Solid Oxide Fuel Cells: How they work and their current position as

a low carbon energy alternative

Austin Mills

Student Number: 2142380

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1 TABLE OF CONTENTS
2 Table of Figures .............................................................................................................. 3
3 Abstract ......................................................................................................................... 4
4 Introduction ................................................................................................................... 5
5 Working Principles of SOFCs .......................................................................................... 7
6 High Temperature Operation and Efficiency .................................................................... 9
7 Fuel Flexibility and Internal Reforming ........................................................................... 10
8 Challenges and Considerations .................................................................................... 10
9 Future Directions for SOFC Technology ......................................................................... 12
10 Conclusion .................................................................................................................. 13
11 References .................................................................................................................. 14

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2 TABLE OF FIGURES
Figure 1 - IDTechEx Research on SOFC installations (Dr Conor O'Brien, 2023) .......................... 5
Figure 2 - Comparison of Fuel Cell Technologies (Office of Energy Efficiency and Renewable
Energy, 2019) ......................................................................................................................... 6
Figure 3 - Diagram of a SOFC (Dwivedi, 2020) .......................................................................... 8
Figure 4 - Diagram showing effects of delamination (anon, 2001) .......................................... 11

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3 ABSTRACT
Solid Oxide Fuel Cells (SOFCs) are a promising and versatile technology prospect for low
carbon emission energy systems. SOFCs can be defined as high temperature electrochemical
devices that convert chemical energy directly into electricity with high efficiency. A variety of
fuels can be used to operate them such as hydrogen, natural gas and biogas, this is one of
their many advantages. This report explores the working principles of SOFCs, focusing on the
electrochemical reactions occurring at the anode and cathode, the role of key materials such
as yttria-stabilised zirconia (YSZ) electrolytes and perovskite-based cathodes, and the
thermodynamic considerations that impact performance. Despite numerous advantages,
SOFCs currently have limitations that need to be overcome such as: material degradation,
high operating temperatures, and cost barriers. The report also covers current applications of
SOFCs in stationary power generation, combined heat and power systems (CHPs) and
auxiliary power systems (APUs) for transportation. Finally, future prospects are discussed with
regard to advancements in materials, low temperature operation, hybrid systems and the use
of renewable fuels. By addressing the challenges presented and leveraging ongoing research,
SOFCs have the potential to play a critical role in the global transition to sustainable energy
systems.

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4 INTRODUCTION
The energy sector is undergoing significant transformation as global powers are striving to
reduce carbon emissions and transition to sustainable energy systems. Among emerging
technologies, fuel cells have gained considerable attention for their ability to efficiently convert
chemical energy directly into electricity with minimal environmental impact. The European
strategic Energy Technology Plan (SET Plan), which promotes coordinated national research
in the European union (European Commission, n.d.), has included fuel cells and hydrogen as
part of their portfolio of technologies that are expected to contribute to a sustainable and
secure energy supply system in the medium but primarily long-term (Niakolas et al., 2015).
This can be evidenced in research as the amount of SOFC Installations (in MW) has increased
by more than 4 times over since 2016 and the global market value is set to grow to US$6.8
Billion by 2033 (Dr Conor O'Brien, 2023).

Figure 1 - IDTechEx Research on SOFC installations (Dr Conor O'Brien, 2023)

According to Mekhilefa et al. 2012 fuel cells can be classified into six major categories based
on the choice of fuel and electrolyte. These fuel cells also differ regarding their operating
temperatures, applications, efficiencies and cost. These are: Alkaline fuel cells (AFCs),
Phosphoric acid fuel cells (PAFCs), Molten carbonate fuel cells (MCFCs), Proton exchange
membrane fuel cells (PEMFCs), Solid oxide fuel cells (SOFCs) and direct methanol fuel cells
(DMFCs) (Niakolas et al., 2015). A comparison of some of these different fuel cell types can
be found below in Figure 2 .

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Figure 2 - Comparison of Fuel Cell Technologies (Office of Energy Efficiency and Renewable Energy, 2019)

As shown in Figure 2, two of the primary advantages of SOFCs is that they maintain the
highest efficiency of energy conversion whilst having the flexibility to use many different fuel
types where other types of fuel cells cannot. As well as this, when combined heat and power
systems (CHPs) are implemented when using SOFCs the efficiency has the potential to reach
values over 85% (Smith et al., 2019). Currently, applications of SOFCs are based around its
current limitations surrounding long start-up times, limited number of shutdowns and high
operating temperatures. Therefore, it is optimal for applications and sectors that require a
continuous power supply such as but not limited to: Utilities, Commercial, Industrial, Data
centres and hospitals. As seen in Figure 1, the market share is domination by application in
power grids (utility) and commercial use. Many of these applications can also benefit directly
from CHPs and use the SOFCs as heating sources.

Despite numerous advantages, SOFCs face several technical challenges that hinder their
widespread adoption. These include the high operating temperatures that cause material
degradation, long start-up times and high costs associated with materials and manufacturing.
These challenges are being addressed through ongoing research and development and is
critical to unlocking the full potential of SOFCs and allowing for their wider integration as a low
carbon energy system.

This report aims to provide a comprehensive overview of SOFCs, focusing on their working
principles, key materials, technical challenges, and current applications.

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5 WORKING PRINCIPLES OF SOFCS
The working principles of SOFCs are based on the electrochemical reactions that occur at the
positive and negative electrodes inside a fuel cell. The key components of a fuel cell are the
positive electrode, the cathode, the negative electrode, the anode, and an electrolyte to
conduct the ions between them. This section provides an in-depth explanation of these
components and the electrochemical processes that drive SOFC operation.

Basic Components

Anode

The anode is the electrode where the fuel oxidation occurs. Typically, in a SOFC, it is made
of a nickel-based cermet. A cermet being a composite material made up of ceramic (cer) and
metal (met) components (Naser Kordani, 2023). Cermets combine the advantageous
properties of metal and ceramic such as hardness, high temperature resistance and the ability
to undergo plastic deformation. In this case, Nickel is chosen as the metal for its excellent
catalytic properties for fuel oxidation and high electronic conductivity. The ceramic component
is usually chosen to be nickel-yttria-stabilized zirconia (Ni/YSZ) or gadolinia-doped ceria
(GDC) and these components provides ionic conductivity and structural stability for the anode.
The anode must be porous to allow for fuel gases to diffuse into the reaction sites and for the
products to escape (Aravind & de Jong, 2012).

Cathode

The cathode is the electrode where oxygen reduction takes place. It is typically composed of
materials like lanthanum strontium manganite (LSM), which are mixed ionic-electric
conductors (MIECs). The cathode must also be porous to allow oxygen from the air to reach
the reaction sites and for the oxide ions to migrate through the electrolyte. The cathode’s
primary role is to reduce the oxygen molecules from the air, forming oxide ions that are
transported through the electrolyte to the anode (Aravind & de Jong, 2012).

Electrolyte

The electrolyte is a dense, solid oxide material (hence ‘SOFC’), most commonly yttritia-
stabilized zirconia (YSZ) which allows the conduction of oxygen ions whilst being impermeable
to electrons. This ensures that the electrons, generated by the reaction at the anode, travel
through the external circuit to reach the cathode, thus preventing direct electronic contact
between the two (Aravind & de Jong, 2012).

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Figure 3 - Diagram of a SOFC (Dwivedi, 2020)

Electrochemical Reactions in SOFCs

Operation of a SOFC involves a series of electrochemical reactions at the anode and cathode
which are facilitated by the solid oxide electrolyte. The reactions are driven by high operating
temperatures (typically 500-10000C), which aids ion conductivity and enables more efficient
fuel utilisation.

This section will explain the reactions occurring at each part within the fuel cell which can be
referenced to the diagram in Figure 3.

Cathode Reaction

At the cathode, air is supplied where oxygen molecules are reduced to form oxide ions, which
migrate through the solid electrolyte to the anode, supplying it with the oxide ions needed for
the oxidation reactions.

1
𝑂 + 2𝑒 − → 𝑂2−
2 2
Reaction equation 1

Oxygen molecules are reduced by the electrons that have travelled through the external
circuit, forming oxide ions. These ions then diffuse into the electrolyte and participate in the
anode reactions (Aravind & de Jong, 2012).

Anode Reaction

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At the anode, fuel gases (such as hydrogen, carbon monoxide, biogas, etc.) are oxidised. The
process of oxidisation releases electrons which travel through an external circuit to the
cathode. This produces the electrical power. The specific reactions and byproducts depend
on the choice of fuel.

Hydrogen Oxidation:

𝐻2 + 𝑂2− → 𝐻2 𝑂 + 2𝑒 −

Reaction equation 2

Hydrogen molecules are reacting with oxide ions from the electrolyte. This releases two
electrons and one molecule of water as a by-product.

Carbon Monoxide Oxidation:

𝐶𝑂 + 𝑂2− → 𝐶𝑂2 + 2𝑒 −

Reaction equation 3

Carbon monoxide reacts with the oxide ions. This again releases two electrons but with one
molecule of carbon dioxide as the by-product.

The oxidation reaction occurs at the triple-phase boundaries where the anode, electrolyte and
fuel gas converge. The porous structure of the anode promotes diffusion of the fuel gas to the
active sites and allows the by-products to escape (Aravind & de Jong, 2012).

Overall Reaction

The overall reaction in a SOFC depends on the fuel used but in both cases the reaction
produces water or carbon dioxide, electricity and heat. The electricity is produced by the
movement of reactions from the negative to the positive terminal and heat is produced by the
reactions themselves taking place within the fuel cell.

6 HIGH TEMPERATURE OPERATION AND EFFICIENCY

The high operating temperatures of SOFCs are a defining characteristic that sets them apart
from other types of fuel cells. These elevated temperatures, usually ranging from 500-10000C,
are not just a byproduct of the reaction enthalpies within the cell but are integral to their
performance, efficiency and functionality.

One of the primary benefits of the high temperature operation is the significant enhancement
in ionic conductivity within the electrolyte. As at high temperatures, there is a dramatic increase

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in the movement of oxide ions which in turn reduces the ohmic resistance of the electrolyte.
This is one of the main reasons that SOFCs are so efficient.

As mentioned previously, using combined heat and power systems with SOFCs greatly
increases their efficiency (by ~20%). This can be achieved by integrating the system with gas
turbines in combined cycles. Certain applications will take the waste heat from the SOFC and
use it for heating purposes such as space heating, heating in industrial processes, or hot water
production. When using integrated gas turbines, the hot exhaust gases from the SOFC can
be used to drive a turbine, generating additional electricity (Azizi & Brouwer, 2018).

7 FUEL FLEXIBILITY AND INTERNAL REFORMING

As previously stated, one of the key advantages of SOFCs is their ability to operate using a
variety of fuels. This fuel flexibility is largely due to the high operating temperatures, which
enable internal reforming of hydrocarbons directly at the anode. For example, methane can
be reformed within the reactor using either of the byproducts of the anode reaction producing
hydrogen and carbon monoxide that can then be subsequently reused as a fuel for the SOFC.
This ability to internally reform hydrocarbons simplifies the fuel processing requirements and
enhances the overall efficiency of the system (Aravind & de Jong, 2012). These reformation
reactions can be seen as follows:

𝐶𝐻4 + 𝐻2 𝑂 → 𝐶𝑂 + 3𝐻2

Reaction equation 4 – Steam Reforming

𝐶𝐻4 + 𝐶𝑂2 → 2𝐶𝑂 + 2𝐻2

Reaction equation 5 – Dry Reforming

8 CHALLENGES AND CONSIDERATIONS

Contaminants

One of the more significant challenges in SOFC operation is the presence of contaminants in
the fuel. These can poison the anode which then degrades the cells’ performance. Common
contaminants include: Sulphur compounds (e.g. H2S), halides (e.g. HCl) and tars (aromatic
hydrocarbons). Contaminants such as these can greatly impact performance of the SOFC and
general tolerance limits have been experimentally evidenced to be <10ppmv for tar and
<1mmpv for sulphur compounds, halides and alkalis (Marcantonio et al., 2022).

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Hydrogen Sulphide (H2S) is a particularly problematic contaminant. It adsorbs strongly to the
nickel surface which blocks active sites for the fuel oxidation. Even at low concentrations it
can cause a significant drop in cell voltage and increase polarization resistance. At low
concentrations the nickel poisoning effect is reversable but at high concentrations can lead to
the formation of nickel sulphides, causing irreversible damage to the anode (Marcantonio et
al., 2022).

Halide contamination is another harmful contaminant that reacts with the anode. Hydrogen
chloride (HCl) reacts with the nickel, forming nickel chloride which reduces the anodes
catalytic activity. At high concentrations, this again leads to performance degradation and the
corrosion of the anode (Marcantonio et al., 2022).

Tar deposition is the condensation of complex aromatic hydrocarbons on the anode surface
or within the porous structure. This blocks fuel access to the active sites. (Marcantonio et al.,
2022)

Material Degradation due to high temperatures

As previously discussed, high operating temperatures are necessary for effective ion transport
and internal reforming, but they also pose a significant challenge related to material stability
and durability.

Nickel-based anodes are prone to sintering at high temperatures., where nickel particles
agglomerate, reducing the active surface area and increasing polarization resistance. This
sintering effect is exacerbated by prolonged operation and thermal cycling. Leading to a
gradual decline in cell performance (Liu et al., 2021).

The solid oxide electrolyte (usually YSZ) is susceptible to cracking due toi thermal stresses
and mechanical shock. Cracks in the electrolyte can lead to gas crossover, where the air and
fuel gases seep into the electrolyte. This reduces cell efficiency and potentially could cause a
catastrophic failure.

The cathode can experience delamination from the

electrolyte due to thermal expansion mismatches or
chemical reactions at the high temperatures. Thermal
expansion mismatches occur when the values for
thermal expansion of two materials are different and
their relative change in size differs, causing
delamination, fractures and buckling of the cathode .
This delamination increases interfacial resistance and
reduces cell performance (Yang et al., 2024).
Figure 4 - Diagram showing effects of
delamination (anon, 2001) 11
9 FUTURE DIRECTIONS FOR SOFC TECHNOLOGY
While SOFCs have already demonstrated their potential in various applications, ongoing
research and development are essential to address the existing challenges and expand their
applications.

Advanced materials development

Currently nickel based anodes (Ni/YSZ, Ni/GDC) are widely used but are susceptible to
sulphur poisoning and tar deposition. Research is focused on developing alternative anode
materials , such as ceramic anodes (lanthanum strontium titanate, LST) or mixed ionic
electronic conductors (MIECs). These materials offer improved tolerance to contaminants and
reduced degradation (Hanif et al., 2023).

While YSZ is the most common electrolyte material, its ionic conductivity decreases at lower
temperatures. Research is underway to develop alternative electrolytes, such as doped ceria
(GDC, SDC) or proton-conducting ceramics which offer higher conductivity coefficients and
enable SOFCs to operate at lower temperatures (Zhang et al., 2020).

Intermediate Temperature SOFCs

Reducing the operating temperatures of SOFCs to a more intermediate range (500-7000C) is

of major focus. It would enable the use of cheaper materials, reduce thermal stresses, improve
system durability and increase its applications.

The developments in this aspect are focused on achieving similar performance at lower
temperatures and trialling combinations of different materials for the cathode, anode and
electrolyte. This is done to find the materials with the best ionic conductivity and catalytic
activity at the preferred temperatures with a focus on optimising the electrode-electrolyte
interfaces to order to reduce interfacial resistances.

Manufacturing and Costs

Advancements in manufacturing techniques such as tape casting, screen printing and additive
manufacturing are reducing costs and the complexity of SOFC production. These innovations
enable larger scale production of SOFC components with consistent quality and performance
(Li et al., 2024).

As SOFCs approach larger scale production and adoption, government policies and
incentives, such as subsidies, tax credits and renewable energy mandates can help accelerate
this process as public-private partnerships and international collaborations are critical to
driving innovation and deployment.

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Emerging Applications

As SOFC technology continues to evolve, emerging applications are being explored to expand
its impact. SOFCs can be integrated with carbon capture systems to produce electricity whilst
capturing CO2 emissions. The captured CO2 can be captured from existing industrial
processes and converted into green energy and heat for the plant. Smaller scale SOFC
systems for residential CHP are being developed to provide homeowners with efficient clean
energy and heating sources. These systems will reduce energy bills and carbon footprints
whist also enhancing energy security which in this day and age is becoming a higher and
higher priority. SOFCs are also being considered for use in space exploration missions. Their
high efficiency and ability to operate on a variety of fuels make them ideal for providing power
in remote and extreme environments.

10 CONCLUSION
SOFC technology has already demonstrated its potential in a wide range of applications from
stationary power generation to remote and industrial systems. However, to fully realise its
potential, ongoing research and development are needed to address the numerous technical
challenges, overall cost and expand its applications. By overcoming the challenges mentioned
in this report, SOFCs can play a critical role in the global transition to sustainable and low-
carbon energy future.

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