JP2008262853A - Proton conduction film, manufacturing method for same and fuel cell - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a proton conduction film with high proton conductivity, durability and mechanical strength and to provide a manufacturing method for same and a fuel cell. <P>SOLUTION: The proton conduction film is provided with a network structure with Si-O bonding. In addition, the proton conduction film is provided with an aryl group bonded to an Si atom composing the network structure or an allylene group bridging the Si atoms and the aryl group or the allylene group is provided with a proton supplying group. Furthermore, the manufacturing method and the fuel cell using the proton conductive film are provided. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a proton conducting membrane, a method for producing the same, and a fuel cell, and more particularly to an organic-inorganic hybrid proton conducting membrane, a method for producing the same, and a fuel cell.

  For fuel cells, sensors, etc., polymer membranes such as perfluorosulfonic acid membranes (trade name Nafion, manufactured by DuPont) having fluorine in the polymer skeleton as proton conductive membranes that operate at temperatures from room temperature to 100 ° C. Is used. Further, as a similar one, there is a proposal such as a perfluorosulfonic acid membrane having different perfluorovinyl ether side chains.

  Silica-based materials have attracted attention as materials for proton conductive membranes that are more heat resistant than the perfluorosulfonic acid membrane. An example in which fine particles made of silica are dispersed in the perfluorosulfonic acid film and used in a fuel cell is also disclosed (for example, see Patent Document 1). In this case, silica improves the moisture retention of the film. And is not involved in proton conductivity.

  As an electrolyte for a fuel cell, a proton conductive membrane made of an amorphous silica molded body having high proton conductivity in a temperature range from room temperature to about 200 ° C. has been proposed (see, for example, Patent Documents 2 and 3).

  Moreover, it has been reported that the silica glass produced with the sol-gel method has high proton conductivity as glass (for example, refer nonpatent literatures 1 and 2).

Further, phosphorus pentoxide (P ₂ O ₅ ) -zirconium oxide (ZrO ₂ ) -silicon oxide (SiO ₂ ) (P ₂ O ₅ : ZrO ₂ : SiO ₂ = 5: 5: 90 (mol%) whose composition is mainly composed of silica. )) Is reported to have a high proton conductivity of about 10 ⁻³ S / cm at 50 ° C. (see, for example, Non-Patent Documents 3 and 4).

Japanese Patent Laid-Open No. 6-1111827 JP 2000-272932 A JP 2001-143723 A `` Physical Review B '', 1997, Vol.55, p.12108 `` The Journal of Physical Chemistry '' 1998, Vol.102, p.5772 `` Journal of The Electrochemical Society '' 1997, Vol.144, p.2175 "Applied Physics Letters" 1997, Vol.71, p.1323

  However, although the proton conductive membrane using the silica-based material described above has high heat resistance and mechanical strength, there is a problem that proton donating property is low and proton conductivity is not sufficient.

  Therefore, the present invention relates to a proton conductive membrane that improves proton conductivity and has heat resistance and mechanical strength, a method for manufacturing the same, and a fuel cell.

  In order to solve the above-described problems, the proton conducting membrane of the present invention is a proton conducting membrane composed of a network structure having a Si—O bond, and an aryl coupled to Si atoms constituting the network structure. It has an arylene group that bridges between groups or Si atoms, and is characterized in that a proton donating group is bonded to the aryl group or the arylene group.

  According to such a proton conductive membrane, since the aryl group or the arylene group is included in the network structure having the Si—O bond, it is possible to bond the proton donating group. As a result, it is possible to increase the number of proton donating groups as compared with a proton conductive membrane made of a conventional silica-based material, so that proton conductivity can be improved. Moreover, by being comprised by the network structure which has a Si-O bond, it is excellent also in heat resistance and mechanical strength like a silica type material.

  The first method for producing a proton conducting membrane of the present invention is characterized by sequentially performing the following steps. First, a step of preparing a solution containing a polysilane compound having at least one aryl group and a proton donating group-containing compound is performed. Next, by irradiating the solution with light in an atmosphere containing oxygen, the aryl group bonded to Si atoms or the arylene group that bridges Si atoms is obtained by photopolymerization, and the aryl group or the A step of generating a network structure of Si—O bonds in which a proton donating group is bonded to an arylene group is performed. Next, a step of applying a solution containing a network structure in which a proton donating group is bonded via an aryl group or an arylene group onto a substrate is performed. Then, the process of forming a proton conductive film is performed by heat-treating the substrate after coating.

  Furthermore, the second method for producing a proton conducting membrane of the present invention is characterized by sequentially performing the following steps. First, a step of preparing a solution containing a polysilane compound having an aryl group is performed. Next, by irradiating the solution with light in an atmosphere containing oxygen, a photo-polymerization forms a network structure of Si-O bonds having aryl groups bonded to Si atoms or arylene groups that bridge Si atoms. A process of generating is performed. Next, a step of bonding the proton donating group to the aryl group or the arylene group in the network structure is performed by adding the proton donating group-containing compound to the solution containing the network structure. Then, the process of apply | coating the solution containing the network structure to which the proton donor group was couple | bonded through the aryl group or the arylene group on a board | substrate is performed. Then, the process of forming a proton conductive film is performed by heat-processing to the board | substrate after application | coating.

  The third method for producing a proton conducting membrane of the present invention is characterized by sequentially performing the following steps. A step of preparing a solution containing a polysilane compound having at least one aryl group and a proton donating group-containing compound is performed. Next, the process of apply | coating the said solution on a board | substrate is performed. Next, the substrate after coating is irradiated with light in an atmosphere containing oxygen to have an aryl group bonded to Si atoms or an arylene group that bridges Si atoms by photopolymerization. A step of generating a network structure of Si—O bonds in which a proton donating group is bonded to an arylene group is performed. Subsequently, a heat treatment is performed on the substrate after light irradiation to perform a step of forming a proton conductive membrane having the above network structure to which proton donating groups are bonded.

  According to the first to third manufacturing methods of such a proton conductive membrane, a proton conductive membrane in which a proton donating group is bonded via an aryl group or an arylene group in a network structure of Si—O bonds is formed. Therefore, it is possible to increase the number of proton donating groups as compared with a conventional proton conductive membrane made of a silica-based material. As a result, a proton conducting membrane with improved proton conductivity can be manufactured. Moreover, by being comprised by the network structure which has a Si-O bond, the proton conductive film excellent also in heat resistance and mechanical strength like a silica type material can be manufactured. Furthermore, since the proton conducting membrane can be formed by a coating method, the manufacturing process of the proton conducting membrane is simplified.

  The present invention is also a fuel cell using the above proton conductive membrane, in which an electrolyte layer composed of a proton conductive membrane having a Si—O bond network structure is sandwiched between a cathode and an anode. And it has the aryl group couple | bonded with Si atom which comprises the said network structure, or the arylene group which bridge | crosslinks between Si atoms, The proton donor group is couple | bonded with the aryl group or the arylene group, It is characterized by the above-mentioned.

According to such a fuel cell, since the proton conductivity can be improved by having the proton conductive membrane, the electromotive force can be increased.
.

  As described above, the proton conducting membrane of the present invention can improve the proton conductivity, and is excellent in heat resistance and mechanical strength as well as the silica-based material. Quality can be improved. Further, according to the method for producing a proton conducting membrane of the present invention, the proton conducting membrane can be produced by a coating method, so that the production apparatus and the production process can be simplified and the productivity is excellent. Furthermore, according to the fuel cell of the present invention, since the electromotive force can be increased, the fuel cell can be made highly efficient and have a long life.

  Hereinafter, an example of a proton conductive membrane of the present invention, a manufacturing method thereof, and a fuel cell using the proton conductive membrane will be described in detail.

(First embodiment)
<Proton conducting membrane>
The proton conducting membrane of the present invention has a network structure of Si—O bonds made of a polymer in which silicon (Si) and oxygen (O) are three-dimensionally crosslinked. Since this network structure has an aryl group bonded to Si atoms constituting the network structure or an arylene group that bridges Si atoms, the proton conducting membrane is configured as an organic-inorganic hybrid membrane. Here, the ratio of the organic component and the inorganic component of the proton conducting membrane is appropriately determined depending on the raw material, as will be described in detail in the production method described later.

  Here, the aryl group or the arylene group may be monocyclic or condensed, may have a substituent, or may be unsubstituted. Since these bond to Si atoms constituting the network structure or bridge between the Si atoms, they are preferably not high molecular weight, for example, aryl groups and arylene groups having 6 to 24 carbon atoms. Specifically, the aryl group is preferably a phenyl group or a naphthyl group, and the arylene group is preferably a phenylene group or a naphthylene group.

  In addition, a proton donating group is bonded to the aryl group or the arylene group. In the above-described network structure of Si—O bonds, proton conductivity is improved by bonding a proton donating group to an aryl group or an arylene group.

The proton donating group is preferably an acid residue having a pKa of 4 or less. For example, a sulfonic acid group (—SO ₃ H), a phosphoric acid group (—POOH, OP (O) (OH) ₂ ), a carboxyl group (—COOH) Etc. Among these, a sulfonic acid group (—SO ₃ H) having a low pKa is particularly preferable. In this case, since water (H ₂ O) is coordinated around the sulfonic acid group in the proton conductive membrane, proton (H ⁺ ) is conducted in the form of H ₃ O ⁺ .

  Examples of the substituent other than the proton donating group bonded to the arylene group include a hydroxyl group, a ketone group, an ester group, an alkyl group, an alkenyl group, an alkoxyl group, an aryl group, a heterocyclic group, a cyano group, a nitro group, An amino group, an amide group, a thiol group, etc. are mentioned.

Here, the partial structure in the case where the aryl group is a phenyl group, the arylene group is a phenylene group, and the proton donating group is a sulfonic acid group (—SO ₃ H) is shown in the following structural formula (1). However, parts other than those bonded to the sulfonic acid group of the aryl group or arylene group shall be unsubstituted.

  As shown in the structural formula (1), a phenyl group is bonded as a side chain to a Si atom constituting the network structure of the Si—O bond, and a phenylene group that bridges between the Si atoms is, for example, at the para position. Are combined. In addition, a sulfonic acid group is bonded to the phenyl group or the phenylene group.

  In the structural formula (1), the phenylene group that bridges the Si atoms is bonded at, for example, the para position, but may be in the ortho position or the meta position, and the sulfonic acid group is bonded. The bonding position of the phenyl group or phenylene group and the number of bonds are not particularly limited.

  According to such a proton conductive membrane, since the aryl group or the arylene group is included in the network structure having the Si—O bond, it is possible to bond the proton donating group. As a result, it is possible to increase the number of proton donating groups as compared with a proton conductive membrane made of a conventional silica-based material, so that proton conductivity can be improved. Moreover, by being comprised by the network structure which has a Si-O bond, it is excellent also in heat resistance and mechanical strength like a silica type material. Therefore, the quality of the proton conducting membrane can be improved.

<Proton conductive membrane production method>
An example of the above-described method for producing a proton conducting membrane will be described with reference to the flowchart of FIG. First, the polysilane compound used as a raw material and the proton donating group-containing compound will be described.

The polysilane compound used in the present invention is represented by the following general formula (1), and may be cyclic or chain-shaped.

R ₁ and R ₂ in the general formula (1) represent an alkyl group or an aryl group. These may have a substituent and may be unsubstituted. The alkyl group is preferably a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms. Specific examples include a methyl group, an ethyl group, an isopropyl group, an n-butyl group, a 2-ethylhexyl group, an n-decyl group, a cyclopropyl group, a cyclohexyl group, and a cyclododecyl group. Moreover, as a preferable example of the said aryl group, a C6-C20 substituted or unsubstituted phenyl group, a naphthyl group, etc. are mentioned. N is an integer.

  Examples of the substituent for the alkyl group or aryl group include hydroxyl group, ketone group, ester group, alkyl group, alkenyl group, alkoxyl group, aryl group, heterocyclic group, cyano group, nitro group, amino group, amide group, Examples include thiol groups.

Here, decaphenylcyclopentasilane represented by the following structural formula (3) is used as the polysilane compound.

On the other hand, as the proton-donating group-containing compound, a compound represented by the following general formula (2) is used.

In the general formula (2), the proton donating group A is preferably an acid residue having a pKa of 4 or less, as described above, such as a sulfonic acid group (—SO ₃ H), a phosphoric acid group (—POOH, OP (O)). (OH) ₂ ) or a carboxyl group (—COOH). R ₃ is a substituted or unsubstituted alkyl group or aryl group.

  Examples of the substituent of this alkyl group or aryl group include hydroxyl group, ketone group, ester group, alkyl group, alkenyl group, alkoxyl group, aryl group, heterocyclic group, cyano group, nitro group, amino group, amide group, thiol Groups and the like.

Here, a proton-donating group-containing compound comprising dodecylbenzenesulfonic acid in which proton-donating group A is a sulfonic acid group and R ₃ is a dodecyl group is used.

  A polysilane compound composed of decaphenylpentasilane and a proton donating group-containing compound composed of dodecylbenzenesulfonic acid as described above are mixed, and mixed with a solvent composed of, for example, toluene, thereby including the polysilane compound and the proton donating group-containing compound. A solution is prepared (S101).

  Here, the composition of the proton conductive membrane to be formed is controlled by the ratio of mixing the polysilane compound and the proton donating group-containing compound. For this reason, it is preferable to mix the said polysilane compound in 50 mol%-90 mol%, and a proton donor group containing compound in the range of 10 mol%-50 mol%. When the polysilane compound is less than 50 mol%, a Si—O network structure is not formed, and heat resistance and mechanical strength are lowered. Moreover, there is a tendency not to become a practical glass excellent in chemical durability. When the amount of the polysilane compound is more than 90 mol%, the number of proton donating groups decreases, so that sufficient proton conductivity cannot be obtained.

  The solvent is not particularly limited as long as it dissolves a polysilane compound and a proton donating group-containing compound, but preferably a nonpolar solvent (toluene, xylene, etc.), a chain hydrocarbon compound (hexane, octane, etc.) , Heterocyclic compounds (3-methyl-2-oxazolidinone, N-methylpyrrolidone, etc.), cyclic ethers (dioxane, tetrahydrofuran, etc.), chain ethers (diethyl ether, ethylene glycol dialkyl ether, propylene glycol dialkyl ether, polyethylene glycol) Dialkyl ether, polypropylene glycol dialkyl ether, etc.), alcohols (methanol, ethanol, isopropanol, 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, glutarodinitrile, methoxyacetonitrile, propionitrile) , Benzonitrile, etc.), esters (carboxylic acid ester, phosphoric acid ester, phosphonic acid ester, etc.), aprotic polar substances (dimethyl sulfoxide, sulfolane, dimethylformamide, dimethylacetamide, etc.), chlorinated solvents (methylene chloride, ethylene chloride, etc.) Etc.), water, etc. can be used. These may be used alone or in combination of two or more.

  Next, this solution is irradiated with light in an atmosphere containing oxygen (S102). Here, for example, ultraviolet rays are irradiated in the air. Here, generally, when a polysilane compound is irradiated with ultraviolet rays in an atmosphere containing oxygen, such as in the air, an Si—Si bond as a main chain is cleaved to generate an active species such as a silyl radical. Thereafter, it reacts with oxygen in the air to form siloxane bonds. Moreover, active species such as this silyl radical react with an aryl group (aromatic hydrocarbon group). Thus, by photopolymerization, there is an aryl group bonded to Si atoms or an arylene group that bridges between Si atoms, and a network structure of Si—O bonds in which proton donating groups are bonded to the aryl groups or arylene groups. Generated.

  The reaction temperature in the photopolymerization is related to the reaction rate, and can be selected according to the reactivity and type of the precursor and the amount thereof. Preferably it is 50-500 degreeC, More preferably, it is 100-300 degreeC.

  Next, a solution containing the network structure is applied on the substrate (S103). Although this board | substrate is not specifically limited, As a preferable example, a glass substrate, a metal substrate, a polymer film, a reflecting plate, etc. can be mentioned. Examples of the polymer film include cellulose polymer films such as TAC (triacetyl cellulose), ester polymer films such as PET (polyethylene terephthalate) and PEN (polyethylene naphthalate), and PTFE (polytrifluoroethylene). And fluorine polymer films, polyimide films and the like.

  The coating method may be a known method, for example, curtain coating method, extrusion coating method, roll coating method, spin coating method, dip coating method, bar coating method, spray coating method, slide coating method, print coating method, etc. be able to.

Next, the coated film is baked by performing heat treatment on the coated substrate at 100 ° C. to 1000 ° C. (S104). The heating time varies depending on the heating temperature and composition, but a range of 1 hour to 24 hours is substantially preferable. The heating atmosphere is not particularly limited, but a stronger Si—O bond network structure is formed by performing in air. The heating conditions in this case are selected so that the specific surface area of the product after heating is 10 m ² / g or more, preferably 50 m ² / g or more. For example, by selecting a range of 600 ° C. to 800 ° C., an amorphous material having a specific surface area of 600 m ² / g or more can be obtained, and a proton conductive membrane having high proton conductivity can be obtained. Stability is also increased.

  As described above, a proton conductive membrane having an Si—O bond network structure in which a sulfonic acid group is bonded via a phenyl group or a phenylene group is formed. Thereafter, the obtained proton conducting membrane is allowed to stand, for example, in an atmosphere having a relative humidity of 50%, so that the proton conducting membrane contains water. The water content in this case is 1% by weight to 20% by weight.

  According to such a first method for producing a proton conducting membrane, the proton conducting membrane as described above can be produced, so that proton conductivity is improved and protons having excellent heat resistance and mechanical strength are also provided. A conductive film can be obtained. In addition, since the proton conducting membrane can be formed by a coating method, the manufacturing process of the proton conducting membrane is simplified.

  In the method for producing a proton conducting membrane of this embodiment, the example in which both the polysilane compound and the proton donating group-containing compound have an aryl group has been described. However, at least one of the polysilane compound and the proton donating group-containing compound has an aryl group. It only has to be.

<Fuel cell>
Next, a fuel cell using the proton conductive membrane described above will be described with reference to FIG. The fuel cell 1 is a hydrogen concentration cell, and is configured by sandwiching an electrolyte layer 4 between a cathode 2 and an anode 3. The cathode 2 and the anode 3 are connected to an external circuit 5. The electrolyte layer 4 is composed of the proton conductive membrane containing moisture.

In this fuel cell 1, the proton supply unit 6 provided on the cathode 2 side is set to a high hydrogen partial pressure, and the proton consumption unit 7 on the anode 3 side is set to a low hydrogen partial pressure. Specifically, for example, hydrogen gas is flowed to the proton supply unit, and oxygen gas is flowed to the proton consumption unit 7 to consume protons. With such a configuration, protons (H ⁺ ) move from the cathode 2 side to the anode 3 side through the electrolyte layer 4.

  According to such a fuel cell, since the proton conductive membrane is used as the electrolyte layer 4, a high electromotive force can be obtained, and the fuel cell can be highly efficient and have a long life.

(Modification 1)
The proton conducting membrane of the present invention can also be manufactured by the method shown in the flowchart of FIG. In addition, as a polysilane compound and a proton donating group containing compound, the same compound as the said embodiment can be used.

  First, for example, a polysilane compound made of decaphenylpentasilane is dissolved in a solvent made of toluene, for example, to prepare a solution containing the polysilane compound (S201).

  Next, by irradiating this solution with ultraviolet rays, a network structure of Si—O bonds having a phenyl group bonded to Si atoms or a phenylene group that bridges Si atoms is generated by photopolymerization (S202). .

  Next, a proton donating group-containing compound made of, for example, dodecylbenzenesulfonic acid is added to the solution (S203). Thereby, a sulfonic acid group is bonded to a phenyl group or a phenylene group in the network structure.

  Subsequently, a solution containing a network structure of Si—O bonds in which sulfonic acid groups are bonded via phenyl groups or phenylene groups is applied on the substrate (S204).

  Thereafter, the substrate coated with the above solution is subjected to a heat treatment, whereby the coating film is baked to form a proton conductive film (S205).

  Even with such a second method for producing a proton conducting membrane, the proton conducting membrane of the present invention can be produced, and the same effects as those of the first producing method can be achieved.

(Modification 2)
Furthermore, the proton conducting membrane of the present invention can also be manufactured by the method shown in the flowchart of FIG. In addition, as a polysilane compound and a proton donating group containing compound, the same compound as the said embodiment can be used.

  First, for example, a polysilane compound made of decaphenylpentasilane and a proton donating group-containing compound made of, for example, dodecylbenzenesulfonic acid are dissolved in a solvent made of, for example, toluene to prepare a solution containing the polysilane compound and the proton donating group-containing compound ( S301).

  Next, the solution is applied on the substrate (S302).

  Subsequently, by irradiating the substrate with ultraviolet rays, a photopolymerization has a phenyl group bonded to Si atoms or a phenylene group that bridges Si atoms, and a sulfonic acid group is bonded to the phenyl group or phenylene group. A network structure of Si-O bonds is generated (S303).

  Next, the substrate after light irradiation is subjected to heat treatment to form a proton conductive membrane having a network structure of Si—O bonds in which sulfonic acid groups are bonded via phenyl groups or phenylene groups (S304).

  Even with such a third method for producing a proton conducting membrane, the proton conducting membrane of the present invention can be produced, and the same effects as those of the first producing method described above can be achieved.

  Next, the above embodiment will be described in detail using examples.

<Example 1>
10 g of the polysilane compound (P-1) in which R ₁ and R ₂ in the above general formula (1) are composed of combinations shown in Table 1 below, and A and R ₃ in the above general formula (2) are as follows: A solution in which 5 g of a proton-donating group-containing compound (G-1) composed of combinations shown in Table 2 was mixed and dissolved in 100 g of toluene was prepared. This solution was irradiated with ultraviolet rays for 30 minutes. Next, a film was formed by applying the obtained solution on a glass substrate by spin coating. Then, after prebaking at 120 degreeC with a hotplate for 5 minutes, it baked at 300 degreeC for 1 hour, and formed the proton conductive film with the film thickness of 0.1 mm.

<Examples 2 to 9>
A proton conducting membrane was formed by the same method as in Example 1 except that the polysilane compound shown in Table 1 and the proton-donating group-containing compound shown in Table 2 were combined as shown in Table 3 below.

<Comparative Example 1>
As Comparative Example 1 with respect to Examples 1 to 9, a proton conductive membrane was formed by the same method as Example 1 except that a solution in which only 10 g of the polysilane compound (P-1) was dissolved in 100 g of toluene was prepared. .

<Comparative example 2>
A proton conducting membrane was formed by the same method as in Comparative Example 1 except that the polysilane compound was changed to P-3 shown in Table 1 above.

(Evaluation methods)
For the proton conducting membranes of Examples 1-9 and Comparative Examples 1-2, after pre-processing the sample in an atmosphere with a relative humidity of 30% or more, silver paste was applied to both sides of the sample having a thickness of about 0.1 mm Alternatively, a gold electrode was attached by a vacuum deposition method or the like, placed in a constant humidity atmosphere, and the proton conductivity (mS / cm) of the sample at 25 ° C. was measured by an AC impedance method. The results of measuring the samples of Examples 1 to 9 and Comparative Examples 1 and 2 are shown in Table 3 above. As a result, it was confirmed that the proton conducting membranes of Examples 1 to 9 had proton conductivity higher by one digit or more than the proton conducting membranes of Comparative Examples 1 and 2.

<Example 10>
A fuel cell comprising the hydrogen concentration cell shown in FIG. 2 was produced using the proton conducting membrane formed in Example 1.

<Examples 11 to 18>
Using the proton conductive membranes formed in Examples 2 to 9, hydrogen concentration batteries were produced in the same manner as in Example 10.

<Comparative Examples 3 and 4>
As Comparative Examples 3 and 4 for the fuel cells of Examples 10 to 18, the proton concentration membranes formed in Comparative Examples 1 and 2 were used to manufacture the hydrogen concentration cell shown in FIG.

(Evaluation method 2)
The electromotive forces of the fuel cells of Examples 10 to 18 and Comparative Examples 3 and 4 were measured. The results are shown in Table 4. As shown in this table, it was confirmed that the fuel cells of Examples 10 to 18 exhibited significantly higher electromotive force than the fuel cells of Comparative Examples 3 and 4.

It is a flowchart for demonstrating 1st Embodiment which concerns on the manufacturing method of the proton conductive film of this invention. It is a block diagram for demonstrating 1st Embodiment which concerns on the fuel cell using the proton conductive film of this invention. It is a flowchart for demonstrating the modification 1 of 1st Embodiment which concerns on the manufacturing method of the proton conductive film of this invention. It is a flowchart for demonstrating the modification 2 of 1st Embodiment which concerns on the manufacturing method of the proton conductive film of this invention.

Explanation of symbols

  DESCRIPTION OF SYMBOLS 1 ... Fuel cell, 2 ... Cathode, 3 ... Anode, 4 ... Electrolyte layer (proton conductive membrane)

Claims (8)

A proton conducting membrane having a network structure of Si-O bonds,
Having an aryl group bonded to Si atoms constituting the network structure or an arylene group that bridges Si atoms;
A proton donating group is bonded to the aryl group or the arylene group. The proton conductive membrane according to claim 1, wherein the aryl group is a phenyl group, and the arylene group is a phenylene group. The proton conducting membrane according to claim 1, wherein the proton donating group is a sulfonic acid group. The proton conductive membrane according to claim 1, wherein moisture is contained in the proton conductive membrane. Preparing a solution containing a polysilane compound having at least one aryl group and a proton donating group-containing compound;
By irradiating the solution with light in an atmosphere containing oxygen, it has an aryl group bonded to Si atoms or an arylene group that bridges Si atoms by photopolymerization, and the aryl group or the arylene group has Generating a network structure of Si-O bonds to which proton donating groups are bonded;
Applying the solution containing the network structure to which the proton donating group is bonded via the aryl group or the arylene group onto a substrate;
And a step of forming a proton conducting membrane by performing a heat treatment on the substrate after coating. A method for producing a proton conducting membrane. Preparing a solution containing a polysilane compound having an aryl group;
By irradiating the solution with light in an atmosphere containing oxygen, a network structure of an Si—O bond having an aryl group bonded to Si atoms or an arylene group that bridges between Si atoms is generated by photopolymerization. Process,
Adding a proton-donating group-containing compound to the solution containing the network structure to bind a proton-donating group to the aryl group or the arylene group in the network structure;
Applying the solution containing the network structure to which the proton donating group is bonded via the aryl group or the arylene group onto a substrate;
And a step of forming a proton conducting membrane by performing a heat treatment on the substrate after coating. A method for producing a proton conducting membrane. Preparing a solution containing a polysilane compound having at least one aryl group and a proton donating group-containing compound;
Applying the solution onto a substrate;
By irradiating the substrate after coating with light in an atmosphere containing oxygen, photopolymerization has an aryl group bonded to Si atoms or an arylene group that bridges Si atoms, and the aryl group or the Generating a network structure of Si-O bonds in which a proton-donating group is bonded to an arylene group;
And a step of forming a proton conducting membrane by performing a heat treatment on the substrate after the light irradiation. A method for producing a proton conducting membrane. A fuel cell comprising an electrolyte layer composed of a proton conducting membrane having a network structure of Si-O bonds between a cathode and an anode,
Having an aryl group bonded to Si atoms constituting the network structure or an arylene group that bridges Si atoms;
A fuel cell, wherein a proton-donating group is bonded to the aryl group or the arylene group.

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