JPH06203840A - Solid polyelectrolyte fuel cell - Google Patents
Solid polyelectrolyte fuel cellInfo
- Publication number
- JPH06203840A JPH06203840A JP5001674A JP167493A JPH06203840A JP H06203840 A JPH06203840 A JP H06203840A JP 5001674 A JP5001674 A JP 5001674A JP 167493 A JP167493 A JP 167493A JP H06203840 A JPH06203840 A JP H06203840A
- Authority
- JP
- Japan
- Prior art keywords
- catalyst layer
- fuel cell
- conductive material
- group
- electrode
- 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.)
- Withdrawn
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
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、固体高分子電解質型燃
料電池（ＰＥＦＣ）に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a solid polymer electrolyte fuel cell (PEFC).
【０００２】[0002]
【従来の技術】低公害性と高効率という特徴により、燃
料電池が注目されている。燃料電池は水素やメタノール
等の燃料を酸素や空気を用いて電気化学的に酸化し、燃
料の化学エネルギーを電気エネルギーとして取り出すも
のである。用いる電解質の種類によりリン酸型、溶融炭
酸塩型、固体酸化物型等に分類される。この中で、低温
作動性と高出力密度という特徴から、近年特にＰＥＦＣ
が注目されてきた。2. Description of the Related Art Fuel cells have been attracting attention due to their characteristics of low pollution and high efficiency. A fuel cell electrochemically oxidizes a fuel such as hydrogen or methanol using oxygen or air to take out the chemical energy of the fuel as electric energy. Depending on the type of electrolyte used, it is classified into phosphoric acid type, molten carbonate type, solid oxide type and the like. Among these, PEFC has been particularly popular in recent years due to its characteristics of low temperature operation and high power density.
Has been attracting attention.
【０００３】図２にてＰＥＦＣの基本構造について説明
する。同図に示すように電池本体は固体高分子電解質膜
の両側にガス拡散電極が接合されることにより構成され
ている。ガス拡散電極は少なくとも触媒が担持されてい
る層（触媒層）を有しており、従って電池反応は膜と触
媒層の接合界面にて生じる。例えば電極２に水素ガスを
流すと膜の接合界面で２Ｈ2 →４Ｈ+ ＋４ｅ- の反応が
生じる。Ｈ+ は固体高分子電解質膜３を通って対極１
に、またｅ- は電極と電極をむすんだ回路を通じて対極
１に移動する。この電極１に酸素ガスを流すとＯ2 ＋４
Ｈ+ ＋４ｅ- →２Ｈ2 Ｏの反応が膜と電極内触媒の界面
で生じ、水が生成すると同時に電気エネルギーが得られ
る。The basic structure of PEFC will be described with reference to FIG. As shown in the figure, the battery main body is constructed by joining gas diffusion electrodes to both sides of the solid polymer electrolyte membrane. The gas diffusion electrode has at least a layer on which a catalyst is supported (catalyst layer), and therefore a cell reaction occurs at the bonding interface between the membrane and the catalyst layer. For example, when hydrogen gas is supplied to the electrode 2, a reaction of 2H 2 → 4H + + 4e − occurs at the bonding interface of the film. H + passes through the solid polymer electrolyte membrane 3 and the counter electrode 1
In addition, e − moves to the counter electrode 1 through the electrode and the circuit including the electrode. When oxygen gas is passed through this electrode 1, O 2 +4
The reaction of H + + 4e − → 2H 2 O occurs at the interface between the membrane and the catalyst in the electrode, and water is generated, and at the same time, electric energy is obtained.
【０００４】界面で電極反応が生じることから、プロト
ン導伝材を溶媒に溶かして電極表面に塗布してからイオ
ン交換膜と接合したり、電極構成カーボンにあらかじめ
混合した後に電極作成（特開昭６１−６７７８７号公
報、同６１−６７７８８号公報）したりの工夫がされて
いる。これらの電極と電解質膜の接合は加熱しながら圧
をかけるホットプレス法が用いられている。しかし、接
合のためのホットプレス操作により、ガス拡散電極内の
触媒担持部分（触媒層）の細孔がつぶされ、結果として
充分な反応ガスの供給ができなくなり出力の低下を生じ
るという問題がある。Since an electrode reaction occurs at the interface, the proton conductive material is dissolved in a solvent and applied on the surface of the electrode and then bonded to the ion exchange membrane, or the electrode constituent carbon is preliminarily mixed to prepare the electrode (Japanese Patent Laid-Open Publication No. Sho. 61-67787 and 61-67788). A hot press method in which pressure is applied while heating is used to bond these electrodes and the electrolyte membrane. However, there is a problem that the pores of the catalyst supporting portion (catalyst layer) in the gas diffusion electrode are crushed by the hot pressing operation for joining, and as a result, sufficient reaction gas cannot be supplied and the output is reduced. .
【０００５】[0005]
【発明が解決しようとする課題】本発明は、反応ガスを
反応点に充分供給せしめ、出力性能を大きく向上させる
ことを目的とする。SUMMARY OF THE INVENTION It is an object of the present invention to sufficiently supply a reaction gas to a reaction point and greatly improve output performance.
【０００６】[0006]
【課題を解決するための手段】本発明者らは、イオン交
換膜と触媒層を含むガス拡散電極との接合及び接合体の
物性と出力特性の関係を鋭意検討した結果、接合後の触
媒層内の細孔の大きさが出力に関係することを見い出
し、本発明に至った。すなわち、本発明は電解質である
イオン交換膜と、少なくとも触媒層を有するガス拡散電
極とを接合した燃料電池において、上記触媒層がプロト
ン導伝材を含有し、かつ、接合後の上記触媒層内の空孔
率が６５から９０容量％であることを特徴とするもので
ある。Means for Solving the Problems The inventors of the present invention have made earnest studies on the bonding between the ion exchange membrane and the gas diffusion electrode including the catalyst layer and the relationship between the physical properties and the output characteristics of the bonded body. The inventors have found that the size of the inner pores is related to the output, and completed the present invention. That is, the present invention is a fuel cell in which an ion exchange membrane which is an electrolyte and a gas diffusion electrode having at least a catalyst layer are joined, and the catalyst layer contains a proton conductive material, and the inside of the catalyst layer after joining Is characterized by having a porosity of 65 to 90% by volume.
【０００７】本発明において電解質として用いるイオン
交換膜は含フッ素高分子を骨格とし、スルホン酸基、カ
ルボキシル基、リン酸基、ホスホン酸基から選ばれる少
なくとも１種を有するものである。例えば、テトラフル
オロエチレン、トリフルオロモノクロロエチレン、トリ
フルオロエチレン、フッ化ビニリデン、１、１−ジフル
オロ−２，２−ジクロロエチエン、１，１−ジフルオロ
−２−クロロエチレン、ヘキサフルオロプロピレン、
１，１，１，３，３−ペンタフルオロプロピレン、オク
タフルオロイソブチレン、エチレン、塩化ビニルおよび
アルキルビニルエステルの第１群のモノマー、並びに、
下記一般式（１）で表される第２群のモノマーで表され
るものから、第１群モノマーの１種以上を必須として選
ばれた２種以上、通常は２ないし３種類の共重合体であ
る。 Ｙ−（ＣＦ2 ）a −（ＣＦＲf ）b −（ＣＦＲf ′）c −Ｏ− −｛ＣＦ（ＣＦ2 Ｘ）−ＣＦ2 −Ｏ｝n −ＣＦ＝ＣＦ2 ……（１） （式中、Ｙは−ＳＯ3 Ｈ，−ＣＯＯＨ，−ＰＯ3 Ｈ2 ま
たは−ＰＯ3 Ｈである。ａは０〜６の整数であり、ｂは
０〜６の整数であり、ｃは０または１である。但しａ＋
ｂ＋ｃは０に等しくはならない。Ｘはｎ≧１のときＣ
ｌ，Ｂｒ，Ｆまたはそれらの混合物である。ｎは０〜６
の整数であり、Ｒf およびＲf ′は独立にＦ，Ｃｌ，１
〜１０個の炭素原子を有するペルフルオロアルキル基お
よび１〜１０個の炭素原子を有するフルオロクロロアル
キル基からなる群から選択されるものである。）プロト
ン導伝材はプロトンを導伝する材料であれば良く、好ま
しくはスルホン酸基、カルボキシル基、リン酸基、およ
びホスホン酸基から選ばれた少なくとも１種を含有する
含フッ素炭化水素である。The ion exchange membrane used as an electrolyte in the present invention has a fluorinated polymer as a skeleton and has at least one selected from a sulfonic acid group, a carboxyl group, a phosphoric acid group and a phosphonic acid group. For example, tetrafluoroethylene, trifluoromonochloroethylene, trifluoroethylene, vinylidene fluoride, 1,1-difluoro-2,2-dichloroethene, 1,1-difluoro-2-chloroethylene, hexafluoropropylene,
1,1,1,3,3-pentafluoropropylene, octafluoroisobutylene, ethylene, vinyl chloride and alkyl vinyl esters of the first group of monomers, and
Copolymers of two or more kinds, usually 2 to 3 kinds, selected from those represented by the second group of monomers represented by the following general formula (1), in which at least one kind of the first group of monomers is essential. Is. Y- (CF 2) a - ( CFR f) b - (CFR f ') c -O- - {CF (CF 2 X) -CF 2 -O} n -CF = CF 2 ...... (1) ( Formula In the formula, Y is —SO 3 H, —COOH, —PO 3 H 2 or —PO 3 H. a is an integer of 0 to 6, b is an integer of 0 to 6 and c is 0 or 1. Where a +
b + c does not equal 0. X is C when n ≧ 1
1, Br, F or a mixture thereof. n is 0 to 6
And R f and R f ′ are independently F, Cl, 1
It is selected from the group consisting of perfluoroalkyl groups having from 10 carbon atoms and fluorochloroalkyl groups having from 1 to 10 carbon atoms. ) The proton conducting material may be any material that conducts protons, and is preferably a fluorine-containing hydrocarbon containing at least one selected from a sulfonic acid group, a carboxyl group, a phosphoric acid group, and a phosphonic acid group. .
【０００８】例えば、前記第１群のモノマーと前記第２
群のモノマーから選ばれた、第２群モノマーを必須モノ
マーとする２種類あるいは３種類以上のモノマーの共重
合体；前記第２群のモノマーの１種類以上の重合体；前
記第２群のモノマーである、トリフルオロメタンスルホ
ン酸，フルオロエタン，スルホン酸，トリフルオロエタ
ンスルホン酸，テトラフルオロプロパンスルホン酸，パ
ーフルオロアルキル（Ｃ4 〜Ｃ12）スルホン酸，３−
〔フルオロアルキル（Ｃ6 〜Ｃ11）オキシン〕−１−ア
ルキル（Ｃ3 〜Ｃ4 ）スルホン酸，３−〔ω−フルオロ
アルカノイル（Ｃ 6 〜Ｃ8 ）−Ｎ−エチルアミノ〕−１
−プロパンスルホン酸などの一官能性含フッ素ハイドロ
カーボンスルホン酸類；ジフルオロメタンジスルホン
酸，テトラフルオロエタンジスルホン酸などの二官能性
含フッ素ハイドロカーボンスルホン酸類；トリフルオロ
メタンベンゼンスルホン酸などの含フッ素芳香族スルホ
ン酸誘導体；トリフルオロ酸類，フルオロアルキル（Ｃ
2 〜Ｃ20）カルボン酸，パーフルオロアルキル（Ｃ7 〜
Ｃ13）カルボン酸などの一官能性含フッ素ハイドロカー
ボンカルボン酸類；テトラフルオロエタンジカルボン酸
などの二官能性含フッ素ハイドロカーボンカルボン酸
類；ジフルオロメタンジカルボン酸などの含フッ素ハイ
ドロカーボンホスホン酸類；チオスルホン酸類；トリフ
ルオロメタンスルホンイミドなどのフルオロスルホンイ
ミド類；モノパーフルオロアルキル（Ｃ6 〜Ｃ16）リン
酸などであり、これらは単独、あるいは２種類以上の混
合で用いられる。For example, the first group of monomers and the second group of monomers
Group 2 monomers selected from the group of monomers are essential
Co-weight of two or more types of monomers
A polymer; one or more polymers of the second group of monomers;
The second group of monomers, trifluoromethanesulfone
Acid, fluoroethane, sulfonic acid, trifluoroethane
Sulfonic acid, tetrafluoropropane sulfonic acid,
-Fluoroalkyl (CFour~ C12) Sulfonic acid, 3-
[Fluoroalkyl (C6~ C11) Oxine] -1-a
Rukiru (C3~ CFour) Sulfonic acid, 3- [ω-fluoro
Alkanoyl (C 6~ C8) -N-Ethylamino] -1
-Monofunctional fluorine-containing hydro such as propanesulfonic acid
Carbon sulfonic acids; difluoromethane disulfone
Bifunctionality of acid, tetrafluoroethanedisulfonic acid, etc.
Fluorine-containing hydrocarbon sulfonic acids; trifluoro
Fluorine-containing aromatic sulfo such as methanebenzenesulfonic acid
Acid derivatives; trifluoro acids, fluoroalkyl (C
2~ C20) Carboxylic acid, perfluoroalkyl (C7~
C13) Monofunctional fluorine-containing hydrocar such as carboxylic acid
Boncarboxylic acids; tetrafluoroethanedicarboxylic acid
Bifunctional fluorine-containing hydrocarbon carboxylic acid such as
Kinds; Fluorine-containing high, such as difluoromethanedicarboxylic acid
Drocarbonphosphonic acids; Thiosulfonic acids; Trif
Fluorosulfones such as luoromethanesulfonimide
Mides; monoperfluoroalkyl (C6~ C16)Rin
Acids, etc., which can be used alone or as a mixture of two or more kinds.
Used in combination.
【０００９】重合体はモノマー２分子以上結合しておれ
ばよく、好ましくはその分子量が５０００以上である。
分子量が大きい方が触媒層の導電材への絡まりが良好と
なり耐久性の点でより好ましい。これらは、例えばメタ
ノール、エタノール、プロパノール、ブタノール等のア
ルコール類、Ｎ，Ｎ′−ジメチルアセトアミド、Ｎ，
Ｎ′−ジメチルホルムアミド、ジメチルスルホキシド、
スルホラン等の極性溶媒、テトラヒドロフラン等の環状
エーテル類、および上記溶媒群から選ばれた２種類以上
の混合物、さらには、上記溶媒群と水との混合物等の水
溶性媒体に溶解して用いることができる。It is sufficient that the polymer has two or more molecules of the monomer bonded thereto, and the molecular weight thereof is preferably 5,000 or more.
The larger the molecular weight, the better the entanglement of the catalyst layer with the conductive material, which is more preferable in terms of durability. These include alcohols such as methanol, ethanol, propanol, butanol, N, N'-dimethylacetamide, N,
N'-dimethylformamide, dimethyl sulfoxide,
It may be used by dissolving in a polar solvent such as sulfolane, cyclic ethers such as tetrahydrofuran, and a mixture of two or more kinds selected from the above solvent group, and further dissolved in an aqueous medium such as a mixture of the above solvent group and water. it can.
【００１０】本発明のガス拡散電極は、少なくとも触媒
金属の微粒子を担持した導電材を必須構成物とする多孔
性触媒層を有しており、必要に応じて撥水剤と結着剤を
含んでもよい。触媒金属としては、水素の酸化反応ある
いは酸素の還元反応に触媒作用を有するものであれば良
く、例えば、鉛、鉄、マンガン、コバルト、クロム、ガ
リウム、バナジウム、タングステン、ルテニウム、イリ
ジウム、パラジウム、ロジウム、又はそれらの合金から
選択することができる。触媒粒径は、１０Åから３００
Åが良く、好ましくは１５Åから１００Åである。触媒
粒径１０Å未満のものは現実的に作成が困難であり、一
方３００Åより大きいと触媒性能が低下する。The gas diffusion electrode of the present invention has at least a porous catalyst layer having an electrically conductive material carrying fine particles of catalytic metal as an essential component, and optionally contains a water repellent and a binder. But it's okay. The catalyst metal may be any one that has a catalytic action on the hydrogen oxidation reaction or the oxygen reduction reaction, and for example, lead, iron, manganese, cobalt, chromium, gallium, vanadium, tungsten, ruthenium, iridium, palladium, rhodium. , Or their alloys. Catalyst particle size is 10Å to 300
Å is good, preferably 15 Å to 100 Å. If the catalyst particle size is less than 10Å, it is practically difficult to prepare, while if it is larger than 300Å, the catalyst performance is deteriorated.
【００１１】導電材への触媒の担持は、粉末状カーボン
に担持しても良いし、触媒層成形後に担持しても良い。
触媒担持量は電極成形後において０．０１〜１０mg/cm2
であり、好ましくは０．１〜０．５mg/cm2である。触媒
が０．０１mg/cm2未満では性能が低下し、一方、１０mg
/cm2より大では触媒によるコストが大きい。触媒層を構
成する導電材は電子導伝性物質であればよく、例えば各
種金属やカーボン材料などがある。カーボン材料として
は、例えばファーネスブラック、チャンネルブラック、
アセチレンブラック等のカーボンブラック、活性炭、黒
鉛等があり、単独あるいは混合して使用できる。必要に
応じて用いる撥水剤は撥水性を有していれば良く、例え
ば、フッ素化カーボン等が好ましい。必要に応じて用い
る結着剤は結着性を有していれば良く、例えば、各種樹
脂などが用いられる。これらの中で一般に用いられるの
が撥水剤と結着剤を兼ねるテフロン系化合物であり、好
ましくは融点が４００℃以下の物が適しており、より好
ましくはポリテトラフルオロエチレン、テトラフルオロ
エチレン−パーフルオロアルキルビニルエーテル共重合
体、テトラフルオロエチレン−ヘキサフルオロプロピレ
ン共重合体などがある。The catalyst may be supported on the conductive material by powdery carbon or after forming the catalyst layer.
The amount of catalyst supported is 0.01 to 10 mg / cm 2 after forming the electrode.
And preferably 0.1 to 0.5 mg / cm 2 . If the catalyst is less than 0.01 mg / cm 2 , the performance will decrease, while 10 mg
If it is larger than / cm 2, the cost of the catalyst is large. The conductive material forming the catalyst layer may be an electron conductive material, and examples thereof include various metals and carbon materials. Examples of carbon materials include furnace black, channel black,
There are carbon black such as acetylene black, activated carbon, graphite and the like, which can be used alone or in combination. The water repellent that is used if necessary has water repellency, and for example, fluorinated carbon or the like is preferable. The binder used as necessary may have a binding property, and for example, various resins are used. Of these, a Teflon-based compound that also serves as a water repellent and a binder is generally used, preferably one having a melting point of 400 ° C. or less is suitable, and more preferably polytetrafluoroethylene or tetrafluoroethylene- Examples include perfluoroalkyl vinyl ether copolymers and tetrafluoroethylene-hexafluoropropylene copolymers.
【００１２】プロトン導伝材を電極原料粉末に溶液ある
いは粉末で混合した後触媒層として成形してもよいし、
電極成形後に電極の触媒を担持している側からプロトン
導伝材溶液を含浸してもよい。また、電極は触媒を担持
した導電材を含有する触媒層だけから成っていても良い
し、該触媒層と触媒を担持しない導電材層との積層でも
よい。さらに、この電極と導電材を用いたクロスとの複
合物として使用してもよい。The proton conductive material may be mixed with the electrode raw material powder as a solution or powder and then formed into a catalyst layer,
After forming the electrode, the proton conducting material solution may be impregnated from the side of the electrode supporting the catalyst. Further, the electrode may be composed only of a catalyst layer containing a catalyst-supporting conductive material, or may be a laminate of the catalyst layer and a catalyst-free conductive material layer. Further, it may be used as a composite of this electrode and a cloth using a conductive material.
【００１３】膜とガス拡散電極の接合は加温、加圧でき
る装置を用いて実施される。特定の装置はなく、一般的
には例えばホットプレス機、ロールプレス機等が用いら
れる。プレス温度は使用した電解質膜のガラス転移温度
以上であれば良く、好ましくは１２０℃から２５０℃で
ある。プレス圧力は使用するガス拡散電極（触媒層）の
固さに依存し、約５ｋｇ／ｃｍ2 から２００ｋｇ／ｃｍ
2 であり、好ましくは２０ｋｇ／ｃｍ2 から１００ｋｇ
／ｃｍ2 である。５ｋｇ／ｃｍ2 より小さい圧力では膜
と電極の接着が不充分になり、一方、２００ｋｇ／ｃｍ
2 以上では触媒層内空孔の減少が大きい。ホットプレス
時に電極の厚さより薄いスペーサーを入れると効果が大
きい。また、水の共存下で電解質膜を湿潤させた状態で
ホットプレスするのもよい。接合された触媒層の空孔率
は６５から９０容量％であり、より好ましくは７０から
８０容量％のものである。空孔率６５容量％より小さい
と原料ガスの供給が不充分となり、一方９０容量％より
大では触媒を担持した反応点の絶対量が少なくなって性
能の低下の原因となる。Bonding of the membrane and the gas diffusion electrode is carried out by using a device capable of heating and pressurizing. There is no specific device, and, for example, a hot press machine, a roll press machine or the like is generally used. The pressing temperature may be higher than the glass transition temperature of the used electrolyte membrane, and is preferably 120 ° C to 250 ° C. The pressing pressure depends on the hardness of the gas diffusion electrode (catalyst layer) used, and is about 5 kg / cm 2 to 200 kg / cm 2.
2 , preferably from 20 kg / cm 2 to 100 kg
/ Cm 2 . If the pressure is less than 5 kg / cm 2, the adhesion between the membrane and the electrode will be insufficient, while the pressure of 200 kg / cm
When it is 2 or more, the number of voids in the catalyst layer is greatly reduced. Inserting a spacer thinner than the thickness of the electrode during hot pressing has a great effect. Further, hot pressing may be performed while the electrolyte membrane is wet in the coexistence of water. The bonded catalyst layers have a porosity of 65 to 90% by volume, more preferably 70 to 80% by volume. If the porosity is less than 65% by volume, the supply of the raw material gas will be insufficient, while if it is more than 90% by volume, the absolute amount of the reaction points supporting the catalyst will be small, which will cause deterioration in performance.
【００１４】前述のように電気化学反応が生じるのは、
液体（水）、固体（電子、及びプロトン）、気体（水素
ガスあるいは酸素ガス）の三相界面であり、この中で気
体及び液体は、電極内の孔を通って反応点に移動あるい
は反応点から排出される。従って電極内の孔の量及び形
状が重要であり、特に、触媒が存在する層（触媒層）の
孔量が最も性能に影響を与える。ガス拡散電極の構成物
により、固さ（孔の保持力）が各々異なってくる。従っ
てその接合条件が同一であっても、得られる触媒層内孔
量は電極によって全く違う。燃料電池として使用する状
態での触媒層内孔量を制御したガス拡散電極を用いるこ
とは燃料電池の発電メカニズムに直結した発想であり、
性能向上に大きく寄与するものである。As described above, the electrochemical reaction occurs
It is a three-phase interface of liquid (water), solid (electrons and protons), and gas (hydrogen gas or oxygen gas), in which the gas and liquid move or react to the reaction point through the pores in the electrode. Emitted from. Therefore, the amount and shape of the holes in the electrode are important, and in particular, the amount of holes in the layer in which the catalyst is present (catalyst layer) has the greatest effect on the performance. The hardness (holding force of the holes) varies depending on the composition of the gas diffusion electrode. Therefore, even if the bonding conditions are the same, the amount of pores in the obtained catalyst layer is completely different depending on the electrode. The use of a gas diffusion electrode in which the amount of pores in the catalyst layer is controlled when used as a fuel cell is an idea directly connected to the power generation mechanism of the fuel cell.
It greatly contributes to performance improvement.
【００１５】[0015]
【００１６】[0016]
【実施例１】本実施例で使用したガス拡散電極（米国Ｅ
−ＴＥＫ Ｉｎｃ．社製）は、触媒層とカーボンファイ
バー織布部から成っており、触媒層が５２重量％を占め
ること、及び触媒層は、直径１０μｍ以下の孔のみ有
し、カーボンファイバー層はそれより大きな孔のみ有し
ていることを水銀圧入法ポロシメーターポアサイザー９
３２０（（株）島津製作所製）による測定で確認した。Example 1 The gas diffusion electrode used in this example (US E
-TEK Inc. (Made by the company) consists of a catalyst layer and a carbon fiber woven cloth portion, the catalyst layer occupies 52% by weight, and the catalyst layer has only pores with a diameter of 10 μm or less, and the carbon fiber layer has pores larger than that. Mercury porosimetry porosimeter Poisizer 9
It was confirmed by measurement with 320 (manufactured by Shimadzu Corporation).
【００１７】面積が１０ｃｍ2 のガス拡散電極（米国Ｅ
−ＴＥＫ Ｉｎｃ．社製）、白金担持量の０．３８ｍｇ
／ｃｍ2 を６枚用意し、５重量％濃度のナフィオン溶液
（米国Ａｌｄｒｉｃｈ社製）を電極表面に０．１６２ｍ
ｌ塗布後７０℃にて２時間減圧乾燥した。乾燥後重量測
定したところ、ナフィオン塗布量は０．６ｍｇ／cm2で
あった。得られた電極の２枚で厚み１２０μｍのアシプ
レックス膜（商標 旭化成工業（株）製）をはさみ、加
えて電極の大きさに穴をあけた厚み２７０μｍのガラス
繊維を含むテフロンシートを膜の両側にスペーサーとし
て用いて、３０ｋｇ／ｃｍ2 の圧力で１４０℃、９０秒
間プレスした。同様な方法で合計２枚の接合体を作成し
た。接合しない電極及び接合後の電極を水銀圧入法ポロ
シメーターポアサイザー９３２０（（株）島津製作所
製）にて測定したところ、接合前の触媒層空孔率７７
％、接合後の触媒層空孔率７４％であった。この接合体
を用いて、図３に示す評価装置にて出力評価を行った。
セル温度９０℃圧力３ａｔｍである。限界電流密度が
２．３Ａ／ｃｍ2 であった。A gas diffusion electrode having an area of 10 cm 2 (US E
-TEK Inc. Manufactured by the company), 0.38 mg of platinum loading
6 sheets / cm 2 are prepared, and a Nafion solution having a concentration of 5% by weight (manufactured by Aldrich, USA) is applied to the electrode surface for 0.162 m.
After coating, the coating was dried under reduced pressure at 70 ° C. for 2 hours. When dried and weighed, the amount of Nafion applied was 0.6 mg / cm 2 . A 120 μm thick aciplex film (trade name, manufactured by Asahi Kasei Kogyo Co., Ltd.) was sandwiched between two of the obtained electrodes, and a Teflon sheet containing glass fibers with a thickness of 270 μm in which a hole was formed in the size of the electrode was added to both sides of the film. Was used as a spacer at 140 ° C. for 90 seconds at a pressure of 30 kg / cm 2 . A total of two bonded bodies were prepared by the same method. The non-bonded electrode and the electrode after bonding were measured with a mercury porosimetry porosimeter Poisizer 9320 (manufactured by Shimadzu Corporation), and the porosity of the catalyst layer before bonding was 77.
%, And the porosity of the catalyst layer after bonding was 74%. Using this bonded body, output evaluation was performed with the evaluation device shown in FIG.
The cell temperature is 90 ° C. and the pressure is 3 atm. The limiting current density was 2.3 A / cm 2 .
【００１８】[0018]
【実施例２】実施例１と同じ濃度のナフィオン溶液を塗
布したガス拡散電極を４枚用意した。２枚の電極でアシ
プレックス膜をはさみ、そのまま、２０ｋｇ／ｃｍ2 の
圧力にて１４０℃、９０秒間ホットプレスした。同様に
合計２枚の接合体を作成した。１枚の接合体の触媒層内
空孔率を測定したところ７３％であった。他の１枚を用
いて、図３の評価装置にて出力評価を行なった。限界電
流密度は２．１Ａ／ｃｍ2 であった。Example 2 Four gas diffusion electrodes coated with the Nafion solution having the same concentration as in Example 1 were prepared. The aciplex film was sandwiched between two electrodes, and hot pressed at 140 ° C. for 90 seconds at a pressure of 20 kg / cm 2 as it was. Similarly, a total of two joined bodies were prepared. The porosity in the catalyst layer of one bonded body was 73%. Output evaluation was performed using the other one with the evaluation device of FIG. The limiting current density was 2.1 A / cm 2 .
【００１９】[0019]
【比較例１】実施例１，２と同じナフィオン溶液を塗布
した電極を４枚用意した。２枚の電極でアシプレックス
膜をはさみ、そのまま８０ｋｇ／ｃｍ2 の圧力にて１４
０℃、９０秒間ホットプレスした。同様に合計２枚の接
合体を作成した。１枚の接合体の触媒層内空孔率を測定
したところ６０％であった。他の１枚を用いて、図３の
評価装置にて出力評価を行なったところ限界電流密度は
１．５Ａ／ｃｍ2 であった。Comparative Example 1 Four electrodes coated with the same Nafion solution as in Examples 1 and 2 were prepared. Sandwich the Aciplex membrane with two electrodes, and press it at a pressure of 80 kg / cm 2 for 14
It was hot pressed at 0 ° C. for 90 seconds. Similarly, a total of two joined bodies were prepared. When the porosity in the catalyst layer of one bonded body was measured, it was 60%. When the output was evaluated by using the other one with the evaluation device of FIG. 3, the limiting current density was 1.5 A / cm 2 .
【００２０】実施例１，２と比較例１における接合体の
触媒層内空孔率及び評価結果の限界電流密度を表１、ま
た出力特性を図１にまとめて示した。Table 1 shows the porosity in the catalyst layer of the bonded bodies of Examples 1 and 2 and Comparative Example 1 and the limiting current density of the evaluation results, and the output characteristics are shown in FIG.
【００２１】[0021]
【表１】 [Table 1]
【００２２】[0022]
【発明の効果】以上説明したように本発明の燃料電池で
は反応界面への反応ガスの供給が充分行なわれ、その結
果として出力電圧の急激な減少がなく、性能が大幅に向
上する効果を奏する。As described above, in the fuel cell of the present invention, the reaction gas is sufficiently supplied to the reaction interface, and as a result, the output voltage does not suddenly decrease and the performance is greatly improved. .
【図１】実施例１〜２及び比較例１における出力電圧と
電流密度の関係を示すグラフ図である。FIG. 1 is a graph showing the relationship between output voltage and current density in Examples 1 and 2 and Comparative Example 1.
【図２】固体高分子電解質型燃料電池の接合体の説明図
である。FIG. 2 is an explanatory view of a joined body of a solid polymer electrolyte fuel cell.
【図３】接合体の評価装置図の説明図である。FIG. 3 is an explanatory diagram of an evaluation device diagram of a bonded body.
１：酸素極のガス拡散電極 ２：水素極ガス拡散電極 ３：固体高分子電解質膜 ４：燃料電池セル ５：加湿器 ６：純水 1: Gas diffusion electrode of oxygen electrode 2: Hydrogen gas diffusion electrode 3: Solid polymer electrolyte membrane 4: Fuel cell 5: Humidifier 6: Pure water
Claims (1)
も触媒層を有するガス拡散電極とを接合した燃料電池に
おいて、上記触媒層がプロトン導伝材を含有し、かつ、
接合後の上記触媒層内の空孔率が６５から９０容量％で
あることを特徴とする固体高分子電解質型燃料電池。1. A fuel cell in which an ion exchange membrane, which is an electrolyte, and a gas diffusion electrode having at least a catalyst layer are joined, wherein the catalyst layer contains a proton conductive material, and
A solid polymer electrolyte fuel cell, wherein the porosity in the catalyst layer after joining is 65 to 90% by volume.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5001674A JPH06203840A (en) | 1993-01-08 | 1993-01-08 | Solid polyelectrolyte fuel cell |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5001674A JPH06203840A (en) | 1993-01-08 | 1993-01-08 | Solid polyelectrolyte fuel cell |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH06203840A true JPH06203840A (en) | 1994-07-22 |
Family
ID=11508067
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP5001674A Withdrawn JPH06203840A (en) | 1993-01-08 | 1993-01-08 | Solid polyelectrolyte fuel cell |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH06203840A (en) |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1997050143A1 (en) * | 1996-06-25 | 1997-12-31 | The Dais Corporation | Gas diffusion electrode |
| JP2001189155A (en) * | 1995-10-06 | 2001-07-10 | Dow Chem Co:The | Electrochemical fuel cell |
| JP2005044815A (en) * | 2004-10-05 | 2005-02-17 | Asahi Glass Co Ltd | Manufacturing method of solid polymer electrolyte fuel cell |
| US7094492B2 (en) | 2001-10-11 | 2006-08-22 | Honda Giken Kogyo Kabushiki Kaisha | Electrode for polymer electrolyte fuel cell |
| US7842432B2 (en) | 2004-12-09 | 2010-11-30 | Nanosys, Inc. | Nanowire structures comprising carbon |
| US7939218B2 (en) | 2004-12-09 | 2011-05-10 | Nanosys, Inc. | Nanowire structures comprising carbon |
| US8278011B2 (en) | 2004-12-09 | 2012-10-02 | Nanosys, Inc. | Nanostructured catalyst supports |
| US8357475B2 (en) | 2004-12-09 | 2013-01-22 | Nanosys, Inc. | Nanowire-based membrane electrode assemblies for fuel cells |
| US10490817B2 (en) | 2009-05-19 | 2019-11-26 | Oned Material Llc | Nanostructured materials for battery applications |
-
1993
- 1993-01-08 JP JP5001674A patent/JPH06203840A/en not_active Withdrawn
Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001189155A (en) * | 1995-10-06 | 2001-07-10 | Dow Chem Co:The | Electrochemical fuel cell |
| WO1997050143A1 (en) * | 1996-06-25 | 1997-12-31 | The Dais Corporation | Gas diffusion electrode |
| US7094492B2 (en) | 2001-10-11 | 2006-08-22 | Honda Giken Kogyo Kabushiki Kaisha | Electrode for polymer electrolyte fuel cell |
| DE10247452B4 (en) * | 2001-10-11 | 2007-08-16 | Honda Giken Kogyo K.K. | Electrode for polymer electrolyte fuel cell |
| JP2005044815A (en) * | 2004-10-05 | 2005-02-17 | Asahi Glass Co Ltd | Manufacturing method of solid polymer electrolyte fuel cell |
| US8357475B2 (en) | 2004-12-09 | 2013-01-22 | Nanosys, Inc. | Nanowire-based membrane electrode assemblies for fuel cells |
| US7939218B2 (en) | 2004-12-09 | 2011-05-10 | Nanosys, Inc. | Nanowire structures comprising carbon |
| US8278011B2 (en) | 2004-12-09 | 2012-10-02 | Nanosys, Inc. | Nanostructured catalyst supports |
| US7842432B2 (en) | 2004-12-09 | 2010-11-30 | Nanosys, Inc. | Nanowire structures comprising carbon |
| US8440369B2 (en) | 2004-12-09 | 2013-05-14 | Nanosys, Inc. | Nanowire-based membrane electrode assemblies for fuel cells |
| USRE45703E1 (en) | 2004-12-09 | 2015-09-29 | Oned Material Llc | Nanostructured catalyst supports |
| USRE46921E1 (en) | 2004-12-09 | 2018-06-26 | Oned Material Llc | Nanostructured catalyst supports |
| USRE48084E1 (en) | 2004-12-09 | 2020-07-07 | Oned Material Llc | Nanostructured catalyst supports |
| US10490817B2 (en) | 2009-05-19 | 2019-11-26 | Oned Material Llc | Nanostructured materials for battery applications |
| US11233240B2 (en) | 2009-05-19 | 2022-01-25 | Oned Material, Inc. | Nanostructured materials for battery applications |
| US11600821B2 (en) | 2009-05-19 | 2023-03-07 | Oned Material, Inc. | Nanostructured materials for battery applications |
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