JPH06231780A - Improved solid high polymer electrolytic fuel cell - Google Patents
Improved solid high polymer electrolytic fuel cellInfo
- Publication number
- JPH06231780A JPH06231780A JP5039418A JP3941893A JPH06231780A JP H06231780 A JPH06231780 A JP H06231780A JP 5039418 A JP5039418 A JP 5039418A JP 3941893 A JP3941893 A JP 3941893A JP H06231780 A JPH06231780 A JP H06231780A
- Authority
- JP
- Japan
- Prior art keywords
- warp
- fuel cell
- weft
- sulfonic acid
- parfluorocarbon
- 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
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Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Landscapes
- Fuel Cell (AREA)
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.
【０００２】[0002]
【従来の技術】近年プロトン伝導性の高分子膜を電解質
として用いる燃料電池（固体高分子電解質型燃料電池）
の研究が進んでいる。固体高分子電解質型燃料電池は、
低温で作動し出力密度が高く小型化が可能であるという
特徴を有し、車載用電源等の用途に対し有力視されてい
る。2. Description of the Related Art Recently, a fuel cell using a proton-conducting polymer membrane as an electrolyte (solid polymer electrolyte fuel cell)
Research is progressing. The solid polymer electrolyte fuel cell is
It operates at low temperature, has a high output density, and can be downsized, and is regarded as a promising candidate for applications such as in-vehicle power supplies.
【０００３】[0003]
【発明が解決しようとする課題】本用途に用いられる高
分子膜は、通常厚さ１００〜２００μｍのプロトン伝導
性イオン交換膜が用いられ、特にスルホン酸基を有する
パーフルオロカーボン重合体からなる陽イオン交換膜が
基本特性に優れ広く検討されている。しかし、現在提案
されている陽イオン交換膜の電気抵抗は、より高出力密
度の電池を得る観点から必ずしも十分に低いとは言えな
い。As the polymer membrane used for this purpose, a proton conductive ion exchange membrane having a thickness of 100 to 200 μm is usually used, and in particular, a cation composed of a perfluorocarbon polymer having a sulfonic acid group. Exchange membranes have been widely studied because of their excellent basic properties. However, the electrical resistance of currently proposed cation exchange membranes is not necessarily sufficiently low from the viewpoint of obtaining batteries with higher power density.
【０００４】陽イオン交換膜の電気抵抗を低減する方法
としてはスルホン酸基濃度の増加と膜厚の低減がある
が、スルホン酸基濃度の著しい増加は膜の機械的強度を
低下させたり、長期運転において膜がクリープし易くな
り耐久性を低下させるなどの問題点が生じる。一方膜厚
の低減は膜の機械的強度を低下させたり、更にガス拡散
電極との接合等の加工性・取扱い性を低下させるなどの
問題点が生じる。As a method for reducing the electric resistance of the cation exchange membrane, there is an increase in the concentration of sulfonic acid groups and a reduction in the film thickness. During operation, the film easily creeps, which causes problems such as deterioration of durability. On the other hand, the reduction of the film thickness causes problems such as deterioration of the mechanical strength of the film and further deterioration of workability and handleability such as bonding with the gas diffusion electrode.
【０００５】上記の問題点を解決する方法として、スル
ホン酸基を含有するパーフルオロカーボン重合体のフィ
ルムとポリテトラフルオロエチレン（ＰＴＦＥ）の多孔
体との複合陽イオン交換膜が提案された（マーク．Ｗ．
バーブルッジら、AIChE ジャーナル、1992年,38,93）
が、膜厚は薄くできるものの多孔体状のＰＴＦＥでは膜
の電気抵抗が十分に低下しないことがわかった。As a method for solving the above problems, a composite cation exchange membrane of a film of a perfluorocarbon polymer containing a sulfonic acid group and a porous body of polytetrafluoroethylene (PTFE) has been proposed (Mark. W.
Barbudge et al., AIChE Journal, 1992, 38,93)
However, it was found that although the film thickness can be reduced, the electrical resistance of the film is not sufficiently reduced in porous PTFE.
【０００６】[0006]
【課題を解決するための手段】本発明は前述の問題点を
解決すべくなされたものであり、所定の網目構造を有す
るパーフルオロカーボン重合体織布で補強されたスルホ
ン酸基を含有するパーフルオロカーボン重合体からなる
陽イオン交換膜を固体高分子電解質とする固体高分子電
解質型燃料電池を提供するものである。The present invention has been made to solve the above-mentioned problems, and is a perfluorocarbon containing a sulfonic acid group reinforced with a perfluorocarbon polymer woven fabric having a predetermined network structure. It is intended to provide a solid polymer electrolyte fuel cell using a cation exchange membrane made of a polymer as a solid polymer electrolyte.
【０００７】本発明において補強材として用いられるパ
ーフルオロカーボン重合体としては、テトラフルオロエ
チレン、ヘキサフルオロプロピレン、クロロトリフルオ
ロエチレン、パーフルオロアルコキシビニルエーテルの
如きパーフルオロオレフィンの単独又は共重合体が例示
される。その具体例としてはポリテトラフルオロエチレ
ン（ＰＴＦＥ）、ポリテトラフルオロエチレン−ヘキサ
フルオロプロピレン（ＦＥＰ）、ポリテトラフルオロエ
チレン−パーフルオロプロピルビニルエーテル（ＰＦ
Ａ）、ポリクロロトリフルオロエチレン、ポリテトラフ
ルオロエチレン−パーフルオロ−２, ２−ジメチル−
１, ３−ジオキソール、ポリパーフルオロブテニルビニ
ルエーテルなどが挙げられるが、特にＰＴＦＥが特性上
好ましい。Examples of the perfluorocarbon polymer used as the reinforcing material in the present invention include homopolymers or copolymers of perfluoroolefins such as tetrafluoroethylene, hexafluoropropylene, chlorotrifluoroethylene, and perfluoroalkoxy vinyl ether. . Specific examples thereof include polytetrafluoroethylene (PTFE), polytetrafluoroethylene-hexafluoropropylene (FEP), polytetrafluoroethylene-perfluoropropyl vinyl ether (PF).
A), polychlorotrifluoroethylene, polytetrafluoroethylene-perfluoro-2,2-dimethyl-
Examples thereof include 1,3-dioxole and polyperfluorobutenyl vinyl ether, but PTFE is particularly preferable in terms of characteristics.
【０００８】かかる重合体は特定の網目構造を有する織
布状の形態で補強材とされる。これらの織布形態は上記
文献で知られたＰＴＦＥ多孔体と比較して補強の割合が
網目構造として任意に選定可能であること、織布の開口
率を高めても補強効果が高く電気抵抗の上昇が低いこ
と、更に寸法安定性に優れていること等の利点を有す
る。Such a polymer is used as a reinforcing material in the form of a woven cloth having a specific network structure. Compared with the PTFE porous body known in the above-mentioned literature, these woven fabric forms can be arbitrarily selected for the reinforcement ratio as a mesh structure, and even if the opening ratio of the woven fabric is increased, the reinforcement effect is high and the electrical resistance is high. It has advantages such as low rise and excellent dimensional stability.
【０００９】本発明においては、パーフルオロカーボン
重合体織布は、縦糸のデニール数が２０〜１００、好ま
しくは３０〜７５、横糸のデニール数が２０〜２００、
好ましくは３０〜１００であり、縦糸及び横糸密度が１
０〜５０本／インチ、好ましくは１５〜３０本／インチ
であり、さらに縦糸及び横糸の交点が偏平化されて、厚
みが４０〜１２０μｍ、好ましくは５０〜８５μｍにせ
しめられた構造を有する。縦糸、横糸のデニール数が上
記範囲より小さい場合には補強効果が不十分となり、一
方大きい場合にはピンホールやクラックが発生し易いと
いう欠点が生じる。In the present invention, the perfluorocarbon polymer woven fabric has a warp yarn denier number of 20 to 100, preferably 30 to 75, and a weft yarn denier number of 20 to 200,
It is preferably 30 to 100, and the warp and weft density is 1
It has 0 to 50 yarns / inch, preferably 15 to 30 yarns / inch, and further has a structure in which the intersections of the warp yarns and the weft yarns are flattened to have a thickness of 40 to 120 μm, preferably 50 to 85 μm. When the denier number of the warp yarn and the weft yarn is smaller than the above range, the reinforcing effect is insufficient, while when it is large, there is a drawback that pinholes and cracks are likely to occur.
【００１０】各縦糸、横糸は、上記の範囲の細糸であれ
ばモノフィラメント、マルチフィラメントのいずれも適
用可能であるが、マルチフィラメントの場合には、糸断
面の偏平化による布開口率の減少に伴う膜抵抗の上昇を
極小にできるので、好ましく採用可能である。縦糸及び
横糸密度が上記範囲より小さい場合には目ずれが生じ易
くなるなるとともに、補強効果が不十分である。また上
限より大きい場合には膜抵抗が上昇する。As the warp yarns and the weft yarns, both monofilaments and multifilaments can be applied as long as they are fine yarns in the above range. However, in the case of multifilaments, the cloth opening ratio is reduced by flattening the yarn cross section. Since the increase in the membrane resistance accompanying it can be minimized, it can be preferably adopted. If the warp and weft densities are less than the above range, misalignment is likely to occur and the reinforcing effect is insufficient. If it is larger than the upper limit, the film resistance increases.
【００１１】また、織布は、平板プレスやロールプレス
などにより偏平化され、その厚みを４０〜１２０μ、好
ましくは５０〜８０μｍにせしめられる。織布が偏平化
されない場合には、これにより電気抵抗を増大させず
に、ピンホールやクラックの発生が抑制できることが見
い出された。The woven fabric is flattened by a flat plate press or a roll press and the thickness thereof is set to 40 to 120 μm, preferably 50 to 80 μm. It has been found that if the woven fabric is not flattened, this can suppress the occurrence of pinholes and cracks without increasing the electrical resistance.
【００１２】パーフルオロカーボン重合体織布による陽
イオン交換膜の補強する方法は特に限定されず、スルホ
ン酸型パーフルオロカーボン重合体、又は分散液を織布
に含浸させた後乾燥、造膜を行うキャスティング法や、
スルホン酸型パーフルオロカーボン重合体膜状物と織布
とを熱溶融プレスにより積層する方法等も適用される。
熱溶融プレス法としては平板プレス、真空プレス等のバ
ッチ法や連続ロールプレス法等の連続法が挙げられる。
陽イオン交換膜の全厚みは、７０〜３００μｍ、好まし
くは８０〜１２０μｍが採用される。The method for reinforcing the cation exchange membrane with the perfluorocarbon polymer woven fabric is not particularly limited, and casting is performed by impregnating the woven fabric with the sulfonic acid type perfluorocarbon polymer or the dispersion liquid, followed by drying and film formation. The law,
A method of laminating a sulfonic acid type perfluorocarbon polymer film and a woven fabric by a hot melt press is also applicable.
Examples of the hot-melt pressing method include batch methods such as flat plate pressing and vacuum pressing, and continuous methods such as continuous roll pressing.
The total thickness of the cation exchange membrane is 70 to 300 μm, preferably 80 to 120 μm.
【００１３】本発明で用いられるスルホン酸型パーフル
オロカーボン重合体としては、従来より公知の重合体が
広く採用される。一般式ＣＦ2 ＝ＣＦ−（ＯＣＦ2 ＣＦ
Ｘ）m −Ｏq −（ＣＦ2 ）n −Ａ（式中ｍ＝０〜３、ｎ
＝０〜１２、ｑ＝０又は１、Ｘ＝Ｆ又はＣＦ3 、Ａ＝ス
ルホン酸型官能基）で表されるフルオロビニル化合物
と、テトラフルオロエチレン、ヘキサフルオロプロピレ
ン、クロロトリフルオロエチレン、又はパーフルオロア
ルコキシビニルエーテルの如きパーフルオロオレフィン
との共重合体が例示される。As the sulfonic acid type perfluorocarbon polymer used in the present invention, conventionally known polymers are widely adopted. Formula CF 2 = CF- (OCF 2 CF
X) m -O q - (CF 2) n -A ( wherein m = 0 to 3, n
= 0 to 12, q = 0 or 1, X = F or CF 3 , A = sulfonic acid type functional group) and tetrafluoroethylene, hexafluoropropylene, chlorotrifluoroethylene, or perfluoroethylene. Examples thereof include copolymers with perfluoroolefin such as fluoroalkoxy vinyl ether.
【００１４】上記フルオロビニル化合物の好ましい例と
しては、 ＣＦ2 ＝ＣＦＯ（ＣＦ2 ）1-8 ＳＯ2 Ｆ ＣＦ2 ＝ＣＦＯＣＦ2 ＣＦ（ＣＦ3 ）Ｏ（ＣＦ2 ）1-8 ＳＯ2 Ｆ ＣＦ2 ＝ＣＦ（ＣＦ2 ）0-8 ＳＯ2 Ｆ ＣＦ2 ＝ＣＦ（ＯＣＦ2 ＣＦ（ＣＦ3 ））1-5 Ｏ（ＣＦ2 ）2 ＳＯ2 Ｆ などが挙げられる。かかるスルホン酸型パーフルオロカ
ーボン重合体中のスルホン酸基の濃度、即ちイオン交換
容量としては０．５〜２．０ミリ当量／グラム乾燥樹
脂、更には０．７〜１．６ミリ当量の範囲が好ましい。
イオン交換容量がこの範囲より低い場合には膜の電気抵
抗が大きくなり、一方高い場合には膜の機械的強度が十
分でない。Preferred examples of the fluorovinyl compound include CF 2 ═CFO (CF 2 ) 1-8 SO 2 F CF 2 ═CFOCF 2 CF (CF 3 ) O (CF 2 ) 1-8 SO 2 F CF 2 = CF (CF 2) 0-8 SO 2 F CF 2 = CF (OCF 2 CF (CF 3)) , such as 1-5 O (CF 2) 2 SO 2 F and the like. The concentration of the sulfonic acid group in the sulfonic acid type perfluorocarbon polymer, that is, the ion exchange capacity is 0.5 to 2.0 meq / g dry resin, and further 0.7 to 1.6 meq. preferable.
When the ion exchange capacity is lower than this range, the electric resistance of the membrane becomes large, while when it is high, the mechanical strength of the membrane is not sufficient.
【００１５】補強されたスルホン酸型パーフルオロカー
ボン重合体からなる陽イオン交換膜は通常の、既知の手
法に従ってその表面にガス拡散電極を密着させ、次いで
集電体をとりつけ、燃料電池として組み立てられる。The cation exchange membrane made of the reinforced sulfonic acid type perfluorocarbon polymer is assembled into a fuel cell by adhering a gas diffusion electrode to the surface of the cation exchange membrane according to a known method and then attaching a current collector.
【００１６】ガス拡散電極は通常白金触媒微粒子を担持
させた導電性のカーボンブラック粉末をポリテトラフル
オロエチレンなどの疎水性樹脂結着材で保持させた多孔
質体のシートよりなるが、該多孔質体はスルホン酸型パ
ーフルオロカーボン重合体や該重合体で被覆された微粒
子を含んでいてもよい。The gas diffusion electrode usually comprises a sheet of a porous body in which conductive carbon black powder carrying fine platinum catalyst particles is held by a hydrophobic resin binder such as polytetrafluoroethylene. The body may contain a sulfonic acid type perfluorocarbon polymer or fine particles coated with the polymer.
【００１７】ガス拡散電極はスルホン酸型パーフルオロ
カーボン重合体からなる陽イオン交換膜に対して加熱プ
レス法等により密着される。集電体には燃料ガス又は酸
化剤ガスの通路となる溝が形成された、導電性カーボン
板等が用いられる。The gas diffusion electrode is brought into close contact with a cation exchange membrane composed of a sulfonic acid type perfluorocarbon polymer by a heating press method or the like. For the current collector, a conductive carbon plate or the like in which a groove serving as a passage for the fuel gas or the oxidant gas is formed is used.
【００１８】水素ガス燃料電池では、陽極側に水素ガス
が供給され陰極側には酸素或いは空気が供給され、次の
反応により化学エネルギーが電気エネルギーに変換され
る。 陰極：Ｈ2 → ２Ｈ+ ＋２ｅ- 陽極：１／２Ｏ2 ＋２Ｈ+ ＋２ｅ- → Ｈ2 ＯIn the hydrogen gas fuel cell, hydrogen gas is supplied to the anode side and oxygen or air is supplied to the cathode side, and chemical energy is converted into electric energy by the following reaction. Cathode: H 2 → 2H + + 2e − Anode: 1 / 2O 2 + 2H + + 2e − → H 2 O
【００１９】[0019]
実施例１ 特開平２−８８６４５号公報に記載されている方法に準
拠し、イオン交換容量１．０ミリ当量／ｇ乾燥樹脂であ
る、ＣＦ2 ＝ＣＦＯ（ＣＦ2 ＣＦＣＦ3 ）Ｏ（ＣＦ2 ）
2 ＳＯ2 Ｆとテトラフルオロエチレンとの共重合体を得
た。この共重合体を２２０℃で押し出し製膜し、厚さ５
０μｍのフィルムを得た。According to the method disclosed in Japanese Patent Example 1 JP-A 2-88645, an ion exchange capacity 1.0 meq / g dry resin, CF 2 = CFO (CF 2 CFCF 3) O (CF 2)
A copolymer of 2 SO 2 F and tetrafluoroethylene was obtained. This copolymer was extruded at 220 ° C to form a film, and the thickness was 5
A 0 μm film was obtained.
【００２０】次に縦糸、横糸ともに太さが５０デニー
ル、偏平化後の厚みが６０μｍ、密度が２７本／インチ
のポリテトラフルオロエチレン製織布を用意した。２２
０℃でロールを用いて、上記２枚のフィルムとの間にポ
リテトラフルオロエチレンにより構成される上記織布を
挿入し積層することにより補強陽イオン交換膜を得た。
この膜を、ジメチルスルホキシド３０重量％と、苛性カ
リ１５重量％との混合水溶液中で加水分解を行い、水洗
した後１Ｎの塩酸中に浸漬した。得られた膜を水洗し、
膜の四辺を専用治具で拘束した後６０℃、１時間乾燥し
サンプル陽イオン交換膜を得た。Next, a woven polytetrafluoroethylene cloth having a thickness of 50 denier for both warp and weft, a thickness after flattening of 60 μm and a density of 27 filaments / inch was prepared. 22
A reinforced cation exchange membrane was obtained by inserting the woven fabric composed of polytetrafluoroethylene between the two films using a roll at 0 ° C. and laminating the woven fabric.
This membrane was hydrolyzed in a mixed aqueous solution of 30% by weight of dimethyl sulfoxide and 15% by weight of caustic potash, washed with water, and then immersed in 1N hydrochloric acid. Wash the resulting membrane with water,
After restraining the four sides of the membrane with dedicated jigs, the membrane was dried at 60 ° C. for 1 hour to obtain a sample cation exchange membrane.
【００２１】（強度測定）この陽イオン交換膜を９０℃
の純水中に浸漬した後、引っ張り強度を測定したところ
３．９ｋｇ／ｃｍ幅であった。(Measurement of Strength) This cation exchange membrane was heated at 90 ° C.
After being dipped in pure water, the tensile strength was measured and found to be 3.9 kg / cm width.
【００２２】（膜抵抗測定）陽イオン交換膜を１Ｍの硫
酸に２５℃、２４時間浸漬した後、交流比抵抗を測定し
た。電解液は１Ｍの硫酸であり、白金製の電極を用い
た。有効膜面積は１．８７ｃｍ2 であり、測定温度２５
℃に設定した。横河ヒューレッドパッカー社のＬＣＲメ
ータを用い、交流比抵抗を測定した結果は１２．６Ωｃ
ｍであった。(Measurement of Membrane Resistance) The cation exchange membrane was immersed in 1 M sulfuric acid at 25 ° C. for 24 hours, and then the AC specific resistance was measured. The electrolytic solution was 1 M sulfuric acid, and a platinum electrode was used. The effective membrane area is 1.87 cm 2 and the measurement temperature is 25
It was set to ° C. Using an LCR meter manufactured by Yokogawa Hured Packer, the result of measuring the AC specific resistance was 12.6 Ωc.
It was m.
【００２３】比較例１ 実施例１で得られた、同一のイオン交換容量１．０ミリ
当量／ｇ乾燥樹脂である、ＣＦ2 ＝ＣＦＯ（ＣＦ2 ＣＦ
ＣＦ3 ）Ｏ（ＣＦ2 ）2 ＳＯ2 Ｆとテトラフルオロエチ
レンとの共重合体からなる厚さ５０μｍの押し出しフィ
ルムを２枚を用い、２２０℃でロールを用いて、フィル
ム同志を貼合わせて得られる無補強の陽イオン交換膜を
実施例１と同様な処理を施し、強度測定及び抵抗測定を
実施したところ、引っ張り強度（幅方向）は１．９ｋｇ
／ｃｍ、交流比抵抗は１２．６Ωｃｍであった。Comparative Example 1 CF 2 ═CFO (CF 2 CF), which is the same ion exchange capacity of 1.0 meq / g dry resin obtained in Example 1.
CF 3 ) O (CF 2 ) 2 SO 2 F and a tetrafluoroethylene copolymer having a thickness of 50 μm are used as two extruded films, and the films are stuck together using a roll at 220 ° C. The obtained non-reinforced cation exchange membrane was subjected to the same treatment as in Example 1 and subjected to strength measurement and resistance measurement. The tensile strength (width direction) was 1.9 kg.
/ Cm, the AC specific resistance was 12.6 Ωcm.
【００２４】実施例２ 実施例１で得られた織布で補強された陽イオン交換膜の
燃料電池特性を評価した。白金触媒微粒子を担持させた
カーボンブラック粉末にポリテトラフルオロエチレンを
混入し、ロールプレスを用いて厚さ２５０μｍのシート
状のガス拡散電極を作製した。上記２枚のガス拡散電極
との間に上記陽イオン交換膜を挿入し平板熱プレス機を
用いて積層することにより膜電極接合体を作製した。膜
電極接合体の白金触媒量は膜面積ｃｍ2 あたり１ｍｇで
あった。次に膜電極接合体をチタン製の集電体、ＰＴＦ
Ｅ製のガス供給室、ヒーターの順番ではさみ、有効膜面
積９ｃｍ2 の燃料電池を組み上げた。セルの温度を８０
℃に保ち、正極に酸素、負極に水素をそれぞれ５気圧で
供給した時の電流密度に対する端子電圧を測定したとこ
ろ電流密度１Ａ／ｃｍ2 、セル電圧０．６０Ｖであっ
た。Example 2 Fuel cell characteristics of the cation exchange membrane reinforced with the woven fabric obtained in Example 1 were evaluated. Polytetrafluoroethylene was mixed in carbon black powder supporting platinum catalyst fine particles, and a 250 μm thick sheet-shaped gas diffusion electrode was produced by using a roll press. A membrane electrode assembly was produced by inserting the cation exchange membrane between the two gas diffusion electrodes and stacking them using a flat plate heat press. The amount of platinum catalyst in the membrane electrode assembly was 1 mg per cm 2 of membrane area. Next, the membrane electrode assembly was replaced with a titanium current collector, PTF.
A gas supply chamber made of E and a heater were sandwiched in this order to assemble a fuel cell having an effective membrane area of 9 cm 2 . Set the cell temperature to 80
When the terminal voltage was measured with respect to the current density when oxygen was supplied to the positive electrode and hydrogen was supplied to the negative electrode at 5 atm at 5 ° C., the current density was 1 A / cm 2 , and the cell voltage was 0.60 V.
【００２５】比較例２ 比較例１で製造した補強されていない陽イオン交換膜に
対し、実施例２と同様な方法により燃料電池を組み上げ
た後、同様な条件下で電流密度に対する端子電圧を測定
したところ電流密度１Ａ／ｃｍ2 、セル電圧が０．６０
Ｖであった。Comparative Example 2 After assembling a fuel cell to the unreinforced cation exchange membrane produced in Comparative Example 1 by the same method as in Example 2, the terminal voltage with respect to the current density was measured under the same conditions. As a result, the current density was 1 A / cm 2 and the cell voltage was 0.60.
It was V.
【００２６】上記の結果からわかるように、実施例１の
陽イオン交換膜は比較例１の膜に比べ、大きな引張り強
度を有するにもかかわらず、ほぼ同一の燃料電池を保持
できることがわかった。As can be seen from the above results, the cation exchange membrane of Example 1 can hold almost the same fuel cell as the membrane of Comparative Example 1, although it has a higher tensile strength than the membrane of Comparative Example 1.
【００２７】[0027]
【発明の効果】従来にない低い電気抵抗と高い機械的強
度を有する補強陽イオン交換膜を固体高分子電解質とす
ることにより高性能の固体高分子電解質型燃料電池が得
られる。EFFECTS OF THE INVENTION By using a reinforcing cation exchange membrane having unprecedented low electric resistance and high mechanical strength as a solid polymer electrolyte, a high performance solid polymer electrolyte fuel cell can be obtained.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 三宅 晴久 神奈川県横浜市神奈川区羽沢町1150番地 旭硝子株式会社中央研究所内 ─────────────────────────────────────────────────── ─── Continued Front Page (72) Inventor Haruhisa Miyake 1150, Hazawa-machi, Kanagawa-ku, Yokohama-shi, Kanagawa Asahi Glass Co., Ltd. Central Research Laboratory
Claims (3)
デニール数が２０〜２００、縦糸及び横糸密度が１０〜
５０本／インチであり、縦糸及び横糸の交点が偏平化さ
れて、厚み４０〜１２０μｍにせしめたパーフルオロカ
ーボン重合体織布で補強されたスルホン酸基を含有する
パーフルオロカーボン重合体からなる陽イオン交換膜
を、固体高分子電解質とすることを特徴とする固体高分
子電解質型燃料電池。1. The warp yarn has a denier number of 20 to 100, the weft yarn has a denier number of 20 to 200, and the warp and weft yarn densities are 10 to 10.
Cation exchange consisting of perfluorocarbon polymer containing sulfonic acid groups of 50 threads / inch, flattened at intersections of warp and weft, and reinforced with perfluorocarbon polymer woven fabric having a thickness of 40 to 120 μm A solid polymer electrolyte fuel cell, wherein the membrane is a solid polymer electrolyte.
テトラフルオロエチレン、ポリテトラフルオロエチレン
−パーフルオロアルコキシビニルエーテル、又はポリテ
トラフルオロエチレン−ヘキサフルオロプロピレンから
なる請求項１の固体高分子電解質型燃料電池。2. A solid polymer electrolyte fuel cell according to claim 1, wherein the woven cloth of perfluorocarbon polymer is made of polytetrafluoroethylene, polytetrafluoroethylene-perfluoroalkoxyvinyl ether, or polytetrafluoroethylene-hexafluoropropylene. .
ボン重合体がＣＦ2 ＝ＣＦ2 とＣＦ2 ＝ＣＦ−（ＯＣＦ
2 ＣＦＸ）m −Ｏq −（ＣＦ2 ）n −Ａ（式中ｍ＝０〜
３、ｎ＝０〜１２、ｑ＝０又は１、Ｘ＝Ｆ又はＣＦ3 、
Ａ＝スルホン酸型官能基）との共重合体である請求項１
又は２の固体高分子電解質型燃料電池。3. A perfluorocarbon polymer containing a sulfonic acid group is CF 2 ═CF 2 and CF 2 ═CF— (OCF.
2 CFX) m —O q — (CF 2 ) n —A (where m = 0 to
3, n = 0 to 12, q = 0 or 1, X = F or CF 3 ,
A is a copolymer with a sulfonic acid type functional group).
Or the solid polymer electrolyte fuel cell of item 2.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5039418A JPH06231780A (en) | 1993-02-03 | 1993-02-03 | Improved solid high polymer electrolytic fuel cell |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5039418A JPH06231780A (en) | 1993-02-03 | 1993-02-03 | Improved solid high polymer electrolytic fuel cell |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH06231780A true JPH06231780A (en) | 1994-08-19 |
Family
ID=12552442
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP5039418A Pending JPH06231780A (en) | 1993-02-03 | 1993-02-03 | Improved solid high polymer electrolytic fuel cell |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH06231780A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6224994B1 (en) | 1998-01-19 | 2001-05-01 | Aisin Seiki Kabushiki Kaisha | Solid polyelectrolyte-type fuel cell |
| US6713207B2 (en) | 2000-05-18 | 2004-03-30 | Kabushiki Kaisha Toyota Chuo Kenkyusho | Membrane electrode assembly, and solid polymer fuel cell using the assembly |
| EP1674508A1 (en) * | 2004-12-22 | 2006-06-28 | Asahi Glass Company, Limited | Electrolyte membrane, process for its production and membrane-electrode assembly for polymer electrolyte fuel cells |
| WO2019088299A1 (en) * | 2017-11-06 | 2019-05-09 | Ａｇｃ株式会社 | Solid polymer electrolyte film, membrane electrode assembly and electrolyzer |
| CN113396245A (en) * | 2019-02-08 | 2021-09-14 | Ａｇｃ株式会社 | Membrane electrode assembly and water electrolysis device |
-
1993
- 1993-02-03 JP JP5039418A patent/JPH06231780A/en active Pending
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6224994B1 (en) | 1998-01-19 | 2001-05-01 | Aisin Seiki Kabushiki Kaisha | Solid polyelectrolyte-type fuel cell |
| US6713207B2 (en) | 2000-05-18 | 2004-03-30 | Kabushiki Kaisha Toyota Chuo Kenkyusho | Membrane electrode assembly, and solid polymer fuel cell using the assembly |
| EP1674508A1 (en) * | 2004-12-22 | 2006-06-28 | Asahi Glass Company, Limited | Electrolyte membrane, process for its production and membrane-electrode assembly for polymer electrolyte fuel cells |
| WO2019088299A1 (en) * | 2017-11-06 | 2019-05-09 | Ａｇｃ株式会社 | Solid polymer electrolyte film, membrane electrode assembly and electrolyzer |
| CN111316380A (en) * | 2017-11-06 | 2020-06-19 | Ａｇｃ株式会社 | Solid polymer electrolyte membrane, membrane electrode assembly, and water electrolysis device |
| CN111316380B (en) * | 2017-11-06 | 2022-05-24 | Ａｇｃ株式会社 | Solid polymer electrolyte membrane, membrane electrode assembly, and water electrolysis device |
| US11742507B2 (en) | 2017-11-06 | 2023-08-29 | AGC Inc. | Polymer electrolyte membrane, membrane electrode assembly and water electrolyzer |
| CN113396245A (en) * | 2019-02-08 | 2021-09-14 | Ａｇｃ株式会社 | Membrane electrode assembly and water electrolysis device |
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