||Studies of Electrospun Carbon Nanofiber/Ni-Co oxide Composites as Anodes for Lithium Ion Batteries
||Department of Chemical Engineering
electrospun carbon nanofiber
lithium ion battery
本研究以電紡絲法製備聚丙烯腈(polyacrylonitrile)奈米碳纖維，再以水熱法於纖維表面沉積氫氧化鎳/氫氧化鈷，分別在氮氣氣氛與空氣氣氛下，以不同熱處理溫度觀察其結構變化，並探討結構對於此碳纖維/鎳鈷複合膜之電化學表現。在氮氣氣氛下，複合膜在未經熱處理前，呈現片狀的氫氧化鎳/氫氧化鈷型態附著在纖維表面；經過200 oC熱處理後，複合膜由片狀轉變成為針狀結構，其組成仍為氫氧化物；經過300 oC熱處理後，轉變成為氧化鎳/氧化鈷針狀結構型態，但當在更高溫下的熱處理，纖維上的氧化鈷/氧化鎳會聚集且脫落。300 oC熱處理的樣品所呈現的氧化鎳/氧化鈷針狀結構，具有比片狀氫氧化鎳/氫氧化鈷更高的比表面積與孔洞結構，同時又擁有較佳導電性和氧化鎳/氧化鈷所提供的高理論電容值，因此擁有最佳的電化學效能，充放電測試顯示在150 mA/g電流密度下具有645 mAh/g的比電容量，循環壽命測試顯示在200 mA/g電流密度下循環100次仍具有553 mAh/g的比電容量。複合膜在空氣氣氛下熱處理，觀察到樣品在300 oC下呈現NiCo2O4薄片覆蓋於碳纖維表面，且具有許多孔洞，較多的中孔體積結構幫助鋰離子進入電極內部區域，400 oC熱處理後則出現聚集，但仍有一層NiCo2O4覆蓋於碳纖維之上。經電化學測試後，300 oC熱處理後的碳纖維擁有最佳的電化學效能，充放電測試顯示在150 mA/g電流密度下具有734 mAh/g的比電容量，循環壽命測試顯示在200 mA/g電流密度下循環100次仍具有595 mAh/g的比電容量，這歸因於NiCo2O4擁有比氫氧化鎳/氫氧化鈷更適合做為電極材料的特質，包含較高的理論電容值、高導電度使電子快速傳遞、高比表面積與中孔體積。
In this study, carbon nanofibers were prepared through the polyacrylonitrile precursor by electrospinning. Subsequently, binary nickel-cobalt compounds were co-precipitated on the fiber surface by using a hydrothermal approach. We varied the annealing temperature and environment (nitrogen and air) to study the structural change with the annealing conditions, and aimed at understanding the correlation between the structure and electrochemical performance of the composite fibers. The co-precipitation of Ni and Co resulted in Ni(OH)2/Co(OH)2 nanoflakes vertically attached on the fiber surface. In nitrogen atmosphere, Ni(OH)2/Co(OH)2 nanoflakes were converted to Ni(OH)2/Co(OH)2 nanoneedle at 200 °C. At 300 °C, the composite exhibited the structure composed of NiO/CoO nanoneedles. The NiO/CoO nanoneedles aggregated and peeled off from the fiber surface when annealed at a higher temperature. The composite with a needle-like structure exhibited the higher total pore volume, specific surface area, electrical conductivity, and NiO/CoO theoretical capacities, resulting in the better electrochemical performance than those with a flake-like structure. Galvanostatic chargedischarge tests revealed that the composites annealed at 300 oC delivered a specific capacity of 645 mAh/g at a current density of 150 mA/g. They also exhibited a specific capacity of 553 mAh/g at a current density of 200 mA/g for 100 cycles. By contrast, the composite fibers annealed at 300 °C in air atmosphere yielded the NiCo2O4 sheet-like structure on the fiber surface, and possessed rich pores, which facilitated lithium-ion transfer from electrolyte to the electrode. Annealing at 400 °C resulted in the NiCo2O4 aggregation, forming a thin layer on the fiber surface. Galvanostatic chargedischarge tests show that the composite annealed at 300 °C delivered a specific capacity of 734 mAh/g at a current density of 150 mA/g. The composite also exhibited a specific capacity of 595 mAh/g at a current density of 200 mA/g for 100 cycles. The favorable electrochemical performance indicated that carbon nanofiber/NiCo2O4 composite is more suitable than carbon nanofiber/Ni(OH)2/Co(OH)2 composite as the anode material. This was attributed to the characteristics of the carbon nanofiber/NiCo2O4 composite, including a high theoretical capacity, favorable electrical conductivity for fast electron transfer, high specific surface area, and rich mesopores.
Extended abstract IV
第一章 緒論 1
第二章 文獻回顧 3
2.2.3 PAN纖維熱處理 14
第三章 實驗 31
第四章 結果與討論 39
4.1 CNF/Ni-Co hydroxide@N2複合膜 39
4.1.1 CNF/Ni-Co hydroxide@N2複合膜形態 39
4.1.2 CNF/Ni-Co hydroxide@N2複合膜結構判定 43
4.1.3 CNF/Ni-Co hydroxide@N2複合膜之循環伏安測試 56
4.1.4 CNF/Ni-Co hydroxide@N2複合膜之電化學測試 59
4.2 CNF/Ni-Co hydroxide@air複合膜 71
4.2.1 CNF/Ni-Co hydroxide@air複合膜形態 71
4.2.2 CNF/Ni-Co hydroxide@air複合膜結構判定 74
4.2.3 CNF/Ni-Co hydroxide@air複合膜之循環伏安測試 84
4.2.4 CNF/Ni-Co hydroxide@air複合膜之電化學測試 86
第五章 結論 96
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