在本研究中，將COOH-多壁奈米碳管(COOH-MWCNTs)散佈於水與酒精之溶液中，並取定量溶液滴於已酸處理過之碳纖維布(Carbon fiber)上並退火，使其形成奈米碳管¬¬-碳纖維布之共構物，再利用脈衝電化學沉積法將鎳鈷氫氧化物沉積於碳管上。在本研究中，針對脈衝電化學沉積的參數，做了一系列的改動及討論，並在此基礎上，額外加入鈷做為參雜元素，藉由調整鎳鈷之間的比例來得到能同時具有良好比電容值及維持率之超級電容器，並在最後針對奈米碳管於碳纖維布上之數量多寡對於電容性質表現有何影響。在使用最佳化參數製作之奈米複合材料電極，在5 mV/s時具有高達1151 F/g的高比電容值，並在經過在20 mV/s掃描3000圈以後，依舊有著84.99%的良好的比電容維持率。而在最後，針對退火條件對於電極之電化學性質之改變進行探討，並利用XPS分析溫度及退火持溫時間對於電極之電化學性質產生何種影響。最終得出結論，當退火程度越高，比電容值會隨之下降，然而在循環壽命及倍率放大維持率上則有明顯進步，反之亦然。

In this thesis, a high-performance supercapacitor based on MWCNTs/Ni-Co hydroxide nanocomposites was developed. The MWCNTs on carbon fiber were prepared by the drop-by-drop process, followed by pulse electrodeposition of Ni-Co hydroxide nanoflakes on the surfaces of MWCNTs. The effects of the pulse electrodeposition conditions of Ni-Co hydroxides, including the deposition current density, current-on time, current-off time, deposition cycles and Ni to Co bath ratio, and MWCNTs drop-times were systematically investigated. The optimum deposition conditions were found to be a deposition current density of -0.2 mA/cm2, current-on time of 1 s, current-off time of 3 s, deposition cycles of 600, Ni:Co bath ratio of 3:1, and MWCNTs drop-times of 8. The resulting electrode fabricated under the optimal conditions has exhibited excellent capacitive properties, including a specific capacitance of 1401 F g−1 at 1 A g−1, energy density of ~35 Wh kg−1, power density of ~9 kW kg−1, and capacitance retention of ~85 % after 3000 cycles of operation. The structure-property relationship of the composite electrode was also investigated with different annealing conditions. The results indicate the electrodes subjected to longer annealing time and/or higher annealing temperature would exhibit lower specific capacitance, while better cycling life and rate retention.

[1] Review on supercapacitors: Technologies and materials. Renewable and Sustainable Energy Reviews, 2016, 58, 1189-1206.
[2] Progress of electrochemical capacitor electrode materials: A review, International Journal of Hydrogen Energy, 2009, 34, 4889-4899.
[3] Electrochemical capacitors: Mechanism, materials, systems, characterization and applications, Chemical Society Review, 2016, 45, 5925.
[4] Supercapacitors Performance Evaluation, Advanced Energy Materials, 2015, 5, 14011401
[5] Cobalt sulfide nano sheets coated on NiCo2S4 nanotube arrays as electrode materials for high-performance supercapacitors, Journal of Materials Chemistry A, 2015, 3, 10492-10497,
[6] Nitrogen doped carbon derived from polyimide/multiwall carbon nanotube composites for high performance flexible all-solid-state supercapacitors, Journal of Power Sources, 2018, 380, 55-63.
[7] High electrochemical performance of RuO2–Fe2O3 nanoparticles embedded ordered mesoporous carbon as a supercapacitor electrode material, Energy, 2016, 106, 103-111.
[8] Synthesis and characterization of GO/IrO2 thin film supercapacitor, Journal of Alloys and Compounds, 2018, 754, 14-25.
[9] Activated carbon sandwiched manganese dioxide/graphene ternary composites for supercapacitor electrodes, Electrochimica Acta, 2018, 266, 284-292.
[10] Flexible, silver nanowire network nickel hydroxide core-shell electrodes for supercapacitors, Journal of Power Sources, 328, 167-173.
[11] High performance supercapacitor electrodes from electro-spun nickel oxide nanowires, Journal of Alloys and Compounds, 2014, 610, 143-150.
[12] Doping cobalt hydroxide nanowires for better supercapacitor performance, Acta Materialia, 2015, 84, 20-28.
[13] Collective use of deep eutectic solvent for one-pot synthesis of ternary Sn/SnO2@C electrode for supercapacitor, Journal of Alloys and Compounds, 2018, 732, 694-704.
[14] All solid-state V2O5-based flexible hybrid fiber supercapacitors, Journal of Power Sources, 2017, 371, 18-25.
[15] Preparation and capacitive properties of cobalt–nickel oxides/carbon nanotube composites, Electrochimica Acta, 2007, 52, 2959–2965.
[16] One-Step Synthesis of Ni/Ni(OH)2@Multiwalled Carbon Nanotube Coaxial Nano cable Film For High Performance Supercapacitors, Electrochimica Acta, 2014, 125, 427-434.
[17] A high-performance supercapacitor electrode based on N-doped porous graphene, Journal of Power Sources, 2018, 387, 43-48,
[18] Overview of nanostructured metal oxides and pure nickel oxide (NiO) electrodes for supercapacitors: A review, Journal of Alloys and Compounds, 2018, 734, 89-111.
[19] Thermally oxidized synthesis of hierarchical Co3O4@MnO2 nano sheet arrays on nickel foam with enhanced supercapacitor performance, Journal of Alloys and Compounds, 2017, 708, 524-530.
[20] Construction of hierarchical FeCo2O4@MnO2 core-shell nanostructures on carbon fibers for high-performance asymmetric supercapacitor, Journal of Colloid and Interface Science, 2018, 512, 419-427.
[21] Hybrid Composite Ni(OH)(2)@NiCo2O4 Grown on Carbon Fiber Paper for High-Performance Supercapacitors, Applied Materials & Interface, 2013, 5, 11159-11162.
[22] NiCo2O4 / MnO2 heterostructured nano sheet: influence of preparation conditions on its electrochemical properties, Electrochimica Acta, 2015, 176, 359-368.
[23] Preparation of hierarchical material by chemical grafting of carbon nanotubes onto carbon fibers, Diamond and Related Materials, 2017, 80, 118-124.
[24] Synthesis of Ni(OH)2 nanoflakes on ZnO nanowires by pulse electrodeposition for high-performance supercapacitors, Journal of Power Sources, 2016 308, 29-36.
[25] Supercapacitive composite metal oxide electrodes formed with carbon, metal oxides and conducting polymers, Journal of Alloys and Compounds, 2016, 682, 381-403.
[26] Carbon nanotube–metal oxide nanocomposites: Fabrication, properties and applications, Chemical Engineering Journal, 2016, 302 344-367.
[27] A non-polarity flexible asymmetric supercapacitor with nickel nanoparticle@ carbon nanotube three-dimensional network electrodes, Energy Storage Materials, 2018, 11, 75-82.
[28] Nickel cobalt hydroxide/reduced graphene oxide/carbon nanotubes for high performance aqueous asymmetric supercapacitors, Journal of Alloys and Compounds 2018, 753, 525-531.
[29] Electrodes based on nano-tree-like vanadium nitride and carbon nanotubes for micro-supercapacitors, Journal of Materials Science & Technology, 2018, 34, 976-982.
[30] Solvent-assisted synthesis of carbon nanotubes-manganese oxide hybrid materials
for high voltage aqueous supercapacitor, Journal of Alloys and Compounds, 2018, 763, 62-70.
[31] Arrays of hierarchical nickel sulfides/MoS2 nano sheets supported on carbon nanotubes backbone as advanced anode materials for asymmetric supercapacitor, Journal of Power Sources, 2017, 343, 373-382.
[32] Strongly coupled nickel boride/graphene hybrid as a novel electrode material for supercapacitors, Chemical Engineering Journal, 2017, 327, 1085-1092.
[33] Hydrothermal growth of 3D graphene on nickel foam as a substrate of nickel-cobalt-sulfur for high-performance supercapacitors, Journal of Alloys and Compounds, 2018, 732, 613-623.
[34] Zn–Ni alloy deposits obtained by continuous and pulsed electrodeposition processes, Surface and Coatings Technology, 1999, 122, 10-13.
[35] Electrochemical Methods Fundamentals and Applications, JOHN WILEY & SONS, INC, SECOND EDITION, 2001.
[36] Electrochemical Reduction of Oxygen on Multiwalled Carbon Nanotube Modified Glassy Carbon Electrodes in Acid Media, Electrochemical and Solid-State Letters, 2007, 10, 18-21.
[37] Effects of oxygen-containing functional groups on the supercapacitor performance of incompletely reduced graphene oxides, International Journal of Hydrogen Energy, 2017, 42, 7186-7194.
[38] Nickel cobaltite nano grass grown around porous carbon nanotube-wrapped stainless steel wire mesh as a flexible electrode for high-performance supercapacitor application, Electrochimica Acta , 2015, 182, 31-38.
[39] Cathodic deposition of Ni(OH)2 and Co(OH)2 for asymmetric supercapacitors:
Importance of the electrochemical reversibility of redox couples, Journal of Power Sources, 2013, 221, 128-133
[40] Ultrathin nanosheets of cobalt-nickel hydroxides hetero-structure via electrodeposition and precursor adjustment with excellent performance for supercapacitor, Journal of Energy Chemistry, 2018, 27, 591-599.
[41] Superior capacitive performances of binary nickel-cobalt hydroxide nano network prepared by cathodic deposition, Journal of Power Sources, 2014, 253, 205-213.
[42] Conductive silver nanowires-fenced carbon cloth fibers-supported layered double hydroxide nanosheets as a flexible and binder-free electrode for high-performance asymmetric supercapacitors, Nano Energy, 2017, 36, 58-67
[43] Fabrication of nickel hydroxide electrodes with open-ended hexagonal nanotube arrays for high capacitance supercapacitors, Chemical Communications, 2011, 47, 12122–12124
[44] Rational Design of Nickel Hydroxide-Based Nanocrystals on Graphene for Ultrafast Energy Storage, Advanced Energy Materials, 2017, 8, 1702247.
[45] Effect of Al-doped b-Ni(OH)2 nano sheets on electrochemical behaviors for high performance supercapacitor application, Journal of Power Sources, 2013, 232, 370-375.
[46] Solvothermal synthesis of pompon-like nickel-cobalt hydroxide/graphene oxide composite for high-performance supercapacitor application, Colloids and Surfaces A, 2018, 549, 76-85
[47] Hierarchical NiCo2O4 nano sheets@ hollow micro rod arrays for high-performance asymmetric supercapacitors, Journal of Materials Chemistry A, 2014, 2, 4706.
[48] Review and prospect of NiCo2O4-based composite materials for supercapacitor electrodes, Journal of Energy Chemistry, 2018, 000, 1-25.
[49] One-step preparation of one dimensional nickel ferrites/graphene composites for supercapacitor electrode with excellent cycling stability, Journal of Power Sources, 2018, 396, 41-48.
[50] Interface polarization matters: Enhancing supercapacitor performance of spinel NiCo2O4 nanowires by reduced graphene oxide coating, Electrochimica Acta, 2018, 260, 814-822.