JP4959597B2 - 固体電解質フィルムの製造方法 - Google Patents
固体電解質フィルムの製造方法 Download PDFInfo
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- JP4959597B2 JP4959597B2 JP2008027391A JP2008027391A JP4959597B2 JP 4959597 B2 JP4959597 B2 JP 4959597B2 JP 2008027391 A JP2008027391 A JP 2008027391A JP 2008027391 A JP2008027391 A JP 2008027391A JP 4959597 B2 JP4959597 B2 JP 4959597B2
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- 229920001690 polydopamine Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910001414 potassium ion Inorganic materials 0.000 description 1
- 239000012286 potassium permanganate Substances 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
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- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
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Images
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- 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
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- Manufacture Of Macromolecular Shaped Articles (AREA)
- Moulding By Coating Moulds (AREA)
- Fuel Cell (AREA)
Description
固体電解質としては、プロトン供与基をもつポリマーまたはプロトン受容基をもつポリマーを用いることができる。プロトン供与基をもつポリマーは、特に限定されないが、酸残基をもち、プロトン伝導材料として公知であるものを用いることができる。中でも好ましいポリマーは、酸残基をもつものであり、例えば、側鎖にスルホン酸基を有する付加重合高分子化合物、ポリエーテルエーテルケトンをスルホン化したスルホ化ポリエーテルエーテルケトン、スルホ化ポリベンズイミダゾール、ポリスルホンをスルホン化したスルホ化ポリスルホン、耐熱性芳香族高分子化合物のスルホ化物などが挙げられる。側鎖にスルホン酸基を有する付加重合高分子化合物としては、ナフィオン(登録商標)に代表されるパーフルオロスルホン酸や、スルホ化スチレン、スルホ化ポリアクリロニトリルスチレン、スルホ化ポリアクリロニトリルブタジエンスチレンなどがあり、耐熱性芳香族高分子のスルホ化物としてはスルホ化ポリイミド等がある。
ドープの溶媒には、固体電解質としてのポリマーを溶解させることができる有機化合物が用いられる。例としては、芳香族炭化水素(例えば、ベンゼン,トルエンなど)、ハロゲン化炭化水素(例えば、ジクロロメタン,クロロベンゼンなど)、アルコール(例えば、メタノール,エタノール,n−プロパノール,n−ブタノール,ジエチレングリコールなど)、ケトン(例えば、アセトン,メチルエチルケトンなど)、エステル(例えば、酢酸メチル,酢酸エチル,酢酸プロピルなど)、エーテル(例えば、テトラヒドロフラン,メチルセロソルブなど)、及び窒素を含有する化合物(N−メチルピロリドン(NMP)、N,N−ジメチルホルムアミド(DMF)、N,N’−ジメチルアセトアミド(DMAc)など)、ジメチルスルホキシド(DMSO)などが挙げられる。
固体電解質としてのポリマーが、側鎖にスルホン酸基を有する場合には、ドープに用いられる溶媒と混ぜたときに多価の陽イオンを生じる塩を、ドープ中に含ませることが好ましい。多価の陽イオンを生じる塩がドープ中に含まれることにより、後述の流延膜冷却工程において、スルホン酸基と塩から生じる陽イオンとの間でのクーロン力が生じる。これにより、ポリマー分子同士を、陽イオンを介して架橋させることができる。例えば、2価の陽イオンをM2+として表すときに、「−SO3 −・・・M2+・・・SO3 −−」というようにM2+が−SO3 −同士の橋渡しの役割を果たす。この結果、流延膜の貯蔵弾性率が上昇するので、流延膜の強度が上がり、流延膜の支持体からの剥ぎ取りのタイミングを早めるとともに、剥ぎ取った後の自己支持性をより高めることができる。多価の陽イオンとしてはMg2+,Ca2+,Sr2+,Ba2+,Al 3+ が好ましい。
次に、本発明の固体電解質フィルムの製造方法について説明する。図2に、本発明に係る固体電解質フィルム製造工程60のフローを示す。なお、ここでは、フローの概略のみを説明するものとし、各工程の詳細については別の図面を参照して説明する。
図3は、上記第1フローを実施するフィルム製造設備33の概略図である。ただし、このフィルム製造設備33は本発明の一例であり、本発明を限定するものではない。
理論希釈倍率=(洗浄液121の量[cc/m2 ])÷(酸溶液110の量[cc/m2]・・・(1)
以下に、固体電解質フィルムを電極膜複合体(Membrane and Electrode Assembly,以下、MEAと称する)に使用する例と、この電極膜複合体を燃料電池に用いる例とを説明する。ただし、ここに示すMEA及び燃料電池の様態は本発明の一例であり、本発明はこれに限定されない。図4は、MEAの断面概略図である。MEA161は、固体電解質フィルム78と、このフィルム78を挟んで対向するアノード電極162及びカソード電極163とを備える。
(1)プロトン伝導材料塗布法:活性金属担持カーボン、プロトン伝導材料、溶媒を含む触媒ペースト(インク)を固体電解質フィルム78の両面に直接塗布し、多孔質導電シート132a,133aを(熱)塗布層に圧着して5層構成のMEAを作製する。
(2)多孔質導電シート塗布法:触媒層132b,133bの材料を含んだ液、例えば触媒ペーストを、多孔質導電シート132a,133aの表面に塗布し、触媒層132b,133bを形成させた後、固体電解質フィルム78と圧着し、5層構成のMEA131を作製する。
(3)Decal法:触媒ペーストをPTFE上に塗布し、触媒層132b,133bを形成させた後、固体電解質フィルム78に触媒層132b,133bのみをうつし、3層構造を形成し、これに多孔質導電シート132a,133aを圧着し、5層構成のMEA131を作製する。
(4)触媒後担持法:白金未担持カーボン材料をプロトン伝導材料とともに混合したインクを固体電解質フィルム78、多孔質導電シート132a,133aあるいはPTFE上に塗布・製膜した後、白金イオンを含む液に固体電解質フィルム78を含浸させ、白金粒子をフィルム中で還元析出させて触媒層132b,133bを形成させる。触媒層132b,133bを形成させた後は、上記(1)〜(3)の方法にてMEA131を作製する。
・原料A; 100重量部
・溶媒成分1;DMSO 256重量部
・溶媒成分2;メタノール 171重量部
ドープAからフィルム製造設備33により実験1〜6,比較実験1〜4の各条件で固体電解質フィルムをつくった。表1には、実験1〜6,比較実験1〜4の各条件と、評価結果とを示す。表1における項目番号は、以下の条件及び評価項目の各番号に対応する。
1の(a)・・・ドープに加えた塩の種類、加えなかった場合には「−」を記載する。
1の(b)・・・前駆体であるポリマーの重量を100としたときに、ドープに加えた塩の重量の割合(単位;重量%)
2.ドラム96の温度(単位;℃)
3.流延室81の湿度(単位;%RH)
4.剥ぎ取り時における流延膜の貯蔵弾性率(単位;Pa)
5.形成された流延膜が剥ぎ取られるまでの時間(単位;分)
6.ドラム96からの流延膜の剥ぎ取り性を目視で評価した結果であり、評価基準は以下のとおり。
○;剥ぎ取ることができた
×;自重により変形してしまうあるいは引きちぎれてしまう等で剥ぎ取ることができなかった
7.得られた固体電解質フィルムにおける多価の塩の濃度(単位;ppm)
なお、上記項目6において「×」であったものについては、サンプル片を切り出して、このサンプル片で測定した。
8.プロトン伝導度(単位S/cm);プロトン伝導度の測定は、Journal of the Electrochemical Society 143巻4号1254−1259項(1996年)に従い、4端子交流法を用いて行なった。具体的には、先ず、各固体電解質フィルムから長さ2cm、幅1cmに切り抜いたものをサンプルとした。次に、PTFE板に5mm間隔で白金線を4本固定したものに先のサンプルを載せた後、更にPTFE板を載せてから、これらをビスで固定して試験セルとした。そして、この試験セルと、ソーラトロン製1480型及び1225B型を組合せたインピーダンスアナライザーとを用いて、25℃と80℃との各水中で交流インピーダンス法によりプロトン伝導度を測定した。25℃の水中での結果を(a)欄に、80℃の水中での結果を(b)欄に記す。なお、上記項目6において「×」であったものについては、サンプル片を切り出して、このサンプル片で評価した。
33 フィルム製造設備
96 ドラム
67 湿潤前駆体フィルム67
78 固体電解質フィルム
Claims (3)
- 溶剤と固体電解質でありスルホン酸基を有するポリマーと前記溶剤中で多価の陽イオンを生じる塩とを含むドープを支持体の上に流延して流延膜を形成する工程と、
表面温度を−20℃〜10℃の範囲で一定とした前記支持体により前記流延膜を冷却する工程と、
前記流延膜を前記支持体から剥がして乾燥する工程と、
を有することを特徴とする固体電解質フィルムの製造方法。 - 前記陽イオンは、Mg2+,Ca2+,Sr2+,Ba2+,Al 3+ の少なくともいずれかひとつであることを特徴する請求項1記載の固体電解質フィルムの製造方法。
- 前記流延膜に水を含ませることを特徴とする請求項1または2記載の固体電解質フィルムの製造方法。
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