JP2006134602A - Catalyst structure and film-electrode junction for solid polymer fuel cell using the same - Google Patents
Catalyst structure and film-electrode junction for solid polymer fuel cell using the same Download PDFInfo
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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
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- Fuel Cell (AREA)
- Catalysts (AREA)
- Inert Electrodes (AREA)
Abstract
Description
本発明は、触媒構造体及び該触媒構造体を用いた固体高分子型燃料電池用膜電極接合体に関し、特に固体高分子型燃料電池の膜電極接合体の触媒層に好適な触媒構造体に関するものである。 The present invention relates to a catalyst structure and a membrane electrode assembly for a polymer electrolyte fuel cell using the catalyst structure, and more particularly to a catalyst structure suitable for a catalyst layer of a membrane electrode assembly of a polymer electrolyte fuel cell. Is.
昨今、発電効率が高く、環境への負荷が小さい電池として、燃料電池が注目を集めており、広く研究開発が行われている。燃料電池の中でも、出力密度が高く作動温度が低い固体高分子型燃料電池は、小型化や低コスト化が他のタイプの燃料電池よりも容易なことから、電気自動車用電源、分散発電システム、家庭用のコージェネレーションシステムとして広く普及することが期待されている。 In recent years, fuel cells have attracted attention as a battery with high power generation efficiency and a low environmental load, and extensive research and development has been conducted. Among fuel cells, polymer electrolyte fuel cells with high output density and low operating temperature are easier to reduce in size and cost than other types of fuel cells. It is expected to spread widely as a household cogeneration system.
一般に固体高分子型燃料電池においては、固体高分子電解質膜を挟んで一対の電極を配置すると共に、一方の電極の表面に水素等の燃料ガスを接触させ、もう一方の電極の表面に酸素を含有する酸素含有ガスを接触させ、この時起こる電気化学反応を利用して、電極間から電気エネルギーを取り出している(非特許文献1及び2参照)。また、上記電極の高分子電解質膜に接する側には触媒層が配設されており、高分子電解質膜と触媒層とガスとの三相界面で電気化学反応が起こる。そのため、固体高分子型燃料電池の発電効率を向上させるためには、上記電気化学反応の反応場を拡大する必要がある。 In general, in a polymer electrolyte fuel cell, a pair of electrodes are arranged with a polymer electrolyte membrane sandwiched between them, a fuel gas such as hydrogen is brought into contact with the surface of one electrode, and oxygen is applied to the surface of the other electrode. The oxygen-containing gas contained is brought into contact, and electric energy is taken out between the electrodes by using an electrochemical reaction that occurs at this time (see Non-Patent Documents 1 and 2). A catalyst layer is disposed on the electrode in contact with the polymer electrolyte membrane, and an electrochemical reaction occurs at the three-phase interface between the polymer electrolyte membrane, the catalyst layer, and the gas. Therefore, in order to improve the power generation efficiency of the polymer electrolyte fuel cell, it is necessary to expand the reaction field of the electrochemical reaction.
上記電気化学反応の反応場を拡大することが可能な触媒層を形成するために、一般に、白金等の貴金属触媒をカーボンブラック等の粒状カーボン上に担持した触媒粉を含有するペースト又はスラリーを、カーボンペーパー等の導電性の多孔質支持体上に塗布する方法が採られている。しかしながら、この方法で形成された触媒層を備える固体高分子型燃料電池であっても、依然として発電効率の点で改善の余地があり、上記電気化学反応の反応場を更に拡大することが可能な触媒層の開発が求められている。 In order to form a catalyst layer capable of expanding the reaction field of the electrochemical reaction, generally, a paste or slurry containing catalyst powder in which a noble metal catalyst such as platinum is supported on granular carbon such as carbon black, The method of apply | coating on electroconductive porous supports, such as carbon paper, is taken. However, even a polymer electrolyte fuel cell including a catalyst layer formed by this method still has room for improvement in terms of power generation efficiency, and the reaction field for the electrochemical reaction can be further expanded. Development of a catalyst layer is required.
このような状況下、本発明の目的は、従来試みられることのなかった新規な方法で担体に触媒材料を担持してなる触媒構造体及び該触媒構造体を用いた固体高分子型燃料電池用膜電極接合体を提供することにある。 Under such circumstances, an object of the present invention is to provide a catalyst structure in which a catalyst material is supported on a support by a novel method that has not been attempted in the past, and a polymer electrolyte fuel cell using the catalyst structure. The object is to provide a membrane electrode assembly.
本発明者らは、種々の触媒担持方法を試みた結果、ガスフロースパッタリング法で触媒を担体にコーティングすることにより、高い触媒活性を有する触媒構造体が得られ、その中に固体高分子型燃料電池用膜電極接合体の触媒層として十分に機能するものが存在することを見出し、本発明を完成させるに至った。 As a result of trying various catalyst loading methods, the present inventors have obtained a catalyst structure having high catalytic activity by coating a catalyst on a support by gas flow sputtering, in which a solid polymer fuel is obtained. The inventors have found that there is a material that functions sufficiently as a catalyst layer of a membrane electrode assembly for a battery, and completed the present invention.
即ち、本発明の触媒構造体は、担体表面にガスフロースパッタリング法により触媒材料をコーティングしてなることを特徴とする。 That is, the catalyst structure of the present invention is characterized in that the catalyst surface is coated with a catalyst material by a gas flow sputtering method.
本発明の触媒構造体としては、前記触媒材料が金属又は金属化合物であり、一種又は複数の金属又は金属化合物を同時にスパッタリングして前記担体表面にコーティングしたものが好ましい。ここで、本発明の触媒構造体としては、前記複数の金属又は金属化合物をスパッタリングするに際し、複数のカソードを用い同時に放電させて、前記担体表面に複数の金属又は金属化合物をコーティングしたもの、並びに、前記複数の金属又は金属化合物をスパッタリングするに際し、複数のターゲットを一つのカソードに取り付け、放電時に該カソードにおいて同時に複数の金属をスパッタリングして前記担体表面に前記複数の金属又は金属化合物をコーティングしたものが更に好ましい。なお、前記複数の金属又は金属化合物をスパッタリングするに際し、複数のターゲットを一つのカソードに取り付け、放電時に該カソードにおいて同時に複数の金属をスパッタリングして前記担体表面に前記複数の金属又は金属化合物をコーティングした後に、該コーティングされた複数の金属又は金属化合物の少なくとも1種を酸及び/又はアルカリで除去することも好ましい。また、前記複数のターゲットを一つのカソードに取り付けるに際し、該ターゲットが二つの場合は、該ターゲットを対面させて配置し、前記ターゲットが三つ以上の場合は、該ターゲットを多面体状に配置することが好ましい。 As the catalyst structure of the present invention, it is preferable that the catalyst material is a metal or a metal compound, and one or a plurality of metals or metal compounds are simultaneously sputtered and coated on the support surface. Here, as the catalyst structure of the present invention, when sputtering the plurality of metals or metal compounds, a plurality of cathodes are used to discharge simultaneously, and the support surface is coated with a plurality of metals or metal compounds, and When sputtering the plurality of metals or metal compounds, a plurality of targets are attached to one cathode, and a plurality of metals are simultaneously sputtered on the cathode during discharge to coat the plurality of metals or metal compounds on the surface of the carrier. More preferred. When sputtering the plurality of metals or metal compounds, a plurality of targets are attached to one cathode, and the plurality of metals or metal compounds are coated on the surface of the carrier by simultaneously sputtering a plurality of metals at the cathode during discharge. Then, it is also preferable to remove at least one of the plurality of coated metals or metal compounds with an acid and / or an alkali. Further, when attaching the plurality of targets to one cathode, when there are two targets, the targets are arranged to face each other, and when there are three or more targets, the targets are arranged in a polyhedral shape. Is preferred.
本発明の触媒構造体の好適例においては、前記触媒材料が、Na,Mg,Al,Si,K,Ca,Sc,Ti,V,Cr,Mn,Fe,Co,Ni,Cu,Zn,Ga,Ge,Rb,Sr,Y,Zr,Nb,Mo,Ru,Rh,Ag,Cd,In,Sn,Sb,Cs,Ba,La,Hf,Ta,W,Re,Os,Ir,Tl,Pb,Bi,Ce,Pr,Nd,Sm及びEuからなる群から選択される少なくとも1種の金属である。 In a preferred embodiment of the catalyst structure of the present invention, the catalyst material is Na, Mg, Al, Si, K, Ca, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga. , Ge, Rb, Sr, Y, Zr, Nb, Mo, Ru, Rh, Ag, Cd, In, Sn, Sb, Cs, Ba, La, Hf, Ta, W, Re, Os, Ir, Tl, Pb , Bi, Ce, Pr, Nd, Sm and Eu.
本発明の触媒構造体の他の好適例においては、前記触媒材料が貴金属である。ここで、該貴金属が、Ag,Pt及びAuからなる群から選択される少なくとも1種であることが好ましい。 In another preferred embodiment of the catalyst structure of the present invention, the catalyst material is a noble metal. Here, it is preferable that the noble metal is at least one selected from the group consisting of Ag, Pt and Au.
本発明の触媒構造体の他の好適例においては、前記触媒材料が金属酸化物である。ここで、該金属酸化物が、AlOx,SiOx,TiOx,FeOx,CoOx,NiOx,CuOx,ZnOx,NbOx,MoOx,LaOx,TaOx,WOx及びPbOxからなる群から選択される少なくとも1種であり、前記xの値をスパッタリング時の酸素流量で制御することが好ましい。 In another preferred embodiment of the catalyst structure of the present invention, the catalyst material is a metal oxide. Here, the metal oxide is AlO x , SiO x , TiO x , FeO x , CoO x , NiO x , CuO x , ZnO x , NbO x , MoO x , LaO x , TaO x , WO x and PbO x. It is preferable that the value of x is controlled by the oxygen flow rate during sputtering.
本発明の触媒構造体の他の好適例においては、前記触媒材料が金属窒化物である。ここで、該金属窒化物が、AlNx,SiNx,TiNx,FeNx,CoNx,NiNx,CuNx,ZnNx,NbNx,MoNx,LaNx,TaNx,WNx及びPbNxからなる群から選択される少なくとも1種であり、前記xの値をスパッタリング時の窒素流量で制御することが好ましい。 In another preferred embodiment of the catalyst structure of the present invention, the catalyst material is a metal nitride. Here, the metal nitride is AlN x , SiN x , TiN x , FeN x , CoN x , NiN x , CuN x , ZnN x , NbN x , MoN x , LaN x , TaN x , WN x and PbN x. It is preferable that the value of x is controlled by a nitrogen flow rate during sputtering.
本発明の触媒構造体の他の好適例においては、前記触媒材料が金属炭化物である。ここで、該金属炭化物が、AlCx,SiCx,TiCx,FeCx,CoCx,NiCx,CuCx,ZnCx,NbCx,MoCx,LaCx,TaCx,WCx及びPbCxからなる群から選択される少なくとも1種であり、前記xの値をスパッタリング時の炭化水素流量で制御することが好ましい。 In another preferred embodiment of the catalyst structure of the present invention, the catalyst material is a metal carbide. Here, the metal carbide is composed of AlC x , SiC x , TiC x , FeC x , CoC x , NiC x , CuC x , ZnC x , NbC x , MoC x , LaC x , TaC x , WC x and PbC x. It is preferable that the value of x is controlled by the hydrocarbon flow rate during sputtering.
本発明の触媒構造体の他の好適例においては、前記触媒材料が金属酸化窒化物である。ここで、該金属酸化窒化物が、AlOxNy,SiOxNy,TiOxNy,FeOxNy,CoOxNy,NiOxNy,CuOxNy,ZnOxNy,NbOxNy,MoOxNy,LaOxNy,TaOxNy,WOxNy及びPbOxNyからなる群から選択される少なくとも1種であり、前記x及びyの値をスパッタリング時の酸素流量及び窒素流量で制御することが好ましい。 In another preferred embodiment of the catalyst structure of the present invention, the catalyst material is a metal oxynitride. Here, the metal oxynitride is AlO x N y , SiO x N y , TiO x N y , FeO x N y , CoO x N y , NiO x N y , CuO x N y , ZnO x N y , NbO x N y , MoO x N y , LaO x N y , TaO x N y , WO x N y, and PbO x N y , and at least one of the values of x and y are sputtered. It is preferable to control by the oxygen flow rate and the nitrogen flow rate.
本発明の触媒構造体においては、前記ガスフロースパッタリングで用いたターゲット材の使用効率が80%以上であることが好ましい。 In the catalyst structure of the present invention, the use efficiency of the target material used in the gas flow sputtering is preferably 80% or more.
本発明の触媒構造体の他の好適例においては、前記担体がカーボン繊維集合体である。ここで、該カーボン繊維集合体としては、カーボンペーパー、直径1nm〜1μmのフィブリル状カーボン繊維集合体、並びに前記カーボンペーパー上に直径1nm〜1μmの前記フィブリル状カーボン繊維集合体を配設してなる複合カーボン集合体が好ましい。 In another preferred embodiment of the catalyst structure of the present invention, the carrier is a carbon fiber aggregate. Here, as the carbon fiber aggregate, carbon paper, a fibrillar carbon fiber aggregate having a diameter of 1 nm to 1 μm, and the fibrillar carbon fiber aggregate having a diameter of 1 nm to 1 μm are disposed on the carbon paper. A composite carbon aggregate is preferred.
本発明の触媒構造体の担体としては、芳香環を有する化合物を酸化重合してフィブリル状ポリマーを得、該フィブリル状ポリマーを焼成、好ましくは非酸化性雰囲気中で焼成して得た3次元連続状炭素繊維が特に好ましい。ここで、前記芳香環を有する化合物がベンゼン環又は芳香族複素環を有する化合物であることが好ましく、アニリン、ピロール、チオフェン及びそれらの誘導体からなる群から選択された少なくとも一種の化合物であることが更に好ましい。 As the carrier of the catalyst structure of the present invention, a three-dimensional continuous product obtained by oxidative polymerization of a compound having an aromatic ring to obtain a fibril-like polymer, and firing the fibril-like polymer, preferably in a non-oxidizing atmosphere. A carbon fiber is particularly preferred. Here, the compound having an aromatic ring is preferably a compound having a benzene ring or an aromatic heterocyclic ring, and is at least one compound selected from the group consisting of aniline, pyrrole, thiophene and derivatives thereof. Further preferred.
また、本発明の固体高分子型燃料電池用膜電極接合体は、固体高分子電解質膜と、該固体高分子電解質膜の両側に配置した触媒層と、該触媒層の両側に配置した拡散層とからなる固体高分子型燃料電池用膜電極接合体において、前記触媒層に上記触媒構造体を用いたことを特徴とする。 Further, a membrane electrode assembly for a polymer electrolyte fuel cell of the present invention comprises a solid polymer electrolyte membrane, a catalyst layer disposed on both sides of the solid polymer electrolyte membrane, and a diffusion layer disposed on both sides of the catalyst layer In the membrane electrode assembly for a polymer electrolyte fuel cell comprising the above, the catalyst structure is used for the catalyst layer.
本発明によれば、触媒材料をガスフロースパッタリング法で担体にコーティングした新規な触媒構造体、並びに該触媒構造体を用いた固体高分子型燃料電池用膜電極接合体を提供することができる。 ADVANTAGE OF THE INVENTION According to this invention, the novel catalyst structure which coated the catalyst material on the support | carrier by the gas flow sputtering method, and the membrane electrode assembly for polymer electrolyte fuel cells using this catalyst structure can be provided.
以下に、本発明を詳細に説明する。本発明の触媒構造体は、担体表面にガスフロースパッタリング法により触媒材料をコーティングしてなる。ガスフロースパッタリング法により触媒材料を担体表面にコーティングすることにより、通常のスパッタリング方式(プレーナー型マグネトロンスパッタリング)対比、金属膜の場合、10倍以上の製膜速度で、金属化合物、特に金属酸化物薄膜の場合、10〜1000倍の成膜速度で膜を形成することができる。高速成膜法としては、真空蒸着法がポピュラーであるが、基材との密着性が悪く、これに対し、ガスフロースパッタ法で形成した膜は、スパッタリング法の特徴である密着性に富んでいる。従って、触媒性能を発揮するためのある膜厚を得るのに、ガスフロースパッタ法では短時間で成膜が可能であるため、低温での形成が可能となり、また、担持体との密着性に優れた触媒担持材料を形成することができる。一方、成膜時に流す反応性ガス流量の制御により、本願にも記載するように、例えば、MeOx(Meは金属を示す、以下同じ)等のx値、MeOxNy等のx、y値を制御することができ、この制御は真空蒸着法では不可能である。なお、本発明の触媒構造体は、種々の化学反応の触媒として有効であるが、特に固体高分子型燃料電池の触媒層として好適である。 The present invention is described in detail below. The catalyst structure of the present invention is formed by coating the support surface with a catalyst material by gas flow sputtering. By coating the catalyst surface with a catalyst material by gas flow sputtering method, compared to the usual sputtering method (planar type magnetron sputtering), in the case of metal film, the metal compound, especially metal oxide thin film, at a film formation speed of 10 times or more In this case, the film can be formed at a film formation rate of 10 to 1000 times. As a high-speed film formation method, the vacuum deposition method is popular, but the adhesion to the substrate is poor. On the other hand, the film formed by the gas flow sputtering method is rich in the adhesion characteristic of the sputtering method. Yes. Therefore, in order to obtain a certain film thickness for exerting the catalytic performance, the gas flow sputtering method can form the film in a short time, so that it can be formed at a low temperature, and the adhesion to the carrier is improved. An excellent catalyst support material can be formed. On the other hand, the control of reactive gas flow to flow during film formation, as described in the present application, e.g., MeO x (Me represents a metal, hereinafter the same) x values such, MeO x N y or the like of the x, y The value can be controlled, and this control is not possible with vacuum deposition. The catalyst structure of the present invention is effective as a catalyst for various chemical reactions, but is particularly suitable as a catalyst layer of a polymer electrolyte fuel cell.
本発明で担体表面に触媒材料をコーティングするのに用いるガスフロースパッタリング法は、比較的高い圧力下でスパッタリングを行い、スパッタ粒子をガスの強制流により担体まで輸送し堆積させる方法である。図1に、本発明の実施に好適なガスフロースパッタ装置の概略図を示す。図示例のガスフロースパッタ装置では、スパッタガス導入口1からアルゴン等の希ガス等を導入し、DC電源2に接続されたアノード3及びカソード4間での放電で発生したプラズマPをカソード4のターゲット5に衝突させ、はじき飛ばされたスパッタ粒子をアルゴン等の希ガス等の強制流により触媒担持用の担体6まで輸送し堆積させる。なお、図示例において、担体6は、ホルダー7に支持されており、担体6の近傍には、反応性ガスの導入口8が配置されており、反応性スパッタリングを行うことが可能である。また、スパッタガス導入口1は、図2の側面図に示すように上部及び下部から導入されたスパッタガスが側面の開口から流れる構造を有する。
The gas flow sputtering method used for coating the catalyst material on the surface of the support in the present invention is a method in which sputtering is performed under a relatively high pressure, and sputtered particles are transported to the support by a forced flow of gas and deposited. FIG. 1 shows a schematic diagram of a gas flow sputtering apparatus suitable for carrying out the present invention. In the gas flow sputtering apparatus of the illustrated example, a rare gas such as argon is introduced from the sputtering gas inlet 1, and plasma P generated by discharge between the anode 3 and the cathode 4 connected to the DC power source 2 is supplied to the cathode 4. The sputtered particles collided with the target 5 are transported and deposited on the catalyst-supporting
本発明の触媒構造体を構成する触媒材料としては、金属及び金属化合物が挙げられ、これらは一種単独であっても、二種以上の混合物であってもよい。また、複数の金属又は金属化合物をスパッタリングして担体表面にコーティングする場合、複数の金属又は金属化合物を同時にスパッタリングすることが好ましい。 Examples of the catalyst material constituting the catalyst structure of the present invention include metals and metal compounds, which may be used alone or in a mixture of two or more. When a plurality of metals or metal compounds are sputtered and coated on the surface of the support, it is preferable to simultaneously sputter the plurality of metals or metal compounds.
上記複数の金属又は金属化合物をスパッタリングする場合は、複数のカソード4を用い同時に放電させて、前記担体表面に複数の金属又は金属化合物をコーティングすることが好ましい。ここで、各カソード4に、異種の金属からなるターゲット5を配設することで、複数の金属又は金属化合物を同時に担体表面にコーティングすることが可能となる。 When sputtering the plurality of metals or metal compounds, it is preferable that the plurality of cathodes 4 are simultaneously discharged to coat the support surface with the plurality of metals or metal compounds. Here, it is possible to coat a plurality of metals or metal compounds simultaneously on the surface of the carrier by disposing a target 5 made of a different metal on each cathode 4.
また、上記複数の金属又は金属化合物をスパッタリングする場合は、複数のターゲット5を一つのカソード4に取り付け、放電時に該カソード4において同時に複数の金属をスパッタリングして担体表面に複数の金属又は金属化合物をコーティングすることも好ましい。ここで、上記カソード4において同時に複数の金属をスパッタリングして担体表面に複数の金属又は金属化合物をコーティングした後、コーティングされた複数の金属又は金属化合物の少なくとも1種を酸及び/又はアルカリで除去してもよい。ここで、金属又は金属化合物を除去するために用いる酸及びアルカリは、除去対象の金属又は金属化合物と、残留させる金属又は金属化合物との種類に応じて適宜選択され、例えば、酸としては、塩酸、硫酸、硝酸、リン酸、酢酸、フッ酸、クロム酸、過酸化水素、過塩素酸、塩素酸、亜塩素酸、次亜塩素酸、クエン酸、シュウ酸、臭化水素等が挙げられ、これらを単体で又はこれらを混合した混酸で水溶液として用いることができる。また、溶解する金属によっては、混酸と塩化第二鉄のような金属塩化物、金属硫化物との混合水溶液を用いることもできる。一方、アルカリ水溶液としては、水酸化ナトリウム、水酸化カリウム等の水溶液やアンモニア水等を用いることができる。なお、酸水溶液、アルカリ水溶液の濃度、組成は、溶解する金属の種類に応じて適宜選定することができる。 In the case of sputtering the plurality of metals or metal compounds, a plurality of targets 5 are attached to one cathode 4, and a plurality of metals or metal compounds are simultaneously sputtered on the cathode 4 during discharge to sputter a plurality of metals or metal compounds on the surface of the carrier. It is also preferable to coat. Here, after a plurality of metals are simultaneously sputtered on the cathode 4 and a plurality of metals or metal compounds are coated on the support surface, at least one of the plurality of coated metals or metal compounds is removed with an acid and / or alkali. May be. Here, the acid and alkali used for removing the metal or metal compound are appropriately selected according to the type of the metal or metal compound to be removed and the metal or metal compound to be left. For example, the acid is hydrochloric acid. , Sulfuric acid, nitric acid, phosphoric acid, acetic acid, hydrofluoric acid, chromic acid, hydrogen peroxide, perchloric acid, chloric acid, chlorous acid, hypochlorous acid, citric acid, oxalic acid, hydrogen bromide, etc. These can be used as an aqueous solution alone or with a mixed acid obtained by mixing them. Further, depending on the metal to be dissolved, a mixed aqueous solution of a mixed acid, a metal chloride such as ferric chloride, and a metal sulfide can be used. On the other hand, as the alkaline aqueous solution, an aqueous solution such as sodium hydroxide or potassium hydroxide, aqueous ammonia, or the like can be used. In addition, the density | concentration and composition of acid aqueous solution and alkali aqueous solution can be suitably selected according to the kind of metal to melt | dissolve.
また、上記複数のターゲット5を一つのカソード4に取り付けるに際しては、該ターゲット5が二つの場合は、ターゲット5を対面させて配置し、ターゲット5が三つ以上の場合は、ターゲット5を多面体状に配置することが好ましく、例えば、ターゲット5が三つの場合は、ターゲット5を三角形状に配置し、ターゲット5が四つの場合は、ターゲット5を四角形状に配置することが好ましい。 Further, when attaching the plurality of targets 5 to one cathode 4, when there are two targets 5, the targets 5 are arranged facing each other, and when there are three or more targets 5, the targets 5 are in a polyhedral shape. For example, when there are three targets 5, it is preferable to arrange the targets 5 in a triangular shape, and when there are four targets 5, the targets 5 are preferably arranged in a quadrangular shape.
上記触媒材料として用いられる金属は、Na,Mg,Al,Si,K,Ca,Sc,Ti,V,Cr,Mn,Fe,Co,Ni,Cu,Zn,Ga,Ge,Rb,Sr,Y,Zr,Nb,Mo,Ru,Rh,Ag,Cd,In,Sn,Sb,Cs,Ba,La,Hf,Ta,W,Re,Os,Ir,Tl,Pb,Bi,Ce,Pr,Nd,Sm及びEuからなる群から選択されることが好ましく、本発明の触媒構造体には、これら金属を一種単独で用いてもよいし、これら金属の二種以上を用いてもよい。なお、これら金属を担体表面にコーディングする場合は、ターゲット5に上記金属を用いてガスフロースパッタリングを行う。 The metal used as the catalyst material is Na, Mg, Al, Si, K, Ca, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, Ge, Rb, Sr, Y. , Zr, Nb, Mo, Ru, Rh, Ag, Cd, In, Sn, Sb, Cs, Ba, La, Hf, Ta, W, Re, Os, Ir, Tl, Pb, Bi, Ce, Pr, Nd , Sm and Eu are preferably selected, and the catalyst structure of the present invention may be used alone or in combination of two or more of these metals. In addition, when coding these metals on the support | carrier surface, gas flow sputtering is performed using the said metal for the target 5. FIG.
また、触媒構造体の使用目的によっては、上記金属として、貴金属が好ましく、該貴金属としては、Ag,Pt及びAu等が挙げられる。本発明の触媒構造体においては、これら貴金属の一種若しくは複数を使用することができる。なお、触媒構造体を固体高分子型燃料電池用膜電極接合体の触媒層に用いる場合、貴金属の中でもPtが特に好ましい。貴金属としてPtを用いることで、100℃以下の低温でも水素を高効率で酸化することができる。また、PtをRu等の他の金属との合金として用いることで、COによるPtの被毒を防止して、触媒の活性低下を防止することができる。 Further, depending on the purpose of use of the catalyst structure, a noble metal is preferable as the metal, and examples of the noble metal include Ag, Pt and Au. One or more of these noble metals can be used in the catalyst structure of the present invention. In addition, when using a catalyst structure for the catalyst layer of the membrane electrode assembly for polymer electrolyte fuel cells, Pt is particularly preferable among noble metals. By using Pt as the noble metal, hydrogen can be oxidized with high efficiency even at a low temperature of 100 ° C. or lower. Further, by using Pt as an alloy with other metals such as Ru, it is possible to prevent poisoning of Pt by CO and prevent a decrease in the activity of the catalyst.
上記触媒材料として用いる金属化合物としては、金属酸化物、金属窒化物、金属炭化物及び金属酸化窒化物等が挙げられ、触媒構造体を固体高分子型燃料電池用膜電極接合体の触媒層に用いる場合は、金属化合物として金属酸化窒化物を用いることが好ましい。なお、これら金属化合物を担体表面にコーディングする場合は、ターゲット5に上記金属を用い、反応性ガスを導入口8から導入して反応性スパッタリングを行うことが好ましい。
Examples of the metal compound used as the catalyst material include metal oxides, metal nitrides, metal carbides, and metal oxynitrides, and the catalyst structure is used as a catalyst layer of a membrane electrode assembly for a polymer electrolyte fuel cell. In this case, it is preferable to use a metal oxynitride as the metal compound. When these metal compounds are coded on the surface of the carrier, it is preferable to perform reactive sputtering by using the above metal for the target 5 and introducing a reactive gas from the
上記金属酸化物としては、AlOx,SiOx,TiOx,FeOx,CoOx,NiOx,CuOx,ZnOx,NbOx,MoOx,LaOx,TaOx,WOx及びPbOx等が挙げられ、本発明の触媒構造体には、これら金属酸化物を一種単独で用いてもよいし、これら金属酸化物の二種以上を用いてもよい。ここで、上記反応性スパッタリングによれば、上記各化学式中のxの値をスパッタリング時において導入口8から導入される酸素の流量を調整することで所望の値に制御することが可能となる。
The metal oxide, AlO x, SiO x, TiO x, FeO x, CoO x, NiO x, CuO x, ZnO x, NbO x, MoO x, LaO x, TaO x, etc. WO x and PbO x is In the catalyst structure of the present invention, these metal oxides may be used alone, or two or more of these metal oxides may be used. Here, according to the reactive sputtering, the value of x in each chemical formula can be controlled to a desired value by adjusting the flow rate of oxygen introduced from the
また、上記金属窒化物としては、AlNx,SiNx,TiNx,FeNx,CoNx,NiNx,CuNx,ZnNx,NbNx,MoNx,LaNx,TaNx,WNx及びPbNx等が挙げられ、本発明の触媒構造体には、これら金属窒化物を一種単独で用いてもよいし、これら金属窒化物の二種以上を用いてもよい。ここで、上記反応性スパッタリングによれば、上記各化学式中のxの値をスパッタリング時において導入口8から導入される窒素の流量を調整することで所望の値に制御することが可能となる。
Further, as the metal nitride, AlN x, SiN x, TiN x, FeN x, CoN x, NiN x, CuN x, ZnN x, NbN x, MoN x, LaN x, TaN x, WN x and PbN x In the catalyst structure of the present invention, these metal nitrides may be used alone, or two or more of these metal nitrides may be used. Here, according to the reactive sputtering, the value of x in each chemical formula can be controlled to a desired value by adjusting the flow rate of nitrogen introduced from the
上記金属炭化物としては、AlCx,SiCx,TiCx,FeCx,CoCx,NiCx,CuCx,ZnCx,NbCx,MoCx,LaCx,TaCx,WCx及びPbCx等が挙げられ、本発明の触媒構造体には、これら金属炭化物を一種単独で用いてもよいし、これら金属炭化物の二種以上を用いてもよい。ここで、上記反応性スパッタリングによれば、上記各化学式中のxの値をスパッタリング時において導入口8から導入される炭化水素の流量を調整することで所望の値に制御することが可能となる。なお、反応性スパッタリングにおいて使用する炭化水素としては、特に制限はなく、メタン、エタン、エチレン、アセチレン等が挙げられる。
The metal carbide, AlC x, SiC x, TiC x, FeC x, CoC x, NiC x, CuC x, ZnC x, NbC x, MoC x, LaC x, TaC x, WC x and PBC x or the like can be mentioned In the catalyst structure of the present invention, these metal carbides may be used alone, or two or more of these metal carbides may be used. Here, according to the reactive sputtering, the value of x in each chemical formula can be controlled to a desired value by adjusting the flow rate of hydrocarbon introduced from the
また、上記金属酸化窒化物としては、AlOxNy,SiOxNy,TiOxNy,FeOxNy,CoOxNy,NiOxNy,CuOxNy,ZnOxNy,NbOxNy,MoOxNy,LaOxNy,TaOxNy,WOxNy及びPbOxNy等が挙げられ、本発明の触媒構造体には、これら金属酸化窒化物を一種単独で用いてもよいし、これら金属酸化窒化物の二種以上を用いてもよい。ここで、上記反応性スパッタリングによれば、上記各化学式中のx及びyの値をスパッタリング時において導入口8から導入される酸素及び窒素の流量を調整することで所望の値に制御することが可能となる。なお、触媒構造体を固体高分子型燃料電池用膜電極接合体の触媒層に用いる場合は、これら金属酸化窒化物の中でも、TiOxNyを用いることが更に好ましい。
Examples of the metal oxynitride include AlO x N y , SiO x N y , TiO x N y , FeO x N y , CoO x N y , NiO x N y , CuO x N y , ZnO x N y , NbO x N y , MoO x N y , LaO x N y , TaO x N y , WO x N y, PbO x N y and the like can be mentioned. The catalyst structure of the present invention includes one of these metal oxynitrides. You may use independently and 2 or more types of these metal oxynitrides may be used. Here, according to the reactive sputtering, the values of x and y in each chemical formula can be controlled to desired values by adjusting the flow rates of oxygen and nitrogen introduced from the
本発明の好適態様においては、上記ガスフロースパッタリングで用いたターゲット材の使用効率が80%以上であり、本発明では、担体表面への金属又は金属化合物のコーティングにガスフロースパッタリング法を採用するため、ターゲット材の使用効率が高い。 In a preferred embodiment of the present invention, the use efficiency of the target material used in the gas flow sputtering is 80% or more, and in the present invention, the gas flow sputtering method is used for coating a metal or metal compound on the support surface. The use efficiency of the target material is high.
本発明の触媒構造体における上記触媒材料の担持量は、その材料の触媒性能によって大きく変わるが、0.001mg/cm2〜10g/cm2の範囲が好ましい。担持量が0.001mg/cm2未満では、触媒としての働きが不十分であり、一方、10g/cm2を超えると、触媒としての有効面積が取れず、触媒性能が飽和する。 The supported amount of the catalyst material in the catalyst structure of the present invention varies greatly depending on the catalyst performance of the material, but is preferably in the range of 0.001 mg / cm 2 to 10 g / cm 2 . When the supported amount is less than 0.001 mg / cm 2 , the function as a catalyst is insufficient. On the other hand, when it exceeds 10 g / cm 2 , the effective area as a catalyst cannot be obtained and the catalyst performance is saturated.
本発明の触媒構造体を構成する担体としては、カーボン繊維集合体が好ましい。ここで、該カーボン繊維集合体としては、カーボンペーパー及び直径1nm〜1μmのフィブリル状カーボン繊維集合体等が更に好ましい。また、上記担体としては、カーボンペーパー上に直径1nm〜1μmのフィブリル状カーボン繊維集合体を配設してなる複合カーボン集合体も特に好ましい。 The carrier constituting the catalyst structure of the present invention is preferably a carbon fiber aggregate. Here, as the carbon fiber aggregate, carbon paper and a fibrillar carbon fiber aggregate having a diameter of 1 nm to 1 μm are more preferable. Further, as the carrier, a composite carbon aggregate obtained by disposing fibrillar carbon fiber aggregates having a diameter of 1 nm to 1 μm on carbon paper is particularly preferable.
また、上記担体として用いるフィブリル状カーボン繊維集合体としては、芳香環を有する化合物を酸化重合してフィブリル状ポリマーを得、該フィブリル状ポリマーを焼成、好ましくは非酸化性雰囲気中で焼成して得た3次元連続状炭素繊維が特に好ましい。なお、上記芳香環を有する化合物としては、ベンゼン環を有する化合物、芳香族複素環を有する化合物を挙げることができ、ベンゼン環を有する化合物としては、アニリン及びアニリン誘導体が好まく、芳香族複素環を有する化合物としては、ピロール、チオフェン及びこれらの誘導体が好ましい。これら芳香環を有する化合物は、一種単独で用いても、二種以上の混合物として用いてもよい。 The fibrillar carbon fiber aggregate used as the carrier is obtained by oxidatively polymerizing a compound having an aromatic ring to obtain a fibrillar polymer, and firing the fibrillated polymer, preferably in a non-oxidizing atmosphere. Particularly preferred is a three-dimensional continuous carbon fiber. In addition, examples of the compound having an aromatic ring include a compound having a benzene ring and a compound having an aromatic heterocyclic ring. As the compound having a benzene ring, aniline and aniline derivatives are preferable, and the aromatic heterocyclic ring. As the compound having pyrrole, pyrrole, thiophene and derivatives thereof are preferable. These compounds having an aromatic ring may be used alone or as a mixture of two or more.
上記芳香環を有する化合物を酸化重合して得られるフィブリル状ポリマーは、直径が30〜数百nmで、好ましくは40〜500nmであり、長さが0.5〜100000μmで、好ましくは1〜10000μmである。 The fibrillar polymer obtained by oxidative polymerization of the compound having an aromatic ring has a diameter of 30 to several hundred nm, preferably 40 to 500 nm, and a length of 0.5 to 100,000 μm, preferably 1 to 10,000 μm. .
上記酸化重合法としては、電解酸化重合法が好ましい。また、酸化重合においては、原料の芳香環を有する化合物と共に、酸を混在させることが好ましい。この場合、酸の負イオンがドーパントとして合成されるフィブリル状ポリマー中に取り込まれ、導電性に優れたフィブリル状ポリマーが得られ、このフィブリル状ポリマーを用いることにより最終的に得られる炭素繊維の導電性を向上させることができる。なお、重合の際に混在させる酸としては、特に限定されるものではなく、HBF4、H2SO4、HCl、HClO4等を例示することができ、該酸の濃度は、0.1〜3mol/Lの範囲が好ましく、0.5〜2.5mol/Lの範囲が更に好ましい。 As the oxidative polymerization method, an electrolytic oxidative polymerization method is preferable. Moreover, in oxidative polymerization, it is preferable to mix an acid with the compound which has a raw material aromatic ring. In this case, the negative ion of the acid is taken into the fibril polymer synthesized as a dopant to obtain a fibril polymer excellent in conductivity, and the conductivity of the carbon fiber finally obtained by using this fibril polymer is obtained. Can be improved. The acid mixed in the polymerization is not particularly limited, and examples thereof include HBF 4 , H 2 SO 4 , HCl, HClO 4 , and the concentration of the acid is 0.1 to 3 mol / The range of L is preferable, and the range of 0.5 to 2.5 mol / L is more preferable.
上記電解酸化重合によりフィブリル状ポリマーを得る場合には、芳香環を有する化合物を含む溶液中に、作用極及び対極を浸漬し、両極間に上記芳香環を有する化合物の酸化電位以上の電圧を印加するか、または該芳香環を有する化合物が重合するのに充分な電圧が確保できるような条件の電流を通電すればよく、これにより作用極上にフィブリル状ポリマーが生成する。ここで、作用極及び対極としては、ステンレススチール、白金、カーボン等の良導電性物質からなる板や多孔質材などを用いることができる。また、電解酸化重合における電流密度は、0.1〜1000mA/cm2の範囲が好ましく、0.2〜100mA/cm2の範囲が更に好ましく、芳香環を有する化合物の電解溶液中の濃度は、0.05〜3mol/Lの範囲が好ましく、0.25〜1.5mol/Lの範囲が更に好ましい。なお、電解溶液には、上記成分に加え、pHを調製するために可溶性塩等を適宜添加してもよい。 When a fibrillated polymer is obtained by the electrolytic oxidation polymerization, the working electrode and the counter electrode are immersed in a solution containing the compound having an aromatic ring, and a voltage higher than the oxidation potential of the compound having the aromatic ring is applied between both electrodes. Or a current having such a condition that a voltage sufficient to polymerize the compound having an aromatic ring may be passed, whereby a fibril-like polymer is formed on the working electrode. Here, as the working electrode and the counter electrode, a plate made of a highly conductive material such as stainless steel, platinum, or carbon, a porous material, or the like can be used. Also, the current density in the electrolytic oxidation polymerization is preferably in the range of 0.1~1000mA / cm 2, more preferably in the range of 0.2~100mA / cm 2, the concentration of the electrolytic solution of the compound having an aromatic ring, 0.05 to 3 mol / The range of L is preferable, and the range of 0.25 to 1.5 mol / L is more preferable. In addition to the above components, a soluble salt or the like may be appropriately added to the electrolytic solution in order to adjust the pH.
上記のようにして作用極上に得られたフィブリル状ポリマーを、水や有機溶剤等の溶媒で洗浄し、乾燥させた後、焼成、好ましくは非酸化性雰囲気中で焼成して炭化することで、フィブリル状で3次元連続状の炭素繊維が得られる。ここで、乾燥方法としては、特に制限されるものではないが、風乾、真空乾燥の他、流動床乾燥装置、気流乾燥機、スプレードライヤー等を使用した方法を例示することができる。また、焼成条件としては、特に限定されるものではなく、最適導電率となるように適宜設定すればよいが、特に高導電率を必要とする場合は、温度500〜3000℃、好ましくは600〜2800℃で、0.5〜6時間焼成することが好ましい。更に、非酸化性雰囲気としては、窒素雰囲気、アルゴン雰囲気、ヘリウム雰囲気等を挙げることができ、場合によっては水素雰囲気とすることもできる。なお、非酸化性雰囲気は、フィブリル状ポリマーが完全に酸化されない限り、少量の酸素を含んでもよい。 The fibrillated polymer obtained on the working electrode as described above is washed with a solvent such as water or an organic solvent, dried, then fired, preferably fired in a non-oxidizing atmosphere and carbonized. A fibril-like three-dimensional continuous carbon fiber is obtained. Here, the drying method is not particularly limited, and examples thereof include a method using a fluidized bed drying device, an air dryer, a spray dryer, etc., in addition to air drying and vacuum drying. In addition, the firing conditions are not particularly limited, and may be set as appropriate so as to obtain the optimum conductivity. Particularly, when high conductivity is required, the temperature is 500 to 3000 ° C., preferably 600 to Baking is preferably performed at 2800 ° C. for 0.5 to 6 hours. Further, examples of the non-oxidizing atmosphere include a nitrogen atmosphere, an argon atmosphere, and a helium atmosphere, and in some cases, a hydrogen atmosphere can also be used. The non-oxidizing atmosphere may contain a small amount of oxygen as long as the fibrillated polymer is not completely oxidized.
上記3次元連続状炭素繊維は、直径が30〜数百nm、好ましくは40〜500nmであり、長さが0.5〜100000μm、好ましくは1〜10000μmであり、表面抵抗が106〜10-2Ω、好ましくは104〜10-2Ωである。また、該炭素繊維は、残炭率が95〜30%、好ましくは90〜40%である。該炭素繊維は、カーボン全体が3次元に連続した構造を有するため、粒状カーボンよりも導電性が高い。 The three-dimensional continuous carbon fiber has a diameter of 30 to several hundred nm, preferably 40 to 500 nm, a length of 0.5 to 100,000 μm, preferably 1 to 10,000 μm, and a surface resistance of 10 6 to 10 −2 Ω. It is preferably 10 4 to 10 −2 Ω. The carbon fiber has a residual carbon ratio of 95 to 30%, preferably 90 to 40%. Since the carbon fiber has a structure in which the entire carbon is three-dimensionally continuous, the carbon fiber has higher conductivity than the granular carbon.
また、本発明の固体高分子型燃料電池用膜電極接合体は、固体高分子電解質膜と、該固体高分子電解質膜の両側に配置した触媒層と、該触媒層の両側に配置した拡散層とからなり、上記触媒層に上述した本発明の触媒構造体を用いたことを特徴とする。ここで、固体高分子電解質膜の各側に位置する触媒層及びガス拡散層の組は、燃料極及び空気極をそれぞれ構成し、燃料極では、2H2→4H++4e-で表される反応が起こり、発生したH+が固体高分子電解質膜を経て空気極に至る一方、発生したe-が外部に取り出されて電流となる。また、空気極では、O2+4H++4e-→2H2Oで表される反応が起こり、水が発生する。ここで、上記触媒構造体の担体が、カーボンペーパーと、該カーボンペーパー上に配設されたフィブリル状カーボン繊維集合体とからなる複合カーボン集合体であり、該集合体のフィブリル状カーボン繊維集合体の表面に触媒材料がガスフロースパッタリング法でコーティングされている場合、触媒材料がコーティングされたフィブリル状カーボン繊維集合体が触媒層に相当し、カーボンペーパーが拡散層として機能する。なお、固体高分子電解質膜としては、イオン伝導性のポリマーを使用することができ、該イオン伝導性のポリマーとしては、スルホン酸、カルボン酸、ホスホン酸、亜ホスホン酸等のイオン交換基を有するポリマーを挙げることができ、該ポリマーはフッ素を含んでも、含まなくてもよい。該イオン伝導性のポリマーとしては、ナフィオン(登録商標)等のパーフルオロカーボンスルホン酸系ポリマー等が挙げられる。 Further, a membrane electrode assembly for a polymer electrolyte fuel cell of the present invention comprises a solid polymer electrolyte membrane, a catalyst layer disposed on both sides of the solid polymer electrolyte membrane, and a diffusion layer disposed on both sides of the catalyst layer The catalyst structure of the present invention described above is used for the catalyst layer. Here, the combination of the catalyst layer and the gas diffusion layer located on each side of the solid polymer electrolyte membrane constitutes a fuel electrode and an air electrode, respectively, and the reaction expressed by 2H 2 → 4H + + 4e − at the fuel electrode. The generated H + reaches the air electrode through the solid polymer electrolyte membrane, and the generated e − is taken out to become an electric current. In the air electrode, a reaction represented by O 2 + 4H + + 4e − → 2H 2 O occurs, and water is generated. Here, the support of the catalyst structure is a composite carbon aggregate including carbon paper and a fibrillar carbon fiber aggregate disposed on the carbon paper, and the fibrillar carbon fiber aggregate of the aggregate When the catalyst material is coated on the surface of the substrate by gas flow sputtering, the fibrillar carbon fiber aggregate coated with the catalyst material corresponds to the catalyst layer, and the carbon paper functions as a diffusion layer. As the solid polymer electrolyte membrane, an ion conductive polymer can be used, and the ion conductive polymer has an ion exchange group such as sulfonic acid, carboxylic acid, phosphonic acid, and phosphonous acid. Mention may be made of polymers, which may or may not contain fluorine. Examples of the ion conductive polymer include perfluorocarbon sulfonic acid polymers such as Nafion (registered trademark).
以下に、実施例を挙げて本発明を更に詳しく説明するが、本発明は下記の実施例に何ら限定されるものではない。 Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to the following examples.
(実施例1)
[担体の作製]
アニリンモノマー0.5mol/LとHBF4 1.0mol/Lとを含む酸性水溶液中に、作用極としてカーボンペーパー[東レ製]を設置し、対極として白金板を使用し、室温にて10mA/cm2の定電流で10分間電解重合を行い、ポリアニリンを作用極上に電析させた。得られたポリアニリンをイオン交換水で洗浄後、24時間真空乾燥した後、SEMで観察したところ、カーボンペーパーの白金板に面した側に直径が50〜100nmのフィブリル状ポリアニリンが生成していることを確認した。
Example 1
[Production of carrier]
In an acidic aqueous solution containing 0.5 mol / L of aniline monomer and 1.0 mol / L of HBF 4 , carbon paper [manufactured by Toray] was installed as a working electrode, a platinum plate was used as a counter electrode, and 10 mA / cm 2 at room temperature. Electropolymerization was performed at a constant current for 10 minutes, and polyaniline was electrodeposited on the working electrode. The obtained polyaniline was washed with ion-exchanged water, vacuum-dried for 24 hours, and then observed with SEM. As a result, fibrillar polyaniline having a diameter of 50 to 100 nm was formed on the side of the carbon paper facing the platinum plate. It was confirmed.
次に、上記ポリアニリンをカーボンペーパーごとAr雰囲気中3℃/分の昇温速度で950℃まで加熱し、その後950℃で1時間保持して焼成処理した。得られた焼成物をSEMで観察したところ、直径が40〜100nmのフィブリル状で3次元連続状の炭素繊維が、カーボンペーパー上に生成していることを確認した。なお、得られた炭素繊維は、残炭率が45%で、表面抵抗が1.0Ωであった(三菱油化製, Loresta IP又はHiresta IPで測定)。 Next, the polyaniline was heated to 950 ° C. at a rate of 3 ° C./min in an Ar atmosphere together with the carbon paper, and then calcined by holding at 950 ° C. for 1 hour. When the obtained fired product was observed by SEM, it was confirmed that fibril-like and three-dimensional continuous carbon fibers having a diameter of 40 to 100 nm were formed on the carbon paper. The obtained carbon fiber had a residual carbon ratio of 45% and a surface resistance of 1.0Ω (measured by Mitsubishi Yuka, Loresta IP or Hiresta IP).
[触媒の担持]
図1に示すガスフロースパッタ装置を用い、下記の条件でTiOxNy薄膜を成膜し、触媒構造体を作製した。
<DCガスフロースパッタ条件>
・ターゲット寸法: 100mm×160mm×5mmt
・カソード形状: 平行平板(上記ターゲットを2枚平行に配置、距離30mm)
・スパッタ圧力: 13.3Pa(1Torr)
・スパッタ電力: 3kW
・Arガス流量: 5slm
・O2ガス流量: 0〜250sccm
・N2ガス流量: 0〜250sccm
・基板温度: 室温(基板加熱なし)
・基板移動速度: 50cm/min、往復、移動距離10cm
・スパッタ成膜時間: 1秒〜10分
・TiOxNy触媒担持量:0.4mg/cm2
[Supporting catalyst]
Using the gas flow sputtering apparatus shown in FIG. 1, a TiO x N y thin film was formed under the following conditions to produce a catalyst structure.
<DC gas flow sputtering conditions>
・ Target dimensions: 100mm × 160mm × 5mmt
・ Cathode shape: Parallel plate (two above targets are arranged in parallel, distance 30mm)
・ Sputtering pressure: 13.3Pa (1Torr)
・ Sputtering power: 3kW
・ Ar gas flow rate: 5slm
・ O 2 gas flow rate: 0 ~ 250sccm
・ N 2 gas flow rate: 0 ~ 250sccm
・ Substrate temperature: Room temperature (no substrate heating)
・ Board moving speed: 50cm / min, reciprocating, moving distance 10cm
Sputtering deposition time: 1 second to 10 minutes, TiO x N y catalyst loading: 0.4 mg / cm 2
[燃料電池の作製及び評価]
上記カーボンペーパー上に形成した触媒構造体に、5質量%のナフィオン(登録商標)溶液を塗布した後、乾燥して、カーボンペーパー上に触媒層を形成した。次に、ナフィオン(登録商標)からなる固体高分子電解質膜(膜厚:175μm)の両面に上記触媒層が接触するように触媒層付きカーボンペーパーをそれぞれ配置し、ホットプレスにより膜電極接合体(MEA)を作製した。得られた膜電極接合体は、触媒層の厚さが10μm、触媒構造体/ナフィオン=4/1(質量比)である。該膜電極接合体をエレクトロケミカル社製の試験セル(EFC25−01SP)に組み込み、燃料電池を作製した。該燃料電池の電圧-電流特性を、H2流量300cm3/分、O2流量300cm3/分、セル温度80℃、加湿温度80℃の条件で測定した。結果を表1に示す。
[Production and evaluation of fuel cells]
A 5 mass% Nafion (registered trademark) solution was applied to the catalyst structure formed on the carbon paper, and then dried to form a catalyst layer on the carbon paper. Next, carbon paper with a catalyst layer is arranged so that the catalyst layer is in contact with both surfaces of a solid polymer electrolyte membrane (film thickness: 175 μm) made of Nafion (registered trademark), and the membrane electrode assembly ( MEA) was prepared. In the obtained membrane / electrode assembly, the thickness of the catalyst layer was 10 μm, and the catalyst structure / Nafion = 4/1 (mass ratio). The membrane electrode assembly was incorporated into a test cell (EFC25-01SP) manufactured by Electrochemical Co., to produce a fuel cell. The voltage-current characteristics of the fuel cell were measured under the conditions of an H 2 flow rate of 300 cm 3 / min, an O 2 flow rate of 300 cm 3 / min, a cell temperature of 80 ° C., and a humidification temperature of 80 ° C. The results are shown in Table 1.
(比較例1〜2)
比較として、反応性ガスを導入しなかった例(比較例1)と、反応性ガスとして酸素のみを導入した例(比較例2)とを行った。これらの結果を1に示す。
(Comparative Examples 1-2)
For comparison, an example in which no reactive gas was introduced (Comparative Example 1) and an example in which only oxygen was introduced as a reactive gas (Comparative Example 2) were performed. These results are shown in 1.
表1から明らかなように、3次元連続状炭素繊維上にTiOxNyをコーティングした触媒構造体は、固体高分子型燃料電池用膜電極接合体の触媒層として作用し、電流掃引により電圧が発生したが、チタンのみ又は酸化チタンからなる膜を配設したものでは、電圧が発生しなかった。 As is apparent from Table 1, the catalyst structure in which TiO x N y is coated on three-dimensional continuous carbon fiber acts as a catalyst layer of a membrane electrode assembly for a polymer electrolyte fuel cell, and voltage is generated by current sweep. However, no voltage was generated when a film made of only titanium or titanium oxide was provided.
1 スパッタガス導入口
2 DC電源
3 アノード
4 カソード
5 ターゲット
6 担体
7 ホルダー
8 反応性ガスの導入口
P プラズマ
1 Sputtering gas introduction port 2 DC power source 3 Anode 4 Cathode 5
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