JP2020032697A - Laminate and method for producing the same and use thereof - Google Patents
Laminate and method for producing the same and use thereof Download PDFInfo
- Publication number
- JP2020032697A JP2020032697A JP2018163549A JP2018163549A JP2020032697A JP 2020032697 A JP2020032697 A JP 2020032697A JP 2018163549 A JP2018163549 A JP 2018163549A JP 2018163549 A JP2018163549 A JP 2018163549A JP 2020032697 A JP2020032697 A JP 2020032697A
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- Prior art keywords
- graphene oxide
- sulfonic acid
- mass
- layer
- fuel cell
- Prior art date
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- 238000004519 manufacturing process Methods 0.000 title claims description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical class [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 124
- 239000010410 layer Substances 0.000 claims abstract description 78
- 239000012528 membrane Substances 0.000 claims abstract description 51
- 239000003792 electrolyte Substances 0.000 claims abstract description 38
- 239000011247 coating layer Substances 0.000 claims abstract description 36
- 239000004449 solid propellant Substances 0.000 claims abstract description 31
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims abstract description 24
- 125000000542 sulfonic acid group Chemical group 0.000 claims abstract description 20
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims abstract description 14
- 239000000758 substrate Substances 0.000 claims abstract description 10
- 229910021389 graphene Inorganic materials 0.000 claims description 77
- 238000000034 method Methods 0.000 claims description 60
- 239000000463 material Substances 0.000 claims description 45
- 239000002585 base Substances 0.000 claims description 38
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 34
- 229910052751 metal Chemical class 0.000 claims description 21
- 239000002184 metal Chemical class 0.000 claims description 21
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- 239000012078 proton-conducting electrolyte Substances 0.000 claims description 20
- 239000007788 liquid Substances 0.000 claims description 19
- -1 alkali metal salt Chemical class 0.000 claims description 16
- 229920002313 fluoropolymer Polymers 0.000 claims description 15
- 239000002243 precursor Substances 0.000 claims description 15
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 11
- 150000003460 sulfonic acids Chemical group 0.000 claims description 11
- 229910052717 sulfur Inorganic materials 0.000 claims description 11
- 239000011593 sulfur Substances 0.000 claims description 11
- 150000003839 salts Chemical class 0.000 claims description 9
- NLVXSWCKKBEXTG-UHFFFAOYSA-N vinylsulfonic acid Chemical class OS(=O)(=O)C=C NLVXSWCKKBEXTG-UHFFFAOYSA-N 0.000 claims description 9
- 238000000576 coating method Methods 0.000 claims description 8
- 238000000921 elemental analysis Methods 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 7
- 239000003505 polymerization initiator Substances 0.000 claims description 7
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- 229910052783 alkali metal Inorganic materials 0.000 claims description 4
- 239000004811 fluoropolymer Substances 0.000 claims description 3
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- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 abstract description 9
- 239000011737 fluorine Substances 0.000 abstract description 9
- 229910052731 fluorine Inorganic materials 0.000 abstract description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 36
- 239000000446 fuel Substances 0.000 description 33
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- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
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- 230000000052 comparative effect Effects 0.000 description 6
- 125000000524 functional group Chemical group 0.000 description 6
- 229910052759 nickel Inorganic materials 0.000 description 6
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- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 229910052742 iron Inorganic materials 0.000 description 5
- 229910052708 sodium Inorganic materials 0.000 description 5
- 239000011734 sodium Substances 0.000 description 5
- 239000006228 supernatant Substances 0.000 description 5
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
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- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
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- 238000002156 mixing Methods 0.000 description 4
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- 229920001343 polytetrafluoroethylene Polymers 0.000 description 4
- 239000004810 polytetrafluoroethylene Substances 0.000 description 4
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 4
- 238000010248 power generation Methods 0.000 description 4
- 239000002356 single layer Substances 0.000 description 4
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 4
- BWYYYTVSBPRQCN-UHFFFAOYSA-M sodium;ethenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C=C BWYYYTVSBPRQCN-UHFFFAOYSA-M 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 3
- 150000001491 aromatic compounds Chemical class 0.000 description 3
- 239000003575 carbonaceous material Substances 0.000 description 3
- 229910017052 cobalt Inorganic materials 0.000 description 3
- 239000010941 cobalt Substances 0.000 description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 3
- 239000003999 initiator Substances 0.000 description 3
- 239000010416 ion conductor Substances 0.000 description 3
- 239000007800 oxidant agent Substances 0.000 description 3
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- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 2
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- LXEKPEMOWBOYRF-UHFFFAOYSA-N [2-[(1-azaniumyl-1-imino-2-methylpropan-2-yl)diazenyl]-2-methylpropanimidoyl]azanium;dichloride Chemical compound Cl.Cl.NC(=N)C(C)(C)N=NC(C)(C)C(N)=N LXEKPEMOWBOYRF-UHFFFAOYSA-N 0.000 description 2
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- TXCDCPKCNAJMEE-UHFFFAOYSA-N dibenzofuran Chemical compound C1=CC=C2C3=CC=CC=C3OC2=C1 TXCDCPKCNAJMEE-UHFFFAOYSA-N 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
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- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 2
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- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
- H01M8/102—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer
- H01M8/1032—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer having sulfur, e.g. sulfonated-polyethersulfones [S-PES]
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Abstract
Description
本発明は、固体燃料電池セルのプロトン伝導電解質膜などに利用できる積層体ならびにその製造方法および用途に関する。 The present invention relates to a laminate that can be used as a proton conductive electrolyte membrane of a solid fuel cell, a method for producing the same, and a use thereof.
燃料電池は、正極である空気極と、負極である燃料極（触媒極）と、両極の間に介在する電解質とを有する電池セルを備えている。この燃料電池では、燃料極に供給された水素ガスが水素イオンと電子とに分かれ、水素イオン（プロトン）が電解質中を移動し、電子が外部回路を通って空気極に移動して酸素と反応して水が生成され、このときに外部回路に移動する電子がエネルギーとして取り出される。燃料電池の出力および安定性向上のために様々な電解質が検討されている。例えば、高プロトン性を得るために、スルホン酸基を有するフッ素系ポリマーを電解質として用いる技術が知られているが、室温でのプロトン伝導性には問題があり、高出力を得ることが難しい。 The fuel cell includes a battery cell having an air electrode serving as a positive electrode, a fuel electrode (catalyst electrode) serving as a negative electrode, and an electrolyte interposed between the two electrodes. In this fuel cell, the hydrogen gas supplied to the fuel electrode is split into hydrogen ions and electrons, hydrogen ions (protons) move through the electrolyte, and electrons move to the air electrode through an external circuit and react with oxygen. As a result, water is generated, and at this time, electrons moving to an external circuit are extracted as energy. Various electrolytes have been studied to improve the output and stability of fuel cells. For example, a technique using a fluorinated polymer having a sulfonic acid group as an electrolyte in order to obtain high protonicity is known, but there is a problem in proton conductivity at room temperature, and it is difficult to obtain high output.
特開２０１１−９８８４３号公報（特許文献１）には、スルホ基を導入するために、スルホン化試剤として硫酸を用いてスルホン化した酸化グラフェン（ＧＯ）が記載されている。しかし、このような材料をプロトン伝導電解質として燃料電池デバイスに使用した場合、電極に含まれる白金触媒層などの金属または金属含有触媒層と電解質との界面密着性が低下して燃料電池出力も低下する。 Japanese Patent Application Laid-Open No. 2011-98843 (Patent Document 1) describes graphene oxide (GO) that has been sulfonated using sulfuric acid as a sulfonating reagent to introduce a sulfo group. However, when such a material is used as a proton conducting electrolyte in a fuel cell device, the interfacial adhesion between a metal such as a platinum catalyst layer included in the electrode or a metal-containing catalyst layer and the electrolyte is reduced, and the fuel cell output is also reduced. I do.
また“A poly(ethylene oxide)/graphene oxide electrolyte membrane for low temperature polymer fuel cells”（非特許文献１）では、高プロトン伝導性および機械的性質向上のために、酸化グラフェンとポリエチレンオキサイドとの混合物を電解質として用いる。しかし、この電解質で燃料電池の駆動を続けると、燃料電池反応から生じた水によりポリエチレンオキサイドが溶解し、電解質の機械的強度が低下する。 In “A poly (ethylene oxide) / graphene oxide electrolyte membrane for low temperature polymer fuel cells” (Non-Patent Document 1), a mixture of graphene oxide and polyethylene oxide is used to improve high proton conductivity and mechanical properties. Used as an electrolyte. However, if the operation of the fuel cell is continued with this electrolyte, the polyethylene oxide is dissolved by the water generated from the fuel cell reaction, and the mechanical strength of the electrolyte decreases.
従って、本発明の目的は、固体燃料電池セルのプロトン伝導電解質膜として用いると、室温で固体燃料電池を駆動でき、かつ出力安定性を向上できる積層体ならびにその製造方法および用途を提供することにある。 Therefore, an object of the present invention is to provide a laminate capable of driving a solid fuel cell at room temperature and improving output stability when used as a proton-conducting electrolyte membrane of a solid fuel cell, and a method for producing the laminate and its use. is there.
本発明の他の目的は、固体燃料電池セルのプロトン伝導電解質膜に利用でき、容易かつ安価に製造できる積層体ならびにその製造方法および用途を提供することにある。 It is another object of the present invention to provide a laminate which can be used for a proton conducting electrolyte membrane of a solid fuel cell, can be easily and inexpensively manufactured, and a method for manufacturing the same and its use.
本発明者らは、前記課題を達成するため鋭意検討した結果、ビニル基を有するスルホン酸類で変性された変性酸化グラフェンを含む基材層の少なくとも一方の面に、スルホン酸基を有するフッ素系ポリマーを含む被覆層が積層された積層体を固体燃料電池のプロトン伝導電解質膜として用いると、室温での電池の駆動が可能となり、プロトン伝導性および出力安定性も向上できることを見出し、本発明を完成した。 The present inventors have conducted intensive studies to achieve the above object, and found that at least one surface of a base material layer containing a modified graphene oxide modified with a sulfonic acid having a vinyl group has a fluorine-based polymer having a sulfonic acid group. It was found that, when a laminate having a coating layer containing is used as a proton conducting electrolyte membrane of a solid fuel cell, the battery can be driven at room temperature, and the proton conductivity and output stability can be improved, thus completing the present invention. did.
すなわち、本発明の積層体は、ビニル基を有するスルホン酸類で変性された変性酸化グラフェンを含む基材層と、この基材層の少なくとも一方の面に積層され、かつスルホン酸基を有するフッ素系ポリマーを含む被覆層とを含む。前記基材層の両面に、それぞれ第１の被覆層および第２の被覆層が積層されていてもよい。前記変性酸化グラフェン中の元素分析での硫黄含有量は０．５〜１０Ａｔｏｍ％であってもよい。前記ビニル基を有するスルホン酸類はビニルスルホン酸またはその金属塩であってもよい。前記基材層の平均厚みと、前記被覆層総厚みの平均厚みとの比は、前者／後者＝１０／１〜１００／１程度である。前記積層体は、固体燃料電池セルのプロトン伝導電解質膜であってもよい。 That is, the laminate of the present invention is a base material layer containing modified graphene oxide modified with sulfonic acids having a vinyl group, and a fluorine-based material having a sulfonic acid group laminated on at least one surface of the base material layer. A coating layer containing a polymer. A first coating layer and a second coating layer may be respectively laminated on both surfaces of the base material layer. An elemental analysis of the modified graphene oxide may have a sulfur content of 0.5 to 10 atom%. The sulfonic acids having a vinyl group may be vinyl sulfonic acid or a metal salt thereof. The ratio of the average thickness of the base material layer to the average thickness of the total thickness of the coating layer is about the former / the latter = about 10/1 to 100/1. The laminate may be a proton conductive electrolyte membrane of a solid fuel cell.
本発明には、重合開始剤および溶媒の存在下で酸化グラフェンとビニル基を有するスルホン酸類とを反応させて得られた変性酸化グラフェンを含む液状基材層前駆体を製膜する基材層形成工程と、得られた基材層の少なくとも一方の面に、スルホン酸基を有するフッ素系ポリマーを含む液状被覆層前駆体をコーティングする被覆層形成工程とを含む、前記積層体の製造方法も含まれる。基材層形成工程における酸化グラフェンとビニル基を有するスルホン酸類との反応温度は１００℃以下であってもよい。前記ビニル基を有するスルホン酸類は、ビニルスルホン酸アルカリ金属塩であってもよい。前記溶媒は水を含んでいてもよい。 The present invention provides a method for forming a substrate layer for forming a liquid substrate layer precursor containing a modified graphene oxide obtained by reacting graphene oxide with a sulfonic acid having a vinyl group in the presence of a polymerization initiator and a solvent. The method for producing a laminate also includes a step and a coating layer forming step of coating a liquid coating layer precursor containing a fluorinated polymer having a sulfonic acid group on at least one surface of the obtained base material layer. It is. The reaction temperature between the graphene oxide and the sulfonic acids having a vinyl group in the base layer forming step may be 100 ° C. or lower. The sulfonic acids having a vinyl group may be an alkali metal salt of vinyl sulfonic acid. The solvent may include water.
本発明には、前記プロトン伝導電解質膜と電極とが一体化した固体燃料電池セルも含まれる。 The present invention also includes a solid fuel cell unit in which the proton conductive electrolyte membrane and an electrode are integrated.
本発明では、ビニル基を有するスルホン酸類で変性された変性酸化グラフェンを含む基材層の少なくとも一方の面に、スルホン酸基を有するフッ素系ポリマーを含む被覆層が積層されており、酸点が高く、プロトン伝導性に優れるため、この積層体を固体燃料電池セルのプロトン伝導電解質膜として用いると、室温で固体燃料電池を駆動でき、取扱性を向上できるとともに、前記基材層と前記被覆層との層間密着性が高く、界面状態が良好であるため、固体燃料電池の最大出力密度を高め、安定な出力密度を確保できる。さらに、慣用の方法を用いて、温和な条件で製造できるため、固体燃料電池セルのプロトン伝導電解質膜に利用できる積層体を容易かつ安易に製造できる。 In the present invention, a coating layer containing a fluorinated polymer having a sulfonic acid group is laminated on at least one surface of a substrate layer containing modified graphene oxide modified with a sulfonic acid having a vinyl group, Since this laminate is used as a proton conducting electrolyte membrane of a solid fuel cell because of its high proton conductivity, the solid fuel cell can be driven at room temperature, handling can be improved, and the base layer and the coating layer can be improved. Since the interlayer adhesion between the solid fuel cell and the interface is good, the maximum output density of the solid fuel cell can be increased and a stable output density can be secured. Furthermore, since it can be manufactured under mild conditions using a conventional method, a laminate that can be used as a proton conductive electrolyte membrane of a solid fuel cell can be easily and easily manufactured.
［基材層］
本発明の積層体は、変性酸化グラフェンを含む基材層を含む。本明細書および特許請求の範囲において、変性酸化グラフェンを構成する酸化グラフェンは、カルボニル基、ホルミル基、ヒドロキシル基、カルボキシル基、エポキシ基などの酸素含有官能基で修飾されたグラフェンを意味する。酸化グラフェンは、天然または人工グラファイトを酸化し、単層または多層に剥離させることにより、ナノメータサイズの厚みのシート形状に調製された酸化グラフェンである。
[Base material layer]
The laminate of the present invention includes a base material layer containing modified graphene oxide. In this specification and the claims, graphene oxide constituting modified graphene oxide means graphene modified with an oxygen-containing functional group such as a carbonyl group, a formyl group, a hydroxyl group, a carboxyl group, or an epoxy group. Graphene oxide is a graphene oxide prepared by oxidizing natural or artificial graphite and exfoliating it into a single layer or a multilayer to form a sheet having a thickness of nanometer size.
グラファイトの酸化方法としては、特に限定されず、慣用の方法を利用できる。慣用の製造方法としては、例えば、ハマーズ（Hummers）法、ブローディー（Brodie）法、スタウデンマイヤー（Staudenmaier）法などが挙げられる。 The method for oxidizing graphite is not particularly limited, and a conventional method can be used. Conventional production methods include, for example, the Hummers method, the Brodie method, the Staudenmaier method, and the like.
ハマーズ法は、W. S Hummers, Jr. et al., J. Am. Chem. Soc., 1958, 80, 1339.に記載の方法であってもよく、例えば、酸化剤として、硫酸、過マンガン酸塩（過マンガン酸カリウムなど）および硝酸塩（硝酸ナトリウムなど）を使用して酸化する方法であってもよい。 The Hummers method may be the method described in W. S Hummers, Jr. et al., J. Am. Chem. Soc., 1958, 80, 1339. An oxidation method using an acid salt (such as potassium permanganate) and a nitrate (such as sodium nitrate) may be used.
ブローディー法は、B. C. Brodie, Philos. Trans. R. Soc., London, 1859, 149, 249.やB. C. Brodie, Ann. Chim. Phys., 1860, 59, 46に記載の方法であってもよく、例えば、酸化剤として、発煙硝酸および塩素酸（塩素酸カリウムなど）を使用して酸化する方法であってもよい。 The Brodie method may be the method described in BC Brodie, Philos. Trans. R. Soc., London, 1859, 149, 249. or BC Brodie, Ann. Chim. Phys., 1860, 59, 46. For example, a method of oxidizing using fuming nitric acid and chloric acid (such as potassium chlorate) as an oxidizing agent may be used.
スタウデンマイヤー法は、L. Staudenmaier, Ber. Dtsch. Chem. Ges., 1898, 31, 1481.に記載の方法であってもよく、酸化剤として、硫酸、硝酸および塩素酸（塩素酸カリウムなど）を使用して酸化する方法であってもよい。 The Staudenmeier method may be a method described in L. Staudenmaier, Ber. Dtsch. Chem. Ges., 1898, 31, 1481. As an oxidizing agent, sulfuric acid, nitric acid and chloric acid (potassium chlorate) are used. Etc.) to perform oxidation.
これらのうち、プロトン伝導電解質としての特性を向上できる点から、ハマーズ法が好ましい。 Among them, the Hummers method is preferable from the viewpoint that the characteristics as a proton conducting electrolyte can be improved.
得られた酸化グラファイトは、酸素含有官能基が付加されているため、親水性であり、かつ層間が拡大し易い性質に改質されている。そのため、酸化グラファイトは、水などの水性溶媒中で超音波を照射する方法や、遠心分離と再分散とを繰り返す方法などにより、層間を剥離して、単層または多層酸化グラフェンに分解できる。得られた酸化グラフェンは、酸素含有官能基として、前述の酸素含有官能基を有している。 Since the obtained graphite oxide has an oxygen-containing functional group added thereto, it has been modified to have a hydrophilic property and to easily expand the interlayer. Therefore, graphite oxide can be decomposed into single-layer or multilayer graphene oxide by exfoliating layers by a method of irradiating ultrasonic waves in an aqueous solvent such as water or a method of repeating centrifugation and re-dispersion. The obtained graphene oxide has the above-mentioned oxygen-containing functional group as the oxygen-containing functional group.
酸化グラフェンの厚みは、原子１層の厚み（例えば、０．４ｎｍ程度）または複数層（例えば２〜１０層、特に２〜５層程度）の厚みを有していてもよい。酸化グラフェンは、炭素原子１個の厚みを有する単層構造であってもよく、複数の単層硫黄含有（酸化）グラフェンが所定の間隔で重なり合った多層（例えば２〜１０層、好ましくは２〜５層、さらに好ましくは２〜３層）構造であってもよい。 Graphene oxide may have a thickness of one atomic layer (for example, about 0.4 nm) or a plurality of layers (for example, about 2 to 10, especially about 2 to 5 layers). The graphene oxide may have a single-layer structure having a thickness of one carbon atom, and may be a multilayer in which a plurality of single-layer sulfur-containing (oxide) graphenes are overlapped at a predetermined interval (for example, 2 to 10 layers, preferably 2 to 2 layers). (5 layers, more preferably 2 to 3 layers).
酸化グラフェンの面方向の平均径は、０．１〜１０００μｍ程度の範囲から選択してもよく、例えば１〜５００μｍ（例えば５〜３００μｍ）、好ましくは５〜１００μｍ（例えば１０〜１００μｍ）程度であり、さらに好ましくは５〜５０μｍ（特に１０〜３０μｍ）程度であってもよい。 The average diameter of the graphene oxide in the plane direction may be selected from a range of about 0.1 to 1000 μm, for example, about 1 to 500 μm (eg, 5 to 300 μm), and preferably about 5 to 100 μm (eg, 10 to 100 μm). And more preferably about 5 to 50 μm (particularly 10 to 30 μm).
なお、本明細書および特許請求の範囲において、酸化グラフェンの面方向の平均径の測定には、電子顕微鏡、光学顕微鏡などが利用できる。なお、異形の酸化グラフェンにおいて、平均径は、各酸化グラフェンについて長軸径と短軸径との平均値を算出し、１００個程度の酸化グラフェンの平均値について加算平均することにより算出できる。 Note that, in this specification and the appended claims, an electron microscope, an optical microscope, or the like can be used for measuring the average diameter of graphene oxide in the plane direction. Note that in the irregular-shaped graphene oxide, the average diameter can be calculated by calculating the average value of the major axis diameter and the minor axis diameter for each graphene oxide, and averaging the average values of about 100 graphene oxides.
このような酸化グラフェンとしては、（株）仁科マテリアル製：品名「Rap GO (TQ-11)」、「GO-TQ2」、「Exfoliated GO」など、Graphenea社製：品名「Graphene Oxide Water Dispersion（０．４重量％濃度）」、「Highly Concentrated Graphene Oxide（２．５重量％濃度）」などの市販品で入手することができる。 Examples of such graphene oxide include: “Rap GO (TQ-11)”, “GO-TQ2”, and “Exfoliated GO” manufactured by Nishina Materials Co., Ltd .; and “Graphene Oxide Water Dispersion (0)” manufactured by Graphenea. 0.4% by weight) "and" Highly Concentrated Graphene Oxide (2.5% by weight) ".
酸化グラフェンは還元物であってもよい。酸化グラフェンの還元物は、還元処理により部分的に還元されたグラフェン（部分酸化グラフェン）であってもよい。 Graphene oxide may be a reduced product. The reduced product of graphene oxide may be graphene partially reduced by reduction treatment (partial graphene oxide).
酸化グラフェンの酸素含有官能基量を調整する方法としては、酸化グラフェンを酸素またはヒドラジンなどの雰囲気下において、キセノンランプにより光照射することで光還元する方法やヒドラジン蒸気により還元する方法、熱還元する方法などが挙げられる。 As a method of adjusting the amount of oxygen-containing functional groups of graphene oxide, a method of photoreducing graphene oxide by irradiating light with a xenon lamp in an atmosphere of oxygen or hydrazine, a method of reducing with hydrazine vapor, a method of performing thermal reduction And the like.
変性酸化グラフェンは、重合開始剤および溶媒の存在下で酸化グラフェンとビニル基を有するスルホン酸類とを反応させて得られた変性酸化グラフェンであればよく、酸化グラフェンとビニル基を有するスルホン酸類とは、共有結合を介して結合（グラフト結合）していてもよい。 The modified graphene oxide may be any modified graphene oxide obtained by reacting graphene oxide with a sulfonic acid having a vinyl group in the presence of a polymerization initiator and a solvent. And a bond (graft bond) via a covalent bond.
ビニル基を有するスルホン酸類としては、例えば、ビニルスルホン酸、アリルスルホン酸などのアルケンスルホン酸；スチレンスルホン酸などのビニルアリールスルホン酸；またはこれらの金属塩などが挙げられる。金属塩としては、ナトリウム塩、カリウム塩などのアルカリ金属塩などが挙げられる。これらのビニル基を有するスルホン酸類は、単独でまたは二種以上組み合わせて使用できる。これらのうち、ビニルスルホン酸またはその金属塩が好ましく、ビニルスルホン酸ナトリウムなどのビニルスルホン酸アルカリ金属塩が特に好ましい。 Examples of sulfonic acids having a vinyl group include alkene sulfonic acids such as vinyl sulfonic acid and allyl sulfonic acid; vinyl aryl sulfonic acids such as styrene sulfonic acid; and metal salts thereof. Examples of the metal salt include an alkali metal salt such as a sodium salt and a potassium salt. These sulfonic acids having a vinyl group can be used alone or in combination of two or more. Of these, vinyl sulfonic acid or a metal salt thereof is preferable, and an alkali metal salt of vinyl sulfonic acid such as sodium vinyl sulfonate is particularly preferable.
変性酸化グラフェンにおいて、ビニル基を有するスルホン酸類と酸化グラフェンとの組成比率は特に限定されないが、変性酸化グラフェン中の元素分析での硫黄含有量は０．５〜１０Ａｔｏｍ％程度の範囲から選択でき、例えば１〜８Ａｔｏｍ％、好ましくは１．５〜５Ａｔｏｍ％、さらに好ましくは２〜３Ａｔｏｍ％程度である。硫黄含有量が多すぎると、水との親和性が高まり、膜としての形状保持が困難となる虞がある。一方、硫黄含有量が少なすぎると、プロトン伝導性が低下し燃料電池デバイスとしての機能が発現しなくなる虞がある。 In the modified graphene oxide, the composition ratio of the sulfonic acid having a vinyl group and the graphene oxide is not particularly limited, but the sulfur content in the modified graphene oxide by elemental analysis can be selected from a range of about 0.5 to 10 atom%, For example, it is about 1 to 8 atom%, preferably about 1.5 to 5 atom%, and more preferably about 2 to 3 atom%. If the sulfur content is too high, affinity with water increases, and it may be difficult to maintain the shape of the film. On the other hand, if the sulfur content is too small, the proton conductivity may decrease, and the function as a fuel cell device may not be exhibited.
変性酸化グラフェン中の金属含有量は１０Ａｔｏｍ％以下であってもよく、例えば５Ａｔｏｍ％以下、好ましくは３Ａｔｏｍ％以下、さらに好ましくは１Ａｔｏｍ％以下であり、検出限界以下であってもよい。特に、ビニル基を有するスルホン酸類として、金属塩を使用した場合であっても、金属塩を用いて酸化グラフェンを変性して得られた変性酸化グラフェンの金属含有量は、前記範囲であってもよい。 The metal content in the modified graphene oxide may be 10 Atom% or less, for example, 5 Atom% or less, preferably 3 Atom% or less, more preferably 1 Atom% or less, and may be below the detection limit. In particular, even when a metal salt is used as the sulfonic acid having a vinyl group, the metal content of the modified graphene oxide obtained by modifying graphene oxide with the metal salt is within the above range. Good.
なお、本明細書および特許請求の範囲において、変性酸化グラフェン中の硫黄含有量や金属含有量は、慣用の元素分析、例えば、エネルギー分散型Ｘ線分光器（ＥＤＳ）による元素分析によって測定できる。 In the specification and the claims, the sulfur content and the metal content in the modified graphene oxide can be measured by a conventional elemental analysis, for example, an elemental analysis using an energy dispersive X-ray spectrometer (EDS).
本発明では、変性酸化グラフェン中のスルホ基と酸素含有官能基（エポキシ基など）とがプロトン伝導部位機能として働くことで、高プロトン伝導性を発現できる。そのため、基材層は、変性酸化グラフェンを含んでいればよいが、プロトン伝導性を向上できる点から、変性酸化グラフェンを主成分として含むのが好ましい。変性酸化グラフェンの割合は、基材層中５０質量％以上であってもよく、例えば７０質量％以上、好ましくは７５質量％以上、さらに好ましくは８０質量％以上（特に９０質量％以上）であり、１００質量％（変性酸化グラフェンのみ）であってもよい。 In the present invention, high proton conductivity can be exhibited by the fact that the sulfo group and the oxygen-containing functional group (such as an epoxy group) in the modified graphene oxide function as a proton conduction site function. Therefore, the base material layer only needs to contain modified graphene oxide, but preferably contains modified graphene oxide as a main component from the viewpoint of improving proton conductivity. The ratio of the modified graphene oxide may be 50% by mass or more in the base material layer, for example, 70% by mass or more, preferably 75% by mass or more, more preferably 80% by mass or more (especially 90% by mass or more). , 100% by mass (only modified graphene oxide).
基材層は、変性酸化グラフェンに加えて、他の成分をさらに含んでいてもよい。他の成分は、燃料電池などの電解質成分として慣用的に利用されるプロトン伝導体であってもよい。具体的に、他の成分としては、例えば、金属酸化物（例えば、酸化鉄、酸化チタンなど）、オキソ酸またはその塩［例えば、リン酸、二リン酸、チオリン酸、硝酸、硫酸、またはこれらのオキソ酸の希土類金属塩など］、芳香族化合物（例えば、ビフェニル、ターフェニル、シクロヘキシルベンゼン、ｔ−ブチルベンゼン、ｔ−アミルベンゼン、ジフェニルエーテル、ジベンゾフランなどの低分子芳香族化合物；ポリイミド、ポリスチレンなどの高分子芳香族化合物など）などが挙げられる。変性酸化グラフェンに他の成分を組み合わせると、積層し易くなり、連続的なプロトン伝導のパスを形成し易くなって好ましい場合がある。これら他の成分は、単独でまたは二種以上組み合わせて使用できる。他の成分の割合は、基材層中５０質量％以下であってもよく、例えば０．５〜３０質量％、好ましくは１〜２５質量％、さらに好ましくは２〜２０質量％程度であり、金属酸化物の場合、基材層中０．５〜２５質量％（特に１〜２０質量％）程度である。他の成分を適切な割合で含むことにより、燃料電池の発電性能が向上し、成膜性も維持できる。 The base layer may further include other components in addition to the modified graphene oxide. Another component may be a proton conductor commonly used as an electrolyte component in fuel cells and the like. Specifically, as other components, for example, metal oxides (eg, iron oxide, titanium oxide, etc.), oxo acids or salts thereof [eg, phosphoric acid, diphosphoric acid, thiophosphoric acid, nitric acid, sulfuric acid, or these Rare earth metal salts of oxo acids, etc.], aromatic compounds (for example, low molecular aromatic compounds such as biphenyl, terphenyl, cyclohexylbenzene, t-butylbenzene, t-amylbenzene, diphenylether, dibenzofuran; polyimides, polystyrene, etc. High molecular aromatic compounds, etc.). When another component is combined with the modified graphene oxide, lamination becomes easy and a continuous proton conduction path is easily formed, which is preferable in some cases. These other components can be used alone or in combination of two or more. The proportion of the other components may be 50% by mass or less in the base material layer, for example, 0.5 to 30% by mass, preferably 1 to 25% by mass, more preferably about 2 to 20% by mass, In the case of a metal oxide, it is about 0.5 to 25% by mass (particularly 1 to 20% by mass) in the base material layer. By including other components in an appropriate ratio, the power generation performance of the fuel cell is improved, and the film formability can be maintained.
基材層中において、変性酸化グラフェンは、薄膜（フレーク）が積層し、密な構造を形成していてもよい。 In the base material layer, the modified graphene oxide may have a dense structure in which thin films (flakes) are laminated.
基材層の平均厚みは１０μｍ以上であってもよく、例えば１０〜１００μｍ、好ましくは２０〜８０μｍ、さらに好ましくは３０〜７０μｍ（特に４０〜６０μｍ）程度である。基材層の厚みが薄すぎると、プロトン伝導性が低下する虞がある。 The average thickness of the substrate layer may be 10 μm or more, for example, about 10 to 100 μm, preferably about 20 to 80 μm, and more preferably about 30 to 70 μm (particularly about 40 to 60 μm). If the thickness of the base material layer is too thin, the proton conductivity may decrease.
［被覆層］
本発明では、前記基材層の少なくとも一方の面に、スルホン酸基を有するフッ素系ポリマーを含む被覆層を積層することにより、電極などとの層間密着性を向上できる。被覆層は、前記基材層の少なくとも一方の面に積層されていればよいが、固体燃料電池セルのプロトン伝導電解質膜として用いると、燃料電池の正極および負極との層間密着性を向上でき、電池の出力安定性を向上できる点から、前記基材層の両面に積層されているのが好ましい。
[Coating layer]
In the present invention, by laminating a coating layer containing a fluorinated polymer having a sulfonic acid group on at least one surface of the base material layer, interlayer adhesion with an electrode or the like can be improved. The coating layer may be laminated on at least one surface of the base material layer.However, when used as a proton conducting electrolyte membrane of a solid fuel cell, interlayer adhesion between a positive electrode and a negative electrode of a fuel cell can be improved, From the viewpoint that the output stability of the battery can be improved, it is preferable to be laminated on both surfaces of the base material layer.
スルホン酸基を有するフッ素系ポリマーを構成するフッ素系ポリマーは、少なくとも一部の水素原子がフッ素原子に置換されたフルオロ炭化水素樹脂であってもよい。フッ素系ポリマーとしては、例えば、ポリテトラフルオロエチレン（ＰＴＦＥ）、テトラフルオロエチレン−パーフルオロアルキルビニルエーテル共重合体（ＰＦＡ）、テトラフルオロエチレン−ヘキサフルオロプロピレン共重合体（ＦＥＰ）などのフッ素樹脂や、（２−テトラフルオロエトキシヘキサフルオロプロポキシ）トリフルオロエチレンとテトラフルオロエチレンとの共重合体、ポリスチレン−グラフト−ポリテトラフルオロエチレン共重合体、ポリスチレン−グラフト−ポリテトラフルオロエチレン共重合体などが挙げられる。これらのフッ素系ポリマーは、単独でまたは二種以上組み合わせて使用できる。これらのうち、電気陰性度の高いフッ素原子の導入による化学的な安定性が高い点から、パーフルオロ脂肪族炭化水素樹脂が好ましい。 The fluorine-containing polymer constituting the fluorine-containing polymer having a sulfonic acid group may be a fluorohydrocarbon resin in which at least a part of hydrogen atoms is substituted by fluorine atoms. Examples of the fluorine-based polymer include fluorine resins such as polytetrafluoroethylene (PTFE), tetrafluoroethylene-perfluoroalkylvinyl ether copolymer (PFA), and tetrafluoroethylene-hexafluoropropylene copolymer (FEP); (2-tetrafluoroethoxyhexafluoropropoxy) copolymer of trifluoroethylene and tetrafluoroethylene, polystyrene-graft-polytetrafluoroethylene copolymer, polystyrene-graft-polytetrafluoroethylene copolymer, and the like. . These fluoropolymers can be used alone or in combination of two or more. Of these, perfluoroaliphatic hydrocarbon resins are preferred because of their high chemical stability due to the introduction of fluorine atoms having high electronegativity.
スルホン酸基を有するフッ素系ポリマーの市販品としては、例えば、デュポン社製「登録商標：ナフィオン（Ｎａｆｉｏｎ）」、旭硝子（株）製「Ｆｌｅｍｉｏｎ」、旭化成（株）製「Ａｃｉｐｌｅｘ」、ゴア（Ｇｏｒｅ）社製「Ｇｏｒｅ Ｓｅｌｅｃｔ」などが挙げられる。スルホン酸基を有するフッ素系ポリマーは、［２−（２−スルホテトラフルオロエトキシ）ヘキサフルオロプロポキシ］トリフルオロエチレンとテトラフルオロエチレンとの共重合体（ブロック共重合体など）であってもよい。 Commercially available fluoropolymers having a sulfonic acid group include, for example, "Registered trademark: Nafion" manufactured by DuPont, "Flemion" manufactured by Asahi Glass Co., Ltd., "Aciplex" manufactured by Asahi Kasei Corporation, Gore (Gore) And "Gore Select" manufactured by the Company. The fluorinated polymer having a sulfonic acid group may be a copolymer of [2- (2-sulfotetrafluoroethoxy) hexafluoropropoxy] trifluoroethylene and tetrafluoroethylene (eg, a block copolymer).
スルホン酸基を有するフッ素系ポリマーの割合は、被覆層中５０質量％以上であってもよく、例えば７０質量％以上、好ましくは７５質量％以上、さらに好ましくは８０質量％以上（特に９０質量％以上）であり、１００質量％（スルホン酸基を有するフッ素系ポリマーのみ）であってもよい。スルホン酸基を有するフッ素系ポリマーの割合が少なすぎると、電極などとの層間密着性が低下する虞がある。 The proportion of the fluorinated polymer having a sulfonic acid group may be 50% by mass or more in the coating layer, for example, 70% by mass or more, preferably 75% by mass or more, more preferably 80% by mass or more (particularly 90% by mass or more). Above), and may be 100% by mass (only the fluorine-based polymer having a sulfonic acid group). If the proportion of the fluorinated polymer having a sulfonic acid group is too small, the interlayer adhesion to an electrode or the like may be reduced.
被覆層は、スルホン酸基を有するフッ素系ポリマーに加えて、他の成分をさらに含んでいてもよい。他の成分としては、基材層の項で例示された他の成分などが挙げられる。他の成分の割合は、基材層中５０質量％以下であってもよく、例えば０．５〜３０質量％、好ましくは１〜２５質量％、さらに好ましくは２〜２０質量％程度であり、金属酸化物の場合、基材層中０．５〜２５質量％（特に１〜２０質量％）程度である。他の成分を適切な割合で含むことにより、燃料電池の発電性能が向上し、成膜性も維持できる。 The coating layer may further include other components in addition to the fluorinated polymer having a sulfonic acid group. Other components include the other components exemplified in the section of the base material layer. The proportion of the other components may be 50% by mass or less in the base material layer, for example, 0.5 to 30% by mass, preferably 1 to 25% by mass, more preferably about 2 to 20% by mass, In the case of a metal oxide, it is about 0.5 to 25% by mass (particularly 1 to 20% by mass) in the base material layer. By including other components in an appropriate ratio, the power generation performance of the fuel cell is improved, and the film formability can be maintained.
被覆層総厚み（基材層の両面に被覆層が積層されている場合、両層の合計厚み）の平均厚みは、例えば０．１〜１０μｍ、好ましくは０．３〜５μｍ、さらに好ましくは０．５〜３μｍ（特に０．８〜２μｍ）程度である。被覆層の厚みが薄すぎると、電極などとの層間密着性が低下する虞があり、逆に厚すぎると、プロトン伝導性が低下する虞がある。 The average thickness of the coating layer total thickness (when the coating layers are laminated on both surfaces of the base material layer, the total thickness of both layers) is, for example, 0.1 to 10 μm, preferably 0.3 to 5 μm, and more preferably 0 to 10 μm. It is about 0.5 to 3 μm (particularly 0.8 to 2 μm). If the thickness of the coating layer is too thin, the interlayer adhesion to electrodes and the like may decrease, and if it is too thick, the proton conductivity may decrease.
基材層の平均厚みと、被覆層総厚みの平均厚みとの比は、前者／後者＝５／１〜２００／１程度の範囲から選択でき、例えば１０／１〜１００／１、２０／１〜８０／１、さらに好ましくは３０／１〜７０／１（特に４０／１〜６０／１）程度である。被覆層総厚みの比率が小さすぎると、電極などとの層間密着性が低下する虞があり、逆に厚すぎると、プロトン伝導性が低下する虞がある。 The ratio of the average thickness of the base material layer to the average thickness of the total thickness of the coating layer can be selected from the former / latter = about 5/1 to 200/1, for example, 10/1 to 100/1, 20/1. To 80/1, more preferably about 30/1 to 70/1 (particularly about 40/1 to 60/1). If the ratio of the total thickness of the coating layer is too small, the interlayer adhesion to the electrode or the like may decrease, and if it is too large, the proton conductivity may decrease.
［積層体の製造方法］
本発明の積層体は、重合開始剤および溶媒の存在下で酸化グラフェンとビニル基を有するスルホン酸類とを反応させて得られた変性酸化グラフェンを含む液状基材層前駆体を製膜する基材層形成工程、得られた基材層の少なくとも一方の面に、スルホン酸基を有するフッ素系ポリマーを含む液状被覆層前駆体をコーティングする被覆層形成工程とを経て製造される。
[Production method of laminate]
The laminate of the present invention is a substrate for forming a liquid substrate layer precursor containing a modified graphene oxide obtained by reacting graphene oxide and a sulfonic acid having a vinyl group in the presence of a polymerization initiator and a solvent. It is manufactured through a layer forming step and a coating layer forming step of coating at least one surface of the obtained base material layer with a liquid coating layer precursor containing a fluorinated polymer having a sulfonic acid group.
基材層形成工程において、変性酸化グラフェンを調製するための重合開始剤としては、特に限定されず、ラジカルを発生させる慣用のラジカル重合開始剤を利用でき、例えば、２，２’−アゾビスブチロニトリル（ＡＩＢＮ）、２，２’−アゾビス（２−メチルプロピオンアミジン）二塩酸塩、２，２’−アゾビス［２−（２−イミダゾリン−２−イル）プロパン］二塩酸塩などのアゾ化合物；過酸化ベンゾイル（ＢＰＯ）、ペルオキソ二硫酸カリウム、リチウムフェニル（２，４，６−トリメチルベンゾイル）ホスフィン酸塩、２−ヒドロキシ−４’−（２−ヒドロキシエトキシ）−２−メチルプロピオフェノンなどの過酸化物などが挙げられる。これらの重合開始剤は、単独でまたは二種以上組み合わせて使用できる。これらのうち、水溶性でラジカルを発生する開始剤、例えば、２，２’−アゾビス（２−メチルプロピオンアミジン）二塩酸塩などのアゾ化合物、ペルオキソ二硫酸カリウムなどの過酸化物が好ましい。重合開始剤の割合は、ビニル基を有するスルホン酸類１００質量部に対して、例えば１〜１００質量部、好ましくは１０〜８０質量部、さらに好ましくは３０〜６０質量部程度である。 In the substrate layer forming step, the polymerization initiator for preparing the modified graphene oxide is not particularly limited, and a conventional radical polymerization initiator that generates a radical can be used. For example, 2,2′-azobisbutyi Azo compounds such as lonitrile (AIBN), 2,2′-azobis (2-methylpropionamidine) dihydrochloride, and 2,2′-azobis [2- (2-imidazolin-2-yl) propane] dihydrochloride Benzoyl peroxide (BPO), potassium peroxodisulfate, lithium phenyl (2,4,6-trimethylbenzoyl) phosphinate, 2-hydroxy-4 ′-(2-hydroxyethoxy) -2-methylpropiophenone and the like And the like. These polymerization initiators can be used alone or in combination of two or more. Among these, a water-soluble initiator that generates a radical, for example, an azo compound such as 2,2'-azobis (2-methylpropionamidine) dihydrochloride and a peroxide such as potassium peroxodisulfate are preferable. The ratio of the polymerization initiator is, for example, 1 to 100 parts by mass, preferably 10 to 80 parts by mass, and more preferably about 30 to 60 parts by mass with respect to 100 parts by mass of the sulfonic acids having a vinyl group.
変性酸化グラフェンを調製するための溶媒としては、酸化グラフェンおよびビニル基を有するスルホン酸類を溶解または分散させ易い点から、水性溶媒（極性溶媒）を好ましく利用できる。水性溶媒としては、例えば、水、低級アルコール（メタノール、エタノール、イソプロパノール、プロパノールなどのＣ１−４アルカノールなど）、ケトン類（アセトンなど）、エーテル類（ジエチルエーテル、ジオキサン、テトラヒドロフランなど）、セロソルブ類、セロソルブアセテート類、カルビトール類、カルビトールアセテート類、ニトリル類（アセトニトリルなど）、アミド類（Ｎ，Ｎ−ジメチルホルムアミド、Ｎ，Ｎ−ジメチルアセトアミドなど）などが挙げられる。これらの水性溶媒は、単独でまたは二種以上組み合わせて使用できる。これらのうち、水、エタノールなどのＣ１−４アルカノールが好ましく、水を含むのが特に好ましい。水の割合は、溶媒中５０質量％以上であってもよく、好ましくは８０質量％以上、さらに好ましくは９０質量％以上であり、１００質量％（水のみ）であってもよい。 As a solvent for preparing the modified graphene oxide, an aqueous solvent (a polar solvent) can be preferably used because the graphene oxide and the sulfonic acid having a vinyl group are easily dissolved or dispersed. Examples of the aqueous solvent include water, lower alcohols (eg, C 1-4 alkanols such as methanol, ethanol, isopropanol, and propanol), ketones (eg, acetone), ethers (eg, diethyl ether, dioxane, tetrahydrofuran), and cellosolves. , Cellosolve acetates, carbitols, carbitol acetates, nitriles (eg, acetonitrile), amides (eg, N, N-dimethylformamide, N, N-dimethylacetamide) and the like. These aqueous solvents can be used alone or in combination of two or more. Of these, water and C 1-4 alkanols such as ethanol are preferable, and water is particularly preferable. The proportion of water in the solvent may be 50% by mass or more, preferably 80% by mass or more, more preferably 90% by mass or more, and may be 100% by mass (water only).
溶媒の割合は、酸化グラフェン１質量部に対して、例えば１０〜１０００質量部、好ましくは３０〜５００質量部、さらに好ましくは５０〜３００質量部（特に８０〜２００質量部）程度である。 The ratio of the solvent is, for example, about 10 to 1000 parts by weight, preferably about 30 to 500 parts by weight, more preferably about 50 to 300 parts by weight (particularly about 80 to 200 parts by weight) with respect to 1 part by weight of graphene oxide.
酸化グラフェンとビニル基を有するスルホン酸類との反応温度は、１５０℃未満が好ましく、ビニル基を有するスルホン酸類による酸化グラフェンの変性効率を向上できる点から、１００℃以下（例えば５０〜１００℃、特に６０〜８０℃程度）が特に好ましい。反応温度が高すぎると、前記変性効率が低下する虞があり、例えば１００℃を超え、特に１５０℃以上になると酸化グラフェンの一部還元などにより溶媒への溶解性に変化が起こり、凝集や析出などが発生して、ビニル基を有するスルホン酸類の変性導入に影響を及ぼす虞がある。 The reaction temperature of the graphene oxide with the sulfonic acids having a vinyl group is preferably less than 150 ° C., and the reaction temperature of the graphene oxide can be improved by the sulfonic acids having a vinyl group. (About 60 to 80 ° C.) is particularly preferred. If the reaction temperature is too high, the denaturation efficiency may decrease. For example, when the temperature exceeds 100 ° C., and particularly when the temperature exceeds 150 ° C., the solubility in the solvent is changed due to partial reduction of graphene oxide, and aggregation and precipitation occur. This may affect the modification and introduction of sulfonic acids having a vinyl group.
得られた変性酸化グラフェンは、必要に応じて他の成分や溶媒を加えて、液状基材層前駆体に調製される。酸化グラフェンと他の成分との混合方法としては、特に限定されず、酸化グラフェンと他の成分をコンパウンドする方法、酸化グラフェンと他の成分を同時に溶液に溶解または分散させる方法、酸化グラフェン分散液に他の成分を添加し、必要に応じて再分散処理を行う方法、酸化グラフェン分散液と他の成分分散液を混合する方法など利用できる。 The obtained modified graphene oxide is prepared into a liquid base material layer precursor by adding other components and a solvent as needed. The method for mixing graphene oxide and other components is not particularly limited, and a method for compounding graphene oxide and other components, a method for simultaneously dissolving or dispersing graphene oxide and other components in a solution, a method for dispersing graphene oxide, A method of adding another component and performing a re-dispersion treatment as needed, a method of mixing a graphene oxide dispersion with another component dispersion, and the like can be used.
溶媒としては、変性酸化グラフェンを調製するための溶媒として例示された溶媒を利用できる。前記溶媒のうち、水を含む溶媒が好ましく、水と低級アルコール（特にメタノールなどのＣ１−４アルカノール）との組み合わせが特に好ましい。水と低級アルコールとの質量比は、水／低級アルコール＝１００／０〜１０／９０程度の範囲から選択でき、例えば、９９／１〜３０／７０、好ましくは９０／１０〜５０／５０、さらに好ましくは８０／２０〜７０／３０程度である。 As the solvent, the solvents exemplified as the solvent for preparing the modified graphene oxide can be used. Among the above solvents, a solvent containing water is preferable, and a combination of water and a lower alcohol (particularly, a C 1-4 alkanol such as methanol) is particularly preferable. The mass ratio of water to lower alcohol can be selected from the range of water / lower alcohol = about 100/0 to 10/90, for example, 99/1 to 30/70, preferably 90/10 to 50/50, and furthermore Preferably it is about 80/20 to 70/30.
液状基材層前駆体において、溶媒の割合は、変性酸化グラフェン１質量部に対して、例えば１０〜２０００質量部、好ましくは１００〜１０００質量部、さらに好ましくは２００〜８００質量部（特に３００〜５００質量部）程度である。 In the liquid base material layer precursor, the ratio of the solvent is, for example, 10 to 2000 parts by mass, preferably 100 to 1000 parts by mass, more preferably 200 to 800 parts by mass, and more preferably 200 to 800 parts by mass, based on 1 part by mass of the modified graphene oxide. 500 parts by mass).
液状基材層前駆体の製膜方法としては、慣用の製膜方法、例えば、ろ過成膜法、スピンコート法、ドロップキャスト法、電解泳動法等、バーコート法などを利用できる。 As a method of forming the liquid base material layer precursor, a conventional film forming method, for example, a filtration film forming method, a spin coating method, a drop casting method, an electrophoresis method, a bar coating method, or the like can be used.
前記製膜方法によって膜状に形成された液状基材層前駆体は、乾燥することによって基材層を形成できる。乾燥は、自然乾燥であってもよく、４０℃以上（例えば５０〜９０℃、特に６０〜８０℃程度）の温度で加熱して乾燥してもよい。加熱時間は１分以上（例えば５〜２０分程度）であってもよい。 The base material layer can be formed by drying the liquid base material layer precursor formed into a film by the film forming method. The drying may be natural drying, or may be performed by heating at a temperature of 40 ° C. or more (for example, about 50 to 90 ° C., particularly about 60 to 80 ° C.). The heating time may be 1 minute or more (for example, about 5 to 20 minutes).
被覆層形成工程において、スルホン酸基を有するフッ素系ポリマーは、必要に応じて他の成分や溶媒を加えて、液状被覆層前駆体に調製される。スルホン酸基を有するフッ素系ポリマーと他の成分との混合方法は、酸化グラフェンと他の成分との混合方法と同様の方法を利用できる。 In the coating layer forming step, the fluorinated polymer having a sulfonic acid group is prepared into a liquid coating layer precursor by adding other components and a solvent as necessary. As a method for mixing the fluorine-based polymer having a sulfonic acid group with other components, the same method as the method for mixing graphene oxide with other components can be used.
液状被覆層前駆体の溶媒としては、例えば、低級アルコール（メタノール、エタノール、イソプロパノール、プロパノールなどのＣ１−４アルカノールなど）、ケトン類（アセトンなど）、エーテル類（ジエチルエーテル、ジオキサン、テトラヒドロフランなど）などが挙げられる。これらの溶媒は、単独でまたは二種以上組み合わせて使用できる。これらのうち、エタノール、イソプロパノールなどのＣ１−３アルカノール、ジエチルエーテルなどのジＣ１−３アルキルエーテルが好ましい。 Examples of the solvent for the liquid coating layer precursor include lower alcohols (eg, C 1-4 alkanols such as methanol, ethanol, isopropanol, and propanol), ketones (eg, acetone), and ethers (eg, diethyl ether, dioxane, and tetrahydrofuran). And the like. These solvents can be used alone or in combination of two or more. Of these, C 1-3 alkanols such as ethanol and isopropanol, and di C 1-3 alkyl ethers such as diethyl ether are preferred.
液状被覆層前駆体において、溶媒の割合は、スルホン酸基を有するフッ素系ポリマー１質量部に対して、例えば１〜５００質量部、好ましくは３〜１００質量部、さらに好ましくは５〜５０質量部（特に１０〜３０質量部）程度である。 In the liquid coating layer precursor, the ratio of the solvent is, for example, 1 to 500 parts by mass, preferably 3 to 100 parts by mass, and more preferably 5 to 50 parts by mass with respect to 1 part by mass of the fluorinated polymer having a sulfonic acid group. (Particularly 10 to 30 parts by mass).
液状被覆層前駆体の製膜方法としては、慣用の製膜方法、例えば、スピンコート法、ドロップキャスト法、バーコート法などを利用できる。 As a method of forming the liquid coating layer precursor, a conventional film forming method, for example, a spin coating method, a drop casting method, a bar coating method, or the like can be used.
前記製膜方法によって膜状に形成された液状被覆層前駆体は、乾燥することによって被覆層を形成できる。乾燥は、自然乾燥であってもよく、４０℃以上（例えば４０〜８０℃、特に５０〜７０℃程度）の温度で加熱して乾燥してもよい。加熱時間は１分以上（例えば５〜２０分程度）であってもよい。 The coating layer can be formed by drying the liquid coating layer precursor formed into a film by the film forming method. Drying may be natural drying, or drying may be performed by heating at a temperature of 40 ° C. or higher (for example, about 40 to 80 ° C., particularly about 50 to 70 ° C.). The heating time may be 1 minute or more (for example, about 5 to 20 minutes).
［固体燃料電池セルのプロトン伝導電解質膜］
本発明の積層体は、固体燃料電池セルのプロトン伝導電解質膜として利用できる。本発明の固体燃料電池セルは、プロトン伝導電解質膜として積層体を含んでいればよく、このプロトン伝導電解質膜は電極と一体化することにより、電極との層間密着性を向上させている。本発明の固体燃料電池セルは、必要に応じて、触媒、セパレーター、電流の取り出し線などをさらに備えていてもよい。
[Proton conductive electrolyte membrane of solid fuel cell]
The laminate of the present invention can be used as a proton conducting electrolyte membrane of a solid fuel cell. The solid fuel cell of the present invention only needs to include a laminate as a proton conductive electrolyte membrane, and the proton conductive electrolyte membrane is integrated with the electrode to improve interlayer adhesion with the electrode. The solid fuel cell of the present invention may further include a catalyst, a separator, a current extraction line, and the like, if necessary.
固体燃料電池セルの一例を模式的に図１に示し、具体的に説明する。図１に示すように、固体燃料電池セルは、セル中心部に位置する電解質膜１と、この電解質膜１の両面に隣接して積層された燃料極（負極）２および空気極（正極）３と、さらに燃料極２および空気極３の各々の外側に積層された負極側セパレーター４および正極側セパレーター５とで形成されている。両セパレーターには、燃料ガスや酸化剤を送り込むための流路が形成されていてもよい。図１では、燃料電池の反応の一例を示しており、燃料極では、水素ガスが供給されて、水素イオンと電子（プロトン）に分解され、空気極では、酸素ガスが供給され、反応生成物として水が生成している。
One example of the solid fuel cell is schematically shown in FIG. 1 and will be specifically described. As shown in FIG. 1, the solid fuel cell includes an
燃料極および空気極は、図２に示すように、それぞれ電解質膜１１と接触する側の触媒層１２ｂおよび１３ｂと、その外側に積層された拡散層１２ａおよび１３ａとで形成されていてもよい。この例では、電解質膜１１と、電解質膜１１の一方の面に配置された燃料極側の触媒層１２ｂと、電解質膜１１の他方の面に配置された空気極側の触媒層１３ｂとで膜電極接合体（Ｍｅｍｂｒａｎｅ Ｅｌｅｃｔｒｏｄｅ Ａｓｓｅｍｂｌｙ；通称ＭＥＡ）と呼ばれる接合体を構成している。本発明では、基材層の両面に被覆層が積層された積層体を電解質膜として用いると、燃料極側および空気極側の両方の触媒層との層間密着性を向上でき、燃料電池の出力特性を安定化できる。この例では、触媒層は、電解質膜の両面に形成されているが、電解質膜の少なくとも一方の面に形成されていればよく、片面のみに形成されていてもよい。また、燃料極および空気極は、触媒層単体で形成されていてもよい。拡散層は、多孔質炭素材料などで形成されていてもよい。
As shown in FIG. 2, the fuel electrode and the air electrode may be formed by catalyst layers 12b and 13b on the side in contact with the
燃料極を構成する触媒層の材質としては、固体燃料電池の燃料極の触媒層として利用される慣用の触媒を利用できる。触媒は、金属触媒単体、金属触媒とカーボン材料の混合物、金属触媒と酸化物イオン導電体からなるセラミックス粉末材料との混合物であってもよい。 As a material of the catalyst layer constituting the fuel electrode, a conventional catalyst used as a catalyst layer of a fuel electrode of a solid fuel cell can be used. The catalyst may be a metal catalyst alone, a mixture of a metal catalyst and a carbon material, or a mixture of a metal catalyst and a ceramic powder material composed of an oxide ion conductor.
前記金属触媒としては、例えば、白金、パラジウム、ルテニウム、イリジウム、ロジウム、オスミウムの貴金属の他、ニッケル、鉄、鉛、銅、クロム、コバルト、マンガン、バナジウム、モリブデン、ガリウム、アルミニウムなどの金属、またはこれらの合金、酸化物、複酸化物、炭化物などが挙げられる。これらのうち、還元性雰囲気において安定で水素酸化活性を有する材料、例えば、白金、ルテニウム、パラジウムなどの貴金属；ニッケル、鉄、コバルトなどが好ましい。 Examples of the metal catalyst include, for example, platinum, palladium, ruthenium, iridium, rhodium, and other noble metals such as nickel, iron, lead, copper, chromium, cobalt, manganese, vanadium, molybdenum, gallium, and metals such as aluminum. These alloys, oxides, double oxides, carbides and the like can be mentioned. Among these, a material that is stable in a reducing atmosphere and has a hydrogen oxidation activity, for example, a noble metal such as platinum, ruthenium, or palladium; nickel, iron, or cobalt is preferable.
このような金属触媒はカーボン材料としてカーボンブラック、グラファイト、またはグラファイト化カーボンブラックと混合して使用してもよい。 Such a metal catalyst may be used in combination with carbon black, graphite, or graphitized carbon black as a carbon material.
前記酸化物イオン導電体は、蛍石型構造またはペロブスカイト型構造を有する材料が好ましい。前記蛍石型構造を有する材料としては、例えば、サマリウムやガドリニウムなどをドープしたセリア系酸化物、スカンジウムやイットリウムを含むジルコニア系酸化物などが挙げられる。前記ペロブスカイト型構造を有する材料としては、例えば、ストロンチウムやマグネシウムをドープしたランタン・ガレード系酸化物などが挙げられる。これらのうち、酸化物イオン導電体とニッケルとの混合物で、燃料極の触媒層を形成するのが好ましい。 The oxide ion conductor is preferably a material having a fluorite structure or a perovskite structure. Examples of the material having the fluorite structure include a ceria-based oxide doped with samarium or gadolinium, and a zirconia-based oxide containing scandium or yttrium. As the material having the perovskite structure, for example, a lanthanum-garde-based oxide doped with strontium or magnesium may be used. Of these, it is preferable to form the catalyst layer of the fuel electrode with a mixture of an oxide ion conductor and nickel.
なお、触媒層が金属触媒（特にニッケル）とセラミックス粉末材料との混合物である場合、混合形態は、物理的な混合形態であってもよく、金属触媒を粉末セラミックス材料で修飾した形態であってもよい。また、セラミックス材料は、１種類を単独で使用してもよく、２種類以上を混合して使用してもよい。 When the catalyst layer is a mixture of a metal catalyst (particularly nickel) and a ceramic powder material, the mixed form may be a physical mixed form, or a form in which the metal catalyst is modified with a powder ceramic material. Is also good. In addition, one type of ceramic material may be used alone, or two or more types may be used in combination.
空気極を構成する触媒層の材質としては、固体燃料電池の空気極の触媒層として利用される慣用の触媒を利用できる。触媒としては、燃料極で例示された金属触媒単体、金属酸化物であってもよい。これらのうち、金属酸化物が好ましい。 As a material of the catalyst layer constituting the air electrode, a conventional catalyst used as a catalyst layer of an air electrode of a solid fuel cell can be used. The catalyst may be a metal catalyst alone or a metal oxide exemplified for the fuel electrode. Of these, metal oxides are preferred.
金属酸化物としては、例えば、ペロブスカイト型構造等を有するコバルト、鉄、ニッケル、クロムまたはマンガンなどからなる金属酸化物を用いることができる。そのような金属酸化物としては、例えば、（Ｓｍ，Ｓｒ）ＣｏＯ３，（Ｌａ，Ｓｒ）ＭｎＯ３，（Ｌａ，Ｓｒ）ＣｏＯ３，（Ｌａ，Ｓｒ）（Ｆｅ，Ｃｏ）Ｏ３，（Ｌａ，Ｓｒ）（Ｆｅ，Ｃｏ，Ｎｉ）Ｏ３などの酸化物が挙げられ、好ましくは、（Ｌａ，Ｓｒ）ＭｎＯ３である。これらの金属酸化物は、単独でまたは二種以上組み合わせて使用できる。 As the metal oxide, for example, a metal oxide made of cobalt, iron, nickel, chromium, manganese, or the like having a perovskite structure or the like can be used. Examples of such a metal oxide include (Sm, Sr) CoO 3 , (La, Sr) MnO 3 , (La, Sr) CoO 3 , (La, Sr) (Fe, Co) O 3 , (La) , Sr) (Fe, Co, Ni) O 3 and the like, and preferably (La, Sr) MnO 3 . These metal oxides can be used alone or in combination of two or more.
空気極および燃料極は、例えば、スクリーン印刷法、ドクターブレード法、スプレーコート法、スピンコ−ト法、ディップコート法、泳動電着法、ロールコート法、グラビアロールコート法、ディスペンサーコート法、ＣＶＤ，ＥＶＤ，スパッタリング法、転写法などの一般的な印刷法を用いて作製できる。 For the air electrode and the fuel electrode, for example, a screen printing method, a doctor blade method, a spray coating method, a spin coating method, a dip coating method, a migration electrodeposition method, a roll coating method, a gravure roll coating method, a dispenser coating method, CVD, It can be manufactured by using a general printing method such as an EVD, a sputtering method, and a transfer method.
以下に、実施例に基づいて本発明をより詳細に説明するが、本発明はこれらの実施例によって限定されるものではない。なお、実施例および比較例で得られた積層体（プロトン伝導性電解質膜）を調製するために使用した各材料の詳細および調製方法は、以下の通りである。 Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples. The details and preparation methods of each material used for preparing the laminate (proton conductive electrolyte membrane) obtained in Examples and Comparative Examples are as follows.
［酸化グラフェン］
（酸化グラフェン水溶液Ａ）
（株）仁科マテリアル製「Ｅｘｆｏｌｉａｔｅｄ ＧＯ」、１質量％水溶液を用いた。
[Graphene oxide]
(Aqueous graphene oxide solution A)
"Exfoliated GO" manufactured by Nishina Material Co., Ltd., 1% by mass aqueous solution was used.
（酸化グラフェン水溶液Ｂ）
酸化グラフェン水溶液Ａを乾燥した粉末酸化グラフェン１ｇに硫酸２６ｍｌを加えて４℃に冷却して、硝酸ナトリウム（ＮａＮＯ３）１．１ｇを少しずつ加えた。さらに過マンガン酸カリウム（ＫＭｎＯ４）３．３ｇを加えて、１０分間撹拌し、液温度３５℃で２時間撹拌した。次に、水冷した状態で水５１ｍＬを滴下しつつ、３０分間撹拌した。さらに、水２８ｍｌを添加した後、過酸化水素（Ｈ２Ｏ２）５．６ｍｌを滴下した。最後に、９０℃で３０分間撹拌した後、１００ｍＬの水を加えて希釈して遠心分離に供した。上澄みが中性になるまで遠心分離を繰り返し行い、上澄みが中性になったところで完了とした。なお、得られた酸化グラフェンを水溶液として濃度調整し１質量％水溶液を調製した。
(Graphene oxide aqueous solution B)
26 ml of sulfuric acid was added to 1 g of the dried graphene oxide aqueous solution A, and 1 g of the dried graphene oxide was cooled to 4 ° C., and 1.1 g of sodium nitrate (NaNO 3 ) was added little by little. Further, 3.3 g of potassium permanganate (KMnO 4 ) was added, and the mixture was stirred for 10 minutes, and stirred at a liquid temperature of 35 ° C. for 2 hours. Next, the mixture was stirred for 30 minutes while dropping 51 mL of water in a water-cooled state. Furthermore, after adding 28 ml of water, 5.6 ml of hydrogen peroxide (H 2 O 2 ) was added dropwise. Finally, the mixture was stirred at 90 ° C. for 30 minutes, diluted with 100 mL of water and centrifuged. Centrifugation was repeated until the supernatant became neutral. When the supernatant became neutral, the process was completed. The concentration of the obtained graphene oxide was adjusted as an aqueous solution to prepare a 1% by mass aqueous solution.
［変性酸化グラフェンの調製］
製造例１
ビニルスルホン酸ナトリウム２５質量％水溶液（東京化成工業製）４質量部を酸化グラフェン水溶液Ａ１００質量部に添加し攪拌を行ない７０℃に加温した状態でペルオキソ二硫酸カリウム（開始剤）０．５質量部を添加し窒素気流中で８時間反応した。その後、室温にした状態で硫酸を添加しｐＨ０．５に調整した後、遠心分離して上澄みを除去した。さらに、イオン交換水で洗浄して変性酸化グラフェンＡを得た。得られた変性酸化グラフェンＡをエネルギー分散型Ｘ線分光器（ＥＤＳ）により元素分析した結果、硫黄成分含有率は１．０Ａｔｏｍ％、ナトリウム成分は検出されなかった。イオン交換水で変性酸化グラフェン水溶液Ａ（固形分濃度０．５質量％）を調製した。
[Preparation of modified graphene oxide]
Production Example 1
4 parts by mass of a 25% by mass aqueous solution of sodium vinyl sulfonate (manufactured by Tokyo Chemical Industry Co., Ltd.) was added to 100 parts by mass of the aqueous solution of graphene oxide A, and the mixture was stirred and heated to 70 ° C., and 0.5 mass of potassium peroxodisulfate (initiator) Then, the mixture was reacted for 8 hours in a nitrogen stream. Thereafter, sulfuric acid was added at room temperature to adjust the pH to 0.5, followed by centrifugation to remove the supernatant. Further, it was washed with ion-exchanged water to obtain modified graphene oxide A. Elemental analysis of the resulting modified graphene oxide A with an energy dispersive X-ray spectrometer (EDS) revealed that the sulfur component content was 1.0 atom% and the sodium component was not detected. A modified graphene oxide aqueous solution A (solid content concentration: 0.5% by mass) was prepared with ion-exchanged water.
製造例２
酸化グラフェン水溶液Ａを酸化グラフェン水溶液Ｂに変更する以外は製造例１と同様にして変性酸化グラフェンＢを得た。得られた変性酸化グラフェンＢをエネルギー分散型Ｘ線分光器（ＥＤＳ）により元素分析した結果、硫黄成分含有率は２．３Ａｔｏｍ％、ナトリウム成分は検出されなかった。イオン交換水で変性酸化グラフェン水溶液Ｂ（固形分濃度０．５質量％）を調製した。
Production Example 2
A modified graphene oxide B was obtained in the same manner as in Production Example 1, except that the aqueous graphene oxide solution A was changed to the aqueous graphene oxide solution B. Elemental analysis of the resulting modified graphene oxide B by an energy dispersive X-ray spectrometer (EDS) revealed that the sulfur component content was 2.3 Atom% and no sodium component was detected. A modified graphene oxide aqueous solution B (solid content concentration: 0.5% by mass) was prepared with ion-exchanged water.
［プロトン伝導電解質膜の調製］
比較例１
酸化グラフェン水溶液Ａ１５質量部にメタノール／水（質量比１／１）混合溶媒３０質量部を添加し、ろ過成膜法でプロトン伝導電解質膜を得た。
[Preparation of proton conducting electrolyte membrane]
Comparative Example 1
30 parts by mass of a mixed solvent of methanol / water (
参考例１
酸化グラフェン水溶液Ａ１５質量部にメタノール／水（質量比１／１）混合溶媒３０質量部を添加し、ろ過成膜法で酸化グラフェン膜を作製し、得られた酸化グラフェン膜（５ｃｍ×５ｃｍ）の片面に５質量％ナフィオン分散液（エレクトロケム社製）３００μＬをコーティングし、６０℃で１５分乾燥し、さらにもう片面も同様にコート処理したプロトン伝導電解質膜を得た（計算上、片面の各厚み０．５μｍのナフィオン膜形成）。
Reference Example 1
30 parts by mass of a mixed solvent of methanol / water (
実施例１
変性酸化グラフェン水溶液Ａ３０質量部にメタノール／水（質量比１／１）混合溶媒３０質量部を添加し、ろ過成膜法で変性酸化グラフェン膜を作製し、得られた変性酸化グラフェン膜（５ｃｍ×５ｃｍ）の両面に参考例１と同様の方法でナフィオン分散液を両面コート処理したプロトン伝導電解質膜を得た。
Example 1
30 parts by mass of a methanol / water (
参考例２
酸化グラフェン水溶液Ａ１００質量部にビニルスルホン酸ナトリウム１質量部を添加し、攪拌した後、硫酸を添加しｐＨ０．５に調整し、遠心分離して上澄みを除去した。さらに、イオン交換水を添加し、酸化グラフェンとビニルスルホン酸とからなる水溶液を調製した（固形分濃度０．５質量％）。得られた水溶液を乾燥し、エネルギー分散型Ｘ線分光器（ＥＤＳ）により元素分析した結果、硫黄成分含有率は０．３Ａｔｏｍ％、ナトリウム成分は検出されなかった。前記水溶液３０質量部にメタノール／水（質量比１／１）混合溶媒３０質量部を添加し、ろ過成膜法で酸化グラフェン系膜を作製し、得られした酸化グラフェン系膜（５ｃｍ×５ｃｍ）の両面に参考例１と同様の方法でナフィオン分散液を両面コート処理したプロトン伝導電解質膜を得た。
Reference example 2
1 part by mass of sodium vinyl sulfonate was added to 100 parts by mass of the aqueous solution of graphene oxide A, and the mixture was stirred, adjusted to pH 0.5 by adding sulfuric acid, and centrifuged to remove the supernatant. Further, ion-exchanged water was added to prepare an aqueous solution composed of graphene oxide and vinyl sulfonic acid (solid concentration 0.5% by mass). The obtained aqueous solution was dried and subjected to elemental analysis using an energy dispersive X-ray spectrometer (EDS). As a result, the sulfur component content was 0.3 Atom%, and no sodium component was detected. 30 parts by mass of a methanol / water (1/1 by mass) mixed solvent was added to 30 parts by mass of the aqueous solution, and a graphene oxide-based film was formed by a filtration film forming method, and the obtained graphene oxide-based film (5 cm × 5 cm) was obtained. In both cases, a proton conducting electrolyte membrane was obtained by coating both surfaces with a Nafion dispersion liquid in the same manner as in Reference Example 1.
参考例３
ビニルスルホン酸ナトリウム２５質量％水溶液（東京化成工業製）１００質量部にペルオキソ二硫酸カリウム（開始剤）５質量部を添加し窒素気流中で７０℃、８時間反応させ、ポリビニルスルホン酸ナトリウム水溶液を作製した。得られたポリビニルスルホン酸ナトリウム水溶液４質量部に酸化グラフェン水溶液Ａ１００質量部を添加して攪拌した。その後、硫酸を添加しｐＨ０．５に調整し、遠心分離して上澄みを除去した。さらに、イオン交換水を添加し、酸化グラフェンとポリビニルスルホン酸からなる水溶液を調製した（固形分濃度０．５質量％）。得られた水溶液を乾燥し、エネルギー分散型Ｘ線分光器（ＥＤＳ）により元素分析した結果、硫黄成分含有率は０．２Ａｔｏｍ％、ナトリウム成分は検出されなかった。前記水溶液３０質量部にメタノール／水（質量比１／１）混合溶媒３０質量部を添加し、ろ過成膜法で酸化グラフェン系膜を作製し、得られた酸化グラフェン系膜（５ｃｍ×５ｃｍ）の両面に参考例１と同様の方法でナフィオン分散液を両面コート処理したプロトン伝導電解質膜を得た。
Reference Example 3
5 parts by mass of potassium peroxodisulfate (initiator) was added to 100 parts by mass of a 25% by mass aqueous solution of sodium vinyl sulfonate (manufactured by Tokyo Kasei Kogyo Co., Ltd.), and the mixture was reacted in a nitrogen stream at 70 ° C. for 8 hours. Produced. 100 parts by mass of the aqueous solution of graphene oxide A was added to 4 parts by mass of the obtained aqueous solution of sodium polyvinyl sulfonate, followed by stirring. Thereafter, the pH was adjusted to 0.5 by adding sulfuric acid, and the supernatant was removed by centrifugation. Further, ion-exchanged water was added to prepare an aqueous solution comprising graphene oxide and polyvinyl sulfonic acid (solid concentration: 0.5% by mass). The obtained aqueous solution was dried and subjected to elemental analysis by an energy dispersive X-ray spectrometer (EDS). As a result, the sulfur component content was 0.2 Atom%, and no sodium component was detected. 30 parts by mass of a methanol / water (
実施例２
変性酸化グラフェン水溶液Ｂ３０質量部にメタノール／水（質量比１／１）混合溶媒３０質量部を添加し、ろ過成膜法で変性酸化グラフェン膜を作製し、得られた変性酸化グラフェン膜（５ｃｍ×５ｃｍ）の両面に参考例１と同様の方法でナフィオン分散液を両面コート処理したプロトン伝導電解質膜を得た。
Example 2
30 parts by mass of a methanol / water (
参考例４
酸化グラフェン水溶液Ｂ１５質量部にメタノール／水（質量比１／１）混合溶媒３０質量部を添加し、ろ過成膜法で酸化グラフェン膜を作製し、得られた酸化グラフェン膜（５ｃｍ×５ｃｍ）の両面に参考例１と同様の方法でナフィオン分散液を両面コート処理したプロトン伝導電解質膜を得た。
Reference example 4
30 parts by mass of a mixed solvent of methanol / water (
比較例２
酸化グラフェン水溶液Ａ１００質量部にｐ−トルエンスルホン酸０．１５質量部を配合した。さらにメタノール／水（質量比１／１）混合溶媒３０質量部を添加し、ろ過成膜法でプロトン伝導電解質膜を得た。
Comparative Example 2
0.15 parts by mass of p-toluenesulfonic acid was mixed with 100 parts by mass of the aqueous solution of graphene oxide A. Further, 30 parts by mass of a mixed solvent of methanol / water (
参考例５
酸化グラフェン水溶液Ａ １００質量部にｐ−トルエンスルホン酸０．１５質量部を配合した。さらにメタノール／水（質量比１／１）混合溶媒３０質量部を添加し、ろ過成膜法で酸化グラフェン系膜を作製した。得られた酸化グラフェン系膜（５ｃｍ×５ｃｍ）の両面に参考例１と同様の方法でナフィオン分散液を両面コート処理したプロトン伝導電解質膜を得た。
Reference Example 5
0.15 parts by mass of p-toluenesulfonic acid was blended with 100 parts by mass of the aqueous solution of graphene oxide A. Further, 30 parts by mass of a mixed solvent of methanol / water (
比較例３
プロトン電解質膜としてナフィオンシート（エレクトロケム社製「ナフィオン２１２」、厚み５０μｍ）を用いた。
Comparative Example 3
A Nafion sheet (“Nafion 212” manufactured by Electrochem, thickness 50 μm) was used as the proton electrolyte membrane.
［燃料電池試験］
得られたプロトン伝導電解質膜を用いて燃料電池の発電特性を評価した。発電特性評価では、（株）東陽テクニカ製シングルセルハードウェア ＦＣ−０５−０２で単セルを構築し、電流電圧（Ｉ−Ｖ）測定を行った。プロトン伝導性電解質膜の両面を電極膜材料（アノード用、カソード用）［（株）東陽テクニカ製「ＥＣ−Ｅ２０−１０−０７」、触媒層：触媒粒子（Ｐｔ／Ｃ）（１．０ｍｇ／ｃｍ２）、拡散層：カーボンペーパー］で触媒層と電解質膜とを接触させて挟み、ＭＥＡを作製した。室温下でアノードに加湿（ＲＨ１００％）水素１００ｍＬ／ｍｉｎ、カソードに加湿（ＲＨ１００％）酸素１００ｍＬ／ｍｉｎを供給した。電池電圧およびオーム抵抗を常時測定した。プロトン伝導率は、膜厚／（セルオーム抵抗×電極面積）の式にて算出した。実施例２および参考例３については、５〜１０回のサイクル試験を実施した。得られた評価結果を表１に示す。
[Fuel cell test]
The power generation characteristics of the fuel cell were evaluated using the obtained proton conductive electrolyte membrane. In the power generation characteristic evaluation, a single cell was constructed with a single cell hardware FC-05-02 manufactured by Toyo Technica Co., Ltd., and the current-voltage (IV) was measured. Both surfaces of the proton conductive electrolyte membrane are electrode membrane materials (for anode and cathode) [“EC-E20-10-07” manufactured by Toyo Corp., catalyst layer: catalyst particles (Pt / C) (1.0 mg / cm 2 ), a diffusion layer: carbon paper], and the catalyst layer and the electrolyte membrane were contacted and sandwiched to produce an MEA. At room temperature, humidified (RH 100%) hydrogen 100 mL / min was supplied to the anode, and humidified (RH 100%) oxygen 100 mL / min was supplied to the cathode. Battery voltage and ohmic resistance were constantly measured. The proton conductivity was calculated by the formula of film thickness / (cell ohmic resistance × electrode area). For Example 2 and Reference Example 3, 5 to 10 cycle tests were performed. Table 1 shows the obtained evaluation results.
表１の結果から明らかなように、実施例１および２は参考例４よりも優れる固体燃料電池としての出力密度が確保された。 As is clear from the results in Table 1, Examples 1 and 2 ensured a higher power density as a solid fuel cell than Reference Example 4.
また、比較例１と参考例１との比較、参考例２と参考例３との比較から、プロトン伝導電解質膜としての酸化グラフェン系膜の両面にナフィオンコートすると、固体燃料電池としての出力密度が高まった。 Also, from the comparison between Comparative Example 1 and Reference Example 1 and Comparison between Reference Example 2 and Reference Example 3, when the Nafion coat is applied to both surfaces of the graphene oxide-based membrane as the proton conducting electrolyte membrane, the output density as a solid fuel cell is reduced. Heightened.
ビニルスルホン酸を酸化グラフェンに反応させ変性した実施例１は、比較例２および３のように、反応していない単なる組成物とは異なり、固体燃料電池としての高い出力密度が確保できた。 In Example 1 in which vinyl sulfonic acid was reacted with graphene oxide and modified, unlike a simple composition that did not react as in Comparative Examples 2 and 3, a high output density as a solid fuel cell could be secured.
実施例２で得られた固体燃料電池を用いてＩ−Ｖ試験を繰り返し測定したが出力密度が安定していた。一方、参考例３に示すｐ−トルエンスルホン酸と酸化グラフェンの組成物では初期の出力密度は高くても繰り返し測定により出力密度が著しく低下した。 The IV test was repeated using the solid fuel cell obtained in Example 2, and the output density was stable. On the other hand, in the case of the composition of p-toluenesulfonic acid and graphene oxide shown in Reference Example 3, even though the initial output density was high, the output density was significantly reduced by repeated measurement.
本発明の積層体は、各種の電気・電子機器（例えば、電池やキャパシタなどの蓄電素子など）に利用されるプロトン伝導電解質膜として利用でき、特に、固体燃料電池セルのプロトン伝導電解質膜（固体電解質）として好適である。 The laminate of the present invention can be used as a proton conductive electrolyte membrane used for various electric / electronic devices (for example, a storage element such as a battery and a capacitor). (Electrolyte).
１，１１…電解質膜
２…燃料極
３…空気極
４…負極側セパレーター
５…正極側セパレーター
１２ａ，１３ａ…拡散層
１２ｂ，１３ｂ…触媒層
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| JP2015140312A (en) * | 2014-01-28 | 2015-08-03 | 旭化成ファインケム株式会社 | Sulfonic acid group-containing compound and method for producing same |
| JP2015529936A (en) * | 2012-07-10 | 2015-10-08 | ジョンソン、マッセイ、フュエル、セルズ、リミテッドＪｏｈｎｓｏｎ Ｍａｔｔｈｅｙ Ｆｕｅｌ Ｃｅｌｌｓ Ｌｉｍｉｔｅｄ | Ion conductive membrane |
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| JP2011098843A (en) * | 2009-11-04 | 2011-05-19 | Fuji Electric Holdings Co Ltd | Solid acid and method for producing the same |
| JP2015529936A (en) * | 2012-07-10 | 2015-10-08 | ジョンソン、マッセイ、フュエル、セルズ、リミテッドＪｏｈｎｓｏｎ Ｍａｔｔｈｅｙ Ｆｕｅｌ Ｃｅｌｌｓ Ｌｉｍｉｔｅｄ | Ion conductive membrane |
| JP2015140312A (en) * | 2014-01-28 | 2015-08-03 | 旭化成ファインケム株式会社 | Sulfonic acid group-containing compound and method for producing same |
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| WO2018110846A2 (en) * | 2016-12-14 | 2018-06-21 | 주식회사 엘지화학 | Functionalized graphene preparing method |
| JP2018106957A (en) * | 2016-12-27 | 2018-07-05 | 旭硝子株式会社 | Method for manufacturing solid polymer electrolyte film, method for manufacturing membrane-electrode assembly, and method for manufacturing solid polymer fuel cell |
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| WO2022246442A1 (en) * | 2021-05-20 | 2022-11-24 | Nabors Energy Transition Solutions Llc | Proton exchange membranes and methods of preparing same |
| GB2621073A (en) * | 2021-05-20 | 2024-01-31 | Nabors Energy Transition Solutions Llc | Proton exchange membranes and methods of preparing same |
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| WO2020044942A1 (en) | 2020-03-05 |
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