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研究生：	粘喬琳 Nian, Ciao-Lin
論文名稱：	定電流陽極沉積錳氧化物之電極製備及其特性研究 Preparation and characteristics of manganese oxides electrode by galvanostatic anodic deposition
指導教授：	黃啟祥 Hwang, Chii-Shyang
學位類別：	碩士 Master
系所名稱：	工學院 - 材料科學及工程學系 Department of Materials Science and Engineering
論文出版年：	2006
畢業學年度：	94
語文別：	中文
論文頁數：	106
中文關鍵詞：	定電流、田口式實驗計畫法、超高電容器、錳氧化物
外文關鍵詞：	manganese oxides, electrode, galvanostatic anodic deposition
相關次數：	點閱：83 下載：2
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超高電容器電極材料之研發，最近深受注目。錳氧化物為可期待的電極材料之ㄧ。影響錳氧化物比電容值的因子甚多，但這些因子對錳氧化物比電容值的貢獻度，以往並未被做定量的描述。本研究目的旨在以定電流陽極沉積法在鈦金屬基板上沉積出錳氧化物薄膜，並將之作為電化學電容器之電極材料。在電化學特性分析方面，主要是以循環伏安法於0.1M Na2SO4溶液中進行擬電容行為測試及比電容值之評估，其中是先以田口方法檢討陽極沉積溫度、電流密度、醋酸錳濃度及pH值對錳氧化物比電容值貢獻度之大小。其結果顯示，當溫度範圍5℃～25℃、pH值範圍5.3～7.3、濃度範圍0.05～0.5 M及電流密度範圍0.25～2.25 mA/cm2時，貢獻度由大而小依序為:沈積溫度、電流密度、陽極沉積溫度與電流密度的交互作用、鍍液濃度，而pH值貢獻度小於1 %。其中值得注意的是陽極沉積溫度與電流密度的交互作用佔了15.04 %。
由於沉積溫度為最主要的影響因子，本研究更進一步檢討沉積溫度對所得錳氧化物之影響。實驗結果顯示當沉積溫度為15℃時所得之錳氧化物有最佳之比電容値225.3 F/g；此錳氧化物電極經300圈循環伏安測試後，仍保有85 %的比電容值，顯示穩定性頗佳。

The electrode materials of supercapacitor are important research targets, recently. Manganese oxide is one of the promising electrode materials. The specific capacitance of manganese oxide are affected by many factors, however, until now there is no any report about the contribution of each factor to the specific capacitance of manganese oxides. This study tries to prepare the manganese oxide film on the titanium metal plate by galvanostatic anodic deposition to get the electrode membrane of capacitors. The Taguchi method was used to analyze the contribution of deposition temperature、current density、Mn(CH3COO)2．4H2O concentration and pH to the specific capacitance of manganese oxides. The cyclic voltammetry was used to test the pseudocapacitor behavior and specific capacitance in 0.1 M Na2SO4 solution. The results showed that the sequence of factors with respect to the contribution to specific capacitance of manganese oxides were the deposition temperature、current density、interaction between deposition temperature and current density, and concentration of Mn(CH3COO)2 solution, when the deposition temperature ranges from 5 ℃ to 25 ℃, pH ranges from 5.3 to 7.3, Mn(CH3COO)2．4H2O concentration ranges from 0.05 M to 0.5 M and current density ranges from 0.25 mA/cm2 to 2.25 mA/cm2. The interaction between deposition temperature and current density was important, and its contribution to specific capacitance of manganese oxides was 15.04 %.
Effect of the deposition temperature(5~80℃) on the specific capacitance of manganese oxides was also discussed because the deposition temperature was the main factor. The experimental results showed that the manganese oxides deposited at 15 ℃ exhibited the highest specific capacitance of 225.3 F/g and the specific capacitance remained 85 % after 300 CV cycles.

總目錄

中文摘要………………………………………………………………….…Ⅰ
英文摘要………………………………………………………………….…Ⅱ
目錄……………………………………………………………………….…Ⅳ
表目錄………………………………………………………………….……Ⅶ
圖目錄…………………………………………………………………….…Ⅷ
第一章 緒論…………………………………………………………….....1
第二章 理論基礎與文獻回顧………………………………………….....5
  2-1 儲能元件簡介…………………………..……………………………5
  2-2 電化學電容器 ……………………………………………………….6
    2-2-1 電化學電容器之特性……………………………………………6
    2-2-2 電化學電容器之分類……………………………………………7
  2-3 電化學電容器之電極材料……………………………………………8
    2-3-1 金屬氧化物電極材料……………………………………………9
    2-3-2 錳氧化物電極製備方法……………………………………..…10
  2-4 錳氧化物的儲能機構………………………….………….…………13
  2-5 田口式品質工程…………………………………………………..…14
第三章 實驗方法及步驟…………….……………………..………………28
  3-1電極材料製備………………….…………………..…………………28
    3-1-1 鈦箔電極片前處理………………………….………………….28
    3-1-2 陽極沈積錳氧化物………………………………………..……28
      3-1-2-1 第一部份:田口式實驗計畫法…………………….………29
      3-1-2-2 第二部份:探討單一變因對比電容值的影響…………….29
  3-2藥品與裝置…………………………………………………...………30   
  3-3錳氧化物薄膜電極製作流程………………...………………………31
    3-3-1第一部份：田口式實驗計畫法…………………..………….…31
    3-3-2第二部分：探討單一變因對比電容值的影響………….………32
  3-4錳氧化物之性質分析………………………..………….……………33
    3-4-1 電容特性分析…………………………………………………..33
    3-4-2 晶體結構分析…………………………………………………..34
    3-4-3 微觀組織分析…………………………………………………..34
    3-4-4 表面形貌分析…………………………………………………..35
    3-4-5 化學性質分析 ……………………………………………...…35 
    3-4-6 熱性質分析………………………………………………..……36
第四章 結果與討論…………………………………………...……………39
  4-1 田口式品質工程……………………………..……………………..39
    4-1-1 實驗規劃……………………………………………………..…39
    4-1-2 實驗結果與S/N比…………………………………………..….40
    4-1-3 變異數分析……………………………………………..………40
    4-1-4 錳氧化物之晶體結構分析……………………….…………….42
    4-1-5 錳氧化物之微觀組織分析………………………..……………42
    4-1-6 錳氧化物之表面形貌分析……………………………………..43
    4-1-7 結語……………………………………………………………..44
  4-2沉積溫度對錳氧化物性質之影響……………………..….…………45
    4-2-1 陽極沉積條件的選擇…………………………………………..45
    4-2-2 錳氧化物之電容特性分析………………………….………….46
    4-2-3 錳氧化物之穩定性分析………………………………………..47
    4-2-4 錳氧化物晶體結構的低掠角XRD分析…………….………....47
    4-2-5 錳氧化物化合狀態的XPS分析………………………….……..48
    4-2-6 錳氧化物電極表面微觀組織的SEM分析……………….……..50
    4-2-7 錳氧化物微觀組織結構的TEM分析………….….……….....51
4-2-8 錳氧化物之表面形貌分析………………………………..…......55
    4-2-9 錳氧化物的熱重與熱差分析…………………………………..56
    4-2-10 結語…………………………………………………………...57
第五章 結論………………………………………………………….......100
參考文獻…………………………….……………………………………...102

表目錄

Table 2-1 Auxiliary table………………………………………………............18

Table 4-1 Factors and levels for Taguchi Method…………………………......59

Table 4-2 L27 matrix of Taguchi Method and experimental data of specific   capacitance (Cs) and S/N ratio…………………………………................ 60

Table 4-3 Auxiliary table…………………………………….………….......……61

Table 4-4 Analysis of Variance, degree of freedom and contribution of the factors……………………………………….………………….....................62

Table 4-5 Surface characteristics and the specific capacitance of the          manganese oxides formed with different deposition conditions…………………………...…………………………..…................63

Table 4-6 O 1s orbital XPS analytical results of the manganese oxides deposited at various temperatures……………...……….…...……...........64

Table 4-7 Surface characteristics and the specific capacitance of the manganese oxides formed with various deposition temperatures………………………………………………….......................65

Table 4-8 Comparative characteristics of the manganese oxides formed at various deposition temperatures…………………………………................66

圖目錄

Fig. 1-1 Sketch of dielectric capacitor………………………………………....4
.
Fig. 2-1 The electronic circuit of a electrochemical capacitor in a power        source system………………………………………………….……....19

Fig. 2-2 The specific power and the specific energy of various energy 
storage devices………………………………………………….….................20

Fig. 2-3 Structure of electric double-layer capacitor………………..………21

Fig. 2-4 Cyclic voltammograms at a scan rate of  2mV/s in 1M Na2SO4 for 
two-electrode cells made of the pristine carbon nanotubes and a-MnO2, respectively…………………………...……….……...…......................22

Fig. 2-5 CV of dip-coated sol-gel MnO2 films was measured in 0.1M 
Na2SO4 solution with a potential scanning rate of 50mV/s…….…..........23

Fig. 2-6 The potential of the film as a function of oxidation time. Four   oxidations have been done, each stopped during a different stage of oxidation……………………….……...………………………....................24

Fig. 2-7 Current vs. potential plots for samples oxidized to various end potentials and then cycled 100 times. A scan rate of 50mV/s was  used in
 a 1M Na2SO4 electrolyte. The tenth cycle is shown……….................25


Fig. 2-8 Cyclic voltammograms of a-MnO2．nH2O measured in 0.1M 
Na2SO4 at 25mV/s with the upper and lower potential limits of CV equal 
to (1) (0.8, 0.2)；(2) (1.0, 0)；and (3) (1.2, -0.2) V…………...........26

Fig. 2-9 Variation of anodic current density of the electrodes formed at various deposition potential in 0.25M Mn(CH3COO)2 solution at 25℃…………………………………………………………...……......................27

Fig.3-1 Schematic diagram of (a) anodic deposition and (b) Potentiostat 
/ Galvanostat analyzer……………………………………………..….............37

Fig. 3-2 Photoelectrons occur principle figure………………………………...38

Fig. 4-1 The contribution of various factors effected on specific  capacitance..............................................................67

Fig. 4-2 GAXRD patterns of the oxide electrodes formed with different deposition conditions (a) NO.12 (4.2F/g), (b) NO.16 (160.6F/g), NO.23 (225.3F/g)……….………………………………………..…......................68

Fig. 4-3 XPS spectra of Mn 2p3/2 orbit for the manganese oxides formed
 with different deposition conditions………………………………............69

Fig. 4-4 SEM micrographs of the manganese oxides formed with different deposition conditions (a) NO.12 (4.2 F/g), (b) NO.16 (160.6 F/g), 
NO.23 (225.3 F/g)……………………………………….………….................71

Fig. 4-5 Surface topography of the manganese oxides formed with 
different deposition conditions (a) NO.12 (4.2 F/g),
 (b) NO.16 (160.6F/g),NO.23(225.3F/g)………...………………….…………....72

Fig. 4-6 Potential-pH equilibrium diagram for the manganese-water 
system, at 25℃……………………………..……….……………………...........73

Fig. 4-7 Variations of deposition potential with deposition time in 
0.1M Mn(CH3COO)2‧4H2O solution at various deposition temperatures…..….74

Fig. 4-8 Cyclic voltammograms of the manganese oxides deposited in 
0.1 M manganese acetate aqueous solution at various   temperatures. 
CV curves were measured in 0.1M Na2SO4    solution at 25℃, with a 
potential scanning rate of 20mV/s………………………………………………....75

Fig. 4-9 The effect of the deposition temperature on the specific 
capacitance of the manganese oxides……………………….……...............76

Fig. 4-10 Variations of specific capacitance with CV cycle number of the manganese oxide electrodes deposited at various temperatures………………………………………………………...................77

Fig. 4-11 Variations of specific capacitance ratio with CV cycle number
of the manganese oxide electrodes deposited at various temperatures……..78

Fig. 4-12 GAXRD patterns of the oxide electrodes deposited at various temperatures…………………………………………………….…..................79

Fig. 4-13 GAXRD patterns of the oxide electrodes deposited at 80℃ after 
10 cycles and 300 cycles of CV test……………….……...…................80

Fig. 4-14 XPS spectra of Mn 2p3/2 orbit for the manganese oxides 
deposited atvarious temperatures…………….………….………...............81

Fig. 4-15 XPS spectra of O 1s orbit for the manganese oxides deposited       at various temperatures…………………………………………..................82

Fig. 4-16 SEM micrographs showing surface morphologies of the  manganese oxides deposited at various temperatures and then after 10 cycles of CV 
test: (a)(b) 5℃, (c)(d) 15℃, (e)(f) 40℃ and (g)(h) 80℃………………….83

Fig 4-17 (a) SEM of the manganese oxides deposited at 15℃.(b) and (c) 
are the map of Mn and O of the manganese oxides deposited at 15℃.....................................................................85

Fig. 4-18 SEM micrographs showing surface morphologies of the 
manganese oxides deposited at various temperatures and then 
after 300 cycles of CV test: (a)(b) 15℃, (c)(d) 40℃, and (e)(f)80℃………………………………………………………….............................86

Fig. 4-19 (a) TEM image of the manganese oxides deposited at 5℃, (b) 
SAED pattern of region B, (c1) and (d1) lattice images    taken from 
regions C and D, respectively. (c2) and (d2) SAED patterns taken from 
regions C and D, respectively……...………...............................89

Fig. 4-20 (a) TEM image with low magnification and (b) TEM image with 
high magnification of the manganese oxides deposited at 15℃.(c) and (d1) 
TEM image with higher magnification of regions C and D, respectively. (d2) 
and (e) SAED patterns  taken from regionsD and E, respectively……….....90

Fig. 4-21 (a) and (b) TEM image with low and high magnification of the manganese oxides deposited at 15℃ , respectively. (c) SAED pattern 
taken from region C . (d) and (e) lattice images taken 
from regions D and E, respectively…………………..…………….............92

Fig. 4-22 (a) and (b) are TEM bright field image and dark field image of 
the manganese oxides deposited at 40℃, respectively.(c) SAED pattern 
taken from the same area……………………………….…......................94

Fig. 4-23 (a) TEM image of the manganese oxides deposited at 80℃ and 
(b) SAED pattern taken from region B ……………………...…….............95

Fig. 4-24 (a) TEM image of the manganese oxides deposited at 80℃ and 
(b) SAED pattern taken from region B . (c) lattice images taken from 
regions C……………………………………………………........................96

Fig. 4-25 Surface topography of the manganese oxides formed with 
various deposition temperatures: (a) 5℃, (b) 15℃, (c) 40℃and (d)80℃…………………………………………………….....……........................98

Fig. 4-26 TGA and DTA curves of manganese oxides deposited at various temperatures: (a) 15℃ and (b) 80℃…...………….…......................99

                                    

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校內：2008-07-31公開
校外：2011-07-31公開

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