M274656 八、新型說明： 【新型所屬之技術領域】 本創作係-種具引出導線之細管型 兀，係指在圓管型質子導通膜内外 ，，且口早 具引出導線的導電敷層管，經加熱二 之細管型薄膜電極組合單元，可應用於燃料電池、贿^8線 【先前技術】 習：的高分子電解膜製成之氫氣燃料電池⑽fc)由於 直去克服1111燃料儲存與運補的困難，致使直接甲醇 燃料電池⑽《成為後繼最具市場潛力㈣料電池能源項 :之一。但是直接甲醇燃料電池⑽FG)受限於其對應之薄膜 極組合(MEA)的單位面積出電功率遠不如氫氣燃料 成為發展上的—項弱點。f之—種解決的方法為 增加單位體積内的薄膜電極組合(_面積數量，細管型薄 ^電極組合的幾合結構便是具有較多膜面積的最佳設計之< —，此原理已應用在氫氣燃料電池（PEMFC)的研製上，如美 國專利US 3, 228, 797，係針對氫氣燃料電池已說明具有增加 膜面積之功效’其原理在直接甲醇燃料電池（，〇依然適 用。後繼發展的細管型電極觸媒塗敷方法，如美國專利肋 ^ 331’758及US 3, 351，487 ’係以化學鑛膜搭配後續電解槽 電鑛的方式，其中舰之!D著性與觸媒經電解製程產生觸媒 催化特性變易等，為廣受爭議且一直未見上市之可能原因。 M274656 出導她)包括薄膜與電極組合之後的引 ⑽3,423,243，㈣疋上^專利不足的地方。如美國專利 焊接到刷域的方法，^插軸線，並在軸線上配接側線或 燃料電池以〜1 官内的流體阻力’在當時氫氣 軋怨進料的流體阻力或可不予重 1:=Γ(_)等類，以液體為進料的實用上:阻力= -次插桿導:。二在製程上’-次觸媒製獏’加上另 係-種具_線::;型=有電本創作 引出導㈣道“ 玉/專膜電極組合早7L’其設計使具 =純者官膜壁面貼管引出，具有不阻塞心轴空 間，〉又有側刷絨毛等阻力之優點。 【新型内容】 .…本11作係提供—種具引出導線之細管型薄膜電極組合 2:本1作係將含顆粒狀_系高分子離子化合物或碳氣 t機=子之離子化合物之高分子以融擠法經高溫融播製 成官型貝子父換膜原胚’該管型質子交換膜原胚，經離子交 換法轉型為—具質子交換功能之圓管型質子導通膜（PEM)， 該離子交換法轉型的程料，至少含有—㈣酸型化合物藥 劑或強鹼型與一種強酸型化合物在轉型程序中使用；在圓管 型質子導通膜（圈的管内壁塗敷—電極觸賴液，該電極 觸媒衆液中含有氟碳系離子化合物或碳氫類離子化合物之 6 M274656 ^夜或此σ ;^與燃料電池用觸媒（或電極觸媒及其載體）妹 超音波_或機械婦，成泥聚狀固液混合物，或含氣體: 内的αι氣相均勾混合物的調製’使該電極觸媒衆液介於具 引出導$的導電敷層管(或孔管)與該圓管型質子導通膜 (PEM)的g内壁之間。另’使另—電極觸媒漿液敷 管 壁與另一具引出導線的導電敷層 :(或孔官)之間。插入模具内桿使圓管型質子導通膜⑽） μ璧之具引出導線的導電敷層管（或孔管）擴大貼合圓管 型質^導通膜(ΡΕΜ)的管内壁，並收合圓管型質子導通膜· (PEM)官外之具引出導線的導電敷層管（或孔管），最後置入 於，.’、C膜具中壓合，使電極衆液將圓管型質子導通膜 (PEM) t極觸媒及具引出導線的導電敷層管緊密貼合，一 體完成-具引出導線之細管型薄膜電極組舍單元，可應用於 燃料電池，尤其是液態燃料（如DMFC)之用。 【實施方式】 α…本㈤作係提供種具引出導線之細管型薄膜電極組合 單元，其細官型薄膜電極組合單元之材料製備如下： 1·具引出導線的導電敷層管（或孔管）1 ·· 本創作選用管型編織之導電碳纖維織管，以24股之碳 纖編織^，置於Naflon溶液SE 5112或Teflon 含浸乾 固成擴官4〜5mm尺寸做為圓管型質子導通膜（pEM)管外璧之 具引出導線的導電敷層管（或孔管）。 2·電極觸媒漿液 2 M274656 本創作以DMFC常用之陰陽極觸媒電極用料為例，取陽 極觸媒 Pt/Ru/C，60/30/10，（Johnson Matthey，Hispec #6000)配 pt/Ru/C，30/15/55，（J〇hns〇nMatthey，Hispec #7000)及 Nafion Solution(Dupont SE： 5112)，重量混合比 例為1:1:10 ,在超音波均質機均勻混合成漿泥狀後，供為 陽極觸媒漿料，做為圓管型質子導通膜（pEM)之管外璧的電 極觸媒漿液。 3·圓管型質子導通膜（PEM) 3 本創作之圓管型質子導通膜係指可以為任何可做為質籲 子父換膜的材料。以Nafion融擠型原料（如R11〇〇或 R1 000)，在250 °C下熱融擠，經環型擠製模頭，環型内管吹 入氮氣，播出之R11〇〇或R1 〇〇〇成為内部中空的細管，經冷 部捲取，為本創作使用之圓管型質子導通膜材，調整RU〇〇 或R1 000膠粒的進料量與氮氣的吹入量及捲取的收線速度 可得各式不同尺寸管徑與壁厚的細管。本創作取Rn〇〇, 1/8// 顆粒狀膠粒，以Randcastle螺桿融擠機（M〇del RCp—〇5〇〇)， 進料螺杯轉速〇· 75rpm ,拉速〇.45ft/min，吹氮氣 3.45cc/min可得管徑2_，膜厚〇· 1_之中空細管融擠製成 圓官型質子導通膜。將圓管型質子導通膜取15公分長，經 以15%K0H及35%DMS0在6(TC至80t自該圓管型質子導通^ 之管内與管外同時浸潤卜4小時，再以去離子水洗淨，至少 洗淨二回，再以15%HN03反覆浸潤與水洗至少二回，得一圓 管型質子導通膜（PEM)。 4·電極觸媒漿液 4 M274656 本創作以DMFC常用之陰陽極觸媒電極用料為例，取陰 極觸媒以 Pt/C，50/5〇，（Johnson Mat they #8000)及 Naf ion S〇luti〇n(Dupont SE 5112)重量混合比例為1:1〇，經超音 波均質機（Sonifier，Branson Ultrasonics，Model 250) 均勻混合成漿泥狀後，供為陰極觸媒漿料，做為圓管型質子 導通膜（PEM)之管内璧的電極觸媒漿液。 5·具引出導線的導電敷層管（或孔管）5 本創作選用管型編織之導電碳纖維織管，以16股之碳 纖編織管，置於Nafion溶液SE 5112或Teflon 30B乾固成· 縮管0.8〜1.2mm尺寸做為圓管型質子導通膜（pEM)管内璧之 具引出導線的導電敷層管（或孔管）。 上述之電極觸媒漿液為燃料電池適用之電極觸媒，專指 直接曱醇燃料電池適用之觸媒及包含貴金屬系狀觸媒，^ 貝金屬系列之觸媒係特指包含鉑金屬在内之觸媒。而上述之 具引出導線的導電敷層管，以導電材編織製成孔洞、網格之 方式，具有可通過氣體、非氣體阻絕性之特徵，且在未與圓 官型質子導通膜做成組合單元之前具有可伸縮之特性外觀春 型狀，形成具有管型、管壁有空隙可通透氣體之具引出 的導電敷層管。 '' 請參閱『第1〜3圖』所示，係本創作之正視圖、本創 作之側視圖、本創作之立體圖。如圖所示：係指在圓管型質 子導通膜（ΡΕΜ) 3的管㈣塗敷—電極觸媒漿液4，該介於 具引出導線的導電敷層管（或孔管）5與該圓管型質 謂咖管内壁之間，完成插内管之中間品。使另：二 9 M274656 極觸媒聚液敷2在該圓管型質子導通膜（pEM) 3之管外壁與 另一具引出導線的導電敷層管（或孔管）1之間，並將該圓管 型貝子導通膜（PEM) 3空留兩端為無陽極觸媒塗敷區，作為 MEA組裝成電池時之配接之用。插入模桿直徑為15咖之模 ί内桿’使具引出導線的導電敷層管（或孔管）5擴大貼合圓 官型質子導通膜（ΡΕΜ) 3的管㈣，並收合具引出導線的導 電敷層管U孔管U，最後置入於熱壓膜具中，使模具均勻 升溫至12G〜127°c〔圓管型f子導通膜的玻璃轉移溫度㈤ 至融點溫度（Tm)之間。〕’ 3〜5分鐘，模具壓力大於如/㈣修 以上壓合’使將圓管型質子導通膜（pEM)、電極觸媒及且引 出導：的導電敷層管緊密貼合，一體完成一具引出導線之細 官型薄膜電極組合單元。如第3圖所示，引出導線H 5可視再接線之需求剪裁成較細小之導線。該具引 線之、’.田s型核電極組合單元之外圍之直徑與管厚範圍如 U.)外圍之直徑範圍介於1随至5cm之間，管厚介於 :，1。倍直fe至0.45倍直徑之間或〇 〇5mm至〇 45倍直徑之 (2.)外圍之直徑範圍介於2随至3cm 〇. 1倍直徑至〇 4S位古"+ S与"於 .45 L直偟或〇. 〇7mm至〇 45倍直徑之間。 )外圍之直彳空範圍介於3_至2cm之間，管厚 倍直徑至。.45倍直徑或0.1随至0.45倍直徑之間。、. 惟以上所述者’僅為本發明之較 以此限定本發明實斿$浐R c田不月匕 貫％之摩巳圍，故，凡依本發明申請專利範圍 M274656 及發明說明書内容所作之簡單的等效變化與修飾，皆應仍屬 本發明專利涵蓋之範圍内。 M274656 【圖式簡單說明】 第1圖 本創作之正視圖 第2圖 本創作之側視圖 第3圖本創作之立體圖 【主要元件符號說明】 具引出導線的導電敷層管（或孔管）1 電極觸媒聚液 2、4 圓管型質子導通膜.3、5 極觸媒漿液 4 引出導線 1 . a、5. a 係指具引出導線的導電敷層管（或孔管）的尾端，預留 做為導出線長度與數量的具引出導線的導電敷層管（或 孔管）之延伸部份，亦即為本創作之引出導線。M274656 8. Description of the new type: [Technical field to which the new type belongs] This creative type is a thin tube type with a lead wire, which refers to a conductive laminated tube with a lead tube inside and outside the proton conducting membrane, and a lead wire leading to the mouth. The thin-tube thin-film electrode combination unit after heating can be applied to fuel cells and wires. [Previous technology] Xi: Hydrogen fuel cell made of polymer electrolyte membrane (fc) Because it has been to overcome the 1111 fuel storage and transportation Difficulties caused direct methanol fuel cells to become one of the most promising battery energy sources in the future: However, the direct methanol fuel cell (FG) is limited by its corresponding thin-film electrode assembly (MEA). The output power per unit area is far inferior to that of hydrogen fuel. This has become a development weakness. f—A solution is to increase the number of thin-film electrode combinations per unit volume (_area number, thin tube-type thin electrode combination is the best design with more film area < —, this principle has been It is applied to the development of hydrogen fuel cells (PEMFC), such as US Patent No. 3,228,797, which has been shown to have the effect of increasing the membrane area for hydrogen fuel cells. Its principle is still applicable to direct methanol fuel cells. Developed thin tube electrode catalyst coating methods, such as U.S. patent ribs 331'758 and US 3,351,487 'are chemical ore membranes and subsequent electrolytic cell power ore methods, of which the surface and contact The catalytic properties of the catalyst produced by the electrolytic process are changed, which is widely controversial and has not been seen as a possible reason for listing. M274656 leads her) Including 3,423,243 after the combination of film and electrode, the lack of patents For example, the method of welding to the brush field in the U.S. patent, inserting the axis, and attaching a side line or a fuel cell on the axis with a fluid resistance of ~ 1 in the official's fluid resistance at the time of the hydrogen rolling may or may not Weight 1: = Γ (_) and other types, practical use of liquid as feed: resistance =-secondary plunger guide: two in the process '-secondary catalyst system 貘' plus another line-species with _ line ::; Type = An electric book creation leads to the guideway "The jade / special membrane electrode combination is as early as 7L ', and its design enables = pure official membrane wall sticking tube to lead out, which does not block the mandrel space, and has side brush fluff The advantages of equal resistance. [New content] ... This 11 series provides-a thin tube type thin film electrode combination with a lead wire 2: This 1 series will contain granular _ series of polymer ion compounds or carbon gas The polymer of the ionic compound is melted and extruded at high temperature to produce the official mother-of-pearl replacement membrane protoembryo. The tubular proton exchange membrane protoembryo is transformed by ion exchange into a proton-exchange round tube proton Conduction membrane (PEM), a process material for the ion-exchange conversion process, which contains at least a phosphonate-type compound agent or a strong base-type compound with a strong acid-type compound for use in the transformation process; Coating—electrode contact solution, which contains fluorocarbon-based ionic compounds or hydrocarbons 6 of the ionic compounds M274656 ^ night or this σ; ^ and ultrasonics of fuel cell catalysts (or electrode catalysts and their carriers) _ or mechanical women, into a mud-like solid-liquid mixture, or containing αι The modulation of the gas-phase homogeneous mixture 'causes the electrode catalyst liquid to be interposed between the conductive coating tube (or perforated tube) with a lead and the inner wall of the circular tube-type proton conducting membrane (PEM). Another' Make another-between the electrode catalyst slurry coating tube wall and another conductive coating: (or hole official) with a lead wire. Insert the inner rod of the mold to make the tube-shaped proton conductive membrane ⑽) μ 璧 conductive with lead wire The laminated tube (or perforated tube) enlarges the inner wall of the tube and attaches the tube-shaped proton conductive film (PEM), and collapses the tube-shaped proton conductive film (PEM). Or hole tube), and finally put it in the. ', C membrane with pressure, so that the electrode liquid will closely adhere the round tube-type proton conduction membrane (PEM) t-pole catalyst and the conductive coating tube with the lead wire , One-piece complete-thin-tube type thin-film electrode assembly unit with lead wires, which can be applied to fuel cells, especially liquid fuels (such as DMFC) Use. [Embodiment] [...] The present invention provides a thin tube type thin film electrode combination unit with a lead wire, and the material of the thin official type thin film electrode combination unit is prepared as follows: 1. A conductive coating tube (or a hole tube) with a lead wire ) 1 ·· This selection uses a tubular braided conductive carbon fiber braided tube, braided with 24 strands of carbon fiber ^, placed in Naflon solution SE 5112 or Teflon impregnated dry solidification expansion 4 ~ 5mm size as a round tube proton conduction membrane (PEM) A conductive cladding tube (or perforated tube) with a lead wire outside the tube. 2 · electrode catalyst slurry 2 M274656 This work takes the anode and cathode catalyst electrode materials commonly used in DMFC as an example, taking the anode catalyst Pt / Ru / C, 60/30/10, (Johnson Matthey, Hispec # 6000) with pt / Ru / C, 30/15/55, (Johnson Matthey, Hispec # 7000) and Nafion Solution (Dupont SE: 5112), with a weight mixing ratio of 1: 1: 10, uniformly mixed in an ultrasonic homogenizer After being slurried, it is used as the anode catalyst slurry, which is used as the electrode catalyst slurry of the outer tube of the circular tube-type proton conducting membrane (pEM). 3. Round Tube Type Proton Conduction Membrane (PEM) 3 The round tube type proton conductivity membrane refers to any material that can be used as a membrane for the son and father. Use Nafion melt-extrusion raw materials (such as R1100 or R1 000), hot melt extrusion at 250 ° C, through the ring-type extrusion die, nitrogen is blown into the ring-shaped inner tube, broadcast R11OO or R1 0. 〇〇Become a hollow thin tube inside, coiled by the cold section, the round tube-type proton conduction membrane used for this creative work, adjust the feed amount of RU〇〇 or R1,000 rubber particles and the amount of nitrogen blowing and the coiled Take-up speed can obtain a variety of thin tubes with different diameters and wall thickness. This work takes Rn〇〇, 1/8 // granular rubber particles, using a Randcastle screw melt extruder (M〇del RCp-〇500), feed screw cup rotation speed 0.75rpm, pull speed 0.45ft / Min, blowing nitrogen at 3.45cc / min can obtain hollow diameter tube with diameter of 2mm and film thickness of 0.1mm. It is melted and extruded to form a circular proton conduction membrane. Take the tube-shaped proton conducting membrane 15 cm long, and infiltrate the tube-shaped proton conducting tube with 15% K0H and 35% DMS0 at 6 (TC to 80t) simultaneously and outside the tube for 4 hours, and then deionize Wash with water, wash at least two times, and then repeatedly infiltrate and wash with 15% HN03 for at least two times to obtain a round tube-type proton conducting membrane (PEM). 4 · electrode catalyst slurry 4 M274656 This work uses the anode and cathode commonly used in DMFC. The catalyst electrode material is taken as an example. The weight ratio of the cathode catalyst is Pt / C, 50 / 5〇 (Johnson Mat they # 8000) and Naf ion Solutión (Dupont SE 5112). After being uniformly mixed into a slurry form by a Sonifier, Branson Ultrasonics (Model 250), it is used as the cathode catalyst slurry and used as the electrode catalyst slurry in the tube of the proton conducting membrane (PEM) of the round tube type. 5 · Conductive cladding tube (or perforated tube) with lead wire 5 This creation uses tubular braided conductive carbon fiber braided tube, 16 strands of carbon fiber braided tube, placed in Nafion solution SE 5112 or Teflon 30B to dry and solidify. The shrink tube is 0.8 ~ 1.2mm in size as a lead with a lead in the tube-shaped proton conducting membrane (pEM) tube. Electro-laminated tube (or perforated tube). The above electrode catalyst slurry is suitable for fuel cell electrode catalysts, and specifically refers to catalysts suitable for direct methanol fuel cells and catalysts containing precious metal-based catalysts. The medium refers to a catalyst including platinum metal. The above-mentioned conductive coated tube with lead wires is woven with conductive materials to form holes and grids. It has the characteristics of gas and non-gas barrier properties. And before it is combined with the official proton conductive membrane to form a combined unit, it has a retractable characteristic spring shape, forming a conductive coated tube with a tube shape and a wall with a gap to allow air to pass through. '' Please Refer to "Figures 1 to 3", which are the front view of this creation, the side view of this creation, and the perspective view of this creation. As shown in the figure: Refers to the tube in the tube-shaped proton conduction membrane (PEM) 3 Coating-electrode catalyst slurry 4, which is between the conductive coating tube (or perforated tube) 5 with a lead wire and the inner wall of the round tube-type quality coffee tube to complete the intermediate product of the inner tube. Two 9 M274656 polar catalyst polymer solution 2 in this round tube type proton Between the outer wall of the tube (pEM) 3 and another conductive cladding tube (or perforated tube) 1 with a lead wire, and leave the round tube-shaped shell conductive film (PEM) 3 without anode contact at both ends The medium coating area is used for mating when the MEA is assembled into a battery. Insert the mold rod with a diameter of 15 coffee. The inner rod 'makes the conductive coating tube (or hole tube) with lead wires 5 to expand and fit the circle. The proton-conducting membrane (PEM) 3 tube is closed, and the conductive cladding tube U with a lead wire U hole tube U is folded, and finally placed in a hot-pressing film tool, so that the mold is uniformly heated to 12G ~ 127 ° c [round The glass transition temperature of the tubular f-conducting film is between ㈤ and the melting point temperature (Tm). 〕 '3 ~ 5 minutes, the mold pressure is greater than the pressure of / / repair and press' to make the tube-shaped proton conductive membrane (pEM), electrode catalyst and lead-out: The conductive coating tube is closely attached to complete one Thin official thin-film electrode combination unit with lead wire. As shown in Figure 3, the lead wire H 5 can be cut into smaller wires according to the needs of rewiring. The outer diameter and tube thickness range of the leaded ′ -field s-type nuclear electrode assembly unit is U.) The outer diameter range is between 1 and 5 cm, and the tube thickness is between: 1 and 1. The diameter of the outer diameter range between 2 times the diameter to 0.45 times or 0.05mm to the diameter of 0.45 times (2.) The outer diameter ranges from 2 to 3cm. 0.1 times the diameter to 〇4S Wei " + S and " Straight at .45 L or between 0.07 mm and 0.45 times the diameter. ) The outer empty space ranges from 3 cm to 2 cm, and the tube thickness is twice the diameter. .45 times diameter or 0.1 to 0.45 times diameter. However, the above-mentioned ones are only for the purpose of the present invention. This is to limit the scope of the present invention. The scope of the invention is not limited. Therefore, according to the scope of the present invention, the scope of patent application M274656 and the contents of the invention specification The simple equivalent changes and modifications made should still fall within the scope of the patent of the present invention. M274656 [Schematic description] Figure 1 Front view of this creation Figure 2 Side view of this creation 3 Dimensional view of this creation [Description of main component symbols] Conductive coated tube (or hole tube) with lead wires 1 Electrode catalyst polymer liquid 2, 4 round tube type proton conducting membrane. 3, 5 pole catalyst slurry 4 lead wire 1. a, 5. a refers to the tail end of the conductive coating tube (or hole tube) with lead wire , Reserved as the extension part of the length and quantity of the conductive coated tube (or perforated tube) with the lead wire, that is, the lead wire for the creation.
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