JPH06111827A - Polymer solid-electrolyte fuel cell - Google Patents
Polymer solid-electrolyte fuel cellInfo
- Publication number
- JPH06111827A JPH06111827A JP4256805A JP25680592A JPH06111827A JP H06111827 A JPH06111827 A JP H06111827A JP 4256805 A JP4256805 A JP 4256805A JP 25680592 A JP25680592 A JP 25680592A JP H06111827 A JPH06111827 A JP H06111827A
- Authority
- JP
- Japan
- Prior art keywords
- silica
- fuel cell
- catalyst layer
- ion exchange
- exchange membrane
- 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.)
- Granted
Links
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1007—Fuel cells with solid electrolytes with both reactants being gaseous or vaporised
-
- 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
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Sustainable Development (AREA)
- Sustainable Energy (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Inert Electrodes (AREA)
- Fuel Cell (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、イオン交換膜を有する
高分子固体電解質型燃料電池の電池性能の改良に関す
る。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to improvement of cell performance of polymer electrolyte fuel cells having an ion exchange membrane.
【０００２】[0002]
【従来の技術】燃料電池は天然ガス等の化学エネルギー
を化学反応によって直接に電気エネルギーに変換するも
ので、他の発電機（ガスエンジン、ガスタービン、ディ
ーゼルエンジン等）に比べてクリーン且つ発電効率が高
いという大きな特徴を有している。2. Description of the Related Art A fuel cell directly converts chemical energy such as natural gas into electric energy through a chemical reaction, and is cleaner and more efficient in power generation than other generators (gas engine, gas turbine, diesel engine, etc.). It has a great feature that it is high.
【０００３】燃料電池の種類にはリン酸型、アルカリ水
溶液型、溶融炭酸塩型、固体電解質型、高分子固体電解
質型等があるが、本発明に関する高分子固体電解質型燃
料電池は他の燃料電池と比べてコンパクトで高い電流密
度を取り出せることから、電気自動車、宇宙船用の電源
として注目されている。そして、この高分子固体電解質
型燃料電池の電池性能は以下に示す要因により大きく支
配される。 （１）イオン交換膜はイオン伝導性が良いこと。即ち、
イオン交換膜自体の比抵抗が小さいほどイオン伝導性は
良くなり、高い電流密度を得ることができる。このこと
から、イオン交換膜のイオン伝導性の改良方法として、
イオン交換膜の膜材である炭化水素系イオン交換樹脂、
又はナフィオン（商品名…米国デュポン社が開発したパ
ーフルオロカーボンスルホン酸）等のフッ素化樹脂等の
高分子固体電解質中のイオン交換基の濃度を増すことが
提案されている。あるいは、膜を機械加工することによ
りイオン交換膜のイオン伝導性を改良する試みもなされ
ている。 （２）イオン交換膜、アノード、及びカソードの水分管
理が適正であること。即ち、イオン交換膜が乾燥する
と、そのイオン伝導性が著しく低下し、電池の内部抵抗
が増大して電池性能が低下する。また、アノード、カソ
ードの水分状態について見ると、イオン交換膜中をアノ
ードからカソードに向かってＨ+ イオンが水分子を同伴
する為、アノード側の水分が欠乏して乾燥しやすくＨ+
イオンの移動を低下させる。一方、カソード側では電極
反応により生成される水が過剰になると、反応ガスの流
入を妨げスムーズな電極反応を阻害する。この為、アノ
ード側では加湿を行い、カソード側では除湿を行って水
分を適正に維持することが必要である。即ち、イオン交
換膜、アノード、及びカソードの水分管理を適正に行う
ことより、電池性能を向上させることができる。このこ
とから水分管理対策の１つとして、イオン交換膜に縒糸
状の繊維を挟んでサンドイッチ構造にすることにより、
繊維を介してイオン交換膜を加湿する方法が提案されて
いる。また別の対策として、アノード側の反応ガスを水
蒸気で加湿することにより間接的にイオン交換膜を加湿
する方法が提案されている。There are various types of fuel cells, such as phosphoric acid type, alkaline aqueous solution type, molten carbonate type, solid electrolyte type, polymer solid electrolyte type, etc., but the polymer solid electrolyte type fuel cell of the present invention uses other fuels. It is more compact than a battery and can draw high current density, so it is attracting attention as a power source for electric vehicles and spacecraft. The cell performance of this polymer electrolyte fuel cell is largely controlled by the following factors. (1) The ion exchange membrane has good ionic conductivity. That is,
The smaller the specific resistance of the ion exchange membrane itself, the better the ionic conductivity and the higher current density can be obtained. From this, as a method for improving the ion conductivity of the ion exchange membrane,
Hydrocarbon-based ion exchange resin, which is the membrane material of the ion exchange membrane,
Alternatively, it has been proposed to increase the concentration of ion exchange groups in a polymer solid electrolyte such as a fluorinated resin such as Nafion (trade name: perfluorocarbon sulfonic acid developed by DuPont, USA). Alternatively, attempts have been made to improve the ionic conductivity of the ion exchange membrane by machining the membrane. (2) Water management of the ion exchange membrane, anode, and cathode is appropriate. That is, when the ion exchange membrane is dried, its ion conductivity is remarkably lowered, the internal resistance of the battery is increased, and the battery performance is lowered. The anode, regarding the cathode moisture conditions, since H + ions entrained water molecules toward the cathode of the ion exchange membrane from the anode, easily water on the anode side is dry deficient H +
Reduces ion migration. On the other hand, on the cathode side, when the water produced by the electrode reaction becomes excessive, the reaction gas is prevented from flowing in and the smooth electrode reaction is hindered. Therefore, it is necessary to perform humidification on the anode side and dehumidify on the cathode side to appropriately maintain the water content. That is, the battery performance can be improved by appropriately managing the water content of the ion exchange membrane, the anode, and the cathode. From this, as one of the water management measures, by sandwiching the filament-shaped fibers in the ion exchange membrane to form a sandwich structure,
A method of humidifying an ion exchange membrane through fibers has been proposed. As another measure, there has been proposed a method of indirectly humidifying the ion exchange membrane by humidifying the reaction gas on the anode side with steam.
【０００４】[0004]
【発明が解決しようとする課題】しかしながら、高分子
固体電解質のイオン交換基の濃度を増すと、炭化水素系
イオン交換樹脂は高分子の特徴である柔らかさが失わ
れ、イオン交換膜とアノード又はイオン交換膜とカソー
ドの接合が困難となり、燃料電池の製作が困難になると
いう問題がある。また、ナフィオン等のフッ素化樹脂の
場合は、膜が流動化してしまう為、多くのイオン交換基
の導入が技術的に困難であるという問題がある。However, when the concentration of ion-exchange groups in the polymer solid electrolyte is increased, the hydrocarbon-type ion-exchange resin loses the softness characteristic of the polymer, and the ion-exchange membrane and the anode or There is a problem that it becomes difficult to join the ion exchange membrane and the cathode, which makes it difficult to manufacture a fuel cell. Further, in the case of a fluorinated resin such as Nafion, since the membrane is fluidized, there is a problem that it is technically difficult to introduce many ion exchange groups.
【０００５】また、イオン交換膜の膜厚を薄くすると膜
自体の機械的強度が小さくなり、イオン交換膜が損傷し
やすいという問題がある。従って、現在、用い得るイオ
ン交換膜のイオン伝導性は満足すべきものではなく、イ
オン伝導性の良いイオン交換膜が要望されている。一
方、水分管理対策において、縒糸状の繊維をサンドイッ
チした構造にする方法は、イオン交換膜への加湿はでき
るものの、繊維を挟んでサンドイッチにする分だけ膜厚
が厚くなりイオン伝導性の低下を招く為、根本的な解決
にはなりにくい。また、反応ガスを水蒸気で加湿する方
法は、水蒸気分だけ反応ガスが希釈される為、反応ガス
の分圧低下を招くと共に、電極触媒層中の反応ガスの拡
散も阻害される為、電池性能が低下する要因になる。更
には、変動する負荷に追従して加湿する水蒸気の量を変
動させることが難しい為、水分を充分供給できずに膜が
乾燥したり、逆に触媒層を濡らし過ぎたりして、電池性
能を低下させるという問題がある。Further, if the thickness of the ion exchange membrane is made thin, the mechanical strength of the membrane itself becomes small, and there is a problem that the ion exchange membrane is easily damaged. Therefore, the ion exchange membranes that can be used at present are not satisfactory in ion conductivity, and there is a demand for ion exchange membranes having good ion conductivity. On the other hand, as a moisture management measure, the method in which the filament-shaped fibers are sandwiched allows the ion exchange membrane to be humidified, but the sandwiching of the fibers causes the film thickness to increase and the ion conductivity to decrease. Because it invites, it is hard to be a fundamental solution. In addition, the method of humidifying the reaction gas with water vapor dilutes the reaction gas by the water vapor content, so that the partial pressure of the reaction gas is lowered and the diffusion of the reaction gas in the electrode catalyst layer is hindered. Will be a factor to decrease. Furthermore, since it is difficult to change the amount of steam to be humidified by following a changing load, it is not possible to supply sufficient water, the membrane may dry, or conversely, the catalyst layer may be excessively wetted, resulting in poor battery performance. There is a problem of lowering it.
【０００６】本発明はこのような事情に鑑みてなされた
もので、イオン交換膜の比抵抗を小さくしてイオン伝導
性を改良することができると共に、無加湿運転が可能な
水分管理のできる高分子固体電解質型燃料電池を提供す
ることを目的とする。The present invention has been made in view of the above circumstances, and it is possible to improve the ionic conductivity by reducing the specific resistance of the ion exchange membrane, and at the same time, it is possible to manage moisture without humidification. An object is to provide a molecular solid oxide fuel cell.
【０００７】[0007]
【課題を解決する為の手段】本発明を概説すれば、本発
明は高分子固体電解質型燃料電池の電池性能を改良する
発明であって、カソード用集電体、カソード用触媒層、
イオン交換膜、アノード用触媒層、及びアノード用集電
体が積層された高分子固体電解質型燃料電池に於いて、
前記イオン交換膜、カソード用触媒層、及びアノード用
触媒層のうち少なくともその１つに微細粒子のシリカ及
び／又は繊維状のシリカファイバーが含有されているこ
とを特徴とする。Means for Solving the Problems The present invention will be described in brief. The present invention is an invention for improving the cell performance of a polymer electrolyte fuel cell, comprising a cathode current collector, a cathode catalyst layer,
In a polymer electrolyte fuel cell in which an ion exchange membrane, an anode catalyst layer, and an anode current collector are laminated,
At least one of the ion exchange membrane, the cathode catalyst layer, and the anode catalyst layer contains fine particles of silica and / or fibrous silica fibers.
【０００８】本発明者らは表１に示すように、シリカ及
び／又はシリカファイバーが含有された高分子固体電解
質（ナフィオンを使用）は比抵抗が小さくなりイオン伝
導性が改良されると共に含水率を高めることを見いだし
た。そして、これに基づいてイオン交換膜、カソード触
媒層、及びアノード触媒層のうち、少なくともその１つ
に微細粒子のシリカ及び／又は繊維状のシリカファイバ
ーが含有されていることにより、高分子固体電解質型燃
料電池の電池性能を向上させたものである。 表１ 高分子固体電解質の含水率及び比抵抗 シリカ含有率（％）含水率（％）比抵抗（Ωｃｍ）８０°Ｃ ０．００ ２．５ １０．５ ０．０１ ２０．０ １０．０ ０．１０ ２８．０ ７．４ １．００ ３１．０ ５．５ ３．００ − ５．４ １０．００ ３４．０ ６．０ ２０．００ − ６．８ ３０．００ − ７．５ ５０．００ − ９．８ （備考）表１では微細粒子のシリカを用いたが繊維状の
シリカファイバーでも同様の結果が得られた。As shown in Table 1, the present inventors have found that the solid polymer electrolyte (using Nafion) containing silica and / or silica fiber has a small specific resistance, improved ionic conductivity and water content. Found to raise. Then, based on this, at least one of the ion exchange membrane, the cathode catalyst layer, and the anode catalyst layer contains fine particles of silica and / or fibrous silica fiber, so that the solid polymer electrolyte The cell performance of the fuel cell is improved. Table 1 Water content and specific resistance of solid polymer electrolyte Silica content (% ) Water content (% ) Specific resistance (Ωcm) 80 ° C 0.00 2.5 10.5 0.01 20.0 10.0 0 .10 28.0 7.4 1.00 31.0 5.5 3.0-5.4 10.00 34.0 6.0 20.00-6.8 30.00-7.5 50.00 -9.8 (Remarks) In Table 1, fine particles of silica were used, but similar results were obtained with fibrous silica fibers.
【０００９】即ち、本発明の高分子固体電解質型燃料電
池によれば、イオン交換膜には、微細粒子のシリカ及び
／又は繊維状のシリカファイバーが含有されている。こ
れにより、イオン交換膜自体の比抵抗を小さくすること
ができるので、イオン交換膜のイオン伝導性が改良され
電池性能を向上させることができる。そして、前記シリ
カ及び／又はシリカファイバーの含有によりイオン交換
膜自体のイオン伝導性が改良される理由は、膜を構成す
る高分子固体電解質のクラスター構造モデルにより説明
することができる。即ち、高分子固体電解質のイオン伝
導機構はイオン交換基同志が集まって４ｎｍ程度の空間
を形成し、この空間同志が１ｎｍ程度の連通管で接続さ
れている。そして、前記空間に水が存在することにより
イオンの移動が起こるとされている。一方、微粒子すな
わち高比表面積のシリカは高い吸湿性を示す。このこと
から、イオン交換膜にシリカ及び／又はシリカファイバ
ーが含有されることにより、前記空間における水の存在
率が高まり、イオン交換膜のイオン伝導性が改良される
ものと考えられる。That is, according to the polymer solid oxide fuel cell of the present invention, the ion exchange membrane contains fine particles of silica and / or fibrous silica fibers. As a result, the specific resistance of the ion exchange membrane itself can be reduced, so that the ion conductivity of the ion exchange membrane is improved and the battery performance can be improved. The reason why the ion conductivity of the ion exchange membrane itself is improved by containing the silica and / or silica fiber can be explained by the cluster structure model of the polymer solid electrolyte constituting the membrane. That is, in the ionic conduction mechanism of the solid polymer electrolyte, the ion exchange groups are gathered to form a space of about 4 nm, and the spaces are connected by a communication tube of about 1 nm. The existence of water in the space causes the movement of ions. On the other hand, fine particles, that is, silica having a high specific surface area, exhibits high hygroscopicity. From this, it is believed that the presence of silica and / or silica fibers in the ion exchange membrane increases the abundance of water in the space and improves the ion conductivity of the ion exchange membrane.
【００１０】また、シリカ及び／又はシリカファイバー
が含有されることにより、イオン交換膜全体が保持でき
る保水量を大きくすることができるので、イオン交換膜
の乾燥を防止することができる。更には、シリカファイ
バーが含有された場合には、イオン交換膜の機械的強度
を大きくすることができる。これにより、イオン交換膜
の膜厚を薄くしても膜の損傷が起きにくいので、膜厚を
薄くすることによりイオン伝導性を改良することができ
る。Further, by containing silica and / or silica fibers, the amount of water retention that can be held by the entire ion exchange membrane can be increased, so that the ion exchange membrane can be prevented from drying. Furthermore, when silica fibers are contained, the mechanical strength of the ion exchange membrane can be increased. As a result, even if the film thickness of the ion exchange film is made thin, damage to the film is unlikely to occur, so that the ion conductivity can be improved by making the film thickness thin.
【００１１】本発明において、含有される微細粒子のシ
リカは無定形の結晶構造を有し、平均一次粒度が０．１
μｍ以下、好ましくは０．０１μｍ以下が望ましい。ま
た、シリカファイバーは太さが５μｍ以下であることが
望ましい。なぜなら、平均一次粒度が０．１μｍ以上の
シリカ及び太さが５μｍ以上のシリカファイバーの場合
は、イオン交換膜の比抵抗を低下させる効果が小さく実
用的でない。また、含有量としては、高分子固体電解質
の重量に対して０．０１〜５０重量％であり、好ましく
は０．１〜２０重量％であることが望ましい。なぜな
ら、前記表１に示すように、高分子固体電解質に含有さ
れるシリカの含有率が０．０１重量％以下又は５０重量
％以上では、比抵抗の改良効果が認められなくなる。ま
た、シリカ及び／又はシリカファイバーをイオン交換膜
に含有させる場合は、シリカ及び／又はシリカファイバ
ー及びイオン交換樹脂を夫々メタノール、エタノール、
イソプロパノール、ブタノール等の親水性の溶剤に懸濁
又溶解させた状態で混合すると、イオン交換膜の比抵抗
が小さくなるので望ましい。この理由としては、親水性
の溶剤を用いることにより、含有されるシリカが高分子
固体電解質のイオン交換基（親水性）で形成される前記
クラスター構造に近接した状態で含有され易くなること
が推定される。In the present invention, the fine particles of silica contained have an amorphous crystal structure and an average primary particle size of 0.1.
It is desirable that the thickness be less than or equal to μm, preferably less than or equal to 0.01 μm. The silica fiber preferably has a thickness of 5 μm or less. This is because in the case of silica having an average primary particle size of 0.1 μm or more and silica fiber having a thickness of 5 μm or more, the effect of lowering the specific resistance of the ion exchange membrane is small and not practical. The content is 0.01 to 50% by weight, preferably 0.1 to 20% by weight, based on the weight of the solid polymer electrolyte. This is because, as shown in Table 1, when the content of silica contained in the polymer solid electrolyte is 0.01% by weight or less or 50% by weight or more, the effect of improving the specific resistance cannot be recognized. When silica and / or silica fiber is contained in the ion exchange membrane, the silica and / or silica fiber and the ion exchange resin are respectively methanol, ethanol,
Mixing in a state of being suspended or dissolved in a hydrophilic solvent such as isopropanol or butanol is desirable because the specific resistance of the ion exchange membrane becomes small. The reason for this is presumed that the use of a hydrophilic solvent makes it easier for the contained silica to be contained in a state close to the cluster structure formed by the ion exchange groups (hydrophilic) of the solid polymer electrolyte. To be done.
【００１２】また、イオン交換膜の膜材である高分子固
体電解質としては、種々の電気化学装置にイオン交換膜
として用いられるパーフルオロカーボンスルホン酸、ポ
リサルフォン、パーフルオロカルボン酸、スチレン─ビ
ニルベンゼンスルフォン酸のカチオン交換樹脂、またス
チレン−ブタジエン系アニオン交換樹脂等を用いること
ができる。特に、パーフルオロカーボンスルホン酸（ナ
フィオン）は、耐薬品性、耐熱性に優れており好適であ
る。Further, as the polymer solid electrolyte which is the membrane material of the ion exchange membrane, perfluorocarbon sulfonic acid, polysulfone, perfluorocarboxylic acid, styrene-vinylbenzene sulfonic acid used as an ion exchange membrane in various electrochemical devices. The above cation exchange resin, styrene-butadiene type anion exchange resin and the like can be used. In particular, perfluorocarbon sulfonic acid (Nafion) is preferable because it has excellent chemical resistance and heat resistance.
【００１３】次に、カソード触媒層、アノード触媒層に
おけるシリカ及び／又はシリカファイバーの含有につい
て説明する。本発明によれば、カソード触媒層にはシリ
カ及び／又はシリカファイバーが含有されている。これ
により、カソード触媒層での電極反応で生成される水が
ガス気相に揮散するの防止することができるので、電池
の作動の停止時又は低負荷時のようにカソードでの水の
生成量が少ない時には、電池系内に一定の水分を保持す
ることができる。また、高負荷時のようにカソードでの
水の生成量が多い時（アノードやイオン交換膜の乾燥が
発生し易い時）には、カソードの過剰水分がアノード側
に逆拡散して、イオン交換膜及びアノードの水源として
の役目を行うことができる。また、アノード触媒層にシ
リカ及び／又はシリカファイバーが含有されていること
により、アノードの乾燥を防止すると共に、カソード側
からアノード側への水分の逆拡散を助長する役目を行う
ことができる。Next, the content of silica and / or silica fiber in the cathode catalyst layer and the anode catalyst layer will be described. According to the present invention, the cathode catalyst layer contains silica and / or silica fibers. As a result, the water generated by the electrode reaction in the cathode catalyst layer can be prevented from volatilizing into the gas vapor phase, so the amount of water generated at the cathode can be reduced, such as when the battery is not operating or when the load is low. When the amount is small, a certain amount of water can be retained in the battery system. Also, when the amount of water produced at the cathode is large, such as when the load is high (when drying of the anode and ion exchange membrane is likely to occur), excess water in the cathode is diffused back to the anode side and ion exchange is performed. It can serve as a water source for the membrane and the anode. Further, by containing silica and / or silica fiber in the anode catalyst layer, it is possible to prevent the anode from drying and to promote the reverse diffusion of water from the cathode side to the anode side.
【００１４】また、カソード触媒層、アノード触媒層に
含有されるシリカ及び／又はシリカファイバーは、イオ
ン交換膜に含有されたものと同じである。また、触媒層
において電極反応を円滑に進行させる為には、触媒粒子
（又は炭素粒子表面に白金を還元法で析出させた触媒）
／高分子固体電解質を１／９〜５／５の重量比率になる
ようにすることが望ましい。ところで表１に示した如く
高分子固体電解質の重量に対してシリカが０．０１〜５
０重量％の範囲で含有されることが触媒層の比抵抗及び
含水率を改良できるので、触媒層に対して０．０００６
〜３１重量％に相当するシリカを含有させることが望ま
しい。また、高分子固体電解質はイオン交換膜に用いた
のと同じものを用いることが好ましい。また、シリカを
触媒層に含有させる場合は、イオン交換膜で記載したと
同様に、触媒粒子（又は炭素粒子表面に白金を還元法で
析出させた触媒）、高分子固体電解質、シリカ及び／又
はシリカファイバーを夫々メタノール、エタノール、イ
ソプロパノール、ブタノール等の親水性の溶剤に懸濁又
溶解させた状態で混合すると、触媒層の比抵抗が小さく
なるので望ましい。The silica and / or silica fibers contained in the cathode catalyst layer and the anode catalyst layer are the same as those contained in the ion exchange membrane. Further, in order to smoothly proceed the electrode reaction in the catalyst layer, catalyst particles (or a catalyst in which platinum is deposited on the surface of carbon particles by a reduction method)
It is desirable that the solid polymer electrolyte has a weight ratio of 1/9 to 5/5. By the way, as shown in Table 1, the silica content is 0.01 to 5 relative to the weight of the solid polymer electrolyte.
Since the content of 0% by weight can improve the specific resistance and the water content of the catalyst layer,
It is desirable to include silica corresponding to ˜31 wt%. Further, it is preferable to use the same solid polymer electrolyte as that used for the ion exchange membrane. When silica is contained in the catalyst layer, the catalyst particles (or the catalyst in which platinum is deposited on the surface of carbon particles by the reduction method), the polymer solid electrolyte, silica and / or silica are used as described in the ion exchange membrane. It is desirable to mix the silica fibers in a state of being suspended or dissolved in a hydrophilic solvent such as methanol, ethanol, isopropanol, butanol, etc., because the specific resistance of the catalyst layer becomes small.
【００１５】以上説明したように、本発明の高分子固体
電解質型燃料電池では、イオン交換膜、カソード触媒
層、アノード触媒層のうち、その１つにシリカ及び／又
はシリカファイバーが含有される場合にも、夫々の効果
により電池性能を高めることができるが、少なくとも、
イオン交換膜には含有されていることが望ましい。しか
し、本発明の高分子固体電解質型燃料電池の大きな特徴
は、イオン交換膜、カソード触媒層、アノード触媒層の
全てにシリカ及び／又はシリカファイバーが含有される
ことにより電池性能を顕著に向上させることができると
共に、無加湿で運転を行うことができることである。即
ち、このシリカ含有により、カソード触媒層での電極反
応により水が生成されると、カソード触媒層では生成水
の反応ガス中への揮散を防止し、また、カソード触媒層
の余剰水のイオン交換膜及びアノード触媒層側への逆拡
散を助ける。これにより、本発明の高分子固体電解質燃
料電池は、電池系内の水分がクローズドシステムで移
動、逆拡散が行われるので、電池系外からの加湿を必要
とせずに運転することができる。As described above, in the solid polymer electrolyte fuel cell of the present invention, when one of the ion exchange membrane, the cathode catalyst layer and the anode catalyst layer contains silica and / or silica fiber. Also, each effect can improve the battery performance, but at least,
It is desirable that it is contained in the ion exchange membrane. However, the major feature of the solid polymer electrolyte fuel cell of the present invention is that the ion exchange membrane, the cathode catalyst layer, and the anode catalyst layer all contain silica and / or silica fiber to significantly improve the cell performance. In addition to being able to operate, it is possible to operate without humidification. That is, when water is generated by the electrode reaction in the cathode catalyst layer due to the silica content, the generated water is prevented from volatilizing into the reaction gas in the cathode catalyst layer, and the excess water in the cathode catalyst layer is ion-exchanged. Helps back diffusion to the membrane and anode catalyst layer side. As a result, the polymer electrolyte fuel cell of the present invention can be operated without the need for humidification from outside the cell system, because the water in the cell system moves and back diffuses in the closed system.
【００１６】尚、イオン交換膜、カソード用触媒層、ア
ノード用触媒層に含有されるシリカ及び／又はシリカフ
ァイバーの各含有率は、電池系内の水分の移動、逆拡散
のバランスから上記した含有率の範囲内で変えることが
望ましい。例えば乾燥し易いアノード用触媒層側にシリ
カ及び／又はシリカファイバーを多く含有させ、水が生
成されるカソード用触媒層にシリカ及び／又はシリカフ
ァイバーを少なめに含有させることができる。この場
合、アノード触媒層とイオン交換膜の接合面の少なくと
も一面に塗布したシリカ及び／又はシリカファイバーを
ホットプレス等の加熱圧着処理等により表面層に埋め込
んだ構造にすることも可能である。同様に、アノード用
触媒層とアノード集電体の接合面、イオン交換膜とカソ
ード用触媒層の接合面、カソード用触媒層とカソード集
電多体の接合面においてもシリカ及び／又はシリカファ
イバーを埋め込んだ構造にすることが可能である。The respective contents of silica and / or silica fiber contained in the ion exchange membrane, the catalyst layer for the cathode and the catalyst layer for the anode are determined as described above from the balance of the movement of water in the battery system and the reverse diffusion. It is desirable to change within the range of rates. For example, a large amount of silica and / or silica fibers can be contained on the side of the anode catalyst layer that is easily dried, and a small amount of silica and / or silica fibers can be contained on the cathode catalyst layer where water is produced. In this case, it is also possible to have a structure in which silica and / or silica fiber applied to at least one of the joint surfaces of the anode catalyst layer and the ion exchange membrane is embedded in the surface layer by a heat compression treatment such as hot pressing. Similarly, silica and / or silica fibers are also used on the joint surface between the anode catalyst layer and the anode current collector, the joint surface between the ion exchange membrane and the cathode catalyst layer, and the joint surface between the cathode catalyst layer and the cathode current collector. It is possible to have an embedded structure.
【００１７】以上の如く本発明の高分子固体電解質型燃
料電池によれば、イオン交換膜自体のイオン伝導性を改
良することができると共に、高分子固体電解質燃料電池
の無加湿運転を可能にすることができる。As described above, according to the solid polymer electrolyte fuel cell of the present invention, the ion conductivity of the ion exchange membrane itself can be improved and the solid polymer electrolyte fuel cell can be operated without humidification. be able to.
【００１８】[0018]
【作用】本発明の高分子固体電解質型燃料電池を構成す
るイオン交換膜、カソード触媒層、アノード触媒層に夫
々シリカ及び／又はシリカファイバーが含有されている
ので、電池のイオン伝導性が改良され、電池性能を向上
させることができる。また、含水率が高くなることによ
り、カソード用触媒層で生成された水分はアノード用触
媒層側に拡散され、イオン交換膜及びアノード用触媒層
に水分を供給する。これにより、電池内の水分がクロー
ズドシステムで移動、拡散するので、無加湿運転を行う
ことができる。Since the ion exchange membrane, cathode catalyst layer and anode catalyst layer constituting the polymer electrolyte fuel cell of the present invention contain silica and / or silica fiber, the ionic conductivity of the cell is improved. The battery performance can be improved. In addition, since the water content is increased, the water generated in the cathode catalyst layer is diffused to the anode catalyst layer side, and the water is supplied to the ion exchange membrane and the anode catalyst layer. As a result, the moisture in the battery moves and diffuses in the closed system, so that non-humidified operation can be performed.
【００１９】[0019]
【実施例１】次に、本発明に係わる高分子固体電解質型
燃料電池の好ましい実施例を記載するが、本実施例は本
発明を限定するものではない。本発明の高分子固体電解
質型燃料電池に用いたイオン交換膜は次の製法によって
作った。EXAMPLE 1 Next, a preferred example of the polymer solid oxide fuel cell according to the present invention will be described, but this example does not limit the present invention. The ion exchange membrane used in the solid polymer electrolyte fuel cell of the present invention was produced by the following production method.
【００２０】先ず、ナフィオンの５重量％イソプロパノ
ール溶液（アルドリッチ社製）と、前記ナフィオン重量
に対して５重量％相当のシリカ（商品名…アエロジル３
８０、日本アエロジル社製、平均一次粒度０．００７μ
ｍ）のイソプロピルアルコール分散液（濃度…５ｇ／
ｌ）とを混合して超音波ホモジナイザーで良く攪拌し
た。次に、この溶液を膜成型容器に流し込み、６０°Ｃ
で減圧乾燥してイソプロパノールを除去して成膜し、シ
リカ含有率５重量％及び膜厚０．１ｍｍのイオン交換膜
を作成した。尚、押出し成型又はスクリーン印刷による
成膜も可能である。First, a 5% by weight solution of Nafion in isopropanol (manufactured by Aldrich) and 5% by weight of silica (commercial name ... Aerosil 3) based on the weight of Nafion.
80, manufactured by Nippon Aerosil Co., Ltd., average primary particle size 0.007μ
m) isopropyl alcohol dispersion (concentration: 5 g /
1) and were mixed well with an ultrasonic homogenizer. Next, this solution is poured into a membrane forming container, and the temperature is 60 ° C.
Was dried under reduced pressure to remove isopropanol to form a film, thereby forming an ion exchange membrane having a silica content of 5% by weight and a film thickness of 0.1 mm. Film formation by extrusion molding or screen printing is also possible.
【００２１】また、本発明の高分子固体電解質型燃料電
池に用いたカソード触媒層、アノード触媒層は次の製法
で作った。先ず、炭素粒子の表面に白金を還元法で析出
させた触媒と、ナフィオンと、シリカとが１：１：０．
０５の重量比率になる各エタノール溶液を混合して超音
波ホモジナイザーで良く攪拌した。次に、この液を６０
°Ｃで減圧乾燥してエタノールを除去した後、乾燥物を
破砕し、濾過転写法で集電極のカーボンペーパに転写
し、１３０°Ｃ、５ｋｇ／ｃｍ2 で３秒間ホットプレス
して薄板状に成形した。使用したシリカは前記イオン交
換膜で使用したものと同じである。この時の触媒層のシ
リカ含有率は、触媒層の重量に対して２．４重量％であ
り、カソード触媒層、アノード触媒層ともに同じ含有率
とした。The cathode catalyst layer and the anode catalyst layer used in the polymer electrolyte fuel cell of the present invention were prepared by the following manufacturing method. First, a catalyst in which platinum is deposited on the surface of carbon particles by a reduction method, Nafion, and silica are mixed in a ratio of 1: 1: 0.
Each ethanol solution having a weight ratio of 05 was mixed and well stirred with an ultrasonic homogenizer. Next, add 60
After drying under reduced pressure at ° C to remove ethanol, the dried material is crushed, transferred to carbon paper of the collecting electrode by filtration transfer method, and hot pressed at 130 ° C and 5 kg / cm 2 for 3 seconds to form a thin plate. Molded. The silica used is the same as that used for the ion exchange membrane. The silica content of the catalyst layer at this time was 2.4% by weight based on the weight of the catalyst layer, and the same content was used for both the cathode catalyst layer and the anode catalyst layer.
【００２２】そして、上記の如く作成した２枚の触媒電
極間に上記の如く作成したイオン交換膜を挟み、図１及
び図２に示す高分子固体電解質燃料電池を組み立てた。
図１及び図２において、１はイオン交換膜、２はカソー
ド触媒層、３はアノード触媒層、４は酸素の供給通路５
を有するカソード集電体、６は水素の供給通路７を有す
るアノード集電体、８はシール材を示している。Then, the ion exchange membrane prepared as described above was sandwiched between the two catalyst electrodes prepared as described above, and the polymer electrolyte fuel cell shown in FIGS. 1 and 2 was assembled.
1 and 2, 1 is an ion exchange membrane, 2 is a cathode catalyst layer, 3 is an anode catalyst layer, 4 is an oxygen supply passage 5.
Is a cathode collector, 6 is an anode collector having a hydrogen supply passage 7, and 8 is a sealant.
【００２３】また、比較例として、シリカを含有しない
以外は、上記と同様にイオン交換膜、カソード触媒層、
及びアノード触媒層を作製して、図２と同様に高分子固
体電解質燃料電池を組み立てた。そして、本発明の高分
子固体電解質燃料電池と従来の高分子固体電解質燃料電
池との電池性能の評価方法として、以下に示す比較テス
トを実施した。 （１）本発明の高分子固体電解質型燃料電池は無加湿で
運転して比抵抗を測定した。一方、比較例として作成し
た高分子固体電解質型燃料電池は、水素ガスに加湿した
場合及び無加湿の場合について比抵抗を測定した。電池
の作動条件は以下の通りであり、比較結果を図３に示
す。In addition, as a comparative example, an ion exchange membrane, a cathode catalyst layer, and
Then, an anode catalyst layer was prepared, and a polymer electrolyte fuel cell was assembled in the same manner as in FIG. Then, as a method of evaluating the cell performance of the polymer solid electrolyte fuel cell of the present invention and the conventional polymer solid electrolyte fuel cell, the following comparative tests were carried out. (1) The solid polymer electrolyte fuel cell of the present invention was operated without humidification to measure the specific resistance. On the other hand, in the polymer electrolyte fuel cell prepared as a comparative example, the specific resistance was measured when humidified with hydrogen gas and when not humidified. The operating conditions of the battery are as follows, and the comparison result is shown in FIG.
【００２４】 反応ガス…水素（アノード側）、酸素（カソード側） セル運転温度…８０°Ｃ 加湿温度…８０°Ｃ（加湿した場合） セル運転圧力…大気圧 図３の結果から明らかなように、本発明の高分子固体電
解質型燃料電池は無加湿にも係わらず、その比抵抗は比
較例の高分子固体電解質型燃料電池の加湿した時の比抵
抗より小さくイオン伝導性が良いことを示した。また、
比較例の高分子固体電解質型燃料電池の無加湿した時の
比抵抗は、明らかに高い値を示した。Reaction gas: hydrogen (anode side), oxygen (cathode side) Cell operating temperature: 80 ° C Humidification temperature: 80 ° C (when humidified) Cell operating pressure: atmospheric pressure As is apparent from the results of FIG. Despite the fact that the solid polymer electrolyte fuel cell of the present invention is not humidified, its specific resistance is smaller than the specific resistance of the solid polymer electrolyte fuel cell of the comparative example when it is humid, and shows that the ion conductivity is good. It was Also,
The specific resistance of the solid polymer electrolyte fuel cell of Comparative Example when it was not humidified was obviously high.
【００２５】このことから、本発明の高分子固体電解質
型燃料電池は無加湿でも、比較例の高分子固体電解質型
燃料電池の加湿した時と比べ同等以上の電池性能を有す
ることが分かった。 （２）また、前記両者の高分子固体電解質型燃料電池と
もに無加湿の条件の下に、電流密度３５０ｍＡ／ｃｍ2
で運転した場合の電池寿命を比較した結果を図４示す。From this, it was found that the solid polymer electrolyte fuel cell of the present invention has a cell performance equivalent to or higher than that of the solid polymer electrolyte fuel cell of the comparative example when not humidified. (2) Further, both of the polymer electrolyte fuel cells have a current density of 350 mA / cm 2 under non-humidified conditions.
FIG. 4 shows the result of comparing the battery lifespan when the battery was operated at.
【００２６】図４の結果から明らかなように、本発明の
高分子固体電解質燃料電池は、比較例の高分子固体電解
質燃料電池と比べ明らかに電池性能が高いことが分か
る。また、本発明の高分子固体電解質燃料電池は、無加
湿運転にも係わらず５００時間後でも安定した電池性能
を維持していた。以上の結果から、本発明の高分子固体
電解質燃料電池は無加湿運転が可能なことを確認するこ
とができた。As is clear from the results shown in FIG. 4, the polymer solid electrolyte fuel cell of the present invention clearly has higher cell performance than the polymer solid electrolyte fuel cell of the comparative example. Further, the polymer electrolyte fuel cell of the present invention maintained stable cell performance even after 500 hours despite the non-humidified operation. From the above results, it could be confirmed that the polymer electrolyte fuel cell of the present invention can be operated without humidification.
【００２７】[0027]
【実施例２】前記ナフィオンの重量に対して太さ３μｍ
のシリカ短繊維を５重量％含有させたイオン交換膜を実
施例１と同様の成膜方法で成膜し、高分子固体電解質型
燃料電池を作った。尚、イオン交換膜以外は実施例１の
高分子固体電解質型燃料電池と同じ構成とした。そし
て、この高分子固体電解質型燃料電池について、無加湿
運転又は加湿運転での比抵抗を測定した。その結果、無
加湿運転での比抵抗は７Ωｃｍとなり、シリカ繊維を含
有させた場合も実施例１と同様の結果を得た。また、加
湿運転での比抵抗は５．５Ωｃｍとなり、更に小さな比
抵抗を得ることができた。Example 2 Thickness of 3 μm with respect to the weight of Nafion
An ion-exchange membrane containing 5% by weight of the silica short fiber of 5 was formed by the same film-forming method as in Example 1 to prepare a polymer electrolyte fuel cell. It should be noted that, except for the ion exchange membrane, the polymer solid oxide fuel cell of Example 1 had the same structure. Then, the specific resistance of the polymer solid oxide fuel cell in the non-humidified operation or the humidified operation was measured. As a result, the specific resistance in non-humidified operation was 7 Ωcm, and the same results as in Example 1 were obtained when silica fiber was contained. Further, the specific resistance in the humidifying operation was 5.5 Ωcm, and a further smaller specific resistance could be obtained.
【００２８】[0028]
【発明の効果】以上説明したように、本発明に係る高分
子固体電解質燃料電池によれば、イオン交換膜、カソー
ド用触媒層、及びアノード用触媒層のうち少なくともそ
の１つに微細粒子のシリカ及び／又は繊維状のシリカフ
ァイバーが含有されていることにより、良好な水分管理
ができるので、電池内抵抗を小さくでき、電池の高性能
化が図れる。As described above, according to the solid polymer electrolyte fuel cell of the present invention, at least one of the ion exchange membrane, the cathode catalyst layer, and the anode catalyst layer has fine particle silica. By containing and / or fibrous silica fiber, good water content management can be achieved, so that the internal resistance of the battery can be reduced and the battery performance can be improved.
【００２９】イオン交換膜、カソード用触媒層、及びア
ノード用触媒層の全てに微細粒子のシリカ及び／又は繊
維状のシリカファイバーが含有されることにより、無加
湿で運転を行うことができる。Since the ion-exchange membrane, the cathode catalyst layer and the anode catalyst layer all contain fine particles of silica and / or fibrous silica fibers, the operation can be performed without humidification.
【図１】本発明に係る高分子固体電解質型燃料電池の構
成を示す斜視図FIG. 1 is a perspective view showing the structure of a polymer electrolyte fuel cell according to the present invention.
【図２】シール構造を持つ単セルに組立てた本発明に係
る高分子固体電解質型燃料電池の断面図FIG. 2 is a sectional view of a polymer electrolyte fuel cell according to the present invention assembled into a single cell having a seal structure.
【図３】本発明の実施例における本発明の高分子固体電
解質型燃料電池と比較例の高分子固体電解質型燃料電池
との比抵抗を比較したグラフFIG. 3 is a graph comparing the specific resistances of the solid polymer electrolyte fuel cell of the present invention and the solid polymer electrolyte fuel cell of the comparative example in the examples of the present invention.
【図４】本発明の実施例における本発明の高分子固体電
解質型燃料電池と比較例の高分子固体電解質型燃料電池
の電池寿命を比較したグラフFIG. 4 is a graph comparing the cell life of the polymer solid oxide fuel cell of the present invention in the example of the present invention and the polymer solid electrolyte fuel cell of the comparative example.
１…イオン交換膜 ２…カソード触媒層 ３…アノード触媒層 ４…カソード集電体 ５…酸素供給通路 ６…アノード集電体 ７…水素供給通路 ８…シール材 DESCRIPTION OF SYMBOLS 1 ... Ion exchange membrane 2 ... Cathode catalyst layer 3 ... Anode catalyst layer 4 ... Cathode collector 5 ... Oxygen supply passage 6 ... Anode collector 7 ... Hydrogen supply passage 8 ... Sealing material
───────────────────────────────────────────────────── フロントページの続き (71)出願人 000218166 渡辺 政廣 山梨県甲府市和田町2421番地の８ (72)発明者 ポール・ストンハルト アメリカ合衆国 06443 コネチカット州 マジソン コテッジ・ロード 17、ピ ー・オー・ ボックス 1220 (72)発明者 渡辺 政廣 山梨県甲府市和田町2412番地８ ─────────────────────────────────────────────────── ─── Continuation of the front page (71) Applicant 000218166 Masahiro Watanabe 8241, 2421 Wada-cho, Kofu-shi, Yamanashi Prefecture (72) Inventor Paul Stonhardt United States 06443 Madison Cottage Road, Connecticut 17, 17 P-O Box 1220 (72) Inventor Masahiro Watanabe 2412 Wadacho, Kofu City, Yamanashi Prefecture 8
Claims (4)
イオン交換膜、アノード用触媒層、及びアノード用集電
体が積層され、前記カソード用触媒層に酸化性ガスが、
前記アノード用触媒層に燃料ガスが供給される固体電解
質燃料電池に於いて、 前記イオン交換膜、カソード用触媒層、及びアノード用
触媒層のうち少なくともその１つに微細粒子のシリカ及
び／又は繊維状のシリカファイバーが含有されているこ
とを特徴とする高分子固体電解質型燃料電池。1. A cathode current collector, a cathode catalyst layer,
An ion exchange membrane, an anode catalyst layer, and an anode current collector are laminated, and an oxidizing gas is added to the cathode catalyst layer,
In a solid electrolyte fuel cell in which fuel gas is supplied to the anode catalyst layer, fine particles of silica and / or fibers are present in at least one of the ion exchange membrane, the cathode catalyst layer, and the anode catalyst layer. A solid polymer electrolyte fuel cell characterized by containing silica fibers in the form of particles.
以下であると共に、前記シリカファイバーは太さが６μ
ｍ以下であることを特徴とする請求項１の高分子固体電
解質型燃料電池。2. The silica has an average primary particle size of 0.1 μm.
In addition to the following, the silica fiber has a thickness of 6 μm.
The solid polymer electrolyte fuel cell according to claim 1, wherein the solid polymer electrolyte fuel cell has a thickness of m or less.
シリカファイバーの含有率はイオン交換膜の重量に対し
て０．０１〜５０重量％であることを特徴とする請求項
１の高分子固体電解質型燃料電池。3. The polymer solid according to claim 1, wherein the content of silica and / or silica fiber in the ion exchange membrane is 0.01 to 50% by weight based on the weight of the ion exchange membrane. Electrolyte fuel cell.
触媒層のシリカ及び／又はシリカファイバーの含有率は
触媒槽の重量に対して０．０００６〜３１重量％である
ことを特徴とする請求項１の高分子固体電解質型燃料電
池。4. The content of silica and / or silica fiber in the cathode catalyst layer and the anode catalyst layer is 0.0006 to 31% by weight based on the weight of the catalyst tank. 1. The solid polymer electrolyte fuel cell of item 1.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP25680592A JP3498321B2 (en) | 1992-09-25 | 1992-09-25 | Polymer solid oxide fuel cell |
| US08/126,337 US5523181A (en) | 1992-09-25 | 1993-09-24 | Polymer solid-electrolyte composition and electrochemical cell using the composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP25680592A JP3498321B2 (en) | 1992-09-25 | 1992-09-25 | Polymer solid oxide fuel cell |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH06111827A true JPH06111827A (en) | 1994-04-22 |
| JP3498321B2 JP3498321B2 (en) | 2004-02-16 |
Family
ID=17297687
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP25680592A Expired - Fee Related JP3498321B2 (en) | 1992-09-25 | 1992-09-25 | Polymer solid oxide fuel cell |
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