TWI343669B - A method to manufacture the membrane electrode assembly in fuel cell - Google Patents
A method to manufacture the membrane electrode assembly in fuel cell Download PDFInfo
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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1343669 九、發明說明: 【發明所屬之技術領域】 ^ 本發明屬化學化工之材料製作技術領域,係關於一種 簡易製作燃料電池組所需之膜電極組,主要係利用惰性氣體 多道次噴搶噴覆法將觸媒漿液均勻分散在碳氣體擴散層表 面,直到所需觸媒含量,再與質子交換膜熱壓組合成膜電極 組等步驟。 、 【先前技術】 對質子交換膜燃料電池(PEMFC)而言,將陽極、質子 交換膜、與陰極結合成三明治結構的單一元件稱為膜電極組 (MEA)。MEA是PEMFC的核心部份,電池主要的電化學反應都 發生在此,因此MEA的性能好壞直接決定了PEMFC效能觸 媒層設計直接影響反應氣體與電解質介面間的有效觸媒總表 面積,此觸媒層必須兼含兩種機能:一為離聚物成^分 (ionomer component),負責提供電化學反應中的離子(H+)傳 導通道;另一則為供應氣體組成(gas supplying component),為促使反應氣體能迅速通暢傳抵觸媒表面的诵 道。在質子交換膜燃料電池中,通常是採用質子傳導高分子 (proton conducting polymer)為接合劑(Binder),其中最常 用的NafionC商品名),Nafion中負責離子傳導的磺^根官能 基是親水性’而聚四氟乙締 (Polytetrafluoroethylene,PTFE)主鏈則是疏水性,疏水性 的鏈結團即為電極觸媒層中的主要氣體通道,所製得的必 須要能平衡親水性的離子傳導通道與疏水性的氣體通道,才 能發揮最大效率。 陽極主要是由碳布(或碳紙)與觸媒所組成。通常是將 碳布(或碳紙)’塗上一層鉑和碳粉混合的觸媒所製成。依照 其中機制不同,可分為氣體擴散層(diffUSi〇n 'lay^r)和作用 5 碳紙)等層的材_為碳布(或 用區域與面積外,並可將7電揮,與擴大觸媒的作 達反應區域的通道。出’及提供氫分子到 時,需藉糾廣散電極到達觸媒附近的過程 体擴散層。作二式㈣,因此稱此區域為氣 中七生電化學反應的地方,也就 PEMFC並、盒;ρ由。山卩伤,為了增加反應面積與減少鉑含量, 與降低二木f、作為觸媒載體(s_〇r t)以提高電催化性 ;匕釋放出二用ί中’氫氣會經由_媒的催 好則穿過質由碳布或破紙導離’氣 構成。陽極相同’也是由氣體擴散層和作用層所 紙)所廣散層與陽極側一樣,都是使用碳布(或碳 近,在淨纟子雌也是藉由擴散对雜到達觸媒附 極中的碳布(或碳紙)是將參與反應的電子導入, 吸收石成f水導出。在陰極的作用層中,氧分子在 t導入的電子後’與穿過質子交換膜的氫離 、$二二二’這個反應過程較陽極慢,因此陰極的觸媒含量 。,電極組耐久性問題主要為陰極觸媒凝結與 昧化料紐概能降低,自麵齡陰極高溫長 夺=作時會有凝結現象,降低了觸絲面積及造成膜電極 ΐίί下ϊ’目前傾向研發雙相及三相觸媒來提高操作溫度 及時間,陰蝴賴_需有抗腐純化能力,因此碳 目前研是將其石墨化,以增加其抗雜能力。 貝子父換膜的基本功能在阻絕兩側電極,伸能值道 離子完成反應。其結構基本上是多孔狀的固態氧 虱離子以遷移(migrati〇n)和擴散的方式移動至氧氣側。 最常使用的是由美國杜邦⑽P〇n t)公司生產的Na f i 〇n 貝子父換膜’内部結構是由聚四氟乙婦(pTFE)與氟化項酸離 1343669 聚物(perfluorosulfonic acid ionomers)組成的全氟化高分 子聚合體’分子結構與聚四氟乙烯相似,具有體型網絡結 構,其中有很多微孔(孔徑約lnm)。除了Nafion外,日本1343669 IX. Description of the invention: [Technical field to which the invention pertains] ^ The invention belongs to the technical field of material fabrication of chemistry and chemical industry, and relates to a membrane electrode assembly required for simple production of a fuel cell stack, mainly by using a multi-pass spray of inert gas The spraying method uniformly disperses the catalyst slurry on the surface of the carbon gas diffusion layer until the required catalyst content, and then combines with the proton exchange membrane to form a membrane electrode group. [Prior Art] For a proton exchange membrane fuel cell (PEMFC), a single element that combines an anode, a proton exchange membrane, and a cathode into a sandwich structure is called a membrane electrode assembly (MEA). MEA is the core part of PEMFC. The main electrochemical reaction of the battery occurs here. Therefore, the performance of MEA directly determines the PEMFC performance catalyst layer design directly affects the total effective surface area of the effective catalyst between the reaction gas and the electrolyte interface. The catalyst layer must have two functions: one is the ionomer component, which is responsible for providing the ion (H+) conduction channel in the electrochemical reaction; the other is the gas component, The reaction gas can be quickly and smoothly transmitted to the channel of the catalyst surface. In proton exchange membrane fuel cells, proton conducting polymers are commonly used as binders, the most commonly used NafionC trade name, and the sulfonate functional group responsible for ion conduction in Nafion is hydrophilic. 'The polytetrafluoroethylene (PTFE) backbone is hydrophobic, and the hydrophobic chain is the main gas channel in the electrode catalyst layer. It must be able to balance the hydrophilic ion conduction. Channels and hydrophobic gas channels are used for maximum efficiency. The anode is mainly composed of carbon cloth (or carbon paper) and a catalyst. It is usually made by coating a carbon cloth (or carbon paper) with a catalyst mixed with platinum and carbon powder. According to the different mechanisms, it can be divided into layers of gas diffusion layer (diffUSi〇n 'lay^r) and 5 carbon paper). It is a carbon cloth (or outside the area and area, and can be used for 7 waves, Expanding the channel of the reaction zone of the catalyst. When the hydrogen molecule is supplied, the diffusion layer of the process is required to reach the diffusion layer of the process body near the catalyst. As a second formula (4), the region is called the gasification in the gas. The place where the reaction is studied, that is, the PEMFC and the box; ρ by. Hawthorn injury, in order to increase the reaction area and reduce the platinum content, and reduce the diwood f, as a catalyst carrier (s_〇rt) to improve electrocatalytic;匕 匕 匕 ί ί ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' As with the anode side, carbon cloth (or carbon is used, and in the net scorpion, the carbon cloth (or carbon paper) in the catalyst-attached pole is diffused to the electrons that will participate in the reaction, and the absorption stone is formed. f water is derived. In the active layer of the cathode, the oxygen molecules are 'after and after the electrons introduced by t The hydrogen separation of the proton exchange membrane and the reaction process of the disulfonate are slower than that of the anode, so the catalyst content of the cathode. The durability of the electrode group is mainly due to the reduction of cathode catalyst condensation and bismuth flux. The high temperature of the cathode will cause condensation, reduce the area of the contact wire and cause the membrane electrode to ΐ ί ί ϊ 目前 'currently inclined to develop dual-phase and three-phase catalyst to improve the operating temperature and time, the need to have anti-corrosion The ability to purify, so carbon is currently graphitized to increase its anti-vibration ability. The basic function of Bezier's membrane replacement is to block the two sides of the electrode, and the extension energy ions complete the reaction. The structure is basically porous solid state. The oxonium ions move to the oxygen side by migration and diffusion. The most commonly used is the Na fi 〇n shell-female replacement film produced by DuPont (10) P〇nt). The internal structure is made of polytetrafluoroethylene. The perfluoropolymerized polymer composed of pTFE and perfluorosulfonic acid ionomers has a molecular structure similar to that of polytetrafluoroethylene, and has a bulk network structure, many of which Pores (pore size of about lnm). In addition to Nafion, Japan
Asahi Chemical 的Aciplex-S 膜、Asahi Glass 的Flemion 膜、日本Chlorine Engineers的C 膜 '美國Dow Chemical 的Asahi Chemical's Aciplex-S film, Asahi Glass's Flemion film, Japan's Chlorine Engineers' C film 'Dow Chemical'
Dow膜均以聚氟化磺酸(pFSA)為主要材料,結構與Nafi〇n 膜相似、以及日本Honda stack燃料電池組進展研發速度相 當快’質子交換膜主要採用芳香族電解膜(Ar〇matic electrolytic membrane),其操作溫度高Dupont pem約 i5°c, 其操作耐用性高DuPont PEM約4倍。 目則联電極組表大的技術瓶頸為成本(c〇st)、性能 (performance)與耐久性(durability),降低成本主要可由量 產技巧開發著手,性能則由改進觸媒、質子交換膜、氣體擴 月欠層等性質著手,耐久性則需藉由改進材料本質及燃料電池 組設計,並經長時間測試單電池或電池組,進行極^ 循環伏安、電池阻抗、排放水分析等。 在MEA專利技術相關領域研究中,以BaUar_d pQwer_ Systems專利之產出最多,約佔專利總數之2〇%,為投入MEA 專利技術研發最活躍的公司,Uard p〔)wer如娜在_ 之技術研發料有12細上,投人之發日狀高翁位以上, 也是投入研發團隊最多的公司,專利屬於近期專利。 共計17件以上,專利活動年期有約_ 年另外The Dow Chemical Company專利件數不多(約6 件)。 " 膜電極組主要製程有觸媒塗佈於氣體擴散 佈或轉印至質子交換膜上。利用刷子塗佈(以咖直接言 Painting)、超音波噴覆(lHtras〇nic Spraying)、 (Doctor Blading)或轉印(Decal如阳㈣等方法 料均勻塗佈或轉印至氣難制,然祕氣體崎電 7 ^熱壓,如E-Tek公司。而本發明採用 在氣體擴散層上的製程。 早、贺杈貝復塗佈 刷子塗佈的優點為簡單、無需複雜設備 差、大1生產時人X昂貴及大量生產時觸媒㈣量變 轉印的優點為可精確控制觸媒含量、 ;,大量生產速度及電極與質子交換膜匕== 為製程步驟多及慢,自動化大量生產困難。 強缺”、占 刮刀的優點為觸媒分布均勻性佳及可減少塗佈 ,點為自動化需要昂貴設備、在不損失性能時 ==多道次薄膜塗佈較困難,可能不是最好 超音波喷覆的優點為觸媒分布均勻性佳、 多道次薄膜塗佈應用佳及可自動化大量生產 ▲ 雜及昂貴設備、㈣混合物易分離及如果設計不佳 量將很明顯。 、 另外有關層壓法是本領域衆所周知的且在MEA製造的情 况下疋&其中使用熱、壓力和/或#合劑將兩種組分例如PE% 和電極結合在一起的方法。B〇nsi丨等人的美國專利 NO. 6197147公開了用於生産MEAs的層壓方法。該方法包括將 離子傳導膜、催化活性物質和氣體可滲透的電子導電材料層 壓。公開了膜和/或導電材料可與化合物如六氣鈾酸接觸,其 然後被還原形成鉑金屬。 〃 轉印法(deca 1 coman i a) —般定義爲用於將印刷在特別 製備的轉移基底上的圖樣轉移至材料如玻璃或金屬上的方 法。在MEA元件的情況下,圖樣爲用於產生MEA的各種層的沈 積圖案,其然後被轉移至MEA基底如PEM、氣體或流體分佈層 或雙極板。特別地,將油墨組合物沈積在空彈(blank cartridge)上,這裏稱作轉移基底。轉移基底和MEA基底然後 夾在一起並在加熱的環境中壓制。熱將油墨固化至該基底, 由此將其從轉移基底上脫離並沈積到該基底上。然後通過將 轉移基底從沈積的油墨層上剝離將其除去。Dow membranes are mainly composed of polyfluorinated sulfonic acid (pFSA), the structure is similar to that of Nafi〇n membrane, and the development of Honda stack fuel cell stack in Japan is quite fast. The proton exchange membrane mainly uses aromatic electrolytic membrane (Ar〇matic). Electrolytic membrane), its operating temperature is high, Dupont pem is about i5 °c, its operation durability is about 4 times higher than DuPont PEM. The technical bottleneck of the joint electrode group is cost (c〇st), performance (performance) and durability. The cost reduction can be started by mass production techniques, and the performance is improved by catalyst, proton exchange membrane, The nature of the gas expansion and the underlying layer is required. The durability is improved by the nature of the material and the design of the fuel cell stack, and the battery cells or battery packs are tested for a long time, and the cyclic voltammetry, battery impedance, and water discharge analysis are performed. In the research of related fields of MEA patent technology, the BaUar_d pQwer_ Systems patent has the largest output, accounting for 2% of the total number of patents. It is the most active company in the research and development of MEA patent technology. Uard p[) wer is in the technology of _ The research and development materials have 12 fines, and the investment is more than the high-end of the day. It is also the company with the most research and development team. The patent belongs to the recent patent. A total of 17 or more, the patent activity period is about _ years, and the number of patents of The Dow Chemical Company is small (about 6 pieces). " The main process of the membrane electrode group is to apply a catalyst to a gas diffusion cloth or transfer it to a proton exchange membrane. Uniform coating or transfer to gas-tolerance by brush coating (Painting), ultrasonic coating (Doctor Blading), or transfer (Decal, etc.) The gas is 7 hot pressing, such as E-Tek. The invention adopts the process on the gas diffusion layer. The advantages of early and Hebeibei coating brush coating are simple, no complicated equipment, and large 1 The production of human X is expensive and the catalyst is produced in large quantities. (IV) The advantage of variable transfer is that it can accurately control the catalyst content, and the mass production speed and electrode and proton exchange membrane 匕 == more and slower process steps, automatic mass production difficulties The advantage of the strong and the scraper is that the distribution of the catalyst is uniform and the coating can be reduced. The point is that the automation requires expensive equipment, and when the performance is not lost, the multi-pass film coating is difficult, and may not be the best. The advantages of sound wave spray coating are good distribution of catalyst distribution, good application of multi-pass film coating and automatic mass production ▲ miscellaneous and expensive equipment, (4) easy separation of mixture and if the design is not good, it will be obvious. Pressure method It is well known in the art and in the case of MEA manufacture, a method in which two components, such as PE% and electrodes, are combined using heat, pressure and/or # mixture. B〇nsi丨 et al. U.S. Patent No. 6,197,147 discloses a lamination process for the production of MEAs. The method comprises laminating an ion-conducting membrane, a catalytically active material, and a gas-permeable electronically conductive material. It is disclosed that the membrane and/or the electrically conductive material can be combined with a compound. Lithium uranium is contacted, which is then reduced to form platinum metal. 转印 The transfer method (deca 1 coman ia) is generally defined as the transfer of a pattern printed on a specially prepared transfer substrate to a material such as glass or metal. In the case of MEA elements, the pattern is a deposition pattern for the various layers used to produce the MEA, which is then transferred to an MEA substrate such as a PEM, gas or fluid distribution layer or bipolar plate. In particular, the ink composition is deposited On a blank cartridge, referred to herein as a transfer substrate, the transfer substrate and the MEA substrate are then clamped together and pressed in a heated environment. Heat heats the ink to the substrate, thereby transferring it from the substrate. The substrate is detached and deposited onto the substrate, which is then removed by peeling the transfer substrate from the deposited ink layer.
Wilson的美國專利N0.52U984公開了通過轉印法生產 MEAs的方法。將包括支撐的鉑催化劑和質子傳導聚合物的油 墨組合物塗在脫模空白(release blank)上以形成薄膜貼花 臈。然後使用熱壓機該貼花膜轉移至PEM表面。 轉印法和層壓法是有利的,由於它們可在易碎表面上 ,積材料且操作相對簡單。層壓法還提供高産量。然而,印 花法和層壓法不經過另外的加工無法生產精細圖案或組成中 的梯度。而且,對準各種MEA層是困難的。U.S. Patent No. 5,029,984 to Wilson discloses a method of producing MEAs by a transfer process. An ink composition comprising a supported platinum catalyst and a proton conducting polymer is applied to a release blank to form a film decal. The decal is then transferred to the PEM surface using a hot press. Transfer methods and lamination methods are advantageous because they can be deposited on fragile surfaces and are relatively simple to handle. The lamination process also provides high yields. However, the printing method and the lamination method cannot produce a fine pattern or a gradient in composition without additional processing. Moreover, it is difficult to align various MEA layers.
Zhang等人的美國專利No. 6丨8 74 6 7公開了使用連續浸透 和印刷製造電極。首先,將質子傳導聚合物浸透在基底=碳 ,維紙的表面上。該浸透可使用各種技術完成,如將該基底 =入包括質子傳導聚合物的溶液中。然後將電催化劑塗覆於 浸透的基底。據公開電催化劑可以在包括在溶液中的質子傳 導聚合物的含水油墨的形式通過任何已知的方法包括噴 絲網印刷和噴墨印刷塗覆於該基底。 、The use of continuous impregnation and printing to produce electrodes is disclosed in U.S. Patent No. 6,8,742, the disclosure of which is incorporated herein. First, the proton conducting polymer is impregnated on the surface of the substrate = carbon, paper. The impregnation can be accomplished using a variety of techniques, such as substituting the substrate into a solution comprising a proton conducting polymer. The electrocatalyst is then applied to the impregnated substrate. It is disclosed that the electrocatalyst can be applied to the substrate by any known method including spray screen printing and ink jet printing in the form of an aqueous ink of a proton conducting polymer included in the solution. ,
Starz等人在美國專利NO. 6500217中公開了使用含有石户 顆粒和零價Pt化合物的油墨組合物生産MEAs的方法。該= 公開了用於在聚合物電解質膜帶(strip)的前面和背 極層的方法。 後电A method for producing MEAs using an ink composition containing stone particles and a zero-valent Pt compound is disclosed in U.S. Patent No. 6,500,217. This = discloses a method for the front and back layers of a polymer electrolyte membrane strip. After power
Shah 等人(Langmuir,1999, Vol. 15, ρρ·1584_1587) 開了紐溶膠㈣墨沈積’用作用於微電子應用的化學 積中的催化劑。 ^Shah et al. (Langmuir, 1999, Vol. 15, ρρ·1584_1587) opened a neosol (tetra) ink deposit' as a catalyst used in chemical stacks for microelectronic applications. ^
Wi lkinson等人的美國專利Να 5672439公開了用於⑽ 的MEA,其中降低了液體甲醇從陽極到陰極的跨 (crossover)。爲了降低跨接,可在陽極表面上對催化劑 進行濃縮,其中該催化劑顆粒促進甲醇在陽極中的氧化。,U.S. Patent No. 5,672,439 to Wilkinson et al. discloses an MEA for (10) wherein the crossover of liquid methanol from the anode to the cathode is reduced. To reduce bridging, the catalyst can be concentrated on the surface of the anode, wherein the catalyst particles promote oxidation of the methanol in the anode. ,
Dufer等人的美國專利·. 6〇24848公開了電化學電池如 PEMFC。該電池可包括用於增強在電池内流體傳輸的雙層。該 雙層於笔極接觸且包括炭黑和疏水聚合物的疏水相以及包括 厌黑和質子交換樹脂的混合物的親水相。該雙層可通過過濾 轉移法形成。An electrochemical cell such as PEMFC is disclosed in U.S. Patent No. 6,24,848 to Dufer et al. The battery can include a dual layer for enhancing fluid transport within the battery. The bilayer is in contact with the pen tip and comprises a hydrophobic phase of carbon black and a hydrophobic polymer and a hydrophilic phase comprising a mixture of anisotropic and proton exchange resins. The double layer can be formed by a filtration transfer method.
Zuber等人的美國專利N〇. 6156449公開了如在PEMFC中 的催化劑層,其包括質子傳導聚合物、導電碳顆粒和貴金屬 如鉑的細粒。該層由油墨組合物形成,該油墨組合物包括碳 顆粒和至少一種在離聚物的溶液中的有機貴金屬配位化合 物。將該組合物塗覆並乾燥,其中配位化合物在乾燥過程中 熱分解以形成貴金屬顆粒。U.S. Patent No. 6,156,449 to Zuber et al. discloses a catalyst layer as in a PEMFC comprising a proton conducting polymer, conductive carbon particles and fine particles of a noble metal such as platinum. The layer is formed from an ink composition comprising carbon particles and at least one organic precious metal coordination compound in a solution of the ionomer. The composition is coated and dried, wherein the coordination compound thermally decomposes during drying to form noble metal particles.
Susan G. Yan等人在美國專利put) no. Us 喷覆後不產生變形或皺摺等問題,大量生產及自動生產較困 難。 本發明開發膜電極組時,採用惰性氣體噴搶喷覆將觸 媒皇佈在氣肢擴政層上’氣體擴散層表面底部加熱溫度控制 玉白白,描很縮碰古六今0 iMi :太认A /丄,“ 2005/,_3讀1巾公開叫塗再上燈光加熱,簡媒直接噴 覆在膜上,缺點在於不易控制燈加熱的均勻性且需考量膜在 優點為觸媒 多道次薄膜塗佈應用佳、可大面 均勻,提供觸媒有效且快速均勻分佈在觸媒層 分布均勻性佳、再現性佳、多道次蒗眩涂 ^ 塗佈、製作容易及可自動化大量生產。缺點為如果只有少 量的MEA製作觸媒浪費量將很明顯。 【發明内容】 奈米微孔碳氣體擴散層技術上的提升,可_塞.賴Susan G. Yan et al. in the US patent put) no. Us no problems such as deformation or wrinkles after spraying, mass production and automatic production are more difficult. When the membrane electrode assembly of the invention is developed, the inert gas is sprayed and sprayed to spray the catalyst on the air-expansion layer of the gas diffusion layer, and the bottom temperature of the gas diffusion layer is controlled by the temperature control jade white, which is very confined to the ancient six today 0 iMi: too A / 丄, "2005 /, _3 read 1 towel openly painted and then heated on the light, the direct spray directly on the film, the disadvantage is that it is not easy to control the uniformity of lamp heating and the film is considered to have the advantage of multi-channel The secondary film coating application is good, and the surface can be evenly distributed, providing the catalyst with effective and rapid uniform distribution in the catalyst layer, good distribution uniformity, good reproducibility, multi-pass glare coating, easy coating and automatic mass production. The disadvantage is that if only a small amount of MEA production catalyst waste amount will be obvious. [Summary of the Invention] Nano microporous carbon gas diffusion layer technology improvement, can _ 塞.
1343669 但其機械财㈣及㈣量觸優點。碳布i有 凹凸不平,需進行整平處理,峨奈米碳氣職散層之= 孔洞大小、·分佈、導電性與疏水躲,使射適合= 體通适、電子通道和水的通道。本發明主要以碳布 ^ 體擴散層為主,细填充高導電度顆粒大小、_固體^ 量、預浸製程次數及輾壓條件來控制碳氣體擴散層 = 及分佈等性質。製作流程如圖二所示。 、、小 280〜360 C熱處理’使浸潰在碳布巾的氟碳高分子乳液 的表面活性劑被除掉,同時使氟碳高分子熱熔燒結並岣又 散在碳布上。 77 本發明所使用>ε反布規格如表一所示,碳布先進 處理,碳布浸於經稀釋過之氟化丙烯高分子(FEp)f= (Dupont公司之FEP120J產品),取出於空氣中乾燥後/浏 - Carbon cloth specifirptinn construction Plain Yarn input 2/27 Count(WxF) 48x44yarns/in Area weight 3, 4oz/yd2 Standard widths 33in thickness 15mil(〇. 38mm) density 1. 75g/cc Carbon content 99% Oxidation rate(%per hour)at500°C 1.0 Surface resistivity(ohms/square) Outside:0. 3 Inside :〇· 29 因碳布表面不平有孔,對於製作觸媒催化層有影響,因此需要對 11 1343669 ^進行整平處理。將聚四氟乙烯乳劑(PTFE)與導電粉末調配為固 定比例’其中聚四氟乙烯乳劑採用Dupont PTFE 30B之產品。其 中導電粉末可為碳黑、石墨粉、活性碳或惰性金屬粉等,導電粉 士漿液的調配為氣體擴散層製作的關鍵技術,選擇以蒸餾水當作 溶劑,力:入導電粉末、聚四氟乙烯乳劑與分散劑混合,調整漿液 固體含量約5〜40wt%。為了增加漿液的黏度,添加約〇. 5〜2wt%之 曱基,維素。以超音波震盪或機械均勻混合漿液。混合好的漿液 預浸製,塗佈在已疏水處理的碳布上、經輾壓成型、重複預浸 製程及輾壓步驟-至五次,直到所料電碳固體含量及納米孔洞 大小與分佈,使其表面平整,每次預浸製程經過6〇至12〇艽去除 水分後,再經冷軋壓或熱軋壓60至18〇t步驟,最 $ 處f使得剛鱗燒結絲結與疏樣,即製ΐ炭氣體 末的含f在3_12mg/Cm2之間。碳氣體擴散層之體 m、比表面積、孔隙總體積及平均孔徑大小(BET測得〉等 性賀如表二所示。1343669 But its mechanical wealth (4) and (4) touch the advantages. The carbon cloth i has irregularities and needs to be leveled. The carbonized carbon layer is the size, distribution, conductivity and hydrophobicity of the hole, making it suitable for the body, the passage of the electron channel and the water. The invention mainly adopts a carbon cloth diffusion layer, and finely fills a high conductivity particle size, a solid amount, a pre-dip process number and a rolling condition to control the carbon gas diffusion layer = and distribution properties. The production process is shown in Figure 2. , 280~360 C heat treatment' The surfactant of the fluorocarbon polymer emulsion impregnated in the carbon cloth was removed, and the fluorocarbon polymer was hot-melted and sintered and dispersed on the carbon cloth. 77 The anti-clothing specifications used in the present invention are as shown in Table 1. The carbon cloth is advanced, and the carbon cloth is immersed in the diluted fluorinated propylene polymer (FEp) f = (FEP120J product of Dupont Company), and taken out. After drying in the air / Carbon cloth specifirptinn construction Plain Yarn input 2/27 Count (WxF) 48x44yarns / in Area weight 3, 4oz / yd2 Standard widths 33in thickness 15mil (〇. 38mm) density 1. 75g / cc Carbon content 99 % Oxidation rate(%per hour)at500°C 1.0 Surface resistivity(ohms/square) Outside:0. 3 Inside :〇· 29 Because the surface of the carbon cloth is uneven, it has an effect on the catalytic layer of the catalyst, so it is necessary to 1343669 ^ Perform leveling. The polytetrafluoroethylene emulsion (PTFE) and the conductive powder were formulated to a fixed ratio, wherein the polytetrafluoroethylene emulsion was a product of Dupont PTFE 30B. The conductive powder may be carbon black, graphite powder, activated carbon or inert metal powder. The preparation of the conductive powder slurry is the key technology for the production of the gas diffusion layer, and the distilled water is selected as the solvent. The force: into the conductive powder, polytetrafluoroethylene The ethylene emulsion is mixed with a dispersing agent to adjust the slurry solid content to about 5 to 40% by weight. In order to increase the viscosity of the slurry, add about 5 to 2 wt% of the sulfhydryl group, the vitamin. Mix the slurry with ultrasonic vibration or mechanically. The mixed slurry is pre-impregnated, coated on the hydrophobically treated carbon cloth, subjected to rolling forming, repeated pre-dip process and rolling step-to-five times until the charged carbon solid content and nanopore size and distribution are obtained. , to make the surface flat, each time the pre-dip process is removed from 6〇 to 12〇艽, and then subjected to cold rolling or hot rolling to 60 to 18〇t steps, the most f is so that the scales are sintered and thinned. For example, the content of f at the end of the preparation of the carbon gas is between 3 and 12 mg/cm2. The body m, specific surface area, total pore volume and average pore size (BET measured) of the carbon gas diffusion layer are shown in Table 2.
1343669 組合成膜電極組等步驟。在觸職舰置上採 媒、5—溶液與異兩醇,pt/c與% 。= f 1 2〜3:卜其中20_/(:與__體二:重里 較,,將以上三成份以機械方式混合均勻後,以喷“覆法將觸 ΐίΐΓ4Γ=在5層表面上,此時碳氣體擴散廣表溫 須達到45〜85C ’其中U 65ΐ較佳,陽極 5wt/〇 Nafion溶液薄薄噴覆—次。電極與質子交‘膜二,將質 =換膜置於㈣極中間’以熱壓的方式將結“,執 fnt為加2熱至,〜靴保持6㈣秒再熱壓秒,動、 70〜85kg/cm ’即製得膜電極組。 單電如下,為了單電池性能達到最触條件, ffi氧氣或空氣’以—定化學當量比之預 氡;L二々::’,在壓下(latm)氣體溫度(即氫氣, ^或Γ 皿度"^於電池本體溫度’以保持其刻性。 =溫度設在紙,放電模式狀電壓,其初始設 2路電壓時,再將電壓奴在㈣,時間ί8 开/人視電流汝度上升趨勢而定),期間並觀察電流變化情 ^^=溫2至阶’諸條件同上所述,待二忿 #〜°又疋.時間〇. 5小時,並觀察電流變化情形,待其電流 H :寺’即可進行測試,定電壓放電等實驗。本測試 :。、士 - v測試條件為,溫度:氫極增濕瓶溫度為如賓c, 或電池組)溫度為4(rc〜7Gt,氣體流量可變。背壓:1 式乳麼(視需要而定),增濕:外部濕潤,放電電愿方 【實施方式】 貫施例1 13 1343669 碳布先進行疏水處理,碳布浸於經稀釋過之5wt%FEP 乳劑(Dupont公司之FEP120J產品),取出於空氣中乾燥後, 進行100°C ’ 10分鐘乾燥處理,再進行35(TC,20分鐘熱處 理’使氟碳高分子熱炼燒結並均勻分散在碳布上。 預/¾料έ周配’取1039. 5g秦賴水,加入3. 7g Triton, 均勻混合後’加人57. 5g之碳黑(ENSACO 250 Power,average particle size 40nm,BET 62mVg),放入球磨罐球磨 2 小時。 再加入聚四氟乙烯乳劑(PTFE)3〇B後球磨5分鐘。取出混合物 l〇71g放入pp燒杯内,加入〇.⑽伐或8. 57g之曱基纖維素, 巧燒杯放入80 C熱水浴攪拌2小時,之後在不加熱條件下持 縯攪拌12小時,最後靜置6小時。所得預浸料之固體含 7〜。 久机姐僻驭滑心杈忭,混合好的預浸料經預浸製程塗 佈在已疏水處理的碳布上,預浸後之碳布經卯它及洲分鐘烘 乾’再經12(TC熱乾壓,滾輪間隙〇 3刪 報 壓步驟―次,直到所需導電碳 ί 表面平整’再經35Gt及3G分鐘熱處理使得服、妖 熔k、、·。具黏結與疏水性,即製得碳氣體擴散層。 將24 作流程如圖三所示,在觸賴液配置上先 雷溶液與30克異丙醇放入玻璃瓶内,置於 ,,熱,上混合i如夺後,玻璃瓶内通入惰性氣體, 以上三成份以機械方式混合^ ΐ 熱用鐵板放置於電磁加娜器 溫度,放上碳氣體擴散層,待 J于°又疋所肩1343669 The steps of synthesizing membrane electrode sets and the like. On the contact ship, the medium, 5-solution and iso-alcohol, pt/c and % were placed. = f 1 2~3: Bu 20_/(: with __ body 2: heavy and medium, after the above three components are mechanically mixed evenly, spray "covering method will touch ΐ ΐΓ 4Γ = on the surface of 5 layers, this When the carbon gas diffuses, the surface temperature must reach 45~85C. Among them, U 65ΐ is better, and the anode 5wt/〇Nafion solution is thinly sprayed-time. The electrode and the proton are crossed, and the membrane is placed in the middle of the (four) pole. 'Take the knot by hot pressing method, hold fnt to add 2 heat to ~, hold the boot for 6 (four) seconds and then pressurize the second, move, 70~85kg/cm 'that is the membrane electrode set. Single electricity is as follows, for the single battery The performance reaches the most sensitive condition, ffi oxygen or air 'to determine the stoichiometric ratio of the pre-twist; L 々:: ', under the pressure (latm) gas temperature (ie hydrogen, ^ or 皿 度 degree " ^ battery The body temperature 'to maintain its engraving. = Temperature is set on the paper, discharge mode voltage, when the initial set of 2 voltage, then the voltage slave (4), time ί8 open / people depending on the current trend of rising trend), During the period and observe the current change ^^=temperature 2 to the order 'the conditions are the same as above, wait for the second ##°°又疋.time〇. 5 hours, and Check the current change situation, wait for its current H: Temple' to test, set voltage discharge and other experiments. This test: ., - v test condition is, temperature: hydrogen extreme humidification bottle temperature is such as Bin C, or battery Group) The temperature is 4 (rc~7Gt, the gas flow rate is variable. Back pressure: 1 type milk (depending on the need), humidification: external wetting, discharge electric power [Embodiment] Example 1 13 1343669 Carbon The cloth is first subjected to hydrophobic treatment, and the carbon cloth is immersed in the diluted 5 wt% FEP emulsion (FEP120J product of Dupont Co., Ltd.), taken out in the air and dried, and then dried at 100 ° C for 10 minutes, and then 35 (TC, 20). After the heat treatment of the fluorocarbon polymer, the fluorocarbon polymer is heat-sintered and uniformly dispersed on the carbon cloth. The pre-/3⁄4 material is mixed with a '39g. 5g Qin Lai water, added 3. 7g Triton, evenly mixed, 'additional 57. 5g The carbon black (ENSACO 250 Power, average particle size 40nm, BET 62mVg) was ball milled in a ball mill for 2 hours. After adding 3 times of polytetrafluoroethylene emulsion (PTFE), the ball was milled for 5 minutes. The mixture was taken out and placed at 71 g. In a pp beaker, add 〇.(10) fell or 8.57g of thiol cellulose, The cup was placed in an 80 C hot water bath for 2 hours, then stirred for 12 hours without heating, and finally allowed to stand for 6 hours. The solid of the obtained prepreg contained 7~. The mixed prepreg is coated on the hydrophobically treated carbon cloth by pre-dip process, and the pre-impregnated carbon cloth is dried by simmering it and drying in the continent for a while (12) (TC hot dry pressing, roller gap 〇 3 deletion The pressure-receiving step - times, until the required conductive carbon ί surface is flat - and then heat treated by 35Gt and 3G minutes to make clothes, demon melt k,, ·. With a bonding and hydrophobicity, a carbon gas diffusion layer is obtained. The process of 24 is shown in Figure 3. In the contact liquid configuration, the first solution of thunder and 30 grams of isopropyl alcohol are placed in a glass bottle, placed, heated, and mixed. Gas, the above three components are mechanically mixed ^ ΐ The hot iron plate is placed at the temperature of the electromagnetic jianer, and the carbon gas diffusion layer is placed.
時,利用舰氣體,如氮氣,以噴"^ θ表溫達到65°C 次均勻分散在碳氣體擴散:表: 發乾後,再重複噴覆動作-次,直㈣極及陰 1343669 ΐ里將觸媒電極片放人真空烘箱,抽真空後7『c保持60分 $ .片·35mm厚度冷.1,表面再經2. 5wt%Nafion /谷、液/彝Λ h —人。接著將觸媒電極5cmx5cm與7cmx7cmWhen using a ship gas, such as nitrogen, to spray the surface temperature to 65 ° C, the temperature is uniformly dispersed in the carbon gas diffusion: Table: After drying, repeat the spraying action - times, straight (four) pole and Yin 1343669 ΐ The catalyst electrode is placed in a vacuum oven, and after vacuuming, 7 "c is kept for 60 minutes. The film is 35 mm thick and cold. 1. The surface is further 2. 5 wt% Nafion / valley, liquid / 彝Λ h - person. Then the catalyst electrode is 5cmx5cm and 7cmx7cm
Dupont f^3之212質子交換膜產品進行熱壓,將質子交換膜 置於陰陽極中間’以熱壓的方式將三片結合成_體。熱壓條 件為加熱至14『c保持1分鐘10秒,壓力8Gkg/cm2,即製得 5cmx5cm膜電極組,膜電極組在空氣與氧氣中的功率,如圖四 與圖五所示。 實施例2 同^施例1製程’此實施例將20wt% Pt/C與Nafion固體含量 重罝比由2:1改為1. 75:1,製得膜電極組,膜電極組在空氣 與氧氣中的功率’如圖六與圖七所示。 實施例3 同實施例1製程,此實施例將2〇wt% Pt/C與Nafi〇n固體含量 重里比由2:1改為1.5:1,製得膜電極組,膜電極組在空氣與 氧氣中的功率,如圖八與圖九所示。 實施例4 同實施例1製程,將Dupont公司之212質子交換膜改為50" 厚度的含吸水性陶瓷微粉之複合質子交換膜製成之MEA之電 性極化曲線,如圖十所示。 【圖式簡單說明】 圖一、膜電極組噴塗製作圖。 圖二、碳氣體擴散層製作流程。 圖三、膜電極組製作流程。 圖四、20wt% Pt/C與Nafion固體含量重量比由2:1製成之 15 mea在空氣中極化曲線。 圖五、20wt% Pt/C與Nafion固體含量重量比由2:1製成之 MEA在氧氣中極化曲線。 圖六、20wt% Pt/C與Nafion固體含量重量比由丨,75:1製成 之MEA在空氣中極化曲線。 圖七、20wt% Pt/C與Nafion固體含量重量比由1.75:1製成 之MEA在氣中極化曲線。 圖八、20wt% Pt/C與Nafion固體含量重量比由丨.5:1製成 之MEA在空氣中極化曲線。 圖九、20wt% Pt/C與Nafion固體含量重量比由1. 5:1製成 之MEA在氧氣中極化曲線。 圖十、50"厚度的複合質子交換骐製成之MEA極化曲線。 【主要元件符號說明】 十、申請專利範圍: 1· 一種燃料電池膜電極組之製作方法,其製程為碳氣體擴散 層製作、觸媒漿液調配、多道次噴搶噴覆法將觸媒漿液分散 在碳氣體擴散層表面’直到所需觸媒含量(陽極白金用量控制 在〇.卜0. 3mg/cm2 ’陰極白金用量0. 3〜0. 6mg/cni2)、觸媒電極 片乾燥’最後再與質子交換膜熱壓組合成膜電極組等步驟。 2. 如申請專利範圍第1項所述之燃料電池膜電極組之製作方 法’其中觸媒漿液調配之Pt/C與Nafion固體含量重量比為 1.2至3:卜 3. 如申請專利範圍第2項所述之燃料電池膜電極組之製作方 法’其中Pt/C與Nafion固體含量重量比以1. 75:1較佳。Dupont f^3's 212 proton exchange membrane product was hot pressed, and the proton exchange membrane was placed in the middle of the anode and cathode. The three sheets were combined into a body by hot pressing. The hot pressing conditions were heated to 14 『c for 1 minute and 10 seconds, and the pressure was 8 Gkg/cm2, that is, a 5 cm×5 cm membrane electrode group, and the power of the membrane electrode group in air and oxygen, as shown in FIG. 4 and FIG. Example 2 Same as Example 1 Process 'This example changed the weight ratio of 20 wt% Pt/C to Nafion solid content from 2:1 to 1.75:1 to prepare a membrane electrode group, and the membrane electrode group was in air and The power in oxygen is shown in Figure 6 and Figure 7. Example 3 The same as the process of Example 1, this example changed the solid content ratio of 2〇wt% Pt/C and Nafi〇n solid content from 2:1 to 1.5:1 to prepare a membrane electrode group, and the membrane electrode group was in air and The power in oxygen is shown in Figure 8 and Figure 9. Example 4 The same procedure as in Example 1 was carried out, and the electrochemical propolar polarization curve of the MEA of Dupont's 212 proton exchange membrane was changed to 50" thickness of the composite proton exchange membrane containing water-absorbing ceramic micropowder, as shown in Fig. 10. [Simple description of the diagram] Figure 1. Photograph of the membrane electrode assembly. Figure 2, carbon gas diffusion layer production process. Figure 3. Process of making a membrane electrode assembly. Figure 4. Polarization curve of 15 mea in air at a weight ratio of 20 wt% Pt/C to Nafion solid content of 2:1. Figure 5. Polarization curve of MEA in oxygen at a weight ratio of 20 wt% Pt/C to Nafion solid content of 2:1. Figure 6. The weight ratio of 20 wt% Pt/C to Nafion solids by 丨, 75:1 MEA in air. Figure 7. Polarization curve of MEA in a gas ratio of 20 wt% Pt/C to Nafion solid content by 1.75:1. Figure 8. Polarization curve of MEA in a weight ratio of 20 wt% Pt/C to Nafion solid content by 丨.5:1. Figure 9. Polarization curve of MEA in oxygen ratio of 20 wt% Pt/C to Nafion solid content by weight ratio of 1.5:1. Figure 10, 50 " thickness of composite proton exchange enthalpy MEA polarization curve. [Description of main component symbols] X. Patent application scope: 1. A method for fabricating a fuel cell membrane electrode assembly, the process of which is a carbon gas diffusion layer preparation, a catalyst slurry preparation, and a multi-pass spray blasting method. Disperse on the surface of the carbon gas diffusion layer until the required catalyst content (the anode platinum amount is controlled at 〇. 0. 3mg/cm2 'the cathode platinum amount is 0. 3~0. 6mg/cni2), the catalyst electrode sheet is dried' last Then, a step of forming a membrane electrode group by hot pressing with a proton exchange membrane is carried out. 2. The method for producing a fuel cell membrane electrode assembly according to claim 1, wherein the ratio of Pt/C to Nafion solid content in the catalyst slurry is 1.2 to 3: b. The method for producing the fuel cell membrane electrode assembly of the present invention, wherein the Pt/C and Nafion solid content weight ratio is preferably 1.75:1.
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