JP2007242524A - Organic-inorganic hybrid electrolyte membrane, its manufacturing method, and fuel cell - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To form an independent organic-inorganic hybrid electrolyte membrane by using an organic-inorganic hybrid electrolyte having high ion conductivity even at low temperatures; and to provide a high-performance fuel cell allowing the organic-inorganic hybrid electrolyte membrane to be used in a polymer electrolyte fuel cell. <P>SOLUTION: This organic-inorganic hybrid electrolyte membrane is formed by filling a mesoporous organic-inorganic hybrid material in pores of a porous membrane. The mesoporous organic-inorganic hybrid material has minute pores each having a center pore diameter of 1-50 nm, and has a skeleton comprising an organic group having one or more metal atoms, oxygen atoms bonded to the metal atoms, and carbon atoms bonded to the metal atoms or the oxygen atoms, and a functional group bonded to the organic group in the minute pores and having ion exchange capacity. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to an organic-inorganic hybrid electrolyte membrane, a method for producing the membrane, and a fuel cell using these. More specifically, the present invention relates to an organic-inorganic hybrid electrolyte membrane that is suitable for an electrolyte membrane used in a fuel cell and has both self-supporting property, strength, durability, and chemical stability.

  Conventionally, studies are being made to apply a solid electrolyte such as β-alumina, lithium nitride, and stabilized zirconia having ion conductivity to an electrolyte membrane of a fuel cell, an electrolyte of an all-solid battery, a sensor, and the like. The ionic conductivity of these solid electrolytes is considered to be manifested by ions moving between lattices or defects in the solid.

  Also, in polymer electrolytes such as perfluorosulfonic acid and hydrocarbon polymers that have been studied as electrolyte membranes for polymer electrolyte fuel cells, polymer chain gaps when wetted with an electrolyte solution such as water. It is known that ion conductivity is exhibited by movement of ions in an electrolyte solution existing in the field, and these are called quasi-solid electrolytes. These polymer electrolytes have advantages such as ion conductivity at a relatively low temperature; excellent formability to a thin film, etc .; good contact with electrodes, etc. It is attracting attention as an electrolyte membrane for fuel cells.

  However, in conventional solid electrolytes, the activation energy for moving ions between lattices or defects is usually large, so that sufficient ionic conductivity is not always exhibited under low temperature conditions. Therefore, in order to obtain sufficiently high ionic conductivity, there is a problem in that it must be maintained under a high temperature condition (for example, 700 ° C. or more in the case of stabilized zirconia) using a heating device or the like.

  On the other hand, conventional polymer electrolytes usually exhibit ionic conductivity at a lower temperature than the above-mentioned conventional solid electrolytes, but are not necessarily sufficient when the electrolyte solution is not sufficiently filled in the gaps between the polymer chains. It does not show ionic conductivity. Therefore, when using a polymer electrolyte, it is necessary to set the vapor pressure of the electrolyte solution to a saturated vapor pressure.For example, when water is used as the electrolyte solution, the relative pressure of water vapor in the atmosphere is set using a humidifier or the like. There is a problem that it must be maintained at 1.0 (that is, humidity 100% RH).

  Therefore, Patent Document 1 below discloses a solid electrolyte that exhibits sufficiently high ionic conductivity at a lower temperature than conventional solid electrolytes such as stabilized zirconium even when the relative pressure of water vapor in the atmosphere is less than 1.0. For the purpose of providing, an organic-inorganic hybrid material having a pore whose central pore diameter is within a specific range is used as a solid electrolyte material, and an ion exchange capacity is formed on an organic group constituting the skeleton of the organic-inorganic hybrid material. An organic-inorganic hybrid electrolyte to which a functional group having s is bonded is disclosed. That is, it has a pore having a central pore diameter of 1 to 30 nm and comprises a metal atom, an oxygen atom bonded to the metal atom, and an organic group having one or more carbon atoms bonded to the metal atom or the oxygen atom. An organic-inorganic hybrid electrolyte having a skeleton and a functional group having ion exchange ability bonded to the organic group in the pores is disclosed.

  According to Patent Document 1, an organic-inorganic hybrid material having a pore whose central pore diameter is in the specific range and having a skeleton having the above characteristics is used as a solid electrolyte material. By bonding the functional group having ion exchange capacity and the organic group in the pores, even if the relative pressure of water vapor in the atmosphere is less than 1.0, the pores are sufficiently filled with water due to the capillary condensation phenomenon. It is filled. And, in the pores sufficiently filled with water in this way, it is possible to sufficiently conduct ions in water by the same ion conduction mechanism as in the case of the polymer electrolyte by the functional group having ion exchange ability Therefore, even if the relative pressure of water vapor in the atmosphere is less than 1.0, it is said that sufficiently high ion conductivity can be obtained at a lower temperature than conventional solid electrolytes such as stabilized zirconium. .

  About 10 years have passed since the discovery of various mesoporous materials synthesized using surfactants (for example, Non-Patent Documents 1 to 3 below). In particular, since Toyota Chuken and Mobil reported new mesoporous materials, research on various mesoporous materials has been conducted, and there are many reports accompanying it. Since introduction of an organic group into the surface or skeleton of these pores can be expected to have a function corresponding to the characteristics of the organic group, it has attracted much attention. On the other hand, in taking advantage of these functions and developing applications, a self-supporting film configuration in which the film is not a coating film but has a self-supporting structure is very important. For example, it is considered that a mesoporous material is supported on various supports or complexed with a polymer.

  By the way, the basic structure of a polymer electrolyte fuel cell is composed of an electrolyte membrane and a pair of gas diffusion electrodes having a catalyst layer bonded to both sides thereof, and a structure in which current collectors are arranged on both sides thereof. It has become. Then, hydrogen or methanol as fuel is supplied to one gas diffusion electrode (anode), oxygen or air as oxidant is supplied to the other gas diffusion electrode (cathode), and an external load is applied between both gas diffusion electrodes. By connecting the circuit, it operates as a fuel cell. At this time, protons generated at the anode move to the cathode side through the electrolyte membrane, and react with oxygen at the cathode to generate water.

  Here, the electrolyte membrane functions as a proton transfer medium and a hydrogen gas or oxygen gas diaphragm. Therefore, the electrolyte membrane is required to have high proton conductivity, strength, and chemical stability. In particular, as an electrolyte membrane used for a polymer electrolyte fuel cell, it is desired to reduce the film thickness in order to reduce membrane resistance and promote water movement in the membrane. However, since the film strength decreases as the film thickness decreases, there is a problem in that the handling property when the film is handled decreases.

International Publication WO2002-037506 C. T. T. et al. Kresge et al. , Nature, 359, 710 (1992). J. et al. S. Beck et a1. , J .; Am. Chem. Soc. , 114, 10834 (1992) S. Inagaki et al. , Chem. Commun. , 680 (1993)

  Conventionally obtained organic / inorganic hybrid films having mesoporous pores have a hard skeletal structure and poor flexibility, and thus cannot stand by themselves and cannot be used only as a coating film. For example, the structure of a self-supporting film obtained by using a conventional sol-gel synthesis method using an alkoxysilane, an organic-containing alkoxysilane, or an organic crosslinked alkoxysilane as a raw material is configured with a three-dimensional network of -O-Si-O- bonds ( As a result, a very rigid cured product is obtained. In order to expand the use range of the organic-inorganic hybrid mesoporous material, it is desirable that it can be used as a self-supporting film as well as a coating film.

  For example, the organic-inorganic hybrid electrolyte disclosed in Patent Document 1 cannot form a self-supporting film by itself, and the organic-inorganic hybrid electrolyte powder cannot be solidified and used as a solid electrolyte.

  Therefore, the present invention makes it possible to form a self-supporting organic-inorganic hybrid electrolyte membrane by using an organic-inorganic hybrid electrolyte having high ionic conductivity even at low temperatures, and the organic-inorganic hybrid electrolyte membrane can be used as a solid polymer fuel cell. The purpose is to realize a high-performance fuel cell that can be applied.

  As a result of intensive studies, the present inventors have found that the above problems can be solved by an electrolyte membrane having both the pores of the porous membrane and the fine pores of the organic-inorganic hybrid electrolyte, and have reached the present invention.

  Specifically, first, the present invention is an invention of an organic-inorganic hybrid electrolyte membrane in which pores of a porous membrane are filled with a mesoporous organic-inorganic hybrid material, and the mesoporous organic-inorganic hybrid material has a central pore diameter of 1 A skeleton having a fine pore of ˜50 nm and comprising a metal atom, an oxygen atom bonded to the metal atom, and an organic group having one or more carbon atoms bonded to the metal atom or the oxygen atom; And a functional group having an ion exchange ability bonded to the organic group.

  As the mesoporous organic-inorganic hybrid material constituting the electrolyte part in the organic-inorganic hybrid electrolyte membrane of the present invention, those having the above structure are widely used. Among them, an organic inorganic group comprising an organic group having one or more carbon atoms, two or more metal atoms bonded to the same or different carbon atoms in the organic group, and one or more oxygen atoms bonded to the metal atoms. Those having a skeleton of a hybrid material are preferred.

（上記式（１）中、Ｒ^１は炭素原子を１以上有する有機基を表し、Ｍは金属原子を表す。Ｒ^２は水素原子、水酸基又は炭化水素基を表す。ｘは金属Ｍの価数から１を差し引いた整数、ｎは１以上ｘ以下の整数、ｍは２以上の整数を表す。なお、Ｍが結合するＲ^１の炭素は同一でも異なっていてもよい。また、−Ｏ_１／２−は、これらが２つ結合することにより−Ｏ−となる基を表す。）
で表される構成単位の少なくとも１種からなるものが好ましく例示される。 Specifically, the skeleton of the organic-inorganic hybrid material has the following general formula (1):

(In the above formula (1), R ¹ represents an organic group having one or more carbon atoms, M represents a metal atom, R ² represents a hydrogen atom, a hydroxyl group or a hydrocarbon group. X represents the valence of the metal M. from minus 1 integer, n represents 1 or x an integer, m is an integer of 2 or more. in addition, the carbon of R ¹ that M is bonded may be the same or different. Further, -O 1 _{/ 2-} represents a group which becomes -O- when two of these are bonded.
What consists of at least 1 type of the structural unit represented by these is illustrated preferably.

  Preferred examples of the functional group having ion exchange ability include at least one selected from the group consisting of a sulfonic acid group, a phosphoric acid group and a carboxylic acid group.

  In the present invention, a surfactant may be contained in the micropores of the mesoporous organic-inorganic hybrid material.

  As the porous membrane having micron-order pores, which is the main component of the organic-inorganic hybrid electrolyte membrane of the present invention, inorganic materials such as silica gel and various polymer porous materials can be used.

  Specifically, as the porous film, polyimide (PI), polyetheretherketone (PEEK), polyethyleneimide (PEI), polysulfone (PSF), polyphenylsulfone (PPSU), polyphenylene sulfide (PPS), cross-linking One or more kinds selected from polyethylene (CLPE) are preferably exemplified.

  Examples of the porous membrane include polytetrafluoroethylene (PTFE) represented by the following general formula or a tetrafluoroethylene copolymer containing 10 mol% or less of a copolymer component.

（式中、Ａは下記から選択される１種以上であり、ａ：ｂ＝１：０〜９：１である）

(In the formula, A is one or more selected from the following, and a: b = 1: 0 to 9: 1)

  Further, the porous film is preferably polysiloxane, and the organic group in the polysiloxane is preferably at least one group selected from methyl group, phenyl group, hydrogen group or hydroxyl group. Is done.

  2ndly, this invention is invention of the manufacturing method of said organic-inorganic hybrid electrolyte membrane. That is, a step of filling a precursor of a mesoporous organic-inorganic hybrid material in the pores of the porous membrane, a step of forming a mesoporous organic-inorganic hybrid material in the pores of the porous membrane, and the mesoporous organic-inorganic hybrid material A method for producing an organic-inorganic hybrid electrolyte membrane having a micron-order pore, wherein the mesoporous organic-inorganic hybrid material is filled in the pore, the method comprising: The inorganic hybrid material has a fine pore having a central pore diameter of 1 to 50 nm, and has an organic atom having at least one metal atom, an oxygen atom bonded to the metal atom, and one or more carbon atoms bonded to the metal atom or the oxygen atom. A step of synthesizing a polymer skeleton composed of a group, and a functional group having ion exchange ability for a part of the organic group in the micropore Characterized by a step of converting the.

  Another method for producing an organic-inorganic hybrid electrolyte membrane includes a step of filling a mesoporous organic-inorganic hybrid material into pores of a porous membrane and a step of protonating the mesoporous organic-inorganic hybrid material. A method for producing an organic-inorganic hybrid electrolyte membrane having a pore and a mesoporous organic-inorganic hybrid material filled with a mesoporous organic-inorganic hybrid material, wherein the mesoporous organic-inorganic hybrid material has a central pore diameter of 1 to 50 nm. Synthesizing a polymer skeleton having micropores and comprising a metal atom, an oxygen atom bonded to the metal atom, and an organic group having one or more carbon atoms bonded to the metal atom or the oxygen atom; And a step of converting a part of the organic group into a functional group having ion exchange ability in the micropore.

  In the method for producing an organic / inorganic hybrid electrolyte membrane of the present invention, the skeleton of the organic / inorganic hybrid material includes an organic group having one or more carbon atoms and two or more metals bonded to the same or different carbon atoms in the organic group. What consists of an atom and one or more oxygen atoms couple | bonded with the said metal atom is illustrated preferably.

（上記式（２）中、Ｒ^１は炭素原子を１以上有する有機基を表し、Ｍは金属原子を表す。Ｒ^２は水素原子、水酸基又は炭化水素基を表す。Ａはアルコキシ基またはハロゲン原子を表す。ｘは金属Ｍの価数から１を差し引いた整数、ｎは１以上ｘ以下の整数、ｍは２以上の整数を表す。なお、Ｍが結合するＲ^１の炭素は同一でも異なっていてもよい。）
で表される少なくとも１種の化合物を、界面活性剤を含む水溶液に加え、酸性またはアルカリ性の条件下に重縮合して得られた、界面活性剤を含むことを特徴とする有機無機ハイブリッド電解質膜の製造方法が好ましく例示される。 As a synthesis procedure of the skeleton of the organic-inorganic hybrid material, the following general formula (2):

(In the above formula (2), R ¹ represents an organic group having one or more carbon atoms, M represents a metal atom, R ² represents a hydrogen atom, a hydroxyl group or a hydrocarbon group. A represents an alkoxy group or a halogen atom. X represents an integer obtained by subtracting 1 from the valence of the metal M, n represents an integer of 1 to x, and m represents an integer of 2. The carbons of R ¹ to which M is bonded are the same or different. May be.)
An organic-inorganic hybrid electrolyte membrane comprising a surfactant obtained by polycondensation under acidic or alkaline conditions with at least one compound represented by the formula: The production method is preferably exemplified.

（上記式（２）中、Ｒ^１は炭素原子を１以上有する有機基を表し、Ｍは金属原子を表す。Ｒ^２は水素原子、水酸基又は炭化水素基を表す。Ａはアルコキシ基またはハロゲン原子を表す。ｘは金属Ｍの価数から１を差し引いた整数、ｎは１以上ｘ以下の整数、ｍは２以上の整数を表す。なお、Ｍが結合するＲ^１の炭素は同一でも異なっていてもよい。）
で表される少なくとも１種の化合物を、界面活性剤を含む水溶液に加え、酸性またはアルカリ性の条件下に重縮合し、得られた多孔質前駆体から該界面活性剤を除去する方法が好ましく例示される。 As another procedure for synthesizing the skeleton of the organic-inorganic hybrid material, the following general formula (2):

(In the above formula (2), R ¹ represents an organic group having one or more carbon atoms, M represents a metal atom, R ² represents a hydrogen atom, a hydroxyl group or a hydrocarbon group. A represents an alkoxy group or a halogen atom. X represents an integer obtained by subtracting 1 from the valence of the metal M, n represents an integer of 1 to x, and m represents an integer of 2. The carbons of R ¹ to which M is bonded are the same or different. May be.)
A method in which at least one compound represented by the formula (1) is added to an aqueous solution containing a surfactant, polycondensed under acidic or alkaline conditions, and the surfactant is removed from the resulting porous precursor is preferably exemplified. Is done.

  In the step of filling the mesoporous organic-inorganic hybrid material or the mesoporous organic-inorganic hybrid material precursor in the pores of the porous film, the mesoporous organic-inorganic hybrid material or the mesoporous organic-inorganic hybrid material precursor is irradiated with ultrasonic waves, deprocessed, It is preferable to use one or more means selected from solvent replacement, use of a surfactant, and surface modification of the porous membrane.

  The functional group having ion exchange ability of the organic-inorganic hybrid electrolyte membrane is preferably exemplified by at least one selected from the group consisting of a sulfonic acid group, a phosphoric acid group and a carboxylic acid group.

  Specific examples of the porous membrane that is the main component of the organic-inorganic hybrid electrolyte membrane of the present invention include polyimide (PI), polyetheretherketone (PEEK), polyethyleneimide (PEI), polysulfone (PSF), and polyphenylsulfone. One or more types selected from (PPSU), polyphenylene sulfide (PPS), and crosslinked polyethylene (CLPE) are preferably exemplified.

  Examples of the porous membrane include polytetrafluoroethylene (PTFE) represented by the following general formula or a tetrafluoroethylene copolymer containing 10 mol% or less of a copolymer component.

（式中、Ａは下記から選択される１種以上であり、ａ：ｂ＝１：０〜９：１である）

(In the formula, A is one or more selected from the following, and a: b = 1: 0 to 9: 1)

  Further, the porous film is preferably polysiloxane, and the organic group in the polysiloxane is at least one group selected from methyl group, phenyl group, hydrogen group or hydroxyl group. Illustrated.

  3rdly, this invention is invention of the electrolyte membrane for fuel cells which consists of said organic-inorganic hybrid electrolyte membrane.

  4thly, this invention is invention of the film for chemical processes which consists of said organic-inorganic hybrid electrolyte membrane.

  Fifth, the present invention is an invention of a fuel cell using the above organic-inorganic hybrid electrolyte membrane, and is a polymer solid electrolyte membrane (a) and a conductive carrier carrying a catalyst metal that is joined to the electrolyte membrane. In a polymer electrolyte fuel cell having a membrane / electrode assembly (MEA) composed of a gas diffusion electrode (b) whose main constituent material is an electrode catalyst made of a proton conductive material and the polymer solid electrolyte membrane Is the above-mentioned organic-inorganic hybrid electrolyte membrane.

  An organic / inorganic hybrid material that could not be formed by a conventional film can be used as a self-supporting electrolyte membrane, and the organic / inorganic hybrid electrolyte membrane of the present invention can be used for a fuel cell, resulting in excellent mechanical strength. In addition, a fuel cell having improved durability, excellent chemical stability, excellent proton conductivity, easy manufacturing, low cost, and excellent high-temperature operability can be obtained.

  Conventionally obtained organic-inorganic hybrid membranes having mesoporous pores have a hard skeletal structure and poor flexibility, and thus cannot stand by themselves and cannot be used only as a coating membrane. For example, the structure of a free-standing film obtained from an organic silane as a raw material by a conventional sol-gel synthesis method is such that —O—Si—O bonds are formed in a three-dimensional network, and as a result, a very rigid cured product is obtained. . In order to expand the use range of the organic-inorganic hybrid mesoporous material, it is desirable that it can be used not only as a coating film but also as a self-supporting film. Therefore, in the present invention, by using a monomer or polymer of an organic-inorganic hybrid material that is a raw material of the self-supporting membrane, and further by filling the raw material monomer or polymer into the pores in the porous reinforcing membrane (pore filling method), A flexible cured product having a mesostructure (a mesoporous structure or a surfactant may be contained in the mesoporous) is obtained.

Thereby, the operations and effects of the organic-inorganic hybrid electrolyte membrane of the present invention are as follows.
(1) A mesoporous organic-inorganic hybrid material that does not form itself as a film can be formed into a film.
(2) By forming a mesoporous organic-inorganic hybrid material as a self-supporting membrane, it is possible to form an electrolyte membrane having proton conductivity that can be operated with lower humidification than before.
(3) The self-supporting membrane in which the surfactant is held in the micropores of the mesoporous organic-inorganic hybrid material makes it possible to form an electrolyte membrane having proton conductivity that can be operated at a lower humidity than in the past.
(4) By forming a mesoporous organic-inorganic hybrid material as a self-supporting film, it is possible to form a film for a chemical process having both a separation function and a catalytic function.
(5) The pore surface can be functionalized by using, as the mesoporous skeleton, a Si source into which an organic group has been introduced or a Si source having a crosslinked organic group.

  As the porous membrane used in the present invention, a polymer porous membrane is desirable. Specifically, polyimide (PI), polyether ketone ketone (PEKK), polyether ether ketone (PEEK), polyether imide (PEI), PAI, polyphenylene sulfide (PPS), PPSU, PAR, PBI, PA, polyphenylene Ether (PPO), polycarbonate (PC), PP, polyethersulfone (PES), PVDC, PSF, PAN, polyethylene terephthalate (PET), polyethylene (PE), high density polyethylene (HDPE), polytetrafluoroethylene (PTFE) A material such as PVDF can be used.

  Further, methacrylate resins such as polymethyl methacrylate (PMMA); styrene resins such as polystyrene, acrylonitrile-styrene copolymer (AS resin), acrylonitrile-butadiene-styrene copolymer (ABS resin); polyamide; polyamideimide; Polyacetals; Polyarylates; Polyaryls; Polysulfones; Polyurethanes; Polyetherketones; Polyacrylates such as polybutyl acrylate and polyethyl acrylate; Polyvinyl esters such as polybutoxymethylene; Polysiloxanes Polysulfides; polyphosphazenes; polytriazines; polycarboranes; polynorbornene; epoxy resins; polyvinyl alcohol; polyvinylpyrrolidone; Polydienes such as polypropylene and polybutadiene; Polyalkenes such as polyisobutylene; Fluorine resins such as vinylidene fluoride resin, hexafluoropropylene resin, hexafluoroacetone resin, polytetrafluoroethylene resin; polyethylene, polypropylene, ethylene- A porous body of a resin such as a polyolefin resin such as a propylene copolymer may be mentioned, but is not limited thereto.

  The technique for opening pores in the above polymer material is not particularly limited, and various methods such as a stretching method, a solution casting method, an etching method by chemical treatment, and a laser beam irradiation method can be used.

  Hereinafter, the mesoporous organic-inorganic hybrid material constituting the electrolyte portion in the organic-inorganic hybrid electrolyte membrane of the present invention will be specifically described.

  The organic-inorganic hybrid material used in the present invention has a pore having a central pore diameter of 1 to 50 nm, and is bonded to a metal atom, an oxygen atom bonded to the metal atom, and the metal atom or the oxygen atom. It has a skeleton composed of an organic group having one or more carbon atoms and a functional group having an ion exchange ability bonded to the organic group in the pores.

In the organic-inorganic hybrid material used in the present invention, the center pore diameter of the pores is 1 to 50 nm as described above, preferably 1 to 30 nm, more preferably 1 to 10 nm. When the central pore diameter of the pores exceeds 50 nm, the capillary condensation phenomenon becomes difficult to occur, and when the relative pressure of the electrolyte solution in the atmosphere is less than 1.0, the pores are sufficiently filled with the electrolyte solution. Can not be. In general, the capillary condensation phenomenon is likely to occur with a decrease in the center pore diameter of the pores. However, if the center pore diameter is less than 1 nm, the electrolyte solution becomes not a liquid but a solid state, which is sufficient. Ion conductivity becomes difficult to express. The relationship between the relative pressure (p / p ₀ ) at which capillary action occurs and the pore diameter (D) is the following formula (Kelvin formula):
ln (p / p ₀ ) = − (2γV _L cos θ) / {(D / 2) RT}
(Wherein γ represents the surface tension of the flocculated liquid, V _L represents the molar molecular volume of the flocculated liquid, θ represents the contact angle between the pore wall and the flocculated liquid, R represents the gas constant, and T is (Represents absolute temperature)
It can be expressed as From the above equation, it can be seen that the smaller the pore diameter, the lower the relative pressure at which capillary action occurs.

  The central pore diameter here is a curve (pore diameter) in which the value (dV / dD) obtained by differentiating the pore volume (V) with respect to the pore diameter (D) is plotted against the pore diameter (D). It is the pore diameter at the maximum peak of the distribution curve. The pore size distribution curve can be obtained by the method described below. That is, the organic-inorganic composite material is cooled to liquid nitrogen temperature (-196 ° C.), nitrogen gas is introduced, the adsorption amount is obtained by the constant volume method or the gravimetric method, and then the pressure of the introduced nitrogen gas is gradually increased. Then, the adsorption amount of nitrogen gas with respect to each equilibrium pressure is plotted, and an adsorption isotherm is obtained. Using this adsorption isotherm, a pore size distribution curve can be obtained by a calculation method such as Cranston-Inklay method, Pollmore-Heal method, BJH method.

  The organic-inorganic hybrid material used in the present invention preferably contains 60% or more of the total pore volume in the range of ± 40% of the central pore diameter in the pore diameter distribution curve. Here, “60% or more of the total pore volume is included in the range of ± 40% of the pore diameter showing the maximum peak in the pore diameter distribution curve” means that the central pore diameter is 3.00 nm, for example. In this case, it means that the total volume of pores in the range of ± 40% of 3.00 nm, that is, 1.80 to 4.20 nm occupies 60% or more of the total pore volume. An organic-inorganic hybrid material that satisfies this condition means that the pore diameter is very uniform.

Moreover, there is no restriction | limiting in particular about the specific surface area of the organic inorganic hybrid material used in this invention, However, It is preferable that it is 700 m < ² > / g or more. The specific surface area can be calculated as a BET specific surface area from the adsorption isotherm using the BET isotherm adsorption equation.

  Furthermore, the organic-inorganic hybrid material used in the present invention preferably has one or more peaks at a diffraction angle corresponding to a d value of 1 nm or more in the X-ray diffraction pattern. The X-ray diffraction peak means that a periodic structure having a d value corresponding to the peak angle is present in the sample. Therefore, having one or more peaks at a diffraction angle corresponding to a d value of 1 nm or more means that the pores are regularly arranged at intervals of 1 nm or more.

  The pores of the organic-inorganic hybrid material used in the present invention are formed not only on the surface of the particles but also inside. The shape of the pores is not particularly limited, but may be, for example, one that penetrates in a tunnel shape, or may have a shape in which spherical or polygonal cavities are connected to each other.

As described above, the organic-inorganic hybrid material used in the present invention has a skeleton composed of a metal atom, an oxygen atom bonded to the metal atom, and an organic group having one or more carbon atoms bonded to the metal atom or the oxygen atom. It is what you have. Examples of such a skeleton include the following skeletons (a) and (b):
(A) a skeleton (hereinafter referred to as an organic group having one or more carbon atoms, two or more metal atoms bonded to the same or different carbon atoms in the organic group, and one or more oxygen atoms bonded to the metal atoms) , “Organic inorganic hybrid skeleton”);
(B) In an inorganic skeleton composed of a metal atom and an oxygen atom bonded to the metal atom, a skeleton in which an organic group having one or more carbon atoms is bonded to the metal atom or the oxygen atom (hereinafter referred to as “surface-modified organic-inorganic hybrid skeleton” ")
Is mentioned.

  (A) The organic group in the organic-inorganic hybrid skeleton needs to have a valence of 2 or more in order to bond to 2 or more metal atoms. Examples of such an organic group include divalent or higher valent organic groups generated by elimination of two or more hydrogen atoms from hydrocarbons such as alkanes, alkenes, alkynes, benzenes, and cycloalkanes. In addition, the organic-inorganic hybrid skeleton according to the present invention may contain only one kind of the above organic group or may contain two or more kinds.

In the present invention, since an organic-inorganic hybrid material having an appropriate degree of crosslinking can be obtained, the valence of the organic group is preferably divalent. Examples of the divalent organic group include a methylene group (—CH ₂ —), an ethylene group (—CH ₂ CH ₂ —), a trimethylene group (—CH ₂ CH ₂ CH ₂ —), and a tetramethylene group (—CH ₂ CH ₂ CH ₂ CH ₂ —), 1,2-butylene group (—CH (C ₂ H ₅ ) CH—), 1,3-butylene group (—CH (CH ₃ ) CH ₂ CH ₂ —), phenylene group (— C ₆ H ₄ -), diethyl phenylene group _{(-C 2 H 4 -C 6 H} 4 -C 2 H 4 -), vinylene group (-CH = CH-), the propenylene group _{(-CH 2} -CH = CH 2 -), butenylene _{(-CH 2 -CH = CH-CH} 2 -), amide group (-CO-NH-), dimethylamino group _(-CH 2 _-NH-CH 2 -), trimethylamine group (-CH _{2 -N (CH 3) -CH 2 -} ) and the like Among these, a methylene group, an ethylene group, and a phenylene group are preferable because porous particles having high crystallinity can be obtained.

  Two or more metal atoms are bonded to the same or different carbon atoms in the above organic group, but the type of the metal atom is not particularly limited. For example, silicon, aluminum, titanium, magnesium, zirconium, tantalum, niobium, molybdenum , Cobalt, nickel, gallium, beryllium, yttrium, lanthanum, hafnium, tin, lead, vanadium, and boron. Of these, silicon, aluminum, and titanium are preferable because of their good bondability with organic groups and oxygen. In addition, although said metal atom couple | bonds with an organic group and couple | bonds with an oxygen atom, an oxide is formed, This oxide may be complex oxide which consists of 2 or more types of metal atoms.

  The organic-inorganic hybrid skeleton is formed by the above-described organic group, metal atom, and oxygen atom bond, but the type of bond is not limited, and examples thereof include a covalent bond and an ionic bond. Further, organic-inorganic composite materials having different skeletons (straight, ladder, network, branched, etc.) are generated depending on the number of metal atoms bonded to the organic group and the number of oxygen atoms bonded to the metal atom.

  In the organic-inorganic hybrid skeleton, the organic group is bonded to two or more metal atoms, and the metal atom is bonded to one or more oxygen atoms. Therefore, the organic group is incorporated into the skeleton of the metal oxide. As a result, the organic-inorganic composite material according to the present invention exhibits both organic / inorganic surface characteristics.

で表される構成単位の少なくとも１種からなるものが好ましい。 Among such organic-inorganic hybrid skeletons, the following general formula (1):

What consists of at least 1 type of the structural unit represented by these is preferable.

In the above formula (1), R ¹ represents an organic group having one or more carbon atoms, and M represents a metal atom. Specific examples of R ¹ and M include the groups and atoms exemplified in the above description of the organic group and metal atom.

In the above formula (1), R ² represents a hydrogen atom, a hydroxyl group or a hydrocarbon group. When R ² is a hydrocarbon group, the type thereof is not limited. Examples of R ² include an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 1 to 10 carbon atoms, a phenyl group, and a substituted phenyl group. Etc.

In the general formula (1), x represents an integer obtained by subtracting 1 from the valence of the metal M, n represents an integer of 1 to x, and m represents an integer of 2 or more. The carbons of R1 to which M is bonded may be the same or different. -O _1/ 2-represents a group which becomes -O- by bonding two of them.

で表され、上記化学式（３）の構成単位が２個連結した骨格は下記化学式（４）： In the general formula (1), when R ¹ , M, R ² , n, and m are an ethylene group, a silicon atom, a methyl group, and 1, 2, respectively, the general formula (1) is represented by the following chemical formula (3). :

And a skeleton in which two structural units of the chemical formula (3) are linked is represented by the following chemical formula (4):

で表される。

It is represented by

In the general formula (1), when R ¹ , M, n, and m are an ethylene group, a silicon atom, and 3, 2, respectively, the general formula (1) is represented by the following chemical formula (5):

で表され、上記化学式（５）の構成単位が複数個連結すると網状構造を形成する。下記化学式（６）：

When a plurality of structural units of the chemical formula (5) are connected, a network structure is formed. The following chemical formula (6):

はその網状構造の一例として上記化学式（５）の構成単位の４個が連結した場合示すものである。

Shows an example of the network structure when four of the structural units of the chemical formula (5) are linked.

The organic-inorganic hybrid skeleton used in the present invention may be composed of a plurality of structural units having different R ¹ , M, R ² , n, and m in the general formula (1). It may consist of a structural unit represented by the chemical formula (3) and a structural unit represented by the chemical formula (5). In addition, when the organic-inorganic composite material according to the present invention has a structural unit represented by the general formula (1) as an organic-inorganic hybrid skeleton, other than the structural unit, for example, Si— (O _1/2 ) _{4 -, Ti- (O 1/2) 4} - may have a constitutional unit, and the like.

で表される化合物の少なくとも１種類を重縮合することにより得ることができる。 An organic-inorganic hybrid material having an organic-inorganic hybrid skeleton is, for example, the following general formula (2):

It can obtain by carrying out the polycondensation of at least 1 type of the compound represented by these.

^{Wherein, R} 1, M and ^{R 2} is ^R 1, M, is the same as ^{R 2} in each of the above general formula (1). A represents an alkoxyl group or a halogen atom, x represents an integer obtained by subtracting 1 from the valence of the metal M, n represents an integer of 1 to x, and m represents an integer of 1 or more. The carbons of R1 to which M is bonded may be the same or different.

When A in the general formula (2) is an alkoxyl group, the type of hydrocarbon group bonded to oxygen in the alkoxyl group is not particularly limited. For example, chain, cyclic, and alicyclic hydrocarbons may be used. Can be mentioned. This hydrocarbon group is preferably a chain alkyl group having 1 to 5 carbon atoms, and more preferably a methyl group or an ethyl group.
In addition, when A in the general formula (6) is a halogen atom, the type thereof is not particularly limited, and examples thereof include a chlorine atom, a bromine atom, a fluorine atom, and an iodine atom. And bromine are preferred.

In the general formula (2), when R ¹ , M, A, n, and m are ethylene group, silicon, methoxy group, 3, and 2, respectively, the compound represented by the general formula (2) is ( It becomes 1,2-bis (trimethoxysilyl) ethane represented by CH ₃ O) ₃ Si—CH ₂ —CH ₂ —Si (OCH ₃ ) ₃ .

In the general formula (2), when R ¹ , M, A, n, and m are each an ethylene group, silicon, chlorine, 3, 2, the compound represented by the general formula (2) is: It becomes 1,2-bis (trichlorosilyl) ethane represented by Cl ₃ Si—CH ₂ —CH ₂ —SiCl ₃ .

  In the present invention, alkoxysilane, titanium alkoxide, aluminum alkoxide or the like may be added to the compound represented by the general formula (2) for polycondensation.

  As the alkoxysilane, tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, or the like can be used. In addition, alkoxysilane having a functional group such as an amino group, a carboxyl group, a mercapto group, or an epoxy group can also be used.

As the titanium alkoxide, for example, titanium butoxide, titanium isopropoxide, and titanium ethoxide can be used. As the aluminum alkoxide, for example, aluminum isopropoxide can be used. Various metal halides such as chlorinated silicon (SiCl ₄ ) can also be used.

Further, by adding pseudoboehmite, sodium aluminate, aluminum sulfate, dialkoxyaluminotrialkoxysilane and the like to the compound represented by the above general formula (2), alkoxysilane, and the like, and reacting them, SiO ₂ —Al ₂ O _Three skeletons can be introduced. Further, V, B, and Mn can be introduced into the skeleton by adding vanadyl sulfate (VOSO ₄ ), boric acid (H ₃ BO ₃ ), manganese chloride (MnCl ₂ ), and the like to cause a reaction.

  When producing an organic-inorganic composite material having an organic-inorganic hybrid skeleton, the compound represented by the general formula (2) may be added to an aqueous solution containing a surfactant and polycondensed under acidic or alkaline conditions. preferable.

As the surfactant, any of cationic, anionic and nonionic surfactants can be used. Such surfactants, such as alkyl trimethyl ammonium _{[C n H 2n + 1 N} (CH 3) 3], alkylammonium, dialkyldimethylammonium chloride benzyl ammonium bromide, such as iodide or hydroxide Other examples include fatty acid salts, alkyl sulfonates, alkyl phosphates, polyethylene oxide nonionic surfactants, primary alkyl amines, and the like.

As alkyltrimethylammonium [C _n H _{2n + 1} N (CH ₃ ) ₃ ], it is preferable to use an alkyl group having 8 to 18 carbon atoms.

Examples of the nonionic surfactant include a polyethylene oxide nonionic surfactant having a hydrocarbon group as a hydrophobic component and a polyethylene oxide chain as a hydrophilic component. Examples of such a surfactant include C ₁₆ H ₃₃ (OCH ₂ CH ₂ ) ₂ OH, C ₁₂ H ₂₅ (OCH ₂ CH ₂ ) ₄ OH, C ₁₆ H ₃₃ (OCH ₂ CH ₂ ) ₁₀ OH, C ₁₆ H ₃₃ (OCH ₂ CH ₂ ) ₂₀ OH, C ₁₈ H ₃₇ (OCH ₂ CH ₂ ) ₁₀ OH, C ₁₈ H ₃₅ (OCH ₂ CH ₂ ) ₁₀ OH, C ₁₂ H ₂₅ (OCH ₂ CH ₂ ) ₂₃ OH etc. are mentioned.

  A surfactant having a sorbitan fatty acid ester component and a polyethylene oxide component can also be used. As such surfactants, Triton X-100 (Aldrich), polyethylene oxide (20) sorbitan monolaurate (Tween 20, Aldrich), polyethylene oxide (20) sorbitan monopalmitate (Tween 40), polyethylene oxide (20) sorbitan Examples thereof include monostearate, polyethylene oxide (20) sorbitan monooriate (Tween 60), sorbitan monopalmitate (Span 40), and the like.

As the surfactant, a triblock copolymer comprising three polyalkylene oxide chains can also be used. Among these, a triblock copolymer represented by a polyethylene oxide (EO) chain-polypropylene oxide (PO) chain-polyethylene oxide (EO) chain is preferable. When the number of EO chain repeats is x and the number of PO chain repeats is y, this triblock copolymer can be represented as (EO) _x (PO) _y (EO) _x . The x and y of the triblock copolymer used in the present invention are not particularly limited, but x is preferably 5 to 110, y is preferably 15 to 70, x is 15 to 20, and y is 50 to 60. More preferably.

Furthermore, as a surfactant, a polypropylene oxide (PO) chain-polyethylene oxide (EO) chain-polypropylene oxide (PO) chain triblock copolymer ((PO) _x (EO) _y (PO) _x ) can also be preferably used. Here, x and y are not particularly limited, but x is preferably 5 to 110, and y is preferably 15 to 70, more preferably 15 to 20, and y is 50 to 60.

Examples of the triblock copolymer include (EO) ₅ (PO) ₇₀ (EO) ₅ , (EO) ₁₃ (PO) ₃₀ (EO) ₁₃ , (EO) ₂₀ (PO) ₃₀ (EO) ₂₀ , (EO). ₂₆ (PO) ₃₉ (EO) ₂₆ , (EO) ₁₇ (PO) ₅₆ (EO) ₁₇ , (EO) ₁₇ (PO) ₅₈ (EO) ₁₇ , (EO) ₂₀ (PO) ₇₀ (EO) ₂₀ , ( EO) ₈₀ (PO) ₃₀ (EO) ₈₀ , (EO) ₁₀₆ (PO) ₇₀ (EO) ₁₀₆ , (EO) ₁₀₀ (PO) ₃₉ (EO) ₁₀₀ , (EO) ₁₉ (PO) ₃₃ (EO) ₁₉ , (EO) ₂₆ (PO) ₃₆ (EO) ₂₆ . Among these, (EO) ₁₇ (PO) ₅₆ (EO) ₁₇ and (EO) ₁₇ (PO) ₅₈ (EO) ₁₇ are preferably used. These triblock copolymers are available from BASF, etc., and triblock copolymers having desired x and y values can be obtained at a small scale production level. The above triblock copolymers can be used alone or in combination of two or more.

Also, a star diblock copolymer in which two polyethylene oxide (EO) chains-polypropylene oxide (PO) chains are bonded to two nitrogen atoms of ethylenediamine can be used. As such a star diblock copolymer, ((EO) ₁₁₃ (PO) ₂₂ ) ₂ NCH ₂ CH ₂ N ((PO) ₂₂ (EO) ₁₁₃ ) ₂ , ((EO) ₃ (PO) ₁₈ ) ₂ NCH ₂ CH ₂ N ((PO) ₁₈ (EO) ₃ ) ₂ , ((PO) ₁₉ (EO) ₁₆ ) ₂ NCH ₂ CH ₂ N ((EO) ₁₆ (PO) ₁₉ ) _{2 and the} like. The above star diblock copolymers can be used alone or in combination of two or more.

  An organic-inorganic hybrid material having an organic-inorganic hybrid skeleton is obtained by adding the compound represented by the general formula (2) (and an inorganic compound such as alkoxysilane if necessary) to an aqueous solution containing a surfactant, Although it can be obtained by polycondensation under alkaline conditions, the pH of the aqueous solution is preferably 7 or more.

  In addition, an organometallic compound (and inorganic compound if necessary) is polycondensed in the absence of a surfactant under acidic or alkaline conditions to form an oligomer, and the surfactant is added to an aqueous solution containing this oligomer. Further, polycondensation can be performed under acidic or alkaline conditions.

  In polycondensation in the presence of a surfactant, polycondensation under alkaline conditions and polycondensation under acidic conditions can be performed alternately. At this time, the order of the alkaline condition and the acidic condition is not particularly limited. However, when polycondensation is performed under acidic conditions and polycondensation is performed under alkaline conditions, the degree of polymerization tends to increase. In the polycondensation reaction, it is preferable to perform stirring and standing alternately.

  The reaction temperature of the polycondensation is preferably in the range of 0 to 100 ° C., but the lower the temperature, the higher the regularity of the structure of the product. A preferable reaction temperature is 20 to 40 ° C. in order to increase the regularity of the structure. On the other hand, the higher the reaction temperature, the higher the degree of polymerization tends to increase the structural stability. In order to increase the degree of polymerization, a preferable reaction temperature is 60 to 80 ° C.

  After the polycondensation reaction, the precipitate or gel produced after aging is filtered, and if necessary washed and dried, the porous precursor with the surfactant filled in the pores is obtained. can get.

  This porous particle precursor is used in an aqueous solution containing the same surfactant as that used in the polycondensation reaction (typically with a surfactant concentration equal to or lower than that in the polycondensation reaction) or water. The precursor can be dispersed in an electrolyte solution and hydrothermally treated at 50 to 200 ° C. In this case, the solution used in the polycondensation reaction can be heated as it is or after dilution. The heating temperature is preferably 60 to 100 ° C, and more preferably 70 to 80 ° C. Moreover, it is preferable that pH at this time is weak alkalinity, and it is preferable that pH is 8-8.5, for example. Although there is no restriction | limiting in particular in the time of this hydrothermal treatment, 1 hour or more is preferable and 3-8 hours are more preferable.

  After this hydrothermal treatment, the porous body precursor is filtered and then dried to remove excess treatment liquid. In addition, before dispersing the porous body precursor in the above aqueous solution or solvent and starting the hydrothermal treatment after pH adjustment, a stirring treatment may be previously performed at room temperature for several hours to several tens of hours.

  Next, the surfactant is removed from the porous precursor. Examples of the method include a method by firing and a method of treating with a solvent such as water or alcohol.

  In the method by firing, the porous particle precursor is heated at 300 to 1000 ° C, preferably 400 to 700 ° C. The heating time may be about 30 minutes, but it is preferable to heat for 1 hour or longer in order to completely remove the surfactant component. Firing can be performed in the air, but since a large amount of combustion gas is generated, it may be performed by introducing an inert gas such as nitrogen.

  When removing the surfactant from the porous particle precursor using a solvent, for example, the porous material precursor is dispersed in a solvent having a high solubility of the surfactant, and the solid content is recovered after stirring. As the solvent, water, ethanol, methanol, acetone or the like can be used.

  When a cationic surfactant is used, the porous material precursor is dispersed in ethanol or water to which a small amount of hydrochloric acid is added, and stirred while heating at 50 to 70 ° C. Thereby, a cationic surfactant is ion-exchanged and extracted by protons. When an anionic surfactant is used, the surfactant can be extracted in a solvent to which an anion has been added. In addition, when a nonionic surfactant is used, extraction can be performed only with a solvent. In addition, it is preferable to irradiate an ultrasonic wave at the time of extraction. Further, it is preferable to combine or repeat stirring and standing.

  The shape of the organic-inorganic hybrid material used in the present invention can be controlled by the synthesis conditions. The shape of the organic-inorganic hybrid material reflects the arrangement structure of the pores of the particles, and the shape is determined by determining the crystal structure. For example, the crystal structure of spherical particles is three-dimensional hexagonal, and the crystal structure of hexagonal columnar particles is two-dimensional hexagonal. The crystal structure of the octahedral particles is cubic.

  Examples of the synthesis conditions that affect the shape (crystal structure) of the organic-inorganic hybrid material include the reaction temperature and the length of the surfactant (carbon number). For example, when alkyltrimethylammonium is used as the surfactant, the carbon number of the alkyl group and the reaction temperature affect the shape of the organic-inorganic composite material. For example, when the reaction temperature is 95 ° C. and the carbon number of the alkyl group is 18, hexagonal columnar particles are easily formed, and when the reaction temperature is 95 ° C. and the carbon number of the alkyl group is 16, the octahedron -Like particles are easily generated. In addition, when the reaction temperature is 25 ° C., spherical particles are likely to be produced when the alkyl group has 18 or 16 carbon atoms. On the other hand, when the reaction temperature is 2 ° C. and the alkyl group has 18 carbon atoms, a layered structure is formed. When the reaction temperature is 2 ° C. and the alkyl group has 16 carbon atoms, spherical particles are likely to be formed.

  On the other hand, the (b) surface-modified organic-inorganic hybrid skeleton has an inorganic oxide polymer main chain composed of metal atoms and oxygen atoms. Here, examples of the metal atom constituting the main chain include the metal atoms exemplified in the description of the organic-inorganic hybrid skeleton, and among them, silicon, Aluminum and titanium are preferred. In the surface-modified organic-inorganic composite skeleton, metal atoms are combined with oxygen atoms to form an oxide, but this oxide may be a composite oxide containing two or more metal atoms. Further, the main chain of the inorganic skeleton may be linear, branched, ladder-like, or network-like.

  Specific examples of the organic group in the surface-modified organic-inorganic hybrid skeleton include an alkyl group having 1 to 6 carbon atoms such as a methyl group and an ethyl group; an aryl group having 6 to 12 carbon atoms such as a phenyl group, and the like. . The bonding position of these organic groups may be either a metal atom or an oxygen atom constituting the inorganic skeleton.

  The method for producing the organic-inorganic hybrid material having the surface-modified organic-inorganic hybrid skeleton is not particularly limited. For example, when forming a silicate skeleton (—Si—O—), the following formula (7):

（式中、Ｒは炭素数１〜６のアルキル基又は炭素数６〜１２のアリール基を表し、Ｒ’はメチル基又はエチル基を表す）
で表されるオルガノシラン、並びに必要に応じて用いられるテトラメトキシシラン、テトラエトキシシラン、テトラプロポキシシラン等のアルコキシシラン、をテンプレートとしての界面活性剤を用いて縮重合し、その後、界面活性剤を除去することによって得ることができる。また、上記のアルコキシシランや、ケイ酸ソーダ、カネマイト（ｋａｎｅｍｉｔｅ、ＮａＨＳｉ_２Ｏ_５・３Ｈ_２Ｏ）等の無機骨格成分を界面活性剤を用いて縮重合し、界面活性剤を除去して無機多孔体とした後、無機系骨格の表面に存在するシラノール基（Ｓｉ−ＯＨ）に上記のオルガノシランやトリメトキシクロロシラン［Ｃｌ−Ｓｉ−（ＯＣＨ_３）_３］等のハロゲン化オルガノシランを反応させることによって、無機系骨格の表面に有機基を導入することもできる。

(In the formula, R represents an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 12 carbon atoms, and R ′ represents a methyl group or an ethyl group).
In addition, a surfactant is used as a template for the polysilanes, and the alkoxysilanes such as tetramethoxysilane, tetraethoxysilane, and tetrapropoxysilane that are used as necessary. It can be obtained by removing. In addition, inorganic skeleton components such as alkoxysilane, sodium silicate, kanemite (Kanemite, NaHSi ₂ O ₅ .3H ₂ O) and the like are polycondensed using a surfactant, and the surfactant is removed to form an inorganic porous material. Then, the silanol group (Si—OH) present on the surface of the inorganic skeleton is reacted with a halogenated organosilane such as the above organosilane or trimethoxychlorosilane [Cl—Si— (OCH ₃ ) ₃ ]. Thus, an organic group can be introduced into the surface of the inorganic skeleton.

In addition, an inorganic skeleton containing aluminum can be formed by using pseudo-bomalite, sodium aluminate, aluminum sulfate, dialkoxyaluminotrialkoxysilane, or the like. Furthermore, various metals (Mn +; M is Ti) can be obtained by using oxides in which Si of the inorganic skeleton component exemplified in the formation of the silicate skeleton is replaced with a metal such as Ti, Zr, Ta, Nb, Sn, and Hf. , Zr, Ta, Nb, Sn, Hf, etc., where n represents the charge of the metal) in the silicate skeleton, a metallosilicate skeleton (SiO ₂ —MO _{n / 2} ) can be obtained. Specifically, a titanate compound such as Ti (OC ₂ H ₅ ) ₄ , vanadyl sulfate (VOSO ₄ ), boric acid (H ₃ BO ₃ ) or manganese chloride (MnCl ₂ ) is added to the alkoxysilane to carry out a copolymerization reaction. By performing, a metallosilicate porous body into which Ti, V, B, or Mn is introduced can be obtained.

  In the formation of the surface-modified organic-inorganic hybrid skeleton, the surfactants exemplified in the explanation of the organic-inorganic hybrid skeleton can be used as a template, and the surface-modified organic-inorganic hybrid skeleton can be reduced in the same manner as the formation of the organic-inorganic hybrid skeleton. Polymerization and surfactant removal can be performed.

  In order for the organic-inorganic hybrid material to function as a solid electrolyte in the present invention, the organic-inorganic hybrid material having the above-described configuration needs to have a configuration in which a functional group having ion exchange ability is bonded to an organic group in the pores. . Thereby, even if the relative pressure of water vapor is less than 1.0, sufficiently high ionic conductivity is exhibited at a lower temperature than conventional solid electrolytes such as stabilized zirconium.

  Here, the functional group having ion exchange ability has a function of easily causing a phenomenon that the pores are filled with an electrolyte solution such as water in addition to the function of imparting ion conductivity to the solid electrolyte. . That is, even when the functional group having ion exchange ability is not arranged in the pores of the organic-inorganic hybrid material used in the present invention, the capillary condensation phenomenon appears. By disposing a functional group having ion exchange capacity therein, the pores can be sufficiently filled with the electrolyte solution under conditions where the relative pressure of the electrolyte solution is lower.

Specific examples of the functional group having ion exchange ability include a sulfonic acid group, a phosphoric acid group, a carboxylic acid group, and a sulfonimide group. The functional group is a sulfonic acid group (—SO ₃ H), When at least one selected from the group consisting of a phosphoric acid group (—PO ₄ H ₂ or> PO ₄ H) and a carboxylic acid group (—COOH), the pores can be formed in a pore under a condition where the relative pressure of the electrolyte solution is lower. Can be sufficiently filled with the electrolyte solution, and higher ionic conductivity can be obtained.

In addition, the method for binding the functional group having ion exchange capacity with the organic group is not particularly limited.
(1) When the functional group having ion exchange ability is a sulfonic acid group, a sulfonic acid oxidizing agent such as fuming sulfuric acid, sulfuric anhydride (sulfur acid oxide, SO ₃ ), chlorosulfonic acid (chlorosulfuric acid, ClSO ₃ H), etc. A method using
(2) When the functional group having ion exchange ability is a phosphate group, a method using a phosphorylating agent such as phosphorus oxychloride (POCl ₃ ), or after reacting triethyl phosphite after chloromethylation Hydrolyzing with water;
(3) When the functional group having ion exchange ability is a carboxylic acid group, a method of introducing a group whose side chain group or terminal group is a methyl group as an organic group and oxidizing the methyl group, etc. It is done.

  The content of the particles of the organic-inorganic hybrid material in the organic-inorganic hybrid electrolyte membrane of the present invention is not particularly limited as long as the excellent ion conductivity is not impaired, but preferably 40-80 based on the total amount of the organic-inorganic hybrid electrolyte membrane. % By weight. When the content of the solid electrolyte in the organic-inorganic hybrid electrolyte membrane is less than the lower limit, a sufficiently high ionic conductivity tends not to be obtained when the relative pressure of the electrolyte solution in the atmosphere is less than 1.0. On the other hand, if it exceeds the upper limit, it tends to be difficult to mold into a film or the film strength tends to decrease.

  The organic-inorganic hybrid electrolyte membrane of the present invention having the above configuration is sufficiently low at a temperature lower than that of a conventional solid electrolyte such as stabilized zirconium even when the relative pressure of the electrolyte solution in the atmosphere is less than 1.0. It makes it possible to obtain high ion conductivity, and can be suitably used for applications such as electrolyte membranes of solid polymer fuel cells and oxide fuel cells, electrolytes of all solid state batteries, and sensors. In addition, it does not restrict | limit especially as electrolyte solution used in this invention, Specifically, although water, alcohol, a pyridine, imidazole etc. are mentioned, Among these, it is preferable to use water. Moreover, the use conditions of the organic-inorganic hybrid electrolyte membrane of the present invention are not particularly limited, but the relative pressure of the electrolyte solution is preferably 0 to 70%, and the use temperature is in the range of 0 to 100 ° C. Is preferred.

The present invention will be described in more detail with reference to the following examples.
[Example 1]
BTEB condensate polymerized gas inlet tube, exhaust tube, 200 mL four-necked flask equipped with a stirrer was cooled for 10 minutes in an ice bath containing BTEB (1,4-bistrioxysilylbenzene) as a Si source, and then ethanol ( Solvent), distilled water and hydrochloric acid (catalyst) were introduced into the flask using a syringe so as to have a predetermined molar ratio (Table 1). The reaction was performed at 150 rpm, a nitrogen flow rate of 360 mL / min, and 80 ° C. (oil bath) for 1.5 hours. The molar ratio of HCI to BTEB is 0.005, 0.01, 0.02, 0.03 (EtOH / BTEB = 40 molar ratio constant), and the molar ratio of H ₂ O to BTEB at each HCI / BTEB ratio. (R) was changed (r = 1.0-2.0).

Evaluation Method GPC (liquid chromatography: manufactured by Tosoh Corporation, column: Super AW, solvent: 10 mM H ₃ PO ₄ in 2-methoxyethanol, flow rate: 0.6 / min, detector: HLC-8120 GPC internal RI for measuring sol molecular weight Detector, standard sample: polymethyl methacrylate) was used. The route of the sol structure was ²⁹ Si-NMR (JNM-LA500, manufactured by JEOL Ltd.) (solvent: CDDI ₃ , Ref: TMS was used).

Results Figure 1 of high molecular weight indicates the molecular weight of the sol obtained in each condition (weight average molecular weight). Table 2 shows the yield of the sol obtained by the reaction obtained under each condition and the molecular weight of the sol (Mn: number average molecular weight, Mw: weight average molecular weight). The molecular weight dispersity (Mw / Mn) increased with increasing r. Moreover, the yield decreased as the water ratio (r) to BTEB increased (the amount of BTEB raw material charged: 2.01 g common to each condition). It can be considered that as r increases, the hydrolysis reaction proceeds faster, and the remaining Etoxy groups are relatively reduced (see Tables 2a, b, c, and d).

[Example 2]
BTEB / BDEB condensate polymerized gas inlet tube, exhaust tube, 200 mL four-necked flask equipped with a stirrer and cooled for 10 minutes in an ice bath containing BTEB (1,4-bistrioxysilylbenzene) as Si source, followed by Ethanol (solvent), distilled water and hydrochloric acid (catalyst) were introduced into the flask using a syringe so as to have a predetermined molar ratio (Table 3). After reacting for 1 hour under the conditions of a rotational speed of 150 rpm, a nitrogen flow rate of 360 mL / min, and room temperature (15 ° C.), the reaction was further carried out at 80 ° C. (oil bath) for 1.5 hours. The molar ratio (r) of H ₂ O corresponding to BTEB is r = 1.0, 1.5, 2.0, 30 (constant molar ratio of EtOH and HCI). After completion of the reaction, the sol obtained by allowing to cool for 10 minutes under RT was adjusted to a 20 wt% acetone ethanol solution (acetone and ethanol were weighed and mixed respectively) and poured into a PFA petri dish. Further, in order to lower the crosslink density of the BTEB film, a sol solution was prepared by the same method using BDEB (1,4-Bistrioxysilylbenzene) as a Si source and the mixing ratios shown in Tables 4 and 5. The molar ratio (r) of water to the substrate (Si raw material: BTEB + BDEB) was constant at r = 1.0 (Table 4) and 1.5 (Table 5). The sol cast in the PFA petri dish was kept at 80 ° C. for 2 weeks with a dryer.

Evaluation Method GPC (liquid chromatography: manufactured by Shimadzu Corporation, column: Polymer Science Mixed D, solvent: THF, flow rate: 1.0 / min, detector: SPD-10A, standard sample: polystyrene) was used to measure the sol molecular weight. Using.

As a result of the high molecular weight FIG. 2 shows the molecular weight of the sol adjusted with the mixing ratios described in Tables 4 and 5. By adding BDEB for r = 1.5, the molecular weight increased, the weight average molecular weight was 51,300, and it was possible to polymerize up to about 120-mer.

[Example 3]
BTEB / BMEB condensate polymerized gas introduction tube, exhaust tube, 200 mL four-necked flask equipped with a stirrer was charged with BTEB and BMEB as Si sources and cooled in an ice bath for 10 minutes, followed by ethanol (solvent) and distillation Water and hydrochloric acid (catalyst) were charged into the flask using a syringe so as to have a predetermined molar ratio (Table 6). The reaction was performed at 150 rpm, a nitrogen flow rate of 360 mL / min, and 80 ° C. (oil bath) for 1.5 hours. The mixing ratio (molar ratio) of BTEB and BMEB is BTEB: BMEB = 1: 0, 0.7: 0.3, 0.5: 0.5, 0.3: 0.7, 0.2: 0.8 It was. After completion of the reaction, ethanol was added to the sol obtained by allowing to cool at room temperature for 10 minutes (adjusted to a 20 wt% ethanol solution), poured into a Teflon petri dish, and dried at 60 ° C. for 24 hours.

Evaluation method In order to measure the sol molecular weight before casting, GPC (liquid chromatography: manufactured by Tosoh Corporation, column: Super AW, solvent: 10 mM LiBr + 10 mM H ₃ PO ₄ in 2-methoxyethanol, flow rate: 0.6 / min, detector: HLC-8120GPC visceral RI detector, standard sample: polymethylmethacrylate) was used. The strength of the self-supporting film was measured using an all-purpose sample testing machine (INSTRON-5564), the test piece was cut into a 5 × 50 mm square strip, and the tensile speed of the test piece was 120 mm / min.

As a result of high molecular weight FIG. 3 shows the weight average molecular weight of BTEB / BMEB sols with different catalysts under a constant r (H ₂ O / Si) = 1.0. The molecular weight of the sol obtained with HCI / Si = 0.02 and BTEB: BMEB = 0.5: 0.5 reached 30,000. Similarly, the molecular weight of the sol obtained with HCI / Si = 0.01 and BTEB: BMEB = 0.2: 0.8 reached 8,900.

FIG. 4 shows the weight average molecular weight of the BTEB / BMEB sol obtained under different conditions of r (H ₂ O / Si) with HCI / Si = 0.02 constant. For r = 1.0 and 1.3, copolymerization was possible until BTEB: BMEB = 0.5: 0.5 and 0.3: 0.7, respectively. The weight average molecular weight reached about 30,000 in both conditions.

FIG. 5 shows the weight average molecular weight of the BTEB / BMEB sol obtained under different conditions of r (H ₂ O / Si) with HCI / Si = 0.01 constant. For r = 1.0 and 1.5, copolymerization was possible up to BTEB: BMEB = 0.3: 0.7, respectively, and the weight average molecular weight was Mw = 51,300 (BTEB: BMEB = 0.3: 0) .7 composition r = 1.5).

[Example 4]
One-pot sol in which tetraethoxysilane (TEOS), 3-mercaptopropyltriethoxysilane (MPTES), ethanol, hydrochloric acid, water-retaining nonionic surfactant (F127), and hydrogen peroxide (mercapto group oxidizing agent) are mixed. A membrane was prepared by filling the solution with a polyethylene porous film (Teijin Solfil).

Raw Material FIG. 6 shows a procedure for producing a one-pot impregnated membrane using a polyethylene porous film. The reagent used was a special grade reagent purchased from Wako Pure Chemical Industries, Ltd., Tokyo Chemical Industry Co., Ltd., and Aldrich. The polyethylene porous film is a Teijin Solfil porous body (weight: 7 g / m ² , thickness: 50 μm, porosity: 85%, air permeability: 15 s / 50 mL, average pore size: 0.3 μm, maximum pore size: 0.4 μm, tensile (Strength: 15 MP, elongation: 15%) was used.

Pretreatment of polyethylene porous film A polyethylene porous film (PE-film) was cut into 30 mm x 30 mm and immersed in ethanol (2 mL) for 5 minutes. This was degassed at 35 Pa at room temperature for 10 minutes, so that ethanol was immersed in the pores of PE-film. The pretreated PE-film was used in the next experiment in a normal state where ethanol remained.

Preparation of TEOS / MPTES / F127 / H ₂ O ₂ / Impregnated Membrane (Sol-1 / PE-film) Tetraethoxysilane: TEOS (0.83 g, 4 mmol) and 3-mercaptopropyltriethoxysilane: MPTES (0.239 g) 1 mmol) was stirred at room temperature for 30 minutes, and this was designated as Solution A. Next, a mixed solution of nonionic surfactant F127 (0.641 g), ethanol (10 ml), 6 mol / L hydrochloric acid aqueous solution (8.35 μL) and distilled water (443 μL) was stirred at room temperature for 30 minutes, B. Solution A was added to solution B with ethanol (1.1 mL) and stirred at room temperature for 1.5 hours. 30% hydrogen peroxide solution (0.681 mL) was added thereto, and the mixture was stirred at room temperature for 1.5 hours. The obtained reaction solution was designated as Sol-1. Sol-1 (4 mL) was poured into a pretreated PE-film and dried at 60 ° C. for 24 hours.

Impregnated membrane for comparison (Sol-2 / PE-film , Sol-3 / PE-film, Sol-4 / PE-film) surfactant-free system as impregnated membrane for regulating made comparisons (Sol-2 / PE-film), a system without hydrogen peroxide (Sol-3 / PE-film), and a system without MPTES (Sol-4 / PE-film) were prepared by the above-described methods. Table 7 shows the raw material composition of each sol solution.

Evaluation method X-ray diffraction (XRD) was performed using a RINT-TTR powder X-ray analyzer (Rigaku) at a tube voltage of 50 kV, a tube current of 300 mA, and an operation speed of 2 ° / min. The slits were a diffusion slit 1/6 deg, a scattering slit 1/6 deg, and a light receiving slit 0.15 mm.

The conductivity measurement sample was immersed in distilled water (room temperature for 24 hours), and then set in a conductivity measurement cell. Conductivity measurement of a free-standing film at a humidity of 100% (25 ° C.) was performed using an LCR meter while sandwiching the vertical (thickness) direction of the free-standing film between electrodes and applying a pressure of 32 kg / cm ² (0.25 MPa). The AC resistance at 1 kHz was measured. In addition, the conductivity of the free-standing film at a relative humidity of 80% or less (25 ° C.) is adjusted to the target humidity (20, 40, 60, 80%) in a constant humidity chamber by attaching electrodes in the horizontal direction of the film, The AC resistance at 1 kHz was measured using an LCR meter.

Structure and conductivity of organic-inorganic hybrid film As shown in FIG. 7, Sol-1 / PE-film (a) had higher transparency and higher flexibility than PE-film (b). The change in the transparency of the base material before and after the impregnation indicates that Sol-1 was sufficiently impregnated into PE-film. Further, the high flexibility of Sol-1 / PE-film shows the reinforcing effect. Moreover, the transparent and flexible impregnation film | membrane was obtained also in the other sol solution (Sol-2, Sol-3, Sol-4).

  The formation of the mesostructure of the impregnated film was investigated using the bulk of each sol solution. FIG. 8 shows an X-ray diffraction pattern of each sol solution. Sol-1 showed diffraction derived from a mesostructure at 2θ = 0.780 ° (d = 133.1 A). This indicates that a mesostructure can be formed at the Sol-1 raw material ratio. Similarly, also in the bulk bodies of Sol-3 and Sol-4, diffraction derived from the mesostructure at 2θ = 0.799 ° (d = 1110.4 A) and 2θ = 0.780 ° (d = 1113.1 A). Showed a peak. On the other hand, since the Sol-2 bulk body has no surfactant, no mesostructure was formed. These results suggest that a mesostructure is also formed in Sol-1 / PE-film, Sol-3 / PE-film, and Sol-4 / PE-film.

Table 8 shows the results of measuring proton conductivity (relative humidity 100%, room temperature) of four types of one-pot impregnated membranes and PE-film. The conductivity of PE-film was 2.1 × 10 ⁻⁷ S / cm, and the substrate alone showed almost no conductivity. The conductivity of Sol-1 / PE-film was 6.7 × 10 ⁻² S / cm, and the conductivity was improved by 5 digits by impregnating PE-1 film with Sol-1. The conductivity of Sol-2 / PE-film (system without surfactant) was 1.9 × 10 ⁻³ S / cm. This is a conductive performance of about 3% of Sol-1 / PE-film (system with a surfactant). This result suggests that the presence or absence of mesostructure has a great influence. Further, the conductivity of Sol-3 / PE-film (system without hydrogen peroxide solution) and Sol-4 / PE-film (system without MPTES) are 1.9 × 10 ⁻⁴ S / cm and 1.1, respectively. × 10 ^-4 S / cm. These results indicate that the “mercapto group oxidized with hydrogen peroxide solution = sulfonic acid group” in the impregnated organic silica is a conductor.

  FIG. 9 shows the results of measuring the conductivity of Sol-1 / PE-film under relative humidity of 20, 40, 50, 60, 80, and 90% (25 ° C.) and comparing the humidity dependency with Nafion. The conductivity of Sol-1 / PE-film at each relative humidity was 1-2 orders of magnitude lower than Nafion. In particular, the conductivity dropped rapidly in the region of relative humidity 60-100%. However, at a relative humidity of 20 to 60%, it was not affected by the ambient humidity and showed a substantially constant conductivity. On the other hand, the conductivity of Nafion changed linearly in proportion to humidity. The organic-inorganic hybrid electrolyte membrane in which the surfactant was held in the mesopores exhibited a water retention effect that was not present in Nafion on the low-humidity side, and showed a certain conductivity.

  Conventionally obtained organic-inorganic hybrid membranes having mesoporous pores have a hard skeletal structure and poor flexibility, so that they could not be maintained independently and could not be used only as a coating membrane. The organic-inorganic hybrid electrolyte membrane can be obtained. Thereby, the organic-inorganic hybrid electrolyte membrane of the present invention can be used in various fields as a functional membrane. In particular, the organic-inorganic hybrid electrolyte membrane of the present invention is suitable as an electrolyte membrane for fuel cells, and has a high strength, high proton conductivity, excellent chemical stability, and flexibility (strong against deformation). can get. As a result, a high-performance fuel cell can be realized, which contributes to the practical use and spread of fuel cells.

The molecular weight (weight average molecular weight) of the sol obtained under each condition is shown. The molecular weight of the sol adjusted by the mixing ratio described in Table 4 and Table 5 is shown. r (H ₂ O / Si) = 1.0 shows the weight average molecular weight of BTEB / BMEB sols with different catalysts under constant conditions. The weight average molecular weight of the BTEB / BMEB sol obtained under different conditions of r (H ₂ O / Si) with HCI / Si = 0.02 constant is shown. The weight average molecular weight of the BTEB / BMEB sol obtained under different conditions of r (H ₂ O / Si) with HCI / Si = 0.01 constant is shown. The preparation procedure of the one pot impregnation film | membrane using a polyethylene porous film is shown. The photograph which shows the transparency and flexibility of Sol-1 / PE-film (a) and PE-film (b). The X-ray diffraction pattern of each sol liquid is shown. The results of measuring the conductivity of Sol-1 / PE-film under relative humidity of 20, 40, 50, 60, 80, 90% (25 ° C.) and comparing the humidity dependency with Nafion are shown.

Claims (21)

  An organic-inorganic hybrid electrolyte membrane in which pores of a porous membrane are filled with a mesoporous organic-inorganic hybrid material, the mesoporous organic-inorganic hybrid material having a fine pore with a central pore diameter of 1 to 50 nm, and a metal A skeleton composed of an atom, an oxygen atom bonded to the metal atom, and an organic group having one or more carbon atoms bonded to the metal atom or the oxygen atom, and an ion exchange ability bonded to the organic group in the micropore. An organic-inorganic hybrid electrolyte membrane having a functional group.   The skeleton of the organic-inorganic hybrid material has an organic group having one or more carbon atoms, two or more metal atoms bonded to the same or different carbon atoms in the organic group, and one or more oxygen atoms bonded to the metal atoms The organic-inorganic hybrid electrolyte membrane according to claim 1, comprising: The skeleton of the organic-inorganic hybrid material has the following general formula (1):

(In the above formula (1), R ¹ represents an organic group having one or more carbon atoms, M represents a metal atom, R ² represents a hydrogen atom, a hydroxyl group or a hydrocarbon group. X represents the valence of the metal M. from minus 1 integer, n represents 1 or x an integer, m is an integer of 2 or more. in addition, the carbon of R ¹ that M is bonded may be the same or different. Further, -O 1 _{/ 2-} represents a group which becomes -O- when two of these are bonded.
The organic-inorganic hybrid electrolyte membrane according to claim 1 or 2, comprising at least one of the structural units represented by   The organic / inorganic according to any one of claims 1 to 3, wherein the functional group having ion exchange ability is at least one selected from the group consisting of a sulfonic acid group, a phosphoric acid group and a carboxylic acid group. Hybrid electrolyte membrane.   The organic-inorganic hybrid electrolyte membrane according to any one of claims 1 to 4, wherein a surfactant is contained in the micropores of the mesoporous organic-inorganic hybrid material.   The porous membrane is made of polyimide (PI), polyetheretherketone (PEEK), polyethyleneimide (PEI), polysulfone (PSF), polyphenylsulfone (PPSU), polyphenylene sulfide (PPS), or crosslinked polyethylene (CLPE). The organic-inorganic hybrid electrolyte membrane according to any one of claims 1 to 5, comprising at least one selected from the above. 6. The porous film according to claim 1, wherein the porous film is made of polytetrafluoroethylene (PTFE) represented by the following general formula or a tetrafluoroethylene copolymer containing 10 mol% or less of a copolymer component. An organic-inorganic hybrid electrolyte membrane according to claim 1.

(In the formula, A is one or more selected from the following, and c: d = 1: 0 to 9: 1)

  The porous film is made of polysiloxane, and the organic group in the polysiloxane is at least one group selected from methyl group, phenyl group, hydrogen group and hydroxyl group. Item 6. The organic-inorganic hybrid electrolyte membrane according to any one of Items 1 to 5.   A step of filling a precursor of a mesoporous organic-inorganic hybrid material in the pores of the porous membrane, a step of forming a mesoporous organic-inorganic hybrid material in the pores of the porous membrane, and a proton of the mesoporous organic-inorganic hybrid material A method for producing an organic-inorganic hybrid electrolyte membrane having a pore-filled porous membrane filled with a mesoporous organic-inorganic hybrid material, the mesoporous organic-inorganic hybrid material comprising: Polymer having a fine pore having a central pore diameter of 1 to 50 nm and comprising a metal atom, an oxygen atom bonded to the metal atom, and an organic group having at least one metal atom or carbon atom bonded to the oxygen atom A step of synthesizing a skeleton, and a step of converting a part of the organic group into a functional group having ion exchange ability in the micropore. Process for producing an organic-inorganic hybrid electrolyte membrane, characterized in that.   A porous membrane having pores comprising a step of filling a mesoporous organic-inorganic hybrid material in pores of a porous membrane and a step of protonating the mesoporous organic-inorganic hybrid material. A method for producing an organic-inorganic hybrid electrolyte membrane filled with an inorganic hybrid material, wherein the mesoporous organic-inorganic hybrid material has a fine pore having a central pore diameter of 1 to 50 nm, and is bonded to a metal atom and the metal atom And a step of synthesizing a polymer skeleton composed of an organic group having one or more oxygen atoms and one or more carbon atoms bonded to the metal atom or the oxygen atom; And a method for producing an organic-inorganic hybrid electrolyte membrane, comprising: converting the functional group into a functional group.   The skeleton of the organic-inorganic hybrid material has an organic group having one or more carbon atoms, two or more metal atoms bonded to the same or different carbon atoms in the organic group, and one or more oxygen atoms bonded to the metal atoms The method for producing an organic-inorganic hybrid electrolyte membrane according to claim 9 or 10, wherein: Synthesis of the skeleton of the organic-inorganic hybrid material is represented by the following general formula (2):

(In the above formula (2), R ¹ represents an organic group having one or more carbon atoms, M represents a metal atom, R ² represents a hydrogen atom, a hydroxyl group or a hydrocarbon group. A represents an alkoxy group or a halogen atom. X represents an integer obtained by subtracting 1 from the valence of the metal M, n represents an integer of 1 to x, and m represents an integer of 2. The carbons of R ¹ to which M is bonded are the same or different. May be.)
A surfactant obtained by polycondensation under acidic or alkaline conditions is added to an aqueous solution containing a surfactant and at least one compound represented by the formula: A method for producing an organic-inorganic hybrid electrolyte membrane according to any one of the above. Synthesis of the skeleton of the organic-inorganic hybrid material is represented by the following general formula (2):

(In the above formula (2), R ¹ represents an organic group having one or more carbon atoms, M represents a metal atom, R ² represents a hydrogen atom, a hydroxyl group or a hydrocarbon group. A represents an alkoxy group or a halogen atom. X represents an integer obtained by subtracting 1 from the valence of the metal M, n represents an integer of 1 to x, and m represents an integer of 2. The carbons of R ¹ to which M is bonded are the same or different. May be.)
At least one compound represented by the formula (1) is added to an aqueous solution containing a surfactant, polycondensed under acidic or alkaline conditions, and the surfactant is removed from the resulting porous precursor. A method for producing an organic-inorganic hybrid electrolyte membrane according to any one of claims 9 to 11.   In the step of filling a mesoporous organic-inorganic hybrid material or a mesoporous organic-inorganic hybrid material precursor in the pores of the porous film, the mesoporous organic-inorganic hybrid material or the mesoporous organic-inorganic hybrid material precursor is irradiated with ultrasonic waves, a detreatment method, 14. The production of an organic-inorganic hybrid electrolyte membrane according to claim 9, wherein one or more means selected from surface modification of a porous membrane, solvent replacement, and use of a surfactant are used. Method.   The organic / inorganic according to any one of claims 9 to 14, wherein the functional group having ion exchange ability is at least one selected from the group consisting of a sulfonic acid group, a phosphoric acid group, and a carboxylic acid group. A method for producing a hybrid electrolyte membrane.   The porous membrane is made of polyimide (PI), polyetheretherketone (PEEK), polyethyleneimide (PEI), polysulfone (PSF), polyphenylsulfone (PPSU), polyphenylene sulfide (PPS), or crosslinked polyethylene (CLPE). The method for producing an organic-inorganic hybrid electrolyte membrane according to any one of claims 9 to 15, comprising at least one selected. The porous film is made of polytetrafluoroethylene (PTFE) represented by the following general formula or a tetrafluoroethylene copolymer containing 10 mol% or less of a copolymer component. A method for producing an organic-inorganic hybrid electrolyte membrane according to claim 1.

(In the formula, A is one or more selected from the following, and a: b = 1: 0 to 9: 1)

  The porous film is made of polysiloxane, and the organic group in the polysiloxane is at least one group selected from methyl group, phenyl group, hydrogen group and hydroxyl group. Item 16. A method for producing an organic-inorganic hybrid electrolyte membrane according to any one of Items 9 to 15.   An electrolyte membrane for a fuel cell comprising the organic-inorganic hybrid electrolyte membrane according to any one of claims 1 to 8.   A chemical process film comprising the organic-inorganic hybrid electrolyte film according to claim 1.   A solid polymer electrolyte membrane (a), and a gas diffusion electrode (b) mainly composed of an electroconductive carrier carrying a catalytic metal and an electrocatalyst made of a proton conductive material joined to the electrolyte membrane A polymer electrolyte fuel cell having a membrane / electrode assembly (MEA) that is formed, wherein the polymer solid electrolyte membrane is the organic-inorganic hybrid electrolyte membrane according to any one of claims 1 to 8. Solid polymer fuel cell.

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