200810223 (1) 九、發明說明 【發明所屬之技術領域】 本發明係關於一種對可攜式機器之動作有效之平面配 置的燃料電池。 【先前技術】 近年來，個人電腦、行動電話等各種電子機器，與半 Φ 導體技術之發達一起小型化，並嘗試將燃料電池使用於此 等小型機器用之電源。燃料電池，係僅供應燃料及氧化劑 即可發電，並具有僅補充/更換燃料即可連續發電之優點 。因此，若能小型化則可說是對行動電子機器之動作極爲 有利的系統。特別是直接甲醇燃料電池（DMFC : Direct Methanol Fuel Cell)，由於使用能量密度高之甲醇爲燃料 ，可在電極觸媒上直接從甲醇取出電流，因此可小型化， 又，燃料之處理亦較使用氫氣燃料容易，故極有希望作爲 馨 小型機器用電源’因此期待其實用化作爲筆記型電腦、行 動電話、可攜式音響、可攜式遊戲機等無線可攜式機器之 最佳電源。 例如日本特開2004 — 014148號公報及日本國際公開 編號20Ό5Π 12 172 A1公報掲示有一種直接甲醇燃料電池 ’其係具有以質子導電性之固體電解質膜、具有陽極觸媒 層及陽極氣體擴散層，並自燃料與水產生電荷與質子之陽 極、及具有陰極觸媒層及陰極氣體擴散層，並自質子與氧 產生水之陰極所形成的薄膜電極組（MEa : Membrane 200810223 (2)200810223 (1) Description of the Invention [Technical Field] The present invention relates to a fuel cell which is arranged in a plane effective for the operation of a portable machine. [Prior Art] In recent years, various electronic devices such as personal computers and mobile phones have been miniaturized with the development of semi-Φ conductor technology, and attempts have been made to use fuel cells for power sources such as small machines. Fuel cells are powered by only fuel and oxidant, and have the advantage of continuous power generation by supplementing/replacement of fuel. Therefore, if it can be miniaturized, it can be said to be a system that is extremely advantageous for the operation of the mobile electronic device. In particular, a direct methanol fuel cell (DMFC) uses a high energy density methanol as a fuel to extract current directly from methanol on the electrode catalyst, so that it can be miniaturized, and the fuel treatment is also used. Hydrogen fuel is easy, so it is very promising as a power source for small-sized machines. Therefore, it is expected to be practically used as the best power source for wireless portable devices such as notebook computers, mobile phones, portable audio players, and portable game consoles. For example, a direct methanol fuel cell having a proton conductive solid electrolyte membrane, an anode catalyst layer, and an anode gas diffusion layer is disclosed in Japanese Laid-Open Patent Publication No. 2004-014148, the disclosure of which is incorporated herein by reference. And an anode for generating charge and proton from fuel and water, and a thin film electrode group having a cathode catalyst layer and a cathode gas diffusion layer, and a cathode formed by proton and oxygen generating water (MEa : Membrane 200810223 (2)
Electrode Assembly)爲單元電池，於單元電池周邊具備液 體燃料槽，並以保護蓋覆蓋單數個或複數個單元電池。 雖於DMFC之陰極側在觸媒之存在下使燃料之甲醇與 氧反應，但由於該反應係產生水與二氧化碳之燃燒反應（ 發熱反應），因此該反應熱會蓄積於保護蓋內部，如圖8 特性曲線C所示，於發電初期電池溫度會急遽上升。之後 ，雖隨著時間經過進行放熱電池溫度會緩緩下降，但隨著 φ 電池溫度之下降，如特性曲線D所示，發電輸出亦降低。 如上述在DMFC有自發電開始起隨著時間經過產生輸出不 均的課題。 又，因發電初期電池溫度急遽上升造成DMFC之保護 蓋的表面溫度亦可能超過約60 °C，亦擔心對周邊構件之熱 影響，進而有輸出特性降低之問題。 【發明內容】 Φ 〔發明欲解決之課題〕 本發明係爲解決上述課題而構成，提供能有效防止發 電初期急遽之溫升，並可抑制從發電初期直至後期止隨時 間產生輸出不均的燃料電池。 〔用以解決課題之手段〕 〔發明效果〕 本發明者等對燃料電池之溫升，特別是抑制保護蓋表 面溫度之上升，且抑制輸出隨時間產生不均之技術銳意硏 -5- 200810223 (3) 究的結果，完成了以下所述之本發明。 本發明之燃料電池，係具備··電池結構，具有將質 子傳導膜配置於陰極觸媒層與陽極觸媒層之間所構成之薄 膜電極組、以及保護蓋，具有用以將空氣供應至此電池結 構之陰極側之空氣導入孔所設開口的主面；其特徵爲：具 備內藏於前述保護蓋之主面且用以將發電反應在陰極側所 產生之熱能吸收/蓄積/釋出的蓄熱劑。 φ 空氣導入孔係配置成空氣導入孔彼此間距離較長以使 保護蓋主面之中央部較疎，空氣導入孔彼此間距離較短以 使保護蓋主面之周邊部較密較佳（圖5 A)。由於發電初期在 陰極側產生之熱能集中於電池結構之中央部，因此若使空 氣導入孔與空氣導入孔彼此間之距離較長而將空氣導入孔 設置成較疎（減少空氣導入孔之開口數量）時，由於中央部 之蓄熱劑的量增加，因此可使中央部之熱容量較週邊部之 熱容量大，並提升保護蓋整體之溫度均一性。 • 蓄熱劑係具有在保護蓋主面之中央部容量爲最大，自 保護蓋主面之中央部向周邊部容量爲逐漸減少的容量分布 較佳（圖6)。由於所產生之熱能在電池結構之中央部較大 ，與此鄰近對面之保護蓋係中央部接受到較周邊部多之熱 能，西此與此對應使蓄熱劑之熱容量在中央_部較大，在周 邊部較小，即能提升保護蓋整體之溫度均一性。 蓄熱劑之熔點在30〜50 °C之範圍內較佳（表1)。蓄熱 劑係具有於發電初期吸收所產生之熱（吸熱功能），於發電 中期將所吸收之熱暫時蓄積（蓄熱功能），於發電中期〜後 200810223 (4) 期將所蓄積之熱釋出（放熱功能）諸功能者。若蓄熱劑之熔 點超過50°C時，由於接近於保護蓋表面之最高到達溫度， 因此會立即釋出所吸收之熱能蓄熱期間會變短。另一方面 ，若蓄熱劑之熔點低於3 (TC時，由於在室溫狀態亦會從固 體改變成液體，因此無法吸收發電所產生之熱能。 於蓄熱劑可使用碳原子數目爲20以上之石臘、硫代 硫酸鈉水合物、硫酸鈉水合物等。然而，碳原子數目爲1 8 以下之石臘、氯化鈣水合物等因熔點過低故不適合使用作 爲蓄熱劑。相反地，醋酸鈉水合物等因熔點過高此亦不適 合於蓄熱劑。 保護蓋可設爲具有以下之結構體：蓋子本體，備有爲 容納蓄熱劑而設有開口之收容部、以及蓋體，用以覆蓋蓋 子本體之開口且形成保護蓋主面之一部分。 此外，具有介設於前述保護蓋之前述蓋子本體與前述 蓋體之間’以使前述蓄熱劑不會漏出的密封材料較佳。於 密封材料可使用從硬質到軟値之各種橡膠系材料、樹脂材 料、或金屬材料，其中橡膠系材料（例如EPDM(乙丙橡膠 )、FKM(氟橡膠）、NBR(丁苯橡膠）、SBR(苯乙烯—丁二烯 橡膠））最合適。 保護蓋可具有例如藉由鉚接加工一體安襞於電池結構 t #P胃部。當將該鉚接部鉚接加工於電池結構之周邊部以 胃#_蓋固定於電池結構時，無法鎖付按壓保護蓋之中央 ^ ° ’當熱自電池結構傳導至保護蓋時，保護蓋之中 @ 膨脹變形爲凸狀。然而，本發明係使用蓄熱劑從 -7- 200810223 (5) 保護蓋強制移除熱，因此抑制或防止保護 【實施方式】 以下’參照附加之圖式說明用來實施 態。 (第一實施形態） 首先，參照圖1、圖2A、圖2B、及圖 池整體之槪要。燃料電池1具備作爲發電部 及具有覆蓋電池結構1 0之陰極側之主面的^ 結構1 0具有平面配置於內部並串列連接之 池。單元電池，如圖3所示，具備質子傳_ 質膜11、以及陽極觸媒層12及陰極觸媒層 膜電極組，此外，並具備陽極氣體擴散層1 散層15、正極引線（陰極集電體）i6a、以及 集電體）16b。 於燃料電池1內部，藉由密封構件18 空間或間隙。該等空間或間隙中，例如陰稻 爲保1板26使用，陽_側之空間係作爲箱 2 7及氣化室（未圖示）使用。於保濕板2 6，| 率例如爲20〜60 %之多孔性薄膜。於液體 於適當位置設有連通於液體接受口 21之燃 。於液體接受口 21例如安裝有插接式耦合 之熱膨脹變形 發明之各種形 3說明燃料電 之電池結構1 〇 呆護蓋2。電池 :複數個單元電 I性之固體電解 1 3 —體化之薄 4、陰極氣體擴 負極引線（陽極 等形成有各種 i側之空間係作 [體燃料收容室 芝佳爲使用氣孔 燃料收容室2 7 料供給流路19 器2 3，將未圖 -8 - 200810223 (6) 示之燃料卡匣的噴嘴插入於該耦合器23，以將液體燃料補 給於液體燃料收容室27。 此外，液體燃料可使用甲醇水溶液或純甲醇等甲醇燃 料、乙醇水溶液或純乙醇等乙醇燃料、丙醇水溶液或純丙 醇等丙醇燃料、乙二醇水溶液或純乙二醇等乙二醇燃料、 蟻酸、蟻酸水溶液、犠酸鈉水溶液、醋酸水溶液、硼氫化 鈉水溶液、硼氫化鉀水溶液、氫化鋰水溶液、乙二醇水溶 φ 液、及二甲醚等含氫之有機系水溶液。總之，收納依照燃 料電池之液體燃料。 其中，由於甲醇以一個碳原子反應時所產生者爲二氧 化碳氣體，且能於低溫產生發電反應，並比較容易從工業 廢棄物來製造因此較佳。又，燃料可使用從濃度100%至 數％範圍內之各種濃度者。較佳係當使用濃度爲80%以上 之甲醇作爲液體燃料時，特別能發揮其性能或效果。因此 ’各實施形態應用使用濃度爲80%以上之甲醇作爲液體燃 Φ 料之燃料電池較佳。 於陰極側之保護蓋2的主面，以各既定間隔設有複數 個空氣導入孔24之開口並分別連通於保濕板26。該等空 氣導入孔24雖形成外氣所通過之開口，但係經仔細設計 成不會妨礙外氣之通過且能防止微小或針狀異物從-外部侵 入/接觸陰極氣體擴散層1 5的形狀。 如圖4所示，保護蓋2內包有用來蓄積發電初期所產 生之過剩熱能的蓄熱劑3。亦即，於保護蓋2之蓋子本體 2d覆蓋有蓋體2c，並於蓋子本體2d之凹處與蓋體2c間 -9 - 200810223 (7) 所形成的密閉空間，收納蓄熱劑3。於蓋子本體2d與蓋體 2c間插人橡膠系材料（例如EpDM(乙丙橡膠）、fkm(氟橡 膠）、NBR(丁本橡膠）、SBR(苯乙烯—丁二烯橡膠》等具有 耐甲醇性之密封材料4，並密封成熔解後之液狀蓄熱劑3 不會從保護蓋2漏出至外部。 由於畜熱劑3係內藏於保護蓋2內，相較於只配置於 保護蓋2外部（與陰極之間）之情形，由於使陰極側產生 φ 之熱能首先鞯由保護蓋2下部先擴散於平面方向並蓄積於 蓄熱劑3，因此可在廣大範圍蓄熱並使熱分布均勻。 蓄熱劑3可使用碳原子數目爲20以上之石臘、硫代 硫酸鈉水合物、及硫酸鈉水合物等。該等蓄熱劑材料，如 表1所示，熔點在30〜50T：之範圍內，在保護蓋2之發電 開始前的溫度（室溫）爲固體，在發電開始後的溫度（約60 °C )則熔解成液體。 保護蓋2之材料，雖較佳爲使用不銹鋼或鎳金屬等耐 • 腐蝕性優異之金屬材料，但不限於金屬材料亦可使用樹脂 材料，例如（聚醚醚酮）（PEEK:英國威格斯（Victrex pic)公 司之商標）、聚苯硫（PPS)、聚四氟乙烯（PTFE)等在液體不 易產生膨潤等之硬質樹脂。 …本實施形態中，將保護蓋2之板厚tl設—爲0.5mm， 將密封材料4之厚度t2設爲〇.2mm，將蓄熱劑3之厚度 t3設爲l.〇mm。此外，蓄熱劑3之板厚t3可在0·8〜3 ·〇 之範圍內適當改變。 爲了可從陽極氣體擴散層14於負極引線16b取出電 -10- 200810223 (8) 子，並以最佳效率利用發電能量，形成有既定空間之氣化 室（未圖示）。氣化室（未圖示）係與液體燃料收容室27鄰接 設置，兩者之間藉由氣液分離膜（未圖示）隔開。此外，氣 液分離膜係由具有多數個細孔之聚四氟乙嫌（PTFE)薄片所 構成，用來隔斷液體燃料並使燃料氣體透過。 液體燃料收容室27 ’係由藉由作爲陽極保護側保護蓋 之筐體外飾板25及液體燃料供給框以界定周圍之既定容 φ 量的空間所構成，液體接受口 21開口於該空間之適當位 置（例如燃料槽之側面）。於液體接受口 2 1例如安裝有插接 式耦合器23，除補給燃料時以外藉由耦合器23以封閉燃 料供應口 2 1。該燃料電池本體側之耦合器2 3係形成爲能 與另外之燃料卡匣側之耦合器（未圖示）液密卡合的形狀 。例如若使燃料卡匣側耦合器之槽（未圖示）卡合於燃料 電池本體側之耦合器2 3之突起，並一邊導引一邊押入於 燃料電池本體側之鍋合器2 3之內時，內藏閥即開啓卡匣 • 側之流路便連通至燃料電池本體側之流路，藉由燃料卡匣 之內壓液體燃料（甲醇液等）通過輸送管自液體接受口流入 於液體燃料收容室27內。 亦可將液體燃料含浸層（未圖示）收納於液體燃料收容 室H內。較隹爲於液體燃料含寖層，使用例如多孔貧聚 酯纖維、多孔質烯烴系樹脂等多硬質纖維、或連續氣泡多 孔質樹脂。液體燃料含浸層係配置於氣液分離膜（未圖示） 與形成燃料供應口 21之液體燃料供給框間，在燃料槽內 之液體燃料減少時或燃料電池本體傾斜導致所裝載之燃料 -11 - 200810223 (9) 供應偏移時，亦能將燃料均質地供應至氣液分離膜，其結 果，便能將經氣化之液體燃料均質地供應於陽極觸媒層1 4 。除聚酯纖維外，亦可藉由丙烯酸系樹脂等各種吸水性聚 合物構成，利用海綿或纖維之集合體等液體之滲透性藉由 能保持液體之材料來構成。本液體燃料含浸部能不拘本體 之姿勢以供應適量之燃料。 氣化室（未圖示）係藉由間隔器與氣液分離膜（未圖示） φ 來界定周圍。複數個氣化燃料供應口開口在間隔器之上面 。該等氣化燃料供應口係貫通負極引線1 6b並分別連通於 陽極氣體擴散層1 4側。當液體燃料收容室內之液體燃料 的一部分氣化時，該燃料氣體成分即通過氣液分離膜進入 氣化室，並進一步自氣化室通過氣化燃料供給口導入於陽 極氣體擴散層1 4側，有助於發電反應。 燃料電池1之單元電池具備電解質膜11、陽極及陰極 。陽極與陰極係將電解質膜1 1包夾於中間並對向配置。 # 陽極具有陽極觸媒層12及陽極氣體擴散層14。 電解質膜11係用來將在陽極觸媒層12產生之質子輸 送至陰極觸媒層13，不具電子傳導性，由能輸送質子之材 料所構成。例如，聚全氟颯酸系之樹脂膜，具體而言，由 • 杜邦公司屬之納菲（Maflon)薄膜、旭硝子公司製之Flemion 膜、或旭化成工業社製之Axiplex膜等所構成。此外，除 聚全氟礪酸系之樹脂膜外，亦能以三氟苯乙烯之共聚合膜 、含浸磷酸之聚苯并咪唑膜、芳香族聚醚酮楓酸膜、或脂 肪族碳氫化合物系樹脂膜等構成可輸送質子之電解質膜11 -12- 200810223 (10) 陽極觸媒層1 2係將透過氣體擴散層1 4所供應之燃料 氧化後從燃料取出電子與質子，陽極觸媒層1 2與氣體擴 散層14構成重疊堆積之層積構造。陽極觸媒層12例如係 由包含觸媒之碳粉末所構成。觸媒可使用例如白金（Pt)之 微粒子、鐵（Fe)、鎳（Ni)、鈷（Co)、釕（Ru)或錳（Mo)等過 渡金屬或其氧化物或該等合金等之微粒子。然而，若藉由 釕與白金之合金構成觸媒時，由於可防止因一氧化碳（CO) 之吸附所造成之觸媒非活性化因此較佳。 又，陽極觸媒層1 2若包含使用於電解質膜1 1之電解 質更佳。係爲了使所產生之質子容易移動。陽極氣體擴散 層14例如以多孔質之碳材料構成之薄膜來構成，具體而 言，以碳紙或碳纖維等構成。 此外，於與陽極氣體擴散層1 4之電解質膜1 1相反側 的面配置有集電體16b，自該集電體16b之端部往外側延 伸作爲負極引線。該集電體可分別使用例如將金等優良導 電性金屬被覆於金、鎳等金屬材料所構成之多孔質層（例 如篩網）、或箔體、或不銹鋼（SUS)等導電性金屬材料的複 合材料。 陰極具有陰極觸媒層〗3及陰極擴散層15。陰極觼媒 層13,係將氧還原使電子與在陽極觸媒層12產生之質子 反應而產生水，例如以與上述陽極觸媒層12及氣體擴散 層14相同方式所構成。亦即，陰極構成層積構造，依照 自固體電解質膜1 1側之順序其係由包含觸媒之碳粉末構 -13- 200810223 (11) 成之陰極觸媒層I2及多孔質碳材料構成之陰極氣體擴散 層15(氣體透過層）所重疊堆積。使用於陰極觸媒層13之 觸媒，與陽極觸媒層12之觸媒相同，陽極觸媒層12有包 含使用於固體電解質膜1 1之電解質的情形，亦與陽極觸 媒層1 2相同。此外，於與陰極氣體擴散層丨5之電解質膜 1 1相反側的面配置有集電體16a ’自該集電體16a之端部 往外側延伸作爲正極引線。 # 圖5A及圖5B中，爲了使本發明之空氣導入孔之配置 的說明易於理解’係以數目較實際上少之空氣導入孔來顯 示以方便說明配置。 在本實施形態之燃料電池1，如圖5A所示，相較於 保護蓋2之中央部分係將空氣導入孔2 4集中配置於外周 部。以此方式，由於以高密度將空氣導入孔2 4配置於保 護蓋2之周邊部，因此能使收納於保護蓋2內部之蓄熱材 料3的熱容量在中央部較大在周邊部較小。由於產生之熱 • 能在電池結構的中央部較大，與此近接對面之保護蓋2相 較於周邊部中央部接受較多熱能，因此藉由本構成能提升 保護蓋2整體之溫度均一性。 相對於此，在習知燃料電池1 0 0，如圖5 B所示，係 ‘ 以等間隔將空氣導入孔24配置於保護蓋2。在習知型式之 燃料電池，於9個空氣導入孔24之間隔無疎密，空氣導 入孔24與空氣導入孔24之間爲等間距間隔。因此當自發 電開始經過某段時間後，保護蓋2整體之溫度便呈現不均 ，且因陰極側之反應熱導致保護蓋2中央部分熱膨脹變形Electrode Assembly is a unit cell with a liquid fuel tank around the unit cell and covering a single or multiple unit cells with a protective cover. Although the methanol of the fuel reacts with oxygen in the presence of a catalyst on the cathode side of the DMFC, since the reaction produces a combustion reaction (heating reaction) between water and carbon dioxide, the heat of reaction is accumulated inside the protective cover, as shown in the figure. 8 Characteristic curve C shows that the battery temperature will rise sharply at the beginning of power generation. After that, although the temperature of the exothermic battery gradually decreases with the passage of time, as the temperature of the φ battery decreases, as shown by the characteristic curve D, the power generation output also decreases. As described above, the DMFC has a problem of uneven output over time since the start of self-generation. In addition, the surface temperature of the protective cover of the DMFC may increase by more than about 60 °C due to a sudden rise in battery temperature in the initial stage of power generation, and there is also a concern about the thermal influence on the peripheral members and the problem of lowering the output characteristics. [Problem to be Solved by the Invention] The present invention has been made to solve the above problems, and to provide a fuel that can effectively prevent a sudden rise in temperature at the initial stage of power generation, and can suppress an output unevenness from the initial stage of power generation to the end of time. battery. [Means for Solving the Problem] [Effect of the Invention] The inventors of the present invention have a technique for suppressing the temperature rise of the fuel cell, particularly suppressing the rise of the surface temperature of the protective cover, and suppressing the occurrence of unevenness in output over time 硏-5-200810223 ( 3) As a result of the study, the present invention described below was completed. The fuel cell of the present invention includes a battery structure, a thin film electrode assembly including a proton conductive membrane disposed between a cathode catalyst layer and an anode catalyst layer, and a protective cover for supplying air to the battery a main surface of the opening provided in the air introduction hole on the cathode side of the structure; characterized in that it has a heat storage built in the main surface of the protective cover and used for absorbing/accumulating/releasing the heat energy generated by the power generation reaction on the cathode side Agent. φ The air introduction hole is arranged such that the air introduction holes are long apart from each other such that the central portion of the main surface of the protective cover is relatively narrow, and the air introduction holes are shortly spaced from each other to make the peripheral portion of the main surface of the protective cover denser (Fig. 5 A). Since the heat generated on the cathode side at the initial stage of power generation is concentrated in the central portion of the battery structure, if the distance between the air introduction hole and the air introduction hole is long, the air introduction hole is set to be relatively thin (reducing the number of openings of the air introduction hole) In the case where the amount of the heat storage agent in the central portion is increased, the heat capacity of the central portion can be made larger than the heat capacity of the peripheral portion, and the temperature uniformity of the entire protective cover can be improved. • The heat storage agent has the largest capacity at the center of the main surface of the protective cover, and the capacity distribution is gradually reduced from the central portion of the main surface of the protective cover to the peripheral portion (Fig. 6). Since the generated thermal energy is large in the central portion of the battery structure, the central portion of the protective cover adjacent to the opposite side receives more heat energy than the peripheral portion, and accordingly, the heat capacity of the heat storage agent is larger in the central portion. The smaller the peripheral portion, the higher the temperature uniformity of the protective cover. The melting point of the heat storage agent is preferably in the range of 30 to 50 ° C (Table 1). The heat storage agent has heat generated during the initial stage of power generation (endothermic function), and temporarily accumulates the absorbed heat in the middle of power generation (heat storage function), and releases the accumulated heat in the middle of power generation and after 200810223 (4) ( Exothermic function). If the melting point of the heat accumulating agent exceeds 50 ° C, the heat absorption during the heat storage period will be shortened due to the fact that the maximum temperature reached the surface of the protective cover is reached. On the other hand, if the melting point of the heat storage agent is lower than 3 (TC, since it changes from solid to liquid at room temperature, it cannot absorb the heat generated by power generation. The number of carbon atoms in the heat storage agent can be 20 or more. Paraffin, sodium thiosulfate hydrate, sodium sulfate hydrate, etc. However, paraffin, calcium chloride hydrate, etc. having a carbon number of 18 or less are not suitable for use as a heat storage agent because of a too low melting point. Conversely, acetic acid The sodium hydrate or the like is not suitable for the heat storage agent because the melting point is too high. The protective cover may be configured to have a structure in which the cover body is provided with a housing for opening the heat storage agent, and a cover for covering The opening of the cover body forms a part of the main surface of the protective cover. Further, a sealing material is provided between the cover body and the cover body disposed between the protective cover so that the heat storage agent does not leak out. Various rubber-based materials, resin materials, or metal materials ranging from hard to soft, such as EPDM (ethylene propylene rubber), FKM (fluoro rubber), NBR (butyl benzene) can be used. Glue), SBR (styrene-butadiene rubber) is most suitable. The protective cover can be integrally attached to the battery structure t #P stomach by riveting, for example, when the riveted portion is riveted to the periphery of the battery structure. When the stomach is fixed to the battery structure with the stomach #_ cover, the center of the protective cover cannot be locked. When the heat is transmitted from the battery structure to the protective cover, the expansion cover is convex and convex. However, the present invention is Use of a heat storage agent to forcibly remove heat from the protective cover of -7-200810223 (5), so that the protection is suppressed or prevented. [Embodiment] The following description is made with reference to the attached drawings. (First Embodiment) First, reference is made to the drawings. 1. Fig. 2A, Fig. 2B, and the entire pool. The fuel cell 1 is provided with a power generating portion and a main surface having a main surface covering the cathode side of the battery structure 10, and has a plane disposed inside and connected in series. As shown in FIG. 3, the unit cell includes a proton-transporting membrane 11, an anode catalyst layer 12, and a cathode catalyst layer membrane electrode group, and further includes an anode gas diffusion layer 1 and a negative electrode layer. (cathode collector) ) i6a, and current collector) 16b. Inside the fuel cell 1, space or gap is provided by the sealing member 18. Among these spaces or gaps, for example, the yin rice is used as the Bao 1 plate 26, and the space on the yang side is used as the tank 27 and the vaporization chamber (not shown). The moisture-reducing sheet 2 6,| is, for example, a porous film of 20 to 60%. The liquid is connected to the liquid receiving port 21 at a suitable position. The liquid receiving port 21 is mounted with, for example, a thermal expansion deformation of the plug coupling. Various forms of the invention 3 describe the fuel cell structure 1 呆 the cover 2. Battery: a plurality of units of solid electrolysis 1 3 - thin body 4, cathode gas expansion negative lead (anode, etc. formed a variety of i side space system [body fuel storage room Zhijia for the use of stomatal fuel storage room 2 7 material supply flow path 19 2, a nozzle of the fuel cartridge not shown in Fig. -8 - 200810223 (6) is inserted into the coupler 23 to supply liquid fuel to the liquid fuel containing chamber 27. Further, the liquid As the 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, glycol fuel such as ethylene glycol aqueous solution or pure ethylene glycol, and formic acid may be used. An aqueous solution of an aqueous solution containing an aqueous solution of formic acid, an aqueous solution of sodium citrate, an aqueous solution of acetic acid, an aqueous solution of sodium borohydride, an aqueous solution of potassium borohydride, an aqueous solution of lithium hydride, a solution of ethylene glycol water-soluble φ, and a hydrogen-containing organic solvent such as dimethyl ether. Liquid fuel. Among them, since methanol is produced by reacting with one carbon atom, it is carbon dioxide gas, and can generate a power generation reaction at a low temperature, and is relatively easy to be industrialized. It is preferred that the waste is manufactured. Further, the fuel may be used in various concentrations ranging from 100% to several % by concentration. It is preferred to use methanol having a concentration of 80% or more as a liquid fuel, particularly to exert its performance or Therefore, it is preferable to use a fuel cell having a concentration of 80% or more of methanol as a liquid fuel absorbing material in each embodiment. On the main surface of the protective cover 2 on the cathode side, a plurality of air introduction holes 24 are provided at predetermined intervals. The openings are respectively communicated with the moisturizing plate 26. The air introducing holes 24 form an opening through which the outside air passes, but are carefully designed so as not to hinder the passage of the outside air and prevent the intrusion of minute or needle-shaped foreign matter from the outside. / Contacting the shape of the cathode gas diffusion layer 15. As shown in Fig. 4, the protective cover 2 is provided with a heat storage agent 3 for accumulating excess heat energy generated at the initial stage of power generation. That is, the cover body 2d of the protective cover 2 is covered with a cover. The body 2c accommodates the heat storage agent 3 in a sealed space formed by the recess of the cover main body 2d and the cover 2c -9 - 200810223 (7). A rubber-based material is inserted between the cover main body 2d and the cover 2c (for example) EpDM (B A sealing material 4 having a methanol resistance such as rubber), fkm (fluororubber), NBR (butyl rubber), or SBR (styrene-butadiene rubber), and sealed to form a liquid heat storage agent 3 after melting The protective cover 2 leaks to the outside. Since the heat generating agent 3 is housed in the protective cover 2, compared with the case where it is disposed only outside the protective cover 2 (between the cathodes), the heat energy of φ is generated on the cathode side first. The lower portion of the protective cover 2 is first diffused in the plane direction and accumulated in the heat storage agent 3, so that heat can be stored in a wide range and the heat distribution is uniform. The heat storage agent 3 can use paraffin or sodium thiosulfate hydrate having a carbon number of 20 or more. And the sodium sulphate hydrate, etc., as shown in Table 1, the melting point is in the range of 30 to 50 T:, the temperature (room temperature) before the start of power generation of the protective cover 2 is solid, and the power generation starts. The latter temperature (about 60 ° C) melts into a liquid. The material of the protective cover 2 is preferably a metal material excellent in corrosion resistance such as stainless steel or nickel metal, but not limited to a metal material, and a resin material such as (polyetheretherketone) (PEEK: Victrex, UK) (Victrex pic) company's trademark), polyphenylene sulfide (PPS), polytetrafluoroethylene (PTFE) and other hard resins that are less likely to swell in liquids. In the present embodiment, the thickness t1 of the protective cover 2 is set to 0.5 mm, the thickness t2 of the sealing material 4 is set to 〇2 mm, and the thickness t3 of the heat storage agent 3 is set to 1. 〇mm. Further, the thickness t3 of the heat storage agent 3 can be appropriately changed within the range of 0·8 to 3 · 。. In order to take out the electricity - 10 200810223 (8) from the anode gas diffusion layer 14 to the negative electrode lead 16b, and to utilize the power generation energy with an optimum efficiency, a vaporization chamber (not shown) having a predetermined space is formed. A vaporization chamber (not shown) is provided adjacent to the liquid fuel storage chamber 27, and is separated by a gas-liquid separation membrane (not shown). Further, the gas-liquid separation membrane is composed of a polytetrafluoroethylene (PTFE) sheet having a plurality of pores for blocking the liquid fuel and allowing the fuel gas to permeate. The liquid fuel accommodating chamber 27' is constituted by a space which is defined by the outer fascia 25 of the anode protective side protective cover and the liquid fuel supply frame to define a predetermined volume φ around the liquid receiving opening 21 in the space. Position (eg side of the fuel tank). For example, a plug-in coupler 23 is attached to the liquid receiving port 2, and the fuel supply port 21 is closed by a coupler 23 in addition to refueling. The coupler 23 on the fuel cell main body side is formed in a shape that can be fluid-tightly engaged with a coupler (not shown) on the other fuel cartridge side. For example, a groove (not shown) of the fuel cartridge side coupler is engaged with the protrusion of the coupler 23 on the fuel cell main body side, and is guided while being guided into the potter 2 3 on the fuel cell main body side. When the built-in valve opens the flow path on the side of the cassette, it is connected to the flow path on the side of the fuel cell body, and the liquid fuel (methanol liquid, etc.) in the fuel cartridge flows into the liquid from the liquid receiving port through the conveying pipe. Inside the fuel containing chamber 27. A liquid fuel impregnation layer (not shown) may be housed in the liquid fuel storage chamber H. More preferably, the liquid fuel impregnated layer is a multi-hard fiber such as a porous polyester fiber or a porous olefin resin, or a continuous cell porous resin. The liquid fuel impregnation layer is disposed between the gas-liquid separation membrane (not shown) and the liquid fuel supply frame forming the fuel supply port 21, and the fuel fuel is loaded when the liquid fuel in the fuel tank is reduced or the fuel cell body is inclined. - 200810223 (9) When the supply is shifted, the fuel can be homogeneously supplied to the gas-liquid separation membrane, and as a result, the vaporized liquid fuel can be uniformly supplied to the anode catalyst layer 14 . In addition to the polyester fiber, it may be composed of various water-absorbent polymers such as an acrylic resin, and the liquid permeability of the sponge or the fiber assembly may be constituted by a material capable of retaining the liquid. The liquid fuel impregnation section can supply an appropriate amount of fuel regardless of the posture of the body. The gasification chamber (not shown) is defined by a spacer and a gas-liquid separation membrane (not shown) φ. A plurality of gasification fuel supply ports are open above the spacer. The vaporized fuel supply ports pass through the negative electrode lead 16b and communicate with the anode gas diffusion layer 14 side, respectively. When a part of the liquid fuel in the liquid fuel storage chamber is vaporized, the fuel gas component enters the gasification chamber through the gas-liquid separation membrane, and is further introduced into the anode gas diffusion layer 14 from the gasification chamber through the vaporization fuel supply port. To help generate electricity. The unit cell of the fuel cell 1 is provided with an electrolyte membrane 11, an anode, and a cathode. The anode and the cathode are sandwiched between the electrolyte membranes 1 and disposed in the middle direction. # anode has an anode catalyst layer 12 and an anode gas diffusion layer 14. The electrolyte membrane 11 is for transporting protons generated in the anode catalyst layer 12 to the cathode catalyst layer 13, and is made of a material capable of transporting protons without electron conductivity. For example, a polyperfluorophthalic acid-based resin film is specifically composed of a Maflon film of DuPont, a Flemion film manufactured by Asahi Glass Co., Ltd., or an Axiplex film manufactured by Asahi Kasei Kogyo Co., Ltd. In addition, in addition to the polyperfluorodecanoic acid resin film, a copolymer film of trifluorostyrene, a polybenzimidazole film impregnated with phosphoric acid, an aromatic polyetherketone maple acid film, or an aliphatic hydrocarbon can also be used. An electrolyte membrane that can transport protons such as a resin film. 11-1210210223 (10) The anode catalyst layer 1 2 oxidizes the fuel supplied through the gas diffusion layer 14 to extract electrons and protons from the fuel, and the anode catalyst layer The gas diffusion layer 14 and the gas diffusion layer 14 have a laminated structure in which they are stacked. The anode catalyst layer 12 is composed of, for example, a carbon powder containing a catalyst. As the catalyst, for example, a platinum (Pt) fine particle, a transition metal such as iron (Fe), nickel (Ni), cobalt (Co), ruthenium (Ru) or manganese (Mo) or an oxide thereof or a fine particle such as the alloy may be used. . However, when a catalyst is formed by an alloy of ruthenium and platinum, it is preferable to prevent the catalyst from being deactivated by adsorption of carbon monoxide (CO). Further, the anode catalyst layer 1 2 preferably contains the electrolyte used for the electrolyte membrane 1 1 . In order to make the generated protons easy to move. The anode gas diffusion layer 14 is formed, for example, of a film made of a porous carbon material, and specifically, is made of carbon paper or carbon fiber. Further, a current collector 16b is disposed on a surface opposite to the electrolyte membrane 11 of the anode gas diffusion layer 14 and extends outward from the end portion of the current collector 16b as a negative electrode lead. Each of the current collectors may be a porous layer (for example, a mesh) made of a metal material such as gold or nickel, or a conductive metal material such as a foil or stainless steel (SUS). Composite material. The cathode has a cathode catalyst layer 3 and a cathode diffusion layer 15. The cathode tantalum layer 13 is formed by reacting oxygen with a proton generated in the anode catalyst layer 12 to generate water, for example, in the same manner as the anode catalyst layer 12 and the gas diffusion layer 14. That is, the cathode constitutes a laminated structure which is composed of a cathode catalyst layer I2 composed of a catalyst-containing carbon powder structure-13-200810223 (11) and a porous carbon material in the order from the side of the solid electrolyte membrane 1 1 . The cathode gas diffusion layer 15 (gas transmission layer) is stacked and stacked. The catalyst used for the cathode catalyst layer 13 is the same as the catalyst of the anode catalyst layer 12, and the anode catalyst layer 12 has the same electrolyte as that used for the solid electrolyte membrane 11, and is also the same as the anode catalyst layer 12 . Further, the current collector 16a' is disposed on the surface opposite to the electrolyte membrane 1 of the cathode gas diffusion layer 丨5, and extends from the end of the current collector 16a to the outside as a positive electrode lead. In Fig. 5A and Fig. 5B, in order to make the description of the arrangement of the air introduction holes of the present invention easy to understand, it is shown by a relatively small number of air introduction holes to facilitate the explanation of the arrangement. In the fuel cell 1 of the present embodiment, as shown in Fig. 5A, the air introduction hole 24 is disposed in a concentrated manner on the outer peripheral portion of the center portion of the protective cover 2. In this way, since the air introduction hole 24 is disposed at a peripheral portion of the protective cover 2 at a high density, the heat capacity of the heat storage material 3 accommodated inside the protective cover 2 can be made larger at the center portion and smaller at the peripheral portion. Since the generated heat can be made larger in the central portion of the battery structure, the protective cover 2 that is adjacent to the opposite side receives more heat energy than the central portion of the peripheral portion. Therefore, the temperature uniformity of the entire protective cover 2 can be improved by this configuration. On the other hand, in the conventional fuel cell 100, as shown in Fig. 5B, the air introduction hole 24 is disposed at equal intervals in the protective cover 2. In the conventional fuel cell, the interval between the nine air introduction holes 24 is not dense, and the air introduction holes 24 and the air introduction holes 24 are equally spaced. Therefore, when the self-energizing starts for a certain period of time, the temperature of the protective cover 2 as a whole is uneven, and the central portion of the protective cover 2 is thermally expanded and deformed due to the reaction heat on the cathode side.
A -14- 200810223 (12) 成凸狀。 保護蓋2，25及支柱29，雖以例如（聚醚醚酮）（PEEK :英國威格斯（Victrex pic)公司之商標）、聚苯硫（PPS)、 聚四氟乙烯（PTFE)等在液體燃料不易產生膨潤之硬質塑膠 製作較佳，但若施以耐腐蝕性優異之鍍膜時亦可以不銹鋼 或鎳金屬等耐腐飩性優異之金屬材料來製作。當保護蓋2 採用金屬材料時，必須將未圖示之絕緣構件插入於負極彼 φ 此間，以防止配置於同一電池容器內之各負極彼此短路。 (第二實施形態） 參照圖6說明第二實施形態。此外，省略本實施形態 與上述第一實施形態重複部分之說明。 在第二實施形態，依照電池結構之發熱部位改變內包 於保護蓋2 A之蓄熱劑3的厚度。亦即，使蓄熱劑3之厚 度在保護蓋2A之中央部最厚，在保護蓋2A之周邊部逐 # 漸減少而變薄。藉此，在進熱量大之保護蓋中央部分熱容 量較大’在進熱量小之保護蓋周邊部分熱容量較小，整體 保護蓋2呈良好之熱平衡。 在本實施形態，將保護蓋2之板厚u設爲〇 5mm， 將密封枒料4之厚度t2設爲0.2mm，將蓄-熱劑3乏最大 厚度t設爲1 · 〇 m m。此外，蓄熱劑3厚度增減之程度可依 照電池結構1 0之構成作各種改變。 於保護蓋2A內部之剩餘空間塡充有隔熱材料$。由 於隔熱材料5阻斷來自內部之熱，因此具有防止發電初期 -15- 200810223 (13) 保護蓋之異常升溫的效果。又’由於藉由隔熱材料5之存 在，在發電中期〜後期使蓄積於蓄熱劑3之熱能緩緩釋出 ，因此具有安定輸出的效果。 (實施例與比較例） 表1分別表示各種實施例及比較例之蓄熱劑的熔點（ °C )與熔解熱（kJ/kg)。石躐係熔點位於較室溫稍高之溫度 區域，在呈現適度之熔解熱量，容易獲得且低價位等各點 非常優異。此外，石躐在即使萬一漏出於外部時，具有無 毒性且安全性高之優異特性。如上述石躐可說是本發明之 蓄熱劑最合適的材料之一。 實施例1之石蠟（C22H46)，由於熔點（441)低於燃料 電池發電初期之過熱溫度，且熔解熱（157kJ/kg)爲適度之 大小，因此能保有足夠之蓄熱量。 實施例2之石蠟（C2()H42)，熔點（36.4°C )雖較實施 低，但由於熔解熱（247kJ/kg)較大，因此可在發電初期預 先蓄積所欲程度之熱量，並在發電中期〜後期緩緩消耗其 所蓄積之熱能，可抑制燃料電池之溫度降低，並能防止輸 出降低。 另一方面，比較例1之石蠟（C18H38)，由於溶點 (28.2 °C )較低且接近於室溫，因此無法在發電中期〜後期 緩緩消耗其所蓄積之熱能，且不能發揮所欲之蓄熱效果。 除石蠟之外，硫代硫酸鈉或硫酸鈉等各種水合物亦可 使用於本發明之蓄熱劑。由於該等水合物熔點位於較室溫 •16- 200810223 (14) 稍高之溫度區域，並呈現適度之熔解熱量，因此適合使用 於本發明之蓄熱劑。 實施例3之硫代硫酸鈉水合物（Na2S203.5H2〇)，由於 熔點（48 °C )低於燃料電池發電初期之過熱溫度，且熔解 熱（197kJ/kg)爲適度之大小，因此能保有足夠之蓄熱量。 該硫代硫酸鈉水合物與實施例1之石蠟（C22H46)，由於熔 點適度高於室溫（23 ± 1 °C )，因此適合於作爲蓄熱劑之材料 φ ，並能得到優異之蓄熱效果。 實施例4之硫酸鈉水合物（Na2S04· 1〇H20)，熔點（32.4 °C)雖較實施例3低，但由於熔解熱（251kJ/kg)較大，因此 可在發電初期預先蓄積所欲程度之熱量，並在發電中期〜 後期緩緩消耗其所蓄積之熱能，而可抑制燃料電池之溫度 降低，並能防止輸出之降低。 另一方面，比較例2之氯化鈣水合物 （CaCl2.6H20) ，由於熔點（29.7 °C )較低且接近於室溫，因此無法在發電 • 中期〜後期緩緩消耗其所蓄積之熱能，不能發揮所欲之蓄 熱效果。 與此相反，比較例3之醋酸鈉水合物（C H3 C Ο Ο Η _ 3Η20)，由於熔點（5 8°C)較高且接近於燃料電池發電初期 之過熱溫度，其全量未必一定液化，因此不能發揮所欲之 蓄熱效果。 -17- 200810223 (15)A -14- 200810223 (12) It is convex. The protective covers 2, 25 and the pillars 29 are, for example, (polyetheretherketone) (PEEK: trademark of Victrex pic), polyphenylene sulfide (PPS), polytetrafluoroethylene (PTFE), etc. A hard plastic which is less likely to cause swelling of a liquid fuel is preferably produced. However, when a coating having excellent corrosion resistance is applied, it can be produced by a metal material having excellent corrosion resistance such as stainless steel or nickel metal. When the protective cover 2 is made of a metal material, an insulating member (not shown) must be inserted between the negative electrodes φ to prevent the respective negative electrodes disposed in the same battery container from being short-circuited to each other. (Second Embodiment) A second embodiment will be described with reference to Fig. 6 . Further, the description of the overlapping portions of the present embodiment and the first embodiment will be omitted. In the second embodiment, the thickness of the heat storage agent 3 contained in the protective cover 2A is changed in accordance with the heat generating portion of the battery structure. In other words, the thickness of the heat storage agent 3 is made thickest at the center portion of the protective cover 2A, and is gradually reduced and thinned at the peripheral portion of the protective cover 2A. Thereby, the heat capacity in the central portion of the protective cover having a large heat input is large. The heat capacity in the peripheral portion of the protective cover having a small heat input is small, and the overall protective cover 2 has a good heat balance. In the present embodiment, the thickness u of the protective cover 2 is set to 〇 5 mm, the thickness t2 of the sealing material 4 is set to 0.2 mm, and the maximum thickness t of the heat storage agent 3 is set to 1 · 〇 m m. Further, the degree of increase or decrease in the thickness of the heat storage agent 3 can be variously changed in accordance with the constitution of the battery structure 10. The remaining space inside the protective cover 2A is filled with the heat insulating material $. Since the heat insulating material 5 blocks the heat from the inside, it has an effect of preventing the abnormal temperature rise of the protective cover at the initial stage of power generation -15-200810223 (13). Further, since the thermal energy stored in the heat storage agent 3 is gradually released in the middle to the late stage of power generation by the heat insulating material 5, the effect of stable output is obtained. (Examples and Comparative Examples) Table 1 shows the melting point (°C) and the heat of fusion (kJ/kg) of the heat storage agents of the respective examples and comparative examples. The melting point of the sarcophagus is located in a temperature region slightly higher than the room temperature, and exhibits moderate heat of fusion, is easily available, and is excellent in various points such as low price. In addition, the sarcophagus has excellent properties such as non-toxicity and high safety even if it leaks to the outside. As described above, sarcophagus is one of the most suitable materials for the heat storage agent of the present invention. In the paraffin wax (C22H46) of Example 1, since the melting point (441) is lower than the superheating temperature at the initial stage of power generation of the fuel cell, and the heat of fusion (157 kJ/kg) is moderately large, sufficient heat storage amount can be maintained. In the paraffin wax (C2()H42) of Example 2, although the melting point (36.4 ° C) is lower than that of the implementation, since the heat of fusion (247 kJ/kg) is large, the desired amount of heat can be accumulated in advance at the initial stage of power generation, and During the mid-to-late generation period, the accumulated heat energy is slowly consumed, which can suppress the temperature drop of the fuel cell and prevent the output from being lowered. On the other hand, in the paraffin wax (C18H38) of Comparative Example 1, since the melting point (28.2 °C) is low and close to room temperature, it is impossible to gradually consume the accumulated heat energy in the middle to late stages of power generation, and it is not possible to exert its desired energy. The heat storage effect. In addition to paraffin, various hydrates such as sodium thiosulfate or sodium sulfate can also be used in the heat storage agent of the present invention. Since the melting point of the hydrate is located in a temperature range slightly higher than room temperature •16-200810223 (14) and exhibits moderate heat of fusion, it is suitable for use in the heat storage agent of the present invention. The sodium thiosulfate hydrate (Na2S203.5H2〇) of Example 3 has a melting point (48 ° C) lower than the superheat temperature at the initial stage of power generation of the fuel cell, and the heat of fusion (197 kJ/kg) is moderately sized, so that it can be retained. Enough heat storage. The sodium thiosulfate hydrate and the paraffin wax (C22H46) of Example 1 are suitable as the material φ of the heat storage agent because the melting point is moderately higher than room temperature (23 ± 1 °C), and an excellent heat storage effect can be obtained. The sodium sulfate hydrate (Na2S04·1〇H20) of Example 4 has a lower melting point (32.4 °C) than that of Example 3. However, since the heat of fusion (251 kJ/kg) is large, it can be accumulated in advance in the early stage of power generation. The degree of heat, and in the mid-to-late generation, slowly consumes the accumulated heat energy, which can suppress the temperature drop of the fuel cell and prevent the output from decreasing. On the other hand, the calcium chloride hydrate of Comparative Example 2 (CaCl2.6H20), because the melting point (29.7 °C) is low and close to room temperature, it is not possible to slowly consume its accumulated heat energy in the middle and late stages of power generation. Can not exert the desired heat storage effect. On the contrary, the sodium acetate hydrate of Comparative Example 3 (C H3 C Ο Ο _ _ 3Η20) has a high melting point (58 ° C) and is close to the superheat temperature at the initial stage of power generation of the fuel cell, and the total amount thereof does not necessarily liquefy. Therefore, the desired heat storage effect cannot be exerted. -17- 200810223 (15)
蓄熱劑 組成 熔點 (°C ) 熔解熱 (kJ/kg) 實施例1 石蠟 C22H46 44 157 實施例2 石蠟 C20H42 36.4 247 實施例3 硫代硫酸納 水合物 N a 2 S 2 〇 3 • 5H20 48 197 實施例4 硫酸鈉 水合物 N a2 S 04· 1 0H2〇 32.4 25 1 比較例1 石躐 C 1 8H3 8 28.2 243 比較例2 氯化鈣 水合物 CaCl2 · 6H2〇 29.7 192 比較例3 醋酸鈉 水合物 CH3COO H·3H20 58 264 如圖6所示，亦可依照發熱量來改變蓄熱劑3之量。 亦即，在發熱量較大之電池中央部增加蓄熱劑之厚度t4 ’ 在發熱量較小之電池周邊部減少蓄熱劑之厚度t4 ’以此方 φ 式藉由依各保護蓋2之部位改變蓄熱劑3之量’便能實現 保護蓋2整體的溫度均一性。 圖7，係表示取運作開始起之經過時間（hr)爲橫軸’ 取燃料電池保護蓋表面之溫度（°C )爲縱軸，並分別調查 實施輒與比較例之燃料電池中，保_護蓋表面溫度之·隨勝間 變化之結果的特性曲線圖。溫度係使用數位表面溫度計在 保護蓋之中央部測量。圖中之特性曲線A及特性曲線B係 分別表示實施例1之結果及比較例1之結果。 從圖中明顯可知，藉由將蓄熱劑3內包於保護蓋，即 使在起動時或注入燃料時在電池內部產生急遽之溫度上升 •18- 200810223 (16) 時，保護蓋2之表面溫度能維持在4(TC以下。又，藉由蓄 熱劑3之蓄熱效果，在其後亦不會產生急遽之溫度降低， 而能有效防止發電輸出之降低。 依據本發明，可穩定得到優異之電池性能，並能得到 不均較小的輸出特性以作爲筆記型電腦、行動電話、可攜 式音響、可攜式遊戲機等無線可攜式機器之電源。又，依 據本發明，由於發電初期保護蓋2表面無異常升溫，因此 φ 可緩和對周邊構件之熱影響，進而能改善輸出特性。 此外，本發明並非直接限定於上述實施形態，於實施 階段在不逸脫其要旨之範圍能將構成要素加以變形並予以 具體化。又’藉由適當組合揭示於上述實施形態之複數個 構成要素，可形成各種發明。例如，亦可從揭示於實施形 態之全部構成要素刪除幾個構成要素。進一步，亦可將跨 越不同實施形態之構成要素適當予以組合。 例如，上述說明中，雖以於薄膜電極組（MEA)下部具 Φ 有液體燃料收容室之構造作爲燃料電池之構成而加以說明 ’但自燃料收容部對薄膜電極組之燃料供應以配置流路來 連接之構造亦可。又，雖舉被動型燃料電池爲例作爲燃料 電池本體之構成而加以說明，但對進一步於燃料供應等一 部分使用泵等之稱爲半被動型燃料電池亦可應甩本發明-。 半被動型燃料電池’係將來自燃料收容部供應於MEA之 燃料使用於發電反應，之後並不循環返回燃料收容部。半 被動型燃料電池’因不使燃料循環，與習知主動方式不同 ，並不損及裝置之小型化等。又，燃料電池係於燃料供應 -19- 200810223 (17) 使用泵，與如習知內部氣化型之純被動方式亦不相同。因 此，燃料電池如上述般被稱爲半被動方式。此外，在該半 被動型之燃料電池，只要是進行自燃料收容部對MEA之 燃料供應的構成，亦可設置成配置燃料遮斷閥以取代泵的 構成。於此情況下，燃料遮斷閥係設置成用來控制流路之 液體燃料的供應。 又’在對MEA供應之液體燃料的蒸氣，雖亦可供應 所有液體燃料之蒸氣，但一部分以液體狀態供應時亦可應 用本發明。 【圖式簡單說明】 〔圖1〕係表示燃料電池之槪要的分解立體圖。 〔圖2A〕係表示從陰極側（空氣極）側觀看燃料電池的 外觀立體圖。 〔圖2B〕係表示從陽極側（燃料極）側觀看燃料電池的 外觀立體圖。 〔圖3〕係燃料電池之內部透視截面圖。 〔圖4〕係表示內藏本發明實施形態之蓄熱劑之保護 蓋的截面圖。 〔薗5 A〕係槪略表示本發明之保護篕之空氣導入孔 位置的分解l體圖。 〔圖5 B〕係槪略表示習知之保護蓋之空氣導入孔位 置的分解立體圖。 〔圖6〕係表示內藏其他實施形態之蓄熱劑之保護蓋 -20- 200810223 (18) 的截面圖。 〔圖7〕係比較實施例與比較例以表示本發明之蓄熱 效果的特性曲線圖。 〔圖8〕係表示發電輸出之溫度依存性的特性曲線圖 【主要元件符號說明】 1，1 〇 〇 :燃料電池 2,2A :保護蓋 2c :蓋體 2d :蓋子本體 3 :蓄熱劑 4 :密封材料 5 :隔熱材料 1 0 :電池結構 1 1 :固體電解質膜 1 2 :陽極觸媒層 1 3 :陰極觸媒層 1 4 :陽極氣體擴散層 15 :陰極氣體擴散層 16a :正極引線（陰極集電體） 16b :負極引線（陽極集電體） 1 8 :密封構件 19 :燃料供給流路 -21 - 200810223 (19) 2 1 :液體接受口 23 :耦合器 24 :空氣導入孔 25 :筐體外飾板 2 6 :保濕板 27 :液體燃料收容室 29 :支柱Heat storage agent composition melting point (°C) Heat of fusion (kJ/kg) Example 1 Paraffin wax C22H46 44 157 Example 2 Paraffin wax C20H42 36.4 247 Example 3 Sulfuric acid sulphate N a 2 S 2 〇3 • 5H20 48 197 Example 4 Sodium sulfate hydrate N a2 S 04· 1 0H2 〇 32.4 25 1 Comparative Example 1 Dendrobium C 1 8H3 8 28.2 243 Comparative Example 2 Calcium chloride hydrate CaCl 2 · 6H 2 〇 29.7 192 Comparative Example 3 Sodium acetate hydrate CH 3 COO H·3H20 58 264 As shown in Fig. 6, the amount of the heat storage agent 3 can also be changed in accordance with the amount of heat generation. That is, the thickness t4 of the heat storage agent is increased in the central portion of the battery where the amount of heat generation is large. The thickness t4 of the heat storage agent is reduced in the peripheral portion of the battery where the amount of heat generation is small, and the heat storage is changed by the position of each protective cover 2 The amount of the agent 3 can achieve the temperature uniformity of the protective cover 2 as a whole. Figure 7 shows the elapsed time (hr) from the start of the operation as the horizontal axis 'takes the temperature of the fuel cell protective cover surface (°C) as the vertical axis, and investigates the implementation of the fuel cell in the 辄 and comparative examples, respectively. A characteristic curve of the result of the change in the surface temperature of the cover as a function of the change. The temperature is measured at the center of the protective cover using a digital surface thermometer. The characteristic curve A and the characteristic curve B in the figure show the results of Example 1 and the results of Comparative Example 1, respectively. As is apparent from the figure, by enclosing the heat storage agent 3 in the protective cover, the surface temperature of the protective cover 2 can be generated even when a sudden temperature rise occurs inside the battery at the time of starting or injecting fuel. 18-200810223 (16) It is maintained at 4 (TC or less. Further, by the heat storage effect of the heat storage agent 3, there is no sudden temperature drop, and the power generation output can be effectively prevented from being lowered. According to the present invention, excellent battery performance can be stably obtained. And can obtain uneven output characteristics for use as a power source for a wireless portable device such as a notebook computer, a mobile phone, a portable audio, a portable game machine, etc. Further, according to the present invention, the protective cover is provided at the initial stage of power generation (2) Since the surface is not abnormally heated, φ can alleviate the thermal influence on the peripheral member, and the output characteristics can be improved. Further, the present invention is not limited to the above-described embodiment, and the constituent elements can be removed in the range of the implementation stage. It is modified and embodied. Further, various inventions can be formed by appropriately combining the plurality of constituent elements disclosed in the above embodiments. For example, Several constituent elements are deleted from all the constituent elements disclosed in the embodiment. Further, constituent elements spanning different embodiments may be combined as appropriate. For example, in the above description, the lower portion of the thin film electrode assembly (MEA) has Φ. The structure of the liquid fuel storage chamber is described as a configuration of the fuel cell. However, the fuel supply unit may be connected to the fuel supply of the thin film electrode group by a flow path. Further, the passive fuel cell is used as a fuel. Although the configuration of the battery body is described, the present invention can also be applied to a semi-passive fuel cell that uses a pump or the like for a part of the fuel supply. The semi-passive fuel cell is supplied from the fuel storage unit to the MEA. The fuel is used for the power generation reaction, and then does not circulate back to the fuel accommodating portion. The semi-passive fuel cell 'has not circulated the fuel, unlike the conventional active mode, does not impair the miniaturization of the device, etc. For fuel supply -19- 200810223 (17) The use of pumps is not the same as the passive mode of the internal internal gasification type. Here, the fuel cell is referred to as a semi-passive method as described above. Further, the semi-passive type fuel cell may be provided with a fuel shutoff valve as long as it is configured to supply fuel from the fuel containing unit to the MEA. Instead of the configuration of the pump, in this case, the fuel shut-off valve is provided to control the supply of the liquid fuel in the flow path. Further, the vapor of the liquid fuel supplied to the MEA can supply all the vapors of the liquid fuel, However, the present invention can also be applied to a part of the fuel supply. Fig. 1 is an exploded perspective view showing the fuel cell. Fig. 2A shows the fuel viewed from the cathode side (air electrode) side. Fig. 2B is a perspective view showing the appearance of the fuel cell viewed from the anode side (fuel electrode) side. Fig. 3 is an internal perspective sectional view showing the fuel cell. Fig. 4 is a cross-sectional view showing a protective cover in which a heat storage agent according to an embodiment of the present invention is incorporated. [薗5 A] schematically shows a decomposition of the position of the air introduction hole of the protective crucible of the present invention. Fig. 5B is an exploded perspective view showing the position of the air introduction hole of the conventional protective cover. Fig. 6 is a cross-sectional view showing a protective cover -20- 200810223 (18) incorporating a heat storage agent of another embodiment. Fig. 7 is a characteristic graph showing the heat storage effect of the present invention by comparing the examples and the comparative examples. [Fig. 8] is a characteristic diagram showing the temperature dependence of the power generation output. [Main component symbol description] 1,1 〇〇: Fuel cell 2, 2A: Protective cover 2c: Cover 2d: Cover body 3: Heat storage agent 4: Sealing material 5: heat insulating material 10: battery structure 1 1 : solid electrolyte membrane 1 2 : anode catalyst layer 1 3 : cathode catalyst layer 14 : anode gas diffusion layer 15 : cathode gas diffusion layer 16 a : positive electrode lead ( Cathode current collector) 16b: negative electrode lead (anode current collector) 1 8 : sealing member 19: fuel supply flow path-21 - 200810223 (19) 2 1 : liquid receiving port 23: coupler 24: air introduction hole 25: Basket exterior trim 2 6 : moisturizing plate 27 : liquid fuel containment chamber 29 : pillar
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