1326931 (1) 九、發明說明 【發明所屬之技術領域】 本發明是關於燃料電池用燃料卡匣和使用該卡厘之燃 料電池》 【先前技術】 近年’爲了要使筆記型電腦或行動電話等的各種攜帶 % 用電子機器不必長時間充電仍能夠使用，嘗試將燃料電池 用來作爲該攜帶用電子機器的電源。燃料電池的特徵爲具 有只要供應燃料和空氣就可以發電，又補充燃料的話，可 以長時間連續發電。因而，若是可以將燃料電池小型化的 話’則稱得上極有助於用來作爲攜帶用電子機器的電源之 系統。 使用能量密度很高的甲醇燃料之直接甲醇型燃料電池 (DMFC : direct methanol fuel cell)能夠小型化，再者燃 • 料的處理容易，故期待作爲攜帶機器用的電源》DMFC的 液體燃料供應方式已知有：氣體供給型或液體供給型的主 動方式、使燃料存放部內的液體燃料在電池內部氣化後供 應到燃料極之內部氣化型等的被動型方式。這些供應方式 當中’主動方式由於能夠DMFC的高出力化（大電力化） ’故期待能來作爲筆記型電腦等的電源。 內部氣化型等的被動方式，由於不必要如同燃料幫浦 之動力式的燃料移送手段，所以特別有助於DMFC的小型 化。例如’曰本專利文獻1或專利文獻2中，對於具備有 -5- (2) 1326931 保持液體燃料的燃料浸透層、及使被保持持在燃料浸透層 中之液體燃料的氣化成分擴散來供應到燃料極的燃料氣化 層之被動型DM FC已有記載。這種被動型DMFC期待能成 爲攜帶用音響裝置或行動電話等小型攜帶機器等的電源。 主動型DMFC係將存放液體燃料的燃料卡匣連接到燃 料電池本體’從該燃料卡匣直接或是經由燃料存放部（稀 釋調整槽等）使液體燃料循環，藉此來將液體燃料供應到 φ 燃料電池薄膜電極組。一方面，內部氣化型等的被動型 DMFC ’具備有燃料存放部及使液體燃料氣化的機構，與 主動型同樣’使用燃料卡匣來對於燃料存放部供應液體燃 料。衛星形式（外部注入式）的燃料卡匣，嘗試使用分別 由內部設有閥機構的噴嘴部及插座部所構成的聯結器，進 行液體燃料的阻斷和注入（例如參考日本文獻3 )。 內部氣化型等的被動型DMFC，例如爲了要搭載在攜 帶用電子機器而持續變小型，其結果導致DMFC側的插座 • 部或燃料卡匣側的噴嘴部也有小型化的趨勢。將這種噴嘴 部與插座部予以連接，從燃料卡匣來將液體燃料注入到 DMFC的燃料存放部的情況，會有對燃料卡匣施加彎曲負 荷的力量時導致損壞之虞。 燃料卡匣係利用內設在噴嘴部的閥機構來阻斷液體燃 料’故會有噴嘴損壞導致存放在燃料卡匣中的液體燃料漏 出之虞。即使噴嘴損壞時閥機構沒有損壞，仍會有閥機機 的構成零件突出致使閥機構誤動作而漏出液體燃料的危險 性。 -6- (3) 1326931 對於 DMFC用燃料卡匣的噴嘴部使用聚醚醚酮 (Polyether ether ketone,PEEK)、聚苯硫醚（Polyphenylene Sulfide Ether,PPS) 液晶聚合物（Liquid Crystal Polymer，LCP)等的超級工程塑膠；或聚對苯二甲酸乙二醇 醋（Polyethylene terephthalate ,ΡΕΤ)、聚對苯二甲酸丁二 醇醋（Polybutylene Terephthalate,PBT)、聚縮醒 (P〇lyaCetal，POM)等的泛用工程塑膠，進行檢討。然而， φ 這些工程塑膠既硬又韌性不佳，所以有對彎曲負荷容易折 損的問題點。 〔專利文獻1〕日本專利第3413111號公報 〔專利文獻2〕日本專利特開2004 - 1 7 1 844公報 〔專利文獻3〕日本專利特開2004 — 1 27824公報 【發明內容】 本發明的目的係提供能夠抑制發生噴嘴部損壞的情況 # 的缺失之燃料電池用燃料卡匣、及適用該燃料卡匣之燃料 電池。 ，·匕 ° \ ' ( β . . 本發明形態的燃料電池用燃料卡匣，.其特徵爲具備有 :存放燃料電池用的液體燃料之卡匣本體/及被設羃在前 述卡匣本體，內部設有具有分割構造的閥機構之噴嘴部。 本發明形態的燃料電池，其特徵爲具備有：本發明形 態之燃料電池用燃料卡匣 '及配備有具眘可.拆裝地舆前述 燃料卡匣的前述噴嘴部相連接的插座部之燃料_放部和從 4« , · 前述燃料存放部供應前述液體燃料來進行發怍之‘起電 (4) 1326931 部之燃料電池本體。 【實施方式】 以下，針對用來實施本發明的形態進行說明。第1圖 爲表示本發明的實施形態之燃料電池的構成之圖。第1圖 所示的燃料電池1具備有：主要由成爲起電部之燃料電池 薄膜電極組2和燃料存放部3所構成之燃料電池本體4、 φ 及將液體燃料供應到燃料存放部3之衛星形式（外部注入 式）的燃料卡匣5。在燃料存放部3的下面側，設置具有 成爲液體燃料的供應口之插座部6之燃料供應部7。如同 以下所詳述，插座部6內部設有閥機構，除了供應液體燃 料時之外，成爲閉合狀態。 燃料卡匣5具有存放燃料電池用的液體燃料之卡匣本 體（容器）8。卡匣本體8的前端開口部，設有成爲將該 內部所存放的液體燃料供應到燃料電池本體4時的燃料噴 # 出口之噴嘴部9。噴嘴部9如同後述內部設有閥機構，除 了供應液體燃料時之外，成爲閉合狀態。這種燃料卡匣5 只在液體燃料注入燃料存放部時才連接到液體燃料本體4 〇 燃料卡匣5的卡匣本體8，存放與燃料電池本體4相 對應的液體燃料，例如直接甲醇型燃料電池（DMFC )的 話，則存放各種濃度的甲醇水溶液或純甲醇等的甲醇燃料 。存放在卡匣本體8的液體燃料並不侷限於甲醇燃料，例 如也可以存放乙醇水溶液或純乙醇等的乙醇燃料、丙醇水 -8- (5) 1326931 溶液或純丙醇等的丙醇燃半斗 '乙=醇水溶液或純乙二醇等 的乙二醇燃料、二甲酸、甲酸、其他的液體燃料。無論如 何，存放與燃料電池本體4相對應的液體燃料。 被設置在燃料電池本體4的燃料存放部3之插座部6 及被设置在燃料卡匣5的卡匣本體8之噴嘴部9係構成一 對連接機構（聯結器）。有關插座部6及噴嘴部9所構成 之聯結器的具體構成，參考第2圖來進行說明。第2圖爲 • 表示本發明的實施形態之燃料電池用燃料卡匣5的構成。 第2圖中表示燃料卡匣5的噴嘴部與燃料電池本體4的插 座部6相連接之前的狀態。 燃料電池本體4與燃料卡匣5相連接之聯結器中，作 爲卡匣側連接機構的噴嘴部（公側聯結器）9，具有由基 體部11及插入部12所構成之噴嘴頭。基體部n係裝著 在卡匣本體8的前端開口部。基體部I〗具有與插座部6 相對向之平坦面11a’以突出該平坦面lla的方式設置圓 • 筒狀的插入部12。插入部12的該前端側具有噴嘴口 13。 基體部11的內側設有閥座14。基體部11與插入部丨2則 是一體成形。 在噴嘴頭的內部配置杯狀的閥支架15。閥支架15位 於基體部11的內側，與基體部11共同來限定閥室。閥支 架15係利用卡匣本體8及基體部π夾入該前端外緣部來 予以固定。在利用基體部11及閥支架15所限定之閥室內 配置閥16。閥16具備有：具有閥頭17a之閥本體17、及 被設置在閥本體17的前端部之圓柱狀的閥桿18、及被設 • 9 - (6) 1326931 置在閥本體1 7的後方側之導銷1 9。 如同後述，閥16具有向軸方向分割的構造。具有閥 頭17a之閥本體17，配置在利用基體部11及閥支架15所 限定之閥室內。閥桿18收納在圓筒狀的插入部12內。閥 16能夠向軸方向（噴嘴部9的插入方向）進退。在閥頭 17a與閥座14之間配置〇封圈。例如用如同壓縮彈簧21 的彈性構件，隨時對閥本體17施加強制使閥頭17a推向 # 閥座14的力量，藉此來押壓〇封圈20。 通常狀態（燃料卡匣5脫離燃料電池本體4的狀態） ，經由〇封圈來強制使閥頭17a推向閥座，藉此來使噴嘴 部9內的燃料流路成爲閉合狀態。一方面，如同後述將燃 料卡匣5連接到燃料電池本體4，則閥桿18後退而使閥頭 17a脫離閥座14，使噴嘴部9內的燃料流路成爲開放狀態 。閥支架15的底部設有成爲液體燃料的流路之連通孔i5a 。被設置在閥本體1 7的後方側之導銷1 9則是插進連通孔 φ 15a 內。 閥16的閥桿18具有分割構造。具體上，閥桿18係 如第3圖所示，具有與閥本體17 —體化的桿基部22、及 與該桿基部22分割的桿前端部23。即是閥桿18由桿基部 22及桿前端部23的2種零件所構成，這兩種零件分別被 分割來成爲獨立的零件。該桿基部22與桿前端部23的接 觸面成爲閥桿18的分割面。 桿前端部23具有以不會從閥頭的插入部12脫落的方 式設置在桿基部22側的大徑部23a。閥前端部23具備有 -10- 12 (7) 1326931 配置在插入部12內之小徑部23 b、及具有大於插入部 內徑的外徑之大徑部23a。利用插入部12內的階段狀孔 壓制大徑部23a，藉此來防止桿前端部23脫離插入部 。桿基部22具有與桿前端部23的大徑部23a相同的直 。使這兩基部22與桿前端部23的大徑部23a相接觸來 裝閥1 6，以這狀態來配置到噴嘴頭內。 在閥桿18與插入部12的內壁面之間設置液體燃料 • 流路的情況，桿基部22及桿前端部23可以不必考慮周 向的位置關係，單是接觸來進行組裝。一方面，會有在 方向上形成溝槽來將液體燃料的流路設置在閥桿1 8的 周面的情況。這種情況最好是如第4圖和第5圖所示， 桿前端部23的大徑部及桿基部22(第4圖和第5 中未圖示），設置顯示周方向的位置之導引鍵。 可以藉由使用導引鍵24，對準桿基部22與桿前端 23之周方向的位置來進行閥16的組裝。此處則是顯示 • 有2個導引鍵24的桿前端部23，不過導引鍵24的個數 不侷限於2個，例如也可以是丨個或4個。此外，在插 部12的內壁面’對應於設置在閥桿18側的導引鍵24 設置鍵槽。藉由將閥桿18側導引鍵24與插入部12的 槽相卡合’對準桿基部22與桿前端部23之周方向的位 〇 閥桿18之桿則端部23的構成材料或桿基部22被 體化之桿本體17的構成材料’例如可以使用超級工程 膠或泛用工程塑膠。進而，閥16的構成材料最好是與 來 12 徑 組 的 方 軸 外 在 圖 部 具 並 入 來 鍵 置 塑 甲 -11 - (8) 1326931 醇燃料相接觸，具有耐甲醇性。這樣的材料例如列舉有： 聚對苯二甲酸乙二醇酯、聚對苯二甲酸丁二醇酯、聚縮醒 等的泛用工程塑膠以及聚苯硫醚、聚醚醚酮、液晶聚合物 等的超級工程塑膠。 有關閥16以外的噴嘴部9，最好也是由同樣的超級工 程塑膠或泛用工程塑膠所構成。上述的各材料都具有良好 的耐甲醇性。具體上，經過以ns Κ7ΐ μ的「塑膠的耐藥 φ 品性試驗方法」爲基準之純甲醇的浸漬試驗，符合質量變 化率爲0.3%以下、長度變化率爲0.5%以下、厚度變化率 爲〇 · 5 %以下的條件》各變化率的値未達上述的値，則會 有將甲醇燃料等存放到燃料卡匣5來使用時，在噴嘴部9 發生溶解或應力裂痕等之虞。因此，降低燃料卡匣5實用 上的耐久性或可靠性。 燃料卡匣5側的噴嘴部9有隨著燃料電池本體4的小 型化而被小徑化的趨勢。被小徑化的噴嘴部9會有對燃料 Φ 卡匣5施加彎曲負荷（來自對燃料卡匣5的插入方向具有 角度的方向之力量所造成的負荷）時導致損壞之虞。具體 上，會有如第6圖所示，突出基體部11的插入部12折損 的可能性。噴嘴部9受損壞的危險性則是愈小徑化則愈高 ，尤其，用對於上述過的超級工程塑膠或泛用工程塑膠等 的彎曲負荷之韌性較差的的材料來構成噴嘴部9的情況則 容易損壞。 本實施形態中，使用將閥桿18分割成桿基部22和桿 前端部23的構造。因而，即使如第6圖所示閥頭的插入 -12- (9) 1326931 部12折損’仍只有桿前端部23與插入部一起脫離，藉此 可以防止阻斷液體燃料的閥機構（利用閥頭17a阻斷液體 燃料的機構）受到損壞。即是閥桿1 8與閥本體1 7 —體化 的情況’與閥桿18與插入部12 —起折損，則會有閥機構 也損壞之虞。針對這點’將閥桿18分割成桿基部22和桿 前端部23，藉此就可以防止閥桿18損壞導致閥機構的損 壞。 # 進而’閥桿18與閥本體17 —體化，則即使插入部12 損壞時閥桿18沒有折損，損壞後閥桿18仍突出基體部11 的平坦面1 1 a。這狀態會有誤按壓閥桿1 8的情況漏出液體 燃料之虞。本實施形態中，即使噴嘴部9損壞的情況，桿 前端部23仍與插入部12 —起脫離，故不會損壞後閥桿18 突出基體部11的平坦面11a。因此，能夠抑制發生噴嘴部 9損壞時的缺失（漏出液體燃料）。 如同上述過插入部12損壞的情況，桿前端部23最好 Φ 是以閥桿18的一部份不會突出基體部11的平坦面lla的 方式脫離。因此，桿基部22與桿前端部23的分割面最好 是位於與基體部11的平坦面lla相同的面上，或是比平 坦面1 1 a還要更閥本體17側（卡匣本體8側）。藉此就 可以更加確實地防止插入部12損壞時閥桿18的突出。 適用於閥16的分割構造並不侷限於將閥桿18分割成 桿基部22和桿前端部23的構造。如第7圖所示，也可以 使閥本體17及閥桿18予以分割。即是第7圖所示的閥16 具有：具有閥頭17a之閥本體17、及被配置在該閥本體 -13- 1326931 do) Ϊ7的前端側，且與閥本體17分割之閥桿18。此外，有關 其他的構造則與第2圖同樣。 閥16係由具有閥頭17a之閥本體17及閥桿18的2 種零件所構成，這兩零件分別被分割來成爲獨立的零件。 該閥本體17與閥桿18的接觸面成爲閥16的分割面。閥 桿18具備有配置在插入部12內之小徑部、及具有大於插 入部12內徑的外徑之大徑部。利用插入部12內的階段狀 # 孔來壓制大徑部23a，藉此來防止閥桿I 8脫離插入部12 。使該閥本體17與閥桿18相接觸來組裝閥16，以這狀態 來配置到噴嘴頭內。 如此’將閥16分割成閥本體17和閥桿18的情況， 如第8圖所示，閥桿18與損壞的插入部12 —起脫離，故 可以防止閥機構（利用閥頭17a阻斷液體燃料的機構）受 到損壞。進而，也不會插入部12損壞後閥16的一部份突 出基體部11的平坦面11a。將閥16分割成閥本體17和閥 # 桿18的構造中，尤其，閥本體17的表面（閥本體17與 閥桿18的分割面），位於比基體部11的平坦面11a還要 更閥頭（基體部11)的內側，故可以更加確實地防止閥機 構誤動作造成的洩漏。 作爲燃料電池側連接機構的插座度（母側聯結器）6 ’如第2圖所示，具有圓筒狀的插座本體（外殼）31。插 座本體31具有本體上部31a、本體中部31b、本體下部 31c’這些被一體化來裝塡到燃料電池本體4的燃料供應 部7內。大致圓筒狀的本體上部31a具有插入噴嘴部的插 -14· (11) 1326931 入部12之插座口。 插座本體31的本體中部31b具有向該直徑方向內側 突出之環狀凸部32。在環狀凸部32上，設置彈性體支架 之橡膠支架33。橡膠支架33配置在本體上部31a內。橡 膠支架33係根據形狀（伸縮形狀）及材料特性（橡膠彈 性）來向軸方向施予彈性。橡膠支架33爲在噴嘴部9的 插入部1 2之間形成密封之密封構件，該內側則作爲燃料 φ 流路。 在插座本體31內配置閥34。閥34具備有：具有閥頭 35a之閥本體35、及被設置在閥本體35的前端側之閥桿 36、及被設置在閥本體35的後方側之導銷37。具有閥頭 35a之閥本體35配置在以本體中部31b及本體下部31(；所 形成之閥室內。閥桿36則是收納在橡膠支架33內。閥34 能夠向軸方向（噴嘴部9的插入方向）進退。 在閥頭35a與被形成在環狀凸部32的下面側之閥座 • 38之間配置〇封圈39。對閥本體35，例如藉由如同壓縮 彈環40的彈性構件’隨時施加將閥頭35a強制推向閥座 38的力量，藉此來押壓〇封圈。通常狀態（燃料卡匣5 從燃料電池本體4脫離的狀態）下，經由〇封圈39，閥 頭35a強制推向閥座38 ’藉此插座部6內燃料流路成爲閉 合狀態。 燃料卡匣5連接到燃料電池本體4，則閥桿36後退， 閥頭35a脫離閥座38，插座部6內的燃料流路則成爲開放 狀態。插座本體31的本體下部31c設有經由燃料供應部7 -15- (12) 1326931 內連接到燃料存放部3之連通孔41。此外，被設置在閥本 體35的後方側之導銷3 7插進連通孔41內。 如此’插座部6則使被設置在本體31內之燃料流路 經由被設置在本體下部31c之連通孔41來連接到燃料存 放部3。然後，閥16、34成爲開放狀態來將噴嘴部9和插 座部6內的燃料流路分別予以開放，藉此就能夠經由噴嘴 部9和插座部6將被存放在燃料卡匣5的液體燃料注入到 φ 燃料存放部3內。 當要將存放在燃料卡匣5的液體燃料供應到燃料電池 本體4的燃料存放部3，則要將燃料卡匣5的噴嘴部9插 入插座部6來予以連接。此處，在噴嘴部9之插入部12 的外周面，沿著燃料卡匣5的插入方向（噴嘴部9的軸方 向）’例如形成有2條導引槽25。一方面，在插座部6之 插座本體31的內周面，設置與導引槽25相卡合來導引燃 料卡匣5的插入之鍵部42。鍵部42係依照導引槽25的數 # 量’以向插座本體31的徑方向側突出的方式形成。 導引槽25的形狀，例如列舉有沿著插入部丨2的軸方 向之直線狀形狀。進而，導引槽25也可以將鍵部42沿著 軸方向導引，並且使噴嘴部9鎖定在插座部6，從中途就 向周方向移位。即是導引槽25並不侷限於直線形狀，也 可以是J形狀。與導引槽25相卡合的鍵部42，適用將輪 轂一體形成在插座本體31的內周面的形式、或將與插座 本體31不同構件的鍵插入插座本體31的形式等。鍵部42 也可以用金屬材料來形成。 -16- (13) 1326931 —面將鍵部42卡合到導引槽25，一面將噴嘴部9插 入插座部6，首先，插入部12的前端與橡膠支架33的前 端相接觸，閥16、34成爲開放狀態之前，確實密封燃料 流路的周邊。由插入部12的前端與橡膠支架33的前端相 接觸的狀態，將噴嘴部9插入插座部6，則噴嘴部9的閥 桿18和插座部6的閥桿36的前端彼此間相抵觸。由這狀 態再度將噴嘴部9插入插座部6，則插座部6的閥34後退 • 來將流路開放之後，噴嘴部9的閥16後退來確立燃料流 路。藉由此方式，將被存放在燃料卡匣5的液體燃料供應 到燃料電池本體4的燃料存放部3。 本實施形態中，如同前述過噴嘴部9的閥16中使用 分割構造。因此，將燃料卡匣5的噴嘴部9連接到燃料電 池本體4的插座部6時，即使對燃料卡匣5施加彎曲負荷 致使噴嘴部9(例如，插入部12)損壞，閥16的一部份 (閥桿18的桿前端部23或閥桿18本身）仍會與插入部 • 12 —起脫離，故可以防止閥機構受到損壞。進而，也不會 損壞後閥16的一部分突出基體部11的平坦面11a。藉此 能夠抑制燃料卡匣5的噴嘴部9損壞時造成的缺失（洩漏 液體燃料）。 然則，噴嘴部9損壞的燃料卡匣5則無法直接再度使 用。本實施形態的燃料卡匣5，如第9圖所示，具有被安 裝在損壞之噴嘴部9的外側之備用噴嘴45。備用噴嘴45 具有被配置在閥16的分割面（第3圖所示之桿基部22的 表面或第7圖所示之閥本體17的表面）上之備用的閥桿 -17- (14) 1326931 46。備用噴嘴45係在配置了備用的閥桿45之後裝著在損 壞之基體部1 1的外側。 如此’先準備備用噴嘴45，藉此則能夠再度使用噴嘴 部9損壞的燃料卡匣5。本實施形態中，即使噴嘴部9損 壞的情況，仍可以防止閥機構受到損壞。因此，在損壞之 噴嘴部9的外側，安裝具有備用的閥桿46之備用噴嘴45 ，藉此則不會導致液體燃料洩漏，可以再度使用燃料卡匣 φ 5。此外，第9圖中，圖號47爲密封液體燃料的〇封圈。 其次，針對燃料電池本體4的構造進行說明。燃料電 池本體4並沒有特別的限定，例如可以使用必要時連接衛 星形式的燃料卡匣5之被動型或主動型的DMFC。此處則 是參考第10圖來說明燃料電池本體4使用內部氣化型的 DMFC之實施形態。第10圖所示之內部氣化型（被動型 )的DMFC 4 ’除了具備構成起電部之燃料電池薄膜電極 組2及燃料存放部3，還具備夾在這兩之間之氣體選擇透 # 過膜51。 燃料電池薄膜電極組2具有：由具有陽極觸媒層52 和陽極氣體擴散層53之陽極（燃料極）、及具有陰極觸 媒層54和陰極氣體擴散層54之陰極（氧化劑極/空氣極 )、及用陽極觸媒層52和陰極觸媒層54來夾持之質子（ 氫離子）傳導性的電解質膜56所構成之膜電極接合體（ Membrane Electrode Assembly ： ΜEA )。 含在陽極觸媒層52和陰極觸媒層54的觸媒，例如列 舉有Pt、Ru' Rh、Ir、〇s、Pd等之白金族元素的單體及 •18- (15) 1326931 含有白金族元素的合金等。最好是陽極觸媒層52使用對 甲醇或一氧化碳有很強的耐性之Pt-Ru或Pt-Mo等。陰極 觸媒層54最好是使用Pt或Pt-Ni等。觸媒也可以使用如 同碳材料的導電性受載體之受載觸媒或者非受載觸媒的任 何一種。 構成電解質膜5 6的質子傳導性材料，例如列舉有如 同具有磺酸基的全氟磺酸聚合物之氟系樹脂（Nafion (商 品名’日本Dupont公司製造）或flemion(商品名，日本 旭硝子公司製造）等）、具有磺酸基碳化氫系樹脂、鎢酸 或磷鎢酸等的無機物等。惟，質子傳導性的電解質膜56 並不侷限於這些。 層積在陽極觸媒層52之陽極氣體擴散層53，擔負將 燃料均等供應到陽極觸媒層52的工作，同時還兼負陽極 觸媒層52的集電體。層積在陰極觸媒層54之陰極氣體擴 散層5 5，擔負將氧化劑均等供應到陰極觸媒層54的工作 • ，同時還兼負陰極觸媒層54的集電體。 在陽極氣體擴散層53層積陽極導電層57，在陰極氣 體擴散層55層積陰極導電層58。這兩導電層57、58例如 由以如同金的導電性金屬材料所組成之網目、多孔質膜、 薄膜等所構成。電解質膜56與陽極導電層57之間以及電 解質膜56與陰極導電層58之間，中間設有橡膠製的〇封 圈59、60，藉此來防止從燃料電池薄膜電極組（MEA) 2 洩漏燃料或洩漏氧化劑。 燃料槽等之燃料存放部3的內部’裝塡有甲醇燃料來 -19- (16) 1326931 作爲液體燃料F。燃料存放部3具有存放液體燃料F之箱 狀容器，該箱狀容器中與陽極（燃料極）相對向的面爲開 口著。在燃料存放部3的開口部與燃料電池薄膜電極組2 之間設置氣體選擇透過膜51。氣體選擇透過膜51爲只透 過液體燃料F的氣化成分，不讓液體成分透過之氣液分離 膜。 氣體選擇透過膜51的構成材料，例如列舉有如同聚 φ 四氟乙烯的含氟樹脂。經由氣體選擇透過膜51，對燃料電 池薄膜電極組2只供應液體燃料F的氣化成分。液體燃料 F的氣化成分係指當使用甲醇水溶液來作爲液體燃料F的 情況爲由甲醇的氣化成分和水的氣化成分所組成的混合氣 ，當使用純甲醇的情況則爲甲醇的氣化成分》 陰極導電極58上層積保濕層61，該上面則層積表面 層62。表面層62具有調整氧化劑也就是調整空氣的導入 量之功能，該調整係依據被形成在表面層62之空氣導入 # 口 63的個數或尺寸來進行。保濕層61係擔負浸漬經由陰 極觸媒層54所生成之水的一部份來抑制水的蒸散的工作 ，並且具有將氧化劑均等導入到陰極氣體擴散層55，促進 氧化劑均均等擴散到陰極觸媒層54的功能。保濕層6 1係 由多孔質構造的構件所構成。具體的構成材料，列舉有聚 乙烯或聚丙烯的多孔質體等。 在燃料存放部3上依序層積氣體選擇透過膜51、燃料 電池薄膜電極組2、保濕層61、表面層62’再從該上面例 如組裝不銹鋼製的殼體。用殻體來保持構成要件全體’藉 -20- (17) (17)1326931 此來構成本實施形態的被動型DMFC (燃料電池本體）4 。殼體64上在與被形成在表面層62的空氣導入口 63相 對應的部份設置開口。燃料存放部3設有承接殻體64爪 64a之平台65’將爪64a卡止在平台65上，利用殼體64 來一體保持燃料電池本體4全體。第10圖中雖省略了圖 示’但如同第1圖所示在燃料存放部3的下面側設有具有 插座部6的燃料供應部7。 具有如同上述的構成之被動型D MFC (燃料電池本體 )4係使燃料存放部3內的液體燃料F (例如，甲醇水溶 液）氣化，該氣化成分透過氣體選擇透過膜51供應到燃 料電池薄膜電極組2。燃料電池薄膜電極組2內，液體燃 料F的氣化成分經由陽極氣體擴散層53予以擴散，供應 到陽極觸媒層52。供應到陽極觸媒層52的氣體成分，產 生下述（1)式所示之甲醇的內部改質反應。 CH3OH + H20 — C02 + 6H + + 6e- ------( 1 ) 此外，使用純甲醇來作爲液體燃料F的情況，由於不 會從燃料存放部3供應水蒸氣，故經由陰極觸媒層54所 生成的水或電解質膜56中的水與甲醇起反應，產生（1) 式的內部改質反應。或者不依據（1)式的內部改質反應 ’利用不必水的其他反應機構來產生內部改質反應。 經由內部改質反應所生成的質子（H+ )，傳達到電解 質膜，到達陰極觸媒層54。從表面層62的空氣導入口 63 -21 - (18) 1326931 導入的空氣（氧化劑）’擴散到保濕層61、陰極導電層 58、陰極氣體擴散層55，供應到陰極觸媒層54。供應到 陰極觸媒層54的空氣，產生以下（2)式所示的反應。藉 由該反應’隨著水的生產生發電反應。 (3/2) 02 + 6H + + 6e' 3H2〇 ......( 2) • 隨著根據上述的反應持續進行發電反應，消耗燃料存 放部3內的液體燃料F (例如，甲醇水溶液或純甲醇）。 燃料存放部3內的液體燃料F消耗完畢則停止發電反應， 故在這時候或是在這之前，從燃料卡匣5將液體燃料供應 到燃料存放部3內。從燃料卡匣5供應液體燃料係經由如 前述將燃料卡匣5側的噴嘴部9插入燃料電池本體4側的 插座部6予以連接來實施。 本實施形態的燃料電池（被動型D M F C )，即使燃料 ® 卡匣5連接時噴嘴部9損壞，閥16的一部份仍與插入部 12 —起脫離，故可以防止閥機構受到損壞。進而，也不會 損壞後閥16的一部分突出基體部11的平坦面Ua。藉此 能夠抑制燃料卡匣5的噴嘴部9損壞時的缺失（洩漏液體 燃料）。因此’能夠提供既有可靠性又有實用性的燃料電 池系統1。 本發明適用於演進成小型化之內部氣化型等的被動型 D MFC。惟’本發明若爲用燃料卡匣來供應液體燃料之燃 料電池的話’並沒有對於該方式或機構等有所限定。這種 -22- (19) 1326931 燃料電池或用於該燃料電池的燃料卡匣也是含在本發明中 。另外，本發明的實施形態可以在本發明的技術上的思想 範圍內進行擴張或變更’該擴張、變更的實施形態仍含屬 在本發明的技術上的範圍。 【圖式簡單說明】 第1圖爲表示本發明的實施形態之燃料電池的構成之 Φ 圖。 第2圖爲表示第1圖所示之燃料電池的噴嘴部及插座 部的構成之剖面圖。 第3圖爲表示適用於第2圖所示的噴嘴部之閥之剖面 圖。 第4圖爲表示第3圖所示之閥桿的變形例之正面圖。 第5圖爲第4圖所示的閥桿之平面圖。 第6圖爲表示第2圖所示之噴嘴部的插入部損壞的狀 φ 態之剖面圖。 第7圖爲表示第2圖所示之噴嘴部的變形例之剖面圖 〇 第8圖爲表示第7圖所示之噴嘴部的插入部損壞的狀 態之剖面圖。 第9圖爲表示在損壞後的噴嘴部裝著了備用噴嘴的狀 態之剖面圖。 第10圖爲表示本發明的實施形態之燃料電池本體的 構成例之剖面圖。 -23- (20) 1326931 〔產業上·利用的可能性〕 本發明形態的燃料電池用燃料卡匣，由於內設在噴嘴 部內部的閥機構採用分割構造，故即使對噴嘴部施加彎曲 負荷致使損壞的情況，仍可以抑制發生閥機構損壞或閥機 構誤動作導致液體燃料漏出等的缺失。因此，能夠提供使 用這種燃料卡匣來提高可靠性或實用性之燃料電池。 • 【主要元件符號說明】 1 ： 燃料電池 2 : 燃料電池薄膜電極組 3 ： $料存放部 4 ： 燃料電池本體 5 : 燃料卡匣 6 ： 插座部 8 : 卞匣本體 9 ： 噴嘴部 11 ： 基體部 12 ： :插入部 1 4 ： 閥座 15 ： 閥支架 16 ： 閥 17 ： 閥本體 17a :閥頭 18 : 閥桿 20 ： 0封圈 21 : 壓縮彈簧 22 ： 捭基部 23 : 桿前端部 23a :大徑部 23b :小徑部 -24-1326931 (1) EMBODIMENT OF THE INVENTION [Technical Field] The present invention relates to a fuel cell fuel cartridge and a fuel cell using the same. [Prior Art] In recent years, in order to make a notebook computer or a mobile phone, etc. The various carrying % can be used without using an electronic device for a long time to charge, and attempts to use the fuel cell as a power source for the portable electronic device. The fuel cell is characterized in that it can generate electricity for a long time if it can generate electricity and replenish fuel as long as fuel and air are supplied. Therefore, if the fuel cell can be miniaturized, it is said to be useful as a system for powering a portable electronic device. A direct methanol fuel cell (DMFC) that uses a methanol fuel with a high energy density can be miniaturized, and the treatment of fuel and fuel is easy. Therefore, it is expected to be a liquid fuel supply method for a power source for a portable device. There is known a passive type of a gas supply type or a liquid supply type, and a passive type in which a liquid fuel in a fuel storage portion is vaporized inside a battery and supplied to an internal vaporization type of a fuel electrode. These supply methods are expected to be used as a power source for notebook computers, etc., because they can increase the power of DMFCs (large power). The passive mode of the internal gasification type or the like is particularly advantageous for miniaturization of the DMFC because it is not necessarily a fuel-type fuel transfer means of the fuel pump. For example, in Patent Document 1 or Patent Document 2, a fuel permeation layer containing -5-(2) 1326931 holding liquid fuel and a vaporized component of liquid fuel held in the fuel permeation layer are diffused. Passive DM FC supplied to the fuel gasification layer of the fuel electrode has been described. Such a passive DMFC is expected to be a power source for a portable device such as a portable audio device or a mobile phone. The active DMFC connects the fuel cartridge storing the liquid fuel to the fuel cell body 'from the fuel cartridge directly or via the fuel storage portion (dilution adjustment tank, etc.) to circulate the liquid fuel, thereby supplying the liquid fuel to φ Fuel cell membrane electrode set. On the other hand, the passive DMFC' such as the internal vaporization type has a fuel storage portion and a mechanism for vaporizing the liquid fuel, and uses the fuel cartridge to supply the liquid fuel to the fuel storage portion in the same manner as the active type. In the fuel cartridge of the satellite type (external injection type), it is attempted to block and inject the liquid fuel by using a coupler each composed of a nozzle portion and a socket portion in which a valve mechanism is provided (for example, refer to Japanese Document 3). The passive DMFC, such as the internal vaporization type, is continuously reduced in size in order to be mounted on an electronic device for carrying, and as a result, the nozzle portion on the DMFC side or the nozzle portion on the fuel cartridge side tends to be miniaturized. When such a nozzle portion is connected to the socket portion and liquid fuel is injected into the fuel storage portion of the DMFC from the fuel cartridge, there is a possibility that damage is caused when a bending load is applied to the fuel cartridge. The fuel cartridge uses a valve mechanism built in the nozzle portion to block the liquid fuel. Therefore, there is a possibility that the nozzle is damaged and the liquid fuel stored in the fuel cartridge leaks. Even if the valve mechanism is not damaged when the nozzle is damaged, there is a risk that the components of the valve machine will protrude, causing the valve mechanism to malfunction and leaking liquid fuel. -6- (3) 1326931 Polyether ether ketone (PEEK), Polyphenylene Sulfide Ether (PPS) Liquid Crystal Polymer (LCP) is used for the nozzle portion of the DMFC fuel cartridge. Super engineering plastics; or Polyethylene terephthalate (、), Polybutylene Terephthalate (PBT), P〇lyaCetal (POM), etc. The general engineering plastics are used for review. However, these engineering plastics are hard and tough, so there is a problem that the bending load is easily broken. [Patent Document 1] Japanese Patent No. 3413111 [Patent Document 2] Japanese Patent Laid-Open No. 2004-197-844 (Patent Document 3) Japanese Patent Laid-Open Publication No. 2004- 1274824 Provided is a fuel cell fuel cartridge that is capable of suppressing the occurrence of a nozzle portion damage, and a fuel cell to which the fuel cartridge is applied. The fuel cartridge for a fuel cell according to the aspect of the invention is characterized in that: a cartridge body for storing a liquid fuel for a fuel cell, and a cartridge body provided on the cartridge body; A fuel cell having a valve mechanism having a divided structure is provided in the fuel cell of the present invention, and is characterized in that: the fuel cell fuel cartridge of the present invention is provided with a fuel cartridge for use in a fuel cell a fuel-receiving portion of the socket portion to which the nozzle portion of the cassette is connected, and a fuel cell body that supplies the liquid fuel from the fuel storage portion to generate the electric power (4) 1326931 portion. In the following, a configuration for carrying out the present invention will be described. Fig. 1 is a view showing a configuration of a fuel cell according to an embodiment of the present invention. The fuel cell 1 shown in Fig. 1 is mainly provided with electricity. The fuel cell membrane electrode assembly 2 and the fuel storage unit 3 constitute a fuel cell body 4, φ and a fuel cartridge 5 of a satellite form (external injection type) for supplying liquid fuel to the fuel storage portion 3. A fuel supply portion 7 having a socket portion 6 serving as a supply port for liquid fuel is provided on the lower surface side of the storage portion 3. As will be described in detail below, the socket portion 6 is internally provided with a valve mechanism which is closed except for the supply of liquid fuel. The fuel cartridge 5 has a cartridge body (container) 8 for storing liquid fuel for a fuel cell. The front end opening portion of the cartridge body 8 is provided to supply the liquid fuel stored therein to the fuel cell body 4. The nozzle portion 9 of the fuel injection # outlet. The nozzle portion 9 is provided with a valve mechanism as will be described later, and is closed except when liquid fuel is supplied. This fuel cartridge 5 is connected only when the liquid fuel is injected into the fuel storage portion. The cartridge body 8 to the liquid fuel body 4 〇 fuel cartridge 5 stores liquid fuel corresponding to the fuel cell body 4, such as a direct methanol fuel cell (DMFC), and stores various concentrations of methanol aqueous solution or pure methanol. Methanol fuel. The liquid fuel stored in the cartridge body 8 is not limited to methanol fuel, and for example, an aqueous ethanol solution or pure ethanol may be stored. Alcohol fuel, propanol water-8- (5) 1326931 solution or propanol combustion tank such as pure propanol 'B = alcohol solution or ethylene glycol fuel such as pure ethylene glycol, dicarboxylic acid, formic acid, other liquids In any case, the liquid fuel corresponding to the fuel cell body 4 is stored. The socket portion 6 of the fuel storage portion 3 of the fuel cell body 4 and the nozzle portion 9 of the cartridge body 8 provided in the fuel cartridge 5 are provided. A pair of connection mechanisms (couplings) are formed. The specific configuration of the coupler formed by the socket portion 6 and the nozzle portion 9 will be described with reference to Fig. 2. Fig. 2 is a view showing a fuel cell according to an embodiment of the present invention. The configuration of the fuel cartridge 5 is shown in Fig. 2, which shows the state before the nozzle portion of the fuel cartridge 5 is connected to the socket portion 6 of the fuel cell main body 4. In the coupler in which the fuel cell main body 4 is connected to the fuel cartridge 5, the nozzle portion (male side coupler) 9 as the snap side connecting mechanism has a nozzle head composed of the base portion 11 and the insertion portion 12. The base portion n is attached to the front end opening of the cassette body 8. The base portion I has a circular cylindrical insertion portion 12 so as to have a flat surface 11a' opposed to the socket portion 6 so as to protrude the flat surface 11a. The front end side of the insertion portion 12 has a nozzle opening 13. A valve seat 14 is provided on the inner side of the base portion 11. The base portion 11 and the insertion portion 丨2 are integrally formed. A cup-shaped valve holder 15 is disposed inside the nozzle head. The valve holder 15 is located inside the base portion 11 and cooperates with the base portion 11 to define the valve chamber. The valve holder 15 is fixed by sandwiching the outer peripheral portion of the front end portion with the hook body 8 and the base portion π. The valve 16 is disposed in a valve chamber defined by the base portion 11 and the valve holder 15. The valve 16 is provided with a valve body 17 having a valve head 17a, a cylindrical valve stem 18 provided at a front end portion of the valve body 17, and a rear end of the valve body 17 provided with a 9-(6) 1326931 Side guide pin 1 9. As will be described later, the valve 16 has a structure that is divided in the axial direction. The valve body 17 having the valve head 17a is disposed in a valve chamber defined by the base portion 11 and the valve holder 15. The valve stem 18 is housed in a cylindrical insertion portion 12. The valve 16 can advance and retreat in the axial direction (the insertion direction of the nozzle portion 9). A seal ring is disposed between the valve head 17a and the valve seat 14. For example, the elastic force of the compression spring 21 is applied to the valve body 17 at any time to force the valve head 17a to push against the valve seat 14, thereby pressing the seal ring 20. In the normal state (the state in which the fuel cartridge 5 is separated from the fuel cell main body 4), the valve head 17a is forcibly pushed toward the valve seat via the helium seal, whereby the fuel flow path in the nozzle portion 9 is closed. On the other hand, when the fuel cartridge 5 is connected to the fuel cell main body 4 as will be described later, the valve stem 18 is retracted to disengage the valve head 17a from the valve seat 14, and the fuel flow path in the nozzle portion 9 is opened. A communication hole i5a serving as a flow path of the liquid fuel is provided at the bottom of the valve holder 15. The guide pin 19 provided on the rear side of the valve body 17 is inserted into the communication hole φ 15a. The valve stem 18 of the valve 16 has a split configuration. Specifically, as shown in Fig. 3, the valve stem 18 has a rod base portion 22 that is formed integrally with the valve body 17, and a rod distal end portion 23 that is divided from the rod base portion 22. That is, the valve stem 18 is composed of two types of members, the rod base portion 22 and the rod distal end portion 23, and the two members are divided into separate members. The contact surface of the rod base portion 22 and the rod distal end portion 23 serves as a dividing surface of the valve stem 18. The rod distal end portion 23 has a large diameter portion 23a provided on the rod base portion 22 side so as not to fall off from the insertion portion 12 of the valve head. The valve distal end portion 23 is provided with a small diameter portion 23b in which the -10-12 (7) 1326931 is disposed in the insertion portion 12, and a large diameter portion 23a having an outer diameter larger than the inner diameter of the insertion portion. The large diameter portion 23a is pressed by the stepped hole in the insertion portion 12, whereby the rod distal end portion 23 is prevented from coming off the insertion portion. The rod base 22 has the same straightness as the large diameter portion 23a of the rod front end portion 23. The two base portions 22 are brought into contact with the large diameter portion 23a of the rod distal end portion 23, and the valve 16 is placed in the nozzle head in this state. In the case where the liquid fuel/flow path is provided between the valve stem 18 and the inner wall surface of the insertion portion 12, the rod base portion 22 and the rod distal end portion 23 can be assembled by contact alone without considering the positional relationship in the circumferential direction. On the other hand, there is a case where a groove is formed in the direction to set the flow path of the liquid fuel on the circumferential surface of the valve stem 18. In this case, as shown in Figs. 4 and 5, the large-diameter portion of the rod distal end portion 23 and the rod base portion 22 (not shown in Figs. 4 and 5) are provided to guide the position in the circumferential direction. Lead button. The assembly of the valve 16 can be performed by aligning the position of the rod base portion 22 with the circumferential direction of the rod front end 23 by using the guide key 24. Here, the front end portion 23 of the two guide keys 24 is displayed. However, the number of the guide keys 24 is not limited to two, and may be, for example, one or four. Further, a key groove is provided at the inner wall surface ' of the insertion portion 12 corresponding to the guide key 24 provided on the side of the valve stem 18. By engaging the valve stem 18 side guide key 24 with the groove of the insertion portion 12, the material of the end portion 23 of the stem of the valve stem 18 in the circumferential direction of the alignment rod base portion 22 and the rod front end portion 23 is The constituent material of the rod body 17 in which the rod base 22 is formed can be, for example, a super engineering glue or a general engineering plastic. Further, it is preferable that the constituent material of the valve 16 is in contact with the square shaft of the 12-diameter group and is in contact with the plastic fuel -11 - (8) 1326931 alcohol fuel, and has methanol resistance. Examples of such materials include: general-purpose engineering plastics such as polyethylene terephthalate, polybutylene terephthalate, polycondensation, and polyphenylene sulfide, polyetheretherketone, and liquid crystal polymer. Super engineering plastics. The nozzle portion 9 other than the valve 16 is preferably made of the same super engineering plastic or general engineering plastic. Each of the above materials has good methanol resistance. Specifically, the immersion test of pure methanol based on the "plastic resistance φ quality test method" of ns Κ 7 ΐ μ is in accordance with the mass change rate of 0.3% or less, the length change rate of 0.5% or less, and the thickness change rate. In the condition that the rate of change of 5% or less is less than the above-mentioned enthalpy, when methanol fuel or the like is stored in the fuel cartridge 5, dissolution or stress cracking occurs in the nozzle portion 9. Therefore, the durability or reliability of the fuel cartridge 5 is lowered. The nozzle portion 9 on the side of the fuel cartridge 5 tends to be smaller in size as the fuel cell body 4 is reduced in size. The nozzle portion 9 whose diameter is reduced may cause damage when a bending load is applied to the fuel Φ cassette 5 (a load due to a force in a direction in which the insertion direction of the fuel cartridge 5 is angular). Specifically, as shown in Fig. 6, the insertion portion 12 of the protruding base portion 11 may be broken. The risk of damage to the nozzle portion 9 is that the smaller the diameter is, the higher the diameter is. In particular, the nozzle portion 9 is formed of a material having a poor toughness of a bending load such as the above-mentioned super engineering plastic or general engineering plastic. It is easy to damage. In the present embodiment, a structure in which the valve stem 18 is divided into the rod base portion 22 and the rod distal end portion 23 is used. Therefore, even if the insertion of the valve head -12-(9) 1326931 portion 12 is broken as shown in Fig. 6, only the rod front end portion 23 is separated from the insertion portion, whereby the valve mechanism for blocking the liquid fuel can be prevented (using the valve) The mechanism in which the head 17a blocks the liquid fuel is damaged. That is, when the valve stem 18 is integrated with the valve body 17 and the valve stem 18 and the insertion portion 12 are broken together, the valve mechanism is also damaged. In response to this, the valve stem 18 is divided into the rod base portion 22 and the rod front end portion 23, whereby the damage of the valve stem 18 can be prevented from causing damage to the valve mechanism. # Further, the valve stem 18 is integrated with the valve body 17, so that the valve stem 18 is not broken even if the insertion portion 12 is damaged, and the valve stem 18 still protrudes from the flat surface 11a of the base portion 11 after being damaged. In this state, there is a possibility that the liquid fuel is leaked when the valve stem 18 is pressed. In the present embodiment, even if the nozzle portion 9 is damaged, the rod distal end portion 23 is separated from the insertion portion 12, so that the rear valve stem 18 does not damage the flat surface 11a of the base portion 11. Therefore, it is possible to suppress the occurrence of a loss (leakage of liquid fuel) when the nozzle portion 9 is broken. As in the case where the above-described insertion portion 12 is damaged, the rod front end portion 23 is preferably Φ so that a part of the valve stem 18 does not protrude from the flat surface 11a of the base portion 11. Therefore, it is preferable that the dividing surface of the rod base portion 22 and the rod front end portion 23 is located on the same surface as the flat surface 11a of the base portion 11, or the valve body 17 side is more than the flat surface 11a (the cartridge body 8) side). Thereby, it is possible to more reliably prevent the protrusion of the valve stem 18 when the insertion portion 12 is damaged. The split configuration suitable for the valve 16 is not limited to the configuration in which the stem 18 is divided into the rod base 22 and the rod front end portion 23. As shown in Fig. 7, the valve body 17 and the valve stem 18 can be divided. That is, the valve 16 shown in Fig. 7 has a valve body 17 having a valve head 17a and a valve stem 18 disposed on the front end side of the valve body - 13 - 1326931 do) 7 and divided from the valve body 17. In addition, the other structures are the same as in Fig. 2. The valve 16 is composed of two types of parts including a valve body 17 of the valve head 17a and a valve stem 18, and these two parts are divided into separate parts. The contact surface of the valve body 17 with the valve stem 18 serves as a dividing surface of the valve 16. The valve stem 18 is provided with a small diameter portion disposed in the insertion portion 12 and a large diameter portion having an outer diameter larger than the inner diameter of the insertion portion 12. The large diameter portion 23a is pressed by the stepped hole in the insertion portion 12, thereby preventing the valve stem I8 from coming off the insertion portion 12. The valve body 17 is brought into contact with the valve stem 18 to assemble the valve 16, and is disposed in the nozzle head in this state. Thus, when the valve 16 is divided into the valve body 17 and the valve stem 18, as shown in Fig. 8, the valve stem 18 is disengaged from the damaged insertion portion 12, so that the valve mechanism can be prevented (the liquid is blocked by the valve head 17a). The fuel mechanism is damaged. Further, a part of the valve 16 is protruded from the flat surface 11a of the base portion 11 without the insertion portion 12 being damaged. The valve 16 is divided into the configuration of the valve body 17 and the valve # rod 18, in particular, the surface of the valve body 17 (the dividing surface of the valve body 17 and the valve stem 18) is located at a valve more than the flat surface 11a of the base portion 11. Since the inside of the head (base portion 11) is inside, it is possible to more reliably prevent leakage due to malfunction of the valve mechanism. As shown in Fig. 2, the socket degree (female side coupling) 6' as the fuel cell side connecting means has a cylindrical socket body (case) 31. The socket body 31 has a body upper portion 31a, a body center portion 31b, and a body lower portion 31c' which are integrally assembled into the fuel supply portion 7 of the fuel cell body 4. The substantially cylindrical main body upper portion 31a has a socket opening for inserting the nozzle portion into the nozzle portion 14 (11) 1326931. The body middle portion 31b of the socket body 31 has an annular convex portion 32 that protrudes inward in the diameter direction. On the annular convex portion 32, a rubber bracket 33 of an elastic body holder is provided. The rubber bracket 33 is disposed in the upper portion 31a of the body. The rubber holder 33 applies elasticity in the axial direction in accordance with the shape (expanded shape) and material properties (rubber elasticity). The rubber holder 33 is a sealing member that forms a seal between the insertion portions 1 2 of the nozzle portion 9, and the inner side serves as a fuel φ flow path. A valve 34 is disposed in the socket body 31. The valve 34 includes a valve body 35 having a valve head 35a, a valve stem 36 provided on the front end side of the valve body 35, and a guide pin 37 provided on the rear side of the valve body 35. The valve body 35 having the valve head 35a is disposed in the valve body portion formed by the body middle portion 31b and the body lower portion 31. The valve stem 36 is housed in the rubber bracket 33. The valve 34 can be oriented in the axial direction (insertion of the nozzle portion 9) In the direction of the valve head 35a and the valve seat 38 formed on the lower surface side of the annular convex portion 32, a seal ring 39 is disposed. For the valve body 35, for example, by an elastic member like the compression ring 40 The force of forcibly pushing the valve head 35a toward the valve seat 38 is applied at any time, thereby pressing the seal ring. In the normal state (the state in which the fuel cartridge 5 is detached from the fuel cell body 4), the valve head is closed via the helium seal 39. 35a is forced to the valve seat 38' by which the fuel flow path in the socket portion 6 is closed. When the fuel cartridge 5 is connected to the fuel cell body 4, the valve stem 36 is retracted, the valve head 35a is disengaged from the valve seat 38, and the socket portion 6 is closed. The fuel flow path is in an open state. The body lower portion 31c of the socket body 31 is provided with a communication hole 41 connected to the fuel storage portion 3 via the fuel supply portion 7-15-(12) 1326931. Further, it is disposed in the valve body 35. The guide pin 3 7 on the rear side is inserted into the communication hole 41. Thus The seat portion 6 connects the fuel flow path provided in the body 31 to the fuel storage portion 3 via the communication hole 41 provided in the lower portion 31c of the body. Then, the valves 16, 34 are opened to open the nozzle portion 9 and the socket. The fuel flow paths in the portion 6 are opened, whereby the liquid fuel stored in the fuel cartridge 5 can be injected into the φ fuel storage portion 3 via the nozzle portion 9 and the socket portion 6. When it is to be stored in the fuel card When the liquid fuel of the crucible 5 is supplied to the fuel storage portion 3 of the fuel cell main body 4, the nozzle portion 9 of the fuel cartridge 5 is inserted into the socket portion 6 to be connected. Here, the outer peripheral surface of the insertion portion 12 of the nozzle portion 9 is provided. In the insertion direction of the fuel cartridge 5 (the axial direction of the nozzle portion 9), for example, two guide grooves 25 are formed. On the other hand, the inner circumferential surface of the socket body 31 of the socket portion 6 is provided with a guide groove. The 25-phase engagement is to guide the inserted key portion 42 of the fuel cartridge 5. The key portion 42 is formed so as to protrude toward the radial direction side of the socket body 31 in accordance with the number of the guide grooves 25. The shape, for example, is linear along the axial direction of the insertion portion 丨2 Further, the guide groove 25 may guide the key portion 42 in the axial direction, and lock the nozzle portion 9 to the socket portion 6 to be displaced in the circumferential direction from the middle. That is, the guide groove 25 is not limited. The linear shape may be a J shape. The key portion 42 that engages with the guide groove 25 is adapted to integrally form the hub on the inner circumferential surface of the socket body 31 or to insert a key different from the socket body 31. The form of the socket body 31, etc. The key portion 42 may be formed of a metal material. -16- (13) 1326931 - The key portion 42 is engaged with the guide groove 25, and the nozzle portion 9 is inserted into the socket portion 6, first The front end of the insertion portion 12 is in contact with the front end of the rubber holder 33, and the periphery of the fuel flow path is surely sealed before the valves 16 and 34 are opened. When the tip end of the insertion portion 12 comes into contact with the front end of the rubber holder 33, the nozzle portion 9 is inserted into the socket portion 6, and the valve stem 18 of the nozzle portion 9 and the front end of the valve stem 36 of the socket portion 6 are in contact with each other. When the nozzle portion 9 is again inserted into the socket portion 6 in this state, the valve 34 of the socket portion 6 is retracted. After the flow path is opened, the valve 16 of the nozzle portion 9 is retracted to establish the fuel flow path. In this way, the liquid fuel stored in the fuel cartridge 5 is supplied to the fuel storage portion 3 of the fuel cell body 4. In the present embodiment, a split structure is used as the valve 16 of the over-nozzle portion 9. Therefore, when the nozzle portion 9 of the fuel cartridge 5 is connected to the socket portion 6 of the fuel cell body 4, even if a bending load is applied to the fuel cartridge 5 to cause the nozzle portion 9 (for example, the insertion portion 12) to be damaged, a portion of the valve 16 The portion (the rod front end portion 23 of the valve stem 18 or the valve stem 18 itself) is still disengaged from the insertion portion 12, so that the valve mechanism can be prevented from being damaged. Further, a part of the rear valve 16 is not damaged and the flat surface 11a of the base portion 11 is not damaged. Thereby, the loss (leakage of liquid fuel) caused when the nozzle portion 9 of the fuel cartridge 5 is damaged can be suppressed. However, the fuel cartridge 5 damaged by the nozzle portion 9 cannot be directly reused. As shown in Fig. 9, the fuel cartridge 5 of the present embodiment has a spare nozzle 45 attached to the outside of the damaged nozzle portion 9. The backup nozzle 45 has a spare valve stem -17-(14) 1326931 disposed on the split surface of the valve 16 (the surface of the rod base 22 shown in Fig. 3 or the surface of the valve body 17 shown in Fig. 7). 46. The spare nozzle 45 is attached to the outside of the damaged base portion 11 after the spare valve stem 45 is disposed. Thus, the spare nozzle 45 is prepared first, whereby the fuel cartridge 5 damaged by the nozzle portion 9 can be reused. In the present embodiment, even if the nozzle portion 9 is damaged, the valve mechanism can be prevented from being damaged. Therefore, a spare nozzle 45 having a spare valve stem 46 is attached to the outside of the damaged nozzle portion 9, whereby liquid fuel leakage is not caused, and the fuel cartridge φ 5 can be used again. Further, in Fig. 9, reference numeral 47 is a seal ring for sealing a liquid fuel. Next, the structure of the fuel cell body 4 will be described. The fuel cell body 4 is not particularly limited, and for example, a passive or active type DMFC in which a fuel cartridge 5 in the form of a satellite is connected may be used. Here, an embodiment in which the fuel cell main body 4 uses an internal vaporization type DMFC will be described with reference to Fig. 10. The internal vaporization type (passive type) DMFC 4' shown in Fig. 10 includes a fuel cell membrane electrode group 2 and a fuel storage portion 3 constituting the electrification portion, and a gas selection plate that is sandwiched between the two. Pass through the membrane 51. The fuel cell membrane electrode assembly 2 has an anode (fuel electrode) having an anode catalyst layer 52 and an anode gas diffusion layer 53, and a cathode (oxidant electrode/air electrode) having a cathode catalyst layer 54 and a cathode gas diffusion layer 54. And a membrane electrode assembly (Membrane Electrode Assembly: ΜEA) composed of a proton (hydrogen ion)-conductive electrolyte membrane 56 sandwiched between the anode catalyst layer 52 and the cathode catalyst layer 54. The catalyst contained in the anode catalyst layer 52 and the cathode catalyst layer 54 is, for example, a monomer of a platinum group element such as Pt, Ru' Rh, Ir, 〇s, Pd, etc., and • 18-(15) 1326931 contains platinum. Alloys of family elements, etc. Preferably, the anode catalyst layer 52 is Pt-Ru or Pt-Mo which is highly resistant to methanol or carbon monoxide. The cathode catalyst layer 54 is preferably made of Pt or Pt-Ni or the like. The catalyst may also be any one of a supported carrier or a non-supported catalyst of a conductive material of the same carbon material. The proton conductive material constituting the electrolyte membrane 56 is, for example, a fluorine-based resin such as a perfluorosulfonic acid polymer having a sulfonic acid group (Nafion (trade name: manufactured by Japan Dupont Co., Ltd.) or flemion (trade name, Asahi Glass Co., Ltd., Japan) Manufactured, etc.), an inorganic substance such as a sulfonic acid-based hydrocarbon-based resin, tungstic acid or phosphotungstic acid. However, the proton conductive electrolyte membrane 56 is not limited to these. The anode gas diffusion layer 53 laminated on the anode catalyst layer 52 is responsible for the operation of uniformly supplying the fuel to the anode catalyst layer 52, and also serves as the current collector of the anode catalyst layer 52. The cathode gas diffusion layer 55, which is laminated on the cathode catalyst layer 54, is responsible for the operation of supplying the oxidant uniformly to the cathode catalyst layer 54, and also serves as the current collector of the cathode catalyst layer 54. The anode conductive layer 57 is laminated on the anode gas diffusion layer 53, and the cathode conductive layer 58 is laminated on the cathode gas diffusion layer 55. The two conductive layers 57, 58 are made of, for example, a mesh composed of a conductive metal material such as gold, a porous film, a film, or the like. Between the electrolyte membrane 56 and the anode conductive layer 57 and between the electrolyte membrane 56 and the cathode conductive layer 58, a rubber seal ring 59, 60 is provided therebetween to prevent leakage from the fuel cell membrane electrode assembly (MEA) 2 Fuel or leaking oxidant. The inside of the fuel storage unit 3 such as a fuel tank is equipped with methanol fuel -19-(16) 1326931 as the liquid fuel F. The fuel storage unit 3 has a box-shaped container for storing the liquid fuel F, and a surface of the box-shaped container facing the anode (fuel electrode) is opened. A gas selective permeable membrane 51 is provided between the opening of the fuel storage unit 3 and the fuel cell membrane electrode assembly 2. The gas selective permeation membrane 51 is a gas-liquid separation membrane that passes only the vaporized component of the liquid fuel F and does not allow the liquid component to permeate. The constituent material of the gas selective permeable membrane 51 is, for example, a fluorine-containing resin such as poly φ tetrafluoroethylene. Only the gasification component of the liquid fuel F is supplied to the fuel cell membrane electrode group 2 via the gas selective permeable membrane 51. The gasification component of the liquid fuel F means a mixture gas composed of a gasification component of methanol and a vaporization component of water when a methanol aqueous solution is used as the liquid fuel F, and a methanol gas when pure methanol is used. The composition of the cathode electrode 58 is deposited on the cathode electrode 61, and the surface layer 62 is laminated on the upper surface. The surface layer 62 has a function of adjusting the oxidizing agent, i.e., adjusting the amount of introduction of air, which is performed in accordance with the number or size of the air introduction port 63 formed in the surface layer 62. The moisture retaining layer 61 is responsible for suppressing the evapotranspiration of water by immersing a part of the water generated by the cathode catalyst layer 54, and has an equal introduction of the oxidant into the cathode gas diffusion layer 55 to promote uniform diffusion of the oxidant to the cathode catalyst. The function of layer 54. The moisture retaining layer 61 is composed of a member having a porous structure. Specific constituent materials include porous bodies of polyethylene or polypropylene. A gas selective permeable membrane 51, a fuel cell membrane electrode group 2, a moisture retaining layer 61, and a surface layer 62' are sequentially laminated on the fuel storage portion 3, and a stainless steel casing is assembled from the upper surface, for example. The entire constituting element is held by the casing. By the -20-(17)(17)1326931, the passive DMFC (fuel cell body) 4 of the present embodiment is constructed. An opening is provided in the casing 64 at a portion corresponding to the air introduction port 63 formed in the surface layer 62. The fuel storage portion 3 is provided with a platform 65' that receives the claw 64a of the casing 64 to lock the claw 64a to the platform 65, and integrally holds the entire fuel cell body 4 by the casing 64. Although the illustration is omitted in Fig. 10, the fuel supply portion 7 having the socket portion 6 is provided on the lower surface side of the fuel storage portion 3 as shown in Fig. 1. The passive type D MFC (fuel cell body) 4 having the above-described configuration vaporizes the liquid fuel F (for example, an aqueous methanol solution) in the fuel storage portion 3, and the vaporized component is supplied to the fuel cell through the gas selective permeable membrane 51. Thin film electrode group 2. In the fuel cell membrane electrode group 2, the vaporized component of the liquid fuel F is diffused through the anode gas diffusion layer 53 and supplied to the anode catalyst layer 52. The gas component supplied to the anode catalyst layer 52 produces an internal reforming reaction of methanol represented by the following formula (1). CH3OH + H20 - C02 + 6H + + 6e- (1) Further, in the case where pure methanol is used as the liquid fuel F, since the water vapor is not supplied from the fuel storage portion 3, the cathode catalyst is passed. The water formed in the layer 54 or the water in the electrolyte membrane 56 reacts with methanol to produce an internal reforming reaction of the formula (1). Or the internal reforming reaction of the formula (1) is not used to generate an internal reforming reaction by using other reaction mechanisms that do not require water. The protons (H+) generated by the internal reforming reaction are transmitted to the electrolyte membrane and reach the cathode catalyst layer 54. The air (oxidant) introduced from the air introduction port 63 - 21 - (18) 1326931 of the surface layer 62 is diffused to the moisture retaining layer 61, the cathode conductive layer 58, and the cathode gas diffusion layer 55, and supplied to the cathode catalyst layer 54. The air supplied to the cathode catalyst layer 54 produces a reaction represented by the following formula (2). By this reaction, a power generation reaction occurs as water is generated. (3/2) 02 + 6H + + 6e' 3H2 〇 (2) • The liquid fuel F (for example, aqueous methanol solution) in the fuel storage unit 3 is consumed as the power generation reaction is continued according to the above reaction. Or pure methanol). When the liquid fuel F in the fuel storage unit 3 is consumed, the power generation reaction is stopped. Therefore, at this time or before, the liquid fuel is supplied from the fuel cartridge 5 to the fuel storage unit 3. The supply of the liquid fuel from the fuel cartridge 5 is carried out by connecting the nozzle portion 9 on the side of the fuel cartridge 5 to the socket portion 6 on the side of the fuel cell body 4 as described above. In the fuel cell (passive type D M F C ) of the present embodiment, even if the nozzle portion 9 is broken when the fuel ® cassette 5 is connected, a part of the valve 16 is separated from the insertion portion 12, so that the valve mechanism can be prevented from being damaged. Further, a part of the rear valve 16 is not damaged and the flat surface Ua of the base portion 11 is not damaged. Thereby, the absence (leakage of liquid fuel) when the nozzle portion 9 of the fuel cartridge 5 is damaged can be suppressed. Therefore, it is possible to provide the fuel cell system 1 which is both reliable and practical. The present invention is applicable to a passive type D MFC which has been evolved into a miniaturized internal gasification type or the like. However, the present invention is not limited to this mode or mechanism if it is a fuel cell that supplies a liquid fuel with a fuel cartridge. Such a -22-(19) 1326931 fuel cell or a fuel cartridge for the fuel cell is also included in the present invention. Further, the embodiment of the present invention can be expanded or changed within the scope of the technical scope of the present invention. The embodiment of the expansion and modification is still within the scope of the technical scope of the present invention. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a view showing the configuration of a fuel cell according to an embodiment of the present invention. Fig. 2 is a cross-sectional view showing the configuration of a nozzle portion and a socket portion of the fuel cell shown in Fig. 1. Fig. 3 is a cross-sectional view showing a valve applied to the nozzle portion shown in Fig. 2. Fig. 4 is a front elevational view showing a modification of the valve stem shown in Fig. 3. Figure 5 is a plan view of the valve stem shown in Figure 4. Fig. 6 is a cross-sectional view showing a state in which the insertion portion of the nozzle portion shown in Fig. 2 is damaged. Fig. 7 is a cross-sectional view showing a modification of the nozzle portion shown in Fig. 2. Fig. 8 is a cross-sectional view showing a state in which the insertion portion of the nozzle portion shown in Fig. 7 is damaged. Fig. 9 is a cross-sectional view showing a state in which a spare nozzle is attached to the nozzle portion after the damage. Fig. 10 is a cross-sectional view showing a configuration example of a fuel cell main body according to an embodiment of the present invention. -23- (20) 1326931 [Industrial Applicability] In the fuel cartridge for a fuel cell according to the aspect of the invention, since the valve mechanism provided inside the nozzle portion has a divided structure, even if a bending load is applied to the nozzle portion, In the case of damage, the loss of the valve mechanism or the leakage of the liquid fuel due to malfunction of the valve mechanism can be suppressed. Therefore, it is possible to provide a fuel cell using such a fuel cartridge to improve reliability or practicability. • [Main component symbol description] 1 : Fuel cell 2 : Fuel cell membrane electrode group 3 : $ Material storage unit 4 : Fuel cell body 5 : Fuel cartridge 6 : Socket portion 8 : 卞匣 body 9 : Nozzle portion 11 : Base Part 12 : : Insertion part 1 4 : Seat 15 : Valve holder 16 : Valve 17 : Valve body 17 a : Valve head 18 : Stem 20 : 0 Sealing ring 21 : Compression spring 22 : Base part 23 : Rod front end part 23a : Large diameter portion 23b: small diameter portion -24-