Progress in Energy and Combustion Science 93 (2022) 101011

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Progress in Energy and Combustion Science

journal homepage: www.elsevier.com/locate/pecs

Analysis of solid oxide fuel and electrolysis cells operated in a real-system

environment: State-of-the-health diagnostic, failure modes, degradation
mitigation and performance regeneration
Vanja Subotić *, Christoph Hochenauer
Institute of Thermal Engineering, Graz University of Technology, Inffeldgasse 25/B, Graz 8010, Austria

A R T I C L E I N F O A B S T R A C T

Keywords: Solid oxide cells (SOC) play a major role in strategic visions to achieve decarbonization and climate-neutrality.
Solid oxide fuel cell (SOFC) With its multifuel capability, this technology has received rapidly growing amount of attention from researchers
Solid oxide electrolysis (SOE) degradation worldwide. Due to the great flexibility of SOCs with respect to the fuels that can be used, not only hydrogen, but
State-of-the-health monitoring (SoH)
also biogas, natural gas, diesel reformates and many other conventional and alternative fuels can be used. This
Degradation prevetion
Regeneration
makes it possible to couple SOCs with diverse sustainable fuel sources to generate electricity or to generate
valuable fuels such as syngas when utilizing renewable electricity. In this paper, the reader is provided with a
review of the existing knowledge about solid oxide fuel cell (SOFC) and solid oxide electrolysis (SOE) systems
and how to safely operate them over the long-term, placing a special focus on real-world operating environments.
Both the utilization and generation of real commercially available fuels are taken into consideration. Different
failure modes can appear during the system operation under real-world conditions and reduce the SOC lifetime,
an aspect that is extensively discussed in this review. Firstly, a detailed discussion of the difference between
carbon-free and carbon-containing fuels is presented, considering different impurities and their impacts on the
SOC performance, stability and lifetime. Secondly, unfavorable operating conditions are presented and possi­
bilities for the early identification of different failure modes are explored. An overview of available conventional
and non-conventional diagnostic tools and their applications is provided here. Overall, this review paper presents
a guideline for all relevant degradation issues related to SOCs operated in a real-world environment, describing
(i) how these issues appear and how to understand them, (ii) how to predict them, (iii) how to identify them and
(iv) how to prevent them, as well as, if required, how to reverse them. To achieve this goal, individual chapters
specifically address failure modes, degradation prediction, degradation prevention and performance regenera­
tion. The reader is provided with necessary knowledge about the long-term and short-term operating stability
and the degradation provoked in a compact summary. The available knowledge about specific process fre­
quencies is summarized in one diagram, which is a novel contribution of this review. This enables researchers to
rapidly identify all occurring process mechanisms with SOFCs and SOECs. Moreover, suggestions for how to
accelerate degradation and how to regenerate performance are summarized in several tables.

1. Overview and scope of this review
Solid oxide cells (SOCs) present a great solution for ensuring a sus­
tainable energy future, especially when they are compared with the
available conventional technologies. To achieve a sustainable energy
future, three main technological challenges must be overcome: (i) en­
ergy demand savings, (ii) improving the efficiency of energy generation
technologies and (iii) implementing renewable energy and replacing
fossil fuels. Addressing these challenges means radically rethinking the
available energy system [1–5]. Solid oxide cells enable us to overcome
the second and third challenges. Firstly, they have an electrical effi­
ciency of more than 60% when used in real systems [6], resulting in a
significant emissions decrease. Secondly, they can be operated with a
variety of fuels, such as conventional diesel fuel and natural gas, but also
alternative biogas, biomass gasification products, ammonia, or
hydrogen. SOCs thus embody a synthesis of traditional and radically
new systems and principles. Among other available fuel cell types, SOCs
feature the highest efficiency and fuel flexibility [7]. These features

* Corresponding author.
E-mail address: vanja.subotic@tugraz.at (V. Subotić).

https://doi.org/10.1016/j.pecs.2022.101011
Received 6 October 2021; Received in revised form 11 March 2022; Accepted 30 April 2022
Available online 18 August 2022
0360-1285/© 2022 The Author(s). Published by Elsevier Ltd. This is an open access article under the CC BY license (http://creativecommons.org/licenses/by/4.0/).
V. Subotić and C. Hochenauer
indicate that they bridge the gap between conventional and alternative
technologies, leading us toward the leading future climate-friendly en­
ergy technologies. Moreover, SOCs offer a unique opportunity to employ
a single unit to generate both (i) electricity and heat when operating in a
solid oxide fuel cell (SOFC) mode and (ii) valuable fuels, such as
hydrogen or syngas, when operating in the solid oxide electrolysis (SOE)
mode [8].
Despite the great suitability and flexibility of solid oxide cells for real
system applications, thus including both SOFCs and SOEs, several
challenges presented by degradation, possibilities to identify and reverse
it, material suitability and general lifetime issues must still be addressed
to accelerate their commercialization and use in present and future
energy systems. It is important to fully understand their behavior and
operating issues and to discover options that can improve their opera­
tion and lifetime, especially at the level of industrial-sized cells, stacks
and, ultimately, systems. This paper provides a comprehensive review
that summarizes all of the possible failure modes and their impacts on
SOC performance, suggestions for the early identification of undesired
failures and degradation mechanisms, their mitigation and performance
regeneration. Such a condensed presentation of all these relevant points
in a single paper has been lacking up until now, but is critically neces­
sary for members of the scientific community.
This review was carried out to provide a comprehensive, reliable,
critical and accessible summary of information about SOCs, addressing
the most important issues that affect the improvement of the SOC life­
time. This review paper combines comprehensive aspects of SOCs to
describe how (i) to recognize relevant characteristics of the operating
environment regarding the SOC reliability and durability, (ii) to identify
failure modes and all of the individual degradation mechanisms, (iii) to
apply appropriate SoH diagnostic tools and (iv) to provide strategies that
can be employed to mitigate degradation and improve SOC stability
throughout the entire lifetime. All of these aspects are addressed under
real-system conditions. This review, therefore, is of great importance to
the community, since it presents a preliminary SOC guideline for re­
searchers, students, system applicants and operators, as well as other
interested stakeholders.
1.1. Structure of this work
This review was carried out to summarize information about the
application of SOC single cells, and especially of industrial-sized cells
and cells as they are used in stacks and real systems, under real-life
operating conditions. We discuss the influence of the real system envi­
ronment on the performance and morphological behavior of the cells, as
well as possible degradation mechanisms and the strategies that can be
used to inhibit the undesired negative effects and to reverse degradation
that has already occurred. This paper begins with an introduction, ends
with a concluding discussion, and contains four main thematic sub-
sections:
• Lifetime issues and failure modes encountered when running SOCs
• Failure prediction and accelerated degradation tests
• State-of-the-health diagnostics for running SOCs
• Degradation mitigation and performance regeneration
Lifetime issues and failure modes in running SOCs - The degradation of
electrochemical performance can have different causes, such as the
coarsening of catalytic particles, contamination of active sites by im­
purities, carbon deposition, electrode delamination and system
component degradation. The effects of most of these degradation causes
are closely related to the (i) fuels used, such as the fuel composition, gas
quality and impurities contained, and (ii) set operating conditions,
encompassing the operating temperature, degree of reactant utilization,
operating current and other factors. Identification and quantification of
diverse degradation processes at different levels is required to select
optimal system operating conditions. To achieve this aim, different
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Progress in Energy and Combustion Science 93 (2022) 101011
degradation mechanisms are summarized and discussed in Section 2.
Failure prediction and accelerated degradation tests - This section pro­
vides more detailed insight into diverse strategies used to identify failure
modes that may occur within the SOC systems and to predict their
impact on the performance behavior. The failure prediction can be based
on numerical data, experimental data or even a combination of these.
Therefore, in this section, we focus on: (i) model-driven and data-driven
predictions tools and (ii) accelerating stress testing. Employing such
tools, it is possible to collect information about the expected SOCs life­
time and degradation mechanisms that can occur without having to
perform long-term real-life testing. Accelerating stress testing is of
crucial importance for the further development and commercialization
of SOC technology. This type of test has to be properly designed. The
topic of accelerated degradation testing for SOCs has not yet been
comprehensively addressed, and no review of the current literature was
previously available. Therefore, special attention is given to this topic in
Section 3.
State-of-the-health (SoH) diagnostics for running SOCs - In this section,
we describe how researchers can identify failure modes and degradation
mechanisms in the running SOC systems at an early stage, thus, pre­
venting irreversible degradation. Once reliable online SoH estimate can
be made, and the likely end of life can be anticipated, optimal mainte­
nance actions can be planned to prevent damage to equipment and a loss
of operability. No review of the current literature was previously
available to provide an insight into all available conventional tools for
SOC application and a comparison of their applications with those of
SOC cells, stacks and systems. The results of this review are found in
Section 4.
Degradation mitigation and performance regeneration - This section
contains a summary of strategies used to mitigate, limit and reverse SOC
degradation and extend their durability. Appropriate measures can be
applied to prolong the lifetime of the SOC systems. These, however,
differ in terms of their diverse degradation modes, operating modes and
the types of SOC employed; therefore, they must be carefully designed.
In Section 5, we analyze and summarize the strategies that have already
been used to mitigate, limit and reverse degradation as well as to
regenerate SOC performance.
This review enables the reader/SOC operator to prepare a suitable
operating environment, select an appropriate fuel, gain insight into
possible failure modes, employ appropriate SoH tools to identify all
changes that occur, and finally, to mitigate and reverse degradation.
This is also illustrated in Fig. 1. Here, we present four steps that were
employed on the basis of the knowledge presented in the four sections:
(i) predicting SOC performance under specific operating conditions; (ii)
using performance data to prepare experimental design; (iii) using the
information available in the Section 4, to select appropriate diagnostic
tools; and (iv) selecting suitable mitigation and regeneration strategies
to prolong the SOC lifetime and enable stable long-term operation.
Previous reviews reported only specific topics considered in the
present study. The results of an analysis of the SOFC suitability for
operation with carbon-based fuels and their impact on the performance
degradation was reported by Gür [9], who focussed on methane fuel,
and Lanzini et al. [10], who reviewed the impact of fuel contaminants in
biogas-fed SOFCs. Boldrin et al. [11] provided a comprehensive review
of strategies used with carbon- and sulfur-tolerant SOFC materials, thus
conducting a detailed examination of degradation effects and ap­
proaches taken to increase electrode tolerance. Regarding
high-temperature electrolysis operation, Mocoteguy et al. [12] and
Wang et al. [13] reviewed and analysed degradation mechanisms and
phenomena in SOEs, while Chen and Jiang [14] reviewed material
degradation processes in SOEs. For more information on recent ad­
vances in SOEs, we refer the reader to [15,16]. Huang et al. [17]
reviewed AC impedance modeling and validation, while Fasmin and
Srinivasan [18] reported results of the nonlinear impedance spectros­
copy, although these were not directly correlated with the SOC processes
or mechanisms. In this study, we provide a detailed review of the
V. Subotić and C. Hochenauer Progress in Energy and Combustion Science 93 (2022) 101011

Fig. 1. Illustrated main scope of this review.

Fig. 2. Effect of different impurities on the SOC morphology: (i) phosphine, reprinted from [29] and [30] with permission from Elsevier, (ii) chlorine, reprinted from
[31] and [32] with permission from Elsevier, (iii) sulfur, reprinted from [33] with permission from Elsevier, (iv) chromium, reprinted from [34] and [35] with
permission from Elsevier, and (v) siloxane, reprinted from [32] with permission from Elsevier.

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V. Subotić and C. Hochenauer Progress in Energy and Combustion Science 93 (2022) 101011

following topics: (i) failure modes that occur during the SOC operation
under real-world operating conditions, (ii) options for failure prediction,
(iii) accelerating degradation tests, (iv) state-of-the-health diagnostic
tools, (v) degradation mitigation, and (vi) performance regeneration.
Such a review has not appeared in the available literature until now, but
is critically necessary.
2. Lifetime issues and failures encountered when running SOCs
are optimized for SOFC operation, and their further optimization for use
in an SOE mode is necessary to further avoid undesired degradation.
Long-term degradation processes are beyond scope of this review and
are not further discussed.
In this section, we describe the effects of short-term degradation,
which are mainly influenced by the operating conditions and for which
appropriate counteractions can be taken. Detailed descriptions are
provided below.

In this chapter, we discuss SOC reliability and durability issues, 2.1. Contaminants and their impact on the SOC performance
which can be disturbed by different failure modes and the subsequent
performance and morphology degradation. Depending on the degrada­ The great advantage of SOCs is that variety of fuels can be used.
tion mechanisms, this can be identified as long-term or short-term However, a big challenge is still how to achieve long-term SOC operation
degradation. Long-term degradation is correlated with the perfor­ without experiencing undesired failure modes, which occur due to
mance losses over time that mainly occur as a result of the morphology multifuel capability. The first step is to provide contaminant-free fuels.
degradation. These cannot be significantly adjusted by the operating However, many conventional and alternative fuels appropriate for SOC
environment. This type of degradation still presents the main challenge operation, such as natural gas, diesel or biogas, contain impurities
regarding SOC development and requires improvements in the materials (phosphine, sulfur, siloxane). They mainly influence the fuel electrode.
used or development of new optimized materials. A short overview of On the air electrode, chromium is the most commonly-known contam­
degradation rates observed in both SOFC and SOE operating modes for inant. Different impurities cause both performance and morphological
single-cells and stacks is presented in Table 1. The most recent material degradation of the running cells. The impact of the most common im­
developments decreased the degradation rate for SOFCs down to 0.5%/ purities available in the relevant SOC fuels on the SOC performance is
1,000 h [14,19,20], while the lowest degradation rate for SOEs recorded described below and illustrated in Fig. 2. Moreover, the sources of
is 1.5%/1,000 h after 3,600 h at 1 A/cm2 [21], both of which were specific impurities and their impacts on specific electrodes are summa­
observed for Forschungszentrum Jülich stacks. The materials employed rized in Table 2. Since all of these impurities cause significant perfor­
mance degradation, which is often seen as irreversible, only the impact
on the SOC morphology is summarized in this table.
Table 1
Summary of selected reported degradation rates. 2.1.1. Sulfur poisoning
Operating Operating Degradation rate Operating Source Sulfur is the most commonly present impurity in a number of SOFC-
mode unit conditions relevant fuels, such as natural gas (>1%), coal syngas (100-300 ppm)
SOFC Fuel 3%/1,000 h 750∘ C, 0.7 V, and biogas (50-200 ppm)[36–38]. Sulfurous species are especially
[22]
electrode- 2,000 h, H2 /H2 O/ harmful for SOC fuel electrodes and cause detrimental performance
supported N2 =48.5/48.5/3
degradation [39–41]. Their presence accelerates Ni sintering and carbon
planar cell
SOFC Electrolyte- 0.64%/1,000 h 800∘ C at 0.5 A/ deposition [40,42] and even completely changes the electrode
[23] morphology, as shown in Fig. 2. For this reason, it is important to
supported cm2 , 120 h
button cell remove sulfur from the fuels used, which is possible by using desulfur­
SOFC 4-cell fuel 0.2%/1,000 h 700∘ C, 0.5 A/cm2 , ization units. Nevertheless, although the amount of sulfur is significantly
[19]
electrode- 35,000 h, H2 /
reduced by using desulfurization technologies, residual concentrations
supported H2 O=80/20
stack still fall within the range of a few ppm [43]. Even such low concentra­
SOFC 2-cell fuel 0.6%/1,000 h 700∘ C, 0.5 A/cm2 , tions can cause undesired degradation effects, since Ni-catalysts exhibit
[24]
electrode- 70,000 h, H2 / restricted tolerance toward sulfur [10]. Increasing concentrations of
supported H2 O=80/20, fuel sulfurous species result in rising degradation rates. In general, the
stack utilization 40%
presence of sulfur initially results in a rapid performance drop, which is
SOE Fuel 3.8%/1,000 h 778∘ C± 6∘ C, 1 A/ seen as the first degradation stage. In the second stage, initial degra­
[25,
electrode- cm2 , 80% H2 O,
26] dation is followed either by stable performance without further degra­
supported 36% H2 O
circular cell utilization, 9,000
dation, continuing degradation with a lower degradation rate for only a
h period of several hours, or further continuous degradation [44]. It is also
SOE Electrolyte- 4.26%/1,000 h 800∘ C, 0.5 A/cm2 , interesting to mention at this stage that, although several studies report
[23]
supported 300 h after initial that increasing the amount of sulfur carbon formation is enhanced,
button cell 120 h SOFC
Chattanathan et al. [45] reported contradictory results, namely, that the
operation
SOE Metal- 2.1%/1,000 h 800∘ C, 0.3 A/cm2 ,
presence of H2 S in biogas prevents coking.
[27] Brightman et al. [46] reported that exposure of Ni/CGO electrodes to
supported after initial 1,000 2,000 h, H2 /
circular cell h, 3.9%/1,000h H2 O=57/43 up to 3 ppm H2 S for 90 min causes a rapid increase in losses but also that
after next 1,000 h this process is reversible. Sulfur poisoning as a reversible process under
SOE 2-cell fuel 1.5%/1,000 h 3,600 h, 0.875 A/
electrode-
[21] short exposure times was also reported in [47,48]. In the recently pub­
cm2 , H2 /H2 O=1,
supported H2 O utilization lished study by Pongratz et al. [48], synthetic product gas from wood
stack 44% steam gasification including 1–10 ppm H2 S was used as a fuel for SOFC,
SOE 10-cell 3.2%/1,000 h a 800∘ C, variation
[28]
while the operating temperature varied between 750∘ C and 800∘ C.
electrolyte between 0.25 A/ Although performance deterioration occurred during the operation,
supported cm2 and 0.317 A/
stack
removing the sulfurous species from the fuel enabled the authors to
cm2 , 1,000 h,
H2 O=56% regenerate the overall performance and regain the initial performance.
SOE 5-cell fuel 8.9%/1,000 h a 800∘ C, 0.2 A/cm2 , This conclusion was reached for both fuel electrode- and
[28]
electrode- 1,000 h, electrolyte-supported SOFC. Appari et al. [49], however, reported, that
supported H2 O=56% sulfur poisoning is reversible only at higher temperatures such as 800∘ C,
stack
while the operation at lower temperatures such as 700∘ C resulted in

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V. Subotić and C. Hochenauer Progress in Energy and Combustion Science 93 (2022) 101011

Table 2
Summary of relevant contaminants and their impacts on SOC based on references provided in Section 2.1.
Impurity Operating Impurity source Threshold Affected component Observations
mode

Sulfur SOFC Natural gas, syngas, ∼3 ppm Fuel electrode Irreversible Ni morphology changes, formation of Ni sulfides,
biogas, biomass accelerated Ni sintering and C deposition
Sulfur SOE Inlet CO2 gas ∼ppb Fuel electrode Locally increasing potential and as a consequence higher CO-
concentration and accelerated C deposition, covered Ni sites
Chlorine SOFC Coal gas, biogas, ∼5 ppm Fuel electrode Blocking the Ni catalyst, formation of Ni chlorides, irreversible
biomass morphology change, metal dusting
Chlorine SOE Inlet gas mixture for co- ∼10 ppm @OCV, ∼5 Fuel electrode Cl adsorption on Ni, reduction of the electrochemical activity
electrolysis ppm under and catalytic reactions
polarization
Phosphine SOFC Syngas, coal gas, ∼3 ppb Fuel electrode Formation of Ni phosphides, formation of secondary phases, Ni
biogas, biomass agglomeration
Siloxane/ SOFC Biogas, digester gas ∼ppb Fuel electrode SiO2 formation and deposition within electrode, Si deposition
silicon on fuel electrode support and contact layer, TPB, interconnects,
reduced fuel electrode porosity, Si deposition
Silicon/ SOE Glass sealing, water N/A Fuel electrode, Air Segregation on the electrolyte/fuel electrode interface, fuel
silica electrode, Electrolyte/ fuel electrode passivation, SiO2 deposition, Si deposition, SiO2 /Si
electrode interface inclusion into Ni particles
Chromium SOFC SOE Fe-Cr alloy metallic N/A Air electrode Formation of different secondary phases (e.g., SrCrO4 , CrO2.5 ,
interconnects Cr2 O3 ) on the air electrode and electrolyte, air electrode phase
decomposition, inhibited oxygen reduction reaction, inhibited
oxygen evolution reaction
Boron and SOFC SOE Metallic interconnects, N/A Air electrode Damaging influence on the air electrode stability, its
sulfur air stream, glass sealing disintegration and delamination, boron deposition at electrode/
electrolyte interface, interaction with air electrode materials,
accelerated Sr segregation, formation of secondary phases

irreversible degradation. The reversibility of the degradation, however,
is mainly a function of the H2 S concentration and the SOFC exposure to
it.
Moreover, Brightman et al. [46] reported that increasing the oper­
ating current further decreased the degradation rate. Other studies
indicate that increasing the current density results in an increasing
sulfur coverage [46,50]. Hauch et al. [51] showed that reversible per­
formance losses occurred when operating at a low overpotential, while
the microstructure remained unchanged in this case. However, in­
vestigations performed at high cell overpotential levels showed that
both reversible performance and irreversible morphological degrada­
tion can occur during the SOFC exposure to H2 S. Hagen et al. [52] and
Riegraf et al. [53] claimed that losses caused by sulfur are more severe at
high current densities. The authors identified sulfur as having the most
pronounced impact on mass transfer/fuel reforming processes and
charge transfer/TPB processes.
When operating SOC in a CO2 electrolysis mode, even ppb concen­
trations of sulfur can have detrimental effects on the SOE performance
[54]. Sulfur accelerates carbon deposition in this case and makes it
possible for carbon to occur outside the theoretically calculated range.
The goal is to minimize the amount of sulfur deposited on the fuel
electrode during the SOC operation and, if possible, to reduce it down to
zero. Different purification methods for sulfur removal are available,
including solvent absorption, biofiltration (biotrickling filter, biofilter,
bio scrubber), adsorption for primary (bulk) sulfur removal with a high
capacity based on iron oxide, hot guard beds for achieving ultra-low
amounts of sulfur contaminants, metal organic frameworks (MOFs)
and hydro-desulfurization beds (HDS). Discussing the principles un­
derlying these specific purification technologies is beyond the scope of
this work, but detailed descriptions can be found in the review by
Lanzini et al. [10].
2.1.2. Chlorine poisoning
The effect of chlorine poisoning of the fuel electrode on the SOC
performance has been reported in several studies, most of which refer to
SOFC [55–57]. Available studies show that chlorine poisoning occurs in
two stages, as in the case of sulfur poisoning. The first stage is identified
as reversible adsorption and blocking of the nickel catalyst surface,
while the second stage is observed to be irreversible degradation and
formation of nickel chloride compounds on the surface [58–60]. The
nickel chloride and nickel sulfide compounds formed are volatile, and
their removal results in fuel electrode damage that cause metal dusting
[61]. Marina et al. [62] reported that reversible poisoning was observed
when the Ni/YSZ fuel electrodes of the fuel electrode-supported (FESC)
SOFC were exposed to coal gas containing up to 800 ppm HCl. The
magnitude of this poisoning decreased as the temperature increased.
The authors reported that performance losses were observable up to
concentrations of approximately 100 ppm HCl, but no morphological
changes could be observed due to the HCl poisoning. Moreover,
increasing the HCl amount above 100 ppm resulted in no observable
additional performance deterioration. Xu et al. [31] also reported a
performance loss of approximately 3% for the Ni/YSZ fuel
electrode-supported SOFC fed with a syngas containing 100 ppm HCl,
but unlike to the previous study, this was followed by significant
morphological changes in the Ni catalyst. Moreover, stainless steel
exhaust tubing was used in this study, which was attacked by HCl,
leading to rust deposition on the cell. The study carried out by Reeping
and Walker [63] showed highly aggressive performance degradation
with approximately 15%/hour when chlorine was combined with
methane (CH3 Cl/CH4 =110 sccm/20 sccm=5.5), while the degradation
grade was very low for CH3 Cl/CH4 =110 sccm/100 sccm=1.1 mixture.
The possible reason for these results could be significantly higher vol­
ume fraction of chlorine in methane than in hydrogen. Here, we must
also emphasize that dry methane significantly accelerates degradation,
since methane cracking and thus the carbon formation reaction is
favored. The occurrence of a specific carbon peak observed when
employing operando Raman spectroscopy became less stable when
introducing CH3 Cl, and its intensity was reduced by 50% after 29 min.
When the operating time was increased up to approximately 174 min,
thus increasing the exposure to chlorine, the carbon intensity and
observable carbon accumulation decreased.
The recently published study by Jeanmonod et al. [64] examined the
impact of chlorine on performance during co-electrolysis operation. The
authors reported that exposure of the Ni/YSZ electrode to biogas con­
taining 10 ppm of HCl and at OCV did not impact the SOE performance,
whereby the exposure to biogas containing 5 ppm HCl under polariza­
tion resulted in a significant irreversible performance degradation.
Increasing operating current proportionally increased the losses.

5
V. Subotić and C. Hochenauer
Moreover, durability tests performed at 0.5 A/cm2 under a biogas con­
taining 1 ppmv showed that steadily increasing voltage resulting in a
high degradation rate. Cl was identified as reducing the electrochemical
activity and catalytic reaction of nickel, even causing Ni depletion.
2.1.3. Phosphine poisoning
Phosphine (PH3 ) is another contaminant that can impact the per­
formance of the fuel electrode. It is present in coal syngas at a concen­
tration of approximately 10 ppm. Its presence in an SOFC fuel even in
very low concentrations of 1–10 ppm can be detrimental to the SOFC
performance [65]. A number of studies reported observing morpholog­
ical changes in the Ni/YSZ fuel electrodes in the presence of phosphine
[66–69], all of which are related to the SOFC operation. This exposure
resulted in the formation of new phases, mainly nickel phosphides
[70–72], but also nickel phosphates [73], which is identified as an
irreversible change and negatively affects the overall performance. Xu
et al. [70] reported dramatic irreversible performance degradation as a
result of the functional damage of the Ni/YSZ fuel electrode and espe­
cially the functional layer near the electrolyte. Operation at 10 ppm PH3
caused a loss of porosity, Ni agglomeration and even Ni migration, as
well as a loss of the TPB length. The authors claimed that even much
lower concentrations of < 2 ppm could lead to significant degradation.
Marina et al. [29] reported observing a very strong interaction between
nickel and phosphine, even at very low concentrations of < 0.5 ppm.
Further research by Haga et al. [74] showed that phosphine is detri­
mental even at ppb concentrations, defining a threshold as ∼3 ppb at
800∘ C. The authors reported the formation of the secondary phase on
both the Ni catalyst and current collector as well as subsequent Ni
agglomeration. They also observed that rapid and fatal degradation
occurs at higher operating temperatures, while gradual degradation was
observed at lower operating temperatures. Moreover, if present in
higher concentrations, phosphine can cause immediate degradation,
while it can lead to slow performance and structural degradation at
lower concentrations. The time required to cause the total system
breakdown depends on the fuel electrode thickness and thus the avail­
ability of the catalyst, which means that it will appear earlier for
electrolyte-supported (ESC) than for fuel electrode-supported cells [65].
Based on the observations reported in the previously available studies,
phosphine is not suitable to be converted in SOFCs, but must definitively
be removed from fuel.
2.1.4. Silica poisoning
Silicon based impurities represent another poison that can affect
both the fuel and air electrodes. In biogas or digester gas, siloxanes
appear as the main impurities, but studies report that their impact on
SOFC performance is restricted. Moreover, silicon and/or silica are
present in glass sealing and can also be found in water during the
electrolysis, which may lead to a degradation in SOE performance.
Haga et al. [32] revealed in their study that operation under
3%-humidified hydrogen with 10 ppm siloxane resulted in strong fatal
degradation, independent of the operating temperature. Rapid degra­
dation from the beginning of the operation appeared regardless of the
operating temperature, namely, 800∘ C, 900∘ C and 1,000∘ C. Morpho­
logical changes were observed as SiO2 deposition under and on the
porous fuel electrode surface. Madi et al. [75] observed high degrada­
tion rates even when fueling SOFC with biogas containing several ppb of
siloxanes. Si was deposited within the entire fuel side, and thus in­
terconnects, the fuel electrode contact layer, fuel electrode support and
TPB. Papurello and Lanzini also identified siloxane as reducing the fuel
electrode porosity and disturbing the fuel distribution within the cell
[76]. This resulted in a strong increase in polarization losses. Si con­
denses and deposits everywhere within the fuel electrode, which was
also shown in [77]. The authors suggested that performance recovery is
much more effective at OCV than under polarized cell conditions. Tian
and Milcarek [78] also reported increasing losses and voltage degrada­
tion rate as the siloxane concentration increased. Summarizing all the
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Progress in Energy and Combustion Science 93 (2022) 101011
results published, siloxanes have to be completely removed from the fuel
in order to protect the cell from the irreversible degradation.
Another issue is presence of silica in glass sealing or the water during
the steam electrolysis. Silica-containing impurities can segregate on the
interface between the fuel electrode and electrolyte thus inhibiting
further electrochemical reactions and causing electrode passivation, as
presented in [79,80]. The cause for SiO2 deposition after its evaporation
from the glass sealing was found to be the high steam partial pressure.
The authors identified SiO2 depositions rather than Si deposition, which
was identified only on the interconnects. How SiO2 is deposited on the
nickel and how the inclusion of SiO2 /Si to Ni particles occurs are aspects
described and illustrated in [81]. Silica available in the glass sealing was
further identified to cause the electrolysis deactivation and performance
loss by Schefold et al. [82]. Perz et al. [83] investigated the impact of
silicon poisoning on the LSCF electrode and these authors reported that
even small amounts of silicon resulted in a strong deactivation of the
oxygen reduction.
2.1.5. Chromium poisoning
Chromium poisoning was reported in the literature as one of the
main causes for the air electrode degradation, which is mainly generated
from the Fe-Cr alloy metallic interconnects [34,84]. The presence of
steam in the air can accelerate the process of chromium evaporation
from the interconnect plates and their deposition onto the air electrode,
thus accelerating undesired degradation mechanism, as reported by
Sitte et al. [85–87]. Many of the findings have been obtained under
SOFC operating conditions, during which different Cr phases are formed
due to chromium evaporation from the interconnect, its diffusion into
the porous air electrode and its eventual deposition [88]. The formation
of such phases deteriorates the electrochemical and catalytic perfor­
mance of the SOFC electrodes and may also prevent the diffusion of
oxygen. Moreover, phase decomposition as a consequence of
Cr-poisoning has been observed [89,90]. The deactivation of the elec­
trode activity and performance degradation were observed for different
electrode materials, LSM and LSF in [91] as well as LSCF [92]. More­
over, Wang et al. [93] investigated the impact of operating temperature
on Cr deposition and Sr segregation in LSCF electrodes. The authors
observed that more chromium deposition and SrCrO4 phase was
detected as the temperature increased. Chromium deposits inhibited the
diffusion processes and surface electrochemistry. Next, the authors
assumed that the decrease in chromium depositions that they observed
as the temperature decreased can be correlated directly with the
significantly decreasing Sr segregation.
When taking into consideration SOE operation, chromium oxides
and strontium chromate have been reported in the literature as occur­
ring and depositing both on the electrode inner surface and on the
electrolyte [94]. Based upon the observed results, Chen et al. [94]
claimed that Cr deposition is a chemical process which results in for­
mation of many different secondary phases in the electrode and on the
electrolyte surface. Placing a focus on the LSCF electrode during the SOE
operation, Wei et al. [95] identified the formation of SrCrO4 , CrO2.5 and
Cr2 O3 phases and correlated these with the SrO segregation under air
electrode polarization conditions. The formation of such phases, in turn,
inhibits the oxygen evolution reaction.
In conclusion, the effect of chromium poisoning seems to be inde­
pendent of the operation mode.
Besides chromium, boron and sulfur, which can also be found in
interconnects, the air stream, or glass sealing, were reported in the
literature as having a damaging influence on the activity and stability of
the air electrode in both the SOFC [96–101] and SOE operating mode
[102].
2.2. Impact of carbonaceous species on fuel electrode degradation
Specific impurities can cause detrimental SOC performance degra­
dation and strong morphological changes, as discussed above. However,
V. Subotić and C. Hochenauer Progress in Energy and Combustion Science 93 (2022) 101011

while impurities have an undesired impact on the SOC performance and Table 3
its microstructure, the main fuel components can also cause SOC Possible carbon formation reactions according [123–126].
degradation under specific operating environment. The best example of CH4 + H2 O⇌3H2 + CO (1)
such behavior is the impact of carbon-containing fuels, which can lead to
( )
1 (2)
Cn Hm + nH2 O⇌nCO + n + m H2
carbon deposition, thus damaging and completely destroying the elec­ 2
CH4 + CO2 ⇌2H2 + 2CO (3)
trode morphology and leading to irreversible performance deterioration
CO + H2 O⇌H2 + CO2 (4)
or even an abrupt performance decrease down to zero. C + 2H2 O⇌CO2 + 2H2 (5)

CH4 ⇌C + 2H2 (6)

2.2.1. Carbon deposition 1 (7)
Carbon deposition appears as a major issue when operating SOFCs CH4 + O2 ⇌C + H2 + H2 O
2
with carbon-containing fuels, such as hydrocarbons or carbon monox­ CH4 + O2 ⇌C + 2H2 O (8)
CH4 + CO⇌2C + H2 + H2 O (9)
ide. Fuels such as natural gas, biogas, biomass gasification products and
CH4 + 2CO⇌3C + 2H2 O (10)
diesel reformates contain high concentrations of methane, carbon CH4 + 3CO⇌3C + CO2 + H2 + H2 O (11)
monoxide and carbon dioxide. CO and CO2 are present in a high con­ CH4 + CO2 ⇌2C + 2H2 O (12)
centration also during the co-electrolysis and CO2 -electrolysis processes, m (13)
Cn Hm →nC + H2
2
in which CO and CH4 are produced. For the past few decades, great 2CO⇌C + CO2 (14)
effort has been invested in increasing the understanding of the carbon CO + H2 ⇌C + H2 O (15)
formation and deposition phenomena for SOFC operating under polar­ CO2 + 2H2 ⇌C + 2H2 O (16)
ized conditions as well as under OCV. In the case of the OCV, this is equal CH4 + 2CO⇌3C + 2H2 O (17)
1 (18)
to the pure catalyst deactivation. Regarding the SOE operating mode, C + O2 ⇌CO
2
most studies have been performed on steam electrolysis. More attention C + O2 ⇌CO2 (19)
has recently been directed toward the co-electrolysis of CO2 and H2 O, C + H2 O⇌CO + H2 (20)
but only a limited number of studies provide any insight into carbon
deactivation. The information available for CO2 electrolysis is even
path graphically, claiming that carbon formation always begins at the Ni
more restricted. Nevertheless, the main carbon forming reactions are
catalyst. The carbon type and its amount are a function of the operating
chemical reactions linked to the Ni-based SOC catalysts, and under­
temperature, the fuel composition, polarization state and exposure type.
standing how these processes occur is relevant in both operating modes.
This type can differ significantly for different SOC types. An overview of
CO and CH4 are, in this case, the main carbon-forming species, and their
carbon types extracted from the present literature is summarized in
impact on the carbon formation processes is described below.
Fig. 2.
Taking into account the methane influence, carbon formation and its
Numerous studies have discussed carbon formation in relation to the
deposition on Ni-based catalysts during the natural gas reforming pro­
Ni catalyst. However, this formation has also been confirmed by the fact
cess are well-known phenomena that are frequently reported in the
that methane reforming and carbon formation also occur on the ionic
literature [40,103–109]. Methane reforming reactions are related to the
YSZ surface [119,120]. In contrast, the GDC layer is reported to provide
methane conversion employing steam (Eq. (1) or carbon dioxide (Eq. 3)
more resistance towards carbon deposition [121]. Moreover, numerous
as oxidants, which occur on the catalytic active sites. If higher hydro­
investigations have confirmed that CO and CH4 have different impacts
carbons are employed as a fuel, the reaction illustrated in Eq. (2) is
on the performance degradation and type of carbon formed. Stoeckl
expected to occur. In the steam-reforming process, different steam/­
et al. [111] identified carbon occurrence when fueling SOFCs with either
carbon (S/C) ratios can be utilized. To achieve the maximum efficiency,
methane or carbon monoxide, but its appearance strongly differed as a
researchers attempt to achieve the stoichiometric ratio of S/C=1. The
function of the specific fuel components.
same applies to dry reforming, for which a stoichiometric ratio of
After feeding the cell with CO, carbon covered solely Ni catalytic
CO2 /CH4 =1 is tailored. However, this can lead to undesired hydrocar­
sites, as a solid layer encapsulating the Ni grains. Carbon from CH4 ,
bon dissociation reaction, also known as cracking or pyrolysis, as pre­
however, covered both Ni and YSZ and appeared in the form of amor­
sented in Eq. (6) and Eq. (13).
phous carbon. The difference in the carbon appearance is clearly pre­
If we consider the carbon formation from carbon monoxide, the main
sented in Fig. 2. It seems as though even low concentration of CH4 in fuel
carbon forming reactions are the Boudouard reaction (Eq. (14)) and
enables carbon to cover both Ni and YSZ, a hypothesis supported by
reversible steam gasification (Eq. (15)). Reactions relevant for carbon
[122]. These authors fueled SOFC with diesel reformate with a low
formation are shown in Table 3; based on these reactions, the possibility
methane concentration and amorphous carbon covered both YSZ and Ni
for carbon to form when fueling the porous SOC with CO or CH4 is very
on the fuel electrode surface. Increasing the amount of methane in the
high.
fuel mixture resulted in the additional formation of carbon nanofibers,
Carbon formation mainly begins at the Ni catalyst, whether the
especially along the boundary between the fuel electrode functional
carbon originates from CH4 or CO. Bartholomew [117] examined carbon
layer and the electrolyte, as reported in [115].
deposition during steam reforming and methanation processes and
Chen et al. [113] also examined the carbon deposition phenomenon
discovered that many different types of carbon can be deposited in these
as a function of different syngas variations, testing the effects of the
processes. In 1982, he described these as polymeric, adsorbed, graphitic,
operating temperature factor. At 650∘ C, the authors observed solid
vermicular or filamentous carbon and carbides. In 2014, Yurkiv [118]
carbon depositing inside the fuel electrode, which inhibited further fuel
reviewed the available literature and the already known processes,
diffusion and electrochemical reactions. At 750∘ C, carbon mainly
reporting that all different carbon types can be described as follows: (i)
covered the electrode surface, thus influencing the conductivity. More­
heterogeneous carbon, which deposits on the catalytic Ni sites and
over, when operating the SOFC at 750∘ C with a syngas containing
which is similar to polymeric carbon, whereby such carbon is mainly
approximately 24% CH4 for 2 h, Ni-grains became encapsulated in
formed under OCV and inhibits reactions; (ii) homogeneously/heter­
carbon shell, resulting in loss of available catalytic active sites.
ogeneously formed pyrolytic carbon or soot, which reduces the electrode
Taking into account the effects of dry reforming, Lanzini et al. [110]
porosity by covering the gas channels and increasing the overall resis­
showed that catalyst deactivation cannot be avoided, regardless of the
tance, and eventually (iii) heterogeneously formed carbon on and in the
CO2 amount; lower CO2 concentrations led to carbon depositions,
fuel electrode, which diffuses into Ni-particles. This changes the elec­
whereby carbon deposition could be reduced at higher CO2 concentra­
trode morphology and leads to Ni dusting, explained in more detail
tions, but catalyst deactivation still occurred and carbon was still
below. In the same study, the author illustrated the carbon formation

7
V. Subotić and C. Hochenauer Progress in Energy and Combustion Science 93 (2022) 101011

Fig. 3. Different types of carbon formed as a function of different fuels: (i) CH4 due to dry and steam reforming, reprinted from [110] and [111] with permission
from Elsevier and [112] with the permission of the Royal Society of Chemistry, (ii) different fuel mixtures as syngas (reprinted from [113] with permission from
Elsevier), biomass gasification producer gas (reprinted from [114] with permission from Elsevier) and diesel reformate mixture (reprinted from [115] with
permission from the Journal of the Electrochemical Society), (iii) CO reprinted from [116] and [111] with permission from Elsevier.

formed, mainly as carbon nano-fibers.
Next, rapid degradation due to the presence of long chain hydro­
carbon was reported in [127]. In order to further discuss the impact of
the operating temperature on carbon formation, the equilibrium for
Fig. 4. Calculated equilibrium for the Boudouard-reaction () and methane-
cracking (). Reprinted from [128] with permission from Elsevier.
methane cracking and the Boudouard reaction is shown in Fig. 3. If the
operating temperature is increased, a higher amount of carbon is ex­
pected to occur due to methane cracking, while amount of carbon
formed due to Boudouard reaction is higher at lower operating tem­
peratures. Such equilibrium calculations are also used as simple pre­
diction tools, which enable the user to adjust the operating conditions to
prevent the undesired degradation effects. These are explained in more
detail in Section 5.
Regarding the electrolysis operation, Tao et al. [129] identified the
formation of carbon nanofibers at the electrode/electrolyte interface,
when operating SOE in an electrolysis mode and at operating current
densities of 2.0–2.5 A/cm2 . Carbon fiber deposition resulted in a sub­
sequent interlayer delamination. In [130], the authors stated that car­
bon forming during the CO2 electrolysis process could influence
performance, such as the voltage, gas composition and temperature
distribution, even before it is measured.
While increasing the operating current density during the SOFC
operation increases the number of oxygen ions available and, thus, in­
hibits carbon formation, this increase has an opposite effect during the
SOE operation. While operating SOC in a co-electrolysis mode,
increasing the current density is reflected by the increasing fraction of
CO and possibly CH4 species, which are seen as the main carbon pre­
cursors, thus, accelerating carbon formation and its deposition at the

8
V. Subotić and C. Hochenauer Progress in Energy and Combustion Science 93 (2022) 101011

porous fuel electrode.
2.2.2. Metal dusting
The metal dusting process is as well-known as nickel corrosion and
this phenomenon has already been observed both in the fuel cell and
electrolysis modes. Since carbon-containing fuels are indeed most
commonly used in SOC systems, the metal dusting phenomenon is firstly
correlated with carbon. The reaction initially occurs between the tran­
sition metals on the SOC fuel electrode, such as Ni, and carbon. During
this reaction the amorphous carbon is transformed into graphite, a
process which is known as catalytic graphitization [131]. The phe­
nomenon of catalytic graphitization is generally explained based on the
results reported in [132], namely, that carbon dissolves during a solu­
tion precipitation mechanism and supersaturates nickel, eventually
precipitating as graphite. The overall Ni dusting reaction is driven by the
free energy difference between the amorphous and crystalline carbon
states. Chun et al. reports in [133] that nickel-carbide structures are not
stable at temperatures higher than 350 ∘ C; however, the metal dusting
phenomenon occurs between 350 and 1,100 ∘ C for Ni-based fuel elec­
trodes. Since that study was not performed under polarized conditions,
but under open circuit voltage, the knowledge gained is applicable to
both the SOFC and SOE operating modes. The gas compositions and Ni
surface orientation have strong impacts on the metal dusting process,
while the Ni surface orientation is especially relevant at the initial stage.
For instance, the authors showed that surface graphite intercalates into
Ni particles at CO/H2 =25, causing undesired Ni corrosion. When the
CO/H2 ratio is reduced down to 1, carbon diffusion into the Ni lattice
and the subsequent graphite precipitation in the bulk material occur as
an additional degradation mechanism. This excessive precipitation re­
sults in subsequent Ni disintegration. Increasing the operating temper­
ature accelerates this degradation phenomenon.

Fig. 5. Different types of Ni electrode degradation: (i) Ni reoxidation after (1) SOE operation, reprinted from [134] with permission from Elsevier, (2) reversible SOC
operation, reprinted from [135] with permission from Elsevier, and (3) SOE operation, reprinted from [136] with permission from Elsevier, and (ii) Ni agglomeration
after (1) reversible SOC operation, reprinted from [135] with permission from Elsevier, (2) SOFC operation with biomass gasification producer gas, reprinted from
[114] with permission from Elsevier, and (3) SOE operation, reprinted from [137] with permission from Elsevier.

9
V. Subotić and C. Hochenauer
2.3. Instability of the Ni-based electrodes
Aside from the fact that different contaminants and carbon formation
have harmful impacts on the fuel electrodes, Ni reoxidation and
agglomeration are mechanisms that detrimentally effect the SOC per­
formance. While Ni reoxidation is partly reversible, Ni agglomeration
represents an irreversible degradation phenomenon.
2.3.1. Ni reoxidation
Ni reoxidation affects the fuel electrode structure, after which
occurrence the initial performance and morphological state of the pre-
reduced electrode cannot be met. The phenomenon of Ni reoxidation
can occur due to (i) redox processes that present a circle of reduction and
oxidation processes of the fuel electrode or, (ii) an excessive number of
oxidizing species on the fuel electrode (steam or air) that can diffuse to
the electrode due to leakage, or be caused by high fuel utilization during
SOFC operation and/or low steam utilization during SOE operation.
During the electrolysis operation, a high amount of steam is used
(>80%), which causes Ni reoxidation, if low operating currents are
employed. If the cell is operated at high operating currents in a fuel cell
mode, high numbers of oxygen ions will be generated and conducted to
the fuel electrode, which can accelerate the oxidation of the functional
layer. Specific morphological changes and damage that occur as a
consequence of Ni reoxidation in both operating modes are illustrated in
Fig. 4.
Ni reoxidation under SOFC operating conditions. After reoxidation, the
size of the Ni particles changes, and a significant increase in the volume
of nickel is observable, which happens as a result of the sintering and
coalescing processes [138]. Consequently, the electrode porosity re­
duces due to the increasing size of the nickel particles. The size of the
dimensional change depends most notably on the operating tempera­
ture, as shown by Pihlatie et al. [139]. Reaction reversibility and
re-gaining the initial state after reoxidation was possible at lower
operating temperatures. For example, the authors observed that strong,
irreversible performance degradation occurred when supplying the fuel
electrode with 6% H2 O and a high p(H2 O)/p(H2 )-ratio at 850∘ C, while
no negative effect could be identified at 600∘ C. The reversibility grade
depends both on the electrode microstructure and the sintering tem­
perature, requiring the microstructure optimization [140,141]. The
initial NiO-reduction temperature was also identified as having an
impact on cell conductivity. For example, when reducing the substrates
at 1,000∘ C, the conductivity was twice as high as for the substrates
reduced at 800∘ C [142]. The reducing temperature also has a significant
impact on the mechanical strain; increasing the temperature increases
the mechanical stress that arises during the reduction process [139].
This can also be correlated with sintering processes and coarsening ef­
fects observed at higher temperatures. Similar results were also
observed for the oxidation temperature. Researchers have reported that
microscopic strain increases as the oxidizing temperature increases
[143–147]. Ettler et al. [148] employed Ni-8YSZ substrates to investi­
gate the effects of temperature, the time of reoxidation and the air-flux
on the reoxidation of half-cells. For the purpose of their study, they
varied only one parameter and held the other two parameters constant.
Up to the reoxidation degree of 38%, no cracks were visible. Moreover,
the authors reported that when reoxidation appeared at higher tem­
peratures, a clear border between Ni and NiO was observable. This was
not the case at lower temperatures; after reoxidation at 600∘ C, no border
between the Ni and NiO could be seen. Moreover, the authors observed
that the outside of the Ni was oxidized in samples that were re-oxidized
only to a limited degree, while the core remained metallic nickel. If we
examine studies that addressed the cell level, a significant difference can
be observed between the electrolyte- and fuel electrode-supported cells
[134]. While the reoxidation of FESC results in electrolyte cracking, and
eventually the cell cracking, electrode delamination was only observed
after the re-oxidation of ESC. Summarizing results from different
studies, the authors reported that redox cycling does not influence the
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Progress in Energy and Combustion Science 93 (2022) 101011
OCV of ESC, whereby a strong decrease in OCV was observed for FESC,
and a final and complete failure was observed after 50 cycles, which
correlates with the thickness of the catalyst layer. Moreover, a decrease
in performance was observed after 1000 cycles for both cell types. It is
also important to mention here that a slight increase in performance
may be observed after first redox cycle in specific cases. Moreover, in
[149], the authors reported that high fuel utilization and a subsequent
fuel starvation significantly accelerated Ni reoxidation.
Ni reoxidation under SOE operating conditions. Regarding the SOE
operation, the number of studies that refer to phenomenon of Ni reox­
idation is highly limited. Schefold et al. [82] reported a minor perfor­
mance loss after operating SOE at a reduced operating current density of
0.18 A/cm2 for 66 h, which was correlated with a slight Ni reoxidation
at the rim of the fuel electrode. The Ni reoxidation phenomenon was not
observed at higher operating current densities. In [136], SOE fuel
electrode was supplied with a mixture of H2 /H2 O=20/80 during the
steam electrolysis operation, after which the Ni sites locally reoxidized.
After 80 h operation at 600 mA/cm2 , approximately 50% of the Ni
surface oxidized, while this surface seemed to be reduced after operation
at 1,200 mA/cm2 . However, the re-oxidation that occurred did not
significantly impact the electrode porosity, and the electrochemical re­
actions were thus not influenced. A strong Ni-reoxidation effect was
reported for operation under H2 O/H2 ⩾90/10, even at the limit voltage
of 1.35 V, which presumes high operating currents [137].
In conclusion, steam amount and operating current density present a
decisive factor regarding Ni reoxidation process. Taking into consider­
ation the SOFC operating mode, increasing the operating current in­
creases the steam concentration, which, in turn, can accelerate Ni
reoxidation. In contrast, high operating current densities are considered
to have a positive effect and enable to prevent Ni reoxidation when
operating SOC under electrolysis conditions. Increasing operating cur­
rent density enables to convert steam into hydrogen, thus reducing the
amount of the available steam and the propensity towards Ni
reoxidation.
2.3.2. Ni agglomeration or Ni coarsening
Ni agglomeration or Ni coarsening usually occurs as the operating
time increases because material instability during the long-term opera­
tion and this degradation phenomenon cannot be prevented. However,
specific operating conditions, such as temperature, steam concentration
and, in general, fuel composition, can significantly accelerate Ni-
agglomeration [150]. Applying appropriate ionic conductors within
the fuel electrodes should limit Ni agglomeration at high operating
temperatures [151]. The undesired phenomenon of Ni agglomeration
deteriorates cell performance, since it reduces the available TPB surface
[152–154]. This also causes the appearance of inactive Ni/YSZ regions
[155]. The same negative effect was reported for operation in both the
SOFC [149,156] and SOE modes [137]. In general, Ni agglomeration
occurs independent of the operating mode as a consequence of high
operating temperatures and the specific operating environment [157]. It
can appear even under OCV. Zou et al. [158,159] showed that Ni
coarsening was observed after holding the SOC under OCV for 20 h,
which caused the deterioration of the Ni/YSZ interface. Other studies
show that high steam partial pressure accelerates Ni agglomeration,
which is expected especially during the electrolysis operation [137,
160–162]. The et al. [160] compared the microstructure of SOEs after
operating for 6,100 h and 9,000 h, coming to the conclusion that the
humid atmosphere accelerates Ni coarsening. They also identified a
direct correlation between nickel growth rates and H2 /H2 O.
Holzer et al. [163] quantified the growth of Ni particles after oper­
ating SOFC under both dry (H2 /N2 =3/97) and humidified atmospheric
conditions (H2 O=60%, H2 /N2 varies) and compared these with each
other. They showed that the initial growth rates in the humidified at­
mosphere are high and account for 140%/100 h during the initial 200 h.
Afterwards, during the long-term operation of more than 1,000 h, the
V. Subotić and C. Hochenauer
growth rate seemed to be almost zero for each 100 h. In contrast,
operating under dry atmospheric conditions resulted in lower degra­
dation rates of approximately 1%/100 h, but this degradation rate
remained unchanged over the 2,000 h operating time. Carrying out
simulations for Ni coarsening in both operating modes, Hubert et al.
[153] came to the conclusion that the coarsening rate seems to be
slightly lower in the electrolysis mode, i.e., 25% in comparison to 30% in
the SOFC mode, both at 850∘ C after 1,000-2,000 h of operating time. The
microscopic changes that occur as a result of Ni agglomeration and
different operating environments in both the SOFC and SOE modes are
illustrated in Fig. 4.
2.4. Air electrode degradation
Two air electrode types, LSM and LSCF, are the most common rep­
resentatives among air electrodes. LSM electrodes are mainly employed
at higher operating temperatures (800-900∘ C), due to their thermal and
chemical stability and acceptable performance. At lower operating
temperatures, LSCF electrodes are more appropriate, providing great
performance at intermediate temperatures[13,164,165].
Air electrode degradation under SOFC operating conditions. Tempera­
ture, operating current density and air humidity have been shown to
negatively affect the LSCF-based air electrodes leading to the undesired
degradation mechanisms while operating in a fuel cell mode [166].
Increasing the operating temperature or increasing the air humidity can
significantly accelerate surface segregation, which has been identified as
a primary degradation mechanism that has a detrimental effect on the
LSCF electrodes stability [34,167]. Niania et al. [168] examined the
impact of the air electrode atmosphere on Sr segregation, comparing air,
oxygen and pure steam. Steam significantly accelerated Sr segregation
in comparison to the operation in air or pure oxygen atmosphere.
Operation at high current densities and thus lower oxygen partial
pressures resulted in accelerated performance degradation. This occurs
due to morphological changes that occur at the air electrode; thus, Sr
and Co segregation, the formation of SrCoOx phases from segregated Sr
and Co and subsequently electrode agglomeration occur [169]. Besides
Sr and Co segregation, La depletion was also identified as a further
degradation phenomenon that occurs at LSCF air electrodes during the
SOFC operation [170]. Next, Sr segregation, the formation of a Sr layer
on the air electrode, mainly between the electrolyte and the GDC layer
was reported to occur. This happens even without polarization, and may
appear as a function of the operating time and the operating temperature
[171,172]. However, the main reason for formation of a Sr-layer at the
YSZ/GDC layer could be high sintering temperatures. During the sin­
tering process Sr can diffuse through the GDC, leading to the formation
of the secondary layer [173,174]. Moreover, without presence of a
barrier layer, LSCF shows high propensity to chemically react with YSZ,
forming SrZrO3 phases, which can further cause SOFC degradation
[175]. Taking into account LSM air electrodes while operating in SOFC
mode, the most frequently reported degradation mechanisms are the
formation of LaZrO3 and SrZrO3 [176,177], formation of Mn oxides, air
electrode delamination, densification, or coarsening [177,178]. The
presence of steam has also been reported to have a detrimental effect on
the SOFC performance, causing a continuous loss of the electrolyte/air
electrode contact, an enhanced Mn removal from the LSM/YSZ interface
and an eventual LSM decomposition [178]. Moreover, operating tem­
perature is a further factor that significantly impacts the electrode
degradation. The loss of the interface stability, both chemical and me­
chanical, was more severe at lower temperatures, e.g. 750∘ C [177]. At
850∘ C, the degradation effects were linked mainly to the grain coars­
ening and element diffusion, but their intensity was rather low. [179]
Air electrode degradation under SOE operating conditions. Regarding
electrolysis operation, Graves et al. [180] reported in their study that
fuel electrode degradation was dominant during the SOE operation at
lower current densities (i <0.25Ȧ/cm2 ), while this changed at higher
11
Progress in Energy and Combustion Science 93 (2022) 101011
operating current densities (i >0.5 A/cm2 ), at which oxygen electrode
degradation seems to be dominant. They concluded that high current
densities can significantly accelerate degradation of the air electrode.
Two main degradation mechanisms were determined that deteriorate
the performance and microstructure: the (i) delamination of the elec­
trode/electrolyte interlayer and (ii) formation of the secondary phases.
The intensity of these degradation mechanisms is partially influenced by
the type of the electrode used.
Regarding the LSM electrode, increasing the oxygen partial pressure
during the electrolysis operation is seen as critical parameter that can
accelerate electrode degradation; the appropriate tolerance is not
currently available [14,180]. Oxygen accumulates within the cavities
impacting both the electrolyte and the electrode [181,182]. Increasing
the oxygen partial pressure causes cracks/voids to form within the
electrolyte [183] and within the electrode/electrolyte interlayer [184,
185]. When these accumulate, the effects cause the delamination of the
electrode/electrolyte boundary layer. The LSM degradation is further
accelerated by the high electromotive potential that occurs under the
high operating current when the concentration of oxygen decreases at
the fuel electrode and increases at the air electrode [186]. Chen and
Jiang [187] reported the effect of increasing the oxygen partial pressure,
but also that the local disintegration of LSM particles and subsequent
formation of nanoparticles can occur, causing interlayer delamination.
Regarding LSCF electrodes, their excellent electrical and catalytical
performance at intermediate temperatures is crucial for their applica­
tion at these temperatures. Due to the LSCF’s propensity to react with
YSZ, a barrier layer GDC is mainly used between the electrode and
electrolyte [13,188]. Schefold et al. [25,82,160] carried out extensive
investigations of the SOE durability with different SOE types, all of
which contained LSCF electrode, and observed continuous degradation.
They identified the formation of a secondary phase SrZrO3 as the main
degradation mechanism [189–191]. Another degradation phenomenon
that has been observed in many studies is Sr segregation from the air
electrode and diffusion through the GDC layer to the GDC/electrolyte
interface, which causes morphological changes and performance dete­
rioration [136,192,193]. In [192], the authors also reported that diffu­
sion of Co through the GDC/YSZ layer was observed. The authors
explained that the Sr and Co diffusion was a consequence of the com­
bined air electrode electric field and high p(O2 ). Similar results were
presented in [136], suggesting that increasing p(O2 ) by varying the air
electrode supply between air, O2 /N2 =50/50 and 100% O2 has an
electrode-protecting effect. In contrast, when increasing p(O2 ) in air by
increasing the operating current density, this study revealed strong
degradation of the air electrode and, thus, Sr segregation and diffusion
as well as interlayer delamination. In addition, the authors observed the
formation of a thin Sr layer between the GDC barrier layer and the
electrolyte. The delamination types mentioned in the available literature
as detected by post-mortem analysis are illustrated in Fig. 5.
2.5. Degradation induced by reversible operation
Many investigations have been carried out to understand degrada­
tion mechanisms that occur separately in either the fuel cell or elec­
trolysis mode. However, although no new kinds of degradation
mechanisms are expected to occur during the reversible operation,
recent investigations devoted to reversibly operated SOCs came to two
opposite conclusions: (i) that electrodes and interfaces can be placed
under greater strain when operating in the reversible mode, and (ii) that
degradation could even be reduced due to the reversible operation. The
available knowledge about degradation mechanisms that occur during
the reversible operation is based primarily on conditions under which
the fuel electrode is fed with H2 /H2 O mixtures, mainly with a 50/50
ratio, while the air electrode is fed with air. While almost all of the
studies available reported performance degradation as a consequence of
air electrode degradation [195], Morales-Zapata et al. [196] alluded to a
V. Subotić and C. Hochenauer
Fig. 6. Degradation of the (i) LSM air electrode reprinted from [194] and
[187], and the (ii) LSCF air electrode reprinted from [25] and [136], with
permission from Elsevier.
slight degradation of the fuel electrode as being caused by high steam
partial pressure and mobility of Ni particles, which could be partially
covered in the SOFC mode. In their study, they presented
nickelate-based air electrodes as excellent candidates for air electrodes
and reversible operation. Nickelate-based air electrodes were also
employed in [197], which was the only study found to report perfor­
mance improvement during the electrolysis operation that can be
correlated to the air electrodes employed. Improving materials used in
the air electrode, e.g., Sr-free bismuth oxide-cobaltite [198], resulted in
stable SOFC and SOE operation, followed by stable low degradation
operation, or even enabled the elimination of degradation by using high
oxygen-capacity perovskites [199].
Placing a focus on air electrode degradation, Hughes et al. [200]
examined durability of symmetric LSM-YSZ electrodes at current den­
sities of ±0.5 A/cm2 and ±1.5 A/cm2 and the operating temperature of
800∘ C, comparing reversible operation with applied cycles in a period of
1 and 12 h, with the constant current operation. This investigation also
confirmed the importance of the operating current density and cycling
duration on the degradation rate. During the constant current operation
at ±1.5 A/cm2 significant electrode/electrolyte interface delamination
occurred, which was mapped with an increasing ohmic and polarization
resistance. The cycling at lower current density of ±0.5 A/cm2 resulted
in a stable performance. However, by introducing 12 h cycles, degra­
dation could be significantly reduced. Further degradation reduction
was possible by reducing the cycling duration down to 1 h. In contrast,
He et al. [201] showed that degradation was more intensified for single
cells when reducing the cycling time from 12 h to 4 h, while operating at
±0.5 A/cm2 and 750∘ C. The possibility to employ reversible operation to
partially or even completely regenerate deteriorated electrocatalytic
activity of LSM air electrodes that occurred during the SOE operation,
was also presented by Chen et al. [202]. Here, the SOFC operating mode
was identified to reduce degradation rate, while longer SOE operation
accelerated degradation. Fuel electrode-supported single cell modules
and multicell stacks consisting of Ni/YSZ fuel electrode, YSZ electrolyte
and both LSM and LSCF air electrodes were reversibly operated in [203].
The results obtained show that electrolysis operation accelerated
degradation, which was identified as air electrode/electrolyte interface
delamination of the LSM based air electrodes. Fan et al. [204] reported
degradation of LSCF air electrodes during the reversible operation at
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Progress in Energy and Combustion Science 93 (2022) 101011
±300 mA/cm2 and 800∘ C. Altogether 13 cycles with a cycling duration
of 1 h were applied for each mode. While operating the SOC in the
electrolysis mode, delamination of the GDC layer and YSZ electrolyte
occurred, which resulted in an overall performance degradation of
5.9%. During the fuel cell mode, the degradation rate was observed to be
more than twice as low as 2.7%. Interestingly, by increasing the SOFC
duration cycle over the SOE cycle, researchers could eliminate degra­
dation [205]. Choi et al. [206] claimed that both fuel cell and elec­
trolysis operation are responsible for degradation that occurs during the
reversible operation of cell containing LSCF as an air electrode. The
identified degradation mechanisms were delamination of the air elec­
trode/electrolyte interface, cobalt segregation, compositional variation
and the location of internal pores. The above discussed findings
collected from different studies indicate that the degradation modes
described are mainly related to the degradation of the air electrode and
air electrode/electrolyte interlayer, which, in turn, occurs due to either
the low or high oxygen partial pressure. Detailed description of the air
electrode degradation mechanisms is given in the previous section. On
the fuel electrode, it is necessary to control the operating environment
and H2 /H2 O ratio in order to inhibit undesired Ni reoxidation.
2.6. Thermal stress
Thermal stress is a further issue that lowers SOC stability and causes
undesired performance and morphology degradation. Generally
speaking, SOCs are mainly composed of ceramic materials, which are
brittle and very sensitive to stress. Thermal stress can appear as a
consequence of cooling and restarting the SOC operating units known as
thermal cycling, because of an unexpected gas supply shortage or total
gas supply interruption [207], or due to mismatched thermal expansion
coefficients of individual cell or stack components [208,209]. The latter
one is considered as an extreme case and should be prevented by
appropriate material selection and SOC design. Thermal cycling is
generally a process of cycling between two specified temperature ex­
tremes and, in terms of SOCs, it is mainly related to the range between
ambient temperature and 900∘ C. In the SOFC mode, the main degra­
dation process that occurs as a consequence of thermal cycling was
identified to be delamination of the interface between electrolyte and air
electrode, as shown in [210]. Moreover, in [211], a thermal cycling was
performed on ScSZ/LSCF-GDC half cells. The procedure was designed to
vary the temperature between 400∘ C and 800∘ C with a temperature
gradient of 200∘ C/h for 100 cycles. After each applied thermal cycle, a
voltage between the cathode and the electrolyte of the half-cell was
measured at a constant current density of 1 A/cm2 . A continuous in­
crease in ASR was observed with reference to the performance degra­
dation, while morphological changes were observable as delamination
and changes of the cathode particles, which became finer. Lie et al. [72]
developed a model that could be used to analyze thermal stress and
behavior of both electrolyte- and fuel electrode-supported SOFCs, which
was also validated employing the available experimental data. The
peeling and interfacial stress were found to be concentrated near the
SOFC edges, thus validating the damages observed at the cell edges in
the available experiments. Moreover, they observed more pronounced
fuel electrode delamination after thermal cycling, as confirmed by tests
performed on electrolyte-supported SOFCs. Finally, they found that
porosity and fuel electrode thickness are significantly correlated with
the degradation mechanisms. Increasing porosity and the electrode
thickness reduced a lifetime. Moving towards the stack level, a 5-cell
fuel-electrode supported SOFC stack, consisting of Ni/YSZ fuel elec­
trode, LCN electrode and Fe-16Cr alloy-based bipolar plates [212], was
subjected to thermal stress, but very low degradation rate of 0.8% was
reported after 15 cycles between the ambient temperature and 750∘ C.
Degradation, however, occurred particularly on the air electrode. In
order to reduce stack degradation caused by thermal cycling, Yang et al.
[213] suggested improving stack design, placing a focus on metallic
V. Subotić and C. Hochenauer
interconnect and sealing. This enabled to reduce the degradation rate
from 50%/1,000 h down to 5%/1.000 h. A glass-ceramic sealant was
identified as the most critical part of a stack that accelerates degradation
due to thermal cycling in [214].
If thermal cycling as described above happens in a controlled
manner, slight performance and material degradation are expected;
these, however, do not lead to rigorous SOC degradation. In contrast, e.
g., the intermittent renewable energy and its coupling with SOE, could
pose irregular load changes, causing irregular thermal cycling, local
temperature hot-spots and undesired degradation in SOEs. Kaur et al.
[215] employed LSScM-GDC composite electrodes as fuel electrode for
the purpose of CO2 electrolysis. In order to simulate volatile power
supply, five thermal cycles were applied, varying the temperature be­
tween the ambient temperature and 800∘ C. This resulted in significant
cell degradation. Current collector coarsening and fuel electrode
cracking were determined as major degradation mechanisms. The un­
desired changes in the operating environment and the previously
described degradation mechanisms are more heavily weighted to cause
thermal stress within SOCs than carefully-designed thermal cycles.
Moreover, the degradation mechanisms mentioned in previous sections
can also lead to thermal stresses, especially formation of local hot-spots
and crack nucleation, which are influenced by the changing electrode
morphology and inhibited chemical and electrochemical reactions.
2.7. Concluding remarks
Summarizing the observations presented in this section, we can
divide the failures that occur within cells into two main classes: (i)
physical failures that influence the cell performance, its resistance and
losses and (ii) morphological failures that cause damage and irreversible
morphological changes. The second type of failure always results in
physical failure, visible as performance deterioration. The failures that
occur depend on two main factors: the (i) materials employed and (ii)
operating environment. The first degradation type that depends on the
materials used is intensified as the operating time increases and is
irreversible. To reduce this degradation type or to slow it down, the
development of improved new generation materials or adjustment of
operating conditions is needed. With regard to the latter, operating
conditions and factors such as impurities, the steam concentration,
concentration of carbonaceous species and operating temperature play a
central role. Different impurities, such as sulfur, phosphine and chlorine
can have a detrimental impact on the cell performance, even if present
only in ppb concentrations. They increase the overall losses within both
SOFC and SOE, reduce the available catalytic active sites and block the
gas channel, thus reducing the electrode porosity. Therefore, their
removal from the fuel used is critically necessary in order to enable safe
long-term operation. Moreover, carbonaceous species in the fuel flow
increase the propensity of the Ni-based fuel electrodes to form carbon
and to deposit it on and within the SOC fuel electrode. Ni instability,
such as Ni reoxidation and Ni agglomeration, should be prevented
during the operation as discussed above. Thermal cycling is identified as
a further stress factor that can accelerate undesired degradation. Finally,
regarding the reversible operation, the opposite conclusions have been
reached. While researchers have reported that this can negatively affect
the operating SOC, a number of studies also reported their positive
impact on reducing or even completely eliminating degradation effects
in the SOE mode.
While various sources can cause degradation on the cell level,
degradation can also occur in different system components, such as the
reforming unit, heat exchanger and steam generator; this influences the
stability of the overall system. However, such degradation types are
beyond the scope of this study and are not described here.
Different methods have already been developed to remove undesired
impurities and to mitigate subsequent SOC degradation. These are
described in detail in Section 5.
13
Progress in Energy and Combustion Science 93 (2022) 101011
3. Failure prediction and accelerated degradation tests
The broad commercialization of the SOC technology is still an issue,
since unexpected degradation mechanisms can occur during the opera­
tion deteriorating the cell performance and significantly reducing the
system lifetime. In order to prevent unexpected system shut downs, (i)
performance prediction and (ii) state-of-the-health monitoring appear as
first choice solutions. By properly predicting the expected SOC behavior
and possible failure modes, appropriate countermeasures can be devel­
oped and applied at precisely the right time point, reducing the necessity
for maintenance. This means that we have to identify all the emergen­
cies before they occur by identifying the first signs of changes and un­
desired degradation. To date, performance degradation and lifetime
prediction is possible by employing (i) model-driven prediction, (ii)
data-driven prediction approaches and (iii) accelerating stress testing
(AST). The first approach involves the use and development of complex
numerical models to predict performance and degradation. The second
approach is more closely related to the experimentally observed data
and their classification when compared with a trained data set or a priori
knowledge, thus enabling researchers to build behavior models[216].
The combination of both previously mentioned models is known as
hybrid prognostic, which provides the advantages of both the model-
and data-driven approach [217]. The latter tool is based on experi­
mental investigations that employ accelerating aging tests. While much
effort has been invested to develop different prediction models and
make them available to the scientific community, relatively limited
knowledge about the accelerating degradation is available. Neverthe­
less, if all of the presented principles are applied in a holistic and inte­
grated manner, the expected system lifetime can be precisely
determined, as illustrated in Fig. 6. In this section, both of these possi­
bilities are discussed.
3.1. Model-driven prediction
When predicting the performance with model-driven fault systems,
0D, 1D, 2D and 3D models are available. 0D-models provide information
about the expected cell performance which are based on simple calcu­
lations and consider, e.g., relevant reactions [218]. However, these do
not consider the impact of the cell microstructure and kinetics. In
contrast, 1D-models provide more detailed information about the het­
erogeneous chemistry, mass transport and porous media transport [219]
and, thus, are also appropriate to illustrate dynamic SOFC behavior
[220,221]. Nevertheless, the results gained depend strongly on the input
variables [222], which impact their quality. More precise information
about the system behavior can be gained when using 2D models, which
enable the user to simulate the spatial distribution of the relevant
operating parameters, such as temperature, fuel and oxygen species,
potential and current [223]. In addition, the precision of the information
obtained can be increased when applying 3D modeling [224–227].
Schluckner et al. [228] showed that it is important to define the
boundary conditions first, such as the testing environment and impact of
the setup on the cell performance, before starting to examine SOC per­
formance, since these conditions can influence the cell performance and
behavior. The results reported were supported by both numerical and
experimental investigations. The most important parameters were
identified as the flow configuration and position of electrical contact,
which have to be properly designed to avoid the formation of regions
with excessively high fuel or air starvation. Formation of such regions
can lead to an abrupt decrease in performance and eventually me­
chanically damaging the cell as well as lead to the formation of local hot
spots. Fig. 7a illustrates a comparison between the current density dis­
tribution through the electrolyte for counter-flow and cross-flow con­
figurations, showing that cross-flow leads to the non-homogeneous
profiles, which can cause undesired cell degradation. In comparison,
current density profile in the counter-flow is more homogeneous and
thus can be seen as more appropriate for a degradation-free operation.
V. Subotić and C. Hochenauer
Fig. 7. Model-driven and data-driven methods used to predict the SOC performance.
The same study suggested that the counter-flow configuration and
electrical contacts placed on the air electrode inlet side cause the most
uniform temperature and current density distribution along the fuel
electrode-supported SOFCs, making it the optimal setup combination for
the specific SOFC operation. Therefore, we also suggest examining the
impact of the cell setup as the first step before starting the SOC operation
in order to identify its critical points. Considering the specific operating
environments, equilibrium calculations should be carried out first to
predict the expected SOC behavior, especially if carbon-based fuels are
involved. If the user performs equilibrium calculations, however, they
are assuming that the kinetics are sufficiently rapid, excluding the
impact of the kinetics on the reactions that occur. Moreover, these are
mainly calculated for OCV conditions and do not consider impact of
electrochemistry. Sasaki et al. [229,230] carried out highly detailed
equilibrium calculations in 2003, in order to determine the boundary
conditions for carbon formation as a function of the operating condi­
tions, e.g., operating temperature and, fuel composition. The results
obtained can be used as a first assumption of the applicability in the
defined operating environment. Ten years after these published studies,
in 2013, Lee et al. [231] performed highly detailed equilibrium calcu­
lations to investigate the impact of both methane dissociation (Eq. (6))
and the Boudouard reaction (Eq. (14)) on carbon formation. They
extended the prediction for carbon formation by predicting not only the
formation of graphitic carbon, but also of carbon nano-fibers. Focusing
on the equilibrium calculations given in the three previously mentioned
studies and extending them by considering reactions kinetics, major
carbon precursors in porous SOFC fuel electrodes were precisely iden­
tified in [226]. For S/C=0.5, CO was identified to be critical as a fuel at
operating temperatures lower than 700 ∘ C, and CH4 , at operating tem­
peratures higher than 500 ∘ C. The temperature range at which carbon
nano-fibers could occur was shown to be smaller than the range at which
graphite occurred. Moreover, when a CH4 /CO mixture is used, this
range is significantly extended, graphitic carbon can occur starting all up
to approximately 850 ∘ C, whereas carbon nano-fibers can occur between
500 and 1,000 ∘ C. Afterwards, in 2017, Sasaki and his research group
[232] extended the equilibrium calculations to investigate the impact of
the operating pressure on the equilibrium state with different fuel
compositions. They reported that carbon depositions can be effectively
avoided under high pressure in the steam-reforming processes, whereby
partial oxidation was more suitable for coal gas to prevent carbon
formation.
However, although performing thermodynamic equilibrium calcu­
14
Progress in Energy and Combustion Science 93 (2022) 101011
lations enables users to identify boundaries of the critical operating
environments, the kinetics must be considered to obtain more detailed
information about the expected system behavior. For instance, in [233],
the authors examined the behavior of reversibly operated SOCs with
both steam and syngas, reaching the conclusion that their work is mostly
dominated by the gas diffusion and less by reaction kinetics. Moreover,
one relevant suggestion they provided is that the fuel composition
should not be changed at the mode-switching point, since it is
time-consuming to reach stable gas diffusion and co-redox reactions at
this point. A performance prediction for reversibly operated SOCs was
also presented in [234,235]. Knowing the spatial distribution of single
gaseous species along the cell, as well as the temperature and potential
distribution, supports performance prediction and its optimization, as
shown in [224]. Based on the knowledge gained, the fuel composition
can be adjusted to achieve, e.g., more uniform temperature distribution
or higher power. The availability of such information enables the user to
determine the possible occurrence of different degradation mechanisms,
as reported in [225]. The authors showed that the highest amount of
carbon is expected to occur at the inlet, while the increasing current
significantly reduces amount of the carbon formed, when operating
large industrial-sized SOFCs with carbon-based reformates. The risk that
carbon will be formed when operating cells under high currents is also
shown in [236]. Moreover, knowing the surface coverage and distribu­
tion of all involved species along the cell surface can provide us further
information about distribution of occurring reactions and more impor­
tantly, propensity of the cells towards specific degradation mechanisms,
e.g., Ni re-oxidation. Fuel electrode coverage with oxygen radicals and
the magnitude of the adsorbed species are shown in 7 b. It is clearly
visible that the coverage at the inlet is low, while it is significantly
intensified at the outlet. This refers to the possibility of the enhanced Ni
re-oxidation on the fuel electrode outlet side. Wu et al. [237] employed a
least squares support vector machine (LS-SVM) classifier to design a
diagnosis model to predict different types of SOFC faults, such as
Cl2 -poisoning of the fuel electrode and air electrode humidification by
using humidified air. In addition, the estimation of the remaining useful
lifetime as a function of the faults that occurred was enabled by
employing two hidden semi-Markov models (HSMMs) and resulted in an
accuracy of ±20%.
3.1.1. Data-driven prediction
Another way to predict the cell performance is to employ data-driven
prediction methods. As could be seen in the previous section,
V. Subotić and C. Hochenauer Progress in Energy and Combustion Science 93 (2022) 101011

Fig. 8. Model-driven prediction based on 3D modeling of SOFC performance as a function of flow conditions and SOFC surface coverage with oxygen.

performance prediction based on the physical models is extremely time-
consuming. This often requires the user to have very precise knowledge
about the SOC microstructure, its porosity, electrode thickness, structure
of the individual layers, and other factors. To simplify the prediction of
the SOC performance and reduce the necessary prediction time, artificial
intelligence and the application of artificial neural networks (ANN) have
recently received more of attention. Training brain-inspired neural
networks enables the representation and prediction of real-world
behavior, as proven by several Sillicon Valley giants for different pur­
poses. The applicability of ANNs to predict and control the performance
of SOFC in residential micro-cogeneration installations was confirmed
by Milewski et al. [238]. The ANNs have also been used to predict SOFC

15
V. Subotić and C. Hochenauer
performance as a function of the microstructure, thus offering the pos­
sibility for microstructural optimization [239–241]. Moreover, the
successful prediction of the SOFC performance, [242], SOE performance
[243], or even the prediction of specific losses that can occur when
varying the operating temperature, fuel composition and the operating
current [244] during the operation, verifies the applicability of ANNs for
purposes of electrochemical performance prediction. Wu et al. [245]
employed Elman neural network to predict faults that can occur in the
operating SOFC system, such as heat exchanger breakage and the
instable stack voltage, this enabled a multi-dynamic system response.
Dolenc et al. [246] employed a hybrid approach on a 6 kW stack to
predict the remaining lifetime in non-stationary operating conditions.
Collecting the performance data in-operando, they could predict the
future performance progress and estimate the stack area specific resis­
tance. In another work, Dolenc et al. [247] presented an SoH approach
based on the data-driven degradation model for SOFC performance
prediction, which makes adjustment to new conditions possible. Zhang
et al. [248] presented the following steps as relevant for data-driven
approaches: data acquisition, data processing, feature selection and
distribution, and finally, fault prognostics. To achieve this aim, it is
important to identify the healthy stage during the operation and to
determine different degradation stages that occur. The last aspect is the
critical stage, but before the critical stage occurs, it is important to
identify degradation at an early stage within the prognostic window.
The illustration in Fig. 8 shows that different prediction approaches need
to be combined using both the available measured data and the model
parameters. Combining different prediction approaches enables the user
to increase the reliability of the data obtained and, based on these to
prepare an appropriate experimental design. All of the steps shown in
this illustration are important to ensure the safe long-term operation of
SOC systems.
3.2. Accelerated stress testing
One huge challenge is to achieve long lifetimes for SOC-based sys­
tems in order to make them suitable for system level applications.
Nevertheless, it is also challenging, expensive and time-consuming to
demonstrate the required long lifetimes to identify all the possible fail­
ure modes and degradation mechanisms. As an alternative approach,
degradation mechanisms can be provoked and accelerated by using
specifically designed operating conditions. In this way, the lifetime can
be significantly shortened, the testing can be performed quickly, and the
obtained data - when properly interpreted and analyzed - should deliver
the desired information about the expected lifetime. This means that the
information that is usually gained over a period of months or years can
be obtained in only a few hours, days, or weeks. To achieve this goal,
researchers are developing strategies for accelerating aging or
Fig. 9. Different SoH stages relevant for data-driven SOC performance pre­
diction. Reprinted from Ref. [248] with permission from Elsevier.
16
Progress in Energy and Combustion Science 93 (2022) 101011
accelerating stress testing for SOC technology. Employing the experi­
mental AST data and appropriate stochastic models, it is possible to
estimate the expected lifetime as a function of different operating
parameters.
In 1990, Nelson [249] published a book entitled ”Accelerating
Testing”, which summarized the knowledge and available studies about
different products at that stage and discussed general principles of ac­
celeration and stress loading, statistical considerations, models for life
tests and the graphical data analysis. The author claimed that it is
important to plan the tests appropriately. All of the collected data should
be analyzed and presented, as well as compared to each other, correctly.
Moreover, the comparisons of the impacts of different accelerating pa­
rameters and stressors, respectively, should be compared with each
other. Varying stress is also considered as an important step, since the
different types of stress loading can be applied in various ways. These
include (i) the most common constant stress, (ii) step stress, in which the
stress level successively increases, (iii) cyclic stress with a cyclic stress
loading, which can e.g., be presented as a sine curve and (iv) random
stress with randomly changing stress levels.
In 2006, Escobar et al. [250] reviewed the general accelerated test
models that could be used for different products. As a possible method of
acceleration they reported the increasing use of the following parame­
ters: the use rate of the product, intensity of the exposure to radiation,
aging rate of the product and stress level (e.g., amplitude in voltage,
pressure, temperature cycling). Among the accelerated testing forms,
they also differentiated among response types and listed the following:
accelerated binary tests (ABT), accelerated life tests (ALT) and acceler­
ated destructive degradation tests (ADDT). When considering tempera­
ture as an accelerating stressor, they suggested using the following
Arrhenius based equation:
[ ( )]
EA 1 1
AF(T) = exp − (21)
kB T0 Ts
In the above-mentioned equation, EA represents the thermal degradation
activation energy, kB the Boltzmann constant, T the temperature at the
nominal conditions T0 and under the impact of the specific stressor Ts
[250,251].
Moreover, when considering temperature cycling as an accelerating
stressor, the authors suggested using the following equation as a way to
determine the impact of the degradation type on the overall lifetime:
( )
N(ΔtempU ) Δtemp β1
AF(Δtemp) = = (22)
N(Δtemp) ΔtempU
with Δtemp describing as the temperature range, N as the random
number of cycles to failure, and β1 as property of the test setup and
materials used. Nelson [249] suggested defining β1 as two (2) for some
metals. If we examine the literature addressing specific degradation in
high-temperature applications, Kang described the sintering, grain
growth and densification of Ni-particles, aspects relevant in SOC
manufacturing, in his book [252] published in 2005. In 2006, Sehestad
et al. [253] published a work that considered the effects of time, at­
mosphere, temperature, nickel-carrier interactions and dopants on the
sintering of nickel catalysts.
Accelerated stress testing for SOFC. Summarizing the two above
mentioned studies, Ploner et al. [251] suggested considering the impact
of steam on the sintering processes as follows:
( )n
p(H2 O)s
AF(steam) = (23)
p(H2 O)0
in which p(H2 O)0 is the steam partial pressure at nominal conditions,
p(H2 O)s is the steam partial pressure at stressor conditions and n is the
acceleration exponent.
Ploner et al. [251] generalized the information collected for general
accelerating mechanisms in order to obtain information about the
V. Subotić and C. Hochenauer Progress in Energy and Combustion Science 93 (2022) 101011

expected degradation in SOFCs. They discussed the possibility of using

semi-empirical fitting models to achieve this purpose, in which degra­
dation D can be accelerated by appyling an accelerating factor AF as a
function of a specific stressor s. Thus, a universal degradation function
employing the above mentioned accelerating functions of specific
stressors can be provided as follows.
D(s) = D(s0 )⋅AF(s) (24)

In this function, AF(s0 ) = 1, AF(s) is assumed to be a positive function of

a stressor s, whereby D is a function (e.g., Weibul exponential) rather
than a constant. This describes a distribution of degradation. In [251],
the authors investigated the impact of the operating temperature and the
steam partial pressure on the SOFC performance deterioration. They
noted that increasing the temperature accelerated the Ni-coarsening
process and identified the steam partial pressures higher than 0.15 as
critical regarding morphological fuel electrode changes. The combined
impact of both accelerating stressors is presented in Fig. 9, which are
useful for predicting the accelerating impact.
The importance of the accelerating testing has already been proven
for proton electrolyte membrane (PEM) cells, as shown in numerous
studies [254–257]. Nevertheless, although accelerating testing can yield
important information about the expected cell lifetime and behavior,
and especially regarding the design, manufacture and operation of the
SOCs, only a few experimental studies have been carried out specifically
to investigate accelerated degradation in either SOFC or SOE. To date,
the long-term data for SOFC operation (i.e., longer than 20,000 h) are
mainly available at Forschungszentrum Zentrum Jülich. In their recent
study, Blum et al. [258] compared results for the SOFC stacks operated
at 20,000 h and 40,000 h. Two different stack types were compared with
each other; the first one as a four-layer stack containing cells with a
10x10 cm2 surface area and an active area of 80 cm2 , and the second one
Fig. 11. Changes in electrochemical performance and microstructure of SOFC
as an 18-layer 20x20 cm2 cell (active area of 360 cm2 ). Thus, extended as a function of the operating temperature for stacks (reprinted from Ref. [258]
knowledge about the SOFC long-term behavior, its degradation and with permission from Elsevier) and for single-cells as a function of the air
possible accelerated stacks testing could be gained. The authors volume flow (reprinted from Ref. [149] with permission from Elsevier).
observed that, when increasing the operating temperature from 700∘ C to
800∘ C, the degradation rate was increased from 1%/1,000 h up to influenced by changing specific operating conditions, which may not
1.5%/1,000 h, which was mainly caused by chromium poisoning. The appear as relevant for the real operation. Thus, the authors suggested
performance and morphology degradation described are illustrated in first investigating each degradation process individually under acceler­
Fig. 10. Moreover, they showed that the degradation rate does not ated conditions.
change when increasing fuel utilization from 40% up to 70–80%. They Based on this conclusion, in [149] the same cell type with an active
also reported that different degradation mechanisms could be surface of 80 cm2 was used, and the operating environment was
designed in order to accelerate the following degradation phenomena
separately: carbon deposition, fuel electrode degradation initiated by
high fuel utilization and air electrode degradation caused by high oxy­
gen utilization. S/C=0.5, fuel utilization higher than 90% and air uti­
lization higher than 70% were identified as significantly accelerating
degradation during the SOFC operation. Almost the same conclusion
regarding the carbon deposition degradation was reached in [112] for
electrolyte-supported SOFCs. Bianco et al. [260] investigated the
degradation of stack interconnects as a function of the operating time
and the operating current density. The main conclusion drawn is that
degradation on the interconnect air side stabilizes after 5,000 h.
An interesting fact is presented in [261], in which the authors pre­
sented a link between an initial fuel electrode resistance and degrada­
tion: Low starting ASR values of the fuel electrode could be associated
with faster degradation. This can be easily explained as follows: A low
ASR is associated with high TPB and Ni-particles distribution, which
results in higher activity in the cells used [262,263]. The fuel electrode
deactivation mechanisms that occur due to Ni coarsening and particle
growth are more pronounced for such electrodes with a higher number
of smaller Ni-particles, as stated in [264]. Another interesting approach
was presented by Polverino et al. [259], who proposed using a multi­
scale modelling framework to link SOFC degradation with accelerated
Fig. 10. Comparison of the impact of two different accelerating stressors on (T
stress test protocols. This model is provided to predict (i) Ni agglomer­
and p(H2 O)) under nominal operating conditions. Reprinted from Ref. [251]
with permission from Elsevier.
ation and (ii) SOFC performance as a function of the key mesoscale

17
V. Subotić and C. Hochenauer Progress in Energy and Combustion Science 93 (2022) 101011

Table 4 Table 4 (continued )

Accelerated stress testing for SOFC. Accelerating Observed result Critical operating Source
Accelerating Observed result Critical operating Source parameter conditions
parameter conditions
pressure between degradation, only by
Operating Increasing temperature T↗ 1 bar and 5 bar fuel electrode pressure.
[258] over 5,000 h Degradation rates at
temperature from 700∘ C up to 800∘ C
increases degradation T=800∘ C, i=0.5 A/cm2 :
rate from 1%/1,000 h 5.16 mV/1000 h at 1
up to 1.5%/1,000 h, bar; 2.0 mV/1000 h at
mainly caused by Cr- 2 bar; 1.22 mV/1000 h
poisoning at 3 bar; 0.93 mV/1000
h at 4 bar; 0.8 mV/
Temperature Increasing temperature T > 900∘ C
[251] 1000 h at 5 bar
disregarding accelerates Ni-
steam/hydrogen coarsening
atmosphere

Temperature at high Temperature increase Increasing parameters such as electrode conductivity, fuel electrode TPB length and
[251]
steam partial from 700∘ C to 800∘ C temperature mean hydraulic pore radius. An SOFC performance model was also used
pressure accelerated coarsening in which already well-known equations and principles from other
of Ni-particles by a
studies were applied. The creation of such a model was, however,
factor of four at
p(H2 O)=0.5
necessary, to examine the impact of Ni-agglomeration on performance
degradation. The results observed are discussed in Table 4. Fitting the
Steam at low Degradation rate lower Steam partial
[251] results observed to an appropriate curve, the authors tried to find the
temperatures for the inlet steam pressure p(H2 O)>
pressure of p(H2 O)= 0.15 right transfer function to correlate the accelerating stressor and the
0.04 and p(H2 O)=0.15 degradation rate.
than for p(H2 O)=0.25 Accelerating stressors for the SOFC operation, their impact on the
and p(H2 O)=0.4
observable SOFC performance and especially the critical operating
S/C Very low S/C ratio S/C<0.1 [112, conditions are summarized and discussed in Table 4.
significantly accelerates 149] Accelerated stress testing for SOE. Although the number of available
carbon-formation,
studies that focus on accelerated degradation in SOFC is low, the number
blocking gas channels
and covering the of available studies related to the SOE operation is even more restricted.
catalytic active sites Nechache et al. [265] examined the impact of Si-containing impurities
Fuel utilization High fuel utilization FU>90% [149] on YSZ stability, increasing the operating current density up to 1.7
accelerates Ni- A/cm2 . They came to the conclusion that, when increasing the operating
reoxidation and Ni- current density to the values higher than 0.6 A/cm2 , the YSZ electrolyte
agglomeration
began to be electronic conductive, which is an undesired feature. This
Air utilization High air utilization AU>70% [149] occurs as a result of the formation of numerous micropores within the
accelerates air electrolyte. Moreover, cracks appeared and delamination in the
electrode
decomposition and
YDC/YSZ layer occurred. Such strong YSZ degradation was observed
interlayer delamination only after 350 operating hours. The impact of increasing operating
current density on accelerating degradation was also determined in
Operating time of Ni-agglomeration and not discussed
20,000 h at 800∘ C increase of Ni-particles
[259] [136]. Increasing the current density from 600 mA/cm2 up to 1,200
and 0.5 A/cm2 at: (i) fuel electrode mA/cm2 resulted in more pronounced morphological changes in the air
functional layer by electrode over a period of only 80 h. Those included intensified Sr
3.7%, (ii) fuel electrode
support by 0.8%, (iii)
segregation that was identified while operating at 600 mA/cm2 , but also
decrease in TPB length additional Sr deposition within the GDC layers and delamination of the
by 24%, (iv) decrease in GDC/LSCF interface. Besides the operating current density, a number of
the fuel electrode different parameters can accelerate degradation when using the elec­
interlayer conductivity
trolysis mode, such as high steam partial pressure, load cycling, high
by 70%, (v) decrease in
the fuel electrode voltages, steam starvation and even reversible operation, as reported by
support conductivity by Königshofer at al. [137] in a study performed on 5 single-cells. The
18%, (vi) increase in authors provided accelerated stress test protocols for the SOE operation
ohmic and activation as a function of the previously mentioned parameters and supported
losses by 25%
them by morphological post-mortem analyses. They also showed that
Operating Increasing operating i>1.0 A/cm2 at different accelerating parameters result in different degrees of
[259]
temperature and temperature in a range 600∘ C; i>1.9 A/cm2 degradation.
current density 600–800∘ C and current at 650∘ C; i>3.0 A/
over 5,000 h density in a range 0-0.5 The knowledge gained on a single-cell level was further applied on
cm2 at 700∘ C; i>4.2
mA/cm2 accelerates A/cm2 at 750∘ C; the stack level in [266]. The results observed show that lower temper­
voltage degradation as i>4.8 A/cm2 at atures and higher voltages as well as high steam conversion rates
follows: 1.04 mV/1000 800∘ C; accelerated degradation. In contrast to these results, operation under
h at 600∘ C, 1.63 mV/
high steam partial pressure resulted in a stable degradation rate. The
1000 h at 650∘ C, 2.41
mV/1000 h at 700∘ C, impact of high steam partial pressure on the performance and
3.45 mV/1000 h at morphology of both single-cell and stack is shown in Fig. 11. The data
750∘ C and 5.16 mV/ found regarding the AST for SOE, the observed results and the critical
1000 h at 800∘ C
conditions are summarized and discussed in detail in Table 5.
Fuel electrode and No impact of air lower fuel electrode
[259]
air electrode electrode pressure on pressure

18
V. Subotić and C. Hochenauer
Fig. 12. Changes in electrochemical performance and microstructure of SOE under high steam amount (H2 O/H2 =95/5) and 835∘ C at 500 mA/cm2 for single-cells
and 800 mA/cm2 for stack. Single-cells and stack have same microstructure. Reprinted from Ref. [137,266] with permission from Elsevier.
4. State-of-the-health diagnostics for running SOC
The commercialization and long-term application of SOC-based
systems in the future energy system will be possible, if their reliability
and lifetime can be controlled and prolonged properly. These aspects are
feasible, if important information about the system state of the health
can be determined when undesired changes first occur that could be
fatal for the system operation. By performing reliable online state-of-the-
health (SoH) estimations, likely end of life as well as maintenance ac­
tions can be designed optimally, hence preventing equipment damage
and loss of operability. Much research has already been carried out to
address this issue and much research is still ongoing.
This section provides an overview of different available diagnostic
tools that enable the identification of degradation at an early stage, thus
preventing irreversible degradation. The most commonly used tools,
parameters that can be identified using these tools and information they
provide are shortly summarized in Table 6. The most relevant current/
voltage-based conventional and non-conventional SoH tools that are (i)
applicable in both laboratory and real-operating environment, (ii) time-
and cost-efficient and (iii) can easily be implemented in systems,
namely, polarization curve, electrochemical impedance spectroscopy,
its advanced methodology distribution of relaxation times and total
19
Progress in Energy and Combustion Science 93 (2022) 101011
harmonic distortion analysis, are described and discussed in detail
below. Much attention is especially given to understanding the elec­
trochemical impedance spectroscopy (EIS), since this provides a basis
for all further SoH tools. Its advanced distribution of relaxation times
(DRT) methodology is also explained in detail, since this enables the
identification of specific frequencies to separate the ongoing processes
within SOCs. A comprehensive study on the available DRT was carried
out; these are summarized in Fig. 14 making a novel contribution to the
scientific community. This significantly helps researchers to easily
analyze the SOC processes.
Before a detailed description of the above-mentioned SoH tools is
provided, it is important to mention that the criterion of reliability must
be met both during the electrochemical measurement procedure and
data processing. In this context, e.g., the criterion of the stationary
system behavior must be met, which requires a specific testing speed to
be used. Moreover, the operating conditions should not be changed at
any time, e.g., during the running measurement. For more information
on this topic, we refer the reader to the work of Klotz et al. [286], which
presents a guideline for making reliable electrochemical measurements.
V. Subotić and C. Hochenauer Progress in Energy and Combustion Science 93 (2022) 101011

Table 5 Table 6
Accelerated stress testing for SOE. Summary of available in-operando diagnostic tools applicable for both operating
Accelerating Observed result Critical operating Source
modes and their application.
parameter conditions Diagnostic tool Parameter Information Source
provided
Si-containing For i>0.6 mA/cm2 YSZ i > 0.6 A/cm2
[265]
impurities and becomes electronic Temperature monitoring via Temperature, Reactions [267–270]
operating conductive; appearance of thermocouples, temperature distribution
current density numerous micropores thermography, light imaging distribution along the cell,
within YSZ, cracks and heat losses,
delamination at the YDC/ endothermal
YSZ interface vs. exothermal
Increasing Increasing i from 600 mA/ i > 600 mA/cm2 reactions
[136]
operating cm2 up to 1,200 mA/cm2 Gas analysis, gas Gas Concentration [48,114,
current density intensified Sr-segregation chromatography components of specific gas 271]
and resulted in additional components,
degradation mechanisms: species
Sr deposition withing the distribution,
GDC interlayer and estimation of
damaging of the GDC/ chemical
LSCF interface reactions,
High steam partial Increase of cell voltage, H2 O/H2 ≥ 90/10, equilibrium
[137]
pressure inhibited diffusion of H2 O, V = Vmax (∼1.35 V), state
H2 T = Topt (835∘ C) Mass spectrometry Mass spectra Species [65,80]
Redistribution Ni, traces of t > 200 h of gases concentration,
[137]
Ni-agglomeration and Ni- species
reoxidation, Species distribution
deposition at air electrode Spectrochronopotentionmetry, Wavenumber Carbon [63,
structure Raman vibrational and Signal deposition, Ni- 272–274]
Load cycling Slightly unstable cell H2 O/H2 ⩾ 80/20, spectrometry intensity reoxidation,
[137]
(dynamic voltage, inhibited diffusion V = Vmax (∼1.35 V) degradation
operation) of H2 O, H2 Voltage and current monitoring DC voltage, Voltage and [75,267,
O2 , charge transfer and T = Topt (835∘ C), i1.0 system DC current current 275]
[137]
ionic transfer = i @ Vmax , i0.5 = distribution
i1.0 ⋅ 0.5 Polarization curve Voltage, Power, overall [276–278]
Redistribution of Ni, local Interval ≤ 1 h, t > current losses
[137] Electrochemical impedance AC voltage, Process [279,280]
Ni-agglomeration, surface- 200 h
segregation of Sr spectroscopy analyzer AC current, mechanisms,
High voltages Moderately unstable cell H2 O/H2 = 80/20, V impedance polarization
voltage, slight increase of > Vmax (∼1.35 V), T losses
ohmic resistance and high < Topt (835∘ C), i ⩾ Equivalent circuit model Current, Process [281–283]
frequency -800 mA/cm2 analysis voltage, mechanisms
Big Ni-grains, traces of Ni- t>200 h equivalent
[137] circuit
agglomeration, foam-like
layer on surface of LSM elements
Reversible Improvement of cell H2 O/H2 = 50/50, V Total harmonic distortion Higher System non- [112,149,
operation voltage, more stable = Vmax (∼1.35 V), T analysis harmonics, linearity, 284,285]
operation at lower = Topt (835∘ C) signal degradation
intervals, slight increase of distortion processes
impedance of steam
electrode related processes
Local occurrences of Ni- t ≤1 h, t>200 h When applying the second method, a fast hold time acquisition method
[137]
agglomeration/- is used. The aim of using this method is to avoid sensible temperature
reoxidation
variation, which requires a rapid increase in the current density, not
higher than 10 s. The guidelines for a correct measurement procedure of
4.1. Conventional characterization tools based on linear system analysis polarization curves is described in technical reports, as follows
[288–292].
The examination of electrochemical systems usually starts with an The shape of the characteristic polarization curves enables initial
application of conventional monitoring tools, such as voltage moni­ conclusions to be drawn about the loss mechanisms involved. However,
toring. Voltage monitoring provides information about cell performance further information is required to determine the exact distribution of
at a specific operating point. In order to obtain information about the losses, their origin, or even specific failure modes at their initial stage,
SOC behavior at different operating points, polarization curve mea­ which can be gained when employing more complex measuring prin­
surement is usually employed. The polarization curve measurement is ciples such as linear and non-linear electrochemical impedance
the most widely used method for the electrochemical characterization of spectroscopy.
fuel and electrolysis cells. This measurement can be carried out either (i)
step by step by selecting individual points or (ii) by continuously
changing the specified value for the current or voltage. The choice of test 4.2. Electrochemical impedance spectroscopy (EIS)
speed is mostly a question of a compromise and depends on the re­
quirements to obtain relevant results. Two different methods are used to Electrochemical impedance spectroscopy (EIS) is an established non-
obtain current density profiles, as reported in [287]. Employing the first destructive methodology used to analyze processes and mechanisms that
one, the current density is increased in specific steps from OCV to the occur in electrochemical systems [293]. It is also called impedance
maximum current density at 0.7 V. A stable measurement is carried out spectroscopy or AC impedance. For the purpose of EIS measurements, a
at each current density step with a typical holding time of approximately sinusoidal current or voltage perturbation is superimposed on the sys­
10 minutes, after which the thermochemical equilibrium is reached. tem running under DC conditions, and the corresponding system
response is measured. The measurements are usually carried out in a

20
V. Subotić and C. Hochenauer
range of 1 MHz to 100 mHz. Depending on the processes that are ex­
pected to occur, the frequency range can be adjusted. For instance, if
very slow processes will be examined, the low frequency range is
reduced down to 1 mHz. The high frequency range, however, depends
on the system inductance, which can significantly decrease the upper
frequency limit. Eventually, impedance is calculated as a vector ratio of
the voltage and current for the specified frequency range (see Eq. 25).
u(t) U
Z(jω) = = exp(j(φ − ψ ))
i(t) I
Depending on the system boundaries, the system can be operated in
(i) a pseudo potentionstatic mode in which the voltage is controlled and
the current is measured or in (ii) a pseudo galvanostatic mode, in which
the current is controlled and the voltage is measured. For the SOC sys­
tems, the galvanostatic mode is commonly employed. When operating
the system in the potentiostatic mode, the voltage applied corresponds
to u = uDC + uAC , whereby the current response measured can be pre­
sented as a Fourier series as follows [18]:
i(t) = i0 + i1 sin(ωt + ψ 1 ) + i2 sin(2ωt + ψ 2 ) + … + in sin(nωt + ψ n )
In the opposite case, when operating the system in a galvanostatic mode,
the current applied is equal to i = iDC + iAC . The corresponding system
voltage response can be obtained as follows [18]:
u(t) = u0 + u1 sin(ωt + ξ1 ) + u2 sin(2ωt + ξ2 ) + … + un sin(nωt + ξn )
4.2.1. Basic principles of the EIS measurement
In order to carry out the impedance measurements correctly and to
ensure their quality, several requirements must be fulfilled, including:
steady-state, causality, time-invariance, and linearity [294]. Before
taking the measurements, the criteria of stability and steady-state for
both electrodes must be confirmed, which is achieved for the system in a
thermochemical equilibrium state. If the measured signal response is a
sinusoidal waveform signal and directly corresponds to the applied
input signal, the system is causal. A system function of the electro­
chemical systems under investigation is only indirectly dependent on the
time-domain, meaning that the system is assigned as time-invariant.
Eventually, the linearity criterion must be satisfied. In order to main­
tain system linearity, the signal amplitude must be low enough to attain
the pseudo-linear system response [295,296]. However, amplitudes that
are too small result in poor signal-noise ratio, indicating that a suffi­
ciently high amplitude value should be chosen to reduce the signal
noise. The criterion of system linearity cannot be violated as the
amplitude increases, because the well-known linear system theory needs
to be applied in either the time or frequency domain [17]. If the linearity
criterion is disturbed and nonlinearity appears, a nonlinear analysis
must be applied.
As a perturbation signal both current and voltage can be employed.
Different current amplitudes have already been applied for this purpose,
e.g., 20 mA [297], 10–40 mA [296], 60 mA [298–301] and even 100 mA
[302]. Recently, the measurements were performed with the
AC-amplitude varied as a function of the DC-load, e.g., 4% of the DC load
without violating the system linearity [8,112]. Different AC voltage
amplitudes have also been suggested in the available literature: 10 mV
[303,304], 12 mV [305], 14 mV [304] and, 50 mV [306]. Besides the
conventional principle of setting a constant amplitude while taking one
measurement, the random binary signal (RBS) has recently been
approved as a successful and time-efficient means of taking impedance
measurements [307,308]. This principle is based on the amplitude
variation at random time instances and its adjustment for different
frequencies.
A comprehensive description of the basic impedance principles,
measurements, instrumentation, analysis, fitting procedures, modeling
and much more can be found in recent books published by Orazem
[309], Barsoukov and MacDonald [295], Lvovich [310] and Lasia [311].
Progress in Energy and Combustion Science 93 (2022) 101011
4.2.2. Equivalent circuit model (ECM) analysis
Interpretation of the measured impedance data can be simplified by
utilizing an equivalent circuit model (ECM) to fit the measured data. In
an ECM, different elements are connected with each other to illustrate
the SOC behavior. The elements used illustrate physical and chemical
processes that occur, such as electrochemical reactions, electron and
mass transfer and electrolyte resistance [17]. These elements used can
be classified into two groups: (i) the lumped element model resistance
(25) (R), capacitance (C) and inductance (L) and (ii) frequency-dependent
elements such as the constant-phase element (CPE), Warburg element
(W), Gerisher element (G) and bounded frequency-dependent elements
[17]. Ideal capacitances have rather rarely been observed to illustrate
behavior for solid oxide cell-based electrochemical systems. This is
clearly seen in the measured EIS semi-circles that are depressed and thus
deviate from ideal 90∘ . The constant-phase element is an appropriate
element to be used here, which presents a non-perfect capacitance built
of resistance and capacitance elements and the arc observed is presented
at an angle of (n-1)⋅90∘ . Ricciardi et al. [312], who investigated the
SOFC air electrodes, reported that this element can be correlated with
(26)
the irregular electrode surface, and its roughness as well as distribution
of activation energy can be related to reduction processes. Nevertheless,
Lvovich [310] showed that, depending on the n value, the CPE element
can depict a number of properties and processes in SOCs, e.g., electrode
porosity and thickness, surface coating and its conductivity, slow
(27) adsorption processes, crystal phases and grain boundaries of poly­
crystalline electrodes, and even inhomogeneity in the current and po­
tential distribution along the electrode. If diffusion processes are
dominant, the Warburg element is used for their description instead of
the CPE element [280]. The Warburg element is thus related to the
resistance to the current flow of electroactive species [310], and it is
especially employed for large planar electrodes. When these electro­
active species undergo chemical reactions in the bulk, a Gerischer
element is used. This is mainly related to homogeneous reactions and, at
very low frequencies, it reaches a constant value, which is inversely
proportional to a kinetic rate constant [310]. The Gerischer element is
also often correlated with the air electrode oxygen surface exchange
kinetics and bulk diffusion of O2− [313]. A detailed description and
mathematical explanations for different elements are provided by Lvo­
vich [310], Barsoukov and Macdonald [295], and Stoynov and Vladi­
kova [281].
To date, numerous equivalent circuit models have been developed in
order to evaluate the SOC performance and gain better insights into the
processes that occur. The commonly used EC models are based on the
complex nonlinear least squares (CNLS) principle. The EC presented in
[314] contains five serially connected elements: (i) R0 ohmic losses, (ii)
RQ-elements for gas diffusion and activation polarization in the fuel
electrode functional layers, (iii) G-Gerischer elements to describe the air
electrode activation polarization, (iv) the Warburg element W to illus­
trate the fuel electrode gas diffusion polarization, and (v) the RQ
element, which has a significant impact when p(O2 ) is lower than 0.05
atm on the air electrode. This model is shown in Fig. 12 a. An equivalent
circuit that is exactly the same was presented in another work by the
same research group [315]. However, in that study, the last RQ-unit was
associated with the processes that occur under reformate operation.
Sumi at al. [316] employed a different EC consisting of mainly R, C and
Q elements as presented in Fig. 12 b. L-R depicts the large noise obtained
at high frequencies for the lead wires, and the remaining R-Q elements
present processes that take place in microtubular SOFCs. The same
model that was used by Sumi et al. [316] was used by Nielsen and
Mogensen [178] to investigate degradation in LSM:YSZ air electrodes
induced by steam.
In addition to the fuel cell operation, the authors also analyzed
processes that occur in the electrolysis mode with the EC model as
shown in Fig. 12 c. Yang et al. [299] fitted two equivalent circuits using
the CNLS method and the Ravdav software, both of which were based on
21
V. Subotić and C. Hochenauer Progress in Energy and Combustion Science 93 (2022) 101011

Fig. 13. CNLS equivalent circuits used for SOCs used from different mentioned references with permission from Elsevier.

previously performed studies and a distribution of relaxation times re­
sults. In the second EC variant, mentioned as B, an additional element
consisting of the resistance R6 in series with inductance L6 describes
only the low frequency loop that was observable in specific cases at low
frequencies (f<0.5 Hz). The same EC as presented in [314] (Fig. 12 a)
was successfully implemented to examine the behavior of stacks
operated in a reversible mode [267].
Moreover, the cell impedance for reversibly operated SOCs was
illustrated by linearizing the fundamental equations and approaching
the losses by creating a Taylor series [8]. In that simulation, the cell was
considered as both only one segment and as a unit consisting of several
segments: therefore, two different approaches were used to simulate

22
V. Subotić and C. Hochenauer
impedance losses. The first one is presented as a 1D-model for
one-segment cell, as shown in Fig. 12 d, and the second one is suitable
for the 2D-model, in which one cell consists of several segments, as
presented in Fig. 12 e. Aside from the aforementioned complex equiv­
alent circuits, simpler circuits that use solely R, L, C and/or Q elements
have also been employed to reproduce the SOC behavior. When
increasing the complexity of the EC, thus increasing the number and
diversity of the elements, better overlapping will be achieved. However,
this is not the goal, because the number of the elements used should be
kept as low as possible, and the usage of the elements should be
meaningful. This means that the processes that occur must be explain­
able with the elements used. In this sense, we suggest to initially
compare the cells or stacks used with those available in the literature
and to try to use the already proved ECMs. In the further steps, if these
seem to be inappropriate for the system under investigation, the ele­
ments should be replaced and the new, more appropriate ECM should be
created.
However, before employing the ECM chosen for the process analysis,
the measured and fitted data must be compared in order to verify and
validate the circuit elements used. If such a step is neglected, the further
suitability of the ECM data for the detailed analysis cannot be assessed.
In [296], an interesting approach is proposed to validate the EC used.
Three different ECMs, (i) RL-RC-RC, (ii) RL-RC-RQ and (iii) RL-RQ-RQ,
were used to find the most appropriate one for the system under
investigation. After fitting, the values of the EC individual elements were
calculated and further used to calculate the polarization curves. To
calculate the polarization curves from the data available, different ap­
proaches were utilized for this purpose, such as Euler’s implicit nu­
merical integration, Euler’s explicit numerical integration and
trapezoidal function. After selecting the most suitable calculation
methodology, the polarization curves were calculated using the ohmic
values from the relevant elements of all three different ECs and even­
tually compared with the measured data. Following this strategy, an
excellent choice of the correct EC can be made.
4.2.3. Impedance analysis of SOC systems
An analysis of the solid oxide cell-based systems is currently un­
imaginable without using electrochemical impedance spectroscopy. EIS
is used to characterize SOCs at different levels, starting with the mate­
rials, over individual electrodes, electrolytes and single-cells and up to
the stack level. In specific cases, the losses that occur cannot clearly be
assigned to the individual electrodes, which, in turn, requires mea­
surements involving the reference electrode. However, measuring with
the reference electrode is a very challenging and thus non-trivial
approach, since its position on the electrolyte can significantly affect
the accuracy of the electrochemical measurements. Adler et al. [317,
318] examined impact of the reference electrode on the potential dis­
tribution within a solid electrolyte and near the electrode, both exper­
imentally and numerically. They came to the conclusion that, in order to
avoid undesired potential gradients along the electrolyte, the distance
between the reference electrode and each active electrode should be at
least three electrolyte thicknesses. Moreover, measuring on symmetric
cells seem to be more easily done than measuring on the single-cells.
When employing single-cells, the electrolyte thickness should be
significantly increased. The same distance of at least three electrolyte
thicknesses was also confirmed in [319,320]. In contrast to the results of
those studies, another study [321] claimed that the necessary minimum
distance should account at least 50 electrolyte thicknesses in order to
avoid the potential difference along the electrolyte and, thus, the impact
on the measurements. A discussion on the possible cell configuration for
performance evaluation in SOFCs is reported by Jian [322]. In a general
sense, when starting to characterize SOCs by means of electrochemical
impedance spectroscopy, it is firstly important to perform a reference
measurement in order to observe the initial performance and understand
the SOC behavior under degradation-free conditions. Secondly, a spe­
cific time interval for repeating the measurements should be set to
23
Progress in Energy and Combustion Science 93 (2022) 101011
monitor changes that occur as a function of the operating time.
Impedance analysis of SOC operation in the SOFC mode. Zhu and Kee
[323] simulated impedance spectra for the case of internal methane
reforming, taking into consideration the fuel mixture of
CH4 /H2 O=90/10 and varying the current density between 0.2 A/cm2
and 3 A/cm2 . Initially, two semi-circles were observed, both of which
had similar heights and lengths. Increasing the current density up to 1
A/cm2 , the losses decreased, and it seemed as though the two
semi-circles merged to form one semi-circle. However, when further
increasing the operating current density, the losses started to increase,
and the first semi-circle was larger than the second one, an event that
can be correlated with the rising concentration losses. Barford et al.
[301] studied losses that occur in fuel electrode-supported SOFCs as a
function of the operating time and the operating temperature. The
impedance spectra were measured before and after the change was
carried out, thus calculating differences that occur in the impedance
values. These differences were mainly in the derivate with respect to the
ln(f) of the real impedance part and were related to the specific fre­
quencies. Such an analysis provided information that enabled the three
peaks to be assigned to each electrode. Regarding the LSM/YSZ elec­
trode, peaks of 10 Hz, ∼ 300 Hz and ∼ 10 kHz were identified, and the
analysis results agreed closely with the results shown in [324].
Regarding the Ni/YSZ electrode, the 0.1-10 Hz range was associated
with a gas-conversion arc: the 10 Hz-1 kHz, to a gas-diffusion arc: and
1–10 kHz, to a gas-solid or solid-solid arc. This association corresponds
with the results presented in [325–327]. The same principle of param­
eter variation used to obtain more information about the impedance
alternations was applied in [296]. Three different fuel mixtures were
used on the fuel electrode: (i) H2 /H2 O, (ii) H2 /H2 O/CO, and (iii)
H2 /H2 O/CO/CO2 /CH4 . When varying between the fuel components, the
most relevant changes occurred in the second arc, between approxi­
mately 50 Hz and 100 mHz, enabling these changes to be correlated with
the fuel electrode processes. Mogensen and other researchers from the
same research team investigated both fuel electrode degradation [328,
329] and air electrode degradation [178] by means of electrochemical
impedance spectroscopy. In [178], the impact of moisture on the air
electrode degradation was identified as affecting the YSZ interface and
causing LSM decomposition. Such morphological changes could be
linked to the high frequency arc and increasing capacitance. Gas
cleaning procedures also have important impacts on the SOFC perfor­
mance, e.g., H2 cleaning reduced performance losses even by a factor of
2–3, which was observed by EIS measurement [328]. Moreover, in the
same study, the EIS measurements enabled researchers to gain signifi­
cant knowledge about the impact of p(H2 O) on the Ni/YSZ degradation
and identify the most relevant parameter as the characteristic time.
When increasing the p(H2 O) from 0.2 atm up to 0.4 atm, the degradation
time was reduced from 134 h down to 17 h. Jensen et al. [330] also
varied operating parameters such as temperature and the partial pres­
sure of the reactants to monitor the changes that occurred and separate
the fuel electrode and air electrode processes that overlapped in the
Nyquist plot.
Impedance analysis of SOC operation in the SOE mode. Impedance
monitoring has also often been used to control the performance degra­
dation as a function of the operating time. Yang et al. [299] examined
SOE behavior under thermoneutral voltage of 1.29 V as a function of the
operating time of over 1,000 h and the operating temperature that was
varied between 700 ∘ C, 750 ∘ C and 800 ∘ C. Regardless of the operating
temperature, the impedance and thus the overall losses increased as the
time increased. During the initial 300 h, strong degradation was
observed. After 300 operating hours, the cells operated at 750 ∘ C pro­
vided the same performance as the cells operated at 800 ∘ C. This was,
however, even 74% higher than the cell performance observed at 700 ∘ C.
The results described are presented in Fig. 13. The EIS results observed
clearly indicate enhanced degradation as the time increased, which the
authors correlated with the Ni/YSZ electrode in all the three cases.
V. Subotić and C. Hochenauer
Fig. 14. EIS and the corresponding DRT for SOC. Reprinted from [299] with permission from Elsevier.
Taking into consideration alternations on the air electrode, the LSM
electrode delamination and formation of nanoparticles can be identified
as an increase in both ohmic and polarization resistance. This was pre­
sented by Chen and Jiang in [187], in which they operated the elec­
trodes for 48 h of at 500 mA/cm2 and employed an equivalent circuit for
a subsequent analysis. The main conclusion drawn was that the HF arc is
solely correlated to the electrode/electrolyte interface and O2− migra­
tion from the electrolyte towards the electrode. The increase in both the
ohmic and polarization resistance was also correlated with the silica
segregation on the Ni/YSZ-surface by Hauch et al. [331]. The same ef­
fect of increasing ohmic and polarization resistance was observed in
[136] for the case of strong Sr-segregation within both the LSCF elec­
trode and GDC interlayer, which caused interlayer delamination and the
formation of a Sr-layer on the boundary with the electrolyte. This was
caused by the operation under a high current density of 1.2 A/cm2 for
80 h. Decreasing the operating current density down to 600 mA/cm2 ,
degradation was reduced and resulted in the formation of the Sr-layer
between the electrolyte and the GDC-layer, which displayed the
increasing polarization resistance, whereby the ohmic resistance
remained constant. Knibbe et al. [186] also confirmed that higher cur­
rent densities (>1 A/cm2 ) result in intensified degradation and an
increased number of degradation mechanisms. This was illustrated by
the increasing ohmic resistance presented as the increasing polarization
drop across the oxygen electrode. The latter can be attributed to the O2
formation in YSZ grain boundaries near the oxygen electrode. Never­
theless, the polarization resistance did not show any systematic
behavior.
Considering the stack level, several studies are available in the
literature. When operating the 10-cell SOC stack consisting of
electrolyte-supported cells, as shown in [332], the electrolysis mode
operation resulted in increasing losses - both ohmic and polarization -
when increasing the H2 O/H2 ratio from 80/20, over 90/10 and up to
95/5. As the operating current increased, the difference between the
Nyquist plots reduced significantly for all the three H2 O/H2 -ratios. For
the selected gas mixture of H2 O/H2 =90/10, the impedance spectra
remained unchanged over 40 h. This was indicative of the stable oper­
ation without visible degradation. For the same stack operated in a fuel
cell mode, the reformate mixture was used as a fuel, and several pa­
rameters were varied. This meant that when decreasing the fuel flow
under a current density of 200 mA/cm2 , increasing polarization losses
and a significant increase in the second arc were observed. This was
indicative of the increasing concentration losses. Varying the operating
temperature only shifted the spectrum along the x-axis, which is linked
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Progress in Energy and Combustion Science 93 (2022) 101011
to the temperature dependent electrolyte resistance. Similar behavior
was observed as a function of the operating temperature. When per­
formed on each single cell within the stack, an impedance analysis can
provide useful information about the performance of single cells within
the stack, as reported by Yan et al. [333]. This enables researchers to
identify discrepancies between single cells and to make conclusions
about their state of the health.
4.2.4. Discussion and concluding remarks
Considering the studies available and comparing them to each other,
the conclusion can be made that impedance simulations have primarily
been designed for ideal systems. Nevertheless, the experimental setup
plays a significant role when investigating system processes by means of
EIS. In order to obtain the most representative results, we suggest to
carry out initial measurements for the system used and to vary relevant
operating parameters, such as temperature, partial pressure of gaseous
species and operating current. Analyzing variations related to the spe­
cific electrodes, process mechanisms can be identified and moreover
correlated to the electrodes. In addition, the electrochemical impedance
spectra provide many overlapped processes and easily differentiating
between single electrodes and individual processes is a challenging
approach.
Traditionally, impedance analysis is carried out employing electrical
equivalent circuits; these make the fitting of the measured impedance
possible. Specific groups of elements are assembled to illustrate the
behavior of complex electrochemical processes, representing processes
in different frequency ranges. Nevertheless, although a fitting an ECM
based on the mathematical model can always provide solutions, the
meaning and relation to physical processes are not always completely
clear. Finding a correlation between the model parameters and SOFC
properties is a challenging task. It is also highly challenging to extract all
the complex processes that occur on the microscopic level and their
coefficients from the EIS spectra, in which different physical and
chemical processes overlap, and to correlate them with the EC elements
used. A number of different ECMs are presented in the available litera­
ture, which shows that different ECMs provide the same fitted spectra.
Thus, employing the ECM principle presumes that number of processes
should be known and a priori defined, since increasing complexity of the
ECM can lead to either under- or over-fitting. In order to be able to
clearly differ between the single electrode processes without a necessary
prior knowledge, distribution of relaxation times is gaining increasing
attention as a sophisticated analysis tool. Its basic principles and results
observed for SOFCs and SOEs are presented in the following section.
V. Subotić and C. Hochenauer Progress in Energy and Combustion Science 93 (2022) 101011

Fig. 15. Overview of the process mechanisms as a function of DRT frequency values summarized by the available literature: FE: fuel electrode, AE: air electrode, AE/
FE: both electrodes, FE/E: fuel electrode/electrolyte, red: temperature impact on the cell level. (For interpretation of the references to colour in this figure legend, the
reader is referred to the web version of this article.)

4.3. Distribution of relaxation times (DRT)
Distribution of relaxation times is a sophisticated complementary
tool that enables researchers to extract the most dominant time con­
stants from the measured EIS data and to correlate them with the specific
mechanisms. Employing the DRT principle, it is assumed that at each
measured frequency specific process can be identified, which is usually
represented by a number of RC, or more recently, RQ elements which are
connected in series. The optimization algorithm is applied to find the
lowest number of elements that is appropriate to depict the processes
that occurs in a running SOC system. As reported by Nechahe et al.
[334], DRT analysis is of particular interest, because it excludes the
users’ subjectivity, as in the case of the ECM. Thus, it can be used as a
preliminary step in identifying an appropriate ECM. When making a
detailed comparison between the ECM and DRT, in [313], the authors
claim that two different approaches are applicable with regard to the
impedance data deconvolution. The first one focuses on employing the
simple ECM containing a number of RC elements as a basis for DRT,
without any previous knowledge regarding the physical behavior of the
system under investigation. The second approach proposes the opposite
tactic, which means that DRT combined with the experimentally
observed impedance spectra can be used to establish the appropriate

25
V. Subotić and C. Hochenauer
ECM for describing complex electrochemical processes. In conclusion,
the DRT approach provides insight into specific physical quantities that
are not directly observable from the experimental measurements.
Compared to the traditional tools, it can provide more detailed insights
into process mechanisms and depict the complexity of the systems under
investigation. For this reason, it seems that DRT is becoming a new
standard in impedance data analysis.
4.3.1. Basic principles of the DRT methodology
Jürgen Weese described the basic principle of the DRT approach, up
on which the tools used to analyze the electromical systems are based, in
1992 and provided this as a FTIKREG program [335,336]. The approach
presented by Weese employs Fredholm integral equations of the first
kind (see Eq. 28) based on the Tikhonov regularization.
∫b
∑
m
g(t) = K(t, s)f (s) ds + ai bi (t) (28)
a i=1
In this function, as expected in many electrochemical applications, a
function f and m coefficients a1 , …, am have to be determined from the
experimentally observed data, which are described with the function g.
This function involves the known parameters b1 , …, bm and the Kernel
function K, which is known from theory. In addition, the data presented
in the function g are mainly noisy data, which should be smoothed for
the purpose of further application. Since the Fredholm integral equation
of the first kind intrinsically reflects an ill-posed problem, it means that a
non-unique solution is available or it strongly depends on the system
errors. The author provided the developed code for further usage [335],
which clearly underlines the fact that the calculation and demonstration
of the correct DRT spectra is not an easy task. A number of parameters
that have to be chosen carefully, without violating the physical system
criteria. Among others, the most relevant parameter is the regularization
parameter λ.
An application of the appropriate regularization method, e.g.,
Tikhonov regularization [335,336], is necessary in order to provide a
correct problem solution. Regularization involves a process of both
solving an ill-posed problem and preventing overfitting by integrating
additional information into the problem under consideration [337].
Selecting the appropriate regularization parameter enables the
researcher to smooth the noisy measurement data and also affects the
error of the results. In addition to the Tikhonov regularization used in
[335,336], different regularization methods can be employed for the
same purpose. The Ciucci research group is actively involved in exam­
ining different regularization and discretization approaches to address
the issue of DRT deconvolution interpretation. They confirmed that
different frameworks, such as Bayesian statistical frameworks [338] or
Lasso regularization [337] can be successfully implemented instead of
the Tikhonov regularization. A code developed in Matlab (DRTtools) by
the same research group to calculate DRT spectra using the impedance
data has been made available to researchers. Different parameters can
be selected for the purpose of performing detailed calculations [93,339].
Redirecting the focus toward the Tikhonov regularization, an
approach to find the optimal regularization parameter has already been
presented in the literature. In order to identify the best appropriate
regularization parameter, [340] proposes taking repetitive impedance
measurements and subsequently comparing the respective DRT data.
The authors recommend generating synthetic datasets to reduce the
efforts needed to perform experimental investigations. Proceeding
further, in [341], the authors reported that the level of corrupted data
needs to be known to select an appropriate regularization method.
Single-parameter regularization seems to be appropriate for slightly
corrupted data, whereby a multi-parameter regularization approach is
favorable for the higher degree of data corruption.
The interest inusing DRT methodology to analyze electrochemical
processes has increased recently, and especially because this method­
ology provides detailed insight into separated processes unlike the
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Progress in Energy and Combustion Science 93 (2022) 101011
conventional interpretation of the Nyquist plots. The DRT tool can be
readily used in different disciplines, such as medicine [342,343],
biology [344,345], as well as in the technical field to analyze, e.g., solar
cells [346,347], batteries [348,349], supercapacitors [350] and solid
oxide cells. More detailed information about the applicability of the DRT
methodology to analyze the processes in SOCs is described in sections
4.3.2 and 4.3.3.
SOCs provide highly complex microstructures. In addition, due to
their fuel flexibility and depending on the fuels used, the complexity of
the process identification increases as the number of fuel components
increases. For this purpose, many studies begin with the DRT analysis,
setting the focus on the application of simple fuels. In addition, the
analyses are carried out on different levels, starting with the electrodes
and symmetrical cells, extending to single-cells and on to stacks. When
starting examination at the lowest level, researchers can gain an un­
derstanding of fundamental processes and apply this to more complex
systems. In Fig. 14, we summarized DRT-spectra for SOFC and SOE
based on the literature available. This can be very helpful to find
appropriate processes related to their specific applications. We sum­
marize the results from different DRT based studies performed for both
solid oxide fuel and electrolysis cells to provide an overview of the
processes and to shape a strategy for a simplified process analysis.
4.3.2. DRT for SOFC
In order to fully understand the single processes in SOFC, the in­
vestigations begin with the electrode or electrolyte level, proceed to
symmetric cells, and go on to include single cells and stacks. The in­
fluence of different impurity contents in the polycrystalline proton-
conduction electrolyte was analyzed in [351]. The authors reported
how effectively the DRT analysis could be used to differentiate between
bulk and grain boundary resistance. They noted that the formation of a
silica-based phase between the grains resulted in a strong increase in the
DRT area observed for relaxation times lower than 1 s, indicating that
ion transfer was inhibited. Applying the DRT analysis to the character­
ization of LSCF-based symmetrical cells, other researchers showed that
DRT can be used to identify the underlying processes, such as interfacial
effects and diffusion resistances [352]. Moreover, the application of
SFCM as a potential air electrode material for proton conducting SOFC
was examined in [353] by carrying our the DRT analysis. In the latter
study, four specific peaks were observed. The low frequency peak
observed for frequencies below 1 Hz was associated with a concentra­
tion polarization induced by the gas diffusion. The peak located between
10 and 100 Hz reflected the oxygen reduction and oxygen surface
diffusion toward TPB, whereby the peak observed between 100 Hz and
1 kHz could be associated with the oxygen incorporation into the lattice.
In the same study, the authors reported that high-frequency peaks
observed between 1 kHz and 10 kHz can be correlated with different
overlapped processes, such as coupled charge transfer and ionic trans­
port through the air electrode as well as the electrical contact between
electrolyte and grain boundaries, respectively, and electrode. These re­
sults are supported by several other studies [354–357]. Soltanizade et al.
[358] showed that DRT can be successfully employed to localize the
impact of gas diffusion that inhibits oxygen reduction reaction. This was
not possible by solely applying electrochemical impedance spectros­
copy. Clematis et al. [359] also highlighted the importance of DRT in
their study on the catalytic activity of the BSCF- and LSCF-based air
electrodes. An analysis of the EIS data included in the DRT analysis
provided insight into two kinetic regimes regarding the electrocatalytic
activity of surface oxygen exchange and bulk diffusion, which could not
be identified by applying a common EIS method.
Sumi et al. [360] performed a highly detailed DRT analysis of
micro-tubular SOFCs manufactured as Ni-GDC/YSZ/GDC/LSCF to
extract relevant electrode processes and, subsequently, the undesired
degradation mechanisms. They identified five relevant frequency ranges
that should be monitored to learn more about the fuel electrode and air
electrode processes. These are assigned to (i) the air electrode specific
V. Subotić and C. Hochenauer
processes for the frequencies of 5–20 Hz and 10–100 kHz, and to (ii) the
fuel electrode related processes for the following specific frequencies:
20 Hz-10 kHz 1–10 Hz and less than 1 Hz. In another work by the same
research group [316], further relevant results were reported. The au­
thors observed that the peaks placed at 0.37-5 kHz and 4.8-7.8 Hz
changed due to the fuel electrode sintering processes and/or p(H2 ).
Peaks changes in the range between 10 Hz and 10 kHz were ascribed to
the influence of the air electrode sintering temperature [361]. On the
other hand, gas diffusion processes occurring in the fuel electrode sub­
strates could be identified at lower frequencies starting at 0.5 Hz and
extending to 15 Hz [315]. This depends significantly on the fuel used
and, e.g., for CO/CO2 , fuel diffusion peaks are observed between 0.5-1
Hz, whereby the diffusion of H2 /H2 O fuel is ten times faster and thus
visible at frequencies of 5–10 Hz.
In [362], the authors summarized several sources [363–366] for the
fuel electrode-supported SOFCs and ascribed them to six different pro­
cesses as follows: (i) P1 (f<1 Hz) for fuel electrode diffusion for refor­
mate fuels and air electrode adsorption/desorption; (ii) P2 (f=1-10 Hz)
for gas conversion; (iii) two peaks P3 (f=10-100 Hz) and P4 (f=100-1,
000 Hz) for O2 and transport related processes in the fuel electrode; (iv)
P5 (f=1-10 kHz) for charge transfer in fuel electrode; and (v) P6 (f>10
kHz) no corresponding processes identified. In general, the specific
frequencies fall within a similar range as those summarized in Fig. 14.
Taking into account the process analysis of fuel electrode-supported
single cells, two detailed studies based on the variation of several
operating parameters were found: the first one was published in 2018
[300] and the second one was published in 2019 [362]. In the first study
[300], an FESC-SOFC with an active surface of 81 cm2 was employed,
and the following parameters were varied: partial pressure of nitrogen,
partial pressure of steam, fuel volume flow, air volume flow, and oper­
ating current density. In addition, the phenomena of carbon deposition
and carbon removal were analyzed by employing the DRT tool. The
impact of fuel dilution in nitrogen was mainly identified at low current
densities and for the frequency range 1–10 Hz, which corresponds to the
fuel diffusion in the fuel electrode. Taking into account the impact of
steam partial pressure in the fuel, the frequency range was extended to
the higher frequency of 1 kHz, which was also reported in [362].
Moreover, the impact of fuel and air starvation was investigated; the
authors showed that fuel starvation could be identified between 1–10
Hz, whereby frequencies lower than 0.5 Hz needed to be used to identify
the air starvation. The second study was carried out to analyze 12.56
cm2 FESC-SOFCs when varying the operating temperature, current
density, O2 partial pressure, H2 O partial pressure, fuel composition and
flow rates. The impact of the operating temperature was identified at
frequencies higher than 1 kHz, whereby altering the operating current
resulted in changes in the entire frequency range. The reason for this is
clear, since increasing the current causes changes at both electrodes,
influences the fuel compositions and triggers reduction processes at the
air electrode, as well as eventually impacts the operating temperature.
Taking into consideration more complex fuels, such as carbon
containing-fuels, the literature review provides additional information.
Caliandro et al. [362] correlated processes related to both internal and
external reforming at frequencies lower than 1 Hz. For 50 x 50 mm
Ni/8YSZ fuel electrode substrates Kromp et al. [305] claimed that all
reformate related processes could be identified with a new specific peak
observed at relaxation frequencies lower than 1 Hz. When adding 0.1
ppm H2 S to the fuel over an operating time of 100 h, no significant
changes in the DRT peaks could be observed, indicating that
degradation-free operation was possible in an sulfur-containing fuel
atmosphere [315]. Nevertheless, when increasing the amount of sulfur
from 0.5 ppm to 1 ppm and on 15 ppm, the authors clearly observed a
strong increase in the polarization resistance and performance degra­
dation. When the amount of sulfur in the H2 /H2 O/N2 fuel mixture used
was increased, other authors observed an increase in the amplitude of
the peak visible at 100–400 Hz, and this shifted toward lower
27
Progress in Energy and Combustion Science 93 (2022) 101011
frequencies [367]. Operating large-sized cells with (i) reformate mix­
tures obtained from a methane-reforming unit containing H2 , H2 O, CO,
CO2 , CH4 and N2 and (ii) humidified methane used for internal
reforming, four specific peaks were observed for the following specific
frequencies: (i) 2 kHZ, (ii) 300–700 HZ, (iii) 30–100 Hz, and (iv) 1–10
HZ [368]. When diluting the reformate fuel mixture in nitrogen, two
low-frequency peaks decreased and shifted towards higher frequencies,
whereby two high frequency peaks remained unchanged. This result
may be due to enhanced diffusion processes. Next, during the internal
reforming, the CH4 fraction was increased, thus decreasing the H2 O
fraction. Only the high-frequency peak observed between 1–10 kHz
remained unchanged. Three remaining peaks resulted in slight ampli­
tude increase and were shifted towards lower frequencies. However,
when increasing the operating current, this difference was reduced.
The DRT diagnosis methodology has also been applied to investigate
processes in stacks. Fang et al. [369,370] carried out a DRT analysis on a
two-layer, F10-design SOC stack consisting of Ni-YSZ/YSZ/LSCF elec­
trode-supported cells. For the stacks investigated, the authors reported
that the responses were similar for both operating modes, and a tem­
perature dependence was identified between 10 Hz and 10 kHz. In
comparison, for the frequencies lower than 10 Hz, no temperature
dependence could be recognized. Based on the results of the in­
vestigations carried out, the main conclusions are that (i) impedance at
the air electrode is higher than at the fuel electrode and that (ii) both
electrodes provide higher impedance in the SOE operating mode. In
[333], the authors showed that, within one stack containing of four cells,
different cells can provide different specific frequencies based on, e.g.,
different stability, temperature and gas distribution.
In addition to O2− -conducting SOFCs, DRT has also been used to
investigate the behavior of proton-conducting SOFCs. Shi et al. [354]
reported observing three main peaks and two additional peaks related to
the both electrodes of pSOFCs in the frequency range between 1 Hz and
32 kHz. The proton diffusion is correlated to the high-frequencies be­
tween 630 Hz and 32 kHz, whereby the fuel electrode reactions can also
be identified between 630 Hz and 4 kHz. At lower frequencies, O2−
incorporation in the electrolyte lattice is observed for the
middle-frequency range of 100–630 Hz. As expected, the O2 reduction
was observable at lower frequencies between 15 and 100 Hz, while low
frequencies of 1–15 Hz were ascribed to the impact of the partial pres­
sure of both H2 and O2 species. The intensity of all the peaks except the
high frequency peak (f>4 kHz) increases as the temperature decreases,
whereby the intensity of the high-frequency peak, decreases in contrast
and completely disappears at temperatures lower than 650 ∘ C. Wang
et al. [355] compared two different proton conducting electrode types,
namely, Ni-BZCY and Ni-LCO, employing the DRT tool. This enabled
them to clearly differentiate between the rate-limiting polarization
processes of the two different electrode types. For the first electrode
type, similar values to those observed in [354] were reported. For the
modified Ni-LCO electrodes, the author observed that internal
short-circuit currents could be blocked, thus significantly improving the
open-circuit voltage and the overall efficiency. In addition, the
proton-transfer number could be increased. This could clearly be
recognized in the DRT spectra. Moreover, Chen et al. [371] applied DRT
to examine the performance of a novel layered Nd(Ba0.4 Sr0.4 Ca0.2 )
Co1.6 Fe0.4 O5+δ air electrode for proton-conducting SOFCs and identified
five relevant processes for both electrodes altogether.
Based on the studies that have already been carried out to examine
processes in both oxygen ion- and proton-conducting SOFCs and in
which the DRT analysis has been applied, we summarized the processes
as a function of the specific frequency ranges and illustrate these in
Fig. 14 for O2− -SOFC and in Fig. 14 b for p-SOFC.
4.3.3. DRT for SOE
To date, many studies have been carried out with DRT methodology
to analyze the processes that occur in SOFCs. However, few studies have
V. Subotić and C. Hochenauer
solely analyzed electrolysis operation. Several studies that were carried
out during SOE operation have compared the relaxation times with
those observed for the SOFC, thus associating the processes with those
occurring in SOFCs. In general, specific SOE processes were identified
for similar frequency ranges at those observed for the SOFC processes
(seen diagrams in Fig. 14). For instance, gas diffusion in the fuel elec­
trode substrate was identified to be visible between 0.1-50 Hz [191,372,
373,373,374] for the SOE mode in comparison to 0.7-10 Hz in the SOFC
mode. Moreover, regarding to overlapped processes such as gas diffu­
sion, charge transfer and ionic transport, these processes are visible
between 500 Hz and 100 kHz for the SOE mode [333,369,375] and
between 700 Hz and 10 kHz for the SOFC mode.
The Ni-YSZ/YSZ/LSCF/CGO single cells with an active surface of 16
cm2 were operated in an electrolysis mode in [299]. Initially, they were
fueled with H2 /H2 O=50/50 at the fuel electrode and pure oxygen at the
air electrode. Five specific peaks could be identified: (i) 10–100 kHz
associated with the ion conduction in the composite electrode; (ii) 1–10
kHz associated with the resistance related to the charge transfer re­
actions at the TPB; (iii) 100-1,000 kHz linked with the oxygen evolution
within the oxygen electrode; (iv) two peaks between 1–100 Hz associ­
ated with the mass transport process by gas conversion polarization and
gas diffusion. To increase long-term durability, the steam fraction was
increased to 90% and the hydrogen amount was decreased to 10%. The
air electrode was also supplied with the pure oxygen. The DRT analysis
resulted in five peaks, and the degradation effects that occurred as a
function of the operating time were most dominant for the peak
observed between 50–500 Hz at 800 ∘ C and 750 ∘ C, whereby additional
alternations between 1–10 Hz were observed at the operating temper­
ature of 700 ∘ C. For the single cells of industrial size, i.e., 80 cm2 , only
two specific peaks at approximately 20 Hz and between 200–300 Hz
were identified in the electrolysis mode [135]. These peaks changed as a
function of the H2 /H2 O-ratio and the operating current density. When
the H2 fraction was increased, the processes observed shifted toward the
higher time constants, but the resistance increased in parallel. Such
behavior was associated with the varying fuel diffusion resistance
through the fuel electrode.
Regarding the stack level, a 10-cell stack was investigated in [332].
The low-frequency peak observed between 1–10 Hz changed as a
function of current density, indicating that diffusion losses occurred as a
function of varying hydrogen content in the gas inlet. The peak observed
between 100–300 Hz could be associated with air electrode processes,
such as O2− -bulk diffusion at the air electrode and the chemical surface
exchange of O2 . At lower current densities, only one peak was observed,
whereby it split into two peaks when increasing the current density
above 100 mA/cm2 . Further peaks observed between 0.2-10 kHz could
be associated with fuel electrode processes, e.g., ionic transport in the
functional layer and the charge transfer reaction. When considering the
impact of the operating current, the investigation of 10-cell stacks in
[135] showed that an increase in the current resulted in a decrease in the
peaks observed, and mainly their amplitude. However, if increasing the
operating current leads to an increase in amplitude, this is a clear
indication that fuel or steam starvation and concentration losses,
respectively, are occurring in the stack. Thus, the operating conditions
have to be adjusted to prevent undesired degradation mechanisms.
The identification of specific degradation mechanisms was also
demonstrated when employing the DRT tool. In [174], the authors
examined the behavior of the air electrode in an accelerated degradation
environment and correlated microscopic changes observed with the
specific frequencies that appeared during the accelerated degradation
tests. They showed that Sr-enrichment on the LSCF grains, the micro­
scopic alternation of the LSCF/GDC boundary layer and LSCF decom­
position could be measured in the frequency range of 100–300 Hz. By
doubling the operating current density from 600 mA/cm2 up to 1,200
mA/cm2 the degradation was significantly intensified and identified as
LSCF decomposition and Sr-deposition both within the LSCF and GDC
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Progress in Energy and Combustion Science 93 (2022) 101011
layers, which prevented O2− conduction and subsequent oxygen evo­
lution. These phenomena could be identified by examining the changes
in the peak observed at approximately 2 kHz.
The data related to the specific frequencies and process mechanisms
that occur during SOE operation were extracted from the available
studies and are summarized in Fig. 14 c.
4.3.4. Concluding remarks
In conclusion, our review indicates that the DRT approach represents
a highly relevant methodology that enables researchers to identify
relevant processes in electrochemical systems that cannot be observed
using other conventional monitoring tools. However, DRT peaks are not
unambiguous, and the sufficient knowledge about the system under
investigation is necessary to interpret the results properly. For example,
when changing the system geometry, the size of the cells used, fuels
used, or operating temperature, changes are expected to occur and,
therefore, these need to be associated correctly with the ongoing pro­
cesses. The information gained when employing both the DRT and EIS is
of great importance, as it helps researchers to understand not only the
fundamental processes on the microscopic level, but to employ these
methods - representing the basis for cost-effective and practical SoH
techniques - to monitor performance on a system level and to guide the
control system. Overall, this enables the user to prolong the overall
system lifetime.
4.4. Unconventional diagnostic tools based on nonlinear system analysis
Under specific conditions, the system linearity can be disturbed,
moving the system towards nonlinear state. Two possible causes for the
nonlinear state can be identified: (i) large amplitude perturbation, and
(ii) specific processes that cause SOC deactivation and morphological
changes, resulting in a distortion of the system response. In this case, the
linear system analysis is no longer applicable, and a nonlinear system
analysis must be applied to the acquired data to extract contributions
from both the linear and higher harmonics. Both these can provide
valuable information about the nonlinear processes that occur in the
electrochemical system [376]. This is of great importance for fully un­
derstanding the system behavior, since the information gained by using
linear impedance spectroscopy is insufficient to understand all the
mechanisms in specific cases. For this reason, nonlinear impedance
spectroscopy (NLEIS) or total harmonic distortion (THD) analysis must
sometimes be employed.
Although NLEIS/THD can provide relevant information about the
system behavior that is not contained in the conventional linear EIS,
only a few studies have used this methodology to date. These made a
significant contribution towards (i) fully understanding the process
mechanisms and electrode kinetics, and (ii) enabling the rapid identi­
fication of undesired, faulty system changes at a preliminary stage. The
oxygen exchange kinetics and relation between the oxygen vacancies
and oxygen activity cause nonlinear effects at the oxygen electrode,
phenomena that have been examined and explained in detail by Adler,
Wilson and co-workers [284,376–378]. Back in 2006, they first isolated
the nonlinear effects of O2 exchange on perovskite oxide with NLEIS
[377], revealing that the rate limiting O2 exchange steps at the LSC
electrode on Gd-doped ceria involve the dissociative adsorption of ox­
ygen ions at a limited number of vacant positions. The same conclusion
was reached for LSC air electrodes on Sm-doped ceria; an analysis of the
third-order harmonic spectra revealed this relevant information, which
was not contained in the first harmonic [376]. Such information was
gained by utilizing both models to predict higher harmonics and con­
ducting an experimental analysis. In an experimental study, ten different
amplitudes were applied at the same frequency in the range between 0.1
Hz and 10 kHz.
Taking into consideration single-cells of industrial size with an active
surface of 81 cm2 , the first results that revealed early identification of
V. Subotić and C. Hochenauer Progress in Energy and Combustion Science 93 (2022) 101011

the most relevant fault modes that occur in SOFCs, namely, fuel star­
vation, air starvation and carbon depositions, were published in [112,
149,379]. In [149], the THD tool was demonstrated to be highly suc­
cessful when identifying different failure modes in
fuel-electrode-supported SOFCs. At the air electrode, air starvation led
to LSCF decomposition, interlayer delamination and strong mechanical
damage. This phenomenon was observed for frequencies lower than 10
Hz, with a response signal distortion of 3–4% observed in the frequency
range of 0.5-10 Hz, and a higher distortion of approximately 8% at 0.1
Hz. At the fuel electrode, two failure modes were examined. Fuel star­
vation resulted in Ni-reoxidation and Ni-agglomeration, and signal
distortion could be observed at frequencies lower than 50 Hz; 4% at 20
Hz, 3% between 1–10 Hz and 6% at 0.1 Hz.
Carbon depositions, which blocked the catalytic active surface and
gas channels were also visible at low frequencies. At 0.01 Hz, the signal
distortion accounted for several hundred percentages. However, unlike
the two previously mentioned degradation modes, the carbon deposition
phenomenon was also identified at higher frequencies of 2 kHz, 4 kHz
and 8 kHz, as illustrated in Fig. 16. This enables to perform measure­
ments solely at higher frequencies, significantly reducing the required
measurement time. Carbon deposition and its removal from the
electrolyte-supported cells with the same active surface were reported in
[112]. Signal distortions were observed for the carbon deposition phe­
nomenon at same high-frequency values and also at low frequencies. In
addition, carbon removal could be identified with THD, as shown in
Fig. 15 a.
Malafronte et al. [285] examined the impact of the stack fuel utili­
zation on the THD index for a 6 kW SOFC demonstration system.
Increasing the fuel utilization resulted in an increase in THD distortion,
whereby the changes were most clearly visible in the frequency range
between 1 Hz and 0.01 Hz. The authors proposed to apply excitation
signal amplitude AC of 5% of the DC load to obtain better signal values.
This is illustrated in Fig. 15 b, showing that increasing the fuel utiliza­
tion from 0.85 up to 0.9 increases the observed THD-index. This increase
is higher if the AC amplitude is higher; for example, a slight increase of
<1% is visible for AC=1%. In comparison, when increasing the AC from
1% up to 10%, the THD-index increased from 15% to 20%. The effect of
fuel starvation in a six-cell SOFC stack was also investigated by Mougin
and coauthors in [380]. They came to the same conclusion as authors of
previous studies, showing that the THD index increases as the fuel uti­
lization increases, which is visible at frequencies lower than 1 Hz.
However, they proposed to use small AC amplitudes (<<10% of the DC
current) for this purpose.
Fig. 15 c refers to the results reported in [149], employing THD to
identify carbon deposition at its early stage. The x-axis presents the
operation duration, whereas the y-axis shows the frequency values. The
colors and their intensities are linked to the THD-index. Comparing the
two diagrams presented, we can conclude that the appropriate threshold
should be defined. This is seen as a boundary between a ”degrada­
tion-free state” and a ”degradation state”. This means that, if the
threshold is set to 1%, we could consider that degradation occurs when
experiment begins. Nevertheless, when increasing the threshold up to
10%, we observe that the first signs of degradation can be identified
after approximately six operating hours. Thus, in order to define an
appropriate threshold, initial THD measurements must be made for
different fuels, as shown in Fig. 15 a. This clearly shows that a threshold
is a function of the fuel used.
The studies discussed above demonstrated the potential for applying
non-conventional tools for the rapid identification of undesired failure
modes, both on large single-cell and a stack level. This is a crucial step
towards employing these technologies on the system scale, which could
involve not only SOC monitoring, but also monitoring of the remaining
system components and their influence on the SOC performance.
Nevertheless, validation and recalibration of the presented SoH tools for Fig. 16. Possibilities to present the observed THD data.
the industrial environment would be necessary.

29
V. Subotić and C. Hochenauer
Fig. 17. The identification of carbon deposits employing THD methodology. Reprinted and changed from [379] with permission from Elsevier.
4.5. Species and temperature monitoring approaches
In addition to the techniques described above, other strategies are
available to identify the current state of the health of the cells. The most
relevant are gas analysis and temperature monitoring, which can also be
applied to industrial-sized cells and at a higher stack or system level.
Combining different monitoring tools offers the possibility to reach the
most precise conclusion about reactions that occur [381,382]. The
combination of, e.g., voltage monitoring, electrochemical impedance
spectroscopy, gas analysis and temperature measurement at different
points provides highly detailed information about the processes that
occur and enable to identify different operating issues, [109,115,128,
235,383,384]. If specific impurities are available in the fuel at low ppm
concentrations, a precise gas analysis is the first choice for their iden­
tification. For instance, phosphine (PH3 ) present in ppm concentration
in coal gas was identified by applying a mass spectrometer in [65]. In
[65], it was only possible to detect PH3 in a dry hydrogen, while in the
presence of steam, it reacts if the pressure is higher than few torr at
higher temperatures. Even for dry fuels, steam is generated due to
electrochemical reactions which enhance PH3 reactions. Phosphine re­
actions in SOFCs do not generate the expected equilibrium products
such as P2 , HPO, HPO2 , or HPO3 , but its presence causes irreversible
degradation. In [63], electrochemical impedance spectroscopy (EIS),
linear sweep voltammetry (LSV), which actually corresponds to the
polarization curve, and vibrational Raman spectroscopy were coupled to
examine the impact of chlorine contamination on the SOFC perfor­
mance. The study showed highly aggressive degradation with approxi­
mately 15%/hour when combining chlorine with methane
(CH3 Cl/CH4 =110 sccm/20 sccm=5.5), while the degradation grade was
low for CH3 Cl/CH4 =110 sccm/100 sccm=1.1 mixture. If sulfur needs to
be detected, gas chromatography seems to be a good solution. Khan
et al. [385] employed a gas chromatograph outfitted with a sulfur
chemiluminescence detector to measure extremely low sulfur concen­
trations in air. At the concentration of >2 ppb, precise measurements
were possible, while at lower temperatures, larger measurement un­
certainties were observable. In order to identify ammonia in a fuel
30
Progress in Energy and Combustion Science 93 (2022) 101011
mixture, the application of Fourier-transform infrared spectroscopy
(FTIR) is preferred [386,387]. Casteel et al. [388] proposed to use a
solution conductivity measurement system and a transpiration mea­
surement system to precisely measure chromia evaporation from SOFC
interconnect materials.
Optical in-situ methodology, including non-invasive characteriza­
tion tools, shows a great potential for obtaining information about
spatial species and temperature distribution [269,273,389]. Walker,
Kirtly, Owrutsky et al. performed much research to examine the impact
of different species on SOFC performance and to identify different
degradation types [390–392]. In [274], they used in situ vibrational
Raman scattering to successfully identify the NiO growth on SOFC
Ni/YSZ electrodes. In their further study [393], the authors tried to
identify the impact of butanol on the SOFC performance. For this pur­
pose they employed near-infrared thermal imaging to measure tem­
perature distribution and vibrational Raman spectroscopy to identify
carbon accumulation along and cross the surface. Moreover, the authors
enable to investigate the effectiveness of different gaseous components
on carbon removal from the Ni catalyst.
5. Degradation mitigation and lifetime extension
The use of appropriate measures can prolong the lifetime of the SOC
systems. These, however, differ according to the diverse degradation
modes, operating modes and SOC types employed; therefore, they must
be carefully designed as soon as the first signs of degradation are iden­
tified. In general, we differentiate between two key solutions used to
mitigate degradation and extend the SOC lifetime: the (i) material and
the (ii) operating environment. In this section we are mainly concerned
with the latter one. Nevertheless, material solutions will also be dis­
cussed here, but not in great detail, because this presents the only pos­
sibility to mitigate irreversible degradation in specific degradation
modes.
Initially, before starting the SOC operation, thermochemical equi­
librium calculations are recommended to be performed as the initial
degradation mitigation step. They provide information about the
V. Subotić and C. Hochenauer Progress in Energy and Combustion Science 93 (2022) 101011

Table 7 recirculation and fuel enclosure. However, the authors suggested that
Regeneration approaches provided in [383]. considering redox instability, passive solutions are desired and the
Parameters Value Unit number of redox cycles should be reduced. The second solution pro­
posed by Wood et al. [140] is the material solution, described as more
R1
H2 45 vol% elegant and less expensive with regard to overall system costs.
N2 55 vol% Regarding the material solution, the authors proposed three different
R2
solutions: the use of (i) alternative materials, e.g., an alloy to replace
H2 45 vol% nickel in the cermet fuel electrode and possibly all-ceramic fuel elec­
H2 O 11 vol% trodes, (ii) microstructural modification to retain the great electro­
N2 44 vol% chemical performance of the Ni/YSZ electrodes, but also to reduce the
R2var damage potential, e.g., graded nickel content and/or increased porosity
H2 30 vs. 45 vol% in the fuel electrode functional layer (AFL), and (iii) kinetics, applying
H2 O 40 vs. 20 vol% the knowledge available to reduce the oxidation kinetic, e.g., improved
N2 remainder vol%
sealing, oxidation barrier and lower operating temperatures.
R3 The novel material solutions are proposed to overcome the insta­
i variable mA/cm2
bility issues facing the conventional Ni/YSZ electrodes. Employing
U variable V
H2 variable vol% perovskite-based electrodes, which have all-ceramic mixed ionic-
N2 remainder vol% electronic conductors (MIEC), results in enhanced redox stability, but
R4
also improved chemical and thermal compatibility with other cell
CO2 variable vol% components. Adding metal nanoparticles to the porous electrodes en­
H2 variable vol% ables researchers to significantly increase the active surface, which, in
H2 O variable vol% turn, enables them to enhance electrochemical performance. Alternative
N2 remainder vol%
solutions are to combine MIEC and impregnated metallic nanoparticles,
R4ov which has seemed to gain more attention in recent years [395–397]. A
CO2 25 vol% step toward the fully redox stable electrodes is achieved by replacing the
N2 75 vol%
U 1.4 V
Ni catalyst with noble metals, such as Ru, Rh, Pd, or Pt; this not only
increases redox tolerance, but also prevents catalyst agglomeration
R5var
[398–400].
O2 2 vs. 0.5 vol%
CO2 18.9 vs. 4.7 vol% Regarding the operating environment, the concentration of oxidizing
N2 remainder vol% species, such as steam and oxygen, the H2 O/H2 -ratio and the amount of
oxygen ions that result from the operating current are crucial parame­
ters to prevent undesired reoxidation processes. The highly aggressive
expected degradation modes, such as carbon deposition or reoxidation effect of oxygen was reported in [401], and the authors showed that the
of the catalysts used, which can occur as a function of the designed entire fuel electrode surface can be oxidized at 800∘ C within only 150 s if
operating environment [394]. In the next step, if degradation occurs a high amount O2 or H2 O is available in the gas mixture. Therefore, they
during the operation, specific mitigation strategies can be applied to suggest avoiding H2 O/H2 >1 [383]. Baldinelli et al. [402] also provided
prevent further performance deterioration and morphological changes. a ternary diagram presenting the NiO area; based on the gas composition
In the final step, if reversible degradation has already occurred, specif­ used, researchers can use the diagram to easily calculate whether NiO is
ically designed regeneration strategies can be utilized to bring the expected to occur or not.
overall SOC state back to the initial state.
Taking into consideration different possible failure modes, many of
these, such as contamination due to impurities (e.g., sulfur, chlorine) 5.2. Solutions for carbon depositions
can be inhibited by applying the appropriate purification and fuel
preparation methods, which are beyond the scope of this paper and will Although nickel catalysts display great catalytic performance and
not be discussed here. The three main failure modes that can occur conductivity, they are prone to carbon deposition, which can have a
during both fuel cell and electrolysis operation are Ni reoxidation, car­ detrimental effect on the SOC performance, as discussed in detail in
bon deposition and air electrode degradation. Therefore, possible solu­ Section 2. For this reason, different solutions have been proposed in the
tions for their mitigation and subsequent performance regeneration are literature to mitigate degradation and regenerate deteriorated
discussed below. Moreover, based on our comprehensive literature re­ performance.
view, we summarize the available suggestions that address degradation The first solution is related to material development. Much research
mitigation and performance regeneration for the three selected degra­ has been devoted to the development of new carbon-tolerant electrodes.
dation modes and present them in Table 9. Xu et al. [403] attempted to develop high-catalytic-activity fuel elec­
trode material with a high carbon tolerance that was appropriate for
5.1. Solutions for Ni reoxidation intermediate temperatures. To achieve this goal, they developed a new
material SFCoM, which they designed and prepared from perovskite
In 2006, Wood et al. [140] proposed two possible solutions for sys­ with additional in-situ exsolved Co nanoparticles. This novel material
tem redox instability that occur due to an unexpected shutdown: (i) an provided stable performance even after 200 h of operation under hu­
improvement in the material redox limitations, and (ii) the safety im­ midified C3 H8 . Thus, it seems to be a promising candidate for electrode
plications of using the fuel gas, and especially hydrogen and carbon materials with high carbon tolerance. Next, a double perovskite SMM
monoxide. The authors also divided the system redox solutions into based hybrid catalyst synthetized with SM nanoparticles seems to be
active, passive and dependent concepts. The active solution concepts another promising carbon-tolerant material, as published by Peng et al.
involve the use of a partial oxidation reformer, the thermal cracking of [404]. However, the new materials have to be optimized to achieve
fuel components, a delayed purge of fuel or air, cell reversal, water higher performance. In [404], at the operating temperature of 800∘ C,
electrolysis and activated carbon. Passive solutions involve the use of the maximum power density of 245 mA/cm2 was achieved in humidified
hybrides, a steam purge, high temperature check valves and a reducing CH4 for 250 h, and 183 mW/cm2 for operation in humidified C2 H5 OH
gas cylinder. And dependent solutions involve the use of fuel gas for 70 h. Another proposed possibility to reduce the direct cracking of

31
V. Subotić and C. Hochenauer
hydrocarbons at Ni/YSZ fuel electrodes is to mix copper and nickel,
since copper prevents the Boudouard reaction from occurring [405,
406]. Furthermore, Gavrielatos et al. [407] presented Ni-Au SOFC
carbon-tolerant electrodes even when feeding with steam reforming. As
the most common solution, which has already been implemented in real
case scenarios, the zirconia ionic conductor is replaced with ceria, which
significantly reduces the cracking reaction and increased the carbon
tolerance [408].
Despite all of the advantages offered by new generation materials,
their development requires a great deal of additional research and
several proposed solutions even present much higher costs. Therefore,
the most efficient solution when considering the maximum achievable
performance, durability, reliability and the costs seems to be to combine
the strategies described in the previous sections, i.e., to make predictions
and, based on these, to optimize the operating environment, then to
conduct online-monitoring of the cell behavior and its state-of-the-
health. This enables to identify all of the undesired changes early on
and to take appropriate countermeasures. Initially, predicting the per­
formance and making the subsequent adjustments to the operating
conditions, and thus the fuel compositions, S/C-ratio and the operating
temperature, seems to be the appropriate first steps. As an example, in
[226], thermodynamic calculations were used to predict the impacts of
CO and CH4 on the graphite and carbon nanofibers formation across a
wide temperature range. If humidified methane is used as fuel, the S/C
must be higher than 1.5 to mitigate carbon formation at temperatures
higher than 800 ∘ C. For S/C<1.5 large amounts of both graphite and
carbon nanofibers are expected to be formed. Carbon nanofibers begin
to form at approximately 400 ∘ C, and the amount reaches a peak at
approximately 700 ∘ C. Graphitic carbon can be formed at much lower
temperatures. Its amount increases as the operating temperature in­
creases, reaching a peak at 550 ∘ C. Afterwards, this amount slightly
decreases. In order to prevent the formation of different types of carbon
throughout the operating range, the S/C-ratio should be set to values
higher than 1.5, or, even better, higher than 2. This is important when
unexpected system failures occur, which can, e.g., decrease the oper­
ating temperature. Thus, the safe operation of the systems operated with
humidified methane can be assured. On the other hand, when using
carbon monoxide, more graphite will be formed if the operating tem­
perature is lower. If S/C>2, carbon formation can be avoided. The
higher the operating temperature, the lower the S/C needed for this
purpose. Moreover, if S/C>0.8, CNF formation can be inhibited
throughout the temperature range. Next, if the operating temperature is
higher than 800 ∘ C, carbon is not expected to be formed, regardless of
the S/C ratio.
Moving from the performance prediction to in-operando measures,
several studies have described how to reverse carbon deposition and
regain the initial SOC performance. Mermelstein et al. [409] suggested
increasing the operating current to generate an appropriate number of
oxygen ions to reduce carbon deposition on the fuel electrode. The same
conclusion was also reached in [410], where simulations showed that it
is important to exceed the critical operating current to prevent carbon
formation. Alzate-Restrepo et al. [411] performed experimental exam­
inations to induce carbon depositions, using low current densities of 0.1
mA/cm2 , 10 mA/cm2 and 50 mA/cm2 and varying the operating time
from 6 to 72 h. They came to the conclusion that as soon the current
flowed through the cell, the amount of carbon formed was reduced by
100 times as compared to the amount of carbon formed under OCV
conditions.
Besides using higher operating currents, using a higher amount of
steam can also be advantageous to reduce the amount of the carbon
formed, as shown in [412–414]. Increasing the amount of CO2 in the fuel
mixture is another way to reduce carbon formation [415].
Considering the in-operando gasification of the carbon deposited,
Kirtley et al. [272] examined the impact of H2 O, O2 and CO2 on carbon
removal and identified H2 O as the most efficient species, followed by O2
and CO2 . The authors also showed that, regardless of the gasification
32
Progress in Energy and Combustion Science 93 (2022) 101011
agent used, Ni reoxidation occurred after carbon removal. Snoeck et al.
[416] examined the impact of H2 O, H2 and CO2 on the carbon gasifi­
cation both numerically and experimentally. They reached the main
conclusion that carbon gasification depends primarily on whether car­
bon is formed from methane or carbon monoxide. The same conclusion
was also reached by Takenaka et al. [417–419], but they used only CO2
to remove the carbon formed. However, carbon gasification must not
only be ensured; the SOFC performance must be regenerated, and this
cannot be achieved by using pure CO2 .
For this purpose, the effectiveness of different gaseous species in
combination with current and voltages for carbon removal and perfor­
mance regeneration was examined by Subotić et al. [115,122,383,420].
The goal was to regain the initial cell performance and morphology
state. The regeneration approaches used are summarized in Table 8,
while their cell-protecting effects on performance regeneration are
shown in Table 8. In [122], the authors reported that carbon can be
removed from the porous Ni/YSZ structure, and the initial performance
can be regained after using both H2 /N2 and a H2 /H2 O/N2 -mixture for
44 h under OCV conditions. For the purpose of this study, carbon was
generated under a specific operating current, avoiding rapid carbon
formation under OCV conditions. In [420], in addition to carbon
deposition, Ni reoxidation and air electrode degradation - presented as
the LSCF decomposition - were introduced to investigate the effective­
ness of the carbon removal strategies when multiple degradation modes
are present. Air electrode decomposition did not allow the initial cell
performance to be regained, but regeneration was possible only up to a
specific grade, whereby carbon could be completely removed with
parallel Ni reoxidation, which probably occurred due to the presence of
oxygen species.
The authors went one step further in [115], utilizing CO2 to remove
carbon and regenerate cell performance, but simultaneously applying an
overvoltage of 1.4 V. This is the first study to report both the regenerated
electrochemical cell performance and its microstructure after employing
the CO2 gasification agent for carbon removal over a short time-period,
i.e., approximately 200 s. Cell-protecting carbon removal must be
possible; otherwise irreversible damage to the cell structure can occur.
For example, when utilizing a H2 /H2 O/N2 regeneration mixture with
20% H2 O, regeneration can be achieved. However, increasing the steam
amount up to 40%, Ni reoxidation will occur that can even cause irre­
versible cell damage, as shown in [383]. Han et al. [421] also underlined
the importance of cell-protecting fuel electrode regeneration and carbon
removal. In their study, oxygen ions generated as a result of oxygen
reduction were used to remove carbon, whereas hydrogen was utilized
to prevent undesired Ni reoxidation. Reeping et al. [422] also empha­
sized the palliative effect of H2 during the operation with
carbon-containing fuels. The authors reported that small amounts of
hydrogen effectively prevent the degradation of the Ni catalyst and even
inhibit fuel cracking reactions. They also confirmed that, in addition to
this advantage, hydrogen can also effectively remove adsorbed chlorine
from the Ni surface. Removing hydrogen from the
chlorine-contaminated, carbon-containing fuel can lead to the immedi­
ate chlorine poisoning and carbon deposition on the catalytic active
sites.
Table 8
Effectiveness of different regeneration approaches provided in [383].
Regeneration Regeneration Reus- Cell-protecting
approach time ability effect
R1 and R2 ∼ 44 h ✓ ✓
R mA and R2var 5–40 h ✓ ✓
3,at100
cm2
R1 and R3,overvoltage ∼ 12 h ✓ ✓
R4 1–10 min × ×
R4ov ∼ 200 s ✓ ✓
R3,ov,aesupply 40 s 1–2 × ✓
R5var 30 s - 10 min
× ×
V. Subotić and C. Hochenauer
Table 9
Suggestion of appropriate prevention and regeneration strategies for different
degradation modes.
Degradation mode Prevention/regeneration strategy
Ni reoxidation Employing all ceramic perovskite-based
electrodes
Replacement of Ni with Ru, Rh, Pd or Pt
Coating Ni with Y, Zr, La, Ce or their
oxides
Reduced substrate thickness and
increased electrolyte/substrate ratio
Ni-Co alloy instead of Ni
Prevented intentional air break-in at the
fuel electrode or if not possible strongly
restricted air amount
H2 O/H2 < 1
Carbon Carbon-tolerant perovskite fuel electrodes
deposition
Carbon-tolerant Ni-based materials
Adjust S/C ratio considering the operating
temperature and concentration of CO and
CH4 species
For biomass gasification syngas: (i) if
T<715∘ C, steam is necessary, (ii) if
T<685∘ C, H2 >5% is necessary, (iii) if
T ∼ 600∘ C and i=2.8-3.6, 365 mA/cm2 is
required as a threshold current density
For operation in dry conditions and
0–15 g/m3 benzene use calculated
threshold current densities diagram
i>0.1 mA/cm2
Suggestions For different fuel mixtures (H2 , CO, CO2 ,
H2 O, CH4 ) and various operating
temperatures use proposed ternary
diagram
H2 /H2 O/N2 mixture
CO/CO2 /N2 with/without overvoltage
Application of regeneration strategies
presented in Table 7 and Table 8
Air electrode New electrode materials and designs to
degradation reduce air electrode overpotential
In addition to the experimentally examined regeneration processes
presented in [115,122,383,420], the impact of all the species used on
the fuel electrode surface was numerically examined in [401],
employing detailed heterogeneous reaction mechanisms. The authors
showed that hydrogen/steam mixtures successfully reduced the amount
of adsorbed carbon under OCV conditions. When increasing the oper­
ating current, even faster gasification of both the adsorbed carbon and
carbon monoxide could be achieved in a controlled manner. The nu­
merical study also showed that CO2 is not appropriate as a gasification
agent, since its use results in an increased catalyst coverage with
elementary carbon and carbon monoxide. In this case, even Ni reox­
idation is possible. When mixing CO2 with O2 , significantly higher
carbon oxidation rates are visible, but significantly faster, complete
reoxidation of the catalyst surface occurred.
The impact of both suitable and non-suitable regeneration ap­
proaches on fuel electrode morphology and cell performance is illus­
trated in Fig. 17. In specific cases, e.g., when utilizing only CO2 for fuel
electrode regeneration, carbon gasification could be achieved, but the
performance deteriorated even further. Nevertheless, when combining
CO2 with overvoltage, the full regeneration of both fuel electrode sur­
face and performance was possible.
Progress in Energy and Combustion Science 93 (2022) 101011
5.3. Solutions to mitigate degradation of oxygen electrode
The main reason for accelerated degradation and delamination of the
Source air electrode was identified as the increased pO2 , resulting in increased
[395–397]
air electrode overpotential. This is mainly related to the electrolysis
mode, as described in 2.4. This issue can be considered as the key to
[398–400] mitigate undesired electrode degradation. As suggested by Wang et al.
[436] [13], degradation mitigation can be achieved by decreasing either the
activation overpotential or the concentration polarization. In this way, a
[437]
significant lower overpotential on the air electrode can be achieved,
[438] while simultaneously increasing the operating current.
[134] Starting with adjusting the operating conditions, the pO2 could be
decreased by decreasing the operating current. However, this would
result in reduced hydrogen generation, which does not achieve the
[383] purpose of electrolysis. Therefore, the most appropriate solution seems
[404,439,440] to be to improve the materials and develop new generation materials for
the air electrode [14,423–425]. Song et al. [423] proposed the infil­
[441–444] tration of RuO2 nanoparticles, increasing the operating current density
[226,227] from 0.46 mA/cm2 up to 0.74 mA/cm2 at 1.2 V and 800∘ C, thereby
improving performance by 60%. Moreover, different air electrode
structures - perovskite and Ruddlesden-Propper - were compared with
[409,445]
each other. Shahrokhi et al. [426] reported the greater stability of the
Ruddlesden-Propper in both the fuel cell and electrolysis operating
mode. Moreover, different variations of the Ruddlesden-Propper struc­
ture [427–429] or perovskite structure, such as double perovskite oxide
[445] [430] and layered perovskite [431] appeared as promising candidates
for improving the performance of the air electrodes and decreasing the
overpotential losses. An interested approach that has recently been re­
[411]
ported is the new honeycomb structure, which simplifies the OER ki­
[114]
netics and provides much more stable performance than conventional
LSC/YSZ electrodes [432]. Taking into consideration LSM electrodes,
which are less resistant toward higher pO2 than LSCF, Khan et al. [433]
[112,122,383, proposed using an additional porous YSZ layer between the YSZ elec­
420] trolyte and the LSM electrolyte to release the high oxygen pressure and
reported that no delamination occurred in this case. For proton con­
[115,272,401,
416,417,420] ducting SOCs, the issue of air electrode delamination was also not re­
[112,115,383, ported due to the lower operating temperature, significantly lower
420] activation losses and, finally, the different requirements these cells have
[13,14,423–431, to fulfill [434,435].
433–435]
6. Conclusions and perspectives
This study provided an intense review of the current literature,
considering relevant issues that can occur when operating SOC under
real-world operating conditions as well as options to address them. This
review is useful for researchers, developers and system operators, since
it offers a complete overview of (i) different failure modes, (ii) process
mechanisms that occur and their prediction, as well as (iii) ways to
perform the early identification of various failure modes and (iv)
degradation mitigation and lifetime extension including regeneration.
The focus of this study is directed toward system-relevant operating
conditions, namely, practice-oriented fuels and steam-, CO2 - and Co-
electrolysis. Considering their impact on the SOC performance and
morphology for the running system, three main degradation issues were
determined. These are: (i) impurities in the feed gas and air, (ii)
carbonaceous species present in many conventional and alternative
fuels, and (iii) the propensity of the Ni-based electrodes to suffer from
oxidation and agglomeration. Impurities (e.g., compounds of S, Cl, P, Si)
in the feed gas were identified as having a huge impact on both SOC
performance and the fuel electrode morphology. Even when present in
low concentrations of several ppb, they exert a detrimental impact on
the electrode surface, leading to its damage. The same is observed at the
air electrode in presence of Si, Cr, or S, which are diagnosed as the main
contaminants on the air side. Beside impurities, carbon-containing feed
gases can initiate carbon formation and its subsequent deposition on the
33
V. Subotić and C. Hochenauer
Fig. 18. Effects of CO2 and CO2 in combination with overvoltage on carbon gasification and performance regeneration: (i) effectiveness of CO2 with overvoltage on
both carbon gasification and performance regeneration, reprinted from [115] with permission from the Electrochemcial Society, (ii) effectiveness of CO2 on carbon
gasification, reprinted from [115] with permission from the Electrochemcial Society, and (iii) simulation of adsorbed and oxygenated species over electrode surface
with CO2 , reprinted from [401] with permission from Elsevier.
fuel electrode surface and within the porous gas channels. This happens
if S/C ratio is high. In the available literature, a value of S/C=2 is
accepted as a boundary value between the carbon-free and carbon-
inducing operating environment. However, many numerical and
experimental studies show that this value can vary significantly as a
function of the fuel composition, operating temperature, operating
current density and fuel utilization. The operating environment also
influences the structural impact of carbon formed, and the carbonaceous
fuel components (CO, CH4 , Cx Hy ) and their concentration play major
roles. The last issue that affects the real-system operation is Ni-oxidation
and Ni-agglomeration. Ni-oxidation occurs if the concentration of
oxidizing species (H2 O, O2 , CO2 ) in the feed gas is too high as compared
to the fuel components (H2 , CO and CH4 ). High fuel utilization (>90%)
and high operating current densities which are equal to the high amount
of O2− are causes of Ni-oxidation. The operating temperature of 300 ∘ C is
seen as a threshold value. However, since SOC are operated at temper­
atures >600 ∘ C, the tendency toward Ni-oxidation is usually high.
Moreover, another typical degradation mechanism that affects Ni-
electrodes is Ni-agglomeration, which appears as a consequence of the
high operating temperature and harsh operating conditions and seems to
be inevitable.
This study also provided a reader with (i) a way to understand pro­
cess mechanisms that occur in SOCs and (ii) to predict unexpected
failures. Different approaches can be utilized for this purpose: (i) model-
driven, (ii) data-driven and (iii) accelerated stress testing. Based on the
comprehensive literature review results, we can assert that pure model-
based performance predictions are still inaccurate, since a number of
parameters have to be defined. These, however, cannot be determined
accurately. The accuracy of the SOC behavior prediction seems to in­
crease when numerical and experimental approaches are combined. A
promising approach that can be taken is accelerating stress testing,
focusing on predicting the remaining useful lifetime. By taking this
approach, different degradation modes are specifically induced (e.g.,
increasing the concentration of specific contaminants in the fuel gas) in
running SOC systems. In addition, the effective degradation impact can
be determined by employing the appropriate AST models. In this study,
we carefully summarized the available AST results for both SOFC and
SOE operating modes, giving a detailed insight into accelerating
stressors and their impact on SOC behavior.
34
Progress in Energy and Combustion Science 93 (2022) 101011
With this knowledge about different failure modes and ways to
predict them, we analyzed the options for state-of-the-health identifi­
cation. The extensive literature review revealed that we can differentiate
between conventional and unconventional strategies. The most
commonly used conventional tool is electrochemical impedance spec­
troscopy. This has already been applied in numerous studies; however, it
is often not easy to interpret the results obtained. With this in mind, the
distribution of relaxation times obtained by using this sophisticated tool
is gaining increasing attention and provides more precise information
about process mechanisms that occur during the operation. Using the
measurement data available in the literature that were obtained using
conventional SoH tools, we provided a frequency range for each process
mechanism that can occur in SOFC and SOE and illustrated these in a
form of diagram. This is an enormous advantage for the real system SOC
operation as well as scientific research. Moreover, conventional tools
seem to be more appropriate for analyzing processes in stationary and
fault-free systems. Regarding the fault status, when the system steady-
state and equilibrium are disturbed, unconventional methods seem to
be more suitable for performance monitoring. The unconventional
diagnostic tools require a nonlinear system analysis, and the most
frequently used method is the total harmonic distortion analysis. This
can be used to collect the necessary data more quickly than conventional
tools, thus reducing the measurement time by a factor >20. Neverthe­
less, interpreting the obtained data is still challenging, and more
research is needed in future to reach the full potential of the THD
methodology that seems to be significant. In this review, we structured
the existing knowledge and reported how to reveal the most common
SOC failures.
In the final step needed to ensure safe and long-term operation, we
reviewed the possibilities for degradation mitigation and lifetime
extension, focusing on regeneration strategies. Impurities contained in
the fuel gas and air (e.g., Si, S) should be extracted before entering the
SOC, since they completely change the electrode morphology, cause
permanent damage to the materials employed, and no regeneration
strategies are available here. The development of new-generation ma­
terials and coatings for conventional electrodes could be adequate so­
lutions to reduce undesired degradation, but this increases the costs. We
provided practical solutions for the most common electrode damage. In
order to prevent Ni-reoxidation, the H2 O and CO2 concentration in the
V. Subotić and C. Hochenauer
fuel gas should be minimized, while maintaining the concentration of
H2 , CO and CH4 . Moreover, the presence of pure O2 , e.g., due to leak­
ages, should be avoided in the fuel gas. Fuel utilization should also be
maintained below 90%. Another possibility is to control the current
density, since high current densities are equal to high O2− concentra­
tions and oxidize the electrode functional layer. In order to inhibit
carbon depositions, the concentration of Cx Hy in the fuel gas should be
minimized. It is advantageous to reduce the CH4 concentration at higher
temperatures and to reduce the CO concentration at lower operating
temperature. Furthermore, higher fuel utilization and higher operating
current densities seem to help reduce carbon deposition. Degradation
mitigation of the air electrode seems to be possible when reducing the
amount of chromium available, which is most easily possible when
utilizing dry air which prevents Cr evaporation from interconnects. Si
poisoning of the air electrode could be reduced by maintaining the glass
sealing used.
Overall, these review results provide a guideline for researchers,
developers and operators regarding safe and long-term cell, stack and
system operation.
CRediT authorship contribution statement
Vanja Subotić: Conceptualization, Data curation, Formal analysis,
Investigation, Methodology, Visualization, Writing – original draft,
Writing – review & editing, Funding acquisition, Project administration.
Christoph Hochenauer: Conceptualization, Writing – review & editing.
Declaration of Competing Interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
Acknowledgment
The authors gratefully acknowledge the funding of the project
”Degradation monitoring and performance optimisation of SOECs”
(project number I3994) by the Austrian Science Fund (FWF). Vanja
Subotić also wants to thank to Benjamin Königshofer, Michael Höber
and Gernot Pongratz for useful discussions during the preparation of this
review.
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