JP6471097B2 - 電気化学素子用複合膜 - Google Patents
電気化学素子用複合膜 Download PDFInfo
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- JP6471097B2 JP6471097B2 JP2015551455A JP2015551455A JP6471097B2 JP 6471097 B2 JP6471097 B2 JP 6471097B2 JP 2015551455 A JP2015551455 A JP 2015551455A JP 2015551455 A JP2015551455 A JP 2015551455A JP 6471097 B2 JP6471097 B2 JP 6471097B2
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- 239000002131 composite material Substances 0.000 title claims description 77
- 239000012528 membrane Substances 0.000 claims description 67
- 239000004745 nonwoven fabric Substances 0.000 claims description 59
- 239000000835 fiber Substances 0.000 claims description 52
- 238000005342 ion exchange Methods 0.000 claims description 49
- 239000000463 material Substances 0.000 claims description 33
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 32
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 32
- 238000000034 method Methods 0.000 claims description 26
- -1 polytetrafluoroethylene Polymers 0.000 claims description 25
- 238000001523 electrospinning Methods 0.000 claims description 13
- 229920000642 polymer Polymers 0.000 claims description 13
- 238000009987 spinning Methods 0.000 claims description 13
- 238000001035 drying Methods 0.000 claims description 12
- 239000000446 fuel Substances 0.000 claims description 12
- 239000002904 solvent Substances 0.000 claims description 11
- 238000013329 compounding Methods 0.000 claims description 10
- 239000003792 electrolyte Substances 0.000 claims description 8
- 239000002243 precursor Substances 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 6
- 229910052731 fluorine Inorganic materials 0.000 claims description 6
- 239000011737 fluorine Substances 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 239000011347 resin Substances 0.000 claims description 5
- 229920005989 resin Polymers 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 3
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical class C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 claims description 2
- 239000010408 film Substances 0.000 description 59
- 239000000243 solution Substances 0.000 description 23
- 230000000052 comparative effect Effects 0.000 description 15
- 239000011148 porous material Substances 0.000 description 10
- 239000005518 polymer electrolyte Substances 0.000 description 9
- 238000005259 measurement Methods 0.000 description 8
- 229920000557 Nafion® Polymers 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 6
- 239000007784 solid electrolyte Substances 0.000 description 5
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 230000008961 swelling Effects 0.000 description 4
- 230000037303 wrinkles Effects 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 229910052729 chemical element Inorganic materials 0.000 description 3
- 230000036961 partial effect Effects 0.000 description 3
- 125000001174 sulfone group Chemical group 0.000 description 3
- 229920003937 Aquivion® Polymers 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 238000010304 firing Methods 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
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- 239000011780 sodium chloride Substances 0.000 description 2
- TXEYQDLBPFQVAA-UHFFFAOYSA-N tetrafluoromethane Chemical compound FC(F)(F)F TXEYQDLBPFQVAA-UHFFFAOYSA-N 0.000 description 2
- 238000004448 titration Methods 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical compound C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 1
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- 238000010894 electron beam technology Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 229920002313 fluoropolymer Polymers 0.000 description 1
- 239000004811 fluoropolymer Substances 0.000 description 1
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- 230000005764 inhibitory process Effects 0.000 description 1
- 229910003471 inorganic composite material Inorganic materials 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 239000003014 ion exchange membrane Substances 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 230000005865 ionizing radiation Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000002121 nanofiber Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 229920002493 poly(chlorotrifluoroethylene) Polymers 0.000 description 1
- 239000005023 polychlorotrifluoroethylene (PCTFE) polymer Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920002959 polymer blend Polymers 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000012779 reinforcing material Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
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Description
この構成により、電気化学素子用複合膜は、膜の安定性に優れ、且つ高いイオン交換容量を有する。
この構成により、高い耐熱性や、各種電解液等への高い化学的耐久性を有する。
この構成により、以下の特徴を有する。より高い耐熱性及び安定性を有する。また、より高い空隙率を有し、繊維径及び細孔径の均一性が高いため、多くのイオン交換材料を充填することができ、高いイオン交換容量を有する。さらに、膜厚を薄くしても、十分な強度を有すると共に、膜抵抗を低くすることができる。また、MD方向とTD方向による異方性が生じない。
この構成により、耐久性の高い複合膜とすることができ、またプロトン透過チャンネルが形成されやすい。
この構成により、膜抵抗が低く、膜の安定性に優れ、膜の変形・破壊が生じにくい燃料電池用電解質膜を提供することができる。
この構成により、膜抵抗が低く、膜の安定性に優れ、膜の変形・破壊が生じにくい二次電池用セパレータを提供することができる。
この構成により、膜抵抗が低く、異方性を有しない電気化学素子用複合膜を製造することができる。
この構成により、耐熱性、長期安定性、化学的耐久性に優れ、且つ膜抵抗が低いと共に、強度、耐久性、及び膜抵抗の均一性が高い電気化学素子用複合膜を製造することができる。
この構成により、二次電池の高性能化・長寿命化・小型化・軽量化を図ることができる。
この構成により、燃料電池の高性能化・長寿命化・小型化・軽量化を図ることができる。
本実施形態の実施例1は、フッ素樹脂不織布として、電界紡糸法により生成され、加熱焼成処理された、平均繊維径が900nmのポリテトラフルオロエチレン繊維(以下、PTFE繊維と記す)からなる不織布を用い、イオン交換材料12の溶解溶液として、20質量パーセントのNafion溶液を用いた。当該PTFE繊維からなる不織布は、気孔率が85%、平均細孔径が1.8μm、厚さが60μmであった。ここで、気孔率は、次式にて算出した。
気孔率(%)=[1−{(フッ素樹脂不織布の重量)/(フッ素樹脂不織布の体積×フッ素樹脂の真密度)}]×100
尚、上式中のフッ素樹脂不織布の体積はフッ素樹脂不織布の横幅、縦幅、厚みの測定結果より算出される値とする。また、フッ素樹脂(PTEE)の真密度は2.1g/cm3とした。
◎:シワや丸まりがほとんど見られなかった
○:シワや丸まりが一部見られたが、全体として平面形状を保っていた
△:シワや丸まりが多数発生し、平面形状を一部保てていなかった
×:シワや丸まりにより、全体的に平面形状を保てていなかった
実施例2の電気化学素子用複合膜は、電界紡糸法により生成され、加熱焼成処理された、平均繊維径が900nmであるPTFE繊維からなり、気孔率が85%、平均細孔径が1.8μm、厚さが30μmであるフッ素樹脂不織布を用いた以外は実施例1と同様の手順により、電気化学素子用複合膜を作製した。用いた実施例2のフッ素樹脂不織布の熱収縮、及び作製した実施例2の電気化学素子用複合膜のイオン交換容量、及び寸法変化は、実施例1と同様の方法により測定した。測定結果を表1に示す。
比較例1は、延伸ポリテトラフルオロエチレン(以下、e−PTFEと記す。気孔率:85%、平均細孔径:1.0μm、厚さ:30μm)をフッ素樹脂不織布の代わりに用いた以外は、実施例1と同様の手順により、電気化学素子用複合膜を作製した。用いた比較例1のe−PTFEの熱収縮、及び作製した比較例1の電気化学素子用複合膜のイオン交換容量、及び寸法変化は、実施例1と同様の方法により測定した。測定結果を表1に示す。尚、e−PTFEは、非繊維状形態のノード(結束部)とフィブリル(繊維状部)とから構成されているため、SEM観察による繊維径の測定方法では適切な平均繊維径を算出することができず、表1に示していない。
比較例2は、e−PTFE(気孔率:66%、平均細孔径:0.45μm、厚さ:30μm)をフッ素樹脂不織布の代わりに用いた以外は、実施例1と同様の手順により、電気化学素子用複合膜を作製した。用いた比較例2のe−PTFEの熱収縮、及び作製した比較例2の電気化学素子用複合膜のイオン交換容量、及び寸法変化は、実施例1と同様の方法により測定した。測定結果を表1に示す。
比較例3は、e−PTFE(気孔率:56%、平均細孔径:0.10μm、厚さ:30μm)をフッ素樹脂不織布の代わりに用いた以外は、実施例1と同様の手順により、電気化学素子用複合膜を作製した。用いた比較例3のe−PTFEの熱収縮、及び作製した比較例3の電気化学素子用複合膜のイオン交換容量、及び寸法変化は、実施例1と同様の方法により測定した。測定結果を表1に示す。
比較例4は、電気化学素子用複合膜として、市販のパーフルオロカーボンスルホン酸膜(Nafion NRE212、E. I. du Pont de Nemours and Company社製)を用いた。比較例4の電気化学素子用複合膜のイオン交換容量、寸法変化は、実施例1と同様の方法により測定した。測定結果を表1に示す。
本明細書開示の発明は、各発明や実施形態の構成の他に、適用可能な範囲で、これらの部分的な構成を本明細書開示の他の構成に変更して特定したもの、或いはこれらの構成に本明細書開示の他の構成を付加して特定したもの、或いはこれらの部分的な構成を部分的な作用効果が得られる限度で削除して特定した上位概念化したものを含み、下記の変形例等も包含する。
11…フッ素樹脂不織布
12…イオン交換材料
Claims (8)
- 平均繊維径が300〜5000nmのポリテトラフルオロエチレン繊維からなるフッ素樹脂不織布と、
イオン交換材料と、
を有する電気化学素子用複合膜であって、
前記電気化学素子用複合膜は、90℃の水中に3時間浸漬後の膨張率がMD方向、TD方向、及び厚み方向でそれぞれ6%以下であり、また110℃で3時間乾燥後の収縮率がMD方向、TD方向、及び厚み方向でそれぞれ2%以下であることを特徴とする電気化学素子用複合膜。 - 前記ポリテトラフルオロエチレン繊維が、ポリテトラフルオロエチレンを含む溶液から電界紡糸法により生成されることを特徴とする請求項2に記載の電気化学素子用複合膜。
- 前記イオン交換材料が含フッ素イオン交換樹脂であることを特徴とする請求項1、又は2に記載の電気化学素子用複合膜。
- 前記電気化学素子用複合膜が、燃料電池用電解質膜として用いられることを特徴とする請求項1〜3の何れかに記載の電気化学素子用複合膜。
- 前記電気化学素子用複合膜が、二次電池用セパレータとして用いられることを特徴とする請求項1〜3の何れかに記載の電気化学素子用複合膜。
- 繊維化するポリマー及びポリテトラフルオロエチレンを溶媒に分散・溶解させて、紡糸液を作成する紡糸液作成工程と、
前記紡糸液を用いて電界紡糸法によりフッ素樹脂繊維を生成し、集積することによりフッ素樹脂不織布前駆体を形成する電界紡糸工程と、
前記フッ素樹脂不織布前駆体を加熱焼成することにより前記繊維化するポリマー及び溶媒を除去し、ポリテトラフルオロエチレンのみからなるフッ素不織布を形成する焼成工程と、
前記フッ素樹脂不織布とイオン交換材料とを複合化する複合化工程と、
を有し、
上記各工程により製造された電気化学素子用複合膜は、90℃の水中に3時間浸漬後の膨張率がMD方向、TD方向、及び厚み方向でそれぞれ6%以下であり、また前記電気化学素子用複合膜は、110℃で3時間乾燥後の収縮率がMD方向、TD方向、及び厚み方向でそれぞれ2%以下であることを特徴とする電気化学素子用複合膜の製造方法。 - 請求項1〜3及び請求項5の何れかに記載の電気化学素子用複合膜を有することを特徴とする二次電池。
- 請求項1〜4の何れかに記載の電気化学素子用複合膜を有することを特徴とする燃料電池。
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