臺灣博碩士論文加值系統

研究利用電化學方法在鈦基材上沉積氧化物,以製備超高電容電極,主要是探討電化學沉積反應機制與釕氧化物儲電特性。實驗內容包括,利用CV法分別在-0.2~1.1V及0.7~1.1V電位範圍沉積及定電位法沉積釕氧化物,並對鍍層結構作分析探討,包含SEM和XPS測試,以及電極於H2SO4電解液中之阻抗分析.
實驗結果顯示,在RuCl3.3H2O和HCl水溶液中,以循環伏安法在水分解的電位範圍間(-0.2~1.1V vs. SCE)沉積釕氧化物時,電極電位大於0.7V vs. SCE以上時產生氧化反應,而當電位小於0.5V時則產生還原反應.電極表面RuOx沉積主要由氧化反應產生,還原反應無明顯釕氧化物沉積現象發生。CV法循環過程,還原反應使得電極上沉積層較為堅固.
利用Ru(III)離子在旋轉電極上還原反應的極限電流求得其擴散係數(D),D值範圍為1.05*10-5至2.56*10-6cm2/sec.,其值隨電解液pH值.Ru(III)離子濃度及電解液靜置時間增加而減小,電解液中的KCl的濃度大小對擴散係數則無明顯影響，顯示溶液中,Ru(III)離子形成較大的膠體粒子,反應主要影響因素為溶液pH值.Ru(III)離子濃度及靜置時間.溶液在靜置24小時後擴散係數比新配溶液擴散係數減小25~40％，靜置144小時後約減小30~60％,並漸漸達一穩定值,即約一周後生成穩定膠體溶液.
由釕氧化物沉積之CV測試及XPS分析顯示,陰極還原沉積會使釕氧化物沉積層含較多Ru-O-Ru的結構,結晶水含量降低,鍍層較穩定但氧化還原反應較不可逆;而陽極氧化反應恰好相反,會使鍍層中結晶水含量增加,且含較少Ru-O-Ru的結構,造成鍍層不穩定易溶解,但氧化還原反應可逆性較佳.SEM分析顯示以陰極還原沉積之鍍層表面結構平整,而以CV法沉積之鍍層表面結構有龜裂之現象,顯示沉積層在不斷的氧化還原過程中,體積膨脹收縮會造成表面結構之破裂.
阻抗(Impedance)測試分析結顯示,電化學沉積之釕氧化物電極經熱處理,當熱處理溫度大於200℃時阻抗會因燒結會形成釕氧化物的結晶相,使電極電阻減小.以CV法(-0.2~1.1V)沉積之釕氧化物鍍層，在高電位時法拉第電阻(Rct)較小,在低電位時Rct較大,即其氧化還原可逆性在高電位時較在低電位時佳;而以陰極還原沉積之釕氧化物其Rct在各電極電位無明顯變化,即其氧化還原可逆性在各電極電位下無明顯差異。釕氧化物電極電容器在H2SO4濃度的電解液中，其等效串聯電阻(ESR)隨著電解液H2SO4濃度增加而降低,而當H2SO4濃度大於4M時,則隨H2SO4濃度增加而增加,約在4M時其ESR值最小。

Abstracts
The growth of Ruthenium oxides on Ti substrates in RuCl3.3H2O and HCl aqueous solution by cyclic voltammetric (CV) methods and constant potential deposition are studied in this work. Rotating electrode technology, SEM,XPS and EIS measurements are performed to investigate the growth mechanisms and the properties of ruthenium oxide deposition.
The results of rotating electrode study show that the CV deposition of Ruthenium oxides via anodic and cathodic cycling in the potential range of —0.2 to 1.1 V vs. SCE are mainly contributed by the anodic oxidation of Ru(III) ions, while that via the cathodic reduction of Ru(III) ions are not apparent. The limiting current of the cathodic polarization behaviors on the rotating electrode is in accordance with the Levich’s equation and the diffusivity (D) values of Ru(III) ions calculated accordingly are in the range 1.05*10-5 to 2.56*10-6cm2/sec. D values decrease with the increase of the pH, RuCl3 concentration and aging time of the solution, about 25-40% and 30- 60% decrease of the D values are found after 24 and 144 hours storage of the solution respectively.
The results of XPS analysis show that the ruthenium oxides via cathodic reactions lead to higher Ru-O-Ru and lower H2O composition, and a more stable structure than that via anodic reactions. The SEM photographs show crack phenomena appears in the deposits via CV deposition, while smooth deposits are obtained via cathodic deposition.
The EIS study shows that The impedance of RuOx electrode decreases apparently after annealing at temperature higher than 200℃ due to the crystallization of the deposition. The redox reversibility of CV deposited RuOx electrode is better at higher electrode potential( e.g. 1.0 V vs. SCE) than that at lower electrode potential(e.g. 0V vs. SCE), while that are about equal in the potential range 0 - 1.0 V for cathodically prepared RuOx electrodes. It indicates the properties of ruthenium oxide electrodes are significantly dependent on the electrochemical deposition conditions. The optimum H2SO4 concentration for minimum equivalent series resistance (ESR) for RuOx electrochemical capacitor obtained is 4M.

中文摘要 --------------------------------------------- i
英文摘要 ------------------------------------------ iii
誌謝 --------------------------------------------- v
目錄 --------------------------------------------- vi
表目錄 --------------------------------------------- ix
圖目錄 --------------------------------------------- x
第一章 緒論----------------------------------------- 1
1-1 電化學電容器簡介---------------------------- 1
1-1-1 電化學電容器的沿革與應用----------- 1
1-1-2 電化學電容器的儲能機構-------------- 3
1-2 超高電容器電極材料種類--------------------- 6
1-2-1 碳系材料---------------------------- 8
1-2-2 導電性高分子材料-------------------- 11
1-2-3 金屬化合物材料---------------------- 13
1-3 超高電容器電極製備方法--------------------- 14
1-3-1 活性碳複合電極的製備---------------- 14
1-3-2 導電性高分子電極製備---------------- 16
1-3-3 金屬氧化物電極的製備---------------- 16
1-4 影響電極儲電特性的因素---------------------- 18
1-5 阻抗頻譜分析--------------------------------- 20
1-5-1 EIS理論----------------------------- 20
1-5-2 常見電容器電極之等效電路模式------- 21
1-6 研究動機------------------------------------- 29
第二章 實驗方法與步驟------------------------------ 31
2-1 電極製作------------------------------------- 31
2-1-1 電極基材前處理--------------------- 31
2-1-2 旋轉電極之電極基材製備-------------- 31
2-1-3 鍍浴組成---------------------------- 31
2-2 電化學測試-------------------------- 32
2-2-1 電化學沉積測試-------------------- 32
2-2-2 可逆性及電極老化測試------------------ 32
2-2-3 阻抗分析----------------------------------- 33
2-2-4 鍍層分析----------------------------------- 33
2-3 使用儀器及藥品------------------------------- 34
第三章 釕氧化物在旋轉電極上之沉積行為及Ru(III)在電解液中擴散 係數的探討------------------- 36
3-1 瞬時改變旋轉電極轉速對循環伏安法沉積釕氧化物沉積之 影 響------------------------------- 36
3-1-1 瞬時改變旋轉電極轉速對I-V曲線之影響---------- 36
3-1-2 瞬時改變旋轉電極轉速對沉積速率之影響--------- 37
3-2 Ru(III)離子陰極還原之極化曲線---------------- 44
3-2-1 Ru(III)於電解液中之擴散係數------------ 44
3-2-2 鍍液pH值、靜置時間及電解質濃度對擴散係數的影響---46
第四章 循環伏安法及定電位法製備釕氧化物電極及其電化學特性探討------------------------------- 56
4-1 循環伏安法製備釕氧化物電極---------------- 56
4-1-1 不同循環電位範圍下沉積之I-V 關係 56
4-1-2 循環電位範圍對鍍層特性之影響------ 59
4-2 定電位沉積釕氧化物電極---------------------- 71
4-2-1 不同電位下之I-t曲線及鍍層儲電特性 71
4-2-2 沉積電位對釕氧化物鍍層特性之影響- 75
第五章 電化學沉積釕氧化物電極之阻抗特性-------- 84
5-1 循環伏安法與定電位陰極還原沉積之釕氧化物電極阻抗特性分析----------------------------- 84
5-2 熱處理溫度對釕氧化物電極阻抗之影響------ 92
5-3 硫酸電解液濃度對釕氧化物電極電容器ESR的影響-- 95
第六章 總結----------------------------------------- 99
參考文獻 --------------------------------------------- 102
附錄 --------------------------------------------- 110
作者簡歷 --------------------------------------------- 115
表目錄
表1-1 超高電容器與二次電池之優缺點--------------- 3
表1-2 高性能電容器技術與産品發展趨勢------------ 3
表1-3 介電質與其介電常數--------------------------- 4
表1-4 各種不同型式碳材電極所製成的電容器之性質一覽表----10
表1-5 各種不同金屬氧化物及複合電極材料之電容量比較表----15
表4-1 循環伏安法沉積之鍍層沉積量與擬電容------ 64
表4-2 不同定電位下沉積釕氧化物鍍層之結果------ 74
表5-1 Rct ,Cdl and Cp of Ruthenium oxide electrodes at various potential------------------------------- 89
圖目錄
圖1-1 The schematic diagram of an electrochemical capacitor.------------------------------------------- 5
圖1-2 Ragone plot for various energy storage and conversion devices.--------------------------------------- 7
圖1-3 (A) The equivalent circuit of resistor and capacitor were series.(B) The Nyquist plot for the equivalent circuit (A). ----------------------------------------------23
圖1-4 (A)The equivalent circuit for an electrode without diffusion effect.(B) The Nyquist plot for the equivalent circuit (A).--------------------------------------- 24
圖1-5 (A) The equivalent circuit for an electrode with diffusion effect.(B) The Nyquist plot for the equivalent circuit (A).--------------------------------------- 26
圖1-6 The equivalent circuit of RuOx electrode (A) with Warburg impedance effects; (B) without Warburg impedance effects at high frequency.----------------- 27
圖2-1 (A) The schematic diagram of Ti plate on RDE.(B)The schematic diagram of an electrochemical measurement. --34
圖3-1 The effects of changing rotation rate of electrode on the I-V behaviors of CV deposition for ruthenium oxides in various potential range.------- 38
圖3-2 The effects of changing rotation rate of electrode in anodic potential region on the deposition of ruthenium oxides. --------------------------------------- 41
圖3-3 The effects of changing rotation rate of electrode on the deposition of ruthenium oxides in cathodic potential range.------------------------------------------ 42
圖3-4 (A)Cathodic polarization current of RuCl3.3H2O vs. scan number.(B)Relation of in/i1 and scanning number at various potential .------------------------------------------ 45
圖3-5 Cathodic polarization curves of RuCl3.3H2O at various rotating rate.----------------------------------- 47
圖3-6 Plot of limiting current vs. ω1/2. -------- 49
圖3-7 XPS spectra of the (A) Ru 3d5/2,3/2 (B) O 1s for RuOx deposition via cathodic sweep between 0 to -0.7V for 60 times. ---------------------------------------------------- 50
圖3-8 Plot of diffusivity vs. concentration of RuCl3.3H2O at various rotating speed of electrode. ---------------52
圖3-9 Plot of Ru(III) diffusivity vs. pH.--------- 53
圖3-10 Ru(III) diffusivity vs. [KCl].--------------- 54
圖3-11 Plot of Ru(III) diffusivity vs. aging time of the solution. ------------------------------------- 55
圖4-1 CV behaviors of RuOx growth in 10mM RuCl3. 3H2O between -0.2~1.1V vs. SCE for 100 cycles.----- 57
圖4-2 CV behaviors of RuOx growth in 10mM RuCl3.3H2O between 0.7~1.1V vs. SCE for 100 cycles. ------------- 58
圖4-3 CV behavior of a RuOx electrode with upper potential limits changed from 1.1 to 0.2V. The electrode was prepared by CV method etween —0.2~1.1V for 100 cycles.----------- 60
圖4-4 CV behavior of a RuOx electrode with upper potential limits changed from 1.1 to 0.2V. The electrode was prepared by CV method between 0.7~1.1V for 100 cycles. ----------- 61
圖4-5 The CV behaviors of Ruthenium oxides electrode prepared by CV methods between various potential range for 100 cycles in 10mM RuCl3.3H2O. --------- 63
圖4-6 SEM photographs (10,000x) of the RuOx deposited in the plating bath containing 10mM RuCl3.3H2O by CV method.--65
圖4-7 The plot of charge decay of RuOx films vs. cycle number of anodic and cathodic cycling between -0.2~1.1V in 0.5M H2SO4. ------------------------------ 67
圖4-8 XPS spectra of the O 1s for RuOx electrode prepared by CV method.-------------------------------- 68
圖4-9 SEM photographs (X3,000) of the RuOx prepared by CV method.------------------------------------------- 70
圖4-10 Current vs. deposition time of RuOx deposition in the plating both containing 10mM RuCl3.3H2O at various constant potential. ---------------------------- 72
圖4-11 The CV behaviors of Ruthenium oxide electrodes prepared by constant potential methods in 10 mM RuCl3.3H2O for 1 hour.---------------------------------- 73
圖4-12 SEM photographs (X10,000) of the cathodically deposited RuOx.3H2O in the plating bath containing 10mM RuCl3.3H2O at various potential for 1 hour. ---------- 76
圖4-13 CV behavior of RuOx in 0.5M H2SO4 electrode prepared by cathodic deposition at (A)—0.5V, (B)-0.4V, (C)-0.3V for 1 hr., pH:2; scan rate : 50mV/s. -------------------- 78
圖4-14 XPS spectra of the O 1s for RuOx via cathodic deposition .------------------------------------ 81
圖4-15 The plot of charge decay of RuOx films vs. cycle number of anodic and cathodic cycling between -0.2~1.1V in 0.5M H2SO4. Electrode prepared by cathodic deposition method at (1)-0.5V, (2)-0.4V, (3)0.9V, (4)1.1V for 1 hour.---------- 82
圖4-16 SEM photographs (X3,000) of RuOx deposited at constant potential. The deposits were treated by anodic/cathodic cycling between -0.2 and 1.1V (vs. SCE) for 10 times.--------------------------------------- 83
圖5-1 Nyquist plot of RuOx electrode at various potential in 0.5M H2SO4. Electrodes were prepared by (A) CV method between -0.2~1.1V for 100 cycle; (B)cathodic deposition at —0.5V for 1 hour.--------- 85
圖5-2 Bode plot of RuOx electrodes at various potential in 0.5M H2SO4. Electrodes were prepared by (A) CV method between -0.2~1.1V for 100 cycle, (B) cathodic deposition at —0.5V for 1 hr. and annealed at 200℃ for 3 hours.---------------- 87
圖5-3 I-V behaviors of RuOx electrodes in 0.5M H2SO4. The electrodes were prepared by (A) CV method between -0.2~1.1V for 100 cycle (B) cathodic deposition at —0.5V for 1 hour.--91
圖5-4 Effects of annealing temperature on the impedance of RuOx Electrodes in 0.5 M H2SO4. ohm resistance at Z”=0 annealing time: 3 hours.---------------------- 93
圖5-5 Effect of standing time of Ti substrate in 0.5M H2SO4 electrolyte on the CV behaviors. -------------- 96
圖5-6 SEM photographs (X10,000) of the CV deposited RuOx between -0.2 to 1.1V for 100 cycles in the plating bath containing 10mM RuCl3.nH2O .The deposits have been (A)dried at room temp. (B) annealed at 200℃, (C) annealed at 300℃. ----97
圖5-7 Plot of RuOx capacitor ESR vs. concentration of H2SO4.------------------------------------------------ 98
圖A-1 (A)Crrent of behavior in an RC circuit corresponding to the (B) potential step charge.----- 113
圖A-2 E-t behavior for current step.--------------- 114
圖A-3 I-t behavior for potential sweep.------------ 114

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