臺灣博碩士論文加值系統

本論文中，以電化學沈積法製備CoO前驅物α-Co(OH)2，在前驅物的製備過程中，改變了攪拌速率，改變奈米顆粒的種類，添加量與粒徑，界面活性劑triton X-100的添加，進行製備前驅物α-Co(OH)2之修飾，在500℃高純氮環境下煆燒製得經修飾之CoO/Cu，另一方面，另一方面在本論文亦利用濺鍍Ni於CoO表面製備CoO-Ni/Cu電極。將各種製備所得之電極與Li箔組裝為Li / 1.0 M LiPF6 , EC-DEC (體積比1:1)溶液 / CoO鈕釦型電池，於0.02~3V電位範圍，進行充放電性質探討。在材料性質上利用SEM、XRD、FTIR與EDS等分析其性質。
由SEM觀察前驅物之組態，發現α-Co(OH)2呈現奈米纖維結構，製備前驅物時攪拌速率、SiO2的添加量、SiO2 與TiO2顆粒大小與界面活性劑存在與否，均影響著前驅物及其煆燒後CoO之物性。在pH 3.30~3.14無添加物，攪拌速率50rpm下煆燒所得CoO粒徑為31~27 nm，添加0.05 % 12nm SiO2，晶粒降為16~12 nm，進一步的添加0.065M triton X-100界面活性劑，其粒徑更進一步降為14~11nm。
在pH為3.30~3.14下，電沈積攪拌速率50rpm，CoO薄膜厚度為2.5~3.0μm，不可逆電容百分比為29.9%，其最大電容量1580 mAh g-1，當攪拌速率增加為100rpm時，CoO薄膜厚度與不可逆電容百分比減少為2.0~2.4μm與24.3%，最大電容量增加為3321 mAh g-1。
無添加物下，在pH 3.30~3.14條件下獲得之CoO(薄膜)/Cu，以0.2C充放電，在第30圈可達最高電容量為1580 mAh g-1，但添加0.05% 12nm SiO2下，在第69圈達最高電容量為2471 mAh g-1，添加SiO2時，對電容量的提升主要在於機構III充放電容量的增加，因SiO2扮演奈米Co擔體的角色，催化膠態高分子的生成與消失；另一方面SiO2顆粒具有降低CoO粒徑以及防止生成之Co奈米粒子聚集的效果，故可有效的提升CoO的充放電電容量，以及防止其電容量衰退。在CoO電極上濺鍍Ni可增加電極的導電度，因此可增加其電容量與抑制電容量衰退的作用。

The precursor of CoO (α-Co(OH)2) was prepared by the electrodeposition with various strring rates, nano-particles with different amounts and particle sizes in the presence of surfactant triton X-100 or not. Cobalt oxide (CoO) was obtained by calcinations of α-Co(OH)2 in N2 atmosphere at 500 oC. Furthermore, Ni was sputtered on CoO surface to prepared CoO-Ni/Cu in this thesis. The charge/discharge properties of CoO prepared in this work were investigated by the coin cell of Li/1.0M LiPF6 , EC-DEC (v/v=1:1) / CoO in the potential range of 0.02~3V. The characteristics of CoO were analyzed by SEM, XRD, FTIR and EDS, respectively.
The morphology of α-Co(OH)2 analyzed by SEM were nano-fiber type structures. The properties of CoO and its precursor were affected by the stirring rate, the amount and size of SiO2 and TiO2 nano-particles, and surfactant for electrodeposition of the precursor. Whenα-Co(OH)2was prepared in pH 3.30~3.14 and 50 rpm, the grain size of CoO was found to be 31~27 nm, the grain size of CoO was decreased to 16~12 nm by addition of 0.05% 12nm SiO2 for preparing α-Co(OH)2. By further adding 0.065M triton X-100 to prepare the precursor of α-Co(OH)2 in the electrodeposition, the grain size was decreased to 14~11 nm.
When the precursor was prepared in pH 3.30~3.14, the thickness, the irreversible capacity in the first cycle and the maximum charge capacity of CoO film decreased from 2.5~3.0μm and 29.9 % to 2.0~2.4 μm and 24.3 %, and the maximum charge capacity increased from 1580 to 3321 mAh g-1 with the increase in the stirring rate from 50 to 100 rpm for preparingα-Co(OH)2.
The maximum capacity of CoO (thin film)/Cu was obtained to be 1580 and 2471 mAh g-1 at the charge/discharge cycle of 30 and 69 for preparing the precursor of CoO in the absence and presence of 0.05% 12nm SiO2. The functions of SiO2 in the CoO were deduced to be acted as the support of Co to catalyze the formation/dissolution of the polymeric gel. Moreover, the CoO grain size in the calcination procedure, and the Co particle size in the charge/discharge process were restricted by the presence of the SiO2 nano-particle Hence the charge/discharge capacity of CoO was effectively promoted, and the capacity fading was inhibited by the presence of SiO2 nano-particle. The increase in the capacity and decrease in the capacity fading were also obtained by sputtering Ni on the CoO surface due to the increase in the conductivity of CoO electrode.

中文摘要............................................... I
英文摘要...............................................III
致謝....................................................V
目錄................................................... VI
表目錄................................................. XI
圖目錄................................................. XVI
第一章 緒論............................................ 1
1-1 電池概述及發展現況................................ 1
1-2 鋰二次電池........................................ 4
1-3 鋰二次電池陽極材料................................ 7
1-3-1 碳材料應用於鋰二次電池陽極.................. 7
1-3-2 錫氧化物應用作為鋰二次電池陽極.............. 9
1-3-3 無機與合金材料應用作為鋰二次電池陽極........ 12
1-4 鈷氧化物於鋰電池陽極材料之研究與應用.............. 15
1-4-1 鈷氧化物應用作為鋰電池陽極材料之充放電機構… 15
1-4-2 鈷氧化物於鋰電池中作為陽極材料之應用………… 26
1-5 研究動機與實驗架構………………………………………… 33
第二章 實驗設備、方法與程序……………………………………… 35
2-1 儀器…………………………………………………………… 35
2-2 藥品…………………………………………………………… 37
2-3 實驗程序與步驟……………………………………………… 39
2-3-1 Co(OH)2前趨物之合成……………………………… 42
2-3-1-1含SiO2之Co(OH)2製備……………………45
2-3-1-2含TiO2之Co(OH)2製備…………………… 45
2-3-1-3含介面活性劑Triton X-100與.45
2-3-2陽極CoO(薄膜)/Cu之製備…………………… 46

2-3-3 CoO(薄膜)-Ni/Cu之製備……………………………… 47
2-3-4 鈕扣型電池組裝……………………………………… 47
2-3-5 XRD 繞射分析……………………………………… 48
2-3-6傅立葉紅外線光譜儀(FTIR)………………………… 51
2-3-7 SEM 表面組態分析…………………………………… 51
2-3-8 SEM膜厚分析………………………………………… 51
2-3-9原子吸收光譜儀(AA)分析Ni的重量………………… 52
2-3-10鈕扣型電池充放電測試……………………………… 52
2-3-11交流組抗分析(AC Impedances analysis)…………… 53
2-3-12循環伏安(Cyclic voltammetry, CV)分析…………… 53
2-3-13 電流中斷分析法(current interrupt)……………………54
2-3-14 二次離子質譜儀(SIMS)………………………………56
第三章 結果與討論……………………………………………………57
3-1 以電沈積法製備CoO薄膜前驅物Co(OH)2薄膜之特性……57
3-1-1電沈積次數之影響………………………………………57
3-1-2電沈積所得之α- Co(OH)2 分子組成之鑑定…………63
3-1-3電沈積之共沈積矽化物成份分析………………………68
3-1-4 電沈積時攪拌速率對α- Co(OH)2的影響……………82
3-1-5 電沈積時SiO2添加量對Co(OH)2的影響……………96
3-1-6 電沈積時添加不同SiO2顆粒尺寸對Co(OH)2表面型態的影響………………………………………………… 111
3-1-7電沈積時添加triton X-100與SiO2對Co(OH)2的影響.115
3-1-8電沈積時添加TiO2顆粒對Co(OH)2表面型態的影響.122
3-2 CoO(薄膜)之製備與性質……………………………………126
3-2-1 製備前驅物之攪拌速率對CoO薄膜的影響…………129
3-2-2 電沈積時不同SiO2添加量對CoO薄膜的影響……146
3-2-3 電沈積時不同SiO2顆粒尺寸對CoO薄膜的影響……164
3-2-4 電沈積時添加triton X-100與SiO2對CoO(薄膜)的影響………………………………………………………172
3-2-5 電沈積時添加TiO2顆粒對CoO(薄膜)的影響………181
3-2-6 CoO表面上鍍Ni對CoO(薄膜)表面型態的影響…187
3-3 CoO/Cu為之充放電機構與循環特性…………………………191
3-3-1 充放電機構……………………………………………192
3-3-2 製備前驅物時攪拌速率對CoO(薄膜)/Cu充放電性質的影響…………………………………………………217
3-3-3 製備前驅物時溶液中奈米級SiO2對CoO(薄膜)/Cu充放電性質的影響………………………………………233
3-3-3-1 充放電性質………………………………233
3-3-3-2 電流中斷法分析……………………………249
3-3-3-3 交流阻抗分析………………………………255
3-3-4 製備前驅物時SiO2粒徑對CoO(薄膜)/Cu充放電性質的影響…………………………………………………275
3-3-5製備前驅物時添加triton X-100與12nm SiO2，對CoO(薄膜)/Cu充放電性質的影響……………………………282
3-3-5-1 0.2C-rate充放電………………………………282
3-3-5-2 充放電速率對CoO(薄膜)/Cu充放電性質影響……………………………………………289
3-3-6製備前驅物時添加21nm TiO2對CoO(薄膜)/Cu充放電性質的影響……………………………………………….297
3-3-7 CoO(薄膜)-Ni/Cu之充放電性質影響…………………304
3-4 綜合討論……………………………………………………… 314
3-4-1 製備前驅物時，添加物不同對CoO(薄膜)/Cu為負極之充放電性質影響……………………………………… 314
第四章 結論與建議…………………………………………………323
參考文獻………………………………………………………………330

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