Patent Application
20230193483
The present invention relates to a membrane electrode assembly, a solid polymer electrolyte membrane, a water electrolysis apparatus and an electrolytic hydrogenation apparatus.
A membrane electrode assembly containing a solid polymer electrolyte membrane can be applied to various applications, and various studies have been conducted. For example, the membrane electrode assembly is applied to a solid polymer electrolyte water electrolysis apparatus (Patent Document 1).
Patent Document 1: WO2020/162511
A membrane electrode assembly is sometimes used not only in water electrolysis apparatus but also in electrolytic hydrogenation apparatus for toluene, etc. In recent years, there has been a need to further improve the performance of these apparatuses, specifically, to reduce the electrolysis voltage.
When the present inventors evaluated the water electrolysis apparatus having a membrane electrode assembly as described in Patent Document 1, they found that the range of increase in electrolysis voltage sometimes became large when the current density increased, and that there was room for improvement.
The present invention was made in view of the above circumstances and is concerned with providing a membrane electrode assembly, a solid polymer electrolyte membrane, a water electrolysis apparatus and an electrolytic hydrogenation apparatus, that can reduce the range of increase in electrolysis voltage even when the current density increases when applied to a water electrolysis apparatus or an electrolytic hydrogenation apparatus.
The present inventors have studied the above problem intensively and as a result, have found that in a membrane electrode assembly containing a solid polymer electrolyte membrane, the desired effect can be obtained if the solid polymer electrolyte membrane contains a woven fabric with a predetermined aperture ratio and the ratio TAAVE/TBAVE calculated from the average maximum membrane thickness TAAVE and the average minimum membrane thickness TBAVE of the solid polymer electrolyte membrane is at least a predetermined value, and thus have arrived at the present invention.
That is, the present inventors have found that he above problem can be solved by the following constructions.
—[CF2—CF(L-(SO3M)n)]— Formula (1):
[11] A water electrolysis apparatus including a membrane electrode assembly as claimed in any one of [1] to [10].
[12] An electrolytic hydrogenation apparatus including a membrane electrode assembly as claimed in any one of [1] to [10].
[13] A solid polymer electrolyte membrane comprising a fluorinated polymer having ion-exchange groups and a woven fabric, wherein
[14] The solid polymer electrolyte membrane according to [13], wherein the ion exchange capacity of said fluorinated polymer is from 0.90 to 2.00 meq/g dry resin.
[15] The solid polymer electrolyte membrane according to [13] or [14], wherein the ratio TAAVE/TBAVE is at least 1.95.
[16] The solid polymer electrolyte membrane according to any one of [13] to [15], to be used in a membrane electrode assembly.
According to the present invention, it is possible to provide a membrane electrode assembly, a solid polymer electrolyte membrane, a water electrolysis apparatus and an electrolytic hydrogenation apparatus, whereby, when applied to a water electrolysis apparatus or an electrolytic hydrogenation apparatus, the increase range of the electrolysis voltage can be made small even when the current density is increased.
The definitions of the following terms apply throughout this specification and claims unless otherwise noted.
An “ion-exchange group” is a group that can exchange at least some of the ions contained in this group to other ions, such as the following sulfonic acid type functional group or carboxylic acid type functional group.
A “sulfonic acid type functional group” means a sulfonic acid group (—SO3H) or a sulfonic acid base (—SO3M2, where M2 is an alkali metal or quaternary ammonium cation).
A “carboxylic acid type functional group” means a carboxylic acid group (—COOH) or a carboxylic acid base (—COOM1, where M1 is an alkali metal or quaternary ammonium cation).
A “precursor membrane” is a membrane containing a polymer having groups that can be converted to ion-exchange groups.
The term “groups that can be converted to ion-exchange groups” means groups that can be converted to ion-exchange groups by treatment such as a hydrolysis treatment, acidification treatment or the like.
The term “groups that can be converted to sulfonic acid type functional groups” means groups that can be converted to sulfonic acid type functional groups by treatment such as a hydrolysis treatment, acidification treatment or the like.
A “unit” in a polymer means an atomic group derived from a single monomer molecule, which is formed by polymerization of the monomer. The unit may be an atomic group formed directly by the polymerization reaction, or it may be an atomic group in which a part of the atomic group is converted to another structure by treating the polymer obtained by the polymerization reaction.
A numerical range expressed by using “to” means a range that includes the numerical values listed before and after “to” as the lower and upper limits.
The membrane electrode assembly of the present invention comprises an anode having a catalyst layer, a cathode having a catalyst layer, and a solid polymer electrolyte membrane disposed between the above anode and the above cathode. Further, the above solid polymer electrolyte membrane comprises a fluorinated polymer having ion-exchange groups and a woven fabric. Further, the above woven fabric comprises yarns A extending in one direction and yarns B extending in a direction orthogonal to the yarns A. The aperture ratio of the above woven fabric is at least 50%. The ratio TAAVE/TBAVE calculated from the average maximum membrane thickness TAAVE and the average minimum membrane thickness TBAVE of the above solid polymer electrolyte membrane is at least 1.20.
When applied to a water electrolysis apparatus or an electrolytic hydrogenation apparatus, the membrane electrode assembly of the present invention can reduce the range of increase in electrolysis voltage even when the current density is increased. Although the details of the reason for this have not been clarified, it is assumed to be due to the following reasons.
When the ratio TAAVE/TBAVE is at least 1.20, the surface of the solid polymer electrolyte membrane has an uneven structure with a predetermined height difference. It is assumed that the uneven structure on the surface of the solid polymer electrolyte membrane generates convection of the liquid supplied to the surface of the membrane electrode assembly and improves the diffusion of the liquid, resulting in a smaller increase in the electrolysis voltage even when the current density is increased.
Further, when a woven fabric is present in the solid polymer electrolyte membrane, the membrane resistance of the solid polymer electrolyte membrane may increase, resulting in a problem of high electrolysis voltage. To address this problem, it is assumed that the electrolysis voltage could be reduced by using a woven fabric with the specified aperture ratio.
The ratio TAAVE/TBAVE in the solid polymer electrolyte membrane is at least 1.20, and from the viewpoint that the effect of the present invention is more excellent, at least 1.35 is preferred, at least 1.60 is more preferred, at least 1.95 is further preferred, and at least 2.10 is particularly preferred.
The upper limit of the ratio TAAVE/TBAVE in the solid polymer electrolyte membrane is at most 3.00, preferably at most 2.50 and particularly preferably at most 2.30, from the viewpoint of uniformity of the catalyst layer coated on the uneven surface of the solid polymer electrolyte membrane.
The method of making the ratio TAAVE/TBAVE to be at least 1.20 is not particularly limited, but, for example, a method of sandwiching the precursor membrane for the solid polymer electrolyte membrane by the low melting point films described below at the time of the production of the solid polymer electrolyte membrane, followed by heat pressing. The low melting point films thereby deform to follow the surface shape of the precursor membrane, so that a solid polymer electrolyte membrane having a concavo-convex structure on the surface is obtainable, where the area where the yarns A and B constituting the woven fabric are present is convex and the area where the yarns A and B are not present is concave.
The calculation method of the ratio TAAVE/TBAVE in the solid polymer electrolyte membrane in the present invention will be described.
First, the maximum membrane thickness TA and the minimum membrane thickness TB of the solid polymer electrolyte membrane are measured for each of ten different cross-sections at the time when the solid polymer electrolyte membrane is cut in a direction parallel to the direction in which the yarns A in the solid polymer electrolyte membrane extend and at the midpoint between the yarns A.
Specifically, in the example in
Further, the maximum membrane thickness TA and the minimum membrane thickness TB of the solid polymer electrolyte membrane are measured for each of ten different cross-sections at the time when the solid polymer electrolyte membrane is cut in a direction parallel to the direction in which the yarns B in the solid polymer electrolyte membrane extend and at the midpoint between the yarns B.
Specifically, in the example in
Next, the average maximum membrane thickness TAAVE is obtained by arithmetically averaging the 20 TA obtained, and the average minimum membrane thickness TBAVE is obtained by arithmetically averaging the 20 TB obtained, and the ratio of the average maximum membrane thickness TAAVE to the average minimum membrane thickness TBAVE is taken as the ratio TAAVE/TBAVE.
Here, for the measurement of the membrane thickness in the solid polymer electrolyte membrane, a sample having the solid polymer electrolyte membrane dried at 90° C. for 2 hours is employed.
Further, the maximum membrane thickness TA and the minimum membrane thickness TB are measured by using a magnified image (e.g. 100 magnifications) of a cross-section of the solid polymer electrolyte membrane taken by an optical microscope (product name “BX-51” manufactured by Olympus Corporation).
The average maximum membrane thickness TAAVE of the solid polymer electrolyte membrane is preferably from 60 to 200 μm, more preferably from 60 to 140 μm, further preferably from 60 to 120 μm, particularly preferably from 60 to 100 μm, from such a viewpoint that the electrolysis voltage can be reduced more.
The average minimum membrane thickness TBAVE of the solid polymer electrolyte membrane is preferably from 30 to 130 μm, more preferably from 30 to 100 μm, further preferably from 30 to 80 μm, particularly preferably from 30 to 50 μm, from such a viewpoint that the strength of the membrane electrode assembly can be more improved.
In the example in
The cross-sectional shape of the solid polymer electrolyte membrane is not limited to the cross-sectional shape in
(Woven fabric)
The aperture ratio of the woven fabric is at least 50%, and from such a viewpoint that the electrolysis voltage can be reduced more, at least 55% is more preferred, at least 60% is further preferred, and at least 70% is particularly preferred.
The upper limit of the aperture ratio of the woven fabric is preferably at most 90%, more preferably at most 80%, from such a viewpoint that the strength of the membrane electrode assembly is more excellent.
The aperture ratio of the woven fabric is calculated by the following formula (ε) based on the average diameter R1 of yarns and the average spacing P1 between adjacent yarns (hereinafter referred to also as “pitch P1”).
Here, the average diameter R1 of yarns means the arithmetic average value of the diameters of 10 different yarns selected arbitrarily based on a magnified image (e.g. 100 magnifications) of the woven fabric surface obtained by using a microscope. Further, the pitch P1 means the arithmetic average value of 10 spacing points at different locations selected arbitrarily based on a magnified image (e.g. 100 magnifications) of the woven fabric surface obtained by using a microscope.
Aperture ratio (%) of woven fabric=[P1/(P1+R1)]2×100 (ε)
The denier count of yarns A and the denier count of yarns B constituting the woven fabric are each independently at least 2, and, from such a viewpoint that the strength and dimensional stability of the membrane electrode assembly will be more excellent, preferably at least 10 and particularly preferably at least 15.
The upper limit value for the denier count of yarns A and the denier count of yarns B constituting the woven fabric are, each independently, at most 60, more preferably at most 50, and particularly preferably at most 20, from such a viewpoint that the electrolysis voltage can be reduced more.
Here, the denier count is a value having the mass of 9000 m of yarns expressed in grams (g/9000 m).
The densities of yarns A and yarns B are, each independently, preferably at least 50 yarns/inch, more preferably at least 70 yarns/inch, and particularly preferably at least 90 yarns/inch, from such a viewpoint that the strength and dimensional stability of the membrane electrode assembly will be excellent, while preferably at most 200 yarns/inch, more preferably at most 150 yarns/inch, and particularly preferably at most 100 yarns/inch, from such a viewpoint that the electrolysis voltage can be reduced more.
Yarn A and yarn B may be composed of either a monofilament consisting of one filament or a multifilament consisting of two or more filaments, and the monofilament is preferred.
Yarn A and yarn B are, each independently, preferably made of at least one material selected from the group consisting of polytetrafluoroethylene (hereinafter referred to also as “PTFE”), a tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer (hereinafter referred to also as “PFA”), polyether ether ketone (hereinafter referred to also as “PEEK”) and polyphenylene sulfide (hereinafter referred to also as “PPS”), from such a viewpoint that the durability of the yarn will be more excellent.
Yarn A and yarn B are each preferably composed of slit yarn from such a viewpoint that the durability and strength of the yarn will be more excellent.
In the woven fabric, yarns A and yarns B are orthogonal to each other.
Orthogonal means that the angle between yarns A and yarns B is 90±10 degrees.
Yarns A may be warp yarns or weft yarns of the woven fabric, but if yarns A are weft yarns, yarns B are warp yarns, and if yarns A are warp yarns, yarns B are weft yarns.
In a case where the material that constitutes the woven fabric is PTFE, the fabric weight of the woven fabric is preferably from 20 to 40 g/m2, particularly preferably from 30 to 40 g/m2, from such a viewpoint that the balance between the strength and the handling efficiency of the solid polymer electrolyte membrane will be excellent.
In a case where the material that constitutes the woven fabric is PFA, the fabric weight of the woven fabric is preferably from 10 to 30 g/m2, particularly preferably from 10 to 20 g/m2, from such a viewpoint that the balance between the strength and the handling efficiency of the solid polymer electrolyte membrane will be excellent.
In a case where the material that constitutes the woven fabric is PEEK, the fabric weight of the woven fabric is preferably from 5 to 40 g/m2, particularly preferably from 5 to 30 g/m2, from such a viewpoint that the balance between the strength and the handling efficiency of the solid polymer electrolyte membrane will be excellent.
In a case where the material that constitutes the woven fabric is PPS, the fabric weight of the woven fabric is preferably from 5 to 40 g/m2, particularly preferably from 5 to 30 g/m2, from such a viewpoint that the balance between the strength and the handling efficiency of the solid polymer electrolyte membrane will be excellent.
The electrolyte contains a fluorinated polymer (I).
The ion exchange capacity of the fluorinated polymer (I) is preferably at least 0.90 meq/g dry resin, more preferably at least 1.10 meq/g dry resin, further preferably at least 1.15 meq/g dry resin, particularly preferably at least 1.20 meq/g dry resin, most preferably at least 1.25 meq/g dry resin, from such a viewpoint that the electrolysis voltage can be reduced more.
The upper limit value of the ion exchange capacity of the fluorinated polymer (I) is preferably at most 2.00 meq/g dry resin, more preferably at most 1.50 meq/g dry resin, particularly preferably at most 1.43 meq/g dry resin, from such a viewpoint that the solid polymer electrolyte membrane will be more excellent.
The fluorinated polymer (I) to be used in the solid polymer electrolyte membrane may be of one type, or two or more types may be used as laminated or mixed.
Although the solid polymer electrolyte membrane may contain polymers other than the fluorinated polymer (I), it is preferred that the polymer in the solid polymer electrolyte membrane is substantially composed of the fluorinated polymer (I). Substantially composed of a fluorinated polymer (I) is meant that the fluorinated polymer (I) content is at least 95 mass % to the total mass of polymers in the solid polymer electrolyte membrane. The upper limit of the fluorinated polymer (I) content may be 100 mass % to the total mass of polymers in the solid polymer electrolyte membrane.
Specific examples of other polymers other than fluorinated polymer (I) include one or more polyazole compounds selected from the group consisting of a polymer of a heterocyclic compound containing one or more nitrogen atoms in the ring, as well as a polymer of a heterocyclic compound containing one or more nitrogen atoms and oxygen and/or sulfur atoms in the ring.
Specific examples of polyazole compounds include polyimidazole compounds, polybenzimidazole compounds, polybenzobisimidazole compounds, polybenzoxazole compounds, polyoxazole compounds, polythiazole compounds, and polybenzothiazole compounds.
Further, from the viewpoint of the oxidation resistance of the solid polymer electrolyte membrane, as other polymers, polyphenylene sulfide resins and polyphenylene ether resins may also be mentioned.
The fluorinated polymer (I) has ion-exchange groups. As specific examples of ion-exchange groups, sulfonic acid type functional groups and carboxylic acid type functional groups may be mentioned, and sulfonic acid type functional groups are preferred, from such a viewpoint that the electrolysis voltage can be reduced more.
In the following, detailed descriptions will be made mainly about embodiments of a fluorinated polymer having sulfonic acid type functional groups (hereinafter referred to also as a “fluorinated polymer (S)”).
The fluorinated polymer (S) preferably contains units based on a fluorinated olefin and units having sulfonic acid type functional groups and fluorine atoms.
As the fluorinated olefin, for example, a C2-3 fluoroolefin having at least one fluorine atom in the molecule may be mentioned. Specific examples of the fluoroolefin include tetrafluoroethylene (hereinafter referred to also as “TFE”), chlorotrifluoroethylene, vinylidene fluoride, vinyl fluoride, and hexafluoropropylene. Among them, TFE is preferred from such a viewpoint that it is excellent in the cost of monomer production, reactivity with other monomers, and properties of the obtainable fluorinated polymer (S).
As the fluorinated olefin, one type may be used alone, or two or more types may be used in combination.
As the units having sulfonic acid type functional groups and fluorine atoms, units represented by the following formula (1) are preferred.
—[CF2—CF(L-(SO3M)n)]— Formula (1):
In the formula, L is an n+1-valent perfluorohydrocarbon group which may contain an etheric oxygen atom.
The etheric oxygen atom may be located at the terminal or between carbon-carbon atoms in the perfluorohydrocarbon group.
The number of carbon atoms in the n+1-valent perfluorohydrocarbon group is preferably at least 1, particularly preferably at least 2, and preferably at most 20, particularly preferably at most 10.
As L, an n+1-valent perfluoroaliphatic hydrocarbon group which may contain an etheric oxygen atom is preferred, and a divalent perfluoroalkylene group which may contain an etheric oxygen atom, as an embodiment of n=1, or a trivalent perfluoroaliphatic hydrocarbon group which may contain an etheric oxygen atom, as an embodiment of n=2, is particularly preferred.
The above divalent perfluoroalkylene group may be linear or branched-chain.
M is a hydrogen atom, an alkali metal or a quaternary ammonium cation.
n is 1 or 2. When n is 2, the plurality of M may be the same or different.
As the units represented by the formula (1), units represented by the formula (1-1), units represented by the formula (1-2), units represented by the formula (1-3) or units represented by the formula (1-4), are preferred.
Rf1 is a perfluoroalkylene group which may contain an oxygen atom between carbon-carbon atoms. The number of carbon atoms in the above perfluoroalkylene group is preferably at least 1, particularly preferably at least 2, and preferably at most 20, particularly preferably at most 10.
Rf2 is a single bond or a perfluoroalkylene group which may contain an oxygen atom between carbon-carbon atoms. The number of carbon atoms in the above perfluoroalkylene group is preferably at least 1, particularly preferably at least 2, and preferably at most 20, particularly preferably at most 10.
Rf3 is a single bond or a perfluoroalkylene group which may contain an oxygen atom between carbon-carbon atoms. The number of carbon atoms in the above perfluoroalkylene group is preferably at least 1, particularly preferably at least 2, and preferably at most 20, particularly preferably at most 10.
r is 0 or 1.
m is 0 or 1.
M is a hydrogen atom, an alkali metal or a quaternary ammonium cation.
As the units represented by the formula (1-1) and the units represented by the formula (1-2), units represented by the formula (1-5) are more preferred.
—[CF2—CF(—(CF2)x—(OCF2CFY)y—O—(CF2)z—SO3M)] Formula (1-5):
x is 0 or 1, y is an integer of from 0 to 2, z is an integer of from 1 to 4, and Y is F or CF3. M is as described above.
As specific examples of the units represented by the formula (1-1), the following units may be mentioned. In the formulas, w is an integer of from 1 to 8, and x is an integer of from 1 to 5. The definition of M in the formulas is as defined above.
—[CF2—CF(—O—(CF2)w—SO3M)]—
—[CF2—CF(—O—CF2 CF(CF3)—O—(CF2)w—SO3M)]—
—[CF2—CF(—(O—CF2CF(CF3))x—SO3M)]—
As specific examples of the units represented by the formula (1-2), the following units may be mentioned. In the formulas, w is an integer of from 1 to 8. The definition of M in the formulas is as defined above.
—[CF2—CF(—(CF2)w—SO3M)]—
—[CF2—CF(—CF2—O—(CF2)w—SO3M)]—
As the units represented by the formula (1-3), units represented by the formula (1-3-1) are preferred. The definition of M in the formula is as defined above.
Rf4 is a C1-6 linear perfluoroalkylene group, and Rf5 is a single bond or a C1-6 linear perfluoroalkylene group which may contain an oxygen atom between carbon-carbon atoms. The definitions of r and M are as defined above.
As specific examples of the units represented by the formula (1-3-1), the following may be mentioned.
As the units represented by the formula (1-4), units represented by the formula (1-4-1) are preferred. The definitions of Rf1, Rf2 and M in the formula are as defined above.
As specific examples of the units represented by the formula (1-4-1), the following may be mentioned.
As the units having sulfonic acid type functional groups and fluorine atoms, one type may be used alone, or two or more types may be used in combination.
In the case of a fluorinated polymer having carboxylic acid type functional groups (hereinafter referred to as a “fluorinated polymer (C)”), one containing units based on a fluorinated olefin and units having carboxylic acid type functional groups and fluorine atoms, is preferred.
As specific examples of the fluorinated polymer (C), the following compounds may be mentioned.
CF2═CFOCF2 CF(CF3)OCF2CF2COOCH3,
CF2═CFOCF2CF2COOCH3,
CF2═CFOCF2CF2CF2COOCH3,
CF2═CFOCF2CF2CF2OCF2CF2COOCH3,
CF2═CFOCF2CF2CF2CF2CF2COOCH3,
CF2═CFOCF2CF(CF3)OCF2CF2CF2COOCH3.
The fluorinated polymer (I) may contain units based on other monomers, other than units based on a fluorinated olefin and units having sulfonic acid type functional groups and fluorine atoms.
As specific examples of other monomers, CF2═CFRf6 (where Rf6 is a C2-10 perfluoroalkyl group), CF2═CF—ORf7 (where Rf7 is a C1-10 perfluoroalkyl group) and CF2═CFO(CF2)vCF═CF2 (where v is an integer of from 1 to 3) may be mentioned.
The content of the units based on other monomers is preferably at most 30 mass % to all units in the fluorinated polymer (I), from the viewpoint of maintaining the ion exchange performance.
The solid polymer electrolyte membrane may have a monolayer or multilayer structure. In the case of a multilayer structure, for example, an embodiment wherein a plurality of layers containing the fluorinated polymer (I) and having different ion exchange capacities are laminated, may be mentioned.
As a method for producing a solid polymer electrolyte membrane, a method may be mentioned, in which a membrane (hereinafter referred to also as a “precursor membrane”) containing a polymer of a fluorinated monomer having groups which can be converted to ion-exchange groups (hereinafter referred to also as a “fluorinated polymer (I′)”) and a woven fabric, is produced, and then the groups which can be converted to ion-exchange groups in the precursor membrane, are converted to ion-exchange groups.
Here, a suitable embodiment for the method of producing the precursor membrane is, for example, a method of sandwiching both sides of a laminate in which the fluorinated polymer (I′) is placed on both sides of a woven fabric, by transfer base materials such as low melting point films with a melting point of from 70 to 180° C., followed by heat pressing.
As specific examples of the low melting point films, polyethylene films, polypropylene films, and polystyrene films may be mentioned.
The form of the woven fabric is as described above.
The fluorinated polymer (I′) is preferably a polymer (hereinafter referred to also as a “fluorinated polymer (S′)”) of a fluorinated monomer (hereinafter referred to also as a “fluorinated monomer (S′)”) having a group which can be converted to a sulfonic acid type functional group, and particularly preferably a copolymerized polymer of a fluorinated olefin and a monomer having a group which can be converted to a sulfonic acid type functional group and a fluorine atom.
In the following, the fluorinated polymer (S′) will be described in detail.
As a method of copolymerization for the fluorinated polymer (S′), a known method such as solution polymerization, suspension polymerization, emulsion polymerization, or the like, may be employed.
As the fluorinated olefin, those exemplified earlier may be mentioned, and TFE is preferred from such a viewpoint that it is excellent in the cost of monomer production, reactivity with other monomers, and properties of the obtainable fluorinated polymer (S).
As the fluorinated olefin, one type may be used alone, or two or more types may be used in combination.
As the fluorinated monomer (S′), a compound which has at least one fluorine atom in the molecule, has an ethylenic double bond, and has a group which can be converted to a sulfonic acid type functional group, may be mentioned.
As the fluorinated monomer (S′), a compound represented by the formula (2) is preferred from such a viewpoint that it is excellent in the cost of monomer production, reactivity with other monomers, and properties of the obtainable fluorinated polymer (S).
CF2═CF-L-(A)n Formula (2):
The definitions of L and n in the formula (2) are as defined above.
A is a group which can be converted to a sulfonic acid type functional group. As the functional group which can be converted to a sulfonic acid type functional group, a functional group which can be converted to a sulfonic acid type functional group by hydrolysis is preferred. As specific examples of the group which can be converted to a sulfonic acid type functional group, —SO2F, —SO2Cl and —SO2Br may be mentioned.
As the compound represented by the formula (2), a compound represented by the formula (2-1), a compound represented by the formula (2-2), a compound represented by the formula (2-3), and a compound represented by the formula (2-4) are preferred.
CF2═CF—O—Rf1-A Formula (2-1):
CF2═CF—Rf1-A Formula (2-2):
The definitions of Rf1, Rf2, r and A in the formulas are as defined above.
The definitions of Rf1, Rf2, Rf3, r, m and A in the formula are as defined above.
As the compound represented by the formula (2-1) and the compound represented by the formula (2-2), a compound represented by the formula (2-5) is preferred.
CF2═CF—(CF2)x—(OCF2CFY)y—O—(CF2)z—SO3M Formula (2-5):
The definitions of M, x, y, z and Y in the formula are as defined above.
As specific examples of the compound represented by the formula (2-1), the following compounds may be mentioned. In the formulas, w is an integer of from 1 to 8, and x is an integer of from 1 to 5.
CF2═CF—O—(CF2)w—SO2F
CF2═CF—O—CF2CF(CF3)—O—(CF2)w—SO2F
CF2═CF—[O—CF2CF(CF3)]x—SO2F
As specific examples of the compound represented by the formula (2-2), the following compounds may be mentioned. In the formulas, w is an integer of from 1 to 8.
CF2═CF—(CF2)w—SO2F
CF2═CF—CF2—O—(CF2)w—SO2F
As the compound represented by the formula (2-3), a compound represented by the formula (2-3-1) is preferred.
The definitions of Rf4, Rf5, r and A in the formula are as defined above.
As specific examples of the compound represented by the formula (2-3-1), the following may be mentioned.
As the compound represented by the formula (2-4), a compound represented by the formula (2-4-1) is preferred.
The definitions of Rf1, Rf2 and A in the formula are as defined above.
As specific examples of the compound represented by the formula (2-4-1), the following may be mentioned.
As the fluorinated monomer (S′) one type may be used alone, or two or more types may be used in combination.
For the production of a fluorinated polymer (S′), other monomers may be used in addition to the fluorinated olefin and the fluorinated monomer (S′). As such other monomers, those exemplified above may be mentioned.
The ion exchange capacity of the fluorinated polymer (I′) can be adjusted by changing the content of groups which can be converted to ion-exchange groups in the fluorinated polymer (I′).
As a specific example of the production method for the precursor membrane, an extrusion method may be mentioned. More specifically, a method may be mentioned, in which a membrane (I′) consisting of a fluorinated polymer (I′) is formed, and then, the membrane (I′), a woven fabric, and the membrane (I′) are arranged in this order, and they are laminated by using a stacking roll or a vacuum stacking device.
As a specific example of the method for converting groups which can be converted to ion-exchange groups in the precursor film, a method of applying a hydrolysis treatment or acidification treatment to the precursor membrane may be mentioned.
Among them, the method of contacting the precursor membrane with an alkaline aqueous solution is particularly preferred.
As specific examples of the method of contacting the precursor membrane with the alkaline aqueous solution, a method of immersing the precursor membrane in the alkaline aqueous solution and a method of spray coating the precursor membrane surface with the alkaline aqueous solution, may be mentioned.
The temperature of the alkaline aqueous solution is preferably from 30 to 100° C., particularly preferably from 40 to 100° C. The contact time between the precursor membrane and the alkaline aqueous solution is preferably from 3 to 150 minutes, particularly preferably from 5 to 50 minutes.
The alkaline aqueous solution preferably contains an alkali metal hydroxide, a water-soluble organic solvent and water.
As the alkali metal hydroxide, sodium hydroxide and potassium hydroxide may be mentioned.
In this specification, a water-soluble organic solvent is an organic solvent which is readily soluble in water, and specifically, an organic solvent with a solubility of 0.1 g or more in 1,000 ml (20° C.) of water is preferred, and an organic solvent with a solubility of 0.5 g or more is particularly preferred. The water-soluble organic solvent preferably contains at least one type selected from the group consisting of a non-protonic organic solvent, an alcohol and an amino alcohol, and it is particularly preferred to contain a non-protonic organic solvent.
As the water-soluble organic solvent, one type may be used alone, or two or more types may be used in combination.
As specific examples of the non-protonic organic solvent, dimethyl sulfoxide,
N,N-dimethylformamide, N,N-dimethylacetam ide, N-methyl-2-pyrrolidone and N-ethyl-2-pyrrolidone may be mentioned, and dimethyl sulfoxide is preferred.
As specific examples of the alcohol, methanol, ethanol, isopropanol, butanol, methoxyethoxyethanol, butoxyethanol, butylcarbitol, hexyloxyethanol, octanol, 1-methoxy-2-propanol and ethylene glycol may be mentioned.
As specific examples of the aminoalcohol, ethanolamine, N-methyl ethanolamine, N-ethyl ethanolamine, 1-amino-2-propanol, 1-amino-3-propanol, 2-aminoethoxyethanol, 2-amino thioethoxyethanol and 2-amino-2-methyl-1-propanol may be mentioned.
The concentration of the alkali metal hydroxide in the alkaline aqueous solution is preferably from 1 to 60 mass %, particularly preferably from 3 to 55 mass %.
The concentration of the water-soluble organic solvent in the alkaline aqueous solution is preferably from 1 to 60 mass %, particularly preferably from 3 to 55 mass %.
The concentration of water is preferably from 39 to 80 mass % in the alkaline aqueous solution.
After contact of the precursor membrane with the alkaline aqueous solution, treatment to remove the alkaline aqueous solution may be performed. As a method of removing the alkaline aqueous solution, for example, a method of washing the precursor membrane contacted with the alkaline aqueous solution, with water, may be mentioned.
After contact of the precursor membrane with the alkaline aqueous solution, the obtained membrane may be contacted with an acidic aqueous solution to convert the ion-exchange groups to the acid form.
As a specific example of the method of contacting the precursor membrane with the acidic aqueous solution, a method of immersing the precursor membrane in the acidic aqueous solution, or a method of spray coating the precursor membrane surface with the acidic aqueous solution, may be mentioned.
The acid aqueous solution preferably contains an acid component and water.
As a specific example of the acid component, hydrochloric acid or sulfuric acid may be mentioned.
<Anode and Cathode>
The anode and the cathode each have a catalyst layer. In the example in
As a specific example of the catalyst layer, a layer containing a catalyst and a polymer having ion-exchange groups may be mentioned.
As specific examples of the catalyst, a supported catalyst having a catalyst containing platinum, a platinum alloy or platinum having a core-shell structure supported on a carbon carrier, an iridium oxide catalyst, an alloy containing iridium oxide, and a catalyst containing iridium oxide having a core-shell structure, may be mentioned. As the carbon carrier, carbon black powder may be mentioned.
As the polymer having ion-exchange groups, a fluorinated polymer having ion-exchange groups may be mentioned.
The gas diffusion layer has a function of diffusing gas uniformly to the catalyst layer and a function as a current collector. As specific examples of the gas diffusion layer, carbon paper, carbon cloth and carbon felt may be mentioned.
The gas diffusion layer is preferably one treated for water repellency by PTFE or the like.
In the membrane electrode assembly in
The membrane thicknesses of the anode and the cathode are each independently preferably from 5 to 100 μm, more preferably from 5 to 50 μm, further preferably from 5 to 30 μm, particularly preferably from 5 to 15 μm, from such a viewpoint that the effect of the present invention will be more excellent.
The membrane thicknesses of the anode and the cathode are measured by using images obtained by measuring by an optical microscopy of cross-sections cut toward the membrane thickness direction of the membrane electrode assembly and are the arithmetic average values at optional 20 locations.
As a method for producing a membrane electrode assembly, for example, a method of forming catalyst layers on a solid polymer electrolyte membrane and further sandwiching the obtained assembly by gas diffusion layers, and a method of forming a catalyst layer on a gas diffusion layer to form electrodes (anode, cathode) and sandwiching a solid polymer electrolyte membrane with such electrodes, may be mentioned.
Here, as the method of forming the catalyst layer, a method of applying a coating liquid for forming the catalyst layer at a predetermined position and drying it as the case requires, may be mentioned. The coating liquid for forming the catalyst layer is a liquid having a polymer having ion-exchange groups and a catalyst dispersed in a dispersant.
The membrane electrode assembly of the present invention can be used in a water electrolysis apparatus (specifically, a solid polymer water electrolysis apparatus). Further, the membrane electrode assembly of the present invention can also be used as a diaphragm in an electrolytic hydrogenation apparatus for an aromatic compound (e.g. toluene).
The water electrolysis apparatus of the present invention contains the membrane electrode assembly as described above. Since the water electrolysis apparatus of the present invention contains the above-described membrane electrode assembly, the increase range of the electrolysis voltage is small even when the current density is increased.
The water electrolysis apparatus may have the same construction as known water electrolysis apparatuses, except that it contains the above-described membrane electrode assembly.
The electrolytic hydrogenation apparatus of the present invention contains the above-described membrane electrode assembly. The electrolytic hydrogenation apparatus of the present invention can have the same construction as known electrolytic hydrogenation apparatuses, except that it contains the above-described membrane electrode assembly.
The solid polymer electrolyte membrane of the present invention is a solid polymer electrolyte membrane containing a fluorinated polymer having ion-exchange groups and a woven fabric.
The above woven fabric comprises yarns A extending in one direction and yarns B extending in a direction orthogonal to the yarns A, and the aperture ratio of the above woven fabric is at least 50%. Further, the ratio TAAVE/TBAVE calculated from the average maximum membrane thickness TAAVE and the average minimum membrane thickness TBAVE of the above solid polymer electrolyte membrane is at least 1.20.
The solid polymer electrolyte membrane of the present invention is suitable for a solid polymer electrolyte membrane contained in the above-described membrane electrode assembly, and when applied to a water electrolysis apparatus or an electrolytic hydrogenation apparatus, the increase in electrolysis voltage can be reduced even when the current density is increased.
The description of the suitable solid polymer electrolyte membrane of the present invention is omitted since it is similar to the solid polymer electrolyte membrane contained in the membrane electrode assembly of the present invention as described above.
In the following, the present invention will be described in detail with reference to Examples. Ex. 1 to Ex. 4 are Examples of the present invention, and Ex. 5 to Ex. 7 are Comparative Examples. However, the present invention is not limited to these Examples.
The average maximum membrane thickness TAAVE, the average minimum membrane thickness TBAVE and the ratio TAAVE/TBAVE of the solid polymer electrolyte membrane were calculated in accordance with the methods described in the above-described section for description of the solid polymer electrolyte membrane.
The fluorinated polymer was placed in a glove box with dry nitrogen flowing through it for 24 hours, and the dry mass of the fluorinated polymer was measured. Then, the fluorinated polymer was immersed in a 2 mol/L sodium chloride solution at 60° C. for 1 hour. After washing the fluorinated polymer with ultrapure water, it was taken out, and the ion exchange capacity (meq/g dry resin) of the fluorinated polymer was determined by titrating the solution in which the fluorinated polymer was immersed, with a 0.1 mol/L sodium hydroxide solution.
[Fabric Weight of Woven Fabric]
The woven fabric raw material used was cut into a 20×20 cm size and its mass was measured. The above measurement was performed five times, and the average value was used as the basis for determining the fabric weight (g/m2) of the woven fabric.
The densities of warp yarns and weft yarns constituting the woven fabric were calculated according to the following method. For each of the warp yarns and the weft yarns, the average value of five measurements of the length of 10 yarns was calculated as the density (yarns/inch), from the observation image of an optical microscope.
Calculated in accordance with the method described in the above section for description of the woven fabric, by using a sample obtained by cutting the woven fabric raw material into a 20×20 cm size.
The denier counts of warp yarns and weft yarns constituting the woven fabric ere calculated in accordance with the following method. By randomly selecting five aperture areas, the aperture ratio was calculated from the observed images of the optical microscope, and the average value was used as the aperture ratio.
A polymer (ion exchange capacity: 1.10 meq/g dry resin) obtained by copolymerizing TFE and the monomer (X) described below, followed by hydrolysis and acid treatment, was dispersed in a water/ethanol=40/60 (mass %) solvent at a solid concentration of 25.8% to obtain a dispersion (hereinafter referred to also as a “dispersion X”). To the obtained dispersion liquid X (19.0 g), ethanol (0.52 g) and water (3.34 g) were added, and an iridium oxide catalyst (manufactured by Tanaka Kikinzoku Kogyo K.K.) (13.0 g) containing 76 mass % of iridium in the dispersion, was also added. The obtained mixture was treated in a planetary bead mill (rotation speed 300 rpm) for 30 minutes, then water (4.49 g) and ethanol (4.53 g) were added, and further treated in a planetary bead mill (rotation speed 200 rpm) for 60 minutes to obtain an anode catalyst ink with a solid content of 40 mass %.
On one surface of the solid polymer electrolyte membrane obtained by the procedure described below, the anode catalyst ink was applied by a bar coater to bring iridium to be 2.0 mg/cm2, dried at 80° C. for 10 minutes, and then heat treated at 150° C. for 15 minutes to obtain an electrolyte membrane provided with an anode catalyst layer.
To a supported catalyst (“TEC10E50E” manufactured by Tanaka Kikinzoku Kogyo K.K.) (11 g) having 46 mass % of platinum supported on carbon powder, water (59.4 g) and ethanol (39.6 g) were added, followed by mixing and pulverization by using an ultrasonic homogenizer to obtain a dispersion of the catalyst.
To the dispersion of the catalyst, a mixture (29.2 g) having the dispersion X (20.1 g), ethanol (11 g) and Zeorora-H (manufactured by ZEON Corporation) (6.3 g) preliminarily mixed and kneaded, was added. Further, to the obtained dispersion, water (3.66 g) and ethanol (7.63 g) were added, followed by mixing by using a paint conditioner for 60 minutes to obtain a cathode catalyst ink with a solid content concentration of 10.0 mass %.
The cathode catalyst ink was applied to an ETFE sheet by a die coater, dried at 80° C., and further heat treated at 150° C. for 15 minutes to obtain a cathode catalyst layer decal with a platinum content of 0.4 mg/cm2.
The surface of the electrolyte membrane with the anode catalyst layer, on which no anode catalyst layer is formed, and the surface of the cathode catalyst layer decal, on which the catalyst layer is present, were faced to each other, and heated and pressed under conditions of a pressing temperature of 150° C., a pressing time of 2 minutes and a pressure of 3 MPa to bond the anode catalyst layer-attached electrolyte membrane and the cathode catalyst layer, and then the temperature was lowered to 70° C. and the pressure was released, whereupon the ETFE sheet of the cathode catalyst layer decal was peeled off to obtain a membrane electrode assembly with an electrode area of 25 cm2.
The membrane electrode assembly obtained by the above procedure was heat-treated at 150° C. for 15 minutes and then set in a water electrolysis evaluation jig EH50-25 (manufactured by Greenlight innovation).
Next, first, in order to sufficiently hydrate the solid polymer electrolyte membrane and both electrode ionomers, pure water with a conductivity of at most 1.0 μS/cm at a temperature of 80° C. under normal pressure was supplied to the anode side and the cathode side at a flow rate of 50 mL/min for 12 hours. Then, the cathode side was purged with nitrogen.
After the nitrogen purge, to the anode side, pure water with a conductivity of at most 1.0 μS/cm at a temperature of 80° C. under normal pressure was supplied at a flow rate of 50 mL/min, and while the gas pressure formed on the cathode side was kept at atmospheric pressure, the current was increased in steps of 2.5 A, in the range of from 0 to 50 A (current density of from 0 to 2 A/cm2) by a direct current power source PWR1600L manufactured by Kikusui Electronics Corporation. At each stage, the current was held for 10 minutes, and the electrolysis voltage Vx (unit V) at a current density of 2 A/cm2 and the electrolysis voltage Vy (unit V) at a current density of 4 A/cm2 were measured and evaluated by the following standards.
CF2═CF2 and a monomer (X) represented by the following formula (X) were copolymerized to obtain a fluorinated polymer (S′-1) (ion exchange capacity: 1.25 meq/g dry resin).
CF2═CF—O—CF2CF(CF3)—O—CF2CF2—SO2F (X)
Here, the ion exchange capacity described in the above [Production of fluorinated polymer (S′-1)] represents the ion exchange capacity of the fluorinated polymer obtainable by hydrolyzing the fluorinated polymer (S′-1) by the procedure as described below.
The fluorinated polymer (S′-1) was deposited by a melt-extrusion method on a base material consisting of a linear low-density polyethylene (LLDPE) film (melting point: 110 to 120° C.) to obtain a film-attached base material Y1 having a film α1 (membrane thickness: 45 μm) consisting of the fluorinated polymer (S′-1) formed on the base material.
The fluorinated polymer (S′-1) was deposited by a melt-extrusion method on a base material consisting of a linear low-density polyethylene (LLDPE) film (melting point: 110 to 120° C.) to obtain a film-attached base material Y2 having a film α2 (membrane thickness: 30 μm) consisting of the fluorinated polymer (S′-1) formed on the base material.
The fluorinated polymer (S′-1) was deposited by a melt-extrusion method on a base material consisting of a linear low-density polyethylene (LLDPE) film (melting point: 110 to 120° C.) to obtain a film-attached base material Y3 having a film α3 (membrane thickness: 15 μm) consisting of the fluorinated polymer (S′-1) formed on the base material.
The fluorinated polymer (S′-1) was deposited by a melt-extrusion method on a base material consisting of a polyethylene terephthalate (PET) film (melting point: 250 to 260° C.) to obtain a film-attached base material Y4 having a film α1 (membrane thickness: 45 μm) consisting of the fluorinated polymer (S′-1) formed on the base material.
The fluorinated polymer (S′-1) was deposited by a melt-extrusion method on a base material consisting of a polyethylene terephthalate (PET) film (melting point: 250 to 260° C.) to obtain a film-attached base material Y5 having a film α2 (membrane thickness: 30 μm) consisting of the fluorinated polymer (S′-1) formed on the base material.
49.8 denier yarns made of PTFE were used for the warp yarns and the weft yarns, and woven plainly to obtain woven fabric A1 so that the density of PTFE yarns became 90 yarns/inch. The fabric weight of the woven fabric A1 was 39.2 g/m2. Here, the warp yarns and the weft yarns were constituted by slit yarns.
Woven fabrics A2 to A3 were produced in the same manner as the production of the woven fabric A1, except that the type and denier of the material constituting the warp yarns and the weft yarns, as well as the density and fabric weight of the woven fabric, were changed to the values listed in Table 1.
The film-attached base material Y1/woven fabric A1/film-attached base material Y1 were overlapped in this order. Here, the film-attached base material Y1 was placed so that the film α1 in the film-attached base material Y1 was in contact with the woven fabric A1.
After heating and pressing the respective overlapped members for 10 minutes by a flat press machine at a temperature of 160° C. under a surface pressure of 30 MPa/m2, the base materials on both sides were peeled off at a temperature of 50° C. to obtain a precursor membrane.
The precursor membrane was immersed in a solution of dimethyl sulfoxide/potassium hydroxide/water=30/5.5/64.5 (mass ratio) at 95° C. for 30 minutes to hydrolyze the groups in the precursor membrane which can be converted to sulfonic acid type functional groups to convert them to K-type sulfonic acid type functional groups, followed by washing with water. Then, the obtained membrane was immersed in 1M sulfuric acid to convert the terminal groups from K-type to H-type, followed by drying to obtain a solid polymer electrolyte membrane.
Using the obtained solid polymer electrolyte membrane, measurement of the membrane thickness of the solid polymer electrolyte membrane and an evaluation test for an electrolysis voltage were conducted. The results are shown in Table 1.
Except that the types of the film-attached base material and the woven fabric were changed as described in Table 1, in the same manner as in Ex. 1, solid polymer electrolyte membranes were prepared, and measurement of the membrane thicknesses of the solid polymer electrolyte membranes and an evaluation test for an electrolysis voltage were conducted.
The film-attached base material Y4/woven fabric A1/film-attached base material Y4 were overlapped in this order. Here, the film-attached base material Y4 was placed so that the film α1 in the film-attached base material Y4 was in contact with the woven fabric A1.
After heating and pressing the respective overlapped members for 10 minutes in a flat press machine at a temperature of 200° C. under a surface pressure of 30 MPa/m2, the base materials on both sides were peeled off at a temperature of 50° C. to obtain a precursor membrane.
Except that the precursor membrane obtained in this manner was used, in the same manner as in Ex. 1, a solid polymer electrolyte membrane was prepared, measurement of the membrane thickness of the solid polymer electrolyte membrane and an evaluation test for an electrolysis voltage were conducted.
Except that the types of the film-attached base material and the woven fabric were changed as described in Table 1, in the same manner as in Ex. 5, solid polymer electrolyte membranes were prepared, and measurement of the membrane thicknesses of the solid polymer electrolyte membranes and an evaluation test for an electrolysis voltage were conducted.
The “denier count (g/9000 m)” in Table 1 represents the denier count of the warp yarns and the weft yarns constituting the woven fabric. In all of Ex. 1 to 7, the denier counts of the warp yarns and the weft yarns constituting the woven fabric were the same.
As shown in Table 1, it was confirmed that in a membrane electrode assembly containing a solid polymer electrolyte membrane, if the solid polymer electrolyte membrane contains a woven fabric with an aperture ratio of at least 50% and the ratio TAAVE/TBAVE of the solid polymer electrolyte membrane is at least 1.20, the increase in electrolysis voltage can be reduced even when the current density is increased (Ex. 1 to 4).
This application is a continuation of PCT Application No. PCT/JP2021/032352, filed on Sep. 2, 2021, which is based upon and claims the benefit of priority from Japanese Patent Application No. 2020-148732 filed on Sep. 4, 2020. The contents of those applications are incorporated herein by reference in their entireties.
| Number | Date | Country | Kind |
|---|---|---|---|
| 2020-148732 | Sep 2020 | JP | national |
| Number | Date | Country | |
|---|---|---|---|
| Parent | PCT/JP21/32352 | Sep 2021 | US |
| Child | 18108763 | US |
