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系統識別號 U0026-0108201712073300
論文名稱(中文) 電紡絲奈米碳纖維與鎳鈷氧化物複合膜於鋰離子電池負極材料之研究
論文名稱(英文) Studies of Electrospun Carbon Nanofiber/Ni-Co oxide Composites as Anodes for Lithium Ion Batteries
校院名稱 成功大學
系所名稱(中) 化學工程學系
系所名稱(英) Department of Chemical Engineering
學年度 105
學期 2
出版年 106
研究生(中文) 徐嘉敏
研究生(英文) Jia-Min Syu
學號 N36044254
學位類別 碩士
語文別 中文
論文頁數 107頁
口試委員 指導教授-羅介聰
口試委員-陳東煌
口試委員-李建良
口試委員-關旭強
中文關鍵字 電紡絲奈米碳纖維  鋰離子電池  負極材料  鎳/鈷氧化物 
英文關鍵字 electrospun carbon nanofiber  lithium ion battery  anode material  nickel/cobalt oxide 
學科別分類
中文摘要 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。
英文摘要 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 chargedischarge 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 chargedischarge 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.
論文目次 摘要 I
Abstract II
Extended abstract IV
誌謝 IX
目錄 X
表目錄 XIII
圖目錄 XIV
第一章 緒論 1
1.1前言 1
1.2研究動機與目的 2
第二章 文獻回顧 3
2.1鋰離子電池 3
2.1.1鋰離子電池簡介 3
2.1.2鋰離子電池工作原理 7
2.1.3碳材料作為負極材料 10
2.2電紡絲技術 12
2.2.1電紡絲簡介 12
2.2.2影響纖維型態之參數 12
2.2.3 PAN纖維熱處理 14
2.2.4電紡絲碳纖維應用於鋰電池負極材料 16
2.3碳纖維/鎳鈷氧化物複合膜 18
2.3.1導電性基材/過渡金屬氧化物之複合材料 18
2.3.2鎳/鈷氧化物特性 20
2.3.3製備碳材/鎳鈷氧化物複合材料 24
2.3.4充放電測試後之材料表面分析 30
第三章 實驗 31
3.1實驗藥品與儀器 31
3.1.1實驗藥品 31
3.1.2實驗儀器 32
3.1.3電紡絲裝置 33
3.2實驗步驟 33
3.2.1製備奈米纖維薄膜 34
3.2.2碳纖維之表面改質 35
3.2.3碳纖維/鎳鈷氧化物複合膜的製備 35
3.2.4極片製作與電化學分析 36
3.2.5儀器參數設定 37
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
參考文獻 98
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