JP4864107B2 - ブロック共重合体並びにこれを用いた燃料電池用固体高分子電解質、燃料電池用固体高分子電解質膜、膜電極接合体及び燃料電池 - Google Patents
ブロック共重合体並びにこれを用いた燃料電池用固体高分子電解質、燃料電池用固体高分子電解質膜、膜電極接合体及び燃料電池 Download PDFInfo
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- JP4864107B2 JP4864107B2 JP2009033771A JP2009033771A JP4864107B2 JP 4864107 B2 JP4864107 B2 JP 4864107B2 JP 2009033771 A JP2009033771 A JP 2009033771A JP 2009033771 A JP2009033771 A JP 2009033771A JP 4864107 B2 JP4864107 B2 JP 4864107B2
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- BDAWXSQJJCIFIK-UHFFFAOYSA-N potassium methoxide Chemical compound [K+].[O-]C BDAWXSQJJCIFIK-UHFFFAOYSA-N 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 125000004964 sulfoalkyl group Chemical group 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- YNHJECZULSZAQK-UHFFFAOYSA-N tetraphenylporphyrin Chemical compound C1=CC(C(=C2C=CC(N2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3N2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 YNHJECZULSZAQK-UHFFFAOYSA-N 0.000 description 1
- 125000000101 thioether group Chemical group 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- CNUJLMSKURPSHE-UHFFFAOYSA-N trioctadecyl phosphite Chemical compound CCCCCCCCCCCCCCCCCCOP(OCCCCCCCCCCCCCCCCCC)OCCCCCCCCCCCCCCCCCC CNUJLMSKURPSHE-UHFFFAOYSA-N 0.000 description 1
- HVLLSGMXQDNUAL-UHFFFAOYSA-N triphenyl phosphite Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)OC1=CC=CC=C1 HVLLSGMXQDNUAL-UHFFFAOYSA-N 0.000 description 1
- QQBLOZGVRHAYGT-UHFFFAOYSA-N tris-decyl phosphite Chemical compound CCCCCCCCCCOP(OCCCCCCCCCC)OCCCCCCCCCC QQBLOZGVRHAYGT-UHFFFAOYSA-N 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
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Description
撹拌機、温度計及び塩化カルシウム管を接続した還流冷却器を付設した300mlの四つ口丸底フラスコの内部を窒素置換した後、4、4−ジクロロジフェニルスルホン、4、4−ビフェノール及び炭酸カリウムをそれぞれ、mol比で1.00:1.05:1.15に調製して投入した。共沸材としてトルエン、溶媒としてN−メチル−2−ピロリドン(NMP)を用いて200℃で24時間反応させ、末端基がOHのポリマーを合成した。
カラム:東ソー株式会社製 TSKgel SuperAWM−H×2本
溶離液:N−メチル−2−ピロリドン(NMP、10mmol/L臭化リチウム添加)
(2)ポリマーb(親水性セグメント)の作製
撹拌機、温度計及び塩化カルシウム管を接続した還流冷却器をつけた1000mlの四つ口丸底フラスコの内部を窒素置換した後、スルホン化4、4−ジクロロジフェニルスルホン、4、4−チオビスベンゼンチオール及び炭酸カリウムをそれぞれ、mol比で1.05:1.00:1.15に調製して投入した。溶媒としてトルエン、ジメチルスルホキシド(DMSO)とN−メチル−2−ピロリドン(NMP)の混合溶媒を用いて200℃で12時間反応させて末端基がCl(塩素)であるポリマーを合成した。親水性セグメントの数平均分子量Mnは3.6×104、重量平均分子量Mwは8.0×104であった。
上記の(1)及び(2)で合成したポリマーa及びポリマーbを混合し、200℃で10時間反応させた。なお、ポリマーaとポリマーbとの配合比は、イオン交換容量が2.0meq/gになるように調合した。得られた溶液を水に投入し、再沈することでブロック共重合体Aを得た。得られたブロック共重合体Aの数平均分子量Mnは1.2×105、重量平均分子量Mwは4.7×105であった。酸塩基滴定により測定したイオン交換容量は1.9meq/gであった。
上記(3)で得られたブロック共重合体Aを15重量%の濃度になるようにNMPに溶解した。この溶液をガラス上に流延塗布、加熱乾燥し、次いで硫酸及び水に浸漬、乾燥して膜厚40μmの高分子電解質膜を得た。さらに、非特許文献1に記載の方法でこの高分子電解質膜のチオエーテル結合部位を酸化させ、すべてスルホニル結合とし、高分子電解質膜を得た。
上記(4)で作製した高分子電解質膜を非特許文献1に記載の方法で架橋させて、架橋高分子電解質膜を得た。
炭素担体上に白金微粒子を70wt%分散担持した触媒粉末と5wt%のポリパーフルオロスルホン酸とを1−プロパノール、2−プロパノール及び水で構成された混合溶媒に混合してスラリーを調整し、触媒重量が0.4g/cm2になるように上記の高分子電解質膜の上にスプレー塗布し、約20μm、幅30mm、長さ30mmのカソード及びアノードを作製した。その後、120℃、13MPaでホットプレスすることにより、上記の高分子電解質膜の両面にアノード及びカソードを有する膜電極接合体(MEA)を作製した。
図1は、本発明の燃料電池の内部構造を示す分解斜視図である。
(参考例)
実施例1の(2)と同様の方法で、スルホン化4、4−ジフルオロベンゾフェノン、4、4−ビフェノール及び炭酸カリウムの比をそれぞれ、mol比で1.05:1.00:1.15に調製して投入した。溶媒としてトルエン、ジメチルスルホキシド(DMSO)及びN−メチル−2−ピロリドン(NMP)の混合溶媒を用いて200℃で12時間反応させて末端基がFのポリマーcを合成した。
実施例1の(3)と同様の方法で、本参考例の(1)及び実施例1の(1)で合成したポリマーc及びポリマーaを混合し、200℃で10時間反応させた。なお、ポリマーcとポリマーaとの配合比は、イオン交換容量が2.0meq/gになるように調合した。得られた溶液を水に投入し、再沈することでブロック共重合体Bを得た。
実施例1の(4)と同様の方法で、上記のブロック共重合体Bから高分子電解質膜を得た。この高分子電解質膜を80℃の水中に8時間浸漬させた後の面積方向への寸法変化率は4%であり、80℃、60RH%で4端子交流インピーダンス法により測定した10KHzにおけるイオン伝導度は、5.0×10−2S/cmであった。また、耐酸化性試験として高分子電解質膜をFe2+を3ppm含む3%H2O2溶液に80℃で90分浸漬するFenton試験を行うと、Fenton試験後の重量残存率は96%であった。
本参考例の(3)で作製した高分子電解質膜を実施例1の(5)と同様の方法で架橋させて、架橋高分子電解質膜を得た。この架橋高分子電解質膜を80℃の水中に8時間浸漬させた後の面積方向への寸法変化率は0%であり、80℃、60RH%で4端子交流インピーダンス法により測定した10KHzにおけるイオン伝導度は、4.2×10−2S/cmであった。また、耐酸化性試験として高分子電解質膜をFe2+を3ppm含む3%H2O2溶液に80℃で90分浸漬するFenton試験を行うと、Fenton試験後の重量残存率は99%であった。
実施例1の(6)と同様の方法で、本参考例の(4)で得られた高分子電解質膜からMEAを得た。
実施例1の(7)と同様の方法で、本参考例の(6)で得られたMEAを用いたPEFCの電池性能を測定した。MEAを用いたPEFCは0.73V以上の出力を示し、800時間以上安定して発電可能であった。
撹拌機、温度計及び塩化カルシウム管を接続した還流冷却器を付設した1000mlの四つ口丸底フラスコの内部を窒素置換した後、スルホン化4、4−ジクロロジフェニルスルホン、4、4−ビフェノール及び炭酸カリウムをそれぞれ、mol比で1.60:1.65:1.15に調製して投入した。溶媒としてトルエン、N−メチル−2−ピロリドン(NMP)を用いて200℃で12時間反応させて末端基がOHのポリマーを合成した。親水性セグメントの数平均分子量Mnは3.5×104、重量平均分子量Mwは8.5×104であった。
本比較例1の(1)及び(2)で合成したポリマーd、ポリマーeを混合し、140℃で2時間反応させた。なお、ポリマーdとポリマーeとの配合比は、イオン交換容量が2.0meq/gになるように調合した。得られた溶液を水に投入し、再沈することでブロック共重合体Cを得た。
実施例1の(4)と同様の方法で、ブロック共重合体Cから高分子電解質膜を得た。この高分子電解質膜を80℃の水中に8時間浸漬させた後の面積方向への寸法変化率は13%であり、80℃、60RH%で4端子交流インピーダンス法により測定した10KHzにおけるイオン伝導度は、7.0×10−2S/cmであった。また、耐酸化性試験として、高分子電解質膜を、Fe2+を3ppm含む3%H2O2溶液に80℃で90分浸漬するFenton試験を行うと、Fenton試験後の重量残存率は18%であった。
(5)架橋高分子電解質膜の作製とその特性
高分子電解質膜を実施例1の(5)と同様の方法で架橋させ、架橋高分子電解質膜を得た。この架橋高分子電解質膜を80℃の水中に8時間浸漬させた後の面積方向への寸法変化率は12%であり、80℃、60RH%で4端子交流インピーダンス法により測定した10KHzにおけるイオン伝導度は、6.8×10−2S/cmであった。
Claims (6)
- 下記化学式(1)で表される構造単位を含み、さらに、下記化学式(8)で表される構造単位及び下記化学式(9)で表される構造単位のうち少なくともいずれかを含み、前記化学式(1)で表される構造単位が親水性セグメントであり、下記化学式(8)又は下記化学式(9)で表される構造単位は疎水性セグメントであり、前記親水性セグメントが水溶性であり、イオン交換容量が0.3〜5.0meq/gであり、三次元架橋構造を有することを特徴とするブロック共重合体。
(下記化学式(1)において、X、Y1及びY2はそれぞれ、直接結合、−SO2−及び−CO−の群から選択される1種類であり、Y1とY2とは同一でも異なっていてもよく、a及びcは0又は1以上の整数であり、bは0〜1の有理数である。Ar1は下記化学式(2)〜(7)で表される結合基の群から選択される1種類であり、下記化学式(2)〜(7)には置換基が導入されていてもよい。この置換基は、−C6H5、−OH、−Br、−Cl、−I、−CH3及び−Fの群から選択される。
下記化学式(8)において、Wは、直接結合、−C(CH3)2−、−C(CF3)2−、−O−、−S−及び前記化学式(7)で表される結合基の群から選択される1種類であり、Zは、直接結合、−SO2−及び−CO−の群から選択される1種類の結合基であり、V1及びV2は、直接結合、−O−及び−S−の群から選択される1種類であり、V1とV2とは、同一でも異なっていてもよい。c、d及びgは0又は1以上の整数であり、e及びfは0〜1の有理数である。
下記化学式(9)において、Zは、直接結合、−SO2−及び−CO−の群から選択される1種類であり、V1及びV2は、直接結合、−O−及び−S−の群から選択される1種類であり、V1とV2とは、同一でも異なっていてもよい。c及びgは0又は1以上の整数であり、eは0〜1の有理数である。Ar2は、下記化学式(10)〜(14)で表される結合基の群から選択される1種類であり、下記化学式(10)〜(14)で表される結合基には置換基が導入されていてもよい。この置換基は、−C6H5、−OH、−Br、−Cl、−I、−CH3及び−Fの群から選択される。Ar3及びAr4は、少なくとも1つの芳香環を有する4価の基である。T1及びT2は、−O−、−S−及び−NR−の群から選択される1種類である。ここで、Rは、水素原子、炭化数1〜6のアルキル基、炭素数1〜10のアルコキシ基、又は炭素数6〜10のアリール基を表し、これらのアルキル基、アルコキシ基及びアリール基は置換基を有していてもよい。この置換基は、−C6H5、−OH、−Br、−I、−CH3及び−Fの群から選択される。T1とT2とは、同一でも異なっていてもよい。)
- 請求項1記載のブロック共重合体を用いたことを特徴とする燃料電池用固体高分子電解質。
- 請求項2記載の燃料電池用固体高分子電解質を用いたことを特徴とする燃料電池用固体高分子電解質膜。
- 水、N−メチルピロリドン、ジメチルアセトアミド、ジメチルホルムアミド、ジメチルスルホキシド、エタノール若しくはメタノール又はそれらの混合物に80℃で24時間浸漬した場合に、その浸漬の前後における重量減少が10%以下であることを特徴とする請求項3記載の燃料電池用固体高分子電解質膜。
- 請求項3又は4に記載の燃料電池用固体高分子電解質膜と、カソード電極と、アノード電極とを含み、前記カソード電極と前記アノード電極との間に前記燃料電池用固体高分子電解質膜を挟んで形成したことを特徴とする膜電極接合体。
- 請求項5記載の膜電極接合体を含むことを特徴とする燃料電池。
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JP5892653B2 (ja) | 2011-04-14 | 2016-03-23 | 株式会社カネカ | 高分子電解質およびその利用 |
WO2013153696A1 (ja) * | 2012-04-13 | 2013-10-17 | 株式会社カネカ | 高分子電解質およびその利用 |
JP6108587B2 (ja) * | 2012-03-29 | 2017-04-05 | 国立大学法人東京工業大学 | 高分子電解質、膜電極接合体、固体高分子形燃料電池、及び、高分子電解質の製造方法 |
KR101546816B1 (ko) | 2012-11-09 | 2015-08-25 | 한국화학연구원 | 부분 가지형 블록 공중합체를 포함하는 이온전도성 고분자 및 이의 용도 |
JP6206048B2 (ja) * | 2013-09-30 | 2017-10-04 | 凸版印刷株式会社 | 高分子電解質用のジフェニル化合物、高分子電解質、膜電極接合体、固体高分子形燃料電池、及び、高分子電解質の製造方法 |
JP2015122308A (ja) * | 2013-11-21 | 2015-07-02 | 凸版印刷株式会社 | 高分子電解質、膜電極接合体、および固体高分子形燃料電池 |
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