本研究主要對超級電容器之碳電極材料進行改質，以提升其高速操作的效能。首先於中孔碳（mesoporous carbon, MPC）表面成長奈米碳纖維（carbon nanofibers, CNFs），成長CNFs所使用之Fe觸媒以熱迴流法擔載至MPC上，以H2氣氛還原Fe催化劑後分別於800、900℃下成長CNFs；CNFs的存在，促進了MPC間的良好電性接觸，可使MPC之電阻減少32.6 %。但是，於CNFs成長過程中，Fe容易與MPC反應生成Fe3C，導致MPC的孔洞阻塞，而使得成長CNFs後的MPC比電容下降。為了改善以上的缺點，碳電極材料改用活性碳纖維布（activated carbon cloth, ACC），以濺鍍法將Ni鍍於ACC表面作為成長奈米碳管之（carbon nanotubes, CNTs）觸媒，利用濺鍍法，僅將催化劑鍍於ACC表面，因此成長CNTs後，CNT/ACC系列樣品避免了孔洞阻塞皆保有ACC原始之比表面積。再則於成長CNTs程序中通入5% NH3，不但增進了CNTs的品質，也保留了ACC表面的含氧官能基團；由於CNTs使得活性碳纖維間有良好的電性接觸，CNT/ACC樣品在高掃描速率之循環伏安測試之比電容維持率優於ACC，在500 mV/s下，CNT/ACC之效能最高可提升達239 %。
擬電容電極材料之效能改善部份，有別於一般擔載奈米顆粒於碳材表面的方式，本研究開發出水熱沉積法來擔載RuO2及Ni奈米顆粒；於水熱過程中，CNFs表面會受到輕微氧化而在其表面產生孔洞，這些孔洞便成為奈米顆粒之成核點，經由水熱程序，奈米顆粒尺寸均一（~2 nm）且均衡的散佈於CNFs表面。將所獲得之RuO2/CNF電極材料進行電化學測試，RuO2因擔載於導電性優異之CNFs表面，CNFs的存在不但降低了整體材料的電阻也提供了良好的電子傳輸網路；使得RuO2/CNF之效能增加，於200 mV/s下，效能較純RuO2奈米顆粒提升638%，其比電容達155 F/g。同時，RuO2/CNF也具有長程高速操作的穩定性，經掃描速率500 mV/s掃描1000圈後，電容維持率達98.9 %。於Ni/CNF電極材料的研究中，同樣確認水熱程序有利於擔載奈米粒子於碳材表面，但由於Ni前驅物在水熱反應後是生成Ni(OH)2，其尺寸過大（200~400 nm），將限制Ni化合物所能提供進行氧化還原反應之表面。因此將水熱後之產物進行H2還原，所得即Ni/CNF樣品，Ni奈米顆粒尺寸均一且均衡的散佈於CNFs表面；於電化學測試中，Ni/CNF之比電容值於200 mV/s下，仍高於CNF電極；當Ni於鹼性電解質中表面形成Ni(OH)2，不但提供擬電容同時也增進CNFs的親水性，有利電雙層形成。相同地，Ni/CNF電容器也能穩定的長程高速操作，經掃描速率500 mV/s掃描1000圈後，電容維持率達96.6 %。於交流阻抗分析中，Ni/CNF系列電容器之阻抗小於CNF電容器，Ni存在使得電阻下降，且改善CNF對於電荷的親和力。

In this research, carbonaceous materials are modified in order to be high performance electrode materials in super capacitor. Carbon nanofibers (CNFs) were grown on catalyst-seeded mesoporous carbons using thermal chemical vapor deposition. The iron catalyst was applied to the mesoporous carbons (MPC) by a reflux process followed by a high temperature reduction. The growth of CNFs then took place through the thermal decomposition of methane at temperatures of 800 °C or 900 °C. CNFs grown on MPC provide interconnects among the particles. Intimate contacts between the CNFs and the MPC were also observed. Due to these interconnects and the intimate contacts, the electrical resistance MPC having CNFs is approximately 32.6% lower than that of MPC. In spite of electrical resistance reducing by CNFs existing, but the specific capacitance of CNF-grafted MPC is decreased due to pore blockage by Fe3C. These Fe3C particles were formed under CNFs growth stage. In order to improve above disadvantages, activated carbon cloth (ACC) was used as electrode material. The catalyst used for the growth of CNTs was sputter-deposited Ni. It was found that the use of sputter-deposited catalyst for the growth CNTs prevents normally observed surface pore blockage on the ACC. The growth of CNTs also took place in a thermal chemical vapor deposition chamber. During the CNT growth, ammonia was introduced into the growth chamber for enhancing the CNT growth and limiting the formation of pyrolytic carbon. The resulting CNTs were found to follows the tip growth mode, leading to direct contacts between the CNTs and the ACC fiber surfaces. Due to this and the high electrical conductivity of CNTs, the obtained CNT-grafted ACC electrodes exhibit significantly enhanced electrical conductivity and improved capacitance retention. The enhancement of capacitance is as high as 239% at a potential sweep of 500 mV/s.
The performances of electrode materials (RuO2 and Ni nanoparticles) in pseudo capacitor were also improved by loading onto CNF surface using a hydrothermal deposition method. The obtained RuO2 nanoparticles have very small particle sizes, averaging at 2 nm with a narrow size distribution, and are homogenously distributed on the CNF surfaces. Electrochemical capacitors were fabricated using RuO2 grafted CNFs as the electrodes. The existence of CNFs leads to reduced contact resistance among the RuO2 nanoparticles and therefore provides a network for fast electron transport, which then results in enhanced electrochemical performance. The enhancement was found to be proportional to the RuO2 content and can be as high as 638% at a high sweep rate of 200 mV/s, at which a capacitance of 155 F/g was obtained. Stability of the RuO2-grafted CNF capacitor has also been demonstrated by subjecting the capacitor to a potential sweep at 500 mV/s for 1000 cycles. The Ni nanoparticles also have a narrow size distribution and are well dispersed the CNF surfaces. The electrochemical capacitance was enhanced due to the presence of the Ni nanoparticles. This is attributed to the occurrence of pseudocapacitance effect, enhanced electric double layer capacitance, and increased electrical conductivity. The enhancement was found to be proportional to the Ni content and can be as high as 214%. Stability of the Ni grafted CNF capacitor has been demonstrated by subjecting the capacitor to a potential sweep at 500mV/s for 1000 cycles.

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