JP2004207228A - Catalyst material, electrode, and fuel cell using this - Google Patents
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Abstract
Description
本発明は燃料電池に関する。 The present invention relates to a fuel cell.
近年、化石燃料の大量消費による地球温暖化・環境汚染問題は深刻な問題となっている。この問題に対する対処手段として、化石燃料を燃やす内燃機関に代わり、固体高分子型燃料電池（ＰＥＦＣ）を始めとする水素を燃料とした燃料電池が注目を集めている。また電子技術の進歩によって、年々、情報端末機器などが小型化され、携帯用電子機器として急速な普及が進んでいる。現在、携帯用電子機器の情報量の増加とその高速処理に伴う消費電力の増加を補う次世代電源として、メタノールを燃料とした直接メタノール型燃料電池（ＤＭＦＣ）が開発されている。 In recent years, the problem of global warming and environmental pollution due to mass consumption of fossil fuels has become a serious problem. As a solution to this problem, a fuel cell using hydrogen as a fuel, such as a polymer electrolyte fuel cell (PEFC), has been attracting attention instead of an internal combustion engine burning fossil fuel. Also, with the advance of electronic technology, information terminal devices and the like have been reduced in size year by year, and are rapidly spreading as portable electronic devices. At present, a direct methanol fuel cell (DMFC) using methanol as a fuel has been developed as a next-generation power supply to compensate for an increase in the amount of information of a portable electronic device and an increase in power consumption due to its high-speed processing.
これら燃料電池の電極等に使われる触媒材料は、一般的に触媒を触媒担体上に分散させた構成になっている（特許文献１）。また、触媒担体には炭素材料が用いられている。 The catalyst material used for these fuel cell electrodes and the like generally has a structure in which a catalyst is dispersed on a catalyst carrier (Patent Document 1). Further, a carbon material is used for the catalyst carrier.
触媒材料の活性度は、触媒材料に含まれる触媒金属の粒子径に大きく依存する。触媒金属の粒子径が小さいほど触媒金属の比表面積（触媒金属粒子の表面積／触媒金属粒子の重さ）が大きくなり、同量の触媒金属を用いた場合、触媒として作用する面積が大きくなるため、触媒の活性度が高まる。 The activity of the catalyst material largely depends on the particle diameter of the catalyst metal contained in the catalyst material. The smaller the particle diameter of the catalyst metal, the larger the specific surface area of the catalyst metal (the surface area of the catalyst metal particle / the weight of the catalyst metal particle). When the same amount of the catalyst metal is used, the area acting as a catalyst increases. As a result, the activity of the catalyst increases.
しかしながら、これまでの触媒材料では、触媒金属が触媒担体に主に物理吸着で担持されているため、触媒材料作製時および電池使用環境下で、触媒金属の凝集，粗大化が起こる。その結果、触媒金属の粒径は大きくなり、比表面積は小さくなる。この凝集，粗大化により、粒子径の小さい触媒金属を作製すること、あるいは電池使用環境下で触媒金属の粒径を小さく維持することは困難であった。 However, in the conventional catalyst materials, since the catalyst metal is mainly supported on the catalyst carrier by physical adsorption, aggregation and coarsening of the catalyst metal occur during the preparation of the catalyst material and in a battery operating environment. As a result, the particle size of the catalyst metal increases, and the specific surface area decreases. Due to the aggregation and coarsening, it has been difficult to produce a catalyst metal having a small particle diameter, or to keep the particle diameter of the catalyst metal small in a battery operating environment.
本発明は、高い比表面積を有した粒子径の小さい触媒金属を電極に用いることにより出力密度が向上した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 fuel cell having an improved power density by using a catalyst metal having a high specific surface area and a small particle diameter for an electrode.
ここで「触媒金属」とは、触媒作用を持つ金属あるいは金属化合物等のことであり、
「触媒担体」とは前記触媒を担持するもので、燃料電池用の触媒担体の場合には、カーボンブラック，カーボンナノチューブ等の炭素材料が用いられる。
Here, "catalytic metal" refers to a metal or metal compound having a catalytic action,
The "catalyst carrier" supports the above-mentioned catalyst. In the case of a catalyst carrier for a fuel cell, a carbon material such as carbon black or carbon nanotube is used.
本願に係る発明の主な特徴は、触媒担体と触媒金属とを含む触媒材料における触媒担体に触媒金属と共有結合可能な原子を含むことである。 A main feature of the invention according to the present application is that a catalyst carrier in a catalyst material containing a catalyst carrier and a catalyst metal contains an atom capable of being covalently bonded to the catalyst metal.
また、触媒担体は炭素を主成分とする触媒担体であれば、燃料電池用の触媒材料として好適である。 Further, any catalyst carrier containing carbon as a main component is suitable as a catalyst material for a fuel cell.
ここで、「炭素」とは、構造上、非晶質のものからグラファイトのような結晶質のものまで含むものもある。 Here, the term “carbon” includes from structurally amorphous to crystalline such as graphite.
「配位結合可能な原子を含む」とは、触媒金属と共有結合可能な原子が触媒担体を構成する原子（例えば炭素原子）と共有結合して、触媒担体中に存在することを意味する。ただし、触媒担体を構成する原子が炭素原子の場合は、炭素結晶の結晶子径は大きくても、小さくても良く、また非晶質であっても良い。また、触媒金属と共有結合可能な原子は、炭素原子と共有結合していると同時に、水素原子と共有結合している場合もある。ここで共有結合には配位結合も含まれる。 “Including an atom capable of coordinating” means that an atom capable of covalently bonding to a catalyst metal is covalently bonded to an atom (for example, a carbon atom) constituting the catalyst support and is present in the catalyst support. However, when the atoms constituting the catalyst support are carbon atoms, the crystallite diameter of the carbon crystal may be large or small, or may be amorphous. In addition, an atom that can be covalently bonded to a catalyst metal may be covalently bonded to a carbon atom and also to a hydrogen atom in some cases. Here, the covalent bond includes a coordinate bond.
本発明にかかる触媒材料を燃料電池に用いることにより出力密度の高い燃料電池を提供することができる。 By using the catalyst material according to the present invention for a fuel cell, a fuel cell having a high output density can be provided.
以下の触媒材料の作製方法はＤＭＦＣに適用する場合について記述するが、本実施例に係る触媒材料はＤＭＦＣに適用する場合に限定されずＰＥＦＣ等、炭素原子を主成分とする触媒担体に触媒を分散する構成をとる触媒材料であれば適用可能である。尚、本実施例の「触媒材料」とは、触媒担体に触媒金属を担持させたものを意味する。 The following method for producing a catalyst material is described for a case where the catalyst material is applied to a DMFC. However, the catalyst material according to this example is not limited to a case where the catalyst material is applied to a DMFC, and a catalyst is applied to a catalyst carrier mainly containing carbon atoms, such as PEFC. As long as the catalyst material is configured to be dispersed, it can be applied. The “catalyst material” in the present embodiment means a catalyst carrier on which a catalyst metal is supported.
本実施例に係る触媒材料および電極の作製方法を示す。 A method for manufacturing a catalyst material and an electrode according to this example will be described.
本実施例では触媒金属と配位結合可能な原子として窒素原子を用いる。 In this embodiment, a nitrogen atom is used as an atom capable of coordinating with the catalyst metal.
窒素を５原子％含んだカーボンブラック３.５ｇ と、アルカリ性水溶液と、還元剤とを容器に入れ、スターラにて３０分間攪拌し混合する。ここで、アルカリ性水溶液としては例えば、水酸化カリウム水溶液，水酸化ナトリウム水溶液，アンモニア水等を用いることができ、還元剤としては水素化ホウ素ナトリウム，ホルマリン等を用いることができる。本実施例ではアルカリ性水溶液として水酸化ナトリウム水溶液，還元剤としてホルマリンを用いる。これに触媒金属塩の水溶液を加え、ウォーターバスを用いて容器を４０℃に保ち、更に１時間スターラにて攪拌を行う。触媒金属塩は、例えば塩化物を用いることができ、本実施例では塩化白金酸２.１ｇ を用いる。ガラスフィルターを用いて攪拌後の溶液を、濾過する。得られた物質に純水を加え洗浄，濾過する作業を７回行い最終的に得られた物質を恒温槽にて８０℃で２日間、乾燥を行う。乾燥後、乳鉢にて粉砕し、窒素原子を含んだ炭素に白金が担持された触媒材料４.５ｇ を得る。作製法は本実施例の方法以外にも、例えばアルコール還元法を用いることもできる。 3.5 g of carbon black containing 5 atomic% of nitrogen, an alkaline aqueous solution, and a reducing agent are put in a container, and mixed by stirring with a stirrer for 30 minutes. Here, as the alkaline aqueous solution, for example, an aqueous potassium hydroxide solution, an aqueous sodium hydroxide solution, aqueous ammonia or the like can be used, and as the reducing agent, sodium borohydride, formalin, or the like can be used. In this embodiment, an aqueous sodium hydroxide solution is used as an alkaline aqueous solution, and formalin is used as a reducing agent. An aqueous solution of a catalytic metal salt is added thereto, and the vessel is kept at 40 ° C. using a water bath, and further stirred for 1 hour with a stirrer. As the catalyst metal salt, for example, chloride can be used. In this embodiment, 2.1 g of chloroplatinic acid is used. The solution after stirring is filtered using a glass filter. Pure water is added to the obtained substance, washing and filtration are performed seven times, and the finally obtained substance is dried at 80 ° C. for 2 days in a thermostat. After drying, the mixture is pulverized in a mortar to obtain 4.5 g of a catalyst material in which platinum is supported on carbon containing nitrogen atoms. As a manufacturing method, for example, an alcohol reduction method can be used in addition to the method of this embodiment.
得られた触媒材料１.０ｇ と、プロトン伝導性材料であるパーフルオロカーボンスルホン酸０.６ｇ及び水／アルコール（１／４）混合溶媒のスラリーとを調製し、カーボンペーパー上にスクリーン印刷法で電極を形成する。 1.0 g of the obtained catalyst material and a slurry of perfluorocarbon sulfonic acid (0.6 g), which is a proton conductive material, and a mixed solvent of water / alcohol (1/4) were prepared, and the electrodes were formed on carbon paper by screen printing. To form
図１，図２に本実施例に係る触媒担体の模式図を示す。炭素中の炭素原子の一部は主に図１と図２との２種の形で窒素原子と置換される。図１は、ピリジン構造をとる形で炭素原子１０１と窒素原子１０２とが置換している。図２は、六員環構造を保ったままの形で、炭素原子２０１と窒素原子２０２とが置換している。ただし、結晶子径が非常に小さい場合では、炭素原子と窒素原子との結合が必ずしも図１、図２の形態をとっているとは限らず、非晶質炭素中に存在する炭素原子に窒素原子が結合しているような場合、また、五員環を形成している場合もあるため、これらに限定されるものではない。
1 and 2 are schematic views of the catalyst carrier according to the present embodiment. Some of the carbon atoms in the carbon are replaced by nitrogen atoms in two main forms, FIGS. In FIG. 1, a
このような炭素と窒素とを有する触媒担体は例えば気相化学蒸着（ＣＶＤ）法でＣ2Ｈ2とＮ2 との混合ガスをフローさせ、得ることができる。あるいはＡｒガスとＮ2 ガスとの混合雰囲気中でグラファイトターゲットを用いてＤＣマグネトロンスパッタ法でも得ることができる。また窒素原子を含んだ有機物をＡｒガス雰囲気中で、加熱することでも得ることができる。 Such a catalyst carrier having carbon and nitrogen can be obtained, for example, by flowing a mixed gas of C 2 H 2 and N 2 by a chemical vapor deposition (CVD) method. Alternatively, it can also be obtained by DC magnetron sputtering using a graphite target in a mixed atmosphere of Ar gas and N 2 gas. Alternatively, it can be obtained by heating an organic substance containing a nitrogen atom in an Ar gas atmosphere.
ここで窒素原子と触媒金属の粒子との結合は、共有結合であり、この結合により触媒金属粒子は炭素表面上に安定に担持されると考えられる。 Here, the bond between the nitrogen atom and the particles of the catalyst metal is a covalent bond, and it is considered that the catalyst metal particles are stably supported on the carbon surface by this bond.
したがって窒素原子を含んだ炭素を触媒担体に用いることで、触媒金属の粒子は窒素原子との結合により運動を束縛される。そのため触媒材料の作製時あるいは電池使用環境下における触媒金属の粒子の凝集，粗大化を防ぐことができる。 Therefore, by using carbon containing a nitrogen atom for the catalyst carrier, the movement of the catalyst metal particles is restricted by the bond with the nitrogen atom. Therefore, it is possible to prevent the catalyst metal particles from agglomerating and coarsening during the preparation of the catalyst material or in the battery operating environment.
触媒金属の粒子の凝集，粗大化を防ぐことができるという利点はアノード電極，カソード電極のいずれにおいても有効である。 The advantage that the aggregation and coarsening of the catalyst metal particles can be prevented is effective for both the anode electrode and the cathode electrode.
また、分散した触媒金属の粒子それぞれに燃料が十分に供給される範囲であれば、触媒担体に担持される触媒金属の担持量は、多いほどよい。 Also, as long as the fuel is sufficiently supplied to each of the dispersed catalyst metal particles, the larger the amount of the catalyst metal supported on the catalyst carrier, the better.
しかし、触媒担体として従来用いられてきたカーボンブラックでは触媒金属の担持量を増加させすぎると、触媒金属の粒子同士が凝集しやすくなってしまい、触媒金属が触媒作用を起こす表面積である有効面積が減少してしまう。そのため触媒金属の担持量は５０重量％（触媒金属の重量／触媒材料の重量）程度が最大であった。 However, in the case of carbon black that has been conventionally used as a catalyst carrier, if the amount of the supported catalyst metal is excessively increased, the particles of the catalyst metal tend to aggregate, and the effective area, which is the surface area where the catalyst metal performs a catalytic action, is reduced. Will decrease. Therefore, the maximum amount of the supported catalyst metal was about 50% by weight (weight of the catalyst metal / weight of the catalyst material).
しかし、窒素原子を含んだ触媒担体を用いると、上述のように触媒金属は触媒担体に含まれる窒素原子との共有結合により動きが束縛されるため、凝集を防ぐことができ、更に触媒金属の担持量を増加させることが可能となる。 However, when a catalyst carrier containing a nitrogen atom is used, the movement of the catalyst metal is restricted by the covalent bond with the nitrogen atom contained in the catalyst carrier as described above, so that aggregation can be prevented, and furthermore, the catalyst metal It is possible to increase the carrying amount.
なお、本実施例で作成される触媒材料はある確率で触媒金属の一部が小さな粒径（２
ｎｍ程度）を保ったまま窒素原子と共有結合をすることにより動きが束縛される。
In the catalyst material prepared in this example, a part of the catalyst metal has a small particle size (2
The movement is constrained by forming a covalent bond with the nitrogen atom while maintaining the same (about nm).
しかし、一部の触媒金属の粒子は依然として熱エネルギなどを得て動き回ることができる状態にある。これらの触媒金属の粒子は動き回る過程で窒素原子に近づいたものは共有結合により動きを束縛されるし、またある確率で触媒金属の粒子同士がある程度凝集，粗大化した後、窒素原子の近傍で動きを束縛されるものもある。触媒金属の粒子が小さな粒径を保ったまま動きを束縛されるか、ある程度凝集した後動きを束縛されるかは窒素原子が触媒担体上にどの程度の割合で分散しているか、あるいは作製時の触媒金属の粒子の粒子径に依存すると考えられる。 However, some catalyst metal particles are still in a state where they can move around by obtaining heat energy or the like. Those catalyst metal particles that approach the nitrogen atom in the process of moving are bound by covalent bonds, and at a certain probability, the catalyst metal particles are aggregated and coarsened to some extent, and then near the nitrogen atom. Some are restricted in movement. Whether the catalytic metal particles are constrained to move while maintaining a small particle size, or constrained to a certain degree after aggregating to some extent depends on how much nitrogen atoms are dispersed on the catalyst support, or during production. Of the catalyst metal particles.
触媒金属の粒子の動きが束縛され凝集を防ぐことができるということは、触媒金属の粒子同士の距離を従来よりも近づけることができるという利点がある。すなわち、従来では触媒金属の粒子同士が近すぎて凝集してしまうような距離であっても、本実施例の触媒材料によれば触媒金属の粒子の動きが束縛されるため隣同士の触媒金属の粒子は凝集しない。したがって、従来に比べ同一の触媒金属の量を電極内に含ませたときに、触媒担体の量をより少なくすることが可能となる。触媒担体の量を少なくできるということは、同一の電極面積であれば、電極の厚さをより薄くすることが可能となり、電極における燃料の拡散性，電子の伝導性，プロトンの伝導性を向上させることが可能となる。このように物質易動抵抗を減少させることができるため、膜電極接合体（以下、ＭＥＡ８０４）の出力密度を向上させることが可能となる。また出力密度の高いＭＥＡを用いることで、ＰＥＦＣやＤＭＦＣの出力を向上させることが可能となる。また、出力を一定とすれば小型化することもできる。 The fact that the movement of the catalyst metal particles is restricted and aggregation can be prevented has the advantage that the distance between the catalyst metal particles can be made shorter than before. That is, even if the distance is such that the particles of the catalyst metal are conventionally too close to agglomerate, the movement of the particles of the catalyst metal is restricted according to the catalyst material of the present embodiment, so that the adjacent catalyst metal Do not agglomerate. Therefore, when the same amount of the catalyst metal is included in the electrode as compared with the related art, the amount of the catalyst carrier can be further reduced. The fact that the amount of catalyst carrier can be reduced means that if the electrode area is the same, the thickness of the electrode can be reduced, and the fuel diffusion, electron conductivity, and proton conductivity at the electrode are improved. It is possible to do. Since the material mobility resistance can be reduced in this manner, the output density of the membrane electrode assembly (hereinafter, MEA 804) can be improved. Further, by using MEA having a high output density, the output of PEFC or DMFC can be improved. If the output is fixed, the size can be reduced.
窒素原子による触媒金属を束縛する効果は、触媒担体の表面層にある窒素原子によるものである。ここで表面の窒素原子の濃度は目標とする触媒金属の担持量や触媒金属の粒子径によって左右されるため、特に規定されるものではないが、好ましくはＸ線光電子分光法（ＸＰＳ）による触媒担体の表面の窒素原子の濃度分析において０.１ 〜３０原子％程度が良い。これは触媒担体の表面の窒素原子の濃度が０.１ 原子％以下であると、実用的に必要な量である０.０１ 重量％以上の触媒を担持する際に、効果が得られにくい。また、３０原子％以上であると、窒素原子がカーボンブラック中にグラファイト構造を保って安定に含まれることが困難となり、触媒担体の機械的強度が弱くなってしまう。また、ダイヤモンドのような立体構造になり、グラファイト的な構造の割合が減少するため、電子伝導性が低くなる。更に好ましくは、１〜１０原子％である。 The effect of binding the catalyst metal by nitrogen atoms is due to the nitrogen atoms in the surface layer of the catalyst support. Here, the concentration of nitrogen atoms on the surface is not particularly limited since it depends on the target amount of supported catalytic metal and the particle diameter of the catalytic metal, but is preferably determined by X-ray photoelectron spectroscopy (XPS). In the analysis of the concentration of nitrogen atoms on the surface of the carrier, it is preferably about 0.1 to 30 atomic%. This is because if the concentration of nitrogen atoms on the surface of the catalyst carrier is 0.1 atomic% or less, it is difficult to obtain an effect when supporting a practically necessary amount of 0.01% by weight or more of the catalyst. On the other hand, if the content is 30 atomic% or more, it becomes difficult for nitrogen atoms to be stably contained in the carbon black while maintaining the graphite structure, and the mechanical strength of the catalyst carrier is reduced. In addition, a three-dimensional structure such as diamond is formed, and the proportion of a graphite-like structure is reduced, so that electron conductivity is reduced. More preferably, it is 1 to 10 atomic%.
本実施例では、窒素原子を含ませる触媒担体の主成分としてはカーボンブラックを用いたが、カーボンブラックは直径数十〜数百ｎｍ程度の一次粒子の凝集体である二次粒子から構成され、その表面には凹凸があり、比表面積が大きいため、触媒を担持するサイト、ここでは触媒担体の表面に存在する窒素原子、が多く、単位体積あたりの触媒金属の担持量を増やすことができると考えられる。 In the present embodiment, carbon black was used as the main component of the catalyst carrier containing nitrogen atoms, but carbon black is composed of secondary particles which are aggregates of primary particles having a diameter of about several tens to several hundreds of nm, Since the surface has irregularities and a large specific surface area, there are many sites for supporting the catalyst, here, nitrogen atoms present on the surface of the catalyst carrier, and it is possible to increase the amount of the catalyst metal carried per unit volume. Conceivable.
したがってここからも電極を薄くすることが可能となり、燃料拡散性や電子，プロトン導電性が高くなると考えられる。また一般にカーボンブラックは生産が容易であるためコストを低く抑えることができる。 Therefore, it is considered that the electrode can be made thinner, and the fuel diffusivity and the electron and proton conductivity are increased. In general, carbon black is easy to produce, so that the cost can be kept low.
比較例１として本実施例にて作成した電極を評価するため、窒素原子を含んだ炭素の代わりに、窒素原子を含まない炭素を用いて実施例１と同様の方法で電極を作成した。 In order to evaluate the electrode prepared in this example as Comparative Example 1, an electrode was prepared in the same manner as in Example 1 except that carbon containing no nitrogen atom was used instead of carbon containing a nitrogen atom.
実施例１の電極と、比較例１の電極と、をメタノール含有電解質水溶液（１.５Ｍ（Ｍはmol ／ｌの略）硫酸，２０重量％メタノール）中に浸し、単極測定（電流／電圧測定）を行った。ここで参照電極には飽和カロメル電極、対極には金板を用いた。 The electrode of Example 1 and the electrode of Comparative Example 1 were immersed in a methanol-containing electrolyte aqueous solution (1.5 M (M is mol / l) sulfuric acid, 20% by weight methanol), and subjected to unipolar measurement (current / voltage Measurement). Here, a saturated calomel electrode was used as a reference electrode, and a gold plate was used as a counter electrode.
その結果、比較例１の電極に比べ、実施例１の電極は同一電位で約１.２ 倍程度の電流密度が得られ、電極性能が高いと考えられる。 As a result, compared to the electrode of Comparative Example 1, the electrode of Example 1 has a current density of about 1.2 times at the same potential, and is considered to have high electrode performance.
触媒担体として窒素原子を５原子％含んだカーボンブラック２０重量％に、窒素原子を５原子％含んだカーボンナノチューブ（以下、ＣＮＴ）が８０重量％となるように混合した以外は、実施例１と同様とする。 Example 1 was repeated except that 20% by weight of carbon black containing 5 atomic% of nitrogen atoms and 80% by weight of carbon nanotubes containing 5 atomic% of nitrogen atoms (hereinafter referred to as CNT) were mixed as a catalyst carrier. The same shall apply.
ＣＮＴを用いた場合は、複数のＣＮＴ同士が複数の接点を持ち、接触するため電極内の抵抗率を低減させることができる。 When CNT is used, the plurality of CNTs have a plurality of contact points and come into contact with each other, so that the resistivity in the electrode can be reduced.
本実施例に係るＣＮＴを図３，図４に示す。図３はグラフェンシート３０１が筒状になったもので単層ＣＮＴ（ＳＷＣＮＴ）と呼ばれるものである。図４は、外側グラフェンシート４０１の内部に内側グラフェンシート４０２を有する多層ＣＮＴ（ＭＷＣＮＴ）と呼ばれるものである。
FIGS. 3 and 4 show a CNT according to the present embodiment. FIG. 3 is a
なおＭＷＣＮＴには２層だけのものではなく、３層若しくはそれ以上のものがある。 Note that the MWCNT has not only two layers but also three layers or more.
また、ＳＷＣＮＴ，ＭＷＣＮＴはいずれも五員環を有する半球状のキャップで覆われているものもあり、これはフラーレンキャップとも呼ばれている。 Some of SWCNT and MWCNT are both covered with a hemispherical cap having a five-membered ring, and this is also called a fullerene cap.
また、カーボンナノファイバーと呼ばれるグラフェンシートがチューブの長手方向と平行でないものもあり、これを用いることもできる。 Some graphene sheets called carbon nanofibers are not parallel to the longitudinal direction of the tube, and can be used.
一般的にＳＷＣＮＴは比表面積が大きいため、触媒を担持するサイトが多いという利点がある。また、ＭＷＣＮＴは電子伝導性が高く、電子移動のロスが少ないという利点がある。 Generally, SWCNT has a large specific surface area, and thus has an advantage that there are many sites for supporting a catalyst. In addition, MWCNT has the advantage that electron conductivity is high and electron transfer loss is small.
図５に本実施例に係る窒素原子を含んだＣＮＴを示す。窒素原子５０２はＣＮＴを構成する炭素原子５０１と置換される形でドーピングされる。
FIG. 5 shows a CNT containing a nitrogen atom according to the present embodiment. The
図６に本実施例に係る触媒材料の模式図を示す。窒素原子を含んだＣＮＴ６０１上に触媒金属６０２が粒子状に担持されている。触媒金属６０２が担持されている場所は窒素原子を含んだＣＮＴ６０１に含まれる窒素原子の近傍である。この場所で触媒金属６０２はその動きが束縛される。窒素原子を含んだＣＮＴ６０１は、電子伝導性が高く、尚且つ繊維構造を持っているため、電極内で良い電子伝導パスとなり得る。触媒金属６０２としては、マンガン，鉄，コバルト，ニッケル，ルテニウム，ロジウム，パラジウム，レニウム，オスミウム，イリジウム，白金から選ばれる少なくとも一種以上の金属あるいはその化合物が望ましく、更に望ましくはこれらが合金化している方が良い。
FIG. 6 shows a schematic diagram of the catalyst material according to the present example. The
燃料電池のアノード，カソードに用いられる触媒金属としては白金が好ましい。ただし、一酸化炭素が存在する場合や、メタノールを酸化する場合には、白金とルテニウムを触媒金属に用いることで、より高い性能を示す。また、白金とルテニウムの他に、白金，ルテニウム，マンガン，鉄，コバルト，ニッケル，ロジウム，パラジウム，レニウム，オスミウム，イリジウムを組み合わせることで近い性能を持たすことが可能となる。 Platinum is preferred as the catalytic metal used for the anode and cathode of the fuel cell. However, when carbon monoxide is present or methanol is oxidized, higher performance is exhibited by using platinum and ruthenium as the catalyst metal. In addition, in addition to platinum and ruthenium, it is possible to obtain similar performance by combining platinum, ruthenium, manganese, iron, cobalt, nickel, rhodium, palladium, rhenium, osmium, and iridium.
一般にアノード電極に用いる場合は、白金とルテニウムの合金が望ましく、カソード電極に用いる場合は白金が望ましい。 Generally, when used for an anode electrode, an alloy of platinum and ruthenium is desirable, and when used for a cathode electrode, platinum is desirable.
実施例１と同様な手法で比較例１と実施例２とを比較すると比較例１の電極に比べ、実施例２の電極は同一電位で約１.５ 倍程度の電流密度が得られ、電極性能が高いと考えられる。 Comparing Comparative Example 1 and Example 2 with the same method as in Example 1, compared with the electrode of Comparative Example 1, the electrode of Example 2 has about 1.5 times the current density at the same potential, and It is considered that the performance is high.
触媒金属塩として塩化白金酸２.１ｇ，塩化ルテニウム１.１ｇを用いる以外は実施例１と同様とした。 Example 1 was repeated except that 2.1 g of chloroplatinic acid and 1.1 g of ruthenium chloride were used as catalyst metal salts.
比較例２として、触媒金属塩として塩化白金酸２.１ｇ，塩化ルテニウム１.１ｇを用いる以外は比較例１と同様の電極を用いた。 As Comparative Example 2, the same electrode as in Comparative Example 1 was used except that 2.1 g of chloroplatinic acid and 1.1 g of ruthenium chloride were used as the catalyst metal salts.
実施例３の触媒材料と比較例２の触媒材料とを透過型電子顕微鏡で観察した結果を図９に示す。比較例２の触媒金属の平均粒径は約５ｎｍ、実施例３の触媒の平均粒径は約２
ｎｍであり、実施例３の触媒粒子の方がより微細に担持されていることがわかる。
FIG. 9 shows the results of observing the catalyst material of Example 3 and the catalyst material of Comparative Example 2 with a transmission electron microscope. The average particle size of the catalyst metal of Comparative Example 2 was about 5 nm, and the average particle size of the catalyst of Example 3 was about 2 nm.
nm, which indicates that the catalyst particles of Example 3 are more finely supported.
実施例１と同様な手法で実施例３の電極と比較例２の電極について、単極測定を行った。その結果、比較例２の電極に比べ、実施例３の電極は同一電位で約３倍の電流密度が得られ、電極性能が高かった。 The unipolar measurement was performed on the electrode of Example 3 and the electrode of Comparative Example 2 in the same manner as in Example 1. As a result, as compared with the electrode of Comparative Example 2, the electrode of Example 3 had about three times the current density at the same potential, and the electrode performance was high.
したがって、触媒金属として白金の他に白金とルテニウムを用いても効果があることがわかった。その他、白金とマンガン，白金と鉄等でも同様であった。 Therefore, it was found that the use of platinum and ruthenium in addition to platinum as the catalytic metal was also effective. The same applies to platinum and manganese, platinum and iron, and the like.
また、白金と、ルテニウム，マンガン，鉄などは触媒担体上に単体で存在しているものから合金となって存在しているものもある。さらに、これらの金属は何らかの化合物であっても良く、例えば酸化物や塩化物であっても良い。 Platinum, ruthenium, manganese, iron, and the like may be present on the catalyst carrier alone or in the form of an alloy. Further, these metals may be any compounds, for example, oxides and chlorides.
本実施例に係るＭＥＡ８０４の断面模式図を図８に示す。図８はわかりやすくするため電極及び膜の厚さを大きく描いているが、実際に作成するＭＥＡはシート状で、その厚さは７０〜５００μｍ程度（電極の厚さ１０〜１００μｍ，電解質膜の厚さ５０〜３００
μｍ）であり、本実施例に係るＭＥＡは１００μｍである。本実施例のＭＥＡはアノード電極８０１とカソード電極８０２とその中間に位置する電解質膜８０３から構成される。次に本実施例に係るＭＥＡ８０４の作製方法を示す。
FIG. 8 is a schematic cross-sectional view of the
μm), and the MEA according to the present example is 100 μm. The MEA according to the present embodiment includes an
実施例３の電極をアノード電極、実施例１の電極をカソード電極とし、両電極が電解質膜８０３として用いるパーフルオロスルホン酸膜に接するように両側に配置し、これをホットプレスにより熱圧着，転写することでＭＥＡ８０４を作製する。
The electrode of the third embodiment is an anode electrode, the electrode of the first embodiment is a cathode electrode, and both electrodes are arranged on both sides so as to be in contact with a perfluorosulfonic acid film used as the
比較例３に係るＭＥＡの作製法であるが、比較例２の電極をアノード電極、比較例１の電極をカソード電極とする以外は、実施例４と同様である。 The method of manufacturing the MEA according to Comparative Example 3 is the same as that of Example 4 except that the electrode of Comparative Example 2 is an anode electrode and the electrode of Comparative Example 1 is a cathode electrode.
図７に本実施例に係るＤＭＦＣの模式図を示す。前記ＤＭＦＣは、アノード電極７０１と、カソード電極７０３と、その中間に位置するプロトン伝導性を備えた電解質膜７０２と、からなるＭＥＡを中心に構成され、アノード電極７０１側には、メタノールと水とを主成分とする燃料７０５が供給され、二酸化炭素と水７０６が排出される。カソード電極７０３側には、空気等の酸素を含む気体７０７が供給され、導入した気体中の未反応気体と水とを含む排ガス７０８が排出される。またアノード電極７０１と、カソード電極703は外部回路７０４へ接続される。
FIG. 7 shows a schematic diagram of the DMFC according to the present embodiment. The DMFC mainly includes an MEA including an
前述のような構成のＤＭＦＣに本実施例のＭＥＡと比較例４のＭＥＡを用い、出力密度を比較した。比較例４のＭＥＡを用いたＤＭＦＣの出力密度に比べ、本実施例のＭＥＡを用いたＤＭＦＣの出力密度は約２倍程度であると考えられる。 The output density was compared by using the MEA of the present example and the MEA of Comparative Example 4 for the DMFC having the above-described configuration. It is considered that the output density of the DMFC using the MEA of this example is about twice that of the DMFC using the MEA of Comparative Example 4.
窒素原子による触媒束縛効果は、主として触媒担体の表面に存在する窒素原子に依存する為、カーボンブラックの表面を、窒素原子を含んだ炭素で覆うような構造をもったものを触媒担体に用いることで同様の効果がある。この場合、触媒担体の形状は用いたカーボンブラックの形状にある程度依存する為、カーボンブラックの形状を選択することで触媒担体の最終的な形状を選択できるという利点がある。 Since the catalyst binding effect of nitrogen atoms depends mainly on the nitrogen atoms present on the surface of the catalyst carrier, use a catalyst carrier with a structure that covers the surface of carbon black with carbon containing nitrogen atoms. Has the same effect. In this case, since the shape of the catalyst carrier depends to some extent on the shape of the carbon black used, there is an advantage that the final shape of the catalyst carrier can be selected by selecting the shape of the carbon black.
以下に作成方法を示す。カーボンブラックとヘキサメトキシメチルメラミンとを重量比にして１：４にてエタノール中で１時間混合し、大気中、８０℃で２４時間乾燥させた。得られた物体をアルゴン雰囲気中、８００℃で１時間焼成し、カーボンブラックの表面が、窒素原子を含んだ炭素で被覆された触媒担体を得た。 The creation method is described below. Carbon black and hexamethoxymethyl melamine were mixed in ethanol at a weight ratio of 1: 4 in ethanol for 1 hour, and dried in air at 80 ° C. for 24 hours. The obtained object was baked at 800 ° C. for 1 hour in an argon atmosphere to obtain a catalyst carrier having a carbon black surface coated with nitrogen-containing carbon.
得られた触媒担体をＸＰＳで分析した結果、窒素原子の含有濃度は５原子％であった。これを、窒素を５原子％含んだ炭素のかわりに用いる以外は実施例３と同様とし、触媒材料を得た。 As a result of analyzing the obtained catalyst carrier by XPS, the nitrogen atom content was 5 atom%. A catalyst material was obtained in the same manner as in Example 3 except that this was used instead of carbon containing 5 atomic% of nitrogen.
本実施例の触媒材料と比較例２の触媒材料とを透過型電子顕微鏡で観察した結果、本実施例で得られた触媒材料に担持された触媒金属の平均粒径は約２ｎｍであり、本実施例の触媒金属の方がより微細に担持されていた。 As a result of observing the catalyst material of this example and the catalyst material of Comparative Example 2 with a transmission electron microscope, the average particle size of the catalyst metal supported on the catalyst material obtained in this example was about 2 nm. The catalyst metal of the example was more finely supported.
窒素原子を含んだ炭素の前駆体と触媒金属塩とを事前に混合し、その後焼成を行うことでも窒素原子を含んだ炭素に触媒が担持された触媒材料を得ることができる。フェニレンジアミン０.３ｇ とポリアミック酸０.７ｇ とＮ−メチル−２−ピロリジノン１００ｍｌと塩化白金酸０.２ｇ と塩化ルテニウム０.１ｇ とを混合し、１時間攪拌を行う。これを２００℃で２時間真空乾燥する。得られた固形物をアルゴン雰囲気中、８００℃で１時間焼成する。 A catalyst material in which a catalyst is supported on carbon containing nitrogen atoms can also be obtained by preliminarily mixing a carbon precursor containing nitrogen atoms and a catalyst metal salt and then performing calcination. 0.3 g of phenylenediamine, 0.7 g of polyamic acid, 100 ml of N-methyl-2-pyrrolidinone, 0.2 g of chloroplatinic acid and 0.1 g of ruthenium chloride are mixed and stirred for 1 hour. This is vacuum dried at 200 ° C. for 2 hours. The obtained solid is fired at 800 ° C. for 1 hour in an argon atmosphere.
実施例６の触媒材料と比較例２の触媒材料とを透過型電子顕微鏡で観察した結果、触媒の大きさはほぼ同等（約５ｎｍ）であったが、実施例６の触媒の方が均一に分散していると考えられる。 As a result of observing the catalyst material of Example 6 and the catalyst material of Comparative Example 2 with a transmission electron microscope, the size of the catalyst was almost the same (about 5 nm), but the catalyst of Example 6 was more uniform. It is thought to be dispersed.
触媒金属と共有結合可能な原子として硫黄原子を用い、窒素原子を５原子％含んだカーボンブラックの代わりに硫黄原子を５原子％含んだカーボンブラックを用いること以外は実施例３と同様とする。 Example 3 is the same as Example 3 except that a sulfur atom is used as an atom that can be covalently bonded to the catalyst metal, and a carbon black containing 5 atomic% of sulfur is used instead of a carbon black containing 5 atomic% of nitrogen.
実施例１と同様の手法で本実施例の電極と比較例２の電極とを単極測定により測定する。ここで参照電極には飽和カロメル電極、対極には金板を用いる。その結果、比較例２の電極に比べ、本実施例の電極は同一電位で約３倍程度の電流密度が得られ、電極性能が高いと考えられる。 The electrode of this example and the electrode of Comparative Example 2 are measured by monopolar measurement in the same manner as in Example 1. Here, a saturated calomel electrode is used as a reference electrode, and a gold plate is used as a counter electrode. As a result, compared to the electrode of Comparative Example 2, the electrode of this example can obtain about three times the current density at the same potential, and is considered to have higher electrode performance.
本実施例の触媒材料と比較例２の触媒材料を透過型電子顕微鏡で観察した結果、本実施例の触媒粒子の方がより微細に担持されている。 As a result of observing the catalyst material of this example and the catalyst material of Comparative Example 2 with a transmission electron microscope, the catalyst particles of this example are more finely supported.
硫黄原子を含んだ触媒担体の代わりに酸素原子を含んだ触媒担体を用いる以外は、実施例７と同様とする。 Example 7 is the same as Example 7 except that a catalyst carrier containing an oxygen atom is used instead of a catalyst carrier containing a sulfur atom.
実施例１と同様な手法で本実施例の電極と比較例２の電極について、単極測定を行う。その結果、比較例２の電極に比べ、本実施例の電極は同一電位で約３倍の電流密度が得られ、電極性能が高いと考えられる。したがって硫黄原子を含む触媒担体の他に酸素原子を含む触媒担体を用いても効果があることがわかる。その他、燐原子を含む触媒担体を用いても同様であると考えられる。 The unipolar measurement is performed on the electrode of this example and the electrode of Comparative Example 2 in the same manner as in Example 1. As a result, compared to the electrode of Comparative Example 2, the electrode of this example can obtain about three times the current density at the same potential, and is considered to have higher electrode performance. Therefore, it can be seen that the use of a catalyst carrier containing an oxygen atom in addition to the catalyst carrier containing a sulfur atom is also effective. In addition, it is considered that the same applies even when a catalyst carrier containing a phosphorus atom is used.
１０１，２０１，５０１…炭素原子、１０２,２０２,５０２…窒素原子、３０１…グラフェンシート、４０１…外側グラフェンシート、４０２…内側グラフェンシート、６０１…窒素原子を含んだＣＮＴ、６０２…触媒金属、７０１，８０１…アノード電極、７０２，８０３…電解質膜、７０３，８０２…カソード電極、７０４…外部回路、７０５…燃料、７０６…二酸化炭素と水、７０７…酸素を含む気体、７０８…排ガス、８０４…ＭＥＡ。
101, 201, 501: carbon atom, 102, 202, 502: nitrogen atom, 301: graphene sheet, 401: outer graphene sheet, 402: inner graphene sheet, 601: CNT containing nitrogen atom, 602: catalytic metal, 701 801: anode electrode, 702, 803: electrolyte membrane, 703, 802: cathode electrode, 704: external circuit, 705: fuel, 706: carbon dioxide and water, 707: gas containing oxygen, 708: exhaust gas, 804: MEA .
Claims (11)
In a fuel cell having an anode electrode for oxidizing a liquid fuel, a cathode electrode for reducing oxygen, and an electrolyte membrane formed between the anode electrode and the cathode electrode, at least one of the anode electrode and the cathode electrode is A fuel cell comprising a catalyst material containing a catalyst carrier having carbon and a catalyst metal, wherein the catalyst carrier contains at least one of a nitrogen atom, a sulfur atom, an oxygen atom, and a phosphorus atom.
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