JP2002298859A - Fuel cell - Google Patents
Fuel cellInfo
- Publication number
- JP2002298859A JP2002298859A JP2001102895A JP2001102895A JP2002298859A JP 2002298859 A JP2002298859 A JP 2002298859A JP 2001102895 A JP2001102895 A JP 2001102895A JP 2001102895 A JP2001102895 A JP 2001102895A JP 2002298859 A JP2002298859 A JP 2002298859A
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- JP
- Japan
- Prior art keywords
- water
- gas flow
- anode
- gas
- layer
- 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
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Landscapes
- Separation Using Semi-Permeable Membranes (AREA)
- Inert Electrodes (AREA)
- Fuel Cell (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、電解質膜を用いた
燃料電池の陽極構造に関する。[0001] The present invention relates to an anode structure of a fuel cell using an electrolyte membrane.
【０００２】[0002]
【従来の技術】燃料電池は、一般に、電解質膜を挟んで
陽極と陰極を配置した単位セルを多数積層してなり、各
単位セルにおいて、陽極に接して設けたガス流路に酸素
を含む酸化性ガスを、陰極に接して設けたガス流路に水
素を含む燃料ガスを供給して、発電を行うものである。
陽極および陰極における反応は、それぞれ下記式
（１）、（２）のようになり、 陽極：（１／２）Ｏ2 ＋２Ｈ+ ＋２ｅ- →Ｈ2 Ｏ・・・（１） 陰極： Ｈ2 →２Ｈ+ ＋２ｅ- ・・・（２） これをまとめると、電池全体では下記式（３）のようになる。 Ｈ2 ＋（１／２）Ｏ2 →Ｈ2 Ｏ・・・（３）2. Description of the Related Art In general, a fuel cell is formed by stacking a large number of unit cells each having an anode and a cathode with an electrolyte membrane interposed therebetween. In each unit cell, a gas flow path provided in contact with the anode contains an oxidizing gas containing oxygen. The fuel gas containing hydrogen is supplied to a gas flow path provided in contact with the cathode with the reactive gas to generate power.
The reactions at the anode and the cathode are represented by the following formulas (1) and (2), respectively: Anode: (1/2) O 2 + 2H + + 2e − → H 2 O (1) Cathode: H 2 → 2H + + 2e − (2) In summary, the following formula (3) is obtained for the whole battery. H 2 + (１ ／) O 2 → H 2 O (3)
【０００３】陽極および陰極は、導電性かつガス透過性
の材料、例えば、カーボンクロスからなり、陽極および
陰極とその外側に配設されるセパレータとの間にガス流
路が形成される。ここで、上記式（１）に示されるよう
に、陽極では、電極反応により水が生成するので、生成
水で電極が覆われてガスの供給が妨げられないように、
これを速やかに取り除くことが発電を安定して継続する
ために重要となる。そこで、従来より電極の排水機能を
向上させるために、種々の方法が提案されており、例え
ば、陽極の構成材中に、撥水効果をもつフッ素樹脂を混
合したり（特開平７−１０５９５７号公報）、親水性炭
素繊維からなる縦糸と、撥水性炭素繊維からなる横糸を
織り込んで電極を形成したりすることが行われている
（特開平７−１０５９５７号公報等）。The anode and the cathode are made of a conductive and gas-permeable material, for example, carbon cloth, and a gas flow path is formed between the anode and the cathode and a separator provided outside the cathode and the cathode. Here, as shown in the above formula (1), since water is generated by the electrode reaction at the anode, the electrode is covered with the generated water so that the supply of gas is not hindered.
It is important to remove this promptly for stable and continuous power generation. Therefore, various methods have been conventionally proposed to improve the drainage function of the electrode. For example, a fluorine resin having a water-repellent effect is mixed in the constituent material of the anode (Japanese Patent Laid-Open No. 7-105957). Japanese Patent Application Laid-Open No. 7-105957 discloses a method of weaving a warp yarn made of a hydrophilic carbon fiber and a weft yarn made of a water-repellent carbon fiber to form an electrode.
【０００４】ただし、電解質膜は湿潤状態を保つ必要が
あるため、生成水が排出されすぎることは好ましくな
い。このため、特開平９−２４５８００号公報には、陽
極の基材に親水処理を施し、その表面に撥水層を形成す
ることが開示されている。この構造を、図４に示すと、
陽極１１は、基材となるカーボンクロスを親水処理して
親水性基材層１２を形成するとともに、親水性基材層１
２の電解質膜１３側の表面に撥水性カーボンを塗布して
なる撥水層１５と、親水性基材層１２のガス流路１４側
の表面に撥水性カーボンを塗布してなる撥水層１６とを
有している。However, since the electrolyte membrane needs to be kept in a wet state, it is not preferable that generated water is discharged too much. For this reason, Japanese Unexamined Patent Publication No. 9-245800 discloses that a base material of an anode is subjected to a hydrophilic treatment to form a water-repellent layer on the surface thereof. This structure is shown in FIG.
The anode 11 forms a hydrophilic substrate layer 12 by subjecting a carbon cloth serving as a substrate to hydrophilic treatment and forms the hydrophilic substrate layer 1.
2, a water-repellent layer 15 formed by applying water-repellent carbon to the surface on the electrolyte membrane 13 side, and a water-repellent layer 16 formed by applying water-repellent carbon to the surface of the hydrophilic base layer 12 on the gas flow path 14 side. And
【０００５】ガス流路１４から供給されるＯ2 は、陽極
１１を透過して電解質膜１３へ達し、陰極側から電解質
膜１３内を拡散してきた水素イオンと上記（１）のよう
に反応して水を生成する。生成するＨ2 Ｏの一部は、撥
水層１５によって電解質膜１３側へ戻されて、電界質膜
１３の湿潤を保つ。残るＨ2 Ｏの一部は親水性基材層１
２に吸入され、水蒸気のみ撥水層１６を透過してガス流
路１４を流れるガス中へ放散される。[0005] O 2 supplied from the gas passage 14 passes through the anode 11 and reaches the electrolyte membrane 13, and reacts with hydrogen ions diffused in the electrolyte membrane 13 from the cathode side as described in (1) above. To produce water. Part of the generated H 2 O is returned to the electrolyte membrane 13 side by the water-repellent layer 15 to keep the electrolyte membrane 13 wet. Part of the remaining H 2 O is the hydrophilic substrate layer 1
2, only the water vapor is transmitted through the water-repellent layer 16 and diffused into the gas flowing through the gas flow path 14.
【０００６】[0006]
【発明が解決しようとする課題】図４の従来構成は、反
応の初期状態あるいは一定条件の下で生成水のバランス
が取れている時には、効果が大きい。しかしながら、高
負荷運転時のように多量に生成水が生じる場合や、長時
間運転時に、親水性基材層１２が生成水で一杯になって
しまい、その結果、発電効率が悪化してしまうことが判
明した。また、ガス過剰率（燃料電池を稼働させて所定
の電力を得るために理論的に必要なガス量に対する実際
に供給するガス量の割合）を下げることによって、発電
に費やすエネルギーを減少させ、発電効率を高める方法
があるが、ガス過剰率が下がると、ガス流量そのものが
減少するため、ガス流速が低下する。このため、発電に
よって生成された水が、ガス流路１４を流れるガスによ
って持ち去られにくくなり、排水性が低下してしまうと
いう問題があった。The conventional structure shown in FIG. 4 has a large effect when the generated water is balanced in the initial state of the reaction or under certain conditions. However, when a large amount of generated water is generated as in a high-load operation, or during a long-time operation, the hydrophilic base material layer 12 becomes full of the generated water, and as a result, the power generation efficiency is deteriorated. There was found. In addition, by reducing the excess gas ratio (the ratio of the amount of gas actually supplied to the amount of gas theoretically required to operate the fuel cell to obtain the predetermined power), the energy consumed for power generation is reduced, Although there is a method of increasing the efficiency, when the excess gas ratio decreases, the gas flow rate itself decreases, and the gas flow rate decreases. For this reason, there has been a problem that water generated by power generation is less likely to be carried away by the gas flowing through the gas flow path 14, and the drainage performance is reduced.
【０００７】本発明は上記実情に鑑みなされたもので、
その目的は、燃料電池における陽極の構造を改良して、
電解質膜の保湿性を保持しつつ、高負荷運転時や長時間
運転時に過剰に生じる生成水を効率よく排水し、親水層
に生成水が滞留するのを防止して、発電効率を向上する
ことにある。[0007] The present invention has been made in view of the above circumstances,
The aim is to improve the structure of the anode in fuel cells,
Improving power generation efficiency by maintaining the moisture retention of the electrolyte membrane, efficiently draining excessively generated water during high-load operation or long-time operation, and preventing the generated water from staying in the hydrophilic layer. It is in.
【０００８】[0008]
【課題を解決するための手段】上記課題を解決するため
に、本発明請求項１の燃料電池は、電解質膜を挟んで陽
極と陰極を設置し、陽極に接して設けたガス流路に酸化
性ガスを、陰極に接して設けたガス流路に燃料ガスを供
給して、発電を行うものである。上記陽極は、親水性の
基材層と、該基材層の上記ガス流路側の表面に部分的に
形成される撥水層を有しており、上記撥水層は、陽極反
応で生成した過剰の生成水が滞留する部分を除く上記基
材層表面に形成されている。According to a first aspect of the present invention, there is provided a fuel cell comprising: an anode and a cathode provided with an electrolyte membrane interposed therebetween; and an oxidizing gas passage provided in contact with the anode. The fuel gas is supplied to a gas flow path provided in contact with the cathode with the reactive gas to generate power. The anode has a hydrophilic substrate layer and a water-repellent layer formed partially on the surface of the substrate layer on the gas flow path side, and the water-repellent layer is formed by an anodic reaction. It is formed on the surface of the base material layer except for the portion where excess generated water stays.
【０００９】上記構成によれば、陽極反応で生成した過
剰の生成水が、上記基材層の表面にスムーズに移動し、
上記ガス流路を流れるガス中に蒸散して、ガスとともに
排出されるので、上記基材層中に生成水が滞留すること
がなく、排水性が大幅に向上する。他の部分では上記撥
水層により必要以上に生成水が排水されることがなく、
電解質膜および陽極を適度に保湿することができる。よ
って、生成水を効率よく排水し、発電効率を向上するこ
とができる。According to the above configuration, excess water generated by the anodic reaction smoothly moves to the surface of the base material layer,
Since the water evaporates into the gas flowing through the gas flow path and is discharged together with the gas, the generated water does not stay in the base material layer, and the drainage property is greatly improved. In other parts, the generated water is not drained more than necessary by the water repellent layer,
The electrolyte membrane and the anode can be appropriately moisturized. Therefore, the generated water can be efficiently drained, and the power generation efficiency can be improved.
【００１０】請求項２のように、上記陽極を、親水性の
基材層と、該基材層の上記ガス流路側の表面に形成され
る撥水層とで構成し、上記基材層の、陽極反応で生成し
た過剰の生成水が滞留する部分の表面に形成される上記
撥水層の厚さを、他の表面に形成される上記撥水層の厚
さよりも薄くすることもできる。According to a second aspect of the present invention, the anode comprises a hydrophilic substrate layer and a water-repellent layer formed on the surface of the substrate layer on the gas flow path side. Alternatively, the thickness of the water-repellent layer formed on the surface of the portion where excess water generated by the anodic reaction stays may be smaller than the thickness of the water-repellent layer formed on the other surface.
【００１１】上記撥水層を部分的に形成する請求項１の
構成の他、上記撥水層を上記ガス流路側の表面に形成し
て、その厚さを部分的に変更するようにしてもよい。こ
の場合、生成水が滞留する部分に形成される上記撥水層
を十分薄くすることによって、同様の効果が得られる。[0011] In addition to the constitution of claim 1, wherein the water-repellent layer is partially formed, the water-repellent layer may be formed on the surface on the gas flow path side and the thickness thereof may be partially changed. Good. In this case, the same effect can be obtained by sufficiently reducing the thickness of the water-repellent layer formed in the portion where the generated water stays.
【００１２】請求項３のように、上記生成水が滞留する
部分は、例えば、使用姿勢において自重で下方に移動し
た水が滞留する部分、具体的には、請求項４のように、
上記基材層の下部であり、この部分を除いて上記撥水層
を形成し、または厚さを薄くすることで、上記効果が得
られる。The portion where the generated water stays is, for example, a portion where the water which has moved downward by its own weight in the use posture stays, and more specifically, as in claim 4,
The above effect can be obtained by forming the water-repellent layer at a lower portion of the base material layer except for this portion or reducing the thickness.
【００１３】あるいは、請求項５のように、上記生成水
が滞留する部分は、上記陽極に隣接する上記ガス流路の
ガス流れが停滞する部分、具体的には、請求項６のよう
に、上記ガス流路の屈曲部に対応する部分であり、この
部分を除いて上記撥水層を形成し、または厚さを薄くす
ることもできる。Alternatively, as in claim 5, the portion where the generated water stays is a portion where the gas flow in the gas flow path adjacent to the anode stagnates, specifically, as in claim 6, The portion corresponding to the bent portion of the gas flow path. Excluding this portion, the water-repellent layer can be formed or the thickness can be reduced.
【００１４】請求項７のように、上記撥水層を、上記陽
極に隣接する上記ガス流路のガス流れのパターンに応じ
て形成すると、より排水性を良好にすることができ、好
ましい。It is preferable that the water-repellent layer is formed in accordance with the gas flow pattern of the gas flow path adjacent to the anode, as the drainage can be further improved.
【００１５】請求項８のように、上記陽極を、上記基材
層の上記電解質膜側の表面に撥水層を有する構成とする
こともできる。このようにすると、陽極反応の生成水の
一部が上記撥水層の表面ではじかれて上記電解質膜側へ
戻ることにより、湿潤を保持する効果がある。[0015] The anode may have a water-repellent layer on the surface of the base material layer on the electrolyte membrane side. In this case, a part of the water generated by the anodic reaction is repelled on the surface of the water-repellent layer and returns to the electrolyte membrane side, thereby having an effect of maintaining wetness.
【００１６】[0016]
【発明の実施の形態】以下、図面により本発明の第１の
実施の形態を説明する。図１（ｂ）、（ｃ）は燃料電池
の主要部を構成する単位セル１の概略図で、単位セル１
は、電解質膜２と、電解質膜２の一方の面側に設けられ
た陽極３と、電解質膜２の他方の面側に設けられた陰極
４とを有し、陽極３および陰極４の外側にはセパレータ
５、６がそれぞれ配置されている。セパレータ５、６
は、陽極３または陰極４との間にガス流路５１、６１を
形成するとともに、隣り合うセル間を分離するもので、
燃料電池はこの単位セル１を多数積層したスタック構造
を有している。DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, a first embodiment of the present invention will be described with reference to the drawings. FIGS. 1B and 1C are schematic views of a unit cell 1 constituting a main part of a fuel cell.
Has an electrolyte membrane 2, an anode 3 provided on one side of the electrolyte membrane 2, and a cathode 4 provided on the other side of the electrolyte membrane 2. Are provided with separators 5 and 6, respectively. Separator 5, 6
Is to form gas flow paths 51 and 61 between the anode 3 and the cathode 4 and to separate adjacent cells.
The fuel cell has a stack structure in which many unit cells 1 are stacked.
【００１７】電解質膜２には、例えば、フッ素樹脂系の
プロトン導電性固体高分子電解質膜が用いられる。この
種の固体高分子電解質膜は、水和プロトンが電荷担体と
なって陰極４側から陽極３側へ移動するため、通常、含
水状態で使用され、不足する水を必要に応じて補給す
る。また、固体高分子電解質膜を用いた燃料電池は、比
較的作動温度が低く、通常、触媒を用いて電極反応を促
進している。触媒としては、例えば、白金または白金合
金等が用いられ、該触媒金属を含むカーボン粉をペース
ト化して電解質膜２の表面に塗布することにより担持さ
れる。あるいは、触媒金属を含むカーボン粉を陽極３ま
たは陰極４の電解質膜２側の表面に塗布するか、構成材
料中に添加することもできる。As the electrolyte membrane 2, for example, a fluororesin-based proton conductive solid polymer electrolyte membrane is used. This type of solid polymer electrolyte membrane is usually used in a water-containing state because hydrated protons serve as charge carriers and move from the cathode 4 side to the anode 3 side, and replenish insufficient water as needed. In addition, a fuel cell using a solid polymer electrolyte membrane has a relatively low operating temperature and usually promotes an electrode reaction using a catalyst. As the catalyst, for example, platinum, a platinum alloy, or the like is used, and carbon powder containing the catalyst metal is made into a paste and applied to the surface of the electrolyte membrane 2 to be supported. Alternatively, carbon powder containing a catalytic metal can be applied to the surface of the anode 3 or the cathode 4 on the side of the electrolyte membrane 2 or can be added to the constituent material.
【００１８】陽極３および陰極４は、導電性とガス透過
性を兼ね備えた材料、例えば、炭素繊維を平織にしたカ
ーボンクロスからなる。その他、炭素繊維を用いたカー
ボンペーパ等を、電極材料に用いることもできる。これ
ら陽極３および陰極４は、電解質膜２のほぼ全面に形成
され、陽極３には、ガス流路５１から酸素を含む酸化性
ガスが、陰極４には、ガス流路６１から水素を含む燃料
ガスがそれぞれ供給される。この時、陽極３では、下記
式（１）に示す電極反応により水が生成し、陰極４で
は、下記式（２）に示す電極反応により水素イオンが生
成する。 （１／２）Ｏ2 ＋２Ｈ+ ＋２ｅ- →Ｈ2 Ｏ・・・（１） Ｈ2 →２Ｈ+ ＋２ｅ- ・・・（２） 電池全体の反応は、式（３）のようになる。 Ｈ2 ＋（１／２）Ｏ2 →Ｈ2 Ｏ・・・（３）The anode 3 and the cathode 4 are made of a material having both conductivity and gas permeability, for example, a carbon cloth formed by plain weaving of carbon fibers. In addition, carbon paper using carbon fiber or the like can be used as the electrode material. The anode 3 and the cathode 4 are formed on almost the entire surface of the electrolyte membrane 2. The anode 3 is provided with an oxidizing gas containing oxygen from a gas passage 51, and the cathode 4 is provided with a fuel containing hydrogen from a gas passage 61. Gas is supplied respectively. At this time, water is generated at the anode 3 by an electrode reaction represented by the following formula (1), and hydrogen ions are generated at the cathode 4 by an electrode reaction represented by the following formula (2). (1/2) O 2 + 2H + + 2e − → H 2 O (1) H 2 → 2H + + 2e − (2) The reaction of the whole battery is as shown in equation (3). H 2 + (１ ／) O 2 → H 2 O (3)
【００１９】セパレータ５、６は、ガス不透過性の材
料、例えば、圧縮カーボン等からなる。セパレータ５、
６の、陽極３または陰極４側の表面には、ガス流路５
１、６１形状に応じてリブ５２、６２が突出形成してあ
り、例えば、図１（ｂ）のように、セパレータ６の外周
縁に沿う矩形のリブ６２ａと、その左右側縁から交互に
水平方向に延びるリブ６２ｂによって、蛇行する一続き
のガス流路６１が形成される。ガス流路６１の一端側
は、セパレータ６の上側部に設けたガス導入口６３に接
続され、他端側は、セパレータ６の下側部に設けたガス
導出口６４に接続される。ガス流路５１も、ガス流路６
１と同様の形状に形成され、その一端側は、セパレータ
５の上側部に設けたガス導入口５３に、他端側は、セパ
レータ５の下側部に設けたガス導出口５４に接続されて
いる。The separators 5 and 6 are made of a gas-impermeable material, for example, compressed carbon or the like. Separator 5,
6, a gas flow path 5 is provided on the surface of the anode 3 or the cathode 4 side.
The ribs 52 and 62 are formed so as to protrude according to the shapes of the ribs 1 and 61. For example, as shown in FIG. The meandering continuous gas flow path 61 is formed by the rib 62b extending in the direction. One end of the gas flow channel 61 is connected to a gas inlet 63 provided on an upper portion of the separator 6, and the other end is connected to a gas outlet 64 provided on a lower portion of the separator 6. The gas flow path 51 is also connected to the gas flow path 6.
1, one end of which is connected to a gas inlet 53 provided in the upper part of the separator 5 and the other end thereof is connected to a gas outlet 54 provided in the lower part of the separator 5. I have.
【００２０】ここで、図１（ａ）に陽極３の詳細構造を
示す。陽極３は、カーボンクロスを親水処理してなる親
水性の基材層３１と、そのガス流路５１側の表面に部分
的に形成される撥水層３２と、電解質膜２側の表面の全
面に形成される撥水層３３からなる。カーボンクロスの
親水処理は、具体的には、ＳｉＯ2 等の親水性物質を含
む溶液に、カーボンクロスを浸漬することによって行う
ことができる。基材層３１中の親水性物質の含有量は、
溶液中の親水性物質の濃度によって調節することができ
るが、ＳｉＯ2 は絶縁性物質であり含有量が多いと導電
性が低下するので、必要な導電性と親水性が得られるよ
うに適宜設定すればよい。このように、基材層３１に親
水性を付与することにより、陽極反応で生成する水をガ
ス流路５１側の表面へ速やかに移動させることができ
る。Here, FIG. 1A shows a detailed structure of the anode 3. The anode 3 includes a hydrophilic base layer 31 formed by subjecting a carbon cloth to a hydrophilic treatment, a water-repellent layer 32 partially formed on the surface on the gas flow path 51 side, and the entire surface on the electrolyte membrane 2 side. And a water-repellent layer 33 formed on the substrate. Specifically, the hydrophilic treatment of the carbon cloth can be performed by immersing the carbon cloth in a solution containing a hydrophilic substance such as SiO 2 . The content of the hydrophilic substance in the base material layer 31 is:
It can be adjusted by the concentration of the hydrophilic substance in the solution, but SiO 2 is an insulating substance, and if the content is large, the conductivity is reduced. Therefore, it is appropriately set so that necessary conductivity and hydrophilicity can be obtained. do it. By imparting hydrophilicity to the base layer 31 in this manner, water generated by the anodic reaction can be promptly moved to the surface on the gas flow path 51 side.
【００２１】撥水層３２と、撥水層３３は、基材層３１
の表面に撥水処理を施すことによって形成される。撥水
処理は、撥水性のフッソ系樹脂、例えば、ポリテトラフ
ルオロエチレン（ＰＴＦＥ）等を表面に付着させた撥水
性カーボンを用い、これをエタノール等に分散させた溶
液を、基材層３１の表面の所定部位に塗布することによ
って行う。この溶液を塗布した後、焼成することによっ
てエタノール等を除去し、撥水性カーボンからなる撥水
層３２、３３を形成することができる。なお、撥水性カ
ーボンは、例えば、ＰＴＦＥ等のフッソ系樹脂とカーボ
ン粉を分散剤とともに水に添加、混合し、濾過すること
によって作製される。The water-repellent layer 32 and the water-repellent layer 33 are
Is formed by performing a water-repellent treatment on the surface of the substrate. The water-repellent treatment uses a water-repellent fluorine-based resin, for example, water-repellent carbon having polytetrafluoroethylene (PTFE) or the like adhered to the surface, and disperses the solution in ethanol or the like to form a solution for the base layer 31. It is carried out by applying it to a predetermined portion of the surface. After applying this solution, baking is performed to remove ethanol and the like, whereby water-repellent layers 32 and 33 made of water-repellent carbon can be formed. The water-repellent carbon is produced by, for example, adding a fluorine resin such as PTFE and carbon powder to water together with a dispersant, mixing, and filtering.
【００２２】ここで、本実施の形態では、図１（ｂ）に
示すように、ガス流路５１側の撥水層３２を、上記式
（１）の陽極反応で過剰の生成水が生じた時に、生成水
が滞留しやすい基材層３１の下部を除く表面に形成す
る。図示するように、単位セル１の電解質膜２を立てた
状態で使用する場合、生成水は、親水性の基材層３１を
伝って自重で下方へ移動するので、この部分に撥水層３
２を形成しないことで、排水をスムーズに行うことがで
きる。具体的には、ガス流路５１の最下流部、すなわ
ち、ガス導出口５４に連続する直線状の流路に対応する
基材層３１の表面には撥水層３２を形成せず、これより
上方の表面にのみ撥水層３２を形成している。Here, in the present embodiment, as shown in FIG. 1B, the water-repellent layer 32 on the gas flow path 51 side generated excessive water by the anodic reaction of the above formula (1). Occasionally, it is formed on the surface of the base material layer 31 except for the lower part where the generated water is likely to stay. As shown in the figure, when the electrolyte membrane 2 of the unit cell 1 is used in an upright state, the generated water moves downward by its own weight along the hydrophilic base material layer 31.
By not forming 2, drainage can be performed smoothly. Specifically, the water-repellent layer 32 is not formed on the most downstream portion of the gas flow path 51, that is, on the surface of the base material layer 31 corresponding to the linear flow path continuous to the gas outlet 54. The water-repellent layer 32 is formed only on the upper surface.
【００２３】上記構成の燃料電池の作動を以下に説明す
る。図１（ｂ）において、ガス導入口５３に酸素を含む
酸化性ガス（通常、空気）を、ガス導入口６３に水素を
含む燃料ガスを供給すると、これらガスはガス流路５
１、６１に沿って流れる間に、上記式（１）、（２）の
ように反応し、ガス導出口５４、６４から排出される。
この時、陽極３では、図１（ａ）のように、酸素
（Ｏ2 ）がガス流路５１側から陽極３内を電解質膜２側
へ移動し、電解質膜２を拡散してきた水素イオンと反応
して水（Ｈ2 Ｏ）を生成する。生成するＨ2 Ｏの一部
は、基材層３１の電解質膜２側に形成された撥水層３３
によって電解質膜２側へ戻されて、電界質膜２の湿潤を
保つ。残るＨ2 Ｏは、撥水層３３を通過して親水性の基
材層１２に吸入され、水蒸気のみ撥水層３２を透過して
ガス流路５１中へ蒸散する。The operation of the fuel cell having the above configuration will be described below. In FIG. 1B, when an oxidizing gas (normally, air) containing oxygen is supplied to a gas inlet 53 and a fuel gas containing hydrogen is supplied to a gas inlet 63, these gases are supplied to a gas passage 5.
While flowing along 1 and 61, they react as shown in the above formulas (1) and (2) and are discharged from the gas outlets 54 and 64.
At this time, in the anode 3, as shown in FIG. 1 (a), oxygen (O 2 ) moves from the gas flow path 51 side to the electrolyte membrane 2 side in the anode 3, and reacts with hydrogen ions diffused through the electrolyte membrane 2. Reacts to produce water (H 2 O). Part of the generated H 2 O is supplied to the water-repellent layer 33 formed on the electrolyte membrane 2 side of the base material layer 31.
Is returned to the electrolyte membrane 2 side to keep the electrolyte membrane 2 wet. The remaining H 2 O passes through the water repellent layer 33 and is sucked into the hydrophilic base material layer 12, and only water vapor passes through the water repellent layer 32 and evaporates into the gas flow path 51.
【００２４】ここで、高負荷運転時のように多量にＨ2
Ｏが生成される時には、基材層３１中のＨ2 Ｏが自重で
下方へ移動して、基材層３１の下部に滞留する。滞留す
る水が過剰になると、ガス流路５１から供給される酸化
性ガスが通過しにくくなるなど、電極反応が阻害される
おそれがあるが、上記構成では、基材層３１の下部に撥
水層３２を形成していないので、基材層３１表面に達し
たＨ2 Ｏが蒸発しやすくなる。蒸発したＨ2 Ｏは、ガス
流路５１のガス流れによって持ち去られる。このように
して、良好な排水性を実現でき、結果として発電効率を
向上させることができる。Here, as in the case of high load operation, a large amount of H 2
When O is generated, H 2 O in the base layer 31 moves downward by its own weight and stays below the base layer 31. If the amount of retained water is excessive, the electrode reaction may be hindered, for example, the oxidizing gas supplied from the gas flow path 51 may be difficult to pass. Since the layer 32 is not formed, H 2 O reaching the surface of the base material layer 31 is easily evaporated. The evaporated H 2 O is carried away by the gas flow in the gas flow path 51. In this way, good drainage can be realized, and as a result, power generation efficiency can be improved.
【００２５】上記第１の実施の形態では、撥水層３２の
形成部位を、自重で下方へ移動した生成水が滞留する基
材層３１の下部を除く部分としたが、必ずしもこれに限
るものではない。単位セル１の構成、例えば、ガス流路
５１の形状によっては、ガス流れが停滞して対応する陽
極３表面の排水性が低下するので、このようにして生成
水が滞留しやすくなる部分に撥水層３２を形成しないこ
とで、同様の効果が得られる。これを以下に説明する。In the first embodiment, the formation site of the water-repellent layer 32 is a portion excluding the lower portion of the base material layer 31 in which the generated water moved downward by its own weight stays. However, the present invention is not limited to this. is not. Depending on the configuration of the unit cell 1, for example, the shape of the gas flow path 51, the gas flow stagnates and the drainage property of the corresponding anode 3 surface is reduced. The same effect can be obtained by not forming the water layer 32. This will be described below.
【００２６】図２（ａ）は、ガス流路５１のガス流れの
パターンの一例を示すもので、このように、流路の途中
に屈曲部５５（図では２ヵ所）を有する場合、屈曲部５
５では、流れが停滞するために、対応する陽極３表面の
排水性が低下し、基材層３１に生成水が滞留しやすくな
る。そこで、この部分についても撥水層３２を形成しな
いことで、基材層３１に生成水が滞留するのを防止する
ことができる。図２（ｂ）の第２の実施の形態では、自
重での生成水の移動で、より水が滞留しやすい下流側の
屈曲部５５に対応する基材層３１の表面と、上記第１の
実施の形態と同様の基材層３１の下部を除く部分に、撥
水層３２を形成している。FIG. 2A shows an example of a gas flow pattern in the gas flow path 51. As described above, when the flow path has a bent portion 55 (two places in the drawing), 5
In No. 5, since the flow is stagnant, the drainage property of the surface of the corresponding anode 3 is reduced, and the generated water is easily retained in the base material layer 31. Therefore, by not forming the water-repellent layer 32 in this portion as well, it is possible to prevent generated water from staying in the base material layer 31. In the second embodiment shown in FIG. 2B, the surface of the base material layer 31 corresponding to the bent portion 55 on the downstream side where water is more likely to stay due to the movement of the generated water by its own weight, The water-repellent layer 32 is formed in a portion except for the lower portion of the base material layer 31 similar to the embodiment.
【００２７】また、図２（ｃ）の第３の実施の形態のよ
うに、２ヵ所の屈曲部５５の両方に対応する基材層３１
の表面を除いて、撥水層３２を形成する構成とすること
もできる。この場合は、屈曲部５５に対応する部分を除
く、基材層３１の下部（ガス流路５１の最下流部に対応
する部分）にも撥水層３２を形成している。あるいは、
図２（ｄ）の第４の実施の形態のように、ガス流路５１
全長に渡って、流路下半部に対応する部分に撥水層３２
を形成しないようにしてもよく、この部分と屈曲部５５
に対応する基材層３１の表面にのみ撥水層３２を形成し
ている。Further, as in the third embodiment shown in FIG. 2C, the base material layers 31 corresponding to both of the two bent portions 55 are provided.
It is also possible to adopt a configuration in which the water-repellent layer 32 is formed except for the surface of. In this case, the water-repellent layer 32 is also formed on the lower portion of the base layer 31 (the portion corresponding to the most downstream portion of the gas flow path 51) except for the portion corresponding to the bent portion 55. Or,
As in the fourth embodiment shown in FIG.
A water-repellent layer 32 is provided on a portion corresponding to the lower half of the flow path over the entire length.
May not be formed, and this portion and the bent portion 55
The water-repellent layer 32 is formed only on the surface of the base material layer 31 corresponding to.
【００２８】上記各実施の形態では、撥水層３２を部分
的に形成し、生成水が滞留する部分に、撥水層３２を形
成しないようにしたが、図３のように、基材層３１のガ
ス流路５１側の全面に撥水層３２、３４を形成して、そ
の厚さを変更することもできる。図３（ａ）はガス流れ
のパターンの一例で（図２（ａ）と同じ）、これに対
し、図３（ｂ）の第５の実施の形態では、上記図２
（ｂ）の第２の実施の形態と同様、下流側の屈曲部５５
に対応する基材層３１の表面と基材層３１の下部を除く
部分に撥水層３２を形成するとともに、それ以外の部分
に撥水層３２より薄い撥水層３４を形成する。あるい
は、図３（ｃ）の第６の実施の形態のように、上記図２
（ｃ）の第３の実施の形態と同様、２ヵ所の屈曲部５５
の両方に対応する基材層３１の表面を除いて撥水層３２
を形成するとともに、それ以外の部分に撥水層３２より
薄い撥水層３４を形成することもできる。撥水層３４の
厚さは、基材層３１内の生成水の排水性を損なわないよ
うに、撥水層３２より十分薄くするのがよい。In each of the above embodiments, the water-repellent layer 32 is partially formed, and the water-repellent layer 32 is not formed in the portion where the generated water stays. However, as shown in FIG. The water-repellent layers 32 and 34 can be formed on the entire surface of the gas channel 51 on the side of the gas channel 51, and the thickness thereof can be changed. FIG. 3A shows an example of a gas flow pattern (same as that of FIG. 2A). On the other hand, in the fifth embodiment of FIG.
As in the second embodiment (b), the downstream bent portion 55
The water-repellent layer 32 is formed on the portion excluding the surface of the substrate layer 31 and the lower portion of the substrate layer 31 corresponding to the above, and the water-repellent layer 34 thinner than the water-repellent layer 32 is formed on other portions. Alternatively, as in the sixth embodiment shown in FIG.
As in the third embodiment (c), two bent portions 55 are provided.
The water-repellent layer 32 except for the surface of the base material layer 31 corresponding to both
And a water-repellent layer 34 thinner than the water-repellent layer 32 can be formed in other portions. The thickness of the water-repellent layer 34 is preferably sufficiently smaller than that of the water-repellent layer 32 so as not to impair the drainage of the generated water in the base material layer 31.
【図１】本発明の第１の実施の形態を示し、（ａ）は陽
極の詳細構造を示す拡大断面図、（ｂ）は単位セルの分
解斜視図、（ｂ）は単位セルの部分断面図である。1A and 1B show a first embodiment of the present invention, wherein FIG. 1A is an enlarged sectional view showing a detailed structure of an anode, FIG. 1B is an exploded perspective view of a unit cell, and FIG. FIG.
【図２】（ａ）はガス流れのパターンの一例を示す図、
（ｂ）は本発明の第２の実施の形態における撥水層の形
成パターンを示す図、（ｃ）は本発明の第３の実施の形
態における撥水層の形成パターンを示す図、（ｄ）は本
発明の第４の実施の形態における撥水層の形成パターン
を示す図である。FIG. 2A is a diagram showing an example of a gas flow pattern;
(B) is a diagram showing a water repellent layer formation pattern according to the second embodiment of the present invention, (c) is a diagram showing a water repellent layer formation pattern according to the third embodiment of the present invention, (d) () Is a diagram showing a formation pattern of a water-repellent layer in the fourth embodiment of the present invention.
【図３】（ａ）はガス流れのパターンの一例を示す図、
（ｂ）は本発明の第５の実施の形態における撥水層の形
成パターンを示す図、（ｃ）は本発明の第６の実施の形
態における撥水層の形成パターンを示す図、（ｄ）は本
発明の第４の実施の形態FIG. 3A is a diagram showing an example of a gas flow pattern;
(B) is a diagram showing a pattern for forming a water-repellent layer according to the fifth embodiment of the present invention, (c) is a diagram showing a pattern for forming a water-repellent layer according to the sixth embodiment of the present invention, (d) ) Is the fourth embodiment of the present invention.
【図４】従来の燃料電池の陽極の詳細構造を示す拡大断
面図である。FIG. 4 is an enlarged sectional view showing a detailed structure of an anode of a conventional fuel cell.
１ 単位セル ２ 電解質膜 ３ 陽極 ３１ 基材層 ３２、３３、３４ 撥水層 ４ 陰極 ５、６ セパレータ ５１、６１ ガス流路 ５２ 屈曲部 ５２、６２ リブ ５３、６３ ガス導入口 ５４、６４ ガス導出口 DESCRIPTION OF SYMBOLS 1 Unit cell 2 Electrolyte membrane 3 Anode 31 Base layer 32, 33, 34 Water repellent layer 4 Cathode 5, 6 Separator 51, 61 Gas channel 52 Bent 52, 62 Rib 53, 63 Gas inlet 54, 64 Gas guide exit
───────────────────────────────────────────────────── フロントページの続き (72)発明者 菊地 哲郎 愛知県西尾市下羽角町岩谷14番地 株式会 社日本自動車部品総合研究所内 (72)発明者 曽 一新 愛知県豊田市トヨタ町１番地 トヨタ自動 車株式会社内 (72)発明者 高橋 剛 愛知県豊田市トヨタ町１番地 トヨタ自動 車株式会社内 Ｆターム(参考） 4D006 GA41 MA03 MA06 MB10 MC28 PB66 PC80 5H018 AA06 AS03 BB05 BB08 CC06 DD06 EE00 EE05 EE12 EE19 HH02 5H026 AA06 BB03 BB04 CC01 CX03 CX05 EE00 EE05 EE12 EE19 HH02 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Tetsuro Kikuchi 14 Iwatani, Shimowasumi-cho, Nishio-shi, Aichi Prefecture Inside the Japan Auto Parts Research Institute, Inc. (72) Inventor Takeshi Takahashi 1 Toyota Town, Toyota City, Aichi Prefecture F-term (reference) 4D006 GA41 MA03 MA06 MB10 MC28 PB66 PC80 5H018 AA06 AS03 BB05 BB08 CC06 DD06 EE00 EE05 EE12 EE19 HH02 5H026 AA06 BB03 BB04 CC01 CX03 CX05 EE00 EE05 EE12 EE19 HH02
Claims (8)
陽極に接して設けたガス流路に酸化性ガスを、陰極に接
して設けたガス流路に燃料ガスを供給して、発電を行う
燃料電池であって、上記陽極が、親水性の基材層と、該
基材層の上記ガス流路側の表面に部分的に形成される撥
水層を有し、上記撥水層を、陽極反応で生成した過剰の
生成水が滞留する部分を除く上記基材層表面に形成した
ことを特徴とする燃料電池。An anode and a cathode are provided with an electrolyte membrane interposed therebetween.
An oxidizing gas is supplied to a gas flow path provided in contact with an anode, and a fuel gas is supplied to a gas flow path provided in contact with a cathode to generate power, wherein the anode has a hydrophilic base material. Layer, and a water-repellent layer formed partially on the surface of the substrate layer on the gas flow path side, wherein the water-repellent layer excludes a portion where excess water generated by the anodic reaction stays. A fuel cell formed on the surface of a base material layer.
陽極に接して設けたガス流路に酸化性ガスを、陰極に接
して設けたガス流路に燃料ガスを供給して、発電を行う
燃料電池であって、上記陽極が、親水性の基材層と、該
基材層の上記ガス流路側の表面に形成される撥水層を有
し、上記基材層の、陽極反応で生成した過剰の生成水が
滞留する部分の表面に形成される上記撥水層の厚さを、
他の表面に形成される上記撥水層の厚さよりも薄くした
ことを特徴とする燃料電池。2. An anode and a cathode are provided with an electrolyte membrane interposed therebetween,
An oxidizing gas is supplied to a gas flow path provided in contact with an anode, and a fuel gas is supplied to a gas flow path provided in contact with a cathode to generate power, wherein the anode has a hydrophilic base material. And a water-repellent layer formed on the surface of the base material layer on the gas flow path side, and formed on the surface of the base material layer where excess water generated by the anodic reaction stays. The thickness of the water-repellent layer,
A fuel cell, wherein the thickness of the water-repellent layer formed on another surface is smaller than that of the water-repellent layer.
において自重で下方に移動した水が滞留する部分である
請求項１または２記載の燃料電池。3. The fuel cell according to claim 1, wherein the portion in which the generated water stays is a portion in which water moved downward by its own weight in the use posture stays.
層の下部である請求項３記載の燃料電池。4. The fuel cell according to claim 3, wherein the portion where the generated water stays is a lower portion of the base layer.
に隣接する上記ガス流路のガス流れが停滞する部分であ
る請求項１または２記載の燃料電池。5. The fuel cell according to claim 1, wherein the portion where the generated water stays is a portion where the gas flow in the gas passage adjacent to the anode stagnates.
流路の屈曲部に対応する部分である請求項５記載の燃料
電池。6. The fuel cell according to claim 5, wherein the portion where the generated water stays is a portion corresponding to a bent portion of the gas flow path.
ガス流路のガス流れのパターンに応じて形成する請求項
１ないし６のいずれか記載の燃料電池。7. The fuel cell according to claim 1, wherein the water-repellent layer is formed according to a gas flow pattern of the gas flow path adjacent to the anode.
側の表面に形成される撥水層を有する請求項１ないし５
のいずれか記載の燃料電池。8. The anode according to claim 1, wherein the anode has a water-repellent layer formed on the surface of the base material layer on the electrolyte membrane side.
The fuel cell according to any one of the above.
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| Application Number | Priority Date | Filing Date | Title |
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| JP2001102895A JP4372370B2 (en) | 2001-04-02 | 2001-04-02 | Fuel cell |
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| JP2001102895A JP4372370B2 (en) | 2001-04-02 | 2001-04-02 | Fuel cell |
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| JP2002298859A true JP2002298859A (en) | 2002-10-11 |
| JP4372370B2 JP4372370B2 (en) | 2009-11-25 |
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| JP2001102895A Expired - Fee Related JP4372370B2 (en) | 2001-04-02 | 2001-04-02 | Fuel cell |
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Cited By (10)
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| JP2002313359A (en) * | 2001-04-17 | 2002-10-25 | Mitsubishi Heavy Ind Ltd | Solid polymer fuel cell |
| JP2003092112A (en) * | 2001-09-14 | 2003-03-28 | Toshiba International Fuel Cells Corp | Solid polymer fuel cell |
| WO2004006364A1 (en) * | 2002-07-03 | 2004-01-15 | Nec Corporation | Liquid fuel feed fuel cell, electrode for fuel cell and methods for manufacturing same |
| JP2005078975A (en) * | 2003-09-01 | 2005-03-24 | Matsushita Electric Ind Co Ltd | Polymer electrolyte membrane-electrode junction and polymer electrolyte fuel cell using this |
| JP2006134886A (en) * | 2004-11-03 | 2006-05-25 | Samsung Sdi Co Ltd | Electrode for fuel cell, its manufacturing method, membrane-electrode assembly comprising the same and and fuel cell system comprising the same |
| JP2008509521A (en) * | 2004-08-06 | 2008-03-27 | ゼネラル・モーターズ・コーポレーション | Hydrophobic and hydrophilic diffusion media |
| JP2008166260A (en) * | 2006-12-04 | 2008-07-17 | Toyota Motor Corp | Fuel cell |
| US7482089B2 (en) | 2003-03-10 | 2009-01-27 | Honda Motor Co., Ltd. | Fuel cell |
| JP2009076423A (en) * | 2007-09-25 | 2009-04-09 | Nippon Soken Inc | Fuel cell |
| WO2009078302A1 (en) * | 2007-12-17 | 2009-06-25 | Kabushiki Kaisha Toshiba | Fuel cell |
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| JPH08167416A (en) * | 1994-12-14 | 1996-06-25 | Fuji Electric Co Ltd | Cell for solid high polymer electrolyte fuel cell |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002313359A (en) * | 2001-04-17 | 2002-10-25 | Mitsubishi Heavy Ind Ltd | Solid polymer fuel cell |
| JP4610815B2 (en) * | 2001-09-14 | 2011-01-12 | 東芝燃料電池システム株式会社 | Polymer electrolyte fuel cell |
| JP2003092112A (en) * | 2001-09-14 | 2003-03-28 | Toshiba International Fuel Cells Corp | Solid polymer fuel cell |
| WO2004006364A1 (en) * | 2002-07-03 | 2004-01-15 | Nec Corporation | Liquid fuel feed fuel cell, electrode for fuel cell and methods for manufacturing same |
| US7482089B2 (en) | 2003-03-10 | 2009-01-27 | Honda Motor Co., Ltd. | Fuel cell |
| JP2005078975A (en) * | 2003-09-01 | 2005-03-24 | Matsushita Electric Ind Co Ltd | Polymer electrolyte membrane-electrode junction and polymer electrolyte fuel cell using this |
| JP4493954B2 (en) * | 2003-09-01 | 2010-06-30 | パナソニック株式会社 | Polymer electrolyte membrane-electrode assembly and polymer electrolyte fuel cell using the same |
| JP2008509521A (en) * | 2004-08-06 | 2008-03-27 | ゼネラル・モーターズ・コーポレーション | Hydrophobic and hydrophilic diffusion media |
| JP4860616B2 (en) * | 2004-08-06 | 2012-01-25 | ゼネラル・モーターズ・コーポレーション | Hydrophobic and hydrophilic diffusion media |
| JP2006134886A (en) * | 2004-11-03 | 2006-05-25 | Samsung Sdi Co Ltd | Electrode for fuel cell, its manufacturing method, membrane-electrode assembly comprising the same and and fuel cell system comprising the same |
| US7998638B2 (en) | 2004-11-03 | 2011-08-16 | Samsung Sdi Co., Ltd. | Electrode for fuel cell, and membrane-electrode assembly and fuel cell system comprising the same |
| JP2008166260A (en) * | 2006-12-04 | 2008-07-17 | Toyota Motor Corp | Fuel cell |
| JP2009076423A (en) * | 2007-09-25 | 2009-04-09 | Nippon Soken Inc | Fuel cell |
| WO2009078302A1 (en) * | 2007-12-17 | 2009-06-25 | Kabushiki Kaisha Toshiba | Fuel cell |
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