本研究以靜電輔助超波霧化沉積法(EAUSP) 在氧化釓摻雜氧化鈰(CGO)基材上沉積鑭鍶鈷鐵La0.6Sr0.4Co0.2Fe0.8O3 (LSCF)氧化物膜。在高壓靜電場作用下，霧氣會在沉積過程中會向基材集中，不因上升熱氣流影響而散逸在大氣中。由此可知，施加高壓靜電場有助於薄膜之沉積。由XRD結果可知，所沉積之LSCF薄膜為立方晶鈣鈦礦結構。由SEM結果可知，靜電場強度影響薄膜之孔隙度，弱電場沉積之薄膜孔隙度較高。而在LSCF//CGO//LSCF對稱電池以交流阻抗法量測，所獲得之介面阻抗ASR及活化能，均與傳統製程之數值相當。由於EAUSP法是簡單，高效率又經濟的鍍膜法，由目前所獲得的薄膜及電化學性質可知，EAUSP法適合用來製備SOFC電極膜。
除了EAUSP法，靜電輔助噴塗（ESD）法，亦用來沉積LSCF薄膜。藉由一系列變化沉積時間與沉積溫度以了解LSCF膜在矽晶片之成長機制。結果顯示薄膜之初始成膜過程與沉積溫度有關。但沉積溫度略低於先驅物溶液的沸點時，可獲得單一多孔結構的薄膜。
經由系統化地改變沉積參數，將LSCF陰極膜沉積SDC基材上並製作成對稱電池。薄膜之微結構及表面形貌分別以XRD及SEM觀察。電化學阻抗譜技術用以量測對稱電極的介面電阻area specific resistance (ASR)，在700oC 時可獲得最低之介面ASR為 0.25 Ω-cm2。
在NiO-SDC/SDC半電池上,製作並測試單層及雙層陰極之性能，單層陰極以網印法製作，雙層陰極是在SDC電解質上以ESD沉積一層LSCF膜再以網印製作另一層LSCF陰極。雙層陰極在700 oC時最大功率密度由單層陰極之1.04 提升至1.18 W/cm2, 而介面電阻ASR結果顯示, ESD雙層電極之介面阻抗為單層陰極的一半。
Ω

In this study, deposition of La0.6Sr0.4Co0.2Fe0.8O3 (LSCF) oxide films on Gd-doped ceria (CGO) substrates by an electrostatic assisted ultrasonic spray pyrolysis (EAUSP) method was demonstrated for the first time. The electrostatic field employed for directing the aerosol stream towards the substrate was shown to be indispensable for film deposition. The XRD result indicates that a single phase of cubic perovskite was obtained in the calcined films. SEM examination reveals that the electric field strength had a profound effect on film porosity with weaker field resulting in higher porosity. The results of impedance measurement on LSCF//CGO//LSCF cells indicate that the area specific resistance (ASR) values of current LSCF films and their activation energies are comparable to that obtained by conventional sample preparation routes. In view of the simplicity, efficiency and economy of film deposition and the sound electrochemical characteristics of the obtained films manifested in current work, it is concluded that EAUSP method is a promising method for preparation of SOFC electrode films.
Besides the EAUSP method, electrostatic spray deposition (ESD) method was also employed to deposit LSCF films. The growth mechanism of LSCF films deposited on silicon wafer was studied by examining a series of films obtained with increasing deposition durations. The results show that the film formation mechanism in the initial stage depends on the deposition temperature, and films with a unique porous structure were obtained when a deposition temperature lower than the boiling point of the precursor solution was used.
Deposition parameters were also varied systematically to deposit LSCF cathode films on CGO substrates to obtain symmetrical cells. The microstructure and morphology of obtained films were investigated by X-ray diffraction and SEM, and the area specific resistances of the symmetrical cells measured by electrochemical impedance spectroscopy (EIS). The minimum interfacial ASR value associated with the LSCF cathodes was 0.25 ohm•cm2 at700 °C.
NiO-SDC (Sm0.2Ce0.8O1.9)/SDC/LSCF (La0.6Sr0.4Co0.2Fe0.8O3-δ) cells with either single
layer or double layer cathode were also fabricated and tested. The single layer LSCF cathode
was made by stencil printing while the double layer one was prepared by depositing a thin
porous layer on the SDC electrolyte by ESD before stencil printing LSCF. The maximum
power density increased from 1.04 to 1.18 Wcm-2 at 700°C when the LSCF inter-layer was
introduced. The results showed that the ASRs of the cells reduced to half with the addition of
the LSCF inter-layer.

Table of contents
List of Figures v
List of Tables xii
List of Tables xii
摘 要 xiv
Abstract xvi
Chapter 1 Introduction 1
1.1 What are fuel cells ? 1
1.1.1 Fuel cell Types 2
1.1.2 The solid oxide fuel cell 3
1.1.2 The solid oxide fuel cell 4
1.2 Electrode polarization of SOFC 6
1.3 The Objective of this study 14
Chapter 2 Literature review 15
2.1 Electrostatic spray deposition (ESD) method 15
2.1.2 Growth models of ESD films 21
2.2 LSCF for SOFC cathode 24
2.2.1 Lattice Structure of LSCF 24
2.2.2 Crystallography of La1-xSrxCo1-yFeyO3-δ 27
2.2.3 Thermal analysis 31
2.2.3 Electrical conductivity 35
2.3 Kinetics of cathode 40
2.4 Electrochemical impedance spectroscopy (EIS) analysis 45
2.4.2 Equivalent Circuit fitting 49
Chapter 3 Experimental procedures 54
3.1 Experimental Procedures 54
3.2 EAUSP Experimental procedure 55
3.2.1 EASUP setup 56
3.2.2 EAUSP deposition parameters 58
3.2.3 Characterization of EAUSP films 61
3.3 ESD experimental procedure 63
3.3.1 ESD system setup 65
3.3.2 ESD deposition parameters 66
3.3.3 Characterization of ESD films 71
3.4 SOFC Cell performance test 73
3.4.1 Fabrication of NiO-YSZ cermet supported half cell 73
3.4.2 Fabrication of cathode films 76
3.4.3 Cell performance test 77
Chapter 4 Results 79
4.1 EAUSP Results 79
4.1.1 Deposition of LSCF/CGO composite films on CeO2 79
4.1.2 Deposition of LSCF films on CGO 88
4.2 ESD results 96
4.2.1 TGA/DSC results of precursor solution 96
4.2.2 Deposition of LSCF films on silicon wafers 97
4.2.3 Deposition of LSCF films on SDC substrates 110
4.3 Results of cell performance test 128
4.3.1 SEM morphology 128
4.3.2 EDS analysis 132
4.3.3 AC impedance analysis 134
4.3.4 Cell performance test 137
Chapter 5 Discussion 139
5.1 EAUSP films 139
5.1.1 LSCF/CGO composite films 140
5.1.2 LSCF film deposited on CGO pellet 142
5.2 ESD films 147
5.2.1 LSCF films deposited on silicon wafer 147
5.2.2 LSCF films deposited on SDC pellet 158
5.3 SOFC performance test 160
5.3.1 SEM morphology 160
5.3.2 AC impedance analysis and cell performance test 161
Chapter 6 Conclusion 163
6.1 EAUSP 163
6.2 ESD 164
6.2.1 LSCF films deposited on silicon wafer 164
6.2.2 Deposition of LSCF films on SDC pellet 164
6.3 SOFC performance test 165
Reference 166
CURRICULUM VITAE 174

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