JPH11339815A - Solid polymer electrolyte for cell and its manufacture - Google Patents
Solid polymer electrolyte for cell and its manufactureInfo
- Publication number
- JPH11339815A JPH11339815A JP10149261A JP14926198A JPH11339815A JP H11339815 A JPH11339815 A JP H11339815A JP 10149261 A JP10149261 A JP 10149261A JP 14926198 A JP14926198 A JP 14926198A JP H11339815 A JPH11339815 A JP H11339815A
- Authority
- JP
- Japan
- Prior art keywords
- hydrogen
- electrode
- oxygen
- polymer electrolyte
- water
- 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.)
- Pending
Links
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
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は固体高分子電解質型
燃料電池に関する。The present invention relates to a solid polymer electrolyte fuel cell.
【０００２】[0002]
【従来の技術】固体高分子電解質燃料電池は、水素及び
酸素あるいは空気を燃料とする小型軽量高出力用電源と
して自動車その他への応用が有力視されている。かかる
電池はイオン交換能を有する固体高分子電解質膜とこの
両極側に熱間接合して配置される正極及び負極から構成
される。燃料としての水素ガスは負極において電気化学
的に酸化され、プロトンと電子を生成する。このプロト
ンは高分子電解質膜内を酸素が供給される正極に水とと
もに移動する。一方負極で生成した電子は電池に接続さ
れた負荷を通り、正極に流れ、正極においてプロトンと
酸素と電子が反応して水を生成する。2. Description of the Related Art Solid polymer electrolyte fuel cells are expected to be applied to automobiles and the like as small, lightweight, high-output power supplies using hydrogen, oxygen or air as fuel. Such a battery is composed of a solid polymer electrolyte membrane having ion exchange ability, and a positive electrode and a negative electrode which are hot-joined to both electrode sides. Hydrogen gas as fuel is electrochemically oxidized at the negative electrode to generate protons and electrons. The protons move together with water in the polymer electrolyte membrane to the positive electrode to which oxygen is supplied. On the other hand, the electrons generated at the negative electrode pass through the load connected to the battery and flow to the positive electrode, where protons, oxygen, and electrons react to generate water at the positive electrode.
【０００３】このように、自動車用電力源として固体高
分子電解質型燃料電池が常温作動性や小型で高出力密度
であることからこのタイプの研究が行われているが、一
般には燃料電池用高分子電解質膜としてスルホン酸基を
有するパーフルオロカーボン重合体膜（商品名；ナフィ
オン、デュポン株式会社、商品名；アシプレックス、旭
化成株式会社）等が用いられている。しかしながら、燃
料電池のより高出力化からするとまだ十分なものとはい
えない。また非常に高価であり、実用化の障害になって
いる。As described above, a solid polymer electrolyte fuel cell has been studied as a power source for automobiles because of its operability at room temperature, small size and high power density. As a molecular electrolyte membrane, a perfluorocarbon polymer membrane having a sulfonic acid group (trade name: Nafion, DuPont, trade name: Aciplex, Asahi Kasei Corporation) or the like is used. However, it cannot be said that it is still sufficient in terms of increasing the output of the fuel cell. In addition, they are very expensive and hinder practical use.
【０００４】そのため、パーフルオロカーボン重合体膜
を代替する安価で高性能な高分子イオン交換膜の研究開
発が進められている。放射線グラフト重合法により、Ｅ
ＴＦＥ（エチレンーテトラフルオロエチレン共重合体）
フィルムにスチレンを導入して次いでスルホン化して製
造したイオン交換膜はパーフルオロカーボン重合体膜に
比べて電気抵抗を低くすることが原理的に可能であり、
さらに低コスト化が可能であることから、これを用いた
燃料電池の特性評価が行われている。一般に燃料電池の
性能を向上させるためには、内部抵抗を小さくすること
が、有効であるため、電解質である高分子イオン交換膜
のイオン交換容量を大きくすることが有利であると考え
られる。放射線グラフト重合法によれば、簡単に低電気
抵抗膜を製造することが可能であるが、この場合に、膜
表面が極めて親水性になり、これが、電極反応に悪影響
を及ぼし内部抵抗が低いにもかかわらず、十分な発電を
行う場合、あるいは電極の撥水性が低い場合に顕著にな
るといった問題点があった。[0004] Therefore, research and development of an inexpensive and high-performance polymer ion exchange membrane that substitutes for a perfluorocarbon polymer membrane has been promoted. By radiation graft polymerization, E
TFE (ethylene-tetrafluoroethylene copolymer)
The ion exchange membrane produced by introducing styrene into the film and then sulfonating it is possible in principle to lower the electrical resistance compared to the perfluorocarbon polymer membrane,
Since further cost reduction is possible, the characteristics of fuel cells using the same have been evaluated. In general, it is effective to reduce the internal resistance to improve the performance of the fuel cell. Therefore, it is considered that it is advantageous to increase the ion exchange capacity of the polymer ion exchange membrane as the electrolyte. According to the radiation graft polymerization method, it is possible to easily produce a low electric resistance film, but in this case, the film surface becomes extremely hydrophilic, which adversely affects the electrode reaction and lowers the internal resistance. Nevertheless, there has been a problem that it becomes remarkable when sufficient power generation is performed or when the water repellency of the electrode is low.
【０００５】触媒層とその触媒層に接するガス供給層か
らなる燃料電池のガス拡散電極の前記ガス供給層は、例
えばガーボンブラック微粒子などと撥水性樹脂材料であ
るポリテトラフルオロエチレン（以下ＰＴＦＥ）の微粉
体の混合物を塗布又は圧着するなどした後、使用されて
いる。あるいはカーボンペーパーにＰＴＦＥを付着、焼
結させて使用されている。The gas supply layer of a gas diffusion electrode of a fuel cell comprising a catalyst layer and a gas supply layer in contact with the catalyst layer is made of, for example, fine particles of carbon black and polytetrafluoroethylene (hereinafter, PTFE) which is a water-repellent resin material. Is used after applying or pressing a mixture of fine powders of the above. Alternatively, PTFE is attached to carbon paper and sintered.
【０００６】しかしながら、ガス供給層は長時間にわた
ってガス供給能を維持させるためには多量のＰＴＦＥの
添加を必要として、その結果カーボンブラック微粒子間
の細孔が先のＰＴＦＥにより閉塞されてガス供給能の低
下を招き、燃料電池として使用したとき性能の低下を生
じるものである。However, the gas supply layer needs to add a large amount of PTFE in order to maintain the gas supply capability for a long time. As a result, the pores between the carbon black fine particles are blocked by the PTFE, and the gas supply capability is increased. And when used as a fuel cell, the performance is reduced.
【０００７】他方、前記触媒層はガス流通路と電解質通
路とを有し、前記ガス供給層から供給された反応ガスは
前記触媒層中のガス流通路中を拡散し、これと接する電
解質成分に達し、その電解質成分に隣接する触媒上で電
気化学的な反応を行うようにしている。On the other hand, the catalyst layer has a gas flow passage and an electrolyte passage, and the reaction gas supplied from the gas supply layer diffuses in the gas flow passage in the catalyst layer, and reacts with the electrolyte component in contact with the gas. And perform an electrochemical reaction on the catalyst adjacent to the electrolyte component.
【０００８】触媒層中においても、例えばリン酸型燃料
電池などで見られるように、長時間運転により前記ガス
流通路中の電解液が浸入して、ガス供給能が低下して、
これにより電池性能の極端な低下を生じる。これを回避
するために撥水剤の量を増加させると触媒層中に電解力
が入りにくくなり、触媒が反応に関与できなくなり、燃
料電池の低下を生じせしめることになる。[0008] Even in the catalyst layer, as seen in, for example, a phosphoric acid type fuel cell, the electrolyte in the gas flow passage invades due to long-time operation, and the gas supply capability is reduced.
This results in an extreme decrease in battery performance. If the amount of the water repellent is increased in order to avoid this, it becomes difficult for the electrolysis force to enter the catalyst layer, and the catalyst cannot participate in the reaction, resulting in a decrease in the fuel cell.
【０００９】前記触媒中のガス供給能と触媒反応の能力
を両立させるための手段として、特開昭６２−２４５６
５号公報に示すように、撥水微粒子と触媒を含まないカ
ーボンブラック微粒子の混合物などと、撥水剤を含まな
い触媒微粉末を混合することにより触媒層を形成する方
法が開示されている。Japanese Patent Application Laid-Open No. 62-2456 discloses a means for achieving both the gas supply capability in the catalyst and the catalytic reaction capability.
As disclosed in Japanese Patent Application Publication No. 5 (1993) -5, a method of forming a catalyst layer by mixing a mixture of water-repellent fine particles and carbon black fine particles not containing a catalyst with a catalyst fine powder not containing a water-repellent agent is disclosed.
【００１０】[0010]
【発明が解決しようとする課題】しかしながら、特開昭
６２−２４５６５号公報は、長時間ガス供給能を維持す
るためには前記混合物中の撥水性微粒子の組成比を高く
することが必要であり、必然的にガス供給能の低下を生
じせしめる。However, in Japanese Patent Application Laid-Open No. 24565/1987, it is necessary to increase the composition ratio of the water-repellent fine particles in the mixture in order to maintain the gas supply capability for a long time. Inevitably, the gas supply capacity is reduced.
【００１１】また、一般的に、高分子電解質型燃料電池
の水素電極では、水素ガスが触媒に接触することによ
り、下記の反応が生じる。In general, at the hydrogen electrode of a polymer electrolyte fuel cell, the following reaction occurs when hydrogen gas comes into contact with a catalyst.
【００１２】２Ｈ２→４Ｈ＋＋４ｅ− Ｈ＋は、下記に示すように、電解質中を移動し酸素電極
側に達し空気中の酸素と反応して水となる。As shown below, 2H 2 → 4H + + 4e − H + moves in the electrolyte, reaches the oxygen electrode side, and reacts with oxygen in the air to become water.
【００１３】４Ｈ＋＋４ｅ−＋Ｏ２→２Ｈ２Ｏ 水素電極からのＨ＋の移動に伴い水も移動する。この水
の移動に伴う水分を補うため水素電極に供給する改質ガ
スに水分を含ませて供給する。このため、酸素電極では
反応によって生成する水の他にＨ＋の移動に伴う水分増
加があり、これらを考慮して酸素電極側に供給、排出さ
れる空気（酸素）の温度管理を行わないと空気中の水分
が露点に達し凝縮して酸素電極の空気供給通路に水滴と
なって付着し空気の流れを阻害し電圧降下をきたすとと
もに酸素電極部分を水滴が覆い、電極機能を失う虞があ
った。4H + + 4e − + O 2 → 2H 2 O Water moves with the movement of H + from the hydrogen electrode. The reformed gas supplied to the hydrogen electrode is supplied with moisture contained therein in order to compensate for the moisture accompanying the movement of the water. For this reason, in the oxygen electrode, there is an increase in water due to the movement of H + in addition to the water generated by the reaction, and the temperature of the air (oxygen) supplied to and discharged from the oxygen electrode must be controlled in consideration of these factors. The water in the air reaches the dew point and condenses, forming water droplets on the air supply passage of the oxygen electrode, obstructing the flow of air, causing a voltage drop and, at the same time, water droplets covering the oxygen electrode portion, and the electrode function may be lost. Was.
【００１４】本発明は、上記課題を解決するもので、水
素極側を親水性傾向の電極とし、酸素極側を撥水性傾向
の電極とするように、撥水性効果を水素極と酸素極と変
えることにより、従来の技術では解決できなかったガス
供給能と触媒能との両者をバランスよく併せ持つ固体高
分子電解質型燃料電池及びその製造方法を提供するもの
である。The present invention has been made to solve the above-mentioned problems, and has a water repellency effect between a hydrogen electrode and an oxygen electrode so that the hydrogen electrode side is an electrode having a hydrophilic tendency and the oxygen electrode side is an electrode having a water repellency. The present invention provides a solid polymer electrolyte fuel cell having both gas supply ability and catalytic ability, which cannot be solved by conventional techniques, in a well-balanced manner, and a method for producing the same.
【００１５】[0015]
【課題を解決するための手段】上記技術的課題を解決す
るために、本発明の請求項１において講じた技術的手段
は、イオン交換能を有する固体高分子電解質膜と、前記
高分子電解質膜の一方側に配置される水素電極としての
水素極側集電体及び水素極側導電性多孔質層と、前記高
分子電解質の他方側に配置される酸素電極としての酸素
極側集電体及び酸素極側導電性多孔質層構成とから構成
される固体高分子電解質型燃料電池において、前記酸素
電極の撥水性樹脂材料の含有量は前記水素電極の含有量
より大きいことを特徴とする固体高分子電解質型燃料電
池である。Means for Solving the Problems To solve the above technical problems, the technical measures taken in claim 1 of the present invention are a solid polymer electrolyte membrane having an ion exchange ability, and the polymer electrolyte membrane. A hydrogen electrode-side current collector and a hydrogen electrode-side conductive porous layer as a hydrogen electrode disposed on one side of, and an oxygen electrode-side current collector as an oxygen electrode disposed on the other side of the polymer electrolyte; and A solid polymer electrolyte fuel cell comprising an oxygen electrode side conductive porous layer structure, wherein the content of the water repellent resin material of the oxygen electrode is larger than the content of the hydrogen electrode. It is a molecular electrolyte fuel cell.
【００１６】上記第１の技術的手段による効果は、以下
のようである。The effects of the first technical means are as follows.
【００１７】即ち、水素電極側は、親水性効果が得ら
れ、酸素電極側は撥水性効果が得られ、触媒に近接する
撥水性樹脂材料量を最小限に設定することが可能とな
り、充分なガス供給能と触媒能との両者をバランスよく
併せ持つことができ、自動車用の燃料電池として、十分
な出力性能を有することができる固体高分子電解質型燃
料電池となる。That is, the hydrophilic effect is obtained on the hydrogen electrode side, and the water repellent effect is obtained on the oxygen electrode side, and the amount of the water-repellent resin material close to the catalyst can be set to a minimum. A solid polymer electrolyte fuel cell which can have both gas supply ability and catalytic ability in a well-balanced manner and which has sufficient output performance as an automobile fuel cell.
【００１８】上記技術的課題を解決するために、本発明
の請求項２において講じた技術的手段は、前記水素電極
及び前記酸素電極には２０重量％から４０重量％の撥水
性樹脂材料が含有されていることを特徴とする請求項１
記載の固体高分子電解質型燃料電池である。In order to solve the above technical problem, a technical measure taken in claim 2 of the present invention is that the hydrogen electrode and the oxygen electrode contain 20 to 40% by weight of a water-repellent resin material. 2. The method according to claim 1, wherein
20 is a solid polymer electrolyte fuel cell according to the above.
【００１９】上記第２の技術的手段による効果は、以下
のようである。The effects of the second technical means are as follows.
【００２０】即ち、撥水性樹脂材料が両集電体に２０重
量％から４０重量％のが含有されている範囲内では、請
求項１の効果に加えてさらに、自動車用の燃料電池とし
て、十分な出力性能を有することができる固体高分子電
解質型燃料電池となる。撥水性樹脂材料が２０重量％よ
り低いと、十分な撥水効果が得られないため、ガス供給
ができなくなり、一方４０％重量％より大であると、電
気抵抗値が高くなり、燃料電池としての十分な出力特性
が得られない。That is, within the range where the water-repellent resin material contains 20% by weight to 40% by weight in both current collectors, in addition to the effect of the first aspect, the present invention further provides a fuel cell for automobiles. Thus, a solid polymer electrolyte fuel cell having a high output performance can be obtained. If the water-repellent resin material is less than 20% by weight, a sufficient water-repellent effect cannot be obtained, so that gas cannot be supplied. On the other hand, if the water-repellent resin material is more than 40% by weight, the electric resistance value increases and the fuel cell becomes Output characteristics cannot be obtained.
【００２１】上記技術的課題を解決するために、本発明
の請求項３において講じた技術的手段は、イオン交換能
を有する固体高分子電解質膜と、前記高分子電解質膜の
一方側に配置される水素電極としての水素極側集電体及
び水素極側導電性多孔質層と、前記高分子電解質の他方
側に配置される酸素電極としての酸素極側集電体及び酸
素極側導電性多孔質層構成とから構成される固体高分子
電解質型の製造方法において、前記水素電極は、前記水
素側集電体に撥水性樹脂材料を含有させる第１の焼結工
程と、前記第１の焼結工程と略同一の工程とする第２の
焼結工程と、前記水素極側導電性多孔質層に触媒を担持
する工程とから製造され、前記酸素電極は、前記酸素極
側集電体に撥水性樹脂材料を含有させる第１の焼結工程
と、前記酸素極側導電性多孔質層と前記水素極側集電体
全体に前記第１の焼結工程と略同一とする第２の焼結工
程と、前記酸素極側導電性多孔質層に触媒を担持する工
程から製造されることを特徴とする固体高分子電解質型
燃料電池の製造方法である。[0021] In order to solve the above technical problems, a technical measure taken in claim 3 of the present invention is to dispose a solid polymer electrolyte membrane having an ion exchange ability and one side of the polymer electrolyte membrane. A hydrogen electrode side current collector and a hydrogen electrode side conductive porous layer as a hydrogen electrode, and an oxygen electrode side current collector and an oxygen electrode side conductive porous layer as an oxygen electrode disposed on the other side of the polymer electrolyte. The hydrogen electrode comprises a first sintering step of allowing the hydrogen-side current collector to contain a water-repellent resin material, and the first firing step. A second sintering step, which is substantially the same as a binding step, and a step of supporting a catalyst on the hydrogen electrode-side conductive porous layer, wherein the oxygen electrode is provided on the oxygen electrode-side current collector. A first sintering step in which a water-repellent resin material is contained; A second sintering step in which the entirety of the electrically conductive porous layer and the hydrogen electrode side current collector is substantially the same as the first sintering step, and a step of carrying a catalyst on the oxygen electrode side conductive porous layer And a method for producing a solid polymer electrolyte fuel cell.
【００２２】上記第３の技術的手段による効果は、以下
のようである。The effects of the third technical means are as follows.
【００２３】即ち、上記製造方法は、簡単な製造方法
で、自動車用燃料電池として十分な出力性能が得られる
といった効果を有する。That is, the above manufacturing method has an effect that sufficient output performance can be obtained as a fuel cell for an automobile by a simple manufacturing method.
【００２４】上記技術的課題を解決するために、本発明
の請求項４において講じた技術的手段は、前記第１焼結
工程及び第２の焼結工程の撥水性樹脂材料の含有量は１
０重量％から２０重量％であることを特徴とする請求項
３記載の固体高分子電解質型燃料電池の製造方法であ
る。In order to solve the above technical problem, the technical means taken in claim 4 of the present invention is that the content of the water-repellent resin material in the first sintering step and the second sintering step is 1
4. The method for producing a solid polymer electrolyte fuel cell according to claim 3, wherein the amount is from 0% by weight to 20% by weight.
【００２５】上記第４の技術的手段による効果は、以下
のようである。The effects of the fourth technical means are as follows.
【００２６】即ち、撥水性樹脂材料の含有量は１０重量
％から２０重量％の範囲内では、請求項３の効果に加え
て、自動車用燃料電池として十分な出力性能が得られる
といった効果を有する。That is, when the content of the water-repellent resin material is in the range of 10% by weight to 20% by weight, in addition to the effect of the third aspect, there is an effect that sufficient output performance as a fuel cell for an automobile can be obtained. .
【００２７】撥水性樹脂材料が１０重量％より低いと、
長時間十分な撥水効果が得られず、２０％重量％より大
であると、電気抵抗値が高くなり、燃料電池としての十
分な出力が得られない。When the water-repellent resin material is lower than 10% by weight,
If the water-repellent effect is not sufficient for a long time, and if it is more than 20% by weight, the electric resistance value increases, and a sufficient output as a fuel cell cannot be obtained.
【００２８】上記技術的課題を解決するために、本発明
の請求項５において講じた技術的手段は、前記撥水性樹
脂材料はポリテトラフルオロエチレンであることを特徴
とする請求項１から４記載の固体高分子電解質型燃料電
池およびその製造方法である。According to a fifth aspect of the present invention, in order to solve the above technical problem, the water repellent resin material is polytetrafluoroethylene. And a method for manufacturing the same.
【００２９】[0029]
【発明の実施の形態】以下、本発明の実施例について説
明する。Embodiments of the present invention will be described below.
【００３０】図１は燃料電池セルを表わした図である。
高分子電解質型膜５の一方側（図１の左側）を水素電極
としての水素極側導電性多孔質層７１と水素極側集電体
２１が配設し、他方側（図１の右側）を酸素電極として
の酸素極側導電性多孔質体７２と酸素極側集電体２２が
配設している。一方の第１供給管６１から、上記の酸素
極側集電体２１と酸素極側導電性多孔質層７１に水蒸気
と水素を供給している。また他方の第２供給管６２か
ら、第２集電体２２と水素極側導電性多孔質層７２に水
蒸気と酸素を供給している第１供給管６１から供給され
る空気は、後述する製造によって得られたＰｔ触媒２１
が担持された水素極側集電体２１を通り水素極側導電性
多孔質層７１の細孔内で拡散する。一方、第２供給管６
２から供給される水素は、Ｐｔ／Ｒｕ触媒２２が担持さ
れた酸素極側集電体２２を通り、酸素極側導電性多孔質
層７２の細孔内で拡散する。反応により、生成された水
は水素極側導電性多孔質層７１、酸素極側導電性多孔質
層７２内で細孔内拡散し、供給管６１、６２に循環す
る。同時に、上記部材の間で水素電子の交換が行われ
て、発電が行われる。FIG. 1 is a diagram showing a fuel cell.
One side (left side in FIG. 1) of the polymer electrolyte membrane 5 is provided with a hydrogen electrode side conductive porous layer 71 as a hydrogen electrode and a hydrogen electrode side current collector 21, and the other side (right side in FIG. 1). Are provided with an oxygen electrode side conductive porous body 72 as an oxygen electrode and an oxygen electrode side current collector 22. Water vapor and hydrogen are supplied from one first supply pipe 61 to the oxygen electrode side current collector 21 and the oxygen electrode side conductive porous layer 71. The air supplied from the other second supply pipe 62 from the first supply pipe 61 that supplies water vapor and oxygen to the second current collector 22 and the hydrogen-electrode-side conductive porous layer 72 is produced as described later. Catalyst 21 obtained by
Are diffused in the pores of the hydrogen-electrode-side conductive porous layer 71 through the hydrogen-electrode-side current collector 21 on which hydrogen is carried. On the other hand, the second supply pipe 6
The hydrogen supplied from 2 passes through the oxygen electrode side current collector 22 carrying the Pt / Ru catalyst 22, and diffuses in the pores of the oxygen electrode side conductive porous layer 72. The water generated by the reaction is diffused in the pores in the hydrogen electrode side conductive porous layer 71 and the oxygen electrode side conductive porous layer 72 and circulates through the supply pipes 61 and 62. At the same time, hydrogen electrons are exchanged between the members, and power is generated.
【００３１】以下に、触媒２１、２２が担持される第１
導電性多孔質層７１、第２導電性多孔質層７２の製造方
法について説明する。In the following, the first catalysts 21 and 22 are supported.
A method for manufacturing the conductive porous layer 71 and the second conductive porous layer 72 will be described.
【００３２】（実施例）まず、水素極側の第１導電性多
孔質層７１、酸素側の第２導電性多孔質層７２共通の工
程について説明する。(Embodiment) First, steps common to the first conductive porous layer 71 on the hydrogen electrode side and the second conductive porous layer 72 on the oxygen side will be described.
【００３３】ダイキン工業株式会社製の含有濃度が６０
％のディスパージョン原液（商品名：ポリフロン、Ｄ１
グレード）をテトラフルオロエチレンの含有濃度が１５
重量％になるように、水で希釈する。この溶液の中に東
レ株式会社製カーボンペーパー（商品名：トレカ、ＴＧ
Ｐ−０６０ １８０μｍ）を投入して、十分に上記のデ
ィスパージョン溶液に含浸させる。次に８０°Ｃに温度
を保った乾燥炉で余分な水分を蒸発させた後に、焼結温
度３９０°Ｃで６０分保持して、撥水性樹脂材料（以下
ＰＴＦＥという）焼結をする。なお上記工程は説明をわ
かりやすくするために、第１の焼結工程（１５重量％／
１回塗布工程）と表現する。The content concentration of Daikin Industries, Ltd. is 60
% Dispersion stock solution (trade name: Polyflon, D1
Grade) with a tetrafluoroethylene content of 15
Dilute with water to give weight%. In this solution, carbon paper (trade name: Torayca, TG) manufactured by Toray Industries, Inc.
P-060 180 μm) and sufficiently impregnated with the above dispersion solution. Next, after evaporating excess water in a drying furnace maintained at a temperature of 80 ° C., the sintering temperature is maintained at 390 ° C. for 60 minutes to sinter a water-repellent resin material (hereinafter referred to as PTFE). Note that the above process is performed in the first sintering process (15% by weight /
(One application step).
【００３４】次に水素極側にあたる水素極側集電体２１
と水素極側導電性多孔質層７１の作成工程について図２
を参考にして説明する。Next, the hydrogen electrode side current collector 21 corresponding to the hydrogen electrode side
FIG. 2 shows a process of forming the hydrogen-electrode-side conductive porous layer 71.
This will be described with reference to FIG.
【００３５】第１工程：水素極側導電性多孔質層７１の
素材である東レ株式会社製カーボンペーパー（商品名：
トレカ）を上記のＰＴＦＥ焼結法によって、第１の焼結
工程「１５重量％／１回塗布」を行った。First step: Carbon paper (trade name, manufactured by Toray Industries, Ltd.), which is a material of the hydrogen electrode-side conductive porous layer 71
A first sintering step “15% by weight / one application” was performed by using the above-mentioned PTFE sintering method.
【００３６】第２工程：上記第１の焼結工程「１５重量
％／１回塗布」で実施した作成工程と略同一な焼結工程
を一度実行した。つまりＰＴＦＥ焼結処理済の水素極側
導電性多孔質層７１に上記の第１の焼結工程「１５重量
％／１回塗布」を２回行った。これを第２の焼結工程と
いう。Second step: The same sintering step as the preparation step performed in the first sintering step “15% by weight / one application” was performed once. That is, the above-mentioned first sintering step “15% by weight / one application” was performed twice on the hydrogen electrode side conductive porous layer 71 having been subjected to the PTFE sintering treatment. This is called a second sintering step.
【００３７】第３工程：次にこのＰＴＦＥ焼成後の水素
極側導電性多孔質層７１の片面にスクリーン印刷法など
の薄膜成形法を用いて、厚さ３００μｍ程度のカーボン
ブラック微粒子（粒径約３０μｍ）層の薄膜を成形し
た。図２（ａ）第４工程：その後カーボンブラック微粒
子層にエチレングリコール等の成形助剤を混入させ、８
０°Ｃの温度に保った真空乾燥炉中で２時間乾燥して、
蒸発させた。Third step: Next, carbon black fine particles having a thickness of about 300 μm (having a particle size of about 300 μm) are formed on one surface of the hydrogen-electrode-side conductive porous layer 71 after the PTFE firing by using a thin film forming method such as a screen printing method. A 30 μm) layer of thin film was formed. FIG. 2 (a) Fourth step: Thereafter, a molding aid such as ethylene glycol is mixed into the carbon black fine particle layer,
Dried in a vacuum drying oven maintained at a temperature of 0 ° C. for 2 hours,
Evaporated.
【００３８】第５工程：次に、白金／ルテニウム担持カ
ーボン（以下Ｐｔ／ＲｕＣ）１０ｇとイオン交換膜溶液
１６７ｇ（触媒層とイオン交換膜との間をなじませるた
めの接着剤としての役割を行う溶液で、イオン交換膜を
溶かした溶液）及び成形助剤としてのイソプロピルアル
コール等の有機溶剤２０〜３０ｇとを充分に混合した後
に、未処理な状態のカーボンブラック微粒子層７１の表
面に前記の混合溶液を混入し、３００μｍのシート厚さ
になるように、ドクターブレード法又はスクリーン印刷
法等の薄膜成形法により薄膜成形シートを成形する。こ
の薄膜成形法は撥水処理済の電極基材の上に触媒／溶剤
を載置しスキージの移動により薄膜層を形成させる。で
きた成形品が図２（ｂ）、（ｃ）である。Fifth step: Next, 10 g of platinum / ruthenium-supported carbon (hereinafter referred to as Pt / RuC) and 167 g of an ion-exchange membrane solution (acting as an adhesive for blending the catalyst layer and the ion-exchange membrane) A solution obtained by dissolving an ion exchange membrane in a solution) and 20 to 30 g of an organic solvent such as isopropyl alcohol as a molding aid, and then sufficiently mixed with the surface of the carbon black fine particle layer 71 in an untreated state. The solution is mixed, and a thin film forming sheet is formed by a thin film forming method such as a doctor blade method or a screen printing method so as to have a sheet thickness of 300 μm. In this thin film forming method, a catalyst / solvent is placed on a water-repellent electrode substrate, and a squeegee is moved to form a thin film layer. The resulting molded products are shown in FIGS. 2 (b) and 2 (c).
【００３９】なお図２の下図はカーボンブラック微粒子
を拡大した図である。図２の（ａ）は、未処理のカーボ
ン微粒子を示したもので、図２の（ｂ）はカーボン微粒
子周辺にＰＴＦＥが焼結された図である。図２（ｃ）は
カーボン微粒子周辺にＰＴＦＥが焼結され、さらに触媒
としてのＰｔ／ＲｕＣが担持されている図を表してい
る。The lower part of FIG. 2 is an enlarged view of carbon black fine particles. FIG. 2A shows untreated carbon fine particles, and FIG. 2B shows PTFE sintered around the carbon fine particles. FIG. 2 (c) shows a diagram in which PTFE is sintered around carbon fine particles and Pt / RuC as a catalyst is further supported.
【００４０】次に空気極側の作成工程についてを参考に
して説明する。Next, a description will be given of the production process on the air electrode side with reference to FIG.
【００４１】第１工程：酸素極側導電性多孔質層７２の
素材である東レ株式会社製カーボンペーパー（商品名：
トレカ）を上記のＰＴＦＥ焼結法によって、第１の焼結
工程「１５重量％／１回塗布」を行った。First step: Carbon paper (trade name: manufactured by Toray Industries, Ltd.) as a material of the oxygen-electrode-side conductive porous layer 72
A first sintering step “15% by weight / one application” was performed by using the above-mentioned PTFE sintering method.
【００４２】第２工程：次にこのＰＴＦＥ焼成後の酸素
極側導電性多孔質層７２の片面にスクリーン印刷法によ
る薄膜成形シート法を用いて、厚さ３００μｍ程度のカ
ーボンブラック微粒子層の薄膜を成形した。図３（ａ） 第３工程：その後カーボンブラック微粒子層に混入した
エチレングリコール等の成形助剤を混入させ、８０°Ｃ
の温度に保った真空乾燥炉中で２時間乾燥して、蒸発さ
せた。Second step: Next, a thin film of a carbon black fine particle layer having a thickness of about 300 μm is formed on one surface of the oxygen-electrode-side conductive porous layer 72 after the PTFE firing by using a thin film forming sheet method by a screen printing method. Molded. FIG. 3 (a) Third step: After that, a molding aid such as ethylene glycol mixed into the carbon black fine particle layer is mixed,
Was dried in a vacuum drying oven maintained at a temperature of 2 hours and evaporated.
【００４３】第４工程：上記第１の焼結工程「１５重量
％／１回塗布」で実施した工程と略同一の条件でＰＴＦ
Ｅ焼結処理済の酸素極側集電体２２とカーボンブラック
微粒子層からなる酸素極側導電性多孔質層７２全体を第
１の焼結工程「１５重量％／１回塗布」と略同一な焼結
工程で作成した。図３（ｂ） 第５工程：次に、白金担持カーボン（以下ＰｔＣ）１０
ｇとイオン交換膜溶液１５０ｇ（触媒層とイオン交換膜
との間をなじませるための接着剤としての役割を行う溶
液で、イオン交換膜を溶かした溶液）及び成形助剤とし
てのイソプロピルアルコール等の有機溶剤２０〜３０ｇ
とを充分に混合した後に、ＰＴＦＥ焼結したカーボンブ
ラック微粒子層の表面に前記の混合溶液を設定した３０
０μｍのシート厚さになるように、スクリーン印刷法に
より薄膜成形シートを成形した。図３（ｂ）、（ｃ） なお図３の下図はカーボンブラック微粒子を拡大した図
である。図２の（ａ）未処理のカーボン微粒子を示した
もので、図２の（ｂ）はカーボン微粒子周辺にＰＴＦＥ
が焼結された図である。図２（ｃ）はカーボン微粒子周
辺にＰＴＦＥが焼結され、さらに触媒としてのＰｔＣが
担持されている図を表している。Fourth step: PTF under substantially the same conditions as those performed in the first sintering step “15% by weight / one application”
The entirety of the oxygen-electrode-side current collector 22 and the oxygen-electrode-side conductive porous layer 72 composed of a carbon black fine particle layer subjected to the E-sintering treatment is substantially the same as that in the first sintering step “15% by weight / one application”. Created in the sintering process. FIG. 3 (b) Fifth step: Next, platinum-supported carbon (hereinafter referred to as PtC) 10
g and 150 g of an ion-exchange membrane solution (a solution that functions as an adhesive for dissolving between the catalyst layer and the ion-exchange membrane and is a solution in which the ion-exchange membrane is dissolved) and isopropyl alcohol and the like as a molding aid Organic solvent 20-30g
After sufficiently mixing the mixed solution, the mixed solution was set on the surface of the carbon black fine particle layer sintered with PTFE.
A thin film-formed sheet was formed by a screen printing method so as to have a sheet thickness of 0 μm. FIGS. 3B and 3C The lower diagram of FIG. 3 is an enlarged view of carbon black fine particles. FIG. 2A shows untreated carbon fine particles, and FIG. 2B shows PTFE around the carbon fine particles.
It is the figure which was sintered. FIG. 2C shows a diagram in which PTFE is sintered around carbon fine particles and PtC as a catalyst is further supported.
【００４４】（比較例１）比較例として、従来の電極接
合体による単セル型の高分子電解質型燃料電池を製造し
た。Comparative Example 1 As a comparative example, a single cell type polymer electrolyte fuel cell using a conventional electrode assembly was manufactured.
【００４５】ダイキン工業株式会社製の含有濃度が６０
％のディスパージョン原液（商品名：ポリプロピレン、
Ｄ１グレード）をテトラフルオロエチレンの含有濃度が
５重量％になるように、水で希釈する。この溶液の中に
東レ株式会社製カーボンペーパー（商品名：トレカ、Ｔ
ＧＰ−０６０ １８０μｍ）を投入して、十分に上記の
ディスパージョン溶液に含浸させる。次に８０°Ｃに温
度を保った乾燥炉で余分な水分を蒸発させた後に、焼結
温度３９０°Ｃで６０分保持して、撥水性樹脂材料（以
下ＰＴＦＥという）焼結をする。これは、水素電極およ
び酸素電極両方の電極に使われる。つまり比較例１は、
５％のＰＴＦＥのディスパージョン濃度溶液の水素電極
および酸素電極を有する電極である。The content concentration of Daikin Industries, Ltd. is 60
% Dispersion stock solution (trade name: polypropylene,
D1 grade) is diluted with water such that the concentration of tetrafluoroethylene becomes 5% by weight. In this solution, carbon paper (trade name: Torayca, T
GP-060 180 μm) and sufficiently impregnated with the above dispersion solution. Next, after evaporating excess water in a drying furnace maintained at a temperature of 80 ° C., the sintering temperature is maintained at 390 ° C. for 60 minutes to sinter a water-repellent resin material (hereinafter referred to as PTFE). It is used for both hydrogen and oxygen electrodes. That is, Comparative Example 1
This is an electrode having a hydrogen electrode and an oxygen electrode of a 5% PTFE dispersion concentration solution.
【００４６】次に、塩化白金酸１ｇを２００ｍｌの蒸留
水に溶解し、この白金化合物の水溶液に、硫酸水素ナト
リウム４ｇを含む水溶液を攪拌した。さらに全液量を蒸
留水で７００ｍｌとした後、炭酸ソーダ０．４ｇ水溶液
約１３ｍｌを加え、ＰＨ５に溶液を調整した。この溶液
に過酸化水素水を５０ｍｌ添加し、苛性ソーダ水溶液を
加えることで、この溶液のＰＨを約５に保った。Next, 1 g of chloroplatinic acid was dissolved in 200 ml of distilled water, and an aqueous solution containing 4 g of sodium hydrogen sulfate was stirred in the aqueous solution of the platinum compound. Further, after making the total amount of the solution 700 ml with distilled water, about 13 ml of 0.4 g aqueous solution of sodium carbonate was added to adjust the solution to PH5. To this solution, 50 ml of aqueous hydrogen peroxide was added, and an aqueous solution of caustic soda was added to maintain the pH of this solution at about 5.
【００４７】次に、任意の白金対ルテニウム比になるよ
うに、三塩化ルテニウム水溶液５０ｍｌを加えて、白金
とルテニウム二元系クラスターのコロイド状溶液が得ら
れた。この水溶液中に水素ガスを導入した後、白金とル
テニウムの固溶合金を作成した。Next, 50 ml of an aqueous ruthenium trichloride solution was added so as to obtain an arbitrary ratio of platinum to ruthenium to obtain a colloidal solution of platinum and ruthenium binary cluster. After introducing hydrogen gas into this aqueous solution, a solid solution alloy of platinum and ruthenium was prepared.
【００４８】さらに、このコロイド溶液と２．６８ｇの
カーボンブラック粒子を２００ｍｌに分散した溶液を超
音波ホモナイザー攪拌下で約３０分間混合し、濾過、洗
浄、乾燥などの工程を経てクラスター触媒を担持した。Further, this colloid solution and a solution obtained by dispersing 2.68 g of carbon black particles in 200 ml were mixed for about 30 minutes while being stirred by an ultrasonic homogenizer, followed by filtration, washing, drying and other steps to carry the cluster catalyst. .
【００４９】表１は本実施例と比較例を表わした高分子
電解質型燃料電池の撥水性評価を示したものである。Table 1 shows the evaluation of water repellency of the polymer electrolyte fuel cells according to the present embodiment and the comparative example.
【００５０】[0050]
【表１】 [Table 1]
【００５１】 この表１からわかるように、ＰＴＦＥのデ
ィスパージョン濃度が１５％の２回塗り（ＰＴＦＥの２
回焼結）の実施例では、撥水性もよく、高分子膜と熱間
接合状態がよく、電気抵抗値が低く、車両用（特に自動
車用）の燃料電池の１Ａ／ｃｍ２の出力（Ｈ水素／Ｏ酸
素：２ａｔｍ／２ａｔｍ）の出力を充分に満足する結果
が得られた。なお、ＰＴＦＥが２回塗りが２０％より多
いと、お互いに滑ってしまい、接合状態がよくない。ま
た、電気抵抗値が高くなり、自動車用の燃料電池として
十分な出力性能が得られない。またＰＴＦＥが１０％よ
り多いと、十分な撥水性の効果が得られない。[0051] As can be seen from Table 1, the PTFE data
Two coats with a dispersion concentration of 15% (PTFE 2
In the example of (sintering), water repellency is good,
Good bonding condition, low electric resistance, suitable for vehicles (especially automatic
1A / cm of fuel cell2Output (H hydrogen / O acid
(Element: 2 atm / 2 atm)
was gotten. PTFE is applied twice more than 20%.
If they do, they will slide on each other and the joint will not be good. Ma
In addition, the electric resistance value increases,
Sufficient output performance cannot be obtained. Also, PTFE is 10%
If the amount is too large, a sufficient water repellent effect cannot be obtained.
【００５２】図４は、本実施例１の高分子電解質型燃料
電池での発電性能を評価したものである。電極にリード
線を接合して電圧計を取り付けて評価したもので、面積
２２０ｃｍ２の１００セル積層させたスタックさせ、セ
ルの電圧と電流の関係を評価した図である。図の−○−
は、水素／空気を２．５ａｔｍ／２．５ａｔｍ条件下の
電圧と電流との関係を表わしたグラフである。この条件
下は、水素ボンベによって、水素だけが、供給できる条
件を示したもので、理想的には水素のみの供給が得られ
ることが望まれている。FIG. 4 shows an evaluation of the power generation performance of the polymer electrolyte fuel cell of the first embodiment. FIG. 9 is a diagram in which a lead wire is bonded to an electrode and a voltmeter is attached to evaluate, and a stack is formed by stacking 100 cells having an area of 220 cm 2, and the relationship between the cell voltage and current is evaluated. -○-in the figure
Is a graph showing the relationship between the voltage and the current of hydrogen / air under the conditions of 2.5 atm / 2.5 atm. Under these conditions, only hydrogen can be supplied by the hydrogen cylinder, and ideally, it is desired that only hydrogen can be supplied.
【００５３】自動車に実施される場合には実現上、自動
車に搭載されたメタノールを改質して水素を生成させて
いるが、その際に未反応生成物として発生するＣＯ（一
酸化炭素）が発生している。図の−□−は、本実施例１
から得られたセル電圧と電流密度を表わした図である。
水素と一酸化炭素２０ＰＰＭ含有／空気：２．５ａｔｍ
／２．５ａｔｍの条件下で行われた。In the case where the present invention is applied to an automobile, in practice, methanol mounted on the automobile is reformed to generate hydrogen, and CO (carbon monoxide) generated as an unreacted product at that time is generated. It has occurred. In the figure,-□-indicates the first embodiment.
FIG. 4 is a diagram showing cell voltage and current density obtained from FIG.
Hydrogen and carbon monoxide 20PPM / air: 2.5atm
/2.5atm.
【００５４】この図から本実施例１においては十分な電
圧を発生し、自動車用の高分子電解質型燃料電池として
十分な出力が得られることがわかる。なお電流が０．３
Ａ／ｃｍ２付近では、自動車の定常運転時であり、０．
０Ａ／ｃｍ２付近では自動車のアイドリング状態（無負
荷状態）である。図４の右へいくほど、アクセルの踏む
量が大きくなることを表している。From this figure, it can be seen that in the first embodiment, a sufficient voltage is generated, and a sufficient output is obtained as a polymer electrolyte fuel cell for an automobile. The current is 0.3
In the vicinity of A / cm 2 , it is the time of steady operation of the car,
In the vicinity of 0 A / cm 2 , the vehicle is in an idling state (no-load state). 4 indicates that the amount of stepping on the accelerator increases as going to the right in FIG.
【００５５】なお、本実施例では、導電性多孔質層とし
てカーボンブラック微粒子にて説明したが、カーボンブ
ラックからカーボン成形体を使用することもできる。ま
た撥水性を付与するＰＴＦＥ、あるいは他のフッ素樹脂
がバインダーとされたカーボンブラック微粒子を成形し
たカーボンＰＴＦＥ混合成形体を採用することもでき
る。またカーボンブラック粒子の代りとして、黒鉛等の
炭素粉末や、カーボンファイバー、貴金属粉末、チタン
粉末等の金属微粒子を使うこともできる。In the present embodiment, carbon black fine particles are used as the conductive porous layer. However, a carbon molded body made of carbon black can also be used. It is also possible to employ PTFE that imparts water repellency, or a carbon PTFE mixed molded article obtained by molding carbon black fine particles in which another fluorine resin is used as a binder. Instead of carbon black particles, carbon powder such as graphite, or metal fine particles such as carbon fiber, noble metal powder, and titanium powder can also be used.
【００５６】[0056]
【発明の効果】本発明は、以下の如く効果を有する。The present invention has the following effects.
【００５７】即ち、本発明は、前記酸素電極の撥水性樹
脂材料の含有量は前記水素電極の含有量より大きいこと
を特徴とする固体高分子電解質型燃料電池であるので、
水素極側は、親水性効果が得られ、酸素極側は撥水性効
果が得られ、触媒に近接する撥水性樹脂材料量を最小限
に設定することが可能となり、充分なガス供給能と触媒
能との両者を併せ持つことができ、自動車用の燃料電池
として、十分な電力性能を有することができる固体高分
子電解質型燃料電池となる。That is, the present invention is a solid polymer electrolyte fuel cell characterized in that the content of the water-repellent resin material of the oxygen electrode is larger than the content of the hydrogen electrode.
On the hydrogen electrode side, a hydrophilic effect is obtained, and on the oxygen electrode side, a water-repellent effect is obtained.It is possible to minimize the amount of water-repellent resin material close to the catalyst. Thus, a solid polymer electrolyte fuel cell having sufficient power performance as a fuel cell for an automobile can be obtained.
【００５８】また、前記水素電極は、前記水素側集電体
に撥水性樹脂材料を含有させる第１の焼結工程と、前記
第１の焼結工程と略同一の工程とする第２の焼結工程
と、前記水素極側導電性多孔質層に触媒を担持する工程
とから製造され、前記酸素電極は、前記酸素極側集電体
に撥水性樹脂材料を含有させる第１の焼結工程と、前記
酸素極側導電性多孔質層と前記水素極側集電体全体に前
記第１の焼結工程と略同一とする第２の焼結工程と、前
記酸素極側導電性多孔質層に触媒を担持する工程から製
造されることを特徴とする固体高分子電解質型燃料電池
の製造方法であるので、簡単な製造方法で、自動車用燃
料電池として十分な出力性能が得られるといった効果を
有する。Further, the hydrogen electrode is formed by a first sintering step in which the hydrogen-side current collector contains a water-repellent resin material, and a second sintering step which is substantially the same as the first sintering step. A first sintering step in which the oxygen electrode is made of a water-repellent resin material in the oxygen electrode-side current collector. A second sintering step for making the entirety of the oxygen-electrode-side conductive porous layer and the hydrogen-electrode-side current collector substantially the same as the first sintering step; This is a method for manufacturing a solid polymer electrolyte fuel cell, which is manufactured from a step of supporting a catalyst on a substrate. Have.
【図１】本発明の燃料電池セルの分解図FIG. 1 is an exploded view of a fuel cell unit of the present invention.
【図１】本発明の燃料電池セルの分解図FIG. 1 is an exploded view of a fuel cell unit of the present invention.
【図２】水素極側の水素極側導電性多孔質層と水素極側
集電体の製造方法を表わした図FIG. 2 is a diagram showing a method for manufacturing a hydrogen electrode side conductive porous layer on the hydrogen electrode side and a hydrogen electrode side current collector.
【図３】酸素極側の酸素極側導電性多孔質層と酸素極側
集電体の製造方法を表わした図FIG. 3 is a diagram showing a method for producing an oxygen electrode side conductive porous layer on the oxygen electrode side and an oxygen electrode side current collector.
【図４】本発明の実施例１のセル電圧と電流密度を表わ
したグラフFIG. 4 is a graph showing cell voltage and current density in Example 1 of the present invention.
５…固体高分子電解質 ２１…水素極側集電体 ２２…酸素極側集電体 ７１…水素極側導電性多孔質層 ７２…酸素極側導電性多孔質層 5: solid polymer electrolyte 21: hydrogen electrode side current collector 22 ... oxygen electrode side current collector 71: hydrogen electrode side conductive porous layer 72: oxygen electrode side conductive porous layer
─────────────────────────────────────────────────────
────────────────────────────────────────────────── ───
【手続補正書】[Procedure amendment]
【提出日】平成１０年９月１日[Submission date] September 1, 1998
【手続補正１】[Procedure amendment 1]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】図面の簡単な説明[Correction target item name] Brief description of drawings
【補正方法】変更[Correction method] Change
【補正内容】[Correction contents]
【図面の簡単な説明】[Brief description of the drawings]
【図１】本発明の燃料電池セルの分解図。FIG. 1 is an exploded view of a fuel cell unit of the present invention.
【図２】水素極側の水素極側導電性多孔質層と水素極側
集電体の製造方法を表わした図。 FIG. 2 shows a hydrogen electrode side conductive porous layer on the hydrogen electrode side and a hydrogen electrode side.
The figure showing the manufacturing method of the current collector.
【図３】酸素極側の酸素極側導電性多孔質層と酸素極側
集電体の製造方法を表わした図。FIG. 3 is a diagram showing a method for producing an oxygen electrode side conductive porous layer on the oxygen electrode side and an oxygen electrode side current collector.
【図４】本発明の実施例１のセル電圧と電流密度を表わ
したグラフ。FIG. 4 is a graph showing a cell voltage and a current density according to the first embodiment of the present invention.
【符号の説明】 ５…固体高分子電解質 ２１…水素極側集電体 ２２…酸素極側集電体 ７１…水素極側導電性多孔質層 ７２…酸素極側導電性多孔質層[Description of Symbols] 5 ... Solid polymer electrolyte 21 ... Hydrogen electrode side current collector 22 ... Oxygen electrode side current collector 71 ... Hydrogen electrode side conductive porous layer 72 ... Oxygen electrode side conductive porous layer
Claims (5)
膜と、前記高分子電解質膜の一方側に配置される水素電
極としての水素極側集電体及び水素極側導電性多孔質層
と、前記高分子電解質の他方側に配置される酸素電極と
しての酸素極側集電体及び酸素極側導電性多孔質層構成
とから構成される固体高分子電解質型燃料電池におい
て、 前記酸素電極の撥水性樹脂材料の含有量は前記水素電極
の含有量より大きいことを特徴とする固体高分子電解質
型燃料電池。1. A solid polymer electrolyte membrane having an ion exchange capacity, a hydrogen electrode side current collector and a hydrogen electrode side conductive porous layer as a hydrogen electrode disposed on one side of the polymer electrolyte membrane, A solid polymer electrolyte fuel cell comprising: an oxygen electrode side current collector as an oxygen electrode disposed on the other side of the polymer electrolyte; and an oxygen electrode side conductive porous layer structure. A solid polymer electrolyte fuel cell, wherein the content of the aqueous resin material is larger than the content of the hydrogen electrode.
重量％から４０重量％の撥水性樹脂材料が含有されてい
ることを特徴とする請求項１記載の固体高分子電解質型
燃料電池。2. The hydrogen electrode and the oxygen electrode have 20 electrodes.
2. The solid polymer electrolyte fuel cell according to claim 1, wherein the water-repellent resin material is contained in an amount of from 40% by weight to 40% by weight.
膜と、前記高分子電解質膜の一方側に配置される水素電
極としての水素極側集電体及び水素極側導電性多孔質層
と、前記高分子電解質の他方側に配置される酸素電極と
しての酸素極側集電体及び酸素極側導電性多孔質層構成
とから構成される固体高分子電解質型の製造方法におい
て、前記水素電極は、前記水素側集電体に撥水性樹脂材
料を含有させる第１の焼結工程と、前記第１の焼結工程
と略同一の工程とする第２の焼結工程と、前記水素極側
導電性多孔質層に触媒を担持する工程とから製造され、
前記酸素電極は、前記酸素極側集電体に撥水性樹脂材料
を含有させる第１の焼結工程と、前記酸素極側導電性多
孔質層と前記水素極側集電体全体に前記第１の焼結工程
と略同一とする第２の焼結工程と、前記酸素極側導電性
多孔質層に触媒を担持する工程から製造されることを特
徴とする固体高分子電解質型燃料電池の製造方法。3. A solid polymer electrolyte membrane having an ion exchange ability, a hydrogen electrode side current collector and a hydrogen electrode side conductive porous layer as a hydrogen electrode disposed on one side of the polymer electrolyte membrane, In a method for producing a solid polymer electrolyte type comprising an oxygen electrode side current collector as an oxygen electrode disposed on the other side of the polymer electrolyte and an oxygen electrode side conductive porous layer configuration, the hydrogen electrode is A first sintering step in which the hydrogen-side current collector contains a water-repellent resin material, a second sintering step that is substantially the same as the first sintering step, And supporting the catalyst on the porous porous layer,
The oxygen electrode includes a first sintering step in which the oxygen-electrode-side current collector contains a water-repellent resin material, and a first sintering step in which the oxygen-electrode-side conductive porous layer and the hydrogen-electrode-side current collector are entirely covered with the first sintering step. A second sintering step which is substantially the same as the sintering step, and a step of supporting a catalyst on the oxygen electrode side conductive porous layer. Method.
の撥水性樹脂材料の含有量は１０重量％から２０重量％
であることを特徴とする請求項３記載の固体高分子電解
質型燃料電池の製造方法。4. The content of the water-repellent resin material in the first sintering step and the second sintering step is 10% by weight to 20% by weight.
4. The method for manufacturing a solid polymer electrolyte fuel cell according to claim 3, wherein:
ロエチレンであることを特徴とする請求項１から４記載
の固体高分子電解質型燃料電池およびその製造方法。5. The solid polymer electrolyte fuel cell according to claim 1, wherein the water-repellent resin material is polytetrafluoroethylene.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10149261A JPH11339815A (en) | 1998-05-29 | 1998-05-29 | Solid polymer electrolyte for cell and its manufacture |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10149261A JPH11339815A (en) | 1998-05-29 | 1998-05-29 | Solid polymer electrolyte for cell and its manufacture |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH11339815A true JPH11339815A (en) | 1999-12-10 |
Family
ID=15471388
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP10149261A Pending JPH11339815A (en) | 1998-05-29 | 1998-05-29 | Solid polymer electrolyte for cell and its manufacture |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH11339815A (en) |
Cited By (6)
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|---|---|---|---|---|
| JP2002367655A (en) * | 2001-06-11 | 2002-12-20 | Toyota Motor Corp | Fuel cell |
| JP2004139835A (en) * | 2002-10-17 | 2004-05-13 | Matsushita Electric Ind Co Ltd | Fuel cell |
| JP2005174764A (en) * | 2003-12-11 | 2005-06-30 | Equos Research Co Ltd | Fuel cell system, its manufacturing method, and its operation |
| US6946214B2 (en) | 2001-05-15 | 2005-09-20 | Aisin Seiki Kabushiki Kaisha | Manufacturing method of fuel cell electrode and fuel cell using thereof |
| KR100649088B1 (en) * | 2001-08-16 | 2006-11-24 | 미쓰비시덴키 가부시키가이샤 | Electrochemical element |
| JP2008218131A (en) * | 2007-03-02 | 2008-09-18 | Gs Yuasa Corporation:Kk | Membrane-electrode assembly for polymer electrolyte fuel cell, and polymer electrolyte fuel cell using it |
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