201029254 六、發明說明： 【發明所屬之技術領域】 本發明涉及-種_極及採用該臈電極的生物燃料電池，尤 其涉及-種基於奈米碳管的膜電極及採肋膜電極的生物燃料電 池。 【先前技術】 燃料電池係-種將轉及氧化紙體轉化為電能的電化學發 電裝置，被廣泛顧於軍事國防及民用的電力、汽車、通信等領 域。生物燃料電池係以酶或微生物為催化劑，將有機物中的化學 能直接轉化為電能的裝置。 請參見圖丄，為2003年10月23曰公開的第循993驗號 大陸專辦請（申請人：索尼株式會社；發明人：酒井秀樹等） 揭示的-讎料電池。觸料電池包含祕電極（負極）玉，該燃 料電極1通過酶催化劑分解作為燃料的多糖以獲得電子和產生質 子an;電解層3，用來僅傳導質子；和空氣電極（正極）5，該 空氣電極5通魏_ 3無_極χ _。該空輯極5使經 電解層3傳輸的質子、從燃料電極丄外部電路供給的電子和空氣 中的氧氣反應形成水。燃料電極工包括電極u及固定於該電極u 上的酶。電極U通常為玻璃碳電極。所述電解層3由這樣的材料 構成’其為麟傳輪於燃料電極1產生的質子H+酸氣電極5的 質子傳導膜，該質子料難沒有電子料雜且可傳輸質子 所述工氣電極5包括催化劑層和由多孔碳物質構成的擴散層， 201029254 且催化劑層位於擴散層與電解質層3之間。該催化劑層由負载有 催化劑的故粉或沒有負載於碳上的催化劑顆粒構成。 、 〆/觸燃料電池工作時，燃料電極！ 一端酶催化劑分解生物燃 料以獲得電子和產生質子。所㈣子通過電騎3槪至空氣電 極5 一端。所述電極11用來收集和傳導反應生成的電子，並將電 子通過外電路傳導至空氣電極5。空氣電極5 -端通入氧化劑氣 體，則該氧化諷體與所述電子、質子反應生成水。 ❿然而，上述的燃料電池具有以下不足：第―，電極u通常為 玻璃碳電極。_碳電極係將有機物高溫炭化製得的碳電極，其 比表面積小’電阻率大，制約電極u傳導反應所生成的電子㈣ 能。這些缺點直接影響燃料電池的反應活性。第二，玻璃碳電極 柔韌性差，不易加工。 【發明内容】 有鑒於此’確有必要提供一種具有較高的反應活性且可提 ©高催化劑的利用率的膜電極及採用該膜電極的生物燃料電池。 -種膜電極，其包括：—質子交換膜，一陽極電極及一陰極 電極’所鶴極電贿_電齡職置麟f子賴膜兩個相 對的表面，其中，所述陽極電極包括一擴散層與生物燃料催化劑， 所述擴散層包括奈米碳管。 -種膜電極’其包括：子交換膜…陽極電極及一陰極 電極，所述陽極電極與陰簡極分別設置賴質子交換膜相對的 兩個表面’其巾，所述陽極電極包括_奈米碳管複合結構，該奈 201029254 米碳管複合賴奈米碳管結觀分散碳管結 的生物燃料催化劑。 一種生物燃料電池，其包括：—質子交換膜；-陽極電極與 -陰極電極’所述陽極電極與陰極亟分別設置於該質子 兩個相_表面；-裝杜魏料的容室，且陽極電極浸泡於該 生物燃料巾；—驗板設置於陰極電極雜質子交雜的表面. Φ 及一個供氣和抽氣裝置與該導流板相連通’其中，所述陽極電極 包括-擴散層與生物祕雜劑，所賴散層包括奈米碳管。 、相較於先前技術，所述膜電極及採用該膜電極的生物燃料電 池具有以下優點：第―，所述陽極電極包括奈輕管，奈米碳管 具有較大的比表_和較低㈣_，故，該陽極電極可有效的 收集和料反應所必㈣電子和反應生成的電子，有助於改善燃 料電池膜電極的反應活性。第二，奈米碳管具有較好的柔拿刃性， 易於加工。 【實施方式】 以下將結合賴對本發明提供㈣電極及生物畴電池作進 一步的詳細說明。 月參閱圖2,本發明第一實施例提供一種燃料電池膜電極 3〇0 ’其包括：—質子交換膜3〇2, -陽極電極3〇4及-陰極電極 3〇6所述陽極電極3〇4與陰極電極3〇6分別設置於該質子交換膜 302的兩個相對的表面。其中，所述陽極電極辦包括一擴散層 3〇4a及分散於該槪層施巾的生物燃料催化劑撕卜 201029254 所述擴散層304a包括-奈米碳管結構或奈米碳管複合結構。 所述奈米碳管結構包括複數個均勻分佈的奈純管。該奈米碳管 結構中的奈米碳管有序㈣或無序湖。該奈米碳管結構中的奈 米碳官包括單壁奈米碳管、雙壁奈米礙管及多壁奈米碳管中的— 種或夕種所述單壁奈米碳管的直徑為0.5奈米〜1〇奈米雙壁奈 米碳管的直徑為1.0奈米〜15奈米，多壁奈米碳管的直徑為Μ奈 米〜50奈米。所述奈米碳管的長度大於5〇微米。本實施例中，該 ©奈米後管的長度優選& 2〇〇~9〇〇微米。當奈米碳管結構包括無序 排列的奈米碳管時，奈米碳管相聽繞或者各向雜排列；當奈 米竣管結構包括有序排列的奈米碳管時，奈米碳管沿一個方向或 者複數個方向擇優取向排列。 具體地’所述奈米碳管結構包括至少一層奈米碳管膜、至少 -奈米碳管線狀結構或魏合。#絲碳f結構僅包括—個奈米 碳管線狀結構時，紗轉管植、轉r折疊或魏成一^狀 奈米碳管賴。當奈米碳f結構包括魏财米碳管線狀、轉 時，複數個奈树管線狀結構可相互平行設置，交又設置或編織 設置成-層狀奈米碳管結構。當奈米碳管結構同時包括奈米碳管 膜和奈米碳管線狀結構時，所絲米碳管線狀結構設置於奈米碳 管膜的至少-表面。所述奈純細包括魏綱^分伟的奈= 碳管，具舰’織触㈣分佈的奈料f有序制或血 列’奈米碳管之間通過凡德力連接。該奈米碳管膜純太米 複管絮化膜、奈米碳管賴膜及奈麵管拉财的—種或幾種… 201029254 膜、清2 厚度為α〇1，微米。所述奈米碳管拉 ^通過拉取—奈米碳管_直接獲得。可解，通過將複數個 =炭_平槪_:驗修重_，可製備不同面積 /、厚度的奈米碳管結構。每—絲碳錄膜包括複數個擇優取向 排列的奈米碳管。所述奈米碳f通過凡德瓦爾力首尾相連。請參 閱圖3及圖4 ’具體地’每—奈米碳管拉膜包括複數個連續且定向 ❿ 排列的奈米碳剡段143爾油絲碳”段143通過凡德瓦 爾力耳尾相連。每—奈料管片段⑷包括複數她互平行的奈 米碳管145,該複數個相互平行的奈米碳f 145通過凡德瓦爾力緊 密結合。該絲碳料段143具餘朗紐、厚度、均勾性及 形狀。該奈米碳管拉财的奈米碳管145沿同―方向擇優取向排 列。可以轉，由複數個絲碳餘驗成的奈米碳管結構中， 相鄰兩個奈米碳管拉膜中的奈米碳管的排列方向有-夾角α，且 〇。如90。’從而使相鄰兩層奈米碳管拉膜中的奈米碳管相互交叉 組成-網狀結構’該網狀結構包括複數個微孔，該複數個微孔均 勻且規則分佈於奈米碳管結構中，其中微孔直徑為工奈米〜0.5微 米。該微孔結構可用於擴散氣體。所述奈米碳管拉膜結構及其製 備方法請參見范守善等人於2〇〇7年2月9日申請的，於繼年 8月13公開的第CN1〇1239712A號中國大陸公開專利申請‘‘奈米 碳管薄膜結構及其製備方法”，申請人：清華大學，鴻富錦精密 工業（深圳）有限公司。 所述奈米碳管線狀結構包括至少一非扭轉的奈米碳管線、至 201029254 ^杻轉的奈米*官線或其組合。所述奈米碳管線狀結構包括多 根非扭轉的奈米碳f線或_的奈米碳管斜，_轉的夺米 碳官線或扭轉的絲碳f線可相互平行呈—束狀結構，或相互扭 轉呈一絞線結構。 、，請參閱圖5，該非扭轉的奈米碳管線包括複數個沿該非扭轉的 奈米碳管線長度方轉觸奈米碳管。具舰，該非扭轉的夺米 碳管線包括複數個奈米碳管片段，該複數個奈米破管片段通過凡 ❹德瓦爾力首尾相連’每—奈米碳"段包括複細目互平行並通 過凡德瓦爾力緊密結合的奈米碳管。該奈米碳管片段具有任意的 長度厚度、均勻性及形狀。該非扭轉的奈米碳管線長度不限， 直㈣0.5奈米〜1〇〇微米。非扭轉的奈米碳管線為將奈米碳管拉 ，通過有機賴處理得到。具體地，將有機溶縦騎述奈米碳 官拉膜的整個表面，於揮發性有機溶劑揮發時產生的表面張力的 _下，奈轉管拉财的相互平行的複數個奈米碳管通過凡德 瓦爾力緊餘合’從而使奈米碳管拉敵縮為—非轉的奈米碳 管線。該有機溶劑為揮發性有機溶劑，如乙醇、甲醇、丙嗣、二 氣乙烧或氯仿’本實施例中採用乙醇。通過有機溶劑處理的非扭 轉奈求碳管線與未經有機溶雜理的絲碳管膜相比，比表面積 減小，黏性降低。 所述奈米碳管線狀結構及其製備方法請參見范守善等人於 2002年9月16日申請的，於2〇〇8年8月2〇日公告的第 CN10〇411979C號中國大陸公告專利“一種奈米碳管繩及其製造 8 201029254 方法”，申請人：清華大學，碑& 及於施年12月16日申,有限公司’ c_職號中國大陸利2Q a_第 法”，申請人：清華大學，鴻々辭：：4碳管絲及其製作方 , 瑪田錦精进工業(深圳)有限公司。 兩端^的不米碳"線為翻—機械力將所述奈米碳管拉膜 ❹ t數個繞該扭轉的奈米碳管線轴向螺旋排列的奈米碳管、。: 轉的絲碳料包括她轉米碳管肢，該複數個奈 數^互2通過凡德關力百尾相連，每—奈米碳管片段包括複 平行f通過凡德瓦爾力緊密結合的奈米碳管。該奈米碳 二又具有任意的長度、厚度、均勻性及形狀。該扭轉的奈米碳 吕線長度不限，直徑為〇.5奈米〜_微米^進―步地，可採用一 揮發性有機溶劑處理該扭轉的奈米碳管線。於揮發性有機溶劑揮 發時產生的表面張力的作用下’處理後的扭轉的奈米碳管線中相 鄰的奈米碳管通過凡德瓦爾力緊密結合，使扭轉的絲碳管線的 比表面積減小’密度及強度增大。 所述奈米碳管碾壓膜包括均勻分佈的奈米碳管，奈米碳管各 向同性’沿同_方向或不同方向擇優取向制。請參關7，本實 施例中，奈米碳管碾壓膜中的奈米碳管沿不同方向擇優取向排 列。優選地，所述奈米碳管碾壓膜中的奈米碳管平行於奈米碳管 碾壓膜的表面。所述奈米碳管碾壓膜中的奈米碳管相互交疊，並 通過凡德瓦爾力相互吸引，緊密結合，使得該奈米碳管碾壓膜具 9 201029254 有很好的柔動性，可f曲折疊成任意形狀而不破裂。且由於奈米 碳管碾厘膜中的奈米碳管之間通過凡德瓦爾力相㈣引，緊密結 合，使奈米礙管碾壓膜為-自支樓的結構’可無需基底支撐，自 支撐存在。所述奈米碳管碾壓膜可通過碾壓一奈米碳管陣列獲 得。所述奈米碳管雜财的奈米碳管與形成奈綠管陣列的基 底的表面形成-夾角α，其中，α大於等於〇度且小於等於15度 (〇泥15°)，該㈣α與施加於奈米碳管_上的壓力有關，壓力 ❿越大’該夾肖越小。所述奈米碳管賴膜的長度和寬度不限。所 述碾壓膜包括複數個微孔結構，該微孔結構均勻且規則分佈於奈 米礙管礙壓膜中，其中微孔直徑為工奈米〜〇5微米。該微孔結構 可用於擴散氣體。所述奈米碳管賴膜及其製備方法請參見范守 善等人於2〇〇7年6月1日申請的第2〇〇71〇〇74〇275號中國大陸專 利申明奈米碳官薄膜的製備方法”，申請人：清華大學，鴻富 錦精密工業（深圳）有限公司。 ❹ 所述奈米碳管絮化膜的長度、寬度和厚度不限，可根據實際 需要選擇4翻提供的絲碳管絮賴的長度為㈣厘米，寬 度為1〜10厘米，厚度為丄微米〜2毫米。請參閱圖8,所述奈米碳 S絮化膜包括相互纏繞的絲碳管，奈米碳管長度大於10微米。 所述不米碳官之間通過凡德瓦爾力相互吸引、纏繞，形成網絡狀 結構。所述奈米碳管絮化膜各向·，其中的奈米碳管為均句分 佈’無規則制，形成大量的微孔結構，微孔孔徑為1奈米〜〇 5 微米。該微孔結構可用於擴散氣體。所述奈級管絮化膜及其製 201029254 備方法請參見范守善等人於2GG7年4月13日申請的第 200710074699.6號中國大陸專利申請“奈米碳管薄膜的製備方 法，申請人：清華大學，鴻富錦精密工業（深圳）有限公司。 所述生物燃料催化劑3〇4b指任何能狗對生物燃料進行催化分 解的催化劑，其可為酶催化劑、微生物或其組合。所述酶催化劑 可為含有縣FAD的氧化酶或含有縣NAD(p)+&職酶等。該 酶催化劑均勻·於奈米碳管結射的奈米碳管表面，並通碰 ❿基或羥基無奈米碳管結合。可㈣解，對不_生物燃料所 選用的酶催化劑不同。本實施例中，生物燃料為葡萄糖溶液，酶 催化劑為葡萄糖氧化酶。所述葡萄糖氧化酶均勻分散於奈米碳管 結構中的奈米碳管表面，並與該奈米碳管結構形成一複合結構。 進一步’所述生物燃料催化劑3_中還可包括複數個電子介體， 該電子介_純集反缝生㈣子，並將電子傳輸給奈米碳管201029254 VI. Description of the Invention: [Technical Field] The present invention relates to a bio-fuel cell using the same, and particularly to a bio-fuel cell based on a carbon nanotube-based membrane electrode and a rib membrane electrode . [Prior Art] A fuel cell system, an electrochemical power generation device that converts an oxidized paper body into electric energy, is widely used in the fields of military, national defense, and civil power, automobiles, and communications. Biofuel cells are devices that convert enzymes in organic matter directly into electrical energy using enzymes or microorganisms as catalysts. Please refer to the figure 丄, the 993 test number published for October 23, 2003. The mainland special office (applicant: Sony Corporation; inventor: Sakai Hideki, etc.) revealed the battery. The contact battery comprises a secret electrode (negative electrode) jade which decomposes a polysaccharide as a fuel by an enzyme catalyst to obtain electrons and generates protons an; an electrolytic layer 3 for conducting only protons; and an air electrode (positive electrode) 5, The air electrode 5 is connected to Wei_3 without _ pole χ. The empty electrode 5 causes protons transported through the electrolytic layer 3, electrons supplied from an external circuit of the fuel electrode, and oxygen in the air to react to form water. The fuel electrode worker includes an electrode u and an enzyme immobilized on the electrode u. The electrode U is typically a glassy carbon electrode. The electrolytic layer 3 is composed of a material which is a proton conducting membrane of the proton H+ acid gas electrode 5 generated by the pulsating wheel on the fuel electrode 1, and the proton material is difficult to be free of electrons and can transport protons. 5 includes a catalyst layer and a diffusion layer composed of a porous carbon material, 201029254 and a catalyst layer between the diffusion layer and the electrolyte layer 3. The catalyst layer is composed of a powder loaded with a catalyst or catalyst particles not supported on carbon. , 〆 / touch fuel cell when working, fuel electrode! An enzyme catalyst at one end decomposes the biofuel to obtain electrons and generate protons. (4) The child rides 3 turns to the end of the air electrode 5. The electrode 11 is used to collect and conduct electrons generated by the reaction, and conduct the electrons to the air electrode 5 through an external circuit. When the oxidant gas is introduced into the end of the air electrode, the oxidized iron reacts with the electrons and protons to form water. However, the above fuel cell has the following disadvantages: ―, the electrode u is usually a glassy carbon electrode. The carbon electrode is a carbon electrode obtained by carbonizing an organic substance at a high temperature, and has a small specific surface area and a large resistivity, which restricts electrons generated by the conduction reaction of the electrode u. These shortcomings directly affect the reactivity of the fuel cell. Second, the glassy carbon electrode is poor in flexibility and difficult to process. SUMMARY OF THE INVENTION In view of the above, it is indeed necessary to provide a membrane electrode having a high reactivity and a utilization of a high catalyst, and a biofuel cell using the membrane electrode. a seed electrode comprising: a proton exchange membrane, an anode electrode and a cathode electrode, wherein the anode electrode comprises two opposite surfaces, wherein the anode electrode comprises a first surface a diffusion layer and a biofuel catalyst, the diffusion layer comprising a carbon nanotube. a seed electrode comprising: a sub-exchange membrane, an anode electrode and a cathode electrode, wherein the anode electrode and the cathode electrode are respectively provided with two surfaces opposite to the proton exchange membrane, and the anode electrode comprises _ nanometer Carbon tube composite structure, the Nai 201029254 m carbon tube composite Lai Na carbon tube is a biofuel catalyst for the dispersion of carbon tube junctions. A biofuel cell comprising: a proton exchange membrane; an anode electrode and a cathode electrode, wherein the anode electrode and the cathode cathode are respectively disposed on the two phases of the proton; the chamber containing the Duwei material, and the anode The electrode is immersed in the bio-fuel towel; the test plate is disposed on the surface of the cathode electrode impurity impurity intersection. Φ and a gas supply and extraction device are connected to the baffle plate, wherein the anode electrode comprises a diffusion layer and The biological secret agent, the scattered layer includes a carbon nanotube. Compared with the prior art, the membrane electrode and the biofuel cell using the membrane electrode have the following advantages: first, the anode electrode comprises a nai light tube, and the carbon nanotube has a larger ratio _ and lower (4) _, therefore, the anode electrode can effectively collect and react with the electrons and electrons generated by the reaction, which contributes to improving the reactivity of the fuel cell membrane electrode. Second, the carbon nanotubes have a good flexibility and are easy to process. [Embodiment] Hereinafter, the (four) electrode and the biodomain battery provided by the present invention will be further described in detail in conjunction with Lai. Referring to FIG. 2, a first embodiment of the present invention provides a fuel cell membrane electrode 3'0' which includes: a proton exchange membrane 3〇2, an anode electrode 3〇4, and a cathode electrode 3〇6. The crucible 4 and the cathode electrode 3〇6 are respectively disposed on the opposite surfaces of the proton exchange membrane 302. Wherein, the anode electrode assembly includes a diffusion layer 3〇4a and a biofuel catalyst tearing agent dispersed in the layer coating 201029254. The diffusion layer 304a comprises a carbon nanotube structure or a carbon nanotube composite structure. The carbon nanotube structure includes a plurality of uniformly distributed nematic tubes. The carbon nanotubes in the structure of the carbon nanotubes are ordered (four) or disordered lakes. The carbon carbon in the carbon nanotube structure includes the diameter of the single-walled carbon nanotube, the double-walled nano-tube, and the multi-walled carbon nanotube, or the diameter of the single-walled carbon nanotube. The diameter of the 0.5 nm ~ 1 〇 nano double-walled carbon nanotubes is 1.0 nm ~ 15 nm, and the diameter of the multi-walled carbon nanotubes is Μ nanometer ~ 50 nm. The length of the carbon nanotubes is greater than 5 microns. In this embodiment, the length of the US nanotube is preferably & 2〇〇~9〇〇micron. When the carbon nanotube structure includes a disordered arrangement of carbon nanotubes, the carbon nanotubes are aligned or arranged in an alternating manner; when the nanotube structure includes an ordered arrangement of carbon nanotubes, the nanocarbon The tubes are arranged in a preferred orientation in one direction or in a plurality of directions. Specifically, the carbon nanotube structure comprises at least one layer of carbon nanotube membrane, at least - nanocarbon line-like structure or Wei. The #丝碳f structure only includes a nano carbon line-like structure, the yarn is transferred to the tube, the r-folded or the Wei-cheng-like nano-carbon tube. When the nano carbon f structure includes the Wei Caimi carbon pipeline shape, the plurality of nai tree pipeline structures can be arranged in parallel with each other, and the cross-shaped or layered carbon nanotube structure is disposed or woven. When the carbon nanotube structure includes both a carbon nanotube membrane and a nanocarbon line-like structure, the filamentous carbon line-like structure is disposed on at least a surface of the carbon nanotube membrane. The neat pure fineness includes Wei Gang ^ weiwei's nai = carbon tube, with the ship's woven (four) distribution of the n-fed order or the blood column 'nano carbon tube connected by van der Waals. The carbon nanotube film pure rice metering tube flocculation film, nano carbon tube film and nai tube tube money - kind or several... 201029254 film, clear 2 thickness α 〇 1, micron. The carbon nanotubes are drawn directly by drawing - carbon nanotubes. It can be solved, and the carbon nanotube structure of different area/thickness can be prepared by using a plurality of carbons_flat__: repairing weight_. Each of the carbon recording films includes a plurality of carbon nanotubes arranged in a preferred orientation. The nanocarbons f are connected end to end by van der Waals force. Referring to Figures 3 and 4, 'specifically, each of the carbon nanotube-coated membranes comprises a plurality of continuous and oriented ❿-arranged carbon nanotube segments 143 kerosene carbon segments 143 connected by van der Waals. Each of the tube segments (4) includes a plurality of mutually parallel carbon nanotubes 145, and the plurality of mutually parallel nanocarbons f 145 are tightly bonded by van der Waals force. The wire carbon segments 143 have a residual thickness and thickness. The carbon nanotubes of the carbon nanotubes of the carbon nanotubes are arranged along the same direction. The carbon nanotubes can be transferred, and the carbon nanotubes are formed by a plurality of carbon carbons. The arrangement of the carbon nanotubes in the carbon nanotube film is - the angle α, and 〇, such as 90. 'Therefore, the carbon nanotubes in the adjacent two layers of carbon nanotubes are formed to cross each other - The network structure 'the network structure comprises a plurality of micropores which are uniformly and regularly distributed in the carbon nanotube structure, wherein the micropore diameter is ±0.5 μm. The microporous structure can be used for diffusion Gas. The structure of the carbon nanotube film and its preparation method can be found in Fan Shoushan et al. Application No. CN1〇1239712A, published on February 9th of the year, published in China on August 13th, 'Chinese carbon tube film structure and its preparation method》, applicant: Tsinghua University, Hongfujin Precision Industrial (Shenzhen) Co., Ltd. The nanocarbon line-like structure comprises at least one non-twisted nanocarbon line, a nanowire* line to 201029254, or a combination thereof. The nanocarbon line-like structure comprises a plurality of non-twisted nano-carbon f-lines or _ nanocarbon tube slant, and the _ turn of the carbon-defining official line or the twisted silk-carbon f-line may be parallel to each other in a bundle shape The structure, or twisted to each other, is a twisted wire structure. Referring to Figure 5, the non-twisted nanocarbon pipeline includes a plurality of carbon nanotubes along the length of the non-twisted nanocarbon pipeline. With a ship, the non-twisted rice-removing carbon pipeline includes a plurality of carbon nanotube segments, and the plurality of nano-tube fragments are connected end to end by Van der Deval, 'per-nano carbon" The carbon nanotubes are tightly combined by Van der Valli. The carbon nanotube segments have an arbitrary length thickness, uniformity and shape. The length of the non-twisted nano carbon pipeline is not limited, straight (four) 0.5 nm ~ 1 〇〇 micron. The non-twisted nano carbon pipeline is obtained by pulling the carbon nanotubes through organic treatment. Specifically, the organic solvent dissolves the entire surface of the nano-carbon film, and the surface tension generated when the volatile organic solvent is volatilized is passed, and the plurality of carbon nanotubes that are parallel to each other are passed through. Van der Waals has a tight fit and thus the carbon nanotubes are pulled into a non-transforming nano carbon pipeline. The organic solvent is a volatile organic solvent such as ethanol, methanol, propylene carbonate, ethylene bromide or chloroform. In the present embodiment, ethanol is used. The non-twisted carbon pipeline treated by the organic solvent has a smaller specific surface area and a lower viscosity than the carbon nanotube film which is not organically treated. The nanocarbon line-like structure and its preparation method can be found in the application for publication of the Chinese mainland on September 16, 2002 by Fan Shoushan et al., CN10〇411979C, announced on August 2, 2008. A carbon nanotube rope and its manufacture 8 201029254 method", applicant: Tsinghua University, monument & and on December 16th of the year of application, Ltd. 'c_ job title China mainland profit 2Q a_ law", Applicant: Tsinghua University, Hongxun Ci:: 4 carbon tube wire and its manufacturer, Martian Jinjingjin Industry (Shenzhen) Co., Ltd. Both ends of the non-meter carbon " line for turning - mechanical force will be said Nai The carbon nanotube film is 数t a number of carbon nanotubes arranged axially around the twisted nanocarbon pipeline. The rotating carbon material includes her carbon nanotubes, and the plurality of nanotubes Each of the carbon nanotube segments consists of a carbon nanotube that is tightly coupled by a van der Waals force through a van der Waals force. The nanocarbon has an arbitrary length, thickness, uniformity and shape. The twisted nano-carbon line is not limited in length, and the diameter is 〇.5 nanometer ~ _ micron ^ step by step, one can be used The volatile organic solvent treats the twisted nanocarbon pipeline. Under the action of the surface tension generated by the volatilization of the volatile organic solvent, the adjacent carbon nanotubes in the treated reversed carbon carbon pipeline pass through the van der Waals force. Closely combined, the specific surface area of the twisted silk carbon line is reduced, and the density and strength are increased. The carbon nanotube rolled film includes uniformly distributed carbon nanotubes, and the carbon nanotubes are isotropic. Orientation or orientation is preferred. For reference, in this embodiment, the carbon nanotubes in the carbon nanotube film are arranged in different orientations. Preferably, the carbon nanotube film is laminated. The carbon nanotubes in the middle are parallel to the surface of the carbon nanotubes. The carbon nanotubes in the carbon nanotubes are overlapped with each other and are attracted to each other by the van der Waals force. The carbon nanotube rolled film 9 201029254 has good flexibility and can be folded into any shape without cracking, and the carbon nanotubes in the carbon nanotubes are passed through the van der Waals. Valli phase (four) cited, tightly combined, so that nano-impacted laminated film - The structure of the self-supporting building can be self-supported without the support of the substrate. The carbon nanotube film can be obtained by rolling an array of carbon nanotubes. The carbon nanotubes of the carbon nanotubes are miscellaneous Forming an angle α with the surface of the substrate forming the array of green tubes, wherein α is greater than or equal to 15 degrees and less than 15 degrees (15° of mud), and the pressure is applied to the pressure applied to the carbon nanotubes, pressure The larger the ❿ is, the smaller the clip is. The length and width of the carbon nanotube film are not limited. The laminated film includes a plurality of microporous structures which are uniformly and regularly distributed in the nano tube. In the pressure film, the diameter of the micropores is from work nanometer to 5 micrometers. The microporous structure can be used for diffusing gas. The carbon nanotube membrane and the preparation method thereof can be found in Fan Shoushan et al. The preparation method of the Chinese patent claiming nano carbon official film of the 2nd 〇〇71〇〇74〇275 application filed on June 1st, applicant: Tsinghua University, Hongfujin Precision Industry (Shenzhen) Co., Ltd.长度 The length, width and thickness of the carbon nanotube film are not limited. According to the actual needs, the length of the carbon tube provided by 4 turns is (4) cm, the width is 1~10 cm, and the thickness is 丄μ. ~ 2 mm. Referring to FIG. 8, the nano carbon S flocculation film comprises intertwined carbon carbon tubes having a length of more than 10 micrometers. The non-carbon members are attracted and entangled by van der Waals forces to form a network structure. The carbon nanotube flocculation membranes are oriented, wherein the carbon nanotubes are uniformly distributed, forming a large number of microporous structures having a pore diameter of from 1 nm to 5 μm. The microporous structure can be used to diffuse gases. The preparation method of the nano tube shrinking film and the method for preparing the same can be found in the method of preparing the carbon nanotube film of the Chinese patent application No. 200710074699.6, filed on April 13, 2, 1989. Applicant: Tsinghua University , Hong Fu Jin Precision Industry (Shenzhen) Co., Ltd. The biofuel catalyst 3〇4b refers to any catalyst capable of catalytically decomposing biofuels by dogs, which may be an enzyme catalyst, a microorganism or a combination thereof. The oxidase containing the county FAD or the county NAD(p)+&enzyme. The enzyme catalyst is uniform on the surface of the carbon nanotubes that are formed on the carbon nanotubes, and passes through the thiol or hydroxy carbon nanotubes. The (4) solution may be different for the enzyme catalyst selected for the non-biofuel. In this embodiment, the biofuel is a glucose solution, and the enzyme catalyst is glucose oxidase. The glucose oxidase is uniformly dispersed in the carbon nanotube structure. a surface of the carbon nanotube and forming a composite structure with the carbon nanotube structure. Further, the biofuel catalyst 3_ may further include a plurality of electron mediators, (Iv) sub-set of reverse suture green, and transports the electrons to the carbon nanotube
本實施例中，所述陽極電極3〇4通過以下方法製備： 首先，對上述奈采碳管結構進行功能化處理。 對奈米碳管結構進行功能化處理的方法為將奈卡碳管結構於 強酸溶液中浸泡。本實施财，取濃硫酸和__-定的比例， 1.3犯。於試s巾，將製備好的絲碳管結構裁剪合適的長 度^入混合液中超聲處理2小時左右；取出奈米碳管結構再放 入雙乳水巾超聲處理i何左右；取出後將奈鱗管結構浸泡於 超純水中_超縣理，赵絲碳錄構吨t性為止。 11 201029254 其次，提供一含有酶催化劑的溶液，並將功能化處理後的奈 米碳管結構浸泡於該催化劑的溶液中。 本實施例+，於冰水混合物環境下，配冑版咖丨# 鹽 酸鹽和12mg/ml的葡萄糖氧化酶（G〇D)水溶液。然後將功能化 處理後的奈米碳管結構於該葡萄糖氧化酶水溶液中於溫度條 件下浸泡約1〜5日。可紐解，其他酶催化綱可制類似的方 法，通過選用合適的溶劑配製成一酶催化劑溶液。 最後，將含有催化劑的溶液浸泡後的奈米碳管結構取出烘乾 得到一奈米碳管與酶催化劑的複合結構作為陽極電極3〇4。 所述陰極電極306結構不限，可包括-擴散層及一催化劑層 設置於該紐層上，且該催化獅設置於質子交細與擴散層之 間。所述擴散層可為一碳纖維紙或奈米碳管結構。該催化劑層包 含有催化劑材料（如貴金屬或酶催化劑）及其載體（一般為碳顆 粒’如：石墨、炭黑、碳纖維或奈米碳管）。 所述陰極電極306也可包括至少一個奈米碳管複合結構，且 该奈米碳管複合結構包括奈米碳管結構及分佈於該奈米碳管妗構 中的貴金屬催化劑或酶催化劑。所述貴金屬包括鉑、金及釕中的 一種或其任意組合的混合物。該貴金屬顆粒的直徑尺寸為奈 米。所述貴金屬催化劑的擔載量低於〇.5mg/cm2，且均勻分佈於齐 米碳管結構中的奈米碳管表面。 本實施例中，所述陽極電極304為一奈米碳管結構與酶催化 劑的複合結構。所述陰極電極306為一個奈米碳管結構與貴金屬 12 201029254 催化劑的複合結構，該貴金屬催化劑為_粒。所述陽極電極撕 與陰極電極306中的奈米碳管結構均包括複數個重疊設置的拉 膜。請參閱圖9，編粒均句分佈於奈米碳管拉臈中的奈米礙管表 面。所述奈米碳管複合結構通過自纟的黏性、黏結劑或熱壓= 法固定於質子交換膜302的表面。 知所述質子交換膜302的材料為全氣績酸、聚苯乙稀續酸、聚 三氟苯乙触酸、祕脑雜或錢化合物。本實施例中，質 β 子交換膜302材料為全I確酸。 本實施例提供燃料電池膜電極3〇()具有以下優點：第一，所 述陽極電極翻奈純管複合結構，奈米碳管結構巾的奈米碳管 具有較大的比表面積，故，制該奈米碳管結構可有效且均句的 擔载催化劑’使催化顯生物崎具有較大的接_積，提高催 化劑的利用率。第二，由於奈米碳管具有較大的比表面積和較低 的電阻率’故，採職奈米碳管複合結構的電極可有效的收集和 參傳導反應所必需的電子和反應生成的電子，有助於改善燃料電池 膜電極的反應活性。第三，所述陽極電極採用奈米碳管複合結構， 由於奈米碳管密度小，故，該膜電極3〇〇品質較小，使用更方便。 請參閱圖10,本發明第二實施例提供一種燃料電池膜電極 4〇〇 ’其包括：一質子交換膜4〇2，一陽極電極4〇4及一陰極電極 406。所述陽極電極404與陰極電極4〇6分別設置於該質子交換膜 402的兩個相對的表面所述膜電極4〇〇與本發明第一實施例提供 的膜電極300結構基本相同，其區別在於，所述陽極電極4〇4包 13 201029254 括一擴散層404a及設置於該擴散層304a表面的生物燃料催化劑 層404b °所述生物燃料催化劑層4〇4b設置於所述擴散層4〇如的 至少一表面。本實施例中，所述生物燃料催化劑層404b設置於所 述擴散層404a與質子交換膜402之間。 所述擴散層404a結構與本發明第一實施例提供的擴散層3〇4a 結構相同。 所述生物燃料催化劑層404b包括催化劑及碳顆粒載體。所述 參催化劑與本發明第一實施例提供的生物燃料催化劑3〇4b相同。所 述奴顆粒為石墨顆粒、炭黑顆粒、碳纖維及奈米碳管中的一種或 幾種的混合物，優選為奈米碳管。本實施例中，所述催化劑為酶 催化劑，且酶催化劑分散於後顆粒中，形成催化劑層4〇4b。 所述陰極電極406與本發明第一實施例提供的膜電極3〇〇的 陰極電極306的結構相同。本實施例中，所述陰極電極4〇6為一 個奈米碳管結構與貴金屬催化劑的複合結構，該責金屬催化劑為 ®銘顆粒。 本實施例提供的燃料電池膜電極400中的擴散層4〇4a為一奈 米碳管結構’具有以下優點：第-，由於奈米碳管具有較大的比 表面積和較低的電阻率，故，採用該奈米碳管結構的電極可有效 的收集和傳導反應所必需的電子和反應生成的電子，有助於改善 燃料電池膜電極的反應活性。第二，由於奈米碳管結構包括複數 個均勻分佈的微孔，故，該擴散層可均勻的擴散生物燃料，使生 物燃料與催化劑充分反應。 201029254 請參閱圖11，本發明第三實施例提供一種燃料電池膜電極 500,其包括：一質子交換膜5〇2, 一陽極電極504及一陰極電極 506。所述陽極電極504與陰極電極506分別設置於該質子交換膜 502的兩個相對的表面。所述陽極電極5〇4包括一擴散層5〇4a及 設置於該擴散層504a表面的生物燃料催化劑層504b。所述生物燃 料催化劑層504b設置於所述擴散層504a的至少一表面。本實施 例中’所述生物燃料催化劑層5〇4b設置於所述擴散層5〇4a與質 _子交換膜502之間。所述膜電極500與本發明第二實施例提供的 膜電極400結構基本相同，其區別在於，所述擴散層5〇如包括一 奈米碳管複合結構。 &所述奈米碳管複合結構包括—奈米碳#結構及分散於奈米碳 管結構中的填充材料。所述填充材料均勻分散於奈求碳管結構 卜所述填充材料包括金屬、陶竟、玻璃及纖維中的一種或多種。 可以理解，當奈米碳管結構中分散有金屬時，可增強該奈米碳管 結構的導電性。當奈米碳管結構中分散有填充材料時需確保太 未碳管結構的微孔不被堵塞，以便擴散燃料或氧化劑。可選擇地丁， 管複合結構包括—碳纖維布或碳纖轉及分散於 =或碳編嫩_。瓣_物纖維物 4碳管，可提高其導紐與_性，並增加碳纖維 、 =中小尺寸孔_數量，從而提高碳纖維布或碳_毯的= 地生。所核_布桃_財奈米碳管的添 優 選地，所述碳纖維布或韻維毯中奈米碳管的添加量為Γ〜;L優 201029254 所述陰極電極506的結構與與本發明第一實施例提供的膜電 極300的陰極電極306的結構相同。本實施例中，所述陰極電極 506為-個奈米碳管結構與責金屬催化劑的複合結構，該貴金屬催 化劑為舶顆粒。 本發明第四實施例提供一生物燃料電池，其包括：一質子交 換膜’陽極電極與一陰極電極，所述陽極電極與陰極電極分別 "又置於該質子3C換膜相對的兩個表面；—裝有生物燃料的容室， 罄且所述陽極電極浸泡於該生物燃料中；一導流板設置於陰極電極 遠離質子交換膜的表面；及—個供氣裝置和—個抽氣裝置分別與 該導流板相連通。其中’所述陽極電極包括一擴散層與生物燃料 催化劑，所述擴散層包括一奈米碳管結構。 請參關12 ’具體地’本實施例提供—採用上述燃料電池膜 電極300的生物燃料電池3〇，其包括：一燃料電池膜電極3〇〇， 一個陽極容室314，一個導流板3〇8，一個集流板31〇及一供氣和 抽氣褒置312。所述膜電極3⑻包括一質子交換膜3〇2，一陽極電 4及陰極電極3〇6。所述陽極電極304與陰極電極分別 設置於該質子交換膜3〇2的兩個相對的表面。所述陽極電極3〇4 為-奈米碳管結構與酶催化劑的複合結構。所述陰極電極為 個奈米碳管結構與貴金屬催化劑的複合結構，該責金屬催化劑 為_粒。該奈米碳管結構紐複數健疊設置的城。可以理 解，所述職極還可為本發明第二實施例提供的膜電極或第 二實施例提供的膜電極5Q0。 16 201029254 所述陽極容t 314，設置於燃料電池膜電極3〇〇❾陽極電極 側用來裝載生物燃料316。本實施例中，生物燃料gw為 葡萄糖溶液。所述燃料電池膜電極300將生物燃料316與氧化劑 氣體隔開’且陽極電極3〇4浸泡於該生物燃料316 +，使得酶催 化劑可與生物燃料316接觸。 所述導流板308設置於陰極電極3〇6遠離質子交換膜3〇2的 表面’且於導流板3〇8靠近陰極電極3〇6的表面具有一條或多條 鲁導流槽318 ’用於傳導氧化劑氣體及反應產物水。該導流板308 採用金屬或導電碳材料製作。 所述集流板310採用導電材料製作，設置於導流板3〇8的遠 離質子交換膜302的表面，用於收集和傳導反應所需要的電子。 可以理解，本實施例中’由於奈米碳管結構具有良好的導電性， 可用來收集電流’故，該集流板31〇為一可選擇結構。 *所述供氣和抽氣裝置312包括鼓風機、管路、閥門等(圖中未 標示）。鼓風機通過管路與導流板相連，用來向陰極電極3〇6 提供氧化舰體。本實補巾，氧化舰體域氧氣或含氧的空 氣。 上述生物燃料電池3〇工作時，陽極電極3〇4 一端，生物燃料 316 (以葡萄糖為例）補催化劑的催化作用下發生如下反應：葡 萄糖·>葡萄糖酸咖必。反應生成的質子穿過質子交換膜观到 達陰極電極306，反應生成的電子則進入外電路。 陰極電極306 -端’利用其供氣和抽氣裝置312通過導流板 17 201029254 308向陰極電極306通入氧化劑氣體，如氧氣。氧氣擴散到陰極電 極3〇6的同時，電子則通過外電路到達陰_極306。於貴金屬催 化劑作用下，氧氣與質子及電子發生如下反應：細2+2H++2e— h2o。於此過程中，於陽極電極3〇4舱極電極-之間會形成一 定的電勢差，當外電路接入-負載32〇日夺’將會形成電流。而反 應生成的水則通過導流板排出生物燃料電池3〇。 '综上所述’本發_已符合發明專利之要件，遂依法提出專 ®利申請。惟’以上所述者僅為本發明之較佳實施例，自不能以此 限制本案之申請專利範圍。舉凡熟悉本案技藝之人士援依本發明 之精神所作之等效修飾或變化，技涵蓋触下中請專利範圍内。 【圖式簡單說明】 圖1為先前技術的燃料電池的結構示意圖。 圖2為本發明第—實施例的膜電極的結構示意圖。In this embodiment, the anode electrode 3〇4 is prepared by the following method: First, the above-mentioned carbon nanotube structure is functionalized. The method of functionalizing the carbon nanotube structure is to soak the neka carbon tube structure in a strong acid solution. In this implementation, the proportion of concentrated sulfuric acid and __- is taken, 1.3 is committed. After testing the towel, cut the prepared carbon nanotube structure into a suitable length and sonicate for about 2 hours in the mixture; remove the carbon nanotube structure and put it into the double emulsion water towel for ultrasonic treatment; The Nike tube structure is immersed in ultrapure water _ super county, Zhao silk carbon record structure t to t. 11 201029254 Next, a solution containing an enzyme catalyst is provided, and the functionalized carbon nanotube structure is immersed in the solution of the catalyst. In this example, in an ice-water mixture environment, a sputum version of the curry # hydrochloride and a 12 mg/ml aqueous solution of glucose oxidase (G〇D) were prepared. The functionalized carbon nanotube structure is then immersed in the aqueous glucose oxidase solution under temperature conditions for about 1 to 5 days. A similar method can be used to prepare an enzyme catalyst solution by selecting a suitable solvent. Finally, the carbon nanotube structure after the solution containing the catalyst is taken out and dried to obtain a composite structure of a carbon nanotube and an enzyme catalyst as an anode electrode 3〇4. The cathode electrode 306 is not limited in structure, and may include a diffusion layer and a catalyst layer disposed on the layer, and the catalytic lion is disposed between the protons and the diffusion layer. The diffusion layer may be a carbon fiber paper or a carbon nanotube structure. The catalyst layer contains a catalyst material (e.g., a noble metal or an enzyme catalyst) and a carrier thereof (generally a carbon particle such as graphite, carbon black, carbon fiber or carbon nanotube). The cathode electrode 306 may also include at least one carbon nanotube composite structure, and the carbon nanotube composite structure includes a carbon nanotube structure and a noble metal catalyst or an enzyme catalyst distributed in the nanotube structure. The noble metal includes one of platinum, gold, and rhodium, or a mixture of any combination thereof. The precious metal particles have a diameter of nanometers. The noble metal catalyst has a loading of less than 0.5 mg/cm 2 and is uniformly distributed on the surface of the carbon nanotubes in the carbon nanotube structure. In this embodiment, the anode electrode 304 is a composite structure of a carbon nanotube structure and an enzyme catalyst. The cathode electrode 306 is a composite structure of a carbon nanotube structure and a noble metal 12 201029254 catalyst, which is a granule. The anode electrode tearing and the carbon nanotube structure in the cathode electrode 306 each include a plurality of laminated films disposed in an overlapping manner. Referring to Figure 9, the granules are distributed on the surface of the nanotubes in the carbon nanotubes. The carbon nanotube composite structure is fixed to the surface of the proton exchange membrane 302 by a self-adhesive viscosity, a binder or a hot press method. The material of the proton exchange membrane 302 is known to be a full gas acid, a polystyrene acid, a polytrifluorobenzene acid, a secret brain or a money compound. In this embodiment, the material of the mass β exchange membrane 302 is all I acid. The fuel cell membrane electrode 3〇() has the following advantages: first, the anode electrode has a pure tube composite structure, and the carbon nanotube of the carbon nanotube structure towel has a large specific surface area, so The carbon nanotube structure can be effectively and uniformly supported on the catalyst 'to make the catalytic biosynthesis have a large connection, and improve the utilization of the catalyst. Second, since the carbon nanotubes have a large specific surface area and a low electrical resistivity, the electrodes of the carbon nanotube composite structure can efficiently collect and react electrons and electrons generated by the reaction. It helps to improve the reactivity of the fuel cell membrane electrode. Thirdly, the anode electrode adopts a carbon nanotube composite structure. Since the density of the carbon nanotube is small, the membrane electrode has a small quality and is more convenient to use. Referring to FIG. 10, a second embodiment of the present invention provides a fuel cell membrane electrode 4'' which includes a proton exchange membrane 4〇2, an anode electrode 4〇4, and a cathode electrode 406. The anode electrode 404 and the cathode electrode 4〇6 are respectively disposed on two opposite surfaces of the proton exchange membrane 402. The membrane electrode 4〇〇 is substantially the same as the membrane electrode 300 provided by the first embodiment of the present invention, and the difference is the same. The anode electrode 4〇4 package 13 201029254 includes a diffusion layer 404a and a biofuel catalyst layer 404b disposed on the surface of the diffusion layer 304a. The biofuel catalyst layer 4〇4b is disposed on the diffusion layer 4, for example. At least one surface. In the present embodiment, the biofuel catalyst layer 404b is disposed between the diffusion layer 404a and the proton exchange membrane 402. The structure of the diffusion layer 404a is the same as that of the diffusion layer 3〇4a provided by the first embodiment of the present invention. The biofuel catalyst layer 404b includes a catalyst and a carbon particulate carrier. The reference catalyst is the same as the biofuel catalyst 3〇4b provided by the first embodiment of the present invention. The slave particles are a mixture of one or more of graphite particles, carbon black particles, carbon fibers, and carbon nanotubes, preferably a carbon nanotube. In this embodiment, the catalyst is an enzyme catalyst, and the enzyme catalyst is dispersed in the post particles to form a catalyst layer 4〇4b. The cathode electrode 406 has the same structure as the cathode electrode 306 of the membrane electrode 3 of the first embodiment of the present invention. In this embodiment, the cathode electrode 4〇6 is a composite structure of a carbon nanotube structure and a noble metal catalyst, and the metal catalyst is a granule. The diffusion layer 4〇4a in the fuel cell membrane electrode 400 provided in this embodiment has the advantages of a carbon nanotube structure': the first, since the carbon nanotube has a large specific surface area and a low electrical resistivity, Therefore, the electrode using the carbon nanotube structure can effectively collect and conduct electrons necessary for the reaction and electrons generated by the reaction, and contribute to improvement of the reactivity of the fuel cell membrane electrode. Second, since the carbon nanotube structure includes a plurality of uniformly distributed micropores, the diffusion layer uniformly diffuses the biofuel to sufficiently react the biofuel with the catalyst. Referring to FIG. 11, a third embodiment of the present invention provides a fuel cell membrane electrode 500 comprising: a proton exchange membrane 5〇2, an anode electrode 504 and a cathode electrode 506. The anode electrode 504 and the cathode electrode 506 are respectively disposed on opposite surfaces of the proton exchange membrane 502. The anode electrode 5〇4 includes a diffusion layer 5〇4a and a biofuel catalyst layer 504b disposed on the surface of the diffusion layer 504a. The biofuel catalyst layer 504b is disposed on at least one surface of the diffusion layer 504a. In the present embodiment, the biofuel catalyst layer 5〇4b is disposed between the diffusion layer 5〇4a and the mass-sub-exchange membrane 502. The membrane electrode 500 is substantially identical in structure to the membrane electrode 400 provided by the second embodiment of the present invention, except that the diffusion layer 5 comprises, for example, a carbon nanotube composite structure. & The carbon nanotube composite structure comprises a nanocarbon structure and a filler material dispersed in the carbon nanotube structure. The filler material is uniformly dispersed in the carbon nanotube structure. The filler material comprises one or more of metal, ceramic, glass and fiber. It can be understood that when the metal is dispersed in the carbon nanotube structure, the conductivity of the carbon nanotube structure can be enhanced. When the filler material is dispersed in the carbon nanotube structure, it is necessary to ensure that the pores of the carbon nanotube structure are not blocked to diffuse the fuel or the oxidant. Alternatively, the tube composite structure comprises - carbon fiber cloth or carbon fiber transfer and dispersion in = or carbon braided _. The _ material fiber 4 carbon tube can increase its guide and _ sex, and increase the carbon fiber, = small and medium size hole _ number, thereby increasing the carbon fiber cloth or carbon _ blanket = ground. Preferably, the addition amount of the carbon nanotubes or the carbon nanotubes in the carbon fiber cloth or the rhyme blanket is Γ~; L 优 201029254 The structure of the cathode electrode 506 and the present invention The cathode electrode 306 of the membrane electrode 300 provided by the first embodiment has the same structure. In this embodiment, the cathode electrode 506 is a composite structure of a carbon nanotube structure and a metal catalyst, and the noble metal catalyst is a ship particle. A fourth embodiment of the present invention provides a biofuel cell comprising: a proton exchange membrane 'anode electrode and a cathode electrode, and the anode electrode and the cathode electrode are respectively placed on opposite surfaces of the proton 3C membrane. a chamber containing biofuel, and the anode electrode is immersed in the biofuel; a baffle is disposed on the surface of the cathode electrode away from the proton exchange membrane; and a gas supply device and an air extraction device They are respectively connected to the deflector. Wherein the anode electrode comprises a diffusion layer and a biofuel catalyst, and the diffusion layer comprises a carbon nanotube structure. Please refer to 12 'specifically' this embodiment provides a biofuel cell 3 using the above fuel cell membrane electrode 300, comprising: a fuel cell membrane electrode 3, an anode chamber 314, a baffle 3 〇8, a current collecting plate 31 and a gas supply and evacuation device 312. The membrane electrode 3 (8) comprises a proton exchange membrane 3〇2, an anode electrode 4 and a cathode electrode 3〇6. The anode electrode 304 and the cathode electrode are respectively disposed on opposite surfaces of the proton exchange membrane 3〇2. The anode electrode 3〇4 is a composite structure of a carbon nanotube structure and an enzyme catalyst. The cathode electrode is a composite structure of a carbon nanotube structure and a noble metal catalyst, and the metal catalyst is granule. The carbon nanotube structure has a complex number of cities. It is to be understood that the working electrode may also be the membrane electrode provided in the second embodiment of the invention or the membrane electrode 5Q0 provided in the second embodiment. 16 201029254 The anode capacity t 314 is disposed on the anode electrode side of the fuel cell membrane electrode 3 for loading the biofuel 316. In this embodiment, the biofuel gw is a glucose solution. The fuel cell membrane electrode 300 separates the biofuel 316 from the oxidant gas' and the anode electrode 3〇4 is immersed in the biofuel 316+ such that the enzyme catalyst can be in contact with the biofuel 316. The baffle 308 is disposed on the surface of the cathode electrode 3〇6 away from the surface of the proton exchange membrane 3〇2 and has one or more luer channels 318′ on the surface of the deflector 3〇8 adjacent to the cathode electrode 3〇6. It is used to conduct oxidant gas and reaction product water. The baffle 308 is made of a metal or conductive carbon material. The current collecting plate 310 is made of a conductive material and is disposed on the surface of the deflector 3〇8 away from the proton exchange membrane 302 for collecting and conducting electrons required for the reaction. It can be understood that in the present embodiment, the current collecting plate 31 is an optional structure because the carbon nanotube structure has good conductivity and can be used to collect current. * The air supply and extraction device 312 includes a blower, a line, a valve, etc. (not shown). The blower is connected to the baffle through a conduit for providing an oxidized hull to the cathode electrode 3〇6. This is a real towel, oxidizing the hull domain oxygen or oxygen-containing air. When the above biofuel cell is operated, the reaction of the bioelectrode 316 (in the case of glucose as a catalyst) is catalyzed by the catalyst 3 at the end of the anode electrode 3〇4: glucose·> gluconic acid. The protons formed by the reaction pass through the proton exchange membrane to reach the cathode electrode 306, and the electrons generated by the reaction enter the external circuit. The cathode electrode 306-end' utilizes its gas supply and extraction means 312 to pass an oxidant gas, such as oxygen, through the baffle 17 201029254 308 to the cathode electrode 306. While oxygen diffuses to the cathode electrode 3〇6, electrons pass through the external circuit to the cathode_pole 306. Under the action of noble metal catalyst, oxygen reacts with protons and electrons as follows: fine 2+2H++2e-h2o. During this process, a certain potential difference is formed between the anode electrodes of the anode electrode 3〇4, and a current is formed when the external circuit is connected to the load for 32 days. The water generated by the reaction is discharged from the biofuel cell through the baffle. 'In summary, the 'issued hair _ has already met the requirements of the invention patent, and has filed a special application for profit. However, the above description is only a preferred embodiment of the present invention, and the scope of the patent application of the present invention cannot be limited thereby. Any equivalent modifications or variations made by those skilled in the art to the spirit of the present invention are within the scope of the patent. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a schematic structural view of a prior art fuel cell. Fig. 2 is a schematic view showing the structure of a membrane electrode according to a first embodiment of the present invention.
圖3為本發明第一實施例提供的作為膜電極的擴散層的夺乎 ❿碳管拉膜的掃描電鏡照片。 H 圖4為圖3中的奈米碳管拉膜中的奈米碳管片段的結構示意 圖5為本發明第一實施例提供的作為膜電極的擴散層的 轉的奈米碳管線的掃描電鏡照y。 圖6為本發明第—實施例提供的作為膜電極的擴散層 AA xl> -riU ^ ^ 的奈未碳纽的柄電鏡照片。 圖7為本發㈣—實關提供的作城電極賴散層的奈米 18 201029254 奴管礦麼膜的掃描電鏡照片。 電極的擴散層的奈米 圖8為本發明第一實施例提供的作為膜 碳官絮化膜的掃描電鏡照片。 圖9為本發明第一實施例提供的表面沈積有翻層的奈米碳管 拉膜的局部掃描電鏡照片。Fig. 3 is a scanning electron micrograph of a carbon nanotube-coated film as a diffusion layer of a membrane electrode according to a first embodiment of the present invention. FIG. 4 is a schematic view showing the structure of a carbon nanotube segment in the carbon nanotube film of FIG. 3 . FIG. 5 is a scanning electron microscope of a rotating carbon nanotube line as a diffusion layer of a membrane electrode according to a first embodiment of the present invention. According to y. Fig. 6 is a photograph of a susceptor electron microscope of a Naibu carbon brand as a diffusion layer of a membrane electrode AA xl> - riU ^ ^ according to a first embodiment of the present invention. Fig. 7 is a scanning electron micrograph of the film of the slave electrode of the nano-distribution layer provided by the (4)-Shiguan. Nanoparticles of the diffusion layer of the electrode Fig. 8 is a scanning electron micrograph of the film carbon-based flocculation film provided in the first embodiment of the present invention. Fig. 9 is a partial scanning electron micrograph of a laminated carbon nanotube film deposited on the surface of the first embodiment of the present invention.
圖10為本發明第二 二實施例的膜電極的結構示意圖。 圖11為本發明第三實施例的膜電極的結構示意圖。 圖12為本發明第四實施例的生物燃料電池的結構示意 【主要元件符號說明】 燃料電極 1 電解層 3 空氣電極 5 電極 11 奈米碳管片段 143 奈米碳管 145 生物燃料電池 30 膜電極 300, 400, 500 質子交換膜 302, 402, 502 陽極電極 304, 404, 504 擴散層 304a, 404a, 504a 生物燃料催化劑 304b 生物燃料催化劑層 404b, 504b 19 201029254 陰極電極 306, 406, 506 導流板 308 集流板 310 供氣和抽氣裝置 312 陽極容室 314 生物燃料 316 導流槽 318 負載 320Figure 10 is a schematic view showing the structure of a membrane electrode according to a second embodiment of the present invention. Figure 11 is a schematic view showing the structure of a membrane electrode according to a third embodiment of the present invention. Figure 12 is a schematic view showing the structure of a biofuel cell according to a fourth embodiment of the present invention. [Main component symbol description] Fuel electrode 1 Electrolytic layer 3 Air electrode 5 Electrode 11 Carbon nanotube segment 143 Carbon nanotube 145 Biofuel cell 30 Membrane electrode 300, 400, 500 proton exchange membrane 302, 402, 502 anode electrode 304, 404, 504 diffusion layer 304a, 404a, 504a biofuel catalyst 304b biofuel catalyst layer 404b, 504b 19 201029254 cathode electrode 306, 406, 506 deflector 308 collector plate 310 gas supply and extraction device 312 anode chamber 314 biofuel 316 guide channel 318 load 320
2020