Fb 240715072551

YUAN ZE UNIVERSITY
Department of Chemical Engineering and Material Science
Fabrication of Co-Ionic Conducting Electrolyte for Low Temperature Solid

Oxide Fuel Cell (LT-SOFC) Application
Student: Azam khan
Advisor: I-Ming Hung
May 2022
Fabrication of Co-Ionic Conducting Electrolyte for Low Temperature Solid
Oxide Fuel Cell (LT-SOFC) Application
Student: Azam khan
Advisor: I-Ming Hung
YUAN ZE UNIVERSITY
Department of Chemical Engineering and Material Science
A Dissertation
Submitted to Department of Chemical Engineering and Material Science
Yuan Ze University
In partial Fulfillment of the Requirements for the
Doctor of Philosophy Degree in
Chemical Engineering and Material Science
May 2022
Zhongli, Taiwan (RO
I
Abstract
本研究成功測試了 70% w/w 釤摻雜二氧化鈰與 30% w/w 碳酸鋇 (SDC/BC) 電

解質混合，用作低溫固體氧化物燃料電池 (LT-SOFC) 的改進電解質.討論了
基於這種 SDC/BC 複合電解質的燃料電池的相變、粒度分佈、形貌、電化學
阻抗、電導率和最大功率密度。 SDC/BC 電解液在化學上與 Ni-SDC/BC 陽
極相容。 SDC/BC 在 600 °C 時的電導率為 102.7 mS cm-1，活化能為 36.12 kJ
mol-1。 Ni-SDC-BC/SDC-BC/Pt 電池在 600 °C 時的最大功率輸出為 427 mW
cm-2，這歸因於電解質和負極材料的高電化學活性。這些結果表明 SDC/BC
具有作為 LT-SOFC 的低溫電解質的潛力。
另一方面，利用檸檬酸鹽-乙二胺四乙酸（EDTA）絡合法。 SCZY/SDC 的電
化學性質和結構是在各種氣氛和溫度下確定的。在 1450℃燒結 5h 後，
SCZY/SDC 用作固體氧化物燃料電池的電解質。
SCZY/SDC 複合電解質樣品在 H2 和空氣中的電導率在 800 °C 時分別為 0.228

Scm-1 和 0.00349 Scm-1 。 Pt/SCZY-SDC/Pt 電池的總電導率和活化能由 H2
（陽極）/空氣（陰極）氣氛中的 EIS 數據計算，分別為 0.039-0.223 Scm-1 和
81.87 kJ mol-1, 在 600 oC-800 °C 的溫度範圍內。電解質支持的 Pt/SCZY-
SDC/Pt 電池的功率密度為 21.7 mWcm-2，電解質厚度為 1.19 mm，陰極面積
為 2.54 cm2。
II
Abstract
This research presents the successful testing of 70% w/w samarium-doped ceria
mixed with 30% w/w barium carbonate (SDC/BC) electrolyte for use as an
improved electrolyte for low-temperature solid oxide fuel cells (LT-SOFCs).
The phase changes, particle size distribution, morphology, electrochemical
impedance, conductivity, and maximum power density of the fuel cell based on
this SDC/BC composite electrolyte are discussed. The SDC/BC electrolyte is
chemically compatible with a Ni-SDC/BC anode. The conductivity of the
SDC/BC is 102.7 mS cm−1 at 600 °C with activation energy of 36.12 kJ mol−1.
The maximum power output of the Ni-SDC-BC/SDC-BC/Pt cell is 427 mW
cm−2 at 600 °C, which is attributed to the high electrochemical activity of both
the electrolyte and the anode material. These results demonstrate that SDC/BC
has potential as a low-temperature electrolyte for LT-SOFC.
In other hand, Sr(Ce0.6Zr0.4)0.85Y0.15O3−δ (SCZY)/Sm0.2Ce0.8O1.9 (SDC) co-ionic
conducting (O2−/H+) composite electrolytes are synthesized using the citrate-
ethylene diamine tetra acetic acid (EDTA) complexing method. The
electrochemical properties and structure of the SCZY/SDC is determined at
various atmospheres and temperatures. After sintering at 1450 °C for 5h,
SCZY/SDC is used as electrolyte for solid oxide fuel cell.
III
The conductivity of the SCZY/SDC composite electrolyte sample in H2 and air
is 0.228 S cm−1 and 0.00349 S cm−1 at 800 °C, respectively. The total electrical
conductivity and activation energy of the Pt/SCZY-SDC/Pt cell was calculated
from the EIS data in H2 (anode)/Air (cathode) atmospheres is 0.039-0.223 S
cm−1 and 81.87 kJ mol−1, respectively, at temperature ranging of 600 oC-800 °C.
The power density of the electrolyte supported Pt/ SCZY-SDC/Pt cell is 21.7
mW cm−2 with the thickness of electrolyte of 1.19 mm and area of cathode is
2.54 cm2.
IV
Acknowledgement
I am very grateful to my supervisor prof.I-Ming Hung for his guidance,

supports and in particular his vision and enthusiasm. He always encourages
me to think how to be better in the future and helps me to identify many more
avenues for investigation.
I would like to thanks professor who are the member of my committee and
their valuable comments for my dissertation.
I would also like to thank my colleagues: Tung-Wei Chang, Debabrata

Mohanty, Ko yun Chao, Ya Chen Tsai… They shared their expertise with me
and were always helpful.
My gratitude goes to my parents for their unconditional love and always

supporting me whatever I do.
V
Table of Contents
Title Page …………………………………………………………….….. Ⅰ
Abstract in Chinese………………………………………………………Ⅱ
Abstract in English……………………………………………………….Ⅲ
Acknowledgement………………………………………………………...Ⅴ
Table of Contents…………………………………………………………Ⅵ
List of Table………………………………………………………………Ⅺ
List of Figures…………………………………………………………….Ⅹ
Chapter 1 Introduction………………………………………………….....1
1.1Background…………………………………………………………….1
1.2Research Motivation…………………………………………………...5
Chapter 2 Literature Review……………………………………………....7
2.1 Introduction of Fuel Cells………………………………………..........7
2.2 Solid Oxide Fuel Cell (SOFC) ……………….....................................9
2.2.1 Introduction of Solid Oxide Fuel Cells……………………………..9
2.2.2 Principle of Solid Oxide Fuel Cell………………………………….11
2.2.3 Advantages and disadvantages of solid oxide fuel cells……………13
2.2.4 Structure of Solid Oxide Fuel Cell………………………………….14
2.2.5 Polarization phenomenon of solid oxide fuel cells…………………16
2.3 Development and Type of Solid Oxide Fuel Cell Electrolyte………..22
VI
2.3.1 Fluorite structure of solid oxide fuel cell electrolyte……………….22
2.3.2 Perovskite−structured for solid oxide fuel cell electrolyte………….30
2.4 Development and Properties of Solid Oxide Fuel Cell Cathode……...34
2.4.1 Cathode material properties…………………………………………34
2.4.2 Working principle and characteristics of cathode materials………...37
Chapter 3 Experimental method…………………………………………..40
3.1 Preparation of (SDC/BC) Electrolyte ……………………………….41
3.1.1 Half- and single-cell tests…………………………………………...45
3.1.2 Characterization of composite electrolytes………………………….46
3.2 Preparation of SCZY/SDC composite electrolyte………………….....47
3.2.1 Characterization of Composite Electrolytes………………………...49
3.2.2 Single-cell test………………………………………………………50
Chapter 4 Result and discussion ………………………………………….54
4.1 Preparation of SDC/BC Electrolyte ………………………………….54
4.1.1 XRD and morphology analysis……………………………………..54
4.1.2 Electrical conductivity……………………………………………...61
4.1.3 Fuel cell performance……………………………………………….68
4.2 Preparation of SCZY/SDC composite electrolyte …………………...73
4.2.1 XRD and morphology analysis…………………………………….73
4.2.2 Electrical conductivity……………………………………………..77
VII
4.2.3 Fuel cell performance……………………………………………....83
Chapter 5 Conclusion……………………………………………………88
References………………………………………………………….........90
VIII
List of Table
Table 2.1 Operating conditions in fuel cells……………………………10
Table 2.2 Phase transition temperatures and unit cell parameters
of Bi2O3....................................................................................................29
Table 4.1: The equivalent-circuit analysis results of EIS for
Pt/SCZY-SDC/Pt various temperatures…………………………….......82
IX
List of Figures
Figure 2.1. The structure and principle of SOFC……………….............12
Figure 2.2 Polarization of solid oxide fuel cell…………………………17

Figure 2.3 Illustration of SOFC three phase boundary (TPB) …………20
Figure 2.4 Illustration of the fluorite structure………………………. ...24
Figure 2.5 The structure of bismuth oxide ……………………………..27
Figure 2.6. The stable and Meta stable regions found in Bi2O3………...28
Figure 2.7 Structure of perovskite………………………….. ………….33
Figure 2.8 Schematic representation of oxygen transport around the

O2/cathode/electrolyte interface ………………………………………..39
Figure 3.1 Schematic diagrams for preparation of SDC/BC
Electrolyte……………………………………………………………....43
Figure 3.2. Schematic diagrams for preparation of
Ni-SDC-BC/SDC-BC electrolyte …………………………………….44
Figure 3.3 Schematic diagrams for preparation of SCZY powder ……..51
Figure 3.4 Schematic diagrams for preparation of SDC powder ………52
Figure 3.5 Schematic diagrams for preparation of SCZY/SDC powder..53
Figure 4.1 XRD patterns of the (a) SDC sintered at 1400 oC for 4 h,
X
(b) SDC+BaCO3 composite electrolyte sintered at 700 oC
For 2 h…………………………………………………………………….55
Figure 4.2 Particle size distributions of (a) SDC/BC composite
Electrolyte (b) SDC powders……………………………………………..58
Figure 4.3 (a) SEM micrograph and EDS line scan results of all
Elements and (b) line scan of Ni for cross section of
Ni-SDC-BC/SDC-BC/Pt cell sintered at 700 °C for 2h…………………59
Figure 4.4 (a) selected cross section of Ni-SDC-BC/SDC-BC/Pt cell
(b) EDS spectra…………………………………………………………60
Figure 4.5 Impedance spectra of SDC/BC composite electrolyte
Measured in air at 400–600 C …………………………………………65
Figure 4.6 (a) Re, Rion, Rt resistance values, and the Arrhenius plots
Of (b) Re, (c) Rion, and (d) Rt for the SDC/BC composite electrolyte
at 400–600°C …………………………………………………………..67
Figure 4.7 (a) SEM images of anode supported cell (b) I-V
And I-P characteristics for hydrogen oxygen fuel cell based on
Ni-SDC/BC anode supported, SDC/BC and Pt as an electrolyte
And cathode respectively at 500-600 °C………………………………71
XI
Figure 4.8 More than 100h operation performances of the SDCBC
Composite electrolyte fuel cell at 600 C…………………………….…72
Figure 4.9 XRD patterns of the (a) Sm0.2Ce0.8O1.9,
(b)Sr (Ce0.6Zr0.4)0.85Y0.15O3−δ and (c) Sr(Ce0.6Zr0.4)0.85Y0.15O3−δ/ Sm0.2Ce0.8O1.9
composited electrolyte…………………………………………………..75
Figure 4.10 Particle size distribution of

Sr(Ce0.6Zr0.4)0.85Y0.15O3−δ/Sm0.2Ce0.8O1.9composite electrolyte powder….76
Figure 4.11 (a) Cross-section micrograph, and (b) EDS
Spectra of Pt/ Sr(Ce0.6Zr0.4)0.85Y0.15O3−δ/Sm0.2Ce0.8O1.9/Pt cell…………78
Figure 4.12 The (a) EIS curves, and (b) resistances for
the Pt/ Sr(Ce0.6Zr0.4)0.85Y0.15O3−δ/Sm0.2Ce0.8O1.9/Pt cell in H2
(anode)/Air (cathode) at various temperatures…………………………..81
Figure 4.13The Arrhenius plots of (a) R1, (b) R2, (c)R3 and (d) R4
for the Sr(Ce0.6Zr0.4)0.85Y0.15O3−δ/ Sm0.2Ce0.8O1.9 cell in
H2 (anode)/Air (cathode) at 600-800 C...................................................85
Figure.4.14 The electrical conductivity of the
Sr(Ce0.6Zr0.4)0.85Y0.15O3−δ/ Sm0.2Ce0.8O1.9 as a function of temperature
in (a) H2, (b) Air, and (c) H2 (anode)/Air (cathode) atmospheres………86
Figure.4.15 I-V and I-P characteristics of the
Pt/ Sr(Ce0.6Zr0.4)0.85Y0.15O3−δ/Sm0.2Ce0.8O1.9/Pt cell at 800 C…………..87
XII
Chapter 1
Introduction
1.1 Background
Today’s society faces the exhaustion of oil resources, energy crises, the
greenhouse effect, and the challenges of environmental protection. Awareness
of these environmental issues has increased globally alongside developments
such as the signing of the Kyoto Protocol. The energy problems society is
facing today can be mitigated by developing and utilizing new energy resources,
but environmental protection and energy depletion must be taken into account.
Alternative energy sources, and particularly renewable energy sources, are
widely viewed as solutions to these problems. Renewable energy includes
small-scale hydropower, solar power, and wind power as well as biomass
energy, geothermal power, ocean wave power, and hydrogen fuel cells
including solid oxide fuel cells (SOFCs) and low-temperature SOFCs (LT-
SOFCs) [1-2]. LT-SOFCs have many advantages: (1) the energy value of
hydrogen combustion (up to 140 kJ g−1) is roughly twice that of gasoline, 33.9
times that of alcohol, and 4.5 times that of coke. (2) The byproduct of the
hydrogen combustion reaction in an LT-SOFC is only water, which, unlike the
byproducts of combustion for hydrocarbon fuels such as petroleum, coal, or
natural gas, does not contribute to acid rain, the greenhouse effect, or other
1
pollution. (3) Hydrogen can be produced from water (H2O). Water is the most
abundant resource on Earth, covering 71% of the planet’s surface. Because the
product of the hydrogen combustion reaction is also water, hydrogen could be
an inexhaustible energy source. (4) Compared with stored electric energy,
hydrogen has higher energy density, higher specific energy, is easy to transport
and carry, and is easy to store. (5) Hydrogen has a wide range of uses, it can be
burned for heat or to generate chemical product.
Hydrogen energy can be accessed by using fuel cells that catalyze the reaction
of hydrogen with oxygen to generate energy [3-4]. Fuel cells can generate high
power, have high efficiency, and do not contribute substantially to pollution.
Therefore, the development of fuel cells has high potential to contribute to
sustainable alternative energy. The LT-SOFC is currently the most efficient of
all fuel cells. LT-SOFCs do not require expensive materials as catalysts and can
also use methane-containing fuels such as natural gas or biogas. The LT-SOFC
is cost effective and high efficiency competitive for applications in power
systems and transportation systems that consume large amounts of energy [5-6].
At present, substantial human resources, materials, and financial resources have
been invested globally to research and develop LT-SOFCs [7]. The
performance of the electrolyte determines the key characteristics of the fuel cell:
operating temperature and performance. Yttrium-stabilized zirconium (YSZ) is
2
currently the most widely used electrolyte material in SOFCs. YSZ has
excellent chemical stability and thermal stability, however, at low temperatures;
it has poor conductivity, which causes repulsive oxygen vacancy interactions
with in the cell reducing cell stability. Therefore, researchers have been
developing substances with high ionic conductivity at low temperatures to
replace conventional electrolyte materials [8-10, 11].
Dual-phase electrolyte material containing doped ceria oxides and various
carbonates e.g. SDC-20 wt.% (2Li2CO3: 1Na2CO3), SDC–Li2CO3–K2CO3,
Ce0.93Ca0.05Sr0.02O1.93/Li2CO3–Na2CO3 and Na2CO3-SDC-Li0.2Ni0.7Cu0.1O have
been developed and widely studied as improved electrolytes for low-
temperature SOFCs due to their impressive electrical conductivity and unique
hybrid-ionic conductivity. SOFCs based on dual phase electrolytes of ceria-
carbonate and Ni supported have shown excessive cell performance at below
600°C. The core-shell nanostructure SDC-Na2CO3 composite demonstrated
power density of 200–1150 mW/cm2 at 300–600°C. [12]
Additionally, the structural stability of SrCeO3 based oxide electrolyte material
is as good as BaCeO3 based oxide electrolyte material in a humid atmosphere
[13]. However, the SrCeO3 generally has poor thermal stability and chemical
stability in CO2 containing environment and it will decompose to SrCeO3 and
CeO2. Other oxide material like SrZrO3 was knows as stable proton conductor
3
but it shows low ionic conductivity. Many researches publish that the
substitution of some zirconium ion Zr4+ for Ce4+ component to improve the
chemical stability and mechanical strength of SrCeO3 [14, 15]. Therefore,
SrCe1−xZrxO3 materials have excellent chemical stability and high proton
conductivity. In addition, further improving in the hydrogen permeation and
electrical properties of SrCeO3 by adding of Yb3+, Tm3+ and Y3+ for Ce4+ were
reported [16, 17]. When a small amount of Y3+ ions substituted for Ce4+,
oxygen deficiencies are produce to balance the charge, the reaction as
following:
𝒀𝟐 𝑶𝟑 → 𝟐𝒀𝑪𝒆 ′ 𝟑𝑶𝒐 𝑿 𝑽𝒐 𝟏
𝑪𝒆𝟒 𝒉 . ↔ 𝑪𝒆𝟑 𝟐
Equation (2) represent the electron transfer mechanism of SrCeO3 based
material, Zr has the same valence as Ce and it is very stable both in reduction
and oxidation atmospheres, no exchange of charge, therefore, doping of Zr
could enhance the chemical stability and mechanical properties of SrCeO3
based perovskite in humid or CO2 working atmosphere [18]. In a hydrogen
containing and steam concentration gradient atmosphere, the oxygen ion in the
perovskite material and hydrogen in the gas steam directly produce the electron
and proton from the following equation:
4
𝟏
𝑯𝟐 𝑶𝒐 𝑿 → 𝑶𝑯𝒐 • 𝑒 (3)
𝟐
Where OHo• and Oox are interstitial protons and oxide ions, respectively [19].
Perovskite base oxide powders are usually synthesis by using a solid-state
reaction method, calcinations temperature is always higher than 1200oC with
long duration. In order to prepare a homogeneous powder, sol−gel method, and
wet chemical method [20] are considered. In addition, the citrate-ethylene
diamine tetra acetic acid (EDTA) complex [21] and the hydrothermal technique
[21-22] are preferred for a variety of ceramic materials.
1.2 Research Motivation

This research aimed to develop low-temperature (500-600 °C) SOFC
electrolyte materials to replace YSZ. The mixture of cubic phase samarium-
doped ceria (SDC) and BaCO3 has the highest measured ionic conductivity of
currently known oxides. Therefore, this study employed an SDC and BaCO3
composite as the primary electrolyte material. However, the carbonate is
unstable after heating to 700 °C and can undergo phase transitions that reduce
conductivity when cooling from high temperatures to room temperature.
Several research focus on the improving of ionic conductivity for the widely
used oxide electrolytes such as yttrium stabilized zirconium (YSZ), Scandia
stabilized zirconium (ScSZ) and gadolinium or samarium doped ceria (GDC or
SDC) [23-26, 27]. Numerous studies have attempted to develop a mixed
5
structure Ce-CO3 electrolyte [28] and have reported that a composite structure
with 30% CO3 and 70% SDC will have low porosity after heating at 750 °C,
whereas if the CO3 percentage is increased, the upper surface of the composite
electrolyte is reduced [29]. SDC/BC composite electrolytes are stable during
SOFC operation if the BaCO3 percentage is <40% [30]. The purpose of this
research was therefore to analyze the chemical reaction between SDC and
BaCO3, and a 70% w/w SDC and 30% w/w BaCO3 (SDC/BC) mixed
electrolyte was created to investigate the O2−/H+ conduction behavior of this
SDC/BC mixed-ionic electrolyte material by using electrochemical impedance
spectroscopy.
Also we prepared the SCZY/SDC composited electrolyte for solid oxide fuel
cell. The electrochemical and conduction behavior of SCZY/SDC composited
electrolyte are investigated, and the performance of cell based on Pt/ SCZY-
SDC/Pt in H2/O2 were tested.
6
Chapter 2
Literature Review
2.1 Introduction of Fuel Cells
The earliest basic operating principle of fuel cells was introduced in 1839 by
William Robert Grove Proposed by [31]; he used dilute sulfuric acid as the
electrolyte, at room temperature by the oxidation and reduction of hydrogen
and oxygen, to generate electricity. A fuel cell is an technology that convert
chemical energy with the help of electrochemical reaction directly into
electrical energy, which electrochemical reactions do not require any
combustion process, so it is not restricted by the Carnot cycle and has a higher
energy conversion efficiency, the average power generation efficiency is above
40%, if the waste heat in the reaction is used in steam Electric cogeneration can
increase the overall power generation efficiency to more than 80%.
Fuel cells have high efficiency, low pollution, no noise, no charging, and no
combustion reaction. It has been recognized as the most important new energy
technology in the 21st century due to its excellent performance. Application
range Including laptop computers, electric motor locomotives, spacecraft
power systems, small noise-free power generation stations, large power plants,
7
etc. The fuel cell itself only determines the output power, and the stored energy
is composed of fuel and oxygen depends on the amount of chemical. General
fuel cells, depending on the operating temperature and ion conduction mode, it
can be roughly divided into the following 6 types, and the properties are listed
in Table 2.1[32].
(1) Alkaline fuel cell (AFC).
(2) Direct methanol fuel cell (MCFC).
(3) Proton exchange membrane fuel cell (PEMFC).
(4) Phosphoric acid fuel cell (PAFC).
(5) Molten carbonate fuel cell (MCFC).
(6) Solid oxide fuel cell (solid oxide fuel cell, SOFC).
Among them, solid oxide fuel cells, also known as ceramic fuel cells, due to
their high reaction rate, No platinum catalyst is required, a wide variety of
fuels can be used, and its energy utilization efficiency can reach up to 80 %
Above, there is great competition in power systems and transportation systems
that consume a lot of energy Therefore, all countries in the world have
invested a lot of human, material and financial resources to research and
develop solid−state oxide fuel cell (SOFC) [33].
8
2.2 Solid Oxide Fuel Cell (SOFC)
2.2.1 Introduction of Solid Oxide Fuel Cells
SOFC is one of the types of fuel cells has highest operating temperature
among all fuel cells at present. The biggest feature of SOFC is that the whole
is material is of solid oxides, which has high−temperature resistance; It can be
operated for a long time and is easy to maintain. Its components can be
divided into anode, electrolyte, cathode with the four major parts of the metal
connection plate; each component must have an oxidizing and reducing
atmosphere. They are chemically stable, structurally stable and dimensionally
stable, and must have similar chemical properties to each other.
The current operating temperature of SOFC is 600~1000oC, but the high
operating temperature because of the selectivity of its surrounding materials,
and also makes the mechanical strength, reliability and thermal expansion of
the material.
9
Table 2.1 Operating conditions in fuel cells. [32]
Fuel cell Operating Efficiency Electrolyte Ion transfer

Temp.(oC) (%)
AFC 60~90 50~60 35~45%KOH OH
DMFC 50~80 50~60 Nafion H+
PEMFC 50~80 50~60 Nafion H+
PAFC 160~220 55 100% H3PO4 H+
MCFC 620~660 60~65 Li2CO3/Na2CO3 CO3 2-
SOFC 600~1000 55~65 YSZ O-2
10
The expansion coefficient matching has been great challenged. To increase
material selectivity and ensure electrical properties can operate for a long time,
and reducing the operating temperature has become a major research trend
[34].
SOFC can be divided into three categories according to the different operating
temperature:
(1) High Temperature SOFC (HT−SOFC): 800~1000 oC.
(2) Intermediate Temperature SOFC (IT−SOFC): 600~800 oC.
(3) Low Temperature SOFC (LT−SOFC): 400~600 oC.
2.2.2 Principle of Solid Oxide Fuel Cell
The operating principle of SOFC is similar to that of other fuel cells, as shown
in Fig. 2.1 [35]. Mainly Oxygen ions conduction occurs during operation, fuel
and oxidant needs to be fed into the anode and cathode side respectively. The
oxygen molecules in the oxidant are absorbed by the cathode surface and
decomposed into oxygen atoms, oxygen atoms diffusion to the triple−phase
interface, composed of gas/electrode/electrolyte (Triple Phase Boundary,
TPB), and combine with the electrons passing through the external circuit to
form oxygen ions (O2-), and the oxygen ions (O2-) transferred to the anode
11
Fig 2.1. The structure and principle of SOFC [35].
12
end through the electrolyte, reacts with hydrogen (H2) fuel to generate water
(H2O), and releases electrons come out, reach to the cathode end through the
external loop to form a complete circuit system.
The detailed reaction formula is as follows:
Cathode: 1/2O2 +2e- O2- (4)
Anode reaction: 2H2 +2O2- 2H2O +4e- (5)
Overall: H2 + 1/2O2 H 2O (6)
2.2.3 Advantages and disadvantages of solid oxide fuel cells
SOFC technology has particularly great potential in the field of power
generation, due to the high operating temperature, it can accelerate the
Electrochemical reaction rate, simplicity of element structure, and ability to
manufacture at low cost.
Advantages of SOFC:
(1) The working temperature is high, the electrode reaction speed is fast, and
there is no need to use precious metals as catalysts.
(2) Various fuels such as natural gas, coal gas, and even combustible waste
gas can be used.
13
(3) The high−temperature exhaust gas discharged from SOFC and the turbine
has high−efficiency for co−generation system to generate electricity. The
efficiency can reach 80%.
(4) Using the high temperature of SOFC itself to carry out internal fuel
reforming, the system can be simplified.
(5) SOFC is an all solid−state battery, there is no electrolyte leakage problem,
and no electrolyte management system is required.
Disadvantages of SOFC:
(1) The oxide electrolyte is a ceramic material, which is easy to be brittle and
difficult to assemble the battery stack.
(2) Under the action of high temperature thermal stress, the battery is easy to
crack, so the thermal expansion rate of the main components needs to be
strictly matched.
2.2.4 Structure of Solid Oxide Fuel Cell
The basic structure of SOFC is similar to that of general electrochemical cells,
which are divided into anode, electrolyte and cathode. There are three parts,
all three parts are composed of solid oxides, which have high temperature
14
resistance and can be used for a long time. Time operation, easy maintenance,
Materials structures and electrical conductivity used in each component.
The component introduction as follows:
(1) Anode:
Must have good electronic conductivity, good catalytic ability, and possess
Good stability. The anode mainly catalyzes hydrogen or hydrocarbons into
hydrogen ions, and then reacts with them. Oxygen ions react to generate water
and carbon dioxide in and out, so the anode must have pore in its structure.
The structure (Porous Structure) makes it easy to enter and exit the water
vapor formed after the hydrogenation reaction. At present, the most commonly
used anode material is a mixture of nickel (Ni) and electrolyte (YSZ) material
in an appropriate ratio. [36]
(2) Electrolyte:
The role of electrolyte in SOFC is to conduct ions, so it must have high ionic
conductivity, and it has low electronic conductivity to avoid short circuit in
the internal circuit of the battery. In addition, it is necessary to have It has
good stability in high and low oxygen partial pressure environments. In
addition, in order to prevent the fuel at the anode end is in contact with the air
at the cathode end, and high density is also required for the electrolyte
15
material. One of the current most commonly used electrolyte material is
yttrium stabilized zirconia (YSZ) [37, 38].
(3) Cathode:
The characteristics of cathode materials are similar to those of anode materials,
and they also need to have high electronic conductivity, catalytic chemical
capacity and pore structure. However, the cathode must be in an oxidizing
atmosphere has excellent material stability and with good chemical stability of
the material with the electrolyte, therefore, the general gold Metallic materials
are not suitable, and oxides with electronic conductivity must be used. Most
commonly used cathode material is strontium−doped lanthanum magnate
compound (La1-xSrxMnO3-d) [39−41] and lanthanum strontium cobalt iron
Oxides (La1-xSrxCo1-yFeyO3-d) [42─44].
2.2.5 Polarization phenomenon of solid oxide fuel cells
The efficiency of SOFC is mainly due to the irreversible polarization
phenomenon of the fuel cell Polarization, which varies with the current
density, and its polarization phenomenon is shown in Fig. 2.2 .Polarization
phenomena can be divided into activation polarization, ohmic polarization and
concentration polarization, and the consumption of gas leads to decrease in
battery performance.
16
Fig 2.2 Polarization of solid oxide fuel cell.
17
The following is a description of each polarization phenomenon:
(1) Activation Polarization:
During the electrochemical, reaction catalyzed by SOFC electrodes, gas
molecules, ions and the charge transfer behavior of electrons binding to each
other and dissociating, the rate of reaction between the various reactions and
the polarization phenomenon that causes the accumulation of charges on the
electrode is called activation polarization, and it is represented by ηact .
This activation polarization phenomenon is mainly related to the
electrochemical reaction rate, including air and fuel gas adsorption and
desorption kinetics. High catalytic reaction electrode material and increased
electrochemical reaction area will help to improve the activation polarization
phenomenon. In SOFC the structures of the cathode material is the activation
polarization phenomenon biggest cause. When air diffuses to the surface of
the cathode and electrolyte, the air is extracted from the cathode, electrons to
form oxygen ions (O2-). During the whole reaction process, the position of the
reaction is called the three−phase boundary (Triple Phase Boundary, TPB), as
shown in Fig 2.3 [45], that is gas/electrolyte therefore, increasing the TPB
area of the cathode region is to improve the SOFC activation electrode.
18
(2) Ohmic Polarization：
According to Ohm's law, when a current passes through a material, it affects
the resistance formed by the movement of charge. The value can be
considered as ohmic loss, expressed as ηohm. So, when current flows through
the electrolyte, cathode and anode, there will be ohmic loss inside the material
and the component in contact with the material, this phenomenon called is
ohmic polarization. Usually, the ionic resistivity of the electrolyte is much
greater than the electron electrical resistivity of the cathode and anode
resistivity.
Example: YSZ electrolyte has an ionic resistivity of about 50 Ω•cm2 at 800 oC
and the cathode La0.8Sr0.2MnO3-δ is about 10-2 Ω•cm2, and the Ni−YSZ anode
resistivity is about 10-4Ω•cm2, therefore, the main source of ohmic polarization
is the electrolyte. In the recent years, SOFC has towards to development of
anode support materials, the use of thin film electrolytes with a thickness of
about 5 ~ 30 μm can effectively reduce Low ohmic polarization phenomenon,
in addition to the selection of high conductivity electrolyte materials , E.g.
Sm0.2Ce0.8O2-δ, La0.8Sr0.2Ga0.8Mg0.2O3-δ, Bi0.85-xCa0.15ZrxO1.5-δ, etc., can also
reduce the ohmic polarization.
19
Fig 2.3 Illustration of SOFC three phase boundary (TPB) [45].
20
(3) Concentration Polarization：
During the electrochemical reaction of SOFC, especially at high current
densities, it is necessary to deliver a large amount of oxygen and fuel to the
electrode and electrolyte interface in a short time, and the same time the water
vapor or carbon dioxide produced must also have to be discharged. If the
diffusion rate of these gases in the electrode side is too slow, resulting
insufficient fuel replenishment or concentration polarization caused by too
slow discharge of by−products, It is represented by ηconc in a typical
anode−supported SOFC, the anode thickness is about 0.5–1 mm is much
thicker than the cathode thickness (about 30−50 μm).The type plays a pivotal
role in the concentration polarization, the design of the channels for gas
circulation and the selection of Electrodes with high porosity can effectively
reduce concentration polarization. Therefore, in general, the actual battery
voltage (Cell Voltage) that can be calculated as follows:
Vcell = Eocv – ηact – ηohm – ηconc (7)

△𝑮
E ocv= = 1.23V
𝟐𝑭
Where G：Gibbs free energy，F：Faraday constant
21
2.3 Development and Type of Solid Oxide Fuel Cell Electrolyte
Electrolyte is the main component of SOFC, mostly metal oxides in solid state.
Oxide fuel cell electrolyte materials must have the following characteristics:
(1) High ionic conductivity (σion about 10-4 ~ 10-1 S/cm).
(2) Low electronic conductivity to avoid short circuits.
(3) Good chemical stability not easy to react with fuel.
(4) The thermal expansion coefficient needs to be compatible with other
materials of the battery.
2.3.1 Fluorite structure of solid oxide fuel cell electrolyte
Commonly used as electrolyte materials for solid oxide fuel cells, one of
which is fluorite Structure oxides, a typical fluorite Structure is shown in Fig.
2.4. Fluorite structure is a face−centered structure composed of cations, and
anions occupy tetrahedral positions. Each metal cation is surrounded by eight
anions, and each anion is surrounded by four cations sub−surrounded. Since
there is a very large octahedral lattice hole in the fluorite structure, this
structure has the characteristics of easy diffusion of ions.
22
Common fluorite structure of solid electrolytes mainly includes the following
series:
(1) Yttria−stabilized zirconia, (YSZ).
YSZ is the electrolyte material currently used in commercial SOFC, pure ZrO2
at room temperature Belongs to the monoclinic phase, but after heating at high
temperature 1170 ~ 2300oC , it transformed into tetragonal phase while at
temperatures above 2300 oC it belongs to cubic phase [46].
In order to stabilize the high temperature cubic phase at room temperature, the
Y2O3 is usually doped in ZrO2, which is replaced by low−valent Y3+ yttrium
ion. The high valence Zr4+ produces oxygen vacancies, which reduces the
average anion radius, and the repulsive force, forming a stable cubic phase
YSZ.
The defect chemical equation is as follows:
𝒁𝒓𝑶𝟐
𝒀𝟐 𝑶𝟑 ⎯⎯ 𝟐𝒀𝒁𝒓 𝑽𝒐 .. 𝟑𝑶𝒐 𝒙 (8)
23
Fig 2.4 Illustration of the fluorite structure.[46]
24
(2) CeO2−based System
CeO2 is a stable fluorite structure, and pure CeO2 has very low
oxygen−conducting ability, so it is often Add low−cost Gd3+, Sm3+ ions to
increase the oxygen vacancy concentration and also the ionic conductivity.
The defect chemical equation is as follows:
𝑪𝒆𝑶𝟐
𝑺𝒎𝟐 𝑶𝟑 ⎯⎯ 𝟐𝑺𝒎𝑪𝒆 𝑽𝒐 .. 𝟑𝑶𝒐 𝒙 (9)
𝑪𝒆𝑶𝟐
𝑮𝒅𝟐 𝑶𝟑 ⎯⎯ 𝟐𝑮𝒅𝑪𝒆 𝑽𝒐 .. 𝟑𝑶𝒐 𝒙 (10)
At 700 oC, the conductivity of Sm0.2Ce0.8O2-δ and Gd0.2Ce0.8O2-δ are 3.5×10-2
S/cm and 3.6×10-2 S/cm [47], because they can effectively reduce the
operating temperature of SOFC, currently It has been extensively researched
and developed, and the target will be used in SOFC at medium and low
temperature (500～750 oC) .
(3) Bi2O3−based System
The Bi2O3 has the highest oxygen ion conductivity is that its 25% oxygen
vacancy the concentration and its structure are fluorite structures with large
free space, shown in Fig 2.5. However, due to its excessive defects, the cubic
fluorite structure can only exist at high temperatures (723~ 830 oC), with the
decrease of temperature, cubic phase (Cubic) → tetragonal phase will occur

25
(Tetragonal)→Monoclinic phase change [48, 49], the phase transition
temperature relationship is shown in Fig 2.6, while the unit cell size is shown
in Table 2.2. Therefore, many studies are still devoted to the synthesis of
cubic phase and the inhibition of phase change between high and low
temperature, currently the most common is adding Trivalent cations, such as
yttrium stabilized bismuth oxide, YSB)[50, 51] and erbium stabilized bismuth
oxide,ESB) [52-54].
26
Fig 2.5. The structure of bismuth oxide.
27
Fig 2.6. The stable and Meta stable regions found in Bi2O3. [55]
28
Table 2.2 Phase transition temperatures and unit cell parameters of
Bi2O3. [48, 49]
Phase Structure Transition Cell

Temp. (oC) Parameter(Å)
a= 8.85
α monoclinic δ→α：730 b= 8.16
c= 7.5
β tetragonal δ→β：650 a=b= 7.74
c= 5.73
γ b.c.c. δ→γ：640 10.27
δ f.c.c. -- 5.50
29
2.3.2 Perovskite−structured for solid oxide fuel cell electrolyte
The basic formula of perovskite structure is ABO3, and the crystal structure is
shown in Fig.2.5. It is often occupied by cations with low valence and smaller
ionic radius, and the B site is occupied by cations with high valence and
smaller ionic radius. Occupied by larger cations (B site) form face−centered
cubic (FCC) with oxygen ions closely packed arrangement, oxygen ions are
located in the face−centered position of the cubic unit cell. Therefore, six
Oxygen ions form an octahedral, while smaller B site cations occupy the
center of the octahedral Location (Octahedral Site), a site and B site must
maintain twelve coordination numbers and six coordination numbers
respectively.
In the perovskite structure, the sum of the valences of A site and B site should
be +6, so calcium Titanite oxide can be composed of (+1, +5), (+2, +4), (+3,
+3), or (A'1/2A"1/2)(B'1/2B"1/2)O3 . This complex form is composed of the effect
of combination of various cations can be in order to make perovskite oxides
have multiple properties, very few perovskite oxides have only one
conductivity, most perovskite oxides are usually mixed conductors of
electrons and oxygen ions [56]. These properties can be used on various
components of SOFC. Generally speaking, cubic Symmetry is the ideal state
of perovskite structure, but in fact due to the ionic radius between cations
30
(including A site and B site) and oxygen ions is different causes the
generation of vacancies makes the lattice distortion and deformation in
perovskite structure. It can be exist stably, except that there should be
appropriate valences at the lattice positions of A site and B site, in addition to
cations, the ionic radius ratio between anions and cations must also be within
an appropriate ratio range.
Therefore, RA (A site ion radius), RB (B site ion radius), and RO (oxygen ion
radius) have the following restrictions:
(1) RA ＞0.90 Å
(2) RB ＞0.51 Å
(3) 0.80＜＜1.00 t=

√ √
The above t value is called the tolerance factor, and the size of the t value
depends on A site, the difference in ionic radius between B site ions and
oxygen ions, if t=1, the structure is cubic perovskite, when the t value is
between 0.8 ~1, the perovskite structure is more likely to exist stable, But
there are many Orthorhombic and tetragonal crystals structure, although its t
value deviates from 1, it can simulate an approximate cubic crystal structure.
Tolerate factor formula comes from the difference between cations (including
A site and B site) and oxygen ions in the lattice respectively. Distance ratio
shown in Fig. 2.7 for the cubic phase perovskite structure, B site cation (RB)
31
is the sum of the oxygen ion (RO) radius is 2 times the unit lattice side length
that is the lattice constant a:
a= 2 × (RB+RO) (11)
In the lattice [110] direction, the sum of radius of the A site cation (RA) and
the oxygen ion (RO) is 2 times equal to √2 times the lattice constant:
√𝟐 a= 2 × (RA+RO) (12)
Equation 11 and 12 is the difference between A site, B site and the oxygen
ions relation.
32
Fig 2.7 Structure of perovskite.
33
2.4 Development and Properties of Solid Oxide Fuel Cell Cathode.
2.4.1 Cathode material properties
Generally, the cathode material of SOFC must contain three functions,
(1) Can split O2 covalently bonds to form O2-.
(2) Can accept foreign electrons and provide reaction sites for reduction
reaction.
(3) Allow the reduced O2- to pass through the electrode into the electrolyte and
combine with the H2 of the anode side to form H2O.
Therefore, the cathode material of SOFC must have both conductive electrons
and mixed conductors that conduct oxygen ions. The biggest problem in the
battery is the polarization phenomenon of the cathode material, which
accounts for the whole SOFC.The proportion of bulk polarization is as high as
65%, so how to reduce the polarization of the cathode material is very
important, especially it is at low temperature. Perovskite oxides are
characterized by mixed conductors (Mixed Ion−electron Conductor), can
conduct ions and electrons at the same time, and break the oxygen molecule to
oxygen ion. The distance that the electrons are transported to the electrolyte,
and for this reason the degree of polarization can be effectively reduced.
When the most commonly used material for SOFC cathodes is perovskite
34
oxide La1-xSrxMnO3 (LSM), generally divalent alkaline earth metal ions
(Alkaline earth metal cation, Such as Ca2+, Sr2+) doped with trivalent rare
earth metal ions (Rare Earth Cation, such as La3+, Pr3+, Y3+), used to replace
the A−site lattice sites in the perovskite structure ABO3. [57, 58], Lanthanum
Strontium Cobalt Neutral, B3+cation will oxidize to release an electron to form
a B4+ cation hole, or form a B4+cation hole. Two pathways of Oxygen
Vacancies to compensate for charge Oxides (Lanthanum Strontium Cobalt,
LSC), samarium strontium cobalt oxide (Samarium Strontium Cobalt, SSC)
etc.
At present, the development of solid oxide fuel cells is moving towards
low−temperature batteries, but at lower operating temperature, a serious
activation polarization phenomenon will occur, resulting in a substantial
decrease in the overall battery performance.
To reduce activation polarization, the current requirements for cathode
materials are as follows [59-61]:
(1) It has enough pores to allow sufficient diffusion of oxygen.
(2) High electronic conductivity, reaching over 100 S/cm at operating
temperature.
(3) High ionic conductivity, above 0.01 S/cm at operating temperature.
35
(4) It has high catalytic ability to reduce oxygen.
In order to meet the above requirements, the current research has the
following directions:
(1) Use mixed ion, electronic conductor (Mixed Ionic/electronic Conductor)
as cathode Polar materials, such as La1-xSrxCo1-yFeyO3-δ (LSCF) [60, 62], Sm1-
xSrxCoO3-δ(SSC), etc. Material.
(2) Change the cathode microstructure, such as increasing the porosity and
changing the grain size [40].
(3) Use a composite material, such as a composite of mixed SrSc0.2Co0.8O3-δ
and Sm0.5Sr0.5CoO3-δ Cathode [63], LSM−YSZ cathode and electrolyte hybrid
material [59], adding nanoscale Ag, Pd, Precious metals such as Pt are placed
in the cathode material [64, 65].
(4) Use of bi layer or multilayer cathode materials [66].
(5) Adding the cathode functional layer.
2.4.2 Working principle and characteristics of cathode materials
The oxygen molecules in the air are at the cathode side, and the oxygen atoms
in the adsorbed state are catalyzed by the molecules and then expanded.
Disperse to the three−phase interface (TPB), accept electrons to become
36
oxygen ions, and then diffuse into the oxygen ion electrolyte, the reaction
pathway is shown in Fig. 2.8 [67].
There are three cathodic reaction pathways:
(1) Oxygen molecules are adsorbed on the electrode surface and decomposed
into oxygen atoms, which are then accepted by the electrode through
electrolysis. Electrons from mass conduction to form oxygen ions. Since the
electronic conductivity of electrolyte materials is usually very low, the
electrons are not easy to pass through the electrolyte and react with the
oxygen atoms adsorbed on the surface of the electrolyte. The contribution of
the path is usually very low.
(2) Oxygen molecules are adsorbed on the electrode surface and decomposed
into oxygen atoms, through surface diffusion to the three−phase interface,
accepting electrons and reducing to oxygen ions and diffusing to the
electrolyte.
(3) The oxygen atoms adsorbed on the electrode surface receive electrons to
form oxygen ions on the electrode surface. Surface diffusion or bulk diffusion
to the triple point or electrode/electrolyte interface and then diffusion to the
electrolyte, this reaction pathway can be viewed as an extension of the triple
Point, dividing the region of the reaction by the triple point of the
37
electrode/air/electrolyte extends into the electrode/electrolyte interface;
however, the contribution of this pathway depends on the cathode material
Oxygen ion conductivity of the material.
38
Fig.2.8 Schematic representation of oxygen transport around the
O2/cathode/electrolyte interface:
(1) oxygen dissociate adsorption on cathode surface; (2) surface diffusion of
adsorption oxygen; (3) incorporation of adsorption oxygen via TPB; (4) bulk
diffusion of oxygen through cathode; (5) oxide ion transfer at the
cathode/electrolyte interface.[67]
39
Chapter 3
Experimental method
3.1 Preparation SDC/BC Electrolyte.
SDC powder was synthesized by using the citrate-EDTA technique [68]. The
metal sources were cerium nitrate and samarium nitrate. The 80% v/v of
Ce(NO3)3.6H2O and 20% v/v Sm(NO3)3.6H2O were first dissolved in deionized
H2O and then stirred using a magnetic stirrer at 80 °C. After the complete
dissolution of the metal nitrates, EDTA, and citric acid in 40 mL of H2O, , and
then 40 mL of NH4OH were added to the solution such that the molar ratio of
metal ion to EDTA to citric acid was 1:1:2. The added NH4OH acted as a
buffer to maintain a pH of 6. The solution was continuously stirred at 80 °C
until it became a thick gel. The gel was heated in an oven at 250 °C for 3 h
until the solid precursor was formed. Finally, this precursor was calcined in an
furnace at 800 °C for 3.5 h, and the SDC powder was obtained.
The 70% w/w SDC powder was mixed with 30% w/w BaCO3 by ball milling
for 24 h and then dried at 80 °C in an oven. The powder was calcined at 700 °C
in the presence of air for 2 h to produce the SDC/BC electrolyte. The fine
SDC/BC powder was formed into a disk by using a pressing machine. A
40
pressure of 100 MPa was applied for 15 min to form an SDC/BC disk with a
16.39-mm diameter and 2.4-mm thickness. The compacted disk was heated
again at 700 °C for 2 h. A platinum catalyst was painted on both sides of the
disk as a current collector for electrochemical impedance spectra (EIS). All AC
impedance measurements were made by using a Solatron 1260 Frequency
Response Analyzer (FRA) and a Solatron 1287 Electrochemical Interface (EI)
with an AC signal between 0.01 Hz and 100 MHz and a voltage of 40 mV. An
impedance analysis was then conducted to study the total O2−/H+ ion mobility
in the electrolyte. The impedance data were plotted by using Zview. The O2−/H+
ion conductivity was calculated from the resistance values obtained from the
RC circuit fitting by using equation (13):
𝒍
𝝈 (13)
𝑹𝑨
Where 𝜎 is conductivity (S cm−1), R is electrolyte resistance (), 𝑙 is the
thickness of the SDC/BC electrolyte (cm), and A is the contact area of the
electrode (cm2).
The activation energy of ion mobility was calculated using the Arrhenius
equation as following equation (14):
𝑬𝒂
𝝈𝑻 𝑨𝒆 𝑲𝑻
41
𝐥𝐧 𝝈𝑻 𝐥𝐧 𝑨 𝑬𝒂 /𝑲𝑻 (14)
Where T is temperature (K), Ea is the activation energy (kJ mol−1), A is the pre-
exponential factor, and K is the Boltzmann constant (kJ mol−1 K−1). The
platinum catalyst on the SDC/BC disk had a 2.4-mm thickness and 0.58-cm2
surface area.
A porous NiO–SDC/BC anode-supported SOFC was fabricated by using a
tape-casting process. The NiO (99% w/w) (Alfa Aesar), SDC/BC, and carbon
black (Sigma Aldrich) were mixed at a 65:30:5 ratio, w/w respectively, by ball
milling with zirconia oxide balls in ethanol for 30 h and then dried in an oven
at 80 °C for 12 h to obtain a powder Fig.3.1. The powder was passed through a
100-mesh screen and then mixed with a commercial binder (B73305PF, Ferro,
Taiwan) for 60 min by ball milling to obtain a SDC/BC electrolyte paste for
tape casting. The anode sheets were prepared by using a tape-casting apparatus,
and 300 MPa of pressure was applied for assembling 10 anode layers.
42
Figure 3.1 Schematic diagrams for preparation of SDC/BC electrolyte.
43
Figure 3.2 Schematic diagrams for preparation of Ni-SDC-BC/SDC-BC
electrolyte.
44
The NiO-SDC-BC was heated at 1300 °C to produce the porous anode-
supported LT-SOFC fuel cell Fig.3.2. The NiO-SDC-BC substrate was coated
with the SDC/BC composite electrolyte by spin-coating at 2800 rpm, and then
the half-cell was sintered at 700 °C for 2 h. The electrolyte surface was coated
with a platinum acting as a cathode and was heated at 700 °C for 4 h.
3.1.1 Half- and single-cell tests
The single-cell test apparatus consisted of bar-mounted zirconium tubes,
improving the gas closure from the tube opening, as well as electrical
connection between the current collector and the electrode. Platinum wire was
used for the voltage leads, and platinum mesh was used for the current
collectors. The active area of the platinum was 2.71 cm2, and the thickness of
the cell was 2.4 mm. The voltage-current data were measured for the Ni-SDC-
BC/SDC-BC/Pt cell between 500 and 600 °C at 50 °C intervals by an SOFC
test machine. Air was used as the oxidant, and 100% H2 was used as fuel. The
NiO-SDC-BC anode was reduced to Ni-SDC-BC in 100% H2 at 600 °C for 4 h
before electrochemical performance testing.
45
3.1.2 Characterization of composite electrolytes
X-ray diffraction (XRD, D2 Phaser, Bruker) was used to detect the phase
structure of the SDC/BC composite powder with Ni-filtered Cu Kα radiation
and a diffraction angle ranging from 10o to 90o with a step of 0.01o and a rate of
1o/min. The particle size distribution was measured by using a particle size
analyzer. The morphology of the SDC/BC composite electrolyte and the
microstructure of the sintered sample were obtained by using scanning electron
microscopy (SEM, JEOL JSM-6701F). AC impedance spectroscopy was used
to measure the electrical conductivity of the SDC/BC composite in air/H2
atmospheres. The impedance spectroscopy data were recorded between 400
and 600 °C and at frequencies between 100 MHz and 0.01 Hz with an active
voltage of 40 mV.
46
3.2 Preparation of SCZY/SDC composite electrolyte.
Citrate-Ethylenediaaminetetraacetic acid (EDTA, Riedel de Haen, 98%)
complexing method [69] used to prepare the Sr(Ce0.6Zr0.4)0.85Y0.15O3−δ (SCZY)
and Sm0.2Ce0.8O1.9 (SDC) powders. EDTA was dissolved in 6M NH4OH to
form a solution of EDTA− NH3 solution, whereas Ce(NO3)3• 6H2O,( Alfa
Aesar, 99%), Zr(NO3)2•2H2O ( Alfa Aesar, 99%), Sr(NO3)2•4H2O (Alfa Aesar,
99%), and Y(NO3)3• 6H2O (JT Baker 99%) are added. The final molar ratio of
citric Acid: total metal ion: EDTA was 2: 1: 1. 6M NH4OH added in solution to
adjust the PH to 6 Fig.3.3. After heating at 180 oC on a hot plate magnetic
heater, the water is evaporated from the solution and formed a sticky gel.
Formed sticky gel was heated at 250 oC for 3.5 h and calcined at 1100 oC for
13 h [69].
For SDC, 0.02M Sm2O3 and 0.08 M Ce(NO3)3∙6H2O were dissolved in DI
water and then mixed into an EDTA and citric acid solution at 80oC. The
required amount of EDTA and citric acid were added in a metal nitrate solution
and 40 ml of NH3 and 40ml of H2O were added in the solution, mole ratio of
(EDTA: citrate: metal ions = 1:2:1). 6M NH4OH added in solution to adjust
the PH to 6 Fig.3.4. After heating at 80 °C the solution turned into a transparent
gel. Obtain transparent gel was heated at 250oC on a hotplate magnetic heater
47
to convert gel into a solid precursor. After that the precursor was calcined at an
800oC in air for 3.5h to obtain a pure SDC powder.
50 wt. % of SDC powder and 50 wt. % of SCZY powder was ball milled for
24h. After that mixed powder dried at 80oC on hot plate heater, obtained mixed
powder SCZY/SDC was calcined at 1100 oC for 12h. The resultant powder was
grounded and used for a SCZY/SDC composite electrolyte. The SCZY/SDC
pellets with a thickness of 1.19 mm using high pressure machine under 100
MPa pressure for 15 minutes and were further sintered at 1450oC for 5 h. A
platinum paste was used as current electrode and coated on both the sides of
the pellets with area of 2.58 cm2 sintered at 800 oC Fig.3.5. The DC electrical
conductivity measurement of SCZY/SDC composite electrolyte was performed
(Micro test 6223 and Micro test 6632-10) to study the conduction properties in
H2, Air, and H2 (anode)/Air (cathode) atmospheres, respectively. Activation
energy and total were calculated from the fitting results of the resistance values,
by applying equation (15&16).
𝒍
𝝈 (15)
𝑹𝑨
𝜎 is conductivity (Scm–1), R is electrolyte resistance (Ohm), 𝑙 is the thickness
of electrolyte (cm) and A is an area of the active electrode (cm2).
48
The activation energy of SCZY/SDC composite electrolyte was calculated
using the Arrhenius equation as follows:
𝑬𝒂
𝝈𝑻 𝑨𝒆 𝑲𝑻
𝒍𝒏 𝝈𝑻 𝒍𝒏 𝑨 𝑬𝒂/𝑲𝑻 (16)
Where T is the temperature (K), Ea is the activation energy (kJ/mole), A is the
pre-exponential constant, and K is the Boltzmann constant. The thickness and
active area of Pt/ SCZY-SDC/Pt cell were 1.19 mm and 2.58 cm2, respectively.
3.2.1 Characterization of Composite Electrolytes
XRD (D2 Phaser, Bruker) was used to analyze the phase structure of
SCZY/SDC composite powder in the range of 10o to 90o diffraction angles
with Ni-filtered Cu Kα radiation with a step of 0.01o and a rate of 1o/min. The
particle size analyzer (Beckman Coulter Particle Analyzer, PN A54412) was
used to measure the particle size distribution of SCZY/SDC powder. The
morphology of the powder and the microstructure of the sintered sample were
observed by using field-emission scanning electron microscope (JSM-6701F,
JEOL). Electrochemical Impedance Spectroscopy (VSP-300, Biologic) was
used to measure the resistances of Pt/ SCZY-SDC/Pt in air/H2 atmosphere in
the temperatures range of 600 and 800 °C with 50°C interval at frequencies
49
between 100 MHz and 0.01 Hz with a bias voltage of 40 mV. Zview software
used to fit the Impedance data using Resistor-Capacitor equivalent circuit.
3.2.2 Single-cell test
The thickness of the SCZY/SDC cell was 1.19 mm and the active area of the
cathode was 2.58 cm2. The single cell was sealed on the alumina tube with
glass at 850oC The Pt wire and mesh were used for the current collector both
for anode and cathode electrodes. The I-V and I-P characteristics for the
Pt/SCZY−SDC/Pt cell were performed at 800 °C using an SOFC module. The
gas flow rates of Air/H2 are 600 and 200 ml min-1, respectively.
50
Figure 3.3 Schematic diagrams for preparation of SCZY powder.
51
Figure 3.4 Schematic diagrams for preparation of SDC powder.
52
Figure 3.5 Schematic diagrams for preparation of SCZY/SDC powder.
53
Chapter 4
Result and discussion
4.1 Preparation of SDC/BC Electrolyte.
4.1.1 XRD and morphology analysis
The diffraction patterns of the SDC and the SDC/BC samples are shown in
Fig.4.1. Fig.4.1 (a) displays that the SDC XRD peak is in agreement with the
SDC/BC XRD peak. Fig.4.1 (b) shows the XRD patterns of SDC/BC after heat
treatment at 700 °C for 2 h. The XRD patterns demonstrate that the majority of
the BaCO3 reacted with SDC to form BaCeO3 during heating process, which is
a proton conductor. A small amount of BaCO3 remained after sintering. The
carbonate in the SDC/BC electrolyte acted as an ion interchange barrier
between the SDC/BC electrolyte and the anode or cathode interface during cell
performance measurements at 600 °C. A similar phenomenon has been
reported for sodium carbonate [70]. The amorphous sodium carbonate/barium
carbonate was formed as protective layer for the SDC during thermal treatment
process [71].
54
Fig.4.1 XRD patterns of the (a) SDC sintered at 1400 oC for 4 h ,(b)
SDC+BaCO3 composite electrolyte sintered at 700 oC for 2 h.
55
XRD diffraction patterns confirmed that BaCO3 was in the Composite SDC/BC
powder, indicating that the BaCO3 slightly reacts with SDC in air atmosphere
and forms a new compound of BaCeO3.To characterize the agglomerating
properties of the SDC/BC composite powder, the particle size distributions of
SDC/BC and SDC were measured and the results are shown in Fig.4.2. Two
peaks can be observed on the SDC/BC graph, whereas the SDC graph has one
peak. The main particle sizes of SDC/BC are at 1.97 µm and 8 µm, which is
apparently higher than that of SDC powder at 0.896µm because the chemical
reaction between SDC and BC to form the BeCeO3 during the sintering process.
Fig.4.3 displays the energy-dispersive X-ray spectroscopy (EDS) spectrum and
cross section of the Ni-SDC-BC/SDC-BC/Pt cell, revealing the cathode,
electrolyte, and anode interfaces. The SDC/BC composite electrolyte contained
all of the expected elements in their expected concentrations. The thickness of
SDC/BC electrolyte was about 50 μm, which was determined form the EDS
line scan spectrum (in Fig.4.3 (b), the low-concentration region of Ni
represents the SDC/BC because there is no Ni element in the electrolyte layer.
The higher-concentration of Ni represents the anode supporter of Ni-SDC/BC
[72]. Fig.4.4b displays the EDS spectrum used to determine mass percentages
of the SDC/BC composite elements in a selected cross section of the electrolyte,
as in Fig.4.4a, and also determine that no nickel was present in the SDCBC
56
electrolyte film. The mass percentages of carbon, oxygen, barium, samarium,
and platinum were 2.58%, 13.78%, 13.18%, 41.24%, 6.85%, and 22.36%,
respectively. The contribution from platinum in the spectrum displayed in
Fig.4.4 (b) is primarily due to the platinum coating on the sample for SEM
sample preparation, not from the Pt cathode.
57
Fig.4. 2 Particle size distributions of (a) SDC/BC composite electrolyte (b)
SDC powders
58
Fig.4.3 (a) SEM micrograph and EDS line scan results of all elements, and (b)
line scan of Ni for cross section of Ni-SDC-BC/SDC-BC/Pt cell sintered at 700
°C for 2h.
59
Fig.4. 4 (a) selected cross section of Ni-SDC-BC/SDC-BC/Pt cell (b) EDS
spectra
60
4.1.2 Electrical conductivity
Fig.4.5 displays the results of impedance spectroscopy for the Pt/SDC-BC/Pt
cell taken at 50 °C intervals at 400-600 °C conducted in H2/air (1:3)
atmosphere. Impedance spectroscopy was performed by using an electrical
circuit Re + (Q1/Rc) and Zview software as shown in Fig.4.5 (f). In the equivalent
circuit, Re denotes the series resistance, or the resistance from the electrolyte as
derived from the highest frequencies of impedance at the intercept between the
impedance curve and the real axis. Rc is the polarization electrochemical
resistance obtained by differentiating the semicircular impedance path with
respect to the real axis at both high and low frequencies, therefore, the ion
resistance is equivalent to the polarization resistance. Consequently, Rc is the
ion polarization resistance, and Re is the Ohmic resistance. CPE1 denotes the
constant phase shift, which may change for different electrode-electrolyte
configurations. Rtot is the sum of Re and Rc. The values of Re, Rc, and Rtot are
displayed in Fig.4.6(a), and Fig.4.6(b)-6(d) show the Arrhenius plots of
conductivity against 1/T. The O2−/H+ ion conductivity of the SDC/BC
composite electrolyte, as measured under H2/air atmosphere, varied from 0.030
to 0.104 S/cm between 400 and 600 °C. The conductivity of SDC/BC
measured in this study was much higher than that ever reported, which is about
0.02 S/cm, for a BaZr0.8Y0.2O3-δ (BZY20)-(Li0.62K0.38)2CO3 composite at 400 °C
61
in wet hydrogen atmosphere [73]. However, these two perovskite oxide H+
conductors and the BaCO3 composite should have different conduction
mechanisms in composite electrolytes.
The conduction properties of the SDC/BC composite electrolyte under H2/air
atmosphere were different from those of a BZY20-carbonate composite
electrolyte. Initially, the conductivity-temperature Arrhenius plot is
approximately linear, but after reaching 500 °C during sintering, a conductivity
jump is apparent on the plot due to a superionic phase transition, confirming
that the conductive properties of the SDC/BC composite electrolyte change at
this temperature. H+ conductivity dominates above the superionic transition
temperature, which has low activation energy; above the transition temperature
of approximately 500 °C, the conductivity is relatively high. When the
temperature is below 500 °C, H+ conduction is blocked by insulating solid
carbonate, indicating that the O2−/H+ conduction phase has a substantial effect
on the conductive properties of the SDC/BC composite material due to a
coherence interaction between the carbonate and oxide phases. The activation
energy of the SDC/BC composite sample is approximately 39.65 kJ mol−1 and
31.04 kJ mol−1 at 400-500°C and 500-600 °C, respectively measures in air/H2
atmospheres which is calculated from the Arrhenius graph.
62
63
64
Fig.4.5. Impedance spectra of SDC/BC composite electrolyte measured in air
at 400–600 C.
65
66
Fig. 4.6 (a) Re, Rion, Rt resistance values, and the Arrhenius plots of (b) Re, (c) Rion,
and (d) Rt for the SDC/BC composite electrolyte at 400–600°C
67
4.1.3 Fuel cell performance
Fig.4.7 (a) shows the SEM cross section of an SDC/BC composite electrolyte
based on a Ni-SDC/BC substrate. The substrate was obtained by reducing NiO-
SDC/BC in H2 atmosphere between 400 and 600 °C for 4 h. The porosity of
Ni-SDC/BC anode increased from 12% to 36.7% after reducing in 5% H2
atmosphere. The cross-sectional view of the cell exhibited a uniform SDC/BC
electrolyte, which adhered well with the porous Ni-SDC/BC substrate. Fig4.
7(b) displays the voltage-current and power-current graphs of the SDC/BC fuel
cell. The open-circuit voltage (OCV) of the SDC/BC composite electrolyte was
1.002 V at 600 °C, which is much higher than that of a typical SDC film single
cell, which seldom exceeds 0.96 V above 450 °C due to the electronic
conduction of SDC resulting from the reduction of Ce4+ to Ce3+ in H2
atmosphere [74]. After adding 30% BaCO3 to the SDC, the electronic
conductivity of SDC decreased dramatically. The BaCO3 in the SDC
electrolyte was observed to dissolve at 500-600 °C, and the comparatively
dense layer of electrolyte that developed inhibited gas penetration. When the
fuel cell operating temperature dropped to 450 °C, the BaCO3 in the SDC
electrolyte hardened and produced a number of small pores in the SDC/BC
composite electrolyte resulting in a reduction of the OCV of the material. The
limited O2−/H+ ionic conduction of the SDC/BC composite electrolyte can be
68
determined regardless of the effects of both electrodes, and the internal
resistance of the fuel cell can be found from the slope of the I-V graph. The
O2−/H+ conductivity was 104 mS cm−1 at 600 °C, substantially greater than that
of 100% SDC electrolyte. Therefore, the O2−/H+ ion conduction was increased
by the addition of 30% BaCO3. The improved conductivity of the SDC/BC
composite electrolyte was caused by the interaction between SDC particles to
form the BaCeO3 proton conductor and the molten carbonate, which created an
alternate ionic flow pathway. The current-power characteristics were measured
with a maximum power of 475.7 mA cm−2 at 0.56 V, 686.7 mA cm−2 at 0.51 V,
and 856.3 mA cm−2 at 0.49 V, at 500, 550, and 600 °C, respectively. The fuel
cell based on SDC/BC composite electrolyte had good performance at 500-600
°C, confirming that the SDC/BC composite is suitable used as the electrolyte
for IT-SOFC. The power performance of the fuel cell based on SDC/BC
electrolyte at 600 °C with time was conducted. In the first hour of fuel cell
operation, the performance of the cell decreased to a minimum and then
increased to a steady state by 1.1 h. This phenomenon may be because of the
electrode catalyst activation and the interfaces between the electrolyte and
electrode. The fuel cell was then operated for 4 h with a maximum current
output density of approximately 856.3 mA cm−2 corresponding to the
maximum power output density of approximately 427 mW cm-2 at 600 °C. The
69
high power output of this fuel cell at the low temperatures of 500-600 °C was
primarily due to the high O2−/H+ ion conductivity of the SDC/BC composite
electrolyte. The stability of the cell has been examined for long time testing at
600°C. Fig. 8 shows the current and power density of cell was tested at
100−600 °C for 20 h, and at 600 °C for 90 h. The voltage of cell is constant at
0.6V and flow rate of H2/Air is 200 mL/min and 600mL/min, respectively.
During heating process of 100−600 °C, the current and power is around 0.59
A/cm2 and 0.354 W/cm2 after 10h, and 0.675 A/cm2 and 0.405 W/cm2 after
20h, respectively. After 20h, the power output of this cell is remaining at 0.405
W/cm2 with excellent stability performance at 600 °C until to 90h Fig.4.8.
70
(a)
(b)
Fig.4.7 (a) SEM images of anode supported cell (b) I-V and I-P characteristics
for hydrogen oxygen fuel cell based on Ni-SDC/BC anode supported,
SDC/BC and Pt as an electrolyte and cathode respectively at 500-600 °C.
71
Fig.4.8. More than 100h operation performances of the SDCBC composite
electrolyte fuel cell at 600 C.
72
4.2 Preparation of SCZY/SDC composite electrolyte.
4.2.1 XRD and morphology analysis
Fig.4.9 (a) shows the XRD pattern of SDC sintered at 1400 oC for 5h. All peaks
were assigned to a single phase with crystal structure of cubic fluorite, there is
no peak obtain for the other second phases. Fig.4.9 (b) shows the XRD patterns
of SCZY sintered at 1450 oC for 5h. The diffraction peaks corresponded to the
XRD reflection of well-known orthorhombic perovskite structure of SrCeO3
(JCPDS 82-2370). There is no other peak detected by other phases, indicating
that a single phase of SCZY perovskite has been successfully synthesized by
citrate-EDTA complex method. The lattice parameters of SCZY are a=6.153 Å,
b=6.0118 Å, and c=8.5891 Å, and cell volume=317.72 Å3 corresponding to
results which was reported in the literature [75]. The lattice parameters of
SCZY were slightly larger than that of SrCeO3 (a=6.000 Å, b=6.145 Å,
c=8.575 Å), which due to the substitution of Zr4+ and Ce4+ by Y3+. The radii of
Y3+ is 0.96 Å, which is larger than that of Zr4+ and Ce4+ of 0.72 Å and 0.87 Å,
respectively. Fig.4.9(c) shows the XRD pattern of SCZY/SDC composite
electrolyte sintered at 1450oC for 5h. The peaks corresponding to the SCZY
and SDC phases, which are confirm in Fig.4.9 (a) and Fig.4.9 (b) with small
amount of second phases of Sm2O3, Y2O3 and SrZrO3 in SCZY/SDC composite
73
electrolyte. This XRD result indicated that there is minor chemical reaction
between SCZY and SDC.
The particle size distribution of SCZY/SDC composite powder is shown in
Fig.4.10. It shows two main peaks of 0.6 µm and 6.107 µm, respectively,
which was higher than that of SCZY powder we prepared before [69], due to
the aggregation phenomenon during the high temperature heat treatment
process. Fig.4.11 (a) shows the micrograph of SCZY/SDC composite
electrolyte and Pt electrode. The sintering percentage of SCZY/SDC electrolyte
with small pores, which may be due to chemical reaction between SZCY and
SDC. The interface between Pt electrode and SCZY/SDC composite electrolyte
was defined by the EDS line scan result, which was shown in Fig.4.11 (a).
Fig.4.11 (b) displays the EDS spectrum of the electrolyte. From the cross-
section micrograph, it was confirmed that the adhesion between Pt electrode
and SCZY/SDC composite electrolyte is well, no crack or small gap was
observed.
74
Fig.4.9 XRD patterns of the (a) Sm0.2Ce0.8O1.9, (b) Sr (Ce0.6Zr0.4)0.85Y0.15O3−δ
and (c) Sr(Ce0.6Zr0.4)0.85Y0.15O3−δ/ Sm0.2Ce0.8O1.9 composited electrolyte.
75
Fig.4.10 Particle size distribution of Sr(Ce0.6Zr0.4)0.85Y0.15O3−δ/Sm0.2Ce0.8O1.9
composite electrolyte powder.
76
4.2.2 Electrical conductivity
Fig.4.12(a) displays the results of electrochemical impedance spectroscopy
(EIS) for the Pt/ SCZY-SDC/Pt cell during 600-800 °C with 50 °C intervals of
air and H2 for cathode and anode electrodes, respectively. The EIS was fitting
using an equivalent circuit as shown in Fig.4.12 (a) insert. In the equivalent
circuit, R1 is ohmic resistance, including electrode and electrolyte materials and
conductive wire that is found the intercept point between the semicircle and the
real axis at the highest frequency. R2 and R3 are charge-transfer resistance and
ion diffusion/adsorption resistance, respectively, which are obtained by
subtracting the semicircle to the real axis at the low and high frequencies; Rtot
is the total resistance of R1, R2 and R3. The R1, R2 , R3, and Rtot at various
temperatures are shown in Fig.4.12 (b) and list in Table 4.1. It was found that
the resistance decreases with the temperature increases, especially for ohmic
(R1) and charge-transfer (R2) resistances, which decreases from 1.155 Ωꞏcm2
and 0.847 Ωꞏcm2 to 0.206 Ωꞏcm2 and 0.053 Ωꞏcm2, respectively from 600°C to
800°C. The resistance of ion diffusion/adsorption (R3) did not change
apparently with temperature. The total polarization (Rtot) mainly depends on
ohmic polarization, which the percentage of ohmic polarization is in the range
of 53.3% (600 °C) - 55.9 %( 800 °C), however, the charge-transfer polarization
77
Fig.4.11 (a) Cross-section micrograph, and (b) EDS spectra of Pt/
Sr(Ce0.6Zr0.4)0.85Y0.15O3−δ/Sm0.2Ce0.8O1.9/Pt cell.
78
is in the range of 15.2% (800 °C) to 39.1% (600 °C), and ion
diffusion/adsorption is only in the range of 7.5% (600 °C) to 25.3% (800 °C).
Fig.4.13 shows the Arrhenius plots of conductivity for the Pt/ SCZY-SDC/Pt
cell during 600-800 °C. The activation energy of the R1, R2, R3 and Rtot is 61.37
kJ mol−1, 41.73 kJ mol−1, 38.93 kJ mol−1, and 81.87 kJ mol−1. The activation
energy of ohmic polarization is apparently higher than that of charge-transfer
and ion diffusion/adsorption polarizations, because this cell is based on
electrolyte supported structure, the thickness of electrolyte is as high as 1.19
mm, therefore, the conductivity behavior is mainly depends on ohmic
polarization. The charge-transfer and ion diffusion/adsorption polarizations are
small comparing to ohmic polarization because the Pt was used as the anode
and cathode electrodes.
The conductivity species of SCZY/SDC composite electrolyte maybe contain
oxygen ion, proton, and electron; however, it is difficult to distinguish the ion
transport species in this composite electrolyte. The conductivity behavior of
Pt/SCZY-SDC/Pt in H2, Air, and H2 (anode)/Air (cathode) atmospheres at
various temperatures was shown in Fig.4.14. Fig.4.14 (a) shows the
conductivity of Pt/SCZY-SDC/Pt increases from 0.002 S/cm to 0.228 S/cm as
the temperature increases from 500 °C to 800 °C in H2 atmosphere, which is
much higher than that of SCZY in H2 (0.0082 S/cm at 800 °C) [76]. Even the
79
conductivity of Pt/SCZY-SDC/Pt increases as temperature increases in Air,
which was shown in Fig.4.14 (b), however, the conductivity is only 0.00349
S/cm at 800 oC, which is about 100 times lower than that in H2. Fig.4.14(c)
shows the conductivity of Pt/SCZY-SDC/Pt in H2 (anode)/Air (cathode). The
conductivity behavior and values (0.223 S/cm at 800 °C) of this composite
electrolyte in H2 (anode)/Air (cathode) is similar with that in H2. The main
different of sample in H2 and H2 (anode)/Air (cathode) is there is a voltage,
based on Nernst equation from concentration difference of oxygen partial
pressure, on the Pt/SCZY-SDC/Pt. The proton diffuses from anode to cathode;
inversely the oxygen ion diffuses from cathode to anode due to the
concentration difference of hydrogen and oxygen. From the result of Fig.4.14,
it is believed that the Pt/SCZY-SDC/Pt composite electrolyte exhibits both
oxygen ion and proton conductivity mechanism, but mainly based on proton
conductivity behavior. From the equation (1), oxygen ion vacancies are
developed by doping of Y3+ in Ce4+. In the presence of oxygen atmosphere the
conduction mechanism of SCZY contain of pure of oxygen ion conduction and
increases with operating temperature increases. The proton conductivity in the
SCZY occur because of jumping of protons from an OHo• site to an oxide ion
site [77].
80
Fig.4.12 The (a) EIS curves, and (b) resistances for the Pt/
Sr(Ce0.6Zr0.4)0.85Y0.15O3−δ/Sm0.2Ce0.8O1.9/Pt cell in H2 (anode)/Air (cathode) at
various temperatures.
81
Table 4.1: The equivalent-circuit analysis results of EIS for Pt/SCZY-SDC/Pt
various temperatures.
Temperature(oC) R1 (Ωꞏcm2) R2 (Ωꞏcm2) R3 (Ωꞏcm2) Rtot (Ωꞏcm2)

600 1.155 0.847 0.163 2.165
650 0.794 0.466 0.162 1.421
700 0.544 0.333 0.124 1.001
750 0.272 0.076 0.170 0.518
800 0.206 0.053 0.088 0.347
82
the composite electrolyte SCZY/SDC composite electrolyte show the higher
conductivity comparing than single SCZY or SDC due to the mixed proton and
oxygen ion conductivity species in the H2 (anode)/Air (cathode) atmosphere.
4.2.3 Fuel cell performance
Fig.4.15 illustrates the I−V and I−P curves of the Pt/SCZY-SDC/Pt cell at 800

C. The open circuit voltage is 0.74 V, which is lower than the cell based on
SCZY or SDC SOFC cells, it is due to the composite electrolyte is not dense
enough which contains pores. The maximum power density of Pt/SCZY-
SDC/Pt cell at 800 C is 21.7 mW cm−2. If the sintering density of SCZY/SDC
electrolyte could be improved in the future, it is believed that high
electrochemical performance of SOFC based on SCZY/SDC composite
electrolyte could be approached.
83
84
Fig.4.13 The Arrhenius plots of (a) R1, (b) R2, (c)R3 and (d) R4 for the
Sr(Ce0.6Zr0.4)0.85Y0.15O3−δ/ Sm0.2Ce0.8O1.9 cell in H2 (anode)/Air (cathode) at
600-800 C.
85
Fig.4.14 The electrical conductivity of the Sr(Ce0.6Zr0.4)0.85Y0.15O3−δ/
Sm0.2Ce0.8O1.9 as a function of temperature in (a) H2, (b) Air, and (c) H2
(anode)/Air (cathode) atmospheres.
86
Fig.4.15 I-V and I-P characteristics of the Pt/
Sr(Ce0.6Zr0.4)0.85Y0.15O3−δ/Sm0.2Ce0.8O1.9/Pt cell at 800 C.
87
Chapter 5
Conclusion
SDC/BC composite electrolyte was developed for LT-SOFCs. XRD results
showed the presence of SDC, BaCeO3, and BaCO3 phase in SDC/BC
composite electrolyte. SEM microstructural analysis revealed that the SDC/BC
electrolyte adhered well with the porous Ni-SDC/BC anode support. The
SDC/BC demonstrated the highest O2−/H+ conductivity of 104 mS cm−1 at 600
°C and had low activation energy of 36.12 kJ mol−1 under air/H2 atmosphere. A
fuel cell based on SDC/BC composite electrolyte had excellent electrochemical
performance at low temperatures, and its maximum power output of roughly
427 mW cm−2 would correspond to a current density of approximately 856.3
mA cm−2 at 600 °C. The good power output performance of this fuel cell
proved that this type of SDC/BC composite with excellent O2−/H+ is could be
used as ideal electrolyte for an LT-SOFC.
SCZY/SDC composite electrolyte was developed for SOFCs. XRD results
showed the main structure of SCZY and SDC with small amount of second
phases. SEM microstructure analysis revealed that the SCZY/SDC electrolyte
88
Adhered well with the porous Pt anode and cathode electrodes. The
SCZY/SDC demonstrated the high conductivity of 0.223 S cm−1 at 800oC in H2
(anode)/Air (cathode) atmospheres. A cell based Pt/SCZY-SDC/Pt composite
electrolyte had a maximum power output of 21.7 mW cm−2 at 800 °C.
89
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YUAN ZE UNIVERSITY

Department of Chemical Engineering and Material Science

Fabrication of Co-Ionic Conducting Electrolyte for Low Temperature Solid

Student: Azam khan

Advisor: I-Ming Hung

Student: Azam khan

Advisor: I-Ming Hung

Department of Chemical Engineering and Material Science

Submitted to Department of Chemical Engineering and Material Science

In partial Fulfillment of the Requirements for the

Doctor of Philosophy Degree in

Chemical Engineering and Material Science

Zhongli, Taiwan (RO

本研究成功測試了 70% w/w 釤摻雜二氧化鈰與 30% w/w 碳酸鋇 (SDC/BC) 電

SCZY/SDC 複合電解質樣品在 H2 和空氣中的電導率在 800 °C 時分別為 0.228

improved electrolyte for low-temperature solid oxide fuel cells (LT-SOFCs).

The phase changes, particle size distribution, morphology, electrochemical

this SDC/BC composite electrolyte are discussed. The SDC/BC electrolyte is

chemically compatible with a Ni-SDC/BC anode. The conductivity of the

SDC/BC is 102.7 mS cm−1 at 600 °C with activation energy of 36.12 kJ mol−1.

The maximum power output of the Ni-SDC-BC/SDC-BC/Pt cell is 427 mW

has potential as a low-temperature electrolyte for LT-SOFC.

In other hand, Sr(Ce0.6Zr0.4)0.85Y0.15O3−δ (SCZY)/Sm0.2Ce0.8O1.9 (SDC) co-ionic

conducting (O2−/H+) composite electrolytes are synthesized using the citrate-

ethylene diamine tetra acetic acid (EDTA) complexing method. The

electrochemical properties and structure of the SCZY/SDC is determined at

various atmospheres and temperatures. After sintering at 1450 °C for 5h,

SCZY/SDC is used as electrolyte for solid oxide fuel cell.

conductivity and activation energy of the Pt/SCZY-SDC/Pt cell was calculated

from the EIS data in H2 (anode)/Air (cathode) atmospheres is 0.039-0.223 S

mW cm−2 with the thickness of electrolyte of 1.19 mm and area of cathode is

I am very grateful to my supervisor prof.I-Ming Hung for his guidance,

I would also like to thank my colleagues: Tung-Wei Chang, Debabrata

My gratitude goes to my parents for their unconditional love and always

Title Page …………………………………………………………….….. Ⅰ

Chapter 2 Literature Review……………………………………………....7

2.1 Introduction of Fuel Cells………………………………………..........7

2.2 Solid Oxide Fuel Cell (SOFC) ……………….....................................9

2.2.1 Introduction of Solid Oxide Fuel Cells……………………………..9

2.2.2 Principle of Solid Oxide Fuel Cell………………………………….11

2.2.3 Advantages and disadvantages of solid oxide fuel cells……………13

2.2.4 Structure of Solid Oxide Fuel Cell………………………………….14

2.2.5 Polarization phenomenon of solid oxide fuel cells…………………16

2.3 Development and Type of Solid Oxide Fuel Cell Electrolyte………..22

2.3.2 Perovskite−structured for solid oxide fuel cell electrolyte………….30

2.4 Development and Properties of Solid Oxide Fuel Cell Cathode……...34

2.4.1 Cathode material properties…………………………………………34

2.4.2 Working principle and characteristics of cathode materials………...37

Chapter 3 Experimental method…………………………………………..40

3.1 Preparation of (SDC/BC) Electrolyte ……………………………….41

3.1.1 Half- and single-cell tests…………………………………………...45

3.1.2 Characterization of composite electrolytes………………………….46

3.2 Preparation of SCZY/SDC composite electrolyte………………….....47

3.2.1 Characterization of Composite Electrolytes………………………...49

3.2.2 Single-cell test………………………………………………………50

Chapter 4 Result and discussion ………………………………………….54

4.1 Preparation of SDC/BC Electrolyte ………………………………….54

4.1.1 XRD and morphology analysis……………………………………..54

4.1.2 Electrical conductivity……………………………………………...61