JP2013235665A - Polymer electrolytic film and fuel battery using the same - Google Patents
Polymer electrolytic film and fuel battery using the same Download PDFInfo
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Description
本発明は、高分子電解質膜およびそれを用いた燃料電池に関する。 The present invention relates to a polymer electrolyte membrane and a fuel cell using the same.
固体高分子形燃料電池（ＰＥＦＣ）は、エネルギー密度が高く、家庭用コージェネレーションシステム、携帯機器用電源、自動車用電源などの幅広い分野での使用が期待される。ＰＥＦＣの電解質膜には、燃料極−酸化極間でプロトンを伝導する電解質としての機能、および、燃料極に供給される燃料と酸化極に供給される酸化剤とを分離する隔壁としての機能が求められる。電解質および隔壁としての機能が不十分であると、燃料電池の発電効率が低下する。また、プロトン伝導性、電気化学的安定性および機械的強度に優れ、燃料および酸化剤の透過性が低い高分子電解質膜が望まれる。 The polymer electrolyte fuel cell (PEFC) has a high energy density and is expected to be used in a wide range of fields such as a home cogeneration system, a power source for portable devices, and a power source for automobiles. The electrolyte membrane of PEFC has a function as an electrolyte that conducts protons between the fuel electrode and the oxidation electrode, and a function as a partition that separates the fuel supplied to the fuel electrode and the oxidant supplied to the oxidation electrode. Desired. When the functions as the electrolyte and the partition are insufficient, the power generation efficiency of the fuel cell is lowered. In addition, a polymer electrolyte membrane that is excellent in proton conductivity, electrochemical stability, and mechanical strength and has low fuel and oxidant permeability is desired.
従来、固体高分子形燃料電池の電解質膜として、デュポン社で開発された「ナフィオン（デュポン社の登録商標）」等のパーフルオロスルホン酸膜が一般に用いられていた。しかしながら、「ナフィオン」をはじめとする従来のフッ素系高分子電解質膜は、化学的な安定性には優れるもののイオン交換容量が低いという問題や、保水性が不十分であるため電解質膜が乾燥してプロトン伝導性が低下するという問題があった。この対策としてスルホン酸基を多く導入すると、保水によって強度が極端に低下し、膜が破損しやすくなる。すなわち、ナフィオンのみからなる電解質膜は、乾燥状態と膨潤状態との間の状態変化に対する安定性が低かった。 Conventionally, as an electrolyte membrane for a polymer electrolyte fuel cell, a perfluorosulfonic acid membrane such as “Nafion (registered trademark of DuPont)” developed by DuPont has been generally used. However, conventional fluorine-based polymer electrolyte membranes such as “Nafion” are excellent in chemical stability but have a problem of low ion exchange capacity, and electrolyte membranes are dried due to insufficient water retention. As a result, there is a problem that proton conductivity is lowered. If a large number of sulfonic acid groups are introduced as a countermeasure, the strength is extremely lowered by water retention, and the membrane is easily damaged. That is, the electrolyte membrane composed only of Nafion has low stability against a change in state between the dry state and the swollen state.
含水量の変化に対する耐性が高い膜として、特許文献１（特開平６−２９０３２号公報）は、延伸により作製された高分子多孔膜とその多孔膜の孔内に配置されたイオン交換樹脂とからなる高分子電解質膜を開示している。また、特許文献２（特開２００２−３５２８１９号公報：特許第４０６７３１５号明細書）は、１当量当たりの乾燥重量（ＥＷ）が所定の範囲にある膜を開示している。 As a membrane having high resistance to changes in water content, Patent Document 1 (Japanese Patent Laid-Open No. 6-29032) discloses a polymer porous membrane produced by stretching and an ion exchange resin disposed in the pores of the porous membrane. A polymer electrolyte membrane is disclosed. Patent Document 2 (Japanese Patent Laid-Open No. 2002-352819: Japanese Patent No. 4067315) discloses a membrane having a dry weight (EW) per equivalent in a predetermined range.
しかし、従来の電解質膜は、乾燥状態と膨潤状態との間の状態変化に対する寸法変化が大きく、燃料電池に用いたときの耐久性が不充分であった。 However, the conventional electrolyte membrane has a large dimensional change with respect to a change in state between a dry state and a swollen state, and has insufficient durability when used in a fuel cell.
このような状況において、本発明は、乾燥状態と膨潤状態との間の状態変化に対する寸法変化が小さい新規な高分子電解質膜およびそれを用いた燃料電池を提供することを目的の１つとする。 In such a situation, an object of the present invention is to provide a novel polymer electrolyte membrane with a small dimensional change with respect to a state change between a dry state and a swollen state, and a fuel cell using the same.
上記目的を達成すべく鋭意研究したところ、本発明者らは、特定の構成を有する積層膜に高分子電解質を充填することによって、乾燥状態と膨潤状態との間の状態変化に対する寸法変化が小さい電解質膜が得られることを見出した。本発明は、この新規な知見に基づく発明である。 As a result of diligent research to achieve the above object, the inventors of the present invention have a small dimensional change with respect to a state change between a dry state and a swollen state by filling a polymer electrolyte in a laminated film having a specific configuration. It has been found that an electrolyte membrane can be obtained. The present invention is based on this novel finding.
本発明は、燃料電池に用いられる高分子電解質膜を提供する。その高分子電解質膜は、多孔性の積層膜と、前記積層膜に充填され酸性基を含む高分子電解質とを含み、前記高分子電解質に含まれる前記酸性基は、Ｏ−Ｈ結合を含む酸性基であり、前記積層膜は、多孔性の第１の膜、多孔性の第２の膜、および、前記第１の膜と前記第２の膜との間に配置された多孔性の接着層を含み、前記第１および第２の膜はそれぞれ、方向によって伸び率が異なる膜であり、前記第１の膜の伸び率が最小となる方向と前記第２の膜の伸び率が最小となる方向とがなす角度が４５°〜９０°の範囲にあるように前記第１の膜と前記第２の膜とが積層されている。 The present invention provides a polymer electrolyte membrane used in a fuel cell. The polymer electrolyte membrane includes a porous laminate membrane and a polymer electrolyte filled in the laminate membrane and containing an acidic group, and the acidic group contained in the polymer electrolyte is an acid containing an OH bond. The laminated film includes a porous first film, a porous second film, and a porous adhesive layer disposed between the first film and the second film The first and second films are films having different elongation rates depending on directions, and the direction in which the elongation rate of the first film is minimized and the elongation rate of the second film are minimized. The first film and the second film are laminated so that the angle formed by the direction is in the range of 45 ° to 90 °.
また、本発明は、膜−電極接合体を含む燃料電池を提供する。この燃料電池では、前記膜−電極接合体が本発明の高分子電解質膜を含む。 The present invention also provides a fuel cell including a membrane-electrode assembly. In this fuel cell, the membrane-electrode assembly includes the polymer electrolyte membrane of the present invention.
本発明によれば、乾燥状態と膨潤状態との間の状態変化に対する寸法変化が小さい高分子電解質膜が得られる。この電解質膜を用いることによって、燃料電池において使用したときに剥離などが少ない膜−電極接合体（ＭＥＡ）が得られる。すなわち、本発明の電解質膜を用いることによって、耐久性が高い固体高分子形燃料電池が得られる。 According to the present invention, a polymer electrolyte membrane having a small dimensional change with respect to a change in state between a dry state and a swollen state can be obtained. By using this electrolyte membrane, a membrane-electrode assembly (MEA) with less peeling when used in a fuel cell can be obtained. That is, a solid polymer fuel cell with high durability can be obtained by using the electrolyte membrane of the present invention.
以下、本発明の実施形態について説明する。なお、以下の説明において、特定の材料や特定の数値範囲を例示する場合があるが、本発明はそれらの材料および数値範囲に限定されない。また、例示される材料は、特に記載がない限り、１種を単独で使用してもよいし２種以上を併用してもよい。 Hereinafter, embodiments of the present invention will be described. In the following description, specific materials and specific numerical ranges may be exemplified, but the present invention is not limited to these materials and numerical ranges. Moreover, as long as there is no description in particular, the material illustrated may be used individually by 1 type, and may use 2 or more types together.
（高分子電解質膜）
本発明の高分子電解質膜（複合膜）は、燃料電池に用いられる電解質膜である。この電解質膜は、多孔性の積層膜と、その積層膜に充填され酸性基を含む高分子電解質とを含む。この高分子電解質を、以下では「高分子電解質（Ｅ）」という場合がある。高分子電解質（Ｅ）に含まれる酸性基は、Ｏ−Ｈ結合を含む酸性基である。典型的には、この酸性基は、スルホン酸基、硫酸基、カルボン酸基、リン酸基、ホスホン酸基およびフェノール性水酸基からなる群より選ばれる少なくとも１種である。
(Polymer electrolyte membrane)
The polymer electrolyte membrane (composite membrane) of the present invention is an electrolyte membrane used for a fuel cell. The electrolyte membrane includes a porous laminated film and a polymer electrolyte that is filled in the laminated film and contains an acidic group. Hereinafter, this polymer electrolyte may be referred to as “polymer electrolyte (E)”. The acidic group contained in the polymer electrolyte (E) is an acidic group containing an OH bond. Typically, the acidic group is at least one selected from the group consisting of a sulfonic acid group, a sulfuric acid group, a carboxylic acid group, a phosphoric acid group, a phosphonic acid group, and a phenolic hydroxyl group.
積層膜は、多孔性の第１の膜、多孔性の第２の膜、および、第１の膜と第２の膜との間に配置された少なくとも１層の多孔性の接着層を含む。第１および第２の膜はそれぞれ、方向によって伸び率が異なる膜である。ここで、「方向」とは、積層膜の主面に平行な方向を意味する。また、「伸び率」とは、実施例に記載の引っ張り試験の結果に基づいて実施例に記載の式で算出される伸び率を意味する。第１の膜の伸び率が最小となる方向Ｄ１minと第２の膜の伸び率が最小となる方向Ｄ２minとがなす角度が４５°〜９０°の範囲にあるように第１の膜と第２の膜とが積層されている。 The laminated film includes a porous first film, a porous second film, and at least one porous adhesive layer disposed between the first film and the second film. The first and second films are films having different elongation rates depending on directions. Here, the “direction” means a direction parallel to the main surface of the laminated film. The “elongation rate” means an elongation rate calculated by the formula described in the example based on the result of the tensile test described in the example. The first film has an angle formed by a direction D1 min in which the elongation percentage of the first film is minimum and a direction D2 min in which the elongation ratio of the second film is minimum in the range of 45 ° to 90 °. A second film is stacked.
第１の膜の伸び率が最小となる方向Ｄ１minと第２の膜の伸び率が最小となる方向Ｄ２minとがなす角度は、６０°〜９０°の範囲、７０°〜９０°の範囲、または８０°〜９０°の範囲にあってもよい。この角度が９０°に近い方が、膜の伸び率の異方性が小さい積層膜が得られる傾向がある。 The angle formed by the direction D1 min in which the elongation rate of the first film is minimum and the direction D2 min in which the elongation rate of the second film is minimum is in the range of 60 ° to 90 ° and in the range of 70 ° to 90 °. Or in the range of 80 ° to 90 °. When this angle is close to 90 °, a laminated film having a small anisotropy of the elongation percentage of the film tends to be obtained.
高分子電解質膜の例を、図１に示す。図１の電解質膜１０は積層膜２０を含む。。積層膜２０には、高分子電解質（図示せず）が充填されている。積層膜２０は、「第１の膜１１／接着層１３／第２の膜１２」という積層構造を有する。なお、積層膜は、複数の第１の膜および／または複数の第２の膜を含んでもよい。その場合、第１の膜と第２の膜とは、通常、接着層を挟んで交互に積層される。
An example of the polymer electrolyte membrane is shown in FIG. The
第１の膜の材料および物性と、第２の膜の材料および物性とは異なってもよい。すなわち、第１の膜と第２の膜とは異なる膜であってもよい。典型的な例では、第１の膜の材料および物性は、第２の膜の材料および物性と実質的に同じである。すなわち、第１の膜と第２の膜とは同じ膜である。第１の膜の厚さと第２の膜の厚さとは異なってもよいし、同じでもよい。通常、積層膜に含まれる第１の膜の厚さの合計と、積層膜に含まれる第２の膜の厚さの合計とは実質的に同じであり、前者が後者の０．９〜１．１倍の範囲にあってもよい。また、本発明の効果が得られる限り、積層膜は、第１および第２の膜ならびに接着層に加えて他の膜を含んでもよい。典型的な積層膜は、第１および第２の膜と、それらの間に配置された接着層とからなる。 The material and physical properties of the first film may be different from the material and physical properties of the second film. That is, the first film and the second film may be different films. In a typical example, the material and physical properties of the first film are substantially the same as the material and physical properties of the second film. That is, the first film and the second film are the same film. The thickness of the first film and the thickness of the second film may be different or the same. Usually, the total thickness of the first film included in the multilayer film and the total thickness of the second film included in the multilayer film are substantially the same, and the former is 0.9 to 1 of the latter. It may be in the range of 1 times. Moreover, as long as the effect of the present invention is obtained, the laminated film may include other films in addition to the first and second films and the adhesive layer. A typical laminated film is composed of first and second films and an adhesive layer disposed between them.
（第１および第２の膜）
本発明で用いられる第１および第２の膜はそれぞれ、伸び率に異方性がある膜である。なお、伸び率は、たとえば実施例に記載の方法で測定できる。延伸膜の場合、膜の伸び率の方向依存性は、通常、延伸の条件によって決まる。そのため、２軸延伸で形成された延伸膜は、通常、長手方向（縦方向）とそれに直交する幅方向（横方向）のうちの一方が伸び率が最大となる方向であり、他方が伸び率が最小となる方向である。第１および第２の膜はそれぞれ、伸び率が最小となる方向における伸び率Ｔmin（％）と、伸び率が最大となる方向における伸び率Ｔmax（％）とが、０．０５≦Ｔmin／Ｔmax≦０．７（たとえば、０．０５≦Ｔmin／Ｔmax≦０．５）を満たす膜であってもよい。
(First and second films)
The first and second films used in the present invention are films having anisotropy in elongation. In addition, elongation rate can be measured by the method as described in an Example, for example. In the case of a stretched film, the direction dependency of the elongation rate of the film is usually determined by the stretching conditions. Therefore, in a stretched film formed by biaxial stretching, one of the longitudinal direction (longitudinal direction) and the width direction (lateral direction) perpendicular thereto is usually the direction in which the elongation is maximum, and the other is the elongation. Is the direction in which is minimized. Each of the first and second films has an elongation rate T min (%) in a direction in which the elongation rate is minimum and an elongation rate T max (%) in a direction in which the elongation rate is maximized. A film satisfying min / Tmax ≦ 0.7 (for example, 0.05 ≦ Tmin / Tmax ≦ 0.5) may be used.
第１および第２の膜の材料となる樹脂の例には、ポリテトラフルオロエチレン（ＰＴＦＥ）、およびポリオレフィン樹脂（ポリプロピレン、ポリメチルペンテン、ポリブテンなど）が含まれる。ポリオレフィン樹脂は、１種を単体で使用してもよいし、２種以上をブレンドして用いてもよいし、共重合体として用いてもよい。また、第１および第２の膜はそれぞれ、複数の層で構成されていてもよいし、異なる複数の樹脂で構成されていてもよい。これらの中でも、化学的安定性が高い点、および、プロトン伝導の阻害性が低い点から、第１および第２の膜はそれぞれ、多孔性のポリテトラフルオロエチレン膜であることが好ましい。 Examples of the resin used as the material for the first and second films include polytetrafluoroethylene (PTFE) and polyolefin resin (polypropylene, polymethylpentene, polybutene, etc.). As the polyolefin resin, one kind may be used alone, two or more kinds may be blended and used as a copolymer. Each of the first and second films may be composed of a plurality of layers, or may be composed of a plurality of different resins. Among these, the first and second films are preferably porous polytetrafluoroethylene films from the viewpoints of high chemical stability and low proton conduction inhibition.
多孔性の第１および第２の膜の形成方法に限定はなく、公知の方法で形成してもよく、たとえば以下の方法で形成してもよい。１つの方法では、樹脂を溶融押出し成形したのち、低温延伸してから高温延伸することによって製膜する（乾式製膜法）。他の方法では、樹脂と被抽出剤との混合物を成形・延伸などの処理によって膜状にした後、被抽出剤を溶媒等で抽出して除去することによって製膜する（湿式製膜法）。 The method for forming the porous first and second films is not limited, and may be formed by a known method, for example, by the following method. In one method, a resin is melt-extruded and then formed at a low temperature and then at a high temperature (dry film formation method). In another method, a mixture of a resin and an extractable agent is formed into a film by a process such as molding and stretching, and then the extractable agent is extracted with a solvent or the like and removed to form a film (wet film forming method). .
以下に、第１および第２の膜として好ましいＰＴＦＥ膜を製造するための方法の一例について説明する。ＰＴＦＥ膜は、一般的なＰＴＦＥ多孔膜の製造方法で製造できる。この製造方法において、ＰＴＦＥの結晶融解温度（融点）以上の温度で焼成することが好ましい。そのような焼成によって、ＰＴＦＥ膜を構成するＰＴＦＥは、通常、示差走査熱量測定において吸熱のピークが３２２〜３３２℃の範囲にあり且つ結晶融解熱量が４０Ｊ／ｇ以下であるＰＴＦＥとなる。焼成は、たとえば３４０℃以上の温度で行われ、一例では３５０℃〜３９０℃の範囲にある温度で行われる。結晶融解温度以上の温度に加熱されたＰＴＦＥ膜は、伸び率が小さくなる。しかし、現在、伸び率がより小さい膜が求められている。そのため、本発明の電解質膜は、特定の構成を有する積層膜を用いている。なお、示差走査熱量測定（ＤＳＣ測定）の昇温速度はたとえば１０℃／分である（以下のＤＳＣ測定においても同様である）。 Hereinafter, an example of a method for producing a PTFE film preferable as the first and second films will be described. The PTFE membrane can be manufactured by a general PTFE porous membrane manufacturing method. In this production method, it is preferable to perform firing at a temperature equal to or higher than the crystal melting temperature (melting point) of PTFE. By such firing, the PTFE constituting the PTFE film usually becomes PTFE having an endothermic peak in the range of 322 to 332 ° C. in the differential scanning calorimetry and having a heat of crystal melting of 40 J / g or less. Firing is performed, for example, at a temperature of 340 ° C. or higher, and in one example, is performed at a temperature in the range of 350 ° C. to 390 ° C. A PTFE film heated to a temperature equal to or higher than the crystal melting temperature has a low elongation. However, currently, there is a demand for a film having a smaller elongation rate. Therefore, the electrolyte membrane of the present invention uses a laminated film having a specific configuration. Note that the rate of temperature increase in differential scanning calorimetry (DSC measurement) is, for example, 10 ° C./min (the same applies to the following DSC measurement).
ＰＴＦＥ多孔膜（第１および第２の膜）は、通常の方法で作製できる。具体的には、まず、樹脂（ＰＴＦＥ）に炭化水素系助剤を混合して混合物を得る。次に、その混合物をシート状または円筒状に押し出し、さらに所定の厚さになるように圧延し乾燥する。押し出しおよび圧延を容易にするため、通常、３０〜１００℃の範囲（好ましくは３５〜８０℃の範囲）の温度に材料を加熱して押し出しおよび圧延を行う。押し出しは、通常、押し出しのシリンダーの径のたとえば１／１０〜１／１００の径を有する絞りを通過させることによって樹脂にシェアーをかけて行う。押し出しのシリンダーの径に対する絞りの径の比率によって、延伸膜の長手方向の伸び率や強度がある程度決定される。圧延は、ロールを用いた圧延であってもよいし、ロールを用いない圧延（プレス）であってもよい。圧延によって、膜の厚さおよび幅を所定の範囲とすることができる。ロールを用いた圧延の場合、ロールによって膜を巻き取るときの膜の張力を変えたり、ロール間のギャップを変えながらロールによる圧延を繰り返したりすることによって、膜の厚さおよび幅を調整できる。押し出し後の樹脂を圧延する場合、圧延の条件（膜の幅や厚さの変化）によって、伸び率が高い方向が決定されることがある。 The PTFE porous membrane (first and second membranes) can be produced by a normal method. Specifically, first, a hydrocarbon-based auxiliary is mixed with resin (PTFE) to obtain a mixture. Next, the mixture is extruded into a sheet or cylinder, and further rolled to a predetermined thickness and dried. In order to facilitate extrusion and rolling, the material is usually heated to a temperature in the range of 30 to 100 ° C. (preferably in the range of 35 to 80 ° C.) to perform extrusion and rolling. Extrusion is usually performed by shearing the resin by passing through a throttle having a diameter of, for example, 1/10 to 1/100 of the diameter of the cylinder of the extrusion. The stretch ratio and strength in the longitudinal direction of the stretched film are determined to some extent by the ratio of the diameter of the throttle to the diameter of the extruded cylinder. The rolling may be rolling using a roll or rolling (pressing) without using a roll. By rolling, the thickness and width of the film can be within a predetermined range. In the case of rolling using a roll, the thickness and width of the film can be adjusted by changing the tension of the film when winding the film with the roll, or by repeating the rolling with the roll while changing the gap between the rolls. When the extruded resin is rolled, the direction in which the elongation rate is high may be determined depending on the rolling conditions (changes in film width and thickness).
乾燥された膜は、所定の温度において所定の倍率で延伸される。延伸の方法や延伸の条件によって、得られる膜の伸び率が最大となる方向が決定される。典型的な延伸の一例では、膜の長手方向の延伸（縦延伸）を行った後に、膜の幅方向の延伸（横延伸）が行われる。縦延伸は、たとえば、１００〜３８０℃の範囲の温度において２〜２０倍の範囲の倍率で行われる。また、横延伸は、たとえば、３０〜３８０℃の範囲の温度において、５〜３０倍の範囲の倍率で行われる。ある方向の延伸倍率を高くすると、その方向には伸びにくい膜が得られる傾向がある。そのため、延伸の方向および倍率を変えることによって、伸び率の方向依存性を制御することが可能である。 The dried film is stretched at a predetermined magnification at a predetermined temperature. The direction in which the elongation rate of the obtained film is maximized is determined by the stretching method and stretching conditions. In one example of typical stretching, stretching in the longitudinal direction of the membrane (longitudinal stretching) is performed, and then stretching in the width direction of the membrane (lateral stretching) is performed. The longitudinal stretching is performed, for example, at a magnification in the range of 2 to 20 times at a temperature in the range of 100 to 380 ° C. Further, the transverse stretching is performed at a magnification in the range of 5 to 30 times at a temperature in the range of 30 to 380 ° C., for example. When the stretch ratio in a certain direction is increased, a film that does not easily stretch in that direction tends to be obtained. Therefore, it is possible to control the direction dependency of the elongation rate by changing the stretching direction and the magnification.
通常、ＰＴＦＥの延伸時または延伸後にＰＴＦＥの融点以上の温度にＰＴＦＥを加熱することによって、ＰＴＦＥの焼成を行う。延伸時に焼成を行う場合には、縦延伸時に行ってもよいし、横延伸時に行ってもよい。いずれの場合においても、焼成されたＰＴＦＥは、通常、ＤＳＣ測定における結晶融解熱量が４０Ｊ／ｇ以下となり、吸熱ピークが３２７±５℃の範囲（３２２〜３３２℃の範囲）に現れる。 Usually, PTFE is baked by heating PTFE to a temperature equal to or higher than the melting point of PTFE during or after stretching of PTFE. When firing at the time of stretching, it may be performed at the time of longitudinal stretching or at the time of transverse stretching. In any case, the calcined PTFE usually has a heat of crystal melting in DSC measurement of 40 J / g or less, and an endothermic peak appears in a range of 327 ± 5 ° C. (range of 322 to 332 ° C.).
ＰＴＦＥ以外の樹脂からなる第１および第２の膜も、ＰＴＦＥ膜と同様の方法で形成できる。ただし、押し出し、圧延、および延伸を行う際の温度は、その樹脂に応じた温度を選択する。ＰＴＦＥ以外の樹脂でも、特定の方向の延伸倍率を高くすることによって、通常、その方向における伸び率が小さい膜が得られる。 The first and second films made of a resin other than PTFE can also be formed by the same method as the PTFE film. However, the temperature at the time of extrusion, rolling, and stretching is selected according to the resin. Even with a resin other than PTFE, by increasing the stretching ratio in a specific direction, a film having a low elongation in that direction is usually obtained.
第１および第２の膜の、厚さ、目付量（面密度）、および気孔率は、電解質膜に求められる特性に応じて選択すればよい。第１および第２の膜の一例では、厚さが５μｍ〜１００μｍの範囲（たとえば５μｍ〜５０μｍの範囲）にあり、気孔率が５０％〜９５％の範囲（たとえば６０％〜９５％の範囲）にある。 The thickness, basis weight (area density), and porosity of the first and second films may be selected according to the characteristics required for the electrolyte membrane. In one example of the first and second films, the thickness is in the range of 5 μm to 100 μm (eg, in the range of 5 μm to 50 μm), and the porosity is in the range of 50% to 95% (eg, in the range of 60% to 95%). It is in.
なお、第１および第２の膜には、市販の膜を用いてもよい。同様に、接着層および高分子電解質には市販のものを用いてもよい。 A commercially available film may be used for the first and second films. Similarly, commercially available adhesive layers and polymer electrolytes may be used.
（接着層）
接着層は、多孔性であり、第１の膜および第２の膜を接着できる層であればよい。具体的には、第１および第２の膜の材料よりも低い融点を有する材料を含む多孔性の層を接着層として用いることができる。接着層の形態に限定はなく、たとえば、所定の材料からなる不織布、織布、またはネットであってもよい。
(Adhesive layer)
The adhesive layer may be a layer that is porous and can adhere the first film and the second film. Specifically, a porous layer containing a material having a lower melting point than the materials of the first and second films can be used as the adhesive layer. The form of the adhesive layer is not limited, and may be, for example, a nonwoven fabric, a woven fabric, or a net made of a predetermined material.
接着層に用いることができる材料の例には、ポリエチレン、ポリプロピレン、ポリメチルペンテン、ポリブテン、ポリエチレンテレフタレート、ポリイミド、ポリエーテルケトンケトン、ポリエーテルエーテルケトン、ポリエーテルイミド、ポリアミドイミド、ポリアミド、ポリフェニレンサルファイド、ポリフェニレンエーテル、ポリカーボネート、ポリエーテルスルホン、ポリアクリロニトリル、ポリ塩化ビニリデン、ポリフッ化ビニリデン、ポリテトラフルオロエチレンが含まれる。これらは単独で用いてもよいし、複数種を組み合わせて用いてもよい。接着層の材料は、第１および第２の膜に応じて選択される。 Examples of materials that can be used for the adhesive layer include polyethylene, polypropylene, polymethylpentene, polybutene, polyethylene terephthalate, polyimide, polyetherketone ketone, polyetheretherketone, polyetherimide, polyamideimide, polyamide, polyphenylene sulfide, Polyphenylene ether, polycarbonate, polyether sulfone, polyacrylonitrile, polyvinylidene chloride, polyvinylidene fluoride, and polytetrafluoroethylene are included. These may be used alone or in combination of two or more. The material of the adhesive layer is selected according to the first and second films.
接着層は、融点が１００〜１４０℃の範囲にある熱可塑性樹脂を含むことが好ましい。この構成によれば、接着層よりも高い融点を有する樹脂（たとえばＰＴＦＥ）からなる第１および第２の膜の物性を大きく変化させることなくそれらを容易に接着できる。融点が１００〜１４０℃の範囲にある熱可塑性樹脂の例には、ポリエチレンやポリブテンが含まれる。 The adhesive layer preferably contains a thermoplastic resin having a melting point in the range of 100 to 140 ° C. According to this configuration, the first and second films made of a resin having a higher melting point than the adhesive layer (for example, PTFE) can be easily bonded without significantly changing the physical properties of the first and second films. Examples of the thermoplastic resin having a melting point in the range of 100 to 140 ° C. include polyethylene and polybutene.
接着層は、芯／鞘構造を有する樹脂で形成されてもよい。たとえば、接着層は、熱可塑性樹脂からなる鞘部分と、当該熱可塑性樹脂よりも融点が高い樹脂からなる芯部分とを含む繊維によって構成されていてもよい。鞘部分の材料には、第１および第２の膜よりも融点が低い熱可塑性樹脂を用いることができ、たとえば、融点が１００〜１４０℃の範囲にある樹脂（たとえば上述した樹脂）を用いることができる。このような芯／鞘構造を有する接着層を用い、鞘部分の融点以上で芯部分の融点未満の温度で加熱して第１の膜と第２の膜とを接着することによって、接着層の芯部分の強度を保持したままで積層膜を形成できる。そのため、機械的強度が高い芯部分を含む接着層を用いることによって、機械的強度が高い積層膜（および電解質膜）を得ることが可能である。また、芯／鞘構造を有する接着層を用いることによって、第１の膜と第２の膜とを鞘部分で強固に接着することが可能である。 The adhesive layer may be formed of a resin having a core / sheath structure. For example, the adhesive layer may be composed of fibers including a sheath portion made of a thermoplastic resin and a core portion made of a resin having a melting point higher than that of the thermoplastic resin. As the material of the sheath portion, a thermoplastic resin having a melting point lower than that of the first and second films can be used. For example, a resin having a melting point in the range of 100 to 140 ° C. (for example, the above-described resin) is used. Can do. Using the adhesive layer having such a core / sheath structure, the first film and the second film are bonded by heating at a temperature higher than the melting point of the sheath part and lower than the melting point of the core part. A laminated film can be formed while maintaining the strength of the core portion. Therefore, it is possible to obtain a laminated film (and an electrolyte film) with high mechanical strength by using an adhesive layer including a core portion with high mechanical strength. Further, by using an adhesive layer having a core / sheath structure, the first film and the second film can be firmly bonded at the sheath part.
接着層は、プロトン伝導を阻害しにくい層、すなわち、プロトン伝導阻害性が低い層であることが好ましい。具体的には、接着層は、第１および第２の膜（たとえばＰＴＦＥ多孔膜）よりもプロトン伝導性が低い層であることが好ましい。 The adhesive layer is preferably a layer that does not easily inhibit proton conduction, that is, a layer that has low proton conduction inhibition. Specifically, the adhesive layer is preferably a layer having lower proton conductivity than the first and second membranes (for example, PTFE porous membrane).
接着層に求められる上記の特性、および、燃料電池内で使用するために求められる特性（強度および寸法安定性など）を考慮すると、接着層は、ポリオレフィンを含む層（不織布、織布、またはネット）であることが好ましく、融点が異なる２種類以上の樹脂を有する接着層であることがより好ましい。好ましい接着層の一例は、ポリオレフィンからなる鞘部分と、鞘部分よりも高い融点を有する樹脂からなる芯部分とを含む芯／鞘構造を有する繊維によって構成された接着層である。 In consideration of the above-mentioned properties required for the adhesive layer and the properties required for use in the fuel cell (such as strength and dimensional stability), the adhesive layer is a layer containing a polyolefin (nonwoven fabric, woven fabric, or net). ), And more preferably an adhesive layer having two or more kinds of resins having different melting points. An example of a preferable adhesive layer is an adhesive layer constituted by fibers having a core / sheath structure including a sheath portion made of polyolefin and a core portion made of a resin having a melting point higher than that of the sheath portion.
接着層の、厚さ、目付量、および気孔率は、電解質膜に求められる特性に応じて選択すればよい。たとえば、厚さは、積層膜に含まれる膜を充分な接着強度で接着できる範囲で選択される。接着層の一例では、厚さが１μｍ〜１００μｍの範囲（たとえば１μｍ〜５０μｍの範囲）にあり、目付量が０．１ｇ／ｍ2〜１００ｇ／ｍ2の範囲（たとえば２ｇ／ｍ2〜５０ｇ／ｍ2の範囲）の範囲にあり、気孔率が５０％〜９５％の範囲（たとえば６０％〜９５％の範囲）にある。目付量が小さいと溶融樹脂によるプロトン伝導の阻害性は低くなるが、目付量が小さすぎると、第１および第２の膜との接着性が低下して剥離しやすくなる。一方、目付量が大きいと、第１および第２の膜との接着性は高くなるが、目付量が大きすぎると、溶融樹脂によるプロトン伝導の阻害性が高くなる。接着層の孔径は、第１および第２の膜（たとえばＰＴＦＥ多孔膜）の孔径よりも小さくてもよいが、同じ程度かまたはそれよりも大きいことが好ましい。 The thickness, basis weight, and porosity of the adhesive layer may be selected according to the characteristics required for the electrolyte membrane. For example, the thickness is selected within a range where the films included in the laminated film can be bonded with sufficient adhesive strength. In one example of the adhesive layer is in the range of the thickness is 1 m to 100 m (for example in the range of 1 m to 50 m), range basis weight of 0.1g / m 2 ~100g / m 2 ( e.g. 2g / m 2 ~50g / m 2 range) and the porosity is in the range of 50% to 95% (for example, in the range of 60% to 95%). If the weight per unit area is small, the inhibition of proton conduction by the molten resin will be low, but if the amount per unit area is too small, the adhesiveness with the first and second films will be reduced and peeling will easily occur. On the other hand, if the basis weight is large, the adhesion to the first and second films is high, but if the basis weight is too large, the inhibition of proton conduction by the molten resin is high. The pore diameter of the adhesive layer may be smaller than the pore diameters of the first and second membranes (for example, PTFE porous membrane), but is preferably the same or larger.
（積層膜）
積層膜の厚さは、５μｍ〜２００μｍの範囲にあることが好ましく、高分子電解質膜の強度やプロトン伝導性を考慮すると、１０μｍ〜１００μｍの範囲にあることがより好ましい。積層膜が薄いと、得られる高分子電解質膜のプロトン伝導性は高くなるが、薄すぎると、積層膜の強度が低下し、また、燃料である水素が透過しやすくなるという問題が生じる。一方、積層膜が厚いと、得られる高分子電解質膜の強度が高くなるとともに燃料の透過性が低くなるが、厚すぎると、プロトン伝導性が低下する。
(Laminated film)
The thickness of the laminated film is preferably in the range of 5 μm to 200 μm, and more preferably in the range of 10 μm to 100 μm in view of the strength and proton conductivity of the polymer electrolyte membrane. When the laminated film is thin, the proton conductivity of the obtained polymer electrolyte membrane is high. However, when the laminated film is too thin, the strength of the laminated film is lowered and hydrogen as a fuel is easily transmitted. On the other hand, if the laminated film is thick, the strength of the obtained polymer electrolyte membrane is high and the fuel permeability is low, but if it is too thick, the proton conductivity is low.
積層膜の孔径（第１および第２の膜の孔径）は、高分子電解質の充填性を考慮すると、０．１μｍ〜１０μｍの範囲にあることが好ましく、１μｍ〜５μｍの範囲にあることがより好ましい。孔径が小さすぎると、高分子電解質を均一に充填しにくくなる。一方、孔径が大きすぎると、高分子電解質を保持する機能が弱くなる。高分子電解質の充填量を多くするとプロトン伝導度が高くなるため、プロトン伝導度を高める観点では、積層膜の気孔率は高い方が好ましい。積層膜の気孔率は、５０〜９５％の範囲にあることが好ましく、実用上問題がない限り、６０〜９５％の範囲にあることがより好ましい。積層膜の一例では、気孔率が５０％以上であり、且つ、厚さが５μｍ以上である。 The pore size of the laminated membrane (pore size of the first and second membranes) is preferably in the range of 0.1 μm to 10 μm, more preferably in the range of 1 μm to 5 μm, in consideration of the filling properties of the polymer electrolyte. preferable. When the pore diameter is too small, it becomes difficult to uniformly fill the polymer electrolyte. On the other hand, if the pore diameter is too large, the function of holding the polymer electrolyte is weakened. When the filling amount of the polymer electrolyte is increased, the proton conductivity is increased, and therefore, the porosity of the laminated film is preferably high from the viewpoint of increasing the proton conductivity. The porosity of the laminated film is preferably in the range of 50 to 95%, and more preferably in the range of 60 to 95% unless there is a practical problem. In an example of the laminated film, the porosity is 50% or more and the thickness is 5 μm or more.
（高分子電解質（Ｅ））
上述したように、積層膜に充填される高分子電解質（Ｅ）に含まれる酸性基は、スルホン酸基、カルボン酸基、リン酸基、およびフェノール性水酸基からなる群より選ばれる少なくとも１種である。燃料電池内で使用される際の化学的安定性およびプロトン伝導性を考慮すると、フッ素系高分子電解質が好ましい。電解質の好ましい例には、フッ化炭素鎖とスルホン酸基とを含む高分子が含まれる。そのような高分子の一例は、ナフィオン（登録商標）である。
(Polymer electrolyte (E))
As described above, the acidic group contained in the polymer electrolyte (E) filled in the laminated film is at least one selected from the group consisting of a sulfonic acid group, a carboxylic acid group, a phosphoric acid group, and a phenolic hydroxyl group. is there. In view of chemical stability and proton conductivity when used in a fuel cell, a fluorine-based polymer electrolyte is preferable. Preferred examples of the electrolyte include a polymer containing a fluorocarbon chain and a sulfonic acid group. An example of such a polymer is Nafion®.
本発明の好ましい一例では、第１および第２の膜がＰＴＦＥ多孔膜であり、接着層がポリオレフィン（たとえばポリエチレン）を含む接着層である。この一例では、高分子電解質がスルホン酸基を有する高分子であってもよく、たとえばスルホン酸基とフッ化炭素鎖とを含む高分子であってもよい。そのような高分子の一例はナフィオンである。
（高分子電解質膜の特性）
In a preferred example of the present invention, the first and second membranes are PTFE porous membranes, and the adhesive layer is an adhesive layer containing polyolefin (for example, polyethylene). In this example, the polymer electrolyte may be a polymer having a sulfonic acid group, for example, a polymer containing a sulfonic acid group and a fluorocarbon chain. An example of such a polymer is Nafion.
(Characteristics of polymer electrolyte membrane)
本発明の高分子電解質膜は、高い寸法安定性を有する。好ましい一例では、本発明の電解質膜は、乾燥状態から膨潤状態に変化させたときの、縦方向における寸法変化率Ｌ（％）と横方向における寸法変化率Ｔ（％）との平均が、１０％以下（たとえば５％以下）である。また、好ましい他の一例では、寸法変化率Ｌ（％）および寸法変化率Ｔ（％）が共に１０％以下（たとえば５％以下）である。 The polymer electrolyte membrane of the present invention has high dimensional stability. In a preferred example, the electrolyte membrane of the present invention has an average dimensional change rate L (%) in the vertical direction and dimensional change rate T (%) in the horizontal direction of 10 when the dry state is changed to the swollen state. % Or less (for example, 5% or less). In another preferred example, both the dimensional change rate L (%) and the dimensional change rate T (%) are 10% or less (for example, 5% or less).
また、本発明によれば、乾燥状態から膨潤状態に変化させたときの寸法変化の異方性が小さい電解質膜を得ることが可能である。上記寸法変化ＬおよびＴが共に５％以下である膜は、寸法変化の異方性が小さい膜であるといえる。 Further, according to the present invention, it is possible to obtain an electrolyte membrane having a small anisotropy of dimensional change when changed from a dry state to a swollen state. A film having both the dimensional changes L and T of 5% or less can be said to be a film having a small dimensional change anisotropy.
（高分子電解質膜の製造方法）
本発明の高分子電解質膜を製造するための方法の一例を以下に説明する。なお、本発明の高分子電解質膜について説明した事項は以下の製造方法に適用できるため、重複する説明を省略する場合がある。
(Production method of polymer electrolyte membrane)
An example of the method for producing the polymer electrolyte membrane of the present invention will be described below. In addition, since the matter demonstrated about the polymer electrolyte membrane of this invention is applicable to the following manufacturing methods, the overlapping description may be abbreviate | omitted.
この製造方法は、工程（ｉ）および（ii）を含む。工程（ｉ）では、積層膜を形成する。工程（ii）では、当該積層膜に高分子電解質（Ｅ）を充填する。以下に、工程（ｉ）および（ii）について説明する。 This manufacturing method includes steps (i) and (ii). In step (i), a laminated film is formed. In step (ii), the laminated film is filled with the polymer electrolyte (E). Below, process (i) and (ii) are demonstrated.
この積層膜は、上述したように、第１の膜、第２の膜、および、第１の膜と第２の膜との間に配置された接着層とを含む。積層膜は、積層膜に含まれる膜を接着層で接着して一体化することによって形成できる。接着方法の例には、ホットプレス、ラミネート、圧接、粘着等の方法が含まれる。ただし、得られた高分子電解質膜が膨潤・収縮したときに接着層と膜とが剥離しないような接着性が得られる限り、接着方法に限定はない。接着方法の好ましい一例は、積層膜を構成する膜および層を重ね合わせて一体とした状態で、それらを加熱しながら加圧する方法である。 As described above, this laminated film includes the first film, the second film, and the adhesive layer disposed between the first film and the second film. The laminated film can be formed by bonding and integrating the films included in the laminated film with an adhesive layer. Examples of the bonding method include methods such as hot pressing, laminating, pressure welding, and adhesion. However, there is no limitation on the bonding method as long as the adhesive property that the adhesive layer does not peel off when the obtained polymer electrolyte membrane swells / shrinks can be obtained. A preferred example of the bonding method is a method in which a film and a layer constituting a laminated film are stacked and integrated, and pressed while heating them.
接着の際の加熱・加圧の条件によって、得られる積層膜の膜厚、孔径、および、気孔率が変化し、高分子電解質の充填性に大きく影響する。電解質膜を構成する膜同士の接着性を考慮すると、接着層を構成する材料のうちの少なくとも１つの材料の融点以上の温度に加熱した状態で加圧することが好ましい。加圧時の圧力は、０．０１ＭＰａ〜１ＭＰａの範囲にあることが好ましく、０．１ＭＰａ〜０．８ＭＰａの範囲にあることがより好ましい。圧力が高いと、膜と接着層との接着性が増加するとともに膜厚のバラツキが抑えられる。しかし、圧力が高すぎると、膜の孔径が小さくなるとともに膜の気孔率が低下し、その結果、高分子電解質の充填が難しくなって、得られる電解質膜のプロトン伝導性が低下する。一方、圧力が低いと、膜の孔径および気孔率を維持できるが、圧力が高すぎると、膜と接着層との接着性が低下し、また、膜厚のバラツキも大きくなる。なお、加熱・加圧する時間に限定はなく、充分な接着性が得られる範囲で選択すればよい。 The film thickness, pore diameter, and porosity of the resulting laminated film vary depending on the heating and pressurizing conditions during bonding, and greatly affect the filling properties of the polymer electrolyte. In consideration of the adhesiveness between the membranes constituting the electrolyte membrane, it is preferable to apply pressure in a state of being heated to a temperature equal to or higher than the melting point of at least one of the materials constituting the adhesive layer. The pressure at the time of pressurization is preferably in the range of 0.01 MPa to 1 MPa, and more preferably in the range of 0.1 MPa to 0.8 MPa. When the pressure is high, the adhesiveness between the film and the adhesive layer is increased, and variations in film thickness are suppressed. However, when the pressure is too high, the pore size of the membrane is reduced and the porosity of the membrane is lowered. As a result, it becomes difficult to fill the polymer electrolyte, and the proton conductivity of the obtained electrolyte membrane is lowered. On the other hand, when the pressure is low, the pore size and porosity of the membrane can be maintained. However, when the pressure is too high, the adhesion between the membrane and the adhesive layer is lowered, and the variation in film thickness is increased. In addition, there is no limitation in the time which heats and pressurizes, What is necessary is just to select in the range from which sufficient adhesiveness is acquired.
工程（ii）では、積層膜に高分子電解質（Ｅ）を充填する。高分子電解質の充填方法に限定はなく、公知の方法で充填してもよい。一例の方法では、高分子電解質を含む液体（溶液または分散液）を積層膜に塗布した後、液体中の液媒体（溶媒または分散媒）を除去することによって高分子電解質を積層膜に充填する。この場合、高分子電解質を含む液体の塗布と乾燥とを複数回繰り返してもよい。高分子電解質を含む液体の濃度および液媒体は、高分子電解質および積層膜に応じて選択すればよい。液媒体の例には、アルコール（エタノールやイソプロピルアルコールなど）が含まれる。高分子電解質を含む液体の一例は、濃度が５〜２０重量％の範囲にあるナフィオンの分散液である。 In step (ii), the polymer electrolyte (E) is filled into the laminated film. There is no limitation on the method of filling the polymer electrolyte, and it may be filled by a known method. In an example method, after a liquid (solution or dispersion) containing a polymer electrolyte is applied to the laminated film, the liquid electrolyte (solvent or dispersion medium) in the liquid is removed to fill the laminated film with the polymer electrolyte. . In this case, application and drying of the liquid containing the polymer electrolyte may be repeated a plurality of times. What is necessary is just to select the density | concentration and liquid medium of the liquid containing a polymer electrolyte according to a polymer electrolyte and a laminated film. Examples of the liquid medium include alcohol (such as ethanol and isopropyl alcohol). An example of a liquid containing a polymer electrolyte is a Nafion dispersion having a concentration in the range of 5 to 20% by weight.
以下では実施例によって本発明を詳細に説明するが、本発明は以下の実施例に限定されない。なお、以下の実施例および比較例における膜の評価は、下記の方法で行った。 Hereinafter, the present invention will be described in detail by way of examples. However, the present invention is not limited to the following examples. In addition, evaluation of the film | membrane in a following example and a comparative example was performed with the following method.
（Ａ）引っ張り試験
まず、延伸膜から、１ｃｍ（長手方向）×５ｃｍ（幅方向）のサンプルを切り出した。そして、このサンプルについて、島津製作所製の試験機（オートグラフ）を用いて、引っ張り試験を行った。引っ張り試験は、初期のチャック間距離を２ｃｍとし、引っ張り速度を２０ｃｍ／分として、２５℃で行った。そして、サンプルが破断したときのチャック間距離から、以下の式で伸び率（％）を算出した。
伸び率（％）＝１００×（破断時のチャック間距離−初期のチャック間距離）／（初期のチャック間距離）
(A) Tensile test First, a sample of 1 cm (longitudinal direction) x 5 cm (width direction) was cut out from the stretched film. And about this sample, the tension test was done using the Shimadzu Corporation test machine (autograph). The tensile test was performed at 25 ° C. with an initial chuck distance of 2 cm and a tensile speed of 20 cm / min. And elongation rate (%) was computed with the following formula | equation from the distance between chuck | zippers when a sample fractured | ruptured.
Elongation rate (%) = 100 × (distance between chucks at break−initial distance between chucks) / (initial distance between chucks)
（Ｂ）示差走査熱量測定（ＤＳＣ測定）
まず、膜を直径２ｍｍの円形に打ち抜いた。そして、その円形の膜を、測定用のアルミセルに約１０ｍｇになるように詰めた後、ＮＥＴＺＳＣＨ製の測定器（ＤＳＣ２００Ｆ３）を用いてＤＳＣ測定を行った。測定において、室温から２００℃までは昇温速度を２０℃／分とし、２００℃に達してから５分間２００℃を保持し、その後は昇温速度を１０℃／分とした。結晶融解熱量は、２９５℃〜３４５℃の区間にある吸熱ピークの面積を積分することによって求めた。
(B) Differential scanning calorimetry (DSC measurement)
First, the membrane was punched into a circle with a diameter of 2 mm. And after packing the circular film | membrane so that it might become about 10 mg in the aluminum cell for a measurement, DSC measurement was performed using the measuring device (DSC200F3) made from NETZSCH. In the measurement, the temperature rising rate was 20 ° C./min from room temperature to 200 ° C., 200 ° C. was maintained for 5 minutes after reaching 200 ° C., and then the temperature rising rate was 10 ° C./min. The amount of heat of crystal fusion was determined by integrating the area of the endothermic peak in the interval from 295 ° C to 345 ° C.
（Ｃ）気孔率
まず、面積が２５ｃｍ2となるように膜を打ち抜いて測定用のサンプルを作製した。そして、そのサンプルの厚さ（ｃｍ）および重量（ｇ）を測定した。サンプルの厚さは、尾崎製作所製ダイヤルシックネスゲージＧ−６Ｃ（１／１０００ｍｍ、測定子直径：５ｍｍ）を用いて、室温で６５±２０％ＲＨ（ＲＨ：相対湿度）の環境で測定した（以下の膜厚の測定においても同様である）。そして、測定された厚さおよび重量と、膜の比重とを用いて、以下の式によって気孔率（％）を算出した。なお、膜の比重には、焼成されたＰＴＦＥの比重（２．１８）を用いた。
気孔率（％）＝（１−重量／（厚さ×２５×２．１８））×１００
(C) Porosity First, a measurement sample was prepared by punching the film so that the area was 25 cm 2 . And the thickness (cm) and weight (g) of the sample were measured. The thickness of the sample was measured in an environment of 65 ± 20% RH (RH: relative humidity) at room temperature using a dial thickness gauge G-6C (1/1000 mm, probe diameter: 5 mm) manufactured by Ozaki Mfg. The same applies to the measurement of the film thickness. And the porosity (%) was computed by the following formula | equation using the measured thickness and weight, and the specific gravity of a film | membrane. The specific gravity of the fired PTFE (2.18) was used as the specific gravity of the film.
Porosity (%) = (1−weight / (thickness × 25 × 2.18)) × 100
（Ｄ）イオン交換容量（ＩＥＣ）
実施例および比較例で作製された高分子電解質膜を、面積が約１２ｃｍ2となるように切り出して測定用のサンプルを作製した。このサンプルを濃度が３モル／Ｌの塩化ナトリウム水溶液に浸漬し、浸漬したままの状態で乾燥機中において６０℃で７２時間以上反応させた。その後、この反応によって置換されたプロトン（Ｈ+）の量を電位差自動滴定装置（ＡＴ−５１０：京都電子工業株式会社製）を使用して、０．０５Ｎの水酸化ナトリウム水溶液で滴定することによって測定した。そして、置換されたプロトンの量を酸基の量とした。
(D) Ion exchange capacity (IEC)
Samples for measurement were produced by cutting out the polymer electrolyte membranes produced in Examples and Comparative Examples so that the area was about 12 cm 2 . This sample was immersed in an aqueous sodium chloride solution having a concentration of 3 mol / L, and allowed to react at 60 ° C. for 72 hours or longer in the dryer while being immersed. Thereafter, the amount of proton (H + ) substituted by this reaction is titrated with a 0.05N aqueous sodium hydroxide solution using a potentiometric automatic titrator (AT-510: manufactured by Kyoto Electronics Industry Co., Ltd.). It was measured. The amount of substituted protons was taken as the amount of acid groups.
（Ｅ）プロトン伝導度（σ）
電解質膜のプロトン伝導度（電気伝導度）は、通常の膜抵抗測定セルとＬＣＲメーター（ＨＩＯＫＩ製、Chemical Impedance meter 3532-80）とを使用して、交流法（新実験化学講座１９、高分子化学＜II＞、ｐ９９２、丸善）によって測定した。具体的には、まず、幅１ｃｍで長さ２ｃｍに電解質膜を裁断し、それを３時間以上水中に浸漬した。その電解質膜（サンプル）を、膜の両面のそれぞれに１つずつ白金電極が接触するように、且つ、たわみがないようにプロトン伝導度の測定用の治具にセットした。２つの白金電極間の距離は５ｍｍとした。この白金電極に、ＬＣＲメーターの測定端子を取り付けた。次に、電解質膜をセットした治具を、予め６０℃に設定した恒温水槽で加熱しておいた超純水の入ったビーカーに入れて、ＬＣＲメーターによって抵抗を測定した。そして、測定値をプロットし、極小値の実数部分の値を膜抵抗Ｒ（Ω）とした。膨潤させたときの膜の厚さをｔ（ｃｍ）、サンプルの幅をｈ（ｃｍ）、電極間距離をＬ（ｃｍ）として、膜厚換算したイオン伝導率σ（Ｓ・ｃｍ-1）を以下の式から求めた。
σ＝Ｌ／（Ｒ×ｔ×ｈ） ［Ｓ・ｃｍ-1］
(E) Proton conductivity (σ)
The proton conductivity (electrical conductivity) of the electrolyte membrane can be measured using an alternating current method (New Experimental Chemistry Course 19, Polymer) using a normal membrane resistance measurement cell and an LCR meter (manufactured by HIOKI, Chemical Impedance meter 3532-80). Chemistry <II>, p992, Maruzen). Specifically, first, the electrolyte membrane was cut into a width of 1 cm and a length of 2 cm, and immersed in water for 3 hours or more. The electrolyte membrane (sample) was set on a proton conductivity measurement jig so that one platinum electrode was in contact with each side of the membrane and there was no deflection. The distance between the two platinum electrodes was 5 mm. A measurement terminal of an LCR meter was attached to this platinum electrode. Next, the jig on which the electrolyte membrane was set was placed in a beaker containing ultrapure water that had been heated in a constant temperature water bath set at 60 ° C., and resistance was measured with an LCR meter. Then, the measured values were plotted, and the value of the real part of the minimum value was defined as the membrane resistance R (Ω). When the film thickness when swollen is t (cm), the width of the sample is h (cm), and the distance between electrodes is L (cm), the ion conductivity σ (S · cm −1 ) converted to the film thickness is It calculated | required from the following formula | equation.
σ = L / (R × t × h) [S · cm −1 ]
（Ｆ）寸法変化率
電解質膜を３０ｍｍ（縦方向）×２０ｍｍ（横方向）のサイズに切り出して測定用のサンプルを作製した。このサンプルを、２３℃で５５％ＲＨの環境下に１時間以上放置して乾燥状態とした後、縦方向の２辺の長さ（ＬＤＲＹ１およびＬＤＲＹ２）および横方向の２辺の長さ（ＷＤＲＹ１およびＷＤＲＹ２）を測定した。その後、このサンプルを２３℃の水中に寸法が変化しなくなるまで（１時間以上）浸漬することによって、膨潤状態とした。浸漬後のサンプルについて、縦方向の２辺の長さ（ＬＷＥＴ１およびＬＷＥＴ２）および横方向の２辺の長さ（ＷＷＥＴ１およびＷＷＥＴ２）を測定した。そして、膨潤による、縦方向および横方向の寸法変化率、ならびに、それらの平均の寸法変化率を以下の式から求めた。
縦方向の寸法変化率（％）＝｛（ＬＷＥＴ１＋ＬＷＥＴ２）／（ＬＤＲＹ１＋ＬＤＲＹ２）−１｝×１００
横方向の寸法変化率（％）＝｛（ＷＷＥＴ１＋ＷＷＥＴ２）／（ＷＤＲＹ１＋ＷＤＲＹ２）−１｝×１００
平均寸法変化率（％）＝｛（縦方向の寸法変化率）＋（横方向の寸法変化率）｝／２
(F) Dimensional change rate The electrolyte membrane was cut into a size of 30 mm (vertical direction) × 20 mm (horizontal direction) to prepare a sample for measurement. The sample was left to dry in an environment of 55% RH at 23 ° C. for 1 hour or longer, and then the length of two sides in the vertical direction (LDRY1 and LDRY2) and the length of the two sides in the horizontal direction (WDRY1). And WDRY2) were measured. Thereafter, this sample was immersed in water at 23 ° C. until it no longer changed in size (1 hour or longer) to make it swollen. About the sample after immersion, the length (LWET1 and LWET2) of the two sides of the vertical direction and the length (WWET1 and WWET2) of the two sides of the horizontal direction were measured. And the dimensional change rate of the vertical direction and horizontal direction by swelling, and those average dimensional change rates were calculated | required from the following formula | equation.
Dimensional change rate in the vertical direction (%) = {(LWET1 + LWET2) / (LDRY1 + LDRY2) −1} × 100
Horizontal dimensional change rate (%) = {(WWET1 + WWET2) / (WDRY1 + WDRY2) −1} × 100
Average dimensional change rate (%) = {(vertical dimensional change rate) + (horizontal dimensional change rate)} / 2
（Ｇ）突き刺し強度
測定する膜について、カトーテック（株）製の圧縮試験機「ＫＥＳ−Ｇ５」を使用して針突刺し試験を行った。そして、測定によって得られた荷重変位曲線から最大荷重を読み取り、その値を突刺し強度の値とした。測定には、直径１．０ｍｍ、先端曲率半径０．５ｍｍの針を用い、突刺し速度は２ｍｍ／ｓとした。
(G) Puncture strength The membrane to be measured was subjected to a needle puncture test using a compression tester “KES-G5” manufactured by Kato Tech Co., Ltd. And the maximum load was read from the load displacement curve obtained by measurement, and the value was made into the value of puncture strength. For the measurement, a needle having a diameter of 1.0 mm and a tip curvature radius of 0.5 mm was used, and the piercing speed was 2 mm / s.
（ＰＴＦＥ多孔膜）
ＰＴＦＥ粉末（ダイキン工業株式会社製のＦ１０４）に、イソパラフィン系溶剤（エクソンモービル社製のアイソパーＭ）を２０ｗｔ％となるように配合して、５０℃の温度で、絞り比率を１／５０にして平板状のシート（厚さ１ｍｍ×幅１０ｃｍ）を押出した。これを、幅を変えずにロール２本でギャップを調整して厚さが０．２ｍｍになるまで圧延した後、１５０℃で乾燥して延伸前のシートを作製した。次に、このシートを、長手方向に３００℃で１０倍延伸し、次いで、幅方向に３００℃で１０倍延伸した。さらに、シートの四隅を固定した状態で、３８０℃で６０秒間シートを放置した。このようにして、ＰＴＦＥ多孔膜を作製した。
(PTFE porous membrane)
PTFE powder (F104 manufactured by Daikin Industries, Ltd.) is blended with isoparaffinic solvent (Isopar M manufactured by ExxonMobil Co., Ltd.) at 20 wt%, and the squeezing ratio is 1/50 at a temperature of 50 ° C. A flat sheet (thickness 1 mm ×
得られたＰＴＦＥ多孔膜の長手方向（縦方向）の伸び率は１８％であり、幅方向の伸び率は１００％であった。得られたＰＴＦＥ多孔膜の伸び率が最小となる方向は、長手方向であった。得られたＰＴＦＥ多孔膜についてＤＳＣ測定を行ったところ、結晶融解温度は３２８℃であり、結晶融解熱量は１９Ｊ／ｇであった。 The obtained PTFE porous membrane had an elongation in the longitudinal direction (longitudinal direction) of 18% and an elongation in the width direction of 100%. The direction in which the elongation percentage of the obtained PTFE porous membrane was the minimum was the longitudinal direction. When the obtained PTFE porous film was subjected to DSC measurement, the crystal melting temperature was 328 ° C., and the crystal melting heat amount was 19 J / g.
（比較例１）
比較例１では、上記のＰＴＦＥ膜単体を支持体として電解質膜を作製した。具体的には、まず、ナフィオンの２０ｗｔ％分散液（ＤＥ５３０、デュポン株式会社製）を第１のガラス板上に塗布した。次に、第２のガラス板上に、上記のＰＴＦＥ多孔膜を固定し、このＰＴＦＥ多孔膜上にナフィオンの２０ｗｔ％分散液を塗布した。このＰＴＦＥ多孔膜を第２のガラス板から剥がし、ナフィオン分散液が塗布されていない面を、第１のガラス板上に塗布されたナフィオン分散液に貼り合わせた。そして、ＰＴＦＥ多孔膜上のナフィオン分散液が半乾きの状態で、ナフィオンの２０ｗｔ％分散液をＰＴＦＥ多孔膜上にさらに塗布する作業を２回行った。次に、ＰＴＦＥ多孔膜にナフィオン５ｗｔ％分散液をさらに塗布し、６０℃の乾燥機に１時間置いて乾燥させた。このようにして、高分子電解質膜を得た。得られた高分子電解質膜について、上述した方法で評価を行った。
(Comparative Example 1)
In Comparative Example 1, an electrolyte membrane was produced using the above PTFE membrane alone as a support. Specifically, first, a
（比較例２）
上記のＰＴＦＥ多孔膜を２枚準備し、それらを接着層を用いることなく直接積層して接着し、積層膜を作製した。このとき、２枚のＰＴＦＥ多孔膜は、一方の膜の伸び率が最小となる方向と他方の膜の伸び率が最小となる方向とがなす角度が９０°となるように積層した。接着は、３４０℃の温度、０．２７ＭＰａの圧力で３０秒間加熱・加圧することによって行った。得られた積層膜を支持体とすることを除いて、比較例１と同様の方法で支持体（積層膜）に電解質を充填して高分子電解質膜を作製した。得られた高分子電解質膜について、上述した方法で評価を行った。
(Comparative Example 2)
Two PTFE porous membranes were prepared, and these were directly laminated and bonded without using an adhesive layer to produce a laminated membrane. At this time, the two PTFE porous membranes were laminated so that the angle formed by the direction in which the elongation rate of one membrane was the minimum and the direction in which the elongation rate of the other membrane was the minimum was 90 °. Adhesion was performed by heating and pressing at a temperature of 340 ° C. and a pressure of 0.27 MPa for 30 seconds. A polymer electrolyte membrane was prepared by filling the support (laminate film) with an electrolyte in the same manner as in Comparative Example 1 except that the obtained laminated membrane was used as a support. The obtained polymer electrolyte membrane was evaluated by the method described above.
（実施例１）
上述したＰＴＦＥ多孔膜を２枚準備し、それらを接着層で接着して積層膜を作製した。このとき、２枚のＰＴＦＥ多孔膜は、一方の膜の伸び率が最小となる方向と他方の膜の伸び率が最小となる方向とがなす角度が９０°となるように積層した。また、接着層には、芯部分がポリエチレンテレフタレートで鞘部分がポリエチレンである芯／鞘構造を有する繊維からなる不織布（商品名「エルベス」、ユニチカ株式会社、目付量１５ｇ／ｍ2）を用いた。接着は、１４０℃の温度、０．２７ＭＰａの圧力で３０秒間加熱・加圧することによって行った。
Example 1
Two PTFE porous membranes as described above were prepared, and these were adhered with an adhesive layer to produce a laminated membrane. At this time, the two PTFE porous membranes were laminated so that the angle formed by the direction in which the elongation rate of one membrane was the minimum and the direction in which the elongation rate of the other membrane was the minimum was 90 °. For the adhesive layer, a non-woven fabric (trade name “Elves”, Unitika Ltd., basis weight 15 g / m 2 ) made of fibers having a core / sheath structure in which the core portion is polyethylene terephthalate and the sheath portion is polyethylene was used. . Adhesion was performed by heating and pressurizing for 30 seconds at a temperature of 140 ° C. and a pressure of 0.27 MPa.
得られた積層膜を支持体とすることを除いて、比較例１と同様の方法で支持体（積層膜）に電解質を充填して高分子電解質膜を作製した。得られた高分子電解質膜について、上述した方法で評価を行った。 A polymer electrolyte membrane was prepared by filling the support (laminate film) with an electrolyte in the same manner as in Comparative Example 1 except that the obtained laminated membrane was used as a support. The obtained polymer electrolyte membrane was evaluated by the method described above.
（実施例２）
２枚のＰＴＦＥ多孔膜がなす角度を変えたことを除いて、実施例１と同様の方法で電解質膜を作製した。実施例２では、２枚のＰＴＦＥ多孔膜を、一方の膜の伸び率が最小となる方向と他方の膜の伸び率が最小となる方向とがなす角度が４５°となるように積層した。得られた高分子電解質膜について、上述した方法で評価を行った。
(Example 2)
An electrolyte membrane was produced in the same manner as in Example 1 except that the angle formed by the two PTFE porous membranes was changed. In Example 2, two PTFE porous membranes were laminated so that the angle formed by the direction in which the elongation rate of one membrane was the minimum and the direction in which the elongation rate of the other membrane was the minimum was 45 °. The obtained polymer electrolyte membrane was evaluated by the method described above.
（実施例３）
接着層が異なることを除いて、実施例１と同様の方法で積層膜を作製した。具体的には、上述したＰＴＦＥ多孔膜を２枚準備し、それらを接着層で接着して積層膜を作製した。このとき、２枚のＰＴＦＥ多孔膜は、一方の膜の伸び率が最小となる方向と他方の膜の伸び率が最小となる方向とがなす角度が９０°となるように積層した。実施例２では、接着層として、ポリエチレン製のネット（Ｄｅｌｓｔａｒ Ｔｅｃｈｎｏｌｏｇｉｅｓ社製）の「デルネット（ＤＥＬＮＥＴ：登録商標）」、目付量９．１〜１３．６ｇ／ｍ2）を用いた。接着は、実施例１と同じ条件で行った。
(Example 3)
A laminated film was produced in the same manner as in Example 1 except that the adhesive layers were different. Specifically, two PTFE porous membranes as described above were prepared, and these were adhered with an adhesive layer to produce a laminated film. At this time, the two PTFE porous membranes were laminated so that the angle formed by the direction in which the elongation rate of one membrane was the minimum and the direction in which the elongation rate of the other membrane was the minimum was 90 °. In Example 2, “Delnet (DELNET: registered trademark)” of a net made of polyethylene (manufactured by Delstar Technologies) having a basis weight of 9.1 to 13.6 g / m 2 was used as the adhesive layer. Adhesion was performed under the same conditions as in Example 1.
得られた積層膜を支持体とすることを除いて、比較例１と同様の方法で支持体（積層膜）に電解質を充填して高分子電解質膜を作製した。得られた高分子電解質膜について、上述した方法で評価を行った。 A polymer electrolyte membrane was prepared by filling the support (laminate film) with an electrolyte in the same manner as in Comparative Example 1 except that the obtained laminated membrane was used as a support. The obtained polymer electrolyte membrane was evaluated by the method described above.
（実施例４）
２枚のＰＴＦＥ多孔膜がなす角度を変えたことを除いて、実施例３と同様の方法で電解質膜を作製した。実施例４では、２枚のＰＴＦＥ多孔膜を、一方の膜の伸び率が最小となる方向と他方の膜の伸び率が最小となる方向とがなす角度が４５°となるように積層した。得られた高分子電解質膜について、上述した方法で評価を行った。
Example 4
An electrolyte membrane was produced in the same manner as in Example 3 except that the angle formed by the two PTFE porous membranes was changed. In Example 4, two PTFE porous membranes were laminated so that the angle formed by the direction in which the elongation rate of one membrane was minimized and the direction in which the elongation rate of the other membrane was minimized was 45 °. The obtained polymer electrolyte membrane was evaluated by the method described above.
測定結果を表１に示す。 The measurement results are shown in Table 1.
なお、表１中の「支持体」とは、実施例１〜４および比較例２では積層膜を意味し、比較例１では１枚のＰＴＦＥ多孔膜を意味する。また、表１中の「端部の剥離」とは、寸法変化率の測定を行ったときの、積層膜の端部の剥離の有無を意味する。 The “support” in Table 1 means a laminated film in Examples 1 to 4 and Comparative Example 2, and means a single PTFE porous film in Comparative Example 1. Further, “end peeling” in Table 1 means presence / absence of peeling of the end of the laminated film when the dimensional change rate is measured.
実施例１〜４の高分子電解質膜は、比較例１に比べ、寸法変化率を大きく改善でき、平均寸法変化率を３％以下にまで低減できた。比較例２は多孔接着層を用いていないため、端部の剥離が起こり、さらに寸法変化率も大きかった。また、実施例１〜４で用いられた支持体は、比較例１で用いられた支持体に比べて、突き刺し強度が非常に高くなった。以上のように、本発明の高分子電解質膜は、高いプロトン伝導性および強度と優れた寸法安定性とを有しており、燃料電池作動時の電極との接合性に優れるものであった。 The polymer electrolyte membranes of Examples 1 to 4 were able to greatly improve the dimensional change rate as compared with Comparative Example 1, and the average dimensional change rate could be reduced to 3% or less. Since Comparative Example 2 did not use the porous adhesive layer, the end portion was peeled off and the dimensional change rate was also large. Moreover, the support body used in Examples 1-4 became very high in puncture strength compared with the support body used in Comparative Example 1. As described above, the polymer electrolyte membrane of the present invention has high proton conductivity and strength, and excellent dimensional stability, and has excellent bondability with an electrode during fuel cell operation.
本発明は、高分子電解質膜、ならびに、それを用いた膜−電極接合体および燃料電池に利用できる。 The present invention can be used for a polymer electrolyte membrane, and a membrane-electrode assembly and a fuel cell using the same.
１０ 電解質膜
１１ 第１の膜
１２ 第２の膜
１３ 接着層
２０ 積層膜
DESCRIPTION OF
Claims (10)
多孔性の積層膜と、前記積層膜に充填され酸性基を含む高分子電解質とを含み、
前記高分子電解質に含まれる前記酸性基は、Ｏ−Ｈ結合を含む酸性基であり、
前記積層膜は、多孔性の第１の膜、多孔性の第２の膜、および、前記第１の膜と前記第２の膜との間に配置された多孔性の接着層を含み、
前記第１および第２の膜はそれぞれ、方向によって伸び率が異なる膜であり、
前記第１の膜の伸び率が最小となる方向と前記第２の膜の伸び率が最小となる方向とがなす角度が４５°〜９０°の範囲にあるように前記第１の膜と前記第２の膜とが積層されている、高分子電解質膜。 A polymer electrolyte membrane used in a fuel cell,
A porous laminated film, and a polymer electrolyte filled in the laminated film and containing an acidic group,
The acidic group contained in the polymer electrolyte is an acidic group containing an OH bond,
The laminated film includes a porous first film, a porous second film, and a porous adhesive layer disposed between the first film and the second film,
The first and second films are films having different elongation rates depending on directions,
The first film and the first film are arranged so that an angle formed by a direction in which the elongation ratio of the first film is minimum and a direction in which the elongation ratio of the second film is minimum is in a range of 45 ° to 90 °. A polymer electrolyte membrane in which a second membrane is laminated.
前記膜−電極接合体が請求項１〜９のいずれか１項に記載の高分子電解質膜を含む、燃料電池。 A fuel cell comprising a membrane-electrode assembly,
A fuel cell, wherein the membrane-electrode assembly includes the polymer electrolyte membrane according to any one of claims 1 to 9.
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