JP2002313363A - Solid polymer electrolyte film and its manufacturing method - Google Patents
Solid polymer electrolyte film and its manufacturing methodInfo
- Publication number
- JP2002313363A JP2002313363A JP2001114846A JP2001114846A JP2002313363A JP 2002313363 A JP2002313363 A JP 2002313363A JP 2001114846 A JP2001114846 A JP 2001114846A JP 2001114846 A JP2001114846 A JP 2001114846A JP 2002313363 A JP2002313363 A JP 2002313363A
- Authority
- JP
- Japan
- Prior art keywords
- polymer electrolyte
- solid polymer
- film
- electrolyte membrane
- skin layer
- 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- Withdrawn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
- 239000005518 polymer electrolyte Substances 0.000 title claims abstract description 59
- 239000007787 solid Substances 0.000 title claims abstract description 57
- 238000004519 manufacturing process Methods 0.000 title claims description 4
- 239000011347 resin Substances 0.000 claims abstract description 44
- 229920005989 resin Polymers 0.000 claims abstract description 44
- 239000012528 membrane Substances 0.000 claims description 48
- 239000000758 substrate Substances 0.000 claims description 17
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 14
- TXEYQDLBPFQVAA-UHFFFAOYSA-N tetrafluoromethane Chemical compound FC(F)(F)F TXEYQDLBPFQVAA-UHFFFAOYSA-N 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 5
- 239000000446 fuel Substances 0.000 abstract description 18
- 239000002131 composite material Substances 0.000 abstract description 17
- 229920006254 polymer film Polymers 0.000 abstract description 15
- 239000003792 electrolyte Substances 0.000 abstract description 8
- 239000002737 fuel gas Substances 0.000 abstract description 4
- 239000010408 film Substances 0.000 description 23
- -1 polytetrafluoroethylene Polymers 0.000 description 11
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 11
- 239000004810 polytetrafluoroethylene Substances 0.000 description 11
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 8
- 239000003054 catalyst Substances 0.000 description 7
- 239000001257 hydrogen Substances 0.000 description 7
- 229910052739 hydrogen Inorganic materials 0.000 description 7
- 239000000243 solution Substances 0.000 description 6
- 239000011148 porous material Substances 0.000 description 5
- 150000002500 ions Chemical class 0.000 description 4
- 229920005597 polymer membrane Polymers 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- 238000005342 ion exchange Methods 0.000 description 3
- 239000003456 ion exchange resin Substances 0.000 description 3
- 229920003303 ion-exchange polymer Polymers 0.000 description 3
- 238000010248 power generation Methods 0.000 description 3
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 2
- 229920000049 Carbon (fiber) Polymers 0.000 description 2
- 229920000557 Nafion® Polymers 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 239000004917 carbon fiber Substances 0.000 description 2
- 238000005266 casting Methods 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000007731 hot pressing Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000007784 solid electrolyte Substances 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 1
- KLIDCXVFHGNTTM-UHFFFAOYSA-N 2,6-dimethoxyphenol Chemical compound COC1=CC=CC(OC)=C1O KLIDCXVFHGNTTM-UHFFFAOYSA-N 0.000 description 1
- 239000004962 Polyamide-imide Substances 0.000 description 1
- 239000004697 Polyetherimide Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 229940034040 ethanol / isopropyl alcohol Drugs 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- DWYMPOCYEZONEA-UHFFFAOYSA-N fluorophosphoric acid Chemical compound OP(O)(F)=O DWYMPOCYEZONEA-UHFFFAOYSA-N 0.000 description 1
- UQSQSQZYBQSBJZ-UHFFFAOYSA-N fluorosulfonic acid Chemical compound OS(F)(=O)=O UQSQSQZYBQSBJZ-UHFFFAOYSA-N 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 239000003014 ion exchange membrane Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920000172 poly(styrenesulfonic acid) Polymers 0.000 description 1
- 229920002312 polyamide-imide Polymers 0.000 description 1
- 229920001601 polyetherimide Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229940005642 polystyrene sulfonic acid Drugs 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Landscapes
- Fuel Cell (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、固体高分子電解質
型燃料電池に利用できる固体高分子電解質膜に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a solid polymer electrolyte membrane which can be used for a solid polymer electrolyte fuel cell.
【０００２】[0002]
【従来の技術】固体高分子電解質型燃料電池は、電解質
として固体高分子膜であるイオン交換樹脂膜を用い、こ
の膜の両面に電極を接合した構造を有する。このイオン
交換樹脂膜としては、発生したイオンが速やかに移動で
きるプロトン伝導性固体電解質膜（例えば米国デュポン
社製ナフィオン＃１１７等）や、その溶液をキャストし
て薄膜状に成形された物が使用されている。燃料電池と
して使用する際に高分子固体電解質膜は、それ自体の膜
抵抗が低い必要があり、その為には膜厚はできるだけ薄
い方が望ましい。しかしながら、膜厚をあまり薄くする
と、製膜時にピンホールが生じたり、電極成形時に膜が
破れてしまったり、電極間の短絡が発生したりしやすい
という問題点があった。また、燃料電池使用される高分
子固体電解質膜は、常に湿潤状態で使用されるため、湿
潤による高分子膜の膨潤、変形等による差圧運転時の耐
圧性やクロスリーク等、信頼性に問題が生じるようにな
る。特開平９−１２０８２７号に薄膜化が可能な固体高
分子電解質膜が示されているが、それでも厚さは５０μ
ｍあり、上述の膜抵抗の問題とともに、クロスリークの
問題等が発現する可能性があり、信頼性が不十分であ
る。また、図２は従来の固体高分子電解質膜の断面の模
式図である。図２に示すように、固体高分子電解質膜１
の強度アップを図るため、多孔質樹脂に固体高分子電解
質を担持させた基体膜２を用いる方法があるが、この基
体膜２は網状のためにクロスリークが時間経過とともに
増加し、燃料電池の出力電圧に影響を与えるという問題
がある。2. Description of the Related Art A solid polymer electrolyte fuel cell has a structure in which an ion exchange resin membrane which is a solid polymer membrane is used as an electrolyte, and electrodes are bonded to both surfaces of the membrane. As the ion-exchange resin membrane, a proton-conductive solid electrolyte membrane (for example, Nafion # 117 manufactured by DuPont, U.S.A.) in which generated ions can be quickly transferred, or a thin film formed by casting a solution thereof is used. Have been. When used as a fuel cell, the polymer solid electrolyte membrane needs to have a low membrane resistance itself, and for that purpose, the membrane thickness is desirably as small as possible. However, when the film thickness is too small, there are problems that a pinhole is generated at the time of film formation, the film is broken at the time of forming the electrode, and a short circuit between the electrodes is apt to occur. In addition, since the solid polymer electrolyte membrane used in the fuel cell is always used in a wet state, there are problems in reliability, such as pressure resistance and cross leak during differential pressure operation due to swelling and deformation of the polymer membrane due to wetting. Will occur. Japanese Patent Application Laid-Open No. 9-120827 discloses a solid polymer electrolyte membrane that can be made thinner, but it still has a thickness of 50 μm.
m, there is a possibility that a problem of cross leak may occur along with the above-mentioned problem of the film resistance, and the reliability is insufficient. FIG. 2 is a schematic view of a cross section of a conventional solid polymer electrolyte membrane. As shown in FIG. 2, the solid polymer electrolyte membrane 1
In order to increase the strength of the fuel cell, there is a method of using a base membrane 2 in which a solid polymer electrolyte is supported on a porous resin. There is a problem that the output voltage is affected.
【０００３】[0003]
【発明が解決しようとする課題】本発明は、薄膜化が可
能で、強度が高く、かつ燃料ガスのクロスリーク量が少
ない複合ポリマー膜を提供し、この複合ポリマー膜を固
体高分子電解質膜として用いることによって、出力電圧
および電流密度が向上された燃料電池を提供することを
目的とする。SUMMARY OF THE INVENTION The present invention provides a composite polymer film which can be formed into a thin film, has a high strength, and has a small amount of fuel gas cross leak. This composite polymer film is used as a solid polymer electrolyte membrane. It is an object of the present invention to provide a fuel cell whose output voltage and current density are improved by using it.
【０００４】[0004]
【課題を解決するための手段】本発明に係る固体高分子
電解質膜の製造方法は、多孔質樹脂基体膜に固体高分子
電解質を含浸させて析出させ、該固体高分子電解質の一
部分を該多孔質樹脂基体膜の少なくとも一方の面にスキ
ン層として形成させることを特徴とする。The method for producing a solid polymer electrolyte membrane according to the present invention comprises a step of impregnating and depositing a solid polymer electrolyte into a porous resin substrate membrane, and partially disposing the solid polymer electrolyte in the porous polymer electrolyte membrane. Characterized in that it is formed as a skin layer on at least one surface of the porous resin substrate film.
【０００５】また、本発明は、多孔質樹脂基体膜に固体
高分子電解質を含浸させて析出させ、該固体高分子電解
質の一部分を該多孔質樹脂基体膜の少なくとも一方の面
にスキン層として形成して得られる固体高分子電解質膜
を提供する。さらに、本発明は、多孔質樹脂と固体高分
子電解質とを含んでなる基体膜と、該基体膜の少なくと
も一方の面に一体に置かれる固体高分子電解質スキン層
とからなる固体高分子電解質膜を提供する。The present invention also relates to a porous resin substrate film impregnated with a solid polymer electrolyte and precipitated, and a part of the solid polymer electrolyte is formed as a skin layer on at least one surface of the porous resin substrate film. And a solid polymer electrolyte membrane obtained by the method. Further, the present invention provides a solid polymer electrolyte membrane comprising: a base film comprising a porous resin and a solid polymer electrolyte; and a solid polymer electrolyte skin layer integrally disposed on at least one surface of the base film. I will provide a.
【０００６】上記スキン層の厚さは１．５〜９．０μｍ
が好ましく、２．５〜７．５μｍがより好ましい。ま
た、上記固体高分子電解質として、パーフルオロカーボ
ンスルホン酸樹脂を用いることができる。The skin layer has a thickness of 1.5 to 9.0 μm.
Is preferably, and more preferably 2.5 to 7.5 μm. Further, a perfluorocarbon sulfonic acid resin can be used as the solid polymer electrolyte.
【０００７】本発明によれば、固体高分子電解質膜は、
電解質膜の厚さを前記多孔質樹脂基体膜の厚さで調節す
ることができるので、従来のパーフルオロカーボンスル
ホン酸樹脂を膜状に成形した電解質膜に比べて厚さを薄
くすることが可能である。また、多孔質樹脂を電解質膜
の支持体として用いるため、電解質膜の強度を補強する
ことができる。したがって、本発明に係る固体高分子電
解質膜を備えた燃料電池は、燃料ガスのクロスリーク量
が少なく、電流−電圧特性を向上することができる。According to the present invention, a solid polymer electrolyte membrane
Since the thickness of the electrolyte membrane can be adjusted by the thickness of the porous resin substrate membrane, the thickness can be reduced as compared with a conventional electrolyte membrane formed from a perfluorocarbon sulfonic acid resin in a membrane shape. is there. Further, since the porous resin is used as a support for the electrolyte membrane, the strength of the electrolyte membrane can be reinforced. Therefore, the fuel cell provided with the solid polymer electrolyte membrane according to the present invention can reduce the amount of cross leak of the fuel gas and improve the current-voltage characteristics.
【０００８】[0008]
【発明の実施の形態】添付図面を参照して、本発明の実
施の形態を説明する。図１に、本発明に係る固体高分子
電解質膜の断面の模式図を示す。固体高分子電解質膜１
は、多孔質樹脂基体膜に固体高分子電解質を含浸させて
析出させることにより、前記固体高分子電解質の一部分
が前記多孔質樹脂基体膜の両面にそれぞれ１．５〜９．
０μｍの厚さでスキン層３として形成する複合ポリマー
膜である。スキン層３の厚さを１．５μｍ未満とする複
合ポリマー膜の作製は技術的に難しいが、また、薄すぎ
てもスキン層の役割をなさない。スキン層は、ガスの透
過量をコントロールすることを目的としており、水素ガ
スを遮断する効果も期待される。一方、９μｍを超える
とそれ自体が膜となる程に厚くなり過ぎ、複合ポリマー
膜を作製するのに適さない。より好ましいスキン層３の
厚さは２．５〜７．５μｍである。多孔質樹脂基体膜に
は固体高分子電解質が担持され、多孔質樹脂と固体高分
子電解質とを含んでなる基体膜２を形成する。Embodiments of the present invention will be described with reference to the accompanying drawings. FIG. 1 shows a schematic diagram of a cross section of a solid polymer electrolyte membrane according to the present invention. Solid polymer electrolyte membrane 1
Is a method in which a solid polymer electrolyte is impregnated into a porous resin substrate film and precipitated, so that a portion of the solid polymer electrolyte is 1.5 to 9.
This is a composite polymer film formed as a skin layer 3 with a thickness of 0 μm. Although it is technically difficult to produce a composite polymer film in which the thickness of the skin layer 3 is less than 1.5 μm, if it is too thin, it does not serve as a skin layer. The skin layer is intended to control the gas permeation amount, and is expected to have an effect of blocking hydrogen gas. On the other hand, if it exceeds 9 μm, the film itself becomes too thick to form a film, which is not suitable for producing a composite polymer film. More preferably, the thickness of the skin layer 3 is 2.5 to 7.5 μm. A solid polymer electrolyte is supported on the porous resin base film, and a base film 2 including the porous resin and the solid polymer electrolyte is formed.
【０００９】前記多孔質樹脂基体膜としては、厚さが１
０〜３０μｍ（好ましくは１５〜２５μｍ）で、細孔径
が０．２〜５．０μｍ（好ましくは、０．４５〜３．０
μｍ）で、空隙率が７５〜９５％（好ましくは８０〜９
０％）の多孔質なポリテトラフルオロエチレンシート
（ＰＴＦＥ）を挙げることができる。前記ＰＴＦＥの他
にも、ポリプロピレン（ＰＰ）やポリエチレン（ＰＥ）
等の多孔質体を用いることができ、強度が保たれる多孔
質体であれば特に限定されない。[0009] The porous resin substrate film has a thickness of 1
0 to 30 μm (preferably 15 to 25 μm) and a pore diameter of 0.2 to 5.0 μm (preferably 0.45 to 3.0).
μm) and a porosity of 75 to 95% (preferably 80 to 9%).
0%) porous polytetrafluoroethylene sheet (PTFE). In addition to the PTFE, polypropylene (PP) and polyethylene (PE)
Such a porous body can be used, and is not particularly limited as long as the porous body maintains strength.
【００１０】前記多孔質樹脂基体膜の厚さ、細孔径、空
隙率を前記範囲に限定したのは次のような理由によるも
のである。前記厚さを１０μｍ以下にすると、前述電解
質膜を製造する際にハンドリング等の面で破損等の不良
を生じるのみでなく、スキン層の厚さも厚くなり、電解
質膜のイオン移動抵抗に起因する電気抵抗が増大する。
一方、前記厚さが３０μｍを越えると、固体高分子電解
質を含浸させて析出させる際の均一性が損なわれる恐れ
がある。また、スキン層の厚さは薄くなり、燃料電池を
運転する際に水素および酸素のクロスリークを生じ、燃
料電池の性能が低下するおそれがある。また、前記多孔
質樹脂基体膜の細孔径を０．２μｍ未満にすると固体高
分子電解質の含浸が難しくなり、５．０μｍを超えると
固体高分子電解質の保持が難しくなるとともに基体膜の
強度も低下する。同様に、前記多孔質樹脂基体膜の空隙
率を７５％未満にすると基体膜の強度が低下し、９５％
を超えると膜抵抗が高くなる。The thickness, pore diameter, and porosity of the porous resin substrate film are limited to the above ranges for the following reasons. When the thickness is 10 μm or less, not only defects such as breakage in handling and the like occur when the above-mentioned electrolyte membrane is manufactured, but also the thickness of the skin layer becomes thicker, and the electricity caused by the ion transfer resistance of the electrolyte membrane is increased. The resistance increases.
On the other hand, if the thickness exceeds 30 μm, the uniformity in impregnating and depositing the solid polymer electrolyte may be impaired. Further, the thickness of the skin layer becomes thin, and cross-leakage of hydrogen and oxygen may occur when the fuel cell is operated, and the performance of the fuel cell may be reduced. If the pore diameter of the porous resin substrate membrane is less than 0.2 μm, impregnation with the solid polymer electrolyte becomes difficult, and if it exceeds 5.0 μm, the retention of the solid polymer electrolyte becomes difficult and the strength of the substrate membrane decreases. I do. Similarly, when the porosity of the porous resin substrate film is less than 75%, the strength of the substrate film is reduced,
If it exceeds, the film resistance increases.
【００１１】前記固体高分子電解質としては、パーフル
オロカーボンスルホン酸樹脂が好ましい。パーフルオロ
カーボンスルホン酸樹脂はイオン電導性がある樹脂材料
であり、イオン交換膜として利用されている。また、フ
ッ素系であり耐久性に優れている。前記パーフルオロカ
ーボンスルホン酸樹脂として、例えば、米国のＡｌｄｒ
ｉｃｈ Ｃｈｅｍｉｃａｌ Ｃｏｍｐａｎｙ，Ｉｎｃ．
からＮａｆｉｏｎ Ｓｏｌｕｔｉｏｎとして販売されて
いる５％のパーフルオロカーボンスルホン酸樹脂（イオ
ン交換容量が約０．９ｍｅｑ／ｇ）を含む低級脂肪族ア
ルコール溶液等を挙げることができる。また本発明は、
パーフルオロカーボンスルホン酸樹脂以外のイオン交換
樹脂に対しても適用できる。例えば、スルホン化ポリア
ミドイミド樹脂、スルホン化ポリスルホン酸樹脂、スル
ホン化ポリエーテルイミド半透膜、パーフルオロスルホ
ン酸樹脂、パーフルオロホスホン酸樹脂、ポリスチレン
スルホン酸樹脂、ポリトリフルオロスチレンスルホン酸
樹脂等を用いることができ、特に限定されないがスルホ
ン酸等イオン伝導能を有する基を含む樹脂が望ましい。The solid polymer electrolyte is preferably a perfluorocarbon sulfonic acid resin. Perfluorocarbon sulfonic acid resin is a resin material having ion conductivity, and is used as an ion exchange membrane. Further, it is fluorine-based and has excellent durability. As the perfluorocarbon sulfonic acid resin, for example, US Aldr
ich Chemical Company, Inc.
And a lower aliphatic alcohol solution containing 5% of a perfluorocarbon sulfonic acid resin (ion exchange capacity is about 0.9 meq / g) and sold as Nafion Solution. The present invention also provides
It can be applied to ion exchange resins other than perfluorocarbon sulfonic acid resins. For example, a sulfonated polyamideimide resin, a sulfonated polysulfonic acid resin, a sulfonated polyetherimide semipermeable membrane, a perfluorosulfonic acid resin, a perfluorophosphonic acid resin, a polystyrenesulfonic acid resin, a polytrifluorostyrenesulfonic acid resin, or the like is used. Although not particularly limited, a resin containing a group having ion conductivity such as sulfonic acid is preferable.
【００１２】本発明に係る固体高分子電解質膜を用いる
燃料電池について説明する。前記燃料電池を構成する電
極には、電極触媒が担持された電極を用いることができ
る。例えば、カーボンブラックおよびポリテトラフルオ
ロエチレンの混合物を圧延によりシート状に成形した
後、これに触媒成分を含有する溶液を塗布し、酸化ある
いは熱分解・水素還元処理を施すことにより触媒を担持
した電極や、炭素繊維織物や炭素繊維を抄紙後、焼成に
より成形された紙状の物などの多孔質基体上にポリテト
ラフルオロエチレンと共に電極触媒粉末を担持した電極
や、高分子電解質に電極触媒粉末を分散させた溶液を、
キャスト製膜・乾燥し、これをホットプレスにより直接
固体高分子電解質膜に貼り合わせる電極等が挙げられ
る。なお、前記燃料電池はこれらの電極に限定されるも
のではなく、いかなる電極に対しても適用できる。A fuel cell using the solid polymer electrolyte membrane according to the present invention will be described. An electrode carrying an electrode catalyst can be used as an electrode constituting the fuel cell. For example, after a mixture of carbon black and polytetrafluoroethylene is formed into a sheet by rolling, a solution containing a catalyst component is applied thereto, and the catalyst is supported by oxidation or thermal decomposition / hydrogen reduction treatment. Or, after papermaking a carbon fiber fabric or carbon fiber, an electrode carrying an electrode catalyst powder together with polytetrafluoroethylene on a porous substrate such as a paper-like material formed by firing, or an electrode catalyst powder on a polymer electrolyte. The dispersed solution is
Examples of the electrode include an electrode formed by casting and drying, and then directly bonding this to a solid polymer electrolyte membrane by hot pressing. The fuel cell is not limited to these electrodes, but can be applied to any electrode.
【００１３】[0013]
【実施例】以下、本発明に係る実施例を説明するが、本
発明はこれらの実施例によって何ら限定されるものでは
ない。実施例１ 厚さが１５μｍで、細孔径が３μｍで、気孔率が９０％
のポリテトラフルオロエチレンシートに、１３ｗｔ％の
パーフルオロカーボンスルホン酸樹脂（イオン交換容量
が０．９ｍｅｑ／ｇ）を含むエタノール／イソプロピル
アルコール（４：１ｗ／ｗ）溶液をキャスト・含浸し、
その後、室温で溶媒を蒸発・乾燥させ、パーフルオロカ
ーボンスルホン酸樹脂を析出させ、厚さ３０μｍの複合
ポリマー膜を得た。電子顕微鏡で上記複合ポリマー膜の
断面を観察したところ、中心にポリテトラフルオロエチ
レンシートを配し、その両側に７．５μｍのスキン層を
有し、膜中に貫通部は無く、パーフルオロカーボンスル
ホン酸樹脂がポリテトラフルオロエチレンシートにほぼ
均一に含浸されている複合ポリマー膜であることを確認
した。一方、高分子電解質溶液に電極触媒とカーボンブ
ラックを分散させ、キャスト・乾燥させて電極を得た。
この電極の見かけ面積当たりの白金触媒担持量は、水素
極側は０．３８ｍｇ／ｃｍ2、空気極側は０．４６ｍｇ
／ｃｍ2であった。得られた複合ポリマー膜の両面に、
前記電極を１５０〜２００℃のホットプレスで接合し、
セルを作製した。EXAMPLES Examples according to the present invention will be described below, but the present invention is not limited to these examples. Example 1 The thickness was 15 μm, the pore diameter was 3 μm, and the porosity was 90%.
Cast and impregnated with an ethanol / isopropyl alcohol (4: 1 w / w) solution containing 13 wt% of a perfluorocarbon sulfonic acid resin (ion exchange capacity is 0.9 meq / g) on the polytetrafluoroethylene sheet,
Thereafter, the solvent was evaporated and dried at room temperature to deposit a perfluorocarbon sulfonic acid resin, thereby obtaining a composite polymer film having a thickness of 30 μm. When the cross section of the composite polymer film was observed with an electron microscope, a polytetrafluoroethylene sheet was disposed at the center, a 7.5 μm skin layer was provided on both sides of the sheet, and there was no penetration portion in the film. It was confirmed that the resin was a composite polymer film in which the polytetrafluoroethylene sheet was almost uniformly impregnated. On the other hand, an electrode catalyst and carbon black were dispersed in a polymer electrolyte solution, cast and dried to obtain an electrode.
The platinum catalyst loading per apparent area of this electrode was 0.38 mg / cm 2 on the hydrogen electrode side and 0.46 mg on the air electrode side.
/ Cm 2 . On both sides of the obtained composite polymer membrane,
The electrodes are joined by hot pressing at 150 to 200 ° C.,
A cell was prepared.
【００１４】実施例２ 厚さが２５μｍで、細孔径が０．６μｍで、気孔率が８
５％のポリテトラフルオロエチレンシートを用いること
以外は、実施例１と同様の方法によって複合ポリマー膜
を作製した。電子顕微鏡で上記複合ポリマー膜の断面を
観察したところ、中心にポリテトラフルオロエチレンシ
ートを配し、その両側に２．５μｍのスキン層を有し、
膜中に貫通部は無く、パーフルオロカーボンスルホン酸
樹脂がポリテトラフルオロエチレンシートにほぼ均一に
含浸されている複合ポリマー膜で有ることを確認した。
実施例１と同様に、得られた複合ポリマー膜の両面に電
極を接合し、セルを作製した。 Example 2 The thickness was 25 μm, the pore diameter was 0.6 μm, and the porosity was 8
A composite polymer film was produced in the same manner as in Example 1 except that a 5% polytetrafluoroethylene sheet was used. When the cross section of the composite polymer film was observed with an electron microscope, a polytetrafluoroethylene sheet was disposed at the center, and a 2.5 μm skin layer was provided on both sides thereof.
There was no penetrating portion in the film, and it was confirmed that the film was a composite polymer film in which the perfluorocarbon sulfonic acid resin was almost uniformly impregnated in the polytetrafluoroethylene sheet.
In the same manner as in Example 1, electrodes were bonded to both surfaces of the obtained composite polymer film to prepare a cell.
【００１５】比較例１ 固体高分子電解質膜として、イオン交換容量が０．９ｍ
ｅｑ／ｇで厚さが３０μｍのパーフルオロカーボンスル
ホン酸膜（Ｄｕ Ｐｏｎｔ社製で商品名がＮａｆｉｏ
ｎ）を用いた以外は、実施例１と同様の構成でセルを作
製した。得られた実施例１、２および比較例１の燃料電
池の単セル発電試験を下記表１に示す発電試験条件で行
って電流−電圧特性を求めた。その結果を下記表２に示
す。ここで、水素リーク量は、右の数値が試験開始１日
目、左の数値が試験開始から３日目のリーク量である。 Comparative Example 1 A solid polymer electrolyte membrane having an ion exchange capacity of 0.9 m
eq / g, 30 μm thick perfluorocarbon sulfonic acid membrane (trade name: Nafio, manufactured by Du Pont)
A cell was manufactured in the same configuration as in Example 1 except that n) was used. The single-cell power generation test of the obtained fuel cells of Examples 1 and 2 and Comparative Example 1 was performed under the power generation test conditions shown in Table 1 below, and current-voltage characteristics were obtained. The results are shown in Table 2 below. Here, as for the hydrogen leak amount, the right numerical value is the leak amount on the first day of the test start, and the left numerical value is the leak amount on the third day from the test start.
【００１６】[0016]
【表１】 [Table 1]
【００１７】[0017]
【表２】 [Table 2]
【００１８】表２から明らかなように、実施例１の燃料
電池は、比較例１の燃料電池と同等以上の発電性能を有
し、また水素リーク量も少ないことがわかる。特に、水
素リーク量は、０．０３〜０．０５ｃｃ／ｍｉｎ／ｃｍ
2以上のレベルで出力電圧への影響があることが知られ
ており、実施例１が優れていることがわかる。また、ス
キン層の薄い実施例２でも水素リーク量が同等なことか
ら、スキン層の厚さの最適値は２．５〜７．５μｍであ
る。As is clear from Table 2, the fuel cell of Example 1 has a power generation performance equal to or higher than that of the fuel cell of Comparative Example 1, and the amount of hydrogen leak is small. In particular, the amount of hydrogen leak is 0.03 to 0.05 cc / min / cm.
It is known that there is an effect on the output voltage at two or more levels, and it can be seen that Example 1 is excellent. Further, since the hydrogen leak amount is the same even in Example 2 in which the skin layer is thin, the optimum value of the thickness of the skin layer is 2.5 to 7.5 μm.
【００１９】[0019]
【発明の効果】以上詳述したように、本発明によれば、
薄膜化が可能で、強度が高く、かつ燃料ガスのクロスリ
ーク量が少ない複合ポリマー膜を提供することができ、
この複合ポリマー膜を固体高分子電解質膜として用いる
ことによって、出力電圧および電流密度が向上された燃
料電池を提供することができる。As described in detail above, according to the present invention,
It is possible to provide a composite polymer film that can be thinned, has high strength, and has a small amount of fuel gas cross leak,
By using this composite polymer membrane as a solid polymer electrolyte membrane, a fuel cell with improved output voltage and current density can be provided.
【図１】本発明に係る固体高分子電解質膜の断面の模式
図である。FIG. 1 is a schematic view of a cross section of a solid polymer electrolyte membrane according to the present invention.
【図２】従来の固体高分子電解質膜の断面の模式図であ
る。FIG. 2 is a schematic view of a cross section of a conventional solid polymer electrolyte membrane.
１ 固体高分子電解質膜 ２ 多孔質樹脂基体膜＋固体高分子電解質 ３ スキン層 Reference Signs List 1 solid polymer electrolyte membrane 2 porous resin base film + solid polymer electrolyte 3 skin layer
フロントページの続き (72)発明者 林 俊一 愛知県名古屋市中村区岩塚町字高道１番地 三菱重工業株式会社名古屋研究所内 (72)発明者 森賀 卓也 広島県広島市西区観音新町四丁目６番22号 三菱重工業株式会社広島研究所内 Ｆターム(参考） 5H026 AA06 BB04 CX05 EE18 EE19 HH03 Continued on the front page (72) Inventor Shunichi Hayashi 1 Nagoya Laboratory, Iwazuka-cho, Nakamura-ku, Nagoya City, Aichi Prefecture Inside the Nagoya Research Laboratory, Mitsubishi Heavy Industries, Ltd. No.22 Mitsubishi Heavy Industries, Ltd. Hiroshima Research Laboratory F-term (reference) 5H026 AA06 BB04 CX05 EE18 EE19 HH03
Claims (7)
含浸させて析出させ、該固体高分子電解質の一部分を該
多孔質樹脂基体膜の少なくとも一方の面にスキン層とし
て形成させることを特徴とする固体高分子電解質膜の製
造方法。The present invention is characterized in that a solid polymer electrolyte is impregnated and precipitated in a porous resin substrate film, and a part of the solid polymer electrolyte is formed as a skin layer on at least one surface of the porous resin substrate film. A method for producing a solid polymer electrolyte membrane.
ｍである請求項１記載の固体高分子電解質膜の製造方
法。2. The thickness of the skin layer is 1.5 to 9.0 μm.
The method for producing a solid polymer electrolyte membrane according to claim 1, wherein m is m.
ーボンスルホン酸樹脂である請求項１又は２記載の固体
高分子電解質膜の製造方法。3. The method according to claim 1, wherein the solid polymer electrolyte is a perfluorocarbon sulfonic acid resin.
含浸させて析出させ、該固体高分子電解質の一部分を該
多孔質樹脂基体膜の少なくとも一方の面にスキン層とし
て形成して得られる固体高分子電解質膜。4. A method in which a solid polymer electrolyte is impregnated and precipitated in a porous resin substrate film, and a portion of the solid polymer electrolyte is formed as a skin layer on at least one surface of the porous resin substrate film. Solid polymer electrolyte membrane.
でなる基体膜と、該基体膜の少なくとも一方の面に一体
に置かれる固体高分子電解質スキン層とからなる固体高
分子電解質膜。5. A solid polymer electrolyte membrane comprising a base film comprising a porous resin and a solid polymer electrolyte, and a solid polymer electrolyte skin layer integrally disposed on at least one surface of the base film.
ｍである請求項４又は５記載の固体高分子電解質膜。6. The skin layer has a thickness of 1.5 to 9.0 μm.
The solid polymer electrolyte membrane according to claim 4, wherein m is m.
ーボンスルホン酸樹脂である請求項４又は５記載の固体
高分子電解質膜。7. The solid polymer electrolyte membrane according to claim 4, wherein the solid polymer electrolyte is a perfluorocarbon sulfonic acid resin.
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| JP2001114846A JP2002313363A (en) | 2001-04-13 | 2001-04-13 | Solid polymer electrolyte film and its manufacturing method |
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|---|---|---|---|
| JP2001114846A JP2002313363A (en) | 2001-04-13 | 2001-04-13 | Solid polymer electrolyte film and its manufacturing method |
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