JP7228921B2 - Method for manufacturing electrode structure - Google Patents
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- 238000004519 manufacturing process Methods 0.000 title claims description 19
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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
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Description
本発明は、固体高分子形燃料電池等の電極部材として使用される電極構造体及びその製造方法、並びに当該電極構造体を含む膜電極接合体に関する。 TECHNICAL FIELD The present invention relates to an electrode structure used as an electrode member for polymer electrolyte fuel cells and the like, a method for manufacturing the same, and a membrane electrode assembly including the electrode structure.
燃料電池は、水素の持つ化学エネルギーを効率よく電気エネルギーに変換できるため、燃料電池を利用した発電システムの普及が期待されている。燃料電池の中でも、特に電解質に固体高分子膜を使用した固体高分子形燃料電池（ＰＥＦＣ）は、例えば、車載用電源、家庭用等の小規模な固定電源として導入されている。固体高分子形燃料電池では、以下の電気化学反応によって電力を取り出すことができる。
アノ－ド反応：２Ｈ2 → ４Ｈ+＋４ｅ- （反応１）
カソ－ド反応：Ｏ2＋４Ｈ+＋４ｅ-→２Ｈ2Ｏ （反応２）
全反応 ：２Ｈ2＋Ｏ2→２Ｈ2Ｏ
Since fuel cells can efficiently convert the chemical energy of hydrogen into electrical energy, power generation systems using fuel cells are expected to spread. Among fuel cells, a polymer electrolyte fuel cell (PEFC), which uses a solid polymer membrane as an electrolyte, has been introduced as a small-scale fixed power source for, for example, vehicle-mounted power sources and household use. In polymer electrolyte fuel cells, electric power can be extracted by the following electrochemical reactions.
Anode reaction: 2H 2 → 4H + +4e - (Reaction 1)
Cathode reaction: O 2 +4H + +4e − →2H 2 O (reaction 2)
Total reaction: 2H2 + O2 → 2H2O
ＰＥＦＣは、電解質膜と前記電解質膜の両面に積層された電極（アノード及びカソード）とを含む膜電極接合体（ＭＥＡ）と、前記膜電極接合体の両面に積層されたガス拡散層（ＧＤＬ）とからなる発電モジュールを、ガス流路が形成された２つのセパレータで挟んだ構造のセルを基本単位として構成されている。ＰＥＦＣの構成部材は、一般的に、セパレータは金属材料で形成されており、ガス拡散層は多孔質の炭素材料が使用されている。
また、電極触媒層（アノード及びカソード）は、担体の表面にＰｔ等の貴金属微粒子が担持された構造を有し、担体には一般的に炭素材料が使用されている（例えば、特許文献１，２）。
A PEFC consists of a membrane electrode assembly (MEA) including an electrolyte membrane and electrodes (anode and cathode) laminated on both sides of the electrolyte membrane, and a gas diffusion layer (GDL) laminated on both sides of the membrane electrode assembly. The basic unit is a cell having a structure in which a power generation module composed of is sandwiched between two separators having a gas flow path. As for the constituent members of the PEFC, the separator is generally made of a metal material, and the gas diffusion layer is made of a porous carbon material.
Further, the electrode catalyst layer (anode and cathode) has a structure in which noble metal fine particles such as Pt are supported on the surface of a carrier, and a carbon material is generally used for the carrier (for example,
一方、ＰＥＦＣの膜電極接合体（ＭＥＡ）の電解質膜で使用されるナフィオン（Nafion）は酸性（ｐＨ＝０～３）であるため、ＰＥＦＣの電極材料は超強酸性条件で使用されることになる。また、通常運転しているときのセル電圧は０．４～１．０Ｖであるが、起動停止時にはセル電圧が１．５Ｖまで上昇するため、カソードでは、炭素系担体が電気化学的に酸化されてＣＯ2に分解する反応が起こり、炭素系担体が腐食されて触媒活性成分である貴金属粒子が脱落するという問題があり、アノードにおいても運転初期などに燃料ガスが不足すると、その部分での電圧低下、あるいは濃度分極が生じて局部的に通常と反対の電位となり、炭素系担体の電気化学的酸化分解反応が起こることがある。
上述した炭素系担体の腐食の問題に対し、本発明者らは担体として、強酸性条件、高電位においても安定な電子伝導性酸化物（例えば、酸化スズ）を使用し、これに選択的に電極触媒を担持した電極触媒材料を開発している（特許文献３，４）。
On the other hand, since Nafion, which is used in the electrolyte membrane of PEFC's membrane electrode assembly (MEA), is acidic (pH = 0 to 3), PEFC's electrode material is used under extremely acidic conditions. Become. In addition, the cell voltage during normal operation is 0.4 to 1.0 V, but the cell voltage rises to 1.5 V when starting and stopping, so the carbon-based support is electrochemically oxidized at the cathode. There is a problem that the carbon - based support is corroded and the precious metal particles, which are catalytically active components, fall off. A decrease or concentration polarization may occur, resulting in a local potential opposite to the normal potential, and an electrochemical oxidative decomposition reaction of the carbonaceous support may occur.
In order to solve the problem of corrosion of the carbon-based support described above, the present inventors use an electronically conductive oxide (for example, tin oxide) that is stable even under strongly acidic conditions and at high potentials as the support, and selectively An electrode catalyst material supporting an electrode catalyst is being developed (Patent Documents 3 and 4).
一方、上述のように、ＰＥＦＣの構成部材には、金属材料（セパレータ）や炭素材料（ガス拡散層、電極触媒層）、酸化物材料（電極触媒層）が用いられているが、電子伝導率は一般に、金属材料＞炭素材料＞酸化物材料の関係にある。そして、セパレータや、ガス拡散層、電極触媒層は異なる材料が用いられているため、それぞれの構成部材間における接触抵抗も生じ、ＰＥＦＣの性能を低下させる一因になっていた。 On the other hand, as described above, metal materials (separators), carbon materials (gas diffusion layers, electrode catalyst layers), and oxide materials (electrode catalyst layers) are used for the constituent members of PEFC. generally have a relationship of metal material>carbon material>oxide material. In addition, since different materials are used for the separator, the gas diffusion layer, and the electrode catalyst layer, contact resistance is generated between the constituent members, which has been a factor in lowering the performance of the PEFC.
伝統的に炭素材料が使用されてきた電極触媒層－ガス拡散層の導電パスを酸化物材料や炭素材料からより導電性の高い金属材料にすることで電気抵抗要因をさらに低減できる可能性がある。しかしながら、上述の通り、ＰＥＦＣにおいて、膜電極接合体（ＭＥＡ）に用いられるナフィオンは超強酸性であり、また、ＰＥＦＣでは起動停止時等に高電位にさらされるため、炭素材料の腐食の問題がある。
また、担体として安定な電子伝導性の酸化物材料を使用した、特許文献３，４の電極触媒も導電補助材として炭素材料を使用するため、炭素材料の腐食の問題を完全には解決できない。また、電極触媒層において酸化物材料（電子伝導性酸化物担体）を使用すると、電極触媒層の電気抵抗が炭素系担体を使用した場合より高くなる傾向という課題があった。また、ＰＥＦＣと同様の固体高分子膜を使用した水電解装置に使用される電極やその構成部材においても、上述のＰＥＦＣと同様の課題があった。
There is a possibility that the electrical resistance factor can be further reduced by changing the conductive path between the electrode catalyst layer and the gas diffusion layer, which has traditionally been made of carbon materials, to metal materials with higher conductivity than oxide materials or carbon materials. . However, as mentioned above, Nafion used in the membrane electrode assembly (MEA) in PEFC is an ultra-strong acid, and PEFC is exposed to high potential at the time of starting and stopping, etc., so there is a problem of corrosion of carbon materials. be.
In addition, the electrode catalysts of Patent Documents 3 and 4, which use a stable electronically conductive oxide material as a carrier, also use a carbon material as a conductive auxiliary material, so the problem of corrosion of the carbon material cannot be completely solved. Moreover, when an oxide material (electron conductive oxide support) is used in the electrode catalyst layer, there is a problem that the electrical resistance of the electrode catalyst layer tends to be higher than when a carbon-based support is used. Further, the electrodes and their constituent members used in a water electrolysis device using a solid polymer membrane similar to PEFC have the same problems as those of PEFC.
かかる状況下、本発明の目的は、炭素材料を使用せず、電極触媒層の導電性に優れ、かつ、腐食劣化が生じない電極構造体及びその製造方法、並びに電極構造体を使用した膜電解質接合体を提供することである。 Under such circumstances, an object of the present invention is to provide an electrode structure that does not use a carbon material, has an electrode catalyst layer with excellent conductivity, and does not cause corrosion deterioration, a method for manufacturing the same, and a membrane electrolyte using the electrode structure. It is to provide a zygote.
本発明者は、上記課題を解決すべく鋭意研究を重ねた結果、下記の発明が上記目的に合致することを見出し、本発明に至った。 As a result of earnest research to solve the above problems, the inventors of the present invention have found that the following inventions meet the above objects, and have completed the present invention.
すなわち、本発明は、以下の発明に係るものである。
＜１＞ 金属チタンまたはチタン合金からなる多孔体基材シートと、前記多孔体基材シートに直接または前記多孔体基材の表面のＴｉ酸化物層を介して担持された電極触媒と、を有し、前記多孔体基材シートが、金属チタンまたはチタン合金からなる粒子の焼結体である電極構造体。
＜２＞ 前記電極触媒の少なくとも一部が、前記多孔体基材シートを構成する金属チタンまたはチタン合金に直接接触している前記＜１＞に記載の電極構造体。
＜３＞ 前記電極触媒が、貴金属触媒である前記＜１＞または＜２＞に記載の電極構造体。
＜４＞ 前記電極触媒の形状が、粒子状である前記＜１＞から＜３＞のいずれかに記載の電極構造体。
＜５＞ 前記電極触媒の形状が、島状及び膜状のいずれか１種以上である前記＜１＞から＜３＞のいずれかに記載の電極構造体。
That is, the present invention relates to the following inventions.
<1> A porous substrate sheet made of metallic titanium or a titanium alloy, and an electrode catalyst supported directly on the porous substrate sheet or via a Ti oxide layer on the surface of the porous substrate. and the porous substrate sheet is a sintered body of particles made of titanium metal or a titanium alloy.
<2> The electrode structure according to <1>, wherein at least part of the electrode catalyst is in direct contact with the titanium metal or titanium alloy forming the porous substrate sheet.
<3> The electrode structure according to <1> or <2>, wherein the electrode catalyst is a noble metal catalyst.
<4> The electrode structure according to any one of <1> to <3>, wherein the shape of the electrode catalyst is particulate.
<5> The electrode structure according to any one of <1> to <3>, wherein the shape of the electrode catalyst is one or more of an island shape and a film shape.
＜６＞ 固体高分子電解質膜と、前記固体高分子電解質膜の一方面に接合されたカソードと、前記固体高分子電解質膜の他方面に接合されたアノードと、を有する膜電極接合体であって、
前記カソードとアノードの少なくとも一方として、前記＜１＞から＜５＞のいずれかに記載の電極構造体を用いてなることを特徴とする膜電極接合体。
<6> A membrane electrode assembly comprising a solid polymer electrolyte membrane, a cathode joined to one surface of the solid polymer electrolyte membrane, and an anode joined to the other surface of the solid polymer electrolyte membrane. hand,
A membrane electrode assembly using the electrode structure according to any one of <1> to <5> as at least one of the cathode and the anode.
＜７＞ 前記＜６＞に記載の膜電極接合体を備えてなる固体高分子形燃料電池。
＜８＞ 前記＜６＞に記載の膜電極接合体を備えてなる固体高分子形水電解装置。
<7> A polymer electrolyte fuel cell comprising the membrane electrode assembly according to <6>.
<8> A polymer electrolyte water electrolysis device comprising the membrane electrode assembly according to <6>.
＜９＞ 前記＜１＞から＜５＞のいずれかに記載の電極構造体の製造方法であって、金属チタンまたはチタン合金からなる多孔体基材シートに、電極触媒を担持する工程（Ａ）を有することを特徴とする電極構造体の製造方法。
＜１０＞ 電極触媒を担持する方法が、アークプラズマ蒸着法である前記＜９＞に記載の電極構造体の製造方法。
＜１１＞ 工程（Ａ）の前に金属チタンまたはチタン合金からなる多孔体基材シートを、アルカリエッチング処理したのちに酸洗浄し、さらに熱処理を施す前記＜９＞または＜１０＞に記載の電極構造体の製造方法。
＜１２＞ 酸化雰囲気下で熱処理を行う前記＜１１＞に記載の電極構造体の製造方法。
＜１３＞ 還元雰囲気下で熱処理を行う前記＜１１＞に記載の電極構造体の製造方法。
<9> The method for producing an electrode structure according to any one of <1> to <5>, wherein the step (A) of supporting an electrode catalyst on a porous substrate sheet made of metallic titanium or a titanium alloy. A method for manufacturing an electrode structure, comprising:
<10> The method for producing an electrode structure according to <9>, wherein the method for supporting the electrode catalyst is an arc plasma deposition method.
<11> The electrode according to <9> or <10> above, wherein the porous substrate sheet made of titanium metal or a titanium alloy is subjected to alkali etching treatment, followed by acid washing and heat treatment before the step (A). A method of manufacturing a structure.
<12> The method for producing an electrode structure according to <11>, wherein the heat treatment is performed in an oxidizing atmosphere.
<13> The method for producing an electrode structure according to <11>, wherein the heat treatment is performed in a reducing atmosphere.
本発明の電極構造体は、電極触媒層の導電パスが熱力学的に安定な金属チタンまたはチタン合金からなる多孔体基材シートによって形成されているため、電極触媒層の導電性に優れ、かつ、炭素材料を用いた場合に生じる腐食劣化が生じない。当該電極構造体を用いた膜電極接合体を形成することにより、耐久性に優れ導電性・集電性が向上した膜電極接合体が提供される。 In the electrode structure of the present invention, the conductive path of the electrode catalyst layer is formed of a porous substrate sheet made of thermodynamically stable metal titanium or titanium alloy, so that the electrode catalyst layer has excellent conductivity, and , corrosion degradation that occurs when carbon materials are used does not occur. By forming a membrane electrode assembly using the electrode structure, a membrane electrode assembly having excellent durability and improved electrical conductivity and current collecting properties is provided.
以下、本発明について例示物等を示して詳細に説明するが、本発明は以下の例示物等に限定されるものではなく、本発明の要旨を逸脱しない範囲において任意に変更して実施できる。 Hereinafter, the present invention will be described in detail with reference to examples, etc., but the present invention is not limited to the following examples, etc., and can be arbitrarily modified without departing from the scope of the present invention.
＜１．電極構造体＞
本発明は、金属チタンまたはチタン合金からなる多孔体基材シートと、前記多孔体基材シートに直接または前記多孔体基材シートの表面に形成したＴｉ酸化物層を介して担持された電極触媒と、を有する電極構造体（以下、「本発明の電極構造体」と称す場合がある。）に関する。
本明細書において「電極構造体」は、「電極触媒層」そのものである場合と、「電極触媒層とガス拡散層（ＧＤＬ）とが一体化した電極触媒層/ＧＤＬ一体シートである場合がある。
本発明において「電極構造体」が「電極触媒層」そのものである場合には他のＧＤＬと組み合わせて用いられ、電極触媒層/ＧＤＬ一体シートの場合には他のＧＤＬを必要としない。
<1. Electrode structure>
The present invention provides a porous substrate sheet made of metallic titanium or a titanium alloy, and an electrode catalyst supported directly on the porous substrate sheet or via a Ti oxide layer formed on the surface of the porous substrate sheet. and an electrode structure (hereinafter sometimes referred to as "the electrode structure of the present invention").
In the present specification, the "electrode structure" may be the "electrode catalyst layer" itself, or may be an integrated sheet of the electrode catalyst layer and the gas diffusion layer (GDL) in which the electrode catalyst layer and the gas diffusion layer (GDL) are integrated. .
In the present invention, when the "electrode structure" is the "electrode catalyst layer" itself, it is used in combination with another GDL, and in the case of the electrode catalyst layer/GDL integrated sheet, no other GDL is required.
本発明の電極構造体は、燃料電池、特には固体高分子形燃料電池（ＰＥＦＣ）の電極部材として好適に用いられる。以下、固体高分子形燃料電池の構成について説明するが、本発明の電極構造体は、燃料電池以外の電極部材（例えば、固体高分子形水電解装置の電極部材）としても使用することが可能である。 The electrode structure of the present invention is suitably used as an electrode member for a fuel cell, particularly a polymer electrolyte fuel cell (PEFC). The structure of a polymer electrolyte fuel cell will be described below, but the electrode structure of the present invention can also be used as an electrode member for a polymer electrolyte fuel cell other than a fuel cell (for example, an electrode member for a polymer electrolyte water electrolysis device). is.
図１は固体高分子形燃料電池の代表的な構成を示す概念図である。固体高分子形燃料電池においてアノードには水素が供給され、（反応１）２Ｈ2 → ４Ｈ+＋４ｅ-によって、生成したプロトン（Ｈ+）は固体高分子電解質膜を介してカソードに供給され、また、生成した電子は外部回路（図示せず）を介してカソードへ供給され、（反応２）Ｏ2＋４Ｈ+＋４ｅ-→２Ｈ2Ｏによって、酸素と反応して水を生成する。このアノードとカソードの電気化学反応によって両電極間に電位差を発生させる。 FIG. 1 is a conceptual diagram showing a typical configuration of a polymer electrolyte fuel cell. Hydrogen is supplied to the anode in the polymer electrolyte fuel cell, and protons (H + ) generated by (reaction 1) 2H 2 →4H + +4e − are supplied to the cathode through the solid polymer electrolyte membrane, and , the generated electrons are supplied to the cathode through an external circuit (not shown), and (reaction 2) O 2 +4H + +4e − →2H 2 O react with oxygen to produce water. A potential difference is generated between the two electrodes by the electrochemical reaction between the anode and the cathode.
本発明に係る固体高分子形燃料電池において、アノード及びカソードの少なくとも一方に、本発明の電極構造体を用いていることに特徴がある。なお、本明細書においては、電極（アノード及びカソード）は、「電極触媒層」である場合と、「電極触媒層及びガス拡散層（ＧＤＬ）」である場合とを含む概念とする。 The polymer electrolyte fuel cell according to the present invention is characterized in that the electrode structure of the present invention is used for at least one of the anode and the cathode. In this specification, the concept of the electrodes (anode and cathode) includes the case of being an "electrode catalyst layer" and the case of being an "electrode catalyst layer and gas diffusion layer (GDL)".
電極（アノード及びカソード）以外の構成要素は、公知の固体高分子形燃料電池と同様であるため、詳細な説明を省略する。実際には、本発明の固体高分子形燃料電池（単セル）が発電性能に応じた基数だけ積層された燃料電池スタックが形成され、ガス供給装置、冷却装置などその他付随する装置を組み立てることにより使用される。 Components other than the electrodes (anode and cathode) are the same as those of known polymer electrolyte fuel cells, so detailed descriptions thereof are omitted. In practice, a fuel cell stack is formed in which polymer electrolyte fuel cells (single cells) of the present invention are stacked in a number corresponding to the power generation performance, and a gas supply device, a cooling device, and other accompanying devices are assembled. used.
以下、本発明の電極構造体の構成要素を詳細に説明する。なお、以下の説明において、「金属チタンまたはチタン合金からなる多孔体基材シート」を、「多孔体基材シート」と記載する。 The constituent elements of the electrode structure of the present invention are described in detail below. In the following description, "a porous substrate sheet made of metallic titanium or a titanium alloy" is referred to as a "porous substrate sheet".
１－１．多孔体基材シート
本発明の電極構造体は、基材である多孔体基材シートが、金属チタンまたはチタン合金で構成されるため、電極触媒層における電気抵抗が大幅に低減され（酸化物担体に対する利点）、また、チタンまたはチタン合金は化学的安定性に優れ、ＰＥＦＣ運転条件の電位においても安定であるため、担持された電極触媒の脱落が生じない（炭素系担体に対する利点）。
なお、本発明において、「チタン合金」とは「Ｔｉを４０モル％以上含む合金」を意味する。Ｔｉと合金化させる金属は、本発明の目的を損なわない限り、特に限定されない。
1-1. Porous Substrate Sheet In the electrode structure of the present invention, the porous substrate sheet, which is the substrate, is composed of metallic titanium or a titanium alloy. Also, since titanium or titanium alloys have excellent chemical stability and are stable even at the potential of PEFC operating conditions, the supported electrocatalyst does not fall off (advantage over carbon-based supports).
In the present invention, "titanium alloy" means "an alloy containing 40 mol% or more of Ti". The metal to be alloyed with Ti is not particularly limited as long as it does not impair the purpose of the present invention.
本発明の電極構造体において、多孔体基材シートは、金属チタンまたはチタン合金で構成される。多孔体基材シートの構成要素の金属チタンまたはチタン合金はシート全体で導電性を有する程度に接触していればよくその形状は任意であるが、具体的には以下に説明するチタン粒子焼結体やチタン繊維集合体が挙げられる。 In the electrode structure of the present invention, the porous substrate sheet is composed of metallic titanium or a titanium alloy. The metal titanium or titanium alloy, which is a component of the porous substrate sheet, may be in contact with the whole sheet to the extent that it has conductivity, and the shape is arbitrary. Specifically, titanium particles are sintered as described below and titanium fiber aggregates.
チタン粒子焼結体は、金属チタンまたはチタン合金からなる粒子の焼結体（チタン粒子焼結体」と称す。）である。なお、本明細書において多孔体基材シートにチタン粒子焼結体を使用し、これに電極触媒を担持した電極構造体を、本願発明の電極構造体（第１の態様）と称す場合がある。
チタン粒子焼結体を構成するチタン粒子の大きさは、それぞれの粒子が接触して導電パスを形成し、連通孔を有しており、ガス透過可能な空隙率を有する限り任意であるが、通常、数μｍ～数十μｍの粒子が使用される。
チタン粒子焼結体の場合、機械的強度を保ち、ガス透過可能とする空隙率は４０％程度である。具体的なチタン粒子焼結体の例は、実施例にて開示する。
A sintered body of titanium particles is a sintered body of particles made of titanium metal or a titanium alloy (referred to as a sintered body of titanium particles). In this specification, an electrode structure in which a titanium particle sintered body is used as a porous substrate sheet and an electrode catalyst is supported thereon may be referred to as an electrode structure (first embodiment) of the present invention. .
The size of the titanium particles constituting the titanium particle sintered body is arbitrary as long as the respective particles contact each other to form a conductive path, have communicating pores, and have a gas permeable porosity. Particles of several μm to several tens of μm are usually used.
In the case of a titanium particle sintered body, the porosity that maintains the mechanical strength and allows gas permeability is about 40%. Specific examples of titanium particle sintered bodies are disclosed in Examples.
多孔体基材シートとしてチタン粒子焼結体を使用する場合には、図２に示すように本発明の電極構造体（第１の態様）を電極触媒層とし、よりガス拡散性に優れるガス拡散層（ＧＤＬ）と組み合わせて電極（アノード又はカソード）とすることが好ましい。
この場合、ＧＤＬには、金属系ＧＤＬを用いると、電極触媒層（本発明の電極構造体）を構成する多孔体基材シートとＧＤＬの導電パスがすべて金属材料となるので、電極としての導電性に優れる。金属系ＧＤＬとしてはＰＥＦＣ運転条件で熱力学的に安定なＴｉやＴｉ合金のＧＤＬが好ましく使用できる。後述するチタン繊維集合体をＧＤＬに使用してもよい。
When a titanium particle sintered body is used as the porous base material sheet, the electrode structure (first embodiment) of the present invention is used as an electrode catalyst layer as shown in FIG. It is preferably combined with the layer (GDL) into an electrode (anode or cathode).
In this case, if a metal-based GDL is used for the GDL, the conductive path of the GDL and the porous substrate sheet constituting the electrode catalyst layer (electrode structure of the present invention) are all made of a metal material. Excellent in nature. As the metallic GDL, a Ti or Ti alloy GDL which is thermodynamically stable under PEFC operating conditions can be preferably used. You may use the titanium fiber assembly mentioned later for GDL.
なお、コスト等とのバランスから、カーボンペーパー等の公知の炭素系ＧＤＬを選択する場合もある。炭素系ＧＤＬとしては、例えば、基材層及び前記基材層の片面に形成されたマイクロポーラス層を有するＧＤＬが挙げられる。 It should be noted that a known carbon-based GDL such as carbon paper may be selected in consideration of cost and the like. Carbon-based GDLs include, for example, GDLs having a substrate layer and a microporous layer formed on one side of the substrate layer.
ＧＤＬと組み合わせる場合、本発明の電極構造体（多孔体基材シート）の厚みは、担持される電極触媒の種類や担持量にもよるが、通常、１０～１００μｍ程度である。 When combined with GDL, the thickness of the electrode structure (porous substrate sheet) of the present invention is usually about 10 to 100 μm, depending on the type and amount of supported electrode catalyst.
チタン繊維集合体は、多孔体基材シートが金属チタンまたはチタン合金からなる繊維の集合体である。なお、本明細書において多孔体基材シートにチタン繊維集合体を使用し、これに電極触媒を担持した電極構造体を、本願発明の電極構造体（第２の態様）と称す場合がある。チタン繊維集合体は、金属チタンまたはチタン合金からなる繊維が絡み合い、それぞれが電気的に接続している構造体であり、チタン繊維を焼結したり、圧着して形成することができる。チタン繊維集合体におけるチタン繊維の長さや太さは任意である。具体的なチタン繊維集合体の例は、実施例にて開示する。 A titanium fiber aggregate is an aggregate of fibers whose porous substrate sheet is made of metallic titanium or a titanium alloy. In this specification, an electrode structure in which a titanium fiber assembly is used for a porous substrate sheet and an electrode catalyst is supported thereon may be referred to as an electrode structure (second aspect) of the present invention. A titanium fiber aggregate is a structure in which fibers made of titanium metal or a titanium alloy are entangled and electrically connected to each other, and can be formed by sintering or crimping titanium fibers. The length and thickness of the titanium fibers in the titanium fiber assembly are arbitrary. Examples of specific titanium fiber aggregates are disclosed in Examples.
チタン繊維集合体に電極触媒を担持させることで、本願発明の電極構造体（第２の態様）とすることができるが、チタン繊維集合体は、上述したチタン粒子焼結体と比較して空隙率が大きいため（７０％程度）、チタン繊維集合体そのものをＧＤＬとして使用することができる。
そのため、図３に示すようにチタン繊維集合体の一方の面側に電極触媒を担持させて、当該一方の面側を電極触媒層とし、反対の面側をガス拡散層とする構成とすることにより、電極触媒層／ガス拡散層が一体化したシート部材（電極触媒層／ガス拡散層一体シート）とすることができる。
すなわち、本発明の電極触媒層／ガス拡散層一体シートの好適な態様は、前記多孔体基材シートを構成する繊維状の金属チタンまたはチタン合金の集合体の一方の面側から所定の厚みまで電極触媒を担持させて電極触媒層とし、当該多孔体基材シートにおける電極触媒層以外の部分をガス拡散層とする構成を有することを特徴とする。
このような電極触媒層／ガス拡散層一体シートでは、電極触媒層及びガス拡散層の導電パスが、同一のチタン繊維集合体からなり、異なる部材の電極触媒層とガス拡散層を使用した場合に生じる電気抵抗が生じないため、電極に起因する電気抵抗を小さくすることができ、ＭＥＡ内における導電性、集電性をさらに向上させることができる。
An electrode structure (second aspect) of the present invention can be obtained by supporting an electrode catalyst on a titanium fiber aggregate. Since the ratio is large (about 70%), the titanium fiber assembly itself can be used as the GDL.
Therefore, as shown in FIG. 3, an electrode catalyst is supported on one side of the titanium fiber assembly, and the one side is used as an electrode catalyst layer, and the opposite side is used as a gas diffusion layer. Thus, a sheet member in which the electrode catalyst layer/gas diffusion layer are integrated (electrode catalyst layer/gas diffusion layer integrated sheet) can be obtained.
That is, in a preferred embodiment of the electrode catalyst layer/gas diffusion layer integrated sheet of the present invention, the aggregate of fibrous titanium metal or titanium alloy forming the porous base sheet is formed from one side to a predetermined thickness. It is characterized by having a configuration in which an electrode catalyst is supported to form an electrode catalyst layer, and a portion of the porous substrate sheet other than the electrode catalyst layer is used as a gas diffusion layer.
In such an electrode catalyst layer/gas diffusion layer integrated sheet, the conductive paths of the electrode catalyst layer and the gas diffusion layer are made of the same titanium fiber assembly, and when the electrode catalyst layer and the gas diffusion layer of different members are used, Since no electrical resistance occurs, the electrical resistance caused by the electrodes can be reduced, and the electrical conductivity and current collection in the MEA can be further improved.
電極触媒層／ガス拡散層が一体化したシート部材における電極触媒層の厚みは、チタン繊維集合体を構成する繊維状の金属チタンまたはチタン合金の径や長さ、チタン繊維集合体の空隙率、担持される電極触媒の種類や量等、さらには対象となる用途等を考慮して、電極として実質的に機能できる範囲で決定される。
前記電極触媒層の厚みは、例えば、１０μｍ以上、３０μｍ以上、５０μｍ以上であり、また、これ以上の厚みであってもよい。但し、具体的には電極触媒層の厚みを厚くするほど、電極性能が向上するが内部に担持された電極触媒がうち、電極反応に寄与しない割合が増加するおそれがある。
The thickness of the electrode catalyst layer in the sheet member in which the electrode catalyst layer/gas diffusion layer is integrated depends on the diameter and length of the fibrous metal titanium or titanium alloy constituting the titanium fiber aggregate, the porosity of the titanium fiber aggregate, Considering the type and amount of the electrode catalyst to be supported, the target application, etc., it is determined within a range in which the electrode can substantially function.
The thickness of the electrode catalyst layer is, for example, 10 μm or more, 30 μm or more, or 50 μm or more, and may be greater than this. However, specifically, as the thickness of the electrode catalyst layer is increased, the electrode performance is improved, but there is a possibility that the percentage of the electrode catalyst supported inside that does not contribute to the electrode reaction increases.
また、チタン繊維集合体において、電極触媒層を形成する面側の繊維密度を、反対面側より大きくしてもよい。このように構成することにより、電極触媒層を形成する面側に電極触媒をより多く担持することができ、電極触媒層の厚みを低減させ、電極反応に寄与しない割合を低減させることができる。
電極触媒層を形成する面側の繊維密度を向上させるためには、チタン繊維集合体を構成する繊維状の金属チタンまたはチタン合金から小径の繊維を成長させる方法が挙げられる。また、チタン繊維集合体に金属チタンまたはチタン合金をスパッタして、粒子状のＴｉを形成しチタン繊維集合体の表面積を増加させてもよい。
Moreover, in the titanium fiber assembly, the fiber density on the surface forming the electrode catalyst layer may be higher than that on the opposite surface. With this configuration, more electrode catalyst can be supported on the side where the electrode catalyst layer is formed, the thickness of the electrode catalyst layer can be reduced, and the proportion not contributing to the electrode reaction can be reduced.
In order to improve the fiber density on the side forming the electrode catalyst layer, there is a method of growing small-diameter fibers from the fibrous titanium metal or titanium alloy that constitutes the titanium fiber aggregate. Alternatively, titanium metal or a titanium alloy may be sputtered onto the titanium fiber aggregate to form particulate Ti to increase the surface area of the titanium fiber aggregate.
また、電極触媒層／ガス拡散層一体シートでは多孔体基材シートにおける電極触媒層を形成した反対面側（すなわち、ＧＤＬ側）はセパレータと接触させて導通をとるが、ＧＤＬとセパレータ界面での抵抗を低減させるために、多孔体基材シートにおける電極触媒層を形成した反対面側（すなわち、ＧＤＬの表面側）に、導電補助材を固定化してもよい。
導電補助材は、ＧＤＬとセパレータ界面での抵抗を低減できる状態で多孔体基材シート（ＧＤＬ）の表面に固定化されていればよく、多孔体基材シート（ＧＤＬ）の表面に薄層として固定化されていてもよいし、多孔体基材シート（ＧＤＬ）の表面及び内部に粒子状や島状の形態で固定化されていてもよい。
導電補助材の材質としては、金（Ａｕ）やカーボン等が挙げられる。また、Ｐｔ等の電極触媒として使用される貴金属も使用できる。
In addition, in the electrode catalyst layer/gas diffusion layer integrated sheet, the opposite side of the porous substrate sheet on which the electrode catalyst layer is formed (that is, the GDL side) is brought into contact with the separator for conduction, but the interface between the GDL and the separator is in contact with the separator. In order to reduce the resistance, a conductive auxiliary material may be immobilized on the opposite side of the porous substrate sheet on which the electrode catalyst layer is formed (that is, the surface side of the GDL).
The conductive auxiliary material may be immobilized on the surface of the porous substrate sheet (GDL) in a state where the resistance at the interface between the GDL and the separator can be reduced. It may be immobilized, or it may be immobilized in the form of particles or islands on the surface and inside of the porous substrate sheet (GDL).
Gold (Au), carbon, or the like can be used as the material of the conductive auxiliary material. A noble metal used as an electrode catalyst such as Pt can also be used.
多孔体基材シートの構成材料であるチタンやチタン合金は、表面処理を行ってもよい。
適切な表面処理を行うことにより、表面積が大きくなり、より電極触媒の担持量を増加させることが可能となる。なお、表面処理の有無は、後述する電極触媒の担持方法と併せて適切な方法を選択すればよい。
Titanium and titanium alloys, which are constituent materials of the porous substrate sheet, may be subjected to surface treatment.
Appropriate surface treatment increases the surface area, making it possible to further increase the supported amount of the electrode catalyst. The presence or absence of surface treatment may be determined by selecting an appropriate method together with the method for supporting the electrode catalyst, which will be described later.
表面処理の具体的の方法は、実施例にて開示するが、以下に簡単に説明する。
まず、金属チタンまたはチタン合金からなる多孔体基材シートを、ＮａＯＨ等でアルカリエッチング処理して高表面積化した後、酸洗浄によってアルカリ成分を除去する。表面にはＴｉ水酸化物が形成されているので、熱処理によりＴｉ水酸化物からＴｉ酸化物と変化させると共に結晶性を向上させる。
A specific surface treatment method will be disclosed in Examples, but will be briefly described below.
First, a porous base material sheet made of metallic titanium or a titanium alloy is subjected to alkali etching treatment with NaOH or the like to increase the surface area, and then the alkaline component is removed by acid washing. Since Ti hydroxide is formed on the surface, heat treatment changes the Ti hydroxide to Ti oxide and improves the crystallinity.
この際、熱処理を酸化雰囲気下（例えば、空気雰囲気）で行うことにより、通常のＴｉＯ2より導電率が高いブロンズ型の酸化チタンが形成される。また、より膜厚の薄いＴｉ酸化物層が形成される点で、還元雰囲気下で熱処理を行ってもよい。 At this time, by performing the heat treatment in an oxidizing atmosphere (for example, an air atmosphere), bronze-type titanium oxide having a higher electrical conductivity than ordinary TiO 2 is formed. Further, the heat treatment may be performed in a reducing atmosphere in that a Ti oxide layer having a smaller thickness is formed.
熱処理の有無及び雰囲気は、後述する電極触媒の担持方法と併せて適切な方法を選択すればよい。 An appropriate method may be selected for the presence or absence of the heat treatment and the atmosphere together with the method for supporting the electrode catalyst, which will be described later.
また、形成されるチタン酸化物層にＴｉより価数が高い元素（Ｓｂ，Ｎｂ，Ｔａ，Ｗ，Ｉｎ，Ｖ，Ｃｒ，Ｍｎ，Ｍｏ等）をドープして、酸化チタンの電子導電性を高めることもできる。 Further, the formed titanium oxide layer is doped with an element having a higher valence than Ti (Sb, Nb, Ta, W, In, V, Cr, Mn, Mo, etc.) to increase the electronic conductivity of titanium oxide. can also
１－２．電極触媒
電極触媒は、電極触媒構造体の使用時に化学的に安定であり、酸素の還元（及び水素の酸化）に対する電気化学的触媒活性を有するものであれば、貴金属系触媒、非貴金属系触媒のいずれでもよい。
電極触媒として、好適には、Ｐｔ，Ｒｕ，Ｉｒ，Ｐｄ，Ｒｈ，Ｏｓ，Ａｕ，Ａｇ等の貴金属、及びこれらの貴金属を含む合金が挙げられる。なお、「貴金属を含む合金」とは「上記の貴金属のみからなる合金」と、「上記の貴金属とそれ以外の金属からなる合金で上記の貴金属を１０質量％以上含む合金」を含む。貴金属と合金化させる上記「それ以外の金属」は、特に限定されないが、Ｃｏ，Ｎｉ，Ｔｉ，Ｗ，Ｔａ，Ｎｂ，Ｓｎを好適な例として挙げることができ、これらを１種類あるいは２種類以上を使用してもよい。また、分相した状態で２種類以上の上記貴金属及び貴金属を含む合金を使用してもよい。なお、上記貴金属、及びこれらの貴金属を含む合金を以下、「電極触媒金属」と呼ぶ場合がある。
1-2. Electrocatalyst The electrocatalyst is chemically stable when the electrode catalyst structure is used, and has electrochemical catalytic activity for oxygen reduction (and hydrogen oxidation). Either
Preferred electrode catalysts include noble metals such as Pt, Ru, Ir, Pd, Rh, Os, Au and Ag, and alloys containing these noble metals. The term "alloy containing a noble metal" includes "alloy consisting only of the above noble metal" and "alloy consisting of the above noble metal and other metals and containing 10% by mass or more of the above noble metal". The above "other metals" to be alloyed with the noble metal are not particularly limited, but preferred examples include Co, Ni, Ti, W, Ta, Nb, and Sn, and one or more of these can be used. may be used. In addition, two or more of the noble metals and alloys containing the noble metals may be used in a phase-split state. The above noble metals and alloys containing these noble metals are hereinafter sometimes referred to as "electrode catalyst metals".
非貴金属系触媒としては、例えば、Ｔａ，Ｚｒ，Ｔｉの酸化物（ＴａＯx、ＺｒＯx、ＴｉＯx）、窒化物（ＴａＮx、ＺｒＮx、ＴｉＮx）、酸窒化物（ＴａＯxＮy、ＺｒＯxＮy、ＴｉＯxＮy）等が挙げられる（式中、ｘ、ｙは任意の数）。 Examples of non-precious metal catalysts include oxides of Ta, Zr, and Ti ( TaOx , ZrOx , TiOx ), nitrides (TaNx , ZrNx , TiNx ), oxynitrides ( TaOxNy , ZrO x N y , TiO x N y ) and the like (wherein x and y are arbitrary numbers).
本発明の電極構造体をＰＥＦＣの電極部材として使用する場合には電極触媒金属としてＰｔ及びＰｔを含む合金は、８０℃以上の温度域において、酸素の還元（及び水素の酸化）に対する電気化学的触媒活性に優れるため特に好適である。 When the electrode structure of the present invention is used as a PEFC electrode member, Pt and an alloy containing Pt as an electrode catalyst metal are electrochemically resistant to oxygen reduction (and hydrogen oxidation) in a temperature range of 80 ° C. or higher. It is particularly suitable for its excellent catalytic activity.
また、本発明の電極構造体を固体高分子形水電解装置の電極部材として使用する場合には電極触媒金属として水の電解活性に優れるＩｒやＩｒ合金、ＰｔやＰｔ合金が好適である。この場合、ＩｒやＩｒ合金、ＰｔやＰｔ合金は熱処理等によりＩｒ酸化物やＰｔ酸化物として用いてもよい。 When the electrode structure of the present invention is used as an electrode member of a solid polymer type water electrolysis device, Ir, Ir alloy, Pt, and Pt alloy, which are excellent in water electrolysis activity, are suitable as the electrode catalyst metal. In this case, Ir, Ir alloy, Pt, and Pt alloy may be used as Ir oxide or Pt oxide by heat treatment or the like.
また、電極触媒は、結晶に限定されず、目的とする電気化学的触媒活性を有する限り、非晶質であってよく、結晶と非晶質の混合体であってもよい。 Further, the electrode catalyst is not limited to crystals, and may be amorphous as long as it has the desired electrochemical catalytic activity, or may be a mixture of crystals and amorphous.
本発明の電極構造体において、電極触媒の形状は、特に制限されない。
電極触媒の形状の好適な態様の一つは、電極触媒の形状が粒子状であり、具体的な形状として球形、楕円形、多面体等が挙げられる。
粒子状の電極触媒の大きさは、小さいほど電気化学反応が進行する有効表面積が増加するため、電気化学的触媒活性が高くなる傾向がある。しかし、その大きさが小さすぎると、電気化学的反応活性が低下する。粒子状の電極触媒の大きさは、平均粒子径として１．５～１０ｎｍ以下、好ましくは１．５～５ｎｍである。
なお、本発明における「粒子状の電極触媒の平均粒径」は、電子顕微鏡像より調べられる粒子状の電極触媒（２０個）の粒子径の平均値により得ることができる。電子顕微鏡像による平均粒径算出時は、粒子の形状が、球形以外の場合は、粒子における最大長を示す方向の長さをその粒径とする。
In the electrode structure of the present invention, the shape of the electrode catalyst is not particularly limited.
One of the preferred forms of the shape of the electrode catalyst is that the shape of the electrode catalyst is particulate, and specific shapes include spherical, elliptical, polyhedral, and the like.
The smaller the size of the particulate electrode catalyst, the greater the effective surface area in which the electrochemical reaction proceeds, and thus the electrochemical catalytic activity tends to be higher. However, if the size is too small, the electrochemical reaction activity will decrease. The particle-like electrode catalyst has an average particle size of 1.5 to 10 nm or less, preferably 1.5 to 5 nm.
The "average particle size of the particulate electrode catalyst" in the present invention can be obtained from the average value of the particle sizes of the particulate electrode catalysts (20 particles) examined by an electron microscope image. When the average particle size is calculated from an electron microscope image, when the shape of the particles is other than spherical, the length in the direction of the maximum length of the particles is taken as the particle size.
また、電極触媒の形状の他の好適な態様は、粒子状の電極触媒が結合した状態であり、島状や膜状の状態が挙げられる。ここで、「島状」とは数個の粒子状の電極触媒が固まりになり、それぞれが分離した状態であり、「膜状」とは連続してつながり薄膜を形成した状態を意味する。
島状の電極触媒の大きさや、膜状の電極触媒の大きさ（広さ）や厚みは、十分な導電性と触媒活性を有する限り制限はない。
Another preferred form of the electrode catalyst is a state in which particulate electrode catalysts are bound together, such as an island-like or film-like state. Here, "island-like" means a state in which several particle-like electrode catalysts are aggregated and separated from each other, and "film-like" means a state in which they are continuously connected to form a thin film.
The size of the island-like electrode catalyst and the size (width) and thickness of the film-like electrode catalyst are not limited as long as they have sufficient conductivity and catalytic activity.
電極触媒の担持量は、使用用途、貴金属の種類、担体であるチタン多孔体シートの表面状態（酸化物の有無及び状態、比表面積等）等を考慮して適宜決定される。電極触媒の担持量が少なすぎると電極性能が不十分となり、多すぎると凝集して性能が低下する場合がある。例えば、燃料電池用電極材料の全重量に対して、好ましくは０．１～６０質量％、より好ましくは０．５～２０質量％とすると、単位質量あたりの触媒活性に優れ、担持量に応じた所望の電極反応活性を得ることができる。なお、電極触媒の担持量は、例えば、誘導結合プラズマ発光分析（ＩＣＰ）によって調べることができる。 The amount of the electrode catalyst to be supported is appropriately determined in consideration of the intended use, the type of noble metal, the surface state of the porous titanium sheet as the support (presence or absence and state of oxides, specific surface area, etc.). If the supported amount of the electrode catalyst is too small, the electrode performance will be insufficient, and if it is too large, the performance may deteriorate due to agglomeration. For example, with respect to the total weight of the fuel cell electrode material, preferably 0.1 to 60% by mass, more preferably 0.5 to 20% by mass, the catalyst activity per unit mass is excellent, and depending on the amount supported desired electrode reaction activity can be obtained. The supported amount of the electrode catalyst can be examined by, for example, inductively coupled plasma emission spectroscopy (ICP).
本発明の電極触媒多孔体シートの好適な態様は、多孔体基材シートが、表面にＴｉ酸化物層を有する場合において、電極触媒の少なくとも一部が、多孔体基材シートを構成する金属チタンまたはチタン合金に直接接触している態様である。
チタンまたはチタン合金からなる多孔体の最表面は酸素に触れると自然に酸化されるので、自己組織的にコアシェル構造（内部（コア）が金属Ｔｉ、表面（シェル）がＴｉ酸化物層）になる。Ｔｉ酸化物層は導電率が低く薄膜であっても電気抵抗が高い。
図４に示す模式図のように、多孔体基材シートを構成する金属チタンまたはチタン合金において、表面にＴｉ酸化物層を有する場合、電極触媒がＴｉ酸化物層を介して担持されると（図４左）、Ｔｉ酸化物層に起因する電気抵抗が生じるが、電極触媒の少なくとも一部が、多孔体基材シートを構成する金属チタンまたはチタン合金に直接接触して担持されていると（図４右）、金属―金属接合のため電子移動がスムーズに行われ、ひいては電極触媒層自体の電気抵抗が小さくなる。
なお、図４右では粒子状の電極触媒が多孔体基材シートを構成する金属チタンまたはチタン合金に直接接触している模式図を示したが、電極触媒の形状は島状や膜状であってもよい。
In a preferred embodiment of the electrode catalyst porous sheet of the present invention, when the porous substrate sheet has a Ti oxide layer on its surface, at least a part of the electrode catalyst is metallic titanium constituting the porous substrate sheet. Alternatively, it is in direct contact with the titanium alloy.
Since the outermost surface of a porous body made of titanium or a titanium alloy is naturally oxidized when it comes into contact with oxygen, it self-organizes into a core-shell structure (inside (core) is metal Ti and surface (shell) is a Ti oxide layer). . The Ti oxide layer has low electrical conductivity and high electrical resistance even if it is a thin film.
As shown in the schematic diagram of FIG. 4, when the metal titanium or titanium alloy constituting the porous substrate sheet has a Ti oxide layer on the surface, when the electrode catalyst is carried through the Ti oxide layer ( Fig. 4 left), electrical resistance is caused by the Ti oxide layer, but if at least part of the electrode catalyst is supported in direct contact with the metal titanium or titanium alloy that constitutes the porous substrate sheet ( Fig. 4 (right), metal-to-metal bonding facilitates smooth electron transfer, which in turn reduces the electrical resistance of the electrode catalyst layer itself.
Note that the right side of FIG. 4 shows a schematic diagram in which the particulate electrode catalyst is in direct contact with the metallic titanium or titanium alloy that constitutes the porous substrate sheet, but the shape of the electrode catalyst may be island-shaped or film-shaped. may
電極触媒の少なくとも一部が、多孔体基材シートを構成する金属チタンまたはチタン合金に直接接触して担持する方法としては、アークプラズマ放電蒸着法が好ましく採用される。 An arc plasma discharge vapor deposition method is preferably employed as a method for supporting at least part of the electrode catalyst in direct contact with the metal titanium or titanium alloy constituting the porous substrate sheet.
なお、電極触媒の担持方法は、アークプラズマ放電蒸着法に限定されず、公知の貴金属担持方法を採用することができる。例えば、蒸着（アークプラズマ放電蒸着以外も含む）やスパッタ等の乾式法のみならず、貴金属アセチルアセトナートを使用する貴金属アセチルアセトナート法や貴金属コロイドを使用するコロイド法等の湿式法も選択できる。 Incidentally, the method for supporting the electrode catalyst is not limited to the arc plasma discharge vapor deposition method, and a known noble metal supporting method can be employed. For example, not only dry methods such as vapor deposition (including arc plasma discharge vapor deposition) and sputtering, but also wet methods such as the noble metal acetylacetonate method using noble metal acetylacetonate and the colloid method using noble metal colloid can be selected.
＜２．膜電極接合体（ＭＥＡ）＞
上述した本発明の電極構造体や電極触媒層／ＧＤＬ一体シートは、膜電極接合体（ＭＥＡ）の構成部材として使用できる。
なお、本明細書において、「膜電極接合体（ＭＥＡ）」は、電解質膜、電極（アノード及びカソード）のみならず、ＧＤＬ（アノードＧＤＬ、カソードＧＤＬ）を含み得る概念とする。
<2. Membrane Electrode Assembly (MEA)>
The electrode structure and the electrode catalyst layer/GDL integrated sheet of the present invention described above can be used as a constituent member of a membrane electrode assembly (MEA).
In this specification, "membrane electrode assembly (MEA)" is a concept that can include not only electrolyte membranes and electrodes (anode and cathode) but also GDLs (anode GDL, cathode GDL).
本発明のＭＥＡの第１の態様は、固体高分子電解質膜と、前記固体高分子電解質膜の一方面に接合されたカソードと、前記固体高分子電解質膜の他方面に接合されたアノードと、を有する膜電極接合体であって、前記カソードとアノードの少なくとも一方として、上述した本発明の電極構造体を用いてなることを特徴とする。 A first aspect of the MEA of the present invention comprises a solid polymer electrolyte membrane, a cathode joined to one surface of the solid polymer electrolyte membrane, an anode joined to the other surface of the solid polymer electrolyte membrane, wherein the electrode structure of the present invention described above is used as at least one of the cathode and the anode.
本発明のＭＥＡの第２の態様は、固体高分子電解質膜と、前記固体高分子電解質膜の一方面に接合されたカソードと、前記固体高分子電解質膜の他方面に接合されたアノードと、を有する膜電極接合体と、ガス拡散層（ＧＤＬ）とを有する膜電極接合体/ガス拡散層一体構造であって、前記カソードとアノードの少なくとも一方として、上述した電極触媒層／ガス拡散層一体シートを用いてなることを特徴とする。 A second aspect of the MEA of the present invention includes a solid polymer electrolyte membrane, a cathode joined to one surface of the solid polymer electrolyte membrane, an anode joined to the other surface of the solid polymer electrolyte membrane, and a gas diffusion layer (GDL), wherein at least one of the cathode and the anode is the electrode catalyst layer/gas diffusion layer integrated structure described above. It is characterized by using a sheet.
本発明のＭＥＡにおいて、本発明の電極構造体（電極触媒層／ガス拡散層一体シート）以外の構成要素は、公知の固体高分子形燃料電池と同様であるため、詳細な説明を省略する。 In the MEA of the present invention, the constituent elements other than the electrode structure (electrode catalyst layer/gas diffusion layer integrated sheet) of the present invention are the same as those of known polymer electrolyte fuel cells, so detailed description thereof will be omitted.
また、本発明のＭＥＡは、固体高分子形燃料電池のみならず、固体高分子形水電解装置の構成部材として使用可能である。 Moreover, the MEA of the present invention can be used not only as a polymer electrolyte fuel cell but also as a constituent member of a polymer electrolyte water electrolysis apparatus.
＜３．固体高分子形燃料電池＞
本発明の固体高分子形燃料電池は、本発明の膜電極接合体を備えてなり、通常、膜電極接合体をガス流路が形成されたセパレータで挟持した構造を有する。
<3. Polymer electrolyte fuel cell>
The polymer electrolyte fuel cell of the present invention comprises the membrane electrode assembly of the present invention, and generally has a structure in which the membrane electrode assembly is sandwiched between separators having gas flow paths formed therein.
本発明の固体高分子形燃料電池において、本発明の膜電極接合体以外の構成要素は、公知の固体高分子形燃料電池と同様であるため、詳細な説明を省略する。 In the polymer electrolyte fuel cell of the present invention, the constituent elements other than the membrane electrode assembly of the present invention are the same as those of known polymer electrolyte fuel cells, and detailed description thereof will be omitted.
以上、本発明の電極構造体及びこれを含む電極触媒層/ＧＤＬ一体シート、並びにこれらを含む膜電解質接合体、固体高分子形燃料電池について説明したが、今回開示のすべての点で例示であって制限的なものではないと考えられるべきである。特に、今回開示された形態において、明示的に開示されていない事項、例えば、各種パラメータ、寸法、重量、体積などは、当業者が通常実施する範囲を逸脱するものではなく、通常の当業者であれば、容易に想定することが可能な値を採用している。 As described above, the electrode structure of the present invention, the electrode catalyst layer/GDL integrated sheet containing the same, the membrane electrolyte assembly containing these, and the polymer electrolyte fuel cell have been described, but all points disclosed this time are examples. should be considered non-limiting. In particular, in the embodiments disclosed this time, matters not explicitly disclosed, such as various parameters, dimensions, weights, volumes, etc., do not deviate from the scope normally performed by those skilled in the art, and If there is, a value that can be easily assumed is adopted.
以下に実施例を挙げて本発明をより具体的に説明するが、本発明はこれらに限定されるものではない。 EXAMPLES The present invention will be described in more detail with reference to examples below, but the present invention is not limited to these.
１．電極触媒シートの作製
実施例の電極触媒シートは以下の手順で作製した。図５に作製手順を示すフローチャートを示す。
１－１．Ｔｉ多孔体シート
チタンからなる多孔体基材シートであるＴｉ多孔体シートとして、表１に仕様を示す金属チタン粒子焼結体シート（以下、「Ｔｉ多孔体シート（Ｔｉ（Ｐ））」又は単に「Ｔｉ（Ｐ）」と表記する。）及び金属チタン繊維集合体シート（以下、「Ｔｉ多孔体シート（Ｔｉ（Ｆ））」又は単に「Ｔｉ(Ｆ)」と表記する。）を使用した。
表１にＴｉ多孔体シート（Ｔｉ（Ｐ）及びＴｉ(Ｆ)）の仕様を示す。また、図６にＴｉ（Ｐ）、図７にＴｉ(Ｆ)とのＦＥ－ＳＥＭ像を示す。
1. Production of Electrode Catalyst Sheet Electrode catalyst sheets of Examples were produced by the following procedure. FIG. 5 shows a flow chart showing the manufacturing procedure.
1-1. Ti porous body sheet As a Ti porous body sheet which is a porous body base sheet made of titanium, a metal titanium particle sintered body sheet (hereinafter referred to as "Ti porous body sheet (Ti (P))" whose specifications are shown in Table 1 or simply "Ti(P)") and metal titanium fiber aggregate sheet (hereinafter referred to as "Ti porous sheet (Ti(F))" or simply "Ti(F)") were used.
Table 1 shows specifications of Ti porous sheets (Ti(P) and Ti(F)). FE-SEM images of Ti(P) and Ti(F) are shown in FIG. 6 and FIG. 7, respectively.
実施例１～３にはＴｉ多孔体シート（Ｔｉ（Ｐ））、実施例４にはＴｉ多孔体シート（Ｔｉ（Ｆ））を用い、それぞれに図５に示す処理を行った。以下、各処理を説明する。 A Ti porous sheet (Ti(P)) was used in Examples 1 to 3, and a Ti porous sheet (Ti(F)) was used in Example 4, and the treatment shown in FIG. 5 was performed on each. Each process will be described below.
１－２．ＮａＯＨ処理
実施例２，３はＮａＯＨ処理をおこなった。まず、１０ｍｍ×１０ｍｍにカットしたＴｉ多孔体シート（Ｔｉ（Ｐ））を、６０℃に保持した５ＭのＮａＯＨ水溶液１００ｍＬ中で１時間攪拌した。図８にＮａＯＨ処理前後のＴｉ多孔体シート（Ｔｉ（Ｐ））のＦＥ－ＳＥＭ像を示す。
1-2. NaOH Treatment Examples 2 and 3 were subjected to NaOH treatment. First, a Ti porous sheet (Ti(P)) cut to 10 mm×10 mm was stirred in 100 mL of a 5 M NaOH aqueous solution maintained at 60° C. for 1 hour. FIG. 8 shows FE-SEM images of the Ti porous sheet (Ti(P)) before and after the NaOH treatment.
１－３．酸洗浄（酸洗い）
実施例２，３はＮａＯＨ処理後、０．５ＭのＨＮＯ3水溶液中で１５分超音波をかけ、
Ｎａを除去した。その後、純水で洗い流した。
1-3. Pickling (Pickling)
In Examples 2 and 3, after NaOH treatment, ultrasonic waves were applied for 15 minutes in a 0.5M HNO3 aqueous solution,
Na was removed. After that, it was washed with pure water.
１－４．熱処理
実施例２は、上記処理後のＴｉ多孔体シート（Ｔｉ(Ｐ)）を空気雰囲気で４００℃、５時間の条件で熱処理を行った。実施例３は、上記処理後のＴｉ多孔体シート（Ｔｉ(Ｐ)）を５％Ｈ2－Ｎ2雰囲気で５００℃、３０分の条件で熱処理を行った。
1-4. Heat Treatment In Example 2, the Ti porous sheet (Ti(P)) after the above treatment was heat treated in an air atmosphere at 400° C. for 5 hours. In Example 3, the Ti porous sheet (Ti(P)) after the above treatment was heat-treated in a 5% H 2 -N 2 atmosphere at 500°C for 30 minutes.
１－５．Ｐｔの担持
Ｐｔ微粒子をＴｉシート上に蒸着するためアークプラズマ蒸着法を採用した。実験装置はアークプラズマ成膜装置(アルバック理工株式会社)を使用した。
上記Ｔｉ多孔体シート（未処理の実施例１、又は上記処理を行った実施例２，３のＴｉ多孔体シート）に以下の条件でアークプラズマ蒸着（電圧：１００Ｖ、圧力：１０-3Ｐａ、充放電周波数：３Ｈｚ）を行い、目的とする実施例１～３のＰｔ担持Ｔｉ多孔体シート（Ｐｔ/Ｔｉ多孔体シート）を得た。
1-5. Supporting Pt An arc plasma deposition method was employed to deposit Pt fine particles on a Ti sheet. An arc plasma deposition apparatus (ULVAC-RIKO, Inc.) was used as an experimental apparatus.
Arc plasma vapor deposition (voltage: 100 V, pressure: 10 Pa, charging) was performed on the Ti porous sheet (untreated Example 1, or the Ti porous sheets of Examples 2 and 3 that were subjected to the above treatment) under the following conditions. discharge frequency: 3 Hz) to obtain the intended Pt-supporting Ti porous sheets (Pt/Ti porous sheets) of Examples 1 to 3.
２．物性評価
２－１．Ｘ線回折（ＸＲＤ）による解析
Ｐｔ担持前の実施例１～３のＴｉ多孔質シートのＸＲＤ測定を行った結果を図９に示す。表面処理を行っていない実施例１、空気雰囲気で熱処理を行った実施例２、還元雰囲気で熱処理を行った実施例３において、大きなピークのずれは見られず、金属Ｔｉのピークが大きく検出された。
2. Physical property evaluation 2-1. Analysis by X-Ray Diffraction (XRD) FIG. 9 shows the results of XRD measurement of the Ti porous sheets of Examples 1 to 3 before supporting Pt. In Example 1 in which no surface treatment was performed, Example 2 in which heat treatment was performed in an air atmosphere, and Example 3 in which heat treatment was performed in a reducing atmosphere, no large peak deviation was observed, and a large peak of metal Ti was detected. rice field.
２－２．透過型電子顕微鏡（ＴＥＭ）観察
実施例２のＴｉ多孔体シートについて、ＴＥＭによる微細構造観察を行った。図１０にＴＥＭ観察結果及び制限視野電子回析パターンを示す．ＴＥＭ観察により、ブロンズ型ＴｉＯ2の１１０面の面間隔０．３５６ｎｍとほぼ同等の面間隔０．３６ｎｍが確認されたことから、実施例２のＴｉ多孔体シートにブロンズ型ＴｉＯ2が生成していると判断した。
2-2. Transmission Electron Microscope (TEM) Observation The microstructure of the Ti porous sheet of Example 2 was observed by TEM. Figure 10 shows the TEM observation results and the selected area electron diffraction pattern. TEM observation confirmed that the interplanar spacing of 0.36 nm, which is almost the same as the interplanar spacing of 0.356 nm of the 110 plane of bronze-type TiO 2 , indicates that bronze-type TiO 2 was generated in the Ti porous sheet of Example 2. I decided there was.
２－３．Ｐｔ担持状態の評価
未処理のＴｉ多孔体シート（Ｔｉ（Ｐ）及びＴｉ（Ｆ））へのＰｔの担持はアークプラズマ蒸着法で行った。
図１１にアークプラズマ蒸着法における充放電回数とＰｔ担持量の関係を示す。Ｐｔ担持量は、ＩＣＰ発光分析により求めた。
図１１からからわかるように、充放電回数に比例してＰｔ担持量は増加すること、同じ充放電回数の場合、Ｔｉ（Ｐ）及びＴｉ（Ｆ）の単位面積当たりのＰｔ担持量は、ほぼ同量あることが確認された。
2-3. Evaluation of Pt Carrying State Pt was carried on untreated Ti porous sheets (Ti(P) and Ti(F)) by an arc plasma vapor deposition method.
FIG. 11 shows the relationship between the number of charging/discharging times and the amount of Pt supported in the arc plasma deposition method. The amount of Pt supported was determined by ICP emission spectrometry.
As can be seen from FIG. 11, the supported Pt amount increases in proportion to the number of charge/discharge cycles. Equal amounts were confirmed.
図１２にＰｔ担持後（充放電回数：１０回、２５回、５０回）のＴｉ多孔体シート（Ｔｉ（Ｐ）、未処理）のＴＥＭ像を示す。また、比較のため、Ｐｔ担持なし（充放電回数：０回）のＴＥＭ像も併せて示す。また、図１３にＰｔ担持後（充放電回数：１０回、２５回）のＴｉ多孔体シート（Ｔｉ（Ｐ））の高角度環状暗視野走査透過型電子顕微鏡（ＨＡＡＤＦ-ＳＴＥＭ）観察結果を示す。
図１２のＴＥＭ像において、充放電回数１０回ではＰｔ粒子が明確に確認できなかったが、図１３に示す通り、ＨＡＡＤＦ-ＳＴＥＭ観察では充放電回数１０回においてＰｔが5ｎｍ以下の粒子で存在していることが確認された。ＳＥＭ用画像解析ソフト(Scandium)により、平均粒子径を求めたところ２．４２ｎｍであった．
また、図１２のＴＥＭ像において、充放電回数２５回ではＰｔ粒子と思われるもの (図中の黒い粒子)が確認され、図１３に示す通り、ＨＡＡＤＦ-ＳＴＥＭ観察では充放電回数２５回では、粒子が部分的につながった島状にＰｔは存在していた。
また、図１２のＴＥＭ像において、充放電回数５０回では全体的なアモルファスな膜状のＰｔ(全体的に写る黒い部分)中に、部分的に結晶化したＰｔ(濃く黒く映る粒子)が存在していることが確認できた。また、ＳＥＭ－ＥＤＳの評価（図示せず）により、Ｐｔ担持したＴｉ多孔体シート（Ｔｉ（Ｐ））表面に存在する粒子がＰｔであることを確認した。
FIG. 12 shows TEM images of the Ti porous sheet (Ti(P), untreated) after carrying Pt (the number of charge/discharge cycles: 10, 25, and 50 times). For comparison, a TEM image without supporting Pt (number of charge/discharge cycles: 0) is also shown. In addition, FIG. 13 shows the results of high-angle annular dark-field scanning transmission electron microscope (HAADF-STEM) observation of the Ti porous sheet (Ti(P)) after supporting Pt (the number of times of charging and discharging: 10 times, 25 times). .
In the TEM image of FIG. 12, Pt particles could not be clearly confirmed after 10 charge/discharge cycles, but as shown in FIG. It was confirmed that The average particle size was found to be 2.42 nm using image analysis software for SEM (Scandium).
In addition, in the TEM image of FIG. 12, what seems to be Pt particles (black particles in the figure) were confirmed at 25 charge/discharge cycles, and as shown in FIG. Pt was present in an island shape in which particles were partially connected.
In addition, in the TEM image of FIG. 12, partially crystallized Pt (particles that appear dark and black) are present in the overall amorphous film-like Pt (black portions that appear as a whole) at 50 charge/discharge cycles. I was able to confirm that. Further, by SEM-EDS evaluation (not shown), it was confirmed that the particles present on the surface of the Pt-supported Ti porous sheet (Ti(P)) were Pt.
以上の観察結果より、充放電回数によるＰｔ担持状態の変化は以下であると判断した。
（I）充放電回数１０回未満 :Ｐｔは５ｎｍ以下の粒子で存在
（II）充放電回数１０～２５回 : Ｐｔは粒子もしくは島状で存在
（III）充放電回数２５～５０回: Ｐｔは島状もしくは膜状で存在
（IV）充放電回数５０回以上 : Ｐｔは膜状に存在
From the above observation results, it was determined that the changes in the Pt carrying state due to the number of charge/discharge cycles are as follows.
(I) Less than 10 charge/discharge cycles: Pt exists as particles of 5 nm or less (II) 10 to 25 charge/discharge cycles: Pt exists as particles or islands (III) 25 to 50 charge/discharge cycles: Pt Exists in the form of islands or films (IV) More than 50 charge/discharge cycles: Pt exists in the form of a film
３．電気化学的評価（ハーフセル）
３－１．Ｐｔ担持Ｔｉ多孔体シート（Ｔｉ（Ｐ））
（１）電気化学的表面積（ＥＣＳＡ）の評価
実施例１～３のＰｔ担持Ｔｉ多孔体シート（Ｔｉ（Ｐ））について、サイクリックボルタンメトリー（ＣＶ）を行い、電気化学的表面積（ＥＣＳＡ）の評価を行った。なお、ＥＣＳＡは、担持されたＰｔ触媒粒子の有効表面積に相当する。
3. Electrochemical evaluation (half-cell)
3-1. Pt-supporting Ti porous sheet (Ti(P))
(1) Evaluation of electrochemical surface area (ECSA) Cyclic voltammetry (CV) was performed on the Pt-supported Ti porous sheets (Ti(P)) of Examples 1 to 3 to evaluate the electrochemical surface area (ECSA). did ECSA corresponds to the effective surface area of the supported Pt catalyst particles.
ＣＶの測定条件は以下の通りである。電気化学的表面積（Ｐｔ有効表面積）は、表面のＰｔ原子一つに水素原子が一つ吸着するとの仮定に基づき、ＣＶから求めた水素吸着量から算出した。なお、１原子のＰｔに付き １原子のＨが吸着すると仮定すると２１０μＣ/ｃｍ2の電気量となる。
測定：三電極式セル（作用極：燃料電池用電極材料／ＧＣ、対極：Ｐｔ、参照極：Ａｇ／ＡｇＣｌ）
電解液：０．１Ｍ ＨＣｌＯ4（ｐＨ：約１）
測定電位範囲：０．０５～１．２Ｖ（可逆水素電極基準）
走査速度 ：５０ ｍＶ／ｓ
水素吸着量：０．０５～０．４Ｖの水素吸着を示すピーク面積から算出
電気化学的表面積（ＥＣＳＡ）：下記式より算出
ＥＣＳＡ＝（水素吸着量）[μＣ] / ２１０[μＣ/ｃｍ2]
The CV measurement conditions are as follows. The electrochemical surface area (Pt effective surface area) was calculated from the hydrogen adsorption amount obtained from the CV, based on the assumption that one hydrogen atom is adsorbed to each Pt atom on the surface. Assuming that one atom of H is adsorbed per one atom of Pt, the amount of electricity is 210 μC/cm 2 .
Measurement: Three-electrode cell (working electrode: fuel cell electrode material/GC, counter electrode: Pt, reference electrode: Ag/AgCl)
Electrolyte: 0.1M HClO 4 (pH: about 1)
Measurement potential range: 0.05 to 1.2 V (based on reversible hydrogen electrode)
Scanning speed: 50 mV/s
Hydrogen adsorption amount: Calculated from the peak area indicating hydrogen adsorption at 0.05 to 0.4 V Electrochemical surface area (ECSA): Calculated from the following formula
ECSA = (hydrogen adsorption amount) [μC] / 210 [μC/cm 2 ]
実施例１～３のＣＶにおいて水素の吸脱着に由来するピークが観察された（図示せず）。ＣＶから求めた実施例１～３のＰｔ担持Ｔｉ多孔体シート（Ｔｉ（Ｐ））の電気化学的表面積（ＥＣＳＡ）の評価結果を図１４に示す。
図１４に示されるように電気化学的表面積（ＥＣＳＡ）は、３０～１６０ｍ2/ｇで、従来の炭素系担体を使用した電極触媒（ＥＣＳＡ６０～８０ｍ2/ｇ程度）と同等あるいは同等以上であった。
なお、充放電回数１０回、２５回ではＥＣＳＡは１００ｍ2/ｇ以上と高い値を示しており、これはＰｔが粒子状に存在しているためと判断した。また、充放電回数が増えるとＥＣＳＡが下がる傾向については、Ｐｔの粒子径、もしくは膜厚が増大するためと判断した。また、未処理のＴｉ多孔体シート（Ｔｉ（Ｐ））を使用した実施例１では、充放電回数１０回のＥＣＳＡ １３０ ｍ2/ｇから半球モデルで算出したＰｔ粒子径は２．２ｎｍあり、これは図１３に示したＨＡＡＤＦ-ＳＴＥＭ観察結果より求めたＰｔ平均粒子径２．４ｎｍとほぼ一致している。
A peak derived from adsorption and desorption of hydrogen was observed in the CVs of Examples 1 to 3 (not shown). FIG. 14 shows the evaluation results of the electrochemical surface area (ECSA) of the Pt-supporting Ti porous sheets (Ti(P)) of Examples 1 to 3 obtained from CV.
As shown in FIG. 14, the electrochemical surface area (ECSA) is 30 to 160 m 2 /g, which is equal to or greater than the conventional electrode catalyst using a carbon-based carrier (
It should be noted that ECSA showed a high value of 100 m 2 /g or more at 10 and 25 charge/discharge cycles, and it was determined that this was because Pt was present in the form of particles. In addition, it was determined that the ECSA tended to decrease as the number of charge/discharge cycles increased because the Pt particle size or film thickness increased. Further, in Example 1 using an untreated Ti porous sheet (Ti(P)), the Pt particle diameter calculated by a hemispherical model from ECSA 130 m 2 /g after 10 charge/discharge cycles was 2.2 nm. This substantially agrees with the Pt average particle size of 2.4 nm obtained from the HAADF-STEM observation results shown in FIG.
（２）リニアスイープボルタンメトリー（ＬＳＶ）による評価
実施例１～３のＰｔ担持Ｔｉ多孔体シート（Ｔｉ（Ｐ））についてリニアスイープボルタンメトリー（ＬＳＶ）による評価を行った。Ｐｔ担持のためのアークプラズマ蒸着法の充放電回数は１５０回とした。
まず、Ｏ2を１００ｍＬ/分で３０分間バブリングした後、攪拌子で溶液を攪拌させながら、前処理として１．２０ＶRHEから卑な方向に向けて１０ｍＶ/秒で０．２ＶRHEまで電位を走査し、続けて０．２ＶRHEから貴な方向に向けて１０ｍＶ/秒で１．２０ＶRHEまで電位を走査し、測定を行なった。なお、測定中は常にＯ2を１００ｍＬ/分でパージした。
なお、ＶRHEは可逆水素電極（ＲＨＥ）基準の電位である。
図１５に実施例１～３のＰｔ担持Ｔｉ多孔体シート（Ｔｉ（Ｐ））のリニアスイープボルタモグラムを示す。なお、低電位側に見られるノイズは、酸素ガスの供給の変動によるもので、回転電極で測定を行うと観測されない。
撹拌の影響が少ない電圧０．９ＶRHEの電流値をＰｔ質量で除した値で比較すると、実施例１（未処理）４７．０Ａ/ｇ、実施例２（酸化処理）２８．７Ａ/ｇ、実施例３（還元処理）４１．９Ａ/ｇであり、撹拌回転数の影響を考慮すれば、表面処理を行っていない実施例１と、還元処理を行った実施例３はほぼ同じＯＲＲ活性を示している。これの結果から、Ｐｔ担持前の実施例１，３のチタン多孔体シート（Ｔｉ（Ｐ））はチタン表面の酸化層が薄く、Ｐｔ担持のためのアークプラズマ蒸着法の際にプラズマにより酸化膜が除去され、金属Ｔｉの上に直接Ｐｔが担持されたためであると判断できる。
(2) Evaluation by Linear Sweep Voltammetry (LSV) The Pt-supporting Ti porous sheets (Ti(P)) of Examples 1 to 3 were evaluated by linear sweep voltammetry (LSV). The number of charge/discharge cycles in the arc plasma vapor deposition method for supporting Pt was 150 times.
First, after bubbling O 2 at 100 mL/min for 30 minutes, the potential was scanned from 1.20 V RHE in the negative direction to 0.2 V RHE at 10 mV/sec as a pretreatment while stirring the solution with a stirrer. The potential was then scanned from 0.2 V RHE in the noble direction at 10 mV/s to 1.20 V RHE and measurements were taken. Note that O 2 was always purged at 100 mL/min during the measurement.
Note that V RHE is a reversible hydrogen electrode (RHE) reference potential.
FIG. 15 shows linear sweep voltammograms of the Pt-supporting Ti porous sheets (Ti(P)) of Examples 1-3. The noise seen on the low potential side is due to fluctuations in the supply of oxygen gas, and is not observed when the measurement is performed with a rotating electrode.
Comparing the value obtained by dividing the current value at a voltage of 0.9 V RHE , which is less affected by stirring, by the Pt mass, Example 1 (untreated) 47.0 A / g, Example 2 (oxidized) 28.7 A / g, Example 3 (reduction treatment) is 41.9 A / g, and considering the influence of the stirring rotation speed, Example 1 without surface treatment and Example 3 with reduction treatment have almost the same ORR activity. showing. From these results, it was found that the porous titanium sheets (Ti(P)) of Examples 1 and 3 before supporting Pt had a thin oxide layer on the titanium surface, and the oxide film was formed by plasma during the arc plasma deposition method for supporting Pt. was removed and Pt was supported directly on the metal Ti.
３－２．Ｐｔ担持Ｔｉ多孔体シート（Ｔｉ（Ｆ））（電極触媒／ＧＤＬ一体シート）
（１）電気化学的表面積（ＥＣＳＡ）の評価
実施例４のＰｔ担持Ｔｉ多孔体シート（Ｔｉ（Ｆ））についても、実施例１～３と同じ条件でＣＶを行い、電気化学的表面積（ＥＣＳＡ）を評価した。
実施例４のＣＶにおいて水素の吸脱着に由来するピークが観察された（図示せず）。ＣＶから求めた実施例４のＰｔ担持Ｔｉ多孔体シート（Ｔｉ（Ｆ））の電気化学的表面積（ＥＣＳＡ）の評価結果を図１６に示す。
ＣＶより算出した電気化学的表面積（ＥＣＳＡ）は、４５～６０ｍ2/ｇで、従来の炭素系担体を使用した電極触媒（ＥＣＳＡ６０～８０ｍ2/ｇ程度）と同等であった。
3-2. Pt-supporting Ti porous sheet (Ti(F)) (Electrocatalyst/GDL integrated sheet)
(1) Evaluation of electrochemical surface area (ECSA) For the Pt-supported Ti porous sheet (Ti(F)) of Example 4, CV was performed under the same conditions as in Examples 1 to 3, and the electrochemical surface area (ECSA ) was evaluated.
A peak derived from adsorption and desorption of hydrogen was observed in the CV of Example 4 (not shown). FIG. 16 shows the evaluation results of the electrochemical surface area (ECSA) of the Pt-supporting Ti porous sheet (Ti(F)) of Example 4 obtained from CV.
The electrochemical surface area (ECSA) calculated from the CV was 45 to 60 m 2 /g, which was equivalent to that of an electrode catalyst using a conventional carbon-based carrier (ECSA of about 60 to 80 m 2 /g).
（２）電気化学的評価（単セル、初期性能評価）
以下の通りにＭＥＡを作製し、単セルによる発電実験（ＩＶ測定）を行った。固体電解質膜としてナフィオン膜（デュポン社製、ナフィオン２１２ 厚さ５１μｍ）を使用した。
まず、標準触媒である４６ｗｔ％Ｐｔ／Ｃ（田中貴金属工業株式会社、ＴＥＣ１０Ｅ５０Ｅ）を、ナフィオン溶液を含む所定の有機溶媒に分散させて、アノード形成用の分散溶液を調合した。得られた分散溶液をナフィオン膜上にスプレー印刷して、所定の厚みのアノード（電極触媒層）をナフィオン膜上に作製した。
アノード（電極触媒層）の上には、ガス拡散層として撥水性カーボンペーパー（東レ社製、型番：ＥＣ－ＴＰ１－０６０Ｔ）を配置した。なお、アノードの形成において、Ｐｔ量が０．３ｍｇ／ｃｍ2になるように調整した。
カソードは、実施例４のＰｔ担持Ｔｉ多孔体シート（未処理のＴｉ（Ｆ）にアークプラズマ蒸着法でＰｔ担持した電極触媒層/ＧＤＬ一体シート）を使用した（充放電回数：３００回（０．０１３ｍｇＰｔ／ｃｍ2)又は５００回（０．０２２ｍｇＰｔ／ｃｍ2)）。
実施例４のＰｔ担持Ｔｉ多孔体シートの電極触媒層が形成された面に所定量のナフィオンを含む溶液を滴下して電極触媒層部分にナフィオンを含ませたのちに、アノードを形成したナフィオン膜の反対面に、圧着させて、カソード（電極触媒層／ＧＤＬ）を形成し、目的とするＭＥＡを得た。
(2) Electrochemical evaluation (single cell, initial performance evaluation)
An MEA was produced as follows, and a single cell power generation experiment (IV measurement) was performed. A Nafion membrane (manufactured by DuPont, Nafion 212, thickness 51 μm) was used as the solid electrolyte membrane.
First, 46 wt % Pt/C (Tanaka Kikinzoku Kogyo Co., Ltd., TEC10E50E), which is a standard catalyst, was dispersed in a predetermined organic solvent containing a Nafion solution to prepare a dispersion solution for anode formation. The obtained dispersion solution was spray-printed on the Nafion membrane to form an anode (electrode catalyst layer) having a predetermined thickness on the Nafion membrane.
A water-repellent carbon paper (manufactured by Toray Industries, model number: EC-TP1-060T) was placed as a gas diffusion layer on the anode (electrode catalyst layer). In forming the anode, the amount of Pt was adjusted to 0.3 mg/cm 2 .
The cathode used the Pt-supporting Ti porous sheet of Example 4 (electrode catalyst layer/GDL integrated sheet in which Pt was supported on untreated Ti (F) by an arc plasma deposition method) (the number of charge/discharge cycles: 300 times (0 .013 mg Pt/cm 2 ) or 500 times (0.022 mg Pt/cm 2 )).
A solution containing a predetermined amount of Nafion was added dropwise to the electrode catalyst layer formed surface of the Pt-supporting Ti porous sheet of Example 4 to impregnate the electrode catalyst layer with Nafion, and then the anode was formed on the Nafion membrane. A cathode (electrode catalyst layer/GDL) was formed by pressure bonding on the opposite side of the substrate to obtain the desired MEA.
作製したＭＥＡを組み込んだ単セル発電評価用治具（自作）を８０℃に設定した恒温槽内に設置し、以下の条件で発電試験を行ったところ、所定の起電力を生じ、ＩＶ特性を評価することができた。
なお、燃料電池評価装置（東陽テクニカ社製、型番：ＰＥ－８９００Ｋ）およびポテンショ／ガルバノスタット（Ｓｏｌａｔｒｏｎ社製、型番：ＳＩ１２８７）を用いた。
（アノード条件）
電極面積：１ｃｍ2
供給ガス種 ：１００％ Ｈ2
ガス供給速度 ：１００ｍＬ／分
供給ガス加湿温度 ：８０℃（相対湿度：１００％）
（カソード条件）
電極面積：１ｃｍ2
供給ガス種 ：Ａｉｒ
ガス供給速度 ：１００ｍＬ／分
供給ガス加湿温度 ：８０℃（相対湿度：１００％）
A single cell power generation evaluation jig (self-made) incorporating the fabricated MEA was placed in a constant temperature chamber set at 80° C., and a power generation test was performed under the following conditions. could be evaluated.
A fuel cell evaluation device (manufactured by Toyo Technica, model number: PE-8900K) and a potentio/galvanostat (manufactured by Solatron, model number: SI1287) were used.
(anode conditions)
Electrode area: 1cm2
Supply gas type: 100% H2
Gas supply rate: 100 mL/min Supply gas humidification temperature: 80°C (relative humidity: 100%)
(Cathode conditions)
Electrode area: 1cm2
Supply gas type: Air
Gas supply rate: 100 mL/min Supply gas humidification temperature: 80°C (relative humidity: 100%)
本発明の電極材料は、自動車、電力、ガス、家電業界で使用される固体高分子形燃料電池の電極の構成材料として有望である。特に、負荷変動が激しい燃料電池自動車向けで本材料利用のメリットが大きく、期待される。 INDUSTRIAL APPLICABILITY The electrode material of the present invention is promising as a constituent material for electrodes of polymer electrolyte fuel cells used in the automobile, electric power, gas, and home appliance industries. In particular, the benefits of using this material are great for fuel cell vehicles with severe load fluctuations, and expectations are high.
Claims (6)
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