臺灣博碩士論文加值系統

本研究分成平板電極、旋轉圓盤電極兩類；分別以循環伏安法、穩態動電位掃描法及交流阻抗法測求電化學特性值，並輔以SEM對電極表面進行觀察。研究目的在於瞭解添加Ca(OH)2於KOH溶液中對鋅之陽極溶解及鈍化之影響，以期增進對鋅在KOH中鈍化程序本質的認識。
依據循環伏安法及穩態動電位掃描法等方法得到如下之結果：(1)就陽極溶解速率而言，Ca(OH)2的添加會增加反應電流密度；(2)就鈍化電位而言，Ca(OH)2的添加會稍微提高鈍化電位。另外，就程序變數的影響而言，從溫度效應方面來看，添加Ca(OH)2會促成活化能有所改變；而在濃度效應方面，隨著Ca(OH)2濃度的增加，峰電流密度鈍化電位皆有正向的結果。另外，Tafel斜率在平板電極與旋轉圓盤電極的現象不太相同；(1)在KOH濃度效應方面，前半段和後半段的Tafel斜率皆隨KOH濃度的提高而增大。(2)在流力效應部分，提高轉速，可使質傳速率上升，因此可提高電流密度，並可延長鈍化電位。前半段和後半段的Tafel斜率並不會隨轉速增加而有所改變。

Two categories divided in this study were plate electrode and rotation disk electrode. Linear potential sweep, galvanostayic measurement and alternating current impedance methods were used to obtain the characteristics of the electrochemistry. Moreover, SEM was used to observe the electrode surface. The goal of this study was aimed to investigate the effects of additives Ca(OH)2 on the anodic dissolution and passivation of zinc in KOH solutions in order to gain better understanding of the role of zinc in the process of passivation in KOH solutions.
The findings of this study were: (1) the increasing additives of Ca(OH)2 resulted in higher current density in terms of the anodic dissolution; (2) the higher concentration of Ca(OH)2 additives produced higher passivation potential in terms of passivation potential. Furthermore, the effects of the activation energy changed with the additive of Ca(OH)2 in terms of temperature. On the other hand, both peak current density and passivation potential were dependent on concentration of additive used. In addition, Tafel slopes were not similar between plate electrode and rotation disk electrode. The variation of Tafel slopes was higher with the increasing KOH concentrations. The increasing rotation rate enhanced mass transfer, current density and passivation potential. The former part of Tafel slopes and the latter part didn’t change with the increasing rotation rates.

第一章 緒論 1
第二章 文獻回顧 3
第三章 實驗裝置及方法 10
3-1 實驗儀器 10
3-2 實驗藥品 11
3-3 實驗準備工作 12
3-3-1 反應器 12
3-3-2 鋅金屬電極材料的製作 12
3-4 研究方法 15
3-5 實驗步驟 15
3-5-1 平板電極 15
3-5-2 旋轉圓盤電極 17
3-5-3 掃描電子顯微鏡(SEM)之觀察 20
3-5-4 交流阻抗量測 21
第四章 結果與討論 23
4-1 平板電極 23
4-1-1 純KOH溶液 23
4-1-2 KOH溶液＋Ca(OH)2 25
4-1-2-1 循環伏安法 25
4-1-2-2準穩態動電位掃描法 26
4-1-2-2-1 溫度效應 26
4-1-2-2-2 添加劑Ca(OH)2濃度效應 28
4-1-2-2-3 KOH濃度效應 29
4-2 旋轉圓盤電極 49
4-2-1 純KOH溶液 49
4-2-2 KOH溶液＋Ca(OH)2 50
4-2-2-1 循環伏安法 50
4-2-2-2 準穩態動電位掃描 50
4-2-2-2-1 溫度效應 51
4-2-2-2-2 添加劑Ca(OH)2濃度效應 51
4-2-2-2-3 KOH濃度效應 52
4-2-2-2-4 流力效應 53
4-3 SEM之觀察 72
4-4 交流阻抗量測 88
第五章 結論與建議 94
參考文獻 97
附錄 100
附錄A 100
附錄B 101

1.李季品，“明日之星－鋅空氣電池”，能源報導，8-10 (2001.8) .
2.S. Muller, F. Holzer, O. Haas, “ Optimized zinc electrode
for the rechargeable zinc-air battery, ” Journal of Applied
Electrochemistry,Vol. 28, 895-898 (1998) .
3.Zhang, X. G. , “ Corrosion and Electrochemistry of Zinc, ”
29-91, Plenum Publishing Corporation (1996) .
4.Yu-Chi Chang, “ The effects of sodium metasilicate on the
electrodissolution of zinc in alkaline solutions, ” Journal
of the Chinese Institute of Chemical Engineers, Vol. 27, No.
1, 17-24 (1996) .
5.B. Zaid, S. Aeiyach, P. C. Lacaze and H. Takenouti, “ A two-
step electropolymerization of pyrrole on Zn in aqueous
media, ” Electrochimica Acta, Vol. 43, No. 16-17, 2331-2339
(1998) .
6.A. J. Calandra, N. R. de Tacconi, R. Pereiro and A. J. Arvia,
“ Potentiodynamic current/potential relations for film
formation under ohmic resistance control, ” Electrochimica
Acta, Vol. 19, 901-905 (1974) .
7.P. Bernard, M. Keddam and H. Takenouti, “Effects of ohmic
resistance on the evaluation of faradaic charge in thin films
of redox materials by impedance and voltammetry, ” Journal
of Electroanalytical Chemistry, Vol. 396, 325-332 (1995) .
8.M. Cai and S. M. Park, “ Spectroelectrochemical studies on
dissolution and passivation of Zinc electrodes in alkaline
solutions, ” Journal of the Electrochemical Society, Vol.
143, No. 7, July, 2125-2131 (1996) .
9.Yu-Chi Chang, “ A kinetic model for the anodic dissolution
of zinc in alkaline electrolyte with sodium metasilicate
additions, ” Electrochimica Acta, Vol. 41, No. 15, 2425-2432
(1996) .
10.L. Sziraki, A. Cziraki, I. Gerocs, Z. Vertesy and L. Kiss,
“ A kinetic model of the spontaneous passivation and
corrosion of zinc in near neutral Na2SO4 solutions, ”
Electrochimica Acta, Vol. 43, No. 1-2, 175-186 (1998) .
11.Digby D. Macdonald, Khaled M. Ismail and Elzbieta Sikora, “
Characterization of the passive state on zinc, ” Journal of
the Electrochemical Society, Vol. 145, No. 9, September,
3141-3149 (1998) .
12.M. T. Blanco, C. Andrade and A. Macias, “ SEM study of the
corrosion products of galvanized reinforcements immersed in
solutions in the pH range 12.6 to 13.6, ” Br. Corros. J.,
Vol. 19, No. 1, 41-48 (1984) .
13.A. Macias, C. Andrade, “ Corrosion rate of galvanized steel
immersed in saturated solutions of Ca(OH)2 in pH range 12-
13.8, ” Br. Corros. J., Vol. 18, 82-87 (1983) .
14.E. G. Gagnon, “ Effects of KOH concentration on the shape
change and cycle life of Zn/NiOOH cells, ” Journal of the
Electrochemical Society, Vol. 133, No. 10, 1989-1995 (1986) .
15.JiLing Zhu and YunHong Zhou, “ Effects of ionomer films on
secondary alkaline zinc electrodes, ” Journal of Power
Sources, Vol. 73, 266-270 (1998) .
16.Ram A. Sharma, “ Kintics of calcium zincate formation, ”
Journal of the Electrochemical Society, Vol. 135, No. 8,
1875-1882 (1988) .
17.R. Shivkumar, G. Paruthimal Kalaignan and T. Vasudevan, “
Studies with porous zinc electrodes with additives for
secondary alkaline batteries, ” Journal of Power Sources,
Vol. 75, 90-100 (1998) .
18.格里弟博士編著，鮮棋振博士編譯，“電極動力學”，徐氏基金會出
版，377、104 、79 (1996) .
19.Gordon M. Barrow, “ Physical Chemistry, ” 730, The McGRAW-
HILL Companies (1996) .
20.張裕棋，“鋅在含矽酸鹽的鹼性電解質溶液中電化學行為”，淡江學
報，Vol. 32，513-522 (1993)。