1353679 九、發明說明： 【發明所屬之技術領域】 本發明係有關於一種孔洞性碳材薄膜，特別是有關於一 種具有孔洞規則性的碳材薄膜之製造方法及其作為過濾材、 電極材料、儲氫用途與在燃料電池電極與/或燃料電池膜電極 組(Membrane Electrode Assembly)之應用。 【先前技術】 目則燃料電池電極中觸媒的電子與氣體傳導介面，是以 氣體擴散層(Gas Diffusion Layer，GDL)所建構，通常是以碳紙 或石反布為主要基材，傳統的電極製作認為，GDL的必要處理 是以Teflon進行疏水處理，以避免電極泛溢現象的發生，除 此之外，並未見有關GDL處理的其他特性探討。不過文獻 報導使用外加電場來設計製作具結構規則性的電極，3M公 司的專利揭露酬性的碳材結構作為電鋪躺基材，都宣 稱具有提升電極效率的功能，而目前提供碳紙碳布做為狐 的廠商也已有許多種不_前處理，常見的是以碳黑顆粒塗 覆的碳紙碳布，-般認為有此塗覆層的gdl表面較平整， 因而使得所製錢極效率提升。雜絲顯示，雜gdl的 、”。構會衫響電極的效能，但目前文獻資料並未見有效能提升 真正原因的具體探討。 由電極結射GDL所扮料色而論，GDL f是電子的 6 良好傳導材’才能有效的收集傳導電極反應中的電子，過去 有文獻指出，多孔電極材料的微結構性質—包括孔洞型態、 大J與刀佈、孔洞規則性等—對其電性(electrical pr〇perties) 有非常密_她性。碳紙碳布触賊構讀供為反應 氣體進出的通道’而為了避免電極反應中的水因毛細作用填 滿孔隙’導致氣贿導纽，故需要將紐表面處理成疏水 性。上述的導電性與表面疏水性都是GDL碳材的必備特 性，而理論上孔洞結構體十的氣體傳導是受到孔道尺寸所影 響’孔道愈窄愈長’氣體傳導愈慢，因此孔洞結構體中的孔 道製作可能會是影響氣體傳輸’並進秘響電極反應效能的 個因素。有鑑於此，仍有需要開發新的製程以製造適合燃 料電池使用之具有孔洞規則性的碳材薄膜，並符合高導電性 與表面疏水性之需求’此料目前產#界相t重視的研發方 向0 【發明内容】 鑒於上述之發明背景中，為了符合產業上之要求，本 發明提供一種具有孔洞規則性的碳材薄臈之製造方法及其 應用。 本發明之-目的在於藉由-具有複數個規職孔洞的模 板’以製備具有孔洞規則性之碳材薄膜，其可作為孔洞過遽 與高溫等嚴苛條件下的過濾，也可 散層（GDL)。並延伸此碳材薄膜的 材，適用於強酸、強鹼、與高 作為燃料魏巾的氣體擴散層 擔體的雙功能簡併結構， 功此’兼做為金屬奈_粒的擔體，㈣為氣雜散與觸媒1353679 IX. Description of the Invention: [Technical Field] The present invention relates to a porous carbon material film, and more particularly to a method for producing a carbon material film having regular pores and as a filter material, an electrode material, Hydrogen storage applications and applications in fuel cell electrodes and/or Membrane Electrode Assembly. [Prior Art] The electron and gas conduction interface of the catalyst in the fuel cell electrode is constructed by a Gas Diffusion Layer (GDL), usually based on carbon paper or stone anti-cloth. Electrode fabrication believes that the necessary treatment of GDL is hydrophobic treatment with Teflon to avoid electrode flooding. In addition, no other characteristics of GDL treatment have been discussed. However, the literature reports the use of an external electric field to design and manufacture electrodes with regular structure. The 3M company's patented carbon material structure is used as an electric layup substrate, all of which claim to have the function of improving electrode efficiency. Currently, carbon paper carbon cloth is provided. As a manufacturer of foxes, there are many kinds of non-pretreatments. Commonly, carbon paper carbon cloth coated with carbon black particles is generally considered to have a smooth surface of the gdl of the coating layer, thus making the money Increased efficiency. The miscellaneous silk shows that the miscellaneous gdl, "the structure of the shirt is the performance of the electrode, but the current literature does not see the specific discussion of the effective can enhance the real cause. GDL f is the electron by the electrode gating GDL The 6 good conductive materials can effectively collect the electrons in the conduction electrode reaction. In the past, it was pointed out that the microstructural properties of porous electrode materials—including pore type, large J and knife cloth, and hole regularity—are electrical. (electrical pr〇perties) has a very dense _ her nature. Carbon paper carbon cloth touches the thief to read the passage for the reaction gas to enter and exit 'and in order to avoid the water in the electrode reaction to fill the pores due to capillary action' Therefore, it is necessary to treat the surface of the New Zealand into a hydrophobicity. The above conductivity and surface hydrophobicity are both essential characteristics of the GDL carbon material, and theoretically, the gas conduction of the pore structure is affected by the size of the channel, 'the narrower and longer the channel' The slower the gas conduction, the pore formation in the pore structure may be a factor affecting the gas transmission 'and the efficiency of the reaction of the electrode. In view of this, there is still a need to develop a new system. In order to manufacture a carbon material film with a hole regularity suitable for use in a fuel cell, and to meet the demand for high conductivity and surface hydrophobicity, the current research and development direction of the material is important. In order to meet the requirements of the industry, the present invention provides a method for manufacturing a carbon material thin crucible having a hole regularity and an application thereof. The present invention - the object is to prepare by having a template having a plurality of regular holes A regular carbon film that can be used as a filter under severe conditions such as pores and high temperatures, or as a layer (GDL), and extends the material of the carbon film for strong acid, alkali, and high. As a dual-function degenerate structure of the gas diffusion layer carrier of the fuel Wei towel, it is also used as a carrier of metal naphthalene, and (4) is gas stray and catalyst.
料，作為儲氫、電極材料等應用。 +本發明之另—目的在於提供可關便調控孔洞大小之碳 材薄膜製程’且本發明所形成之氣體傳導通道為直管結構， 以加速氣H傳輸。此外，為喊此储_應驗電極中可 能的泛溢(flooding)現象發生，可關由石墨化絲面疏水處 理碳材結射的孔道表_。據此，本發雜符合經濟上的 效益與產業上的利用性。 根據以上所述之目的，本發明揭示了兩種具有孔洞規則 性之碳材薄蘭製紗法，-種為赌—具有減個規則性 孔/同的模板。然後，以該模板（template)，進行一反模製造 程序以形成一反模，該反模具有與該模板互補之表面型態。 其次，移除該模板。接著，進行一碳材形成程序以形成一碳 材於該反模之孔洞中。最後，移除該反模，以形成該具有孔 洞規則性之碳材薄膜。另一種為提供一具有複數個規則孔洞 的模板，於規則孔洞中進行一管狀碳材形成程序，接著進行 一移除程序，用以形成一環狀孔隙，再於環狀孔隙進行一碳 材形成程序，藉此與該管狀碳材合倂形成一厚壁碳材，重複 進行該移除程序與該碳材職程序，據以形成—具有孔洞規 則性之碳材薄膜。 【實施方式】 *本發明在此所探討的方向為—種具有孔洞規則性的碳 材/專膜之方法及其應S。為了能徹底地瞭解本發明，將 在下列的财中提it}詳盡的製程步驟或組成結構。顯然地， =發明的施行縣蚊於該職之㈣麵熟習的特殊細 即。另-方面，騎周知的組成或製程步驟並未描述於細節 中’以避免造成本發明不必要之限制。本發明的較佳體系會 詳細描述如下，然崎了這轉細描述之外，树明還可以 廣泛地施行在其他的體系中，且本發明的範圍不受限定，以 其之後的專利範圍為準。 文獻中模板方法常見的以奈米孔隙性薄膜如高分子 (Polycarbonate，P〇lyester等)或是具孔洞規則性的氧化物通 常商業級咼分子模板厚度較薄(約6-1〇邮），孔洞密度較低 (約109-10丨2/cm2);具孔洞規則性的氧化物模板種類包括彿石 (zeolite)與 AAO (anodic aluminnum oxide，陽極處理鋁)薄膜， 氧化物模板的種類很多，可以有微孔或中孔、直孔或有歧孔 等的結構差異，故長成的碳材可以有不同的孔洞結構，是其 優點，不過目前沸石製成的薄膜中並無長程的孔洞排列規則 性，故無法製成具有長程孔洞規則性的碳材薄膜結構。相對 1353679 而吕’ AAO薄膜是已成熟的商品(如whatman，， AAO模板的孔洞呈現六角緊密排列(參考第一圖所示），有較 咼的孔洞密度（約1〇9_ 1〇12 /em2)，可以購得大至直徑47 mm、厚60 μιη的薄膜，其中孔洞的大小可以有2〇、1〇〇、 200 nm的選擇，適用於製備碳材薄臈的模板基材。 本發明之第一實施例揭露一種具有孔洞規則性之碳材 薄膜的製造方法，首先提供—具有複數倾雜孔洞的模 板，上述複數個規則性孔洞之孔徑小於或等於丨啤。然後， 以該模板（template) ’進行—反模製造程序以形成一反模， 該反模具有與該具複數個規則性孔洞的模板互補之表面型 態。其次，移除該模拓。垃基，& k . 移除賴板。接著，進行—雜抛程序以形成Materials, as hydrogen storage, electrode materials and other applications. + Another object of the present invention is to provide a carbon film process that can control the size of a hole and that the gas conducting channel formed by the present invention is a straight tube structure to accelerate gas H transmission. In addition, in order to call for the possible flooding phenomenon in the storage electrode, the hole table _ which is formed by the hydrophobicizing of the graphite material by the hydrophobic surface can be closed. Accordingly, this hybrid meets economic benefits and industrial applicability. In accordance with the above objects, the present invention discloses two carbon material thin-blue yarn making methods having a hole regularity, which is a bet--a template having a reduced regular hole/same. Then, using the template, a reverse mold manufacturing process is performed to form a counter mold having a surface pattern complementary to the template. Second, remove the template. Next, a carbon material forming process is performed to form a carbon material in the hole of the counter mold. Finally, the counter mold is removed to form the carbon material film having the regularity of the holes. Another method is to provide a template having a plurality of regular holes, a tubular carbon material forming process in the regular holes, followed by a removal process for forming an annular pore, and then forming a carbon material in the annular pores. The process, in combination with the tubular carbon material, forms a thick-walled carbon material, and the removal process and the carbon material service are repeated to form a carbon material film having a regular hole. [Embodiment] * The direction in which the present invention is discussed herein is a method of carbonaceous material/specific film having a regular hole and its response S. In order to thoroughly understand the present invention, detailed process steps or constituent structures will be mentioned in the following financial statements. Obviously, = the special details of the invention of the county mosquitoes in the position (4). In other instances, well-known components or process steps are not described in detail to avoid unnecessarily limiting the invention. The preferred system of the present invention will be described in detail below. In addition to this detailed description, Shuming can be widely implemented in other systems, and the scope of the present invention is not limited, and the scope of the following patents is quasi. The template method commonly used in the literature is a nanoporous film such as a polymer (Polycarbonate, P〇lyester, etc.) or a regular oxide with a hole. The commercial grade 咼 molecular template is thinner (about 6-1 〇). The density of the holes is low (about 109-10 丨 2 / cm 2 ); the types of oxide templates with regular holes include zeolite and AAO (anodic aluminnum oxide) films, and there are many types of oxide templates. There may be structural differences between micropores or mesopores, straight holes or pores, so the grown carbon material may have different pore structures, which is an advantage, but there is no long-range pore arrangement in the film made of zeolite. Regularity, it is impossible to produce a carbon material film structure having a long-range hole regularity. Relative to 1353679 and Lu 'AAO film is a mature commodity (such as whatman, AAO template hole is arranged in a hexagonal tight arrangement (refer to the first figure), there is a relatively narrow hole density (about 1〇9_ 1〇12 /em2 ), a film having a diameter of 47 mm and a thickness of 60 μm can be purchased, wherein the size of the pores can be selected from 2 Å, 1 Å, and 200 nm, and is suitable for preparing a template substrate of a thin carbon material. The first embodiment discloses a method for manufacturing a carbon material film having a hole regularity, firstly providing a template having a plurality of regular holes, wherein the plurality of regular holes have a pore diameter smaller than or equal to the beer. Then, the template is used. 'Performing-reverse-mold manufacturing process to form a counter-mold having a surface pattern complementary to the template having a plurality of regular holes. Secondly, removing the die-form, the base, & k. In addition to the board. Then, carry out the - parabolic process to form
於本實施例中’上述具有複數個規則性孔洞的模板係選 、高分子模板、沸石。而反 合屬、金屬氧化物、非金屬 自下列族群之一者：陽極氧化鋁、高 模材質包含下列族群中之一者：金屬 氧化物與高分子。上敎反難造料包含下職群中之-者：液相沉積法與氣相沉積法，其中，較佳者：溶膠凝膠法、 …、電鍍電/儿積、化學氣相沉積法與物理氣相沉積法。 於本實施狀-触範射，以轉礙縣為例，首先 提供-金狀氧基單體鱗金魏氧基單⑴說，其中，金 1353679 屬烷氧基單體或非金屬烷氧基單體110A係為液體或溶於一 /谷劑中。然後，導入金屬烷氧基單體或非金屬烷氧基單體 110A於模板丨2〇之孔洞中’以便於金屬烷氧基單體或非金屬 烷氧基單體110A水解與聚合，藉此形成反模11〇B。此外， 參考第二圖所示，上述之導入方式首先塗佈金屬烷氧基單體 或非金屬烷氧基單體110A於模板120的一面，其中，塗佈 方式包含滾筒塗佈（roller coating )、刮刀塗佈（bia(je coating)、浸泡式塗佈(dip_coating)、旋轉式塗佈⑺細幻 …等。接著，於模板120的另一面施加一吸引力（例如：抽 真空）以幫助金屬烷氧基單體或非金屬烷氧基單體ll〇A進 入模板120之孔洞中。 上述之碳材形成程序包含一碳材沈積程序，其包含下列 族群之一者：液相沉積法與氣相沉積法，其中，較佳者：溶 膠-凝膠法、無電鍍、電沉積、化學氣相沉積法與物理氣相沉 積法。 於本實施例之另一較佳範例中，碳材形成程序首先進行 一填料程序以導入至少一碳材前驅物於反模之孔洞中，其 中，碳材前驅物係為液體或溶於一溶劑中。上述之導入方弋 首先塗佈碳材前驅物於反模的一面，其中，塗佈方式包含衷 筒塗佈（roller coating)、刮刀塗佈（blade c〇ating)、浸泡式 11 塗佈(diP-coating)、旋轉式塗佈(spin_c〇ating)等。接著，於 反模的另—面施加—吸引力（例如：抽真空）以幫助碳材前 驅物進入模板之孔洞中。接著，進行一聚合程序以聚合位於 反模孔洞巾之前驅物。織，進行_練_序 以碳化反模孔财之聚合物，觀軸碳材_，其中，上 述之熱裂解程序的溫度大於或等於·。c。於本範例中，可 選擇性的調南上述之熱藤溫度，以石墨化卿成之碳材薄 膜。 於本實_之再-較佳範财，他材料沈積在模板 (如AAO)中’移除从〇製成反模，再進行碳材沈積製作， 如此可以齡絲來从〇相同結構的賴。此外，商講从〇 薄膜的使用問題在於其孔_距過大___，由於碳 材長成後AAO模板需去除，因此原來从〇薄膜的孔洞間 距即成為所得储結射的·，此過大的碳觀洞極有可 能不適於燃料電池咖用。另一方面，當使用AAO模板法 夺沈積的奴材薄膜需要再經連結製作為一個膜片構造。 除了上述製造方法外，本發明也提供了其麵以製造與 模板相同結構之碳臈的形成方法。 本發明之冑二實施侧露-種具有細制性之碳材 薄膜的製&方法’首先提供-具有複數個細孔洞的模板， 其中上述模板係能選自下顺群之—者：陽極氧脑、高分 12 1353679 子模板、彿;δ。其次，於上述規麻财進行—管狀碳材形 成程序’定義上述規則孔洞之孔壁與管狀碳材接觸面為一連 結面，接著，進行-移除程序，由上述之連結面向外移除部 份模板，藉此形成一環狀孔隙。 再者，於環狀孔隙進行一碳材形成程序，以填滿環狀孔 隙並與上述之管狀碳材合倂形成一厚壁碳材，重複進行上述 之移除輕序與上述之碳材形成程序，以移除全部模板，並形 成碳材以填滿厚壁碳材彼此間的碰，藉此形成—具有孔洞 規則性之碳材薄膜。 其中，上述之管狀碳材形成程序包含一第一導入程序與 -第-碳化程序，上述第—導入程序係為導入—碳材前驅物 於該規則孔洞之孔壁表面，並且，上述第一碳化程序，係藉 碳化於孔壁表面之碳材前驅物，以形成該管狀碳材。 於本實施例中，上述之管狀碳材形成程序有三種較佳範 例如下： 管狀奴材形成程序之較佳範例一，上述第一導入程序係 為一塗佈程序，碳材前驅物為一碳源分子，上述塗佈程序係 以一具有適當黏度之碳源分子均勻塗佈於該規則孔洞之孔 壁。其中，上述之碳源分子係選自下列族群之一者：高分子 溶液、醣類分子溶液、碳源氣體。 管狀碳材形成程序之較佳範例二，上述第一導入程序係 13 1353679 為一沈積程序，上述沈積程序係選自下列之一者：液相沉積 法與氣相崎法，其巾，較佳者··溶膠_娜法、無電鍍、電 沉積、化學氣相沉積法與物理氣相沉積法。 官狀碳材形成程序之較佳範例三，於完成第一導入程序 後、進行第-碳化程序之前，更包含一聚合程序以聚合位於 孔壁表面之碳材前驅物。 再者’上述之移除程序係藉由腐蝕性溶液自該連結面向 外洗飯移除纖板，其巾，上稍雜溶㈣選自下列族群 之一者：強酸溶液、強鹼溶液。 而後，上述碳材形成程序包含一第二導入程序與一第二 碳化程序’上述第二導人程序係鱗人—碳材前驅物用以填 充於該環狀孔隙，而上述第二碳化程序，係藉碳化填充於環 狀孔隙之碳材前驅物’並與上述之管狀碳材合倂形成該厚壁 碳材。 於本實施例中，上述之碳材形成程序有三種較佳範例如 下： 碳材形成程序之較佳範例- ’上述第二導入程序係為一 填料程序’碳材前驅物為-碳源分子，上述填料程序係以一 具有適當黏度之碳源分子均勻填充於該於該環狀孔隙。其 中’上述碳源分子係選自下列族群之一者：高分子溶液、餹 類分子溶液、碳源氣體。In the present embodiment, the above-mentioned template having a plurality of regular pores is selected as a polymer template or a zeolite. Anti-genus, metal oxides, non-metals from one of the following groups: anodized aluminum, high-molecular materials containing one of the following groups: metal oxides and polymers. The upper anti-difficult materials include those in the lower-level group: liquid deposition method and vapor deposition method, among which, preferred are: sol-gel method, ..., electroplating electricity/child product, chemical vapor deposition method and Physical vapor deposition. In this embodiment-touching, in order to turn to the county as an example, firstly provide a gold-like oxy-monomer squamous sulphate (1), wherein gold 1353679 is an alkoxy monomer or a non-metal alkoxy group. Monomer 110A is a liquid or soluble in a / granule. Then, a metal alkoxy monomer or a non-metal alkoxy monomer 110A is introduced into the pores of the template 丨2〇 to facilitate hydrolysis and polymerization of the metal alkoxy monomer or the non-metal alkoxy monomer 110A. Form the inverse mold 11〇B. Further, referring to the second drawing, the above-described introduction method first coats a metal alkoxy monomer or a non-metal alkoxy monomer 110A on one side of the template 120, wherein the coating method includes roller coating. , bia (je coating), dip coating (dip_coating), rotary coating (7), etc. Next, an attractive force (for example, vacuum) is applied to the other side of the template 120 to assist the metal. The alkoxy monomer or non-metal alkoxy monomer ll 〇 A enters the pores of the template 120. The carbon material forming procedure described above comprises a carbon material deposition procedure comprising one of the following groups: liquid deposition and gas A phase deposition method, preferably, a sol-gel method, an electroless plating method, an electrodeposition method, a chemical vapor deposition method, and a physical vapor deposition method. In another preferred embodiment of the present embodiment, a carbon material forming program First, a filler program is introduced to introduce at least one carbon precursor into the cavity of the reverse mold, wherein the carbon precursor is liquid or dissolved in a solvent. The above-mentioned introduction square is first coated with a carbon precursor. One side of the mold, where The coating method includes a roller coating, a blade coating, a dip-coating, a spin coating, and the like. Another surface application—attraction—for example, vacuuming—to help the carbon precursor enter the hole in the template. Next, a polymerization process is performed to polymerize the precursor before the reverse mold hole. The carbonization counter-conducting polymer, the axial carbon material _, wherein the temperature of the thermal cracking process is greater than or equal to · c. In this example, the temperature of the above-mentioned hot vine can be selectively adjusted to Graphiteized into a carbon film. In this case, the material is deposited in a template (such as AAO) to remove the anti-mold from the crucible and then deposit the carbon material. The wire comes from the same structure. In addition, the problem with the use of the film is that the hole _ is too large ___, because the AAO template needs to be removed after the carbon material is grown, the hole spacing from the film is the result. It’s very likely that this too large carbon hole will be stored. It is not suitable for fuel cell coffee. On the other hand, when the AAO template method is used to capture the deposited material film, it needs to be connected to make a film structure. In addition to the above manufacturing method, the present invention also provides the surface to manufacture and template. A method for forming a carbon crucible having the same structure. The second embodiment of the present invention is a method for producing a thin carbon film having a fineness. First, a template having a plurality of fine pores, wherein the template is selectable From the next group - the anodic oxygen brain, high score 12 1353679 sub-template, Buddha; δ. Secondly, in the above-mentioned regulation of the money - tubular carbon material formation program 'defined the above-mentioned regular hole hole wall and tubular carbon material contact The face is a joint face, and then a removal-removal process is performed to remove a portion of the formwork from the joint face described above, thereby forming an annular void. Furthermore, a carbon material forming process is performed on the annular pores to fill the annular pores and merge with the tubular carbon material to form a thick-walled carbon material, and the above-mentioned removal of the light order and the formation of the carbon material are repeated. A procedure is to remove all of the stencils and form a carbon material to fill the gaps of the thick-walled carbon materials, thereby forming a carbon material film having a regular hole. Wherein, the tubular carbon material forming program includes a first introduction process and a -carbonization process, wherein the first introduction process is to introduce a carbon material precursor on a surface of the hole wall of the regular hole, and the first carbonization The procedure is to form the tubular carbon material by carbonaceous precursors that are carbonized on the surface of the pore walls. In the present embodiment, the above-mentioned tubular carbon material forming procedure has three preferred examples as follows: In the preferred example of the tubular slave material forming procedure, the first introducing procedure is a coating procedure, and the carbon material precursor is a carbon. The source molecule, the coating procedure described above is uniformly applied to the pore walls of the regular pores by a carbon source molecule having an appropriate viscosity. Wherein the carbon source molecule is one selected from the group consisting of a polymer solution, a saccharide molecule solution, and a carbon source gas. In a preferred example of the tubular carbon material forming procedure, the first introduction program 13 13353679 is a deposition process, and the deposition procedure is selected from one of the following: liquid deposition method and gas phase method, and the towel is preferred. · Sol-Na, electroless plating, electrodeposition, chemical vapor deposition and physical vapor deposition. A preferred example 3 of the official carbon material forming process includes a polymerization process to polymerize the carbon precursor on the surface of the pore wall after the first introduction process and before the first carbonization process. Further, the above-mentioned removal procedure removes the fiberboard from the joint surface by a corrosive solution, and the towel is slightly miscible (4) selected from one of the following groups: a strong acid solution, a strong alkali solution. Then, the carbon material forming process includes a second introduction process and a second carbonization process 'the second guide program is a scale-human carbonaceous precursor for filling the annular pore, and the second carbonization process, The thick-walled carbon material is formed by carbonizing a carbonaceous material precursor filled in an annular pore and combining with the tubular carbon material described above. In the present embodiment, the above carbon material forming procedure has three preferred examples as follows: A preferred example of the carbon material forming procedure - 'The second introduction procedure is a filler procedure' carbon precursor is a carbon source molecule, The above filler program is uniformly filled in the annular pores with a carbon source molecule having an appropriate viscosity. Wherein the above carbon source molecule is selected from one of the following groups: a polymer solution, a hydrazine type molecular solution, and a carbon source gas.
碳材軸程序之魏_二上述第三導人程序係為一 ，積程序’上述沈積程序係選自下列之-者：液相沉積法與 氣相/冗積法其較佳者：溶膠礙膠法、無電n冗積、 化予氣相’"L·積法與物理氣相沉積法。 石反材形成程序之較佳範例三，於完成第二導入程序後、 進行第二碳化辦之前，更包含—聚合辦崎合位於填充 於環狀孔隙之碳材前驅物。 碳材形成程序之較佳_四，於上述具有細規則性之 碳材薄膜形成後’藉由進行一高溫處理程相便於石墨化該 碳材薄膜。 另一方面，上述之第一碳化程序與第二碳化程序皆係為 一熱裂解程序（pyrolysis)，其溫度大於或等於5〇〇〇c。在上 述兩個實施例中，上述之碳材薄膜材料的較佳選擇有奈米碳 管(CNT，carbon nanotube)、奈米碳纖(CNp，carbon nan〇flber) …等。一般而言，化學氣相沉積法(Chemicalvap〇rdep〇siti〇n method)係為製造奈米碳管的常見方法。其特點係在基材上以 離子佈植、熱蒸鑛甚至液相塗佈等方法艘過渡金屬催化劑於 基材上’並於高溫爐中退火或還原，使其成為金屬奈米顆粒， 再以乙块、甲烷等碳氫化合物氣體進行化學氣相沉積奈米碳 管。其優點是製程溫度低，分佈均勻，純度高不需純化，製 程便宜方便’大面積及成長排列整齊之奈米碳管。 15 1353679 化學氣相沉積法(CVD)又可分為(1)高熱分解化學氣相沉 積法(Thermal cvd)與(2)微波電漿化學氣相沉積(Micr〇waveThe carbon material axis program Wei _ 2 above the third person guide program is one, the product program 'the above deposition program is selected from the following: liquid deposition method and gas phase / redundancy method is preferred: Glue method, no electricity n redundant product, chemical phase to gas phase '&L; L method and physical vapor deposition method. The preferred example 3 of the stone counter-material forming procedure is that, after the completion of the second introduction process, before the second carbonization process, the polymerization-containing carbonaceous precursor filled in the annular pores is further included. Preferably, the carbon material forming process is four. After the formation of the fine-grained carbon material film, the carbon material film is easily graphitized by performing a high-temperature treatment process. On the other hand, the first carbonization procedure and the second carbonization procedure described above are both pyrolysis and the temperature is greater than or equal to 5 〇〇〇c. In the above two embodiments, the carbon material film material is preferably selected from the group consisting of carbon nanotubes (CNTs), carbon nanotubes (CNp, carbon nan〇flber), and the like. In general, the chemical vapor deposition method (Chemicalvap〇rdep〇siti〇n method) is a common method for producing carbon nanotubes. The method is characterized in that the transition metal catalyst is sprayed on the substrate by ion implantation, hot steaming or even liquid phase coating on the substrate and is annealed or reduced in a high temperature furnace to make it into a metal nanoparticle, and then A hydrocarbon gas such as a block or a methane is subjected to chemical vapor deposition of a carbon nanotube. The advantages are low process temperature, uniform distribution, high purity without purification, and the process is cheap and convenient. The large-area and well-arranged carbon nanotubes are arranged neatly. 15 1353679 Chemical vapor deposition (CVD) can be further divided into (1) thermal decomposition chemical vapor deposition (Thermal cvd) and (2) microwave plasma chemical vapor deposition (Micr〇wave)
Plasma Chemical Vapor Deposition，MPCVD)，其中，高熱分 解化學氣相沉積法(Thermal CVD)為在高溫爐中汽化分解觸 媒成小顆粒，除去過渡金屬表面的氧化物，再導入碳氫化合 物的奴源氣體合成奈米碳管，此方法不需要鍍有過渡金屬觸 媒基板，因此可以連續式的合成奈米碳管，在高溫爐中，通 入氬氣加熱至100(TC ’然後通入氫氣還原金屬氧化物，沉積 一小時後通入氫氣並冷卻至室溫，可以得到奈米碳管。另一 方面’微波電漿化學氣相沉積(MPCVD)是近絲所發展的新 製程，可控制奈米碳管的成長方向且縮短了成長的時間，做 法是先將金屬催化舰在“上，再將其放人微波化學氣相 沉積裝置t成長奈米碳管，所採用的氣體為甲烧與氫氣的混 合氣體或乙块與魏的混合氣體，此法姻賴解離碳氣化 合物’由於在電渡的系統中，利用高活性的氣體如乂及H2 可以活化金屬觸媒’可以在較低的溫度下製備奈米碳管。 本發明所製造之具有孔洞規則性之碳材薄麟應用於燃 料電池電極與㉖燃料電池膜電極組的製備，特別是應用於氣 體擴散層且/或觸媒擔體層的製備。—般而言，當材料表面的 疏水性高時，1 μιη大小的孔洞就不會有積水泛溢的現象發 生’而1 μΐη大小的孔道中的氣體通透性是相當好的。當孔 16 1353679 道表面的疏水性低時’可預期毛細現象會導致孔道中有積水 泛溢現象，：t小孔道中的積水泛溢會愈嚴重。由此可知碳 材薄膜需要具有表面疏水性以應用於燃料電池中的氣體擴散 層，這可藉由結構的石紐來達成，；δ墨化結_時也具有 較高的導電性’在上述兩個實施例中，於形成該具有孔舰 則性之碳膜後可以進行—高溫處理程相便於石墨化碳 材除了石墨化以外’表面處理也是一個改變表面疏水性質 的處理絲，於具有麵規職之碳_獅錢，可以進 行一疏水性表面改質程序。 如同前面所述’上述之碳材細材料的—個較佳選擇係 為奈米碳管，奈米碳管擁有⑽觸電子和物理性質，其電 子性質會隨著晶體結構料同雜大的改變，如刊的直徑 與螺旋性都會造成奈求碳管的電子性質是半導體 鲁 （―Γ曰)或是金屬(Metal)。奈米碳管是碳的同素異構 體之- ’主要是由碳軒所組成的__觀碳物質，碳原子有 三種可能的混成軌域SP、SP2和sp3，而奈米碳管中的每一個 原子都和相鄰的三個碳原子相連，形成六角形網格結構，因 此奈米碳管中的碳原子主要是以sp2混成軌域來做結合，和 石墨-樣其主要的結構都是以sp2混成軌域為主，所以奈米 碳管擁有好和石墨她的物理、化學性質，但是奈米碳管 的結構比起石細複雜衫，奈米碳管可以想像成是由碳原 Π 1353679 ，所組成的六角形二維蜂巢狀的石墨片，捲曲成—維中空圓 筒…構而直從為幾十奈米㈣但長度卻可達數十微米 m)所以不米碳管有很大的長徑比(均⑽r_)，所以我們 可以視為-維材料，而管壁的碳原子會因為石墨片所捲曲的 角度不同’而使得管壁的六角環和其錄呈現不同的對稱性 質’這些不同的對稱性質造成六角環和其管軸呈現一夾角， 這一個夾角為奈米碳管的螺旋角。依照不同的螺旋角，可以 分成三種不同螺旋性的奈米碳管，並決定奈米碳管具有金屬 傳導特性，或是是為半導體傳導特性。 第一範例具有孔洞規則性之碳材薄膜之製程 步驟一、將具有複數個規則孔洞之AAO (anQdie aluminnum oxide，陽極處理鋁)模板浸泡於溶解於環氧溶液之 碳源分子t，隨後於絕對溫度923度/氮氣下進行一碳化程序； 步驟二、利用強驗溶液-氫氧化鉀溶液餘除部份AAO模 板；以及 步驟三、重複步驟一與步驟二，直至移除全部AAO模 板，形成一完整之具有孔洞規則性之碳材薄膜，參考第三圖 所示。Plasma Chemical Vapor Deposition (MPCVD), in which high thermal decomposition chemical vapor deposition (Thermal CVD) is a source of vaporization of a catalyst into a small particle in a high temperature furnace to remove oxides on the surface of the transition metal and then introduce hydrocarbons. The gas is synthesized into a carbon nanotube. This method does not need to be plated with a transition metal catalyst substrate. Therefore, the carbon nanotube can be continuously synthesized. In a high temperature furnace, argon gas is heated to 100 (TC ' and then hydrogen gas is introduced. Metal oxide, after one hour of deposition, hydrogen is introduced and cooled to room temperature, and a carbon nanotube can be obtained. On the other hand, 'microwave plasma chemical vapor deposition (MPCVD) is a new process developed by the near silk, which can control the naphthalene. The growth direction of the carbon tube has shortened the growth time. The method is to first put the metal catalyst ship on the top, and then put it into the microwave chemical vapor deposition device to grow the carbon nanotubes. A mixed gas of hydrogen or a mixed gas of ethylene and Wei, which is a solution to the dissociation of carbon-gas compounds. 'In the system of electric ferry, high-activity gases such as helium and H2 can activate metal catalysts'. To prepare a carbon nanotube at a lower temperature. The carbon material having a hole regularity manufactured by the present invention is applied to the preparation of a fuel cell electrode and a 26 fuel cell membrane electrode assembly, particularly to a gas diffusion layer. / or the preparation of the catalyst carrier layer. In general, when the surface of the material is highly hydrophobic, there is no water overflow in the pores of 1 μm size, and the gas in the pores of the size of 1 μΐη is transparent. The sex is quite good. When the hydrophobicity of the surface of the hole 16 1353679 is low, it is expected that the capillary phenomenon will cause water overflow in the channel, and the water overflow in the small channel will be more serious. The film needs to have a surface hydrophobicity for use in a gas diffusion layer in a fuel cell, which can be achieved by a structure of a stone; δ inkization also has a higher conductivity' in both embodiments After forming the carbon film with the hole ship, the high temperature treatment process can facilitate the graphitization of the carbon material except for the graphitization. The surface treatment is also a treatment wire for changing the surface hydrophobic property. The carbon of the tactical _ lion money can be subjected to a hydrophobic surface modification procedure. As mentioned above, the preferred choice for the above-mentioned carbon material fine material is a carbon nanotube, and the carbon nanotube has (10) electron contact. And the physical properties, its electronic properties will change with the crystal structure, such as the diameter and the helicity of the publication will cause the electronic properties of the carbon tube is semiconductor Lu (-) or metal (Metal). The carbon nanotubes are the allotropes of carbon - 'mainly consisting of carbonaceous materials, carbon atoms have three possible mixed orbitals SP, SP2 and sp3, while in carbon nanotubes Each atom is connected to three adjacent carbon atoms to form a hexagonal lattice structure. Therefore, the carbon atoms in the carbon nanotubes are mainly combined by the sp2 mixed orbital domain, and the graphite-like main structure. They are mainly sp2 mixed orbital, so the carbon nanotubes have good physical and chemical properties of graphite, but the structure of the carbon nanotubes is more complicated than that of the stone, and the carbon nanotubes can be imagined to be carbon. Original Π 1353679 , composed of hexagonal two-dimensional honeycomb graphite , curled into a dimensional hollow cylinder...the structure is straight from tens of nanometers (four) but the length is up to tens of micrometers m) so the carbon nanotubes have a large aspect ratio (both (10)r_), so we can see It is a dimensional material, and the carbon atoms in the tube wall will cause different symmetry properties of the hexagonal ring of the tube wall and its recording due to the different angles of the curl of the graphite sheet. These different symmetrical properties cause the hexagonal ring and its tube axis to be presented. An angle, this angle is the helix angle of the carbon nanotube. According to different helix angles, it can be divided into three kinds of different helical carbon nanotubes, and it is determined that the carbon nanotubes have metal conduction characteristics or are semiconductor conduction characteristics. The first example is a process for preparing a carbon material film having a regular hole. The first step is to soak an AAO (anQdie aluminum oxide) template having a plurality of regular holes in the carbon source molecule t dissolved in the epoxy solution, followed by absolute a carbonization procedure is carried out at a temperature of 923 degrees/nitrogen; Step 2: using a strong solution-potassium hydroxide solution to remove a portion of the AAO template; and step 3, repeating steps 1 and 2 until all AAO templates are removed to form a A complete carbon film with regular pores is shown in Figure 3.
參考第四圖所示，先前文獻(C.-T. Hsieh，J._M. Chen，R.-R. Kuo, Y.-H· Huang，Appl. Phys. Lett. 84(2004)1186.)使用 AAO 1353679 模版與一步驟移除法所製成之碳材結構係為一具有結構缺陷 之碳材薄膜結構；相對地，本發明使用多步驟移除法所獲得 之碳材結構係為一連續完整之碳材薄膜結構，本發明解決先 前技術中長期存在的薄膜結構缺陷問題，得佐證本發明並非 能輕易完成。 如同則述，本發明所製造之具有孔洞規則性之碳材薄膜 係應用於燃料電池中氣體擴散層且/或觸媒擔體層的製備。因 此’菖元成具有孔洞規則性之碳材薄膜後，更包—觸媒顆 粒沈積程序，以賦予碳材薄膜作為觸媒擔體之功能。當具有 孔洞規則性之碳材薄膜形成後、並經過石墨化或疏水性表面 改質程序’此碳材薄膜已具魏體擴散層之功能，之後再對 上述之碳材薄膜進行觸媒顆粒沈積程序，即可形成具有氣體 擴散與觸媒觀雙魏賴合碳材t料孔洞規則性 之碳材薄膜形成後’直接進行上述觸媒顆粒沈積程序，即形 成具有觸媒擔體功能之複合碳材薄膜。 顯然地，依照上面體系中的描述，本發明可能有許多的 修正與差異。因此需要在其附加的翻要求項之範圍内加以 理解，除了上述詳細的描述外’本發明還可以廣泛地在其他 的體系中施行。上賴為本發明之錄_耐，並制以 限定本發狀巾料赚圍；凡其妹雌树騎揭示之 精神下所完成的等效改變或_，包含在下述中請專利 19 1353679 範圍内Referring to the fourth figure, the previous literature (C.-T. Hsieh, J._M. Chen, R.-R. Kuo, Y.-H. Huang, Appl. Phys. Lett. 84 (2004) 1186.) The carbon material structure prepared by using the AAO 1353679 template and the one-step removal method is a carbon material film structure having structural defects; in contrast, the carbon material structure obtained by the multi-step removal method of the present invention is a continuous The complete carbon material film structure, the present invention solves the problem of long-standing film structure defects in the prior art, and it is corroborated that the present invention is not easily accomplished. As described above, the carbon material film having the hole regularity manufactured by the present invention is applied to the preparation of a gas diffusion layer and/or a catalyst carrier layer in a fuel cell. Therefore, after the carbon material film having the regularity of the hole is formed, the catalyst-particle deposition process is further applied to impart the function of the carbon material film as a catalyst carrier. When a carbon material film having a regular hole shape is formed and subjected to a graphitization or hydrophobic surface modification process, the carbon material film has a function as a Wei body diffusion layer, and then the above-mentioned carbon material film is subjected to catalytic particle deposition. The procedure can form a carbon fiber film having a regularity of a gas diffusion and a catalyst-based double-weilai carbon material, and then directly perform the above-mentioned catalyst particle deposition process to form a composite carbon material film having a catalyst carrier function. . Obviously, the invention may have many modifications and differences in accordance with the description in the above system. Therefore, it is to be understood that within the scope of the appended claims, the invention may be widely practiced in other systems in addition to the detailed description above. The above is the record of the invention _ resistance, and the system is limited to make the hair of the hair towel to make a circle; the equivalent change or _ completed by the spirit of the girl's tree-tree revealing is included in the following patent 19 1353679 Inside
【圖式簡單說明】 第一圖顯示陽極處理鋁（AAO)模板的掃瞄式電子顯微 鏡（SEM)照片；與 第二圖係為金屬烷氧基單體或非金屬烷氧基單體導入具 有複數個規則性孔洞的模板的流程示意圖。 第二圖係為本發明之一較佳範例中，最後所製成之具有 孔洞規則性之碳材薄膜的掃瞄式電子顯微鏡（SEM)照片。 第四圖係為先前文獻所製成的碳材陣列結構之掃瞄式電 子顯微鏡（SEM)照片。 【主要元件符號說明】BRIEF DESCRIPTION OF THE DRAWINGS The first figure shows a scanning electron microscope (SEM) photograph of an anodized aluminum (AAO) template; and the second figure is a metal alkoxy monomer or a non-metal alkoxy monomer introduced with A schematic flow diagram of a template of a plurality of regular holes. The second drawing is a scanning electron microscope (SEM) photograph of a carbon film having a hole regularity which is finally produced in a preferred embodiment of the present invention. The fourth figure is a scanning electron microscope (SEM) photograph of a carbon material array structure prepared in the prior literature. [Main component symbol description]
金屬烷氧基單體或非金屬烷氧基單體ll〇A 反模110B 具有複數個規則性孔洞的模板120 21Metal alkoxy monomer or non-metal alkoxy monomer ll 〇 A inverse mold 110B template having a plurality of regular pores 120 21