200950201 六、發明說明： 【發明所屬之技術領域】 本發明係有關燃料電池及電子機器，特別是有關對於· 使用高濃度之燃料的輸出特性優越之燃料電池，和使用# 燃料電池的電子機器。 【先前技術】 φ 近年，電筆記型電腦，行動電話等之各種電子機器係 隨著半導體技術之發達同時而作爲小型化，並嘗試將燃料 電池使用於此等小型機器用之電源。而燃料電池係只由供 給燃料與氧化劑而即可發電，並具有只交換燃料而即可連 續發電之利點之故，如可小型化，可說對於小型電子機器 之動作極爲有利之系統。特別是，直接甲醇型燃料電池（ DMFC: Direct Methanol Fuel Cell)係將能量密度高之甲 醇使用於燃料，可從甲醇，在電極觸媒上直接取出電流， φ 並從無需改質器情況，有期望可作爲小型電子機器的電源 〇 作爲在DMFC之燃料的供給方式，係知道有有以送風 箱等’將液體燃料氣化者，送入至DMFC內之氣體供給型 ’或直接以幫浦等，將液體燃料送入至DMFC內之液體供 給型的主動方式，將燃料收容部內之液體燃料，在DMFC 內作爲氣化內部氣化型等之被動方式。此等之中，內部氣 化型等之被動方式係對於DMFC之小型化而言特別有利。 作爲內部氣化型DMFC，係例如知道有具備：於陰極 200950201 (空氣極）觸媒層和陽極（燃料極）觸媒層之間，配置具 有質子傳導性之電解質膜之膜電極接合體（MEA : Membrane Electrode Assembly)，和液體燃料收容室，和 配置於此等膜電極接合體與液體燃料收容室之間，只使液 體燃料之氣化成分透過之氣液分離膜所成之燃料氣化層之 構成（例如，參照專利文獻1 )。 但在作爲前述內部氣化型DMFC之以往的燃料電池， 係在使用濃度如成爲50mol %以上之高濃度燃料的情況， 有著無法得到充分之輸出特性者。例如，作爲燃料而使用 甲醇之情況，在陽極觸媒層中係進行如在下述反應式（1 )所示之甲醇的內部改質反應，在陰極觸媒層中係進行如 在下述反應式（2)所示之伴隨產生水的反應。 CH30H + H20^ C〇2 + 6H + + 6e> ( 1 ) (3/2 ) 〇2 + 6H + + 6e*^ 3 Η2〇μ ( 2 ) 作爲燃料而使用高濃度之甲醇水溶液或純甲醇之情況 ，含於燃料中的水爲少，或完全未含有之故，對於內部改 質反應所需的水乃容易不足。然而，在陰極觸媒層中雖產 生水，但由在陰極觸媒層產生的水要確保對於內部改質反 應所需的水之情況係爲困難。因此，使用高濃度的甲醇水 溶液或純甲醇之情況，在內部改質反應的反應阻抗則變高 ，有著未必可得到優越之輸出特性的問題。 〔專利文獻1〕國際公開第2005/1 1 2 1 72號說明書 -6- 200950201 【發明內容】 本發明乃爲了解決如此之問題所作爲之構成，其目的 爲提昇使用高濃度燃料之燃料電池的輸出特性者。 本發明之第1型態之燃料電池係屬於具備：含有陽極 觸媒與具有質子傳導性之電解質的陽極觸媒層，和含有陰 極觸媒與具有質子傳導性之電解質的陰極觸媒層，和夾持 φ 於前述陽極觸媒層與前述陰極觸媒層之間的質子傳導性的 電解質膜’和爲了供給燃料於前述陽極觸媒層之機構的燃 料電池’其特徵乃經由前述陰極觸媒之CO脈衝吸著法所 測定之金屬比表面積乃較經由前述陽極觸媒之CO脈衝吸 著法所測定之金屬比表面積爲大者。 本發明之第2形態之電子機器，其特徵乃將前述之第 1型態之燃料電池作爲電源而使用者。 如根據本發明之燃料電池，經由陰極觸媒之CO脈衝 φ 吸著法所測定之金屬比表面積乃同樣地因呈較經由CO脈 衝吸著法所測定之陽極觸媒的金屬比表面積爲大地加以構 成’故可提昇使用高濃度燃料之燃料電池的輸出特性者。 另外，如根據本發明之電子機器，因具備如此之輸出 特性高的燃料電池，故小型且可發揮安定之高性能者。 【實施方式】 以下，對於本發明之實施型態，將內部氣化型之直接 甲醇型燃料電池（DMFC)舉例加以說明。 200950201 第1實施型態之燃料電池1係如圖1所示，具有備有 由陽極（燃料極）觸媒層2與陽極氣體擴散層3所成之陽 極4，和由陰極（空氣極）觸媒層5與陰極氣體擴散層6 所成之陰極7，以及夾持於陽極觸媒層2與陰極觸媒層5 之間的質子（氫離子）傳導性的電解質膜8之膜電極接合 體（MEA) 9。 陽極觸媒層2與陰極觸媒層5係均含有觸媒與質子傳 導性的電解質。作爲含於陽極觸媒層2之陽極觸媒及含於 陰極觸媒層5之陰極觸媒係可舉出例如白金族元素之Pt， Ru, Rh，Ir，Os，Pd等之單體金屬，含有此等白金族元素之 合金等。具體而言，作爲陽極觸媒，使用對於甲醇或一氧 化碳等而言，具有華耐性之Pt-Ru或Pt-Mo等之合金，而 作爲陰極觸媒層，使用Pt或Pt-Ni等之合金者爲佳，但並 不限於此等。另外，亦可使用將此等觸媒的微粒子載持於 導電性載體的載持觸媒。作爲導電性載體，係使用活性炭 或石墨等之粒子狀的碳或纖維狀的碳。在本發明，經由陰 極觸媒或陽極觸媒之CO脈衝吸著法所測定之金屬比表面 積係指：表示每單位體積之脈衝的金屬比表面積。因此， 對於各含於觸媒層之質子傳導性的電解質之含有量，進行 重量修正。 與此等金屬觸媒同時含於陽極觸媒層2及陰極觸媒層 5係之質子傳導性的電解質係並無特別加以限定。作爲質 子傳導性之電解質，係可舉出Nafion (商品名、DuPont 公司製）或Flemion(商品名、旭硝子公司製）等之具有 -8- 200950201 磺酸基之氟素系樹脂（全氟碳化物聚合物），將磷酸等之 無機酸摻雜於碳化氫系高分子化合物者，一部分乃以質子 傳導性之官能基加以置換之有機/無機混合聚合物，於高 分子矩陣，浸含磷酸溶液或硫酸溶液之質子傳導體等之高 分子電解質者。 並且，在此等觸媒層，經由陰極觸媒之CO脈衝吸著 法所測定之金屬比表面積乃同樣地呈較經由陽極觸媒的 ❹ CO脈衝吸著法所測定之金屬比表面積爲大。爲了得到更 高之輸出特性（輸出密度），陰極觸媒之金屬比表面積乃 陽極觸媒之金屬比表面積的4倍以上爲佳。另外，經由陰 極觸媒之CO脈衝吸著法所測定之金屬比表面積的値乃 5m2/g以上爲佳，而陽極觸媒之金屬比表面積乃l〇m2/g以 下爲佳。 然而，CO脈衝吸著法係於存在在表面之金屬粒子， 斷續性地注入定量之CO (氣體），將穩定地加以溶出之 〇 CO量與開始吸著實之CO量的差分，作爲CO吸著量而測 定之方法。由此方法，可將金屬觸媒之每單位質量的露出 表面積，作爲比表面積而求得者。另外，經由如此之CO 脈衝吸著法的觸媒金屬之比表面積測定係可在既已組裝之 燃料電池進行。即，從將燃料電池的製品解體所取出之 MEA，個別以刀片削落陽極觸媒層與陰極觸媒層，將此等 作爲粉末狀，各塡充於CO脈衝吸著量測定裝置之計量管 內。並且，以特定的溫度（例如5 0 0 °C )，測定C Ο脈衝 吸著量，求取觸媒金屬的比表面積。 -9- 200950201 在陽極觸媒層2及陰極觸媒層5，作爲使觸媒金屬的 比表面積變化的方法’係有（1)調整構成觸媒層之觸媒 與質子傳導性之電解質的調配比例之方法，（2)改變載 持觸媒金屬的碳等之導電性載體的種類之方法，（3)改 變在攪拌觸媒淤漿時所賦予之能量的方法，或者（4)改 變觸媒淤漿之塗布後的乾燥速度的方法等。在此，在觸媒 淤漿攪拌時所賦予的能量係經由例如攪拌葉與觸媒淤漿的 碰撞而進行攪拌、粉碎之情況，成爲攪拌葉的旋轉速度（ 周數）與攪拌時間的積。其能量越大，金屬比表面積係變 越大。另外’觸媒淤漿之塗布後的乾燥速度越慢，金屬比 表面積係變越大。 在本發明之第1實施型態’係於如此所構成之陽極觸 媒層2，層積陽極氣體擴散層3，於陰極觸媒層5，層積陰 極氣體擴散層6。陽極氣體擴散層3乃擔負均一地供給燃 料於陽極觸媒層2之作用同時’亦作用兼具陽極觸媒層2 之集電體。陰極氣體擴散層6乃擔負均一地供給氧化劑於 陰極觸媒層5之作用同時’亦作用兼具陰極觸媒層5之集 電體。此等陽極氣體擴散層3及陰極氣體擴散層6乃例如 經由碳紙所加以構成。 另外’對於陽極氣體擴散層3乃層積陽極導電層1〇, 且對於陰極氣體擴散層6乃層積陰極導電層u。作爲陽極 導電層10及陰極導電層11，係例如可各使用金，鍊等之 導電性金屬材料所成之多孔質膜（例如；網目）或箱體， 或者對於不銹鋼（SUS)等之導電性金屬材料，被覆金等 200950201 良導電性金屬之複合材·等。 對於陽極觸媒層2與陰極觸媒層5之間係夾持有質子 傳導性的電解質膜8。作爲構成電解質膜8之質子傳導性 材料係例如可舉出具有Nafion或Flemion等之磺酸基之氟 素系樹脂（全氟碳化物聚合物），具有磺酸基之碳化氫系 樹脂等之有機系材料，或者鎢酸或磷鎢酸等之無機系材料 等。但’質子傳導性之電解質膜8並不限定於此等之構成 ❿ 在質子傳導性之電解質膜8與陽極導電層10之間， 對於陽極觸媒層2與陽極氣體擴散層3之周圍，設置有例 如剖面爲〇字狀，平面形狀乃矩形框狀之密封材12。另 外’在質子傳導性之電解質膜8與陰極導電層11之間， 對於陰極觸媒層5與陰極氣體擴散層6之周圍，設置有相 同形狀之密封材12。此等密封材12係防止來自ME A9之 燃料洩漏及氧化劑洩漏之構成。 〇 對於MEA9之陽極4側係配置有燃料收容室13。對於 燃料收容部13係收容有液體燃料F。液體燃料F係作爲 最佳的構成可舉出甲醇水溶液或純甲醇，但未必限定於此 等，而亦可使用爲例如，乙醇水溶液或純乙醇等之乙醇燃 料，丙醇水溶液或純丙醇等之丙醇燃料，乙二醇水溶液或 純乙二醇等之乙二醇燃料’二甲醚，蟻酸，其他的燃料者 。另外，作爲液體燃料F係最佳使用濃度乃50mol %以上 之構成，但未必加以限定。對於燃料收容室1 3之開口端 ，係任意地，例如配置只透過液體燃料F的氣化成分，而 -11 - 200950201 不易使液體成分通過之氣液分離膜14。在此，液體燃料F 之氣化成份係指：對於作爲液體燃料F而使用純甲醇之情 況，係指甲醇之氣化成分，對於作爲液體燃料而使用甲醇 水溶液之情況’係指甲醇之氣化成分與水之氣化成分所成 之混合氣體。 對於MEA9之氣液分離膜14之間係配置有樹脂製的 框體15。由框體15所圍繞的空間係作爲將擴散在氣液分 離膜14之氣化燃料，暫時性收容之氣化燃料收容室（所 謂蒸汽積存）而發揮機能。經由其氣液分離膜14及氣化 燃料收容室之透過燃料量抑制效果，控制對於ME A9之急 遽的氣化燃料之流入，進而控制燃料交越的產生。然而， 框體15係具有平面形狀爲格子狀，亦擔負由按壓ME A9 而抑制變形，降低接觸阻抗之作用。因此，框體15係由 例如對於如聚二醚酮（PEEK : Victrex公司之商品名）之 耐藥性或強度優越之工程塑料所構成。 另一方面，對於MEA9之陰極導電層1 1之係任意地 層積·配置有保濕層16。保濕板16係具有防止在陰極觸 媒層5所生成的水之蒸散的機能同時，亦具有均一地導入 氧化劑之空氣於陰極氣體擴散層16，作爲促進對於陰極觸 媒層5的氧化劑（空氣）之均一擴散的補助擴散層之機能 。對於保濕層16上，係層積形成有複數個爲了導入氧化 劑之控氣的空氣導入口 17a之蓋板（表面層）17。蓋板17 乃亦達成將ME A9或保濕層16加壓，提升此等之密著性 的作用，例如如由SUS 3 04之金屬板所構成。 -12- 200950201 在如此之燃料電池1中，如以下作爲而進行發電。首 先，燃料收容室1 3內之液體燃料F的甲醇水溶液或純甲 醇之氣化成分乃擴散在氣液分離膜14，收容於由框體15 所圍繞之氣化燃料收容室。收容於氣化燃料收容室之液體 燃料F的氣化成份係緩慢地擴散在陽極氣體擴散層1〇, 陽極氣體擴散層3而供給至陽極觸媒層2。並且，供給於 陽極觸媒層2之液體燃料F的氣化成份係產生以下之反應 φ 式（1)所示之甲醇的內部改質反應。 CH30H + H20— C〇2 + 6H + + 6e) ( 1) 在此，做爲液體燃料F而使用純甲醇之情況，雖無來 自液體燃料F之水的供給，但對於此情況，利用含於質子 傳導性之電解質膜8或陽極觸媒層2的水，或在陰極觸媒 層5所產生的水而進行內部改質反應。 φ 經由內部改質反應所生成之質子（H+)係經由質子傳 導性之電解質膜8而到達至陰極觸媒層5。另一方面’從 蓋板17之空氣導入口 17a所導入之空氣係依序擴散在保 濕層16，陰極導電層11，及陰極氣體擴散層6’供給至陰 極觸媒層5。在陰極觸媒層5中，經由以下之反應式（1) 所示之反應而生成水。即，產生發電反應。 (3/2) 〇2 + 6H + + 6e，—3 Η2〇μ ( 2) -13- 200950201 當發電反應進行時，經由上述反應$ 應而在陰極觸媒層5生成的水乃到達至保 經由此保濕層16而到達的水之蒸散，作 媒層5的水份保持量則增加。並且，陰極 保持量乃變較陽極觸媒層2之水份保持量 由浸透壓現象，促進從陰極觸媒層5至陽 的移動。經由如此之水的移動，促進內部 輸出特性之同時，高輸出特性則保持長時 如此，經由浸透壓現象，從陰極觸媒 層2使水移動之情況，陰極觸媒層5係水 易引起經由水的閉塞。因此，對於經由含 之質子傳導性的電解質之陰極觸媒的被覆 ，具有5m2/g以上之金屬比表面積者爲佳 媒層2係與陰極觸媒層5做比較，相對地 故，容易引起經由水不足之質子導電性的 於經由含於陽極觸媒層2之質子傳導性的 媒的被覆係75%以上爲佳，具有10m2/g 面積者爲佳。在組合此等條件之實施型態 層5係不易引起經由水的閉塞，從陰極觸 極觸媒層2的水則良好地保持於陽極觸媒 後之內部改質反應，故可得到高的輸出特 〇 本發明之第1實施形態之燃料電池] 的製造方法而製造。首先，將陽極觸媒， ζ ( 2 )所示之反 濕層16。從阻礙 爲結果，陰極觸 觸媒層5之水份 爲多之結果，經 極觸媒層2之水 改質反應，提昇 間維持。 層5至陽極觸媒 保持量變多而容 於陰極觸媒層5 係50%以下爲佳 。另外，陽極觸 水保持量變少之 下降。因此，對 電解質之陽極觸 以下之金屬比表 中，因陰極觸媒 媒層5移動至陽 :層2 ’使用在以 性（輸出密度） I，係可採用公知 例如以以下所示 -14- 200950201 作爲而製造。即，使碳等之導電性載體，與含有構成白金 或白金合金的各金屬成分之化合物的水溶液或淤漿接觸， 使其金屬化合物或其離子吸著或浸含於導電性載體上。並 且，以高速攪拌淤漿的同時徐緩地低下適當之固定化劑， 例如氫氧化鈉，氨，聯胺，蟻酸，福馬林，甲醇，乙醇， 丙醇等之稀釋溶液，作爲金屬鹽，另外或作爲一部分還原 之金屬微粒子而載持於導電性載持體上。更且進行乾燥， Φ 經由在還原氣體或不活性氣體環境下進行熱處理之時，製 造陽極觸媒。 將所得到之陽極觸媒，與質子傳導性的電解質之懸濁 液混合，以甲醇，乙醇，丙醇等之醇，及甘油，乙二醇等 進行黏度調整，作爲陽極觸媒層形成用淤漿（以下，表示 陽極觸媒淤漿）。在此，在所調製之陽極觸媒淤漿，經由 改變陽極觸媒與質子傳道性之電解質之調配比例，或者攪 拌時所賦予之能量之時，可改變構成陽極觸媒層2之觸媒 0 的金屬比表面積者。 接著，將所得到之陽極觸媒淤漿，經由吸引過濾法， 噴射法，滾塗法，棒塗法等而塗布於成爲陽極氣體擴散層 3之碳紙或碳布等之導電性多孔質基材，並使其乾燥而作 爲陽極觸媒層2。然而，由如此作爲而於陽極氣體擴散層 3上，形成陽極觸媒層2之構成乃成爲陽極4。在此，經 由改變陽極觸媒淤漿之塗布後的乾燥速度之時，可改變構 成陽極觸媒層2之觸媒的金屬比表面積者。 另外，形成陰極觸媒層5。即，將陰極觸媒，以與前 -15- 200950201 述陽極觸媒同樣作爲而製造，將所得到之陰極觸媒’與質 子傳導性的電解質之懸濁液混合，以甲醇，乙醇’丙醇等 之醇，及甘油，乙二醇等進行黏度調整，作爲陰極觸媒層 形成用淤漿（以下，表示陰極觸媒淤漿）。在此’在陰極 觸媒淤漿之調製，經由改變陰極觸媒與質子傳道性之電解 質之調配比例，或者攪拌時所賦予之能量之時，可改變構 成陰極觸媒層5之觸媒的金屬比表面積者。 接著，將所得到之陰極觸媒淤漿，經由吸引過濾法， 噴射法，滾塗法，棒塗法等而塗布於成爲陰極氣體擴散層 6之碳紙或碳布等之導電性多孔質基材，並使其乾燥而作 爲陰極觸媒層5。由如此作爲而於陰極氣體擴散層6上， 形成陰極觸媒層5之構成乃成爲陰極7。在此，經由改變 陰極觸媒淤漿之塗布後的乾燥速度之時，可改變構成陰觸 媒層5之觸媒的金屬比表面積者。 接著，於如此作爲所得到之陽極4與陰極7之間夾持 質子傳導性之電解質膜8之後，經由滾輪或噴射熱壓著此 等者，製造膜電極接合體（MEA ) 9。更且，於其MEA9 層積陽極導電層10與陰極導電層11。並且，經由於燃料 收容室13上，依序重合氣液分離膜14，層積陽極導電層 10及陰極導電層11之EMA9，保濕層16，蓋版（表面層 )17而作爲一體化之時，可製造第1實施型態之燃料電池 1者。 在上述之說明中，已說明過作爲燃料電池之構成，於 膜電極接合體（MEA) 9之下部，具有燃料收容室13之構 200950201 造，但亦可爲於燃料收容室與mea之間配置有流路，藉 由其流路而進行燃料之供給的構造。另外’作爲燃料電池 主體之構成，將被動型之燃料電池’舉例進行說明過，但 對於主動型之燃料電池，更加地對於於燃料供給等一部分 使用幫浦等之半被動型之燃料電池’亦可適用本發明者。 半被動型之燃料電池係從燃料收容室供給至MEA之 燃料乃使用於發電反應，之後不會進行循環而返回至燃料 0 收容室者。半被動型之燃料電池係從未循環燃料之情況， 與以往之主動方式不同者，並非損及裝置之小型化等構成 。另外，因對於燃料的供給，使用幫浦，亦與如以往之內 部氣化型之純被動方式不同，故其燃料電池係稱作半被動 方式。 圖2乃顯示本發明之第2實施形態之半被動方式的燃 料電池之構成縱剖面圖。 其燃料電池20係具備作爲發電部之膜電極接合體（ φ ME A ) 21，作爲集電體之陰極導電層22及陽極導電層23 ME A21係將質子傳導性之電解質膜24夾持於其間， 於兩側，以熱壓將陽極25及陰極26作爲一體化而加以構 成。陽極25係於電解質膜24側具有陽極觸媒層27，於其 外側具有陽極氣體擴散層28。陰極26係於電解質膜24側 具有陰極觸媒層29，於其外側具有陰極氣體擴散層30。 並且，在如此之ME A21，陽極觸媒層27與陰極觸媒 層29係與第1實施型態同樣地加以構成。即，在陰極觸 -17- 200950201 媒層29之陰極觸媒之金屬比表面積的値（經由CO脈衝吸 著法所測定）乃變較在陽極觸媒層27之陽極觸媒的之金 屬比表面積的値爲大（經由CO脈衝吸著法所測定）。然 而，爲了得到更高之輸出特性（輸出密度），陰極觸媒之 金屬比表面積的値乃陽極觸媒之金屣比表面積的質之4倍 以上爲佳。另外，陰極觸媒之金屬比表面積的値乃5m2/g 以上爲佳，而陽極觸媒之金屬比表面積乃l〇m2/g以下爲 佳。 對於陽極氣體擴散層28乃呈接觸陽極導電層22地加 以配置，對於陰極氣體擴散層30乃呈接觸陰極導電層23 地加以配置。藉由此等陽極導電層22及陰極導電層23, 在發電部所發電的電力乃成爲輸出於未圖示之負荷。 另外，其燃料電池20係具備蓋板30與燃料供給手段 (燃料分配機構）40。對於質子傳導性之電解質膜24與 蓋板30及之燃料分配機構40間，係各介入存在有如橡膠 製之0環的密封材31，經由此等而防止從燃料電池發電 部之燃料洩漏或氧化劑洩漏。 蓋板30係具有爲了取入氧化劑之空氣的開口（空氣 導入口）3 0a。對於蓋板3 0及陰極2之間，係因應必要而 配置有保濕層或表面層。對於保濕層係浸含有在陰極觸媒 層29所生成的水之一部分，控制水的蒸散的同時’促進 對於陰極觸媒層29之氧化劑（空氣）的均一擴散者。表 面層乃調整空氣之取入量者，並具有對應於空氣之導入而 調整個數或大小等之複數的空氣導入口。 -18- 200950201 對於MEA21之陽極25側係配置有作爲燃料供給手段 之燃料分配機構40。對於燃料分配機構4〇係藉由如配管 之然料的流路41而連接作爲燃料儲藏手段之燃料收容部 42°對於燃料收容部42係收容對應於燃料電池之液體燃 料。 對於燃料分配機構40，係從燃料收容部42，藉由流 路41而導入燃料。流路41係並不限於與燃料分配機構4〇 〇 或燃料收容部42獨立之配管的構成。例如，層積燃料分 配機構40與燃料收容部42而作爲一體化之情況，亦可爲 連繫此等之液體燃料的流路。燃料分配機構4〇係如藉由 流路41而與燃料收容部42連接即可。 在此’燃料分配機構40係如圖3所示，具備具有燃 料藉由流路41而流入之至少1個之燃料注入口 43a，和排 出液體燃料或其氣化成分之複數個燃料排出口 43b之燃料 分配板43。對於燃料分配板43的內部係如圖2所示，設 φ 置有成爲從燃料注入口 43a所引導之燃料的通路之空隙部 43c。複數之燃料排出口 43b係各直接連接於空隙部43c。 從燃料注入口 43a引導於燃料分配機構40之燃料係 進入於做爲燃料通路而發揮機能之空隙部43c，並藉由其 空隙部43c而各引導至複數之燃料排出口 43b。對於複數 之燃料排出口 43b，係亦可例如配置只透過燃料的氣化成 分，無法使液體成分透過之氣液分離膜（無圖示）。由此 ，對於燃料電池發電部之陽極25，係供給燃料之氣化成分 。然而，氣液分離膜係亦可於燃料分配機構40與陽極25 -19 - 200950201 之間加以設置。液體燃料之氣化成分係從複數之燃料排出 口 43b ’朝向陽極25之複數處加以排出。 燃料供給口 43係呈可供給燃料於MEA21之全體地， 複數設置於與燃料分配板43之陽極25接合的面。燃料排 出口 43b之個數係如爲2個以上即可，但在均一化針對在 燃料電池發電部之面內的燃料供給量上，呈存在有0.1〜10 個/cm2之燃料排出口 43b地形成爲佳。 對於連接在燃料分配機構40與燃料收容部42之間的 流路41係插入幫浦44。其幫浦44並非爲使燃料循環之循 環幫浦’徹底來說爲從燃料收容部42，將燃料移送至燃料 分配機構40的燃料供給幫浦。經由以如此之幫浦44在必 要時輸送燃料者，可提昇燃料供給量的控制性者。此情況 ，作爲幫浦44之種類係從控制性佳而可輸送少量之液體 燃料情況’更加地可小型輕量化之觀點，理想爲使用旋轉 葉片幫浦’電性浸透流幫浦，隔片幫浦，汲取幫浦等者。 旋轉葉片幫浦係爲以馬達使葉片旋轉而進行輸送的構成。 電性浸透流幫浦係爲使用引起電性浸透流現象之二氧化矽 等之燒結多孔體之構成。隔片幫浦係爲經由電磁石或壓電 陶瓷而驅動隔片進行輸送的構成。汲取幫浦係壓迫具有柔 軟性之燃料流路的一部分，汲取燃料而進行輸送的構成。 而在此之中’從驅動電力或尺寸等之観點，更理想爲使用 電性浸透流幫浦或具有壓電磁石之隔片幫浦者。 在如此之構成’收容於燃料收容部42之液體燃料係 經由幫浦44，移送在流路而供給至燃料分配機構40。並 -20- 200950201 且，從燃料分配機構40所釋放之燃料係供給至燃料電池 發電部之陽極25。在燃料電池發電部內，燃料係擴散在陽 極氣體擴散層28，供給至陽極觸媒層27。 另外，如爲進行從燃料分配機構40對於MEA2 1之燃 料供給的構成，亦可作爲取代幫浦4 4而作爲配置燃料遮 斷閥之構成者。對於此情況，燃料遮斷閥乃爲了控制經由 流路之液體燃料的供給所設置之構成。 φ 即使爲以上的構成，可得到與第1實施形態相同的作 用、效果。針對在供給於MEA2 1之液體燃料的蒸氣，亦 可所有供給液體燃料之蒸氣，但一部分乃以液體狀態所供 給之情況，亦可適用本發明者。 更且，有關本發明之電子機器係作爲電源，具備前述 實施型態之燃料電池者，其中，可例示個人電腦或行動電 話等之具有半導體元件之小型的電子機器者。本發明之電 子機器，因具備輸出特性高的燃料電池，故具有小型且安 φ 定之高性能者。 接著，對於本發明，參照實施形態更詳細加以說明。 實施例1 於碳載體之科琴（Ketjen) ECP (商品名、LION公司 製），載持陽極觸媒金屬之Pt-Ru合金（Ru60at . % )， 使用鈉硼氫化物而進行液相還原之後，在800 °C不活性環 境下，進行1小時固溶體化處理，製作陽極觸媒。 接著，將其陽極觸媒，和Nafion溶液DE2020 (商品 -21 - 200950201 名、DuPont公司製）與溶劑（1-丙醇，2-丙醇及甘油）， 將Nafion的含有比例，在0〜80重量％之範圍進行改變加 以混合，調製陽極觸媒淤槳。將所得到之陽極觸媒淤漿， 於成爲陽極氣體擴散層之碳紙（商品名 TGP-H-120、 Toray公司製）之一方的面，使用棒塗加以塗布之後，使 其乾燥，形成陽極觸媒層（厚度180μιη)。 另外，於碳載體之科琴ECP，載持陰極觸媒金屬之Pt ，以與陽極觸媒同樣作爲而製造陰極觸媒。接著，將其陰 極觸媒，和Nafion溶液DE2020及溶劑（1-丙醇，2-丙醇 及甘油），將Nafion的含有比例，以成爲26重量％之調 配比加以混合，調製陰極觸媒淤漿（觸媒金屬之含有比例 7重量％)。將其陰極觸媒淤漿，於成爲陰極氣體擴散層 之碳紙（商品名TGP-H-090、Toray公司製）之一方的面 ，使用棒塗加以塗布之後，使其乾燥，形成陰極觸媒層（ 厚度 60μιη )。 然而，在陰極觸媒層之Nafion的含有比例（26重量 % )係從後述之實施例3的測定結果了解到，在改變在陰 極觸媒層之Nafiori含有比例而測定輸出特性時’輸出密 度的値成爲最大時之含有比例。 接著，作爲質子傳導性之電解質膜，使用Nafion NRE-212CS (商品名、DuPont公司製），將其電解質膜與 前述陽極（陽極氣體擴散層與陽極觸媒層）及陰極（陰極 氣體擴散層與陰極觸媒層），各成爲電解質膜側地加以重 合之後，以加熱温度150°C、壓力30kgf/cm2 ' 5分的條件 -22- 200950201 ，加以噴射，製作mea。然而，電極面積係陽極，陰極 26同時作爲12cm2。 接著，使用如此作爲所製造之MEA，製造圖1所示之 燃料電池，於燃料收容部內，作爲液體燃料而加入純甲醇 ，實際進行發電。並且，在温度250C、相對濕度50%的 環境測定輸出之最大値（最大輸出密度）。 另外，將陽極觸媒及陰極觸媒的金屬比表面積，由以 φ 下所示作爲，經由CO脈衝吸著法而加以測定。即，首先 ，從MEA機械性地剝離陰極氣體擴散層與陽極氣體擴散 層。陰極觸媒層與陽極觸媒層係因殘留於電解質膜側或個 氣體擴散層側之故，個別以刀片削落其殘留之陽極觸媒層 與陰極觸媒層。然而，對於以刀片削落時，對於金屬比表 面積的側定値，呈不產生誤差地，呈不會削落電解質膜或 各氣體擴散層地加以注意。接著，將削落之陽極觸媒層及 陰極觸媒層，以硏鉢輕敲作爲粉末狀，塡充於計量管。對 φ 於測定係使用全自動觸媒氣體吸著量測定裝置BEL-CAT ( 日本BEL公司製），以50°C進行測定。然而，在本測定 ，係因重量測定乃對於所得到之結果帶來影響之重要要素 之故，在CO脈衝吸著量之測定前，經由秤錘矯正爲了重 量測定之電子天秤的同時，進行測定樣品之靜電去除。如 此作爲所測定之陰極觸媒的金屬比表面積乃7.8m2/g。 另外，將如此做爲所求得陽極觸媒之金屬比表面積與 燃料電池的最大輸出（最大輸出密度），對於在陽極觸媒 層之Nafion的含有比例而言作爲曲線。將其圖表示於圖4 -23- 200950201 更且，將燃料電池的最大輸出（最大輸出密度），經 由CO脈衝吸著法所測定之陰極觸媒之金屬比表面積與陽 極觸媒之金屬比表面積的比（以下，稱作陰極/陽極比表 面積比）作爲橫軸而畫曲線。將其圖表示於圖5。更且， 將擴大針對在圖5之陰極/陽極比表面積比乃〇〜10之範圍 的圖表示於圖6。 從圖4的圖表，了解到以下的情況。即，在陽極觸媒 層，從Nafion的含有比例超過40重量％，經由CO脈衝 吸著法所測定之陽極觸媒之金屬比表面積的値乃減少爲 Nafion附著前（Nafion含有比例0重量％ )時的値之50% 以下情況，了解到燃料電池之最大輸出密度則大增加，CO 脈衝吸著量乃成爲檢測界限以下，陰極觸媒之金屬比表面 積乃接近於〇時，最大輸出密度的値乃顯示最大値者。 並且，在陽極觸媒層之Nafion的含有比例乃50重量 %以上，陽極觸媒層之金屬比表面積乃7.5m2/g以下時， 了解到顯示最大輸出密度乃高的1 8m W/cm2以上的値。然 而，因在此時之陰極觸媒層之Nafion的含有比例乃26重 量％以上，陰極觸媒層之金屬比表面積乃成爲7.8m2/g， 7.5m2/g以下，故確認到陰極觸媒之金屬比表面積乃變爲 較陽極觸媒之金屬比表面積爲大者。 另外，從圖5及圖6的圖表，了解到陰極/陽極比表 面積比乃4以上時’顯示特別高之輸出特性（輸出密度） 者。 -24- 200950201 實施例2 作爲碳載體，取代科琴ECP而使用火神（Vulcan ) XC72 (商品名、Cabot公司製），以與實施例1同樣作爲 而製造陽極觸媒。 接著，將其陽極觸媒和Nafion溶液DE2020與溶劑（ 1-丙醇，2-丙醇及甘油），將Nafion的含有比例，在〇〜 U 50重量％之範圍進行改變加以混合，調製陽極觸媒淤漿。 之後，將所得到之陽極觸媒淤漿，於成爲陽極氣體擴散層 之碳紙（商品名TGP-H-120 )之一方的面，使用棒塗加以 塗布而使其乾燥，形成陽極觸媒層（厚度180 μηι)。 另外，作爲碳載體，取代科琴ECP而使用火神（ Vulcan) XC72，以與實施例1同樣作爲而製造陰極觸媒。 使用所得到之陰極觸媒，以與實施例1同樣作爲而製造陰 極觸媒淤漿（Nafion含有比例20重量％，媒層金屬之含 φ 有比例9重量％ )。將其陰極觸媒淤漿，於碳紙（商品名 TGP-H-0 90 )之一方的面，使用棒塗加以塗布而使其乾燥 ，形成陰極觸媒層（厚度50μηι)。 然而，在陰極觸媒層之Nafion的含有比例（20重量 %)係從後述之實施例4的測定結果了解到，在改變在陰 極觸媒層之Nafion含有比例而測定輸出特性時，最大輸 出密度的値成爲最大時之含有比例。 接著，在重合質子傳導性之電解質膜之Nafion NRE-212CS與前述陽極（陽極氣體擴散層與陽極觸媒層）及陰 -25- 200950201 極（陰極氣體擴散層與陰極觸媒層）之後，以與實施例1 同樣作爲而製作MEA。 接著，使用如此作爲所製造之MEA，製造圖1所示之 燃料電池，於燃料收容部內，作爲液體燃料而加入純甲醇 ’實際進行發電。並且，在温度25 °C、相對濕度50 %的環 境測定輸出之最大値（最大輸出密度）。 另外，從MEA個別以刀片削落陽極觸媒層及陰極觸 媒層之後，將以硏鉢輕敲作爲粉末狀者，塡充於計量管， 與實施例1同樣地經由CO脈衝吸著法而測定陽極觸媒及 陰極觸媒的金屬比表面積。如此作爲所測定之陰極觸媒的 金屬比表面積乃5m2/g。 將如此做爲所求得陽極觸媒之金屬比表面積，及燃料 電池的最大輸出（最大輸出密度），對於在陽極觸媒層之 Nafion的含有比例而言作爲曲線。將其圖表示於圖7。 從圖7的圖表，了解到以下的情況。即，在陽極觸媒 層，從Nafion的含有比例超過20重量％，經由CO脈衝 吸著法所測定之陽極觸媒之金屬比表面積的値乃減少爲 Nafiori附著前之2/3以下情況，了解到燃料電池之最大輸 出密度則大增加’ CO脈衝吸著量乃成爲檢測界限以下， 陽極觸媒之金屬比表面積乃接近於0時，最大輸出密度的 値乃顯示最大値者。 並且，在陽極觸媒層之Nafion的含有比例乃40重量 %以上，陽極觸媒層之金屬比表面積乃1 m2/g以下時，了 解到顯币最大輸出密度乃高的20mW/cm2以上的値。然而 -26- 200950201 ，此時之陰極觸媒之金屬比表面積乃成爲5m2/g，確認到 陰極觸媒之金屬比表面積乃變爲較陽極觸媒之金屬比表面 積爲大者。 實施例3 作爲碳載體而使用科琴ECP，以與實施例1同樣作爲 而製作陽極觸媒之後，將其陰極觸媒，和Nafion溶液 0 DE2020及溶劑（1-丙醇，2-丙醇及甘油），將Nafion的 含有比例，以成爲60重量％之調配比加以混合，調製陰極 觸媒淤漿（觸媒金屬之含有比例3.5重量％)。接著，將 其陽極觸媒淤漿，於成爲陽極氣體擴散層之碳紙（商品名 TGP-H-120 )之一方的面，使用棒塗加以塗布而使其乾燥 ，形成陽極觸媒層（厚度180μπι)。 然而，在陽極觸媒層之Nafion的含有比例（60重量 %)係從前述實施例1的測定結果了解到，在改變在陽極 φ 觸媒層之Nafion含有比例而測定輸出特性時，最大輸出 密度的値成爲最大之含有比例。 另外，於碳載持體之科琴ECP，將載持陰極觸媒金屬 之Pt所得到之陰極觸媒，和Nafion溶液DE2020與溶劑 (1-丙醇，2 -丙醇及甘油），將Nafion的含有比例，在0 〜40重量％之範圍進行改變加以混合，調製陰極觸媒淤漿 。將所得到之陰極觸媒淤漿，於成爲陰極氣體擴散層之碳 紙（商品名TGP-H-090 )之一方的面，使用棒塗加以塗布 而使其乾燥，形成陰極觸媒層（厚度60 μιη)。 -27- 200950201 接著，在重合質子傳導性之電解質膜之Nafion NRE-212CS與前述陽極（陽極氣體擴散層與陽極觸媒層）及陰 極（陰極氣體擴散層與陰極觸媒層）之後，以與實施例1 同樣作爲而製作MEA。 接著’使用如此作爲所製造之MEA，製造圖1所示之 燃料電池，於燃料收容部內，作爲液體燃料而加入純甲醇 ’實際進行發電。並且，在温度25 °C、相對濕度50%的環 境測定輸出之最大値（最大輸出密度）。 另外，從MEA個別以刀片削落陽極觸媒層及陰極觸 媒層之後，將以硏鉢輕敲作爲粉末狀者，塡充於計量管， 與實施例1同樣地經由CO脈衝吸著法而測定陽極觸媒及 陰極觸媒的金屬比表面積。如此作爲所測定之陽極觸媒的 金屬比表面積乃lm2/g。 另外，將如此做爲所求得陰極觸媒之金屬比表面積與 燃料電池的最大輸出（最大輸出密度），對於在陰極觸媒 層之Nafion的含有比例而言作爲曲線。將其圖表示於圖8 〇 從圖8的圖表，了解到以下的情況。即，在陰極觸媒 層，在Nafion的含有比例超過20重量％，經由CO脈衝 吸著法所測定之陰極觸媒之金屬比表面積的値乃開始減少 時，成爲逐渐得到輸出，陰極觸媒之金屬比表面積乃在比 較於Nafion附著前，約減少20%時，了解到最大輸出密 度的値乃顯示最大値者。並且，陰極觸媒之金屬比表面積 乃成爲Nafion附著前之50%以下時，了解到幾乎無法得 -28- 200950201 到輸出者。 另外，在陰極觸媒層之Nafion的含有比例乃25重量 %，經由CO脈衝吸著法所測定之陰極觸媒層之金屬比表 面積乃 8m2/g時，了解到顯示最大輸出密度乃高的 18mW/cm2以上的値。然而，因在此時之陽極觸媒層之 Nafion的含有比例乃60重量％，陽極觸媒層之金屬比表 面積乃1 m2/g以下，故確認到陰極/陽極比表面積比乃成爲 4以上者。 實施例4 作爲碳載體，取代科琴ECP而使用火神（Vulcan ) XC 72，以與實施例3同樣作爲而製造陽極觸媒。之後，將 其陽極觸媒，和Nafion溶液DE2020與溶劑（卜丙醇，2-丙醇及甘油），以Nafion的含有比例成爲40重量％之調 配比加以混合，調製陽極觸媒淤漿。接著’將其陽極觸媒 ❹ 淤漿，於成爲陽極氣體擴散層之碳紙（商品名TGP-H-120 )之一方的面，使用棒塗加以塗布而使其乾燥，形成陽極 觸媒層（厚度180μπι)。 然而，在其陽極觸媒層之Nafion的含有比例（40重 量％ )係從前述實施例2的測定結果了解到’在改變在陽 極觸媒層之Nafion含有比例而測定輸出特性時’最大輸 出密度的値成爲最大之含有比例。 另外，作爲碳載體，取代科琴ECP而使用火神（ Vulcan) XC72，以與實施例1同樣作爲而製造陰極觸媒。 -29- 200950201 將所得到之陰極觸媒，和Nafion溶液DE2020與溶劑（卜 丙醇，2.丙醇及甘油），將Nafion的含有比例’在〇〜 重量％之範圍進行改變加以混合，調製陰極觸媒淤漿。將 所得到之陰極觸媒淤漿，於成爲陰極氣體擴散層之碳紙（ 商品名TGP-H-090)之一方的面，使用棒塗加以塗布而使 其乾燥，形成陰極觸媒層（厚度60 μιη)。 接著，在重合質子傳導性之電解質膜之Nafion NRE-212CS與前述陽極（陽極氣體擴散層與陽極觸媒層）及陰 @ 極（陰極氣體擴散層與陰極觸媒層）之後，以與實施例1 同樣作爲而製作MEA。 接著，使用如此作爲所製造之MEA，製造圖1所示之 燃料電池，於燃料收容部內，作爲液體燃料而加入純甲醇 ，實際進行發電。並且，在温度25 °C、相對濕度50%的環 境測定輸出之最大値（最大輸出密度）。 另外，從MEA個別以刀片削落陽極觸媒層及陰極觸 媒層之後，將以硏鉢輕敲作爲粉末狀者，塡充於計量管， ◎ 與實施例1同樣地經由CO脈衝吸著法而測定陽極觸媒及 陰極觸媒的金屬比表面積。如此作爲所測定之陽極觸媒的 金屬比表面積乃1 m2/g。 另外，將如此做爲所求得陰極觸媒之金屬比表面積， 以及燃料電池的最大輸出（最大輸出密度），對於在陰極 觸媒層之Nafion的含有比例而言作爲曲線。將其圖表示 於圖9。 從圖9的圖表了解到，在陰極觸媒層，在Nafion的 -30- 200950201 含有比例超過1 〇重量％，經由CO脈衝吸著法所測定之陰 極觸媒之金屬比表面積的値乃開始減少時，開始逐漸出現 輸出，陰極觸媒之金屬比表面積乃在比較於Nafion附著 前，約減少10%時，最大輸出密度的値乃顯示最大値者。 另外，在陰極觸媒層之Nafion的含有比例乃20重量 %，經由CO脈衝吸著法所測定之陰極觸媒層之金屬比表 面積乃 5m2/g時，了解到顯示最大輸出密度乃高的 ❹ 20mW/cm2以上的値。然而，因在此時之陽極觸媒層之金 屬比表面積乃1 m2/g以下，故確認到陰極/陽極比表面積比 乃成爲4以上者。 然而，本發明並非只侷限於上述實施型態者，而在實 施階段中’在不脫離其主旨的範圍，可將構成要素進行變 形而作具體化。另外，經由揭示於上述實施型態之複數之 構成要素的適宜組合，可形成各種發明。例如，亦可從實 施型態所示之全構成要素消除幾個構成要素。更且，亦可 〇 適當組合不同實施型態之構成要素。 【圖式簡單說明】 圖1乃顯示關於本發明之燃料電池的第1實施型態之 構成縱剖面圖。 圖2乃顯示關於本發明之燃料電池的第2實施型態之 構成縱剖面圖。 圖3乃顯示本發明之第2實施形態的燃料分配機構之 斜視圖。 -31 - 200950201 圖4乃在實施例1，將陽極觸媒之金屬比表面積與燃 料電池的最大輸出，對於納菲薄膜的含有比例而言作爲曲 線的圖表。 圖5乃在實施例1，令燃料電池的最大輸出（最大輸 出密度），將陰極/陽極比表面積比作爲橫軸而作爲曲線 的圖表。 圖6乃擴大顯示針對在圖5之陰極/陽極比表面積比 乃〇〜10之範圍的圖表。 圖7乃在實施例2，將陽極觸媒之金屬比表面積與燃 料電池的最大輸出，對於納菲薄膜的含有比例而言作爲曲 線的圖表。 圖8乃在實施例3，將陰極觸媒之金屬比表面積與燃 料電池的最大輸出，對於納菲薄膜的含有比例而言作爲曲 線的圖表。 圖9乃在實施例4，將陰極觸媒之金屬比表面積與燃 料電池的最大輸出，對於納菲薄膜的含有比例而言作爲曲 線的圖表。 【主要元件符號說明】 1 :燃料電池 2 :陽極觸媒層 3 :陽極氣體擴散層 4 :陽極 5 :陰極觸媒層 -32- 200950201 6 :陰極氣體擴散層 7 :陰極 8 :質子傳導性的電解質膜 9 :陽極導電層 10 :陰極導電層 1 2 :燃料收容室 1 3 :氣液分離層 1 5 :保濕層 16 :蓋板200950201 VI. Description of the Invention: [Technical Field] The present invention relates to a fuel cell and an electronic device, and more particularly to a fuel cell excellent in output characteristics for using a high-concentration fuel, and an electronic device using the #fuel cell. [Prior Art] φ In recent years, various electronic devices such as electric notebook computers and mobile phones have been miniaturized with the development of semiconductor technology, and attempts have been made to use fuel cells for power sources such as small machines. On the other hand, the fuel cell can generate electricity only by supplying fuel and oxidant, and has the advantage of continuously exchanging fuel to continuously generate electricity. If it can be miniaturized, it can be said that it is extremely advantageous for the operation of a small electronic device. In particular, a direct methanol fuel cell (DMFC: Direct Methanol Fuel Cell) uses a high energy density methanol for fuel, and can take current directly from the methanol, on the electrode catalyst, φ and without the need for a reformer, there is It is expected that the power supply of a small electronic device can be used as a fuel supply method for the DMFC. It is known that there is a gas supply type in which a liquid fuel is vaporized into a DMFC, such as a blower box, or a direct pump. The liquid fuel is fed into the active mode of the liquid supply type in the DMFC, and the liquid fuel in the fuel containing portion is used as a passive method of vaporizing the internal gasification type or the like in the DMFC. Among these, the passive mode of the internal gasification type or the like is particularly advantageous for miniaturization of the DMFC. As an internal vaporization type DMFC, for example, a membrane electrode assembly (MEA) having a proton conductive electrolyte membrane disposed between a cathode layer 200950201 (air electrode) catalyst layer and an anode (fuel electrode) catalyst layer is known. : Membrane Electrode Assembly), and a liquid fuel storage chamber, and a fuel gasification layer formed between the membrane electrode assembly and the liquid fuel storage chamber, and only the gas-liquid separation membrane through which the vaporized component of the liquid fuel permeates The configuration (for example, refer to Patent Document 1). However, in the conventional fuel cell as the internal vaporization type DMFC, when a high-concentration fuel having a concentration of 50 mol% or more is used, there is a case where sufficient output characteristics cannot be obtained. For example, when methanol is used as the fuel, an internal reforming reaction of methanol as shown in the following reaction formula (1) is carried out in the anode catalyst layer, and a reaction formula such as the following reaction formula is carried out in the cathode catalyst layer ( 2) The reaction shown to produce water. CH30H + H20^ C〇2 + 6H + + 6e> (1) (3/2) 〇2 + 6H + + 6e*^ 3 Η2〇μ ( 2 ) As a fuel, a high concentration aqueous methanol solution or pure methanol is used. In the case where the water contained in the fuel is little or not contained at all, the water required for the internal reforming reaction is easily insufficient. However, although water is generated in the cathode catalyst layer, it is difficult to ensure the water required for the internal reforming reaction by the water generated in the cathode catalyst layer. Therefore, when a high concentration methanol aqueous solution or pure methanol is used, the reaction resistance of the internal reforming reaction becomes high, and there is a problem that superior output characteristics are not necessarily obtained. [Patent Document 1] International Publication No. 2005/1 1 2 1 72-6-1-200950201 SUMMARY OF THE INVENTION The present invention has been made to solve such problems, and an object thereof is to improve a fuel cell using a high-concentration fuel. Output characteristics. A fuel cell according to a first aspect of the present invention is characterized in that it comprises an anode catalyst layer containing an anode catalyst and an electrolyte having proton conductivity, and a cathode catalyst layer containing a cathode catalyst and an electrolyte having proton conductivity, and An electrolyte membrane ′ that sandwiches φ between the anode catalyst layer and the cathode catalyst layer and a fuel cell that supplies a fuel to the anode catalyst layer are characterized by the cathode catalyst described above. The specific surface area of the metal measured by the CO pulse sorption method is larger than the specific surface area of the metal measured by the CO pulse sorption method of the anode catalyst. An electronic device according to a second aspect of the present invention is characterized in that the fuel cell of the first aspect is used as a power source. According to the fuel cell of the present invention, the specific surface area of the metal measured by the CO pulse φ sorption method of the cathode catalyst is similarly caused by the metal specific surface area of the anode catalyst measured by the CO pulse sorption method. It constitutes 'the output characteristics of fuel cells that use high-concentration fuels. Further, according to the electronic device of the present invention, since the fuel cell having such a high output characteristic is provided, it is small and can exhibit stable performance. [Embodiment] Hereinafter, an internal vaporization type direct methanol fuel cell (DMFC) will be described by way of example in the embodiment of the present invention. 200950201 The fuel cell 1 of the first embodiment has an anode 4 formed of an anode (fuel electrode) catalyst layer 2 and an anode gas diffusion layer 3, and is contacted by a cathode (air electrode) as shown in FIG. a cathode electrode 7 formed by the dielectric layer 5 and the cathode gas diffusion layer 6, and a membrane electrode assembly of the electrolyte membrane 8 of proton (hydrogen ion) conductivity sandwiched between the anode catalyst layer 2 and the cathode catalyst layer 5 ( MEA) 9. Both the anode catalyst layer 2 and the cathode catalyst layer 5 contain a catalyst and a proton-conducting electrolyte. The anode catalyst contained in the anode catalyst layer 2 and the cathode catalyst layer contained in the cathode catalyst layer 5 may, for example, be a single metal such as Pt, Ru, Rh, Ir, Os, Pd or the like of a platinum group element. An alloy containing such a platinum group element. Specifically, as the anode catalyst, an alloy such as Pt-Ru or Pt-Mo having a resistance to methanol or carbon monoxide is used, and an alloy such as Pt or Pt-Ni is used as the cathode catalyst layer. It is better, but it is not limited to this. Further, it is also possible to use a carrier supporting the fine particles of the catalyst on the conductive carrier. As the conductive carrier, particulate carbon or fibrous carbon such as activated carbon or graphite is used. In the present invention, the specific surface area of the metal measured by the CO pulse sorption method of the cathode catalyst or the anode catalyst means: the specific surface area of the metal per pulse of the unit volume. Therefore, the weight of each electrolyte containing the proton conductivity of the catalyst layer is corrected. The electrolyte system containing the proton conductivity of the anode catalyst layer 2 and the cathode catalyst layer 5 simultaneously with these metal catalysts is not particularly limited. Examples of the proton conductive electrolyte include a fluorocarbon resin (perfluorocarbon) having a sulfonate group of -8 to 200950201, such as Nafion (trade name, manufactured by DuPont) or Flemion (trade name, manufactured by Asahi Glass Co., Ltd.). a polymer) is an organic/inorganic hybrid polymer in which a mineral acid such as phosphoric acid is doped with a hydrocarbon-based polymer compound, and a part of which is replaced by a proton-conductive functional group, and is impregnated with a phosphoric acid solution or a polymer matrix. A polymer electrolyte such as a proton conductor of a sulfuric acid solution. Further, in these catalyst layers, the specific surface area of the metal measured by the CO pulse sorption method of the cathode catalyst is similarly larger than the specific surface area of the metal measured by the ❹CO pulse sorption method via the anode catalyst. In order to obtain higher output characteristics (output density), the metal specific surface area of the cathode catalyst is preferably 4 times or more of the specific surface area of the anode catalyst. Further, the specific surface area of the metal measured by the CO pulse sorption method of the cathode catalyst is preferably 5 m 2 /g or more, and the metal specific surface area of the anode catalyst is preferably 1 m 2 /g or less. However, the CO pulse sorption method is based on the metal particles present on the surface, intermittently injecting a quantitative amount of CO (gas), and the difference between the amount of CO that is stably dissolved and the amount of CO that starts to be absorbed is used as CO suction. The method of measuring the amount. According to this method, the exposed surface area per unit mass of the metal catalyst can be obtained as the specific surface area. Further, the specific surface area measurement of the catalytic metal by such a CO pulse sorption method can be carried out in a fuel cell which has been assembled. In other words, the MEA taken out from the product of the fuel cell is individually cut by the blade and the cathode catalyst layer and the cathode catalyst layer are cut into powder, and each of the MEA is filled with a measuring tube of the CO pulse sorption amount measuring device. Inside. Further, the C Ο pulse sorption amount is measured at a specific temperature (e.g., 500 ° C) to determine the specific surface area of the catalytic metal. -9- 200950201 The method of changing the specific surface area of the catalytic metal in the anode catalyst layer 2 and the cathode catalyst layer 5 is based on (1) adjusting the electrolyte of the catalyst and proton conductivity constituting the catalyst layer. a method of proportioning, (2) a method of changing the kind of the conductive carrier carrying carbon such as a catalyst metal, (3) changing the energy imparted when the catalyst slurry is stirred, or (4) changing the catalyst A method of drying the slurry after application of the slurry, and the like. Here, the energy supplied when the catalyst slurry is stirred is stirred and pulverized by, for example, a collision between the stirring blade and the catalyst slurry, and becomes a product of the rotation speed (the number of weeks) of the stirring blade and the stirring time. The greater the energy, the greater the specific surface area of the metal. Further, the slower the drying speed after application of the catalyst slurry, the larger the specific surface area of the metal. In the first embodiment of the present invention, the anode gas diffusion layer 3 is laminated on the anode catalyst layer 2 thus constituted, and the cathode gas diffusion layer 6 is laminated on the cathode catalyst layer 5. The anode gas diffusion layer 3 is responsible for uniformly supplying the fuel to the anode catalyst layer 2 while also acting as a current collector having the anode catalyst layer 2. The cathode gas diffusion layer 6 serves to uniformly supply the oxidant to the cathode catalyst layer 5 while also acting as a current collector having the cathode catalyst layer 5. These anode gas diffusion layers 3 and cathode gas diffusion layers 6 are formed, for example, via carbon paper. Further, the anode gas diffusion layer 3 is laminated with the anode conductive layer 1A, and the cathode gas diffusion layer 6 is laminated with the cathode conductive layer u. As the anode conductive layer 10 and the cathode conductive layer 11, for example, a porous film (for example, mesh) or a case made of a conductive metal material such as gold or a chain, or conductivity for stainless steel (SUS) or the like can be used. Metal material, coated gold, etc. 200950201 Composite of good conductive metal, etc. A proton conductive electrolyte membrane 8 is interposed between the anode catalyst layer 2 and the cathode catalyst layer 5. The proton conductive material constituting the electrolyte membrane 8 is, for example, a fluorocarbon resin (perfluorocarbon polymer) having a sulfonic acid group such as Nafion or Flemion, and a hydrocarbon resin having a sulfonic acid group. A material, or an inorganic material such as tungstic acid or phosphotungstic acid. However, the 'proton conductive electrolyte membrane 8 is not limited to the composition ❿ between the proton conductive electrolyte membrane 8 and the anode conductive layer 10, and is disposed around the anode catalyst layer 2 and the anode gas diffusion layer 3 There is, for example, a sealing material 12 having a U-shaped cross section and a rectangular frame shape. Further, between the proton conductive electrolyte membrane 8 and the cathode conductive layer 11, a seal member 12 having the same shape is provided around the cathode catalyst layer 5 and the cathode gas diffusion layer 6. These seal members 12 are configured to prevent fuel leakage from ME A9 and oxidant leakage.燃料 A fuel containing chamber 13 is disposed on the anode 4 side of the MEA 9. The liquid fuel F is housed in the fuel containing portion 13. The liquid fuel F is preferably an aqueous methanol solution or a pure methanol, but is not necessarily limited thereto, and may be, for example, an ethanol fuel such as an aqueous ethanol solution or pure ethanol, an aqueous solution of propanol or pure propanol. A propanol fuel, an ethylene glycol aqueous solution or a glycol fuel such as pure ethylene glycol, dimethyl ether, formic acid, and other fuels. Further, the liquid fuel F is preferably used in an amount of 50 mol% or more, but is not necessarily limited. The open end of the fuel containing chamber 13 is arbitrarily disposed, for example, with a vaporized component that only transmits the liquid fuel F, and -11 - 200950201 is a gas-liquid separation membrane 14 that does not easily pass the liquid component. Here, the gasification component of the liquid fuel F means that the case where pure methanol is used as the liquid fuel F means the gasification component of methanol, and the case where the methanol aqueous solution is used as the liquid fuel means that the methanol is vaporized. a mixture of components and water vaporized components. A frame 15 made of resin is disposed between the gas-liquid separation membranes 14 of the MEA 9. The space surrounded by the frame 15 functions as a vaporized fuel storage chamber (so-called vapor accumulation) that is temporarily stored in the vaporized fuel that is diffused in the gas-liquid separation membrane 14. The permeated fuel amount suppressing effect of the gas-liquid separation membrane 14 and the vaporized fuel storage chamber controls the inflow of the vaporized fuel for the ME A9, and further controls the generation of the fuel crossover. However, the frame body 15 has a planar shape in a lattice shape, and is also responsible for suppressing deformation by pressing ME A9 and reducing contact resistance. Therefore, the frame 15 is composed of, for example, an engineering plastic superior in resistance or strength to, for example, a polydiether ketone (trade name of PEEK: Victrex). On the other hand, the moisture retaining layer 16 is arbitrarily laminated and disposed on the cathode conductive layer 1 of the MEA 9. The moisturizing plate 16 has a function of preventing evapotranspiration of water generated in the cathode catalyst layer 5, and also has air uniformly introduced into the cathode gas diffusion layer 16 as an oxidant (air) for promoting the cathode catalyst layer 5. Uniform diffusion of the function of the subsidized diffusion layer. On the moisture-retaining layer 16, a cover plate (surface layer) 17 of a plurality of air introduction ports 17a for introducing a control gas for introducing an oxidizing agent is laminated. The cover plate 17 also serves to pressurize the ME A9 or the moisture retaining layer 16 to enhance the adhesion of the layers, for example, as a metal plate of SUS 3 04. -12- 200950201 In such a fuel cell 1, power generation is performed as follows. First, the vaporized component of the methanol aqueous solution or the pure methanol of the liquid fuel F in the fuel storage chamber 13 is diffused in the gas-liquid separation membrane 14 and housed in the vaporized fuel storage chamber surrounded by the casing 15. The vaporized component of the liquid fuel F accommodated in the vaporized fuel storage chamber is slowly diffused in the anode gas diffusion layer 1A, and is supplied to the anode catalyst layer 2 by the anode gas diffusion layer 3. Further, the vaporization component of the liquid fuel F supplied to the anode catalyst layer 2 generates an internal reforming reaction of methanol represented by the following reaction φ formula (1). CH30H + H20 - C〇2 + 6H + + 6e) (1) Here, when pure methanol is used as the liquid fuel F, although there is no supply of water from the liquid fuel F, in this case, the use is contained in The proton conductive electrolyte membrane 8 or the water of the anode catalyst layer 2 or the water generated by the cathode catalyst layer 5 undergoes an internal reforming reaction. The proton (H+) generated by the internal reforming reaction of φ reaches the cathode catalyst layer 5 via the proton-conducting electrolyte membrane 8. On the other hand, the air introduced from the air introduction port 17a of the cover plate 17 is sequentially diffused to the moisture retaining layer 16, the cathode conductive layer 11, and the cathode gas diffusion layer 6' to be supplied to the cathode catalyst layer 5. In the cathode catalyst layer 5, water is produced by the reaction represented by the following reaction formula (1). That is, a power generation reaction is generated. (3/2) 〇2 + 6H + + 6e, -3 Η2〇μ ( 2) -13- 200950201 When the power generation reaction proceeds, the water generated in the cathode catalyst layer 5 is reached through the above reaction. The evapotranspiration of the water reached by the moisturizing layer 16 increases the amount of moisture retained as the medium layer 5. Further, the amount of cathode retention is changed to the amount of moisture retained by the anode catalyst layer 2 by the phenomenon of impregnation, which promotes the movement from the cathode catalyst layer 5 to the anode. By the movement of such water, the internal output characteristics are promoted, and the high output characteristics are maintained for a long period of time. When the water is moved from the cathode catalyst layer 2 via the immersion pressure phenomenon, the cathode catalyst layer 5 is easily caused to pass through the water. The occlusion of water. Therefore, in the case of the coating of the cathode catalyst via the proton-conducting electrolyte, the metal specific surface area of 5 m 2 /g or more is compared with the cathode catalyst layer 5 and the cathode catalyst layer 5 is relatively easy to cause It is preferable that the proton conductivity of water deficiency is 75% or more of the coating system via the proton conductive medium contained in the anode catalyst layer 2, and it is preferable to have an area of 10 m 2 /g. In the embodiment in which the above-described conditions are combined, the formation layer 5 is less likely to cause clogging via water, and the water from the cathode contact catalyst layer 2 is favorably maintained in the internal reforming reaction after the anode catalyst, so that a high output can be obtained. It is produced by the method for producing a fuel cell according to the first embodiment of the present invention. First, the anode catalyst, the anti-wet layer 16 shown by ζ (2). As a result of the hindrance, the amount of water in the cathode contact layer 5 is large, and the water is reformed by the polar catalyst layer 2 to maintain the lift. It is preferable that the amount of the layer 5 to the anode catalyst is increased and the cathode catalyst layer 5 is 50% or less. In addition, the amount of anode water contact retention decreases. Therefore, in the ratio of the metal to the anode of the electrolyte, the cathode catalyst layer 5 is moved to the anode: the layer 2' is used in the (output density) I, and can be used, for example, as shown below. 200950201 was manufactured as a. That is, a conductive carrier such as carbon is brought into contact with an aqueous solution or slurry containing a compound constituting each metal component of platinum or a platinum alloy, and the metal compound or its ions are sorbed or impregnated on the conductive carrier. Further, while stirring the slurry at a high speed, slowly lowering a suitable fixing agent such as a diluted solution of sodium hydroxide, ammonia, hydrazine, formic acid, fumarin, methanol, ethanol, propanol or the like as a metal salt, or As a part of the reduced metal fine particles, it is carried on the conductive carrier. Further, drying is carried out, and Φ is produced by heat treatment in a reducing gas or an inert gas atmosphere. The obtained anode catalyst is mixed with a suspension of a proton conductive electrolyte, and the viscosity is adjusted with an alcohol such as methanol, ethanol or propanol, and glycerin or ethylene glycol to form a deposit for the anode catalyst layer. Slurry (hereinafter, represents an anode catalyst slurry). Here, in the prepared anode catalyst slurry, the catalyst constituting the anode catalyst layer 2 can be changed by changing the ratio of the anode catalyst to the proton-passing electrolyte, or the energy imparted during stirring. The specific surface area of the metal. Then, the obtained anode catalyst slurry is applied to a conductive porous substrate such as carbon paper or carbon cloth to be the anode gas diffusion layer 3 by a suction filtration method, a spray method, a roll coating method, a bar coating method, or the like. The material is dried and used as the anode catalyst layer 2. However, by doing so, the anode catalyst layer 2 is formed on the anode gas diffusion layer 3 to form the anode 4. Here, the metal specific surface area of the catalyst constituting the anode catalyst layer 2 can be changed by changing the drying speed after coating of the anode catalyst slurry. In addition, a cathode catalyst layer 5 is formed. That is, the cathode catalyst is produced in the same manner as the anode catalyst described in the above -15-200950201, and the obtained cathode catalyst 'mixes with the suspension of the proton conductive electrolyte to methanol, ethanol 'propanol The alcohol is adjusted, and the viscosity is adjusted as glycerin or ethylene glycol, and is used as a slurry for forming a cathode catalyst layer (hereinafter, a cathode catalyst slurry). Here, in the modulation of the cathode catalyst slurry, the metal constituting the catalyst of the cathode catalyst layer 5 can be changed by changing the ratio of the catalyst of the cathode catalyst to the proton-passing electrolyte or the energy imparted during stirring. Specific surface area. Then, the obtained cathode catalyst slurry is applied to a conductive porous substrate such as carbon paper or carbon cloth to be the cathode gas diffusion layer 6 by a suction filtration method, a spray method, a roll coating method, a bar coating method or the like. The material is dried and used as the cathode catalyst layer 5. As a result, the cathode catalyst layer 5 is formed on the cathode gas diffusion layer 6 to form the cathode 7. Here, the metal specific surface area of the catalyst constituting the negative catalyst layer 5 can be changed by changing the drying speed after coating of the cathode catalyst slurry. Then, the proton conductive electrolyte membrane 8 is sandwiched between the obtained anode 4 and the cathode 7, and then the membrane electrode assembly (MEA) 9 is produced by a roller or a jet heat. Further, the anode conductive layer 10 and the cathode conductive layer 11 are laminated on the MEA9. Then, the gas-liquid separation film 14 is sequentially superposed on the fuel containing chamber 13, and the EMA9 of the anode conductive layer 10 and the cathode conductive layer 11, the moisture-repellent layer 16, and the cover plate (surface layer) 17 are laminated as the integration time. The fuel cell 1 of the first embodiment can be manufactured. In the above description, the configuration of the fuel cell has been made in the lower part of the membrane electrode assembly (MEA) 9 and has the structure of the fuel storage chamber 13 200950201, but it may be arranged between the fuel storage chamber and the mea. There is a flow path, and a structure in which fuel is supplied by the flow path. In addition, as for the fuel cell main body, a passive fuel cell is described as an example. However, for an active fuel cell, a semi-passive fuel cell such as a pump or the like is used for a fuel supply or the like. The inventors are applicable. The semi-passive type fuel cell is used for the power generation reaction from the fuel accommodating chamber to the MEA, and then returns to the fuel 0 storage chamber without circulating. The semi-passive type fuel cell is a case where the fuel is never recycled, and unlike the conventional active method, it does not constitute a miniaturization of the device. In addition, since the pump is used for the supply of fuel, it is also different from the pure passive mode of the internal gasification type, and the fuel cell is called a semi-passive mode. Fig. 2 is a longitudinal sectional view showing the configuration of a semi-passive fuel cell according to a second embodiment of the present invention. The fuel cell 20 includes a membrane electrode assembly (φ ME A ) 21 as a power generation unit, a cathode conductive layer 22 as a current collector, and an anode conductive layer 23 ME A21 in which a proton conductive electrolyte membrane 24 is sandwiched therebetween. The anode 25 and the cathode 26 are integrally formed by hot pressing on both sides. The anode 25 has an anode catalyst layer 27 on the electrolyte membrane 24 side and an anode gas diffusion layer 28 on the outside. The cathode 26 has a cathode catalyst layer 29 on the side of the electrolyte membrane 24 and a cathode gas diffusion layer 30 on the outside. Further, in such ME A21, the anode catalyst layer 27 and the cathode catalyst layer 29 are configured in the same manner as in the first embodiment. That is, the 比 of the metal specific surface area of the cathode catalyst of the cathode layer 17-200950201 (measured by the CO pulse sorption method) is changed to the metal specific surface area of the anode catalyst of the anode catalyst layer 27. The enthalpy is large (measured by the CO pulse sorption method). However, in order to obtain higher output characteristics (output density), the specific surface area of the cathode catalyst is preferably 4 times or more the mass of the surface area of the anode catalyst. Further, the metal specific surface area of the cathode catalyst is preferably 5 m 2 /g or more, and the metal specific surface area of the anode catalyst is preferably 1 m 2 /g or less. The anode gas diffusion layer 28 is disposed in contact with the anode conductive layer 22, and the cathode gas diffusion layer 30 is disposed in contact with the cathode conductive layer 23. By the anode conductive layer 22 and the cathode conductive layer 23, the electric power generated by the power generation unit is output to a load (not shown). Further, the fuel cell 20 is provided with a cover 30 and a fuel supply means (fuel distribution means) 40. Between the proton conductive electrolyte membrane 24 and the cap plate 30 and the fuel distribution mechanism 40, a sealing material 31 such as a rubber ring of 0 is interposed, thereby preventing fuel leakage or oxidant from the fuel cell power generation portion. leakage. The cover plate 30 has an opening (air guide port) 30a for taking in air of the oxidizing agent. A moisture-retaining layer or a surface layer is disposed between the cover 30 and the cathode 2 as necessary. The moisturizing layer is impregnated with a portion of the water generated in the cathode catalyst layer 29 to control the evapotranspiration of the water while promoting the uniform diffusion of the oxidant (air) to the cathode catalyst layer 29. The surface layer is an air inlet for adjusting the amount of air taken in, and has a plurality of air inlets adjusted in accordance with the introduction of air. -18- 200950201 A fuel distribution mechanism 40 as a fuel supply means is disposed on the anode 25 side of the MEA 21. The fuel distribution mechanism 4 is connected to the fuel accommodating portion 42 as a fuel storage means by a flow path 41 such as a piping material. The fuel accommodating portion 42 accommodates the liquid fuel corresponding to the fuel cell. The fuel distribution mechanism 40 introduces fuel from the fuel accommodating portion 42 via the flow path 41. The flow path 41 is not limited to the configuration of a pipe separate from the fuel distribution mechanism 4A or the fuel containing portion 42. For example, when the laminated fuel distribution mechanism 40 and the fuel accommodating portion 42 are integrated, they may be a flow path connecting the liquid fuels. The fuel distribution mechanism 4 may be connected to the fuel containing portion 42 by the flow path 41. As shown in FIG. 3, the fuel distribution mechanism 40 includes at least one fuel injection port 43a through which the fuel flows through the flow path 41, and a plurality of fuel discharge ports 43b that discharge the liquid fuel or its vaporization component. Fuel distribution plate 43. As shown in Fig. 2, the inside of the fuel distribution plate 43 is provided with a gap portion 43c which is a passage for the fuel guided from the fuel injection port 43a. The plurality of fuel discharge ports 43b are each directly connected to the gap portion 43c. The fuel system guided to the fuel distribution mechanism 40 from the fuel injection port 43a enters the gap portion 43c functioning as a fuel passage, and is guided to the plurality of fuel discharge ports 43b by the gap portion 43c. For the plurality of fuel discharge ports 43b, for example, a gas-liquid separation membrane (not shown) that transmits only the vaporized component of the fuel and does not allow the liquid component to pass through may be disposed. Thereby, the vaporization component of the fuel is supplied to the anode 25 of the fuel cell power generation unit. However, the gas-liquid separation membrane can also be disposed between the fuel distribution mechanism 40 and the anodes 25-19 - 200950201. The vaporized component of the liquid fuel is discharged from a plurality of fuel discharge ports 43b' toward the anode 25. The fuel supply port 43 is provided so that the fuel can be supplied to the entire MEA 21, and is provided in a plurality of surfaces that are joined to the anode 25 of the fuel distribution plate 43. The number of the fuel discharge ports 43b may be two or more, but there is a presence of zero in the fuel supply amount in the plane of the fuel cell power generation unit. 1 to 10 / cm2 of fuel discharge port 43b terrain is better. The pump 44 is inserted into the flow path 41 connected between the fuel distribution mechanism 40 and the fuel containing portion 42. The pump 44 is not a fuel supply pump for transferring the fuel from the fuel accommodating portion 42 to the fuel distributing mechanism 40 in order to make the circulation of the fuel cycle. By controlling the fuel to be supplied when such a pump 44 is necessary, it is possible to increase the controllability of the fuel supply amount. In this case, as the type of the pump 44 is based on the controllability and can transport a small amount of liquid fuel, it is more compact and lightweight. It is ideal to use the rotary vane pump 'electrically impregnated flow pump, seperate gang. Pu, grab the pump and so on. The rotary blade pump is configured to convey the blade by rotating the motor. The electrically-impregnated flow pumping system is a sintered porous body using cerium oxide or the like which causes an electric permeation phenomenon. The spacer pump is a structure that drives the separator through electromagnet or piezoelectric ceramic. The pumping system is configured to compress a part of the flexible fuel flow path and draw the fuel for transportation. Among them, from the point of driving power or size, it is more desirable to use an electrically immersed flow pump or a spacer for a pressure electromagnetic wave. In this configuration, the liquid fuel accommodated in the fuel accommodating portion 42 is transferred to the fuel distribution mechanism 40 via the pump 44 via the flow path. Further, -20-200950201, the fuel released from the fuel distribution mechanism 40 is supplied to the anode 25 of the fuel cell power generation unit. In the fuel cell power generation unit, the fuel is diffused in the anode gas diffusion layer 28 and supplied to the anode catalyst layer 27. Further, in order to perform the fuel supply to the MEA 2 1 from the fuel distribution mechanism 40, it may be configured as a fuel shut-off valve instead of the pump 44. In this case, the fuel shutoff valve is configured to control the supply of the liquid fuel via the flow path. φ Even in the above configuration, the same effects and effects as those in the first embodiment can be obtained. The present inventors are also applicable to the case where the vapor of the liquid fuel supplied to the MEA 2 1 is supplied to the vapor of the liquid fuel, but a part thereof is supplied in a liquid state. Furthermore, the electronic device of the present invention is provided with a fuel cell of the above-described embodiment as a power source, and a small electronic device having a semiconductor element such as a personal computer or a mobile phone can be exemplified. Since the electronic device of the present invention has a fuel cell having a high output characteristic, it has a small size and a high performance. Next, the present invention will be described in more detail with reference to the embodiments. Example 1 Ketjen ECP (trade name, manufactured by LION Corporation) on a carbon support, Pt-Ru alloy carrying an anode catalyst metal (Ru60at. %), after liquid phase reduction using sodium borohydride, the solution was solid-solved in an inert atmosphere at 800 ° C for 1 hour to prepare an anode catalyst. Next, the anode catalyst, and Nafion solution DE2020 (commodity-21 - 200950201, manufactured by DuPont) and solvent (1-propanol, 2-propanol and glycerin), Nafion content ratio, 0 to 80 The range of % by weight is changed and mixed to prepare an anode catalyst slurry. The obtained anode catalyst slurry was applied to one of the carbon paper (trade name: TGP-H-120, manufactured by Toray Co., Ltd.) which is an anode gas diffusion layer, and then dried by a bar coating to form an anode. Catalyst layer (thickness 180 μm). Further, in the Kino ECP of the carbon carrier, Pt of the cathode catalyst metal was carried, and the cathode catalyst was produced in the same manner as the anode catalyst. Next, the cathode catalyst, and the Nafion solution DE2020 and the solvent (1-propanol, 2-propanol and glycerin) were mixed with the ratio of Nafion to a ratio of 26% by weight to prepare a cathodic catalyst. The slurry (the content of the catalyst metal is 7 wt%). The cathode catalyst slurry was coated on one of the carbon paper (trade name: TGP-H-090, manufactured by Toray Co., Ltd.) which is a cathode gas diffusion layer, and then dried by a bar coating to form a cathode catalyst. Layer (thickness 60 μιη). However, the content ratio (26% by weight) of Nafion in the cathode catalyst layer was obtained from the measurement results of Example 3 to be described later, and the output density was measured when the Nafiori content ratio of the cathode catalyst layer was changed to measure the output characteristics.値 becomes the maximum proportion of the time. Next, as a proton conductive electrolyte membrane, Nafion NRE-212CS (trade name, manufactured by DuPont) was used, and the electrolyte membrane and the anode (anode gas diffusion layer and anode catalyst layer) and cathode (cathode gas diffusion layer and After the cathode catalyst layer was superposed on the electrolyte membrane side, it was sprayed at a heating temperature of 150 ° C and a pressure of 30 kgf / cm 2 ' 5 minutes - 200950201 to produce mea. However, the electrode area is the anode and the cathode 26 is simultaneously 12 cm2. Then, using the MEA thus produced, the fuel cell shown in Fig. 1 was produced, and pure methanol was added as a liquid fuel in the fuel containing portion to actually generate electricity. Further, the maximum output (maximum output density) of the output was measured in an environment of a temperature of 250 C and a relative humidity of 50%. Further, the metal specific surface area of the anode catalyst and the cathode catalyst was measured by the CO pulse sorption method as indicated by φ. That is, first, the cathode gas diffusion layer and the anode gas diffusion layer are mechanically stripped from the MEA. Since the cathode catalyst layer and the anode catalyst layer remain on the electrolyte membrane side or the gas diffusion layer side, the remaining anode catalyst layer and cathode catalyst layer are individually cut by a blade. However, in the case of cutting with a blade, attention is paid to the side of the metal than the surface area without causing an error, and the electrolyte membrane or the gas diffusion layer is not cut off. Next, the cut anode catalyst layer and the cathode catalyst layer were tapped as a powder and filled in a measuring tube. For φ, the measurement system was measured at 50 ° C using a fully automatic catalyst gas adsorption amount measuring device BEL-CAT (manufactured by Nippon BEL Co., Ltd.). However, in this measurement, since the weight measurement is an important factor affecting the obtained result, the weight is measured and corrected by the scale before the measurement of the CO pulse sorption amount. Static removal of the sample. Thus, the specific surface area of the metal as the cathode catalyst measured was 7. 8m2/g. Further, the metal specific surface area of the anode catalyst and the maximum output (maximum output density) of the fuel cell were determined as a curve for the content ratio of Nafion in the anode catalyst layer. The graph is shown in Fig. 4-23-200950201, and the maximum output (maximum output density) of the fuel cell, the metal specific surface area of the cathode catalyst and the metal specific surface area of the anode catalyst measured by the CO pulse sorption method. The ratio (hereinafter referred to as cathode/anode specific surface area ratio) is plotted as a horizontal axis. A graph is shown in Fig. 5. Further, the graph for the range of the cathode/anode specific surface area ratio of 〇 to 10 in Fig. 5 is shown in Fig. 6. From the chart of Fig. 4, the following cases are known. That is, in the anode catalyst layer, the content of the metal specific surface area of the anode catalyst measured by the CO pulse sorption method is reduced from the Nafion content of more than 40% by weight to the Nafion adhesion (Nafion content ratio 0% by weight) 50% of the time, the maximum output density of the fuel cell is greatly increased, and the CO pulse occlusion is below the detection limit. When the metal specific surface area of the cathode catalyst is close to 〇, the maximum output density 値It is the biggest one. Further, the content ratio of Nafion in the anode catalyst layer is 50% by weight or more, and the metal specific surface area of the anode catalyst layer is 7. When the value is 5 m2/g or less, it is known that the maximum output density is higher than 18 m W/cm2. However, since the content ratio of Nafion in the cathode catalyst layer at this time is 26% by weight or more, the metal specific surface area of the cathode catalyst layer becomes 7. 8m2/g, 7. Below 5 m2/g, it was confirmed that the specific surface area of the metal of the cathode catalyst was larger than the specific surface area of the metal of the anode catalyst. Further, from the graphs of Figs. 5 and 6, it is understood that when the cathode/anode ratio surface area ratio is 4 or more, the output characteristics (output density) which are particularly high are displayed. -24-200950201 Example 2 An anode catalyst was produced in the same manner as in Example 1 except that Vulcan XC72 (trade name, manufactured by Cabot Co., Ltd.) was used as a carbon carrier. Next, the anode catalyst and Nafion solution DE2020 and solvent (1-propanol, 2-propanol and glycerin) were used, and the content ratio of Nafion was changed and mixed in the range of 〇~U 50% by weight to prepare an anode contact. Media slurry. Thereafter, the obtained anode catalyst slurry is applied to one of the carbon paper (trade name: TGP-H-120) which is an anode gas diffusion layer, and is applied by a bar coating to be dried to form an anode catalyst layer. (thickness 180 μηι). Further, as a carbon carrier, a cathode catalyst was produced in the same manner as in Example 1 except that Vulcan XC72 was used instead of Koryo ECP. Using the obtained cathode catalyst, a cathode catalyst slurry (Nafion content ratio: 20% by weight, and dielectric layer metal content φ ratio of 9% by weight) was produced in the same manner as in Example 1. The cathode catalyst slurry was applied to one of the carbon paper (trade name: TGP-H-0 90) by a bar coating and dried to form a cathode catalyst layer (thickness 50 μm). However, the content ratio (20% by weight) of Nafion in the cathode catalyst layer is obtained from the measurement results of Example 4 to be described later, and the maximum output density is measured when the output characteristics are measured by changing the Nafion content ratio in the cathode catalyst layer. The cockroaches become the largest proportion of the time. Next, after the proton-conducting electrolyte membrane of Nafion NRE-212CS and the foregoing anode (anode gas diffusion layer and anode catalyst layer) and cathode-25-200950201 pole (cathode gas diffusion layer and cathode catalyst layer), The MEA was produced in the same manner as in Example 1. Then, using the MEA thus manufactured, the fuel cell shown in Fig. 1 was produced, and in the fuel containing portion, pure methanol was added as a liquid fuel to actually generate electricity. Further, the maximum output (maximum output density) of the output was measured in an environment of a temperature of 25 ° C and a relative humidity of 50 %. Further, after the anode catalyst layer and the cathode catalyst layer were individually cut by the blade from the MEA, the crucible was tapped as a powder, and the tube was filled in the measuring tube, and the CO pulse absorbing method was used in the same manner as in the first embodiment. The metal specific surface area of the anode catalyst and the cathode catalyst was measured. The metal specific surface area thus measured as the cathode catalyst was 5 m 2 /g. The metal specific surface area of the anode catalyst and the maximum output (maximum output density) of the fuel cell were determined as a curve for the content ratio of Nafion in the anode catalyst layer. A graph is shown in Fig. 7. From the chart of Fig. 7, the following cases are known. In other words, in the anode catalyst layer, the content of Nafion is more than 20% by weight, and the specific surface area of the anode catalyst measured by the CO pulse sorption method is reduced to 2/3 or less before Nafiori adhesion. The maximum output density to the fuel cell is greatly increased. 'The CO pulse adsorption amount is below the detection limit. When the metal specific surface area of the anode catalyst is close to zero, the maximum output density is the largest. In addition, when the content ratio of Nafion in the anode catalyst layer is 40% by weight or more, and the specific surface area of the anode catalyst layer is 1 m 2 /g or less, it is known that the maximum output density of the coin is 20 mW/cm 2 or more. . However, -26-200950201, at this time, the specific surface area of the cathode catalyst is 5 m2/g, and it is confirmed that the specific surface area of the metal of the cathode catalyst becomes larger than that of the metal of the anode catalyst. Example 3 A Ketjong ECP was used as a carbon carrier, and after preparing an anode catalyst in the same manner as in Example 1, a cathode catalyst, and a Nafion solution 0 DE2020 and a solvent (1-propanol, 2-propanol and Glycerin), the content ratio of Nafion is mixed at a mixing ratio of 60% by weight to prepare a cathode catalyst slurry (the ratio of the catalytic metal content is 3. 5 wt%). Next, the anode catalyst slurry is applied to one of the carbon paper (trade name: TGP-H-120) which becomes the anode gas diffusion layer, and is applied by a bar coating to be dried to form an anode catalyst layer (thickness). 180μπι). However, the content ratio (60% by weight) of Nafion in the anode catalyst layer was obtained from the measurement results of the above-mentioned Example 1, and the maximum output density was measured when the output characteristics were measured by changing the Nafion content ratio of the anode φ catalyst layer. The cockroach becomes the largest proportion. In addition, the Ketjong ECP in the carbon carrier will carry the cathode catalyst obtained from the Pt of the cathode catalyst metal, and the Nafion solution DE2020 and the solvent (1-propanol, 2-propanol and glycerin), Nafion The content ratio is changed in the range of 0 to 40% by weight and mixed to prepare a cathode catalyst slurry. The obtained cathode catalyst slurry is coated on a surface of one of carbon paper (trade name: TGP-H-090) which is a cathode gas diffusion layer, and dried by a bar coating to form a cathode catalyst layer (thickness). 60 μιη). -27- 200950201 Next, after the proton-conducting electrolyte membrane of Nafion NRE-212CS and the foregoing anode (anode gas diffusion layer and anode catalyst layer) and cathode (cathode gas diffusion layer and cathode catalyst layer), Example 1 An MEA was produced in the same manner. Then, using the MEA thus manufactured, the fuel cell shown in Fig. 1 was produced, and in the fuel containing portion, pure methanol was added as a liquid fuel to actually generate electricity. Further, the maximum enthalpy (maximum output density) of the output was measured in an environment of a temperature of 25 ° C and a relative humidity of 50%. Further, after the anode catalyst layer and the cathode catalyst layer were individually cut by the blade from the MEA, the crucible was tapped as a powder, and the tube was filled in the measuring tube, and the CO pulse absorbing method was used in the same manner as in the first embodiment. The metal specific surface area of the anode catalyst and the cathode catalyst was measured. The metal specific surface area thus measured as the anode catalyst was lm2/g. Further, the metal specific surface area of the cathode catalyst and the maximum output (maximum output density) of the fuel cell were determined as a curve for the content ratio of Nafion in the cathode catalyst layer. The figure is shown in Fig. 8 〇 From the chart of Fig. 8, the following cases are known. In other words, in the cathode catalyst layer, when the content of Nafion exceeds 20% by weight, and the metal specific surface area of the cathode catalyst measured by the CO pulse sorption method starts to decrease, the output is gradually obtained, and the cathode catalyst is gradually obtained. The specific surface area of the metal is about 20% lower than that before the Nafion is attached, and the maximum output density is known to be the largest. Further, when the metal specific surface area of the cathode catalyst is 50% or less before the Nafion is attached, it is known that it is almost impossible to obtain the -28-200950201 to the output. Further, when the content ratio of Nafion in the cathode catalyst layer was 25% by weight, when the specific surface area of the cathode catalyst layer measured by the CO pulse sorption method was 8 m 2 /g, it was found that the maximum output density was 18 mW. /cm2 or more. However, since the content ratio of Nafion in the anode catalyst layer at this time is 60% by weight, and the specific surface area of the anode catalyst layer is 1 m 2 /g or less, it has been confirmed that the cathode/anode specific surface area ratio is 4 or more. . Example 4 An anode catalyst was produced in the same manner as in Example 3, using Vulcan XC 72 as a carbon carrier instead of Koryo ECP. Thereafter, the anode catalyst and the Nafion solution DE2020 and the solvent (bupropanol, 2-propanol and glycerin) were mixed at a mixing ratio of Nafion of 40% by weight to prepare an anode catalyst slurry. Then, the anode catalyst 淤 slurry is applied to one of the carbon paper (trade name: TGP-H-120) which becomes the anode gas diffusion layer, and is applied by a bar coating to be dried to form an anode catalyst layer ( Thickness 180μπι). However, the content ratio (40% by weight) of Nafion in the anode catalyst layer was obtained from the measurement results of the foregoing Example 2, 'the maximum output density when the output characteristics were measured while changing the Nafion content ratio in the anode catalyst layer. The cockroach becomes the largest proportion. Further, as a carbon carrier, a cathode catalyst was produced in the same manner as in Example 1 except that Vulcan XC72 was used instead of Koryo ECP. -29- 200950201 The cathode catalyst obtained, and Nafion solution DE2020 and solvent (bupropanol, 2. Propanol and glycerin were mixed and mixed in a range of 〇 to % by weight of Nafion to prepare a cathode catalyst slurry. The obtained cathode catalyst slurry was coated on a surface of one of carbon paper (trade name: TGP-H-090) which is a cathode gas diffusion layer, and dried by a bar coating to form a cathode catalyst layer (thickness). 60 μιη). Next, after the Nafion NRE-212CS of the proton conductive electrolyte membrane is overlapped with the anode (anode gas diffusion layer and anode catalyst layer) and the cathode current (cathode gas diffusion layer and cathode catalyst layer), 1 Make MEA the same thing. Then, using the MEA thus produced, the fuel cell shown in Fig. 1 was produced, and pure methanol was added as a liquid fuel in the fuel containing portion to actually generate electricity. Further, the maximum enthalpy (maximum output density) of the output was measured in an environment of a temperature of 25 ° C and a relative humidity of 50%. Further, after the anode catalyst layer and the cathode catalyst layer were individually cut by the blade from the MEA, the crucible was tapped as a powder, and the metering tube was filled. ◎ The CO pulse absorbing method was carried out in the same manner as in the first embodiment. The metal specific surface area of the anode catalyst and the cathode catalyst was measured. The specific surface area of the metal as the anode catalyst thus measured was 1 m 2 /g. Further, the metal specific surface area of the cathode catalyst and the maximum output (maximum output density) of the fuel cell were determined as a curve for the content ratio of Nafion in the cathode catalyst layer. The figure is shown in Fig. 9. It is understood from the graph of Fig. 9 that in the cathode catalyst layer, the Nafion -30-200950201 contains more than 1% by weight, and the metal specific surface area of the cathode catalyst measured by the CO pulse sorption method begins to decrease. At the beginning, the output gradually appeared, and the specific surface area of the cathode catalyst was reduced by 10% before the Nafion adhesion, and the maximum output density was the largest. Further, when the content ratio of Nafion in the cathode catalyst layer was 20% by weight, when the specific surface area of the cathode catalyst layer measured by the CO pulse sorption method was 5 m 2 /g, it was found that the maximum output density was high.値 20mW/cm2 or more. However, since the metal specific surface area of the anode catalyst layer at this time is 1 m 2 /g or less, it has been confirmed that the cathode/anode specific surface area ratio is 4 or more. However, the present invention is not limited to the above-described embodiments, and constituent elements may be modified and embodied in the implementation stage without departing from the spirit and scope of the invention. Further, various inventions can be formed by appropriate combination of constituent elements disclosed in the above-described embodiments. For example, several constituent elements may be eliminated from the entire constituent elements shown in the embodiment. Furthermore, it is also possible to appropriately combine the constituent elements of different embodiments. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a longitudinal sectional view showing a first embodiment of a fuel cell according to the present invention. Fig. 2 is a longitudinal sectional view showing a configuration of a second embodiment of the fuel cell of the present invention. Fig. 3 is a perspective view showing a fuel distribution mechanism according to a second embodiment of the present invention. -31 - 200950201 Fig. 4 is a graph showing the ratio of the metal specific surface area of the anode catalyst to the maximum output of the fuel cell and the content ratio of the Nafite film in Example 1. Fig. 5 is a graph showing the maximum output (maximum output density) of the fuel cell in Example 1, and the cathode/anode specific surface area ratio as a horizontal axis. Fig. 6 is a graph showing an enlarged range of the ratio of the cathode/anode specific surface area in Fig. 5 to 1010. Fig. 7 is a graph showing the ratio of the metal specific surface area of the anode catalyst to the maximum output of the fuel cell and the content ratio of the Nafite film in Example 2. Fig. 8 is a graph showing the ratio of the metal specific surface area of the cathode catalyst to the maximum output of the fuel cell and the content ratio of the Nafite film in Example 3. Fig. 9 is a graph showing the ratio of the metal specific surface area of the cathode catalyst to the maximum output of the fuel cell and the content ratio of the Nafite film in Example 4. [Description of main component symbols] 1 : Fuel cell 2 : anode catalyst layer 3 : anode gas diffusion layer 4 : anode 5 : cathode catalyst layer - 32 - 200950201 6 : cathode gas diffusion layer 7 : cathode 8 : proton conductive Electrolyte membrane 9 : anode conductive layer 10 : cathode conductive layer 1 2 : fuel containing chamber 1 3 : gas-liquid separation layer 15 : moisture layer 16 : cover
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