200416067 玖、發明說明 (發明說明應敘明：發明所屬之技術領域、先前技術、內容、實施方式及圖式簡單說明） (一） 技術領域 本發明關係一種基於磷酸鍩之質子傳導陶瓷膜、其製法 及在ME As (膜電極組件）與燃料電池中之用途。 (二） 先前技術 薄膜是燃料電池的中心件。在質子交換膜（p E M s )之情況 中，所用電解質膜主要是經酸基改質之聚合物。於今常用 者爲Nafion(杜邦，具有磺酸官能基之氟化結構）或相關之 | 系統。另一種純爲有機之導質子聚合物是Hoe chst特別說 明以磺化聚醚酮所提供者（E P 0 5 7 4 7 9 1 B 1 )。 所有這些聚合物都有在大氣濕度降低時則導電度陡然跌 落之缺點。因此，在用於燃料電池之前，這些薄膜必須在 水中浸脹。在溫度昇高時，其如在重組燃料電池或直接甲 醇燃料電池（REC或DMFC)中所無可避免者，這些系統因 爲易於乾涸而完全不能再被使用，或僅用於受限之形狀。 用於DMFC之聚合物膜之另一個問題，是對於甲醇有大的修 渗透性°甲醇越過而至陰極側之結果，使燃料電池之功遽 降。 爲了此等原因，使用有機聚合物膜於RFC或DMFC並不 理想’而且@爲燃料電池廣被使用，必須尋求新的解決方 法。 雖然無機之質子導體已見於文獻（例如：Cambridge University Press 1 992 出版 ρ· Colomban 之"Proton -6- 200416067 C ο n d u c t 〇 r s ’’），其大部份所具之傳導性皆太低，或僅在高 溫，通常在5 0 0 °C以上，始達技術上可利用之程度，例如 在殘缺之鈣鈦礦之情形。最後，另一類純爲無機之質子傳 導體，MHS〇4族群，雖然是質子傳導體，然而同時也易溶 於水中。因爲水爲陰極側之生成物而形成，所以薄膜日久 受損，不適合用於燃料電池之用途。長久以來已經討論玻 璃態系統（Abe 等，J. Sol_Gel Sci. Techn. 14(1999)，第 273 頁；Minami 等 ’ Chem. Lett· (2000)，第 1314 頁）或乾凝膠 (Anderson 等，Chem. Mater· 12(1200)第 1762 頁）等作爲質 子傳導材料之適用性。然而這些材料由於傳導性欠佳而不 適合燃料電池之用途。 磷化鉻（ZrPs)，爲α或γ態之ZrP者已久被認知爲質子 導體（Alberti，Solid State Ionics 1 2 5 ( 1 9 9 9 )，第 91 頁）。因 爲此種材料在此情況中之傳導性實質上是由自由之Ο Η基 決定，所以大的表面積爲所重要。對於純的a_ZrP，文獻 (Glipa 等人，Solid State Ionics，97(1997)，第 277 頁）所 報告之傳導性，在平均大氣濕度時，爲1CT5至10_6s/cm (西門子/厘米-Siemens/cm)。磷酸銷可以用於燃料電池膜之 參考文獻見於Linkov(EP 0 838 258)，雖然對於膜之品質 ，尤其是質子傳導性，未有精確詳述。再者，EP 0 8 3 8 2 5 8 所述此種薄膜是基於習用之薄膜，厚而無撓性。因爲厚度 ，只能產生具有高表面阻力之薄膜。反之，對於燃料電池 之用途，傳導性應不低於1 0'3西門子/厘米且厚度應不超過 100微米。對於實際用途，Lin kov所述之堅硬薄膜不適合 200416067 用於燃料電池。 其他問題 於電解質 使有高的 不可能達 膜（WO 性、低膜 可使用性 ，傳導性不 燃料電池 丨狀況中也 種用途之 接反應 再者，因 解質與各 以在兩者 爲無可改 之間極易 ，支持物而 關於在此所指利用無機質子導體於燃料電池之 ，爲此等陶瓷品事實上不可能產生薄的膜片。由 須以極厚之形狀自動製成，電池的整體電阻，即 比傳導性，也常爲極高。結果，例如在汽車內， 到高燃料電池功率密度而合於產業用途。 雖然亦爲已知有具備撓性之大型無機質子傳導 9 9/6 2 6 2 0 )。此等薄膜結合有機膜片之優點（高撓 片厚度）與無機質子傳導系統者（無臨界含水量， 達200 °C ，無甲醇通過）。然而，這些材料也因爲 適合因而無法充份的功率密度，仍然不適合用於 。再者，在WO 99/62620中所述之複合物在理想 不適合用於燃料電池，這是由一項事實，用於此 電解質膜必須絕對無滲透性；否則各反應物將直 (在陽極側的水或甲醇與在陰極側的氧或空氣）。 爲在所已知之ME A (薄膜電極組件）中必須存在電 電極間之接觸以完成燃料電池內的電流迴路，所 內面和兩者表面上具有離子傳導層之多孔支持物 變。另外，因爲在燃料電池之運轉中，於各電極 發生短路，在W 0 9 9 / 6 2 6 2 0所述以鋼質織物作爲 優先使用者，絕對不適合作爲燃料電池用途。 (三）發明內容 因此，本發明之一項目的爲提供一種具有至少1 (Γ3西門 子/厘米傳導度之撓性無機質子傳導膜，以及予以產生之方 200416067 法。 节人馬異者，已發現 用於製成具有夠大的臂 的一類薄膜可供RFCq 因此’本發明提供〜 導膜’含有片狀撓性基 該基板上及其內，基扳 瓷或如此材料所結合之 導質子之奈米級磷酸銷 粒度，且在燃料電池內 本發明提供一種產生 一項之質子傳導膜之方 基板之內與其上設有塗 非傳導性玻璃或陶瓷或 至少含有奈米級磷酸鉻 料至基板上，且經至少 或溶膠被固化於基板之 本發明另提供如申請 薄膜作爲燃料電池內質 請專利範圍第1至1 5項 本發明之薄膜所具優 高之溫度，水位非爲關 質子傳導膜比較，本發 性之形狀而生產之優點 磷酸鉻之奈米級物已可製成，並且 子傳導度之薄膜撓性膜。所以，新 0 D M F C s 使用。 種如申請專利範圍第1項之質子傳 板’備有多個開口具有塗層呈現在 材料選自編織或非編織之坡璃或_ 非傳導性纖維，其中之塗層含有^ 粒子，具有小於5，0 0 0奈米之基本 作爲反應元件而爲不滲透性。 如申請專利範圍第1至1 5項中至少 法’其中在具備有多數開口之片狀 層’基板材料包括編織或非編織之 如此材料所結合之纖維，包括施用 粒子之懸浮液或溶膠之質子傳導塗 一次加熱處理。在該過程內懸浮液 內或其上。 專利範1¾第1至1 5項中至少一項之 子乂換β臭之用途，並提供含有如申 :中至少〜項之薄膜所成之燃料電池。 於聚合物基薄膜之處，並可用於較 鍵’且無甲醇通過。與已知之陶瓷 明薄膜具有能以實質上較薄而有撓 200416067 本發明薄膜對燃料電池內各反應成分如氫、氧、空氣及/ 或甲醇等爲氣密而不滲透。對本發明之目的，各反應成分 之氣密或不滲透性意指每天每巴通過每平方米本發明薄膜 之氫少於5 0公升，氧少於2 5公升；且薄膜對甲醇之滲透 度明顯低於一般認爲是不滲透性之市售Nafion薄膜之情 形。 以某種粒度之奈米級磷酸鍩粒子之懸浮液固化於基板之 內與之上而成爲塗層之事實，確使在整個薄膜上有較爲均 勻之磷酸銷分佈而優於例如在EP 0 3 8 3 2 5 8中所述之方法 所能達成者，其爲以錐鹽滲入多孔之陶瓷膜內，然後用多 元酸，尤其是多元磷酸，處理經已滲透之薄膜。因爲在多 孔陶瓷膜內之粒子分佈與粒子大小兩者有時或多或少是決 定於例如多孔陶瓷膜中孔性和孔度之函數。諒必是因奈米 級基本粒子之大表面積，磷酸銷粒子之較均勻分佈，及/ 或粒子較均勻之大小，以及薄膜之薄化，本發明之薄膜比 現有含磷酸銷陶瓷膜展現明顯較低之質子傳導阻力。 本發明之薄膜以如下之實施例予以說明，然而並無任何 以此等具體例限制本發明之意圖。 本發明之質子傳導膜含有片狀之撓性基板，設有多數開 口，具有塗層於該基板上，基板之材料選自編織或非編織 之非傳導性玻璃或陶瓷或如此材料所結合之纖維，其中之 塗層含有傳導質子之奈米級磷酸鍩粒子，具有小於5微米 之基本粒度，在燃料電池內對各反應成分爲氣密或不滲透 ，反應成分例如爲氫、氧、空氣及/或甲醇。 -10- 200416067 本發明薄膜較佳具有小於1 〇 〇微米之厚度，更佳小於5 0 微米，特別以小於3 0微米爲佳。已被發現特別適用於燃料 電池之本發明薄膜爲具有自1〇至50微米厚度者，即使較 薄而在燃料電池內展現對各反應成分展現充份安定性與氣 密性或不滲透性者同樣可被採用。 由於低厚度，本發明之質子傳導膜特別具有低電阻。織 物、不織布、氈毯或撓性多孔陶瓷膜，其本身被用作供以 磷酸锆滲透之基礎者，自然具有極高之電阻，否則在陽極 與陰極之間將有短路之危險。 爲求獲得本發明具有電絕緣性質之薄膜，其基板材料較 佳含有非傳導性纖維，選自玻璃、氧化鋁、Si02、SiC、Si3N4 、BN、B4N、AIN、Sialons 或 Zr02。 基板材料例如可爲不導電纖維之織物、非編織物或氈毯 ，或備有多孔陶瓷塗層之不導電纖維之另種織物、非編織 物或氈毯，其例如一種微濾膜。爲謀求達到特別良好之質 子傳導性，基板材料以具有無孔陶瓷塗層之玻璃纖維之非 編織物、織物或氈毯者爲佳，這是因爲如若材料不具多孔 塗層，由於實有體積較小，多孔性遠較爲高，因而有較多 之質子傳導性材料可供傳導質子於每單位面積薄膜之中， 基於此種事實而有可能達成較高之傳導度。雖然編織物比 非編織物強固，非編織物之使用，因比編織物更爲多孔， 具有比編織物爲佳之優點。因此，根據所需要之薄膜性質 ，使用玻璃纖維之編織物或非編織物可能比較適合作爲薄 膜基板。 -11- 200416067 原則上可以採用任何可以獲得作爲纖維之玻璃材料，其 如E -、E C R -、C -、D -、R -、S -和Μ -玻璃，例如用作支持 物。較佳者使用Ε -、E C R -或S -玻璃之纖維。較佳之各種 玻璃含有低的BaO、Na20或Κ20含量。較佳之玻璃種類具 有少於5重量％之B a Ο含量，最好少於1重量％ ; N a 0 2含 量少於5重量％，最好少於1重量％ ; Κ2 Ο含量少於5重量 %，最好少於1重量％。最有利之纖維是由不含BaO、Na02 、Κ 2 Ο之玻璃組成，其如爲E玻璃，這是因爲如此型式之 玻璃較耐化學影響。 € 在本發明傳導質子膜之一特佳具體例中，基板之纖維， 尤其爲Ε-或S-玻璃之纖維爲佳，被售以Si02、Zr02、Ti02 或A 1 2 Ο 3或此等氧化物之混合物。氧化物塗層特別適合具 有低的酸安定性之玻璃種類，例如Ε -玻璃。在支特物內氧 化物對玻璃之重量比較較佳爲小於1 5 : 8 5，更佳小於1 0 : 9 0 ，且特佳爲小於5 : 9 5。 若本發明薄膜含有玻璃纖維紡織物基板，其如玻璃纖維 φ 編織物、氈毯或非編織物，例如該紡織物較好產自具有不 大於20tex(毫克/米）直線密度之纖維，纖維之較佳者具有 不大於lOtex之直線密度，特別優良者具有不大於5.5tex 之直線密度。 特別適合之基板含有由有5 . 5或1 1 t e X直線密度之纖維 製成之玻璃纖維編織物。此種纖維之個別紗線具有例如由 5至7微米之直徑。此種適合用作支特物之玻璃纖維編織 物具有5至3 0支緯紗/厘米和自5至3 0支經紗/厘米；較 -12- 200416067 佳自1 〇至3 0支緯紗/厘米和自1 0至3 0支經紗/厘米；等 佳者自1 5至2 5支緯紗/厘米和自1 5至2 5支經紗/厘米。 使用如此之玻璃編織物之確保薄膜有充份強度而保持足夠 之基板多孔性。 本發明薄膜之塗層較佳含有奈米級磷酸锆子，所具基本 粒度爲自1至1 〇 〇 〇奈米，更佳之奈米級磷酸鍩粒子具有自 1至1 0 0奈米之基本粒度，而特別適合之奈米級磷酸鍩粒 子爲具有自10至100奈米之基本粒度者。除了奈米級磷酸 鉻基本粒子外，本發明之塗層亦可含磷酸锆基本粒子之積 聚物。具有1微米或更大之粒度，較佳自1至100微米， 特佳自1至2 5微米。 如果除了奈米級磷酸锆粒子之外，質子傳導膜至少含有 一種Al、Zr、Si或Ti等金屬之氧化物。在塗層內各氧化 物可以以粒子互相連結而呈現，例如用黏著劑結合、燒結 或類似之技術。此對於支特物設有陶瓷塗層之情形特別是 用於產生質子傳導膜。或改之爲使各氧化物形成分離之陶 瓷粒子，此特別是用於使氧化物粒子結合磷酸锆基本粒子 成爲溶膠或懸浮液而施用於支特物上並固化此系統之情形 。分離之氧化物粒子特別是存在於當氧化物對磷酸锆之重 量比爲明顯小於1 : 1之時。氧化物粒子較佳具有5微米或 較小2大小，特別是自0 . 0 1至1微米或自1 0.0 1至0 . 1微 米爲較佳，各該粒子可爲基本粒子或積聚物。 本發明薄膜之一項特點爲具有大於1毫西門子/厘米之 傳導度。本發明薄膜較佳具有自1至1 00毫西門子/厘米之 -13- 200416067 質子傳導度，特別爲佳者自1至1 0毫西門子/厘米，均在 室溫與8 0至9 0 %之相對濕度。本發明薄膜較佳者爲可被彎 曲至250米半徑而不損壞，更佳者爲10厘米，而特佳者爲 5厘米。本發明薄膜之高傳導度和良好之可彎曲性具有使 本發明薄膜可用於可設想之任何幾何形狀於燃料電池之中。 再者，薄膜不溶於水和甲醇，且與例如Nafion比較，展 現對甲醇有極低之滲透性（可想像爲非滲透性）。因此，此 等薄膜特別適用於D M F C s。 本發明薄膜較佳爲得自於一種產生質子傳導膜之方法， 在膜中備有多數開口之片狀撓性基板，於其內與其上設置 塗層。基板之材料包括編織的或非編織的玻璃或陶瓷或此 等材料所結合之非傳導性纖維；包括施加塗層至基板，以 至少含有奈米級磷酸鍩粒子之懸浮液施用，並在懸浮液固 化於基板之上與之內的過程中至少有一次加熱操作。 施於基板之上和之內的懸浮液可用例如印塗、壓印、射 入、輥乳、刀塗、刷塗、浸塗、噴塗或傾淋。 基板材料較佳選自玻璃、氧化鋁、S i Ο 2、S i C、S i 3 Ν 4、 BN、B4N、AIN、Sialons或Zr02，尤其是耐高溫及/或耐酸 之玻璃、或石英玻璃或陶瓷。 基板材料可爲上述材料之非導電纖維之編織物、非編織 物或氈毯。爲求在薄膜內獲得一致之電阻，基板材料最好 使用玻璃纖維非編織物（由非編織之玻璃纖維形成）。 原則上，所有玻璃材料，均可供作纖維而用於基板，例 如 E -、A -、E C R -、C -、D -、R -、S -和 Μ -玻璃。較佳者爲 200416067 使用E -或S -玻璃之纖維。較佳之玻璃種類具有低的B a Ο、 Na20或Κ20含量。較佳之玻璃型式以具有少於5重量％BaO 含量者爲佳，少於1重量％爲最佳；且Na20含量少於5重 量％，最好少於1重量％ ;又κ20含量爲少於5重量％，最 好少於1重量％。組成各種纖維之玻璃型式，其有利者爲 不含有BaO、Na20或Κ20之組成，例如爲Ε-玻璃，是因 爲此型玻璃較耐化學品。 在產生本發明質子傳導膜之方法之一特佳具體例內，基 板之纖維一以Ε-及/或S-玻璃之纖維爲特佳一被塗上一種 Si 02薄膜。此種塗層可以使用例如原矽酸四乙酯（TE0S)施 於個別或成編織物、氈毯或非編織物中之纖維，然後在自 400至6001：之溫度、較佳自420至500 °C，最佳440至460 °C ，烘烤TEOS。烘烤後留下二氧化矽成殘留物於纖維表面上 。已經測知以此方法處理過之纖維實質上比未處理者更合 適用作基板材料。其因後續之塗覆實質上在經處理之纖維 上有較佳之黏著力，因而明顯改善長期之安定性。除了 Si02 之塗層外，Z r Ο 2、T i Ο 2或A 12 Ο 3或此等氧化物之混合物之 各種塗層也可使用，其中可以例如從對應之金屬醇鹽開始 。塗層可以產生於與TEOS塗層相同之方法。 如若所用基板爲玻璃纖維紡織品，其如玻璃纖維編織物 、氈毯或非編織物，例如，較佳者爲產自具有不大於20 teX( 毫克/米）直線密度之纖維，更佳爲自具有不大於1 〇 t e X直 線密度之纖維，且最佳爲自具有不大於5.5 tex直線密度之 纖維。所用基板之最佳者爲織自具有5 . 5或1 1 tex直線密 -15- 200416067 度之纖維所成之玻璃纖維布料。 此等纖維之個別紗線具有例如自5至7微米之直徑。所 用玻璃纖維布料較佳爲具有自5至3 0緯紗/厘米和自5至 3 0經紗/厘米之基板，更佳自1 0至3 0緯紗/厘米而自1 0 至30經紗/厘米，最佳自1 5至25緯紗/厘米而自1 5至25 經紗/厘米。此種玻璃編織物之使用，確保本發明薄膜有充 份強度而持有足夠之基板多孔性。 已經被測知者，當使用市售之玻璃纖維紡織品，尤其玻 璃纖維非編織物、玻璃氈毯或玻璃編織物，其對玻璃纖維 紡織品在製程中所加於纖維之漿料之除去，對於玻璃纖維 紡織品之強度具有實質上之影響。漿料通常以加熱於玻璃 纖維紡織品而除去，尤其是玻璃纖維編織物，在達5 0 (TC 歷經自1至2分鐘，然後在3 0 0 °C熱處理大約4天。令人 驚奇者，已經測知以此方法處理過之玻璃纖維紡織品實質 上比仍有漿料之玻璃纖維紡織品較脆。然而，磷酸锆之塗 層非常難以施加於具有漿料玻璃纖維紡織品基板之上或其 內，其原因是漿料使塗層對紡織品之黏著力劣化。令人驚 奇者爲已發現在5 0 0 °C以下，較佳在4 5 0 °C以下之溫度燒除 漿料歷經2分鐘，較佳經過1分鐘，隨後並用上述ΤΕ Ο S 處理，將足以確保玻璃纖維紡織品有更加耐用之塗層，尤 其是玻璃纖維編織物。 如果所用基板材料爲具有多孔陶瓷塗層之玻璃纖維紡織 品，將可有益。此種陶瓷塗覆之玻璃纖維紡織品見於W 0 9 9/ 1 5 2 62。陶瓷塗層較佳是以含有溶膠和至少一種無機成 200416067 分之懸浮液施於玻璃纖維紡織品上，無機成分至少包含一 種金屬、半金屬或混合之金屬化合物，至少有一元素選自 主族3至7 ;且至少有一次加熱操作，在此過程中至少含 有一種無機成分之懸浮液被固化於玻璃纖維紡織品之上或 其內’或在其上與其內。產生此種陶瓷塗覆之玻璃纖維紡 織品之方法與W Ο 9 9 / 1 5 2 6 2所知者相同。關於不同種類之 陶瓷塗覆玻璃纖維紡織品與其生產可參考WO 9 9/ 1 5 2 6 2。 被用以產生塗層之懸浮液至少含有粒度小於1微米之奈 米級磷酸鉻粒子。用於生產本發明薄膜塗層之懸浮液較佳 含有基本粒度自1至1〇〇〇奈米之奈米級磷酸鉻粒子，更佳 爲具有自1至100奈米基本粒度之奈米級磷酸鉻粒子，而 最佳爲具有自10至1〇〇奈米基本粒度之奈米級磷酸銷粒子 。除了奈米級磷酸鍩基本粒子之外，本發明塗層亦可含有 具有1微米或更大之磷酸鍩粒子之積聚物’較佳爲自1至 1 0 0微米，最佳自1至2 5微米。奈米級磷酸鉻粒子較佳爲 產生上游步驟。原則上，其爲可以產於任何適合生產奈米 級粉末之方法過程，其如氣相方法（與浮質生產法、線爆法 、微波電漿法等等相似），但也可用液相方法。 根據文獻（Penth，WO 00/61275)所知之 MlCr〇-Jet(微噴 射）法而生產者已知特別適宜。在此方法中’用於製備懸浮 液之奈米級磷酸锆粒子是產於一微噴射反應器內’使可溶 之锆化合物與含磷化合物之溶液碰撞。所用可溶銷化合物 可選自硝酸鉻、氯化锆、乙酸锆、乙酶丙嗣酸銷或院氧化 鉻。所用含有磷化物之溶液至少含有一種化合物’選自碟 -17- 200416067 酸及/或磷酸鹽，尤其是鹼金屬之磷酸鹽，其如Na3P04、 Na2HP04 或 NaH2P04。 所用最簡單之溶劑爲水。如若所用反應物對水解敏感， 其如銷烷氧化物，則也可以使用醇類或其他無水溶劑。在 微噴射反應器內，各溶液反應於特定之高壓程序而產生磷 酸鉻，兩溶液在微噴射反應器內從較佳自5 0至5 0 0微米直 徑之噴咀以達數百巴之極高壓力形成薄的噴射流而互相碰 撞。反應生成物可用例如空氣流之方法從反應器取出。 此種方法不致使基本粒子伴生任何成長。以在微噴射反 應器內操作之實驗條件，可以量適當之基本粒度，以及積 聚之大小。此方法直接產生一種含有磷酸锆之膠態懸浮物 。在此懸浮物內磷酸鍩常見之濃度爲〇 . 〇 1 - 5 0重量％，較佳 爲0 . 1 - 5重量％。如若適當，懸浮物也可以進一步蒸發所用 溶劑而濃縮。 懸浮物可以直接使用或施於上述之基板。或改變之，上 述磷酸銷粒子可用噴灑乾燥從微噴射反應器所得之磷酸銷 懸浮物，使轉變成爲包含奈米級磷酸鉻粒子之粉末。噴灑 乾燥可依習知進行，並且較佳發生於自1 〇 〇至2 0 0 °C之溫 度，較佳自1 0 0至1 5 0 °C之溫度。 然而，在本發明方法之另一具體例中，其他材料，其一 部份可爲市售者，如金屬氧化物、氰化物、碳化物或磷酸 锆等粒子，可以以粉狀加入至懸浮物內。金屬氧化物及/ 或其他無機成分之加入有利於使質子傳導度可被設定於所 需之程度，能夠達到基板之最適當之浸透效果，使最後所 -18- 200416067 形成之質子傳導膜在燃料電池內對各反應成分氣密或不滲 透。 如果至少有一種無機成分，其粒度小於5微米，較佳自 10至1000奈米，最佳自100至1000奈米者，被加入至懸 浮物內，則可爲有利。然而也可以加人其他之質子傳導材 料至懸浮物內’其如異多元酸和雜多元酸’或其他奈米級 粉末，來自八丨2〇3、Zr02、Ti02和Si〇2之系列。此外’懸 浮物可以含有Briinsted酸或可固定之矽烷酸。 在本發明方法之另一具體例中，所用懸浮物含有奈米級 磷酸鍩者，可以至少含有一種溶膠、至少一種半金屬溶膠 或至少一種混合之金屬氧化物溶膠，或該各種溶膠之混合 物。 各溶膠是獲自於水解至少一種化合物’較佳爲至少一種 金屬化合物’至少—種半金屬化合物’或至少一種混合的 金屬化合物’至少有一種液體 '固體或氣體’其中可以爲 、液體，例如水、醇或酸，所用固體則爲冰’或所用氣體爲 水蒸汽而有利。於水解前引入待水解之化合物至醇或酸或 等液之混合物中亦可有利。待水解化合物較佳至少爲一 g金屬硝酸鹽、金屬氯化物、金屬碳酸鹽、金屬烷氧化物 等化合物，或至少一種金屬烷氧化物之化合物’選自Zr、 A丨、s i、或T i等元素之化合物，其如锆烷氧化物，如锆異 丙化物，例如’矽烷氧化物’或金屬硝酸鹽’例如硝酸鍩。 其於可水解化合物之可水解基’用至少半容積莫爾比之 水、水蒸汽或冰進行得水解化合物之水解作用爲較有利。 -19- 200416067 經水解之化合物可用至少一種有機或無機酸使行膠化之 處理，較佳爲用選自硫酸、鹽酸、過氯酸、磷酸、和硝酸 、或各該酸之混合物等礦物酸，於自1 0至6 0 %之濃度。 其亦可以不只使用上述所製備各溶膠，而且可用市售溶 膠，其如硝酸锆溶膠或矽石溶膠。 本發明塗層是施用並固化懸浮物於基板之中與之上。爲 了此目的，根據本發明，用刀塗法、輥塗、噴灑或相似技 術將懸浮物施於支持材料。其較佳者進行於連續之方法。 根據本發明可以加熱於自5 0至5 0 0 °C使呈現於基板之上和 其內之懸浮物固化。在本發明方法之一特別變更具體例中 ，呈現於支特物上及其中之懸浮物被加熱於1 〇 〇至4 5 (TC 而固化，較’佳加熱於自1 5 0至4 0 0 °C，特佳爲加熱於自1 5 0 至3 0 (TC。如是加熱進行於自1秒至1 5分，較佳自1 0秒 至5分則爲有利。施用/浸透可以進行一次或多次，其中最 好予以熱處理，較佳在自5 0至5 0 0 °C之溫度，更佳自1 5 0 至3 0 (TC ，歷經1分至1小時而在各個施加步驟之間。若 干單純編織物或非編織物，塗覆多次爲佳。 本發明薄膜構成質子傳導膜之一種新的類別。其係可被 用作燃料電池中的質子交換膜，或爲膜電極組件（ME As)。 在此方面，燃料電池可含有本發明薄膜作爲質子交換膜而 完成。 本發明膜電極組件說用如下。用於燃料電池之撓性膜電 極組件含有一陽極層和陰極層，各設於本發明質子傳導膜 (電解質膜）之相反各面，膜含有片狀撓性基板，設有多數 200416067 開口， 或陶瓷 非編織 子之奈 料電池 爲多孔 導成分 陽極 ⑴ 一 鋁 (ii)-B r ο η 、亞硫 之有機 在一 ΐ夕化合 其R 碳原子 元： 二靥於該基板之上及其內’基板材料選自坡璃 或此寺材料所結合之非傳導性纖維所成之編織物或 物，塗餍含有基本粒度小於5微米之磷酸銷傳導質 米級粒子，且對諸如氫 '氧、空氣及/或甲醇等在燃 內之反應成分有氣密或不滲透性，陽極層和陰極層 性且各含有供陽極反應和陰極反應之觸媒，質子伴 ’和’如若需要之觸媒支特物。 層及/或陰極層之質子傳導膜在各狀況中最好含有； 種硫或磷之固定羥甲矽烷酸或其鹽，並可依需要有 、鈦、鉻及/或磷之氧化物；與/或 種Briinsted酸或鋁、矽、鈦、銷及/或磷之氧化物。 sted酸例如可爲硫酸、磷酸、過氯酸、硝酸、鹽酸 酸、亞磷酸，與其間之酯類，及/或爲單體或聚合體 酸0 較佳具體例中羥甲矽烷酸或其鹽爲通式如下之有機 物； [{(R0)y(R2)z}aSi{R1-S03]a]xMx+ ⑴ 或 [(RO)y(R2)2Si{R1-〇b-P(〇cR3)〇2-}a]xMx+ (丨丨） 1爲一線性或分支之烷基或伸烷基而有自1至1 2個 ，環烷基而有5至8個碳原子者，或如下通式之單 -(CHz)n-\ Η. m 200416067 或 ~(CHb)n 'χΟ) (CH2)m- (IV) 其η和m各爲自0至6之整數， Μ爲Η、ΝΗ4或金屬， X爲自1至4， y爲自1至3，ζ爲自0至2，且a爲自1至3，其條件爲 y + z == 4 _ a， b和c爲0或1， R和R2相同或不同而爲甲基、乙基、丙基或丁基或Η，且 R3爲Μ或甲基、乙基、丙基或丁基。 硫或磷之羥甲矽烷酸較佳爲三羥甲矽丙基磺酸、三羥甲 矽丙基甲基膦酸或4,4_二羥-1，7-二硫-4-矽庚烷。硫或磷之 羥矽烷酸或其鹽較佳是被固定於用經水解之磷化物或用經 水解之金屬或半金屬之硝酸鹽、氧硝酸鹽、氯化物、氧氯 化物、碳酸鹽、醇鹽、乙酸鹽或乙醯丙酮酸鹽。在另一較 佳具體例中，硫或磷之羥矽烷酸或其鹽是被固定於用經水 解之化合物，獲自丙氧化鈦、乙氧化鈦、原矽酸四乙酯 (TEOS)或原矽酸四甲酯（TMOS)，硝酸鍩、氧硝酸鍩、丙氧 化鉻、乙酸锆、乙醯丙酮酸锆、磷酸甲酯、亞磷酸二乙酯 (DEP)或乙基膦酸二乙酯（DEEP)。 陽極層及/或陰極層之質子傳導成分可另含質子傳導物 質，選自磷酸鈦、膦酸鈦、磷酸銷、膦酸鍩、異多元酸和 -22- 200416067 雜多元酸，較佳鎢磷酸或矽鎢酸、或奈米結晶金屬氧化物 ，較佳爲產自Al2〇3、Zr〇2、1^02或Si02粉末。 本發明膜電極組件最好在燃料電池內運作於至少8 之溫度，較佳至少1 〇 ，最佳至少1 2 0 °C。所用燃料可爲 純氫或其他用重組劑產生之氫。然而在一較佳具體例中， 使用甲醇。用於此目的者有水與甲醇之液態或氣態混合物 ，較佳含0 . 5 - 5 %甲醇者用於陽極側。此外，本發明膜電極 組件較佳爲撓性，且最好可調整至彎曲半徑低達5 0 0 0毫米 ，較佳爲100毫米，尤其爲50毫米，特佳爲低至20毫米 。本發明之膜電極組件最佳爲可調整彎曲半徑至低達5毫 米。 在陽極側和陽極側之觸媒可以相同，但最好不同。在一 較佳具體例中在陽極層和陰極層內之觸媒支特物爲有導電 性。 在產生膜電極組件中，電解質膜被以適當方法塗上有觸 媒之活性電極材料。 電解質膜可以用各種方法設置電極。在其過程與順序中 ，導電材料、觸媒、電解質和適當之其他添加物被施加於 薄膜上，爲熟練工匠所易爲。所有須予確定者爲所形成之 氣體空間/觸媒（電極）/電解質之介面。在一特別狀況中，導 電性觸媒支特物材料被省略；於此情形，導電性觸媒直接 供作從膜電極組件傳導電子。 供作生產本發明膜電極組件之本發明方法包含如下各步 驟： -23- 200416067 (A) 提供本發明傳導質子之電解質膜，供燃料電池之用， 並使燃料電池反應各反應成分不滲透， (B) 提供各種組成物，各供產生陽極層和陰極層，各組成 物含有： (B1)—種可縮合之成分，隨縮合作用之後在電極層上 給予質子傳導性， (B 2)—種觸媒，促進陽極反應或陰極反應；或一種觸 媒先驅化合物， (B 3 )如有需要，一種觸媒支特物，和 _ (B 4 )如爲需要，一種孔洞形成物， (C) 施用步驟（B)各組成物至自步驟（A)之電解質膜各側之 一，形成塗層， (D) 在各塗層與電解質膜之間，形成多孔、傳導質子之陽 極層或陰極層，建立堅實之結合，其爲可於陽極層和 陰極層同時或相繼形成。 步驟（C )中組成物之施用可實施於用例如印刷、壓印、噴 φ 塗、輥塗、刀塗、刷塗、浸塗、噴灑或傾淋。 用於產生陽極層或陰極層之步驟（B)組成物較佳得自於 如下之懸浮物= (S 1 )製備一種溶膠，含有： 磷或硫之羥矽烷酸及/或其鹽，和 若合適，磷之一種可水解化合物，其爲固定磷或硫之 羥矽烷酸及/或其鹽， 或金屬或半金屬之一種可水解之硝酸鹽、氧硝酸鹽、 -24- 200416067 氯化物、氧氯化物、碳酸鹽、烷氧化物、乙酸鹽或乙 醯丙酮酸酯，較佳爲磷酸甲酯、亞磷酸二乙酯（DEP) ' 乙基膦酸二乙酯（D E E P)、丙氧化鈦、乙氧化鈦、原石夕 酸四乙酯（TEOS)或原矽酸四甲酯（TMOS)、硝酸锆、氧 硝酸鉻、丙氧化鍩、乙酸锆或乙醯丙酮酸銷， (S 2 )分散觸媒和若爲適合之觸媒支特物，及孔洞形成劑於 (Sl)所成之溶膠內。 用於產生陽極層或陰極層之步驟（B)組成物特別適合爲 懸浮物而獲自於： (Η 1 )水解一種可水解之化合物成爲水解物，可水解化合物 是選自於： 一種可水解之磷化物或可水解之金屬或半金屬硝酸鹽 、氧硝酸鹽、氯化物、氧氯化物、碳酸鹽、院氧化物 、乙酸酯或乙醯丙酮酸酯，較佳爲燒氧化錦、烷氧化 釩、丙氧化鈦、乙氧化鈦、硝酸鉻、氧硝酸錐、丙氧 化鉻、乙酸銷或乙醯丙酮酸锆，或 錦、矽、鈦、釩、銻、錫、鉛、銘、鎢、錦、猛等之 金屬酸，較佳者爲鎢磷酸和矽鎢酸， (H2)用酸膠化水解物使成分散物， (Η 3 )混合分散物與一種奈米結晶之質子傳導金屬氧化物， 較佳爲 Α12〇3、Zr02、Ti〇2 或 Si〇2 粉末， (H4)分解觸媒與適當之支特物和孔洞形成劑。 其可能有利者，如果用於產生陽極靥和陰極層各組成物 在步驟（C )中被印刷並堅固結合於各塗層與電解質膜之間， 200416067 形成多孔之質子傳導性陽極層或陰極層，是完成於步驟（D ) 以加熱至自1 〇 〇至8 0 0 °C之溫度，較佳自1 5 0至5 0 0 °C，最 佳自180至250 °C。 本發明方法也可包含各步驟如： (Μ 1 )施加於產生陽極層或陰極層之組成物至支持薄膜上， 較佳在聚四氟乙烯上， (Μ 2 )局部乾燥（Μ 1 )所得之塗層， (M3)壓合之局部乾燥之塗層於自20至5 0 0 °C之溫度，較佳 自50至300 °C，特佳自100至200 °C，至電解質膜上， (M4)除去支持膜，尤其以機械分離、化學方法破解或予熱 觸，或 (N 1 )施加用於產生陽極層或陰極層之組成物至支持膜上， 較佳用複寫紙或導電性非編織物或編織物， (N2)局部乾燥在（N1)所得之塗層以產生已塗覆之支持膜， (N3)壓合已塗之支持膜於電解質膜上，溫度爲自室溫至50 〇t 上，較佳自50至300 °C ，最佳自100至200 °C。 如果在步驟（B)中結合用於產生陽極層和陰極層各組成 物之條件，可爲有利， (i) 組成物含有觸媒金屬鹽，較佳爲六氯鉑酸， (Π)繼步驟（C)施用組成物之後，還原觸媒金屬鹽成爲促進 陽極反應或陰極反應之觸媒， (i i i)在步驟（D )中之開孔氣體擴散電極，較佳爲開孔複寫紙 ，被壓合至觸媒上，或用導電性黏著劑結合觸媒。 本發明方法中可以視需要完成於重複施加用於產生陽極 -26- 200416067 層或陰極層之組成物與乾燥步驟，較佳在各次重複完成施 用之間，升高溫度於自2 0至5 0 0 °C之範圍，較佳自5 0至 300 °C ，最佳自100至200 °C之升高溫度。 可能有利者，爲如果用於產生陽極層或陰極層之組成物 被施於一原卷展開之撓性支持膜或撓性電解質膜上。尤其 可能有利者，爲若連結施用用於產生陽極層或陰極層之組 成物。可能特別有利者爲若施用用於產生陽極層或陰極層 之組成物至被加熱之電解質膜或支持膜上。 爲求在各塗層與電解質膜之間建立牢固之結合，複合物 最好加熱於自2 0至5 0 0 t之溫度，更佳自5 0至3 0 (TC，最 佳自1 0 0至2 0 0 °C。此項加熱可用熱空氣、加熱之空氣、 紅外線輻射或微波輻射。 爲了產生膜電極組件，在一特別具體例中，有觸媒活性 (氣體擴散）之電極被構成於本發明之電解質膜上。這是用 碳黑觸媒粉末和至少一種質子傳導材料製成之印墨所完成 。然而，印墨也可含有提升膜電極組件性質之其他添加物 。碳黑也可由其他導電性材料取代（其如金屬粉、金屬氧化 物粉、碳、木炭等）。在一特別具體例中，用以替代碳黑之 觸媒支特物是一種金屬或半金屬氧化物（其如例如A e r 〇 s i i) ，然後此印墨使用例如網印法、刀塗法、噴灑、輥輪施加 法或浸入法等施於薄膜上。 印墨可以包含所有亦爲用於浸透支特物的質子傳導材料 。所以印墨可以包含一種酸或其鹽，在印墨被施加於薄膜 之後的固化程序中，被化學反應所固定。這種酸因而可以 -27- 200416067 例如是一種簡單的B r ϋ n s t e d酸，其如硫酸或磷酸，或先爲 矽烷磺酸或矽烷膦酸。可被採用而有助於酸之固化之材料 ，例如包括Si02、Zr02、和Ti02，可以以分子先驅物加至 油墨中。 與對燃料電池反應之反應成分必須爲不滲透之電解質膜 之質子傳導塗層相反，陰極和陽極兩者需要具有高的孔性 以使諸如氫和氧之反應氣體可被引導至觸媒/電解質界面 而無質量傳輸之阻礙。此項孔度可以利用例如具有適當粒 度之金屬氧化物，或利用印墨內之有機成孔劑，或用印墨 內適當之溶劑組分，予以影響。 作爲一種特定之印墨，可以使用含有如下各成分之組成 物： (T1)一種縮合成分，在縮合作用之後，在燃料電池之陽極 層或陰極層上供給質子傳導性， (T2)—種觸媒，促進在燃料電池內之陽極反應或陰極反應 ，或爲觸媒之一種先驅化合物， (T3)如若需要，一種觸媒支特物， (T4)如若需要，一種孔洞形成，和 (T5)如若需要，各種改善泡體性質、黏度、和黏著性之添 力口物。 於縮合作用後，在陽極層或陰極層上供給質子傳導性之 可縮合成分，較佳選自： (I)可水解之磷化物及/或可水解之金屬或半金屬硝酸鹽、 氧硝酸鹽、氯化物、氧氯化物、碳酸鹽、烷氧化物、 -28- 200416067 乙 酸 酯 和 乙 醸 丙 酮 酸 酯 5 較 佳 爲 院 氧 化 鋁 垸 氧 化 釩 氧 化 鈦 乙 氧 化 鈦 硝 酸 锆 氧 硝 酸 m 丙 氧 化 錐 乙 酸 錐 或 乙 醯 丙 酮 酸 5 及 /或鋁、 鈦、 釩、 銻、 鍚 鈴 鉻 鎢 鉬 或 錳 之 金 屬 酸 ， 較 佳 者 爲 鎢 磷 酸 和 矽 鎢 酸 及 /或 一* 種 可 固 定 之 磷 或 硫 之 羥 矽 院 酸. 及- ，或 其 鹽 j 和 此 外 0 在 特 別 較 佳 具 體 例 中 J 一 種 磷 之 可 水 解 化 合 物 其 爲 固 定 磷 或 硫 之 羥 矽 院 酸 或 其 鹽 者 9 一 種 金 屬 或 半 金 屬 之 可 水 解 硝 酸 鹽 、 氧 硝 酸 鹽 > 氯 化 物 氧 氯 化 物 碳 酸 鹽 > 氧 化 物 乙 酸 酯 或 乙 醯 丙 酮 酸 酯 較 佳 爲 磷 酸 甲 酯 亞 磷 酸 二 乙 酯 (DEP)、 乙 基 膦 酸 二 乙 ；酯 (DEEP) 丙 氧 化 鈦 乙 氧 化 鈦 原 矽 酸 四 乙 酯 (TEOS) 或 原 矽 酸四甲酯（Τ Μ O S )、硝酸锆、氧硝酸锆、丙氧化锆、乙 酸锆或乙醯丙酮酸鉻。 然而爲了增加質子傳導度’印墨也可以含有奈米級氧化 物，其如鋁、鈦、鉻或矽者，例如，或其他如磷酸或膦酸 锆或駄。 觸媒或觸媒前驅化合物較佳含有鉑、鈀及/或釕，或含該 等金屬之一或多種之合金。 存在於印墨內之孔洞形成劑可爲有機及/或無機物質，其 爲为解心在5 0與6 0 0 C之間的溫度，較佳在1 〇 〇與2 5 〇。〇 之間。尤其，無機孔洞形成劑可爲碳酸銨或碳酸氫銨。 可存在印墨內之觸媒支特物較佳爲導電性者，且較佳含 有碳黑、金屬粉、金屬氧化物粉、碳或木炭。 -29- 200416067 在另一具體例中，一預鑄之氣 電阻，由導電材料（例如多孔碳非 構成，可直接應用於薄膜。其最 膜用壓合法固定。爲此須使薄膜 具有熱塑性質。或變更之，氣體 薄膜。此黏著劑必須具有離子傳 說明如上之任何種類之材料所構 爲金屬氧化物溶膠另含羥矽烷酸 更爲在生產薄膜或氣體擴散電極 「原位」。在此階段，於氣體分 材料仍未被固化，且可被利用作 中，黏著方法由在隨後之乾燥/固 一種可替代之選項爲直接澱積 放傾注之氣體擴散電極（其如開孔 如，可用金屬鹽或酸施於表面， 屬。例如，鉑可用六氯鉑酸加於 後之步驟中，收集器電極以壓合 含有金屬前驅物之溶液可另含一 爲離子傳導性之化合物於生產程 包括上文已述之質子傳導物質。 以此方法所得膜電極組件可用 接的甲醇燃料電池或重組的燃料 (四）實施方式 本發明之電解質膜可以用於例 體分配器，含有氣體擴散 編織物）、觸煤和電解質 簡單者，氣體分配器和薄 或氣體分配器在壓合溫度 分配器可被黏著劑固定於 導性質，且原則上可由已 成。例如，所用黏著劑可 。最後，氣體分配器可變 之最後階段當中施用於 配器或薄膜內之質子傳導 爲黏著劑。在兩種情況當 化，使溶膠膠化而發生。 觸媒於薄膜上，並設一開 複寫紙）。對此目的，例 並在第二步中還原成爲金 表面並還原成金屬。在最 法或以導電黏著劑固定。 種已爲質子傳導性或至少 序之終點。適合之材料又 於燃料電池，尤其用於直 電池。 如燃料電池，尤其用於直 -30- 200416067 接的甲醇燃料電池或重組的燃料電池。尤其，本發明之電 解質膜可被用於生產膜電極組件、燃料電池、或燃料電池 組。 本發明之電解質膜和本發明之膜電極組件特別可用於生 產燃料電池或燃料電池組，燃料電池中特別是直接的甲醇 燃料電池或用於車輛之重組燃料電池。 所以，本發明也提供含有本發明電解質膜及/或本發明膜 電極組件之燃料電池；並且因而也提供含有本發明含有薄 膜電極組件，含本發明電解質膜或本發明膜電極組件之燃 料電池或燃料電池組等之機動或固定之系統。機動或固定 系統較佳爲車輛或家電系統。 實施例1 : 磷酸和硝酸锆兩者各爲3重量％之水溶液在根據ψ 〇 00/61275之微噴射反應器內各通過3〇〇微米之噴咀，於6〇 巴之壓力互相衝撞。所得生成物爲乳濁狀。粒度分佈顯示 一種雙模式粒子分佈，粒度均爲〇 · 7微米，較小粒子組份 之粒度恰在3微米。此懸浮液經濃縮至約1 〇重量％於一旋 轉蒸發器而除去水，懸浮液變成如溶膠/黏滯但休持乳濁。 此溶膠或懸浮液具有長效安定性，並於稍後使用。 實施例2 : 磷酸（0.2 Μ )和硝酸鉻（〇 . 〇 5 Μ )兩種水溶液在根據W 0 00/61275之微噴射反應器內，通過100微米噴咀，於60 巴壓力互相碰撞。所得生成物爲乳濁。粒度分佈比得上實 施例1之分佈。懸浮液可在旋轉蒸發器中進一步除水濃縮 200416067 ，完成後成爲似溶膠/黏稠狀而保持乳濁。此溶膠或懸浮物 具有長效安定性。 實施例3 : 實施例1之懸浮液與5重量％之Aerosil 2 0 0 (DeguSSa AG) 隨濃縮之後混合。然後用磁攪拌器再攪拌24小時予以勻化。 實施例4 : 以5克Al2〇3和0.23克TODS(2-[2-(2 -甲氧基乙氧基）乙 氧基]乙酸）加至5 0克來自實施例1之懸浮液。用此漿料塗 覆一 S2-玻璃編織物於連續程序中，然後予以乾燥於自1 50 至2 0 (TC於5分鐘內。此薄膜具有非所預期之0.2毫西門 子/厘米之高傳導度，且具有撓性。 實施例5 : 用得自實施例1之懸浮液直接塗覆一玻璃編織物於連續 程序。然後用小刀塗懸浮液於一 S 2 -玻璃編織物（C S -Interglas)上，並在160°C之溫度固化於10分鐘內。所得薄 膜展現大於1毫西門子/厘米之崑好傳導度。薄膜之撓性約 如原始編織物同樣良好。 實施例6 ; 用得自實施例2之懸浮液直接刀塗於一玻璃編織物。然 後固化薄膜於3 0 0 °C之室爐內徑1 5分鐘。現已不溶於水之 薄膜，於92 %相對濕度（RH)和23 t有約2毫西門子/厘米 之傳導度。由於在水和甲醇中的安定性，此薄膜極爲適合 用於DMFC。 -32- 200416067 實施例7 : 一厚度爲7 0微米之S -玻璃編織物被浸透於得自實施例1 之懸浮液，用五重刀塗方法。在各浸透步驟之間，編織物 接受初步固化於用約1 5 0 °C熱空氣風扇。在最後塗覆之後 ，在最後塡充小孔之過程中，薄膜被3 0 0 °C熱空氣最後固 化1 5分鐘。此在水和甲醇內安定之薄膜具有大約4毫西門 子/厘米之傳導度於80%相對濕度，並可用於DMFC。 實施例8 : 一厚度爲7 0微米之S -玻璃編織物用得自實施例3之懸 浮液浸透，用三重刀塗法。在各個浸透步驟之間編織物接 受初步固化於用約1 5 0 °C熱空氣風扇。最後塗覆後，在其 塡充最後小孔之過程中，薄膜被3 0 0 °C熱空氣最後固化1 5 分鐘。此在水和甲醇中安定之薄膜，於8 0 %相對濕度具有 大約1毫西門子/厘米之傳導度，並可用於DMFC。200416067 (1) Description of the invention (The description of the invention should state: the technical field to which the invention belongs, the prior art, the content, the embodiments, and the drawings) (1) Technical Field The present invention relates to a proton-conducting ceramic membrane based on europium phosphate, which Manufacturing method and use in ME As (membrane electrode assembly) and fuel cells. (2) Prior art Thin film is the centerpiece of fuel cells. In the case of a proton exchange membrane (p E M s), the electrolyte membrane used is mainly an acid-modified polymer. Commonly used today is Nafion (DuPont, fluorinated structure with sulfonic acid functional group) or related | system. Another purely organic proton-conducting polymer is Hoe chst, specifically stated to be a sulfonated polyetherketone (EP 0 5 7 4 7 9 1 B 1). All of these polymers have the disadvantage of a sudden drop in conductivity as the atmospheric humidity decreases. Therefore, these films must be swelled in water before being used in fuel cells. As the temperature rises, as is unavoidable in reconstituted fuel cells or direct methanol fuel cells (REC or DMFC), these systems can no longer be used at all because they tend to dry out, or are used only in restricted shapes. Another problem with polymer membranes used in DMFCs is that they have a large repair permeability to methanol. As a result of methanol passing to the cathode side, the power of the fuel cell is reduced. For these reasons, the use of organic polymer membranes in RFCs or DMFCs is not ideal 'and @ is widely used for fuel cells, and new solutions must be sought. Although inorganic proton conductors have been found in the literature (for example: “Proton -6- 200416067 C ο nduct 〇rs” by Cambridge University Press 1 992 ρ · Colomban), most of them have too low conductivity, Or only at high temperatures, usually above 500 ° C, to the extent technically available, such as in the case of incomplete perovskites. Finally, another type of pure inorganic proton conductor, the MHS〇4 group, although it is a proton conductor, is also easily soluble in water at the same time. Since water is formed as a product on the cathode side, the film is damaged over time and is not suitable for use in fuel cells. Glassy systems have been discussed for a long time (Abe et al., J. Sol_Gel Sci. Techn. 14 (1999), p. 273; Minami et al. ’Chem. Lett. (2000), p. 1314) or xerogels (Anderson et al., Chem. Mater 12 (1200), p. 1762), etc. as proton conducting materials. However, these materials are not suitable for fuel cell applications due to their poor conductivity. Chromium phosphate (ZrPs), or γ to state α ZrP who have long been perceived as the proton conductor (Alberti, Solid State Ionics 1 2 5 (1 9 9 9), p. 91). Since the conductivity of this material in this case is essentially determined by the free radicals, a large surface area is important. For pure a_ZrP, literature (Glipa et al., Solid State Ionics, 97 (1997), p. 277) reported the conductivity, while the average atmospheric humidity of 1CT5 to 10_6s / cm (Siemens / centimeter -Siemens / cm ). Phosphate pin may be used to reference the fuel cell membrane found Linkov (EP 0 838 258), although for the quality of the film, particularly proton conductivity, No precise detail. Furthermore, the films described in EP 0 8 3 8 2 5 8 are based on conventional films and are thick and non-flexible. Because of the thickness, only thin films with high surface resistance can be produced. Conversely, for fuel cell applications, the conductivity should be not less than 10'3 Siemens / cm and the thickness should not exceed 100 microns. For practical use, the hard film described by Lin kov is not suitable for 200416067 for fuel cells. Other problems are that the electrolyte makes it impossible to reach the membrane (WO properties, low membrane usability, conductive non-fuel cells, etc.), which is also a reaction in various applications. It is very easy to change the support. Regarding the use of inorganic proton conductors in fuel cells as referred to here, it is virtually impossible for such ceramics to produce thin membranes. They must be made automatically in extremely thick shapes, The overall resistance of a battery, that is, its specific conductivity, is often extremely high. As a result, it is suitable for industrial applications, such as high fuel cell power densities in automobiles. Although it is also known to have large inorganic proton conduction with flexibility9 9/6 2620). These films combine the advantages of organic diaphragms (high baffle thickness) with inorganic proton conduction systems (without critical water content, up to 200 ° C, and no methanol passing). However, these materials are also not suitable for use due to their inadequate power density. Furthermore, the composite described in WO 99/62620 is ideally unsuitable for use in fuel cells due to the fact that it must be absolutely impermeable for use in this electrolyte membrane; otherwise the reactants will be straight (on the anode side) Water or methanol with oxygen or air on the cathode side). Contact between the electrodes must be present in the known ME A (membrane electrode assembly) to complete the current loop within the fuel cell, the ion-conducting layer having a porous support within a variation on the surface of both surfaces. Further, since the operation of the fuel cell, the electrodes in each of the short-circuited at W 0 9 9 / a 62620 steel fabric as a priority to the user, is absolutely not suitable for fuel cell applications. (3) Summary of the Invention Therefore, one of the items of the present invention is to provide a flexible inorganic proton conductive membrane having a conductivity of at least 1 (3 Siemens / cm), and a method for generating the same. 200416067 method. A thin film with a sufficiently large arm can be made available for RFCq. Therefore, 'the present invention provides a guide film' containing a sheet-shaped flexible substrate on and in the substrate, and the substrate is made of ceramic or nanometers of protons combined with this material. Grade phosphoric acid pin particle size, and in the fuel cell, the present invention provides a proton conducting membrane inside a square substrate with non-conductive glass or ceramic coated thereon or containing at least nano-grade chromium phosphate on the substrate, And the invention which has been at least or sol cured on the substrate also provides if the application of the film as the fuel cell internal quality please patent the first to the 15th range of the film of the present invention has a high temperature, the water level is not related to the proton conductive film comparison The advantages of the original shape and the production of nano-grade chromium phosphate can be made, and the sub-conductivity of the thin film flexible film. Therefore, the new 0 DMFC s are used. Species such as The proton transfer plate of item 1 of the patent scope is provided with a plurality of openings and has a coating. The material is selected from woven or non-woven sloped glass or non-conductive fiber, where the coating contains ^ particles and has less than 5, 0 0 0 Nano is basically impervious as a reaction element. For example, in the patent application scope items 1 to 15, at least the method "wherein the sheet layer with most openings" substrate material includes woven or non-woven The fiber to which the material binds, including the suspension of particles or the proton-conducting coating of the sol, is heat-treated once. In this process, the suspension is in or on the suspension. Patent at least one of the first to fifteenth items of the patent is changed to β The use of odor, and provides a fuel cell made of a film containing at least ~ items in the application: in the polymer-based film, and can be used for the bond 'and no methanol through. It has the same performance as known ceramic thin films. Substantially thin and flexible 200416067 The film of the present invention is gas-tight and does not penetrate the reaction components such as hydrogen, oxygen, air, and / or methanol in the fuel cell. For the purpose of the present invention, the gas-tight or Permeability means less than 50 liters of hydrogen and less than 25 liters of oxygen per bar per day per square meter of the film of the present invention; and the permeability of the film to methanol is significantly lower than commercially available Nafion, which is generally considered to be impermeable In the case of thin films, the fact that a suspension of nano-grade phosphoric acid phosphate particles of a certain size is solidified inside and on the substrate to become a coating, indeed, has a more uniform distribution of phosphoric acid pins throughout the film, which is superior to For example, the method described in EP 0 3 8 3 2 5 8 can be achieved by infiltrating the porous ceramic membrane with a cone salt and then treating the permeated membrane with a polyacid, especially a polyphosphoric acid, because Both the particle distribution and the particle size within the porous ceramic membrane are sometimes more or less determined by functions such as porosity and porosity in the porous ceramic membrane. It must be due to the large surface area of the nano-level elementary particles, the more uniform distribution of the phosphoric acid pin particles, and / or the more uniform size of the particles, and the thinning of the thin film. The film of the present invention exhibits significantly more than the existing phosphoric acid pin-containing ceramic film. Low proton conduction resistance. The film of the present invention is illustrated by the following examples, but it is not intended that these specific examples limit the present invention. The proton conductive membrane of the present invention contains a sheet-shaped flexible substrate, which is provided with a plurality of openings and has a coating on the substrate. The material of the substrate is selected from woven or non-woven non-conductive glass or ceramics or fibers combined with such materials. Among them, the coating contains nanometer-grade europium phosphate particles with conductive protons, with a basic particle size of less than 5 microns, which is air-tight or impermeable to various reaction components in the fuel cell. The reaction components are, for example, hydrogen, oxygen, air, and / Or methanol. -10- 200416067 The film of the present invention preferably has a thickness of less than 1000 microns, more preferably less than 50 microns, and particularly preferably less than 30 microns. The film of the present invention which has been found to be particularly suitable for use in fuel cells is those having a thickness of from 10 to 50 microns, even if it is thin and exhibits sufficient stability and airtightness or impermeability to the various reactive components in the fuel cell The same can be used. Due to the low thickness, the proton conductive membrane of the present invention has particularly low resistance. Woven fabrics, non-woven fabrics, felts, or flexible porous ceramic membranes, which are used as the basis for zirconium phosphate infiltration, naturally have extremely high electrical resistance, otherwise there is a danger of a short circuit between the anode and the cathode. In order to obtain the film with electrical insulation properties of the present invention, the substrate material preferably contains non-conductive fibers selected from glass, alumina, SiO2, SiC, Si3N4, BN, B4N, AIN, Sialons or Zr02. The substrate material may be, for example, a fabric, a non-woven fabric or a blanket of non-conductive fibers, or another fabric, a non-woven fabric, or a blanket of non-conductive fibers provided with a porous ceramic coating, such as a microfiltration membrane. In order to achieve particularly good proton conductivity, the substrate material is preferably a non-woven fabric, fabric or blanket with a non-porous ceramic coating of glass fibers. This is because if the material does not have a porous coating, the actual volume is relatively small. It is small and has high porosity, so there are more proton conductive materials available for conducting protons in a thin film per unit area. Based on this fact, it is possible to achieve a higher conductivity. Although knitted fabrics are stronger than non-woven fabrics, the use of non-woven fabrics is more porous than knitted fabrics and has the advantage of being better than knitted fabrics. Therefore, depending on the required film properties, a woven or non-woven fabric using glass fibers may be more suitable as a thin film substrate. May be obtained by any of fiber glass material, which on -11-200416067 principle as E - glass supports, for example, as -, E C R -, C -, D -, R -, S -, and [mu]. Preferred to use Ε -, E C R - or S - glass fibers. Preferred various glasses contain low BaO, Na20 or K20 content. The preferred type of glass having less than 5% by weight of B a Ο content, preferably less than 1 wt%; N a 0 2 content is less than 5 wt%, preferably less than 1 wt%; Κ2 Ο content of less than 5 wt. %, Preferably less than 1% by weight. The most favorable fiber is composed of glass without BaO, Na02, K 2 0, such as E glass, because this type of glass is more resistant to chemical influences. In a particularly preferred embodiment of the conductive proton membrane of the present invention, the fibers of the substrate, especially E- or S-glass fibers, are preferred, and are sold as Si02, Zr02, Ti02, or A 1 2 0 3 or the like. A mixture of things. Oxide coatings are particularly suitable for glass types with low acid stability, such as E-glass. Laid in the branch was oxide glass weight Comparative preferably less than 15: 85, more preferably less than 10: 90, and particularly preferably less than 5: 95. If the film of the present invention contains a glass fiber textile substrate, such as a glass fiber φ knitted fabric, felt, or non-woven fabric, for example, the textile fabric is preferably produced from fibers having a linear density of not more than 20tex (mg / m). The better one has a linear density of no more than lOtex, and the particularly good one has no more than 5. 5tex linear density. Especially suitable for substrates containing 5. 5 or 1 1 t e X linear density fiberglass braid. Individual yarns of such fibers have a diameter of, for example, 5 to 7 microns. This kind of glass fiber knitted fabric suitable for use as a special product has 5 to 30 wefts / cm and 5 to 30 warp / cm; better than -12-200416067 from 10 to 30 wefts / cm and From 10 to 30 warp yarns / cm; top performers from 15 to 25 weft yarns / cm and from 15 to 25 warp yarns / cm. The use of such a glass braid ensures that the film has sufficient strength and maintains sufficient substrate porosity. The coating of the film of the present invention preferably contains nano-grade zirconium phosphate, and has a basic particle size of from 1 to 1,000 nanometers. More preferably, the nano-grade hafnium phosphate particles have a basic size of from 1 to 100 nanometers. Particle size, and particularly suitable nano-grade europium phosphate particles are those having a basic particle size from 10 to 100 nm. In addition to nanoscale chromium phosphate elementary particles, the coating of the present invention may also contain an accumulation of zirconium phosphate elementary particles. It has a particle size of 1 micrometer or more, preferably from 1 to 100 micrometers, particularly preferably from 1 to 25 micrometers. If in addition to nano-sized zirconium phosphate particles, the proton conductive film contains at least one oxide of a metal such as Al, Zr, Si or Ti. The oxides in the coating can be presented as particles connected to each other, such as bonding with an adhesive, sintering or similar techniques. This is particularly the case when the ceramics are provided with a ceramic coating, especially for the production of a proton conducting membrane. Or it can be changed to make the oxides separate ceramic particles, especially for the case where the oxide particles combined with the zirconium phosphate elementary particles become a sol or suspension and applied to the support and solidify the system. The separated oxide particles are particularly present when the weight ratio of oxide to zirconium phosphate is significantly less than 1: 1. The oxide particles preferably have a size of 5 microns or less, especially since 0. 0 1 to 1 micron or from 1 0. 0 1 to 0. 1 micrometer is preferable, and each of the particles may be a basic particle or an aggregate. A feature of the film of the present invention is that it has a conductivity of more than 1 milliSiemens / cm. The film of the present invention preferably has a proton conductivity from 1 to 100 milliSiemens / cm-13-200416067, particularly preferably from 1 to 10 milliSiemens / cm, both at room temperature and 80 to 90%. Relative humidity. The film of the present invention is preferably bendable to a radius of 250 meters without damage, more preferably 10 cm, and particularly preferably 5 cm. The high conductivity and good bendability of the film of the present invention has the advantage that the film of the present invention can be used in any geometric shape conceivable in a fuel cell. Furthermore, the film is insoluble in water and methanol, and exhibits extremely low permeability (conceivable as non-permeability) to methanol compared to, for example, Nafion. Thus, this film is particularly suitable for other D M F C s. The thin film of the present invention is preferably obtained from a method for generating a proton conductive film, and a sheet-shaped flexible substrate having a plurality of openings is provided in the film, and a coating is provided thereon. The material of the substrate includes woven or non-woven glass or ceramics or non-conductive fibers combined with these materials; including the application of a coating to the substrate, which is applied in a suspension containing at least nanometer phosphonium phosphate particles, and in the suspension There is at least one heating operation during curing on and in the substrate. The suspension applied on and in the substrate can be applied, for example, by printing, embossing, injection, roller milking, knife coating, brush coating, dipping, spraying or pouring. Preferably the substrate material is selected from glass, alumina, S i Ο 2, S i C, S i 3 Ν 4, BN, B4N, AIN, Sialons of Zr02 or, in particular, high temperature and / or the acid resistance of glass, quartz glass, or Or ceramic. The substrate material may be a woven, non-woven or felt of non-conductive fibers of the above materials. In order to obtain a consistent resistance in the film, the substrate material is preferably a non-woven glass fiber (formed from non-woven glass fiber). In principle, all the glass material, and it can be made for the fibers used for the substrate, e.g., E -, A -, E C R -, C -, D -, R -, S -, and [mu] - glass. Preferred is 200416067 using E- or S-glass fibers. Preferred glass types have low B a 0, Na20 or K20 content. The preferred glass type is preferably less than 5% by weight BaO content, most preferably less than 1% by weight; and Na20 content is less than 5% by weight, most preferably less than 1% by weight; and κ20 content is less than 5 % By weight, preferably less than 1% by weight. The types of glass that make up various fibers are favorably those that do not contain BaO, Na20, or K20, such as E-glass, because this type of glass is more resistant to chemicals. In a particularly preferred embodiment of the method for producing a proton conducting membrane of the present invention, the substrate fiber is particularly preferably coated with an E- and / or S-glass fiber and is coated with a Si 02 film. Such coatings can be applied, for example, using tetraethyl orthosilicate (TE0S) to individual or woven, felt, or non-woven fibers, and then at temperatures from 400 to 6001 :, preferably from 420 to 500. ° C, best 440 to 460 ° C, baking TEOS. After baking, silicon dioxide remains as a residue on the fiber surface. It has been determined that fibers treated in this way are substantially more suitable as substrate materials than untreated fibers. The subsequent coating substantially improves the long-term stability due to substantially better adhesion on the treated fibers. In addition to the coating of Si02, Z r Ο 2, T i Ο 2 A 12 Ο 3 or coating or various mixtures of these oxides may also be used, which may, for example starting from a metal alkoxide corresponding to the. Coatings can be produced in the same way as TEOS coatings. If the substrate used is a glass fiber textile, such as a fiberglass woven fabric, felt, or non-woven fabric, for example, it is preferably produced from a fiber having a linear density of not more than 20 teX (mg / m), more preferably it has its own Fibers with a linear density of not more than 1 〇te X, and most preferably owns not more than 5. 5 tex linear density fiber. The best substrate to use is woven with 5. 5 or 1 1 tex straight dense -15- 200416067 degree glass fiber cloth. The individual yarns of these fibers have a diameter of, for example, from 5 to 7 microns. The glass fiber cloth used is preferably a substrate having 5 to 30 weft / cm and 5 to 30 warp / cm, more preferably 10 to 30 weft / cm and 10 to 30 warp / cm, most preferably Preferably from 15 to 25 weft / cm and from 15 to 25 warp / cm. The use of such a glass braid ensures that the film of the present invention has sufficient strength and holds sufficient substrate porosity. It has been known that when using commercially available glass fiber textiles, especially glass fiber non-woven fabrics, glass blankets or glass braids, it removes the slurry added to the fiber during the manufacturing process of glass fiber textiles. For glass The strength of fiber textiles has a substantial effect. The slurry is usually removed by heating on glass fiber textiles, especially glass fiber braids, at temperatures up to 50 ° C (from 1 to 2 minutes, and then heat treated at 300 ° C for about 4 days. Surprisingly, it has been It is known that the glass fiber textiles treated in this way are substantially more brittle than glass fiber textiles that still have slurry. However, the coating of zirconium phosphate is very difficult to apply on or in the glass fiber textile substrate with slurry. The reason is that the slurry deteriorates the adhesion of the coating to the textile. The surprising thing is that it has been found that the slurry is burned at a temperature below 500 ° C, preferably below 450 ° C, for 2 minutes. After 1 minute, subsequent treatment with the above TEOS will be sufficient to ensure that the glass fiber textiles have a more durable coating, especially glass fiber braids. If the substrate material used is a glass fiber textile with a porous ceramic coating, it will be beneficial This ceramic-coated glass fiber textile is found in W 0 9 9/1 5 2 62. The ceramic coating is preferably applied to the glass fiber as a suspension containing a sol and at least one inorganic component of 200416067. In U.S. textiles, the inorganic component contains at least one metal, semi-metal or mixed metal compound, and at least one element is selected from the main groups 3 to 7; and at least one heating operation is performed, during which the suspension containing at least one inorganic component is solidified woven glass fiber fabric on top of or within 'or. thereto which is generated in such a method within the glass-ceramic fiber fabric coated with the W Ο 9 9/1 5 2 6 2 are the same known. the different types of ceramic on Coated glass fiber textiles and their production can be referred to WO 9 9/1 5 2 6 2. The suspension used to produce the coating contains at least nanometer grade chromium phosphate particles with a particle size of less than 1 micron. It is used to produce the film coating of the present invention The suspension preferably contains nanoscale chromium phosphate particles having a basic particle size of from 1 to 1000 nanometers, more preferably nanoscale chromium phosphate particles having a basic particle size of from 1 to 100 nanometers, and most preferably has Nano-scale phosphoric acid pin particles with a basic particle size from 10 to 100 nanometers. In addition to the nano-grade phosphonium phosphate basic particles, the coating of the present invention may also contain aggregates having rhenium phosphate particles of 1 micron or larger It is preferably from 1 to 100 microns, and most preferably from 1 to 25 microns. Nanoscale chromium phosphate particles are preferably generated in an upstream step. In principle, it can be produced in any method suitable for the production of nanoscale powders. Process, which is like gas phase method (similar to aerosol production method, line explosion method, microwave plasma method, etc.), but liquid phase method can also be used. According to the literature (Penth, WO 00/61275), MlCr0- The Jet (micro-jet) method is known to be particularly suitable for producers. In this method 'nano-grade zirconium phosphate particles used to prepare suspensions are produced in a micro-jet reactor' to dissolve soluble zirconium compounds with phosphorus The solution of the compound collides. The soluble pin compound used may be selected from chromium nitrate, zirconium chloride, zirconium acetate, acetic acid propionate or chromium oxide. The phosphide-containing solution used contains at least one compound 'selected from the group consisting of acids and / or phosphates, especially phosphates of alkali metals, such as Na3P04, Na2HP04 or NaH2P04. The simplest solvent used is water. If the reactants used are sensitive to hydrolysis, such as alkoxides, alcohols or other anhydrous solvents can also be used. In the micro-jet reactor, each solution is reacted to a specific high-pressure process to produce chromium phosphate. The two solutions in the micro-jet reactor range from a nozzle with a diameter of preferably from 50 to 500 micrometers to a few hundred bar. High pressure forms thin jets and collides with each other. The reaction product can be removed from the reactor by a method such as air flow. This method does not cause any growth to accompany the elementary particles. Based on the experimental conditions of operation in the microjet reactor, the appropriate basic particle size and the size of the accumulation can be measured. This method directly produces a colloidal suspension containing zirconium phosphate. The common concentration of gadolinium phosphate in this suspension is 0. 〇 1-50 0% by weight, preferably 0. 1-5% by weight. If appropriate, the suspension can also be concentrated by further evaporation of the solvent used. The suspension can be used directly or applied to the above substrate. Alternatively, the above-mentioned phosphoric acid pin particles can be spray-dried to dry the phosphoric acid pin suspension obtained from the micro-jet reactor, so as to be converted into a powder containing nano-grade chromium phosphate particles. Conventional spray drying performed to follow, and preferably occurs within 1 billion to 200 billion ° C temperature of from, preferably from 10 to a temperature of 0 of 1 5 0 ° C. However, in another specific example of the method of the present invention, other materials, a part of which may be commercially available, such as particles of metal oxide, cyanide, carbide, or zirconium phosphate, may be added to the suspension in powder form. Inside. The addition of metal oxides and / or other inorganic components is conducive to making the proton conductivity to the required level, and to achieve the most appropriate penetration effect of the substrate, so that the proton conductive film formed in the last -18-200416067 can The battery is airtight or impermeable to each reaction component. It may be advantageous if at least one inorganic component has a particle size of less than 5 microns, preferably from 10 to 1000 nanometers, and most preferably from 100 to 1000 nanometers, added to the suspension. However, it is also possible to add other proton conducting materials to the suspension, such as isopolyacids and heteropolyacids, or other nano-grade powders, from the series of 203, Zr02, Ti02, and SiO2. In addition, the 'suspension' may contain Briinsted acid or fixable silane acid. In another specific example of the method of the present invention, the suspension used contains nano-grade phosphonium phosphate, which may contain at least one sol, at least one semi-metal sol, or at least one mixed metal oxide sol, or a mixture of the various sols. Each sol is obtained by hydrolyzing at least one compound 'preferably at least one metal compound' at least one semi-metal compound 'or at least one mixed metal compound' at least one liquid 'solid or gas', which may be, liquid, for example Advantageously, water, alcohol or acid, the solid used is ice 'or the gas used is water vapor. It may also be advantageous to introduce the compound to be hydrolyzed into a mixture of alcohol or acid or an equivalent before hydrolysis. The compound to be hydrolyzed is preferably at least one g of a metal nitrate, a metal chloride, a metal carbonate, a metal alkoxide, or the like, or at least one metal alkoxide compound 'selected from Zr, A 丨, si, or T i And other elemental compounds such as zirconium oxide, such as zirconium isopropyl, such as' silane oxide 'or metal nitrate' such as hafnium nitrate. It is more advantageous to hydrolyze the hydrolyzable compound 'of the hydrolyzable compound with at least half a volume of Mohrby's water, steam or ice. -19- 200416067 The hydrolyzed compound can be gelatinized with at least one organic or inorganic acid, preferably with a mineral acid selected from the group consisting of sulfuric acid, hydrochloric acid, perchloric acid, phosphoric acid, and nitric acid, or a mixture of these acids. , At a concentration from 10 to 60%. It is also possible to use not only the sols prepared above, but also commercially available sols such as zirconium nitrate sol or silica sol. The coating of the present invention is to apply and cure the suspended matter in and on the substrate. To this end, according to the present invention, the suspension is applied to the supporting material by knife coating, roller coating, spraying or the like. The preferred method is a continuous method. According to the present invention may be heated to from 50 to 5 0 0 ° C and that the presentation on the substrate is cured within the suspension. In a specific modified example of the method of the present invention, the suspended matter present on the support and in it is heated at 1000 to 45 ° C., and is more preferably heated at from 150 to 400. ° C, particularly preferred is heating from 150 to 30 (TC. It is advantageous if heating is performed from 1 second to 15 minutes, preferably from 10 seconds to 5 minutes. Application / soaking can be performed once or times, wherein the heat treatment is preferable to be, preferably at a temperature from 50 to the 5 0 0 ° C, more preferably from 150 to 3 0 (TC, over 1 minute to 1 hour is applied between the respective steps. Several pure woven or non-woven fabrics are better to be applied multiple times. The film of the present invention constitutes a new category of proton conductive membranes. It can be used as a proton exchange membrane in a fuel cell or as a membrane electrode assembly (ME As). In this regard, the fuel cell can be completed by including the thin film of the present invention as a proton exchange membrane. The membrane electrode assembly of the present invention is described as follows. A flexible membrane electrode assembly for a fuel cell includes an anode layer and a cathode layer, each provided On the opposite sides of the proton conductive membrane (electrolyte membrane) of the present invention, the membrane contains a sheet-shaped flexible substrate Most provided with an opening 200 416 067, or non-woven ceramic material son Nai cell porous anode ⑴ an aluminum guide component (ii) -B r ο η, of an organic compound in a thionyl ΐ Xi wherein R membered carbon atoms: two dimple in The substrate material on and inside the substrate is selected from woven fabrics or fabrics made of non-conductive fibers combined with slope glass or this temple material, and coated with phosphoric acid pin conductive rice-level particles with a basic particle size of less than 5 microns. And it is gas-tight or impermeable to reaction components such as hydrogen, oxygen, air and / or methanol, the anode layer and the cathode are layered and each contains a catalyst for the anode reaction and the cathode reaction, and a proton partner 'and 'If catalyst catalyst is required. The proton conductive film of the layer and / or cathode layer should preferably be contained in each state; sulfur or phosphorus fixed hydroxysilicic acid or its salt, and if necessary, titanium, Chromium and / or phosphorus oxides; and / or Briinsted acids or oxides of aluminum, silicon, titanium, pins and / or phosphorus. The sted acid can be, for example, sulfuric acid, phosphoric acid, perchloric acid, nitric acid, hydrochloric acid, Phosphoric acid, its esters, and / or monomers or polymers In a preferred embodiment of the body acid 0, hydroxysilicic acid or a salt thereof is an organic substance having the general formula: [{(R0) y (R2) z} aSi {R1-S03] a] xMx + ⑴ or [(RO) y ( R2) 2Si {R1-〇bP (〇cR3) 〇2-} a] xMx + (丨 丨) 1 is a linear or branched alkyl group or alkylene group with 1 to 12 and cycloalkyl group 5 to 8 carbon atoms, or the following formula-(CHz) n- \ Η. m 200416067 or ~ (CHb) n 'χΟ) (CH2) m- (IV) where η and m are each an integer from 0 to 6, M is Η, ΝΗ4 or a metal, X is from 1 to 4, and y is from 1 to 3, ζ is from 0 to 2, and a is from 1 to 3, provided that y + z == 4_a, b and c are 0 or 1, R and R2 are the same or different and are methyl, Ethyl, propyl or butyl or fluorene, and R3 is M or methyl, ethyl, propyl or butyl. The sulfur or phosphorus hydroxysilyl acid is preferably trimethylsilylsulfonic acid, trimethylsilylmethylphosphonic acid, or 4,4_dihydroxy-1,7-dithio-4-silylheptane. . Sulfur or phosphorus hydroxysilic acid or a salt thereof is preferably fixed to a nitrate, oxynitrate, chloride, oxychloride, carbonate, alcohol using a hydrolyzed phosphide or a hydrolyzed metal or semimetal. Salt, acetate or acetamidine pyruvate. In another preferred embodiment, sulfur or phosphorus hydroxysilicic acid or a salt thereof is immobilized on a hydrolyzed compound obtained from titanium propionate, titanium oxide, tetraethyl orthosilicate (TEOS) or Tetramethyl silicate (TMOS), thorium nitrate, thorium oxynitrate, chromium propoxide, zirconium acetate, zirconium acetamidine pyruvate, methyl phosphate, diethyl phosphite (DEP), or diethyl ethylphosphonate ( DEEP). The proton-conducting component of the anode layer and / or the cathode layer may further contain a proton-conducting substance selected from the group consisting of titanium phosphate, titanium phosphonate, phosphoric acid pin, phosphonium phosphonate, isopolyacid and -22-200416067 heteropoly acid, preferably tungsten phosphoric acid Or silicotungstic acid or nanocrystalline metal oxide, preferably from Al203, Zr02, 1 ^ 02 or Si02 powder. The membrane electrode assembly of the present invention is preferably operated at a temperature of at least 8 in a fuel cell, preferably at least 10 °, and most preferably at least 120 ° C. The fuel used may be pure hydrogen or other hydrogen produced by a recombinant. However, in a preferred embodiment, methanol is used. For this purpose there is a liquid or gaseous mixture of water and methanol, preferably containing 0. 5-5% methanol is used on the anode side. In addition, the membrane electrode assembly of the present invention is preferably flexible, and is preferably adjustable to a bending radius as low as 5000 mm, preferably 100 mm, especially 50 mm, and particularly preferably as low as 20 mm. The membrane electrode assembly of the present invention is preferably an adjustable bending radius as low as 5 mm. The catalysts on the anode side and the anode side may be the same, but preferably different. In a preferred embodiment, the catalyst features in the anode layer and the cathode layer are conductive. In the production of a membrane electrode assembly, an electrolyte membrane is coated with a catalytically active electrode material in an appropriate manner. The electrolyte membrane can be provided with electrodes in various ways. In the process and sequence, conductive materials, catalysts, electrolytes, and other appropriate additives are applied to the film, which is easily done by skilled artisans. All to be determined is the interface of the gas space / catalyst (electrode) / electrolyte formed. In a special case, the conductive catalyst support material is omitted; in this case, the conductive catalyst is directly provided to conduct electrons from the membrane electrode assembly. The method of the present invention is made for the production of a membrane electrode assembly of the present invention also includes the steps of: -23- 200416067 (A) of the present invention is to provide the proton-conducting electrolyte membrane for fuel cell use, the fuel cell reaction and the reaction components with impermeable, (B) Provide various compositions, each for generating the anode layer and the cathode layer. Each composition contains: (B1) —a kind of condensable component that imparts proton conductivity on the electrode layer after condensation, (B 2) — A catalyst that promotes anodic or cathodic reactions; or a catalyst precursor compound, (B 3) if necessary, a catalyst support, and (B 4) if necessary, a hole formation, (C ) Applying each composition in step (B) to one of the sides of the electrolyte membrane in step (A) to form a coating, (D) Between each coating and the electrolyte membrane, forming a porous, proton-conducting anode layer or cathode Layer, to establish a solid combination, which can be formed simultaneously or sequentially on the anode layer and the cathode layer. The application of the composition in step (C) may be performed by, for example, printing, embossing, spray coating, roll coating, knife coating, brush coating, dipping, spraying or pouring. The composition of step (B) for producing the anode layer or the cathode layer is preferably obtained from the following suspensions = (S 1) to prepare a sol containing: hydroxysilicic acid and / or its salt of phosphorus or sulfur, and if suitable A hydrolyzable phosphorus compound, phosphorus or sulfur which is fixed the silicon hydroxyalkyl alkanoic acid and / or salt thereof, or of a metal or semi-metal nitrate may be hydrolyzable, the nitrate oxygen, -24-200416067 chloride, oxygen Chlorides, carbonates, alkoxides, acetates or acetamidine pyruvate, preferably methyl phosphate, diethyl phosphite (DEP) 'diethyl ethylphosphonate (DEEP), titanium acrylate, Titanium oxide, tetraethyl orthoester (TEOS) or tetramethyl orthosilicate (TMOS), zirconium nitrate, chromium oxynitrate, hafnium propionate, zirconium acetate or acetamidine pyruvate, (S 2) disperse contact If the catalyst is a suitable catalyst support, and the hole-forming agent is in the sol formed by (Sl). The composition of step (B) for producing the anode layer or the cathode layer is particularly suitable as a suspension and obtained from: (Η 1) hydrolyzing a hydrolyzable compound into a hydrolysate, the hydrolyzable compound is selected from: a hydrolyzable Phosphides or hydrolyzable metal or semi-metal nitrates, oxynitrates, chlorides, oxychlorides, carbonates, oxides, acetates or acetonylpyruvates, preferably oxidized bromide and alkanes Vanadium oxide, titanium oxide, titanium oxide, chromium nitrate, oxynitrate cone, chromium propionate, acetate or zirconium acetoacetate, or bromide, silicon, titanium, vanadium, antimony, tin, lead, Ming, tungsten, Metallic acids such as bromide and fibrous acid are preferably tungsten phosphoric acid and silicotungstic acid. (H2) uses acid to hydrolyze the hydrolysate to form a dispersion. (Η3) mixes the dispersion with a nanocrystalline proton-conducting metal for oxidation. The material is preferably A1203, Zr02, Ti02 or Si02 powder, (H4) decomposition catalyst and appropriate support and pore-forming agent. It may be advantageous if the components used to produce the anode and cathode layers are printed in step (C) and firmly bonded between each coating and the electrolyte membrane, 200416067 forming a porous proton conductive anode layer or cathode layer is completed in step (D) is heated to from 1 to 800 thousand and to the temperature ° C, preferably from 150 to 5 0 0 ° C, preferred from 180 to 250 ° C. The method of the present invention may also comprise the steps such as: (Μ 1) is applied to the generation of the anode layer or the cathode layer film composition to a support, preferably on a polytetrafluoroethylene, ([mu] 2) partial drying (Μ 1) obtained The coating, (M3) laminated locally dried coating is at a temperature from 20 to 500 ° C, preferably from 50 to 300 ° C, particularly preferably from 100 to 200 ° C, onto the electrolyte membrane, (M4) Remove the support film, especially by mechanical separation, chemical cracking or pre-heating, or (N 1) apply the composition for producing the anode layer or cathode layer to the support film, preferably using carbon paper or conductive non-woven fabric Fabric or braid, (N2) partially dried on the coating obtained in (N1) to produce a coated support film, (N3) laminating the coated support film on the electrolyte membrane, the temperature is from room temperature to 50 ° It is preferably from 50 to 300 ° C, and most preferably from 100 to 200 ° C. It may be advantageous if the conditions for generating the composition of the anode layer and the cathode layer are combined in step (B), (i) the composition contains a catalyst metal salt, preferably hexachloroplatinic acid, (Π) subsequent steps (C) After applying the composition, the reduction catalyst metal salt becomes a catalyst that promotes the anode reaction or the cathode reaction. (Iii) The open-cell gas diffusion electrode in step (D), preferably an open-cell carbon paper, is pressed. To the catalyst, or use a conductive adhesive to bind the catalyst. In the method of the present invention, it may be completed by repeatedly applying the composition for generating the anode-26-200416067 layer or the cathode layer and the drying step as required. It is preferable to increase the temperature from 20 to 5 between each repeated completion of the application. A temperature range of 0 0 ° C, preferably from 50 to 300 ° C, and most preferably from 100 to 200 ° C. It may be advantageous if the composition for producing the anode layer or the cathode layer is applied to a flexible support film or a flexible electrolyte film that is unrolled. It may be particularly advantageous if the composition for producing an anode layer or a cathode layer is applied in combination. It may be particularly advantageous if a composition for producing an anode layer or a cathode layer is applied to a heated electrolyte membrane or a supporting membrane. For the sake of the establishment of a firm bond between the coatings and the electrolyte membrane, the composite is preferably heated at a temperature of from 20 to 5 0 0 t's, more preferably from 50 to 3 0 (TC, best from 100 to 2 0 0 ° C. this is available hot air heating, the heating air, infrared radiation or microwave radiation. to produce the membrane electrode assembly, particularly in a particular embodiment, there is catalytic activity (gas diffusion) electrode is configured in the On the electrolyte membrane of the present invention, this is done by a printing ink made of carbon black catalyst powder and at least one proton conductive material. However, the printing ink may also contain other additives that enhance the properties of the membrane electrode assembly. Carbon black may also be used Replaced by other conductive materials (such as metal powder, metal oxide powder, carbon, charcoal, etc.) In a particular embodiment, the catalyst support used to replace carbon black is a metal or semi-metal oxide (which For example, A er osii), then the printing ink is applied to the film using, for example, screen printing, knife coating, spraying, roller application or immersion. The printing ink may contain all the special properties for soaking. Proton conductive material. So printing ink An acid or a salt thereof to include in the firmware after the ink is applied to the thin film, the chemical reaction is secured. -27-200416067 This acid may thus, for example, is a simple B r ϋ nsted acids, such as sulfuric acid which Or phosphoric acid, or silane sulfonic acid or silane phosphonic acid. Materials that can be used to help acid curing, such as SiO2, Zr02, and Ti02, can be added to the ink as molecular precursors. For fuel cells The reactive component of the reaction must be a proton conductive coating of an impermeable electrolyte membrane. In contrast, both the cathode and anode need to have high porosity so that reactive gases such as hydrogen and oxygen can be directed to the catalyst / electrolyte interface without mass. Impediment to transmission. This porosity can be influenced, for example, by using metal oxides with a suitable particle size, or by using organic pore formers in the ink, or by using appropriate solvent components in the ink. As a specific ink, A composition containing the following components can be used: (T1) A condensation component, which is used to supply proton conductivity to the anode or cathode layer of a fuel cell after condensation (T2) —a catalyst that promotes anodic or cathodic reactions in fuel cells, or is a precursor compound of the catalyst, (T3) if required, a catalyst support, (T4) if required, a Pore formation, and (T5) If necessary, various additives to improve the properties, viscosity, and adhesion of the foam. After condensation, it is better to provide a condensable composition of proton conductivity on the anode layer or the cathode layer. is selected from: (I) the hydrolysable phosphides and / or the hydrolyzable metal or semi-metal nitrates, oxygen nitrates, chlorides, oxychlorides, carbonates, alkoxides, acetates and -28-200416067 Acetylpyruvate 5 is preferably alumina, vanadium oxide, titanium oxide, titanium oxide, zirconium nitrate, oxynitrate, m. Propionate, acetic acid, or acetonylpyruvate 5 and / or aluminum, titanium, vanadium, antimony, halochrome Tungsten molybdenum or manganese metal acid, preferably tungsten phosphoric acid and silicotungstic acid and / or a hydroxysilicic acid that can fix phosphorus or sulfur. And -, or a salt thereof and j 0 Further particularly preferred in specific embodiment of the J one phosphorus compound which is hydrolyzable fixed hydroxyalkyl phosphorus or sulfur acid or a salt thereof Academy of silicon in 9 of a metal or semi-metal nitrate may be hydrolyzed Oxynitrate > Chloride oxychloride carbonate > The oxide acetate or acetamidine pyruvate is preferably methyl ethyl phosphate diethyl phosphite (DEP), ethyl ethyl phosphonate diethyl; ester ( DEEP) propan-acetate titanium dioxide primary tetraethyl silicate (TEOS) or tetramethyl ester original silicate (Τ Μ OS), zirconium nitrate, zirconyl nitrate, zirconium propionate, zirconium acetate or chromium acetyl pyruvic acid. However, in order to increase the proton conductivity, the ink may also contain nano-scale oxides such as aluminum, titanium, chromium or silicon, for example, or others such as phosphoric acid or zirconium or hafnium phosphate. The catalyst or catalyst precursor compound preferably contains platinum, palladium and / or ruthenium, or an alloy containing one or more of these metals. The ink present within the pore former can be organic and / or inorganic substances, which is a solution for the heart 50 with a temperature between 600 C, preferably at 1 billion and 25 billion square. 〇 between. In particular, the inorganic pore-forming agent may be ammonium carbonate or ammonium bicarbonate. The catalyst support that may be present in the ink is preferably conductive, and preferably contains carbon black, metal powder, metal oxide powder, carbon or charcoal. -29- 200416067 In another specific example, the gas resistance of a stack is made of a conductive material (such as porous carbon, which can be directly applied to the film. The most film is fixed by pressing. To this end, the film must be made of thermoplastic Or change it, the gas film. This adhesive must have ion transmission. Any kind of material as described above is constructed as a metal oxide sol and contains hydroxysilicic acid. It is more in situ for the production of films or gas diffusion electrodes. Here At the stage, the gas separation material has not been solidified and can be used as the adhesive method. The alternative method is to dry / solidify it later. An alternative option is to directly deposit and pour the gas diffusion electrode (such as an open hole, available for use). A metal salt or acid is applied to the surface. It is, for example, platinum can be added with hexachloroplatinic acid in the next step. The collector electrode can be pressed to contain a solution containing a metal precursor. Another ion-conducting compound can be included in the production process. Including the above-mentioned proton-conducting substance. The membrane electrode assembly obtained by this method can be used as a methanol fuel cell or a recombined fuel (4) Embodiments of the electrolyte of the present invention Membrane can be used for example distributors (including gas diffusion braids), coal contact and electrolytes simple, gas distributors and thin or gas distributors can be fixed to the conductive properties by adhesives at the lamination temperature, and in principle It can be made. For example, the adhesive used can be. Finally, the proton applied to the dispenser or the film in the final stage of the variable gas distributor can be converted into an adhesive. In two cases, the sol gels. Gelation occurs. Media on the film, and set an open carbon paper). For this purpose, the example is reduced to a gold surface and reduced to a metal in the second step. At most or fixed with conductive adhesive. The species is already the end point of proton conductivity or at least order. Suitable materials are also used for fuel cells, especially for direct batteries. Such as fuel cells, especially for direct methanol fuel cells or recombined fuel cells. In particular, the electrolytic membrane of the present invention can be used for producing a membrane electrode assembly, a fuel cell, or a fuel cell stack. The electrolyte membrane of the present invention and the membrane electrode assembly of the present invention are particularly useful for the production of fuel cells or fuel cell stacks, and among fuel cells, in particular, direct methanol fuel cells or recombined fuel cells for vehicles. Therefore, the present invention also provides a fuel cell comprising the electrolyte membrane of the present invention and / or the membrane electrode assembly of the present invention; and therefore also a fuel cell comprising the thin film electrode assembly of the present invention, the electrolyte membrane of the present invention or the membrane electrode assembly of the present invention, or Motorized or fixed systems for fuel cell stacks, etc. The motorized or fixed system is preferably a vehicle or a home appliance system. Example 1: Both zirconium nitrate and phosphoric acid each of 3% by weight aqueous solution collide with each other in accordance with the ψ square of Micro 00/61275 jet reactor by the pressure of each nozzle 3〇〇 microns, in 6〇 the bar. The obtained product was opaque. A dual display mode of the particle size distribution the particle distribution, particle size of 1.7 microns are square, parts of smaller size particle group just at 3 microns. This suspension was concentrated to about 10% by weight on a rotary evaporator to remove water, and the suspension became like a sol / viscosity but remained opaque. This sol or suspension has long lasting stability and will be used later. Example 2: Phosphoric acid (0. 2 M) and chromium nitrate (0. 〇 5 Μ) The two aqueous solutions collided with each other at a pressure of 60 bar in a micro-jetting reactor according to WO 00/61275 through a 100 micron nozzle. The obtained product was opacified. The particle size distribution is comparable to the distribution of Example 1. The suspension can be further dehydrated and concentrated in a rotary evaporator 200416067. After completion, it will become sol / viscous and remain opaque. This sol or suspension has long-lasting stability. Example 3: The suspension of Example 1 was mixed with 5% by weight of Aerosil 2 0 (DeguSSa AG) after concentration. Then stir with a magnetic stirrer for another 24 hours to homogenize. Example 4: 5 g of Al2O3 and 0. 23 grams of TODS (2- [2- (2-methoxyethoxy) ethoxy] acetic acid) was added to 50 grams of the suspension from Example 1. Coat an S2-glass braid with this slurry in a continuous process and then dry it from 1 50 to 20 (TC in 5 minutes. This film has an unexpected 0. It has a high conductivity of 2 mSiemens / cm and is flexible. Example 5: The suspension obtained from Example 1 was used to directly coat a glass braid in a continuous process. The suspension was then coated with a knife on an S 2 -glass braid (C S -Interglas) and cured at a temperature of 160 ° C within 10 minutes. The resulting film exhibited a good conductivity of more than 1 milliSiemens / cm. The film is about as flexible as the original braid. Example 6; The suspension obtained from Example 2 was directly knife-coated onto a glass braid. The cured film was then placed in a chamber furnace at 300 ° C for 15 minutes. The water-insoluble film now has a conductivity of about 2 milliSiemens / cm at 92% relative humidity (RH) and 23 t. Due to its stability in water and methanol, this film is very suitable for use in DMFC. -32- 200416067 Example 7: An S-glass braid having a thickness of 70 micrometers is impregnated with the suspension obtained from Example 1 and applied by a five-knife coating method. Between the soaking steps, the braid is subjected to preliminary curing in a hot air fan at approximately 150 ° C. After the final coating, the film was finally cured with hot air at 300 ° C for 15 minutes during the final filling of the holes. This stable film in water and methanol has a conductivity of about 4 mSv / cm to a relative humidity of 80% and can be used in DMFC. Example 8: An S-glass braid having a thickness of 70 micrometers was impregnated with the suspension liquid from Example 3 and applied by a triple knife coating method. Between each soaking step, the braid was subjected to preliminary curing using a hot air fan at approximately 150 ° C. After the final coating, the film was finally cured by hot air at 300 ° C for 15 minutes while filling the last hole. This stable film in water and methanol has a conductivity of about 1 milliSiemens / cm at a relative humidity of 80% and can be used in DMFC.