200835036 九、發明說明 【發明所屬之技術領域】 本發明係關於複合電解質膜，以及具備該複合電解質 膜之燃料電池。 【先前技術】 近年來，由於電子技術的進步，電子機器的小型化、 高性能化、可攜帶化正進展中，於攜帶用電子機器中，對 於所使用電池的高能量密度化的要求提高。因此，要求輕 量且小型以及高容量的二次電池。 於該等狀況中，小型的燃料電池受到集中的注目。特 別是直接使用甲醇作爲燃料之直接甲醇型燃料電池（ DMFC : direct methanol fuel cell )使用能量密度高的甲醇 作爲燃料，可於電極觸媒上由甲醇取得直接電流。因此， 不需要爲了作出氫改質有機燃料之改質器，可小型化。再 者，由於輸出密度高，有希望作爲攜帶機器用的電源。 DMFC中，甲醇於燃料極氧化分解，生成二氧化碳、 質子及電子。另一方面，於氧化劑極（空氣極），由空氣 獲得之氧，與經由電解質膜由燃料極所供給之質子、以及 通過外部回路由燃料極所供給之電子，生成水。再者，藉 由通過外部回路之電子供給電力（例如參照專利文獻1及 專利文獻2)。 然而，此方式所構成之燃料電池中，由燃料極至空氣 極的甲醇會通過電解質膜的結果，使發電電位有降低的問 -5- 200835036 題。亦即，Dupont公司之Nafion所代表之高分子電解質 膜的高質子導電性，由於通過含水狀態的簇網絡（cluster network )而發揮，於使用甲醇之燃料電池中，甲醇混於 水中而通過簇網絡，於空氣極（陽極）發生擴散現象（交 叉（crossover))。而於此方式之發生甲醇的交叉之情況 中，所供給之燃料與氧化劑由於直接反應，無法輸出能量 作爲電力，有無法獲得安定的高輸出功率的問題。 φ 爲了解決該問題，已有提案於多孔質膜塡充電解質， 抑制電解質的膨潤，藉此防止甲醇的交叉的技術（例如參 照專利文獻3及非專利文獻1 )。 然而，專利文獻3或非專利文獻1所揭示之技術中， 由於電解質偏在於無機多孔質膜之孔部份，膜全體爲阻抗 (impedance )上昇。爲了降低阻抗，必須只能使膜薄， 而膜薄時則多孔質基材的強度降低，無法充分地抑制電解 質的膨潤。 • 從而，考慮將塡充有電解質之無機多孔質薄膜設置於 支持用的基材上。基材必須爲具有充分地高機械強度，及 . 質子傳導性者。因此，考慮於剛性大之有機多孔質基板的 . 孔中塡充高分子電解質者。 然而，此方式之構造中，電解質的膨潤過高，塡充有 該電解質的基材的膨脹（特別是面的膨脹）過大。因此， 形成於表面之無機多孔質膜有破裂的問題。 [專利文獻1]日本專利第34131 1 1號公報 [專利文獻2]國際專利W0200 5/1 12172號公報 -6- 200835036 [專利文獻3]日本專利特開2002-83 6 1 2號公報 [非專利文獻1]東亞合成硏究年報TREND 2004年， 第7號’ 34至36頁，藉由細孔塡充聚合法之燃料電池用 電解質膜之開發。 【發明內容】 本發明係爲解決該等問題者，以提供具有充份強度不 易破損，且低阻抗（低impedance)之甲醇等燃料穿透度 低之電解質膜爲目的。再者，以提供小型且性能高，可供 給安定輸出的燃料電池爲目的。 爲了達成上述目的，本發明之複合電解質膜係具備： 由具有細孔之有機多孔質體所成之支持基板、塡充於上述 支持基板之上述細孔內之具有質子傳導性之第1電解質、 具有形成於上述支持基板之一面，且於厚方向貫通之貫通 孔之無機多孔質薄膜、塡充於上述無機多孔質薄膜之上述 貫通孔內之具有質子傳導性之第2電解質；其中特徵係該 第1電解質於上述有機多孔質體之上述細孔內，係以形成 空隙之方式塡充。 再者，本發明之燃料電池，係具備燃料極、氧化劑極 、以及配置於上述燃料極與上述氧化劑極之間之電解質膜 ，其特徵係該電解質膜爲本發明之複合電解質膜。 根據本發明，由於第1電解質係以形成空隙之方式塡 充於有機多孔質體所成之支持基板之細孔內，發電時第1 電解質藉由含水而膨脹（膨潤）時，存在於細孔內的空係 200835036 僅藉由第1電解質的埋設，有機多孔質體的細孔無法推壓 展開。因此，有機多孔質的尺寸變化，特別是由於面方向 的膨脹受到抑制，防止於表面所形成之無機多孔質薄膜的 破損。從而，可獲得以高強度不易破損，電阻抗低，且甲 醇等燃料之穿透度低的複合電解質膜。 再者，根據本發明，由於具備該等方式之複合電解質 膜，可實現小型且高性能，可供給安定輸出功率的燃料電 池。 【實施方式】 以下參照圖式說明本發明之實施形態。 第1圖爲模式地顯示本發明複合電解質膜之一實施形 態之構成剖面圖。實施形態之複合電解質膜1，如第1圖 所示方式，具備由具有細孔2a之有機多孔質體所成之支 持基板2、以及形成於該支持基板2之一面的無機多孔質 薄膜3。無機多孔質薄膜3係具有於厚方向貫通之貫通孔 3 a 〇 因此，於支持基板2之細孔2a內，具有質子傳導性 之第1電解質4係以形成空隙4a的方式塡充於細孔2a內 之一部分（於第1圖中爲底部）。再者，無機多孔質薄膜 3之貫通孔3a內，具有質子傳導性之第2電解質5係以實 質上不形成空隙之方式塡充。無機多孔質薄膜3之貫通孔 3 a係藉由該第2電解質5完全地埋設，使貫通孔3 a內全 體無空隙存在的狀態爲較佳。 -8- 200835036 支持基板2由有機多孔質體所構成。作爲有機多孔質 體，使用剛性（機械強度）高，後文所述之藉由電解質的 膨潤而細孔2a受到推壓展開少之合成樹脂等多孔質體。 例如，可列舉多孔質聚醯亞胺或多孔質聚醯胺醯亞胺等。 多孔質聚乙烯或多孔質聚丙烯等多孔質聚烯烴的使用亦爲 可能。該等有機多孔質體之空孔率（細孔2 a之容積於多 孔質體的體積全體中所佔比例）較佳爲20至80%的範圍 〇 由該等方式之有機多孔質體所構成之支持基板2的厚 度爲3至200μηι，較佳爲4至1〇〇μπι，更較佳爲1〇至 50μπι。細孔2a之直徑較佳爲〇·〇ΐ至20μπι，更較佳爲0.1 至5 μ m的範圍。 無機多孔質薄膜3具有於厚方向貫通之多數的貫通孔 3 a。貫通孔3 a係藉由例如精密加工所形成。構成此方式 之無機多孔質薄膜3之無機材料，可列舉氧化鋁（A120 3 )、氧化矽（Si02 )、氧化鍩（Zr02 )等氧化物陶瓷，氮 化矽（Si3N4 )等氮化物陶瓷，碳化矽（SiC )等碳化物陶 瓷。其等之中較佳使用氧化矽。無機多孔質薄膜3的厚度 以薄較佳’爲0.1至20 μπι、更較佳爲0.2至2 μπι。貫通孔 3a的直徑較佳爲〇.〇1至i(^m，特別以1μπ1以下爲佳。貫 通孔3 a的開口率（開口的總面積於面全體總面積中所佔 比例）較佳爲1 5 %以上，特佳爲2 0至8 0 %的範圍。此處 ’貫通孔3 a的直徑爲圍繞貫通孔3 a之最小圓的直徑。再 者’貫通孔3a的開口面積，使用顯微鏡放大表面而求得 -9 - 200835036 。使用顯微鏡放大所獲得影像進行處理，可分別求得開口 部的面積與其以外之面積。 無機多孔質薄膜3的貫通孔3a，係沿著厚方向亦即相 對於主面貫通，較佳爲於垂直方向貫通所形成者，剖面形 狀並無特別限定。考慮爲圓形、四角形、五角形、六角形 等剖面形狀。再者，亦可組合不同大小（直徑）或不同形 狀的孔。縱橫比較佳爲比1大。亦即，於無機多孔質薄膜 3的厚方向所形成的深度，較佳爲比於面方向所形成的孔 徑更大的貫通孔3 a。無機多孔質薄膜3具有孔徑比深度更 大的貫通孔3 a時，壓抑所塡充的第2電解質5的膨潤， 抑制甲醇穿透的效果大。貫通孔3 a的孔徑於面方向擴大 時，由於所塡充的第2電解質5於含水時大爲膨潤，藉由 無機多孔質薄膜3的壓制效果變低。 此方式之無機多孔質薄膜3的管通孔3a，係於由無機 材料所成薄膜的規定位置，藉由光微影術精密地形成。首 先，由有機多孔質體所成之支持基板2的規定面（開口率 低之側的面），例如藉由真空濺鍍法或反應濺鍍法等濺鍍 法，或者CVD或PVD等蒸鍍法，形成氧化矽（Si02)等 無機材料的薄膜。其次，於該薄膜上塗布光阻，其次使用 規定圖型的遮罩曝光，烘烤後，鈾刻無機薄膜，最後剝離 光阻。因此，以規定圖型形成精密地排列之多數的微細貫 通孔3 a。 塡充於支持基板2之細孔2a內的第1電解質4，可使 用以下所示之高分子電解質。 -10- 200835036 亦即，可列舉於（A )主鏈由脂肪族烴所成之高分子 (a)中，導入磺酸基及/或膦酸基之高分子電解質； 於（B)主鏈由使用鹵素取代之脂肪族烴所成之高分 子（b)中，導入磺酸基及/或膦酸基之高分子電解質； 於（C)主鏈具有芳香環之高分子（c)中，導入磺酸 基及/或膦酸基之高分子電解質； 於（D)主鏈實質上不含碳原子之高分子（d)中，導 入磺酸基及/或膦酸基之高分子電解質；以及 於（E)由構成上述（a)至（d)之高分子之重複單 位選出之2種以上之重複單位所成之共聚物中，導入磺酸 基及/或膦酸基之高分子電解質等。此處，「高分子中導 入磺酸基及/或膦酸基」者，意指「於高分子骨架中經由 化學鍵導入磺酸基及/或膦酸基」。 由化學安定性的觀點，該等高分子電解質中，於（B )主鏈由使用鹵素取代之脂肪族烴所成之高分子（b)中 ，導入磺酸基及/或膦酸基之高分子電解質的使用爲較佳 。再者，由耐熱性的觀點，於（C)主鏈具有芳香環之高 分子（c)中，導入磺酸基及/或膦酸基之高分子電解質的 使用爲較佳。 作爲（A )的高分子電解質，例如可列舉聚乙烯基磺 酸、聚苯乙烯磺酸、聚（α_甲基苯乙烯）等。作爲（B) 的高分子電解質，例如可列舉全氟碳磺酸、具有膦酸基之 全氟院基聚合物、聚（三氟苯乙烯）磺酸、聚（三氟苯乙 烯）膦酸等。Nafion (美國Dupont公司製造之商品名） -11 - 200835036 等全氟碳磺酸的使用爲較佳。 (C)的高分子電解質中，亦可爲具有芳香環之主鏈 使用氧原子等雜原子中斷者。作爲（C)的高分子電解質 ，例如可列舉於聚醚醚酮、聚苯乙烯、聚醚、聚（伸芳基 •醚）、聚膦腈（phosphazene)、聚醯亞胺、聚（4-苯氧 基苯甲醯基-1，4-伸苯基）、聚伸苯基硫醚、聚苯基喹喏啉 等聚合物之各者分別導入磺酸基者，芳基磺化聚苯并咪唑 ，烷基磺化聚苯并咪唑、烷基膦化聚苯并咪唑、膦化聚（ 伸苯基醚）等。 作爲（D )的高分子電解質，例如可列舉具有磺酸基 或臉痠機之聚矽氧烷、聚膦腈等。 (E)的高分子電解質，爲無規聚合物中導入磺酸基 及/或膦酸基者，亦可爲交互共聚物中導入磺酸基及/或膦 酸基者，或亦可爲嵌段共聚物中導入磺酸基及/或膦酸基 者。作爲無規聚合物中導入磺酸基及/或膦酸基者，例如 可列舉磺化聚醚颯-二羥基聯苯共聚物。作爲嵌段共聚物 中導入磺酸基及/或膦酸基者，全部的嵌段共聚物的主鏈 爲使用脂肪族烴所構成之嵌段共聚物，例如可爲苯乙烯-(乙烯-丁烯）-苯乙烯三羥段共聚物中導入磺酸基及/或膦 酸基者，但由耐熱性的觀點而言，至少一嵌段係於主鏈具 有芳香環之嵌段共聚物者爲較佳。再者，持有磺酸基及/ 或膦酸基之嵌段，以及不持有磺酸基及/或膦酸基之嵌段 ，各具有一種以上之嵌段共聚物，由於傳導性優異，使用 爲更較佳。 -12- 200835036 作爲塡充於無機多孔質薄膜3之貫通孔3a之第2電 解質5，與上述第1電解質4使用相同材料爲較佳，亦可 使用不同材料。 由有機多孔質體所成支持基板2與無機多孔質薄膜3 ，以及第1與第2電解質4、5所成複合電解質膜1的厚 度，並無特別限制，較佳爲3至200μιη。更較佳爲4至 ΙΟΟμιη，再較佳爲10至50μιη。過薄時無法獲得實用上耐 用之膜強度，過厚時由於電阻抗變高，作爲燃料電池的隔 膜不佳。複合電解質薄膜1的膜厚，可根據支持基板2的 厚度或無機多孔質薄膜3的厚度適當地選擇而調整。 實施形態之複合電解質膜1的製作中，藉由分別進行 對由有機多孔質體所成支持基板2的細孔2a內之第1電 解質4的塡充，以及對無機多孔質薄膜3之貫通孔3a內 之第2電解質5的塡充，可選擇作爲第1電解質4與第2 電解質5之個別最適當者。再者，由於無機多孔質薄膜3 係形成於由有機多孔質體所成支持基板2上，於無機多孔 質薄膜3之形成時，期望有機多孔質體的表面平坦性高。 因此，第1電解質4雖以支持基板2之細孔2a內殘留空 隙4a的方式塡充，支持基板2的無機多孔質薄膜3所形 成之面側，以細孔2a內實質上無空隙之方式塡充第1電 解質4。 亦即，較佳爲以下所示順序進行複合電解質膜的製作 。首先，如第2A圖所示方式，於具有細孔2a之由有機多 孔質體所成支持基板2的下方面，配置剝離性薄膜（圖式 -13- 200835036 中省略）後，由上方面側含浸於含有Nafion溶液之第1 電解質4之液體。考慮溶媒的揮發量而調整含浸量’揮發 溶媒後，如第2B圖所示方式，第1電解質4埋於有機多 孔質體之細孔2a內的下部，於細孔2a內的上部形成空隙 4 a 〇 其次，塡充有第1電解質4之支持基板2’如第2C 圖所示方式，使下方面側成翻轉爲上之方式，將剝離性薄 膜剝離。接著，於細孔2a的開口無間隙地塡充（埋入） 第1電解質4,獲得成爲平坦的面。其次，於該成爲平坦 的面上，形成具有貫通孔3a之無機多孔質薄膜3後，於 貫通孔3a內，含浸於含有Nafion溶液之第2電解質5之 液體。此處，無機多孔質薄膜3的形成，如上文所述方式 ，藉由濺鍍法或蒸鍍法形成由無機材料所成之薄膜後，於 規定位置藉由光微影術形成貫通孔3a而進行。重複含第2 電解質5之液體之含浸與乾燥，以於無機多孔質薄膜3之 貫通孔3a內實質上不產生空隙4a之方式，塡充第2電解 質5。 因此，獲得第1電解質4係於由有機多孔質體所成支 持基板2的細孔2a內殘留空隙4a的方式塡充，且於無機 多孔質薄膜3的貫通孔3a內第2電解質5係以實質上無 空隙地塡充的構造之複合電解質膜1。 由此所得實施形態之複合電解質膜i中，由於由有機 多孔質體所成支持基板2的細孔2a內以形成空隙之方式 塡充第1電解質4，發電時藉由第〗電解質*含水而膨脹 -14-[Technical Field] The present invention relates to a composite electrolyte membrane, and a fuel cell including the composite electrolyte membrane. [Prior Art] In recent years, due to advances in electronic technology, miniaturization, high performance, and portability of electronic devices are progressing, and in portable electronic devices, there is an increasing demand for high energy density of batteries to be used. Therefore, a lightweight and small-sized and high-capacity secondary battery is required. In these situations, small fuel cells have received a lot of attention. In particular, a direct methanol fuel cell (DMFC) that directly uses methanol as a fuel uses a high energy density methanol as a fuel to obtain a direct current from methanol on an electrode catalyst. Therefore, it is not necessary to reduce the size of the reformer for making a hydrogen-modified organic fuel. Furthermore, since the output density is high, it is promising as a power source for carrying the machine. In DMFC, methanol is oxidatively decomposed by fuel to form carbon dioxide, protons and electrons. On the other hand, in the oxidant electrode (air electrode), oxygen obtained from air, and protons supplied from the fuel electrode via the electrolyte membrane, and electrons supplied from the fuel electrode through the external circuit generate water. Further, electric power is supplied through the electrons of the external circuit (see, for example, Patent Document 1 and Patent Document 2). However, in the fuel cell constructed by this method, as a result of the passage of methanol from the fuel electrode to the air electrode through the electrolyte membrane, the power generation potential is lowered. That is, the high proton conductivity of the polymer electrolyte membrane represented by Nafion of Dupont Company is exerted by a cluster network in a hydrated state, and in a fuel cell using methanol, methanol is mixed in water and passed through a cluster network. A diffusion phenomenon (crossover) occurs at the air electrode (anode). On the other hand, in the case where the methanol crosses, the supplied fuel and the oxidant cannot directly output energy as electric power due to direct reaction, and there is a problem that stable high output power cannot be obtained. φ In order to solve this problem, there has been proposed a technique in which the porous membrane is filled with an electrolyte and the swelling of the electrolyte is suppressed, thereby preventing the intersection of methanol (for example, refer to Patent Document 3 and Non-Patent Document 1). However, in the technique disclosed in Patent Document 3 or Non-Patent Document 1, since the electrolyte is biased in the pore portion of the inorganic porous film, the entire film rises in impedance. In order to lower the impedance, it is necessary to make the film thin only, and when the film is thin, the strength of the porous substrate is lowered, and the swelling of the electrolyte cannot be sufficiently suppressed. • Therefore, it is considered to provide an inorganic porous film filled with an electrolyte on a substrate for support. The substrate must be of sufficiently high mechanical strength, and proton conductivity. Therefore, it is considered that the pores of the organic porous substrate having a large rigidity are filled with a polymer electrolyte. However, in the configuration of this mode, the swelling of the electrolyte is too high, and the expansion (especially the expansion of the surface) of the substrate filled with the electrolyte is excessively large. Therefore, the inorganic porous film formed on the surface has a problem of cracking. [Patent Document 1] Japanese Patent No. 34131 1 1 [Patent Document 2] International Patent No. WO200 5/1 12172, -6-200835036 [Patent Document 3] Japanese Patent Laid-Open No. 2002-83 No. 6 1 2 [Non- Patent Document 1] East Asian Synthetic Research Annual Report TREND 2004, No. 7 '34 to 36, development of an electrolyte membrane for a fuel cell by a pore-melting polymerization method. SUMMARY OF THE INVENTION The present invention has been made to solve such problems, and an object of the invention is to provide an electrolyte membrane having a low-impedance (low-impact) methanol and low fuel permeability. Furthermore, it is intended to provide a small and high-performance fuel cell for stable output. In order to achieve the above object, the composite electrolyte membrane of the present invention comprises: a support substrate made of an organic porous body having pores; and a first electrolyte having proton conductivity which is filled in the pores of the support substrate, An inorganic porous film having a through hole formed in one surface of the support substrate and penetrating in a thick direction, and a second electrolyte having proton conductivity filled in the through hole of the inorganic porous film; wherein the feature is The first electrolyte is filled in the pores of the organic porous body so as to form voids. Further, the fuel cell of the present invention comprises a fuel electrode, an oxidant electrode, and an electrolyte membrane disposed between the fuel electrode and the oxidant electrode, wherein the electrolyte membrane is the composite electrolyte membrane of the present invention. According to the present invention, the first electrolyte is filled in the pores of the support substrate formed by the organic porous body so as to form a void, and the first electrolyte is present in the pores when expanded (swelled) by water when generating electricity. The internal hollow system 200835036 is only buried by the first electrolyte, and the pores of the organic porous body cannot be pushed and developed. Therefore, the dimensional change of the organic porous material is suppressed particularly by the expansion in the plane direction, and the inorganic porous film formed on the surface is prevented from being damaged. Therefore, a composite electrolyte membrane which is not easily broken by high strength, has low electrical resistance, and has low penetration of a fuel such as methanol can be obtained. Further, according to the present invention, since the composite electrolyte membrane of these types is provided, it is possible to realize a small and high-performance fuel cell which can supply a stable output. [Embodiment] Hereinafter, embodiments of the present invention will be described with reference to the drawings. Fig. 1 is a cross-sectional view showing the configuration of one embodiment of the composite electrolyte membrane of the present invention. As shown in Fig. 1, the composite electrolyte membrane 1 of the embodiment includes a supporting substrate 2 made of an organic porous body having pores 2a, and an inorganic porous film 3 formed on one surface of the supporting substrate 2. The inorganic porous film 3 has a through hole 3a that penetrates in the thick direction. Therefore, in the pores 2a of the support substrate 2, the first electrolyte 4 having proton conductivity is filled in the pores so as to form the void 4a. One part of 2a (bottom in Figure 1). Further, in the through hole 3a of the inorganic porous film 3, the second electrolyte 5 having proton conductivity is filled so as not to form a void. The through hole 3a of the inorganic porous film 3 is preferably completely embedded in the second electrolyte 5, and a state in which the entire through hole 3a is free of voids is preferable. -8- 200835036 The support substrate 2 is composed of an organic porous body. As the organic porous material, a porous body having a high rigidity (mechanical strength) is used, and the pores 2a are pressed and expanded to a small amount of a synthetic resin such as a synthetic resin. For example, a porous polyimine or a porous polyamidimide may, for example, be mentioned. The use of a porous polyolefin such as porous polyethylene or porous polypropylene is also possible. The porosity of the organic porous material (the ratio of the volume of the pores 2 a to the entire volume of the porous body) is preferably in the range of 20 to 80%, and is composed of the organic porous bodies of the above-described manner. The thickness of the support substrate 2 is 3 to 200 μm, preferably 4 to 1 μm, and more preferably 1 to 50 μm. The diameter of the pores 2a is preferably from 〇·〇ΐ to 20 μm, more preferably from 0.1 to 5 μm. The inorganic porous film 3 has a plurality of through holes 3a penetrating in the thick direction. The through holes 3a are formed by, for example, precision machining. Examples of the inorganic material constituting the inorganic porous film 3 of the present embodiment include oxide ceramics such as alumina (A120 3 ), cerium oxide (SiO 2 ), and cerium oxide (ZrO 2 ), and nitride ceramics such as tantalum nitride (Si 3 N 4 ). Carbide ceramics such as bismuth (SiC). Among them, cerium oxide is preferably used. The thickness of the inorganic porous film 3 is preferably from 0.1 to 20 μm, more preferably from 0.2 to 2 μm. The diameter of the through hole 3a is preferably 〇.1 to i (^m, particularly preferably 1 μπ1 or less. The opening ratio of the through hole 3 a (the total area of the opening in the total area of the entire surface) is preferably 1 5 % or more, particularly preferably in the range of 20 to 80%. Here, the diameter of the through hole 3 a is the diameter of the smallest circle surrounding the through hole 3 a. Further, the opening area of the through hole 3 a is a microscope The surface is enlarged to obtain -9 - 200835036. The image obtained by magnifying the image by the microscope can be used to obtain the area of the opening and the area other than the area. The through hole 3a of the inorganic porous film 3 is relatively thick, that is, relatively The cross-sectional shape is not particularly limited, and the cross-sectional shape is not particularly limited, and may be a cross-sectional shape such as a circle, a quadrangle, a pentagon or a hexagon. Further, different sizes (diameters) may be combined or The hole having a different shape is preferably larger than 1 in the longitudinal direction, that is, the depth formed in the thick direction of the inorganic porous film 3 is preferably a through hole 3 a larger than the hole diameter formed in the plane direction. Porous film 3 has a hole When the through hole 3 a having a larger diameter than the depth is formed, the swelling of the second electrolyte 5 that is filled is suppressed, and the effect of suppressing the penetration of methanol is large. When the diameter of the through hole 3 a is enlarged in the plane direction, (2) The electrolyte 5 is greatly swelled when it contains water, and the pressing effect of the inorganic porous film 3 is lowered. The tube through hole 3a of the inorganic porous film 3 of this embodiment is at a predetermined position of a film formed of an inorganic material. Precisely formed by photolithography. First, a predetermined surface of the support substrate 2 (a surface having a low aperture ratio) made of an organic porous material, for example, by sputtering or reactive sputtering a method, or a vapor deposition method such as CVD or PVD, to form a thin film of an inorganic material such as cerium oxide (SiO 2 ). Secondly, a photoresist is coated on the film, and secondly, a mask of a predetermined pattern is used for exposure, and after baking, the uranium engraved inorganic In the film, the photoresist is finally peeled off. Therefore, a plurality of fine through holes 3a which are precisely arranged in a predetermined pattern are formed. The first electrolyte 4 which is filled in the pores 2a of the support substrate 2 can be used as shown below. Molecular electrolytes. -10- 200835036 In the polymer (a) in which the main chain is composed of an aliphatic hydrocarbon, a polymer electrolyte in which a sulfonic acid group and/or a phosphonic acid group are introduced; (B) an aliphatic group in which a main chain is substituted with a halogen a polymer electrolyte in which a sulfonic acid group and/or a phosphonic acid group are introduced into a polymer (b) formed by a hydrocarbon; and a sulfonic acid group and/or a polymer (c) having an aromatic ring in the (C) main chain; a phosphonic acid-based polymer electrolyte; a polymer electrolyte in which a sulfonic acid group and/or a phosphonic acid group is introduced in the polymer (d) in which the main chain substantially does not contain a carbon atom; and (E) A polymer electrolyte obtained by introducing a sulfonic acid group and/or a phosphonic acid group into a copolymer of two or more kinds of repeating units selected from the repeating units of the polymer of the above (a) to (d). Here, "the introduction of a sulfonic acid group and/or a phosphonic acid group into a polymer" means "introduction of a sulfonic acid group and/or a phosphonic acid group via a chemical bond in a polymer skeleton". From the viewpoint of chemical stability, in the polymer electrolyte (B) in which the main chain is formed of a halogen-substituted aliphatic hydrocarbon, the introduction of a sulfonic acid group and/or a phosphonic acid group is high. The use of a molecular electrolyte is preferred. Further, from the viewpoint of heat resistance, in the high molecular (c) having an aromatic ring in the main chain (C), the use of a polymer electrolyte in which a sulfonic acid group and/or a phosphonic acid group are introduced is preferred. Examples of the polymer electrolyte of (A) include polyvinylsulfonic acid, polystyrenesulfonic acid, and poly(?-methylstyrene). Examples of the polymer electrolyte of (B) include perfluorocarbonsulfonic acid, a perfluorohomopolymer having a phosphonic acid group, poly(trifluorostyrene)sulfonic acid, poly(trifluorostyrene)phosphonic acid, and the like. . Nafion (trade name manufactured by Dupont, USA) -11 - 200835036 The use of perfluorocarbon sulfonic acid is preferred. In the polymer electrolyte of (C), a main chain having an aromatic ring may be interrupted by using a hetero atom such as an oxygen atom. Examples of the polymer electrolyte of (C) include polyetheretherketone, polystyrene, polyether, poly(arylene ether), phosphazene, polyimine, and poly(4- Each of the polymers such as phenoxybenzhydryl-1,4-phenylene), polyphenylene sulfide, and polyphenylquinoxaline is introduced into a sulfonic acid group, and the arylsulfonated polybenzoic acid is introduced. Imidazole, alkylsulfonated polybenzimidazole, alkylphosphonated polybenzimidazole, phosphatized poly(phenylene ether) and the like. Examples of the polymer electrolyte of (D) include polyoxyalkylene having a sulfonic acid group or a face acid machine, and polyphosphazene. The polymer electrolyte of (E) may be a sulfonic acid group and/or a phosphonic acid group introduced into the random polymer, or may be a sulfonic acid group and/or a phosphonic acid group introduced into the alternating copolymer, or may be embedded. The sulfonic acid group and/or the phosphonic acid group are introduced into the segment copolymer. As the sulfonic acid group and/or the phosphonic acid group to be introduced into the random polymer, for example, a sulfonated polyether fluorene-dihydroxybiphenyl copolymer can be mentioned. As the sulfonic acid group and/or the phosphonic acid group introduced into the block copolymer, the main chain of all the block copolymers is a block copolymer composed of an aliphatic hydrocarbon, and may be, for example, styrene-(ethylene-butyl). a sulfonic acid group and/or a phosphonic acid group introduced into the olefin-styrene trihydroxyl segment copolymer, but from the viewpoint of heat resistance, at least one block is a block copolymer having an aromatic ring in the main chain. Preferably. Further, a block having a sulfonic acid group and/or a phosphonic acid group and a block not holding a sulfonic acid group and/or a phosphonic acid group each having one or more block copolymers are excellent in conductivity. Use is better. -12- 200835036 The second electrolyte 5 to be filled in the through hole 3a of the inorganic porous film 3 is preferably the same material as the first electrolyte 4, and a different material may be used. The thickness of the composite substrate 1 and the inorganic porous film 3 which are formed of the organic porous material and the composite electrolyte film 1 formed by the first and second electrolytes 4 and 5 are not particularly limited, but are preferably 3 to 200 μm. More preferably, it is 4 to ΙΟΟμηη, and still more preferably 10 to 50 μm. When the thickness is too thin, the film strength which is practically resistant cannot be obtained, and when the thickness is too large, the electrical resistance becomes high, and the separator as a fuel cell is not preferable. The film thickness of the composite electrolyte film 1 can be appropriately selected depending on the thickness of the support substrate 2 or the thickness of the inorganic porous film 3. In the production of the composite electrolyte membrane 1 of the embodiment, the first electrolyte 4 in the pores 2a of the support substrate 2 formed of the organic porous body is filled, and the through holes of the inorganic porous film 3 are respectively performed. The charge of the second electrolyte 5 in 3a can be selected as the most suitable one of the first electrolyte 4 and the second electrolyte 5. In addition, since the inorganic porous film 3 is formed on the support substrate 2 made of an organic porous body, it is desirable that the surface of the organic porous body is high in flatness when the inorganic porous film 3 is formed. Therefore, the first electrolyte 4 is filled so that the voids 4a remain in the pores 2a of the support substrate 2, and the surface of the inorganic porous film 3 of the support substrate 2 is formed, and the pores 2a are substantially free of voids. The first electrolyte 4 is charged. That is, it is preferred to prepare the composite electrolyte membrane in the order shown below. First, as shown in Fig. 2A, the peeling film (omitted in Fig. 13-200835036) is disposed on the lower side of the support substrate 2 made of the organic porous body having the pores 2a, and the upper side is A liquid impregnated with the first electrolyte 4 containing the Nafion solution. After adjusting the impregnation amount of the solvent to the volatile solvent, the first electrolyte 4 is buried in the lower portion of the pores 2a of the organic porous body, and the voids are formed in the upper portion of the pores 2a as shown in Fig. 2B. a Next, the support substrate 2' filled with the first electrolyte 4 is peeled off from the lower side, and the peelable film is peeled off as shown in Fig. 2C. Then, the first electrolyte 4 is filled (buried) in the opening of the pores 2a without a gap, and a flat surface is obtained. Then, the inorganic porous film 3 having the through hole 3a is formed on the flat surface, and then the liquid is impregnated into the second electrolyte 5 containing the Nafion solution in the through hole 3a. Here, the inorganic porous film 3 is formed by forming a film made of an inorganic material by a sputtering method or a vapor deposition method as described above, and then forming a through hole 3a by photolithography at a predetermined position. get on. The impregnation and drying of the liquid containing the second electrolyte 5 are repeated to fill the second electrolyte 5 so that the voids 4a are not substantially generated in the through holes 3a of the inorganic porous film 3. Therefore, the first electrolyte 4 is obtained by filling the pores 4a in the pores 2a of the support substrate 2 made of the organic porous material, and the second electrolyte 5 is in the through hole 3a of the inorganic porous film 3 The composite electrolyte membrane 1 having a structure that is substantially free of voids. In the composite electrolyte membrane i of the embodiment, the first electrolyte 4 is filled in the pores 2a of the support substrate 2 by the organic porous material, and the first electrolyte 4 is filled by the electrolyte. Expansion-14-
200835036 (膨潤）時，存在於細孔2a內之空隙4a僅藉由 質4而埋入，有機多孔質體的細孔2a無法推壓 此，有機多孔質體的尺寸變化，特別是由於面方 受到抑制，形成於表面之無機多孔質薄膜3不產 由此’可獲得以局強度不易破損，低電阻抗且甲 低的複合電解質膜1。 又，於細孔2 a內之第1電解質4的空隙比 率），以第1電解質4之含水時的膨脹率（膨潤 時，較佳爲α/ ( l+α )。於此方式構成時，發電I 解質4膨潤的結果，如第2D圖所示，經膨潤之 質4不會過與不足地埋入有機多孔質體的細孔： 隙。因此，過於膨潤的細孔2a無法推壓展開， 有機多孔質體所成支持基板2上之無機多孔質薄 產生破損等。 實施形態之複合電解質膜1可如以下所示方 亦即，如第3A圖所示，於具有細孔2a之由有 所成支持基板2的下方面，配置剝離性薄膜（圖 )後，由上方面側含浸於含有Nafion溶液之第 之液體，一邊左右傾斜搖動支持基板2，一邊揖 於揮發溶媒步驟中，因一邊左右傾斜搖動支持S 第3B圖所示，故第1電解質4塡充於細孔2a 0 同時，至細孔2a內壁面的上部爲止形成第1電 被覆層，於細孔2a內的上部中央形成空隙4a。 其次，塡充有第1電解質4之支持基板2In 200835036 (swelling), the void 4a existing in the pore 2a is buried only by the mass 4, and the pores 2a of the organic porous body cannot be pressed, and the size of the organic porous body changes, particularly due to the surface. When the inorganic porous film 3 formed on the surface is inhibited, the composite electrolyte membrane 1 which is less likely to be damaged by local strength and has low electrical resistance and low nail can be obtained. Further, in the void ratio of the first electrolyte 4 in the pores 2 a , the expansion ratio of the first electrolyte 4 in water content (at the time of swelling, α / ( l + α ) is preferable. As a result of the swelling of the power generation I, the swelling 4 does not pass through the pores of the organic porous body. In the organic porous body, the inorganic porous material on the support substrate 2 is thin and damaged. The composite electrolyte membrane 1 of the embodiment can be as shown below, as shown in FIG. 3A, and has pores 2a. After the release film (Fig.) is placed on the lower side of the support substrate 2, the upper side is impregnated with the liquid containing the Nafion solution, and the support substrate 2 is tilted to the left and right while being immersed in the volatile solvent step. In the third embodiment, the first electrolyte 4 is filled with the pores 2a0, and the first electrical coating layer is formed on the upper surface of the inner wall surface of the pores 2a, and the upper portion of the pores 2a is formed in the upper portion of the pores 2a. The gap 4a is formed in the center. Next, the first electrolyte 4 is supported. Substrate 2
第1電解 展開。因 向的膨脹 生破損。 醇穿透度 例（空隙 丨率）爲α 诗第1電 第1電解 2a內的空 形成於由 膜3 ’不 式製作。 多孔質體 式中省略 電解質4 發溶媒。 板2，如 的下部之 解質4的 ，如第3 C -15- 200835036 圖所示，使下方面側成翻轉爲上之方式，將剝離性薄膜剝 離。接著，於細孔2a的開口塡充第1電解質4的結果爲 平坦的面，形成具有貫通孔3a之無機多孔質薄膜3。之後 ，於貫通孔3a內，含浸於含有Nafion溶液之第2電解質 5之液體。因此，重複含浸、乾燥，如第3 D圖所示方式 ，於貫通孔3 a內實質上無空隙地完全塡充第2電解質5。 由此，於所獲得之複合電解質膜1中，第1電解質4 以被覆於有機多孔質體的細孔2a內之內壁面的方式塡充 。因此，第1電解質4藉由含水而膨潤之前，接合於該複 合電解質膜1之電極（電極觸媒）與第1電解質4的接觸 爲完全，可得高輸出功率。再者，第1電解質4藉由含水 而膨潤的結果，由於不會過與不足地埋入有機多孔質體的 細孔2a內的空隙4a，形成於支持基板2上的無機多孔質 薄膜3不產生破損等。 其次，顯示第4圖之具有此方式實施形態之複合電解 質膜 1之膜電極接合體（MEA: Membrane Electrode Assembly )的構成。 實施形態的MEA6，如第4圖所示，具備由燃料極觸 媒層7a與燃料極氣體擴散層7b所成之燃料極7、由空氣 極觸媒層8a與空氣極氣體擴散層8b所成之空氣極8、以 及挾持於燃料極觸媒層7a與空氣極觸媒層8a之間的上述 實施形態之複合電解質膜1。又，複合電解質膜1係以無 機多孔質薄膜3接合於燃料極7側，亦即接合於燃料極觸 媒層7 a爲較佳，亦可接合於空氣極8側。 -16· 200835036 燃料極觸媒層7a及空氣極觸媒層8a中所含有之觸媒 ，例如可列舉鉑族元素之Pt、Ru、Rh、Ir ' Os、Pd等單 體金屬，含有該等鉑族元素之合金等。具體而言，做爲燃 料極觸媒層7a，較佳使用對甲醇或一氧化碳具強耐性的 Pt-Ru或Pt-Mo等合金；作爲空氣極觸媒層8a，較佳使用 鈾或Pt-Ni等合金，但不限定爲該等。再者，於活性碳或 黑鉛等粒子狀碳或纖維狀碳方式之導電性載持體，亦可使 用載持有上述觸媒之微粒子之碳載持觸媒。 層合於燃料極觸媒層7a之燃料極氣體擴散層7b，擔 負均一地供給燃料至燃料極觸媒層7 a之責任之同時，亦 兼具備作爲燃料極觸媒層7a之集電體的機能。層合於空 氣極觸媒層8a之空氣極氣體擴散層8b，擔負均一地供給 氧化劑之空氣至空氣極觸媒層8a之責任之同時，亦兼具 備作爲空氣極觸媒層8a之集電體的機能。 燃料極氣體擴散層7b與空氣極氣體擴散層8b，任一 者皆由導電性物質所構成。作爲導電性物質，雖可使用習 知材料，爲了使原料氣體對觸媒有效地輸送，多孔質的碳 織布或碳紙的使用爲較佳。The first electrolysis is carried out. The expansion due to the direction is broken. The example of the degree of penetration of the alcohol (void ratio) is α. The first electric power of the first electrolysis 2a is formed by the film 3'. In the porous form, the electrolyte 4 is omitted. The peeling film is peeled off from the sheet 2, such as the lower portion of the solution 4 as shown in Fig. 3 C -15-200835036, in such a manner that the lower side is turned upside down. Then, the first electrolyte 4 is filled in the opening of the pores 2a, and the inorganic electrolyte film 3 having the through holes 3a is formed as a flat surface. Thereafter, the liquid is impregnated into the second electrolyte 5 containing the Nafion solution in the through hole 3a. Therefore, the impregnation and drying are repeated, and as shown in Fig. 3D, the second electrolyte 5 is completely filled in the through hole 3a substantially without voids. Thus, in the composite electrolyte membrane 1 obtained, the first electrolyte 4 is filled so as to coat the inner wall surface of the pores 2a of the organic porous body. Therefore, before the first electrolyte 4 is swollen by water, the contact between the electrode (electrode catalyst) bonded to the composite electrolyte membrane 1 and the first electrolyte 4 is completed, and high output can be obtained. In addition, as a result of swelling of the first electrolyte 4 by water, the inorganic porous film 3 formed on the support substrate 2 does not pass through the void 4a which is insufficiently embedded in the pores 2a of the organic porous body. Breakage, etc. Next, a configuration of a membrane electrode assembly (MEA: Membrane Electrode Assembly) having the composite electrolyte membrane 1 of the embodiment of the embodiment shown in Fig. 4 is shown. As shown in Fig. 4, the MEA 6 of the embodiment includes a fuel electrode 7 formed of a fuel electrode catalyst layer 7a and a fuel electrode gas diffusion layer 7b, and an air electrode catalyst layer 8a and an air electrode gas diffusion layer 8b. The air electrode 8 and the composite electrolyte membrane 1 of the above embodiment held between the fuel electrode catalyst layer 7a and the air electrode catalyst layer 8a. Further, the composite electrolyte membrane 1 is bonded to the fuel electrode 7 side by the inorganic porous film 3, that is, it is preferably joined to the fuel electrode catalyst layer 7a, and may be joined to the air electrode 8 side. -16· 200835036 The catalyst contained in the fuel electrode catalyst layer 7a and the air catalyst layer 8a may, for example, be a single metal such as Pt, Ru, Rh, Ir'Os or Pd of a platinum group element. Alloys of platinum group elements, etc. Specifically, as the fuel electrode catalyst layer 7a, an alloy such as Pt-Ru or Pt-Mo which is highly resistant to methanol or carbon monoxide is preferably used; as the air electrode catalyst layer 8a, uranium or Pt-Ni is preferably used. Alloys, etc., but are not limited to these. Further, in the case of the particulate carbon or the fibrous carbon-based conductive carrier such as activated carbon or black lead, a carbon-carrying catalyst carrying the fine particles of the catalyst may be used. The fuel electrode gas diffusion layer 7b laminated on the fuel electrode catalyst layer 7a is responsible for uniformly supplying the fuel to the fuel electrode catalyst layer 7a, and also has the current collector as the fuel electrode catalyst layer 7a. function. The air electrode gas diffusion layer 8b laminated on the air electrode catalyst layer 8a is responsible for uniformly supplying the oxidant air to the air electrode catalyst layer 8a, and also has the current collector as the air electrode catalyst layer 8a. Function. Each of the fuel electrode gas diffusion layer 7b and the air electrode gas diffusion layer 8b is made of a conductive material. As the conductive material, a conventional material can be used, and in order to efficiently transport the material gas to the catalyst, the use of a porous carbon cloth or carbon paper is preferred.
於該Μ E A 6中，由於第1電解質4以於由有機多孔皙 體所成支持基板2的細孔2a內形成空隙4a的方式塡充， 如弟5圖所不方式，發電時第1電解質4藉由含水而膨脹 (膨潤）時’僅埋入存在於細孔2 a內之空隙，有機多孔 質體的細孔2a無法推壓展開。因此，有機多孔質體的尺 寸變化，特別是由於面方向的膨脹受到抑制，形成於表M -17- 200835036 之無機多孔質薄膜3不產生破裂等破損。 此方式所構成之MEA6係設置於燃料電池，藉由燃料 供給與空氣供給而表現電力。燃料電池，由其型態，大致 分爲主動型（active)燃料電池與被動型（passive)燃料 電池。主動型燃料電池中，由甲醇水溶液所成之燃料以供 給量成爲一定之方式，於使用幫浦調整下供給至MEA6的 燃料極7 ’另一方面採用對空氣極8使用幫浦供給空氣之 方式。被動型燃料電池中，MEA6之燃料極7以自然供給 運送經氣化之甲醇，另一方面對空氣極8自然供給外部空 氣’不採用幫浦等多餘機器的裝備的方式。本發明實施形 態之複合電解質膜1可使用其等之任一者，其使用亦無限 制。 以下，說明具備實施形態MEA6之被動方式的燃料電 池。第6圖爲模式地顯示本發明之直接甲醇型燃料電池（ DMFC ) 10之一實施形態的剖面圖。 如該圖所示方式，本發明之一實施形態之燃料電池1 0 ’具有作爲起電部之上述膜電極接合體（MEA ) 6。於 MEA6之燃料極氣體擴散層7b，層合燃料極導電層1 1，於 空氣極氣體擴散層8b，層合空氣極導電層12。燃料極導 電層11與空氣極導電層12，例如可使用於金、鎳等金屬 材料所成之多質層（例如篩網（mesh))或箔體，或於不 鏽鋼（SUS )等導電性金屬材料分別被覆金等良導電性金 屬之複合材等。又，燃料極導電層11與空氣極導電層12 以由邊緣不漏出燃料或氧化劑之方式構成。 -18- 200835036 於實施形態之燃料電池ι〇中，具有矩形外框架狀之 燃料極密封材1 3係圍繞於燃料極觸媒層7a及燃料極氣體 擴散層7b的周圍，配置於MEA6之複合電解質膜1與燃 料極導電層11之間。另一方面，具有矩形外框架狀之空 氣極密封材14係圍繞於空氣極觸媒層8a及空氣極氣體擴 散層8b的周圍，配置於複合電解質膜1與空氣極導電層 1 2之間。燃料極密封材1 3與空氣極密封材1 4，任一者皆 構成爲橡膠製之〇環等，防止由MEA6之燃料漏出與氧化 劑漏出。又，燃料極密封材1 3與空氣極密封材1 4的形狀 ，不限定爲矩形外框架，具有對應於燃料電池1 〇外緣形 之形狀。 因此，以被覆收容液體燃料F之液體燃料槽1 5之開 口部的方式而配設氣液分離膜1 6，於該氣液分離膜1 6上 ，配製而固定有對應於燃料電池1 〇外緣形之形狀的燃料 極側框架1 7 (此處爲矩形框架）。此處，燃料極側框架 1 7係使用電絕緣性材料構成，具體而言，使用聚對苯二甲 酸伸乙酯（PET )等熱可塑性聚酯樹脂等所形成。因此， 於該燃料極側框架1 7的一面連接燃料極導電層1 1之方式 ，配置具備燃料極導電層11與空氣極導電層12之上述 MEA6。 貯留於液體燃料槽1 5內之液體燃料F爲濃度超過50 莫耳％之甲醇水溶液，或純甲醇。純甲醇的純度較佳爲95 重量％以上、1 0 0重量％以下。後文所述之液體燃料F的氣 化成分，作爲液體燃料使用液體甲醇時，意指經氣化之甲 -19 200835036 醇’作爲液體燃料使用甲醇水溶液時，意指甲醇的氣化成 分雨水的氣化成分所成之混合氣。 以燃料極導電層1 1、氣液分離膜1 6與燃料極框架1 7 . 所圍繞的空間1 7a，暫時地收容穿透氣液分離膜1 6之液體 燃料F的氣化成分，進一步地於氣化成份中作爲均一地燃 料的濃度分布空間的機能。又，氣液分離膜1 6係由其等 之邊緣不漏出燃料之方式而構成。 φ 氣液分離膜1 6係使用氧化矽橡膠、氟樹脂等材料所 構成，分離液體燃料F之氣化成分與液體燃料f，使氣化 成分於燃料極7側穿透者。 另一方面’於空氣極導電層1 2上，經由具有對應於 燃料電池1 〇的外緣形之形狀的空氣極側框架1 8 (此處爲 矩形框架），層合保溼層19。再者，於保濕層19上，層 合形成有複數個用於取入氧化劑之空氣之空氣導入口 20a 的表面全覆層20。表面全覆層20係用於提高含MEA6之 ® 層合體之加壓密著性之角色，例如以SUS3 04方式之金屬 形成。再者，空氣極側框架18係使用與上述燃料極側框 - 架17同樣的電絕緣材料所構成，具體而言，使用聚對苯 . 二甲酸伸乙酯（PET )方式之熱可塑性聚酯樹脂等所形成 〇 保濕層19含浸空氣極觸媒層8a中所生成水之一部分 ，抑制水的蒸散作用之同時，藉由於空氣極氣體擴散層8b 均一地導入氧化劑之空氣，亦具有作爲促進對空氣極觸媒 層8a之空氣的均一擴散之補助擴散層的機能。該保濕層 -20- 200835036 19’例如，使用聚乙烯多孔質膜等材料所構成。又，藉由 浸透現象，由空氣極觸媒層8a至燃料極觸媒層7a側之水 的移動，可於設置於保濕層19上之表面全覆層20中藉由 改變空氣導入口 20a之個數與尺寸，調整開口度的面積等 而調控。 根據此方式所構成之本發明實施形態之直接甲醇型燃 料電池10，由於複合電解質膜1的無機多孔質薄膜3不產 生破裂等破損，防止甲醇的交叉，可供給安定的高輸出功 率。 又，所使用之液體燃料不必限定爲甲醇燃料者，例如 亦可使用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、二醇水溶液或純二醇等二醇燃料、二 甲基醚、蟻酸或其他液體燃料。反正爲相應於燃料電池收 容爲液體燃料。 再者，爲了獲得規定的電池輸出功率，可並設複數個 示於第6圖中之燃料電池1 〇，各燃料電池1 0電氣性的串 聯連接，構成燃料電池。此時，例如可以共用1個液體燃 料槽15之方式構成。 其次，以下示實施例說明具有本發明複合電解質膜之 燃料電池獲得優異的輸出功率特性。 (實施例1 ) 示於第1圖之複合電解質膜，如示於第2A圖至第2C 圖之順序製作。亦即，於厚20μηι、空孔率45%之多孔質 -21- 200835036 聚醯亞胺基板（宇部興產公司製；上下面的平均開口徑爲 3 μιη、空孔率45% )的一面（下方面）配置剝離性薄膜後 ，由上方面側含浸全氟碳磺酸的溶液（Nafion溶液），揮 發溶媒。考慮溶媒的揮發而調整含浸量，使溶媒揮發後多 孔質聚醯亞胺基板的細孔內的空隙率成爲α/ ( 1 +α )的方 式。又，α表示含水時Nafion的膨潤率。由於α爲0.25， 多孔質聚醯亞胺基板的細孔內空隙率以成爲20%之方式調 整含浸量。 於該多孔質聚醯亞胺基板的細孔內的下方部塡充 Nafion，於上方部形成空隙。翻轉該多孔質聚醯亞胺基板 之上下，將剝離性薄膜剝離後，於剝離性薄膜貼著的面（ 上方面），藉由濺鍍法形成後0.5 μιη之氧化矽薄膜。 其次，藉由光微影術於氧化矽薄膜形成貫通孔，形成 開口徑0·2μπι、開口率40%之貫通孔圖型。貫通孔的形成 中，於氧化矽薄膜上塗佈光阻後，使用規定圖型的遮罩曝 光，烘烤後，鈾刻氧化矽薄膜，最後剝離光阻。因此於多 孔質聚醯亞胺基板的上方面形成氧化矽多孔質薄膜。 其次，於氧化矽多孔質薄膜之貫通孔內含浸Nafion 溶液。重複含浸、乾燥，使貫通孔內完全地塡充Nafion。 獲得示於第1圖中之複合電解質膜。 (實施例2) 如示於第3A圖至第3D圖之順序歷程，製作複合電 解質膜。亦即，由厚20μιη、空孔率45%之多孔質聚醯亞 -22- 200835036 胺基板（宇部興產公司製；上下面的平均開口徑爲3μπι、 空孔率45%)的上方面側含浸Nafion溶液，於揮發溶媒 的步驟中，一邊使多孔質聚醯亞胺基板左右傾斜搖動，一 邊揮發溶媒，細孔內的下部塡充Nafion之同時，細孔上 部的內壁面亦形成Nafion的被覆層之方式。除此之外與 實施例1同樣方法，製作複合電解質膜。 其次，分別測定實施例1及2所分別製得之複合電解 φ 質膜之甲醇穿透性與質子傳導度。甲醇穿透性之測定，使 用Η型單元，於裝入3 mol/L甲醇水溶液之容器與裝入純 水之容器之間，夾入預先以水膨潤之實施例1之複合電解 質膜，一定時間後於純水測藉由氣相層析術測定穿透之甲 醇量。因此，算出甲醇的穿透度（μιηοΐ/min · cm2 )。質 子傳導度的測定係於含水狀態之複合電解質膜的上下推壓 附著電極，藉由測定1 kHz的交流阻抗而進行。該等測定 結果示於表1。 # 再者，於實施例1及2所分別製得之複合電解質膜的 兩面，分別貼附觸媒層與氣體擴散層所成電極（空氣極與 . 燃料極），製作示於第4圖之Μ E A 6。亦即，於鉑載持碳 t 黑，將添加有全氟碳磺酸溶液與水及甲氧基丙醇所製得之 塗膏，塗佈於複合電解質膜之多孔質聚醯亞胺基板側後， 於常溫乾燥形成觸媒層。於其上貼附氣體擴散層之多孔質 碳紙，形成空氣極。再者，於載持鉛-釕（Pt-Ru )合金微 粒子之碳粒子，將添加有全氟碳磺酸溶液與水及甲氧基丙 醇所製得之塗膏，塗佈於複合電解質膜之氧化矽多孔質薄 -23- 200835036 膜側後，於常溫乾燥形成觸媒層。於其上貼附氣體擴散層 之多孔質碳紙，形成燃料極。又，電極面積與空氣極、燃 料極皆爲12 cm2。 其次，使用所製作之ME A 6，製作示於第6圖之被動 型燃料電池。因此，於該燃料電池1 〇之液體燃料槽注入 10ml純甲醇，於溫度25 °C、相對濕度50%的環境下，測 定變化電流値每單位面積之最大輸出功率。最大輸出功率 的測定分別於發電起始時與1小時後進行。該等測定結果 示於表1。 (比較例） 如以下所示順序製作MEA。亦即，如第7A圖所示方 式，於厚20μιη、空孔率45%之多孔質聚醯亞胺基板21 ( 宇部興產公司製；上下面的平均開口徑爲3μπι、空孔率 45% )的下方面配置剝離性薄膜（圖式省略）後，由上方 面側含浸Nafion溶液，揮發溶媒。爲了埋入溶媒揮發後 的空隙，進一步重複數次含浸•乾燥，於多孔質聚醯亞胺 基板2 1的細孔2 1 a內，以實質上不產生空隙的方式塡充 Nafion22 〇 其次，如第7B圖所示方式，翻轉細孔21a內完全地 塡充Nafi〇n22之多孔質聚醯亞胺基板21的上下後，於上 方面藉由濺鍍法形成厚0.5 μιη的氧化矽薄膜。因此，藉由 光微影術於該氧化矽薄膜形成貫通孔23a，形成具有開口 徑0·2 μιη、開口率40%之貫通孔23a之圖型的氧化矽多孔 -24- 200835036 質薄膜23。 其次，如第7C圖所示方式，於氧化矽多孔質薄膜^ 之貫通孔23a內，含浸Nafi〇n溶液。重複含浸•乾燥，使 Nafi〇n22完全地塡充。因此製作複合電解質膜24。 由此所製得之複合電解質膜24之甲醇穿透性與質子 傳導度，與實施例〗及2同樣的方法測定。再者，於所製 得之複合電解質膜24的兩面，分別貼附由燃料極觸媒胃 7a與燃料極氣體擴散層7b所成之燃料極7，以及由空_ 極觸媒層8a與空氣極氣體擴散層8b所成之空氣極8，製 作第 7D圖所示之MEA25。因此，使用由此所製作& MEA25，與實施例同樣的方法製作被動型燃料電池。分別 測定發電起始時與1小時後之最大輸出功率。該等測定，結 果示於表1。 [表 1 ] 交流 阻抗 (Ω · cm2) 甲醇穿 透度 (μιποΐ/πύη · cm2) 起始時最大 輸出功率 (mW/cm2) 1小時後最 大輸出功率 (mW/cm2) -實施例1 0.24 9 26 34 一實施例2 0.25 7 34 35 一比較例1 0.23 12 29 29 如上述方式，實施例1及2之任一者，以多孔質聚醯 亞胺基板的細孔內形成空隙之方式塡充電解質之Nafion， 電解質（Nafion )的膨潤時，細孔內的空隙緩衝•吸收其 膨潤。其結果，基板全體不產生面積方向的膨脹’形成於 -25-In the EA 6 , the first electrolyte 4 is filled in such a manner that the pores 4 a are formed in the pores 2 a of the support substrate 2 formed by the organic porous body, and the first electrolyte is generated during the generation of the gas. (4) When it is expanded (swelled) by water, it is buried only in the voids existing in the pores 2a, and the pores 2a of the organic porous body cannot be pushed and developed. Therefore, the dimensional change of the organic porous body is suppressed, in particular, the expansion in the plane direction is suppressed, and the inorganic porous film 3 formed in Table M-17-200835036 is not broken by cracking or the like. The MEA 6 constructed in this manner is provided in a fuel cell, and expresses electric power by fuel supply and air supply. Fuel cells, by their type, are broadly classified into active fuel cells and passive fuel cells. In the active fuel cell, the fuel made of the aqueous methanol solution is supplied to the fuel electrode 7 of the MEA 6 by the pump adjustment in a manner that the supply amount is constant, and the air is supplied to the air electrode 8 by means of a pump. . In the passive fuel cell, the fuel electrode 7 of the MEA 6 transports the vaporized methanol in a natural supply, and naturally supplies the external air to the air electrode 8 without using equipment such as a pump. The composite electrolyte membrane 1 of the embodiment of the present invention can be used in any of the above, and its use is also infinite. Hereinafter, a fuel cell including the passive mode of the embodiment MEA 6 will be described. Fig. 6 is a cross-sectional view schematically showing an embodiment of a direct methanol fuel cell (DMFC) 10 of the present invention. As shown in the figure, the fuel cell 10' of one embodiment of the present invention has the membrane electrode assembly (MEA) 6 as an electrification portion. The fuel electrode diffusion layer 7b of the MEA 6 is laminated with the fuel electrode conductive layer 1 1 and the air electrode diffusion layer 8b, and the air electrode conductive layer 12 is laminated. The fuel electrode conductive layer 11 and the air electrode conductive layer 12 can be used for, for example, a multi-layer (for example, mesh) or a foil formed of a metal material such as gold or nickel, or a conductive metal such as stainless steel (SUS). The material is coated with a composite of a good conductive metal such as gold. Further, the fuel electrode conductive layer 11 and the air electrode conductive layer 12 are configured such that no fuel or oxidant is leaked from the edges. -18-200835036 In the fuel cell of the embodiment, a fuel electrode sealing material 13 having a rectangular outer frame shape surrounds the fuel electrode catalyst layer 7a and the fuel electrode gas diffusion layer 7b, and is disposed in the composite of MEA6. The electrolyte membrane 1 is between the fuel electrode conductive layer 11. On the other hand, the air electrode sealing material 14 having a rectangular outer frame shape is disposed around the air electrode catalyst layer 8a and the air electrode gas diffusion layer 8b, and is disposed between the composite electrolyte membrane 1 and the air electrode conductive layer 12. Each of the fuel electrode sealing material 13 and the air electrode sealing material 14 is formed of a rubber ring or the like to prevent leakage of fuel from the MEA 6 and leakage of the oxidizing agent. Further, the shape of the fuel electrode sealing material 13 and the air electrode sealing material 14 is not limited to a rectangular outer frame, and has a shape corresponding to the outer edge shape of the fuel cell 1 . Therefore, the gas-liquid separation membrane 16 is disposed on the gas-liquid separation membrane 16 so as to cover the opening of the liquid fuel tank 15 in which the liquid fuel F is contained, and is fixed to the fuel cell 1 The fuel electrode side frame 1 7 (here, a rectangular frame) in the shape of a rim. Here, the fuel electrode side frame 17 is made of an electrically insulating material, specifically, a thermoplastic polyester resin such as polyethylene terephthalate (PET) or the like. Therefore, the MEA 6 including the fuel electrode conductive layer 11 and the air electrode conductive layer 12 is disposed so that the fuel electrode conductive layer 11 is connected to one surface of the fuel electrode side frame 17. The liquid fuel F stored in the liquid fuel tank 15 is an aqueous methanol solution having a concentration exceeding 50 mol%, or pure methanol. The purity of pure methanol is preferably 95% by weight or more and 100% by weight or less. The gasification component of the liquid fuel F described later, when the liquid methanol is used as the liquid fuel, means that the vaporized group A - 200835036 alcohol "as a liquid fuel using a methanol aqueous solution, means that the vaporized component of methanol is rainwater. A mixture of gasification components. The gasification component of the liquid fuel F penetrating the gas-liquid separation membrane 16 is temporarily accommodated by the space 1 7a surrounded by the fuel electrode conductive layer 1 1 , the gas-liquid separation membrane 16 and the fuel electrode frame 17 , and further The function of the concentration distribution space as a homogeneous fuel in the gasification component. Further, the gas-liquid separation membrane 16 is configured such that the fuel does not leak from the edges thereof. The φ gas-liquid separation membrane 16 is made of a material such as cerium oxide rubber or fluororesin, and separates the vaporized component of the liquid fuel F from the liquid fuel f to cause the vaporized component to penetrate the fuel electrode 7 side. On the other hand, on the air electrode conductive layer 12, the moisture retaining layer 19 is laminated via the air electrode side frame 18 (here, a rectangular frame) having a shape corresponding to the outer edge shape of the fuel cell 1 . Further, on the moisture retaining layer 19, a surface full covering layer 20 of a plurality of air introducing ports 20a for taking in oxidant air is laminated. The surface full coating layer 20 serves to enhance the role of the pressure tightness of the MEA6-containing laminate, for example, a metal of the SUS3 04 method. Further, the air electrode side frame 18 is made of the same electrically insulating material as the fuel electrode side frame 17, and specifically, a thermoplastic resin having a polyparaphenylene terephthalate (PET) method is used. The hydrazine layer 19 formed by the resin or the like is impregnated with a part of the water generated in the air catalyst layer 8a, and the evapotranspiration of the water is suppressed, and the air of the oxidant is uniformly introduced by the air-polar gas diffusion layer 8b. The uniform diffusion of the air of the air extreme catalyst layer 8a is a function of the diffusion diffusion layer. The moisturizing layer -20-200835036 19' is made of, for example, a material such as a polyethylene porous film. Further, by the penetration phenomenon, the movement of the water from the air electrode catalyst layer 8a to the fuel electrode catalyst layer 7a side can be changed in the surface full coating layer 20 provided on the moisture retaining layer 19 by changing the air introduction port 20a. The number and size, the area of the opening degree are adjusted, and the like. According to the direct methanol fuel cell 10 of the embodiment of the present invention, the inorganic porous film 3 of the composite electrolyte membrane 1 is prevented from being broken by breakage or the like, and the crossover of methanol is prevented, so that a stable high output power can be supplied. Further, the liquid fuel to be used is not necessarily limited to a methanol fuel, and for example, an ethanol fuel such as an ethanol aqueous solution or a pure ethanol, a propanol fuel such as an aqueous solution of propanol or a pure propanol, a glycol fuel such as an aqueous glycol solution or a pure glycol, or a glycol fuel may be used. Dimethyl ether, formic acid or other liquid fuels. Anyway, it is corresponding to the fuel cell to be a liquid fuel. Further, in order to obtain a predetermined battery output, a plurality of fuel cells 1 shown in Fig. 6 may be provided in parallel, and each fuel cell 10 is electrically connected in series to constitute a fuel cell. In this case, for example, one liquid fuel tank 15 can be shared. Next, the following examples demonstrate that the fuel cell having the composite electrolyte membrane of the present invention obtains excellent output power characteristics. (Example 1) The composite electrolyte membrane shown in Fig. 1 was produced in the order shown in Figs. 2A to 2C. That is, a porous-21-200835036 polyamidene substrate (manufactured by Ube Industries, Ltd.; average opening diameter of 3 μm and upper porosity of 45%) on a thickness of 20 μm and a porosity of 45% ( In the following aspect, after the release film is disposed, a solution of a perfluorocarbonsulfonic acid (Nafion solution) is impregnated from the upper side to volatilize the solvent. The void ratio in the pores of the porous polyimide substrate after volatilization of the solvent is adjusted in accordance with the volatilization of the solvent to obtain α/(1 + α). Further, α represents the swelling ratio of Nafion at the time of water. Since α is 0.25, the void ratio in the pores of the porous polyimide substrate is adjusted to be 20%. Nafion is filled in a lower portion of the pores of the porous polyimide substrate, and a void is formed in the upper portion. The porous polyimide substrate was turned upside down, and the release film was peeled off, and then a 0.5 μm ruthenium oxide film was formed on the surface of the release film (top side) by sputtering. Next, a through hole was formed in the yttria film by photolithography to form a through hole pattern having an opening diameter of 0·2 μm and an aperture ratio of 40%. In the formation of the through holes, after the photoresist is coated on the ruthenium oxide film, the mask is exposed to light of a predetermined pattern, and after baking, the ruthenium oxide film is etched, and finally the photoresist is peeled off. Therefore, a porous ruthenium oxide film is formed on the upper side of the porous polyimide substrate. Next, the Nafion solution was impregnated into the through holes of the yttria porous film. The impregnation and drying are repeated, so that the through hole is completely filled with Nafion. The composite electrolyte membrane shown in Fig. 1 was obtained. (Example 2) A composite electrolyte membrane was produced as shown in the sequence of Figs. 3A to 3D. That is, the upper side of the porous polysiloxane -22-200835036 amine substrate (manufactured by Ube Industries, Ltd.; average opening diameter of the upper and lower sides is 3 μm, and the porosity is 45%) is 20 μm thick and has a porosity of 45%. The Nafion solution is impregnated, and in the step of volatilizing the solvent, while the porous polyimine substrate is tilted to the left and right, the solvent is volatilized, and the lower portion of the pores is filled with Nafion, and the inner wall surface of the upper portion of the pores also forms a Nafion coating. The way of the layer. A composite electrolyte membrane was produced in the same manner as in Example 1 except the above. Next, the methanol permeability and proton conductivity of the composite electrolytic φ plasma film obtained in each of Examples 1 and 2 were measured. The methanol permeability was measured by using a Η-type unit between a container filled with a 3 mol/L aqueous methanol solution and a container filled with pure water, and the composite electrolyte membrane of Example 1 which was previously swollen with water was sandwiched for a certain period of time. The amount of methanol permeated was determined by gas chromatography after pure water measurement. Therefore, the transmittance of methanol (μιηοΐ/min · cm2 ) was calculated. The proton conductivity was measured by pushing the adhesion electrode up and down in the hydrated composite electrolyte membrane by measuring the AC impedance at 1 kHz. The results of these measurements are shown in Table 1. # Further, the electrodes (air electrode and fuel electrode) formed by the catalyst layer and the gas diffusion layer were attached to both surfaces of the composite electrolyte membranes obtained in each of Examples 1 and 2, and the results are shown in Fig. 4. Μ EA 6. That is, the platinum is carried on the platinum, and the paste prepared by adding the perfluorocarbonsulfonic acid solution and water and methoxypropanol is applied to the porous polyimine substrate side of the composite electrolyte membrane. Thereafter, it is dried at room temperature to form a catalyst layer. A porous carbon paper to which a gas diffusion layer is attached is formed to form an air electrode. Further, a carbon paste containing lead-bismuth (Pt-Ru) alloy fine particles is coated on a composite electrolyte membrane by applying a paste obtained by adding a perfluorocarbonsulfonic acid solution and water and methoxypropanol. The ruthenium oxide porous thin -23- 200835036 After the film side, it is dried at room temperature to form a catalyst layer. A porous carbon paper to which a gas diffusion layer is attached is formed to form a fuel electrode. In addition, the electrode area is 12 cm2 with both the air electrode and the fuel electrode. Next, the passive fuel cell shown in Fig. 6 was produced using the produced ME A 6. Therefore, 10 ml of pure methanol was injected into the liquid fuel tank of the fuel cell 1 to measure the maximum output power per unit area of the varying current 于 at a temperature of 25 ° C and a relative humidity of 50%. The measurement of the maximum output power was performed at the start of power generation and after 1 hour, respectively. The results of these measurements are shown in Table 1. (Comparative Example) The MEA was produced in the order shown below. That is, as shown in Fig. 7A, the porous polyimine substrate 21 having a thickness of 20 μm and a porosity of 45% (manufactured by Ube Industries, Ltd.; the average opening diameter of the upper and lower surfaces is 3 μm, and the porosity is 45%). After the release film (not shown) is disposed in the lower aspect, the Nafion solution is impregnated from the upper side to volatilize the solvent. In order to embed the voids after volatilization of the solvent, the impregnation and drying are repeated several times, and the Nafion 22 is further filled in the pores 2 1 a of the porous polyimine substrate 2 1 so as not to cause voids substantially. In the manner shown in Fig. 7B, the upper and lower sides of the porous polyimine substrate 21 of the Nafi〇n22 were completely filled in the inverted pores 21a, and then a ruthenium oxide film having a thickness of 0.5 μm was formed by sputtering. Therefore, the through-hole 23a is formed in the yttria film by photolithography to form a yttrium oxide porous -24-200835036 film 23 having a pattern of through-holes 23a having an opening diameter of 0.2 μm and an aperture ratio of 40%. Next, as shown in Fig. 7C, a Nafi〇n solution is impregnated into the through hole 23a of the yttria porous film. Repeat the impregnation and drying to completely fill the Nafi〇n22. Thus, the composite electrolyte membrane 24 is produced. The methanol permeability and proton conductivity of the composite electrolyte membrane 24 thus obtained were measured in the same manner as in Examples and 2. Further, on both sides of the prepared composite electrolyte membrane 24, the fuel electrode 7 formed by the fuel electrode catalyst stomach 7a and the fuel electrode gas diffusion layer 7b, and the air-electrode catalyst layer 8a and air are attached, respectively. The air electrode 8 formed by the gas diffusion layer 8b is formed into the MEA 25 shown in Fig. 7D. Therefore, a passive fuel cell was produced in the same manner as in the example using the MEA 25 thus produced. The maximum output power at the start of power generation and after 1 hour was measured separately. The results of these measurements are shown in Table 1. [Table 1] AC impedance (Ω · cm2) Methanol penetration (μιποΐ/πύη · cm2) Maximum output power at the beginning (mW/cm2) Maximum output power after 1 hour (mW/cm2) - Example 1 0.24 9 26 34 A second embodiment 0.25 7 34 35 a comparative example 1 0.23 12 29 29 As in the above embodiment, any of the first and second embodiments is filled with voids in the pores of the porous polyimide substrate. When the electrolyte Nafion and the electrolyte (Nafion) swell, the voids in the pores are buffered and absorbed. As a result, the entire substrate does not have an expansion in the area direction, which is formed in -25-
200835036 基板表面之氧化矽多孔質薄膜的形狀受到保持 損等。此外，實施例1及2中，甲醇的交叉降 的最大輸出功率。實施例1中，燃料電池的發 由於電解質與觸媒層的接觸不必要爲充分，輸 ，但隨著時間經過之同時，電解質膨潤與觸媒 成完全，獲得充分的大的輸出功率。實施例2 起始時，由於電解質與觸媒層的接觸爲完全， 功率。 相對於比較例中，由於多孔質聚醯亞胺基 ，電解質（Nafion )以完全無空隙地塡充，發 藉由含水而膨潤時，基板全體於面積方向膨脹 第8圖所示方式，氧化矽多孔質薄膜23之貫 一部份發生破裂。其結果，發生甲醇的交叉， 時輸出功率變小。 又，本發明不僅限定爲上述實施形態，於 要不超出本發明要指的範疇可具體化改變構成 ’可藉由於上述實施形態所揭示之複數的構成 組合’可形成種種發明。例如，亦可由實施 全構成要素去除些許構成要素。進一步地， 施形態中適當組合主要構成要素。 例如，於上述說明中，作爲燃料電池構 接合體（MEA)的下部具有燃料收容的構造 收容部對MEA之燃料供給亦可配置連接流 者’作爲燃料電池本體構成雖例舉被動型燃 ，不產生破 低，獲得大 電起始時， 出功率變小 層的接觸變 中，由發電 獲得高輸出 板的細孔內 電時電解質 。因此，如 通孔23a的 由發電起始 實施階段只 要素。再者 要素的適當 態所揭示之 可於不同實 :雖以膜電極 :明，由燃料 r的構造。再 卜電池說明， -26- 200835036 但主動型燃料電池，進一步之燃料供給等一部分使用幫浦 等相對稱爲半被動型之燃料電池，亦可適用於本發明。半 被動型燃料電池，由燃料收容部供給於MEA之燃料使用 於發電反應，之後不循環返回燃料收容部。半被動型燃料 電池，由於不循環燃料，與以往之主動型不同，爲不損及 裝置的小型化等。再者，於燃料的供給使用幫浦，由於與 以往之內部氣化型方式之被動方式不同，故稱爲半被動方 式。又，該半被動型燃料電池中，只要由燃料收容部對 MEA之燃料供給可進行之構成即可，亦可配置取代幫浦之 燃料遮斷閥之構成。於此情況中，燃料遮斷閥亦可藉由流 路用於調控液體燃料的供給而設置。 再者，對MEA供給燃料之蒸氣中，雖可全部供給燃 料的蒸氣，部分使用液體狀態供給的情況亦可適用於本發 明。 【圖式簡單說明】 第1圖爲模式地顯示本發明複合電解質膜之一實施形 態之構成剖面圖。 第2A圖爲顯示本發明之一實施形態之複合電解質膜 之製作方法之剖面圖。 第2B圖爲顯示本發明之一實施形態之複合電解質膜 之製作方法之剖面圖。 第2C圖爲顯示本發明之一實施形態之複合電解質膜 之製作方法之剖面圖。 -27- 200835036 第2D圖爲顯示本發明之一實施形態之複合電解質膜 之製作方法之剖面圖。 第3A圖爲顯示一實施形態之複合電解質膜之其他製 作方法之剖面圖。 第3B圖爲顯示一實施形態之複合電解質膜之其他製 作方法之剖面圖。 第3 C圖爲顯示一實施形態之複合電解質膜之其他製 作方法之剖面圖。 第3D圖爲顯示一實施形態之複合電解質膜之其他製 作方法之剖面圖。 第4圖爲模式地顯示具有一實施形態之複合電解質膜 之膜電極接合體（MEA)之構成剖面圖。 第5圖爲模式地顯示一實施形態之MEA中，電解質 藉由含水而膨潤之狀態之剖面圖。 第6圖爲顯示本發明之燃料電池之一實施形態之直接 甲醇型燃料電池（DMFC )的構成剖面圖。 第7A圖爲顯示本發明之比較例中，複合電解質膜之 製作方法之剖面圖。 第7B圖爲顯示本發明之比較例中，複合電解質膜之 製作方法之剖面圖。 第7C圖爲顯示本發明之比較例中，複合電解質膜之 製作方法之剖面圖。 第7D圖爲顯示本發明之比較例中，MEA之製作方法 之剖面圖。 -28- 200835036 第8圖爲模式地顯示比較例中，電解質藉由含水而膨 潤之狀態之剖面圖。 【主要元件符號說明】 1 :複合電解質膜 2 :支持基板 2a :細孔 _ 3 :無機多孔質薄膜 3 a :貫通孔 4 :第1電解質 4a :空隙 5 :第2電解質 6 :膜電極接合體（MEA) 7 :燃料極 7a :燃料極觸媒層 • 7b :燃料極氣體擴散層 8 :空氣極 • 8a :空氣極觸媒層 - 8b :空氣極氣體擴散層 1〇 :燃料電池 11 :燃料極導電層 1 2 :空氣極導電層 1 3 :燃料極密封材 1 4 :空氣極密封材 -29- 200835036 1 5 :液體燃料槽 1 6 :空氣分離膜 17、18 :框架 1 7a :空間 1 9 :保濕層 2 0 :表面全覆層 20a :空氣導入口 # 2 1 :支持基板（多孔質聚醯亞胺基板） 2 1 a :細孔 22 :第1電解質（Nafion ) 23 :無機多孔質薄膜（細氧多孔質薄膜） 23a :貫通孔 24 :複合電解質膜 25 :膜電極接合體（MEA) -30-200835036 The shape of the yttria porous film on the surface of the substrate is kept damaged. Further, in Examples 1 and 2, the maximum output power of the cross-fall of methanol. In the first embodiment, the contact of the electrolyte with the catalyst layer is not necessary to be sufficient, and the electrolyte is swollen and the catalyst is completed as time passes, and a sufficiently large output is obtained. Example 2 Initially, the contact between the electrolyte and the catalyst layer was complete, power. In the comparative example, when the electrolyte (Nafion) is filled with no voids and is swelled by water, the entire substrate expands in the area direction as shown in Fig. 8 and yttrium oxide. A portion of the porous film 23 is broken. As a result, when methanol crosses, the output power becomes small. Further, the present invention is not limited to the above-described embodiments, and various modifications can be made without departing from the scope of the invention, and the various configurations can be formed by the above-described embodiments. For example, some of the constituent elements may be removed by implementing the entire constituent elements. Further, the main constituent elements are appropriately combined in the embodiment. For example, in the above description, the structure accommodating portion having the fuel accommodating portion in the lower portion of the fuel cell structure (MEA) may be configured to connect the flow to the fuel supply of the MEA. When the breakage is generated and the start of the large electric power is reached, the contact of the output power becomes smaller, and the electrolyte in the pores of the high output plate is obtained by power generation. Therefore, for example, the through-hole 23a is only an element of the implementation stage of power generation. Furthermore, the appropriate state of the element reveals that it can be different: although the membrane electrode: Ming, is constructed by the fuel r. Further, the battery description, -26-200835036 However, a part of a fuel cell, a further fuel supply, or the like, which is a semi-passive type fuel cell, such as a pump, can also be applied to the present invention. In a semi-passive fuel cell, the fuel supplied to the MEA by the fuel accommodating portion is used for the power generation reaction, and then is not circulated back to the fuel accommodating portion. The semi-passive fuel cell does not circulate fuel, unlike the conventional active type, so as not to impair the miniaturization of the device. Furthermore, the use of a pump for the supply of fuel is called a semi-passive method because it is different from the passive method of the conventional internal gasification type. Further, in the semi-passive fuel cell, the fuel supply unit may be configured to supply fuel to the MEA, and a fuel shut-off valve in place of the pump may be disposed. In this case, the fuel shutoff valve can also be provided by the flow path for regulating the supply of the liquid fuel. Further, in the case where the vapor of the fuel supplied to the MEA can be supplied to the vapor of the fuel, and the partial supply of the liquid is used, the present invention can also be applied to the present invention. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a cross-sectional view showing the configuration of one embodiment of a composite electrolyte membrane of the present invention. Fig. 2A is a cross-sectional view showing a method of fabricating a composite electrolyte membrane according to an embodiment of the present invention. Fig. 2B is a cross-sectional view showing a method of fabricating a composite electrolyte membrane according to an embodiment of the present invention. Fig. 2C is a cross-sectional view showing a method of fabricating a composite electrolyte membrane according to an embodiment of the present invention. -27- 200835036 Fig. 2D is a cross-sectional view showing a method of manufacturing a composite electrolyte membrane according to an embodiment of the present invention. Fig. 3A is a cross-sectional view showing another manufacturing method of the composite electrolyte membrane of the embodiment. Fig. 3B is a cross-sectional view showing another manufacturing method of the composite electrolyte membrane of the embodiment. Fig. 3C is a cross-sectional view showing another manufacturing method of the composite electrolyte membrane of the embodiment. Fig. 3D is a cross-sectional view showing another method of producing the composite electrolyte membrane of the embodiment. Fig. 4 is a cross-sectional view showing the structure of a membrane electrode assembly (MEA) having a composite electrolyte membrane of an embodiment. Fig. 5 is a cross-sectional view schematically showing a state in which the electrolyte is swollen by water in the MEA of the embodiment. Fig. 6 is a cross-sectional view showing the structure of a direct methanol fuel cell (DMFC) showing an embodiment of the fuel cell of the present invention. Fig. 7A is a cross-sectional view showing a method of fabricating a composite electrolyte membrane in a comparative example of the present invention. Fig. 7B is a cross-sectional view showing a method of fabricating a composite electrolyte membrane in a comparative example of the present invention. Fig. 7C is a cross-sectional view showing a method of fabricating a composite electrolyte membrane in a comparative example of the present invention. Fig. 7D is a cross-sectional view showing a method of fabricating an MEA in a comparative example of the present invention. -28- 200835036 Fig. 8 is a cross-sectional view schematically showing a state in which the electrolyte is swollen by water in the comparative example. [Description of main component symbols] 1 : Composite electrolyte membrane 2 : Support substrate 2a : Fine pores _ 3 : Inorganic porous membrane 3 a : Through-hole 4 : First electrolyte 4 a : Void 5 : Second electrolyte 6 : Membrane electrode assembly (MEA) 7: Fuel electrode 7a: Fuel electrode catalyst layer • 7b: Fuel electrode gas diffusion layer 8: Air electrode • 8a: Air electrode catalyst layer - 8b: Air gas diffusion layer 1〇: Fuel cell 11: Fuel Polar conductive layer 1 2 : Air electrode conductive layer 13 3 : Fuel electrode sealing material 1 4 : Air electrode sealing material -29 - 200835036 1 5 : Liquid fuel tank 1 6 : Air separation film 17, 18: Frame 1 7a: Space 1 9 : Moisture layer 20 : Surface full coating 20a : Air introduction port # 2 1 : Support substrate (porous polyimide substrate) 2 1 a : Fine pore 22 : First electrolyte (Nafion ) 23 : Inorganic porous Thin film (fine oxygen porous film) 23a: through hole 24: composite electrolyte membrane 25: membrane electrode assembly (MEA) -30-