JP5960763B2 - 陰イオン交換樹脂、燃料電池用電解質膜、電極触媒層形成用バインダー、電池電極触媒層および燃料電池 - Google Patents
陰イオン交換樹脂、燃料電池用電解質膜、電極触媒層形成用バインダー、電池電極触媒層および燃料電池 Download PDFInfo
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Description
単数の芳香環からなる、または、2価の炭化水素基、2価のケイ素含有基、2価の窒素含有基、2価のリン含有基、2価の酸素含有基、2価の硫黄含有基、もしくは炭素−炭素結合を介して互いに結合する複数の芳香環からなる2価の疎水性基と、
単数の芳香環からなる、または、2価の炭化水素基、2価のケイ素含有基、2価の窒素含有基、2価のリン含有基、2価の酸素含有基、2価の硫黄含有基、もしくは炭素−炭素結合を介して互いに結合する複数の芳香環からなり、前記芳香環のうち少なくとも1つが陰イオン交換基を有する2価の親水性基と、
下記式で表される2価のフッ素含有基と
からなり、
前記疎水性基が、エーテル結合、チオエーテル結合、または炭素−炭素結合を介して繰り返される疎水ユニットと、
前記親水性基が、炭素−炭素結合を介して繰り返される親水ユニットと
を有し、
前記疎水ユニットと前記親水ユニットとが、エーテル結合、チオエーテル結合、または炭素−炭素結合を介して結合しており、かつ
前記2価のフッ素含有基が、前記疎水ユニットの主鎖中に、エーテル結合、チオエーテル結合、炭素−ケイ素結合、または炭素−炭素結合を介して結合している、あるいは前記親水ユニットの主鎖中に、炭素−炭素結合を介して結合していることを特徴とする。
下記式(3)で示される、前記陰イオン交換基を含む置換基で置換されている、アルキル基で置換されていてもよいビスフェノール残基、および/または、
下記式(3’)で示される、前記陰イオン交換基を含む置換基で置換されているo−、m−もしくはp−フェニレン基
を含むことが好適である。
上記の陰イオン交換樹脂を含む電解質膜と、
前記電解質膜を挟んで対向配置され、含水素燃料が供給される燃料側電極、および、酸素または空気が供給される酸素側電極と、
を備えたことを特徴とする。
電解質膜と、
前記電解質膜を挟んで対向配置され、含水素燃料が供給される燃料側電極、および、酸素または空気が供給される酸素側電極と
を備え、
前記燃料側電極および/または前記酸素側電極が、上記の電池電極触媒層を含むことを特徴とする。
・分子間相互作用の低い主鎖により溶解性・柔軟性が向上する
・撥水性を与え、親水部(イオン交換基周辺)との相分離が発達しイオン導電パスを形成できる
・撥水性により、親水性の水酸化物イオンや酸化剤が主鎖に近づきにくくなる(耐アルカリ性・化学的安定性向上)
・主鎖の剛性を制御できる(電解質膜の柔軟性向上)
・ガラス転移温度が低く、触媒層と接着できる(接触抵抗低下)
・ガス拡散性を制御できる(バインダーで酸素の拡散性増大)
[イオン交換基容量(meq./g)]=親水ユニット当たりの陰イオン交換基導入量×親水ユニットの繰り返し単位×1000/(疎水ユニットの分子量×疎水ユニットの繰り返し単位数+親水ユニットの分子量×親水ユニットの繰り返し単位数+イオン交換基の分子量×親水ユニットの繰り返し単位数) (24)
なお、イオン交換基導入量とは、単位親水性基あたりのイオン交換基の数と定義される。また、陰イオン交換基導入量は、親水性基において主鎖または側鎖に導入された上記陰イオン交換基のモル数(mol)である。
(QPAF6(l1m0.48n0.62)の合成)
<フルオロアルキルモノマーの合成>
窒素インレットおよびディーンスタックトラップを備えた100mLの丸底三口フラスコに、ドデカフルオロ−1,6−ジヨードヘキサン(5.54g、10.0mmol)、3−クロロヨードベンゼン(11.9g、50mmol)、N,N−ジメチルスルホキシド(60mL)を加えた。この混合物を撹拌して均一溶液にした後、銅粉末(9.53g、150mmol)を加え、120℃に昇温して48時間反応を行った。
窒素インレット、メカニカルスターラーおよび冷却管を備えた100mLの丸底三口フラスコに、フルオロアルキルモノマー(0.26g、0.5mmol)、1,4−ジクロロベンゼン(0.020g、0.14mmol)、1,3−ジクロロベンゼン(0.060g、0.41mmol)、2,2’−ビピリジン(0.41g、2.6mmol)、N,N−ジメチルアセトアミド(3mL)を加えた。この混合物を撹拌してフルオロアルキルモノマー、1,4−ジクロロベンゼン、1,3−ジクロロベンゼンを溶解させた後に、ビス(シクロオクタ−1,5−ジエン)ニッケル(0)(0.72g、2.6mmol)を加え、80℃に加熱して3時間反応させた。
(クロロメチル化反応)
100mLのガラス反応容器に陰イオン交換樹脂前駆体ポリマー(0.20g)と1,1,2,2−テトラクロロエタン(9mL)を加えた。この混合物を撹拌して陰イオン交換樹脂前駆体ポリマーを溶解させた後に、アルゴンで置換したグローブボックス中において、クロロメチルメチルエーテル(5mL)、塩化亜鉛(0.5mol/Lテトラヒドロフラン溶液)(1mL)を加えて、80℃で5日間反応させた。
クロロメチル化された陰イオン交換樹脂前駆体ポリマーを、溶液キャスト法により製膜した。
クロロメチル化された陰イオン交換樹脂前駆体ポリマーの膜を、トリメチルアミン45質量%水溶液中に室温で2日間浸漬させると、陰イオン交換樹脂前駆体ポリマーは溶解し、均一な溶液が得られた。この溶液を1M HCl水溶液200mL中に滴下したのち、透析チューブ(分画分子量1kDa)に流し込み透析を行った。透析後の溶液から溶媒を留去することで、褐色の固体を得た。
(QPE−bl−10r(p1m3.13)の合成)
<疎水性モノマーの合成>
窒素インレットおよびディーンスタックトラップを備えた100mLの丸底三口フラスコに、デカフルオロビフェニル(5.00g、14.97mmol)、4−クロロフェノール(4.81g、37.41mmol)、N,N−ジメチルアセトアミド(52mL)を加えた。この混合物を撹拌して均一溶液にした後、炭酸カリウム(12.93g、93.53mmol)を加え、30℃に昇温して3時間反応を行った。
窒素インレット、メカニカルスターラーおよびディーンスタークトラップを備えた100mLの丸底三口フラスコに、疎水性モノマー(2.23g、4.04mmol)、9,9−ビス(4−(−クロロフェニル)フルオレン(1.25g、3.23mmol)、2,2’−ビピリジン(2.84g、18.18mmol)、N−メチルピロリドン(60mL)、トルエン(30mL)を加えた。この混合物を150℃に昇温し3h脱水したのちにトルエンを除去し、反応系を室温まで冷却したのちにビス(1,5−シクロオクタジエン)ニッケル(0)(5.00g、18.18mmol)を加え、60℃に加熱して3時間反応させた。
(クロロメチル化反応)
100mLのガラス反応容器に陰イオン交換樹脂前駆体ポリマー(1.10g)と1,1,2,2−テトラクロロエタン(25mL)を加えた。この混合物を撹拌して陰イオン交換樹脂前駆体ポリマーを溶解させた後に、アルゴンで置換したグローブボックス中において、クロロメチルメチルエーテル(7mL)、塩化亜鉛(0.5mol/Lテトラヒドロフラン溶液)(2mL)を加えて、35℃で5日間反応させた。
クロロメチル化された陰イオン交換樹脂前駆体ポリマーを、溶液キャスト法により製膜した。
クロロメチル化された陰イオン交換樹脂前駆体ポリマーの膜を、トリメチルアミン45質量%水溶液中に室温で2日間浸漬させた。
<溶解性試験>
実施例および比較例で得た陰イオン交換樹脂、QPAF6およびQPE−bl−10rの溶解性は、得られたサンプル100mgを溶媒1mLに溶解することによって評価した。
上記陰イオン交換膜に対し、水酸化物イオン導電率測定を行った。測定は、交流四端子法(300mV、10−100000Hz)で、30℃において水中で実施した。測定装置にはSolartolon1255B/1287を使用し、プローブにはφ1mmの金線を用いた。測定サンプルは、上記得られた陰イオン交換膜を、幅1cm、厚さ50μmに切り出し、プローブ間距離1cmで固定した。上記各温度での水酸化物イオン導電率σ(S/cm)は、次式より、プローブ間距離L(1cm)、インピーダンスZ(Ω)、膜断面積A(cm2)から算出した。
σ=(L/Z)×1/A
得られた結果を図2に示す。
Toshin Kogyo temperature control unit Bethel−3を搭載したShimazu universal testing instrument Autogragh AGS−J500Nを用い、恒温、恒湿に制御されたチャンバー内で行った。測定は、12mm×2mm(サンプル全体の面積:35mm×6mm)のダンベル型サンプル(DIN−53504−S3)を80℃、60%RHの条件下に保持後、10mm/minの速度で引張、得られた応力−歪み曲線(図3)により膜の面内方向の機械強度を評価した。測定条件において、温度および湿度の安定化待ち時間は3時間とした。
2 燃料側電極
3 酸素側電極
4 電解質膜
S 燃料電池セル
Claims (10)
- 単数の芳香環からなる、または、2価の炭化水素基、2価のケイ素含有基、2価の窒素含有基、2価のリン含有基、2価の酸素含有基、2価の硫黄含有基、もしくは炭素−炭素結合を介して互いに結合する複数の芳香環からなる2価の疎水性基と、
単数の芳香環からなる、または、2価の炭化水素基、2価のケイ素含有基、2価の窒素含有基、2価のリン含有基、2価の酸素含有基、2価の硫黄含有基、もしくは炭素−炭素結合を介して互いに結合する複数の芳香環からなり、前記芳香環のうち少なくとも1つが陰イオン交換基を有する2価の親水性基と、
下記式で表される2価のフッ素含有基と
からなり、
前記疎水性基が、エーテル結合、チオエーテル結合、または炭素−炭素結合を介して繰り返される疎水ユニットと、
前記親水性基が、炭素−炭素結合を介して繰り返される親水ユニットと
を有し、
前記疎水ユニットと前記親水ユニットとが、エーテル結合、チオエーテル結合、または炭素−炭素結合を介して結合しており、かつ
前記2価のフッ素含有基が、前記疎水ユニットの主鎖中に、エーテル結合、チオエーテル結合、炭素−ケイ素結合、または炭素−炭素結合を介して結合している、あるいは前記親水ユニットの主鎖中に、炭素−炭素結合を介して結合していることを特徴とする、陰イオン交換樹脂。
- 前記疎水性基が、下記式(2)で示される、ハロゲン原子または擬ハロゲン化物またはアルキル基で置換されていてもよいビスフェノール残基を含むことを特徴とする、請求項1に記載の陰イオン交換樹脂。
- 前記親水性基が、
下記式(3)で示される、前記陰イオン交換基を含む置換基で置換されているビスフェノールフルオレン残基、および/または、
下記式(3’)で示される、前記陰イオン交換基を含む置換基で置換されているo−、m−もしくはp−フェニレン基
であることを特徴とする、請求項1または2に記載の陰イオン交換樹脂。
- 請求項1ないし3のいずれか1項に記載の陰イオン交換樹脂を含むことを特徴とする、燃料電池用電解質膜。
- 請求項1ないし3のいずれか1項に記載の陰イオン交換樹脂を含むことを特徴とする、電極触媒層形成用バインダー。
- 請求項5に記載の電極触媒層形成用バインダーを含むことを特徴とする、電池電極触媒層。
- 請求項1ないし3のいずれか1項に記載の陰イオン交換樹脂を含む電解質膜と、
前記電解質膜を挟んで対向配置され、含水素燃料が供給される燃料側電極、および、酸素または空気が供給される酸素側電極と、
を備えたことを特徴とする、燃料電池。 - 前記含水素燃料が、水素、アルコール、またはヒドラジン類であることを特徴とする、請求項7に記載の燃料電池。
- 電解質膜と、
前記電解質膜を挟んで対向配置され、含水素燃料が供給される燃料側電極、および、酸素または空気が供給される酸素側電極と
を備え、
前記燃料側電極および/または前記酸素側電極が、請求項6に記載の電池電極触媒層を含むことを特徴とする、燃料電池。 - 前記含水素燃料が、水素、アルコール、またはヒドラジン類であることを特徴とする、請求項9に記載の燃料電池。
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