1305966 九、發明說明： 【發明所屬之技術領域】 本發明主要是涉及甲_料電 特別是針對低甲醇穿透率並保有高質子傳導的薄Ϊ製7。技術之改良， 【先前技術】 目前低溫(溫度低於l〇0〇c)操作之子醇燃 氟碳化物(Nafion，Dup〇ntC〇)質子 ^胳’，使用續酸聚 碳化物質子交換薄具有極佳的Hi 電極組。顧聚氣 (>28〇。〇，高質子傳雜力雜:: 安紐，高分解溫度 甲醇由陽極經過薄膜穿透至陰極，°^^效甲=電池，常因燃料 質子交換薄膜的曱醇穿透率並仍保有吏 醇燃料電池的-健要·。 b疋裝作甲 【發明内容】 基於前段所述’本發明之主要目的是提供_新的製健子交換薄 膜技術，使質子交換賴具有較低的甲醇穿轉並仍財良好的質子 傳導能力。 ' 是以本發明提供-種製備微結構排齊的俩化聚合物薄膜的 方法，其包括： (1) 配製磺酸聚氟碳化物溶液； (2) 將純確酸聚氟碳化物固體以有機溶劑溶解配製成績酸聚氟 碳化物溶液； ⑴於溫度低於Tg以下除去溶劑，得到無定形(am〇iph〇us)續酸 聚|L礙化物薄膜； (4) 將磺酸聚氟碳化物薄膜置於電場實驗裝置之電場中；及 (5) 磺酸聚氟碳化物薄膜加熱處理。 1305966 。其中較佳的加熱溫度為〜2贼；更麵加熱溫度為丨成〜 1S0C ’最佳的加熱溫度為1耽’其巾難的電場強度為心⑽·,〜 ;更佳的電場強麟〜;最㈣電場強度為 2kvcm〜Skvem—1。此外本發啊純含其他倾，辭·包含於 驟（5)後進行下列步驟： (6) 使置於電場的磺酸聚氟碳化物薄膜快速降溫； (7) 當磺酸聚氟碳化物薄膜降溫至Tg以下，移除電場；及 (8) 固定磺酸聚氟碳化物薄膜薄膜微結構。 製備顧化聚合物薄膜的時候，其中除去溶劑的方式為將該峰酸 聚氟碳化物溶液真空加熱，其中較佳的加熱溫度為6(rc〜8(rc，一般 的加熱時間為1〜3小時；較佳的加熱時間為2小時。 此外，關於製備本發明的有機溶劑，其中有機溶劑係選自於 Ν,Ν^-dimethyl formamide (DMF) > N,N5-dimethyl acetamide (DMAc) > N-methyl formamide (NMF)^ tetrahydroforane (THF) ； 為 N，N’-dimethyl acetamide (DMAc) 〇 是以本發明另提供-種雜化聚合_膜，其包含微結構排列整 齊的薄膜微結構。該_係可為_巾請專利綱第i項之方法所製 備0 因此本發狀其具赫子導概及低甲醇穿透率。其微結 構的整齊排列是藉纟純電場誘導與加熱來料丨離子轉大小與排列 方向。此外，本發明中，其平面係可平行於電場方向。本發明之薄膜， 其中-般_子導電性為l().3S/em〜2xl().lS/em ;較佳的離子 為 l(T2S/cm。 依照本發明之特色，錢可應祕直接㈣婦電池之薄膜係具 1305966 有低曱醇穿透率，其能使得直接甲_料電池之薄 透率i且錄触高質子料能力。 、有低甲醇穿 是以本發明另提供—種控制確酸聚氟碳化物肖膜 裝置，其包括： 做、$。構的 (1) 根據申請專利範圍第1項薄膜；及 (2) 一組正負電極板， 其中根據中請專利細第丨項之薄膜，雜聚氟碳化物_是置於正 f電極板的中間。此外本發明也可另包括：—個高電壓電源控制器及 —溫度控制箱。本發明之裝置，其中正負電極板之形狀係為圓形、正 方形與長條形，其中正負電極板之距離係可任意調整。 為達^述目的，在本發明實施方式中，係將未經高溫加熱處理或 不含結晶態之磺酸聚氟碳化物，在溫度介於高分子材料的％及融點 (Tm〜220 C)之間加熱，提供高分子鏈運動能量，並同時施以高壓電場 誘導高分子支鏈的磺酸官能基產生規則排列，不會產生大粒徑的離子 聚集’形成孔徑約〜10〜2〇 nm之質子傳導通道，可降低薄膜的甲醇穿透。 根據一般高分子物理教科書記載，在溫度介於高分子材料的％及 融點(Tm=〜220°C)之間加熱可提供高分子鏈適宜的運動能量，促使高分 子鏈運動進而促使互容之分子鏈段產生聚集。磺酸聚氟碳化物疏水性 主鏈的四氟乙烯與其親水性支鏈的磺酸四氟乙醚互不相容，在 110〜200°C之間加熱，會促使親水性支鏈的磺酸官能基互相聚集產生離 子聚集，而疏水性主鏈的四氟乙烯亦會互相聚集，產生無定形 (amorphous)及部份結晶形態(圖一)[參考文獻丨]。文獻報導利用小角χ_ 光及中子散射實驗[參考文獻2及3]，證實此離子聚集成球形，其直徑 約在30〜40nm。球聚集與球聚集之間經由較狹小離子聚集管道連結， 它是薄膜傳導質子的通道(圖二)[參考文獻2]。 若將未含結晶形態之薄膜在溫度介於高分子材料的Tg及融點 1305966 (Tm=~220°C)之間加熱，並同時施以高壓電場誘導高分子支鏈的磺酸官 能基順著電場方向產生規則排列，則可減少大粒徑的離子聚集，形成 孔徑較小之質子傳導通道，降低薄膜的甲醇穿透(圖三）。 參考文獻 1. K. Kordesch and G Simader: Fuel Cells and Their Applications > 1996， VCH Publisher» verlagsgesellschaft mbH. Weinheim (Germany)» page 79. 2. T.D. Gieker，G.E. Munn，and F‘C. Wilson，J. Polym. Sci.，Polym· Phys. Ed. > 19，1687-1704 (1981)，Figure 18. 3. G. Gebe卜 Polymer，41，5829-5838 (2000)，Figure 7. 【實施方式】 本發明所提出之薄膜製作方式，將藉由以下之製作程序的實施方式 及附呈圖示作進一步之說明。 1. 磺酸聚氟碳化物溶液之配製-由杜邦公司購得之磺酸聚氟碳化物溶 液(5 wt%績酸聚氟碳化物+ 95 wt%醇水混合溶劑)以60°c在真空狀態 下加熱’除去溶劑得到純磺酸聚氟碳化物固體。 2. 將純磺酸聚氟碳化物固體以有機溶劑，例如：n，N’-dimethyl formamide (DMF) » N > N?-dimethyl acetamide (DMAc) > N-methyl formamide(NMF)，tetrahydrofUrane(THF)等，溶解配製成濃度約 10〜40 wt%之確酸聚氟破化物溶液。 3·將純續酸聚氟碳化物之有機溶液倒入玻璃蒸發皿，在真空狀態下以 60〜80°C加熱約2小時除去溶劑，得到純磺酸聚氟碳化物之薄膜。 4.將確酸聚氟碳化物之薄膜1 〇 4置於電場實驗裝置(圖四），電場的 1305966 強度可經由高電壓電源供應器i i調整強度及正負電極丄◦ 3 之間的距離來㈣，電場的誠與電縫度成正比，而與兩電極板之 間„献比。並_溫度箱控繼i Q 2將實驗溫度控制在續酸 聚氟碳化物的18與丁„1之間(110〜2O〇0C)，電場強度控制在 之間，實驗時間20〜120分鐘。 5. 薄膜甲醇穿透率量測—如圖五裝置，將膜央至兩玻璃edl中間，膜 材兩側分別裝濃度3M甲醇/水溶液（A槽）和水（B槽），A槽和3槽 的體積皆爲102ml。每隔一固定時間，抽取B槽的溶液（〇 2山），並 以氣相層析儀（GC，HP_859〇A; Agilent capillary column 30m X 〇.53mm x20麵m)測量甲酵濃度，而甲醇滲透率XMe〇H可由式(1)求得。薄膜之 曱醇參透面積為5.31 cm2。 X 妙甲度wt% ^厚 膜面積 6. 薄膜導電度量測一利用頻率應答分析儀(AC_Impedance; SA1125B， Solatron Co.)量測薄膜阻抗。薄膜放置於電極中間於恆溫恆濕箱（溫度 75~90°C相對溼度95%)下進行薄膜阻抗量測實驗。量測之阻抗值代入 式(2)，可求得薄膜的離子導電度。 〇 =L/(RxA) (2) 式(2)中，σ=導電度(ScnT1);!^膜厚(cm);R=膜材阻抗值(Ω);Α=電 極與薄膜接觸的面積(Α= 3.14 cm2)。 實驗例-1 續酸聚氟碳化物以N，N’-dimethyl acetamide (DMAc)溶解配製成10 wt%溶液。將溶液倒入玻璃蒸發皿，在真空狀態下以60〜80°C加熱約5 小時除去溶劑，得到純磺酸聚氟碳化物之薄膜。將磺酸聚氟碳化物薄 1305966 膜1 〇 4置於夾具1 〇 5，並垂直置放於正負電極板i〇2之間，電壓 控制在15KV ’正負電極板1 0 3之間的距離4.35 cm，溫度120oC，實 驗時間30分鐘。 實驗例-2 崎酸聚氟碳化物以N ’ N，-dimethyl acetamide (DMAc)溶解配製成1〇 wt%溶液。將溶液倒入玻璃蒸發皿，在真空狀態下以6〇〜8〇Cc加熱約5 小時除去溶劑’得到純磺酸聚氟碳化物之薄膜。將磺酸聚氟碳化物薄 膜10 4置於夾具1〇 5 ’並水平置放於正負電極板10 2之間，電 壓控制在15KV，正負電極板【〇 3之間的距離4 35 cm，溫度12〇〇c， 實驗時間30分鐘。1305966 IX. Description of the invention: [Technical field to which the invention pertains] The present invention relates mainly to a material, particularly a thin tantalum system 7 which has a low methanol permeability and high proton conduction. Improvement of technology, [Prior Art] At present, the low temperature (lower temperature than l〇0〇c) operation of the fluorocarbon carbide (Nafion, Dup〇ntC〇) protons, using a continuous acid polycarbide sub-exchange thin Excellent Hi electrode set. Gu Juqi (>28〇.〇, high protons are mixed with heterogeneous:: Annu, high decomposition temperature methanol passes through the membrane through the anode to the cathode, °^^effective A = battery, often due to fuel proton exchange membrane The sterol penetration rate still retains the health of the sterol fuel cell. b 疋 作 【 【 【 基于 基于 基于 基于 基于 基于 基于 基于 基于 基于 基于 基于 基于 基于 基于 基于 基于 基于 基于 基于 基于 基于 基于 基于 基于 基于 基于 基于 基于 基于 基于 基于 基于 基于 基于 基于Proton exchange has a lower methanol permeation and still good proton conductivity. 'A method for preparing a microstructured two-component polymer film provided by the present invention, which comprises: (1) preparing a sulfonic acid a polyfluorocarbon solution; (2) dissolving the pure acid polyfluorocarbon solid in an organic solvent to prepare an acid polyfluorocarbon solution; (1) removing the solvent at a temperature below Tg to obtain an amorphous shape (am〇iph〇us a continuous acid poly|L film; (4) a sulfonic acid polyfluorocarbon film placed in an electric field of an electric field experimental device; and (5) a sulfonic acid polyfluorocarbon film heat treated. 1305966. Heating temperature is ~2 thief; more surface heating temperature is 丨成~1S0C 'The best heating temperature is 1耽'. The electric field strength of the towel is the heart (10)·, ~; the better electric field is strong ~; the most (four) electric field strength is 2kvcm~Skvem-1. The following steps are carried out after the step (5): (6) Rapidly lowering the sulfonic acid polyfluorocarbon film placed in the electric field; (7) When the sulfonic acid polyfluorocarbon film is cooled below Tg, remove The electric field; and (8) the microstructure of the fixed sulfonic acid polyfluorocarbon film film. When preparing the polymer film, the solvent is removed by vacuum heating the peak acid polyfluorocarbon solution, wherein the heating is preferred. The temperature is 6 (rc~8 (rc, the general heating time is 1 to 3 hours; the preferred heating time is 2 hours. Further, regarding the preparation of the organic solvent of the present invention, wherein the organic solvent is selected from the group, Ν^ N-methyl formamide (DMF) > N, N5-dimethyl acetamide (DMAc) > N-methyl formamide (NMF) ^ tetrahydroforane (THF) ; N, N'-dimethyl acetamide (DMAc) 〇 is further provided by the present invention - a hybrid polymerization film comprising a thin microstructure of microstructures arranged neatly The _ series can be prepared by the method of the invention of the patent item i. Therefore, the hair style has a Hertzian guide and a low methanol permeability. The microstructure of the hairline is arranged by a pure electric field induction and heating. In addition, in the present invention, the plane can be parallel to the direction of the electric field. The film of the present invention, wherein the general conductivity is l().3S/em~2xl().lS/ Em; a preferred ion is 1 (T2S/cm. According to the characteristics of the present invention, Qian Keying secret directly (4) the film connector of the maternity battery 1305966 has a low sterol permeability, which can make the direct permeability of the battery A and the ability to record high-quality materials. Having low methanol wear is also provided by the present invention as a controlled acid polyfluorocarbon film device comprising: (1) according to the scope of the patent application of the first film; and (2) a set of positive and negative electrode plates, wherein according to the film of the patent application, the heteropolyfluorocarbon _ is placed on the positive f electrode plate intermediate. In addition, the present invention may further comprise: a high voltage power controller and a temperature control box. The device of the present invention, wherein the positive and negative electrode plates are in the shape of a circle, a square and an elongated strip, wherein the distance between the positive and negative electrode plates can be arbitrarily adjusted. For the purpose of the present invention, in the embodiment of the present invention, the sulfonic acid polyfluorocarbon which is not heated at a high temperature or contains no crystalline state, at a temperature between the % of the polymer material and the melting point (Tm~220 C) Between heating, providing polymer chain kinetic energy, and simultaneously applying a high-voltage electric field to induce a polymer chain branching sulfonic acid functional group to produce a regular arrangement, does not produce large particle size ion aggregation 'forming pore size ~ 10 ~ 2 〇 The proton conduction channel of nm reduces the methanol penetration of the film. According to the general polymer physics textbook, heating between the % of the polymer material and the melting point (Tm=~220 °C) can provide suitable energy for the polymer chain, which promotes the movement of the polymer chain and promotes mutual compatibility. The molecular segments produce aggregation. The tetrafluoroethylene of the sulfonic acid polyfluorocarbon hydrophobic backbone is incompatible with its hydrophilic branched sulfonic acid tetrafluoroethyl ether. Heating between 110 and 200 ° C promotes the hydrophilic branched sulfonic acid function. The bases aggregate with each other to produce ion aggregation, and the hydrophobic main chain of tetrafluoroethylene also aggregates with each other to produce an amorphous and partially crystalline morphology (Fig. 1) [Reference 丨]. The literature reports using the small horn _ ray and neutron scattering experiments [Refs. 2 and 3] to confirm that the ions are aggregated into spheres with a diameter of about 30 to 40 nm. The ball aggregation and ball aggregation are connected via a narrower ion-concentrating pipe, which is a channel for proton conduction in the film (Fig. 2) [Reference 2]. If the film containing no crystal form is heated at a temperature between the Tg of the polymer material and the melting point of 1305966 (Tm=~220 °C), and simultaneously applying a high voltage electric field, the sulfonic acid functional group of the polymer branch is induced. The regular arrangement of the electric field direction can reduce the ion concentration of large particle size, form a proton conduction channel with a small aperture, and reduce the methanol penetration of the film (Fig. 3). References 1. K. Kordesch and G Simader: Fuel Cells and Their Applications > 1996, VCH Publisher» verlagsgesellschaft mbH. Weinheim (Germany) » page 79. 2. TD Gieker, GE Munn, and F'C. Wilson, J Polym. Sci., Polym. Phys. Ed. > 19, 1687-1704 (1981), Figure 18. 3. G. Gebe, Polymer, 41, 5829-5838 (2000), Figure 7. [Embodiment] The film production method proposed by the present invention will be further described by the following embodiments of the production process and the accompanying drawings. 1. Preparation of sulfonic acid polyfluorocarbon solution - sulfonic acid polyfluorocarbon solution (5 wt% acid polyfluorocarbon + 95 wt% alcohol water mixed solvent) purchased by DuPont Company at 60 ° C in vacuum The solvent was removed by heating to obtain a pure sulfonic acid polyfluorocarbon solid. 2. Pure sulfonic acid polyfluorocarbon solids in organic solvents, for example: n, N'-dimethyl formamide (DMF) » N > N?-dimethyl acetamide (DMAc) > N-methyl formamide (NMF), tetrahydrofUrane (THF) or the like, dissolved to prepare a polyfluoride solution of a certain acid concentration of about 10 to 40% by weight. 3. The organic solution of the pure acid polyfluorocarbon was poured into a glass evaporating dish, and the solvent was removed by heating at 60 to 80 ° C for about 2 hours under vacuum to obtain a film of pure sulfonic acid polyfluorocarbon. 4. Place the film 1 〇4 of the acid-rich polyfluorocarbon in an electric field experiment device (Fig. 4). The intensity of the electric field of 1305966 can be adjusted by the high voltage power supply ii and the distance between the positive and negative electrodes 丄◦ 3 (4) The electric field is directly proportional to the electrical gap, and is proportional to the two electrode plates. _ Temperature box control followed by i Q 2 to control the experimental temperature between 18 and D1 of the acid-rich polyfluorocarbon. (110~2O〇0C), the electric field strength is controlled between 20 and 120 minutes. 5. Membrane methanol penetration measurement - as shown in Figure 5, the membrane is centered between the two glass edl, and the two sides of the membrane are filled with 3M methanol/water solution (A tank) and water (B tank), A tank and 3 The volume of the tank is 102 ml. At a fixed time, the solution of the B tank (〇2山) was taken, and the concentration of the fermentation was measured by a gas chromatograph (GC, HP_859〇A; Agilent capillary column 30m X 〇.53mm x 20 surface m), and methanol The permeability XMe〇H can be obtained from the formula (1). The film has a sterol penetration area of 5.31 cm2. X Wonderfulness wt% ^ Thick Membrane Area 6. Thin Film Conductivity Measurement 1 The impedance of the film was measured using a frequency response analyzer (AC_Impedance; SA1125B, Solatron Co.). The film was placed in the middle of the electrode in a constant temperature and humidity chamber (temperature 75-90 ° C relative humidity 95%) for film impedance measurement experiments. The measured impedance value is substituted into equation (2) to determine the ionic conductivity of the film. 〇=L/(RxA) (2) In the formula (2), σ = conductivity (ScnT1); !^ film thickness (cm); R = film resistance value (Ω); Α = area of the electrode in contact with the film (Α = 3.14 cm2). Experimental Example-1 A polyacid polyfluorocarbon was dissolved in N,N'-dimethylacetamide (DMAc) to prepare a 10 wt% solution. The solution was poured into a glass evaporating dish, and the solvent was removed by heating at 60 to 80 ° C for about 5 hours under vacuum to obtain a film of pure sulfonic acid polyfluorocarbon. Place the sulfonic acid polyfluorocarbon thin 1305966 membrane 1 〇4 in the clamp 1 〇5 and place it vertically between the positive and negative electrode plates i〇2, and the voltage is controlled at 15KV. The distance between the positive and negative electrode plates 1 0 3 is 4.35. Cm, temperature 120oC, experimental time 30 minutes. Experimental Example-2 Samaramic polyfluorocarbon was dissolved in N ′ N,-dimethyl acetamide (DMAc) to prepare a 1 wt% solution. The solution was poured into a glass evaporating dish, and heated under vacuum for 6 Torr to 8 Torr for about 5 hours to remove the solvent to obtain a film of pure sulfonic acid polyfluorocarbon. The sulfonic acid polyfluorocarbon film 10 4 is placed in the jig 1〇5 ' and placed horizontally between the positive and negative electrode plates 10 2 , the voltage is controlled at 15 kV, and the positive and negative electrode plates [the distance between the 〇 3 is 4 35 cm, the temperature 12〇〇c, experiment time 30 minutes.
表一是實驗例-1，實驗例-2薄膜，與Nafion-117薄膜導電度數據。 圖6是實驗例-卜實驗例-2薄膜，與Nafion-117薄膜的甲醇穿透率量 測實驗數據。圖7是實驗例-1薄膜經硝酸船染色的TEM電子顯微鏡照 片’黑色斑點是離子聚集。照片顯示離子聚集孔徑約〜1()励。圖8是 杜邦公司Nafion-117薄膜的JEM電子顯微鏡照片，顯示較大之離子聚 集孔徑。比較實驗例-1薄膜與Nafl〇n_117薄膜之導電度(表一)及曱醇滲 透率數據(圖六）’我們可發現，實驗例_丨薄膜之導電度是Nafl〇n_117的 2/3 ’但曱醇穿透率在1〇 &之數據卻只有Nafion_li7的1/3。實驗例 之薄膜使用於直接曱醇燃料電池應可獲得較高之發電功率。 表一、薄膜導電度（溫度75°C，濕度95%，量測面積=3.14cm2) 薄膜 厚度 含水率(wt%) 阻抗(Ω) 導電度 (scm'1) 實驗例-1 0.168 24.3 0.2731 ----— 1.96x1 〇·2 實驗例-2 0.170 21.3 0.2361 — 2.30xl〇-2 Nafion-117 . 11， 0.175 7 丄 _L i >ιτ ·\ -i _认 28.0 0.1854 ---- 3.01xl〇-2 ----- 註：Nafion-117—由杜邦公司購得之薄膜 11 1305966 【圖式簡單說明】 圖一、Nafion薄膜之物理微結構形態[ref. 1]。 圖二、Nafion薄膜之離子聚集通道微結構形態[ref.2]。 圖三、經電場誘導實驗之Nafion薄膜的離子聚集通道微結構形態。 圖四、薄膜電場誘導實驗裝置。 圖五、薄膜甲醇滲透量測裝置 圖六、實驗例薄膜與Nafion-117薄膜甲醇穿透率量測實驗數據。 圖七、實驗例薄膜的TEM電子顯微鏡照片，顯示離子聚集孔徑約10nm。 圖八、Nafion-117薄膜的TEM電子顯微鏡照片，顯示較大之離子聚集 孔徑。 【主要元件符號說明】 101 · ••高壓電源供應器 102 · ••溫度控制箱 103 · ••正負電極板 104 · .·續酸聚氟碳化物薄膜 105 · ••薄膜夾具 12Table 1 is the conductivity data of Experimental Example-1, Experimental Example-2 film, and Nafion-117 film. Fig. 6 is an experimental data of the methanol permeability measurement of the experimental example - the experimental example-2 film and the Nafion-117 film. Fig. 7 is a TEM electron micrograph of the experimental example-1 film dyed by a nitric acid vessel. 'Black spots are ion aggregation. The photo shows an ion clustering aperture of ~1 () excitation. Figure 8 is a JEM electron micrograph of DuPont's Nafion-117 film showing a larger ion agglomeration aperture. Comparing the conductivity of the experimental example-1 film with the Nafl〇n_117 film (Table 1) and the sterol permeability data (Fig. 6), we can find that the conductivity of the experimental example 丨 film is 2/3 of Nafl〇n_117. However, the sterol penetration rate of 1 〇 & data is only 1/3 of Nafion_li7. The film of the experimental example should be used for a direct methanol fuel cell to obtain a higher power generation. Table 1. Film conductivity (temperature 75 ° C, humidity 95%, measurement area = 3.14 cm 2 ) Film thickness moisture content (wt%) Impedance (Ω) Conductivity (scm'1) Experimental Example-1 0.168 24.3 0.2731 - ---- 1.96x1 〇·2 Experimental Example-2 0.170 21.3 0.2361 — 2.30xl〇-2 Nafion-117 . 11, 0.175 7 丄_L i >ιτ ·\ -i _ recognize 28.0 0.1854 ---- 3.01 Xl〇-2 ----- Note: Nafion-117—film purchased by DuPont 11 1305966 [Simple illustration] Figure 1. Physical microstructure of Nafion film [ref. 1]. Figure 2. Microstructure morphology of ion-aggregation channels of Nafion films [ref. 2]. Figure 3. Microstructure morphology of ion-aggregation channels of Nafion films subjected to electric field induction experiments. Figure 4. Thin film electric field induction experimental device. Figure 5, film methanol permeation measurement device Figure 6. Experimental sample film and Nafion-117 film methanol permeability measurement experimental data. Figure 7. TEM electron micrograph of the experimental film showing an ion clustering pore size of about 10 nm. Figure 8. TEM electron micrograph of the Nafion-117 film showing a large ion clustering aperture. [Main component symbol description] 101 · •• High-voltage power supply 102 · •• Temperature control box 103 · •• Positive and negative electrode plates 104 ···Continuous acid fluorocarbon film 105 · ••Film holder 12