2003/11/08 多功能碳材料研究室 1 奈米孔洞材料  微小化的反應器 國立成功大學化學工程系 鄧熙聖 ( 教授 ) 、粘耀仁、戴佑理、鄭焙哲、 蔡忠憲、劉信佑、劉啟徵 Nanoporous Materials  Miniaturized Reactors National Cheng Kung University Department of Chemical Engineering

2003/11/08 多功能碳材料研究室 2 孔洞高分子薄膜 電極陣列 MCM 系列 孔洞氧化矽 觸媒反應之 Carbon/metal redox center 孔洞材料電化學儲能機制 孔洞結構結合 吸附能預測吸附量 Gas-carbon 反應之機制 孔洞碳材製備  > 3000 m 2 /g  孔洞形成機制 化學鍍 成膜 感測器 鎳氫電池 電極 高分子充填 成膜 量化 製備 predict 孔徑分佈吸附量

2003/11/08 多功能碳材料研究室 3 Application of Porous Carbon in Supercapacitors (Electrochemical Capacitors) in N 2 in H 2 O or CO 2 mixing ZnCl 2 or H 3 PO 4 in N 2 leaching HCl in N 2 mixing alkali leaching HCl a. Gasification Raw Material char Porous Carbon b. Chemical impregnation Raw Material slurry Porous carbon c. Etching Raw Material partially etched Porous carbon carbonizationgasification (activation)

2003/11/08 多功能碳材料研究室 4 Electrochemical Capacitors Have High Power Density and Energy Capacity R. Kötz, M. Carlen, Electrochimica Acta 45 (2000) 2483–2498

2003/11/08 多功能碳材料研究室 5 Principle of Energy Storage  Conventional capacitors

2003/11/08 多功能碳材料研究室 6  The larger area the electrodes can provide, the more energy can be stored.  Carbon can be made with high surface area and porosity. d = 5 – 10 Å Double Layer Capacitor

2003/11/08 多功能碳材料研究室 7  Conventional Capacitors  Double Layer Capacitors (small d of double Layer) + (porous electrode) Very high capacitance e.g. S.A. = 1000 m 2 /g for porous carbon double-layer capacitance = 10 μF/cm F/g for capacitors with carbon electrodes; more than 1000 times higher than conventional capacitors.

2003/11/08 多功能碳材料研究室 8 Principle of Operation

2003/11/08 多功能碳材料研究室 9 超高電容目前的應用 a. 消費性電子產品的電力支援系統 (backup source)  電視機記憶保護裝置  汽車音響  鬧鐘、程序控制器  相機及攝影機  全球行動通訊系統 (global system for mobile communication, GSM): 每 5 ms 有 0.5 ms 的 pulse power 。 EC 可增加電池壽命。  不斷電系統  筆記型電腦、 行動電話  電動玩具、電動牙刷、電動刮鬍刀

2003/11/08 多功能碳材料研究室 10 b. 各種機械、引擎的啟動器, 尤其寒冬下可取代 電池。 c. 交通號幟的電力供應 d. 電動汽 / 機車 以上應用均是利用其瞬間高放電、 快充電、可靠性高及壽命長等特點。

2003/11/08 多功能碳材料研究室 11 Template Synthesis Method - Principle and Application

2003/11/08 多功能碳材料研究室 12 Preparation of Ordered Mesoporous Carbon and Applications  Mesoporous silica, like MCM48, SBA15…, etc,has been used to synthesis ordered mesoporous carbon in recent years.  Compare with traditional active carbon, mesoporous carbon not only reserves high specific surface (ca cm 2 /g), but also has uniform pore size and regular nanostructure.  It can be used as catalytic supports, electrode materials, … etc.

2003/11/08 多功能碳材料研究室 13 Synthesis Carbonized in the burner at 900  C under N 2 Template Carbon precursor mixed by ultrasonic oscillator Etch template by 1M NaOH at 50  C Washed with D.I. water till pH value under 8 and dry Analyzed by BET,TEM,EA …,etc

2003/11/08 多功能碳材料研究室 14 Mechanism carbonization template pore wallpore mixed with carbon precursor etched by NaOH template/precursor composite template/carbon compositemesoporous carbon

2003/11/08 多功能碳材料研究室 15 TEM image and S BET S BET = 1784 cm 2 /g MCM48 Mesoporous carbon

2003/11/08 多功能碳材料研究室 16 Applications  Anodic catalyst support for direct methanol fuel cell (DMFC).  Electrochemical double layer capacitor.  Separation and purification technology.

2003/11/08 多功能碳材料研究室 17 Materials  (a) Track etch membranes :  (b) Porous alumina membranes polymer Ion beam Porous membrane track-etched PC membrane Anodic Alumina Oxide membrane Pore diameter = 0.2  m Pore diameter = 5 nm

2003/11/08 多功能碳材料研究室 18 (a) cross-section of raw membrane (b) Sn 2+ coated template membrane (c) electroless deposition of Ni-P (d) dissolution of the template membrane. Experimental

2003/11/08 多功能碳材料研究室 19 Characterization of As-deposited Ni-P Films -1 SEM images of Ni-P electrode arrays

2003/11/08 多功能碳材料研究室 20 Ni(OH) 2 + OH - -> NiOOH + H 2 O + e - NiOOH + H 2 O + e - -> Ni(OH) 2 + OH - Characterization of As-deposited Ni-P Films -2

2003/11/08 多功能碳材料研究室 21 Preparation of Nanotube-shaped TiO 2 and Applications  Since the discovery of carbon nanotubes in 1991 by Iijima, much research has been conducted on nanoscale tubular materials with novel properties  TiO 2 is wide application in pigments, catalyst supports, fillers, coating, photoconductors, dielectric materials and so on.  TiO 2 has good characteristics of chemical stability, endurance, thin film transparency and lower production costs.

2003/11/08 多功能碳材料研究室 22 Hydrothermal Method TiO 2 powders NaOH(aq) Heat in autoclave Wash with HCl (aq) and D.I. water ultrasonic Filtering and Drying Analysis with XRD 、 TEM 、 BET…etc.

2003/11/08 多功能碳材料研究室 23 TEM Images

2003/11/08 多功能碳材料研究室 24 Nitrogen Adsorption S BET (m 2 /g)V p (cm 3 /g)

2003/11/08 多功能碳材料研究室 25 Mechanism 1.Raw material treates with NaOH (aq), some of the Ti- O-Ti bonds are broken, and Ti-O-Na and Ti-OH bonds are formed. 2. Treated with HCl (aq) and distilled water, the Ti-O-Na and Ti- OH bonds react with acid and water to form new Ti-O-Ti bonds. 3. More HCl(aq) treatment

2003/11/08 多功能碳材料研究室 26 Applications  Large surface area offer a highly active photo- catalytic material for many applications.  High efficient dye-sensitized solar cell.  Provide a functional catalyst for chemical reaction, and an adsorbents for chemicals.  Environmental purification.  Generation of hydrogen gas.