JP5388979B2 - A fuel cell catalyst, a membrane electrode assembly using the fuel cell, a fuel cell and a method for producing the fuel cell catalyst. - Google Patents
A fuel cell catalyst, a membrane electrode assembly using the fuel cell, a fuel cell and a method for producing the fuel cell catalyst. Download PDFInfo
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- IYDGMDWEHDFVQI-UHFFFAOYSA-N phosphoric acid;trioxotungsten Chemical compound O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.OP(O)(O)=O IYDGMDWEHDFVQI-UHFFFAOYSA-N 0.000 description 1
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Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Description
本発明の実施形態は、触媒、膜電極複合体、燃料電池とこれらの製造方法に関する。 Embodiments described herein relate generally to a catalyst, a membrane electrode assembly, a fuel cell, and a method for producing the same.
燃料電池は、特に、固体高分子型燃料電池は、他の燃料電池に比べて小型軽量化が可能なため、最近では自動車やモバイル機器などの電源としても盛んに研究されている。燃料電池の電池反応は、アノードとカソードの間で生じる酸化還元反応である。いずれの触媒材料も白金族触媒を使っており、燃料電池の本格普及には触媒材料の低コストと高特性が求められている。近年、非白金系触媒としてカーボンアロイ、炭窒化物などが検討されており、白金並みの酸素還元反応の開始電位が報告された。材料の組成と合成プロセスの調整によりこれら材料の表面に高活性を持つ表面構造を形成したと考えられ、活性と活性点密度を更に向上すれば実用化が可能と思われる。炭窒化物についてはカーボン系触媒より高安定性を持つ可能性が高いが、触媒活性、導電性などがまだ不十分である。 In particular, since a polymer electrolyte fuel cell can be reduced in size and weight as compared with other fuel cells, the fuel cell has recently been actively studied as a power source for automobiles and mobile devices. The cell reaction of a fuel cell is a redox reaction that occurs between the anode and the cathode. All the catalyst materials use platinum group catalysts, and low cost and high characteristics of the catalyst materials are required for full-scale spread of fuel cells. In recent years, carbon alloys, carbonitrides, and the like have been studied as non-platinum catalysts, and the onset potential of oxygen reduction reaction similar to platinum has been reported. It is thought that surface structures with high activity were formed on the surface of these materials by adjusting the composition of the materials and the synthesis process, and it would be possible to put it to practical use if the activity and the density of active sites were further improved. Carbon nitrides are likely to have higher stability than carbon-based catalysts, but their catalytic activity, conductivity, etc. are still insufficient.
活性と安定性の双方に優れる低コスト触媒、膜電極複合体及び燃料電池を提供することを目的とする。 An object of the present invention is to provide a low-cost catalyst, a membrane electrode composite, and a fuel cell that are excellent in both activity and stability.
本発明の実施形態にかかる燃料電池用触媒は、金属ワイヤー又は金属シートを担持体とし、担持体上に主触媒として担持された窒化物、炭化物又は炭窒化物とを有することを特徴とする。 A fuel cell catalyst according to an embodiment of the present invention is characterized in that a metal wire or a metal sheet is used as a carrier, and has a nitride, carbide or carbonitride supported as a main catalyst on the carrier .
上記した目的を達成するために、触媒材料の活性度と安定性の向上について鋭意研究を重ねた結果成されたものである。
本発明の実施形態に係る触媒は、例えば、図１の概念図に示すような金属ワイヤー１又は金属シート２とその上に担持された窒化物３、炭化物４又は炭窒化物５を有することを特徴とする。窒化物３、炭化物４又は炭窒化物５は下地である金属ワイヤー１又は金属シート２の影響を受け、単体と異なる原子配置、表面電子状態が得られ、本発明の実施形態にかかる触媒の高耐久性と高活性をもたらしたと考えられる。
In order to achieve the above-mentioned object, it has been made as a result of earnest research on the improvement of the activity and stability of the catalyst material.
The catalyst according to the embodiment of the present invention has, for example, a metal wire 1 or a metal sheet 2 as shown in the conceptual diagram of FIG. 1 and a nitride 3, a carbide 4 or a carbonitride 5 supported thereon. Features. The nitride 3, carbide 4 or carbonitride 5 is affected by the metal wire 1 or the metal sheet 2 as a base, and an atomic arrangement and surface electronic state different from those of a simple substance can be obtained. It is thought that it brought durability and high activity.
まず、本発明の実施形態に係る触媒の材料について説明する。
（窒化物、炭化物又は炭窒化物）
本発明の実施形態に係る窒化物３、炭化物４又は炭窒化物５は主触媒である。これらの表面に触媒の活性点が存在する。窒化物３、炭化物４又は炭窒化物５の単体でも触媒活性を持つが、十分ではない。特に触媒の電極反応には電子の授受が必要であるが、窒化物３、炭化物４又は炭窒化物５の電気伝導性が不十分であるため、電極反応に十分に貢献できない活性サイトが多い。本発明の実施形態では炭化物４、窒化物３又は炭窒化物５の担持体として金属ワイヤー１又は金属シート２を導入する。そして、少なくとも一部の窒化物３、炭化物４又は炭窒化物５は、金属ワイヤー１又は金属シート２と直接接していることを特徴とする。これによって、窒化物３、炭化物４又は炭窒化物５の表面に特異な原子配置、電子状態を形成し、本発明の実施形態に係る触媒の高活性と高耐久性をもたらしたと考えている。
First, the material of the catalyst according to the embodiment of the present invention will be described.
(Nitride, carbide or carbonitride)
The nitride 3, carbide 4 or carbonitride 5 according to the embodiment of the present invention is a main catalyst. There are active sites of the catalyst on these surfaces. Even a simple substance of nitride 3, carbide 4 or carbonitride 5 has catalytic activity, but it is not sufficient. In particular, it is necessary to exchange electrons for the electrode reaction of the catalyst, but since the electrical conductivity of nitride 3, carbide 4 or carbonitride 5 is insufficient, there are many active sites that cannot sufficiently contribute to the electrode reaction. In the embodiment of the present invention, the metal wire 1 or the metal sheet 2 is introduced as a support of the carbide 4, nitride 3 or carbonitride 5. At least a part of the nitride 3, carbide 4 or carbonitride 5 is in direct contact with the metal wire 1 or the metal sheet 2. Thus, it is considered that a unique atomic arrangement and electronic state are formed on the surface of the nitride 3, carbide 4 or carbonitride 5, thereby bringing about high activity and high durability of the catalyst according to the embodiment of the present invention.
窒化物３、炭化物４又は炭窒化物５の粒径は０．２ｎｍ以上１０ｎｍ以下であることが望ましい。粒径が１０ｎｍを超えると、活性低下が顕著になり、金属ワイヤー１又は金属シート２の影響を受けにくくなり、窒化物３、炭化物４又は炭窒化物５の表面に特異な原子配置、電子状態を形成しにくくなり、また、導電パスに存在する活性サイトの数が少なくなると思われる。粒径を０．２ｎｍ未満にすると、耐久性が低下する場合がある。これら粒径は、さらに好ましくは０．２ｎｍ以上５ｎｍ以下である。 The particle size of nitride 3, carbide 4 or carbonitride 5 is preferably 0.2 nm or more and 10 nm or less. When the particle diameter exceeds 10 nm, the activity decrease becomes remarkable, and it becomes difficult to be affected by the metal wire 1 or the metal sheet 2, and the specific atomic arrangement and electronic state on the surface of the nitride 3, carbide 4 or carbonitride 5. It is considered that the number of active sites existing in the conductive path is reduced. If the particle size is less than 0.2 nm, the durability may decrease. These particle sizes are more preferably 0.2 nm or more and 5 nm or less.
窒化物３、炭化物４又は炭窒化物５は、Ｔａ，Ｎｂ，Ｚｒ，Ｔｉ，Ｗ，Ｍｏ，Ｃｅ，Ｈｆ, Ｓｎ，Ａｌ，Ｃｕ，Ｍｎ，Ｌａ，Ｂａ，Ｆｅ，Ｃｏ及びＮｉよりなる群から選ばれる少なくとも一種の元素を含む化合物である。これら元素を含む窒化物３、炭化物４又は炭窒化物５は高い活性と安定性を有する。窒化物３、炭化物４又は炭窒化物５は、それぞれの炭素の含有量が１０〜７０原子％、窒素の含有量が２〜７０原子％であることが望ましい。これら範囲から外れると、活性が低下する可能性が大きくなる。なお、本発明の実施形態に係る触媒はナノサイズであるため、大気中の酸素の吸着が避けられない。これら酸素は本発明の実施形態に係る触媒の窒化物３、炭化物４又は炭窒化物５の表面特異構造または表面電子状態に貢献したと考えている。窒化物３、炭化物４又は炭窒化物５は、０．５〜９０原子％酸素を含むことを特徴とする。また、本発明の実施形態に係る触媒に酸化層が形成することを許容する。なお、窒化物３、炭化物４又は炭窒化物５は、金属ワイヤー１又は金属シート２の構成元素を５〜２０原子％を含むことによって触媒特性が更に向上する場合はある。 The nitride 3, carbide 4 or carbonitride 5 is from the group consisting of Ta, Nb, Zr, Ti, W, Mo, Ce, Hf, Sn, Al, Cu, Mn, La, Ba, Fe, Co and Ni. It is a compound containing at least one element selected. Nitride 3, carbide 4 or carbonitride 5 containing these elements has high activity and stability. The nitride 3, carbide 4 or carbonitride 5 preferably has a carbon content of 10 to 70 atomic% and a nitrogen content of 2 to 70 atomic%. When it deviates from these ranges, the possibility that the activity decreases is increased. In addition, since the catalyst according to the embodiment of the present invention is nano-sized, adsorption of oxygen in the atmosphere is inevitable. It is believed that these oxygens contributed to the surface specific structure or surface electronic state of the nitride 3, carbide 4 or carbonitride 5 of the catalyst according to the embodiment of the present invention. The nitride 3, the carbide 4 or the carbonitride 5 contains 0.5 to 90 atomic% oxygen. In addition, an oxidation layer is allowed to be formed on the catalyst according to the embodiment of the present invention. Note that the nitride 3, the carbide 4 or the carbonitride 5 may further improve the catalyst characteristics by containing 5 to 20 atomic% of the constituent elements of the metal wire 1 or the metal sheet 2.
本発明の実施形態に係る触媒の窒化物３、炭化物４又は炭窒化物５はアモルファス構造を持つことが多いが、表面がアモルファス構造、内部が準結晶構造または結晶構造であるコアシェル構造を持つことも観測され、場合によって触媒特性が向上することもある。 The nitride 3, carbide 4 or carbonitride 5 of the catalyst according to the embodiment of the present invention often has an amorphous structure, but has a core-shell structure in which the surface is an amorphous structure and the inside is a quasicrystalline structure or a crystalline structure. Is observed, and in some cases, the catalytic properties may be improved.
（金属ワイヤー又は金属シート）
ナノサイズの金属ワイヤー１又は金属シート２には粒子と異なる原子配置、電子状態を形成しやすいと報告されている。本発明の実施形態では、炭化物４、窒化物３、炭窒化物５の担持体として金属ワイヤー１又は金属シート２を導入する。金属ワイヤー１又は金属シート２は、助触媒として本発明の実施形態に係る触媒の高活性と高耐久性をもたらしたと考えている。また、触媒の活性点が燃料電池の電極反応に貢献するには触媒層１５の導電パスに存在することは必須であり、金属ワイヤー１又は金属シート２の導電性は、窒化物３、炭化物４又は炭窒化物５より高いため、金属ワイヤー１又は金属シート２である担持体の導入によって本発明の実施形態に係る触媒層担持基板の活性点密度が大幅向上し、高燃料電池特性を齎したと考えられる。
(Metal wire or metal sheet)
It has been reported that the nano-sized metal wire 1 or metal sheet 2 is likely to form an atomic arrangement or electronic state different from the particles. In the embodiment of the present invention, the metal wire 1 or the metal sheet 2 is introduced as a support for the carbide 4, the nitride 3, and the carbonitride 5. The metal wire 1 or the metal sheet 2 is considered to have brought about the high activity and high durability of the catalyst according to the embodiment of the present invention as a promoter. In order for the active site of the catalyst to contribute to the electrode reaction of the fuel cell, it is essential that it exists in the conductive path of the catalyst layer 15, and the conductivity of the metal wire 1 or the metal sheet 2 is nitride 3, carbide 4. Alternatively, since it is higher than carbonitride 5, the active point density of the catalyst layer-carrying substrate according to the embodiment of the present invention is greatly improved by introducing the carrier that is the metal wire 1 or the metal sheet 2, and the high fuel cell characteristics are improved. it is conceivable that.
本発明の実施形態に係る金属ワイヤー１のアスペクト比は、金属ワイヤー１の長さと金属ワイヤー１の平均直径との比で定義する。本発明の実施形態に係る金属シート２のアスペクト比は、金属シート２の長さと金属シート２の厚さとの比で定義する。それぞれのアスペクト比は２．５以上であることが望ましい。金属ワイヤー１のアスペクト比が２．５未満であると、触媒活性または耐久性が低下する恐れがあり、触媒層における導電パスのネットワークが不十分になる。金属ワイヤー１の平均直径または金属シート２の平均厚さが０．２ｎｍ以上１０ｎｍ以下であることが望ましい。アスペクト比は、さらに好ましくは５以上である。
金属ワイヤー１の平均直径又は金属シート２の平均厚さが１０ｎｍを超えると、触媒活性が低くなる場合がある。また、金属ワイヤー１の平均直径または金属シート２の平均厚さが０．２ｎｍ未満であると、触媒耐久性が低下する場合がある。金属ワイヤー１の平均直径または金属シート２の平均厚さは、より好ましくは０．２ｎｍ以上５ｎｍ以下である。
本発明の実施形態に係る金属ワイヤー１又は金属シート２は、Ａｕ，Ｒｕ，Ｐｔ，Ｐｄ，Ｗ，Ｍｏ，Ｔａ，Ｎｂ，Ｚｒ，Ｔｉ，Ｃｒ，Ｎｉ及びＣｏよりなる群から選ばれる少なくとも一種の元素を含むことが望ましい。これら元素を助触媒に用いることで、高い活性と安定性が得られる。
The aspect ratio of the metal wire 1 according to the embodiment of the present invention is defined by the ratio between the length of the metal wire 1 and the average diameter of the metal wire 1. The aspect ratio of the metal sheet 2 according to the embodiment of the present invention is defined by the ratio between the length of the metal sheet 2 and the thickness of the metal sheet 2. Each aspect ratio is preferably 2.5 or more. If the aspect ratio of the metal wire 1 is less than 2.5, the catalyst activity or durability may be lowered, and the network of conductive paths in the catalyst layer becomes insufficient. The average diameter of the metal wire 1 or the average thickness of the metal sheet 2 is preferably 0.2 nm or more and 10 nm or less. The aspect ratio is more preferably 5 or more.
When the average diameter of the metal wire 1 or the average thickness of the metal sheet 2 exceeds 10 nm, the catalytic activity may be lowered. Moreover, catalyst durability may fall that the average diameter of the metal wire 1 or the average thickness of the metal sheet 2 is less than 0.2 nm. The average diameter of the metal wire 1 or the average thickness of the metal sheet 2 is more preferably 0.2 nm or more and 5 nm or less.
The metal wire 1 or the metal sheet 2 according to the embodiment of the present invention is at least one selected from the group consisting of Au, Ru, Pt, Pd, W, Mo, Ta, Nb, Zr, Ti, Cr, Ni, and Co. It is desirable to include an element. By using these elements as promoters, high activity and stability can be obtained.
金属ワイヤー１又は金属シート２の構成元素の元素結合状態については貴金属の場合は金属結合がメインであり、ベースメタルの場合はベースメタルが酸化結合を持つことが多い。窒化物３、炭化物４又は炭窒化物５の炭素又は窒素の拡散によって金属ワイヤー１又は金属シート２の構成元素の一部が炭素又は窒素と結合することも観測された。 As for the element bonding state of the constituent elements of the metal wire 1 or the metal sheet 2, in the case of a noble metal, the metal bond is the main, and in the case of a base metal, the base metal often has an oxidative bond. It was also observed that some of the constituent elements of the metal wire 1 or the metal sheet 2 were bonded to carbon or nitrogen by the diffusion of carbon or nitrogen of the nitride 3, carbide 4 or carbonitride 5.
金属ワイヤー１又は金属シート２の構造については特に限定しないが、結晶構造を持つ場合は、耐久性が向上する場合がある。微結晶、アモルファスとの混合状態で存在する場合は耐久性が若干劣るが、活性は向上することもある。用途に応じて、耐久性と活性とのバランスを顧慮し、プロセス、組成によって金属ワイヤー１又は金属シート２の結合状態又は結晶状態を制御できる。 Although it does not specifically limit about the structure of the metal wire 1 or the metal sheet 2, When it has a crystal structure, durability may improve. When it exists in a mixed state with microcrystals and amorphous, the durability is slightly inferior, but the activity may be improved. Depending on the application, the balance between durability and activity can be taken into account, and the bonding state or crystal state of the metal wire 1 or the metal sheet 2 can be controlled by the process and composition.
金属ワイヤー１の平均直径とアスペクト比と、金属シート２の平均厚さとアスペクト比と、窒化物３、炭化物４又は炭窒化物５の粒径は、透過型電子顕微鏡（ＴＥＭ）分析によって測定したもので、具体的には、本発明の実施形態にかかる触媒を含む触媒層の上部、中部、内部において、それぞれ３箇所の断面（合計９視野）をＴＥＭ観察（２００万倍）し、各視野における全対象物の平均値を用いる。 Average diameter and aspect ratio of metal wire 1, average thickness and aspect ratio of metal sheet 2, and particle size of nitride 3, carbide 4 or carbonitride 5 were measured by transmission electron microscope (TEM) analysis. Specifically, in the upper, middle and inner portions of the catalyst layer containing the catalyst according to the embodiment of the present invention, three cross sections (total 9 fields) are observed by TEM (2 million times), The average value of all objects is used.
造孔材料層１４の平均厚さは１層あたり５ｎｍ以上５００ｎｍ以下とする。５ｎｍ未満では金属材料層１２中の金属材料同士、触媒材料層１３中の触媒材料同士の凝集が顕著になりやすく、触媒特性が低下するほか、造孔処理によって得られる空隙のサイズが小さくなり、燃料電池の燃料供給が困難になり、燃料電池特性が低下する。５００ｎｍを超える場合は更なる触媒凝集の抑制効果または空隙構造改善の効果が少ないうえに、製造プロセスのコスト上昇を招く可能性が高い。この造孔材料層１４の平均厚さは１層あたり１０ｎｍ以上３５０ｎｍ以下とすることが特に好ましい。造孔材料は、酸洗浄、アルカリ洗浄などの造孔工程によって、造孔材料の大部分が除去されるものであればよく、金属又は無機酸化物が挙げられるが限定されない。造孔材料に金属を用いる場合は、短時間で形成できる、除去できるなどプロセスのコストを考えると、Ｍｎ，Ｆｅ，Ｃｏ，Ｎｉ，Ｚｎ，Ｓｎ，Ａｌ，Ｃｕから選択される少なくとも一種の金属が望ましい。造孔材料に無機酸化物を用いる場合は、ＷＯ３、ＺｒＯ２等の酸化物が望ましい。
なお、本発明の実施形態にかかる触媒層１５には、無機酸化物粒子の存在を許容する。それにより触媒粒子の凝集／成長の抑制が高く、触媒利用効率や耐久性を向上させることができる。無機酸化物粒子は造孔処理後に残存の造孔材料によって形成することもできる。また、本発明の実施形態にかかる触媒は他の触媒と混合して使用することも可能であり、混合による相乗効果を期待できる。
The average thickness of the pore-forming material layer 14 is 5 nm or more and 500 nm or less per layer. If the thickness is less than 5 nm, the aggregation of the metal materials in the metal material layer 12 and the catalyst materials in the catalyst material layer 13 are likely to be remarkable, the catalytic properties are deteriorated, and the size of the voids obtained by the pore forming process is reduced. The fuel supply of the fuel cell becomes difficult, and the fuel cell characteristics deteriorate. When it exceeds 500 nm, there is a high possibility that the effect of further suppressing the catalyst aggregation or the effect of improving the void structure is small and the cost of the production process is increased. The average thickness of the pore forming material layer 14 is particularly preferably 10 nm or more and 350 nm or less per layer. The pore forming material may be any material as long as most of the pore forming material is removed by a hole forming step such as acid cleaning or alkali cleaning, and examples thereof include, but are not limited to, metals and inorganic oxides. When a metal is used for the pore forming material, at least one kind of metal selected from Mn, Fe, Co, Ni, Zn, Sn, Al, and Cu is considered in consideration of process costs such as formation and removal in a short time. desirable. When an inorganic oxide is used for the pore forming material, an oxide such as WO 3 or ZrO 2 is desirable.
The catalyst layer 15 according to the embodiment of the present invention allows the presence of inorganic oxide particles. Thereby, the suppression of the aggregation / growth of the catalyst particles is high, and the catalyst utilization efficiency and durability can be improved. The inorganic oxide particles can also be formed from the remaining pore-forming material after the pore-forming treatment. In addition, the catalyst according to the embodiment of the present invention can be used by mixing with another catalyst, and a synergistic effect by mixing can be expected.
次に、本発明の実施形態にかかる触媒の製造方法について、図３の製造方法のプロセスの一例を示す概念図を用いて説明する。
この方法を本発明においては、スパッタ積層法と呼ぶ。
まず、基板１１に金属ワイヤー１又は金属シート２の材料となる金属材料をスパッタもしくは蒸着し、金属材料層１２を形成する（第１の工程）。次に、窒化物３、炭化物４又は炭窒化物５材料をスパッタ又は蒸着して、触媒材料層１３を金属材料層１２上に形成する（第２の工程）。その後、造孔材料をスパッタもしくは蒸着し、造孔材料層１４を触媒材料層１３上に形成する（第３の工程）（図３（Ａ））。この第１から第３の３工程を順番に複数回繰り返して金属材料層１２、触媒材料層１３と造孔材料層１４との積層体を形成する（積層工程）（図３（Ｂ）））。この後に、積層体を造孔処理し、金属材料層１２、触媒材料層１３と造孔材料層１４の一部を溶解除去する（造孔処理工程）（図３（Ｃ））。金属材料層１２と触媒材料層１３に造孔処理工程が施されたものに、本発明の実施形態に係る触媒が含まれる。以下、造孔処理された積層体を触媒層１５と記す。
Next, a catalyst manufacturing method according to an embodiment of the present invention will be described with reference to a conceptual diagram showing an example of a process of the manufacturing method of FIG.
In the present invention, this method is called a sputter lamination method.
First, the metal material used as the material of the metal wire 1 or the metal sheet 2 is sputtered or vapor-deposited on the substrate 11 to form the metal material layer 12 (first step). Next, the nitride 3, carbide 4 or carbonitride 5 material is sputtered or deposited to form the catalyst material layer 13 on the metal material layer 12 (second step). Thereafter, the pore-forming material is sputtered or vapor-deposited to form the pore-forming material layer 14 on the catalyst material layer 13 (third step) (FIG. 3A). The first to third steps are repeated a plurality of times in order to form a laminate of the metal material layer 12, the catalyst material layer 13 and the pore-forming material layer 14 (lamination step) (FIG. 3B)) . Thereafter, the laminate is subjected to pore forming treatment, and a part of the metal material layer 12, the catalyst material layer 13 and the pore forming material layer 14 is dissolved and removed (pore forming treatment step) (FIG. 3C). The catalyst according to the embodiment of the present invention is included in the metal material layer 12 and the catalyst material layer 13 that have been subjected to the pore forming process. Hereinafter, the laminated body that has been subjected to pore forming treatment is referred to as a catalyst layer 15.
基板１１としては、触媒層をサポートできるものであれば、その材料および構成に特に制限されるものではない。例えば、炭素層を有するカーボンペーパー等を用いることができる。また、導電性を持たないもの、多孔質ではないものでもよい。本発明の実施形態に係る触媒が形成した触媒層を基板に形成してからプロトン伝導性膜に転写しても良い。 The substrate 11 is not particularly limited in its material and configuration as long as it can support the catalyst layer. For example, carbon paper having a carbon layer can be used. Moreover, the thing which does not have electroconductivity and the thing which is not porous may be used. The catalyst layer formed by the catalyst according to the embodiment of the present invention may be formed on the substrate and then transferred to the proton conductive membrane.
造孔処理は、具体的には酸洗浄による造孔処理が容易であり望ましい。造孔処理は酸洗浄に限定されるものではなく、本発明の実施形態を維持し、十分な空隙構造を作ることができれば、他のプロセスを採用しても良い。酸洗浄を行なう場合には、例えば、硝酸、塩酸、硫酸、またはこれらの混合液を用い、５分〜５０時間程度の時間で行うことが出来る。このとき、５０〜１００℃程度に加熱して酸処理を行っても良い。また、場合によっては、触媒中の造孔材料の溶解を促進するためにバイアス電圧を加えたり、熱処理などの後処理を加えたりしても良い。酸洗浄以外の造孔処理は、例えばアルカリ溶液による洗浄造孔、または電解法による造孔でも良い。酸洗浄以外の造孔処理は、例えばアルカリ溶液による洗浄造孔、または電解法による造孔でも良い。アルカリの場合は例えばＮａＯＨ水溶液を用い、５分〜５０時間程度の時間で行うことが出来る。 Specifically, the hole making treatment is desirable because the hole making treatment by acid cleaning is easy. The hole making treatment is not limited to acid cleaning, and other processes may be adopted as long as the embodiment of the present invention can be maintained and a sufficient void structure can be formed. When acid cleaning is performed, for example, nitric acid, hydrochloric acid, sulfuric acid, or a mixture thereof can be used in a time of about 5 minutes to 50 hours. At this time, the acid treatment may be performed by heating to about 50 to 100 ° C. In some cases, a bias voltage may be applied or post-treatment such as heat treatment may be applied in order to promote dissolution of the pore-forming material in the catalyst. The hole making treatment other than the acid washing may be, for example, a washing hole making with an alkaline solution or a hole making by an electrolytic method. The hole making treatment other than the acid washing may be, for example, a washing hole making with an alkaline solution or a hole making by an electrolytic method. In the case of an alkali, for example, a NaOH aqueous solution is used, and it can be performed in a time of about 5 minutes to 50 hours.
本発明の実施形態に係る触媒は、スパッタプロセス以外の他のプロセスでも可能である。例えば、溶液錯体法などによって金属ワイヤー１又は金属シート２を作製し、浸漬法によって金属酸化物を金属ワイヤー１又は金属シート２に担持させた後、炭素又は窒素を含む雰囲気において窒化物３、炭化物４又は炭窒化物５を生成する。 The catalyst according to the embodiment of the present invention can be a process other than the sputtering process. For example, the metal wire 1 or the metal sheet 2 is prepared by a solution complex method or the like, and a metal oxide is supported on the metal wire 1 or the metal sheet 2 by an immersion method, and then nitride 3 or carbide in an atmosphere containing carbon or nitrogen. 4 or carbonitride 5 is produced.
なお、本発明の実施形態に係る触媒は後処理によって触媒特性が向上する場合はある。後処理については、例えば、１００℃〜１２００℃の範囲内の温度で、０．０５〜１００時間、ガス雰囲気中において行なう。ガス雰囲気については水素（Ｈ２）ガス、酸素（Ｏ２）、アルゴンガス、アンモニア（ＮＨ３）ガス、また、これらの混合ガスなど等を挙げることができる。後処理によって、窒化物３、炭化物４又は炭窒化物５粒子、金属ワイヤー１又は金属シート２の凝集と粗大化はある程度進行し、表面活性サイトの数が減るが活性点における触媒活性と耐久性が大幅向上し、燃料電池の特性が向上する場合はよくある。 In addition, the catalyst characteristics according to the embodiment of the present invention may improve the catalyst characteristics by post-treatment. The post-treatment is performed, for example, in a gas atmosphere at a temperature in the range of 100 ° C. to 1200 ° C. for 0.05 to 100 hours. Examples of the gas atmosphere include hydrogen (H 2 ) gas, oxygen (O 2 ), argon gas, ammonia (NH 3 ) gas, and mixed gas thereof. By the post-treatment, the aggregation and coarsening of the nitride 3, carbide 4 or carbonitride 5 particles, metal wire 1 or metal sheet 2 proceed to some extent, the number of surface active sites decreases, but the catalytic activity and durability at the active site. It is often the case that the fuel cell characteristics are greatly improved and the characteristics of the fuel cell are improved.
また、触媒材料の利用効率は、触媒材料のサイズのほかに、燃料‐触媒‐プロトン伝導体で形成される三相界面の密度に依存するため、三相界面ができるだけ多くなるよう触媒層１５に空隙を導入すると好ましい。したがって、触媒層１５の空隙率が２０％以上であるものを使用することが好ましい。空隙率が２０％未満では、触媒凝集と触媒成長を十分に抑制できず、触媒サイズが大きく、高い触媒利用効率が得られにくい。触媒層１５の空隙率は４０％以上９０％以下となることが特に望ましい。９０％以上の場合は更なる触媒凝集の抑制効果が少ないため、製造プロセスのコスト上昇を招く可能性が高い。 Further, the utilization efficiency of the catalyst material depends on the density of the three-phase interface formed by the fuel-catalyst-proton conductor in addition to the size of the catalyst material. It is preferable to introduce voids. Therefore, it is preferable to use a catalyst layer having a porosity of 20% or more. When the porosity is less than 20%, catalyst aggregation and catalyst growth cannot be sufficiently suppressed, the catalyst size is large, and high catalyst utilization efficiency is difficult to obtain. The porosity of the catalyst layer 15 is particularly preferably 40% or more and 90% or less. In the case of 90% or more, since the effect of further suppressing the catalyst aggregation is small, there is a high possibility that the cost of the production process is increased.
なお、上記にて空隙率を示したが、本明細書では以下のように空隙率を求める。
試料のＴＥＭ像のコントラストから触媒と空隙を区別できるため、本発明の実施形態にかかる触媒を含む触媒層内の上部、中部、下部においてそれぞれ３箇所の断面（合計９視野）をＴＥＭ観察（２００万倍）し、各視野に含まれた空隙と触媒層の合計面積をそれぞれ計測し、空隙の合計面積／触媒層の合計面積を求め、９視野の平均値を空隙率として用いる。
In addition, although the porosity was shown above, in this specification, a porosity is calculated | required as follows.
Since the catalyst and the void can be distinguished from the contrast of the TEM image of the sample, three cross sections (total of 9 fields) are respectively observed in the upper, middle and lower portions of the catalyst layer containing the catalyst according to the embodiment of the present invention (200 views). The total area of the voids and the catalyst layer included in each visual field is measured, the total area of the voids / the total area of the catalyst layers is obtained, and the average value of nine visual fields is used as the porosity.
（膜電極複合体及び燃料電池）
膜電極複合体（ＭＥＡ）は、図４の概念図に示すように、アノード触媒層２１、カソード触媒層２３、及び前記アノード触媒層２１とカソード触媒層２３の間に介挿されたプロトン伝導性膜２２を有する膜電極複合体である。そして、前記アノード触媒又は前記カソード触媒のいずれか一方は本発明の実施形態に係るいずれかの触媒を具備する。
(Membrane electrode composite and fuel cell)
As shown in the conceptual diagram of FIG. 4, the membrane electrode assembly (MEA) includes an anode catalyst layer 21, a cathode catalyst layer 23, and proton conductivity interposed between the anode catalyst layer 21 and the cathode catalyst layer 23. A membrane electrode assembly having a membrane 22. And either one of the said anode catalyst or the said cathode catalyst comprises the catalyst which concerns on embodiment of this invention.
燃料電池は、前述したＭＥＡと、アノードに燃料を供給する手段と、カソードに酸化剤を供給する手段とを含む。ＭＥＡに加えて、燃料電池流路板を備え、さらにこのＭＥＡと燃料電池流路板との間に多孔質燃料拡散層を備えていてもよい。使用するＭＥＡの数は１つでも、複数でもよい。ＭＥＡを複数使用することにより、より高い起電力を得ることができる。燃料電池の燃料としては、メタノール、エタノール、蟻酸、あるいはこれらから選ばれる１種類以上を含む水溶液等を使用することができる。 The fuel cell includes the above-mentioned MEA, means for supplying fuel to the anode, and means for supplying an oxidant to the cathode. In addition to the MEA, a fuel cell channel plate may be provided, and a porous fuel diffusion layer may be provided between the MEA and the fuel cell channel plate. One or more MEAs may be used. By using a plurality of MEAs, a higher electromotive force can be obtained. As fuel for the fuel cell, methanol, ethanol, formic acid, or an aqueous solution containing one or more selected from these can be used.
図５に、本発明の実施形態にかかる燃料電池の概念図を示す。
燃料電池３０は、プロトン電導性膜３１、およびその膜３１を挟んで２つの電極、すなわち、燃料が供給される燃料極（アノード）３２と酸素が供給される空気極（カソード）３３が配置されたものを基本構成とした膜電極接合体（ＭＥＡ）３８を具備する。アノード３２は、拡散層３４と、その上に積層されたアノード触媒層３５とを含む。カソード３３は、拡散層３６と、その上に積層されたカソード触媒層３７とを含む。アノード３２とカソード３３は、プロトン電導性膜３１を介して、アノード触媒層３５とカソード触媒層３７とが対向するように積層される。
FIG. 5 shows a conceptual diagram of a fuel cell according to an embodiment of the present invention.
The fuel cell 30 includes a proton conductive membrane 31 and two electrodes sandwiching the membrane 31, that is, a fuel electrode (anode) 32 to which fuel is supplied and an air electrode (cathode) 33 to which oxygen is supplied. And a membrane electrode assembly (MEA) 38 having a basic structure. The anode 32 includes a diffusion layer 34 and an anode catalyst layer 35 laminated thereon. The cathode 33 includes a diffusion layer 36 and a cathode catalyst layer 37 stacked thereon. The anode 32 and the cathode 33 are laminated so that the anode catalyst layer 35 and the cathode catalyst layer 37 face each other with the proton conductive film 31 interposed therebetween.
ＭＥＡ３８は図示しない空気（酸素）等の酸化剤を供給する供給機構から空気（酸素）をカソードへ供給するための酸化剤ガス供給溝３９付きのカソードホルダー４０と、燃料である水素等をアノードへ供給するための燃料供給溝４１付きのアノードホルダー４２との内部に組み込んで、図１に示すような単電池を構成して発電を行う。燃料電池３０においては、燃料電池３０が所望する電圧等を得られるように、カソードホルダー４０およびアノードホルダー４２を介してＭＥＡ３８を複数積層して直列に繋いだスタック構造あるいは平面配置構造を形成してもよい。燃料電池３０の形状などは、特に限定されず、所望する電圧などの電池特性が得られるように適宜決定すればよい。 The MEA 38 has a cathode holder 40 with an oxidant gas supply groove 39 for supplying air (oxygen) to the cathode from a supply mechanism for supplying oxidant such as air (oxygen) (not shown), and hydrogen as fuel to the anode. A unit cell as shown in FIG. 1 is built into the anode holder 42 with the fuel supply groove 41 for supply to generate electric power. In the fuel cell 30, a stack structure or a planar arrangement structure in which a plurality of MEAs 38 are stacked and connected in series via the cathode holder 40 and the anode holder 42 so as to obtain a desired voltage or the like is formed. Also good. The shape of the fuel cell 30 is not particularly limited, and may be determined as appropriate so that desired battery characteristics such as voltage can be obtained.
本発明の実施形態の燃料電池は、上記では高分子電解質型燃料電池を例に挙げて説明したがこれに限定されず、ダイレクトメタノール燃料電池、リン酸型燃料電池に代表される酸型電解質の燃料電池など各種燃料電池に対して用いることができる。なかでも、高密度・高出力化が可能であるから、固体高分子型燃料電池に適用されるのが好ましい。
前記燃料電池は、定置用電源の他、搭載スペースが限定される自動車などの移動体用電源などとして有用である。なかでも、製造コストが低減され、かつ、発電性能に優れることから、自動車などの移動体用電源として用いられるのが特に好ましい。
The fuel cell of the embodiment of the present invention has been described above by taking a polymer electrolyte fuel cell as an example, but is not limited thereto, and is not limited to this, and is an acid electrolyte represented by a direct methanol fuel cell and a phosphoric acid fuel cell. It can be used for various fuel cells such as fuel cells. Especially, since it is possible to achieve high density and high output, it is preferably applied to a polymer electrolyte fuel cell.
The fuel cell is useful as a power source for a moving body such as an automobile having a limited mounting space in addition to a stationary power source. Among these, it is particularly preferable to use as a power source for a mobile body such as an automobile because the manufacturing cost is reduced and the power generation performance is excellent.
プロトン伝導性２２に含まれるプロトン伝導性物質は、プロトンを伝達できる材料であれば特に制限されることなく使用することができる。プロトン伝導性物質としては、高分子物質、例えば、デュポン社製のナフィオン（登録商標）、旭硝子社製のフレミオン（登録商標）、旭化成ケミカルズ社製のアシブレック（登録商標）などのスルホン酸基を持つフッ素樹脂や、タングステン酸やリンタングステン酸などの無機物などが挙げられるが、これらに限定されるものではない。 The proton conductive substance contained in the proton conductivity 22 can be used without particular limitation as long as it is a material that can transmit protons. The proton conductive material has a sulfonic acid group such as a polymer material such as Nafion (registered trademark) manufactured by DuPont, Flemion (registered trademark) manufactured by Asahi Glass Co., and Acibreck (registered trademark) manufactured by Asahi Kasei Chemicals. Fluorine resin and inorganic substances such as tungstic acid and phosphotungstic acid can be used, but the invention is not limited to these.
なお、本発明の実施形態に係る触媒が形成した触媒層１５をプロトン伝導性２２に転写して膜電極複合体を作製することにも適用できる。
なお、本発明の実施形態に係る触媒は燃料電池のカソード触媒のほか、燃料電池のアノード触媒、光触媒、水分解触媒などとしても適用できる。
In addition, it is applicable also to producing the membrane electrode assembly by transferring the catalyst layer 15 formed by the catalyst according to the embodiment of the present invention to the proton conductivity 22.
The catalyst according to the embodiment of the present invention can be applied as an anode catalyst, a photocatalyst, a water splitting catalyst, etc. of a fuel cell in addition to a cathode catalyst of a fuel cell.
以下、スパッタ積層法によって積層体を形成する実施形態の実施例について説明する。本発明は以下の実施例に限定されるものではない。 Hereinafter, examples of the embodiment in which the laminated body is formed by the sputtering lamination method will be described. The present invention is not limited to the following examples.
（実施例１〜２０）
表面に厚さが５〜５０μｍの炭素層を持つカーボンペーパー（商品名Ｔｏｒａｙ０６０）を基板１１とし、金属材料ターゲット（複合ターゲットを含む）、窒化物３、炭化物４又は炭窒化物５ターゲット、造孔材料ターゲットをそれぞれ用い、スパッタリングを行い、触媒ローディング量が０．１ｍｇ／ｃｍ２の積層体を形成する。その後８０℃において１０重量％硫酸に積層体を入れ、２時間酸処理を行い、純水によって洗浄し、乾燥させ、触媒層担持基板を得る。表１に実施例１〜１６の構成、金属材料層１２と窒化物３、炭化物４又は炭窒化物５を形成した際の平面相当厚さ、触媒組成（金属部分のみ）を示す。なお、造孔材料層１４の厚さは２００ｎｍの平面相当厚さにする。触媒のローディング量は金属ワイヤーまたはシートと窒化物、炭化物または炭窒化物の単位面積あたりの合計重量（酸洗浄後）である。
(Examples 1-20)
Carbon paper (trade name Toray060) having a carbon layer with a thickness of 5 to 50 μm on the surface is used as a substrate 11, metal material target (including composite target), nitride 3, carbide 4 or carbonitride 5 target, hole making Sputtering is performed using each material target to form a laminate with a catalyst loading of 0.1 mg / cm 2 . Thereafter, the laminate is put into 10% by weight sulfuric acid at 80 ° C., acid-treated for 2 hours, washed with pure water, and dried to obtain a catalyst layer-supporting substrate. Table 1 shows the structures of Examples 1 to 16, the thickness corresponding to the plane when the metal material layer 12 and the nitride 3, carbide 4 or carbonitride 5 were formed, and the catalyst composition (only the metal portion). The thickness of the pore forming material layer 14 is set to a plane equivalent thickness of 200 nm. The loading amount of the catalyst is the total weight (after acid cleaning) per unit area of the metal wire or sheet and the nitride, carbide or carbonitride.
（比較例１〜３）
金属材料層１２、窒化物３、炭化物４又は炭窒化物５層の条件が実施例１〜２０と異なる以外は、実施例と同様な方法によって触媒層担持基板を得る。表１に実施例１〜１６の構成、金属材料層１２と窒化物３、炭化物４又は炭窒化物５を形成した際の平面相当厚さ、触媒組成（金属部分のみ）を示す。なお、造孔材料層１４の厚さは２００ｎｍの平面相当厚さにする。
(Comparative Examples 1-3)
A catalyst layer carrying substrate is obtained by the same method as in Examples except that the conditions of the metal material layer 12, nitride 3, carbide 4 or carbonitride 5 layer are different from those in Examples 1-20. Table 1 shows the structures of Examples 1 to 16, the thickness corresponding to the plane when the metal material layer 12 and the nitride 3, carbide 4 or carbonitride 5 were formed, and the catalyst composition (only the metal portion). The thickness of the pore forming material layer 14 is set to a plane equivalent thickness of 200 nm.
（比較例４）
スパッタ法によってカーボンブラックにＴａＣＮを担持させ、ＴａＣＮ触媒を作製した。溶液法によってＡｕワイヤーを作製し、実施例１と同様な触媒組成になるように上記ＴａＣＮ触媒と混合し、混合触媒を作製する。
(Comparative Example 4)
TaCN was supported on carbon black by sputtering to prepare a TaCN catalyst. An Au wire is prepared by a solution method and mixed with the TaCN catalyst so as to have the same catalyst composition as in Example 1, thereby preparing a mixed catalyst.
（比較例５）
市販のＡｕナノ粒子（平均直径１０ｎｍ）を用いて実施例１と同様な触媒組成になるようにＡｕ粒子にスパッタ法によってＴａＣＮを担持させる。
(Comparative Example 5)
Using commercially available Au nanoparticles (average diameter: 10 nm), TaCN is supported on the Au particles by sputtering so as to have the same catalyst composition as in Example 1.
（触媒の評価）
透過電子顕微鏡（ＴＥＭ）によって各実施例と比較例の触媒層１５を評価する。実施例１〜２０、比較例１、３，４の各触媒には、金属ワイヤー１又は金属シート２が存在し、厚さが表１にまとめた値であることをＴＥＭ画像から確認した。また、比較例５のＡｕのアスペクト比が２．５より小さいことをＴＥＭ観察により確認した。実施例１〜２０の各触媒窒化物３、炭化物４又は炭窒化物５は金属ワイヤー１又は金属シート２によって担持され、窒化物３、炭化物４又は炭窒化物５の少なくとも一部分は金属ワイヤー１又は金属シート２と直接接しており、窒化物３、炭化物４又は炭窒化物５のサイズが表１にまとめた値であることをＴＥＭ画像から確認した。図１、２は実施例４と実施例１１の触媒層１５横断ＴＥＭ写真をそれぞれ示す。平均直径または平均厚さが０．２〜１０ｎｍである金属ワイヤー１と金属シート２をできる。また、各触媒の造孔処理後の組成を蛍光Ｘ線組成分析（ＸＲＦ）によって分析し、その結果を表１にまとめた。造孔処理後の基板のＸ線回折分析（ＸＲＤ）を行い、金属材料層１２は殆ど結晶構造であり、窒化物３、炭化物４又は炭窒化物５は殆どアモルファス構造であることがわかった。
(Evaluation of catalyst)
The catalyst layer 15 of each example and comparative example is evaluated by a transmission electron microscope (TEM). It was confirmed from the TEM images that each of the catalysts of Examples 1 to 20 and Comparative Examples 1, 3 and 4 had the metal wire 1 or the metal sheet 2 and the thickness was a value summarized in Table 1. Further, it was confirmed by TEM observation that the aspect ratio of Au of Comparative Example 5 was smaller than 2.5. Each catalyst nitride 3, carbide 4 or carbonitride 5 of Examples 1 to 20 is supported by metal wire 1 or metal sheet 2, and at least part of nitride 3, carbide 4 or carbonitride 5 is metal wire 1 or The metal sheet 2 was in direct contact, and it was confirmed from the TEM image that the size of the nitride 3, carbide 4 or carbonitride 5 was the value summarized in Table 1. 1 and 2 show TEM photographs across the catalyst layer 15 of Example 4 and Example 11, respectively. A metal wire 1 and a metal sheet 2 having an average diameter or average thickness of 0.2 to 10 nm can be obtained. Further, the composition of each catalyst after the pore-forming treatment was analyzed by fluorescent X-ray composition analysis (XRF), and the results are summarized in Table 1. X-ray diffraction analysis (XRD) of the substrate after the hole forming treatment was performed, and it was found that the metal material layer 12 has almost a crystal structure, and the nitride 3, carbide 4 or carbonitride 5 has almost an amorphous structure.
また、燃料電池電極、膜電極複合体、単セルを以下に示す方法で作製し、評価を行った。 In addition, a fuel cell electrode, a membrane electrode assembly, and a single cell were prepared and evaluated by the following methods.
実施例１〜２０、比較例１〜３の触媒層担持基板に０．５％重量のナフィオン（登録商標）含浸させ、乾燥し、金属触媒のローディング密度が０．１ｍｇ／ｃｍ２のカソード電極を作成する。 The catalyst layer-supported substrates of Examples 1 to 20 and Comparative Examples 1 to 3 were impregnated with 0.5% by weight of Nafion (registered trademark) and dried to obtain a cathode electrode having a metal catalyst loading density of 0.1 mg / cm 2. create.
実施例１〜２０、比較例１〜３の基板を使用したこれらのカソード電極と、標準アノード電極（カーボンブラック担持のＰｔ触媒 田中貴金属社製）を使用し、膜電極複合体及び燃料電池を作成する。 Using these cathode electrodes using the substrates of Examples 1 to 20 and Comparative Examples 1 to 3, and a standard anode electrode (carbon black-supported Pt catalyst manufactured by Tanaka Kikinzoku Co., Ltd.), a membrane electrode composite and a fuel cell were prepared. To do.
比較例４，５の電極は、以下のように作成する。比較例４，５の触媒 ０．５ｇと、純水５ｇと、２０％ナフィオン（登録商標）溶液５ｇと、２−エトキシエタノール２０ｇとを良く攪拌し、分散した後、スラリーを作製する。撥水処理した厚さ１８０μで東レ製のカーボンペーパーに上記のスラリーをコントロールコータで塗布し、乾燥させ、金属触媒のローディング密度が０．１ｍｇ／ｃｍ２のカソード電極を作製する。 The electrodes of Comparative Examples 4 and 5 are prepared as follows. 0.5 g of the catalyst of Comparative Examples 4 and 5, 5 g of pure water, 5 g of 20% Nafion (registered trademark) solution and 20 g of 2-ethoxyethanol are thoroughly stirred and dispersed, and then a slurry is prepared. The slurry is applied to a carbon paper made by Toray with a water repellent thickness of 180 μm using a control coater and dried to produce a cathode electrode having a metal catalyst loading density of 0.1 mg / cm 2 .
標準カソード電極は、以下のように作成する。田中貴金属社製Ｐｔ触媒２ｇと、純水５ｇと、２０％ナフィオン（登録商標）溶液５ｇと、２−エトキシエタノール２０ｇとを良く攪拌し、分散した後、スラリーを作製する。撥水処理した厚さ１８０μで東レ製のカーボンペーパーに上記のスラリーをコントロールコータで塗布し、乾燥させ、貴金属触媒のローディング密度が０．１ｍｇ／ｃｍ２のカソード電極を作製する。標準アノード電極は、撥水処理なしの厚さ１８０μで東レ製のカーボンペーパーを用いた以外は標準カソード電極と同様な方法にて作製する。
各電極を使用した膜電極複合体、燃料電池の製造方法の詳細は以下の通りである。
The standard cathode electrode is prepared as follows. 2 g of Pt catalyst manufactured by Tanaka Kikinzoku Co., 5 g of pure water, 5 g of 20% Nafion (registered trademark) solution and 20 g of 2-ethoxyethanol are thoroughly stirred and dispersed, and then a slurry is prepared. The slurry is applied to a carbon paper manufactured by Toray with a water repellent thickness of 180 μm using a control coater, and dried to prepare a cathode electrode having a noble metal catalyst loading density of 0.1 mg / cm 2 . The standard anode electrode is produced in the same manner as the standard cathode electrode except that Toray carbon paper with a thickness of 180 μ without water repellent treatment is used.
Details of the manufacturing method of the membrane electrode assembly and fuel cell using each electrode are as follows.
（膜電極複合体の作製）
カソード電極、アノード電極それぞれを電極面積が１０ｃｍ２になるよう、３．２×３．２ｃｍの正方形に切り取り、カソード電極とアノード電極の間にプロトン伝導性固体高分子膜としてデュポン社製のナフィオン（登録商標）１１２を挟んで、１２５℃、１０分、３０ｋｇ／ｃｍ２の圧力で熱圧着して、膜電極複合体を作製する。
(Production of membrane electrode composite)
The cathode electrode and the anode electrode are cut into a 3.2 × 3.2 cm square so that the electrode area is 10 cm 2. (Registered Trademark) 112 is sandwiched and thermocompression bonded at 125 ° C. for 10 minutes at a pressure of 30 kg / cm 2 to prepare a membrane electrode assembly.
この膜電極複合体と流路板とを用いて水素高分子電解質型燃料電池の単セルを作製する。この単セルに燃料としての水素、流量０．６ｍｌ／ｍｉｎ．でアノード極に供給すると共に、カソード極に空気を５００ｍｌ／分の流量で供給し、セルを６５℃に維持した状態で２００ｍＡ／ｃｍ２電流密度を放電させ、１００時間後のセル電圧を測定し、その結果を下記表１に併記する。耐久性としては２０００時間発電後のセル電圧を測定し、１００時間後のセル電圧と比較し、低下率が２％以内のものは耐久性◎として、２％より高く５％より低いものは耐久性○として、５％以上のものは耐久性△として、それぞれ表１にまとめた。 A single cell of a hydrogen polymer electrolyte fuel cell is manufactured using the membrane electrode assembly and the flow path plate. Hydrogen as a fuel in this single cell, flow rate 0.6 ml / min. In addition to supplying the cathode electrode with air at a flow rate of 500 ml / min, the cell was maintained at 65 ° C. and a current density of 200 mA / cm 2 was discharged, and the cell voltage after 100 hours was measured. The results are also shown in Table 1 below. As the durability, the cell voltage after 2000 hours of power generation was measured, and compared with the cell voltage after 100 hours, the rate of decrease is within 2%, the durability is ◎, the durability is higher than 2% and lower than 5% As for the property ◯, those with 5% or more are summarized in Table 1 as durability Δ.
表１の結果が示されるように、実施例１〜２０と比較例１，２と比較すると、窒化物３、炭化物４又は炭窒化物５は金属ワイヤー１又は金属シート２に担持させることによって燃料電池単セル電圧と耐久性がいずれも向上したとわかる。実施例１〜２０と比較例３，４と比較すると、実施例の触媒は金属ワイヤー１と炭窒化物５との混合物または球状金属によって担持された炭窒化物５より高い特性を持つことがわかる。また、実施例１と実施例１７〜２０と比較すると、高い燃料電池特性を達成するには金属ワイヤー１と金属シート２の厚さ、窒化物３、炭化物４又は炭窒化物５のサイズを制御する必要があるとわかる。また実施例１と比較例１、実施例１０と比較例３とそれぞれ比較すると、本発明の触媒は同量の貴金属ワイヤーより単セル電圧が高いことがわかる。
なお、本実施形態は、例として提示したものであり、発明の範囲を限定することは意図していない。本実施形態は、その他の様々な形態で実施されることが可能であり、発明の要旨を逸脱しない範囲で、種々の省略、置き換え、変更を行うことができる。本実施形態やその変形は、発明の範囲や要旨に含まれるとともに、特許請求の範囲に記載された発明とその均等の範囲に含まれる。
As shown in Table 1, when Examples 1 to 20 and Comparative Examples 1 and 2 are compared, nitride 3, carbide 4 or carbonitride 5 is fuel by being supported on metal wire 1 or metal sheet 2. It can be seen that both the battery single cell voltage and the durability were improved. Comparing Examples 1-20 with Comparative Examples 3 and 4, it can be seen that the catalyst of the example has higher properties than the mixture of metal wire 1 and carbonitride 5 or carbonitride 5 supported by a spherical metal. . Moreover, compared with Example 1 and Examples 17-20, in order to achieve a high fuel cell characteristic, the thickness of the metal wire 1 and the metal sheet 2, the size of the nitride 3, the carbide 4, or the carbonitride 5 is controlled. I know I need to do it. Moreover, when Example 1 and Comparative Example 1 are compared with Example 10 and Comparative Example 3, respectively, it can be seen that the single cell voltage of the catalyst of the present invention is higher than that of the same amount of noble metal wire.
This embodiment is presented as an example and is not intended to limit the scope of the invention. The present embodiment can be implemented in various other forms, and various omissions, replacements, and changes can be made without departing from the spirit of the invention. This embodiment and its modifications are included in the scope and gist of the invention, and are included in the invention described in the claims and the equivalents thereof.
１…金属ワイヤー、２…金属シート、３…窒化物、４…炭化物、５…炭窒化物、１１…基板、１２…金属材料層、１３…触媒材料層、１４…造孔材料層、２１…アノード触媒層、２２…プロトン伝導性膜、２３…カソード触媒層、３０…燃料電池、３１…プロトン電導性膜、３２…燃料極（アノード）、３３…空気極（カソード）、３４…拡散層、３５…アノード触媒層、３６…拡散層、３７…カソード触媒層、３８…ＭＥＡ、３９…酸化剤ガス供給溝、４０…カソードホルダー、４１…燃料供給溝、４２…アノードホルダー DESCRIPTION OF SYMBOLS 1 ... Metal wire, 2 ... Metal sheet, 3 ... Nitride, 4 ... Carbide, 5 ... Carbonitride, 11 ... Substrate, 12 ... Metal material layer, 13 ... Catalyst material layer, 14 ... Porous material layer, 21 ... Anode catalyst layer, 22 ... proton conductive membrane, 23 ... cathode catalyst layer, 30 ... fuel cell, 31 ... proton conductive membrane, 32 ... fuel electrode (anode), 33 ... air electrode (cathode), 34 ... diffusion layer, 35 ... anode catalyst layer, 36 ... diffusion layer, 37 ... cathode catalyst layer, 38 ... MEA, 39 ... oxidant gas supply groove, 40 ... cathode holder, 41 ... fuel supply groove, 42 ... anode holder
Claims (11)
前記担持体に主触媒として担持された窒化物、炭化物又は炭窒化物とを有することを特徴とする燃料電池用触媒。 With a metal wire or metal sheet as a carrier ,
A fuel cell catalyst comprising a nitride, carbide or carbonitride supported as a main catalyst on the support.
前記アノード触媒層又はカソード触媒層は請求項１乃至７のいずれかに記載の燃料電池用触媒を具備することを特徴とする膜電極複合体。 An anode catalyst layer, a cathode catalyst layer, and a proton conductive membrane interposed between the anode catalyst layer and the cathode catalyst layer,
A membrane electrode assembly, wherein the anode catalyst layer or the cathode catalyst layer comprises the fuel cell catalyst according to any one of claims 1 to 7.
窒化物、炭化物又は炭窒化物材料をスパッタ又は蒸着し、触媒材料層を前記金属材料層上に形成する第２の工程と、
造孔材料をスパッタ又は蒸着し、造孔材料層を前記触媒材料層上に形成する第３の工程と、
前記第１から第３の工程を順番に複数回繰り返して前記金属材料層、前記触媒材料層と前記造孔材料層との積層体を形成する積層工程と、
前記積層工程の後に、前記積層体を造孔処理する造孔処理工程と、を具備することを特徴とする燃料電池用触媒の製造方法。 A first step of sputtering or vapor-depositing a metal on a substrate to form a metal material layer;
A second step of sputtering or evaporating a nitride, carbide or carbonitride material to form a catalyst material layer on the metal material layer;
A third step of sputtering or vapor-depositing a pore-forming material and forming a pore-forming material layer on the catalyst material layer;
A laminating step in which the metal material layer, the catalyst material layer and the pore-forming material layer are formed by repeating the first to third steps in order several times;
A method for producing a catalyst for a fuel cell, comprising: a hole making process step of forming a hole in the laminate after the layering process.
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