JP2793523B2 - Polymer electrolyte fuel cell and method of operating the same - Google Patents
Polymer electrolyte fuel cell and method of operating the sameInfo
- Publication number
- JP2793523B2 JP2793523B2 JP7183081A JP18308195A JP2793523B2 JP 2793523 B2 JP2793523 B2 JP 2793523B2 JP 7183081 A JP7183081 A JP 7183081A JP 18308195 A JP18308195 A JP 18308195A JP 2793523 B2 JP2793523 B2 JP 2793523B2
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- Japan
- Prior art keywords
- fuel
- catalyst
- gas
- platinum
- polymer electrolyte
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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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
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- Fuel Cell (AREA)
- Catalysts (AREA)
- Inert Electrodes (AREA)
Description
【0001】[0001]
【発明の属する技術分野】本発明は、水素イオン伝導性
を有する高分子膜や水素イオン伝導性を有する無機また
は有機材料粉末と高分子結着材料とからなる複合材を電
解質として用いる固体高分子型燃料電池に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a solid polymer using, as an electrolyte, a polymer film having hydrogen ion conductivity or a composite material comprising an inorganic or organic material powder having hydrogen ion conductivity and a polymer binding material. Fuel cell.
【0002】[0002]
【従来の技術】近年、高効率のエネルギ変換装置として
燃料電池が注目を集めている。燃料電池は、これに用い
る電解質の種類により、たとえばアルカリ性水溶液型,
リン酸型,固体高分子型等の低温動作燃料電池と、溶融
炭酸塩型,固体酸化物電解質型等の高温動作燃料電池と
に大別される。2. Description of the Related Art In recent years, fuel cells have attracted attention as high-efficiency energy conversion devices. Depending on the type of electrolyte used for the fuel cell, for example, an alkaline aqueous solution type,
Low-temperature operation fuel cells such as phosphoric acid type and solid polymer type and high temperature operation fuel cells such as molten carbonate type and solid oxide electrolyte type are roughly classified.
【0003】これらの燃料電池のうち、電解質として水
素イオン伝導性を有する高分子電解質膜(Polymer Elec
trolyte Membrane)を用いる固体高分子型燃料電池は、
加圧容器を必要とせず、コンパクトで高出力密度が得ら
れること、優れた起動性が得られ、かつ簡略なシステム
で運転が可能であることなどの理由から、宇宙用、移動
電源用、離島用、定置用などとして注目されている。[0003] Among these fuel cells, a polymer electrolyte membrane (Polymer Elec) having hydrogen ion conductivity as an electrolyte is used.
polymer electrolyte fuel cell using trolyte membrane)
Because it does not require a pressurized container, it is compact, has a high power density, has excellent start-up properties, and can be operated with a simple system. , For stationary use
【0004】固体高分子型燃料電池で用いられる電解質
膜としては、スルホン酸基を持つポリスチレン系の陽イ
オン交換膜、フルオロカーボンスルホン酸とポリビニリ
デンフルオライドとの混合物質、フルオロカーボンマト
リックスにトリフルオロエチレンをグラフト化したもの
等が知られている。最近ではパーフルオロカーボンスル
ホン酸膜(たとえば、ナフィオン:商品名、デュポン社
製)等も用いられている。As the electrolyte membrane used in the polymer electrolyte fuel cell, a polystyrene-based cation exchange membrane having a sulfonic acid group, a mixed substance of fluorocarbon sulfonic acid and polyvinylidene fluoride, and trifluoroethylene as a fluorocarbon matrix are used. Grafted products are known. Recently, a perfluorocarbon sulfonic acid membrane (for example, Nafion: trade name, manufactured by DuPont) or the like is also used.
【0005】このような高分子電解質膜を用いる固体高
分子型燃料電池は、ガス拡散層および触媒層としての機
能を有する一対の多孔質電極、すなわち白金触媒を担持
した多孔質の燃料極と酸化剤極とで高分子電解質膜を挟
持するとともに両極の外側に燃料ガス流路と酸化剤ガス
流路とを備えた集電体を配したものを単セルとし、この
ような単セルを複数個、冷却板等を介して積層した構成
となっている。A polymer electrolyte fuel cell using such a polymer electrolyte membrane is composed of a pair of porous electrodes having functions as a gas diffusion layer and a catalyst layer, that is, a porous fuel electrode carrying a platinum catalyst and an oxidized fuel electrode. A single cell is formed by sandwiching a polymer electrolyte membrane between the electrode and a current collector provided with a fuel gas flow path and an oxidizing gas flow path outside both electrodes. , A cooling plate and the like.
【0006】水素イオン伝導型の燃料電池では、燃料極
側および酸化剤極側において、白金触媒の存在のもとに
電解質と電極との界面で、 燃料極:H2 →2H+ +2e- …(1) 酸化剤極:1/2O2 +2H+ +2e- →H2 O …(2) なる電気化学的な反応が起こる。In a hydrogen ion conduction type fuel cell, on the fuel electrode side and the oxidant electrode side, at the interface between the electrolyte and the electrode in the presence of a platinum catalyst, the fuel electrode: H 2 → 2H + + 2e − . 1) Oxidizer electrode: An electrochemical reaction of 1 / 2O 2 + 2H + + 2e − → H 2 O (2) occurs.
【0007】上記反応式において、電子については燃料
極から外部回路を通して酸化剤極への移動であり、水素
イオンについては電解質中での移動である。そして、反
応生成物として酸化剤極側で水が生成される。In the above reaction formula, electrons move from the fuel electrode to the oxidant electrode through an external circuit, and hydrogen ions move in the electrolyte. Then, water is generated as a reaction product on the oxidant electrode side.
【0008】このような固体高分子型燃料電池の燃料ガ
スとしては、多くの場合、メタノールなどアルコール系
の燃料またはメタンガスなど炭化水素系の燃料を改質し
て得た水素の豊富な改質ガスが用いられる。たとえば、
メタノールの改質の例をとると、(3) 式に示すように、
200〜300℃で水蒸気を加えて炭酸ガスと水素とを
生成させる反応となる。In many cases, the fuel gas for such a polymer electrolyte fuel cell is a hydrogen-rich reformed gas obtained by reforming an alcohol fuel such as methanol or a hydrocarbon fuel such as methane gas. Is used. For example,
Taking an example of methanol reforming, as shown in equation (3),
A reaction is performed in which water vapor is added at 200 to 300 ° C. to generate carbon dioxide gas and hydrogen.
【0009】 CH3 OH+H2 O→CO2 +3H2 …(3) これ以外に、 CH3 OH→CO+2H2 …(4) の反応も起こり、水素以外に副生成物として1数%以下
のCOも生成される。CH 3 OH + H 2 O → CO 2 + 3H 2 (3) In addition to this, a reaction of CH 3 OH → CO + 2H 2 (4) also occurs. Generated.
【0010】ところで、副生成物を含む改質ガスを直接
電池の燃料極に供給すると、含まれているCOが燃料極
の白金触媒に吸着する現象が起こり、白金触媒が被毒さ
れる。触媒がCOによって被毒されると、燃料極での反
応が阻害されて電池性能が大幅に低下する。このため、
通常は改質器を出た燃料ガスをさらにシフトコンバータ
に通したり、CO酸化除去装置(これらを第1段CO除
去装置とする)に通したりしてCO濃度を低減させてか
ら電池の燃料極に供給する方式が採られている。When a reformed gas containing a by-product is directly supplied to the fuel electrode of the battery, a phenomenon occurs in which the contained CO is adsorbed on the platinum catalyst of the fuel electrode, and the platinum catalyst is poisoned. When the catalyst is poisoned by CO, the reaction at the fuel electrode is hindered, and the cell performance is greatly reduced. For this reason,
Normally, the fuel gas discharged from the reformer is further passed through a shift converter or through a CO oxidation removing device (these are referred to as first-stage CO removing devices) to reduce the CO concentration, and then the fuel electrode of the battery is discharged. The method of supplying to the company is adopted.
【0011】リン酸型燃料電池では電池作動温度が20
0℃付近であるため、燃料ガス中のCO濃度が数100
ppm程度でも電池性能にはほとんど影響を与えない。
しかし、固体高分子型燃料電池では作動温度が通常、常
温〜80℃と低いため、燃料ガス中に数100ppmの
COが含まれていると、触媒の被毒が起こる。文献(R.
A.Lemons, J.of Power Souurce, vol.29, pp.251-264
(1990) )によれば固体高分子型燃料電池を80℃で作
動させたときのCO許容濃度は10ppmと報告されて
いる。このため、数100ppmのCOを含む改質ガス
について、CO除去を行うためには、第1段CO除去装
置を通ったガスを、さらに選択的酸化などの第2段CO
除去装置に通す必要がある。しかし、このように第2段
CO除去装置に通しても、CO濃度を確実に許容値の1
0ppm以下に低減させるのは難しい。このため、さら
に第3段CO除去装置に通す必要があり、システム構成
が複雑になってしまう問題があった。In the case of a phosphoric acid type fuel cell, the cell operating temperature is 20
Since the temperature is around 0 ° C., the CO concentration in the fuel gas is several hundreds.
Even about ppm does not substantially affect battery performance.
However, since the operating temperature of the polymer electrolyte fuel cell is usually as low as room temperature to 80 ° C., if the fuel gas contains several hundred ppm of CO, poisoning of the catalyst occurs. Literature (R.
A. Lemons, J. of Power Souurce, vol.29, pp.251-264
(1990)) reports that the allowable concentration of CO when the polymer electrolyte fuel cell is operated at 80 ° C. is 10 ppm. Therefore, in order to remove CO from a reformed gas containing several hundred ppm of CO, the gas that has passed through the first-stage CO removal device is further subjected to second-stage CO such as selective oxidation.
It must be passed through a removal device. However, even if the CO concentration is passed through the second-stage CO removal device, the CO concentration is reliably set to the allowable value of 1.
It is difficult to reduce it to 0 ppm or less. For this reason, it is necessary to further pass through the third stage CO removal device, and there is a problem that the system configuration becomes complicated.
【0012】なお、第3段CO除去装置に代えて、燃料
ガス中のCO濃度に応じて酸化剤を混入することでCO
被毒を抑制する方法(特開平6−251786号)も考
えられている。しかし、この方法では、第3段CO除去
装置を設ける代りに、新たに燃料ガス中のCO濃度を検
知するためのセンサーやCO濃度に応じて酸化剤を供給
するためのガス混合制御装置が必要となる。また、CO
濃度変動に対するセンサーの追従性が要求され、これに
応じて適量の酸化剤がガス混合制御装置で供給されなけ
ればならない。もし、これらの装置に不具合が生じる
と、酸化剤不足で燃料極の白金触媒が被毒したり、酸化
剤の過剰供給で水素との酸化反応が起きて電池電圧が低
下したりする問題が新たに生じることになる。In addition, instead of the third-stage CO removing device, the oxidizing agent is mixed in accordance with the CO concentration in the fuel gas to thereby reduce the CO.
A method of suppressing poisoning (JP-A-6-251786) has also been considered. However, in this method, instead of providing a third-stage CO removal device, a new sensor for detecting the CO concentration in the fuel gas and a gas mixing control device for supplying an oxidant according to the CO concentration are required. Becomes Also, CO
The sensor must be able to follow the concentration fluctuation, and accordingly, an appropriate amount of the oxidizing agent must be supplied by the gas mixing controller. If a malfunction occurs in these devices, there is a new problem that the platinum catalyst of the fuel electrode is poisoned due to insufficient oxidizing agent, and an excessive supply of the oxidizing agent causes an oxidation reaction with hydrogen to lower the battery voltage. Will occur.
【0013】[0013]
【発明が解決しようとする課題】上述の如く、従来の固
体高分子型燃料電池にあっては、燃料ガス中にCOが含
まれていると、このCOによって燃料極触媒が被毒して
電池性能の低下を招くため、使用できる燃料ガスが特定
されたり、あるいはアルコール系の燃料や炭化水素系の
燃料を改質して得た燃料ガスを用いようとした場合には
大掛りな付帯設備を必要とする問題があった。As described above, in a conventional polymer electrolyte fuel cell, if CO is contained in a fuel gas, the fuel electrode catalyst is poisoned by the CO, and the fuel cell is poisoned. In order to reduce the performance, if a fuel gas that can be used is specified, or if an attempt is made to use a fuel gas obtained by reforming an alcohol-based fuel or a hydrocarbon-based fuel, large-scale incidental facilities will be required. There was a problem that needed.
【0014】そこで本発明は、簡単な構成であるにも拘
らず燃料ガス中のCOによる燃料極触媒の被毒を抑制で
き、もって大掛り付帯設備を必要とすることなく、また
使用できる燃料ガスの範囲を拡大できる固体高分子型燃
料電池およびその運転方法を提供することを目的として
いる。Therefore, the present invention can suppress the poisoning of the fuel electrode catalyst by CO in the fuel gas despite having a simple structure, and can therefore use the fuel gas without using large-scale auxiliary equipment. It is an object of the present invention to provide a polymer electrolyte fuel cell capable of expanding the range of the above and a method of operating the same.
【0015】[0015]
【課題を解決するための手段】上記目的を達成するため
に、本発明に係る固体高分子型燃料電池は、白金に対す
るルテニウム含有量が50重量%以上で85重量%以下
の白金−ルテニウム触媒を燃料極が備えており、かつ電
池の作動温度が100℃から120℃の間であることを
特徴としている。In order to achieve the above object, a polymer electrolyte fuel cell according to the present invention comprises a platinum-ruthenium catalyst having a ruthenium content based on platinum of not less than 50% by weight and not more than 85% by weight. The fuel electrode is provided, and the operating temperature of the battery is between 100 ° C. and 120 ° C.
【0016】なお、触媒の担持体としてカーボンが用い
られるが、触媒全体に対するカーボンの含有量は20〜
60重量%であることが好ましい。Although carbon is used as a support for the catalyst, the content of carbon relative to the whole catalyst is 20 to 20%.
Preferably it is 60% by weight.
【0017】また、上記目的を達成するために、本発明
に係る運転方法では、白金に対するルテニウム含有量が
50重量%以上で85重量%以下の白金−ルテニウム触
媒を燃料極が備えており、かつ電池の作動温度が100
℃から120℃の間である固体高分子型燃料電池を運転
するに当たり、前記燃料極を介して高分子電解質膜を加
湿する内部加湿方式を採用するとともに、燃料ガスを2
kg/cm2 〜4kg/cm2 の圧力で供給し、酸化剤
ガスを2kg/cm2 〜4kg/cm2 の圧力で供給
し、一部が上記内部加湿方式の加湿水となる冷却水を上
記燃料ガスの供給圧力に対して同等かもしくはそれ以上
の圧力で供給するようにしたことを特徴としている。Further, in order to achieve the above object, in the operating method according to the present invention, the fuel electrode includes a platinum-ruthenium catalyst having a ruthenium content of 50% by weight or more and 85% by weight or less with respect to platinum, and Battery operating temperature is 100
When operating the polymer electrolyte fuel cell at a temperature between 120 ° C. and 120 ° C., an internal humidification method of humidifying the polymer electrolyte membrane via the fuel electrode is employed, and the fuel gas is supplied to the fuel cell at a temperature of 2 ° C.
was supplied at a pressure of kg / cm 2 ~4kg / cm 2 , the oxidant gas is supplied at a pressure of 2kg / cm 2 ~4kg / cm 2 , the part is cooling water which is a humidifying water of the internal humidifying system The fuel gas is supplied at a pressure equal to or higher than the supply pressure of the fuel gas.
【0018】上記組成の白金−ルテニウム触媒はCOに
被毒され難い。また、電池の作動温度を上記温度まで上
げると、燃料極触媒がCOに被毒され難い方向に一層近
付けることが可能となる。The platinum-ruthenium catalyst having the above composition is hardly poisoned by CO. Further, when the operating temperature of the battery is raised to the above temperature, it becomes possible to bring the fuel electrode catalyst closer to the direction in which CO is less likely to be poisoned.
【0019】また、触媒の担持体であるカーボンの含有
量が少なくなると、触媒での金属濃度が高くなるため、
触媒の製作コストが高くなるばかりか、引火し易くなる
など製造工程上の取扱いが極めて難しく、しかも触媒の
導電性を低下させる。したがって、上記範囲が好まし
い。Further, when the content of carbon, which is a carrier of the catalyst, decreases, the metal concentration in the catalyst increases.
Not only is the production cost of the catalyst high, but it is extremely difficult to handle in the production process, for example, it becomes easy to catch fire, and the conductivity of the catalyst is reduced. Therefore, the above range is preferable.
【0020】上記組成の触媒を持つ燃料極を備え、かつ
上記温度範囲の固体高分子型燃料電池を内部加湿方式で
運転するに当って、燃料ガスおよび酸化剤ガスの供給圧
力は水蒸気分圧より大きな値である必要があるため、2
kg/cm2 以上必要である。また、供給圧力を大きく
すると、加圧動力が大きくなり、電池システム全体の効
率が低下するので、上限を4kg/cm2 に抑える必要
がある。さらに、一部が内部加湿方式の加湿水となる冷
却水の圧力は、加湿水を安定供給するために上記燃料ガ
スの供給圧力に対して同等かもしくはそれ以上である必
要がある。In operating the solid polymer electrolyte fuel cell having the catalyst having the above composition and having the above temperature range in the internal humidification system, the supply pressure of the fuel gas and the oxidizing gas is set to a value lower than the partial pressure of steam. Since it needs to be a large value, 2
kg / cm 2 or more is required. Further, when the supply pressure is increased, the pressurizing power is increased, and the efficiency of the entire battery system is reduced. Therefore, it is necessary to suppress the upper limit to 4 kg / cm 2 . Further, the pressure of the cooling water, part of which is humidification water of the internal humidification method, needs to be equal to or higher than the supply pressure of the fuel gas in order to stably supply the humidification water.
【0021】[0021]
【発明の実施の形態】以下、図面を参照しながら本発明
の実施形態を説明する。Embodiments of the present invention will be described below with reference to the drawings.
【0022】図1には本発明の一実施形態に係る固体高
分子型燃料電池の分解斜視図が示されている。FIG. 1 is an exploded perspective view of a polymer electrolyte fuel cell according to one embodiment of the present invention.
【0023】この固体高分子型燃料電池は、単セル21
を互いの間に後述する加湿水透過板22と冷却水案内機
能およびセパレータ機能を備えた冷却板23とを介在さ
せて複数積層した積層構造に形成されている。This polymer electrolyte fuel cell has a single cell 21
Are formed in a laminated structure in which a plurality of humidified water permeable plates 22 to be described later and a cooling plate 23 having a cooling water guiding function and a separator function are interposed between each other.
【0024】単セル21は、公知のものと同様の材質で
形成された高分子電解質膜24を備えている。この高分
子電解質膜24の両面には高分子電解質膜より小さい面
積に形成された燃料極25と酸化剤極26とが接触配置
されている。燃料極25および酸化剤極26の外周部分
には、各電極とほぼ同じ厚みのシール材で形成されたガ
スシール用のパッキング27,28が配置されている。The single cell 21 has a polymer electrolyte membrane 24 formed of the same material as that of a known cell. On both surfaces of the polymer electrolyte membrane 24, a fuel electrode 25 and an oxidizer electrode 26 formed in areas smaller than the polymer electrolyte membrane are arranged in contact with each other. Gas seal packings 27 and 28 formed of a sealing material having substantially the same thickness as each electrode are arranged on the outer peripheral portions of the fuel electrode 25 and the oxidant electrode 26.
【0025】ここで、燃料極25は次のように形成され
ている。すなわち、図3(a) に示すように、カーボン多
孔質体29の一方の表面にカーボン粉末と撥水剤とのス
ラリーとを塗布し、これを360℃で焼結してガス拡散
層30を形成し、このガス拡散層30上に白金(Pt)
とルテニウム(Ru)とカーボン(C)からなる触媒層
31を設けたものとなっている。触媒層31は、Ptに
対するRuの含有量が50重量%以上で85重量%以下
となるように、たとえば組成比Pt:Ru:C=30:
30:40に配合されたカーボン担持触媒とフッ素系高
分子溶液と水とを混合して燃料極用触媒スラリーを作成
し、これを白金担持量が1.5mg/cm2 となるよう
にガス拡散層30上に塗布して形成されている。そし
て、触媒層31が高分子電解質膜24側に位置するよう
に配置されている。Here, the fuel electrode 25 is formed as follows. That is, as shown in FIG. 3A, a slurry of carbon powder and a water repellent is applied to one surface of the carbon porous body 29, and this is sintered at 360 ° C. to form the gas diffusion layer 30. Formed, and platinum (Pt) is formed on the gas diffusion layer 30.
And a catalyst layer 31 made of ruthenium (Ru) and carbon (C). The catalyst layer 31 has, for example, a composition ratio of Pt: Ru: C = 30:
A catalyst slurry for an anode is prepared by mixing a carbon-supported catalyst, a fluoropolymer solution, and water mixed at a ratio of 30:40, and gas diffusion is performed so that the amount of supported platinum becomes 1.5 mg / cm 2. It is formed by coating on the layer 30. The catalyst layer 31 is arranged so as to be located on the polymer electrolyte membrane 24 side.
【0026】一方、酸化剤電極26は、図3(b) に示す
ように、カーボン多孔質体29の一方の表面にカーボン
粉末と撥水剤とのスラリーを塗布し、これを360℃で
焼結してガス拡散層30を形成し、このガス拡散層30
上に白金(Pt)とカーボン(C)とからなる触媒層3
2を設けたものとなっている。触媒層32は、組成比が
Pt:C=50:50に配合されたカーボン担持触媒と
フッ素系高分子溶液と水とを混合して酸化剤極用触媒ス
ラリーを作成し、これを白金担持量が1.5mg/cm
2 となるようにガス拡散層30上に塗布して形成されて
いる。そして、触媒層32が高分子電解質膜24側に位
置するように配置されている。On the other hand, as shown in FIG. 3 (b), the oxidant electrode 26 is formed by applying a slurry of carbon powder and a water repellent to one surface of a carbon porous body 29 and firing the slurry at 360.degree. To form a gas diffusion layer 30,
Catalyst layer 3 made of platinum (Pt) and carbon (C) on top
2 is provided. The catalyst layer 32 was prepared by mixing a carbon-supported catalyst having a composition ratio of Pt: C = 50: 50, a fluorinated polymer solution, and water to form an oxidant electrode catalyst slurry, Is 1.5mg / cm
It is formed by coating on the gas diffusion layer 30 so as to be 2 . The catalyst layer 32 is arranged so as to be located on the polymer electrolyte membrane 24 side.
【0027】燃料極25の図1中下面側には、燃料極2
5への燃料ガスの供給機能と集電機能とを発揮する燃料
極側集電板33が接触配置されている。この燃料極側集
電板33は、親水性のカーボン多孔質板で形成されてい
る。燃料極側集電板33における燃料極25との接触面
には、図2に示すように、燃料ガスを通流させるための
案内溝34が複数形成されている。同様に、酸化剤極2
6の図1中上面側には、酸化剤極26への酸化剤ガスの
供給機能と集電機能とを発揮する酸化剤極側集電板35
が接触配置されている。この酸化剤極側集電板35は、
緻密なカーボン板で形成されている。酸化剤極側集電板
35における酸化剤極26との接触面には、図2に示す
ように、酸化剤ガスを通流させるための案内溝36が複
数形成されている。On the lower surface side of the fuel electrode 25 in FIG.
A fuel electrode-side current collector plate 33 that has a function of supplying fuel gas to the fuel cell 5 and a function of collecting current is disposed in contact with the fuel electrode 5. The fuel electrode side current collector 33 is formed of a hydrophilic carbon porous plate. As shown in FIG. 2, a plurality of guide grooves 34 for passing fuel gas are formed on the contact surface of the fuel electrode side current collector plate 33 with the fuel electrode 25. Similarly, oxidizer electrode 2
6 on the upper surface side in FIG. 1, an oxidant electrode-side current collector plate 35 that exhibits a function of supplying an oxidant gas to the oxidant electrode 26 and a current collecting function.
Are arranged in contact. This oxidant electrode side current collector plate 35
It is formed of a dense carbon plate. As shown in FIG. 2, a plurality of guide grooves 36 for allowing the oxidant gas to flow are formed on the contact surface of the oxidant electrode side current collector plate 35 with the oxidant electrode 26.
【0028】一方、燃料極側集電板33の図1中下面側
には前述した加湿水透過板22が接触配置されており、
この加湿水透過板22の図1中下面側には冷却板23が
接触配置されている。加湿水透過板22は親水性のカー
ボン多孔質薄板で形成されており、冷却板23は緻密な
カーボン板あるいは金属板で形成されている。冷却板2
3の加湿水透過板22側に位置する面には、冷却水を案
内するための案内溝37が複数形成されている。On the other hand, the above-mentioned humidified water permeable plate 22 is disposed in contact with the lower surface side of the fuel electrode side current collector plate 33 in FIG.
A cooling plate 23 is arranged in contact with the humidified water permeable plate 22 on the lower surface side in FIG. The humidification water permeable plate 22 is formed of a hydrophilic carbon porous thin plate, and the cooling plate 23 is formed of a dense carbon plate or a metal plate. Cooling plate 2
A plurality of guide grooves 37 for guiding the cooling water are formed on the surface of the third humidified water permeable plate 22 side.
【0029】加湿水透過板22の両側部、冷却板23の
両側部、高分子電解質膜24の両側部、パッキング2
7,28の両側部には、それぞれ図1に示すように、燃
料ガスを供給/排出するための孔50,51(ただし、
孔51は図示せず)と、冷却水を供給/排出するための
孔52,53と、酸化剤ガスを供給/排出するための孔
54,55とが積層方向に通じる関係に設けられてい
る。Both sides of the humidified water permeable plate 22, both sides of the cooling plate 23, both sides of the polymer electrolyte membrane 24, the packing 2
As shown in FIG. 1, holes 50 and 51 for supplying / discharging the fuel gas are provided on both sides of the fuel cells 7 and 28, respectively (however,
The holes 51 are not shown), the holes 52 and 53 for supplying / discharging the cooling water, and the holes 54 and 55 for supplying / discharging the oxidizing gas are provided so as to communicate in the stacking direction. .
【0030】そして、燃料極側集電板33に設けられた
案内溝34は燃料ガスを供給/排出するための孔50,
51に通じ、酸化剤極側集電板35に設けられた案内溝
36は酸化剤ガスを供給/排出するための孔54,55
に通じ、冷却板23に設けられた案内溝37は冷却水を
供給/排出するための孔52,53に通じている。The guide groove 34 provided on the fuel electrode side current collector 33 has holes 50 for supplying / discharging the fuel gas.
The guide groove 36 provided in the oxidant electrode side current collector plate 35 is provided with holes 54 and 55 for supplying / discharging the oxidant gas.
The guide groove 37 provided in the cooling plate 23 communicates with holes 52 and 53 for supplying / discharging cooling water.
【0031】このように構成された単セル21、加湿水
透過板22、冷却板23が複数積層されて燃料電池積層
体70が構成されている。燃料電池積層体70の積層方
向に位置する両端面に導電性のエンドプレート71,7
2が当てがわれ、さらにこれらエンドプレート71,7
2の外面にエンドプレートより幅広な図示しない締付け
板が当てがわれ、これら締付け板の周縁部においてバネ
を介在させた条件下で両締付け板を絶縁性のロッドで積
層方向に締付けたものとなっている。The fuel cell stack 70 is formed by stacking a plurality of the single cells 21, the humidified water permeable plate 22, and the cooling plate 23 thus configured. Conductive end plates 71, 7 are provided on both end faces of the fuel cell stack 70 in the stacking direction.
2 and the end plates 71, 7
A clamping plate (not shown) wider than the end plate is applied to the outer surface of the second plate, and both clamping plates are clamped in the laminating direction with insulating rods under the condition that a spring is interposed at the peripheral edge of these clamping plates. ing.
【0032】なお、エンドプレート71の上面には、前
述した孔50,51を介して燃料ガスの供給/排出を行
うための燃料供給管73,燃料排出管74と、前述した
孔52,53を介して冷却水の供給/排出を行うための
冷却水供給管75,冷却水排出管76と、前述した孔5
4,55を介して酸化剤ガスの供給/排出を行うための
酸化剤ガス供給管77,酸化剤ガス排出管78とが対応
する孔に通じる関係に設けられている。The upper surface of the end plate 71 is provided with a fuel supply pipe 73 and a fuel discharge pipe 74 for supplying / discharging the fuel gas through the holes 50 and 51 and the holes 52 and 53 described above. A cooling water supply pipe 75 and a cooling water discharge pipe 76 for supplying / discharging the cooling water through the
An oxidizing gas supply pipe 77 and an oxidizing gas discharge pipe 78 for supplying / discharging the oxidizing gas via the holes 4 and 55 are provided in such a manner as to communicate with the corresponding holes.
【0033】このような構成であると、燃料供給管73
を介して供給された燃料ガス(供給圧力2〜4kg/c
m2 )は、各単セル21において燃料極側集電板33に
設けられた各案内溝34を流れる。そして、一部が燃料
極25に拡散して発電に供され、残りが孔51へと流れ
た後に燃料排出管74へと流れる。また、酸化剤供給管
77を介して供給された酸化剤ガス(供給圧力2〜4k
g/cm2 )は、各単セル21において酸化剤極側集電
板35に設けられた各案内溝36を流れる。そして、一
部が酸化剤極26に拡散して発電に供され、残りが孔5
5へと流れた後に酸化剤排出管78へと流れる。With such a configuration, the fuel supply pipe 73
Gas supplied through the fuel (supply pressure 2 to 4 kg / c
m 2 ) flows through each guide groove 34 provided in the fuel electrode side current collector 33 in each unit cell 21. Then, a part thereof is diffused to the fuel electrode 25 and used for power generation, and the remaining part flows to the hole 51 and then flows to the fuel discharge pipe 74. The oxidizing gas supplied through the oxidizing agent supply pipe 77 (supply pressure 2 to 4 k
g / cm 2 ) flows through each guide groove 36 provided in the oxidant electrode side current collector 35 in each single cell 21. Then, a part is diffused to the oxidizer electrode 26 and is used for power generation, and the rest is
After flowing to 5, it flows to the oxidant discharge pipe 78.
【0034】一方、冷却水供給管75を介して供給され
た冷却水(供給圧力2kg/cm2以上)は、冷却板2
3に設けられた各案内溝37を流れる。そして、一部が
加湿水透過板23、燃料極側集電板33、燃料極25を
それぞれ透過して高分子電解質膜24の加湿に供され、
残りが冷却板23を介して吸熱した後に孔53へと流
れ、その後に冷却水排出管76へと流れる。On the other hand, the cooling water (supply pressure 2 kg / cm 2 or more) supplied through the cooling water supply pipe 75 is
3 flows through each guide groove 37 provided in the guide groove 3. Then, a part of the water passes through the humidified water permeable plate 23, the fuel electrode side current collector 33, and the fuel electrode 25, and is used for humidifying the polymer electrolyte membrane 24,
The remainder flows into the holes 53 after absorbing heat through the cooling plate 23, and then flows to the cooling water discharge pipe 76.
【0035】このとき、燃料電池積層体70は、図示し
ないヒータによって温度が100℃から120℃の間に
保持される。At this time, the temperature of the fuel cell stack 70 is maintained between 100 ° C. and 120 ° C. by a heater (not shown).
【0036】このように、燃料ガス、酸化剤ガスおよび
冷却水の供給によって電池としての機能が発揮される。
そして、この場合には、燃料極25に前記組成の触媒層
31、つまりPtに対するRuの含有量が50重量%以
上で85重量%以下に設定されたカーボン担持の触媒層
31を設けていることと、電池の動作温度を100℃か
ら120℃の間に設定していることとが相俟って、燃料
ガスにCOが含まれている場合であっても触媒層31中
の白金の被毒が抑制され、長期に亘って安定した発電性
能を発揮させることができる。As described above, the function of the battery is exhibited by the supply of the fuel gas, the oxidizing gas and the cooling water.
In this case, the fuel electrode 25 is provided with the catalyst layer 31 having the above-described composition, that is, the carbon-supported catalyst layer 31 in which the content of Ru with respect to Pt is set to 50% by weight or more and 85% by weight or less. And the fact that the operating temperature of the battery is set between 100 ° C. and 120 ° C., so that even if the fuel gas contains CO, the poisoning of platinum in the catalyst layer 31 is prevented. Is suppressed, and stable power generation performance can be exhibited over a long period of time.
【0037】この事実を確認した実験例を以下に説明す
る。An experimental example confirming this fact will be described below.
【0038】実験例1 燃料極25については、カーボン多孔質体29の一方の
表面にカーボン粉末と撥水剤とのスラリーを塗布し、こ
れを360℃で焼結してガス拡散層30を形成した。さ
らに組成比がPt:Ru:C=30:30:40のカー
ボン担持触媒とフッ素系高分子溶液と水とを混合して燃
料極用触媒スラリーを作成した。このスラリーを白金担
持量が1.5mg/cm2 となるようにガス拡散層30
上に塗布して触媒層31を形成した。Experimental Example 1 Regarding the fuel electrode 25, a slurry of carbon powder and a water repellent was applied to one surface of the carbon porous body 29, and this was sintered at 360 ° C. to form the gas diffusion layer 30. did. Further, a carbon-supported catalyst having a composition ratio of Pt: Ru: C = 30: 30: 40, a fluorine-based polymer solution, and water were mixed to prepare a fuel electrode catalyst slurry. The slurry is applied to the gas diffusion layer 30 so that the platinum loading is 1.5 mg / cm 2.
The catalyst layer 31 was formed by coating on the upper surface.
【0039】一方、酸化剤極26については、カーボン
多孔質体29の一方の表面にカーボン粉末と撥水剤との
スラリーを塗布し、これを360℃で焼結してガス拡散
層30を形成した。さらに組成比がPt:C=50:5
0のカーボン担持触媒とフッ素系高分子溶液と水とを混
合して酸化剤極用触媒スラリーを作成した。このスラリ
ーを白金担持量が1.5mg/cm2 となるようにガス
拡散層30上に塗布して触媒層32を形成した。On the other hand, with respect to the oxidizer electrode 26, a slurry of carbon powder and a water repellent is applied to one surface of the carbon porous body 29, and this is sintered at 360 ° C. to form the gas diffusion layer 30. did. Further, the composition ratio is Pt: C = 50: 5.
The carbon-supported catalyst, the fluoropolymer solution, and water were mixed to prepare an oxidant electrode catalyst slurry. This slurry was applied on the gas diffusion layer 30 so that the amount of supported platinum was 1.5 mg / cm 2 , to form a catalyst layer 32.
【0040】これらの燃料極と酸化剤極とでデュポン社
製のフッ素系高分子膜 Nafion R 117を挟み、ホット
プレスして電極面積100cm2 の単位電池を製作し
た。[0040] sandwiched a fluorinated polymer membrane Nafion R 117 manufactured by DuPont in the these fuel electrode oxidant electrode was fabricated unit cell of the electrode area 100 cm 2 by hot pressing.
【0041】製作した単位電池をバイトンパッキンでシ
ールし、ガス流路を設けたホルダーで挟み、電池温度1
10℃で、かつ内部加湿方式で発電試験を行った。この
とき、燃料極ガス圧力を4kg/cm2 とし、燃料ガス
としてはH2 +CO(50ppm)の混合ガスを140
℃でバブリングしてガス利用率30%でフローした。酸
化剤極側ではガス圧力を4kg/cm2 とし、空気をガ
ス利用率50%でフローした。The manufactured unit battery was sealed with Viton packing, sandwiched by a holder provided with a gas flow path, and battery temperature 1
A power generation test was performed at 10 ° C. and by an internal humidification method. At this time, the fuel electrode gas pressure was set to 4 kg / cm 2, and a mixed gas of H 2 + CO (50 ppm) was used as the fuel gas.
The mixture was bubbled at 30 ° C. and flowed at a gas utilization of 30%. On the oxidant electrode side, the gas pressure was 4 kg / cm 2, and air flowed at a gas utilization of 50%.
【0042】電流密度0.4A/cm2 負荷で運転した
ときの電池電圧の経時変化を図4中にAで示す。なお、
参考のために80℃で運転したときの特性を図4中にB
で示す。80℃で運転したときには数時間で電池電圧が
著しく低下したのに比べると、110℃運転時には20
00時間後においても1%の電圧低下であった。A change in the battery voltage with time when the battery was operated at a current density of 0.4 A / cm 2 is indicated by A in FIG. In addition,
For reference, the characteristics when operated at 80 ° C. are shown in FIG.
Indicated by When operating at 80 ° C., the battery voltage dropped significantly in a few hours, compared to 20 hours at 110 ° C.
Even after 00 hours, the voltage dropped by 1%.
【0043】実験例2 実験例1での燃料極用触媒スラリー作成過程において、
組成比がPt:Ru:C=40:20:40のカーボン
担持触媒のスラリーを作成し、これ用いて白金担持量
1.5mg/cm2 の触媒層を持つ燃料極を作成した。
これと白金担持触媒の酸化剤極とでデュポン社製のフッ
素系高分子膜 Nafion R 117を挟みホットプレスで熱
圧着し、単位電池を製作した。Experimental Example 2 In the preparation process of the catalyst slurry for fuel electrode in Experimental Example 1,
A slurry of a carbon-supported catalyst having a composition ratio of Pt: Ru: C = 40: 20: 40 was prepared, and this was used to prepare a fuel electrode having a catalyst layer having a platinum support amount of 1.5 mg / cm 2 .
In between this and the oxidant electrode of the platinum supported catalysts thermocompression bonding by hot pressing to sandwich the fluorinated polymer membrane Nafion R 117 manufactured by DuPont, was fabricated unit cell.
【0044】実験例1と同様のガス圧力条件で、燃料極
にH2 +CO(100ppm)の混合ガスをフローし、
内部加湿方式で加湿を行い、電池作動温度120℃、
0.4A/cm2 負荷で発電試験を行った。燃料極とし
て白金のみを担持した触媒を用いた電池は、発電開始か
ら数時間で電圧が20%低下したのに対し、白金−ルテ
ニウム触媒を用いた電池の電圧は2000時間後におい
てもわずか4%低下しただけだった。Under the same gas pressure conditions as in Experimental Example 1, a mixed gas of H 2 + CO (100 ppm) was flowed through the fuel electrode.
Humidification by internal humidification method, battery operating temperature 120 ° C,
A power generation test was performed at a load of 0.4 A / cm 2 . A battery using a catalyst supporting only platinum as a fuel electrode has a voltage drop of 20% in a few hours from the start of power generation, whereas a battery using a platinum-ruthenium catalyst has a voltage of only 4% even after 2000 hours. It just dropped.
【0045】実験例3 触媒中のルテニウム含有量の影響を調べるため、カーボ
ン重量比を全体の50重量%に固定とし、白金に対する
ルテニウム含有量が20〜90重量%と異なる白金−ル
テニウム担持カーボン触媒を用いて白金担持量が0.6
mg/cm2 となるように実験例1と同様の手順で燃料
極を作成した。これら燃料極と酸化剤極とデュポン社製
のフッ素系高分子膜 Nafion R 117とで電極面積10
0cm2の単位電池をそれぞれ製作し、電池温度110
℃、燃料極側および酸化剤極側ともにガス圧力2kg/
cm2 に加圧し、燃料極側にH2 +CO(100pp
m)の混合ガスをガス利用率40%でフローし、酸化剤
極側には空気をガス利用率50%でフローし、内部加湿
方式によって発電試験を行った。EXPERIMENTAL EXAMPLE 3 In order to investigate the effect of the ruthenium content in the catalyst, the carbon weight ratio was fixed at 50% by weight, and the platinum-ruthenium-supported carbon catalyst having a ruthenium content with respect to platinum different from 20 to 90% by weight. The amount of supported platinum is 0.6
A fuel electrode was prepared in the same procedure as in Experimental Example 1 so as to obtain mg / cm 2 . The electrode area of the fuel electrode, the oxidizer electrode, and the fluorine polymer membrane Nafion R 117 manufactured by DuPont is 10
Each unit battery of 0 cm 2 was manufactured, and the battery temperature was 110
° C, gas pressure 2kg /
cm 2 and H 2 + CO (100 pp) on the fuel electrode side.
m) was flowed at a gas utilization of 40%, and air was flowed at a gas utilization of 50% to the oxidant electrode side, and a power generation test was performed by an internal humidification method.
【0046】表1に初期電池電圧と発電開始から200
0時間後の0.4A/cm2 負荷時の電池電圧を示す。Table 1 shows the initial battery voltage and 200
The battery voltage under a load of 0.4 A / cm 2 after 0 hours is shown.
【0047】[0047]
【表1】 [Table 1]
【0048】表1から判るように、ルテニウムの含有量
が多いほど電池電圧の低下が少なく、白金に対するルテ
ニウム含有量が50〜80重量%の範囲で良好な結果を
示している。中でもルテニウム含有量が78重量%の触
媒を用いた電池の電圧低下が少ないことが判かる。しか
し、ルテニウム含有量が85重量%を越えると、初期の
電池電圧が低くなる。これは燃料極での反応に寄与する
白金量が十分でないことによるものと考えられる。As can be seen from Table 1, as the content of ruthenium increases, the battery voltage decreases less, and good results are shown when the content of ruthenium with respect to platinum is in the range of 50 to 80% by weight. In particular, it can be seen that the voltage drop of the battery using the catalyst having a ruthenium content of 78% by weight is small. However, when the ruthenium content exceeds 85% by weight, the initial battery voltage decreases. This is thought to be due to the insufficient amount of platinum contributing to the reaction at the fuel electrode.
【0049】ルテニウム含有量が90重量%になると、
その傾向が大きく現れ、電池電圧は20%に低下した。
この結果から、燃料極の触媒に適したルテニウム含有量
は、白金に対して50〜85重量%の範囲であるといえ
る。When the ruthenium content reaches 90% by weight,
This tendency was significant, and the battery voltage dropped to 20%.
From these results, it can be said that the ruthenium content suitable for the catalyst of the fuel electrode is in the range of 50 to 85% by weight based on platinum.
【0050】実験例4 組成比がPt:Ru:C=20:10:70(白金に対
するルテニウム含有量67重量%)、Pt:Ru:C=
25:15:60(白金に対するルテニウム含有量63
重量%)、Pt:Ru:C=40:20:40(白金に
対するルテニウム含有量67重量%)の白金−ルテニウ
ム触媒を用い、白金担持量が1.0mg/cm2 となる
ように実験例1と同じ方法でカーボン重量比の異なる燃
料極を作成した。Experimental Example 4 The composition ratio was Pt: Ru: C = 20: 10: 70 (ruthenium content based on platinum: 67% by weight), and Pt: Ru: C =
25:15:60 (ruthenium content 63 with respect to platinum)
Experimental Example 1 using a platinum-ruthenium catalyst having a Pt: Ru: C ratio of 40:20:40 (ruthenium content based on platinum: 67% by weight) and a platinum-supported amount of 1.0 mg / cm 2. Fuel electrodes having different carbon weight ratios were prepared in the same manner as described above.
【0051】これらの燃料極を用いて製作された単位電
池の初期性能から、触媒中にけるカーボン重量比の影響
を調べた。運転条件は実験例3と同じである。触媒全体
に対するカーボン重量比が60重量%、40重量%で
は、0.4A/cm2 負荷時の電池電圧がそれぞれ0.
7V、0.729Vと良好な初期性能が得られたが、カ
ーボン重量比が70重量%の電池電圧では物質拡散律速
の影響のため、0.4A/cm2 負荷時の電池電圧が
0.55Vと著しく低かった。From the initial performance of the unit cells manufactured using these fuel electrodes, the effect of the carbon weight ratio in the catalyst was examined. The operating conditions are the same as in Experimental Example 3. When the weight ratio of carbon to the entire catalyst is 60% by weight and 40% by weight, the battery voltage under a load of 0.4 A / cm 2 is 0.1%.
Although good initial performances of 7 V and 0.729 V were obtained, the battery voltage at a load of 0.4 A / cm 2 was 0.55 V at a load of 0.4 A / cm 2 at a battery voltage of 70% by weight due to the influence of material diffusion control. It was remarkably low.
【0052】このように、たとえばリン酸型燃料電池の
燃料極触媒の組成比(カーボン重量比は80〜90重量
%)にみられるようなカーボン重量比が高いものを固体
高分子型燃料電池の電極触媒に用いた場合は、触媒とし
ての機能が十分に得られず、触媒のカーボン重量比は6
0重量%以下であることが望ましいことが判った。Thus, for example, those having a high carbon weight ratio, such as the composition ratio of the fuel electrode catalyst (carbon weight ratio is 80 to 90% by weight) of the phosphoric acid type fuel cell, are used for the polymer electrolyte fuel cell. When used as an electrode catalyst, the function as a catalyst cannot be sufficiently obtained, and the carbon weight ratio of the catalyst is 6%.
It was found that the content was desirably 0% by weight or less.
【0053】逆に、カーボン重量比が少ない触媒では、
触媒での金属濃度が高くなるため、触媒の製作コストが
高くなるばかりか、引火し易くなるなど製造工程上の取
扱いが極めて難しく、しかも触媒の導電性を低下させ
る。このことから、燃料極触媒に適したカーボン重量比
は20〜60重量%と思われる。Conversely, for a catalyst having a small carbon weight ratio,
Since the metal concentration in the catalyst is increased, not only the production cost of the catalyst is increased, but also it is extremely difficult to handle in the production process such as easy ignition, and the conductivity of the catalyst is reduced. From this, it is considered that the carbon weight ratio suitable for the anode catalyst is 20 to 60% by weight.
【0054】なお、図1に示す実施形態では、燃料ガス
と酸化剤ガスとを並流方式で流しているが、向流方式や
直交流方式で流すようにしてもよい。また、加湿方式も
図1に示す実施形態に限られるものではない。しかし、
図1のような内部加湿方式を採用すると、燃料極におけ
る白金触媒の被毒抑制効果が大きい。In the embodiment shown in FIG. 1, the fuel gas and the oxidizing gas flow in a co-current system, but they may flow in a counter-current system or a cross-current system. Further, the humidification method is not limited to the embodiment shown in FIG. But,
When the internal humidification method as shown in FIG. 1 is adopted, the effect of suppressing the poisoning of the platinum catalyst at the fuel electrode is large.
【0055】また、酸化剤極の電極触媒には、白金触媒
の他に合金触媒を使用してもよい。As the electrode catalyst for the oxidant electrode, an alloy catalyst may be used in addition to the platinum catalyst.
【0056】[0056]
【発明の効果】COに被毒されにくい白金−ルテニウム
触媒層を燃料極に設け、しかも電池を100℃以上で作
動させるようにしているので、燃料極触媒がCOに被毒
されにくい環境を作り出すことができ、CO濃度が10
ppmを越える燃料ガスが供給されても長期にわたって
安定した電池特性を発揮させることができる。したがっ
て、燃料ガス中のCO濃度を10ppm以下に低減する
ための付帯設備を不要化でき、燃料電池システムの簡略
化に寄与できる。According to the present invention, a platinum-ruthenium catalyst layer which is hardly poisoned by CO is provided on the fuel electrode, and the battery is operated at 100 ° C. or higher, so that an environment in which the fuel electrode catalyst is hardly poisoned by CO is created. CO concentration is 10
Even if a fuel gas exceeding ppm is supplied, stable battery characteristics can be exhibited over a long period of time. Therefore, an additional facility for reducing the CO concentration in the fuel gas to 10 ppm or less can be eliminated, which contributes to simplification of the fuel cell system.
【図1】本発明の一実施形態に係る固体高分子型燃料電
池の分解斜視図FIG. 1 is an exploded perspective view of a polymer electrolyte fuel cell according to an embodiment of the present invention.
【図2】同燃料電池を局部的に示す断面図FIG. 2 is a sectional view partially showing the fuel cell;
【図3】同燃料電池に組込まれた燃料極と酸化剤極の構
成説明図FIG. 3 is a configuration explanatory view of a fuel electrode and an oxidizer electrode incorporated in the fuel cell.
【図4】同燃料電池の経時特性を参考例と比較して示す
図FIG. 4 is a diagram showing the aging characteristics of the fuel cell in comparison with a reference example.
21…単セル 22…加湿水透過板 23…冷却板 24…高分子電解質膜 25…燃料極 26…酸化剤極 27,28…パッキング 29…カーボン多孔質体 30…ガス拡散層 31,32…触媒層 33…燃料極側集電板 34,36,37…案内溝 35…酸化剤極側集電板 50,51…燃料ガスを供給/排出するための孔 52,53…冷却水を供給/排出するための孔 54,55…酸化剤ガスを供給/排出するための孔 71,72…エンドプレート DESCRIPTION OF SYMBOLS 21 ... Single cell 22 ... Humidified water permeable plate 23 ... Cooling plate 24 ... Polymer electrolyte membrane 25 ... Fuel electrode 26 ... Oxidizer electrode 27, 28 ... Packing 29 ... Carbon porous body 30 ... Gas diffusion layers 31, 32 ... Catalyst Layer 33: Fuel electrode side current collectors 34, 36, 37 ... Guide grooves 35 ... Oxidizer electrode side current collectors 50, 51 ... Holes for supplying / discharging fuel gas 52, 53 ... Supply / discharge of cooling water Holes 54, 55 ... holes for supplying / discharging the oxidizing gas 71, 72 ... end plates
───────────────────────────────────────────────────── フロントページの続き (58)調査した分野(Int.Cl.6,DB名) H01M 4/90 - 4/92 B01J 23/46 301 H01M 8/00 - 8/24──────────────────────────────────────────────────の Continued on the front page (58) Field surveyed (Int. Cl. 6 , DB name) H01M 4/90-4/92 B01J 23/46 301 H01M 8/00-8/24
Claims (3)
%以上で85重量%以下の白金−ルテニウム触媒を燃料
極が備えており、かつ電池の作動温度が100℃から1
20℃の間であることを特徴とする固体高分子型燃料電
池。1. A fuel electrode comprising a platinum-ruthenium catalyst having a ruthenium content based on platinum of not less than 50% by weight and not more than 85% by weight, and operating temperature of the battery is 100 ° C. to 1%.
A polymer electrolyte fuel cell, wherein the temperature is between 20 ° C.
で、白金に対するルテニウム含有量が50重量%以上で
85重量%以下、全体に対するカーボン含有量が20〜
60重量%の触媒を燃料極が備えており、かつ電池の作
動温度が100℃から120℃の間であることを特徴と
する固体高分子型燃料電池。2. A composition comprising platinum, ruthenium, and carbon, wherein the content of ruthenium with respect to platinum is not less than 50% by weight and not more than 85% by weight, and the content of carbon with respect to the whole is from 20 to 85% by weight.
A polymer electrolyte fuel cell, characterized in that the fuel electrode has a catalyst of 60% by weight and the operating temperature of the cell is between 100 ° C and 120 ° C.
%以上で85重量%以下の白金−ルテニウム触媒を燃料
極が備えており、かつ電池の作動温度が100℃から1
20℃の間である固体高分子型燃料電池を運転するに当
たり、前記燃料極を介して高分子電解質膜を加湿する内
部加湿方式を採用するとともに、燃料ガスを2kg/c
m2 〜4kg/cm2 の圧力で供給し、酸化剤ガスを2
kg/cm2 〜4kg/cm2 の圧力で供給し、一部が
上記内部加湿方式の加湿水となる冷却水を上記燃料ガス
の供給圧力に対して同等かもしくはそれ以上の圧力で供
給するようにしたことを特徴とする固体高分子型燃料電
池の運転方法。3. A fuel electrode comprising a platinum-ruthenium catalyst having a ruthenium content based on platinum of not less than 50% by weight and not more than 85% by weight, and having an operating temperature of the battery of 100 ° C. to 1%.
In operating the polymer electrolyte fuel cell at a temperature between 20 ° C., an internal humidification method of humidifying the polymer electrolyte membrane through the fuel electrode is employed, and the fuel gas is supplied at 2 kg / c.
m 2 -4 kg / cm 2 , and oxidant gas
was supplied at a pressure of kg / cm 2 ~4kg / cm 2 , so a portion of which supplies cooling water to be humidifying water of the internal humidifying system at equal to or higher pressure to the feed pressure of the fuel gas A method for operating a polymer electrolyte fuel cell, comprising:
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP7183081A JP2793523B2 (en) | 1995-07-19 | 1995-07-19 | Polymer electrolyte fuel cell and method of operating the same |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP7183081A JP2793523B2 (en) | 1995-07-19 | 1995-07-19 | Polymer electrolyte fuel cell and method of operating the same |
Publications (2)
Publication Number | Publication Date |
---|---|
JPH0935736A JPH0935736A (en) | 1997-02-07 |
JP2793523B2 true JP2793523B2 (en) | 1998-09-03 |
Family
ID=16129434
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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JP7183081A Expired - Lifetime JP2793523B2 (en) | 1995-07-19 | 1995-07-19 | Polymer electrolyte fuel cell and method of operating the same |
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JP (1) | JP2793523B2 (en) |
Families Citing this family (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE19756880A1 (en) * | 1997-12-19 | 1999-07-01 | Degussa | Anode catalyst for fuel cells with polymer electrolyte membranes |
US6936370B1 (en) | 1999-08-23 | 2005-08-30 | Ballard Power Systems Inc. | Solid polymer fuel cell with improved voltage reversal tolerance |
US6663998B2 (en) | 2001-04-05 | 2003-12-16 | The Technical University Of Denmark (Dtu) | Anode catalyst materials for use in fuel cells |
DE112004000288T5 (en) * | 2003-02-13 | 2006-09-14 | E.I. Dupont De Nemours And Co., Wilmington | Electrocatalysts and methods of preparation |
US7419732B2 (en) * | 2005-02-11 | 2008-09-02 | Gore Enterprise Holdings, Inc. | Method for reducing degradation in a fuel cell |
US7608358B2 (en) | 2006-08-25 | 2009-10-27 | Bdf Ip Holdings Ltd. | Fuel cell anode structure for voltage reversal tolerance |
JP2008243430A (en) * | 2007-03-26 | 2008-10-09 | Tokyo Gas Co Ltd | Method and system for protecting fuel cell |
US8951696B2 (en) | 2008-03-28 | 2015-02-10 | Jx Nippon Oil & Energy Corporation | Fuel electrode catalyst for fuel cell, electrode/membrane assembly, and fuel cell and fuel cell system provided with the electrode/membrane assembly |
-
1995
- 1995-07-19 JP JP7183081A patent/JP2793523B2/en not_active Expired - Lifetime
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JPH0935736A (en) | 1997-02-07 |
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