•1279022 _ 九、發明說明·· 【發明所屬之技術領域】 ·· 、本&明係關於—種直接甲賴料f池構造及其製造 ‘ 方法制疋關於利用—奈米碳管層作為-觸媒層之載體 的直接甲醇簡電池構造及其製造方法。 【先前技術】 f用直接甲醇㈣電池構造及其製造方法，如中華 • 民國公告1232608號「薄型化之平板式直接甲醇燃料電池 結構及其製造方法」發明專利所述，其包含一整合式陰極 電極板、-質子交換膜件單元、—巾間接合層、一整合式 陽極電極板及-流道底板。祕合式陰極電極板設有一第 基材、數個陰極電極區域及數個第一導電通孔，該陰極 、電極區域係以電鍍之方式形成於該第一基材之二侧，且該 陰極電極區域内密佈數個穿孔，而該第一導電通孔係設於 該陰極電極區域以外並以導線連接至該陰極電極區域。該 • 質子交換膜件單元設有數個質子交換膜件，該質子交換膜 件係相對於該陰極電極區域而配置。該中間接合層係由至 少一層接合片〔Bonding Sheet〕所構成，且該中間接合層 設有數個開孔及數個第二導電通孔，該開孔係分別用以容 v 設該質子交換膜件，該第二導電通孔係相對於該第一導電 . 通孔而配置。該整合式陽極電極板設有一第二基材、數個 陽極電極區域及數個第三導電接點，該陽極電極區域係相 對於該陰極電極區域而配置，該第三導電接點儀相對於該 第一導電通孔而配置。 * 1279022 然而，在實際製造上，由 =猶之基材係先進 Γ密佈之該數個穿孔，因而相對增加 構足複雜度、製程困難度，以致降低製程效率。此外，由 於該穿孔之尺寸及密度亦相對受限於鑽孔製程 相對限制電池供電效能。因此，其確實有^要進一丁步改^ 上述直接T醇燃料電池構造及其製造方法。 又 有鑑於此，本發日狀良上述之缺點，其係在一夺米 ，管層之至少-侧形成至少—觸媒層，以分別製成一第一 單元及一第二單元。接著，將該第-單元、第二單无及一 流場板依序結合於一質子交換膜之二侧’以共同組成-ί 、料電池。該奈米碳管層確實可相對提升電化學反應接觸面 積及相對提升該燃料電池之供電能力。 【發明内容】 本發明主要目的係提供一種直接甲醇燃料電池構造 及其製造方法’其係在-奈米碳管層之至少_侧形成一觸 媒層’使得本發明具有提升燃料電池之電化學反應接觸面 積的功效。 本發明次要目的係提供一種直接甲醇燃料電池構造 及其製造方法，其係在一基板上形成一奈米碳管層，並利 用至少一蚀刻液洗除該基板，如此該奈米碳管層之二側用 以分別形成一觸媒層，使得本發明具有減少燃料電池厚度 的功效。 本發明另一目的係提供一種直接、曱醇燃料電池構造•1279022 _ IX, invention description·· 【Technical field to which the invention belongs】 ······················································· - Direct methanol cell structure of a carrier of a catalyst layer and a method of manufacturing the same. [Prior Art] f Direct methanol (four) battery structure and its manufacturing method, as described in the invention patent of "China's Republic of China Announcement No. 1232608 "Thin-type flat-type direct methanol fuel cell structure and its manufacturing method", which includes an integrated cathode The electrode plate, the proton exchange membrane unit, the inter-belt joint layer, an integrated anode electrode plate and a flow channel bottom plate. The cathode electrode plate is provided with a first substrate, a plurality of cathode electrode regions and a plurality of first conductive vias. The cathode and electrode regions are formed on the two sides of the first substrate by electroplating, and the cathode electrode A plurality of perforations are densely arranged in the region, and the first conductive vias are disposed outside the cathode electrode region and are connected to the cathode electrode region by wires. The proton exchange membrane unit is provided with a plurality of proton exchange membranes, and the proton exchange membrane is disposed relative to the cathode electrode region. The intermediate bonding layer is composed of at least one bonding sheet, and the intermediate bonding layer is provided with a plurality of openings and a plurality of second conductive vias for respectively accommodating the proton exchange membrane. The second conductive via is disposed relative to the first conductive via. The integrated anode electrode plate is provided with a second substrate, a plurality of anode electrode regions and a plurality of third conductive contacts, wherein the anode electrode region is disposed relative to the cathode electrode region, and the third conductive contact device is opposite to the cathode conductive electrode region. The first conductive via is disposed. * 1279022 However, in actual manufacturing, the number of perforations of the substrate is advanced, so that the complexity of the structure and the difficulty of the process are relatively increased, so that the process efficiency is reduced. In addition, since the size and density of the perforations are relatively limited by the drilling process, the battery power supply efficiency is relatively limited. Therefore, it does have to be changed to the above-mentioned direct T-alcohol fuel cell structure and its manufacturing method. In view of the above, the above-mentioned shortcomings of the present invention are to form at least a catalyst layer on at least one side of the tube layer to form a first unit and a second unit, respectively. Next, the first unit, the second unit and the flow field plate are sequentially bonded to the two sides of a proton exchange membrane to form a battery. The carbon nanotube layer does increase the electrochemical reaction contact area and relatively enhance the power supply capability of the fuel cell. SUMMARY OF THE INVENTION The main object of the present invention is to provide a direct methanol fuel cell structure and a method for fabricating the same, which form a catalyst layer on at least the side of the carbon nanotube layer, so that the present invention has an electrochemical cell for improving the fuel cell. The effect of the reaction contact area. A secondary object of the present invention is to provide a direct methanol fuel cell structure and a method of fabricating the same, which comprises forming a carbon nanotube layer on a substrate and washing the substrate with at least one etching solution, such that the carbon nanotube layer The second side is used to form a catalyst layer, respectively, so that the present invention has the effect of reducing the thickness of the fuel cell. Another object of the present invention is to provide a direct, sterol fuel cell construction
CiNLindeNPK Pat\PI99I7. doc ~ 6 ~ 05/10/20/12:04 V* -1279022 及其製造方法’其係在一奈米碳管層之至少一侧形成至少 一觸媒層，以分別製成一第一單元及一第二單元，及將該 第一單元、第二單元及二流場板結合於一質子交換膜之二 侧，以共同組成一燃料電池，使得本發明具有提升該燃料 電池供電能力之功效。 根據本發明之直接曱醇燃料電池構造及其製造方法 ，其包含步驟：在一基板上形成一奈米碳管層，並利用至 少一蝕刻液洗除該基板；在該奈米碳管層之至少一侧形成 至少一觸媒層，以分別製成一第一單元及一第二單元；及 將5亥第一及第^一早元分別結合於一質子交換膜之二側，再 將二流場板分別結合於該第一及第二單元遠離該質子交換 膜之一侧，以共同組成一燃料電池。 f【實施方式】 為讓本發明之上述及其他目的、特徵、優點能更明 顯易懂’下文特舉本發明之較佳實施例，並配合所附圖式 ’作詳細說明如下： 請參照第2A至2D圖所示，本發明較佳實施例之直 接甲醇燃料電池構造及其製造方法之第一步驟，其係在一 基板10上形成一奈米碳管層丨，並利用至少一蝕刻液〔 未‘示〕洗除該基板1〇。如第2A圖所示，該基板1〇較 佳係選自石夕晶圓〔Si wafer〕。如第2B圖所示，其較佳係 學氣相沉積法在該基板1G上長成適當長度之該奈 米石反官層卜如2C圖所示，該奈米碳管層〗遠離該基板 1〇之一侧係選擇結合一支撐架π，以供後續支撐該奈米 1279022 碳管層卜言亥支撲架u較佳係選自抗腐騎f〔例如塑 勝，材質〕’以避免在後續侧製程中發生腐餘之情形。 接著，如第2C圖所示’利用該蝕刻液蝕刻該基板1〇，該 ^刻液較佳係選自氫氧倾〔咖〕溶液，以便洗除該 土杈10，如此有利於減少燃料電池整體厚度。如第2D圖 处八^元成钮刻之後’该奈米碳管層1之另一侧可選擇 結合另一支撐架11，。 甲拉請參照第ZE及3圖所示’本發明較佳實施例之直接 電池構造及其製造方法之第二步驟，其係在該奈 二至少一側形成至Γ觸媒層21'22，以分 該觸拔爲Μ早70二及第一單70 b〔如第3圖所示〕。 ^屏、9、22触係獅以雜之枝軸於該奈米 二&曰1之至少’表面或二侧表面竭 2，直接《料辟„、„，；或鄉^鍵前 ==架u、lr。再者，位於該燃料電池〔未標 白&齡_第-單元a之觸媒層2卜η較佳係選 金WU〕朗；位於該燃料電池之陰極側的 2Γ ' Uu 照Ϊ 3圖所示’本發明較佳實施例之直接甲醇 池構造^其製造方法之第三步驟，其係將該第-及 a、Γί別結合於一質子交換膜4之二侧，再將 二=3、3分別結合於該第一及第Μ 、子父換膜4之—側，以共同組成—軸電池〔未標示〕CiNLindeNPK Pat\PI99I7. doc ~ 6 ~ 05/10/20/12:04 V* -1279022 and its manufacturing method's which form at least one catalyst layer on at least one side of a carbon nanotube layer, respectively Forming a first unit and a second unit, and combining the first unit, the second unit and the two flow field plates on two sides of a proton exchange membrane to jointly form a fuel cell, so that the invention has the fuel The power of battery power. A direct sterol fuel cell structure and a method of fabricating the same according to the present invention, comprising the steps of: forming a carbon nanotube layer on a substrate, and washing the substrate with at least one etching solution; in the carbon nanotube layer Forming at least one catalyst layer on at least one side to form a first unit and a second unit, respectively; and combining the first and the first early elements of the 5 Hai to the two sides of a proton exchange membrane, respectively The field plates are respectively coupled to the first and second units away from the side of the proton exchange membrane to collectively form a fuel cell. The above and other objects, features, and advantages of the present invention will become more <RTIgt; </ RTI> <RTIgt; </ RTI> <RTIgt; </ RTI> <RTIgt; 2A to 2D are diagrams showing a first step of a direct methanol fuel cell structure and a method of fabricating the same according to a preferred embodiment of the present invention, which comprises forming a carbon nanotube layer on a substrate 10 and using at least one etching solution. [Not shown] The substrate 1 is washed away. As shown in Fig. 2A, the substrate 1 is preferably selected from the group consisting of Si wafers. As shown in FIG. 2B, the preferred vapor deposition method is formed on the substrate 1G to form an appropriate length of the nano-striped anti-official layer, as shown in FIG. 2C. The carbon nanotube layer is away from the substrate. One side of the 1〇 side is selected to be combined with a support frame π for subsequent support of the nano 1709022 carbon tube layer. The bunhai branch is preferably selected from the anti-corrosion ride f (eg plastic win, material) to avoid The situation of corruption occurs in the subsequent side process. Next, as shown in FIG. 2C, the substrate 1 is etched by the etching solution, and the etching solution is preferably selected from a hydrogen peroxide solution to wash off the soil 10, thereby facilitating the reduction of the fuel cell. Overall thickness. The other side of the carbon nanotube layer 1 may be optionally joined to another support frame 11 as shown in Fig. 2D. Please refer to the second step of the direct battery structure and the manufacturing method thereof according to the preferred embodiments of the present invention, as shown in FIGS. ZE and 3, which are formed on the at least one side of the nanosole to the germanium catalyst layer 21'22. In order to distinguish the touch, it is 702 and the first single 70b (as shown in Figure 3). ^ screen, 9, 22 touch the lion with a miscellaneous branch axis on the surface of the nano 2 & 1 at least 'surface or two sides of the surface 2, direct "material „, „,; or township ^ key before == U, lr. Furthermore, the fuel cell (not labeled & age_the first cell a of the catalyst layer 2 is preferably selected as the gold WU); the second side of the fuel cell is located at the cathode side of the U? The third step of the method for manufacturing a direct methanol cell structure according to a preferred embodiment of the present invention, which combines the first and a, and the two sides of a proton exchange membrane 4, and then two = 3 And 3 are respectively combined on the side of the first and third and the sub-family to change the film 4 to form a shaft battery (not labeled)
c:、Lindn、W 加、_7.細 —8 — 1279022 。藉此，該質子交換膜4、第-單元a、第二單元b及二 流場板3、3’係共同組成該燃料電池。 請參照第4A至4E圖所示，其揭示本發明較佳實施 例之流場板3之製造方法，其包含步驟··⑴、如第4A 圖所示’其係利用丙酮清洗一石夕晶圓3〇〔即晶圓板〕，再 利用異丙醇清洗丙酮，並適當去水烘烤一段時間；〔2〕、 如第4B圖所示，在該石夕晶圓3〇表面機錄一銅金屬薄_ ’以作為金屬犧牲層；〔3〕、如第4C圖所示，利用一阳_ 8光阻32〔即高分子正光阻或稱為第―高分子光阻〕塗佈 於該銅金屬薄膜之表面，該购光阻％先塗佈約· /zrn之厚度’再依序進行旋轉句化、烘烤等處理；〔叫、c:, Lindn, W plus, _7. fine — 8 — 1279022. Thereby, the proton exchange membrane 4, the first unit a, the second unit b, and the two flow field plates 3, 3' together constitute the fuel cell. Referring to FIGS. 4A to 4E, there is disclosed a method for manufacturing a flow field plate 3 according to a preferred embodiment of the present invention, which comprises the steps of (1), as shown in FIG. 4A, which is used to clean a wafer wafer with acetone. 3〇 [ie wafer board], then wash the acetone with isopropyl alcohol, and bake it properly for a period of time; [2], as shown in Figure 4B, record a copper on the surface of the 3D wafer The metal thin _ 'as a metal sacrificial layer; [3], as shown in Fig. 4C, is coated on the copper by a yang 8 photoresist 32 (i.e., a polymer positive photoresist or a first polymer photoresist) On the surface of the metal film, the purchased photoresist is first coated with a thickness of about · / zrn ' and then sequentially rotated, sentenced, baked, etc.;
如第，圖所示’對該SU-8光阻32進行曝光及利用顯影 液進行顯影，以形成數個微孔32〇 ;〔5〕、如第犯圖所示 ，利用-AZ光阻33〔即高分子負光阻或稱為第二高分子 光阻〕塗佈於該⑽光阻32之表面，藉此該仏光阻33 填入該微孔3則及部分覆蓋於該_紘32表面；〔 ==4F _示’ _ AZ光阻33進行曝光及利用顯 ,衫液進行顯影，以除去覆蓋於該_雜32表面之該Μ 光阻33，但仍保留該微孔32〇内之az光阻33部份π =第4G圖所示’在該ΑΖ光阻33之表面鍍一純金金 屬薄膜34〔即金屬電極層〕；〔8〕、如第4Η圖所示，利用 =〔即第-溶液〕侧該ΑΖ光阻33，由於該純金金屬 =34僅與該SU_8植η形錢_結，且該純金金 屬薄膜34與該AZ核33未形成共價鍵結，藉此丙嗣可 —9 C:\Liwta\PK P»t\PK9fll7. doc 05/10/20/1¾.〇4 p 1279022 洗除該純金金屬薄膜34對應於該微孔320之部位，同時 進一步洗除該微孔320内之該AZ光阻33 ;及〔 9〕、如第 41圖所示’利用氣化鐵溶液〔即第二溶液〕蝕刻該銅金屬 薄膜31，藉此可洗除該銅金屬薄膜31及矽晶圓3〇，並保 留該SU-8光阻32及純金金屬薄膜34共同形成該流場板 3。同時，可利用相同之製造方法形成另一該流場板3,〔 如第3圖所示〕。As shown in the figure, the SU-8 photoresist 32 is exposed and developed with a developing solution to form a plurality of micropores 32; [5], as shown in the first diagram, using the -AZ photoresist 33. [ie, a polymer negative photoresist or a second polymer photoresist] is applied to the surface of the (10) photoresist 32, whereby the photoresist 33 is filled into the micropores 3 and partially covered by the 纮32 Surface; [ == 4F _ shows ' _ AZ photoresist 33 for exposure and utilization, the shirt liquid is developed to remove the Μ photoresist 33 covering the surface of the 杂 30, but still retain the micropore 32 〇 The az photoresist 33 is partially π = shown in Fig. 4G. A pure gold metal film 34 (i.e., a metal electrode layer) is plated on the surface of the photoresist 33; [8], as shown in Fig. 4, using = [ That is, the first solution - the side of the photoresist, 33, since the pure gold metal = 34 is only associated with the SU_8, and the pure gold metal film 34 and the AZ core 33 do not form a covalent bond, thereby嗣可—9 C:\Liwta\PK P»t\PK9fll7.doc 05/10/20/13⁄4.〇4 p 1279022 Wash the pure gold metal film 34 corresponding to the portion of the microhole 320 while further washing the The AZ light in the microhole 320 33; and [9], as shown in Fig. 41, etching the copper metal film 31 by using a vaporized iron solution (i.e., a second solution), whereby the copper metal film 31 and the germanium wafer 3 are washed away, and The SU-8 photoresist 32 and the pure gold metal film 34 are retained to form the flow field plate 3. At the same time, another flow field plate 3 can be formed by the same manufacturing method, as shown in Fig. 3.
請參照第5圖所示，當本發明較佳實施例之直接甲 醇燃料電池構造進行電化學反應時，其係將一曱醇〔 CHsOH〕水溶液經由位於陽極之該流場板3的微孔320 流入該燃料電池〔未標示〕内部。接著，該曱醇水溶液係 依序經由該觸媒層22及奈米碳管層丨均勻擴散至該觸媒 丨層21。此時，至少該觸媒層21之部位係產生電化學反應 ’例如1莫耳〔mole〕曱醇與Λ莫耳水〔Η"〕混合，將 產生6個氫離子〔 H+〕、6個電子〔e·〕及i莫耳二氧化碳 〔ccy〕。接著，由於氫離子受到陽極及陰極之間所形成 =電場及該質子交換膜4之孔璧〔未標示〕狀負電荷的 〜響’使彳于氫離子經過該質子交換膜4移動至陰極。位於 陽極之該觸媒層21所產生之電子係依序經由該奈米碳管 層1、觸媒層22、流場板3及一外接電路〔未標示〕到達 位於陰極之該流場板3,、觸媒層22，、奈米碳管層1，及 觸媒層21’。此時，陰極則進行氧氣〔02〕之還原反應， 亦即該燃料電池外部之氧氣進入該燃料電池内並與氫離子 反應，以產生水分子排出該燃料電池外。藉由提供充足之 C:\Linda\PK PHINPK99I7.4«Referring to FIG. 5, when the direct methanol fuel cell structure of the preferred embodiment of the present invention is subjected to an electrochemical reaction, the aqueous solution of monodecyl alcohol [CHsOH] is passed through the micropores 320 of the flow field plate 3 located at the anode. Flow into the inside of the fuel cell [not shown]. Then, the aqueous sterol solution is uniformly diffused to the catalyst layer 21 via the catalyst layer 22 and the carbon nanotube layer. At this time, at least the portion of the catalyst layer 21 is electrochemically reacted, for example, 1 mole of sterol and Λmol water [Η", which will produce 6 hydrogen ions [H+], 6 electrons. [e·] and i mol carbon dioxide [ccy]. Then, hydrogen ions are subjected to an electric field formed between the anode and the cathode and a hole 璧 [unlabeled] negative charge of the proton exchange membrane 4, so that hydrogen ions move to the cathode through the proton exchange membrane 4. The electrons generated by the catalyst layer 21 at the anode are sequentially passed through the carbon nanotube layer 1, the catalyst layer 22, the flow field plate 3, and an external circuit [not shown] to the flow field plate 3 at the cathode. , the catalyst layer 22, the carbon nanotube layer 1, and the catalyst layer 21'. At this time, the cathode performs a reduction reaction of oxygen [02], that is, oxygen outside the fuel cell enters the fuel cell and reacts with hydrogen ions to generate water molecules to be discharged outside the fuel cell. By providing sufficient C:\Linda\PK PHINPK99I7.4«
05/10/20/12:04 I»M —— 10 — .1279022 且整 該曱醇水溶液及氧氣，該燃料電池可持續產生電# 體僅產生無害環境之二氧化碳及水分子。 如上賴，減於制直接甲醇燃料電池構盆 製造方法係預先在該基材上進行鑽孔作業，因而相對^ 製程困難度及降低製概率。此外，藉由·作業所开^ 之該穿孔的尺寸及密度亦姆受限，_降低_料㈣ 之電化學反應面積，進而造成降低該燃料電池之处 _ 特點，第2圖之本翻該奈米碳管層ι作為該^ 反應接觸 層21、22之-载體，其確實可相對增加電化學 、 面積及相對縮小該燃料電池之整體尺寸。05/10/20/12:04 I»M —— 10 — .1279022 And the whole aqueous solution of sterol and oxygen, the fuel cell can continuously produce electricity and only produce environmentally friendly carbon dioxide and water molecules. As described above, the manufacturing method of the direct methanol fuel cell basin is performed on the substrate in advance, thereby making it difficult to control the process and reducing the probability of production. In addition, the size and density of the perforation by the operation are limited, and the electrochemical reaction area of the material (4) is reduced, thereby causing a decrease in the fuel cell _ characteristics, and the second figure is turned over. The carbon nanotube layer ι acts as a carrier for the reaction contact layers 21, 22, which does increase the electrochemical, area and relative reduction of the overall size of the fuel cell.
雖然本發明已則上述較佳實施觸示，然 „發明’任何熟習此技藝者，在不脫離本發J 以二當可作各種更動與修改，因此本發明之 保錄圍請補範_界定者為準。 1279022 【囷式簡單說明】 第1圖：本發明較佳實施例之直接曱醇燃料電池構造 及其製造方法之流程方塊圖。 第2A至2E圖：本發明較佳實施例之直接曱醇燃料電 池構造的奈米碳管層及觸媒層之製造方法的側視圖。 第3圖：本發明較佳實施例之直接甲醇燃料電池構造 之組合剖視圖。 第4A至41圖：本發明較佳實施例之直接曱醇燃料電 池構造的流場板之製造方法的側視圖。 第5圖：本發明較佳實施例之直接曱醇燃料電池構造 進行電化學反應之示意圖。Although the present invention has been described above as a preferred embodiment, the invention may be modified and modified without departing from the scope of the present invention. 1279022 [Simplified simplification] Fig. 1 is a block diagram showing the structure of a direct sterol fuel cell and a method for manufacturing the same according to a preferred embodiment of the present invention. Figs. 2A to 2E are diagrams showing a preferred embodiment of the present invention. Side view of a method for producing a carbon nanotube layer and a catalyst layer of a direct oxime fuel cell structure. Fig. 3 is a sectional view showing a combination of a direct methanol fuel cell structure according to a preferred embodiment of the present invention. Figs. 4A to 41: A side view of a method of fabricating a flow field plate of a direct sterol fuel cell construction in accordance with a preferred embodiment of the invention. FIG. 5 is a schematic illustration of an electrochemical reaction of a direct sterol fuel cell configuration in accordance with a preferred embodiment of the present invention.
【主要元件符號說明】[Main component symbol description]
1 奈米碳管層 V 奈米碳管層 10 基板 11 支撐架 11， 支撐架 21 觸媒層 22 觸媒層 21’觸媒層 22’觸媒層 3 流場板 3， 流場板 30 矽晶圓 31 銅金屬薄膜 32 SU-8光阻 320 微孔 33 AZ光阻 34 純金金屬薄膜 4 質子交換膜 a 第一單元 b 唆一四一 弟一早7L C:\Linda\PK Pat\PK99l7.doc —12 —1 carbon nanotube layer V carbon nanotube layer 10 substrate 11 support frame 11, support frame 21 catalyst layer 22 catalyst layer 21 'catalyst layer 22' catalyst layer 3 flow field plate 3, flow field plate 30 矽Wafer 31 Copper metal film 32 SU-8 photoresist 320 Micro hole 33 AZ photoresist 34 Pure gold metal film 4 Proton exchange membrane a First unit b 唆一一一弟早早 7L C:\Linda\PK Pat\PK99l7.doc —12 —