JP5669432B2 - Membrane electrode assembly, fuel cell, and fuel cell activation method - Google Patents
Membrane electrode assembly, fuel cell, and fuel cell activation method Download PDFInfo
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Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Description
本発明は、水素と酸素の電気化学反応により発電する燃料電池に関する。 The present invention relates to a fuel cell that generates electricity by an electrochemical reaction between hydrogen and oxygen.
近年、エネルギー変換効率が高く、かつ、発電反応により有害物質を発生しない燃料電池が注目を浴びている。こうした燃料電池の一つとして、１００℃以下の低温で作動する固体高分子形燃料電池が知られている。 In recent years, fuel cells that have high energy conversion efficiency and do not generate harmful substances due to power generation reactions have attracted attention. As one of such fuel cells, a polymer electrolyte fuel cell that operates at a low temperature of 100 ° C. or lower is known.
固体高分子形燃料電池は、電解質膜である固体高分子膜をアノード（燃料極）とカソード（空気極）との間に配した基本構造を有し、アノードに水素を含む燃料ガス、カソードに酸素を含む酸化剤ガスを供給し、以下の電気化学反応により発電する装置である。
アノード：Ｈ２→２Ｈ＋+２ｅ−・・・（１）
カソード：１／２Ｏ２+２Ｈ＋+２ｅ−→Ｈ２Ｏ・・・（２）
A polymer electrolyte fuel cell has a basic structure in which a polymer electrolyte membrane, which is an electrolyte membrane, is disposed between an anode (fuel electrode) and a cathode (air electrode). A fuel gas containing hydrogen at the anode and a cathode It is an apparatus that supplies an oxidant gas containing oxygen and generates electricity by the following electrochemical reaction.
Anode: H 2 → 2H + + 2e − (1)
Cathode: 1 / 2O 2 + 2H + + 2e - → H 2 O ··· (2)
アノードおよびカソードは、それぞれ触媒層とガス拡散層が積層した構造からなる。各電極の触媒層が固体高分子膜を挟んで対向配置され、膜電極接合体が構成される。触媒層は、触媒を担持した炭素粒子がイオノマーにより結着されてなる層である。ガス拡散層は酸化剤ガスや燃料ガスの通過経路となる。 The anode and cathode each have a structure in which a catalyst layer and a gas diffusion layer are laminated. The catalyst layers of the electrodes are arranged to face each other with the solid polymer membrane interposed therebetween, thereby forming a membrane electrode assembly. The catalyst layer is a layer formed by binding carbon particles carrying a catalyst with an ionomer. The gas diffusion layer becomes a passage for the oxidant gas and the fuel gas.
アノードにおいては、供給された燃料中に含まれる水素が上記式（１）に示されるように水素イオンと電子に分解される。このうち水素イオンは固体高分子電解質膜の内部を空気極に向かって移動し、電子は外部回路を通って空気極に移動する。一方、カソードにおいては、カソードに供給された酸化剤ガスに含まれる酸素が燃料極から移動してきた水素イオンおよび電子と反応し、上記式（２）に示されるように水が生成する。このように、外部回路では燃料極から空気極に向かって電子が移動するため、電力が取り出される（特許文献１参照）。 At the anode, hydrogen contained in the supplied fuel is decomposed into hydrogen ions and electrons as shown in the above formula (1). Among these, hydrogen ions move inside the solid polymer electrolyte membrane toward the air electrode, and electrons move to the air electrode through an external circuit. On the other hand, in the cathode, oxygen contained in the oxidant gas supplied to the cathode reacts with hydrogen ions and electrons that have moved from the fuel electrode, and water is generated as shown in the above formula (2). Thus, in the external circuit, electrons move from the fuel electrode toward the air electrode, so that electric power is taken out (see Patent Document 1).
従来、触媒層に用いられる触媒として白金触媒が知られている。特に、カソードにおける反応は反応速度が比較的遅いため、カソード触媒層において白金触媒が多用されている。 Conventionally, a platinum catalyst is known as a catalyst used in the catalyst layer. In particular, since the reaction rate at the cathode is relatively slow, platinum catalysts are frequently used in the cathode catalyst layer.
触媒層に用いられる白金は埋蔵量が少なく、高価であるため、燃料電池全体のコスト増の要因となっていた。このため、触媒層に非白金系触媒を適用する試みが進められている。カソード触媒層は酸性質の電解質膜に接触するため、カソード触媒層の環境は酸性雰囲気下となり、カソード触媒層は高電位（約１Ｖの正電位）となる。また、燃料電池が運転中の状態では、カソード触媒層の温度は８０℃程度となる。このため、金以外の非白金系触媒をカソード触媒層に用いた場合には、触媒が溶出するという問題が生じる。 Since platinum used for the catalyst layer has a small reserve and is expensive, it has been a factor in increasing the cost of the entire fuel cell. For this reason, an attempt to apply a non-platinum-based catalyst to the catalyst layer is in progress. Since the cathode catalyst layer is in contact with the acidic electrolyte membrane, the environment of the cathode catalyst layer is in an acidic atmosphere, and the cathode catalyst layer has a high potential (a positive potential of about 1 V). Further, when the fuel cell is in operation, the temperature of the cathode catalyst layer is about 80 ° C. For this reason, when a non-platinum catalyst other than gold is used for the cathode catalyst layer, there arises a problem that the catalyst is eluted.
本発明はこうした課題に鑑みてなされたものであり、その目的は、非白金系触媒を有する燃料電池用電極触媒の耐久性を向上させる技術の提供にある。 This invention is made | formed in view of such a subject, The objective is to provide the technique which improves the durability of the electrode catalyst for fuel cells which has a non platinum catalyst.
本発明のある態様は、膜電極接合体である。当該膜電極接合体は、電解質膜と、電解質膜の一方の面に設けられているカソード触媒層と、電解質膜の一方の面に設けられているアノード触媒層と、を備え、カソード触媒層、アノード触媒層のうち、少なくとも一方の触媒層が、Ｆｅ、Ｃｏ、Ｎｉ、Ｒｕ、Ｒｈ、Ｐｄ、Ａｇ、Ｒｅ、Ｏｓ、Ｉｒからなる群より選ばれる少なくとも１種以上の触媒金属と、触媒金属を担持する導電性の担体粒子と、触媒金属および担体粒子の周囲の少なくとも一部を被覆するＳｉＯ２成分と、プロトン伝導性を有するイオノマーと、を備え、触媒層における、触媒金属、担体粒子およびＳｉＯ２成分の各質量を合計した基準質量に対するＳｉＯ２成分の含有量が１〜３０質量％であり、触媒層の体積抵抗率が１〜３００Ω・ｃｍであることを特徴とする。 One embodiment of the present invention is a membrane electrode assembly. The membrane electrode assembly includes an electrolyte membrane, a cathode catalyst layer provided on one surface of the electrolyte membrane, and an anode catalyst layer provided on one surface of the electrolyte membrane, the cathode catalyst layer, Among the anode catalyst layers, at least one of the catalyst layers includes at least one catalyst metal selected from the group consisting of Fe, Co, Ni, Ru, Rh, Pd, Ag, Re, Os, and Ir, and a catalyst metal. A conductive carrier particle to be supported, a SiO 2 component covering at least a part of the periphery of the catalyst metal and the carrier particle, and an ionomer having proton conductivity, and the catalyst metal, the carrier particle and the SiO in the catalyst layer the content of SiO 2 component to the reference mass of the total of each mass of the two components is 1 to 30 wt%, the volume resistivity of the catalyst layer is characterized in that it is a 1~300Ω · cm.
この態様の燃料電池によれば、非白金系の触媒金属をＳｉＯ２成分で部分的に被覆することにより、発電性能を阻害することなく、触媒金属の溶出を抑制し、燃料電池の耐久性を高めることができる。 According to the fuel cell of this aspect, by partially covering the non-platinum based catalyst metal with the SiO 2 component, the elution of the catalyst metal is suppressed without impeding the power generation performance, and the durability of the fuel cell is improved. Can be increased.
上記態様の燃料電池において、触媒金属の濃度（１００×基準質量に対する触媒金属の質量％／（基準質量に対する触媒金属の質量％＋基準質量に対する担体粒子の質量％））が５〜８０％であってもよい。担体粒子が、カーボンブラック、導電性金属酸化物系のいずれかもしくは両者の混合物であってもよい。担体粒子のＢＥＴ比表面積が１０〜２０００ｍ２／ｇであってもよい。担体粒子のメジアン径が３０ｎｍ〜１μｍであってもよい。膜電極接合体の有効面積に対する、触媒層における触媒金属の量が０．０１〜２ｍｇ／ｃｍ２であってもよい。触媒層における、担体粒子の量に対するイオノマーの量（イオノマー比率）が０．２〜３であってもよい。 In the fuel cell of the above aspect, the concentration of the catalyst metal (100 × mass% of the catalyst metal with respect to the reference mass / (mass% of the catalyst metal with respect to the reference mass + mass% of the support particles with respect to the reference mass)) is 5 to 80%. May be. The carrier particles may be either carbon black, conductive metal oxide, or a mixture of both. The BET specific surface area of the carrier particles may be 10 to 2000 m 2 / g. The median diameter of the carrier particles may be 30 nm to 1 μm. 0.01-2 mg / cm < 2 > may be sufficient as the quantity of the catalyst metal in a catalyst layer with respect to the effective area of a membrane electrode assembly. The amount of ionomer (ionomer ratio) relative to the amount of carrier particles in the catalyst layer may be 0.2 to 3.
本発明の他の態様は、上述したいずれかの態様の膜電極接合体と、カソード触媒層に酸化剤を供給するための酸化剤流路を有するカソード側セパレータと、アノード触媒層に燃料を供給するための燃料流路を有するアノード側セパレータと、を備えることを特徴とする。 In another aspect of the present invention, the membrane electrode assembly according to any one of the aspects described above, a cathode-side separator having an oxidant flow path for supplying an oxidant to the cathode catalyst layer, and fuel to the anode catalyst layer are supplied. And an anode-side separator having a fuel flow path.
本発明のさらに他の態様は、燃料電池の活性化方法である。当該燃料電池の活性化方法は、カソード触媒層が上述した触媒金属、担体粒子およびＳｉＯ２成分を含む燃料電池において、アノード触媒層に燃料を供給し、カソード触媒層に不活性ガスを供給した状態で、カソード触媒層の電位を０．０５〜０．９Ｖから１．０〜１．４Ｖに上昇させた後、０．０５〜０．９Ｖに戻す過程を初期状態において３０〜３００００回繰り返すことを特徴とする。 Yet another embodiment of the present invention is a fuel cell activation method. In the fuel cell activation method, in the fuel cell in which the cathode catalyst layer includes the above-described catalyst metal, support particles, and SiO 2 component, the fuel is supplied to the anode catalyst layer and the inert gas is supplied to the cathode catalyst layer. The process of raising the potential of the cathode catalyst layer from 0.05 to 0.9 V to 1.0 to 1.4 V and then returning to 0.05 to 0.9 V is repeated 30 to 30000 times in the initial state. Features.
なお、上述した各要素を適宜組み合わせたものも、本件特許出願によって特許による保護を求める発明の範囲に含まれうる。 A combination of the above-described elements as appropriate can also be included in the scope of the invention for which patent protection is sought by this patent application.
本発明によれば、非白金系触媒を有する燃料電池の耐久性を向上させることができる。 According to the present invention, the durability of a fuel cell having a non-platinum-based catalyst can be improved.
以下、本発明の実施の形態を図面を参照して説明する。なお、すべての図面において、同様な構成要素には同様の符号を付し、適宜説明を省略する。 Hereinafter, embodiments of the present invention will be described with reference to the drawings. In all the drawings, the same reference numerals are given to the same components, and the description will be omitted as appropriate.
（実施の形態）
図１は、実施の形態に係る燃料電池１０の構造を模式的に示す斜視図である。図２は、図１のＡ−Ａ線上の断面図である。燃料電池１０は、平板状の膜電極接合体５０を備え、この膜電極接合体５０の両側にはセパレータ３４およびセパレータ３６が設けられている。セパレータ３４やセパレータ３６を介して複数の燃料電池１０が積層されることにより、燃料電池スタックを構成する積層体が形成される。
(Embodiment)
FIG. 1 is a perspective view schematically showing the structure of a fuel cell 10 according to an embodiment. FIG. 2 is a cross-sectional view taken along the line AA of FIG. The fuel cell 10 includes a flat membrane electrode assembly 50, and a separator 34 and a separator 36 are provided on both sides of the membrane electrode assembly 50. By stacking a plurality of fuel cells 10 via the separator 34 and the separator 36, a stacked body constituting the fuel cell stack is formed.
膜電極接合体５０は、固体高分子電解質膜２０、アノード２２、およびカソード２４を有する。アノード２２は、アノード触媒層２６とアノードガス拡散層２８とからなる積層体を有する。一方、カソード２４は、カソード触媒層３０とカソードガス拡散層３２とからなる積層体を有する。アノード触媒層２６とカソード触媒層３０は、固体高分子電解質膜２０を挟んで対向するように設けられている。アノードガス拡散層２８は、固体高分子電解質膜２０とは反対側のアノード触媒層２６の面に設けられている。また、カソードガス拡散層３２は、固体高分子電解質膜２０とは反対側のカソード触媒層３０の面に設けられている。 The membrane electrode assembly 50 includes a solid polymer electrolyte membrane 20, an anode 22, and a cathode 24. The anode 22 has a laminate composed of an anode catalyst layer 26 and an anode gas diffusion layer 28. On the other hand, the cathode 24 has a laminate composed of a cathode catalyst layer 30 and a cathode gas diffusion layer 32. The anode catalyst layer 26 and the cathode catalyst layer 30 are provided so as to face each other with the solid polymer electrolyte membrane 20 interposed therebetween. The anode gas diffusion layer 28 is provided on the surface of the anode catalyst layer 26 opposite to the solid polymer electrolyte membrane 20. The cathode gas diffusion layer 32 is provided on the surface of the cathode catalyst layer 30 on the side opposite to the solid polymer electrolyte membrane 20.
アノード２２側に設けられるセパレータ３４にはガス流路３８が設けられている。燃料供給用のマニホールド（図示せず）から改質ガスがガス流路３８に分配され、ガス流路３８を通じて膜電極接合体５０に改質ガスが供給される。同様に、カソード２４側に設けられるセパレータ３６にはガス流路４０が設けられている。酸化剤供給用のマニホールド（図示せず）から酸化剤として空気がガス流路４０に分配され、ガス流路４０を通じて膜電極接合体５０に空気が供給される。 A gas flow path 38 is provided in the separator 34 provided on the anode 22 side. A reformed gas is distributed to a gas flow path 38 from a fuel supply manifold (not shown), and the reformed gas is supplied to the membrane electrode assembly 50 through the gas flow path 38. Similarly, a gas flow path 40 is provided in the separator 36 provided on the cathode 24 side. Air as an oxidant is distributed to the gas flow path 40 from an oxidant supply manifold (not shown), and the air is supplied to the membrane electrode assembly 50 through the gas flow path 40.
固体高分子電解質膜２０は、湿潤状態において良好なイオン伝導性を示し、アノード２２およびカソード２４の間でプロトンを移動させるイオン交換膜として機能する。固体高分子電解質膜２０は、含フッ素重合体や非フッ素重合体等の固体高分子材料によって形成され、例えば、スルホン酸型パーフルオロカーボン重合体、ポリサルホン樹脂、ホスホン酸基又はカルボン酸基を有するパーフルオロカーボン重合体等を用いることができる。スルホン酸型パーフルオロカーボン重合体の例として、ナフィオン（デュポン社製：登録商標）などが挙げられる。また、非フッ素重合体の例として、スルホン化された、芳香族ポリエーテルエーテルケトン、ポリスルホンなどが挙げられる。 The solid polymer electrolyte membrane 20 exhibits good ion conductivity in a wet state, and functions as an ion exchange membrane that moves protons between the anode 22 and the cathode 24. The solid polymer electrolyte membrane 20 is formed of a solid polymer material such as a fluorine-containing polymer or a non-fluorine polymer. A fluorocarbon polymer or the like can be used. Examples of the sulfonic acid type perfluorocarbon polymer include Nafion (manufactured by DuPont: registered trademark). Examples of non-fluorine polymers include sulfonated aromatic polyetheretherketone and polysulfone.
本実施の形態のカソード触媒層３０は、イオノマーと、担体粒子と、触媒金属と、ＳｉＯ２成分とから構成される。イオノマーは、カソード触媒層３０中の触媒金属と固体高分子電解質膜２０を接続し、両者間においてプロトンを伝達する役割を持つ。イオノマーは、固体高分子電解質膜２０と同様の高分子材料から形成されてよい。 The cathode catalyst layer 30 of the present embodiment is composed of an ionomer, support particles, a catalyst metal, and a SiO 2 component. The ionomer connects the catalytic metal in the cathode catalyst layer 30 and the solid polymer electrolyte membrane 20, and has a role of transmitting protons between the two. The ionomer may be formed from the same polymer material as the solid polymer electrolyte membrane 20.
担体粒子として、アセチレンブラック、ケッチェンブラック、フラーレン、カーボンナノチューブ、カーボンナノオニオンなどの導電性の炭素粒子、酸化チタン，酸化スズなどの導電性金属酸化物系、またはこれらの混合物が挙げられる。 Examples of the carrier particles include conductive carbon particles such as acetylene black, ketjen black, fullerene, carbon nanotube, and carbon nano-onion, conductive metal oxides such as titanium oxide and tin oxide, or a mixture thereof.
担体粒子のＢＥＴ比表面積は、１０〜２０００ｍ２／ｇであることが好ましい。担体粒子のＢＥＴ比表面積が１０ｍ２／ｇより小さいと、触媒金属を均一に担持させることが難しくなる。このため、触媒表面の利用率が低下し、触媒性能の低下を招く。担体粒子のＢＥＴ比表面積が２０００ｍ２／ｇより大きいと担体粒子の耐久性が低下する。 The BET specific surface area of the carrier particles is preferably 10 to 2000 m 2 / g. When the BET specific surface area of the carrier particles is smaller than 10 m 2 / g, it becomes difficult to uniformly support the catalyst metal. For this reason, the utilization factor of a catalyst surface falls and it causes the fall of catalyst performance. When the BET specific surface area of the carrier particles is larger than 2000 m 2 / g, the durability of the carrier particles is lowered.
また、担体粒子のメジアン径は３０ｎｍ〜１μｍであることが好ましい。担体粒子のメジアン径が３０ｎｍより小さいと触媒金属（数ｎｍ）を十分に担持することができない。また、担体粒子のメジアン径が１μｍより大きいと比表面積が小さくなるため、触媒金属を十分に担持することができない。 The median diameter of the carrier particles is preferably 30 nm to 1 μm. When the median diameter of the support particles is smaller than 30 nm, the catalyst metal (several nm) cannot be supported sufficiently. On the other hand, if the median diameter of the support particles is larger than 1 μm, the specific surface area becomes small, so that the catalyst metal cannot be supported sufficiently.
触媒金属は、上述した担体粒子に担持される。触媒金属として、Ｆｅ、Ｃｏ、Ｎｉ、Ｒｕ、Ｒｈ、Ｐｄ、Ａｇ、Ｒｅ、Ｏｓ、Ｉｒからなる群より選ばれる少なくとも１種以上の触媒金属が挙げられる。触媒金属の濃度（１００×基準質量に対する触媒金属の質量％／（基準質量に対する触媒金属の質量％＋基準質量に対する担体粒子の質量％））は、５〜８０％であることが好ましい。なお、「基準質量」は、担体粒子、触媒金属およびＳｉＯ２成分各質量を合計した質量である。触媒金属の濃度が５％より低いと、十分な発電性能が得られなくなる。触媒金属の濃度が８０％より高いと、触媒金属を担体粒子上に均一に担持させることが難しくなる。 The catalytic metal is supported on the carrier particles described above. Examples of the catalyst metal include at least one catalyst metal selected from the group consisting of Fe, Co, Ni, Ru, Rh, Pd, Ag, Re, Os, and Ir. The concentration of catalyst metal (100 × mass% of catalyst metal with respect to reference mass / (mass% of catalyst metal with respect to reference mass + mass% of carrier particles with respect to reference mass)) is preferably 5 to 80%. The “reference mass” is the total mass of the carrier particles, the catalyst metal, and the SiO 2 component. When the concentration of the catalytic metal is lower than 5%, sufficient power generation performance cannot be obtained. When the concentration of the catalyst metal is higher than 80%, it becomes difficult to uniformly support the catalyst metal on the support particles.
ＳｉＯ２成分は、上述した触媒金属および担体粒子の周囲の少なくとも一部を被覆する。ここで、ＳｉＯ２成分は、具体的には、シリカである。ＳｉＯ２成分の含有量は、上述した基準質量に対して１〜３０質量％である。ＳｉＯ２成分の含有量が１質量％より少ないと、触媒金属の溶出を十分に抑制することができない。また、ＳｉＯ２成分の含有量が３０質量％より多いと、カソード触媒層において導電パスが形成されにくくなり、発電性の低下を招く。 The SiO 2 component covers at least part of the periphery of the catalyst metal and the support particles described above. Here, the SiO 2 component is specifically silica. The content of SiO 2 component is 1 to 30 wt% with respect to the reference mass as described above. When the content of the SiO 2 component is less than 1% by mass, elution of the catalyst metal cannot be sufficiently suppressed. If the content of SiO 2 component is more than 30 wt%, the conductive path in the cathode catalyst layer becomes is hardly formed, lowering the power generation property.
カソード触媒層３０の体積抵抗率は１〜３００Ω・ｃｍ以下である。カソード触媒層３０の体積抵抗率が１Ω・ｃｍより低い場合には、ＳｉＯ２成分による触媒金属の被覆量が十分でないため、触媒金属の溶出を十分に抑制することができない。カソード触媒層３０の体積抵抗率が３００Ω・ｃｍより高いと、カソード触媒層３０の抵抗が大きすぎるため、十分な発電性能を得ることができない。 The volume resistivity of the cathode catalyst layer 30 is 1 to 300 Ω · cm or less. In the case where the volume resistivity of the cathode catalyst layer 30 is lower than 1 Ω · cm, the coating amount of the catalyst metal by the SiO 2 component is not sufficient, so that elution of the catalyst metal cannot be sufficiently suppressed. If the volume resistivity of the cathode catalyst layer 30 is higher than 300 Ω · cm, the resistance of the cathode catalyst layer 30 is too high, and sufficient power generation performance cannot be obtained.
また、膜電極接合体の有効面積に対する、カソード触媒層３３０における触媒金属の量は、０．０１ｍｇ／ｃｍ２〜２ｍｇ／ｃｍ２であることが好ましい。触媒金属の量が０．０１ｍｇより少ないと、十分な発電性能を得ることができない。触媒金属の量が２ｍｇ／ｃｍ２より多いと、触媒金属に要するコストが必要以上に高くなり、燃料電池１０の製造コストが増大する。また、触媒金属の量が２ｍｇ／ｃｍ２より多いと、カソード触媒層３３０における酸素拡散性やプロトン移動性が悪くなるため、カソード触媒層３３０の内部の触媒金属を有効に利用することができなくなる。 Further, with respect to the effective area of the membrane electrode assembly, the amount of catalyst metal in the cathode catalyst layer 330 is preferably 0.01mg / cm 2 ~2mg / cm 2 . If the amount of catalytic metal is less than 0.01 mg, sufficient power generation performance cannot be obtained. When the amount of the catalyst metal is more than 2 mg / cm 2 , the cost required for the catalyst metal becomes higher than necessary, and the manufacturing cost of the fuel cell 10 increases. On the other hand, if the amount of the catalyst metal is more than 2 mg / cm 2, the oxygen diffusibility and proton mobility in the cathode catalyst layer 330 are deteriorated, so that the catalyst metal in the cathode catalyst layer 330 cannot be effectively used. .
また、カソード触媒層３０における、担体粒子の量に対するイオノマーの量（イオノマー比率）は０．２以上３以下であることが好ましい。イオノマーの量が０．２未満であると、カソード触媒層３０内のプロトン移動性が低下するため、発電性能が低下する。イオノマーの量が３より大きいと、カソード触媒層３０内の酸素拡散性が低下するため、発電性能が低下する。 Further, the amount of ionomer (ionomer ratio) with respect to the amount of carrier particles in the cathode catalyst layer 30 is preferably 0.2 or more and 3 or less. When the amount of ionomer is less than 0.2, the proton mobility in the cathode catalyst layer 30 is lowered, so that the power generation performance is lowered. When the amount of ionomer is larger than 3, the oxygen diffusibility in the cathode catalyst layer 30 is lowered, so that the power generation performance is lowered.
カソードガス拡散層３２は、カソードガス拡散基材により形成される。カソードガス拡散基材は、電子伝導性を有する多孔体で構成されることが好ましく、たとえば、金属板、金属フィルム、導電性高分子、カーボンペーパー、カーボンの織布または不織布などを用いることができる。 The cathode gas diffusion layer 32 is formed of a cathode gas diffusion base material. The cathode gas diffusion base material is preferably composed of a porous body having electron conductivity. For example, a metal plate, a metal film, a conductive polymer, carbon paper, a carbon woven fabric or a non-woven fabric can be used. .
一方、アノード触媒層２６は、イオノマーと、導電性材料と、白金触媒などから構成される。イオノマーは、アノード触媒層２６中の触媒金属と固体高分子電解質膜２０を接続し、両者間においてプロトンを伝達する役割を持つ。イオノマーは、固体高分子電解質膜２０と同様の高分子材料から形成されてよい。導電性材料として、アセチレンブラック、ケッチェンブラック、フラーレン、カーボンナノチューブ、カーボンナノオニオンなどの炭素粒子が挙げられる。 On the other hand, the anode catalyst layer 26 is composed of an ionomer, a conductive material, a platinum catalyst, and the like. The ionomer connects the catalytic metal in the anode catalyst layer 26 and the solid polymer electrolyte membrane 20, and has a role of transmitting protons between the two. The ionomer may be formed from the same polymer material as the solid polymer electrolyte membrane 20. Examples of the conductive material include carbon particles such as acetylene black, ketjen black, fullerene, carbon nanotube, and carbon nano-onion.
アノードガス拡散層２８は、アノードガス拡散基材により形成される。アノードガス拡散基材は、電子伝導性を有する多孔体で構成されることが好ましく、たとえば金属板、金属フィルム、導電性高分子、カーボンペーパー、カーボンの織布または不織布などを用いることができる。 The anode gas diffusion layer 28 is formed of an anode gas diffusion base material. The anode gas diffusion base material is preferably composed of a porous body having electronic conductivity. For example, a metal plate, a metal film, a conductive polymer, carbon paper, a carbon woven fabric or a nonwoven fabric can be used.
以上説明した燃料電池によれば、カソード触媒層に用いられる触媒金属として、非白金系の触媒金属が用いられているため、白金触媒を用いた場合に比べて製造コストを抑制することができる。また、非白金系の触媒金属の周囲にＳｉＯ２成分からなる被覆層が設けられているため、燃料電池の運転時に非白金系の触媒金属が溶出することが抑制される。この結果、燃料電池の耐久性を向上させることができる。 According to the fuel cell described above, since the non-platinum-based catalyst metal is used as the catalyst metal used in the cathode catalyst layer, the manufacturing cost can be suppressed as compared with the case where a platinum catalyst is used. Further, since the coating layer made of the SiO 2 component is provided around the non-platinum-based catalyst metal, it is possible to suppress the non-platinum-based catalyst metal from eluting during the operation of the fuel cell. As a result, the durability of the fuel cell can be improved.
（燃料電池の活性化方法）
上述した構成の燃料電池１０の発電性能を向上させる活性化方法について説明する。
(Fuel cell activation method)
An activation method for improving the power generation performance of the fuel cell 10 having the above-described configuration will be described.
まず、アノード触媒層２６に燃料を供給し、カソード触媒層３０にＮ２などの不活性ガスを供給する。この状態で、カソード触媒層３０の電位を下限電位である０．０５〜０．９Ｖから上限電位である１．０〜１．４Ｖに上昇させた後、下限電位である０．０５〜０．９Ｖに戻す過程を３０〜３００００回繰り返す。この電位サイクルにより、カソード触媒層３０の触媒金属を溶解、再析出させることでカソード触媒層３０の触媒金属を活性化させることができる。 First, fuel is supplied to the anode catalyst layer 26, and an inert gas such as N 2 is supplied to the cathode catalyst layer 30. In this state, the potential of the cathode catalyst layer 30 is increased from 0.05 to 0.9 V which is the lower limit potential to 1.0 to 1.4 V which is the upper limit potential, and then 0.05 to 0. 0 which is the lower limit potential. The process of returning to 9V is repeated 30 to 30000 times. By this potential cycle, the catalyst metal of the cathode catalyst layer 30 can be activated by dissolving and reprecipitating the catalyst metal of the cathode catalyst layer 30.
なお、上述した電位サイクルの下限電位が０．０５Ｖを下回るとプロトン還元による水素発生が起こり、活性化にとって好ましくない。一方、上述した電位サイクルの下限電位が触媒金属の溶解電位を上回ると触媒金属の再析出が生じにくくなる。よって０．９Ｖを電位サイクルの下限電位の上限とすることが好ましい。また、上述した電位サイクルの上限電位が１．０Ｖを下回ると触媒金属の溶解が起こりにくくなり、電位サイクルの上限電位が１．４Ｖを上回ると担体カーボンが腐食するため好ましくない。また、電位サイクルの回数が３０回より少ないと、十分な活性化効果を得ることができない。また、電位サイクルの回数が３００００回を超えると、必要以上に時間がかかり過ぎるため、好ましくない。 If the lower limit potential of the potential cycle described above is less than 0.05 V, hydrogen generation occurs due to proton reduction, which is not preferable for activation. On the other hand, when the lower limit potential of the potential cycle described above exceeds the dissolution potential of the catalyst metal, reprecipitation of the catalyst metal is difficult to occur. Therefore, it is preferable to set 0.9 V as the upper limit of the lower limit potential of the potential cycle. Further, when the upper limit potential of the potential cycle is less than 1.0 V, dissolution of the catalyst metal is difficult to occur, and when the upper limit potential of the potential cycle is more than 1.4 V, the carrier carbon is corroded, which is not preferable. Further, when the number of potential cycles is less than 30, sufficient activation effect cannot be obtained. Further, if the number of potential cycles exceeds 30000, it takes too much time and is not preferable.
上述した燃料電池の活性化処理を製品出荷前に前処理として実施することにより、製品出荷後から直ちに所望の発電性能を発揮させることができる。 By implementing the fuel cell activation process described above as a pre-process before product shipment, desired power generation performance can be exhibited immediately after product shipment.
ここで、各実施例および各比較例の燃料電池の作製方法について説明する。 Here, a manufacturing method of the fuel cell of each example and each comparative example will be described.
（比較例１）
＜カソード触媒の作製＞
ＰｄＣｌ２０．２ｇ、カーボンナノチューブ（以下、ＣＮＴと呼ぶ）２．３ｇを純水中に分散（質量比Ｐｄ：ＣＮＴ＝１：１９）した。得られた分散溶液に超音波を３０分間照射し、６０℃で水分を除去した後、６０℃で一晩乾燥させた。得られた固形物を３５０℃で水素還元して、ＣＮＴにＰｄが担持されたＰｄ／ＣＮＴ触媒（比較例１のカーボン担持金属触媒）を得た。比較例１のカーボン担持金属触媒２０ｍｇをＮａｆｉｏｎ溶液（５ｗｔ％）４５６μｌ、２−プロパノール５００μｌに加え、カソード用の触媒スラリーを得た。
(Comparative Example 1)
<Preparation of cathode catalyst>
0.2 g of PdCl 2 and 2.3 g of carbon nanotubes (hereinafter referred to as CNT) were dispersed in pure water (mass ratio Pd: CNT = 1: 19). The obtained dispersion solution was irradiated with ultrasonic waves for 30 minutes to remove moisture at 60 ° C., and then dried at 60 ° C. overnight. The obtained solid was subjected to hydrogen reduction at 350 ° C. to obtain a Pd / CNT catalyst (carbon-supported metal catalyst of Comparative Example 1) in which Pd was supported on CNTs. 20 mg of the carbon-supported metal catalyst of Comparative Example 1 was added to 456 μl of Nafion solution (5 wt%) and 500 μl of 2-propanol to obtain a catalyst slurry for the cathode.
なお、窒素吸着法で測定したＣＮＴのＢＥＴ比表面積は、４０ｍ２／ｇである。また、沈降法または動的光散乱法で測定したＣＮＴのメジアン径はいずれも２００ｎｍである。 In addition, the BET specific surface area of CNT measured by the nitrogen adsorption method is 40 m < 2 > / g. Moreover, the median diameter of CNT measured by the sedimentation method or the dynamic light scattering method is 200 nm.
＜カソード触媒層の作製＞
上述の手順で得られたカソード用の触媒スラリーを面積５ｃｍ２のカーボンペーパーに塗布した後、一晩乾燥させて、カソード触媒層を作製した。なお、このカソード触媒層におけるイオノマー比率は、１．１である。
<Preparation of cathode catalyst layer>
The cathode catalyst slurry obtained by the above-described procedure was applied to carbon paper having an area of 5 cm 2 and then dried overnight to produce a cathode catalyst layer. In addition, the ionomer ratio in this cathode catalyst layer is 1.1.
＜アノード触媒の作製＞
カソード触媒として、白金担持カーボン（ＴＥＣ１０Ｅ５０Ｅ，田中貴金属工業株式会社）を用い、イオン伝導体として、ＳＳ７００Ｃ溶液（２０％，Ｅｗ＝７８０，含水率＝３６ｗｔ％（２５℃），旭化成ケミカルズ製アイオノマー溶液Ａｃｉｐｌｅｘ（登録商標） ＳＳ７００Ｃ、以下ＳＳ７００と略す）を用いた。白金担持カーボン５ｇに対し、１０ｍＬの超純水を添加し撹拌した後に、１５ｍＬエタノールを添加した。この触媒分散溶液について、超音波スターラーを用いて１時間超音波撹拌分散を行った。所定のＳＳ７００溶液を等量の超純水で希釈を行い、ガラス棒で３分間撹拌した。この後、超音波洗浄器を用いて１時間超音波分散を行い、ＳＳ７００水溶液を得た。その後、ＳＳ７００水溶液をゆっくりと触媒分散液中に滴下した。滴下中は、超音波スターラーを用いて連続的に撹拌を行った。ＳＳ７００水溶液滴下終了後、１−プロパノールと１−ブタノールの混合溶液１０ｇ（重量比１：１）の滴下を行い、得られた溶液をアノード用の触媒スラリーとした。混合中は、すべて水温が約６０℃になるように調整し、エタノールを蒸発、除去した。
<Preparation of anode catalyst>
Platinum-supported carbon (TEC10E50E, Tanaka Kikinzoku Kogyo Co., Ltd.) was used as the cathode catalyst, and SS700C solution (20%, Ew = 780, moisture content = 36 wt% (25 ° C.)), ionomer solution Aciplex manufactured by Asahi Kasei Chemicals Co., Ltd. (Registered trademark) SS700C, hereinafter abbreviated as SS700). 10 mL of ultrapure water was added to 5 g of platinum-supporting carbon and stirred, and then 15 mL of ethanol was added. The catalyst dispersion solution was subjected to ultrasonic stirring and dispersion for 1 hour using an ultrasonic stirrer. A predetermined SS700 solution was diluted with an equal amount of ultrapure water and stirred with a glass rod for 3 minutes. Thereafter, ultrasonic dispersion was performed using an ultrasonic cleaner for 1 hour to obtain an SS700 aqueous solution. Thereafter, the SS700 aqueous solution was slowly dropped into the catalyst dispersion. During the dropping, stirring was continuously performed using an ultrasonic stirrer. After the SS700 aqueous solution was dropped, 10 g (1: 1 by weight) of a mixed solution of 1-propanol and 1-butanol was dropped, and the resulting solution was used as a catalyst slurry for the anode. During mixing, the water temperature was all adjusted to about 60 ° C., and ethanol was evaporated and removed.
＜アノード触媒層の作製＞
上述の手順で得られたアノード用の触媒スラリーを面積５ｃｍ２のカーボンペーパーに塗布した後、一晩乾燥させて、アノード触媒層を作製した。
<Preparation of anode catalyst layer>
The anode catalyst slurry obtained by the above procedure was applied to carbon paper having an area of 5 cm 2 and then dried overnight to produce an anode catalyst layer.
＜膜電極接合体の作製＞
上記の方法で作製したアノードとカソードとの間に固体高分子電解質膜を狭持した状態でホットプレスを行った。固体高分子電解質膜としてＮａｆｉｏｎ２１２（登録商標、デュポン社製）を用いた。１２０℃、５ＭＰａ、１６０秒の接合条件でアノード、固体高分子電解質膜、およびカソードをホットプレスすることによって膜電極接合体を作製した。
<Preparation of membrane electrode assembly>
Hot pressing was performed with the solid polymer electrolyte membrane sandwiched between the anode and the cathode produced by the above method. Nafion 212 (registered trademark, manufactured by DuPont) was used as the solid polymer electrolyte membrane. A membrane electrode assembly was produced by hot pressing the anode, the solid polymer electrolyte membrane, and the cathode under bonding conditions of 120 ° C., 5 MPa, and 160 seconds.
＜燃料電池の作製＞
上記の方法で作成された膜電極接合体のアノード面、カソード面に、それぞれ、燃料流路が設けられた燃料セパレータを、酸化剤流路が設けられたセパレータを配設し、燃料電池を作製した。
<Fabrication of fuel cell>
A fuel cell with a fuel flow path and a separator with an oxidant flow path are arranged on the anode surface and cathode surface of the membrane electrode assembly prepared by the above method, respectively, to produce a fuel cell. did.
（実施例１〜４、比較例２）
実施例１〜４および比較例２の燃料電池は、カーボン触媒を除き比較例１と同様な方法で作製した。
(Examples 1-4, Comparative Example 2)
The fuel cells of Examples 1 to 4 and Comparative Example 2 were produced by the same method as Comparative Example 1 except for the carbon catalyst.
＜カソード触媒の作製＞
上述の手順で得られたＰｄ／ＣＮＴ触媒を純水３００ｍｌに、トリメチルアミン７ｍｌを添加した溶液中に分散（ｐＨ＝１０になるよう調整）させた。得られた分散溶液に６０℃の温浴中で超音波を５分間照射した。その後、分散溶液に３−アミノプロピルエトキシシラン（ＡＰＴＥＳ）を添加し、３０分間攪拌した。さらに、分散溶液にテトラエトキシシラン（ＴＥＯＳ）を添加、２時間攪拌した。得られた混合溶液を遠心分離機を用いて ３０分間遠心分離した。得られた混合溶液を６０℃で一晩乾燥させた後、３５０℃で水素還元して、ＣＮＴに担持されたＰｄがシリカ（ＳｉＯ２成分）で被覆されたＳｉＯ２／Ｐｄ／ＣＮＴ触媒（実施例１〜４のカーボン担持金属触媒）を得た。なお、実施例１〜４および比較例２のカーボン担持触媒金属におけるＡＰＴＥＳの添加量、ＴＥＯＳの添加量を表１に示す。
<Preparation of cathode catalyst>
The Pd / CNT catalyst obtained by the above procedure was dispersed (adjusted so that pH = 10) in 300 ml of pure water and 7 ml of trimethylamine. The obtained dispersion solution was irradiated with ultrasonic waves for 5 minutes in a 60 ° C. warm bath. Thereafter, 3-aminopropylethoxysilane (APTES) was added to the dispersion and stirred for 30 minutes. Further, tetraethoxysilane (TEOS) was added to the dispersion solution and stirred for 2 hours. The obtained mixed solution was centrifuged for 30 minutes using a centrifuge. The obtained mixed solution was dried at 60 ° C. overnight and then reduced at 350 ° C. with hydrogen, and a SiO 2 / Pd / CNT catalyst in which Pd supported on CNT was coated with silica (SiO 2 component) (implemented) The carbon-supported metal catalysts of Examples 1 to 4 were obtained. In addition, Table 1 shows the addition amount of APTES and the addition amount of TEOS in the carbon-supported catalyst metals of Examples 1 to 4 and Comparative Example 2.
＜初期性能評価＞
実施例１〜４、比較例１、２の燃料電池について、下記条件にてそれぞれ電流密度値を測定した。なお、燃料流路および酸化剤流路は、ともに１流路のサーペンタイン型流路であり、燃料流路および酸化剤流路は並行流とした。
膜電極接合体の有効面積：５ｃｍ２
燃料ガス：Ｈ２、流量１００ｍｌ／ｍｉｎ
酸化剤ガス：Ｏ２、流量１００ｍｌ／ｍｉｎ
セル温度：７０℃
燃料ガス用バブラー温度：７０℃
酸化剤ガス用バブラー温度：７０℃
実施例１〜４、比較例１、２の燃料電池における初期電流密度値の測定結果を表１に示す。
なお、実施例１〜４および比較例２の燃料電池については、初期電流密度値の測定前に、後述する電位サイクルによる活性化処理を表１に示す回数だけ実施した。
<Initial performance evaluation>
For the fuel cells of Examples 1 to 4 and Comparative Examples 1 and 2, the current density values were measured under the following conditions. The fuel flow channel and the oxidant flow channel are both serpentine flow channels, and the fuel flow channel and the oxidant flow channel are parallel flow.
Effective area of membrane electrode assembly: 5 cm 2
Fuel gas: H 2 , flow rate 100 ml / min
Oxidant gas: O 2 , flow rate 100 ml / min
Cell temperature: 70 ° C
Fuel gas bubbler temperature: 70 ° C
Bubbler temperature for oxidant gas: 70 ° C
Table 1 shows the measurement results of the initial current density values in the fuel cells of Examples 1 to 4 and Comparative Examples 1 and 2.
In addition, about the fuel cell of Examples 1-4 and the comparative example 2, the activation process by the potential cycle mentioned later was implemented only the frequency | count shown in Table 1 before the measurement of an initial stage current density value.
＜耐久性能評価＞
耐久試験における起動停止の手順を以下に示す。
（１）アノード側に水素を３００ｍｌ／ｍｉｎ、カソード側に酸素を３００ｍｌ／ｍｉｎで約５分間流してバブラー、セル内を置換する。
（２）ＯＣＶ：開回路電圧（Ｖ）の変化が数ｍＶ／１０秒であることを確認したら、１分当たり０．０５Ａ／ｃｍ２の速度で０．２Ａ／ｃｍ２まで電流密度値を増やす。また同時にセル温度を７０℃まで上昇させる。ヒーター性能にもよるが、セル温度の上昇率は５℃／分程度が望ましい。
（３）セル温度が７０℃±１℃で安定するのを確認したら、ガス流量を絞って、アノード側に水素を１００ｍｌ／分、カソード側に酸素を１００ｍｌ／ｍｉｎとし、そのまま３時間維持する。
（４）電流密度値を１分あたり０．０５Ａ／ｃｍ２の速度で減らし、０Ａ／ｃｍ２にする。そのあと、水素のガス流量および酸素のガス流量をともに０ｍｌ／分にする。
（５）そのまま２時間放置。セル温度は室温程度まで低下する。
上記手順を１００サイクル繰り返した後、実施例１〜４、比較例１、２の燃料電池についてそれぞれ電流密度値を測定した。実施例１〜４、比較例１、２の燃料電池における耐久試験後の電流密度値の測定結果を表１に示す。
<Durability evaluation>
The procedure for starting and stopping in the durability test is shown below.
(1) Hydrogen is supplied to the anode side at 300 ml / min and oxygen is supplied to the cathode side at 300 ml / min for about 5 minutes to replace the bubbler and the inside of the cell.
(2) OCV: After confirming that the change in open circuit voltage (V) is several mV / 10 seconds, increase the current density value to 0.2 A / cm 2 at a rate of 0.05 A / cm 2 per minute. . At the same time, the cell temperature is raised to 70 ° C. Although it depends on the heater performance, the cell temperature increase rate is preferably about 5 ° C./min.
(3) When it is confirmed that the cell temperature is stable at 70 ° C. ± 1 ° C., the gas flow rate is reduced, hydrogen is set to 100 ml / min on the anode side, and oxygen is set to 100 ml / min on the cathode side, and maintained for 3 hours.
(4) The current density value is reduced at a rate of 0.05 A / cm 2 per minute to 0 A / cm 2 . Thereafter, the hydrogen gas flow rate and the oxygen gas flow rate are both 0 ml / min.
(5) Leave as it is for 2 hours. The cell temperature drops to about room temperature.
After repeating the above procedure for 100 cycles, current density values were measured for the fuel cells of Examples 1 to 4 and Comparative Examples 1 and 2, respectively. Table 1 shows the measurement results of current density values after endurance tests in the fuel cells of Examples 1 to 4 and Comparative Examples 1 and 2.
表１に示すように、シリカ量、すなわちＳｉＯ２成分の含有量が１〜３０質量％で、かつ体積抵抗率が０．５〜３００Ω・ｃｍの範囲（実施例１〜４）において、耐久試験後の電流密度値が初期電流密度値と同等かそれ以上の値を示すことがわかる。なお、比較例２においても、耐久性能の向上は見られるが、電流密度値自体が低いレベルで安定しており、実用性に欠ける。これは、ＳｉＯ２成分の被覆率が高すぎるため、カソード触媒層において導電パスが形成されにくくなっていることに起因すると考えられる。 As shown in Table 1, in the range (Examples 1 to 4) in which the amount of silica, that is, the content of the SiO 2 component is 1 to 30% by mass, and the volume resistivity is 0.5 to 300 Ω · cm (Examples 1 to 4), It can be seen that the subsequent current density value is equal to or higher than the initial current density value. In Comparative Example 2, although the durability performance is improved, the current density value itself is stable at a low level and lacks practicality. This is considered to be due to the fact that the conductive path is difficult to be formed in the cathode catalyst layer because the coverage of the SiO 2 component is too high.
（触媒金属溶出抑制効果の確認）
比較例１の燃料電池および実施例３の燃料電池について、耐久試験の実施前後における、カソード触媒層の触媒金属の担持状態をＳＥＭ（走査型電子顕微鏡）を用いて確認した。図３（Ａ）、図３（Ｂ）は、それぞれ、耐久試験前、耐久試験後の比較例１のカソード触媒層のＳＥＭ写真である。図４（Ａ）、図４（Ｂ）は、それぞれ、耐久試験前、耐久試験後の実施例３のカソード触媒層のＳＥＭ写真である。
(Confirmation of catalytic metal elution suppression effect)
With respect to the fuel cell of Comparative Example 1 and the fuel cell of Example 3, the catalytic metal loading state of the cathode catalyst layer before and after the endurance test was confirmed using a SEM (scanning electron microscope). 3 (A) and 3 (B) are SEM photographs of the cathode catalyst layer of Comparative Example 1 before and after the durability test, respectively. 4A and 4B are SEM photographs of the cathode catalyst layer of Example 3 before and after the durability test, respectively.
図３（Ｂ）に示すように、比較例１のカソード触媒は、耐久試験後に、ＣＮＴに担時されたＰｄ触媒の量が大幅に減少しており、Ｐｄ触媒の溶出が生じていることがわかる。これに対して、図４（Ｂ）に示すように、実施例３のカソード触媒では、ＣＮＴに担時されたＰｄ触媒の量が初期状態（図４（Ａ）参照）からほとんど変化しておらず、Ｐｄ触媒を部分的に被覆するＳｉＯ２成分によりＰｄ触媒の溶出が抑制されていることがわかる。 As shown in FIG. 3 (B), in the cathode catalyst of Comparative Example 1, the amount of the Pd catalyst carried by the CNT after the endurance test was greatly reduced, and the Pd catalyst was eluted. Recognize. On the other hand, as shown in FIG. 4 (B), in the cathode catalyst of Example 3, the amount of the Pd catalyst carried by the CNTs hardly changed from the initial state (see FIG. 4 (A)). It can be seen that elution of the Pd catalyst is suppressed by the SiO 2 component partially covering the Pd catalyst.
（燃料電池の活性化についての評価）
実施例３の燃料電池を用いて、活性化処理による発電性能の変化を評価した。具体的には、表２に示すように、活性化サイクル数を変化させて、出力電圧０．７Ｖにおける初期電流（ｍＡ／ｃｍ２)およびＯＣＶ（Ｖ）を測定した。活性化サイクルの条件を以下に示す。
・アノードに供給するガス：Ｈ２、流量１００ｍｌ／分
・カソードに供給するガス：Ｎ２、流量１００ｍｌ／分
・セル温度：７０℃
・アノード側バブラー温度：７０℃
・カソード側バブラー温度：７０℃
・カソード電位：１サイクル（０．０５Ｖ→１．２０Ｖ→０．０５Ｖ、５００ｍＶ／ｓ）
(Evaluation of fuel cell activation)
Using the fuel cell of Example 3, the change in power generation performance due to the activation treatment was evaluated. Specifically, as shown in Table 2, the number of activation cycles was changed, and the initial current (mA / cm 2 ) and OCV (V) at an output voltage of 0.7 V were measured. The conditions for the activation cycle are shown below.
Gas supplied to anode: H 2 , flow rate 100 ml / min Gas supplied to cathode: N 2 , flow rate 100 ml / min Cell temperature: 70 ° C.
・ Anode side bubbler temperature: 70 ℃
・ Coverer side bubbler temperature: 70 ℃
・ Cathode potential: 1 cycle (0.05V → 1.20V → 0.05V, 500mV / s)
本発明は、上述の実施の形態に限定されるものではなく、当業者の知識に基づいて各種の設計変更等の変形を加えることも可能であり、そのような変形が加えられた実施の形態も本発明の範囲に含まれうるものである。 The present invention is not limited to the above-described embodiments, and various modifications such as design changes can be added based on the knowledge of those skilled in the art. Embodiments to which such modifications are added Can also be included in the scope of the present invention.
例えば、上述の実施の形態では、カソード触媒層に、担体粒子に担持された触媒金属がＳｉＯ２成分で部分的に被覆された触媒複合体が用いられているが、当該触媒複合体をアノード触媒層に用いてもよい。 For example, in the above-described embodiment, a catalyst composite in which the catalyst metal supported on the carrier particles is partially coated with the SiO 2 component is used for the cathode catalyst layer. The catalyst composite is used as the anode catalyst. May be used for layers.
１０ 燃料電池、２０ 固体高分子電解質膜、２２ アノード、２４ カソード、２６ アノード触媒層、２８ アノードガス拡散層、３０ カソード触媒層、３２ カソードガス拡散層、５０ 膜電極接合体 DESCRIPTION OF SYMBOLS 10 Fuel cell, 20 Solid polymer electrolyte membrane, 22 Anode, 24 Cathode, 26 Anode catalyst layer, 28 Anode gas diffusion layer, 30 Cathode catalyst layer, 32 Cathode gas diffusion layer, 50 Membrane electrode assembly
Claims (9)
前記電解質膜の一方の面に設けられているカソード触媒層と、
前記電解質膜の一方の面に設けられているアノード触媒層と、
を備え、
前記カソード触媒層、前記アノード触媒層のうち、少なくとも一方の触媒層が、
Ｆｅ、Ｃｏ、Ｎｉ、Ｒｕ、Ｒｈ、Ｐｄ、Ａｇ、Ｒｅ、Ｏｓ、Ｉｒからなる群より選ばれる少なくとも１種以上の触媒金属と、
前記触媒金属を担持する導電性の担体粒子と、
前記触媒金属および前記担体粒子の周囲の少なくとも一部を被覆するＳｉＯ２成分と、
プロトン伝導性を有するイオノマーと、
を備え、
前記触媒層における、前記触媒金属、前記担体粒子およびＳｉＯ２成分の各質量を合計した基準質量に対するＳｉＯ２成分の含有量が１〜３０質量％であり、
前記触媒層の体積抵抗率が１〜３００Ω・ｃｍであることを特徴とする膜電極接合体。 An electrolyte membrane;
A cathode catalyst layer provided on one surface of the electrolyte membrane;
An anode catalyst layer provided on one surface of the electrolyte membrane;
With
At least one of the cathode catalyst layer and the anode catalyst layer is
At least one catalyst metal selected from the group consisting of Fe, Co, Ni, Ru, Rh, Pd, Ag, Re, Os, Ir;
Conductive carrier particles carrying the catalytic metal;
An SiO 2 component covering at least a part of the periphery of the catalyst metal and the support particles;
An ionomer having proton conductivity;
With
In the catalyst layer, the content of the SiO 2 component is 1 to 30% by mass with respect to a reference mass obtained by adding the masses of the catalyst metal, the carrier particles, and the SiO 2 component,
A membrane electrode assembly, wherein the catalyst layer has a volume resistivity of 1 to 300 Ω · cm.
前記カソード触媒層に酸化剤を供給するための酸化剤流路を有するカソード側セパレータと、
前記アノード触媒層に燃料を供給するための燃料流路を有するアノード側セパレータと、
を備えることを特徴とする燃料電池。 A membrane electrode assembly according to any one of claims 1 to 7,
A cathode separator having an oxidant flow path for supplying an oxidant to the cathode catalyst layer;
An anode separator having a fuel flow path for supplying fuel to the anode catalyst layer;
A fuel cell comprising:
前記アノード触媒層に燃料を供給し、前記カソード触媒層に不活性ガスを供給した状態で、前記カソード触媒層の電位を０．０５〜０．９Ｖから１．０〜１．４Ｖに上昇させた後、０．０５〜０．９Ｖに戻す過程を初期状態において３０〜３００００回繰り返すことを特徴とする燃料電池の活性化方法。 The method for activating a fuel cell according to claim 8, wherein the cathode catalyst layer includes the catalyst metal, the support particles, and a SiO 2 component.
With the fuel supplied to the anode catalyst layer and the inert gas supplied to the cathode catalyst layer, the potential of the cathode catalyst layer was increased from 0.05 to 0.9 V to 1.0 to 1.4 V. Thereafter, the process of returning to 0.05 to 0.9 V is repeated 30 to 30000 times in the initial state.
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| JP5481297B2 (en) * | 2010-07-16 | 2014-04-23 | Ｊｘ日鉱日石エネルギー株式会社 | Membrane electrode assembly and fuel cell |
| WO2013064640A1 (en) * | 2011-11-04 | 2013-05-10 | Solvicore Gmbh & Co. Kg | Method for the preparation of catalyst-coated membranes |
| JP5956312B2 (en) * | 2012-11-09 | 2016-07-27 | Ｊｘエネルギー株式会社 | Electrode material, membrane electrode assembly, fuel cell stack, and method for producing electrode material |
| JP6086809B2 (en) * | 2013-05-08 | 2017-03-01 | Ｊｘエネルギー株式会社 | Electrode material, membrane electrode assembly, fuel cell stack, and method for producing electrode material |
| WO2015182138A1 (en) * | 2014-05-30 | 2015-12-03 | 日本ゼオン株式会社 | Redox catalyst, electrode material, electrode, membrane electrode assembly for fuel cells, and fuel cell |
| KR20230078519A (en) * | 2021-11-26 | 2023-06-02 | 코오롱인더스트리 주식회사 | Membrane-electrode assembly for fuel cell comprising linear porous silica nanoparticles and fuel cell comprising the same |
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| JPH09167620A (en) * | 1995-12-15 | 1997-06-24 | Toshiba Corp | Electrode catalyst for fuel cell and its manufacture, and electrode and fuel cell using the catalyst |
| US6399231B1 (en) * | 2000-06-22 | 2002-06-04 | Utc Fuel Cells, Llc | Method and apparatus for regenerating the performance of a PEM fuel cell |
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| JP2007273460A (en) * | 2006-03-10 | 2007-10-18 | Sanyo Electric Co Ltd | Activation method of fuel cell, fuel battery cell or membrane electrode assembly for fuel cell activated, cell stack or fuel cell having them, and fuel cell activation device |
| JP5294235B2 (en) * | 2006-05-25 | 2013-09-18 | 日産自動車株式会社 | Electrode material |
| JP2008204799A (en) * | 2007-02-20 | 2008-09-04 | Toyota Motor Corp | Activation method of solid-state polymer type fuel cell |
| JP2009048826A (en) * | 2007-08-17 | 2009-03-05 | Takeshi Takenaka | Electrode material for fuel cell and manufacturing method thereof, electrode for fuel cell, and fuel cell |
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| JP2010027512A (en) * | 2008-07-23 | 2010-02-04 | Toyota Motor Corp | Manufacturing method for membrane-electrode assembly of solid polymer fuel cell, membrane-electrode assembly of solid polymer fuel cell, and solid polymer fuel cell |
| JP5332429B2 (en) * | 2008-09-11 | 2013-11-06 | 日産自動車株式会社 | Electrocatalyst |
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