JP3382654B2 - Solid polymer electrolyte fuel cell - Google Patents
Solid polymer electrolyte fuel cellInfo
- Publication number
- JP3382654B2 JP3382654B2 JP03941993A JP3941993A JP3382654B2 JP 3382654 B2 JP3382654 B2 JP 3382654B2 JP 03941993 A JP03941993 A JP 03941993A JP 3941993 A JP3941993 A JP 3941993A JP 3382654 B2 JP3382654 B2 JP 3382654B2
- Authority
- JP
- Japan
- Prior art keywords
- fuel cell
- polymer electrolyte
- solid polymer
- perfluorocarbon
- water content
- 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.)
- Expired - Fee Related
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
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望視されてい
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
Characterized in that the power density operating at low temperature can be high miniaturization, are promising view to applications such as automotive power.
【０００３】[0003]
【発明が解決しようとする課題】固体高分子電解質型燃
料電池に用いられる高分子膜は、通常厚さ１００〜２０
０μｍ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。[Problems to be Solved by the Invention] Solid polymer electrolyte type fuel
The polymer film used in the charge battery usually has a thickness of 100 to 20.
A 0 μm proton-conducting ion exchange membrane is used, and in particular, a cation exchange membrane made of a perfluorocarbon polymer having a sulfonic acid group has been widely studied because of its excellent basic characteristics. 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
に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やすくなり耐
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。かくして、電気抵抗が低くかつ機械的強度
が高い陽イオン交換膜の開発が望まれていた。Methods for reducing the electrical resistance of cation exchange membranes include increasing the concentration of sulfonic acid groups and reducing the film thickness, but a significant increase in the concentration of sulfonic acid groups reduces the mechanical strength of the membrane, problems such as film reduces the ease no longer durability creep in operation occurs. 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. Thus, either One mechanical strength electric resistance low to develop a high cation exchange membrane has been desired.
【０００５】[0005]
【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、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を
固体高分子電解質として正極と負極の間に配置して有す
る燃料電池において、上記陽イオン交換膜が、異なる含
水率を有するスルホン酸基を有するパーフルオロカーボ
ン重合体フィルム２層以上の積層体からなり、前記パー
フルオロカーボン重合体フィルムは、負極に近いほど含
水率が高くなるように積層されて配置されていることを
特徴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 uses a cation exchange membrane made of a perfluorocarbon polymer having a sulfonic acid group as a solid polymer electrolyte for a positive electrode and a negative electrode. in the fuel cell having disposed between the said cation exchange membrane, Ri Do perfluorocarbon polymer film laminate of two or more layers having a sulfonic acid group having a different moisture content, the par
The fluorocarbon polymer film is included nearer to the negative electrode.
It is intended to provide a solid polymer electrolyte fuel cell, which is characterized in that the solid polymer electrolyte fuel cells are arranged so as to have a high water content.
【０００６】本発明で陽イオン交換膜は、燃料電池にお
いて負極に近いほど含水率が高い重合体フィルムが配置
されるように、含水率の異なる重合体フィルムを積層し
た構造を有する。負極に隣接するパーフルオロカーボン
重合体フィルムの含水率は、正極に隣接するパーフルオ
ロカーボン重合体フィルムの含水率よりも、５〜５０重
量％、特には１０〜３０重量％大きくするのが好まし
い。陽イオン交換膜を構成するパーフルオロカーボン重
合体の各フィルムの含水率は３０〜１１０重量％、特に
は３５〜９５重量％に制御するのが好ましい。[0006] Cation-exchange membranes in the present invention, such that the water content is high polymer film closer to the negative electrode in the fuel cell is arranged, that having a structure obtained by stacking different polymeric films having water content. The water content of the perfluorocarbon polymer film adjacent to the negative electrode is preferably 5 to 50% by weight, more preferably 10 to 30% by weight, higher than the water content of the perfluorocarbon polymer film adjacent to the positive electrode. It is preferable to control the water content of each film of the perfluorocarbon polymer constituting the cation exchange membrane to 30 to 110% by weight, particularly 35 to 95% by weight.
【０００７】本発明で重合体フィルム（スルホン酸型）
の含水率ΔＷは以下のように定義される。
ΔＷ＝（Ｗ1／Ｗ2−１）×１００（重量％）
Ｗ1：９０℃、純水中、２４時間浸漬後の膜重量。
Ｗ2：Ｗ1を測定後、１００℃にて１６時間真空乾燥した
後の膜重量。Polymer film ( sulfonic acid type) according to the present invention
The water content ΔW of is defined as follows. ΔW = (W 1 / W 2 −1) × 100 (wt%) W 1 : 90 ° C., film weight after immersion in pure water for 24 hours. W 2 : The film weight after vacuum-drying at 100 ° C. for 16 hours after measuring W 1 .
【０００８】パーフルオロカーボン重合体フィルムは、
積層して得られる陽イオン交換膜が３０〜３００μｍ、
特には５０〜２５０μｍの膜厚を有するようにするのが
好ましい。膜厚が上記範囲より小さい場合には、膜強度
及び電極接合等における膜取扱い性が低下し、一方上限
値より大きい場合には膜抵抗が上昇し、電池の出力が低
下するため好ましくない。The perfluorocarbon polymer film is
The cation exchange membrane obtained by stacking is 30 to 300 μm,
Preferably, to have a thickness of 50~250μm is especially. When the film thickness is smaller than the above range, the film strength and the film handling property in electrode bonding and the like are deteriorated. On the other hand, when the film thickness is larger than the upper limit, the film resistance is increased and the battery output is decreased, which is not preferable.
【０００９】本発明に用いられるスルホン酸基を有する
（以下、スルホン酸型という。）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とＣＦ2＝Ｃ
Ｆ−（ＯＣＦ2ＣＦＸ）m−Ｏq−（ＣＦ2）n−Ａ（式中
ｍは０〜３、ｎは０〜１２、ｑは０又は１、ＸはＦ又は
ＣＦ3、Ａはスルホン酸基。）で表されるフルオロビニ
ル化合物との共重合体が好ましく採用可能である。[0009] to have a sulfonic acid group to be used in the present invention
(Hereinafter, referred to as sulfonic acid type.) Perfluorocarbon polymers include tetrafluoroethylene and CF 2 ═C
F- (OCF 2 CFX) m -O q - (CF 2) n -A ( wherein m is 0 to 3, n is 0 to 12, q is 0 or 1, X is F or CF 3, A is sulfone A copolymer with a fluorovinyl compound represented by an acid group can be preferably used.
【００１０】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） r ＳＯ 3 Ｈ、ＣＦ2＝Ｃ
ＦＯＣＦ2ＣＦ（ＣＦ3）Ｏ（ＣＦ2） s ＳＯ 3 Ｈ、ＣＦ2＝
ＣＦ（ＣＦ2） t ＳＯ 3 Ｈ、ＣＦ2＝ＣＦ（ＯＣＦ2ＣＦ
（ＣＦ3）） u Ｏ（ＣＦ2）2ＳＯ 3 Ｈ、などが挙げられ
る。ただし、ｒは１〜８であり、ｓは１〜８であり、ｔ
は０〜８であり、ｕは１〜５である。 Preferred examples of the fluorovinyl compound include CF 2 ═CFO (CF 2 ) r SO 3 H and CF 2 ═C.
FOCF 2 CF (CF 3 ) O (CF 2 ) s SO 3 H, CF 2 =
CF (CF 2 ) t SO 3 H, CF 2 ═CF (OCF 2 CF
(CF 3 )) u O (CF 2 ) 2 SO 3 H, and the like. However, r is 1-8, s is 1-8, and t
Is 0 to 8 and u is 1 to 5.
【００１１】なお、スルホン酸型パーフルオロカーボン
重合体を構成するためのコモノマーである上記テトラフ
ルオロエチレンの代わりにヘキサフルオロプロピレンの
如きパーフルオロオレフィン、パーフルオロ（アルキル
ビニルエーテル）等を用いることも可能である。[0011] Incidentally, the tetrafluoroethylene is a co-monomer for constituting the sulfonic acid type perfluorocarbon polymer instead of hexafluoropropylene
It is also possible to use such perfluoroolefin, perfluoro (Al kill <br/> vinyl ether) and the like.
【００１２】上記パーフルオロカーボン重合体フィルム
の積層体である陽イオン交換膜は、フィブリル状、織布
状、又は不織布状のパーフルオロカーボン重合体で補強
することもできる。The cation exchange membrane, which is a laminate of the above-mentioned perfluorocarbon polymer film, can be reinforced with a fibril-like, woven fabric-like or non-woven fabric-like perfluorocarbon polymer.
【００１３】本発明における、異なる含水率を有する重
合体フィルムの積層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、次いで集電体を取り付け、燃料電池として組み立て
られる。[0013] In the present invention, the cation exchange membrane made of a laminate of polymer film having a different water content, on the surface thereof in accordance with conventional known techniques are brought into close contact with the gas diffusion electrode, then fitted with a current collector, a fuel It is assembled as a battery.
【００１４】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（以下、ＰＴＦＥという。）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、該多孔質体がスルホン酸型パーフルオロカーボン重
合体や該重合体で表面を被覆された微粒子を含んでいて
もよい。ガス拡散電極とスルホン酸型パーフルオロカー
ボン重合体とは加熱プレス法等により密着される。The gas diffusion electrode is usually a porous body in which conductive carbon black powder carrying platinum catalyst fine particles is held by a hydrophobic resin binder such as polytetrafluoroethylene (hereinafter referred to as PTFE). Although it is made of a sheet, the porous body may contain a sulfonic acid type perfluorocarbon polymer or fine particles whose surface is coated with the polymer. The gas diffusion electrode and the sulfonic acid type perfluorocarbon polymer are adhered to each other by a hot pressing method or the like.
【００１５】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。As the current collector, there is used a conductive carbon plate or the like in which a groove serving as a passage for fuel gas or oxidant gas is formed.
【００１６】[0016]
【作用】本発明で良好な効果が達成される機構は必ずし
も明らかではないが、以下のように考えられる。水素ガ
ス燃料電池においては以下の反応に従って化学エネルギ
ーが電気エネルギーに変換される。
負極： Ｈ2→２Ｈ+＋２ｅ-
正極： １／２Ｏ2＋２Ｈ+＋２ｅ-→Ｈ2Ｏ
燃料電池における陽イオン交換膜中のプロトンの移動性
は、該膜の含水率に大きく関わっており、含水率が高い
ほどプロトンの移動性は高く、膜抵抗は低下する。Mechanisms good effect is achieved DETAILED DESCRIPTION OF THE INVENTION The present invention is not necessarily clear, Ru is considered as follows. In a hydrogen gas fuel cell, chemical energy is converted into electric energy according to the following reaction. Negative electrode: H 2 → 2H + + 2e − Positive electrode: 1 / 2O 2 + 2H + + 2e − → H 2 O The mobility of protons in the cation exchange membrane in a fuel cell is greatly related to the water content of the membrane. higher rates are high mobility of protons is high, the membrane resistance is lowered.
【００１７】陽イオン交換膜の正極側は上記の反応に従
って水を発生するため、高含水状態となりプロトンの移
動性も高い状態に維持されるが、一方、膜の負極側は相
対的に含水率が低くなり、膜中のプロトンの移動は負極
が律速になると推定される。かかる膜の負極側に高い含
水率を有する層を設置することにより、プロトンの移動
性の低下を防ぐことが可能であり、結果として燃料電池
の高出力化が達成されると考えられる。Since the positive electrode side of the cation exchange membrane generates water in accordance with the above reaction, it is in a high water content state and the mobility of protons is also kept high, while the negative electrode side of the membrane has a relatively high water content. It is estimated that the negative electrode becomes rate-determining for the movement of protons in the film. By installing a layer having a high moisture content in the negative electrode side of such membranes, it is possible to prevent a decrease in mobility of protons, it is believed higher output of the fuel cell as a result is achieved.
【００１８】[0018]
【実施例】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、ＣＦ2＝ＣＦ2とＣＦ2＝ＣＦＯＣＦ2ＣＦ（Ｃ
Ｆ3）Ｏ（ＣＦ2）2ＳＯ2Ｆとの共重合体からなるイオン
交換容量１．０ミリ当量／ｇ乾燥樹脂、及び１．１ミリ
当量／ｇ乾燥樹脂の２種類の共重合体を得た。前者の共
重合体を２２０℃で押し出し製膜し、厚さ８０μｍのフ
ィルムを得た。次に後者の共重合体を２２０℃で押し出
し製膜し、厚さ２０μｍのフィルムを得た。EXAMPLES Example 1 Based on the method described in JP-A-2-88645, CF 2 ═CF 2 and CF 2 ═CF OC F 2 CF ( C
Two types of copolymers having an ion exchange capacity of 1.0 meq / g dry resin and 1.1 meq / g dry resin, which are copolymers with F 3 ) O (CF 2 ) 2 SO 2 F, are prepared. Obtained. The former copolymer was extruded at 220 ° C. to form a film having a thickness of 80 μm. Next, the latter copolymer was extruded at 220 ° C. to form a film, to obtain a film having a thickness of 20 μm.
【００１９】上記２種類の共重合体フィルムを２２０℃
でロールを用いて積層、接合し、ジメチルスルホキシド
３０重量％と苛性カリ１５重量％とを含む水溶液中で加
水分解を行い、水洗した後１Ｎの塩酸中に浸漬して酸型
化した。次に膜を水洗し、膜の四辺を専用治具で拘束し
た後６０℃で１時間乾燥し陽イオン交換膜を製造した。The above two kinds of copolymer films are heated at 220 ° C.
Are laminated and bonded using a roll, hydrolyzed in an aqueous solution containing 30% by weight of dimethyl sulfoxide and 15% by weight of caustic potash, washed with water and then immersed in 1N hydrochloric acid to form an acid form.
It was of. Next, the membrane was washed with water, the four sides of the membrane were restrained by dedicated jigs, and then dried at 60 ° C. for 1 hour to produce a cation exchange membrane.
【００２０】イオン交換容量１．０ミリ当量／ｇ乾燥樹
脂の共重合体フィルム及び１．１ミリ当量／ｇ乾燥樹脂
の共重合体フィルムの９０℃の純水中の含水率はそれぞ
れ、５０重量％及び７０重量％であった。Ion exchange capacity: 1.0 meq / g dry resin copolymer film and 1.1 meq / g dry resin copolymer film have a water content of 50% by weight in pure water at 90 ° C. % and was 70 wt%.
【００２１】この陽イオン交換膜を用いた燃料電池特性
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ＰＴＦＥを混ぜ、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。この
ガス拡散電極２枚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１ｃｍ
2当り１ｍｇであった。Fuel cell characteristics using this cation exchange membrane were evaluated. Ze mixed with PTFE carbon black powder of carrying platinum catalyst particles, to prepare a sheet-shaped gas diffusion electrode having a thickness of 250μm by using a roll press. this
To prepare a membrane electrode assembly by between two gas diffusion electrodes and inserting said cation exchange membrane is laminated using a plate heat press machine. The amount of platinum catalyst in the membrane electrode assembly is 1 cm
It was 1 mg per 2 .
【００２２】次に、膜電極接合体をチタン製の集電体、
ＰＴＦＥ製のガス供給室、ヒーターの順番で両側からは
さみ、有効膜面積９ｃｍ2の燃料電池を組みあげた。こ
のとき負極側に陽イオン交換膜の１．１ミリ当量ｇ／乾
燥樹脂の重合体フィルムが、正極側に１．０ミリ当量／
ｇ乾燥樹脂の重合体フィルムが隣接するように燃料電池
を組みあげた。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気圧で供給したときの電流
密度に対する端子電圧を測定したところ、電流密度１Ａ
／ｃｍ2 においてセル電圧０．６２Ｖであった。Next, the membrane electrode assembly was replaced with a titanium current collector,
A gas supply chamber made of PTFE and a heater were sandwiched in this order from both sides, and a fuel cell having an effective membrane area of 9 cm 2 was assembled. The polymer film of 1.1 meq g / dry resin in this case the cation-exchange membrane on the anode side, the cathode side 1.0 meq /
The fuel cell was assembled with the polymer films of dry resin adjacent . When the cell temperature was maintained at 80 ° C. and oxygen was supplied to the positive electrode and hydrogen was supplied to the negative electrode at 5 atm, the terminal voltage was measured with respect to the current density.
It was the cell voltage 0.62V at / cm 2.
【００２３】比較例１
実施例１で使用したのと同じイオン交換容量１．０ミリ
当量／ｇ乾燥樹脂の共重合体単独を２２０℃で押し出し
製膜し、厚さ１００μｍのフィルムを得た。これに実施
例１と同様な処理を施し、陽イオン交換膜を製造した。
実施例１と同様な方法により燃料電池を組みあげた後、
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 においてセル電圧０．６０
Ｖであった。[0023] Comparative Example 1 A copolymer alone with the same ion exchange capacity 1.0 millimeters as used in Example 1 eq / g dry resin and press and out casting at 220 ° C., to obtain a film having a thickness of 100μm It was This was treated in the same manner as in Example 1 to produce a cation exchange membrane.
After assembling the fuel cell by the same method as in Example 1,
When the terminal voltage with respect to the current density was measured under the same conditions , the cell voltage was 0.60 at a current density of 1 A / cm 2 .
It was V.
【００２４】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、燃料電池を組み
あげたときのエネルギー損失が小さい。As can be seen from the above results, the cation exchange membrane of Example 1 has a smaller energy loss when the fuel cell is assembled than the membrane of Comparative Example 1.
【００２５】[0025]
【発明の効果】燃料電池の作動時に従来膜にない低い電
気抵抗を有する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 A high performance solid polymer electrolyte fuel cell can be obtained by using a cation exchange membrane having a low electric resistance, which is not present in conventional membranes when the fuel cell is operated , as a solid polymer electrolyte.
───────────────────────────────────────────────────── フロントページの続き (56)参考文献 特開 平２−88645（ＪＰ，Ａ) 特開 昭58−199884（ＪＰ，Ａ) 特開 平４−264367（ＪＰ，Ａ) 特開 昭57−25331（ＪＰ，Ａ) 特開 昭54−112398（ＪＰ，Ａ) 特開 平６−84528（ＪＰ，Ａ) 特開 平６−231778（ＪＰ，Ａ) 特開 平４−366137（ＪＰ，Ａ) 特表 昭58−500570（ＪＰ，Ａ) 特表 昭62−500759（ＪＰ，Ａ) (58)調査した分野(Int.Cl.7，ＤＢ名) H01M 8/00 - 8/24 H01M 4/86 - 4/98 ─────────────────────────────────────────────────── ─── Continuation of front page (56) Reference JP-A-2-88645 (JP, A) JP-A-58-199884 (JP, A) JP-A-4-264367 (JP, A) JP-A-57- 25331 (JP, A) JP 54-112398 (JP, A) JP 6-84528 (JP, A) JP 6-231778 (JP, A) JP 4-366137 (JP, A) Special table Sho 58-500570 (JP, A) Special table Sho 62-500759 (JP, A) (58) Fields investigated (Int.Cl. 7 , DB name) H01M 8/00-8/24 H01M 4/86 -4/98
Claims (4)
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
して正極と負極の間に配置して有する燃料電池におい
て、上記陽イオン交換膜が、異なる含水率を有するスル
ホン酸基を有するパーフルオロカーボン重合体フィルム
２層以上の積層体からなり、前記パーフルオロカーボン
重合体フィルムは、負極に近いほど含水率が高くなるよ
うに積層されて配置されてい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 having a cation exchange membrane made of a perfluorocarbon polymer having a sulfonic acid group as a solid polymer electrolyte disposed between a positive electrode and a negative electrode, wherein the cation exchange membranes have different water contents. sul with
Ri Do perfluorocarbon polymer film laminate of two or more layers having acid groups, the perfluorocarbon
The polymer film has higher water content as it approaches the negative electrode.
A solid polymer electrolyte fuel cell, wherein the solid polymer electrolyte fuel cells are arranged so as to be stacked .
体フィルムの含水率が、正極に隣接するパーフルオロカ
ーボン重合体フィルムの含水率よりも５〜５０重量％高
い請求項１に記載の固体高分子電解質型燃料電池。2. The solid polymer electrolyte type according to claim 1, wherein the water content of the perfluorocarbon polymer film adjacent to the negative electrode is 5 to 50% by weight higher than the water content of the perfluorocarbon polymer film adjacent to the positive electrode. Fuel cell.
含水率が３０〜１１０重量％である請求項１又は２に記
載の固体高分子電解質型燃料電池。3. A solid polymer electrolyte fuel cell according to claim 1 or 2 water content of the perfluorocarbon polymer film is 30 to 110% by weight.
Ｆ２とＣＦ２＝ＣＦ−（ＯＣＦ２ＣＦＸ）ｍ−Ｏｑ−
（ＣＦ２）ｎ−Ａ（式中ｍは０〜３、ｎは０〜１２、ｑ
は０又は１、ＸはＦ又はＣＦ３、Ａはスルホン酸基。）
との共重合体からなる請求項１、２又は３に記載の固体
高分子電解質型燃料電池。4. The perfluorocarbon polymer is CF 2 ═C.
F 2 and CF 2 = CF- (OCF 2 CFX ) m -O q -
(CF 2) n -A (wherein m is 0 to 3, n is 0 to 12, q
Is 0 or 1, X is F or CF 3 , and A is a sulfonic acid group. )
Solid polymer electrolyte fuel cell according to claim 1, 2 or 3 comprising a copolymer of.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP03941993A JP3382654B2 (en) | 1993-02-03 | 1993-02-03 | Solid polymer electrolyte fuel cell |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP03941993A JP3382654B2 (en) | 1993-02-03 | 1993-02-03 | Solid polymer electrolyte fuel cell |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH06231781A JPH06231781A (en) | 1994-08-19 |
| JP3382654B2 true JP3382654B2 (en) | 2003-03-04 |
Family
ID=12552469
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP03941993A Expired - Fee Related JP3382654B2 (en) | 1993-02-03 | 1993-02-03 | Solid polymer electrolyte fuel cell |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3382654B2 (en) |
Families Citing this family (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3714766B2 (en) * | 1997-04-04 | 2005-11-09 | 旭化成ケミカルズ株式会社 | Electrode and membrane / electrode assembly for polymer electrolyte fuel cell |
| DE19854728B4 (en) | 1997-11-27 | 2006-04-27 | Aisin Seiki K.K., Kariya | Polymer electrolyte fuel cell |
| JP3485032B2 (en) | 1999-07-02 | 2004-01-13 | トヨタ自動車株式会社 | Fuel cell and solid polymer electrolyte membrane |
| JP2001243964A (en) * | 2000-02-28 | 2001-09-07 | Asahi Glass Co Ltd | Solid polymer electrolyte fuel cell |
| US20040036394A1 (en) * | 2002-08-21 | 2004-02-26 | 3M Innovative Properties Company | Process for preparing multi-layer proton exchange membranes and membrane electrode assemblies |
| US7348088B2 (en) * | 2002-12-19 | 2008-03-25 | 3M Innovative Properties Company | Polymer electrolyte membrane |
| JP2005019041A (en) * | 2003-06-24 | 2005-01-20 | Chiba Inst Of Technology | Battery using solid electrolyte layer and hydrogen permeable metal film, fuel battery, and its manufacturing method |
| KR100684787B1 (en) * | 2005-03-31 | 2007-02-20 | 삼성에스디아이 주식회사 | Polymer membrane for fuel cell, method of preparing the same, and stack for fuel cell and full cell system comprising the same |
| JP2007026819A (en) * | 2005-07-14 | 2007-02-01 | Jsr Corp | Electrode-membrane assembly |
| JP5504552B2 (en) * | 2005-10-28 | 2014-05-28 | 東レ株式会社 | Asymmetric electrolyte membrane, membrane electrode assembly and polymer electrolyte fuel cell using the same |
| JP5109311B2 (en) * | 2005-12-27 | 2012-12-26 | 日産自動車株式会社 | Membrane electrode assembly and fuel cell using the same |
| JP5059341B2 (en) * | 2006-05-09 | 2012-10-24 | 株式会社トクヤマ | Diaphragm for direct liquid fuel cell |
| JP5110348B2 (en) * | 2006-08-14 | 2012-12-26 | 日産自動車株式会社 | Solid polymer electrolyte membrane, production method thereof, and solid polymer fuel cell |
| JP2009070631A (en) | 2007-09-11 | 2009-04-02 | Fujifilm Corp | Electrolyte membrane, membrane electrode assembly, and fuel cell using membrane electrode assembly |
| US10734660B2 (en) | 2016-03-10 | 2020-08-04 | Nissan North America, Inc. | Functionalized carbon layer for membrane degradation mitigation under fuel cell operating conditions |
-
1993
- 1993-02-03 JP JP03941993A patent/JP3382654B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH06231781A (en) | 1994-08-19 |
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