TWI278881B - Method for preparing electrode material and an electrode of a capacitor using the same - Google Patents
Method for preparing electrode material and an electrode of a capacitor using the same Download PDFInfo
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1278881 九、發明說明: 【發明所屬之技術領域】 本發明係關於一種電極材料及其電容器電極之製備方 法,特別係關於一種具有高比電容值之電極材料及其電容 器電極之製備方法。 【先前技術】 超級電容器(supercapacitor)之材料選擇主要有下列二 種:氧化釕(Ru〇2)及碳粉。單純以氧化釕當電極材料是利 用金屬氧化物塊材之氧化還原反應產生電流而達到儲存電 能之功能,雖然其儲電性能優越但價格昂贵。若能進一步 使氧化釕之顆粒尺寸達到奈米尺度,即可增加其使用表面 積而增加塊材之利用效率。另,以碳粉當電極材料是利用 其電雙層排列方式瞬間改變而儲存電荷,具有高表面積和 决速充放電此力、低價格之優點。若配合中孔碳粉 (mesocarbon)使用亦可避免一般碳粉因孔洞大小不均勻或 電阻增加造成使用效能降低之問題。 美國專利US 5,079,674揭示一種超級電容之電極及其製 備方法,其係在金屬塩水溶液中加入高表面積碳粉,使碳 粉表面和孔洞内滲入金屬塩水溶液,再加入氫氧化鈉 (NaOH)或氫氧化鉀(KOH)以形成金屬氧化物,再經除水後 加入聚四氟乙烯(PTFE)即可藉由滾壓形成電極材料。 美國專利US 5,600,535揭示一種非晶形薄膜電極材料之 製備方法,其係將氣化釕(RuC13)溶於醇類並加熱至沸騰且 持續授拌,冷卻至室溫成釕金屬烧氧化物(alkoxide)溶液。 106l79.doc 1278881 以鈦板浸泡塗佈(dip coating)該溶液約5至15次後加熱15分 ,鐘,再浸入沸水後以l〇(TC乾燥,可獲得高比電容值 430F/g(50mV/s)和良好的黏著性。 美國專利US 5,658,355揭示一種超級電容之電極的製備 方法,其係在金屬塩水溶液中加入酒精形成凝膠狀沈澱 物,經洗淨和真空乾燥形成金屬氧化物,加入活性碳至有 機溶液後形成凝膠沈澱物並以200至300eC之溫度在暗性氣 _ 氛下進行熱處理以形成電極材料,可獲得尺寸小於1微米之 顆粒。 美國專利US 5,797,971揭示一種複合電極材料之製備方 法,可用以製備高比電容量、高導電度和高孔隙度之電極 複合電極材料。在高充放電流下保有高能量密度,且具優 良可逆性和循環壽命(cycle life)。 美國專利US 5,851,5 06揭示一種電極材料及其製備方 法’其係由含水金屬及含水金屬氧化物製備氧化釕電極材 | 料,其比電容值高達747F/g,且能量密度高達92J/g。 美國專利US 5,875,092揭示一種換雜質子之氧化釕電極 材料,其在電極材料製程中植入氫原子形成過渡金屬氧化 物電極材料,具有高能量密度、低電阻和較寬的操作溫度 範圍等優點。 美國專利US 6,025,020揭示一種高電容氧化釕之製備方 法,其係在富含水蒸汽之氣氛下合成氧化釕電極材料,可 避免繁複的溶膠-凝膠(sol_gel)製程。 【發明内容】1278881 IX. Description of the Invention: [Technical Field] The present invention relates to an electrode material and a capacitor electrode preparation method thereof, and more particularly to an electrode material having a high specific capacitance value and a method of preparing the same. [Prior Art] There are two main types of materials for supercapacitors: ruthenium oxide (Ru〇2) and carbon powder. The ruthenium oxide electrode material alone uses a redox reaction of a metal oxide block to generate electric current to achieve storage of electric energy, although its storage performance is superior but expensive. If the particle size of cerium oxide can be further increased to the nanometer scale, the surface area can be increased to increase the utilization efficiency of the bulk material. In addition, the use of carbon powder as an electrode material is instantaneously changed by the arrangement of its electric double layer to store electric charge, and has the advantages of high surface area and constant charge and discharge of this force and low price. If used with mesocarbon, it can also avoid the problem that the general toner is degraded due to uneven pore size or increased resistance. U.S. Patent No. 5,079,674 discloses a supercapacitor electrode and a method for preparing the same, which comprises adding a high surface area carbon powder to an aqueous solution of metal ruthenium to infiltrate a surface of a carbon powder into a pore of a metal ruthenium solution, and then adding sodium hydroxide (NaOH) or hydrogen. Potassium oxide (KOH) is used to form a metal oxide, and after removing water, polytetrafluoroethylene (PTFE) is added to form an electrode material by rolling. No. 5,600,535 discloses a method for preparing an amorphous thin film electrode material by dissolving vaporized ruthenium (RuC13) in an alcohol and heating to boiling and continuously mixing, and cooling to room temperature to form alkoxide. Solution. 106l79.doc 1278881 Dip coating the solution with titanium plate for about 5 to 15 times, heating for 15 minutes, clock, and then immersing in boiling water to dry with TC (TC dry, can obtain a high specific capacitance value of 430F / g (50mV) /s) and a good adhesion. US Pat. After the activated carbon is added to the organic solution to form a gel precipitate and heat-treated at a temperature of 200 to 300 eC in a dark atmosphere to form an electrode material, particles having a size of less than 1 μm can be obtained. US Patent No. 5,797,971 discloses a composite electrode. The preparation method of the material can be used to prepare an electrode composite electrode material with high specific capacitance, high conductivity and high porosity, high energy density at high charge and discharge current, excellent reversibility and cycle life. US Pat. No. 5,851,506 discloses an electrode material and a preparation method thereof for preparing a cerium oxide electrode material from an aqueous metal and an aqueous metal oxide. The capacitance is as high as 747 F/g, and the energy density is as high as 92 J/g. U.S. Patent No. 5,875,092 discloses a cerium oxide electrode material for impurity substitution, which implants hydrogen atoms in the electrode material process to form a transition metal oxide electrode material, which has a high Advantages of energy density, low electrical resistance, and wide operating temperature range. US Patent No. 6,025,020 discloses a method for preparing high-capacity yttrium oxide, which is a cerium oxide electrode material synthesized in a water vapor-rich atmosphere to avoid complicated sol. - gel (sol_gel) process. [Summary of the invention]
106179.doc 1278881 本發明之主要目的係提供—種具有高比電容值之電極材 料及其電容器電極之製備方法·,其可改善電極材料之耐用 度及提升比電容特性之優點。 為達成上述目的,本發明第一實施例揭示一種利用化學 滴定技術之電極材料之製備方法,其包含利用齒化訂及破 粉調配成一混合溶液;利用一鹼性溶液滴定該混合溶液以 形成一沈澱物;分離並乾燥該沈澱物以及進行一熱處理製 程以活化該沈澱物而形成該電極材料。函化釕與碳粉之重 量比係介於1 · G.9至1 : G.1之間,而該驗性溶液可為氫氧化 納或氩氧㈣。特而言之,利用_檢性溶液滴定該混合溶 液包含進行一第一滴定程序、靜置該混合溶液一預定時間 以及進行-第二滴定程序,纟中該第一滴定程序之終點為 酸鹼(pH)值6.8且該第二滴定程序之終點為1?11值7 〇。 本發明第二實施例之電極材料製備方法包含利用_化釕 及無機材料調配一第一混合溶液;進行一第一固液分離程 序,從該第一混合溶液十分離出一第一沈澱物;利用一鹼 性溶液及該第一沈澱物調配一第二混合溶液;進行一第一 固液分離程序,從該第二混合溶液中分離出一第二沈澱 物;燒結該第二沈澱物以及去除該第二沈澱物之無機材料 以形成該氧化釕。較佳地,該無機材料係呈六方堆積或立 方堆積或其他可能堆積方式之氧化矽粉末,而去除該第二 沈澱物之無機材料係利用利用一蝕刻液,其中該蝕刻液包 含氫氟酸。 本發明之電容器電極之製備方法包含利用該電極材料 106179.doc 1278881 (亦可使用該氧化釕)及一黏結劑調配一成膠狀物;塗佈該膠 狀物於一金屬基板;利用紅外線加熱烘乾塗佈該膠狀物之 金屬基板以及利用滚輪輾壓該金屬基板上之膠狀物。較佳 地,該金屬基板在塗佈前可先浸泡於經加熱之酸性溶液(例 如:塩酸、硫酸或硝酸溶液)中,加熱溫度可為50至100eC, 溶液濃度可為30wt%至80wt°/〇,這些條件可依電極材料所 要塗佈的厚度決定之)。此外,該黏結劑可選自聚偏二氟 乙烯、聚四氟6烯及聚乙烯酵,而該金屬基板可由鈦金屬 構成。 【實施方式】 圖1係本發明第一實施例之電容器電極之製備流程圖。本 發明之製備方法首先乾燥碳粉之後,再利用鹵化釕(RuX3) 及乾燥之碳粉調配一混合溶液,其中豳化釕可為三氟化釕 (R11F3)、二氣化釕(RuCl3)、三溴化釕(RuBr3或)或三碘化釕 (R11I3) ’且齒化釕與碳粉之重量比較佳地係介於1 ·· 2至1 ·· 0.125之間。 之後,利用一鹼性溶液以5至4〇秒/立方公分(s/cc)之滴定 速率滴定該混合溶液以形成—由碳與釕氧化物構成之沈殿 物,其中該驗性溶液可為氫氧化納或氫氧化卸水溶液。較 佳地,利用一驗性溶液滴定該混合溶液包含進行一第一滴 定程序、靜置該混合溶液—職時間以及進行—第二滴定 程序其中》亥第-滴疋程序之終點約為阳值6.8且該第二滴 疋程序之終點約為P H值7 . Q。由於酸驗滴定反應需要時間使 反應更趨完全’因此本發明利用:階段滴定料以確保酸 106179.doc •10· 1278881 驗滴定反應能完全W。靜置該混合溶液之預定時間係取 決於容積㈣、濃度(M)和滴定速率,如表—所示其中該 預定時間至少10分鐘。106179.doc 1278881 The main object of the present invention is to provide an electrode material having a high specific capacitance value and a method for preparing the capacitor electrode thereof, which can improve the durability of the electrode material and the advantages of the specific capacitance characteristics. In order to achieve the above object, a first embodiment of the present invention discloses a method for preparing an electrode material by using a chemical titration technique, which comprises mixing a powder into a mixed solution by using a tooth and a powder; and titrating the mixed solution with an alkaline solution to form a a precipitate; separating and drying the precipitate and performing a heat treatment process to activate the precipitate to form the electrode material. The weight ratio of the functionalized bismuth to the carbon powder is between 1 · G.9 and 1: G.1, and the test solution may be sodium hydroxide or argon oxygen (four). In particular, titrating the mixed solution with the _detective solution comprises performing a first titration procedure, allowing the mixed solution to stand for a predetermined time, and performing a second titration procedure, wherein the end of the first titration procedure is an acid-base The (pH) value is 6.8 and the end point of the second titration procedure is 1?11 value 7 〇. The electrode material preparation method of the second embodiment of the present invention comprises: arranging a first mixed solution by using cerium and inorganic materials; performing a first solid-liquid separation process, separating a first precipitate from the first mixed solution; Disposing a second mixed solution by using an alkaline solution and the first precipitate; performing a first solid-liquid separation process, separating a second precipitate from the second mixed solution; sintering the second precipitate and removing The inorganic material of the second precipitate forms the cerium oxide. Preferably, the inorganic material is a cerium oxide powder in a hexagonal or vertical packing or other possible deposition manner, and the inorganic material from which the second precipitate is removed utilizes an etching solution in which the etching solution contains hydrofluoric acid. The method for preparing the capacitor electrode of the present invention comprises: using the electrode material 106179.doc 1278881 (the yttrium oxide can also be used) and a binder to prepare a gel; coating the gel on a metal substrate; heating by infrared rays The metal substrate coated with the gel is dried and the gel on the metal substrate is pressed by a roller. Preferably, the metal substrate may be immersed in a heated acidic solution (for example, citric acid, sulfuric acid or nitric acid solution) before coating, the heating temperature may be 50 to 100 eC, and the solution concentration may be 30 wt% to 80 wt ° / Oh, these conditions can be determined by the thickness of the electrode material to be coated). Further, the binder may be selected from the group consisting of polyvinylidene fluoride, polytetrafluoroethylene, and polyethylene fermentation, and the metal substrate may be composed of titanium metal. [Embodiment] FIG. 1 is a flow chart showing the preparation of a capacitor electrode according to a first embodiment of the present invention. The preparation method of the present invention firstly disperses the carbon powder, and then mixes a mixed solution with lanthanum halide (RuX3) and dried carbon powder, wherein the antimony telluride may be lanthanum trifluoride (R11F3) or ruthenium disulfide (RuCl3). Lanthanum tribromide (RuBr3 or) or lanthanum triiodide (R11I3)' and the weight of the toothed bismuth and carbon powder is preferably between 1 ·· 2 to 1 ·· 0.125. Thereafter, the mixed solution is titrated with an alkaline solution at a titration rate of 5 to 4 sec/cm 3 (s/cc) to form a smear composed of carbon and cerium oxide, wherein the test solution may be hydrogen Oxidation of sodium or hydroxide to remove aqueous solution. Preferably, titrating the mixed solution with an assay solution comprises performing a first titration procedure, quenching the mixed solution, and performing a second titration procedure wherein the endpoint of the Dijon-Drip procedure is approximately positive 6.8 and the end of the second drip program is approximately pH 7. Q. Since the acid titration reaction takes time to make the reaction more complete, the present invention utilizes a stage titration to ensure acid 106179.doc •10·1278881. The titration reaction can be completely W. The predetermined time for standing the mixed solution depends on the volume (4), the concentration (M), and the titration rate, as shown in the table, wherein the predetermined time is at least 10 minutes.
• 完成滴定程序後,連續攪拌約12小時,再以去離子水進 行複數次清洗程序以去除不純物,其中不純物以鹵化鈉 (N a X)佔絕大部分且其為強電解質。將不純物金屬離子去除 可降低電性測試時電化學因素干擾。之後,利用高速離心 機分離該沈殿物,再以真空乾燥該沈殺物以形成釕氧化 物。接著,在氧氣環境中180至25(TC熱處理該沈澱物1至4 小時以活化該沈殿物而形成該電極材料。 # 完成該電極材料之後,利用一黏結劑與有機溶劑將該電 極材料調配成一膠狀物,並將該膠狀物塗佈於一鈦金屬基 板上。該鈦金屬基板較佳地係先浸泡於經適當溫度加熱之 咼濃度酸性溶液一段時間(例如:進酸、硫酸或硝酸溶液 中,加熱溫度可為50至100°C,溶液濃度可為3〇wt%至 80wt%),以使表面粗糙利於該膠狀物的塗佈。之後,利用 紅外線加熱烘乾塗佈該膠狀物之鈦金屬基板,並利用滾輪 輾壓該鈦金屬基板上之膠狀物。接著,裁切適當尺寸之成 品,並接上導線即完成該電容器電極^較佳地,該黏結劑 106179.doc •11- fn 1278881 係選自聚偏二氟乙烯、聚四氟乙烯及聚乙烯醇。 表二為以不同滴定速率製備之電容器電極,在不同掃描 速率下所測得該電容器電極之比電容值。反應開始以Na〇H 滴定RuCU水溶液,以不同滴定速率由快至慢分別為 20s/cc、60s/cc、240s/cc測試,終點偵測由pH值來控制。如 表一所示,滴定速率20s/cc可以達到較高之比電容值。若滴 定速率過快反而不利反應進行,其應是反應不及進行或產 物不均勻所致。若滴定速率太慢亦導致比電容值較差,其 應是產生其他衍生化合物產生所致。 表二 ^滴定速率 電壓掃瞄速 20 s/cc 60 s/cc 240 s/cc 2 mV/s 436 F/g 362 F/g 350 F/g 表三為以不同清洗程度製備該電容器電極,其電容特性 之變異情形。表三中所示之中等洗淨係將完成滴定程序之 混合溶液經加水攪拌重覆三次而得,清洗乾淨係將混合溶 液經加水攪拌重覆三次後再經高速離心機分離固液層而 得。由表三得知清洗程度越乾淨,比電容值下降程序越低, 這是因為材料中之不純物以NaCl佔絕大部分且其為強電解 質,將不純物金屬離子去除可降低測試時電化學因素干 擾’所以也讓原有之電極材料特性出現,而呈現循環穩定 現象。 ____年三_ 中等洗淨 清洗乾淨 106179.doc -12-• After the titration procedure is completed, stirring is continued for about 12 hours, and then a plurality of cleaning procedures are performed with deionized water to remove impurities, wherein the impurities are mostly sodium halide (N a X) and are strong electrolytes. Removal of impurity metal ions can reduce electrochemical interference during electrical testing. Thereafter, the sediment was separated by a high speed centrifuge, and the precipitate was vacuum dried to form a cerium oxide. Next, the electrode material is formed by heat-treating the precipitate for 1 to 4 hours in an oxygen atmosphere to form the electrode material. After the electrode material is completed, the electrode material is prepared into a one by using a binder and an organic solvent. Glue and apply the gel to a titanium metal substrate. The titanium metal substrate is preferably immersed in a cerium concentration acidic solution heated at a suitable temperature for a period of time (for example, acid, sulfuric acid or nitric acid) In the solution, the heating temperature may be 50 to 100 ° C, and the solution concentration may be 3 〇 wt% to 80 wt%), so that the surface roughness is favorable for the coating of the gel. Thereafter, the gel is dried by infrared heating. a titanium metal substrate, and using a roller to press the gel on the titanium metal substrate. Then, cutting the finished product of appropriate size, and connecting the wire to complete the capacitor electrode ^ preferably, the bonding agent 106179. Doc •11- fn 1278881 is selected from polyvinylidene fluoride, polytetrafluoroethylene and polyvinyl alcohol. Table 2 shows capacitor electrodes prepared at different titration rates. The specific electrode voltage of the capacitor is measured at different scanning rates. The initial value of the reaction was started with Na〇H titration of RuCU aqueous solution, which was tested at different titration rates from 20s/cc, 60s/cc and 240s/cc, respectively. The endpoint detection was controlled by pH. The titration rate of 20s/cc can reach a higher specific capacitance value. If the titration rate is too fast and the reaction proceeds, the reaction should not be carried out or the product is not uniform. If the titration rate is too slow, the specific capacitance value is poor. It should be caused by the production of other derivative compounds. Table 2 ^ Titration rate voltage sweep speed 20 s / cc 60 s / cc 240 s / cc 2 mV / s 436 F / g 362 F / g 350 F / g Table 3 In order to prepare the capacitor electrode with different degree of cleaning, the variation of the capacitance characteristics thereof is as shown in Table 3. The cleaning solution shown in Table 3 is obtained by repeating the mixing solution of the titration procedure by adding water and stirring three times, and cleaning the mixed solution. Adding water and stirring three times and then separating the solid-liquid layer by high-speed centrifuge. It is known from Table 3 that the cleaner the cleaning degree, the lower the specific capacitance drop procedure, because the impurities in the material account for the majority of NaCl. It is a strong electrolyte, it will not The removal of pure metal ions can reduce the interference of electrochemical factors during the test. Therefore, the original electrode material properties appear and the cycle is stable. ____Year 3 _ Medium wash Clean and clean 106179.doc -12-
1278881 10 mV/s 2 mV/s 10 mV/s 2 mV/s 比電容值經100圈 下降16% 比電容值經100圈 下降4% 表四為製備該電容器電極之過程中,在不同氣體氣氛中 進行熱處理之效應。以氧氣、氮氣或氩氣氣氛經200 °C/2Hr 熱處理後顯示比電容值循環特性有所差異,經氧氣氣氛熱 處理後所得到材料之循環耐用性最好,可能原因是氧氣氛 下可產生較穩定氧化物,且造成電極材料整體結構較為鬆 散,活絡了非晶相氧化釕之電化學特性而使其電子傳輸更 為順暢’增加電極材料電雙層反應和塊材活性區域之利 用。若使用氮氣和氩氣則不利於結晶水之存在,而使比電 容值較低和較差之循環耐用度。 表四 烘乾環境 氧氣 氮氣 氬氣 烘乾溫度/時間 200 eC/2Hr 200 °C/2Hr 200 °C/2Hr 比電容值 280 F/g 200 F/p 244 F/g 比電容 循環特性 比電容值 不變 比電容值 下降 比電容值 下降 圖2及圖3顯示電極材料之重量對電容之影響。無論單純 以碳粉或電極材料作測試’皆可獲知重量較小(即相當於厚 度較薄)可以得到較大之比電容值,這是因為反應為一整體 區塊,非僅限制於表面區域,厚度較薄之塊材其整體能被 電解液包覆和滲透之範圍越大,利用效率越高,厚度較厚 之塊材其整體利用率反而降低,不利電解㈣子之進出反 106179.doc -13- 1278881 • 應,所以造成阻值加大,比電容值降低。然而當厚度越來 - 越小並未導致比電容無限制地增大,因受限於金屬氧化物 中氫質子之傳輸有其最大之數目,其將有一極限值。 圊4和囷5例示本發明第一實施例之電容器電極之循環伏 安測試圓(Cyclic Voltammetry)。圓4和圖5係分別以10mV/s 和50mV/s之掃瞄速率進行循環伏安測試,換算成比電容值 約400法拉/克。亦即,在不同掃瞄速率下,本發明製備之 •電容器電極可維持優良的電容特性及比電容值。 囷6和圖7例示本發明第一實施例之電容器電極之定電流 測試圖。囷6和囷7係分別以l〇mA/cm2和50mA/cm2之電流密 度進行測試,本發明製備之電容器電極之電容行為亦沒有 明顯變動,且其壓降減小。 圖8例示本發明第一實施例之電容器電極之循環測試 圖,其係以10mV/S進行200次循環測試。如圖所示,本發明 之電容器電極之比電容值並未隨著循環測試之進行而降 _ 低,顯示其具有較佳之耐用度。換言之,本發明之電容器 電極具有改善電極材料之耐用度及提升比電容特性之優 點0 電極材料之比表面積對電容值有相對的影響,吾人進行 此實驗希望以降低起始溶液濃度,長出之釕氧化物顆粒聚 集度較小以提高電極材料之比表面積。因起始溶液之碳材 和釕化合物以50%重量比調配,實驗完成後以TGA檢測 Ru〇2的剩餘含量亦接近50%,故相同比例的電極材料,以 降低起始液濃度的方法可提高電極材料比表面積進而增加 106179.doc • 14- 1278881 比電容值,如下表五所示。 表五 實驗 起始溶 滴定 比表 比電容值 ---- TGA量測 編5虎 液濃度 速率 面積 Exp 1 0.1Μ 20s/cc 250m2/g 312F/g®10mV/s ^ 1 0 / Εχρ2 0.01Μ 20s/cc 338m2/g 349F/g(%10mV/s — J JL /〇 47% Εχρ3 0.001Μ 20s/cc 45 lm2/g 404F/g(5)y10mV/s 52%1278881 10 mV/s 2 mV/s 10 mV/s 2 mV/s The specific capacitance value decreases by 16% over 100 turns. The specific capacitance value decreases by 4% over 100 turns. Table 4 shows the process of preparing the capacitor electrode in different gas atmospheres. The effect of heat treatment is carried out. After heat treatment at 200 °C/2Hr in an oxygen, nitrogen or argon atmosphere, the cycle characteristics of the specific capacitance are different. The heat cycle of the material obtained after heat treatment in oxygen atmosphere is the best. The possible reason is that it can be produced under oxygen atmosphere. Stabilizing the oxide, and causing the overall structure of the electrode material to be loose, and the electrochemical properties of the amorphous phase yttrium oxide are activated to make the electron transport smoother. 'The electric double layer reaction of the electrode material and the active area of the bulk material are increased. The use of nitrogen and argon is detrimental to the presence of water of crystallization, resulting in lower specific capacitance and poorer cycle durability. Table 4 Drying Environment Oxygen Nitrogen Argon Drying Temperature/Time 200 eC/2Hr 200 °C/2Hr 200 °C/2Hr Specific capacitance value 280 F/g 200 F/p 244 F/g Specific capacitance cycle characteristic specific capacitance value The constant ratio of capacitance decreases compared to the capacitance value. Figure 2 and Figure 3 show the effect of the weight of the electrode material on the capacitance. Whether it is simply tested with toner or electrode material, it is known that a smaller weight (ie, equivalent to a thinner thickness) can result in a larger specific capacitance value because the reaction is an integral block, not limited to the surface area. The larger the thickness of the bulk material can be coated and infiltrated by the electrolyte. The higher the utilization efficiency, the lower the overall utilization of the thicker bulk material, and the lower the electrolysis (4). -13- 1278881 • Yes, so the resistance is increased and the specific capacitance is reduced. However, as the thickness becomes smaller - the smaller it does not result in an indefinite increase in specific capacitance, which is limited by the maximum number of transfers of hydrogen protons in the metal oxide.圊4 and 囷5 exemplify a Cyclic Voltammetry of the capacitor electrode of the first embodiment of the present invention. Circle 4 and Figure 5 were subjected to cyclic voltammetry at scan rates of 10 mV/s and 50 mV/s, respectively, and converted to a specific capacitance of about 400 Farads/gram. That is, the capacitor electrode prepared by the present invention maintains excellent capacitance characteristics and specific capacitance values at different scanning rates.囷6 and Fig. 7 illustrate a constant current test chart of the capacitor electrode of the first embodiment of the present invention. The 囷6 and 囷7 series were tested at a current density of 10 mA/cm 2 and 50 mA/cm 2 , respectively, and the capacitance behavior of the capacitor electrode prepared by the present invention did not change significantly, and the pressure drop thereof was reduced. Fig. 8 is a view showing a cycle test chart of the capacitor electrode of the first embodiment of the present invention, which was subjected to 200 cycles of testing at 10 mV/s. As shown, the specific capacitance value of the capacitor electrode of the present invention does not decrease as the cycle test progresses, indicating that it has better durability. In other words, the capacitor electrode of the present invention has the advantages of improving the durability of the electrode material and improving the specific capacitance characteristics. 0 The specific surface area of the electrode material has a relative influence on the capacitance value, and it is desirable for us to reduce the concentration of the starting solution and grow it. The cerium oxide particles are less concentrated to increase the specific surface area of the electrode material. Since the carbon material and the cerium compound of the starting solution are formulated in a 50% by weight ratio, the residual content of Ru 〇 2 is also close to 50% by TGA after the completion of the experiment, so the same ratio of the electrode material can be used to reduce the concentration of the starting liquid. Increase the specific surface area of the electrode material and increase the specific capacitance value of 106179.doc • 14-1278881, as shown in Table 5 below. Table 5 Experimental initial titration ratio Table capacitance value---- TGA measurement code 5 Tiger liquid concentration rate area Exp 1 0.1Μ 20s/cc 250m2/g 312F/g®10mV/s ^ 1 0 / Εχρ2 0.01Μ 20s/cc 338m2/g 349F/g (%10mV/s - J JL /〇47% Εχρ3 0.001Μ 20s/cc 45 lm2/g 404F/g(5)y10mV/s 52%
圖9例不本發明第二實施例之電容器電極之製備流程 圖。首先,利用鹵化釕及無機材料調配一第一混合溶液, 較佳地,該無機材料係呈六方堆積或立方堆積或其他可能 之型態,而其中齒化釕可為三氟化釕、三氣化釕、三漠化 釕或三碘化釕。之後,在真空抽氣環境靜置該第_混合溶 固液分離程序,從 液一段時間(例如24小時)後,進行一第一 心機從該第一混合溶液中分離出該第一沈澱物,其係鹵化 釘與氧化梦之混合物。 該第混合溶液中分離出一第一沈澱物,其中第一固液分 離程序可為利用超音波振盈攪拌該第—混合溶液再利用離 々之後’利用—驗性溶液及該第—沈澱物調配—第二混合 溶液q巾祕性溶液錢氧化鉀水溶液或氫氧化納水溶 液較佳地,利用該驗性溶液滴定該第一沈殿物之水溶液 之滴定速率介於5至40秒/立方公分(s㈣之間,其步驟可包 含進行-第-滴定程序;靜置該混合溶液—預定時間以及 進仃一第二滴定程序,其中該第一滴定程序之終點約為阳Fig. 9 is a flow chart showing the preparation of the capacitor electrode of the second embodiment of the present invention. First, a first mixed solution is prepared by using a bismuth halide and an inorganic material. Preferably, the inorganic material is hexagonal or cubic, or other possible forms, and wherein the dentate can be cesium trifluoride or trigas. Huayu, three desertification or triiodide. Thereafter, the first mixed solution separation process is allowed to stand in a vacuum pumping environment, and after the liquid is subjected to a period of time (for example, 24 hours), a first core machine separates the first precipitate from the first mixed solution. It is a mixture of halogenated nails and oxidized dreams. Separating a first precipitate from the first mixed solution, wherein the first solid-liquid separation procedure may be to stir the first mixed solution by ultrasonic vibration and then use the use-test solution and the first precipitate after the separation The second mixed solution q towel secret solution solution potassium hydroxide aqueous solution or sodium hydroxide aqueous solution is preferably used, the titration rate of the aqueous solution of the first sediment is titrated by 5 to 40 seconds / cubic centimeter. Between (s), the steps may include performing a -first-titration procedure; quenching the mixed solution - a predetermined time and entering a second titration procedure, wherein the end of the first titration procedure is about yang
106179.doc 100210 \ 100179 005029515-1 •15- 1278881 值6·8且該第二滴定程序之終點約為pH值7〇。由於酸鹼滴 定反應需要時間使反應更趨完全,因此本發明利用二階段 滴定程序以確保酸鹼滴定反應能完全i勺勻。靜置該第二混 合溶液之預定B寺間係取決於容積(cc)、濃度(M)和滴定速 率,其中該預定時間至少10分鐘。 接著’利用高速離心機進行一第二固液分離程序,從該 第二混合溶液中分離出一第二沈殿物,其係氧化訂(Ru〇x) ,與氧化矽之混合物。之後,以120至16(TC(較佳地為15〇。〇 之高溫燒結該第二沈澱物約20至40小時(較佳地為24小 時),以形成二氧化釕(Ru〇2)與氧化矽之混合物。較佳地, 可將燒結之第二沈澱物磨碎後,重覆上述步驟以獲得較高 產率。之後’利用一蝕刻液(包含氫氟酸)去除該第二沈澱物 之無機材料(即氧化矽),再以去離子水清洗烘乾後即可獲得 氧化釕’如圖10之繞射圖所示(其係利用六方堆積之氧化石夕 粉末製備該氧化釕)。此外,去除該氧化石夕之後,可在含氧 • 環境中以18 0至2 5 0 C之溫度進行1至4小時之熱處理製程以 活化該第二沈澱物。 完成該氧化釕之後,利用一黏結劑與有機溶劑將該氧化 釕調配成一膠狀物,並將該膠狀物塗佈於一鈦金屬基板 上。此鈦金屬基板係先浸泡於經適當溫度加熱之高濃度酸 性溶液一段時間,以使表面粗糙利於該膠狀物的塗佈。之 後,利用紅外線加熱烘乾塗佈該膠狀物之鈦金屬基板,並 利用滾輪輾壓該鈦金屬基板上之膠狀物。接著,裁切適當 106179.doc -16 - 1278881 尺寸之成品,並接上導線即完成該電容器電極。較佳地, 該黏結劑係選自聚偏二氟乙烯、聚四氟乙烯及聚乙烯醇, 該酸性溶液可為鹽酸、硫酸或硝酸溶液。 圖11例示本發明第二實施例之電容器電極之循環伏安測 試圖。分別以lmV/s、10mV/s、50mV/s以及100mV/s之掃瞄 速率進行循環伏安測試,換算成比電容值,並與習知技藝 比較如下表六所示。亦即,在不同掃瞄速率下,本發明製 備之電容器電極可維持優良的電容特性及比電容值。特而 言之,本發明第二實施例製備之電容器電極之比電容值較 習知技藝之比電容值大約二倍。 掃瞄速率(mV/s) 比電容值(F/e) 習知技藝(F/g) 1 1360 670 10 1233 620 50 1030 100 904 460 200 639 460106179.doc 100210 \ 100179 005029515-1 •15- 1278881 The value is 6.8 and the end of the second titration procedure is approximately pH 〇7〇. Since the acid-base titration reaction takes time to complete the reaction, the present invention utilizes a two-stage titration procedure to ensure that the acid-base titration reaction is completely uniform. The predetermined B-situ relationship in which the second mixed solution is allowed to stand depends on the volume (cc), the concentration (M), and the titration rate, wherein the predetermined time is at least 10 minutes. Next, a second solid-liquid separation process is carried out by means of a high-speed centrifuge, and a second sediment is separated from the second mixed solution, which is a mixture of ruthenium (Ru〇x) and ruthenium oxide. Thereafter, the second precipitate is sintered at a high temperature of 120 to 16 (preferably 15 Torr. for about 20 to 40 hours (preferably 24 hours) to form ruthenium dioxide (Ru〇2) and Preferably, the sintered second precipitate is ground and the above steps are repeated to obtain a higher yield. Then the second precipitate is removed by using an etching solution (including hydrofluoric acid). The inorganic material (ie, cerium oxide) is washed and dried with deionized water to obtain cerium oxide as shown in the diffraction diagram of FIG. 10 (which is prepared by using a hexagonal stacked oxidized stone powder). After removing the oxidized stone, a second heat treatment process may be performed in an oxygen-containing environment at a temperature of 18 0 to 250 ° C for 1 to 4 hours to complete the second precipitate. After the yttrium oxide is completed, a bond is utilized. The cerium oxide is formulated into a gel with an organic solvent, and the gel is coated on a titanium metal substrate. The titanium metal substrate is first immersed in a high concentration acidic solution heated at a suitable temperature for a period of time. Roughening the surface to facilitate coating of the gel Thereafter, the titanium metal substrate coated with the gel is dried by infrared heating, and the gel on the titanium metal substrate is pressed by a roller. Then, the finished product of the size of 106179.doc -16 - 1278881 is cut and The capacitor electrode is completed by connecting a wire. Preferably, the binder is selected from the group consisting of polyvinylidene fluoride, polytetrafluoroethylene and polyvinyl alcohol, and the acidic solution may be a hydrochloric acid, sulfuric acid or nitric acid solution. The cyclic voltammetry test chart of the capacitor electrode of the second embodiment of the invention is performed by cyclic voltammetry at a scan rate of lmV/s, 10 mV/s, 50 mV/s, and 100 mV/s, respectively, converted into a specific capacitance value, and The conventional art comparison is shown in Table 6. That is, the capacitor electrode prepared by the present invention can maintain excellent capacitance characteristics and specific capacitance values at different scanning rates. In particular, the second embodiment of the present invention is prepared. The specific capacitance value of the capacitor electrode is approximately twice the specific capacitance of the prior art. Scan rate (mV/s) Specific capacitance value (F/e) Conventional skill (F/g) 1 1360 670 10 1233 620 50 1030 100 904 460 200 639 460
圖12例示本發明第二實施例之電容器電極之定電流測試 圖。分別以 lOmA/cm2、30 mA/cm2、50 mA/cm2、8〇 mA/cm2 以及100mA/cm2之電流密度進行測試,本發明第二實施例 製備之電容器電極之電容行為亦沒有明顯變動,且其壓降 隨著測試電流之降低而減小。 本發明之技術内容及技術特點已揭示如上,然而熟悉本 項技術之人士仍可能基於本發明之教示及揭示而作種種不 106179.doc •17· I27888l 背離本發明精神之替換及修飾。因此,本發明之保護範圍 應不限於實施例所揭示者,而應包括各種不背離本發明之 替換及修飾,並為以下之申請專利範圍所涵蓋。 【囷式簡單說明】 囷1係本發明第-實施例之電容器電極之製備流程圓,· 囷2及囷3顯示電極材料之重量對電容之影響;Fig. 12 is a view showing a constant current test chart of the capacitor electrode of the second embodiment of the present invention. Tested at a current density of 10 mA/cm 2 , 30 mA/cm 2 , 50 mA/cm 2 , 8 〇 mA/cm 2 , and 100 mA/cm 2 , respectively, the capacitance behavior of the capacitor electrode prepared in the second embodiment of the present invention does not change significantly, and Its voltage drop decreases as the test current decreases. The technical content and technical features of the present invention have been disclosed as above, but those skilled in the art can still make various alternatives and modifications from the spirit and scope of the present invention based on the teachings and disclosures of the present invention. Therefore, the scope of the present invention should be construed as being limited by the scope of the appended claims. [Simplified Explanation of 囷] 囷1 is a preparation flow of the capacitor electrode of the first embodiment of the present invention, and 囷2 and 囷3 show the influence of the weight of the electrode material on the capacitance;
囷4和圖5例示本發明第一實施例之電容器電極之循環伏 安測試圓; 囷6和囷7例示本發明第一實施例之電容器電極之定電流 圓8例示本發明第-實施例之電容器電極之循環測試圖,· 圖9例示·揭明第二實施例之電容器電極之製備流程圖; 囷10例不本發明第二實施例之電極材料之繞射圖譜; 囷11例不本發明第二實施例之電容器電極之循環伏安測 圖12例示本發明第二實施例之電容器電極U電流測試 0 【主要元件符號說明】 (無) 106179.doc • 18 -囷4 and FIG. 5 illustrate a cyclic voltammetry test circle of the capacitor electrode of the first embodiment of the present invention; 囷6 and 囷7 illustrate a constant current circle 8 of the capacitor electrode of the first embodiment of the present invention, which is exemplified by the first embodiment of the present invention. Cycle test diagram of the capacitor electrode, FIG. 9 illustrates a flow chart for preparing the capacitor electrode of the second embodiment; 绕10 diffraction patterns of the electrode material not according to the second embodiment of the present invention; 囷11 cases not according to the invention The cyclic voltammetry 12 of the capacitor electrode of the second embodiment exemplifies the capacitor electrode U current test of the second embodiment of the present invention. [Key element symbol description] (none) 106179.doc • 18 -
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