201103184 六、發明說明： 【發明所屬之技術領域】 本發明係關於一種高活性及穩定性電極材料的結構，尤其 是中孔鎳電極材料，以及該電極材料之製備方法。利用電沉 積技術在具有高表面積的中孔洞電極上鐘上-些異類金屬201103184 VI. Description of the Invention: [Technical Field] The present invention relates to a structure of a highly active and stable electrode material, particularly a mesoporous nickel electrode material, and a method of preparing the electrode material. Electrodeposition technology on a mesoporous electrode with a high surface area
元素可以、♦持原有的中孔結構’不受氧化作用影響，同時 保有原本的高表面積與高反應電流。 【先前技術】 中孔/同電極材料具有極高的表面積，可以大幅提升接觸面 積，增加反應電流。所謂中孔洞材料（mes〇p〇r〇us materials)係指孔洞直徑介於2奈米和5〇奈米之間的材 料。此外，只要長、寬、高任一維的尺度小至奈米尺度，並 具有介面及特殊功能的材料，結構中最少有一維之介面對於 電子的運動造成限制，就是奈米結構材料。 在1997年，Attard G. S.的研究團隊使用非離子型界面 活性劑（UE〇8)，並添加無機六氯餘酸（H2PtCh)水溶液， 以電沉積技術成功合成得中孔鉑電極（Science Vol. 278, 838 (1997))。中孔洞奈米結構材料可以廣泛地應用在吸附 劑、觸媒載體、超高電容、燃料電池、感測器等領域（Phillip A. Nelson, Joanne M. Elliott, George S. Attard, and John R. Owen, Chem. Mater. (2002), 14，524-529)，其 合成可以使用包括許多金屬材料、半導體、合金，例如鉑、 TT984505 3 201103184 把、錢、鐵、錄、舶/把。 其中，鎳是一種重要的村料，而在電化學技術領域中廣泛 地應用在電池材料，如燃料電池、感測材料等。中孔洞電極 雖然具有高活性表面積，但是由鎳金屬製成之中孔洞電極的 南表面積極易與空氣中的氧分子產生作用，在室溫下進行氧 化作用’進而阻礙電子傳遞，使得電極的反應電流降低，產 生極快的活性衷退現象。當電極的面積越大（即粗糖度大） 則電流衣退得相對越快，造成應用上大打折扣及實用上的困 擾。 現有文獻對於中孔洞電極感測材料的活性衰退少有著 墨，而對於氧化作用所產生的電流降低亦缺乏相關研究，尤 其在感測器上的應用方面。相關專利文獻又大多著重在奈米 電極材料其他方面的改質上，例如：台灣專利公^第 1247345號揭示-種多孔性碳材表面孔隙結構之改質方 法，藉由氣相沉積法成長奈米碳纖於碳材表面進行碳材表面 改質’以增加碳材的中孔比例；US__89AU?示一種 在非液態結晶相中製造中孔洞金屬電極的方法；肋 7, 144, 658揭示-種使用於能量儲存之具有+孔結構的電 極及其製造方法’㈣極包含奈米結構化之中孔導電金 化物和塗覆在該金屬氧化物上的超薄聚合物。 因此，有必要提供一種可以不受氧化作用影響，同時 原來高表面積與高反應電流，叫著長時間的暴露減緩產生 TF984505 201103184 时衰退現象的 【發明内容】 高活性及穩定性之電極材 以及談電極材料之製備方 基於上述目的，本發明提供一種 料結構’尤其是巾孔㈣極材料， 法。 例如鎳做為^表^積可幅提高反應電流’本發明即使月 ^^0^^ tnmH"，J^ 6SI} ^^" 一些異類金Ufl/、而4_的中孔㈣極上鑛』 受氧化作用的影=:::維持原有的中孔…^ 電流等特性。隨著長時^保有原本的絲面積與高反肩 分具有實際應用触。…、路不會產生活性衰退現象，寸 電==金屬元素’其氧化電位必須高於錄· 降低感應電流，亦須適當選擇鑛轉度。了不汾響或 徵=Γ發明之一態樣，提供-種中孔鎳電極，其特 =:ΓΓ之具有高表面積的中孔洞中，藉由電 "L積技咖鑛有—層異類金屬元素。 保護中孔鎳電極不被氧化，且可二、金屬π素可以 層的錄跟表層欲感敎物進行反應。g子轉移作用，使底 該異類金屬元素係具有高於錄的氧化電位的金屬元素。 較佳地，該相金屬—由金、成之群 TF984505 201103184 組，且更佳地，該異類金屬元素係為 在該異類金屬元素電鍍層中，所缝異金。 至少20%或以上，且較佳係為 、員金屬與錄的比例為 根據本發明之另'態樣，提二，^ 法，其特徵在於藉由電沉積技術，在具中孔鎳電極之製備方 的鎳電極上鍍上-層異類金屬元素=有高表面積之中孔洞 的保護，中孔鎳電極不會被氧化、，'由該層異類金屬元素 用，使底層的錄跟表層欲感測 ^可以產生電子轉移作 該異類金屬元素係且有古 订反應。 τ 1尔兵有间於鎳的氧 較佳地，該異類金屬元素係選自 的金屬元素。 組，且更佳地，該異類金屬元素係為金麵和鋅所組成之群 在該異類金屬元素電鍍層 至少20%或以上，且較佳 1異類金屬與錄的比例為 【實施方式】㈣係為至少_或以上。 底下將以實施例的方式 備以及在其上鑛上-層異類金屬元法孔洞錄電極的製 <中孔洞鎳電極之製借> 首先配置50 wt.%的Bri · 5廿 (由〇.2請酸鎳、0.2_ ^添加“肩錄溶液 的正庚烧，此時PH4 7… 醋酸她成）與2wt.% 進行% ’將贿㈣超音波震盪器 進仃冋酿均勻池合，此時 45俄之間㈣三級，：皮震^之溫度係控制在 ―、式電極，並將溶液系統之溫度固定 TF984505 201103184 在45C。使用恆電位電流儀p〇TENTI〇STATIC儀器以 AMPEROMETRIC I-t CURVE之方法進行沉積中孔洞模版，其 中固定電壓在-〇.8v(vs. AG/AGCL)，沉積庫命量為〇.2c。 田錄/冗積在JL作電極上後，將初步得到的巾孔錄電極用異丙 醇溶液在超音波震盤器震I清洗隔夜，清洗後置放在乾燥箱 晾乾’即可得中孔鎳電極。 <在中孔洞鎳電極上電鍍異類金屬元素〉 首先配製氧化電位比錄高的異類金屬元素的溶液，例如. 金、白金、鋅等金屬溶液。在常溫下，這些具有較高氧化電 位的金屬在空氣中比錦金屬不易被氧化。接著，將上述製備 好的中孔錄電極放人該溶液中進行電錢，固定沉積—定 異類金屬元^結果可得如圖1所示之中孔洞電極結構，其 中，兀件符號1G表示中孔洞電極，元件符號u表示今The element can, ♦ retain the original mesoporous structure' without being affected by oxidation, while maintaining the original high surface area and high reaction current. [Prior Art] The mesoporous/same electrode material has an extremely high surface area, which can greatly increase the contact area and increase the reaction current. The so-called mesop material (mes〇p〇r〇us materials) refers to a material having a pore diameter between 2 nm and 5 nm. In addition, as long as the dimensions of any dimension of length, width and height are as small as nanometer scale and have interfaces and special functions, at least one dimension of the interface in the structure limits the movement of electrons, which is a nanostructured material. In 1997, Attard GS's research team successfully synthesized a mesoporous platinum electrode by electrodeposition using a nonionic surfactant (UE〇8) and an aqueous solution of inorganic hexachloroacid (H2PtCh) (Science Vol. 278) , 838 (1997)). The mesoporous nanostructured materials can be widely used in adsorbents, catalyst carriers, ultra-high capacitance, fuel cells, sensors, etc. (Phillip A. Nelson, Joanne M. Elliott, George S. Attard, and John R. Owen, Chem. Mater. (2002), 14, 524-529), its synthesis can be used including many metal materials, semiconductors, alloys, such as platinum, TT984505 3 201103184, money, iron, record, ship / handle. Among them, nickel is an important village material, and is widely used in battery materials such as fuel cells and sensing materials in the field of electrochemical technology. Although the mesoporous electrode has a high active surface area, the south surface of the hole electrode made of nickel metal actively interacts with oxygen molecules in the air, and performs oxidation at room temperature, thereby hindering electron transfer and causing electrode reaction. The current is reduced, resulting in an extremely fast activity. When the area of the electrode is larger (i.e., the degree of coarse sugar is large), the current garment retreats relatively quickly, resulting in a great compromise in application and practical trouble. The existing literature has less ink for the decay of the activity of the mesoporous electrode sensing material, and there is no relevant research on the current reduction caused by the oxidation, especially in the application of the sensor. Most of the related patent documents focus on the modification of other aspects of the nano-electrode material. For example, Taiwan Patent Publication No. 1247345 discloses a modification method for the surface pore structure of a porous carbon material, which is grown by vapor deposition. The carbon fiber surface is modified on the surface of the carbon material to increase the mesoporous ratio of the carbon material; US__89AU? shows a method for manufacturing the mesoporous metal electrode in the non-liquid crystal phase; the rib 7, 144, 658 reveals An electrode having a +-hole structure for energy storage and a method for producing the same (4) electrode comprises a nanostructured mesoporous conductive metallization and an ultrathin polymer coated on the metal oxide. Therefore, it is necessary to provide an electrode material which can be protected from oxidation and has a high surface area and a high reaction current, which is called a long-term exposure mitigation to produce a TF984505 201103184. The preparation of the electrode material is based on the above object, and the present invention provides a material structure, in particular a towel hole (four) electrode material, method. For example, nickel is used as a table to increase the reaction current. In the present invention, even if ^^0^^ tnmH", J^6SI} ^^" some heterogeneous gold Ufl/, and 4_ medium hole (four) poles on the mine Shadow by oxidation =::: Maintain the original mesopores...^ current and other characteristics. With the long-term guarantee, the original silk area and the high reverse shoulder have practical application touches. ..., the road will not produce an activity decay phenomenon, the electric charge == metal element 'the oxidation potential must be higher than the record · reduce the induced current, and the ore rotation degree must be properly selected. In the case of one of the inventions, a kind of mesoporous nickel electrode is provided, which has a high surface area in the middle hole, and is made by electric "L. metal element. The protective mesoporous nickel electrode is not oxidized, and the metal π can be reacted with the surface layer and the sputum. The g-sub-transfer action causes the heterogeneous metal element to have a metal element higher than the recorded oxidation potential. Preferably, the phase metal is composed of gold, a group of TF984505 201103184, and more preferably, the heterogeneous metal element is in the heterometal element plating layer. At least 20% or more, and preferably, the ratio of the metal to the recording is according to another aspect of the present invention, which is characterized by an electrodeposition technique in which a nickel electrode is used. The nickel electrode on the preparation side is plated with a layer of heterogeneous metal element = the protection of the hole in the high surface area, the mesoporous nickel electrode is not oxidized, 'uses the layer of the heterogeneous metal element, so that the bottom layer is recorded with the surface layer The measurement can produce electron transfer as the heterogeneous metal element system and has an ancient reaction. Preferably, the τ 1 soldier has oxygen in the nickel. Preferably, the heterogeneous metal element is selected from the group consisting of metal elements. And, more preferably, the heterogeneous metal element is a group consisting of gold face and zinc at least 20% or more of the heterometal metal plating layer, and preferably 1 heterogeneous metal and recorded ratio is [Embodiment] (4) Is at least _ or above. The system will be prepared as follows and in the above-mentioned system of the upper-layer heterogeneous metal element method of the hole recording electrode. The first hole 50%. .2 Please use nickel acid, 0.2_ ^ to add "grafting solution of the shoulder recording solution, at this time PH4 7... acetic acid to her) and 2wt.% for the % 'will bribe (four) ultrasonic oscillator into the uniform pool, At this time between 45 Russian (four) and three levels, the temperature of the skin shock is controlled at the "--type electrode", and the temperature of the solution system is fixed at TF984505 201103184 at 45C. Using a potentiostat current meter p〇TENTI〇STATIC instrument with AMPEROMETRIC It The CURVE method is used to carry out the deposition of the hole template, in which the fixed voltage is -〇.8v (vs. AG/AGCL), and the sedimentation life is 〇.2c. The field record/redundancy is obtained on the JL electrode. The towel hole electrode is cleaned with an isopropyl alcohol solution in an ultrasonic disk shaker overnight, and then placed in a dry box to be dried to obtain a mesoporous nickel electrode. <Electrometallurgical elements are plated on the mesoporous nickel electrode. 〉 First prepare a solution of heterogeneous metal elements with higher oxidation potential than recorded, for example. gold, white Metal solution such as zinc, etc. At normal temperature, these metals having a higher oxidation potential are less susceptible to oxidation in the air than the ruthenium metal. Then, the prepared mesoporous electrode is placed in the solution for electricity, fixed deposition - Determining the metal element ^ results can be obtained as shown in Figure 1 hole structure, where the symbol 1G represents the hole in the hole, the symbol u represents today
屬元素電鍍層。 IIt is an elemental plating layer. I
本發明之在中孔洞錄電極上電錢異類金屬元素的電極姓 構’可以達到保護中孔錄電極不被氧化，而且可以產: 轉移作用，使底層_可以跟表層上欲感社反應物作用， 具有優異的感測能力（電流靈敏度）。 習知未錄有·金屬元素之巾電極，如圖2所示， 空氣中活性衰退得相當快，但如圖3所示，在本發明之」 施例中，使關沉賴職，中極的雜變二 定’可以_縣中孔賴不受氧化翻影響㈣具有^ TF984505 201103184 來南表面積與高反應電流，隨著長時間的暴露不會產生活性 衰退現象。 如圖4所示，使用習知未鍍有異類金屬元素之中孔鎳電極 對〇〜5_之乙醇進行感測，發現到其在$氣中活性衰退快， 仁如圖5所不，根據本發明之一實抱例’使用细沉積鍵膜 後’活性則相對地變得很穩定。 圖6為中孔鎳電極之粗糙度對空氣暴露時間的關係圖，其 中⑷為根據本發明之—實施例所製得的鍍有異類金屬元素 之中孔鎳電極，（b)為習知未鍍有異類金屬元素之中孔鎳電 極可以發現到習知中孔鎳電極在空氣中的活性衰退得相當 快’本發明則有相對穩定的活性表現。 圖7為較長時間暴露在空氣中之電極粗M度與時間的關 係圖’其中根據本發明之製備方法，分別在中孔㈣極上鑛 上不同量的黃金層：（a)(). 8C’⑽.c，（e)Q· %，⑷請c， (e)0· 02C，（f)〇C 〇 如圖7所示，在較長時間的觀察下，在中孔錄電極上錢上 異類金屬元素層仍财以相電流衰退或者崎度下^等 現象；然而’當黃金祕層越厚縣退越慢。以粗輪产約 400的中孔鎳電極為例，工作電極面積讀2鑛上q ^的 鎳，經清洗Brij 56後，再鍍上從〇 〇2C到〇 8(：不同電量 的黃金。當黃金鍍層為〇.8c時（圖7之曲線（a))，經過Μ 天後沒有觀察到衰退現象。因此，在黃金鍍層中，黃金與鎳 TF984505 201103184 電鍍量的比例較佳係大於4以上，其在14天的觀察中沒有 看到明顯的衰退。 雖然本發明已就其特定具體例作詳細說明，但應了解對熟 悉該項技術之人士可在不背離本發明之精神和範圍内對其 做出各種變化和修改。 【圖式簡單說明】 圖1係本發明之鍍有異類金屬元素的中孔鎳電極結構示 φ 意圖。 圖2為習知中孔鎳電極的循環伏安圖，其中電極在空氣中 暴露的時間：（a)0小時、（b)24小時；水溶液：4 Μ Κ0Η ; 掃瞄速率：20 mV s_1。 圖3為本發明之中孔鎳電極的循環伏安圖，其中電極在空 氣中暴露的時間：（a)0小時、（b)24小時；水溶液：4MK0H ; 掃猫速率：20 mV s_1。 ^ 圖4為習知中孔鎳電極對乙醇的感測I-t圖，其中電極在 空氣中暴露的時間：（a)0小時、（b)24小時；水溶液：4 Μ Κ0Η ;在電壓0. 45V下，乙醇濃度0〜5mM。 圖5為本發明之中孔鎳電極對乙醇的感測I-t圖，其中電 極在空氣中暴露的時間：（a)0小時、（b)24小時；水溶液： 4 Μ KOH ;在電壓0. 45V下，乙醇濃度0〜5mM。 圖6為暴露在空氣中之電極粗糙度與時間關係圖：（a)根 據本發明之製備方法，以0.2C鎳沉積在工作電極上，再鍍 TF984505 9 201103184 上0. 02C黃金而獲得之中孔鎳電極；（b)習知中孔鎳電極。 粗糙度以CV在4 Μ KOH水溶液下量測。 圖7為較長時間暴露在空氣中之電極粗糙度與時間關係 圖，其中中孔鎳電極上分別鍍有：（a)0.8C、（b)0.4C、 (c)0.2C、（d)0.04C、（e)0.02C、（f)0C 等不同量的黃金層。 粗糙度以CV在4 M KOH水溶液下量測。 【主要元件符號說明】 10 中孔洞電極 11 異類金屬元素電鍍層 TF984505 10The electrode name structure of the electric metal of the heterogeneous metal element on the middle hole recording electrode can achieve the protection of the mesoporous electrode without being oxidized, and can produce: transfer effect, so that the bottom layer can act on the surface layer , has excellent sensing ability (current sensitivity). Conventionally, there is no metal element of the towel electrode. As shown in Fig. 2, the activity in the air decays quite rapidly, but as shown in Fig. 3, in the embodiment of the present invention, the depression is lowered, the middle pole The heterozygous dimorphic 'can be _ county Zhongkong Lai is not affected by oxidation (4) has ^ TF984505 201103184 to the south surface area and high reaction current, with long-term exposure will not produce activity decline. As shown in FIG. 4, the well-known nickel metal electrode which is not plated with a heterogeneous metal element is used to sense the ethanol of 〇~5_, and it is found that its activity decays rapidly in the gas, and the kernel is as shown in FIG. One of the practical examples of the present invention is that the activity becomes relatively stable after the use of a finely deposited bond film. 6 is a graph showing the relationship between the roughness of the mesoporous nickel electrode and the air exposure time, wherein (4) is a nickel-plated electrode with a heterogeneous metal element prepared according to the embodiment of the present invention, and (b) is a conventional one. The hole nickel electrode plated with a heterogeneous metal element can be found that the activity of the conventional mesoporous nickel electrode in the air decays quite rapidly. The present invention has a relatively stable activity performance. Figure 7 is a graph showing the relationship between the thickness of the electrode and the time of exposure to air for a long time. [In the preparation method according to the present invention, different amounts of gold layers are respectively deposited on the mesoporous (four) pole: (a) (). 8C '(10).c, (e)Q· %, (4) Please c, (e)0· 02C, (f)〇C 〇 As shown in Fig. 7, under the observation of a long time, the money is recorded on the mesoporous electrode. The upper layer of the metal element is still in the phase current decay or the phenomenon of sagging under the law; however, 'the thicker the gold secret layer, the slower the county. Take a medium-bore nickel electrode with a rough rotation of about 400 as an example. The area of the working electrode reads 2% of the nickel on the mine. After cleaning the Brij 56, it is plated from 〇〇2C to 〇8 (: different amounts of gold. When the gold plating is 〇.8c (curve (a) of Fig. 7), no decay is observed after Μ天. Therefore, in the gold plating, the ratio of gold to nickel TF984505 201103184 is preferably more than 4, It has not seen a significant decline in the 14-day observation. Although the present invention has been described in detail with reference to the specific embodiments thereof, it should be understood that those skilled in the art can practice the invention without departing from the spirit and scope of the invention. Various changes and modifications are made. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a schematic diagram showing the structure of a mesoporous nickel electrode plated with a heterogeneous metal element according to the present invention. Fig. 2 is a cyclic voltammogram of a conventional mesoporous nickel electrode, wherein The time during which the electrode was exposed to air: (a) 0 hours, (b) 24 hours; aqueous solution: 4 Μ Κ 0 Η; scanning rate: 20 mV s_1. Figure 3 is a cyclic voltammogram of a mesoporous nickel electrode of the present invention, The time during which the electrode is exposed to air: (a) 0 small (b) 24 hours; aqueous solution: 4MK0H; sweeping cat rate: 20 mV s_1. ^ Figure 4 is a sensing It diagram of a conventional mesoporous nickel electrode for ethanol, in which the electrode is exposed to air: (a) Hour, (b) 24 hours; aqueous solution: 4 Μ Κ 0 Η; ethanol concentration 0 to 5 mM at a voltage of 0.45 V. Figure 5 is a schematic diagram of the sensing of ethanol in a mesoporous nickel electrode of the present invention, wherein the electrode is in the air Exposure time: (a) 0 hours, (b) 24 hours; aqueous solution: 4 Μ KOH; ethanol concentration 0 to 5 mM at a voltage of 0.45 V. Figure 6 is a graph showing the relationship between electrode roughness and time exposed to air. : (a) According to the preparation method of the present invention, nickel is deposited on the working electrode with 0.2 C of nickel, and a mesoporous nickel electrode is obtained by plating 0. 02 C gold on TF984505 9 201103184; (b) a conventional mesoporous nickel electrode. The degree is measured by CV in an aqueous solution of 4 Μ KOH. Figure 7 is a graph showing the relationship between the roughness of the electrode exposed to air for a long time and time, wherein the mesoporous nickel electrode is plated with: (a) 0.8C, (b) Different amounts of gold layer such as 0.4C, (c) 0.2C, (d) 0.04C, (e) 0.02C, (f) 0C, etc. Roughness with CV at 4 M KOH water Measurement under solution. [Main component symbol description] 10 hole electrode 11 heterogeneous metal element plating layer TF984505 10