本論文係有關三維磷化鎳/還原氧化石墨烯奈米複合物之製備及電容性能之探討。第一部份以兩步電化學沉積法製備三維之磷化鎳/還原氧化石墨烯/氧化鎳/發泡鎳(NP/rGO/NiO/NF)複合物作為超級電容器之電極材料，首先將發泡鎳在0.1 M硫酸水溶液中以10伏特電壓進行電化學處理，在其表面垂直生長三維多孔性氧化鎳奈米片，所得氧化鎳/發泡鎳(NiO/NF)較未經處理之發泡鎳在2M氫氧化鉀電解液中有明顯較高的電容值。其次，在氧化石墨烯存在下進行發泡鎳的電化學處理，製備還原氧化石墨烯/氧化鎳/發泡鎳(rGO/NiO/NF)。結果顯示rGO可沉積在NiO/NF表面並進一步提高電容值，最佳電化學處理時間約為10分鐘。最後，在含有次磷酸鈉的電鍍液中，將磷化鎳電化學沉積在rGO/NiO/NF表面製得NP/rGO/NiO/NF。結果發現，Ni2.55P的沉積可導致更高的電容值。定電流充放電測試顯示，在電流密度7 mA/cm2下，最大的比電容值1648 F/g與7.98 F/cm2分別發生在電鍍時間10與30分鐘時，且經循環測試2000後，仍保有約80 %的比電容值。NP/rGO/NiO/NF良好的電化學性能顯示其確實可作為有潛力的超級電容器電極材料。
第二部分係在含GO、硫酸鎳與次磷酸鈉的乙二醇溶液中以微波輔助法製備磷化鎳/氫氧化鎳/還原氧化石墨烯(NP/Ni(OH)2/rGO)複合物作為超級電容器之電極材料，結果顯示磷化鎳與氫氧化鎳奈米粒子同時生成，且GO還原為rGO並有助於磷化鎳與氫氧化鎳奈米粒子的分散。將此複合物塗佈於發泡鎳上作為超級電容器的電極，在2M氫氧化鉀電解液中，其電容值在電流密度為5、7、10與15 mA/cm2時分別可達到1476、1393、1142與738 F/g，顯示以本製程製得之NP/Ni(OH)2/rGO奈米複合物確實可作為超級電容器之電極材料。

This thesis concerns the fabrication and capacitor performance of three-dimensional (3-D) nickel phosphide/reduced graphene oxide nanocomposites. In the first part, 3-D nickel phosphide/reduced graphene oxide/nickel oxide on nickel foam (NP/rGO/NiO/NF) has been fabricated as a supercapacitor electrode material via the two-step electrochemical deposition. At first, nickel foam was electrochemically treated at 10 V in 0.1 M sulfuric acid to grow vertically 3D porous NiO nanosheets on the surface of Ni foam. The resulting NiO/NF showed a significantly larger capacitance than the un-treated nickel foam in 2M KOH. Secondly, the rGO/NiO/NF was fabricated by the electrochemical treatment of nickel foam in the presence of graphene oxide (GO). It was found that rGO was deposited on the surface of NiO/NF and could further increase the capacitance. The optimal electrochemical treatment time was determined to be about 10 min. Finally, nickel phosphide was electrochemically deposited on the surface of rGO/NiO/NF in the sodium hypophosphite-based aqueous solution to yield the NP/rGO/NiO/NF. It was found that the deposition of Ni2.55P led to a much higher capacitance. Also, galvanostatic charge-discharge showed that the optimal specific capacitances of 7.98 F/cm2 and 1648 F/g at the current density of 7 mA/cm2 could be obtained at the electrochemical deposition time of 30 and 10 min, respectively. After 2000 cycles at a current density of 30 mA/cm2, about 80% of specific capacitance was retained. The good electrochemical performance revealed that the NP/rGO/NiO/NF indeed could be a potential supercapacitor electrode material.
In the second part, the nickel phosphide/nickel hydroxide/reduced graphene oxide (NP/Ni(OH)2/rGO) nanocomposite was fabricated as a supercapacitor electrode material via the microwave-assisted method in the ethylene glycol solution of GO, nickel sulfate and sodium hypophosphite. It was found that NP and Ni(OH)2 nanoparticles were formed simultaneously and GO was reduced to rGO whose presence was helpful for the dispersion of NP and Ni(OH)2 nanoparticles. By coating this nanocomposite on the nickel foam as the supercapacitor electrode, the specific capacitances of 1476, 1393, 1142 and 738 F/g were obtained at the current densities of 5, 7, 10 and 15 mA/cm2, respectively, in 2 M KOH electrolyte solution. This revealed that the NP/Ni(OH)2/rGO nanocomposite fabricated by the process developed in this work indeed could be used as the electrode material for supercapacitors.

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