TEESSIDE UNIVERSITY

School of Computing, Engineering

and Digital Technologies

Engineering Research Project

2023

Hammed Oluwaseyi Idris

(A0325958@live.tees.ac.uk)

Understanding Solid Oxide Electrolyser Cell

Performance Through Post-Test Analysis of
Degradation Mechanism

Supervisor: Dr Krishnan Venkatesan

1
 ABSTRACT
Defects associated with the degradation mechanisms of a metal supported CGO
(gadolinium doped cerium oxide) Solid Oxide Electrolysis Cell was analysed from
3 cell samples. The cells were operated at different temperatures at applied
voltages of 1.2V, 1.12V and 1.10V with a fuel utilisation of 50% for a mixture of
hydrogen and steam.

The observed degradation/defects were characterised using optical microscopy.

Air electrode delamination and the so-called volcano defect were the
predominant defects observed. The results show that the electrochemical
performance of the cell gradually drops overtime due to the start and growth of
these defects. Cell 1, 2 and 3 for a test duration of 5000h gave an average current
density of 0.199A/cm2, 0.201A/cm2 and 0.285A/cm2 with a corresponding
normalised area specific resistance (ASR) growth rate of 0.972Ωcm/kh,
0.626Ωcm/kh and 1.00Ωcm/kh.

Two other cells operated at 5000h were also quantified for Nickel area fraction
with a reference non-operated cell still at optimal condition. The result showed
that the extent of Ni depletion starting at the electrode-electrolyte interface is not
significant. The relative Nickel area fraction between the operated samples and
the reference are somewhat close with a standard deviation of 0.0796, 0.2554,
and 0.0792 for the reference cell, cell A and cell B respectively, with a
corresponding average area-nickel-distributed normalised value of 0.77, 0.83 and
0.85. The analysis of the degradation data in the study shows that there is ASR
fluctuation resulting from cell arrangement, and the fluctuating ASR decreases
with increasing temperature.

2
 ACKNOWLEDGEMENT
The work done in this thesis originates from the kind cooperation of many people
that shared their time, knowledge, abilities, and guidance. Everyone was so
essential and unique, and everyone was so kind and helpful. For all these
reasons and more, I kindly acknowledge you, with the hope that this thesis could
somehow be useful to give first insights towards performance and degradation in
SOEC for the fight against climate change and increasing energy demand.
In particular I would like to thank Dr Per Hjalmarsson for his time and oversight
and his weekly insights into prospective root-causes, they are invaluable towards
understanding how various degradation mechanisms may arise. A big thank you
also goes to Dr Laura Rios for her incessant and unwavering efforts and support
towards the completion of this thesis and making sure that all objectives of the
studies are catered for.
Lastly, I would like to thank my industrial and academic supervisors in person of
Dr Uyime Donatus and Dr Krishnan Venkatesan for their mentorship and
guidance every step of the way. I thank you both for taking time out of your busy
schedule to always give support, advice and mentorship whenever needed. I also
acknowledge all the people that contributed one way or the other starting with Dr
Mehdi Choolaei and Dr Chandra Macauley by readily being available for
discussion of concepts, and everyone else at Ceres Power Limited who
contributed towards the completion of this thesis. I pray you all shall continue to
find favour in all your endeavours.

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Contents
ABSTRACT...................................................................................................................... 2
ACKNOWLEDGEMENT ................................................................................................ 3
Contents ............................................................................................................................ 4
List of Tables .................................................................................................................... 6
List of Figures ................................................................................................................... 7
Chapter 1 ........................................................................................................................... 9
1 INTRODUCTION ................................................................................................. 9
1.1 SOEC- Principle and materials ........................................................................ 10

1.2 Electrode-membrane components introduction ............................................... 12

1.2.1 Cathode ..................................................................................................... 12

1.2.2 Electrolyte ................................................................................................. 13
1.2.3 Anode ........................................................................................................ 14
1.3 Stack Configuration ......................................................................................... 14

1.4 Research Objectives ......................................................................................... 15

1.5 Research Outline .............................................................................................. 16

Chapter 2 ......................................................................................................................... 17
2 REVIEW OF LITERATURE ............................................................................... 17
2.1 Electrolyte degradation .................................................................................... 17

2.2 Anode degradation ........................................................................................... 20

2.3 Cathode degradation......................................................................................... 22

2.4 Poisoning .......................................................................................................... 24

Chapter 3 ......................................................................................................................... 27
3 METHODOLOGY .............................................................................................. 27
3.1 Overview of post-test analysis ......................................................................... 27

3.2 Post-test data approach ..................................................................................... 28

3.3 Characterization methods ................................................................................. 29

3.3.1 Leak Test................................................................................................... 29

3.3.2 Optical microscopy and visual inspection ............................................... 29
3.3.3 Scanning Electron Microscopy (SEM) ..................................................... 31
3.3.4 Energy Dispersive X-ray Spectroscopy (EDS) ......................................... 31

4
 3.4 Experimental ......................................................................................................... 31

3.4.1 Stack construction ..................................................................................... 31

3.4.2 Stack operation and post-operation analysis ............................................. 33
Chapter 4 ......................................................................................................................... 34
4 RESULT AND DISCUSSION ............................................................................. 34
4.1 Results from Post-test Analysis ....................................................................... 34

4.1.2 Area Specific Resistance (ASR) ............................................................... 38

4.1.3 Adhesion test............................................................................................. 39
4.1.3 ........................................................................................................................ 40
4.2 Quantifying Nickel depletion ........................................................................... 43

4.3 In-situ Degradation Data Analysis Result ........................................................ 47

4.3.1 Fluctuating behaviour of ASR start-of-life value. .................................... 47

4.3.2 Effect of stack operating temperature on ASR start-of-life. .......................... 49
4.3.3 Odd and even layers comparison .............................................................. 50
4.4 Discussion ........................................................................................................ 52

Chapter 5 ......................................................................................................................... 54
5 CONCLUSION AND RECOMMENDATIONS ................................................... 54
5.1 Conclusion........................................................................................................ 54

5.2 Recommendation.............................................................................................. 55

References ....................................................................................................................... 56
APPENDICES ................................................................................................................ 61
Appendix- A1 ......................................................................................................... 61
Appendix- A2 ......................................................................................................... 63
Appendix- A3 ......................................................................................................... 65
Appendix- B ............................................................................................................ 67

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List of Tables
Table 3.1- Operating conditions used for test. ........................................................ 33
Table 4.1- Operating condition for cell testing ......................................................... 39
Table 4.2- Nickel distribution result for reference cell, cell A and cell B.............. 44

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List of Figures
Figure1.1- Schematic of membrane-electrode assembly of a SOEC ............... 12
Figure1.2- Pictorial view of a stack build .......................................................... 14
Figure 3.1- Flow chart of post-test analysis characterization techniques ......... 30
Figure 3.2- Schematic representation of a.) a steel cell from Ceres Power b.) a
stack repeating unit (Leah, et al., 2015) ........................................................... 32
Figure 4.1- Electrical Performance for Cell 1 ................................................... 35
Figure 4.2- Electrical Performance for Cell 2 ................................................... 36
Figure 4.3- Electrical Performance for Cell 3 ................................................... 37
Figure 4.4- Area Specific Resistance (ASR) for cell samples .......................... 38
Figure 4.5- Tape casting to observe variation in air-electrode adhesion properties.
......................................................................................................................... 39
Figure 4.6- Optical microscopy of cell defects in two lighting: A- Delamination
accompanied by an eruption, B- Volcano defect, C- Advent of volcano defect
eruption. ........................................................................................................... 41
Figure 4.7- Optical microscopy of air electrode degradation in two lighting: A-
Combustion marks, B and C- Electrode delamination ...................................... 41
Figure 4.8- Electrolyte degradation in form of volcano defects in the same area
on cell samples under two lighting ................................................................... 42
Figure 4.9- SEM image and the binary image (Left and Right respectively) of the
Reference cell, Cell A and Cell B ..................................................................... 45
Figure 4.10- Plot of Nickel Distribution ............................................................. 46
Figure 4.11. This is the fluctuating behaviour as seen in 3 different stacks having
the same material composition and the same test purpose of ASR degradation in
stamped and post-form coated interconnect. ................................................... 48
Figure 4.12. A and B effect Predominant in Stack A1 and A2 than in B1 and B2
(Stack A1, A2 have the same composition and are tested for the same purpose.
So does Stack B1 and B2) ............................................................................... 48
Figure 4.13- Effect of temperature on global ASR behaviour ........................... 49
Figure 4.14- ASR behaviour for a stack operated at 610C. .............................. 50
Figure 4.15- ASR behaviour for a stack operated at 630C. .............................. 51

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8
 Chapter 1

1 INTRODUCTION
It has become increasingly apparent over the last few decades that the issue of
climate change can no longer be neglected which make one wonder if the climate
has always changed rendering the argument somewhat inconsequential.
According to meteorology studies (Treut, et al., 2007), it is apparent that the
climate has always changed, but the effects of adverse changes in climate
condition is being felt now more than ever in form of global warming and
ecological degradation.
The burning of fossil fuel for energy generation has upset the carbon cycle by
significantly increasing the amount of CO2 and other green-house gases in the
atmosphere. This increasing concern has sparked a worldwide interest in
development of other energy and power generation substitutes with minimal to
no carbon footprint. This power generation technologies offer prospective and
feasible routes in implementing the Paris agreement (United Nations, 2016)
which sets out a global framework to achieve a better climate condition through
global warming reduction strategies to attain an ambient temperature below 2°C.
To achieve this, renewables play an important role as they can be possible
sources of low-carbon electricity, but In reality, to achieve the objectives set out
by the United Nations, the share portion of electricity in the total amount of energy
consumed by the end user worldwide would need to increase by 40% by the year
2050 (IRENA, 2018).
Also, the means of using electricity to decarbonise certain sectors such as the
transport, steel, fertiliser, refinery, and the chemical industry may be too difficult
to achieve due to their requirement in high-grade heat. A promising route to
address the decarbonisation of these sectors is by the development of hydrogen
production technologies such as solid oxide fuel cells (SOFCs) and solid oxide
electrolysers (SOECs) which can generate hydrogen through gravimetry of
hydrogen-laden chemical and electrolysis respectively.
The potential of the technology to play a pivotal role by producing hydrogen for
use as energy carrier is gradually being accepted and researched all around the
world. Hydrogen as energy carrier is the storing of electrical or thermal energy in
9
form of the amount of hydrogen produced from hydrogen-containing resources
mainly water when solid oxide fuel cells are run in reverse mode- Solid Oxide
Electrolyser. The produced hydrogen can then be combusted and used to power
machines or produce electricity. (Bossel & Eliasson, 2021) Solid oxide fuel cells
are electrochemical conversion devises that converts the chemical energy of
hydrogen-laden compounds such as hydrogen and hydrocarbon into electrical
energy with very low pollution and very high efficiency.
There are different types of fuel cells depending on the operating temperature,
architecture, and the maximum power output over a period. For all this mode of
operation, the production of hydrogen by splitting water though the passage of
electricity is favourable because the hydrogen evolution reaction (HER) is
electrochemically reversible in the presence of catalysts such as Platinum. This
simply translates that hydrogen kinetics is comparably fast which makes the
conversion process operate with very high efficiency.
However, most of the hydrogen used in the world is generated from fossil fuels
such that 6 percent and 2 percent of global natural gas and global coal supply
respectively are used to produce hydrogen (Patonia & Poudineh, 2022). As such,
the production of hydrogen through the conventional coal gasification or steam-
methane reforming accounts for about 830million tonnes of CO 2 emitted into the
atmosphere annually by the UK and Indonesia combined (IRENA, 2018). In this
sense, hydrogen production from this route becomes counterintuitive in the fight
to enable decarbonisation which leads to integration of carbon capture
technology with the process and the hydrogen so gotten as a result is referred to
as- blue hydrogen.
Another plausible hydrogen frontier is the production of hydrogen via water
electrolysis using energy collected from renewables making the entire hydrogen
production pathway carbon-free thus ‘green hydrogen’. This is a very enticing
route for industrial decarbonisation as up to 96% of hydrogen used industrially
are gotten from fossil fuel (Jiang & Li, 2022)

1.1 SOEC- Principle and materials

Water in form of steam enters at the hydrogen electrode (cathode) usually made
of a metal and ceramic for a good match of electronic/ionic conductivity and

10
thermal resilience due to the severe operating condition of solid oxide fuel cells
and electrolysers. Upon entry, the steam is reduced and dissociated into
hydrogen molecule and oxygen ion due to high reducing environment of the
cathode, the presence of a catalyst which is a good promoter of hydrogen
evolution and the voltage supplied to initiate the water splitting reaction.
In between the cathode and the anode is the dense, ionic-conducting electrolyte
which allows the passage of oxygen ion from the cathode (hydrogen electrode)
to the anode (air electrode). The porous electrolyte must be able to withstand the
reducing and oxidising environment and insulative to electronic transfer to
prevent electron leakage which may lead to a short circuit and eventually a local
combustion. Oxidation reaction of oxide ion takes place at the anode. The oxide
ion on getting to the anode becomes oxidised by releasing electrons due to high
oxidising environment, which are transported from the anode to the cathode
through a metallic conductor. The transport of electrons via the conductor closes
the circuit and give rise to the production of electron flow creating electricity which
can be used to power a load.

11
 Figure1.1- Schematic of membrane-electrode assembly of
a SOEC

Hydrogen electrode: H2 O + electric energy → H2 + O= +2e− (i)

1
Air electrode: O= +2e− → 2 O2 (ii)
1
Overall reaction: 2H2 + O2 → H2 O (iii)
2

Several material investigations have been carried out for use in SOFC systems,
only a few widely known ones will be introduced in the following subsections. The
materials are described in terms of SOFC operation. The mode of operation can
be reversed to evaluate features when used as SOEC.

1.2 Electrode-membrane components introduction

1.2.1 Cathode
There are a lot of investigation that has been done to evaluate material
performance and fitness for use as SOFC cathodes, examples are cathode
materials which have the perovskite structure ABO3 that shows admirable
properties when incorporated with A- and B-cations which correspond to cations
of group-1, 2, the rare earth metals and group 13 to 15 cations on the A-site.

12
(Hussain & Yangping, 2024) The close lattice structure of such perovskite is
joined by large cations on the A-site which arise due to the presence of O2- ion
octahedral void where the B-cations are located.
A good advantage of the perovskite structured cathode is that their electronic
features can be altered and improved due to the replaceability of the A- and B-
cations in the sub-lattice of the system.
Cobalt-based and cobalt-free perovskite cathodes have also been looked at for
their use in SOFC systems. (Ding & Xue, 2010) Cathode containing Co can
perform effectively at high temperature compared to cobalt-free cathodes. To use
the former at lower temperature rather than intermediate temperature may result
in failure due to the possibility of thermal coefficient expansion mismatch (TEC).
(Lee, et al., 2012) also reported that employing Co-free cathode is a good way to
operate SOFC in the range of intermediate to low temperature and still have a
good electrochemical efficiency.
1.2.2 Electrolyte
(Mahato, et al., 2015) Yttria stabilised zirconia is one of the widely used
electrolyte material for SOFC. It is made by adding yttrium oxide (Y 2O3) to
zirconium oxide (ZrO2) in other to make the latter stable at room temperature.
(Jiang & Li, 2022) Materials which are perovskite-based such as Lanthanum
Gallate (LaGaO3) are also used as electrolyte owning to their higher electronic
conductivity at low temperature, their performance could also be optimised by
doping the materials with Mg on the Ga site and Sr on the La site (La1-x Sax))(Ga1-
yMgy)O3. (Laosinpojana, et al., 2009) Another interesting material for use as
electrolyte is the Gadolinium oxide doped with ceria (GDC) which shows higher
conductivity compared with YSZ. (Basu, 2007) as compared to Scandia which is
effective for use as electrolyte material but due to availability and pricing its
application for electrolytes in SOFC is limited.
Ceria for use as main electrolyte as also been investigated by (Fergus , 2006). It
was also reported that ceria has a better conductivity as compared to YSZ (yttria
stabilised zirconia) and CSSs’ (Scandium supported zirconia) at reduced
temperature and an improved polarisation resistance (Dalslet, et al., 2006).
Doping the widely used ceria (Ce1−x Gdx O2 ) is a way to improve the conductivity
because it tends to increase with increasing dopant though this is by (Yahiro, et
13
al., 1989) at low temperature which means that the stability of the doped ceria
structure may be questioned at increased temperature
1.2.3 Anode
(Bastidas , et al., 2006) LSCM composite (La0.75Sr0.25)Cr0.5Mn0.5O3 is a well-
researched material for use in SOFCs for both anode and cathode. The material
is sought after due to its ability to withstand both oxidation and reduction cycles
combined with its conductive ability and good performance. (Chavan, et al., 2012)
There are also reported cases where Ni-GDC nano composite are used for anode
material, the study of their microstructure depicted that the material lowered the
activation energy and the NiO content at the anode.
(Benamira, et al., 2023) Perovskite material such as BLITIM
(Ba0.5La0.5In0.3Ti0.3Mn0.7O3) and BLTM (Ba0.5La0.5Ti0.3Mn0.7O3) are also SOFC
anode candidates, the use of such materials showed reasonable electronic
conductivity in oxidative atmosphere.

1.3 Stack Configuration

The pictorial view of a stack layout is depicted in Figure1.2 it is made up of
numerous single cells repeating units, each repeating unit is serially connected
to the other from the first layer up to the last layer.

Figure1.2- Pictorial view of a stack build

14
Theoretically, say if some sort of degradation mechanism should occur in the
stack this will increase the area specific resistance of the cells involved which
may eventually cascade to other repeating units which will eventually affect the
overall performance of the system.

1.4 Research Objectives

The overall performance of a SOEC/SOFC is strongly influenced by the operating
conditions and the stringent structural requirements of the system, such as stable
chemical structure, design of architecture to prevent thermal mismatch,
thermal/chemical cyclability, high temperature and porosity to allow for mass
transport. This makes different part of the system subject to different corrosion
and degradation mechanisms which affect the durability, performance and
eventually lifespan of the system.
The objective of this research is to contribute to the general body of available
knowledge about the degradation forms including delamination and defects which
a solid oxide electrolyser cell may be susceptible to under varied operating
voltage conditions and by so doing predict the performance of the SOEC at
certain time span of interest. This could be useful in implementing degradation
prevention methods which may be integrated into the architecture of the cell
improving cell performance, reliability, durability, and an increased amount of
power generation.
The specific empirical research objective is to investigate electrode and
electrolyte defects and delamination of SOE-cells tested at different conditions in
a controlled environment.
The main research question is:
• What are the contributing degradation modes in a short stack of SOEC
which eventually lead o system failure?
The main sub-question is:
• How does this degradation affect the electrochemical performance of the
cells in SOEC system?

15
1.5 Research Outline

This study was carried out at Ceres Power Limited in in collaboration with
Teesside University. The bulk of the study consist of degradation and defect
analyses and how they impact SOEC performance. The other part which is the
in-situ data analysis consist of analysing A and B effect from start-of-life ASR
values arising from stack arrangement and its behaviour with temperature. The
following section of this thesis is organised as follows.
In chapter two, I gave a review of literature of some of the degradation
mechanism that are prominent to both SOFC and SOEC and reported on anode,
cathode, electrolyte degradation and poisoning. In chapter three I described the
methodology used during the study and reported on the characterisation
techniques employed and how results are tracked and compiled. In chapter four,
I reported my findings and analysed the results to show how they impact
performance. I then discussed my results and findings at length. I also
enumerated synergies between the potential causes of degradation mechanism
and how they affect the overall cell performance degradation. In chapter five I
gave my conclusions and a recommendation. In other not to breach confidentiality
and intellectual property agreement, all data sets reported in the appendix have
been normalised.

16
 Chapter 2
2 REVIEW OF LITERATURE
2.1 Electrolyte degradation
This thesis mainly talks about degradation reported from post-test analysis. The
gradual decrease in cell performance is globally considered as a result of ageing
process of the whole SOFC/SOEC system, but the extent of the overall
degradation mechanism depends locally on the contribution of individual
degradation which different materials in the system are susceptible to. (Ciacchi,
et al., 1994) SOFC degradation may vary between individual components viz
from electrolyte degradation which may be observed as decrease in phase
stability of the electrolyte leading to a decrease in its ionic conductivity, (The, et
al., 2015) as the formation of pores in the cathode which eventually deposits and
combine leading to defect in the microstructure, (Zekri, et al., 2017)
Agglomeration and coarsening of Nickel in Ni-cermet anodes, (Yang, 2013)
corrosion of the air/fuel separator interconnect and very often poisoning such as
Chromium and Strontium poisoning diffusing into other layers and lowering
overall system performance (Stanislowski, et al., 2007).
(The, et al., 2015) tested two circular cathode-supported cells for 9000hr and
6000hr and compared them with a cell that was not operated. The cell is made
up of an 8µm thick nickel doped yttria supported zirconia (Ni/8YSZ) hydrogen
electrode, 10µm thick YSZ electrolyte, a barrier layer of CGO (Ce0.8 Gd0.2O1.9)
and a 30µm LSCF oxygen anode (La0.58Sr0.4Co0.2Fe0.8O3). All layers were screen-
printed on the Ni/8YSZ substrate with an active layer of 45cm 2. The solid oxide
electrolyser cell which ran at 9000hr and 6000hr were denoted as cell1 and cell2
respectively and their PTA results compared with cell that were not operated. The
SEM analysis of the operated and non-operated cells showed that the electrolyte
of both cells contains voids which arises from the production process and whose
number and dimensions do not vary during operation. (The, et al., 2015)
therefore, assumed that the voids have negligible impact on degradation. The
TEM/EDS analysis carried out on the non-operated cells depicted that the
chemical composition of the cell only shows minimal variation and no abnormality
which corresponds to irregularities in form of nano-sized pores. On the other

17
hand, in cell 1, a considerable amount of SrZrO3 and nano-sized pores were
formed in the diffusion barrier and the electrolyte respectively, this corresponds
to a degradation phenomenon with a degradation rate of 11mV/kh with no change
in chemical composition of the electrolyte. The micro sized pores show a
distinctive grey coloration located at the diffusion barrier layer.
(Tiets, et al., 2013) also carried out a similar test only on an anode supported
solid oxide electrolyser cells. The cell is run for 9000h showing an increase in the
total electrolyser voltage up to 40mV/kh while showing similar degradation
phenomenon as PTA done by (The, et al., 2015). Here, two forms of degradation
were observed, the first appear as a form of change in the microstructure-
Changes in fracture mode along the grain boundary is observed which is
indicated as a distinct and increased grain structure of the electrolyte. Voids are
seen on the surface of each grain and the dimension of these voids is dependent
on the orientation of the grain. The voids are also observed to come together and
combine to form more irregular features.
Loss of contact area and loss of mechanical stability may arise because of these
microstructural changes which contributes to the voltage increase because of
increase in contact resistance induced due to loss of contact area. The second
degradation feature is the horizontal alignment of pores throughout the electrolyte
which may arise due to an increase in the partial pressure of oxygen gradient
p(O2) corresponding to an increased electrochemical gradient due to oddly
distributed contact resistance which causes a pore formation in the electrolyte
layer. The EDS analysis of the observed grey area by (The, et al., 2015) gives a
1:1 ration of Strontium and Zirconium which corresponds to the formation of
SrZrO3 during operation period of 6100h. The cell 2 also depicted pore formation
in the electrolyte preferably near the CGO/8YSZ interface with no indication of
any changes in chemical composition of the electrolyte. Similarly, the grey areas
were observed in the diffusion barrier at the pores and corresponds to the
formation of SrZrO3.
SOFC/SOEC electrolyte particularly doped ceria (Ce1-x Mx O2-(x/2)-ɗ) also often
degrade during testing and operation. (Lenser, et al., 2022) postulated that the
degradation in doped ceria electrolyte happens through chemical expansion of

18
electrolyte, which is when mechanical failure happens in the cell (or stack) due to
explosion by short circuit caused by the cracking of the electrolyte which arise
due to the expansion of doped ceria electrolyte when exposed to elevated
temperature and varying partial pressure in reducing environment. This is also
confirmed by (Kim, et al., 2020) during a study to understand the electro-chemo-
mechanical behaviour of ceria-based electrolyte. (Kim, et al., 2020) described
that ceria-based electrolyte is open to mechanical stress which is followed by
macroscopic bulk expansion and contraction because of oxygen activity which
can also be seen as a measure of current density in the reducing environment at
elevated temperature which may eventually lead to ceria electrolyte degradation
that emanates on the surface of the electrolyte as cracks and eventually causing
a mechanical failure in the system.
(Kim, et al., 2020) elucidated on this chemical expansion which is showed by
performing an experiment and operated a fuel cell at 3 different current densities
which are a constant load of 0.2A/cm2, a load cycle of 0.2 to 0.12 A/cm 2 and a
load trip of 0.7 to 0 A/cm2. It was observed that the performance of the SOFC
system when it ran in the latest load of 0.7 A/cm 2 gave rise to accelerated cell
degradation compared to others, while minimum degradation is observed when
the cell ran a constant reduced current density of 0.2A/cm 2. According to this test,
the differences in acceleration of degradation in the anode supported cell is as a
result of increase in the water activity (aH2O ) at increased current density which
makes the cell susceptible to electrochemical and mechanical stresses from
increased oxygen partial pressure gradient (aO2 ) through redox cycling.
In other words, (Marochelli, et al., 2012) described chemical expansion as
changes in lattice parameters arising from defects which are caused by
mechanical stresses due to fluctuation between reducing and oxidising
environment, temperature and power demand leading to changes in phase
stability and electrical properties. According to this studies, additional design
consideration is required when cerium oxide is used for electrolyte in
SOFC/SOEC systems because the electrolyte at high gradients in oxygen partial
pressure p(O2) is observed to undergo chemical expansion due to a reduction in
its elastic modulus as a result of increment in lattice parameter. (Marochelli, et

19
al., 2012) Ceria chemical expansion is believed to result from two effects which
are said to happen concurrently along with the formation of a defect. The first is
the ceria reduction process from Ce4+ to Ce3+ leading to an increment in ionic
radius when the valence state of the cation decreases from 4+ to 3+, while the
second effect is the formation of oxygen vacancies which is follow suit by the
electrostatic repulsion of the cations surrounding it.

2.2 Anode degradation

It is observed and of interest the optimisation of the oxygen electrode because
of its large contribution to electrode polarisation which affects the efficiency of
operation by causing a large voltage loss in the system. (Chauveau, et al., 2011)
experimentally observed that the use of oxygen electrode which has the ability to
perform as a mixed ionic and electronic conductor is advantageous for the system
because they tend to reduce the activation polarisation giving rise to a better
electrode performance due to the fact that they extend the reaction zone when
they are employed as MIEC (mixed ionic electronic conductor). (Chauveau, et al.,
2011) confirmed the use of mixed electronic ionic oxygen electrode by using the
Ln2 Ni4+δ type oxide that has the K2NiF4 structure.
This material was selected because of its improved capacity to accommodate an
increased amount of over stoichiometry compared to conventional or
commercially available oxygen electrode such as Sr-doped LaMnO3 (LSM) and
Nd2 Ni4+δ studied by (Chauveau, et al., 2010). The result showed that, over a wide
range of temperature, the oxygen electrode being investigated show a better cell
performance compared to the LSM. This is evident in the evident in the
measurement of current density from the system when using the 3 electrodes
being compared. For Nd2 Ni4+δ a current density of -0.40A/cm2, -0.6 A/cm2 and -
0.87A/cm2 were measured from the SOEC output at temperature of 750°C,
800°C, and 850°C respectively, the cells which Ln2 Ni4+δ was used the current
density obtained were -0.16 A/cm2, -0.39A/cm2 and -0.58A/cm2 for the same
temperature while for LSM the measured current densities were 1.8, 1.8 and 1.1
times larger than Ln2 Ni4+δ and 1.6, 2.9, and 4.4 times larger than Nd2 Ni4+δ. It is
also confirmed that when using Ln2 Ni4+δ and Nd2 Ni4+δ in high temperature

20
steam electrolysis operation the post-test analysis showed no delamination which
is different from when LSF is used.
(Simwonis, et al., 2000) performed a series of experiment test on Ni/8YSZ anode
to study Nickel coarsening in cermet anodes and observed changes in its
electrical conductivity and microstructure. Uniaxial pressing was used to prepare
the powder mixture which is described in (Simwonis, et al., 2011). It appears that
the resistivity of the Ni/8YSZ cermet increases with increasing temperature
because of the metallic conductivity of the Nickel. Due to ferromagnetic-
paramagnetic transition of the metallic phase the decrease in electrical
conductivity appears to be more at 20°C to about 400°C compared to 400 to
900°C. Ceramographic cross section was employed to investigate this decrease
in electrical conductivity, and it shows that the coarsening of Nickel increases with
increasing exposure time, also, Nickel particle distribution also increased i.e., with
increasing exposure period essentially from about 2 to 2.6µm after annealing time
of about 4000h. This is evident in the amount of nickel measured before and after
exposure. It was evaluated that the nickel amount increased by 0.04% to reach
a value of 0.79% after 4000h annealing period.
According to Siemens (Gubner, et al., 1997) another degradation mechanism
which should be noted is the anode cermet degradation through Ni migration,
they investigated the degradation mechanisms in cermet anodes operated in
solid oxide fuel cell mode for a duration of 2000h at a temperature of 950°C in
the ration 1 to 2 of methane to water vapor or in simpler form 1 to 1 for water
vapor to hydrogen. The result depicted no structural changes in the anode except
for a white homogeneous grey surface.
However, observable changes to a mixture of water and methane were seen
which were depicted in a form white coloration of about 0.5-2mm wide found in a
region along the edge next to the fuel inlet and these white shiny crystals
according to EDX consisted of Nickel.
Observable increase in ohmic resistance and anodic polarisation as a result of
nickel loss were noted which leads to a loss in electronic and electrochemical
contact. The result of the experiment simply shows that there is transport of nickel
by volatile species hydroxide in the system and the effect of this transport can be

21
reduced by operating the system at oxygen potential not more than -0.8V which
corresponds to a fuel utilization of 80% at a lowered operating temperature and
it is also advisable according to the study (Gubner, et al., 1997) to partly reform
the fuel if methane is to be used.
(Trini, et al., 2020) also investigated and compared the degradation mechanisms
of anode in both SOFC and SOEC modes and observed that during SOEC mode
Nickel depletion occurs predominantly which is somewhat not seen in SOFC
mode, however, Ni coarsening tend to occur in both operations modes with SOEC
showing more decrement in the amount of percolating triple phase boundary.

2.3 Cathode degradation

The high temperature operation principle of SOFCs offers numerous advantages
and reducing this temperature have drastic effects on the operation which include
an increase in the electrochemical resistance of major components including a
spike in the resistance of the oxygen evolution reaction.
(Ovtar, et al., 2018) studies La0.6 Sr0.4 CoO3−d and LaNi0.6 C𝑜0.4 𝑂3−𝑑 infiltrated
oxygen electrode and reported their differences and similarities in order to
improve the material and structure of oxygen electrode by increasing their
catalytic activity. By this way it is suggested that the surface of oxygen electrodes
can be modified through the introduction of nano-sized catalysts via infiltration.
For LCN infiltrated cells, an increase in polarisation resistance (Rp) was observed
during operation and this is believed to be as a result of loss of contact of the
active surface region as a result of grain growth for the oxygen
reduction/oxidation reaction and it has also been reported to arise due to changes
in the microstructure of the fuel electrode and Nickel migration (Hauch, et al.,
2014).
The addition to the ohmic resistance arises from different processes happening
in different aspects of the bulk of the materials, electronic and oxide-ion transport,
and the permissible contact area of the cell which may be as a result of the cell
set-up. (Ovtar, et al., 2018) Also suggested that the Rs value is complemented
and increased as a result of the growth of nano particles that were infiltrated, this
is said to be caused due to changes in oxide ion transport path which result from
losing percolation in the phase that was electron conducting in the electrolyte.

22
However, a different effect is seen in the activation energy of polarisation in LCN
and LSN symmetrical cells that are made when oxygen is sprayed on both sides
of an electrode on the dense CGO plate. (Liu, et al., 2009) studied microstructural
degradation of YSZ electrolyte and LSM-YSZ interfaces in anode supported
SOFCs. 3 cells were studied at 750°C with a cathode gas of oxygen and air under
a high current density. The nano sized LSM crates reduces in size and flattens
which happens when the chemistry on nanoscale and interfacial structure varies
leading to the degradation of the cathode polarisation resistance. The formed
insulating phases are found in the contact areas of LSM, and they appear in the
nanosized crystals. There is appreciable loss of contact in the LSM which may
account for the increase in the serial resistance Rs in the air cell. While the
interfacial resistance may be held accountable for the high contributions from the
frequency of the cathode electrode process, the interfacial resistance is said to
arise from contact area of LSM/YSZ interface. In the current study (Liu, et al.,
2009) a reduced amount of 50% in the LSM coverage in the air cell correlates
approximately to a rise of 33% in Rs and 90% in Rp.
(Park, et al., 2010) investigated cathode electrode delamination using a single
SOFC with CGO91 electrolyte and a NiO/CGO91 anode in the presence of
PSCF373 cathode. From the result of the experiment, it was observed that the
area specific resistance increases which may be due to different reasons. One
possibility is the propensity of the reaction between the anode and the cathode.
According to the study another credible reason for increase in the area specific
resistance may be as a result of cathode delamination which may occur after
extended time of operation, the thermal expansion coefficient of the cathode and
the electrolyte in the system is quite different which may have given rise to a
thermal mismatch causing the detachment of the cathode material from the
interface which will eventually lead to a loss of active sites or active regions giving
rise to an increase in ASR. This is evident in the SEM analysis which shows
cracks in the PSCF373 cathode at the cathode-electrolyte interphase, these
cracks appear to be the main reason for delamination even though other plausible
reasons such as chromium poisoning and cathode agglomeration may also
contribute to the increase in ASR, which was later confirmed not to be the case

23
from the SEM analysis done after 1000h operation during testing. It shows that
there is no poisoning by chromium because a platinum current collector was
employed.
Numerical analysis was also carried out by (Park, et al., 2010) to better
understand the pathway to degradation in the study by incorporating only
cathodic polarisation resistance which was done to replicate the performance
degradation of the SOFC. As opposed, what was observed in the SEM after test,
there appear to be an increasing difference between experimental result and
analytical result as the time progresses which goes to show that numerically other
degradation mechanisms such as Ni fracture and agglomeration contribute to the
overall degradation factor.
(Tietz, et al., 2006) also performed a long-term SOFC testing whose duration was
about 3000h using La0.58 Sr0.4 Fe0.8 Co0.2 O0.3 (LSCF) cathodes in the presence of
8YSZ electrolyte and Ni/8YSZ anode. The test was carried out to compare the
cathode material performance under deficiency of active sites, that is,
La0.6 Sr0.4 Co0.2 Fe0.8 O3−ɗ and La0.8 Sr0.2 Co0.2 Fe0.8 O3−ɗ . The result showed that the
performance was improved with higher strontium content. According to the study
the presence of active sites with trivalent lanthanum compared to Sr2+ ions on the
active site shows that the latter is better which is observed through the increment
in surface exchange of oxygen as a result of increment in ionic and electronic
conductivity. However, the tendency to compromise on mechanical stability is
also increased.

2.4 Poisoning
(Chen, et al., 2015) first studied the performance of SOEC when it is incorporated
with a chromium forming stainless steel alloy interconnect due to its high thermal
and electrical conductivity together with its ease of fabrication. Electrochemical
behaviour of La0.8 Sr0.2 Co0.2 MnO3 (LSM) oxygen electrode was investigated at
800°C under a current density of 200 and 500A/cm 2 in a simulate SOEC condition
incorporated with a chromium containing steel type interconnect. The
performance of the system was compared when interconnect was used to when
it was not. The result of the study indicated that chromium deposition occurs on
the entire bulk of the of the electrode and in the electrode/electrolyte interphase.

24
The chromium content in these regions was quantified and it appeared that the
amount of chromium in present in the interface was more compared to that in the
bulk of the electrode. This result by (Chen, et al., 2015) goes to show that the Fe-
Cr interconnect poisons the LSM oxygen electrode by affecting the
electrocatalytic activity of the electrode when operated in SOFC mode. This is
similar to observed in the work carried out by (Chen, et al., 2011) in SOFC
operating condition.
However, it has also been reported by (Zhen, et al., 2008) that the deposition of
chromium is not preferentially observed at the interface of the electrode and
electrolyte and on the YSZ electrolyte but are also seen in the electrode bulk. The
result for the preferential deposition of chromium in the interface but not in the
electrode bulk is accompanied by the formation of the Cr3O4 and Mn3O4 spinel
which in SOFC mode is contrary to the work carried out by (Chen, et al., 2011).
Sulphur poisoning is also one of those poisonings that induce the effects of
degradation. (Kushi, 2017) also studied the effects of sulphur poisoning on the
extent of degradation in oxygen electrodes of a solid oxide electrolysers and fuel
cells. The oxygen electrode employed is that lanthanum strontium cobalt oxide
(LSC) with an active area of 0.785cm2. Generally, the result during durability
testing showed that there is high degradation rate in both modes of operation and
the main cause of degradation in both modes is said to be as a result of the
polarisation overpotential.
However, changes were seen in voltage drops in both SOFC and SOEC mode
during current interruption which points to differences in degradation mechanism.
The degradation differences in high resistance arc may be due to the migration
of oxygen ion between oxygen electrode and the electrolyte while that seen in
the low resistance in the impedance spectra is said to be as a result of surface
diffusion and dissociation of oxygen since it continues to increase with increase
in steam content. (Yang, et al., 2017) summarised the effect of chromium
poisoning on cathode material to include that it reduces the surface segregation
of the cathode material which induces chromium decomposition by increasing
material resistance while also enhancing the stability.

25
Silicon poisoning and its effects have also been extensively studied in literature.
(Zhao, et al., 2015) experimented to examine the Silicon induced degradation
effect on a Pr0.1Ce0.9O2−δ (PCO) electrode that was prepared using the Pechini
method. The result showed that the electrode quickly degrades by a factor of 40
times initial degradation rate which could be attributed to the accumulation and
deposition of siliceous phase onto the surface of the PCO film. The aging process
was reversed by depositing oxides of La and Sm, however, treating the surface
with other oxides (such as Tn, Al, Nb, Zn) did not seem to recover the aging effect
of the electrode which is done by recovering the oxygen exchange kinetics. On
the other hand, (Schrodl, et al., 2015) studied the combined chromium and silicon
poisoning effect on the long-term stability of La0.6Sr0.4Co𝑂3−𝛿 (LSC) and
La2NiO4+δ operated at intermediate temperature upon exposure to humid air that
contains silicon and chromium elements. The result showed that the oxygen
surface exchange coefficient reduces in both of the cathode materials which is
said to be as a result of the formation of crystallites on the surface of the sample
which goes to depict the decomposition of the perovskite phase caused by the
formation of SrCrO4.

26
 Chapter 3

3 METHODOLOGY
This chapter describes the methods and approaches followed including test to
address the research objectives around defects and degradation hypotheses.
The starting section of the chapter includes a review of the purpose of the study
and restatement of the research objectives. The subsequent section includes cell
and stack analysis and concept including testing procedures.
The purpose of this study is to analyse degradation mechanism and
microstructural changes which arise as a result of operating conditions and other
factors. The following research questions were investigated to cater for the
proposed aim of the study.
i. What are the observable degradation modes in SOEC which eventually
lead to system failure?
ii. What microstructural changes can be observed in the cells after
failure?
iii. Analysis of test data to understand what effects cell arrangement have
on the resistance offered to the flow of current towards the
interconnect.

3.1 Overview of post-test analysis

In other to envisage reliable and cost-effective solid oxide electrolysers and fuel
cells and to further improve upon their performance for long-term operation and
mobile applications, it is therefore important to understand plausible underlying
reasons behind stack failures and long-term degradation. To do this it is
necessary to put post-operational inspection technologies and activities in place,
such post-test analyses may include advance characterisation methods which
are essential to understand cell performance under the framework of systemic
testing. Stack experiments are initiated to better understand different degradation
and performance inhibition mechanisms contributing to the overall stack failure;
thus, it is important to consider not only the stack operation details but also all
details from individual stack assembly and production stages and components
with respect to quality assurance and other changes in the inlet conditions. Stack

27
dissembling is part of post-test analysis which is carried out by experts depending
on the prospective result of the stack operation after failure.
(Batfalsky, et al., 2016) summarized the reasons for post-test analysis to include
the need to understand typical and unusual operational behaviour.
- The need to characterize operational failures emanating from short
circuiting, voltage breakdown, leakages, low open circuit voltage and other
external factors.
- The investigation of specific mechanisms and how they affect stack
operation, examples include metal dusting, poisoning by chromium and
degradation phenomena which different component of the stack is
susceptible to which may also be induced from changes in operational
conditions.
- The need to observe microstructural changes and/or material chemistry
and geometrical changes as compared to initial design.

3.2 Post-test data approach

The initial approach of the post-test analysis to be followed is dependent on
the objective which the experiment was carried out to investigate. One of the
initial important questions which is posed prior to stack dissembling is: Will the
components of the stack be analysed individually? which means the stack
should be dissected plane-by-plane or a section of the stack should be kept
intact for analysis to extract certain performance and degradation information
which means that part of the stack may be retained by embedding it in
polymeric resin to keep the geometry and contact situation of such part
In this study the reason for carrying out a post-test analysis aligns well with
one of those suggested by (Batfalsky, et al., 2016), which is to investigate and
analyse defects, degradation mechanisms and changes in microstructure and
how they affect cell performance. The dissembling follows that the cell be
analysed individually, and subsequent layers inspected one after the other to
understand what is going on anomaly in each layer. An efficient tracking
system of materials and components must be available to allow for a good
comparison between pretested and post tested materials and changes in
processes and procedures. The reproducibility of materials and processes are

28
 maintained by ensuring that all cells and its component are tracked and
numbered sequentially including handling procedures for processing steps
and standardized stack operation and dissembling protocols. All information
is collected and stored on a central server which allows for an effective
uninterrupted chain of information from the initial starting stages to material
conditions after post-test analysis, this also allows for reasonable fact-based
inferences to be made.

3.3 Characterization methods

3.3.1 Leak Test
One of the first tests in system fault diagnostics is leak testing, which is done on
cells and stack to check for cracks and mechanical faults between layers causing
degradation. The driving force for leakages in cells may be as a result of pressure
difference leading to a viscous leak in which the leak has the same composition
as the gas flowing in their different designated channel or as a result of
concentration difference whose leak often does not have the same composition
as the bulk of the gas. For this leak driver (Halinen & Pennanen, 2015) elucidated
that the composition of leak arising due to concentration changes depends on the
diffusivity of various components of the bulk gas. In both leak driver there is a
resultant change in the composition of the air and fuel gas systems in an identical
manner i.e., combustion of fuel to carbon dioxide occurs in fuel leaking into the
air system while flammable substances are oxidized in the fuel gas which
happens when air leaks into the fuel system. It is thus important to have sufficient
gas tightness in order to realize a robust SOEC and SOFC systems.
3.3.2 Optical microscopy and visual inspection
Optical microscopy is used to characterise contact surfaces to evaluate
geometrical issues of the cell. Changes in material topology and surfaces are
assessed via different surface analytical method. This method of characterisation
is chosen because components of the SOEC system and cells show behaviours
or characteristics at the near-surface region whose properties tend to differ from
those of the bulk of the material. Mostly all surfaces of cells in a stack contains
some form of defects which may occur as a result of contamination, deformation,
delamination, cracking, heating. Having access to surface topography data

29
provides valuable information of surface properties of materials of the
SOEC/SOFC system.
(Miyoshi, 2002) also highlighted that occurrences such as corrosion, oxidation,
fracture, and contamination are also affected to a large degree by surface
characteristics which comprises of a few hundred atomic layers. Visual inspection
is also a curious way to first see what defects or characteristics on the cells post
operation, defects such as corrosion, sealing wear and other visible gross
delamination.

Figure 3.1- Flow chart of post-test analysis characterization techniques

30
3.3.3 Scanning Electron Microscopy (SEM)
The scanning electron microscopy is one of the available characterization
techniques that is used in this study for cell characterization. The SEM technique
is superior to the optical microscopy in the analysis and interpretation of
topography and changes in microstructure of materials. The working principle of
scanning electron microscopy is based on the analysis of dislodged electrons
from their orbitals as a result of bombardment of a solid specimen with an incident
primary electron beam. The sophistication of the analysis of the microstructure or
the depth of the microstructure which will be observed is dependent on the energy
of bombardment in volts in the incident electron beam giving rise to different types
of dislodged electrons such as secondary electrons, backscattered electrons, and
characteristic x-rays.
3.3.4 Energy Dispersive X-ray Spectroscopy (EDS)
Energy dispersive x-ray spectroscopy is a type of spectroscopy that is used for
chemical characterization by analysing the sample through the capturing of
photonic energy emitted in order of x-ray detector from the sample when the
sample is bombarded with primary electron beam. The photonic x-ray captured
are then used to characterize the elemental composition of the said specimen.
Every element has their own characteristic photonic x-ray energy transition, by
knowing this, the machine is able to seamlessly analyse the elemental
composition of the specimen.

3.4 Experimental
3.4.1 Stack construction
All the materials used for the construction of the metal supported cell including
the steel substrate are carefully selected in other to eliminate thermal mismatch
from non-related coefficient of thermal expansion. The ceramic material is printed
onto the top of the ferritic stainless-steel substrate. The steel substrate is made
porous by laser drilling holes in the materials to allow for gas transport where
required and the corresponding cell chemistry is then printed on top and then
fired. The ceramic layer is deposited onto the surface by screen printing
processes which does not require temperatures typically above 1000°C. The
detailed description of the cell constructed is reported by (Bance, et al., 2003).

31
Figure 3.2 also showed the schematic representation of the stack repeating unit.
(Leah, et al., 2013) highlighted that one of the advantages of a metal supported
cell design is that it enhances the sealing of the cell and the metal interconnect
by conventional metal joining techniques which overcome a major problem by
avoiding the use of ceramic-metal seals which have the tendency to be inherently
fragile.

Figure 3.2- Schematic representation of a.) a steel cell from Ceres Power b.) a
stack repeating unit (Leah, et al., 2015)

32
3.4.2 Stack operation and post-operation analysis
Three stacks were built and tested at different voltages of 1.12V, 1.2V and 1.10V.
The stacks were operated at 3 different temperatures with the third stack
operated at the highest temperature at 1.10V. The 20-cell stack operated such
that a mixture of steam and hydrogen was fed to the hydrogen electrode (H2 O/H2 -
0.5). The current density of the stack was measured over the hot hours of 5000h
for first two stacks operated at 1.12V and 1.2V and 12000h for that operated at
1.10V though the timespan of interest in this study is however 5000h. During the
operation, flammable gas detectors were present in the test area to detect
hydrogen leakages. The stack was then cooled down to room temperature by a
robust balance of plant that supplies ambient air to the stack.
The stack was dissembled and examined post-test. Three cell samples in total
from different stacks were chosen in this study for post-operation analysis. The
cell microstructure, topology of air electrode, electrolyte cracking, and changes
were characterised with scanning electron microscopy and optical microscope.
The sample cells were leak tested prior to other characterisation analysis.
Adhesive test was also done on the air electrode to detect any adhesive changes
in the electrode which might indicate high tendency of the electrode to dust or
delaminate.

Table 3.1- Operating conditions used for test.

Cells Voltage [V] Fuel Utilisation [%] Duration of interest [h]

1 1.20 50 5000
2 1.12 50 5000
3 1.10 50 5000

33
 Chapter 4

4 RESULT AND DISCUSSION

4.1 Results from Post-test Analysis
Electrical Performance
Figure 4.1, Figure 4.2, Figure 4.3 shows each cell voltages and their
corresponding current density for cells 1, 2 and 3 respectively. An average current
density of 0.199Ω/cm2, 0.201Ω/cm2 and 0.285Ω/cm2 was achieved respectively
at their different temperature dependent open-circuit voltage (OCV) of 1.153V,
1.170V and 1.217V as mentioned. According to the high OCV value it can be
drawn that various parts of the cell(s) were not severely damaged during
operation and a good electrode/electrolyte interface contact is present.
However, it can be observed that over time along the duration of 5000h the
current density falls gradually which can be associated to some sort of
performance degradation as the lifespan grows. A drop or a sharp increase in the
applied voltage may be a sign indicating that there is some sort of anomalous
occurrence at that instance in the lifespan of the cells which may be as a result
of stack structure, compression forces, material combination,
delamination/defects and degradation leading to loss of a portion of the
electrochemical active contact area, other problems may also arise from
poisoning, gas distribution and sealant material.

34
 Vap=1.2
Jav=0.199

Figure 4.1- Electrical Performance for Cell 1

35
 Vap=1.12
Jav=0.201

Figure 4.2- Electrical Performance for Cell 2

36
 Vap=1.10
Jav=0.285

Figure 4.3- Electrical Performance for Cell 3

37
4.1.2 Area Specific Resistance (ASR)
Another measure of performance is the Area Specific Resistance, which is the
resistance offered to the flow of electrons and a measure of performance
degradation of the cell over a given period of time. This is depicted in Figure 4.4
for up to a period of 1000h. It appears that cell 3 has the lowest ASR-evolution
followed by cells 1 and 3 with a rate ration of 1, 1.54, 1.60 in order of cell2: cell1:
cell3. The reason for the lowest ASR value of the third cell may be due to the
operating voltage of 1.1V which Is lower than those of the other cells.
Furthermore, temperature has been reported to decrease ASR evolution in cells
with semiconductor and superconductor electrochemical components (Megel, et
al., 2011) as cell 3 was operated with the highest temperature.

Figure 4.4- Area Specific Resistance (ASR) for cell samples

38
4.1.3 Adhesion test
To check if the air electrode of the cell retained their denseness a tape casting
test was done on the cell samples. The result showed that Cell-3 had the most
loosened air electrode which might be as a result fuel or other material infiltration.
This is also supported by the leak test result in Table 4.1. The leak test result
showed that Cell 3 compared to other samples had a gross leakage.

Figure 4.5- Tape casting to observe variation in air-electrode adhesion

properties.

Table 4.1- Operating condition for cell testing

TP=50.07mba, Pass≤ 0.15

Cells 1 2 3
Leak rate sccm Pass Pass Fail

39
4.1.3 Optical Microscopy

The cell samples were optically inspected. Attention was particularly paid to the
air electrode and the electrolyte for defects and delamination on each sample.
Cells 1 and 3 typically show the same but with varied sizes of the so-called
volcano defects. The volcano defect is so named because it appears to be a
result of eruption of components from layers below the affected layer, this defect
was also seen on the electrolytes of the cell samples using microscopy. The air
electrode was removed prior to inspecting the electrolyte to gain access to the
electrolyte. Debris were also seen on the defects and cell area which may have
arisen during operation or perhaps due to cell handling. The advent of this defect
which has not fully broken out is also seen on Cell 3 as shown in Figure 4.6
Cell 2 is characterized by delamination marks; local combustion marks were also
seen on the cell air electrode in Figure 4.7 which could have arisen as a result of
short circuit emanating from electron leakage. All these defects, delamination and
cracks reduces the electrochemical active contact which is in line with (Yan, et
al., 2017) in buttressing that the reduction or loss in active area of a cell electrode
plays a pivotal role towards the overall performance of the scaled-up cell.
According to (Dey, et al., 2011) the loss of active area on the anode and cathode
of up to 2.5% and 6.7% respectively typically starts to have a staggering effect
on the performance of the cell. The difference in the electrochemical performance
of the cell at the start of the test can be ascribed to the resistance that exists
between the cell and the adjacent component when the cell is still unaffected at
the start of the operation.

40
Figure 4.6- Optical microscopy of cell defects in two lighting: A- Delamination
accompanied by an eruption, B- Volcano defect, C- Advent of volcano defect
eruption.

Figure 4.7- Optical microscopy of air electrode degradation in two lighting: A-

Combustion marks, B and C- Electrode delamination

41
Figure 4.8- Electrolyte degradation in form of volcano defects in the same area
on cell samples under two lighting

42
4.2 Quantifying Nickel depletion
To understand the extent of Nickel depletion on the Hydrogen electrode, Cells A
and B which were operated for 5000h were quantified to evaluate the depletion
of Ni from the Ni-cermet electrode-electrolyte interface. Ni depletion and
migration has previously been studied and reported (Uchida, et al., 2021). The
effect of this depletion or migration affects the availability of TBP and directly
affect performance degradation. The cells A and B were operated at varied
operating conditions and compared with a non-operated reference cell.
Scanning electron microscopy images of the hydrogen electrode were taken at
the inlet and further Ni quantification was done using a special Fiji-Image-J
software (the characteristic black and white images as seen in (Error! Reference
source not found.)). The software is used to isolates Nickel distribution in the
electrode. The amount of Ni at a 1µm distance starting at the interface with the
electrolyte to a tenth-µm was computed for the cells as seen in (Table 4.2). This
result shows that there is somewhat an even distribution of Nickel in the non-
operated cell, however cells A and B appear to have an increased Ni distribution
over a 10µm length from the interface with their corresponding standard deviation
of 3.34 and 4.40 respectively. The normalised plot of this distribution is shown in
Error! Reference source not found.

43
Table 4.2- Normalised Nickel distribution result for reference cell, cell A and B

%Area occupied by Ni distribution for each µm area away from

interface
µm Reference Cell Cell A Cell B
1 0.783 0.80 0.76
2 0.797 0.89 0.75
3 0.876 0.08 0.84
4 0.932 0.81 0.90
5 0.716 0.69 1.00
6 0.816 0.87 0.79
7 0.845 0.86 0.75
8 0.856 0.81 0.90
9 1.000 1.00 0.82
10 0.876 0.88 0.76

44
Figure 4.9- SEM image and the binary image (Left and Right respectively) of the
Reference cell, Cell A and Cell B

45
Nickel Area Fraction (%)

0 2 4 6 8 10 12
Height
Cell A Cell B Refence Cell

Figure 4.10- Plot of Nickel Distribution

46
4.3 In-situ Degradation Data Analysis Result
4.3.1 Fluctuating behaviour of ASR start-of-life value.
The area specific resistance associated with different tests is analysed to further
understand resistance to current flow in relation to interconnect arrangement in
stacks. In a stack the cells are arranged in an alternating manner to give space
for the protruding dimple and prevent dimples from crushing one another, this
arrangement enables us to group the cells into layers such as odd and even
layers, such that all odd-layer (A-layers) cells align and have the same
arrangement and all even layer cells also align in the same manner (B-layers).
The result showed that there is a fluctuating behaviour of ASR start-of-life value
within a stack as depicted in Figure 4.11. The fluctuation was analysed such that
ASR data for stacks that were built for the same test purpose were grouped and
examined together. However, not all stacks with the same test purpose showed
similar fluctuating behaviour, the behaviour is predominant in some stacks than
others, an example of this is depicted in Figure 4.12

47
Figure 4.11. This is the fluctuating behaviour as seen in 3 different stacks having
the same material composition and the same test purpose of ASR degradation in
stamped and post-form coated interconnect.

Figure 4.12. A and B effect Predominant in Stack A1 and A2 than in B1 and B2

(Stack A1, A2 have the same composition and are tested for the same purpose.
So does Stack B1 and B2)

48
4.3.2 Effect of stack operating temperature on ASR start-of-life.
There are certain operating conditions which affect the resistance to current
density in SOFC/SOEC one of which is the temperature. The effect of
temperature on the ASR start-of-life behaviour of 6 stacks operated at 610C,
630C and 650C were analysed. Globally, the analysis depicted that as the
temperature increases the resistance offered to the flow of current decreases.
This is this is shown in Figure 4.13

Figure 4.13- Effect of temperature on global ASR behaviour

49
4.3.3 Odd and even layers comparison
Tests that were done at a single temperature were analysed to observe the
behaviour of odd and even layers to ASR at that temperature. It was observed
that ASR generally increases in even layers i.e., the odd layers offer less ASR to
the stack than the even layers. The result Is shown in Figure 4.14 for experiments
at 610°C and Figure 4.15 for 630°C.

Figure 4.14- ASR behaviour for a stack operated at 610C.

50
Figure 4.15- ASR behaviour for a stack operated at 630C.

51
4.4 Discussion
Figure shows that the area specific resistance of the cells reduces as the
temperature increases from 605C to 660C which can be attributed to the
behaviour of semiconductors and superconductors as majority of the printed
layers are semiconducting in nature. Also, looking at each cell’s ASR evolution,
it shows that the ASR growth can be fitted best linearly over time which may be
caused by different factors including electrode delamination after prolong
operation. The interface between the air electrode and the electrolyte may also
become detached during a 5000h-test at 605C arising from increased difference
in the thermal expansion coefficient (TEC).
Delamination and defect as seen in Figure 4.6 in the microscopy analysis of each
cell causes the electrochemical performance of the cell to depreciate gradually
by making it lose electrochemically active reaction sites. The presence of cracks
in the electrode topography also indicates that there is tendency for fuel crossover
and diffusion and migration of substances in-between layers to have happened
which further polarises the electrodes. The cell design however is a metal
interconnect supported system; therefore, the most important electrolyte
degradation is those resulting in phase instability and non-compatibility with
electrode materials and atmosphere.
The use of ceria electrode offers some drawbacks, this is because ceria alone as
an electrolyte is a mixed ionic-electronic conductor. This simply means that in the
presence of a strong reducing environment there is tendency of electron leakage
to take place in the cell at about 500C causing a significant drop in efficiency
through electronic short-circuiting. However, a significant and needed advantage
of ceria is its resistance to interfacial reactions with neighbouring materials used
for high performance oxygen electrodes which are employed in most commercial
SOFCs and SOECs
For the Perovskite air electrode, most electrodes for SOC are the mixed-
conducting perovskite type oxides with a general composition of AB𝑂3−𝛿 . The A-
site are usually tri-valent lanthanide ion (La3+, Gd3+…) while the B-site is often
occupied by one or more tri-or tetra-valent 3-d transition metal ions, for example.,
Mn3+/4+, Co3+/4+, N3+/4+. The oxygen stoichiometry or oxygen deficiency, 𝛿, varies
by order of magnitude depending on the oxygen partial pressure. In SOEC mode
52
the oxygen activity is expected to increase because of the transport of ionic
oxygen for oxygen molecule formation at the electrode, therefore, the local partial
pressure of oxygen tends to influence the oxygen electrode conductivity and
eventually its mechanical stability (in worse cases) through fuel starvation arising
from low steam utilization. This is detected during testing as a drop in OCV (When
OCV remains constant, it means that there is no gaseous or electronic leakage)
However, for the Ni-cermet anode. A promising Ni-cermet anode is the LCN
(LaCo1−x Nix O3−δ ) which when x=0.4 and 0.6 (LCN40 and LCN60) were reported
by (Hjalmarsson & Mogensen, 2011) to possess a good electronic conductivity
with a small thermal expansion mismatch with a variety of neighbouring materials.
It has previously been mentioned that loss of active sites or TPB causes cell
performance degradation, but this is not the only causing leading up to cell
performance degradation. In Ni-cermet hydrogen electrode, the Ni structure tend
to percolate through the support structure onto the electrochemically active triple
phase boundary sites which also affects cell performance. This phenomenon has
been studied by (Tanasini, et al., 2009)and the mechanism behind Ni percolation
and loss is attributed to Ni particle growth; formation of volatile Ni species leading
to evaporation and the relocation of impurities to Ni-Ni connection points.
Another contributing factor which has also been reported in literature is the
contribution of inlet gas Impurity concentration (ppb level). This has been reported
(Knibbe, et al., 2011) to exacerbate the degradation in electrodes in SOEC mode,
that is, a continuous supply of gas/water vapor allows the accumulation of
impurities on the active triple phase bouse (TPB) sites which over time worsens
the degradation and eventually affecting the overall cell performance.

53
 Chapter 5

5 CONCLUSION AND RECOMMENDATIONS

5.1 Conclusion
Post-test analysis of degradation, defects, and delamination and how they
contribute to performance degradation was investigated. When defects grow or
cell delaminates it leads to loss of available area for electrochemical activities
which leads to the accumulation of current locally in areas that are still intact. This
in turn give rise to an increased activation loss and increased ohmic resistance
in the electrodes and electrolyte respectively. Based on observed degradation
phenomena from microscopy analysis, it is evident that cell delamination, volcano
defects, and cracks all contribute to the total performance degradation of the cells
which will eventually lead to stack failure resulting from short circuiting
Furthermore, design/architecture and interconnect degradation and corrosion
also affect the overall system performance. From the in-situ data analysis it is
evident that the fluctuating A and B effect is present in the stacks, and it is more
visible in some than others. It is also observed that the ASR decreases globally
with increasing temperature. Based on statistical data, at a given operating
temperature the ASR increases towards the even layers compared to its
behaviours in odd layers. Some of the data that were also compiled were not
representative which may be due to irreproducibility of the experiments,
stochastic nature of corrosion and/or impact of debris or other contaminants.
All of this affect the electrochemical performance of the cell by lowering the
amount of power or current density which can be drawn from the system. This
performance degradation can be attributed to a gradual reduction in the chemical
potential of the reactive species and activation loss of the electrolyte which is
evident as seen in the increasing area specific resistance in Figure 4.4.
In conclusion, it is worth mentioning that a lot of factors goes into the kind of
degradation phenomena which is seen during post-test analysis of an SOEC
system, some of these factors include operating condition, fluctuation in fuel
utilisation, thermal expansion coefficient mismatch, a reduction or increment in
material thermal expansion coefficient during operation, flow pattern, impurities
from environment and balance of plant etc. Material research to optimise
54
performance and improve the durability of the SOEC/SOFC system for fight
against climate change and the growing energy demand is still ongoing. However,
significant contributions have been made towards making this a reality and
commercialising SOEC and SOFC systems by some businesses namely Ceres
Power Limited in the United Kingdom and Bloom Energy in the United States.

5.2 Recommendation

There are currently no ways to probe SOEC/SOFC stacks during operation which
makes shut down important for post-mortem analysis. Methods and technologies
should be researched towards probing during operation to better understand the
evolution of degradation from the early stages. This will further increase the
understanding real-time performance and degradation.

55
References
Bance, P. et al., 2003. Spinning-out a fuel cell company from a UK University-"
years of progress at Ceres Power. Journal of Power Sources, pp. 1-5.
Bastidas , D. M., Tao, S. & Irvine , J. T., 2006. A symmetrical solid oxide fuel cell
demonstrating redox stable perovskite electrodes. Journal of Material Chemistry,
Issue 17.
Basu, R. N., 2007. Recent Trends in Fuel Cell Science and Technology. In:
Materials for Solid Oxide Fuel Cells. New York: Springer, pp. 286-331.
Batfalsky, P., Malzbender, J. & Menzler, N. H., 2016. Post-operational
characterization of solid oxide fuel cell stacks. International Journal of Hydrogen
Energy, pp. 1-13.
Benamira, M. et al., 2023. New anode materials for IT- SOFC derived from
elctrolyte Ba_0.5 La_0.5 〖In_0.3 Ti〗_0.1 Mn_0.7 O_3 by lanthanum
manganese doping. Solid State Ionics, pp. 1-8.
Bossel, U. & Eliasson, B., 2021. Energy and the Hydrogen Economy. p. 36.
Chauveau, F. et al., 2010. A new anode material for solid oxide electrolyser: The
neodymium nickelate Nd_2 Ni_(4+ɗ). Journal of Power Sources, pp. 744-749.
Chauveau, F., Mougin, J., Mauvy, F. & Bassat, J.-M., 2011. Development and
operation of alternative oxygen electrode materials for hydrogen production by
high temperature steam electrolysis. International Journal of Hydrogen Energy,
pp. 1-6.
Chavan, A. U. et al., 2012. Effect of variation of NiO in properties of NiO/GDC
(gadolinium doped ceria) nano-composite. SciVerse ScienceDirect- Ceramic
International, pp. 3191-3196.
Chen, K. et al., 2015. Chromium deposition and poisoning of La_0.8 Sr_0.2
Co_0.2 MnO_3 oxygen electrodes of solid oxide electrolysis cells. Faraday
Discussion, pp. 1-20.
Chen, X., Zhang, L., Liu, E. & Jiang, P. S., 2011. A fundermental study of
chromium deposition and poisoning at (La_0.8 Sr_0.2 )_0.95 (Mn_(1-x) Co_x )
O_(3±δ) (0.0≤x≤1.0) cathodes of solid oxide fuel cells. International Journal of
Hydrogen Energy, pp. 1-17.

56
Ciacchi, F. T., Crane, K. M. & Badwal, S. P., 1994. Evaluation of commercial
zirconia powders for solid oxide fuels. Solid State Ionics, 73(1-2).
Dalslet, B. et al., 2006. Assessment of doped ceria as electrolyte. Journal of Solid
State Electrochemistry, pp. 547-561.
Dey, T. et al., 2011. Diagnosis of scale up issues associated with planar solid
oxide fuel cells. International Journal of Hydrogen Energy, pp. 1-10.
Ding, H. & Xue, X., 2010. Cobalt-free layered perovskite GdBaFe_2 O_(5+x) as
a novel cathode for intermediate temperature solid oxide fuel cells. Journal of
Power Sources, pp. 4718-4721.
Fergus , J. W., 2006. Electrolytes for solid oxide fuel cells. Journal for Power
Source, pp. 30-40.
Gubner, A. et al., 1997. Investigations into the degradation of cermet anode of a
solid oxide fuel cell. Proceedings of the electrochemical society, pp. 1-8.
Halinen, M. & Pennanen, J., 2015. Analysis of Leakages in a Solid Oxide Fuel
Cell in a System Environment. In: Fuel Cells, pp. 1 -12.
Hauch, A., Hagen, A., Hjelm, J. & Ramos, T., 2014. Sulfur Poisoning of SOFC
Anodes: Effect of Overpotential on Long-Term Degradation. Journal of The
Electrochemical Society, pp. 1-11.
Hjalmarsson, P., Sogaard, M., Hagen, A. & Mogensen, M., 2008. Structural
properties and electrochemical performance of strontium- and nickel-substituted
lanthanum cobaltite. Solid State Ionics, pp. 636-646.
Hussain, S. & Yangping, L., 2024. Review of solid oxide fuel cell materials:
cathode, anode, and electrolyte. Energy Transition, pp. 113-126.
IRENA, 2018. Hydrogen from renewable power- Technology outlook for the
energy transition. [Online]
Available at: www.irena.org
[Accessed Monday February 2023].
Jiang, S. P. & Li, Q., 2022. Introduction to Fuel Cells. Singapore: Springer.
Kim, Y.-D.et al., 2020. Degradation studies of ceria-based solid oxide fuel cells
at intermediate temperature under various load conditions. Journal of Power
Sources, pp. 1-10.

57
Knibbe, R. et al., 2011. Durability of Solid Oxide Cells. Green, Volume 1, pp. 1-
29.
Kushi, T., 2017. Effects of sulfur poisoning on degradation phenomena in oxygen
electrodes of solid oxide electrolysis cells and solid oxide fuel cells. Internaional
Journal of Hydrogen Energy, pp. 1-10.
Laosinpojana, N. et al., 2009. Reviews on Solid Oxide fuel cell technologies.
Engineering Journal, 13(1), pp. 1-19.
Leah, R. et al., 2013. Low-Cost, REDOX-Stable, Low-Temperature SOFC
Developed by Ceres Power for Multiple Application: Latest Development Update.
ECS Transactions- The Electrochemical Society, pp. 1-10.
Leah, R. et al., 2015. Ceres Power Steel Cell Technology: Rapid Progress
Towards a Truly Commercially Viable SOFC. ECS Transactions, pp. 1-13.
Lee, J. S., Yong, S.-M., Kim, D. S. & Kim, D. K., 2012. Cobalt free composite
cathode for SOFC: Brownmillerite-type calcium ferrite and gadolinnum-doped
ceria. International Journal of Hydrogen Energy, pp. 17217-17224.
Lenser, C. et al., 2022. Electro-chemo-mechanical analysis of a solid oxide cell
based on doped ceria. Journal of Power Spurces, pp. 1-11.
Liu, Y. L. et al., 2009. Microstructural studies on degradation of interface between
LSM–YSZ cathode and YSZ electrolyte in SOFCs. Solid State Ionics, pp. 1-7.
Mahato, N. et al., 2015. Progress in material selection for solid oxide fuel cell
technology: A review. Progress in Materials Science, pp. 141-337.
Marochelli, D., Bishop, S. R., Harry, T. L. & Yildiz, B., 2012. Understanding
Chemical Expansion in Non-Stoichiometric Oxides: Ceria and Zirconia Case
Studies. Advance functional Materials, pp. 1-8.
Megel, S. et al., 2011. Area specific resistance of oxide scales grown on ferritic
alloys for solid oxide fuel cell interconnects. Journal of Power Sources, 196(17),
pp. 7136-7143.
Miyoshi, K., 2002. Surface Characterization Techniques: An Overview.
NASA/TM, pp. 1-51.
Nations, United;, 2016. The Paris Agreement. Denmank, s.n.

58
Ovtar, S., Hauch, A., Veltze, S. & Chen, M., 2018. Comparison between La_0.6
Sr_0.4 CoO_(3-d) and LaNi_0.6 Co_0.4 O_(3-d) infiltrated oxygen electrodes for
long-term durable solid oxide cells. Electrochemical Acta, pp. 1-12.
Park, K. et al., 2010. Fast performance degradation of SOFC caused by cathode
delamination in long-term testing. International Journal of Hydrogen Energy, pp.
1-8.
Patonia, A. & Poudineh, R., 2022. Cost-competitive green hydrogen: how xto
lower the cost of electrolyser?. Oxford Institute of Energy Studies, pp. 1-45.
Schrodl, N. et al., 2015. Long-term stability of the IT-SOFC cathode materials
La0.6Sr0.4CoO3 − δ and La2NiO4 + δ against combined chromium and silicon
poisoning. Solid State Ionics, pp. 1-10.
Simwonis, D. et al., 2011. Material characterization in support of the development
of an anode substrate for solid oxide fuel cells. Journal of material research, pp.
1508-1518.
Simwonis, D., Tietz, F. & Stover, D., 2000. Nickel coarsening in annealed
Ni/8YSZ anode substrates for solid oxide fuel cells. Solid State Ionics, pp. 1-11.
Stanislowski, M. et al., 2007. Reduction of chromium vaporisation from SOFC
interconnectors by highly effective coatings. Journal of Poer Source, 164(2), pp.
578-579.
Tanasini, P. et al., 2009. Expeimental and Theoretical Investigation of
Degradation Mechanisms by Particle Coarsening in SOFC Electrode. Fuel Cells:
From Fundermental to Systems, 9(5), pp. 740-752.
The, D. et al., 2015. Microstructural comparison of solid oxide electrolyser cells
operated for 6100h and 9000h. Journal of Power Sources, pp. 1-11.
Tiets, F., Sebold, D., Brisse, A. & Schefold, J., 2013. Degradation phenomenon
in a solid oxide electrolysis cell after 9000h of oper. Journal of Power Source, pp.
1-7.
Tietz, F. et al., 2006. Performance of LSCF cathodes in cell tests. Journal of
Power Sources, pp. 1-3.
Treut, H. L. et al., 2007. Historical Overview of Climate Change Science. p. 36.

59
Trini, M. et al., 2020. Comparison of microstructural evolution of fuel electrodes
in solid oxide fuel cells and electrolysis cells. Journal of Power Sources , pp. 1-
10.
Uchida, H., Brito, M. E. & Nishino, H., 2021. Depth-direction analysis of nickel
depletion in a Nigadolinia-doped ceria hydrogen electrode after steam
electrolysis operation. Journal of Ceramic Society of Japan, pp. 1-7.
United Nations, 2016. The Paris Agreement, Denmanrk: s.n.
Yahiro, H., Eguchi, K. & Arai, H., 1989. Electrical properties and reducibilities of
ceria-rare earth oxides system and their application to solid oxide fuel cell. Solid
State Ionics, 36(1-2), pp. 71-75.
Yan, D. et al., 2017. Performance degradation and analysis of 10-cell anode
supported SOFC stack with external manifold structure. Energy, pp. 1-8.
Yang, Z., 2013. Recent advances in metallic interconnects for solid oxide fuel
cells. Materials review, pp. 39-54.
Yang, Z. et al., 2017. A short review of cathode poisoning and corrosion in solid
oxide fuel cell. International Journal of Hydrogen Energy, pp. 1-12.
Zekri, A. et al., 2017. Nickel Depletion and Agglomeration in SOFC Anodes
During Long-Term Operation. Fuel Cells- From Fundermentals to Systems.
Zhao, L. et al., 2015. Improving the Si impurity tolerance of Pr0.1Ce0.9O2-δ
SOFC electrodes with reactive surface additives. Chemistry of Materials, pp. 1-
10.
Zhen, Y., Tok, A. Y., Boey, F. Y. & Jiang, S. P., 2008. Development of Cr-Tolerant
Cathodes of Solid Oxide Fuel Cells. Electrochemical and Solid State Letters,
Volume 11.

60
APPENDICES (NORMALISED DATA SETS)
Appendix- A1
Appendix A1 - Temperature at its corresponding applied voltage and current
density data in real time used in analysing electrical performance for Cell 1

Cell1
Tv [Kh] V [Volt] Tj [Kh] J [Ω/cm2]
0.0005 0.953025 0.001123 1.43E-05
0.1 1.005161 0.001126 1.43E-05
0.265998 1.03203 0.001155 1.47E-05
0.3 1.052957 0.001178 1.5E-05
0.323 1.05369 0.001179 1.5E-05
0.5 1.000938 0.00112 1.43E-05
0.6 0.999411 0.001119 1.43E-05
0.7 0.999634 0.001119 1.43E-05
0.8 0.998795 0.001119 1.43E-05
0.9 0.999446 0.001119 1.43E-05
1 0.999812 0.00112 1.43E-05
1.1 0.999214 0.001119 1.43E-05
1.2 1.000205 0.00112 1.43E-05
1.3 0.999696 0.00112 1.43E-05
1.4 0.997995 0.00112 1.43E-05
1.5 0.997595 0.00112 1.43E-05
1.6 1.000125 0.00112 1.43E-05
1.7 1.000554 0.00112 1.43E-05
1.83 1.001482 0.001122 1.43E-05
1.98 1.00233 0.001123 1.43E-05
2 0.999554 0.00112 1.43E-05
2.14 0.999473 0.001119 1.43E-05
2.2 1.000822 0.00112 1.43E-05
2.3 1.000607 0.00112 1.43E-05
2.4 1.000473 0.00112 1.43E-05

61
 2.5 1.000348 0.00112 1.43E-05
2.663 0.99992 0.001119 1.43E-05
2.7 0.999866 0.00112 1.43E-05
2.8 0.999991 0.00112 1.43E-05
2.9 0.99992 0.001119 1.43E-05
3 0.999955 0.00112 1.43E-05
3.1 1.000304 0.00112 1.43E-05
3.2 0.999036 0.00112 1.43E-05
3.3 1.000197 0.00112 1.43E-05
3.4 1.000143 0.00112 1.43E-05
3.5 1.001655 0.001119 1.43E-05
3.6 1.000732 0.001121 1.43E-05
3.71 0.99917 0.001119 1.43E-05
3.8 1.000134 0.001119 1.43E-05
4.00701 0.997251 0.001118 1.42E-05
4.02 1.000608 0.00112 1.43E-05
4.114 1.000947 0.00112 1.43E-05
4.21 0.999134 0.001119 1.43E-05
4.4475 1.000822 0.001121 1.43E-05
4.453 1.006534
4.5 0.999304
4.6 1.000321
4.7 0.949903
4.8 0.992799
4.95 1.000938
5 1.000974

62
Appendix- A2
Appendix A2 - Temperature at its corresponding applied voltage and current
density data in real time used in analysing electrical performance for Cell 2

Cell2
Tv [Kh] V [Volt] Tj [Kh] J [Ω/cm2]
0 1.045 0.6 0.212073
0.1 0.9813 0.7 0.210104
0.2 1.0006 0.8 0.210052
0.3 0.9996 0.9 0.209298
0.4 1 1 0.208144
0.5 0.9997 1.1 0.206219
0.6 1.0002 1.2 0.206187
0.7 1 1.34912 0.197346
0.8 0.9997 1.4 0.195228
0.9 1.0005 1.455 0.194659
1 0.9998 1.66112 0.20508
1.1 0.9801 1.711 0.202273
1.2 0.9799 1.85562 0.198907
1.3 0.9971 1.9 0.197062
1.4 0.9988 2 0.198143
1.66 0.9989 2.07862 0.195961
1.7 0.9991 2.16492 0.197092
1.795 0.997 2.3 0.195945
1.9 1 2.4 0.202972
2 0.9998 2.5 0.202752
2.08 1.0003 2.6 0.202783
2.2 0.9996 2.7 0.203456
2.3 1.1484 2.8 0.202162
2.4 1.148 2.855 0.247247
2.5 1.1259 2.9 0.201766
2.6 1.1267 3 0.201293

63
 2.7 1.1264 3.1 0.201345
2.8 1.1265 3.244 0.198278
2.9 1.1258 3.3 0.198346
3 1.1258 3.4 0.199685
3.1 1.1259 3.5 0.197889
3.2 1.1255 3.6 0.19749
3.3 1.1263 3.7 0.198926
3.4 0.9813 3.82 0.198701
3.505 0.9947 3.9 0.198716
3.6 1.0004 4.177 0.196639
3.7 0.9995 4.191 0.196292
3.825 1.0001 4.284 0.197017
3.9 1.0004 4.4 0.196785
4.16 1.02 4.5 0.195846
4.17 1.0197 4.6 0.194897
4.2 1 4.7 0.194078
4.32 1.0011 4.75708 0.198233
4.4 1.0001 4.9 0.193545
4.5 0.9809 5.014 0.192273
4.6 0.9807
4.7 0.9999
4.83 0.9993
4.91 0.9992
5.02 0.9998

64
Appendix- A3
Appendix A3 - Temperature at its corresponding applied voltage and current
density data in real time used in analysing electrical performance for Cell 3

Cell3
Tv [Kh] V [Volt] Tj [Kh] J [Ω/cm2]
0 0.9595 0.6 0.329103
0.091303 1.0683 0.7 0.326439
0.2 1.0024 0.8 0.323527
0.3 1.003 0.9 0.321545
0.4 1.0031 1.015 0.314078
0.5 0.9969 1.114 0.309162
0.6 0.998 1.327 0.304766
0.7 0.9981 1.423 0.303373
0.8 0.9984 1.487 0.297734
0.9 0.9979 1.9748 0.306804
1 1.0404 2.1 0.29826
1.1 1.0426 2.2 0.295878
1.32638 0.9974 2.3 0.290102
1.344 0.998 2.4 0.293436
1.421 0.9975 2.5 0.289396
1.4868 0.9965 2.6 0.284539
2 1.0027 2.7 0.285594
2.1 1.0011 2.8 0.279056
2.2 1.0006 2.96 0.280192
2.3 0.9829 3 0.27633
2.4 1.0005 3.1 0.27868
2.5 1.0005 3.2 0.277534
2.6 0.9981 3.3 0.277085
2.7 1.0001 3.4 0.27242
2.81 0.9993 3.822 0.270869
65
2.95 0.9991 3.9 0.269274
3 0.9994 4 0.268641
3.1 0.9993 4.1 0.260938
3.2 0.9996 4.2 0.264315
3.3 0.9996 4.3 0.265944
3.45 1.0168 4.4 0.265256
3.5 0.9994 4.5 0.264586
3.82 0.999 4.6 0.263367
3.9 0.999 4.7 0.260954
4 0.9609 4.8 0.25998
4.11 1.0025 4.9 0.258948
4.2 1.0025 5 0.260406
4.3 1.0039
4.4 1.0041
4.5 0.998
4.6 0.9995
4.7 1.0002
4.8 1.0003
4.9 1
5 1.0008

66
Appendix- B
Appendix B - ASR data in real time used to evaluate degradation rate for the
cell samples.

Cell-1 Cell-2 Cell-3

Time ASR
(kh) ASR (Ωm) Time (kh) ASR (Ωm) Time (kh) (Ωm)
0.176331 0.9479181 0.21136 0.964424 0.126407 0.901287
0.273562 0.9625956 0.307189 0.970053 0.140493 0.903182
0.48202 0.9692542 0.403018 0.973527 0.154579 0.904305
0.690477 0.9854035 0.498847 0.974263 0.168665 0.907664
0.898935 0.9905556 0.594676 0.980625 0.182751 0.908566
1.10739 1 0.690506 0.984311 0.196838 0.909482
0.786335 0.985649 0.22501 0.911364
0.882164 0.98863 0.239096 0.911468
0.977993 0.992747 0.407015 0.909223
1.07382 1 0.472363 0.910554
0.60423 0.922777
0.653534 0.92853
0.80144 0.938434
0.850785 0.948077
0.890053 0.974519
0.910409 0.977967
0.930284 0.972569
0.950159 0.987017
0.970033 0.98327
0.989908 0.981494
1.00978 1

67