau hybride conducteur de protons et couche catalytique pour une pile à combustible l’utilisant
JP2009016267A (ja) * 2007-07-06 2009-01-22 Nagoya Institute Of Technology プロトン伝導性膜及びその製造方法並びにこれを用いた燃料電池及び化学センサ
WO2011018905A1 (fr) * 2009-08-13 2011-02-17 国立大学法人 東京工業大学 Procédé de production de particules de zirconium fortement acides, procédé de production d’un matériau conducteur de protons et d’un film conducteur de protons, et film conducteur de protons

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2007029346A1 (fr) * 2005-08-19 2007-03-15 The University Of Tokyo Matériau hybride conducteur de protons et couche catalytique pour une pile à combustible l’utilisant
JP2009016267A (ja) * 2007-07-06 2009-01-22 Nagoya Institute Of Technology プロトン伝導性膜及びその製造方法並びにこれを用いた燃料電池及び化学センサ
WO2011018905A1 (fr) * 2009-08-13 2011-02-17 国立大学法人 東京工業大学 Procédé de production de particules de zirconium fortement acides, procédé de production d’un matériau conducteur de protons et d’un film conducteur de protons, et film conducteur de protons

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