200828661 九、發明說明 【發明所屬之技術領域】 本發明係有關有效於攜帶機器之動作的平面配置之串 聯連接的燃料電池。 【先前技術】 作爲行動電話或電筆記型電腦等之攜帶積氣的電源， 無須充電之小型燃料電池則被注目，一般，作爲攜帶積氣 的電源所使用之二次電池係對於使用完電池容量的情況， 則需要進行充電，但，對此’燃料電池係只由補充燃料 即可，作爲使用方便性佳，但，小型的燃料電池係有著單 電池的輸出爲低之一個缺點，因此，爲了得到使積氣驅動 之輸出，例如如記載於日本特開2004-01 4 148號公報及國 際公開號碼2005/ 1 1 2 1 72A1號公報，必須串聯連接複數之 電池，而對於此情況，爲了控制輸出的下降，必須極力縮 小在連接部產生之電性阻抗。 對於單電池間之連接部的電性阻抗，係關連到需多的 參數，但其中特別是集電體與擴散層之材料與構造乃對於 連接部之電性阻抗，具有相當的影響力，隨之，由設法作 爲集電體與擴散層的構造情況，如可縮小連接部的電性阻 抗，則有材料選擇的幅度大，設計自由度增加等之優點。 【發明內容】 本發明係爲爲了解決上述課題所作爲之構成’其目的 -5- 200828661 爲提供可減少連接單電池間之連接部的電性阻抗之燃料電 池者。 有關本發明之燃料電池係屬於具備：於電解質膜的兩 面，各配置含有觸媒層與擴散層之電極的膜電極接合體， 和爲了取出發電輸出而於前述兩電極之擴散層，各進行面 接觸之集電體的燃料電池，其特徵乃前述集電體之至少一 部分則深入於擴散層之中者。 【實施方式】 [爲了實施發明之最佳型態] 對於爲了使集電體深入於擴散層，係需要擴散層作爲 較集電體爲軟而容易變形者，而對於擴散層係使用碳纖維 紙或碳纖維織布，而對於集電體係理想爲使用白金，金等 貴金屬，鎳，不銹鋼等耐蝕性金屬等之金屬材料而成之多 孔質層（例如，金屬篩孔）或箔體者，另外，可各自使用以 異種金屬，將金或碳纖維等之導電性金屬進行表面處理之 材料，例如，被覆金等之良導電性金屬於銅或不銹鋼的複 合材等，而碳纖維紙係因有做爲供給於陽極的燃料或供給 於陰極的空氣之擴散層之作用而使用多孔體，但，爲了均 一地使燃料或空氣擴散而細孔分佈係期望爲均一者，另外 ， 碳纖維紙係因亦擔負作爲導電體之作用而體積阻抗率 爲小則佳，例如，可使用TORAY公司製之TGP(Toray Graphite Paper:商品名）或JGI公司製之CARBEL(商品名）等，而集 電體的厚度係爲3 0㈣以上，理想爲作爲200，以下之範圍 200828661 者’而作爲更理想的範圍爲5 〇〜10 0 μιη，而當集電體的厚 度爲達30μπι時，雖經由材料種，但剛性不足而容易產生 變形’並成爲無法使其深入於擴散層者，另一方面，當集 電體的厚度超過200μιη時，因燃料電池本身的厚度則變厚 ’而空間線率則產生惡化。 對於使集電體深入於擴散層之中的方法，係做爲簡易 W方法’可舉出經由如由壓力加工所代表之壓力而進行按 11的方法，例如，由配置於膜電極接合體的兩側之集電體 ’夾持膜電極接合體，並在其狀態，經由壓力機而按壓使 其深入的方法，此時，壓力加工係亦可將功率加熱至1 〇〇 °C(例如，100〜150°c)在熱間進行，而亦可加溫至較室溫 微高的溫度（例如40〜60 °C )，在溫熱間進行，另外亦可在 室溫進行，另外，由其集電體所夾入之膜電極接合體係在 最後，內藏於外裝材而成爲燃料電池，但在期內藏的過程 ，亦可按壓集電體而使其深入，具體而言係經由鉚接或螺 栓等而固定外裝材，但此時，集電體則可作爲呈深入於膜 電極接合體之擴散層，加上壓力。 對於如前述，經由前述集電體壓入於前述擴散層之情 況，前述集電體之至少一部分則深入於前述擴散層之中的 情況，在將押入前述集電體於前述擴散層之前的體積平均 空孔率，作爲α，而押入前述集電體於擴散層時的前述擴 散層潰散部分之潰散率，作爲^之情況’理想爲滿足^ α /3的關係者，在偏移其之/5 > α /3的範圍中，係因有著 經由擴散層過度擴散之情況而阻礙了擴散’以及另外’在 -7- 200828661 邊緣的罩體中，係擴散層過度地變形而產生破裂之虞，在 此’ 「體積平均空孔率」係指每單位體積之平均的空孔率 ’押入集電體於擴散層之前的擴散層之空孔率，但，對於 平價壓入集電體於擴散層之後的構成情況，係可置換於未 壓入集電體於擴散層之部分的空孔率而定義者，而體積平 均空孔率係例如可使用孔隙度分析儀而側定者，另外，「 潰散率」係指與將對於未壓入集電體之部分的擴散層厚度 之集電體，押入於擴散層之部分的擴散層厚度減少部分的 比例（押入集電體於擴散層之部分的擴散層厚度/未壓入集 電體之部分的擴散層厚度），例如，對於擴散層爲矩形之 情況’將5點（部分之中央部附近，與各邊的中央附近）測 定未壓入集電體於擴散層之部分的結果平均，作爲未壓入 集電體之部分之擴散層厚度，另外，對於將集電體多數串 聯配置於同一擴散層之情況，係將在存在各集電體之中央4 附近的集電體之部分所測定之結果平均，·作爲壓入集電體 於擴散層之部分的擴散層厚度減少部分。 作爲集電體，可使用開口有爲了使燃料或空氣流通之 複數孔的有孔平板者，而理想爲將其有孔平板之開口率， 作爲35%以上者，更理想爲作爲50%以上者，即，將二維 投影複數孔之合計面積，對於二維投影集電體全體之全面 積而言，作爲3 5 %以上，而當開口率未達3 5 %時，經由集 電體的壓入，增加擴散層之潰散部分，相反，因使燃料電 池之輸出特性下降，如將開口率，作爲50%以上，更加地 輸出特性則提升，得到安定之輸出特性。 -8- 200828661 在本發明之燃料電池中，係因重疊集電體於擴散層之 上方，並經由壓力等加上面壓而使集電體深入於擴散層之 中，故兩者的密著性提升的同時，兩者的相互接觸面積增 加，因此，針對在集電體/擴散層間之連接部的接觸阻抗 則變小，發電輸出的損失則變少。 另外，集電體之深入部分則因較以往的構造，呈位置 於接近於觸媒層處，故縮短在發電內部之電流路徑，並內 部阻抗則變小，由此，發電輸出的損失亦變少。 以下，參照附加的圖面而說明爲了實施本發明之各種 形態。 (第1實施形態） 首先，關於燃料電池之全體槪要，參照圖1而進行明 〇 燃料電池1係爲由外裝罩體2 1被覆外側，並具有平面 配置·串聯連接於內部之複數的單電池之構成，而燃料電 池1係例如，亦可作爲經由將外裝罩體2 1的端部，鉚接加 工於燃料收容室構造體2 0之外面情況，將複數之單電池作 爲一體化之1個單元而構成，亦可作爲經由以螺絲與螺帽 緊固外裝罩體2 1與燃料收容室構造體20之情況，將此等作 爲一體化形成。 燃料電池1係具備作爲發電部之膜電極接合體〗0，作 爲集電體之陰極集電體7及陽極集電體9，作爲氣化膜之氣 液分離膜13，形成液體燃料空間14之燃料收容室構造體2〇 200828661 ，而膜電極接合體10係將質子傳導性之固體電解質膜6夾 持於其間，於其兩側，以熱壓力法一體形成陰極觸媒層2 與陽極觸媒層3，更加地’於其外側，具有陰極氣體擴散 層4與陽極氣體擴散層5，而更加地，對於膜電極接合體10 之陰極氣體擴散層4，係導通有正極集電體7，並對於陽極 氣體擴散層5，係導通有負極集電體9，成爲藉由此等正負 一對的集電體7’ 9，輸出由發電部所發電之電力爲未圖示 之負載。 對於燃料電池1之內部，係經由密封橡膠8或Ο環（未 圖示），形成有各種的空間或間隙，在此等空間或間隙之 中，例如陰極側之空間係作爲具有保濕板之空氣導入部所 使用’而陽極側之空間係作爲藉由氣液分離膜1 3而連通於 液體燃料空間1 4之氣化室所使用。 氣化室（未圖示）係鄰接設置於液體燃料空間1 4，兩室 間係經由氣液分離膜13所間隔，而氣液分離膜13係由夾入 其周緣部於密封構件（未圖示）與燃料收容室構造體2 0之突 緣之間的狀態所支撐，而氣液分離膜13係爲由具有多數之 細孔的聚四氟乙烯（PTFE)薄片而成，遮斷液體燃料（甲醇 液或其水溶液等）’使氣化燃料（甲醇氣體）透過之構成。 對於外裝罩體2 1的主面係對各特定間距間隔，將複數 的通氣孔22進行開口，各連通於內部的保濕板19，此等通 氣孔22係形成外氣通過的開口，但設法作爲不阻礙外氣的 通過’而可防止從外部對於陰極氣體擴散層4之微小或針 狀的異物侵入.接觸之形狀。 -10- 200828661 對於外裝罩體2 1之材料，係期望使用對於不銹鋼或鎳 合金等之耐蝕性優越之金屬材料者，但不限於金屬材料， 而亦可使用樹脂材料，例如，亦可使用由聚醚醚酮 (PEEK:VicUex公司的商標）、聚苯硫醚（PPS)、聚四氟乙 烯（PTFE)等之液體燃料不易產生膨潤等之硬質的樹脂。 對於密封構件係可採用從硬質到軟質之各種橡膠系材 料，樹脂系材料或金屬材料，但在此之中，最適合爲橡膠 系材料（例如，EPDM(乙丙橡膠）、FKM(氟橡膠）、NBR(腈 丁二烯橡膠）、SBR(苯乙烯橡膠）)。 針對在燃料電池1的內部，將1個單電池之負極集電體 9，表示於圖2，而對於負極集電體9係開口有複數之開口 部1 6，此等之開口部1 6係各連通於陽極氣體擴散層3側， 當液體燃料收容室1 4內之液體燃料的一部分產生氣化時， 氣化燃料係通過氣液分離膜1 3而進入至氣化室內，更加地 從氣化室，通過集電體9之開口部16而導入至陽極氣體擴 散層5及陽極氣體擴散層3，貢獻於發電反應。 同樣地，對於正極集電體7亦開口有複數之開口部1 6 ，而此等開口部16係藉由保濕板（未圖示）而連通於外裝罩 體21之通氣孔22，而當空氣從通氣孔導入時，通過空氣調 整空間的保濕板而進行加濕，並通過集電體7之開口部1 6 而導入至陰極氣體擴散層4及陰極氣體擴散層2，貢獻於發 電反應。 集電體7，9係如圖2所示，全體的形狀則幾乎爲正方 形，並從其一邊的中央，延伸出有導線7a，9a，導線7a， -11 - 200828661 9a係各連接於未圖示之負荷的兩極端子，而集電體之開 口部1 6係實質上爲相同尺寸之長方形，並規則排列縱5列X 橫4列之合計20爲格子狀。 從發電部1 0之陽極側，取出電子於負極集電體9，爲 了作爲可發電能量之有效利用，如圖3所示，將集電體9之 一部分，深入至擴散層5之中，而針對在陰極側，亦同樣 地，將正極集電體7的一部分，深入至擴散層4之中，而在 本實施形態中，經由使用壓力加工機，以約1 00 °C的溫度 進行溫間加壓的情況，使各集電體7，9，至厚度的一半 (t 1/2)爲至，各自深入於擴散層4，5，而當將集電體7，9 的厚度tl，例如作爲Ο.ΙπΐΓη(ΙΟΟμιη)時，對於擴散層4，5 之集電體7，9的深入深度dl係成爲50μηι。 另外，圖4係爲使集電體9Α之一部分深入於擴散層5Α 之中的例，而針對在陰極側，亦同樣地，使正極集電體 7 Α的一部分，深入於擴散層5 Α之中，而在本實施形態中 ，係經由使用壓力加工機，以約150艽的溫度進行熱壓之 情況，使各集電體7A，9A，至厚度tl爲至，各自深入於 擴散層4，5，而當將集電體7A，9A的厚度tl，例如作爲 0.1〇1111(100，)11)時，對於擴散層4人，5人之集電體7人，9八 的深入深度cil係成爲50μπι。 對於集電體7，9係使用施以金電鍍於〇.1 min厚之不銹 鋼板的構成，並各實施有爲了不妨礙供給於陽極之燃料， 與在陰極所需要之空氣的導入之孔加工，而此等集電體7 ，9之一部分係導出於燃料電池外部，作爲外部端子之作 -12- 200828661 用。 於固體高分子膜6的兩面，塗佈由白金或白金與其他 金屬而成之觸媒而形成觸媒層2，3，並對於配置於其兩側 之擴散層4，5係使用碳纖維紙，而作爲使用之碳纖維紙的 厚度t2係陽極側，陰極側，均作爲0.4mm厚，並貢獻於發 電之觸媒部分及碳纖維紙的大小係作爲40mm角之正方形 ，針對在其發電部之各邊，固體高分子膜6則呈5mm突 出地，將固體高分子膜6的尺寸，作爲50mmx50mm角。 對於液體燃料收容室1 4係開口有燃料導入口 1 5，對於 燃料導入口 1 5，係例如安裝有鎖匙溝形之偶合器，並於其 偶合器，插入有無圖示之燃料匣之噴嘴，補充役體燃料於 液體燃料收容室1 4。 對於液體燃料收容室1 4係收容有液體燃料浸含層（未 圖示），對於液體燃料浸含層，係例如理想爲使用多孔質 聚酯纖維，多孔質烯烴系樹脂等多硬質纖維，或連續氣泡 多孔質體樹脂者，而液體燃料浸含層係針對在燃料容器內 的液體燃料減少之情況，或燃料電池主體傾斜而配置，燃 料供給偏移之情況，亦均質地燃料供給於氣液分離膜，其 結果，可作爲供給均質地氣化於陽極觸媒層3之液體燃料 者，而除了聚酯纖維外，亦可經由丙烯酸系之樹脂等之各 種吸水性聚合物而構成，而亦可經由，利用海綿或纖維之集 合體等液體浸透性而保持液體之材料而構成，本液體燃料 浸含部係無關於主體之姿勢，而對於供給適量之燃料的情 況爲有效。 -13- 200828661 然而，對於液體燃料係使用甲醇水溶液或純甲醇等之 甲醇燃料，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，蟻酸水溶液，蟻酸鈉水溶液，醋 酸水溶液，氫化硼鈉水溶液，氫化硼鉀水溶液，氫化 鋰水溶液，乙二醇水溶液，含有二甲醚等之氫的有機系 之水溶液，其中甲醇水溶液係碳素數爲1，在反應時產生 之情況爲碳酸氣體的同時，可作爲在低溫之發電反應，並 因從產業廢棄物可比較容易地製造情況，故爲理想，另外 ，燃料係在從濃度100%至數％爲止的範圍，可使用各種濃 度之構成者。 固體高分子膜6係爲爲了輸送在陽極觸媒層3產生之質 子於陰極觸媒層2之構成，並經由不具有電子傳導性，而 可輸送質子之材料所構成，例如，經由聚全氟磺酸系之 樹脂膜，具體而言，係DUPONT公司製之Nafion膜，旭 硝子公司製之Flemion膜，旭化成工業公司製之Aciplex 膜等所構成，然而，除了聚全氟磺酸系之樹脂膜之外，亦 可作爲構成可輸送三氟苯乙烯衍生物之共聚合膜，含浸磷 酸之聚并咪唑膜，芳香族聚醚酮磺酸膜，或脂肪族碳化氫 樹脂膜等可輸送質子之電解質膜6。 陽極觸媒層3係爲氧化藉由氣體擴散層5所供給之氣化 燃料，從燃料取出電子與質子之構成，而陽極觸媒層3係 例如經由包含觸媒之碳素粉末所構成，而對於觸媒係例如 使用白金（Pt)之微粒子’鐵（Fe)，鎳（Ni)，鈷（Co)，釕（Ru) -14- 200828661 或鉬（Mo)等之過渡金屬或其氧化物或此等之合金等之微粒 子，但，如作爲經由釕與白金之合金構成觸媒，因可防止 經由一氧化碳（CO)之吸附的觸媒之不活性化者，故爲理想 〇 另外，陽極觸媒層3係包含使用於電解質膜6之樹脂 的情況，則更爲理想，因爲容易進行產生之質子的移動， 而陽極氣體擴散層5係例如以由多孔質之碳素材料而成之 薄膜所構成，具體而言，係以碳纖維紙或碳纖維等所形成 〇 陰極觸媒層2係爲還元氧，使電子與在陽極觸媒層3產 生之質子進行反應而生成水之構成，例如，與上述之陽極 觸媒層3及陽極氣體擴散層5同樣地加以構成，即，陰極係 構成從固體電解質膜11側，依序重疊包含觸媒之碳粉末而 成之陰極觸媒層3與多孔質之碳素材料而成之陰極氣體擴 散層5之層積構造，而使用於陰極觸媒層2之觸媒係爲與陽 極觸媒層3同樣，並陽極觸媒層3爲含有使用於電解質膜6 之樹脂的微粒子之情況，亦與陽極觸媒層3同樣，即， 電解質膜6的厚度係可從10〜25 0 W選擇最佳値，陰極觸 媒層2， 陽極觸媒層3的厚度係可從5 0〜1 〇 〇 //m選擇最佳値 ’ 陰極氣體擴散層4，陽極氣體擴散層5的厚度係可從 2 5 0〜5 0 0 ,選擇最佳値，正極集電體7， 負極集電體9的 厚度係可從30〜200卵選擇最佳値。 外裝罩體2 1及燃料收容室構造體20係可由對於不銹鋼 或鎳合金等之耐蝕性優越之金屬材料而製作，而此情況， -15- 200828661 爲了防止金屬離子之溶出，期望施以樹脂包覆者，而可由 將此等，以聚醚醚酮（PEEK: Victrex公司的商標）、聚苯 硫醚（PPS)、聚四氟乙烯（PTFE)等之液體燃料不易產生膨 潤等之硬質的塑料構成者。 (第2實施形態） 接著，參照圖5而說明本發明之第2實施形態，然而， 本實施形態與上述第1實施形態重覆的部分之說明係省略 之。 燃料電池1A係實質上於內部，具有配置於同一平面 上之複數的單電池，而此等平置於同一平面所配置之複數 的單電池係藉由正負兩極的集電體7A，9A而串聯地加以 連接，而在攜帶機器之中，係因嚴格限制厚度尺寸，故對 於內藏於其之燃料電池，亦有同樣的要求，並因採用重疊 複數之單電池之存儲棧構造情況則爲困難，故採用排列於 同一平面上而配置之平置配置構造，而經由串聯地連接如 此平置配置之複數的單電池情況，形成組電池。 在本實施形態之燃料電池1 A之中，集電體7 A，9 A 係爲如圖5所示，6列排列略長方形之集電體7 A，9 A的構 成，並從其一邊的中央，延伸出有導線7a，9a， 導線 7a，9a係各連接於未圖示之負荷的兩極端子。 對於集電體7A，9A係使用施以金電鍍於O.lmm厚之 不銹鋼板的構成，並各實施有爲了不妨礙供給於陽極之燃 料，與在陰極所需要之空氣的導入之孔加工，而此等集電 體7A，9A之一部分係導出於燃料電池外部，作爲外部端 -16- 200828661 子之作用。 集電體7A，9A之開口部16係實質上爲相同尺寸之長 方形，並以縱8個加以列。 從發電部1 〇之陽極側，取出電子於負極集電體9，爲 了作爲可發電能量之有效利用，與第1實施形態同樣地如 圖3或圖4所示，將集電體之一部分，深入至擴散層之中。 [實施例1〜5] 在一般的燃料電池之中，係成爲由串聯地連接複數之 單電池的組電池，確保輸出電壓之情況，但，在以下所述 之實施例1〜5之中，係爲了作爲確認本發明之效果的目的 ，作爲由單電池構成燃料電池者。 於固體高分子膜6的兩面，塗佈由白金或白金與其他 金屬而成之觸媒而形成觸媒層2，3，並對於配置於其兩側 之擴散層4，5係使用碳纖維紙，而作爲使用之碳纖維紙的 厚度t2係陽極側，陰極側，均作爲0.4mm厚，並貢獻於發 電之觸媒部分及碳纖維紙的大小係作爲40mm角之正方形 ，針對在其發電部之各邊，固體高分子膜6則呈5mm突 出地，將固體高分子膜6的尺寸，作爲5 〇 m m X 5 0 m m角。 對於集電體7，9係使用施以金電鍍於0.1mm厚之不銹 鋼板的構成，並各實施有爲了不妨礙供給於陽極之燃料， 與在陰極所需要之空氣的導入之孔加工，而此等集電體7 ，9之一部分係導出於燃料電池外部，作爲外部端子之作 用。 經由成爲外裝材之塑料構件，藉由密封橡膠8夾入此 -17- 200828661 等層積體，並經由螺絲固定之情況而密封，作爲燃料電池 ，而密封橡膠8係呈觸碰到從碳纖維紙4，5之固體高分膜6 之露出部分地設置，並在其部分，進行密封。 作爲夾入之陽極側外裝材2 〇的材質係作爲PP S，而經 由外裝材20的內側臨接於陽極側之情況，形成液體燃料收 容室1 4，並設置有從外部的燃料供給口 1 5，另外，對於陰 極側外裝材2 1亦使用PP S，並呈從外部取入空氣地，開口 (I 有複數之通氣孔22。 更加地，在本實施例中，以補助對於陽極之均一的燃 料供給之目的，配置可於燃料保持部與陽極側集電體之間 ，吸收·保持燃料之不織布1 3。 但，關於對於陽極之燃料供給及對於陰極之空氣供給 ’係亦可使用閥等補助機而供給，另外，亦可利用在其情 況形成流路之構件而供給燃料及空氣。 [實施例1] # 作爲實施例1，作成5 0個以下之燃料電池。 如上述所述，陽極側，陰極側，均對於膜電極構造體 之擴散層4，5，係使用厚度〇.4mm之碳纖維紙，但其碳纖 維紙係選擇空孔率75%之構成，而配置於其外側之集電體 的厚度係作爲0.1 mm，但，在實施例1之燃料電池之中， 係在以集電體夾入膜電極構造體之狀態，進行加壓，並使 集電體之厚度全體埋設於碳纖維紙，並碳纖維紙與集電體 之合計厚度則作爲呈0.4 m m。 此情況的潰散率Θ係成爲未壓入集電體之部分的擴散 -18- 200828661 層厚度0.4mm，和押入集電體於擴散層之部分的擴散層厚 度減少部分0.1mm的比例（0.1/0.4)，爲25%，隨之，因空 孔率α爲75%，成爲沒S α /3的關係，然而，押入集電 體於擴散層之部分的擴散層厚度減少部分係爲（加壓前之 碳纖維紙與集電體合計厚度Μ加壓後之碳纖維紙與集電 體合計厚度）。 關於集電體的形狀，係於與碳纖維紙尺寸相同40mm 角的部分，延伸出成爲外部端子之端子部，但作爲爲了供 給對於陽極之燃料與對於陰極之空氣的供給的孔，如圖2 所示，開啓2 0處5 X 8 m m尺寸的孔，而此時的孔間隔係成 爲〇1=1.6111111，〇7 = 2.5111111，集電體的開口率係成爲50%。 [實施例2] 作爲實施例2，在將集電體，經由壓力埋設於碳纖維 紙時’將深入於碳纖維紙的集電體厚度，作爲〇.〇 5 mm， 作成5 0個只有陽極側，陰極側各自之碳纖維紙與集電體合 計厚度成爲〇.45mm的情況，與實施例1不同之燃料電池。 電極膜構造體與集電體合計厚度係成爲較實施例1爲 厚，但將鎖住外裝材之螺絲的轉矩，作爲相同，而緊固係 作爲與實施例相同，關於後述之厚度的不同的例，亦施以 同樣的處置。 此情況的潰散率Θ係成爲未壓入集電體之部分的擴散 層厚度0.4mm，和押入集電體於擴散層之部分的擴散層厚 度減少部分0 · 0 5 m m的比例（〇 . 〇 5 / 0.4)，爲1 2 · 5 %，隨之， -19- 200828661 因空孔率α爲7 5 %，成爲泠€ α / 3的關係。 [實施例3] 作爲實施例3，將集電體的孔尺寸，作爲5x6mm，孔 間隔係成爲Dx = 3.2mm，Dy = 2.5mm ’ 將集電體的開口率 ，變更爲37.5%之外係製做50個與實施例1相同之燃料電池 [實施例4] 作爲實施例4，將集電體的孔尺寸，作爲5x5mm，孔 間隔係成爲Dx = 4.0mm，Dy = 2.5mm， 將集電體的開口率 ，變更爲31.2%之外係製做50個與實施例1相同之燃料電池 [實施例5] # 作爲實施例5 ’將集電體厚度，變更爲〇.15mm，經由 與實施例1相同進行壓力加工，使集電體的厚度全體，埋 設於碳纖維紙，作成5 〇個碳纖維紙與集電體合計作爲成爲 0.4mm之燃料電池。 此情況的潰散率Θ係成爲未壓入集電體之部分的擴散 層厚度0.4mm，和押入集電體於擴散層之部分的擴散層厚 度減少部分〇.15mm的比例（〇·ΐ5/〇·4)，爲37.5%,隨之， 因空孔率α爲7 5 %，成爲沒$ ^ / 3的關係。 •20- 200828661 [比較例1] 作爲比較例1，構成實施例1與燃料電池的構件係爲同 樣’但唯電極膜構造體，進行壓力，將碳纖維紙的厚度作 爲成爲0.3mm，並於兩側，配置集電體，作成50個唯將 碳纖維紙與集電體合計厚度作爲呈0.4mm之情況，與實施 例1不同之燃料電池。 [比較例2] 作爲比較例2，實施例1與構成燃料電池的構件係爲同 樣，但未作爲將集電體深入於碳纖維紙，而作成5 0個唯將 碳纖維紙與集電體合計厚度作爲呈0.5mm之情況，與實施 例1不同之燃料電池。 各作成5 0個各實施例及比較例之燃料電池，確認輸出 ，而確認輸出的條件係對於。燃料，使用5質量％之甲醇水 溶液，確認到0.2V之定電壓輸出。 於表1表示將比較例1之輸出平均値作爲1 00之情況的 經由實施例1〜5及比較例1，2之燃料電池的輸出平均値。 表1 輸出平均値(％) 實施例1 118.1 實施例2 115.8 實施例3 107.3 實施例4 105.0 實施例5 106.5 比較例1 100 比較例2 98.8 -21 - 200828661 從表1的結果了解到，在實施例1〜5之中，係確認到較 比較例1，2良好的輸出，其中，關於集電體的開口率爲 3 1·2%小之實施例4，擴散層之潰散部分爲多，而輸出平均 値105.0%，成爲效果稍微小之結果，而在經由本發明之燃 料電池所使用之集電體的開口率係期望爲3 5 %，而更理想 爲 5 0 %。 另外，雖使用空孔率75%之碳纖維紙，但集電體則該 H 部分的碳纖維紙之潰散比例爲37.5 %之實施例5的燃料電池 ， 輸出平均値則爲1 〇 6 · 5 %，成爲效果稍微小之結果，並 經由碳纖維紙的過度潰散，而可確認到效果爲薄之情況。 [實施例6〜10] 在以下所述之實施例6〜1 0，係爲串聯地連接複數之單 電池之組電池的例，而爲組電池之外，作爲基本的燃料電 池之構成係爲與實施例1〜5相同。 φ 作爲實施例6，作成50個具有如圖5所示之發電部的燃 料電池。 集電體7，9係全體的形狀則爲短冊狀且細長的長方形 ，並從其一邊的中央，延伸出有導線7a，9a，導線7a，9a 係各連接於未圖示之負荷的兩極端子，而集電體之開口部 1 6係實質上爲相同尺寸之長方形，並規則排列縱8列X橫6 列之合計48爲格子狀。 作爲使用之膜電極複合體係由配置於同一平面之6個 發電部而成，但，固體電解質膜係使用共通之構成，而固 •22- 200828661 體電解質膜的尺寸係爲1 06mmx 1 1 1 mm的大小，且於其配 置6個長度Gy=l〇〇mm，寬度Gx=15mm之電極，但電極間 的距離Mx或從電極之固體電解質膜之露出]viy係所有作 爲 3 mm 〇 對於各電極之陽極側，陰極側各自，配置長度 Ey=l 00mm，寬度Ex=l 1mm之集電體，而所配置的集電體 ，藉由導出於電極外部之端子部（導線）7 a，9 a而鄰接之電 ϋ 極的陽極與陰極則電性地加以連接，並串聯地連接6個電 極，而在本實施形態中，集電體的寬度Ex係較電極的寬 度爲窄，但集電體的寬度方向之中心則呈一致於電極之寬 度方向地配置集電體，而對於各集電體，係開口有爲了取 入燃料或空氣的孔1 6，在本實施例，於長度方向，鑿開8 處長度Hy = 8 mm，寬度Hx = 5 mm的孔，而孔的長度方向之 間隔Dy = 4mm，寬度方向係於集電體的中央呈設置孔，框 部分的寬度Dx = 3mm。 • 佔各電極的面積之集電體的面積係成爲52%，開口率 係爲4 8 %。 對於陽極側，陰極側的擴散層，係各自使用厚度 0.4mm，空孔率75%之碳纖維紙，而對於集電體係使用施 以鍍金於不銹鋼表面之材料，並電鍍後之材料係作爲 0.1mm，並在以集電體夾入此等電極膜構造體之狀態，進 行加壓，使集電體的厚度全體埋設於碳纖維紙，陽極側， 陰極側各自之碳纖維紙與集電體合計厚度則作爲呈〇.4mm -23- 200828661 此情況的潰散率Θ係成爲未壓入集電體之部分的擴散 層厚度0.4mm，和押入集電體於擴散層之部分的擴散層厚 度減少部分0.1mm的比例（〇.1/0.4)，爲25%，隨之，因空 孔率α爲75 %，成爲 /SSa/3的關係，然而，押入集 電體於擴散層之部分的擴散層厚度減少部分係爲（加壓前 之碳纖維紙與集電體合計厚度）-(加壓後之碳纖維紙與集 電體合計厚度）。 [實施例7] 作爲實施例7在將集電體，經由壓力埋設於碳纖維紙 時，將深入於碳纖維紙的集電體厚度，作爲〇.〇5mm，作 成5 0個只有陽極側，陰極側各自之碳纖維紙與集電體合計 厚度成爲〇.45mm的情況，與實施例6不同之燃料電池。 電極膜構造體與集電體合計厚度係成爲較實施例6爲 厚，但將鎖住外裝材之螺絲的轉矩，作爲相同，而緊固係 # 作爲與實施例相同，關於後述之厚度的不同的例，亦施以 同樣的處置。 [實施例8] 作爲實施例8，除了將配置於各電極之陽極側，陰極 側各自之集電體尺寸’變更爲如以下之外，係製作5〇個與 實施例6相同燃料電池。 作爲使用之集電體係作爲長度Ey=l〇〇mm，寬度 Ex=13m ’孔的尺寸係作爲長度Hy = 4m，寬度Hx = 5mm， -24- 200828661 而孔係配置於實施例6同樣長度方向1列，但孔的數量係作 爲〗2處，孔的長度方向之間隔Dy = 4mm，寬度方向係於 集電體的中央呈設置孔，框部分的寬度Dx = 3mm。 佔各電極的面積之集電體的面積係成爲64.3%，開口 率爲3 5.7 %。 [實施例9] 除了將配置於各電極之陽極側，陰極側各自之集電體 尺寸，變更爲如以下之外，係製作50個與竇施例6相同燃 料電池。 作爲使用之集電體係作爲長度 Ey=100mm，寬度 Ex=13m，孔的尺寸係作爲長度Hy = 2mm， 寬度係作爲 Hx = 5 mm，而孔係配置於實施例1同樣長度方向1歹!J，但孔 的數量係作爲1 6處，孔的長度方向之間隔D y = 4 m m，寬度 方向係於集電體的中央呈設置孔，框部分的寬度Dx = 3mir 〇 佔各電極的面積之集電體·的面積係成爲71.8%，開口 率爲3 5.7 %。 [實施例10] 作爲實施例10，除了將集電體的厚度’作爲〇.15mm 以外係作爲與實施例6相同，經由壓力加工而埋設集電體 之厚度全體埋設於碳纖維紙，作成50個在各陽極側，陰極 側，碳纖維紙與集電體合計厚度成爲0.4 m m的燃料電池 -25- 200828661 [比較例3] 作爲比較例3，實施例6與構成燃料電池的構件係爲同 樣’但唯將電極膜構造體進行加壓，將碳纖維紙作爲呈 0 · 3 mm ’並於其兩側，配置集電體，作成5 0個唯纖維紙與 集電體合計厚度成爲0.4mm的情況，與實施例1不同之燃 料電池。 [比較例4 ] 作爲比較例4，實施例6與構成燃料電池的構件係爲同 樣’但作成50個唯不使集電體深入於碳纖維紙，而碳纖維 紙與集電體合計厚度成爲0.5 m m的情況，與實施例6不同 之燃料電池。 於表2彙整表示上述之實施例6〜10及比較例3，4之集 電體7，9的各部尺寸。 -26- 200828661 表2各例之尺寸表 各電極的尺寸 集電體的尺寸 開口 率 (%) 長度 Gy (mm) 寬度 Gx (mm) 面積 (mm2) 長度 Ey (mm) 寬度 Ex (mm) 孔長 度Hy (mm) 孔寬 度Hx (mm) 孔 數 孔間 隔Dy (mm) 尺寸 框Dx (mm) 面積 (mm2) 實施 例6 100 15 1500 100 11 8 5 8 4 3 780 48.0 實施 例6 100 15 1500 100 11 8 5 8 4 3 780 48.0 實施 例6 100 15 1500 100 13 4 7 12 4 3 964 35.7 實施 例6 100 15 1500 100 13 2 7 16 4 3 1076 28.3 實施 例6 100 15 1500 100 11 8 5 8 4 3 780 48.0 比較 例3 100 15 1500 100 11 8 5 8 4 3 780 48.0 比較 例4 100 15 1500 100 11 8 5 8 4 3 780 48.0200828661 IX. Description of the Invention [Technical Field] The present invention relates to a fuel cell connected in series in a planar configuration effective for carrying the action of a machine. [Prior Art] As a power source for carrying a gas, such as a mobile phone or an electric notebook computer, a small fuel cell that does not need to be charged is attracting attention. Generally, a secondary battery used as a power source for carrying gas is used for battery capacity. In this case, charging is required. However, the fuel cell is only supplemented with fuel, and it is convenient to use. However, a small fuel cell has a disadvantage that the output of the single cell is low, and therefore, In order to control the output of the gas, for example, as described in Japanese Laid-Open Patent Publication No. 2004-01 4 148 and International Publication No. 2005/1 1 2 1 72A1, a plurality of batteries must be connected in series, and in this case, for control The drop in output must minimize the electrical impedance generated at the connection. The electrical impedance of the connection between the single cells is related to a large number of parameters, but in particular, the material and structure of the current collector and the diffusion layer have a considerable influence on the electrical impedance of the connection portion. In the case of a structure in which the current collector and the diffusion layer are tried, for example, the electrical impedance of the connection portion can be reduced, there is an advantage that the material selection width is large and the design freedom is increased. SUMMARY OF THE INVENTION The present invention has been made in order to solve the above problems. The object of the present invention is to provide a fuel cell that can reduce the electrical impedance of the connection portion between the cells. A fuel cell according to the present invention is a membrane electrode assembly including an electrode including a catalyst layer and a diffusion layer on both surfaces of an electrolyte membrane, and a diffusion layer on the both electrodes for taking out a power generation output. A fuel cell in contact with a current collector is characterized in that at least a part of the current collector penetrates into the diffusion layer. [Embodiment] [In order to carry out the best mode of the invention] In order to make the current collector deep into the diffusion layer, it is necessary to use a diffusion layer as a softer collector and to be easily deformed, and to use a carbon fiber paper for the diffusion layer or Carbon fiber woven fabric, and the collector system is preferably a porous layer (for example, a metal mesh) or a foil made of a metal material such as platinum, gold or the like, a corrosion-resistant metal such as nickel or stainless steel, or a foil. Each of the materials which are surface-treated with a conductive metal such as gold or carbon fiber by using a dissimilar metal, for example, a composite material of copper or stainless steel coated with gold or the like, is used, and the carbon fiber paper is supplied as a material. The porous body is used for the action of the fuel of the anode or the diffusion layer of the air supplied to the cathode. However, in order to uniformly diffuse the fuel or the air, the pore distribution is desirably uniform, and the carbon fiber paper is also responsible for the conductor. It is preferable that the volume resistivity is small, and for example, TGP (Toray Graphite Paper: trade name) manufactured by TORAY Co., Ltd. or CARBEL (made by JGI Co., Ltd.) can be used. Product name), etc., and the thickness of the current collector is 30 (four) or more, and is preferably 200, the following range is 200828661' and the more desirable range is 5 〇 to 10 0 μιη, and when the thickness of the current collector is up to When the thickness is 30 μm, the material is likely to be deformed due to insufficient rigidity, and it is impossible to penetrate the diffusion layer. On the other hand, when the thickness of the current collector exceeds 200 μm, the thickness of the fuel cell itself becomes thick. 'And the spatial line rate is deteriorating. The method of making the current collector deep in the diffusion layer is a simple W method, and a method of performing 11 according to the pressure represented by the press working, for example, by the film electrode assembly. The current collectors on both sides sandwich the membrane electrode assembly and press it in a state where it is pressed through the press. At this time, the press processing system can also heat the power to 1 〇〇 ° C (for example, 100~150°c) can be carried out in the hot room, and can be heated to a temperature slightly higher than room temperature (for example, 40~60 °C), in the warm room, or at room temperature, in addition, The membrane electrode bonding system in which the current collector is sandwiched is finally contained in the exterior material and becomes a fuel cell. However, during the period of storage, the current collector can be pressed and deepened, specifically The outer casing is fixed by riveting or bolting, but in this case, the current collector can be used as a diffusion layer deep in the membrane electrode assembly, and pressure is applied thereto. In the case where the current collector is press-fitted into the diffusion layer as described above, at least a part of the current collector penetrates into the diffusion layer, and the volume before the current collector is pushed into the diffusion layer The average porosity is α, and the collapsibility of the diffusion layer collapsed portion when the current collector is applied to the diffusion layer is regarded as the case where it is desirable to satisfy the relationship of ^α /3. 5 > In the range of α /3, the diffusion is prevented by the excessive diffusion of the diffusion layer, and in the case of the edge of -7-200828661, the diffusion layer is excessively deformed to cause cracking. Here, "volume average porosity" means the average porosity per unit volume 'the porosity of the diffusion layer before the collector is applied to the diffusion layer, but for the parity intrusion into the collector. The configuration after the layer is defined by the porosity of the portion where the current collector is not pressed into the diffusion layer, and the volume average porosity can be determined, for example, by using a porosity analyzer. " Collapse rate The ratio of the thickness of the diffusion layer to the portion of the diffusion layer that is to be applied to the collector of the thickness of the diffusion layer that is not pressed into the collector (the thickness of the diffusion layer that is applied to the portion of the collector in the diffusion layer) / thickness of the diffusion layer which is not pressed into the current collector), for example, when the diffusion layer is rectangular, '5 points (near the central portion of the portion, and the vicinity of the center of each side) are measured without being pressed into the current collector. The results of the portions of the diffusion layer are averaged as the thickness of the diffusion layer that is not pressed into the current collector, and in the case where a large number of current collectors are arranged in series in the same diffusion layer, the center of each current collector is present. The results of the measurement of the portion of the nearby current collector are averaged as the portion of the thickness of the diffusion layer that is pressed into the portion of the current collector in the diffusion layer. As the current collector, a perforated flat plate having a plurality of holes for circulating fuel or air may be used, and it is preferable that the aperture ratio of the perforated flat plate is 35% or more, and more preferably 50% or more. That is, the total area of the two-dimensional projection complex holes is 35 % or more for the entire area of the entire two-dimensional projection current collector, and the voltage of the current collector when the aperture ratio is less than 35 % In addition, the collapsed portion of the diffusion layer is increased. On the contrary, when the output characteristics of the fuel cell are lowered, if the aperture ratio is 50% or more, the output characteristics are further improved, and the output characteristics of the stability are obtained. -8- 200828661 In the fuel cell of the present invention, since the current collector is superposed on the diffusion layer and the upper surface is pressed by pressure or the like to make the current collector penetrate the diffusion layer, the adhesion between the two is tight. At the same time as the increase, the mutual contact area between the two increases. Therefore, the contact resistance at the connection portion between the current collector/diffusion layer becomes small, and the loss of power generation output decreases. In addition, since the deep portion of the current collector is positioned closer to the catalyst layer than the conventional structure, the current path inside the power generation is shortened, and the internal impedance is reduced, whereby the loss of power generation output is also changed. less. Hereinafter, various aspects of the present invention will be described with reference to the accompanying drawings. (1st Embodiment) First, the fuel cell 1 is the outer side covered with the exterior cover 21, and has the planar arrangement and the serial connection in the inside of the whole of the fuel cell with reference to FIG. In the case of the unit cell, the fuel cell 1 may be integrated into the outer surface of the fuel containing chamber structure 20 by caulking the end portion of the exterior cover 21, for example. One unit is configured, and the outer cover body 21 and the fuel containing chamber structure 20 may be fastened by screw and nut, and these may be integrally formed. The fuel cell 1 includes a membrane electrode assembly body 0 as a power generation unit, a cathode current collector 7 and an anode current collector 9 as a current collector, and a gas-liquid separation membrane 13 as a vaporization membrane to form a liquid fuel space 14 The fuel containing chamber structure 2 is 200828661, and the membrane electrode assembly 10 sandwiches the proton conductive solid electrolyte membrane 6 therebetween, and the cathode catalyst layer 2 and the anode catalyst are integrally formed on both sides by a heat pressure method. The layer 3 is further disposed on the outer side thereof with the cathode gas diffusion layer 4 and the anode gas diffusion layer 5, and more specifically, the cathode gas diffusion layer 4 of the membrane electrode assembly 10 is electrically connected to the cathode current collector 7, and In the anode gas diffusion layer 5, the negative electrode current collector 9 is turned on, and the electric power generated by the power generation unit is output as a load (not shown) by the positive and negative pair current collectors 7'. In the interior of the fuel cell 1, various spaces or gaps are formed through the sealing rubber 8 or an annulus (not shown), and among these spaces or gaps, for example, the space on the cathode side serves as air having a moisturizing plate. The space on the anode side used in the introduction portion is used as a vaporization chamber that communicates with the liquid fuel space 14 by the gas-liquid separation membrane 13 . The vaporization chamber (not shown) is disposed adjacent to the liquid fuel space 14 and is interposed between the two chambers via the gas-liquid separation membrane 13, and the gas-liquid separation membrane 13 is sandwiched between the peripheral portions thereof and the sealing member (not shown). The gas-liquid separation membrane 13 is formed by a sheet of polytetrafluoroethylene (PTFE) having a plurality of pores, and the liquid fuel is blocked. (Methanol liquid or an aqueous solution thereof, etc.) A configuration in which a vaporized fuel (methanol gas) is passed through. The main surface of the exterior cover 21 is spaced apart from each other by a specific pitch, and a plurality of vent holes 22 are opened, each communicating with the inner moisturizing plate 19, and these vent holes 22 form an opening through which the outside air passes, but try to As a result of not obstructing the passage of the outside air, it is possible to prevent intrusion of tiny or needle-like foreign matter from the outside to the cathode gas diffusion layer 4. The shape of the contact. -10- 200828661 For the material of the exterior cover 21, it is desirable to use a metal material excellent in corrosion resistance such as stainless steel or nickel alloy, but it is not limited to a metal material, and a resin material may be used, for example, may also be used. A liquid resin such as polyetheretherketone (PEEK: a trademark of VicUex Co., Ltd.), polyphenylene sulfide (PPS), or polytetrafluoroethylene (PTFE) is less likely to generate a hard resin such as swelling. For the sealing member, various rubber-based materials, resin-based materials or metal materials, from hard to soft, may be used, but among them, rubber-based materials (for example, EPDM (ethylene propylene rubber), FKM (fluororubber)) are most suitable. , NBR (nitrile butadiene rubber), SBR (styrene rubber)). In the inside of the fuel cell 1, the negative electrode current collector 9 of one single cell is shown in Fig. 2, and the opening of the negative electrode current collector 9 is plural, and the opening portion 16 is the same. Each of the liquid fuel in the liquid fuel containing chamber 14 is vaporized when it is connected to the side of the anode gas diffusion layer 3, and the vaporized fuel passes through the gas-liquid separation membrane 13 to enter the gasification chamber, and more gas is supplied. The chemical chamber is introduced into the anode gas diffusion layer 5 and the anode gas diffusion layer 3 through the opening 16 of the current collector 9, and contributes to the power generation reaction. Similarly, a plurality of openings 16 are also opened in the positive electrode current collector 7, and the openings 16 are communicated with the vent holes 22 of the exterior cover 21 by a moisturizing plate (not shown). When the air is introduced from the vent hole, it is humidified by the moisturizing plate of the air-conditioning space, and introduced into the cathode gas diffusion layer 4 and the cathode gas diffusion layer 2 through the opening portion 16 of the current collector 7, thereby contributing to the power generation reaction. The current collectors 7, 9 are as shown in Fig. 2. The overall shape is almost square, and the wires 7a, 9a are extended from the center of one side, and the wires 7a, -11 - 200828661 9a are connected to each other. The two poles of the load are shown, and the opening portion 16 of the current collector is substantially rectangular having the same size, and the total arrangement of the vertical column 5 columns and the horizontal column 4 is a lattice shape. From the anode side of the power generation unit 10, electrons are taken out to the negative electrode current collector 9. In order to effectively utilize the power generation energy, as shown in FIG. 3, one portion of the current collector 9 is deep into the diffusion layer 5, and In the same manner, a part of the positive electrode current collector 7 is further penetrated into the diffusion layer 4 on the cathode side. In the present embodiment, the temperature is applied at a temperature of about 100 ° C by using a press machine. In the case of pressurization, each of the current collectors 7, 9 is made to a half (t 1/2) of thickness, each of which is deep in the diffusion layers 4, 5, and when the thickness of the current collectors 7, 9 is t1, for example As a beggar. In the case of ΙπΐΓη (ΙΟΟμιη), the depths d1 of the collectors 7, 9 of the diffusion layers 4, 5 are 50 μm. In addition, FIG. 4 is an example in which one part of the current collector 9 is deep in the diffusion layer 5, and similarly, a part of the positive electrode current collector 7 is deep in the diffusion layer 5 on the cathode side. In the present embodiment, each of the current collectors 7A and 9A is brought to a depth of t1 to the diffusion layer 4 by using a press machine to perform hot pressing at a temperature of about 150 Torr. 5, and when the current collector 7A, 9A has a thickness t1, for example, as 0. In the case of 1〇1111(100,)11), for the diffusion layer of 4 people, the collector of 5 people is 7 people, and the deep depth cil of 9-8 is 50 μm. For the current collector 7, 9 is applied by gold plating on the crucible. The structure of the 1 minute thick stainless steel plate is processed in order to prevent the fuel supplied to the anode from being introduced into the hole required for the cathode, and one of the collectors 7 and 9 is derived from the fuel. The outside of the battery is used as an external terminal for -12-200828661. On both sides of the solid polymer film 6, a catalyst layer made of platinum or platinum and another metal is applied to form the catalyst layers 2, 3, and carbon fiber paper is used for the diffusion layers 4 and 5 disposed on both sides thereof. The thickness t2 of the carbon fiber paper used is the anode side and the cathode side, both of which are 0. The size of the catalyst portion which contributes to the power generation and the size of the carbon fiber paper is a square of 40 mm angle. For each side of the power generation section, the solid polymer film 6 protrudes by 5 mm, and the solid polymer film 6 is formed. Dimensions, as a 50mm x 50mm angle. A fuel introduction port 15 is opened in the liquid fuel storage chamber 14 , and a key groove coupling is attached to the fuel introduction port 15 , and a nozzle of a fuel cartridge (not shown) is inserted into the coupling. The supplementary body fuel is in the liquid fuel containment chamber 14 . In the liquid fuel storage chamber 14 , a liquid fuel impregnated layer (not shown) is contained, and for the liquid fuel impregnated layer, for example, a porous polyester fiber or a porous olefin resin or the like is used, or In the case of a continuous-cell porous resin, the liquid fuel-impregnated layer is disposed in such a manner that the liquid fuel in the fuel container is reduced, or the fuel cell body is inclined, and the fuel supply is shifted, and the fuel is uniformly supplied to the gas-liquid. As a result, the separation membrane can be used as a liquid fuel which is supplied to the anode catalyst layer 3 in a homogeneous manner, and can be composed of various water-absorbent polymers such as an acrylic resin in addition to the polyester fiber. It is possible to maintain a liquid material by liquid permeability such as a sponge or an aggregate of fibers, and the liquid fuel impregnation portion has no posture with respect to the main body, and is effective for supplying an appropriate amount of fuel. -13- 200828661 However, for the liquid fuel, methanol fuel such as methanol aqueous solution or pure methanol, ethanol fuel such as ethanol aqueous solution or pure ethanol, propanol fuel such as aqueous solution of propanol or pure propanol, ethylene glycol aqueous solution or pure Ethylene glycol fuel such as ethylene glycol, aqueous solution of formic acid, aqueous solution of sodium formate, aqueous solution of sodium acetate, aqueous solution of sodium borohydride, aqueous solution of potassium borohydride, aqueous lithium hydride solution, aqueous solution of ethylene glycol, organic system containing hydrogen such as dimethyl ether An aqueous solution in which the number of carbon atoms in the aqueous methanol solution is 1, and it is a carbonic acid gas generated during the reaction, and can be used as a reaction at a low temperature, and is easily produced from industrial waste, which is preferable. The fuel is in a range from 100% to several % of the concentration, and various concentrations of the constituents can be used. The solid polymer film 6 is formed by transporting protons generated in the anode catalyst layer 3 to the cathode catalyst layer 2, and is formed of a material capable of transporting protons without electron conductivity, for example, by polyfluorination. The sulfonic acid-based resin film is specifically composed of a Nafion membrane manufactured by DUPONT Co., Ltd., a Flemion membrane manufactured by Asahi Glass Co., Ltd., an Aciplex membrane manufactured by Asahi Kasei Kogyo Co., Ltd., and the like, except for a polyperfluorosulfonic acid-based resin film. In addition, it can also be used as a copolymer film which can transport a trifluorostyrene derivative, a polyimidazole film impregnated with phosphoric acid, an aromatic polyether ketone sulfonic acid film, or an aliphatic hydrocarbon film which can transport protons. 6. The anode catalyst layer 3 is formed by oxidizing a vaporized fuel supplied from the gas diffusion layer 5, and extracting electrons and protons from the fuel, and the anode catalyst layer 3 is formed, for example, by carbon powder containing a catalyst. For the catalyst system, for example, a platinum (Pt) microparticle "iron (Fe), nickel (Ni), cobalt (Co), ruthenium (Ru) -14-200828661 or molybdenum (Mo) or the like transition metal or oxide thereof or Fine particles such as alloys, etc., as a catalyst formed by an alloy of ruthenium and platinum, it is preferable to prevent the catalyst from being adsorbed by carbon monoxide (CO), and therefore, the anode catalyst The layer 3 includes a resin used for the electrolyte membrane 6, and is more preferably because the protons are easily moved, and the anode gas diffusion layer 5 is formed, for example, of a film made of a porous carbon material. Specifically, the cathode catalyst layer 2 formed of carbon fiber paper or carbon fiber is a reductive oxygen, and reacts electrons with protons generated in the anode catalyst layer 3 to form water. For example, Anode catalyst layer 3 and In the same manner, the cathode gas diffusion layer 5 is formed by a cathode catalyst layer 3 in which a carbon powder containing a catalyst is sequentially superposed on the solid electrolyte membrane 11 side and a porous carbon material. The cathode gas diffusion layer 5 has a laminated structure, and the catalyst used in the cathode catalyst layer 2 is the same as the anode catalyst layer 3, and the anode catalyst layer 3 is a microparticle containing the resin used for the electrolyte membrane 6. Also, similarly to the anode catalyst layer 3, that is, the thickness of the electrolyte membrane 6 can be selected from 10 to 25 W, and the thickness of the cathode catalyst layer 2 and the anode catalyst layer 3 can be from 5 0 to 1 〇〇//m selects the best 値' cathode gas diffusion layer 4, the thickness of the anode gas diffusion layer 5 can be selected from 205 to 50,000, the optimum enthalpy, the positive current collector 7, and the negative current collector 9 The thickness of the system can be selected from 30 to 200 eggs. The exterior cover body 21 and the fuel containing chamber structure 20 can be made of a metal material excellent in corrosion resistance such as stainless steel or a nickel alloy. In this case, -15-200828661, in order to prevent elution of metal ions, it is desirable to apply a resin. For the coating, it is possible to make the liquid fuel such as polyetheretherketone (PEEK: Victrex company's trademark), polyphenylene sulfide (PPS), or polytetrafluoroethylene (PTFE) hard to produce swelling such as swelling. Plastic constructor. (Second Embodiment) Next, a second embodiment of the present invention will be described with reference to Fig. 5. However, the description of the portions of the present embodiment and the above-described first embodiment will be omitted. The fuel cell 1A is substantially internal and has a plurality of unit cells disposed on the same plane, and the plurality of unit cells disposed on the same plane are connected in series by the collectors 7A, 9A of the positive and negative poles. The ground is connected, and in the portable machine, since the thickness is strictly limited, the same requirements are imposed on the fuel cell built therein, and it is difficult to use the storage stack structure of the overlapping plurality of single cells. Therefore, the assembled battery is formed by connecting a plurality of unit cells arranged in such a flat configuration in series by using a flat configuration configured to be arranged on the same plane. In the fuel cell 1 A of the present embodiment, the current collectors 7 A, 9 A are arranged in a six-column arrangement of the rectangular current collectors 7 A, 9 A as shown in Fig. 5, and are formed on one side thereof. In the center, the wires 7a, 9a are extended, and the wires 7a, 9a are connected to the terminals of the load (not shown). For current collectors 7A, 9A is applied by gold plating to O. The lmm thick stainless steel plate is configured to be processed in order to prevent the fuel supplied to the anode from being introduced into the anode, and one of the current collectors 7A, 9A is derived from the fuel cell. External, as the role of the external end-16-200828661. The openings 16 of the current collectors 7A, 9A are substantially rectangular in the same size and are arranged in eight vertical rows. In the same manner as in the first embodiment, as shown in FIG. 3 or FIG. 4, a part of the current collector is taken out, as shown in FIG. 3 or FIG. 4, in order to use the negative electrode current collector 9 as the power generation energy. Go deep into the diffusion layer. [Embodiment 1 to 5] In a general fuel cell, a battery pack in which a plurality of battery cells are connected in series is provided, and an output voltage is secured. However, in Examples 1 to 5 described below, For the purpose of confirming the effects of the present invention, a fuel cell is constituted by a single cell. On both sides of the solid polymer film 6, a catalyst layer made of platinum or platinum and another metal is applied to form the catalyst layers 2, 3, and carbon fiber paper is used for the diffusion layers 4 and 5 disposed on both sides thereof. The thickness t2 of the carbon fiber paper used is the anode side and the cathode side, both of which are 0. The size of the catalyst portion which contributes to the power generation and the size of the carbon fiber paper is a square of 40 mm angle. For each side of the power generation section, the solid polymer film 6 protrudes by 5 mm, and the solid polymer film 6 is formed. Dimensions, as 5 〇mm X 5 0 mm angle. For the current collector 7, the 9 series is applied with gold plating at 0. The structure of a 1 mm-thick stainless steel plate is processed in order to prevent the fuel supplied to the anode from being introduced into the hole required for the cathode, and one of the collectors 7 and 9 is derived from the fuel cell. External, acting as an external terminal. By the plastic member which is an exterior material, the laminated body such as -17-200828661 is sandwiched by the sealing rubber 8 and sealed by screwing as a fuel cell, and the sealing rubber 8 is in contact with the carbon fiber. The exposed portion of the solid high-part film 6 of the paper 4, 5 is partially disposed, and is sealed at its portion. The material of the anode-side exterior material 2 夹 that is sandwiched is PP S, and the liquid fuel storage chamber 14 is formed via the inner side of the exterior material 20 to the anode side, and the fuel supply from the outside is provided. In addition, PP S is also used for the cathode-side exterior material 21, and air is taken in from the outside, and the opening (I has a plurality of vent holes 22. Further, in the present embodiment, For the purpose of uniform fuel supply of the anode, a non-woven fabric 13 that can absorb and hold the fuel between the fuel holding portion and the anode-side current collector is disposed. However, the fuel supply to the anode and the air supply to the cathode are also It can be supplied by using a auxiliary machine such as a valve, and the fuel and the air can be supplied by the member which forms the flow path in this case. [Example 1] # As Example 1, a fuel cell of 50 or less was produced. The anode side and the cathode side are both used for the diffusion layers 4, 5 of the membrane electrode structure. 4mm carbon fiber paper, but the carbon fiber paper is selected to have a porosity of 75%, and the thickness of the current collector disposed outside is 0. 1 mm, in the fuel cell of the first embodiment, the film electrode structure is sandwiched by the current collector, and the thickness of the current collector is entirely embedded in the carbon fiber paper, and the carbon fiber paper is placed. The total thickness with the current collector is taken as 0. 4 m m. In this case, the collapse rate is a diffusion that is not pressed into the collector. -18- 200828661 Layer thickness 0. 4 mm, and the diffusion layer thickness of the portion of the current collector in the diffusion layer is reduced by 0. 1mm ratio (0. 1/0. 4), which is 25%, and accordingly, since the porosity α is 75%, there is no relationship of S α /3, however, the thickness of the diffusion layer which is pushed into the portion of the current collector in the diffusion layer is reduced (pressurization) The total thickness of the carbon fiber paper and the current collector before the total thickness of the carbon fiber paper and the current collector after pressing). The shape of the current collector is a terminal portion that becomes an external terminal at a portion having the same 40 mm angle as the carbon fiber paper, but as a hole for supplying the fuel for the anode and the air for the cathode, as shown in FIG. Show, open 20 0 5 8 mm size holes, and the hole spacing at this time is 〇 1 = 1. 6111111, 〇7 = 2. 5111111, the aperture ratio of the current collector is 50%. [Example 2] As Example 2, when the current collector was buried in the carbon fiber paper via pressure, the thickness of the current collector of the carbon fiber paper was made deep as a crucible. 〇 5 mm, made 50 only on the anode side, the total thickness of each carbon fiber paper and current collector on the cathode side becomes 〇. In the case of 45 mm, a fuel cell different from that of the first embodiment. The total thickness of the electrode film structure and the current collector is thicker than that of the first embodiment, but the torque of the screw that locks the outer material is the same, and the fastening system is the same as the embodiment, and the thickness is described later. Different cases are also treated the same. In this case, the collapse rate is the thickness of the diffusion layer that is not pressed into the collector. 4mm, and the ratio of the diffusion layer thickness of the collector to the diffusion layer is reduced by 0·0 5 m m (〇. 〇 5 / 0. 4), which is 1 2 · 5 %, and then, -19-200828661 has a relationship of 泠 € α / 3 due to the porosity α of 7 5 %. [Example 3] As Example 3, the pore size of the current collector was set to 5 x 6 mm, and the pore spacing system was Dx = 3. 2mm, Dy = 2. 5mm ’ The aperture ratio of the collector is changed to 37. 50 fuel cells identical to those of the first embodiment were fabricated in 5%. [Example 4] As Example 4, the pore size of the current collector was set to 5 x 5 mm, and the pore spacing system was Dx = 4. 0mm, Dy = 2. 5mm, change the aperture ratio of the current collector to 31. 50% of the same fuel cell as that of the first embodiment was fabricated in 2% [Example 5] # As Example 5', the thickness of the current collector was changed to 〇. 15 mm, pressure processing was carried out in the same manner as in Example 1, and the entire thickness of the current collector was placed on the carbon fiber paper to make a total of 5 carbon fiber papers and current collectors. 4mm fuel cell. In this case, the collapse rate is the thickness of the diffusion layer that is not pressed into the collector. 4mm, and the thickness of the diffusion layer that is pushed into the collector layer in the diffusion layer is reduced. The ratio of 15mm (〇·ΐ5/〇·4) is 37. 5%, and then, because the porosity α is 7 5 %, it becomes a relationship of no $ ^ / 3. 20-200828661 [Comparative Example 1] As a comparative example 1, the components of the fuel cell of the first embodiment were constructed in the same manner as the fuel cell structure, and the pressure was applied to make the thickness of the carbon fiber paper 0. 3mm, and on both sides, the current collector is arranged, and the total thickness of 50 carbon fiber papers and current collectors is made to be 0. In the case of 4 mm, a fuel cell different from that of Embodiment 1 is used. [Comparative Example 2] As a comparative example 2, the first embodiment is the same as the member constituting the fuel cell, but the thickness of the carbon fiber paper and the current collector is not made as the current collector is deep in the carbon fiber paper. As 0. In the case of 5 mm, a fuel cell different from that of Embodiment 1 is used. Each of the fuel cells of each of the examples and the comparative examples was prepared, and the output was confirmed, and the conditions for confirming the output were correct. For the fuel, use a 5% by mass methanol water solution to confirm that it is 0. 2V constant voltage output. Table 1 shows the output average 値 of the fuel cells of Examples 1 to 5 and Comparative Examples 1 and 2 in the case where the output average 値 of Comparative Example 1 was taken as 100. Table 1 Output Average 値 (%) Example 1 118. 1 Example 2 115. 8 Example 3 107. 3 Example 4 105. 0 Example 5 106. 5 Comparative Example 1 100 Comparative Example 2 98. 8 - 21 - 200828661 It is understood from the results of Table 1 that among Examples 1 to 5, a good output is obtained in Comparative Example 1, 2, in which the aperture ratio with respect to the current collector is 3 1 · 2%. In the fourth embodiment, the diffusion layer has a large number of broken portions, and the output average is 値105. 0% is a result of a slightly small effect, and the aperture ratio of the current collector used in the fuel cell of the present invention is desirably 35 %, and more desirably 50%. In addition, although a carbon fiber paper having a porosity of 75% is used, the current ratio of the carbon fiber paper of the H portion is 37. In the fuel cell of Example 5 of 5%, the average output enthalpy was 1 〇 6 · 5 %, which was a result of a slight effect, and it was confirmed that the effect was thin by excessive collapse of the carbon fiber paper. [Embodiment 6 to 10] In the following Examples 6 to 10, an example of a battery unit in which a plurality of unit cells are connected in series is used, and a configuration of a basic fuel cell other than the assembled battery is The same as Examples 1 to 5. φ As Example 6, 50 fuel cells having a power generation section as shown in Fig. 5 were produced. The current collectors 7 and 9 have a short rectangular shape and a long rectangular shape, and the wires 7a and 9a extend from the center of one side, and the wires 7a and 9a are connected to the terminals of the load (not shown). Further, the opening portion 16 of the current collector is substantially rectangular in the same size, and the total arrangement of eight vertical columns, six horizontal rows and six columns is a lattice shape. The membrane electrode composite system used is composed of six power generation units disposed on the same plane. However, the solid electrolyte membrane system has a common configuration, and the solid electrolyte membrane has a size of 16 mm×1 1 1 mm. The size of the electrode is set to 6 electrodes of length Gy=l〇〇mm, width Gx=15mm, but the distance between the electrodes Mx or the solid electrolyte membrane from the electrode] viy is all as 3 mm 〇 for each electrode On the anode side and the cathode side, a current collector having a length Ey=100 mm and a width Ex=l 1 mm is disposed, and the current collector disposed is guided by a terminal portion (wire) 7 a, 9 a which is external to the electrode. The anode and the cathode of the adjacent electrode are electrically connected, and the six electrodes are connected in series. In the present embodiment, the width Ex of the current collector is narrower than the width of the electrode, but the collector In the center of the width direction, the current collector is disposed in the width direction of the electrode, and for each current collector, there is a hole 16 for taking in fuel or air, in the present embodiment, in the longitudinal direction, chisel Open 8 lengths Hy = 8 mm, width Hx = 5 mm Holes, the longitudinal direction of the Dy spaced holes 4mm, based on the center in the width direction of the current collector is provided as a = aperture width Dx frame portion = 3mm. • The area of the collector that occupies the area of each electrode is 52%, and the aperture ratio is 48%. For the anode side, the diffusion layer on the cathode side is each used with a thickness of 0. 4mm, carbon fiber paper with a porosity of 75%, and for the collector system, a material that is plated with gold on the surface of the stainless steel, and the material after plating is used as 0. In the state in which the electrode film structure is sandwiched by the current collector, the pressure is applied to the carbon fiber paper, the anode side, and the total thickness of the carbon fiber paper and the current collector on the cathode side. Then as a presentation. 4mm -23- 200828661 The collapse rate in this case is the thickness of the diffusion layer that is not pressed into the collector. 4 mm, and the diffusion layer thickness of the portion of the current collector in the diffusion layer is reduced by 0. 1mm ratio (〇. 1/0. 4), which is 25%, and accordingly, since the porosity α is 75%, it becomes /SSa/3, however, the thickness of the diffusion layer which is pushed into the portion of the current collector in the diffusion layer is reduced (before pressurization) The total thickness of the carbon fiber paper and the current collector) - (the total thickness of the carbon fiber paper and the current collector after pressurization). [Example 7] As Example 7, when the current collector was buried in carbon fiber paper by pressure, the thickness of the current collector deep in the carbon fiber paper was taken as 〇. 〇5mm, making 50 only the anode side, the total carbon fiber paper and the collector on the cathode side are thicker. In the case of 45 mm, a fuel cell different from that of Example 6. The total thickness of the electrode film structure and the current collector is thicker than that of the sixth embodiment, but the torque of the screw that locks the outer material is the same, and the fastening system # is the same as the embodiment, and the thickness is described later. The same treatment is applied to different cases. [Embodiment 8] In the eighth embodiment, the same fuel cell size as that of the sixth embodiment was produced by changing the size of the current collectors on the anode side of the respective electrodes to be changed to the following. As the current collecting system used, the length Ey=l〇〇mm, the width Ex=13m', the size of the hole is as the length Hy = 4m, the width Hx = 5mm, -24-200828661, and the hole system is disposed in the same length direction as in the sixth embodiment. 1 column, but the number of holes is 〖2, the interval of the longitudinal direction of the holes is Dy = 4 mm, the width direction is set at the center of the current collector, and the width of the frame portion is Dx = 3 mm. The area of the current collector occupying the area of each electrode is 64. 3%, the opening rate is 3 5. 7 %. [Example 9] In addition to the arrangement of the current collectors on the anode side of each electrode and the cathode side, the same fuel cell as that of the sinus example 6 was produced. As the current collecting system used, the length Ey = 100 mm, the width Ex = 13 m, the size of the hole is the length Hy = 2 mm, the width is Hx = 5 mm, and the hole system is arranged in the same length direction as in the first embodiment. However, the number of holes is taken as 16 points, the distance between the lengths of the holes is D y = 4 mm, the width direction is set at the center of the current collector, and the width of the frame portion is Dx = 3 mir 〇 occupies the area of each electrode. The area of the current collector is 71. 8%, the opening rate is 3 5. 7 %. [Embodiment 10] As Example 10, except that the thickness ' of the current collector is taken as 〇. In the same manner as in the sixth embodiment, the thickness of the current collector was buried in the carbon fiber paper by press working, and the thickness of each of the carbon fiber paper and the current collector was 50. 4 mm fuel cell-25 - 200828661 [Comparative Example 3] As Comparative Example 3, Example 6 is the same as the member constituting the fuel cell. However, only the electrode film structure is pressurized, and carbon fiber paper is taken as 0. 3 mm ' and on both sides, the current collector is arranged, and the total thickness of the 50 fiber-optic paper and the current collector becomes 0. In the case of 4 mm, a fuel cell different from that of Example 1 was used. [Comparative Example 4] As Comparative Example 4, Example 6 was the same as the member constituting the fuel cell. However, 50 were formed so that the current collector was not penetrated into the carbon fiber paper, and the total thickness of the carbon fiber paper and the current collector was 0. In the case of 5 m m, a fuel cell different from that of the embodiment 6 is used. Table 2 shows the dimensions of the respective portions of the current collectors 7, 9 of the above-described Examples 6 to 10 and Comparative Examples 3 and 4. -26- 200828661 Table 2 Dimensions of each case Dimensions of each electrode Dimensions of the current collector Opening ratio (%) Length Gy (mm) Width Gx (mm) Area (mm2) Length Ey (mm) Width Ex (mm) Hole Length Hy (mm) Hole width Hx (mm) Hole number Hole spacing Dy (mm) Size box Dx (mm) Area (mm2) Example 6 100 15 1500 100 11 8 5 8 4 3 780 48. 0 Example 6 100 15 1500 100 11 8 5 8 4 3 780 48. 0 Example 6 100 15 1500 100 13 4 7 12 4 3 964 35. 7 Example 6 100 15 1500 100 13 2 7 16 4 3 1076 28. 3 Example 6 100 15 1500 100 11 8 5 8 4 3 780 48. 0 Comparison Example 3 100 15 1500 100 11 8 5 8 4 3 780 48. 0 Comparison Example 4 100 15 1500 100 11 8 5 8 4 3 780 48. 0
各作成50個各實施例及比較例之燃料電池，確認輸出 ’而確認輸出的條件係對於燃料，使用5質量％之甲醇水 溶液，確認到0.2V之定電壓輸出。 於表3表示將以往例之一的比較例3之輸出平均値作爲 1〇〇之情況的經由實施例6〜10及比較例4之燃料電池的輸出 平均値。 -27- 200828661 表3 輸出平均値(％) 實施例6 117.6 實施例7 113.1 實施例8 109.4 實施例9 101.0 實施例10 103.5 比較例3 100 比較例4 99.1 從表3的結果了解到，在實施例6〜1 0之中，係確認到 較比較例3，4良好的輸出，其中，關於集電體的開口率爲 2 8.3%小之實施例9，擴散層之潰散部分爲多，而輸出平均 値1 01 ·0%，成爲效果稍微小之結果，而在經由本發明之燃 料電池所使用之集電體的開口率係期望爲3 5%，而更理想 爲 50%。For each of the fuel cells of the respective examples and the comparative examples, the output was confirmed and the condition for confirming the output was a 5% by mass methanol aqueous solution for the fuel, and a constant voltage output of 0.2 V was confirmed. Table 3 shows the output average 燃料 of the fuel cells according to Examples 6 to 10 and Comparative Example 4 in the case where the output average 値 of Comparative Example 3 of the conventional example is 1 〇〇. -27- 200828661 Table 3 Output Average 値 (%) Example 6 117.6 Example 7 113.1 Example 8 109.4 Example 9 101.0 Example 10 103.5 Comparative Example 3 100 Comparative Example 4 99.1 It is understood from the results of Table 3 that In Examples 6 to 10, it was confirmed that the output of Comparative Example 3, 4 was good, and in the case of Example 9, in which the aperture ratio of the current collector was 28.3%, the diffusion layer had a large number of broken portions, and the output was large. The average 値1 01 · 0% is a result of a slightly small effect, and the aperture ratio of the current collector used in the fuel cell according to the present invention is desirably 35%, and more desirably 50%.
另外，雖使用空孔率7 5 %之碳纖維紙，但集電體則該 部分的碳纖維紙之漬散比例爲3 7 · 5 %之實施例1 0的燃料電 池，輸出平均値則爲1〇6·5%，成爲效果稍微小之結果， 並經由碳纖維紙的過度潰散，而可確認到效果爲薄之情況 以上之實施例1〜10及比較例1〜4，屬於於發電部，具 有配置由觸媒層及多孔質之擴散層而成之電極於電解質膜 之兩面的膜電極接合體，並通過配置於前述膜電極接合體 之兩側的集電體，取出電性能量之燃料電池，其中，使集 電體深入於擴散層，並由控制漬散碳纖維紙之比例或集電In addition, although a carbon fiber paper having a porosity of 75 % is used, the current collector has a water-fiber paper having a water-spraying ratio of 37.5%. The fuel cell of the embodiment 10 has an average output of 1 〇. 6 to 5%, which was a result of a slight decrease in the effect, and it was confirmed that the effect was thin by the excessive collapse of the carbon fiber paper, and the examples 1 to 10 and the comparative examples 1 to 4 were included in the power generation unit. The electrode formed by the catalyst layer and the porous diffusion layer is applied to the membrane electrode assembly on both surfaces of the electrolyte membrane, and the fuel cell is discharged from the collectors disposed on both sides of the membrane electrode assembly. Wherein, the current collector is penetrated into the diffusion layer, and the proportion or current collection of the carbon fiber paper is controlled
-28- 200828661 體的開孔率之情況，可確認到表示良好地維持燃料或空氣 之供給的本發明燃料電池良好之特性。 在上述之實施形態中，關於作爲燃料電池之構造，於 膜電極接合體（MEA)10之下部，具有液體燃料收容室14之 被動方式的燃料電池，進行過說明，但，亦可將本發明適 用於其他構造之燃料電池，例如，對於如圖6所示之半被 動方式之燃料電池3 0 1，亦可使用本發明。 (第3實施形態） 有關本實施形態之燃料電池的發電部3 0 1 a係具備膜 電極接合體1 〇，和作爲集電體之陰極集電體7及陽極集電 體9，而膜電極接合體10係將質子傳導性之電解質膜6，夾 持其間，於其兩側，以熱加壓法而一體形成陰極觸媒層2 與陽極觸媒層3 ’更加地，於其外側，具有陰極氣體擴散 層4與陽極氣體擴散層5，而更加地對於膜電極接合體1 〇之 # 陰極氣體擴散層4係導通有正極集電體7，並對於陽極氣體 擴散層5係導通有負極集電體9，而正極集電體7係其一部 分’如圖3所示，深入於陰極氣體擴散層4之中，同樣地， 負極集電體9係其一部分，如圖3所示，深入於陽極氣體擴 散層5之中’而藉由此等正負一對之集電體7，9而由發電 部所發電之電力則呈輸出於未圖示之負荷。 對於電解質膜6與後述之燃料分配機構3〇le及蓋板21 之間，係各自插入橡膠製之〇環8，並作爲經由此等一對 之Ο環8 ’防止從燃料電池發電部3〇la之燃料洩漏或氧化 -29· 200828661 劑浅漏。 蓋板21係具有爲了取入氧化劑（空氣）之複述的開□( 未圖示），而對於蓋板21與發電部301a之陰極之間，係因 應必要而配置有保濕層或表面層，而保濕層（未圖示）係爲 浸含有在陰極觸媒層2所生成的水之一部分，控制水的蒸 發之同時，促進對於陰極觸媒層2之空氣的均一擴散之構 成’表面層（未圖示）係爲調整空氣之取入量的構成，並具 有因應空氣之取入量而調整個數或尺寸等之複數的空氣導 入孔。 對於發電部3 0 1 a之陽極側’係配置有燃料分配機構 3 〇 1 e，對於燃料分配機構3 〇〗e，係藉由如配管之燃料的流 路3 0 1 c而連接燃料收容部3 〇丨b，對於燃料收容部3 〇丨b係 收容有對應於發電部3 0 1 a之形式的液體燃料。 對於燃料分配機構301e，係從燃料收容部301b，藉由 流路3 0 1 c而導入燃料，而流路3 〇 1 c係並非限於燃料分配 機構3 0 1 e或與燃料收容部3 0 1 b獨立之配管的構成，例如 ，層積燃料分配機構3 0 1 e與燃料收容部3 〇 1 b而作爲~體 化之情況’亦可爲連結此等之液體燃料的流路，而燃料分 配機構3 0 1 e係如藉由流路3 0 1 c而與燃料收容部3 〇1 b連接 即可。 在此，如圖7所示，燃料分配機構3 0 1 e係具備具有 燃料藉由流路3 0 1 c而流入之至少;i個的燃料注入口 2 5，和 排出液體燃料或其氣化成分之複數個之燃料排出口 26的燃 料分配板23，對於燃料分配板23的內部，係如圖6所示， -30- 200828661 形成有空隙部24，空隙部24係在流通有從燃料注入口 25 所導入之燃料另一方面，兼備暫時性進行滯留之流路的機 能與集管的機能之構成，而複數之燃料排出口 2 6係各自直 接連接於空隙部24。 燃料係從燃料注入口 25導入於燃料分配機構3 〇 1 e，並 進入空隙部24，再從空隙部24各自導入至複數之燃料排出 口 22 ’而對於複數之燃料排出口 22係亦可配置例如，只透 過燃料之氣化成分，而不使液體成分透過之氣液分離膜（ 未圖示）’由此，對於發電部3 〇 ! a之陽極3，5係供給燃料 之氣化成分’然而，亦可作爲將氣液分離膜（未圖示），插 入於燃料分配機構3 0 1 e與發電部3 0 1 a之陽極3，5之間， 而液體燃料的氣化成分係從複數之燃料排出口 2 6，朝發電 部301a之陽極3，5之複數處而排出。 燃料排出口 26係呈可供給燃料於發電部3〇la之全體 地’複數設置燃料分配板2 3於與發電部3 0 1 a之陽極3，5 接觸的面，而燃料排出口 26之個數係如爲2個以上即可， 但在將針對在燃料電池發電部3 〇〗a之面內的燃料供給量 作爲均一化之後，呈存在有〇·〗〜“個/cm2之燃料排出口 26 地形成情況則爲理想。 對於連接燃料分配機構3 0 1 e與燃料收容部3 0 1 b之間 的流路301c係插入有閥3〇ld，而其閥301d係並非爲循環 燃料之循環閥’而爲從燃料收容部3 0 1 b移送燃料於燃料 分配機構301e的燃料供給閥，經由如此閥3〇1(1在必要時 ’輸送燃料之情況，提升燃料供給量之控制性的構成，此 -31 - 200828661 情況，作爲閥3 0 1 d係可控制性佳地輸送少量的燃料，更 加地從可小型輕量化的觀點’理想爲使用旋轉葉片幫浦， 電性浸透流幫浦，隔片幫浦，汲取幫浦之情況，而旋轉葉 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觀點，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。 針對在如此構成，收容於燃料收容部3 0 1 b之液體燃 料係經由閥3 0 1 d而移送至流路3 〇 1 c，再供給至燃料分配 機構3 0 1 e，並且從燃料分配機構3 0 1 e所釋放之燃料係供 給至發電部3 0 1 a之陽極3，5，而針對在發電部3 〇〗a內， 燃料係擴散陽極氣體擴散層5而供給至陽極觸媒層3，作爲 液體燃料而使用甲醇燃料之情況，在陽極觸媒層3，產生 特定之甲醇的內部改質反應’然而，對於作爲甲醇燃料而 使用純甲醇之情況’係產生使在陰極觸媒層2生成的水或 電解質膜6的水，與甲醇進行反應之內部改質反應，或經 由無需水之其他反應機構，使內部改質反應產生。 然而，如爲進行從燃料分配機構301e對於ME A之燃' 料供給的構成’亦可取代閥3 0 1 d ’而作爲配置燃料遮斷閥 之構成者，對於此情況，燃料遮斷閥係爲爲了控制經由 流路之液體燃料的供給所設置之構成。 -32- 200828661 如根據本發明，將提供連接單電池間之連接部的電性 阻抗小之燃料電池，而如根據本發明，可作爲安定得到良 好之電池性能，並可作爲行動電話，筆記型電腦，攜帶播 放器，攜帶遊戲機等之移動機器的電源，得到不均少之輸 出特性。 然而’本發明並非限定於上述實施形態之構成，而在 實施階段，在不脫離其宗旨之範圍，可將構成要素作爲變 形而具體化，另外，經由揭示於上述實施形態之複數構成 要素的適宜之組合，可形成各種發明，例如，可從表示於 實施形態之全構成要素刪除幾個構成要素，更加地亦可適 宜組合遍佈不同實施形態的構成要素 。 另外’針對在供給於MEA之液體燃料的蒸氣，亦可 完全供給液體燃料的蒸氣，但在以液體狀態供給一部分之 情況，亦可適用本發明。 【圖式簡單說明】 [圖1 ]係爲表示有關本發明之實施形態的燃料電池之 內部透視剖面圖。 [圖2]係爲表示集電體之一例的平面圖。 [圖3 ]係有關實施形態之集電體的剖面圖。 [圖4]係有關其他的實施形態之集電體的剖面圖。 [圖5 ]係有關其他的實施形態之集電體（6串聯）的平面 圖。 [圖6 ]係爲表示有關本發明之其他實施形態的燃料電 -33- 200828661 池之內部透視剖面圖。 [圖7]係表示燃料分配機構的斜視圖。 【主要元件符號說明】 1 :燃料電池 2 :陰極觸媒層 3 :陽極觸媒層 4 =陰極氣體擴散層 5 :陽極氣體擴散層 6 :固體高分子膜 6 :電解質膜 7 :正極集電體 7A，9A :集電體 7 a，9 a :導線 8 : 0環 9 :陽極集電體 1 〇 :發電部 1 〇 :膜電極接合體 1 3 :氣液分離膜 14 :液體燃料空間 1 5 :燃料導入口 1 6 :開口部 20:燃料收容室構造體 2 1 :外裝罩體 -34- 200828661 22 :通氣孔 24 :空隙部 25 :燃料注入口 26 :燃料排除口 3 0 1 a :發電部 3 〇 1 b :燃料收容部 3 〇 1 c :流路 30 Id ：閥 3 〇 1 e :燃料分配機構-28- 200828661 In the case of the opening ratio of the body, it was confirmed that the fuel cell of the present invention which satisfactorily maintains the supply of fuel or air has good characteristics. In the above-described embodiment, a passive fuel cell having a liquid fuel storage chamber 14 under the membrane electrode assembly (MEA) 10 as a structure of the fuel cell has been described. However, the present invention can also be applied. A fuel cell suitable for other configurations, for example, the fuel cell 300 in a semi-passive manner as shown in Fig. 6 can also be used. (Third Embodiment) The power generation unit 30 1 a of the fuel cell of the present embodiment includes the membrane electrode assembly 1 〇, and the cathode current collector 7 and the anode current collector 9 as current collectors, and the membrane electrode The bonded body 10 is formed by sandwiching the proton conductive electrolyte membrane 6 on both sides thereof, and further forming the cathode catalyst layer 2 and the anode catalyst layer 3' on the both sides thereof by hot pressurization. The cathode gas diffusion layer 4 and the anode gas diffusion layer 5 are further connected to the cathode electrode diffusion layer 4 of the membrane electrode assembly 1 with the cathode current collector 7 and the anode gas diffusion layer 5 with the anode group. The electric body 9 and the positive electrode current collector 7 are partially "into the cathode gas diffusion layer 4 as shown in FIG. 3, and similarly, the negative electrode current collector 9 is a part thereof, as shown in FIG. In the anode gas diffusion layer 5, the electric power generated by the power generation unit by the positive and negative pair of current collectors 7, 9 is outputted to a load (not shown). The rubber membrane 6 is inserted between the fuel membrane 6 and the fuel distribution mechanism 3〇 and the cover 21, which will be described later, and is inserted into the rubber battery power generation unit 3 as a pair of the ring 8'. La fuel leak or oxidation -29· 200828661 agent shallow leak. The cover plate 21 has an opening (not shown) for taking in a description of the oxidizing agent (air), and a moisture-retaining layer or a surface layer is disposed between the cover plate 21 and the cathode of the power generating portion 301a as necessary. The moisture retaining layer (not shown) is formed by immersing a part of the water generated in the cathode catalyst layer 2, controlling the evaporation of water, and promoting the uniform diffusion of the air to the cathode catalyst layer 2 as a surface layer (not shown). The figure is a configuration for adjusting the amount of intake of air, and has a plurality of air introduction holes for adjusting the number, size, and the like in accordance with the amount of intake of air. The fuel distribution mechanism 3 〇 1 e is disposed on the anode side of the power generation unit 3 0 1 a, and the fuel storage unit 3 〇 e is connected to the fuel storage unit by a flow path 3 0 1 c of the fuel such as a pipe. 3 〇丨b, in the fuel accommodating portion 3 〇丨b, a liquid fuel in a form corresponding to the power generating portion 3 0 1 a is housed. In the fuel distribution mechanism 301e, fuel is introduced from the fuel accommodating portion 301b by the flow path 3 0 1 c, and the flow path 3 〇1 c is not limited to the fuel distribution mechanism 3 0 1 e or the fuel storage portion 3 0 1 b. The configuration of the independent piping, for example, the case where the laminated fuel distribution mechanism 3 0 1 e and the fuel accommodating portion 3 〇1 b are used as the "body" may be a flow path connecting the liquid fuels, and the fuel distribution The mechanism 3 0 1 e may be connected to the fuel containing unit 3 〇 1 b by the flow path 3 0 1 c. Here, as shown in FIG. 7, the fuel distribution mechanism 3 0 1 e is provided with at least one of the fuel injection ports 25 through which the fuel flows in through the flow path 3 0 1 c, and the liquid fuel discharged or its gasification. The fuel distribution plate 23 of the plurality of fuel discharge ports 26 of the components is as shown in Fig. 6 for the inside of the fuel distribution plate 23, and the gap portion 24 is formed by -30-200828661, and the gap portion 24 is flowed from the fuel injection. On the other hand, the fuel introduced into the inlet 25 has a function of a function of temporarily storing the retained flow path and a function of the header, and a plurality of fuel discharge ports 26 are directly connected to the gap portion 24, respectively. The fuel is introduced into the fuel distribution mechanism 3 〇1 e from the fuel injection port 25, enters the gap portion 24, and is introduced into the plurality of fuel discharge ports 22' from the gap portion 24, and can be disposed for the plurality of fuel discharge ports 22 For example, a gas-liquid separation membrane (not shown) that transmits only a vaporized component of a fuel without passing a liquid component 'is a gasification component for the anode 3, 5 of the power generation unit 3 〇! a However, it is also possible to insert a gas-liquid separation membrane (not shown) between the fuel distribution mechanism 3 0 1 e and the anodes 3, 5 of the power generation unit 3 0 1 a, and the vaporization component of the liquid fuel is plural The fuel discharge port 26 is discharged to the plurality of anodes 3, 5 of the power generation portion 301a. The fuel discharge port 26 is provided with fuel to be supplied to the entire power generation unit 3a, and a plurality of fuel distribution plates 23 are provided on the surface in contact with the anodes 3, 5 of the power generation unit 3 0 1 a, and the fuel discharge ports 26 are provided. In the case of the number of the fuel supply in the surface of the fuel cell power generation unit 3 a a, the fuel supply port is present in the fuel cell power generation unit 3 a a. The formation of the ground is ideal. The flow path 301c between the fuel distribution mechanism 3 0 1 e and the fuel storage unit 3 0 1 b is inserted with the valve 3〇ld, and the valve 301d is not a cycle of circulating fuel. The valve is a fuel supply valve that transfers fuel to the fuel distribution mechanism 301e from the fuel accommodating portion 301b, and the controllability of the fuel supply amount is improved by the valve 3〇1 (1 when necessary) , -31 - 200828661 In the case of valve 3 0 1 d, a small amount of fuel can be conveyed with good controllability, and from the viewpoint of small size and light weight, it is ideal to use a rotating blade pump, an electric immersion flow pump, Separate pump, take the situation of the pump, and rotate The sheet pumping system is configured to convey a blade by rotating a motor, and the electrically-impregnated flow pumping system is a sintered porous body using cerium oxide or the like which causes an electrical permeation phenomenon, and the spacer pumping system is via The structure in which the electromagnet or the piezoelectric ceramic drives the separator to be transported is a configuration in which the pumping unit presses a part of the flexible fuel flow path to extract the fuel and transports it. Here, the driving power, the size, and the like are used. In view of the above, it is more preferable to use an electrically immersed flow pump or a spacer pump having a pressure electromagnetic stone. With this configuration, the liquid fuel contained in the fuel accommodating portion 3 0 1 b is transferred to the liquid fuel via the valve 3 0 1 d. The flow path 3 〇1 c is supplied to the fuel distribution mechanism 3 0 1 e, and the fuel released from the fuel distribution mechanism 3 0 1 e is supplied to the anodes 3, 5 of the power generation unit 3 0 1 a, and is generated for power generation. In the third portion, the fuel is diffused into the anode gas diffusion layer 5 and supplied to the anode catalyst layer 3, and the methanol fuel is used as the liquid fuel. In the anode catalyst layer 3, a specific methanol internal reforming reaction is generated. 'Ran On the other hand, in the case where pure methanol is used as the methanol fuel, an internal reforming reaction in which water generated in the cathode catalyst layer 2 or the electrolyte membrane 6 is reacted with methanol or another reaction mechanism that does not require water is generated. The internal reforming reaction is generated. However, if the fuel supply mechanism 301e is configured to supply the fuel to the ME A, it may be replaced by the valve 3 0 1 d' as a component of the fuel shut-off valve. In this case, the fuel shutoff valve is configured to control the supply of the liquid fuel via the flow path. -32- 200828661 According to the present invention, a fuel cell having a small electrical impedance connecting the connection portions between the unit cells is provided. According to the present invention, it is possible to obtain good battery performance as stability, and it can be used as a power source for mobile phones such as mobile phones, notebook computers, portable players, and game machines, and has an uneven output characteristic. However, the present invention is not limited to the configuration of the above-described embodiment, and in the implementation stage, constituent elements may be embodied as modifications without departing from the scope of the invention, and suitable for the plurality of constituent elements disclosed in the above embodiment. In the combination, various inventions can be formed. For example, several constituent elements can be deleted from the entire constituent elements shown in the embodiment, and constituent elements that are spread over different embodiments can be combined as appropriate. Further, the vapor of the liquid fuel may be completely supplied to the vapor of the liquid fuel supplied to the MEA, but the present invention may be applied to a case where a part of the liquid fuel is supplied in a liquid state. BRIEF DESCRIPTION OF THE DRAWINGS [Fig. 1] Fig. 1 is an internal perspective sectional view showing a fuel cell according to an embodiment of the present invention. Fig. 2 is a plan view showing an example of a current collector. Fig. 3 is a cross-sectional view showing a current collector according to an embodiment. Fig. 4 is a cross-sectional view showing a current collector according to another embodiment. Fig. 5 is a plan view showing a current collector (6 series) of another embodiment. Fig. 6 is an internal perspective sectional view showing a pool of fuel electric-33-200828661 according to another embodiment of the present invention. Fig. 7 is a perspective view showing a fuel distribution mechanism. [Description of main components] 1 : Fuel cell 2 : Cathode catalyst layer 3 : Anode catalyst layer 4 = Cathode gas diffusion layer 5 : Anode gas diffusion layer 6 : Solid polymer film 6 : Electrolyte film 7 : Positive electrode collector 7A, 9A: current collector 7 a, 9 a : wire 8 : 0 ring 9 : anode current collector 1 〇 : power generation portion 1 〇 : membrane electrode assembly 1 3 : gas-liquid separation membrane 14 : liquid fuel space 1 5 Fuel introduction port 16: Opening portion 20: Fuel storage chamber structure 2 1 : Exterior cover body - 34 - 200828661 22 : Vent hole 24 : Air gap portion 25 : Fuel injection port 26 : Fuel discharge port 3 0 1 a : Power generation unit 3 〇1 b : fuel accommodating portion 3 〇 1 c : flow path 30 Id : valve 3 〇 1 e : fuel distribution mechanism
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