Solid Oxide Fuel Cells (SOFC)

Dr Waldemar Bujalski
Senior Research Fellow
School of Chemical Engineering
College of Engineering and Physical Sciences
University of Birmingham
 Outline
• PEMFC – Proton Exchange Membrane Fuel Cell
• SOFC - How it works?
• A bit of theory
• Standard SOFC design
• SOFC components and materials
• Cell and stack design
• Planar cell and stacks fabrication methods
• Cell and stack testing
• Tubular SOFC designs (large and micro-tubular)
• Work on SOFC at Chemical Engineering
– FP 6 European Project
– Rolls Royce IP SOFC concept and testing facilities at
Birmingham (some thermal testing results)
PEMFC (Proton Exchange
Membrane Fuel Cell)

Anode reaction: Cathode reaction:

H 2 ⇒ 2 H + + 2e − 2 H + + 1 2 O2 + 2e − ⇒ H 2O
 Nernst equation for EMF
(electromotive force or reversible open circuit voltage)

Overall electrochemical reaction for SOFC:

H 2 + 12 O2 → H 2O( steam )
leads (for pressure given in bar) to:
⎛ pH pO2 ⎞
1

RT
E = E0 + ln ⎜ 2 2 ⎟
2 F ⎜ pH 2O ⎟
where:
⎝ ⎠
E - the electromotive force (or reversible open circuit voltage), V
Eº - the EMF at standard pressure, V
R - the universal gas constant, 8.314 JK-1mol-1
F - Faraday constant (the charge of one mole of electrons), 96485 Coulombs
pi - partial pressure (i - hydrogen, oxygen and steam), bar
PEM Stack
MicroCHP
Micro CHP in House
MicroCHP system at Lye
 Microcab car

Hybrid – Electric/Fuel Cells (1.2kW Ballard)

 Successful Projects
Hydrogen Fuel Cell Narrow Boat
PEM Fuel Cell Batteries & Motor

• 10 large cylinders, each containing

30 kg of metal hydride power.
• Gives about 5 kg of hydrogen.
• Operating pressure is < 10 bar
The Protium Project
How it works?
• The SOFC is a complete
solid-state device that
uses an oxide-conducting
ceramics material as
electrolyte:
– Only two phases involved
i.e. gas and solid;
– Both hydrogen and carbon
monoxide can act as fuels;
– A negatively charged ion
(O=) is transferred from the
cathode through the
electrolyte to the anode
with water produced at the
anode.
Schematic showing reactions and charge transfer in a
typical solid oxide fuel cell fuelled with Hydrogen
Reaction at the anode;

Hydrogen 2H2 + 2O2- → 2H2O + 4e-

H2

Porous anode e-
e-

External
Electrolyte O2-
Load

e-
Porous Cathode e-

O2
Oxygen Reaction at the cathode;

O2 + 4e- → 2O2 -

Development can be traced back to Nernst (1899) who was the first to
describe zirconia (ZrO2) as an oxygen ion conductor.
 Nernst equation for EMF
(electromotive force or reversible open circuit voltage)

Overall electrochemical reaction for SOFC:

H 2 + 12 O2 → H 2O( steam )
leads (for pressure given in bar) to:
⎛ pH pO2 ⎞
1

RT
E = E0 + ln ⎜ 2 2 ⎟
2 F ⎜ pH 2O ⎟
where:
⎝ ⎠
E - the electromotive force (or reversible open circuit voltage), V
Eº - the EMF at standard pressure, V
R - the universal gas constant, 8.314 JK-1mol-1
F - Faraday constant (the charge of one mole of electrons), 96485 Coulombs
pi - partial pressure (i - hydrogen, oxygen and steam), bar
 Standard SOFC
• Based on an electrolyte of zirconia stabilised with the addition of a small
percentage of yttria (Y203). Above temperature of 800ºC zirconia becomes
a conductor of oxygen ions (O=) and typically the state of the art zirconia
based SOFC operates between 800 and 1100ºC (this presents both
challenges for the construction and durability but also opportunities e.g. for
combined cycles application such as CHP, etc.).
• The anode is usually a zirconia cermet (an intimate mixture of ceramic and
metal). The metallic component is usually Ni (nickel chosen amongst other
things because of its high electronic conductivity and stability under
chemically reducing and part reducing conditions; it can also be used as
catalyst for direct internal reforming on the anode!);
• Cathodes proved to be difficult from the point of view of choosing the right
material (initially nobel metals were used but proved too expensive for mass
production!). At present, most cathodes are made from electronically
conducting oxides or mixed electronically conducting and ion-conducting
ceramics. The most common cathode material of the latter type is
strontium-doped-lanthanum manganite (SLM).
 SOFC components
• Electrolytes:
– Zirconia doped with 8 to 10 mole % yttria (yttria-stabilised
zirconia (YSZ)) is still the most effective electrolyte for the high
temperature SOFC (but others such as Bi2O3, CeO2 and Ta2O5
have been also investigated with mixed success). Advantages:
• Zirconia is highly stable in both the reducing and oxidising
environments that are experienced at the anode and cathode,
respectively;
• The ability to conduct O= ions is brought about by th fluorite crystal
structure of zirconia in which some of the Zr4+ ions are replaced by
Y3+ ions. When ion exchange occurs, a number of oxide-ion sites
become vacant because of three O= ions replacing four O= ions.
Oxide-ion transport occurs between vacancies located at tetrahedral
sites in the perovskite lattice.
• The ionic conductivity of YSZ (0.02 Scm-1 at 800ºC and 0.1 Scm-1 at
1000ºC) is comparable with that of liquid electrolytes and it can be
made very thin (25-50 μm) ensuring that the ohmic loss in the
SOFC is comparable with other fuel cell types.
 SOFC components
• Electrolytes:
– Most recently other materials have been produced with enhanced oxide-ion
conductivity at temperatures lower than that required by zirconia. For example,
LaSrGaMgO (LSGM) proved to be a superior oxide-ion electrolyte that provides
performance at 800ºC comparable to YSZ at 1000ºC.

Specific conductivity versus reciprocal temperature Typical single cell performance of LSGM
for selected solid-oxide electrolytes electrolyte (500 μm thick)
 SOFC components
• Anode:
– The anode of state of the art SOFCs is a cermet made of
metallic nickel and a YSZ skeleton. Advantages:
• The zirconia serves to inhibit sintering of the metal particles and
provides a thermal expansion coefficient comparable to that of the
electrolyte;
• The anode has a porosity (20-40%) so that mass transport of
reactants and product gases is not inhibited;
• However, there is some ohmic polarisation loss at the interface
between the anode and the electrolyte and bi-layer anodes have
been introduced in order to overcome this problem (often a small
amount of ceria is added to the anode cermet; this improves the
tolerance of the anodes to temperature and redox cycling );
• Control of the particle size of the YSZ can also improve the stability
of the anode under redox conditions.
 SOFC components
• Cathode:
– The cathode is also a porous structure which must allow rapid
mass transport of reactant and product gases. Strontium-doped
lanthanum manganite (La0.84Sr0.26)MnO3, a p-type
semiconductor, is the most commonly used material;
– Other materials may be also used:
• Particularly attractive is p-type conducting perovskite structure that
exhibits mixed ionic and electronic conductivity. This is especially
important for lower-temperature operation since polarisation of the
cathode increases significantly at those conditions. The advantages
are particularly apparent in cells operating at around 650ºC and as
well as the perovskites, lanthanum strontium ferrite, lanthanum
strontium cobalite and n-type semiconductors are better
electrocatalysts than the state of the art LSM because they are
mixed conductors.
 SOFC components
• Interconnect material (in general):
– The interconnect is the means by which connection is achieved
between neighbouring fuel cells. In planar fuel cell technology this it the
bipolar plate (however, it’s different for tubular geometry).
• Metals can be used as interconnects but they are expensive “inconel” type
stainless steels (particularly for stacks that need to operate above 800ºC);
• Conventional steels also have a mismatch in thermal expansion coefficient
with the YSZ electrolyte;
• Development of new alloys (e.g. Cr-5Fe-1Y2O3 Siemens/Plansee alloy) lead
to poisoning the cathode with chromium leading to its deposition at the three
phase (LSM/YSZ/gas) boundary and causing rapid de-activation of the
cathode;
• An advantage for the low temperature SOFC is that cheaper materials may
be used (such as austenitic steels, which do not contain chromium);
• Metal interconnects also tend to form oxide coatings which can limit their
electrical conductivity and acts as a barrier to mass transport.
 SOFC components
• Interconnect material (tubular design):
– The use of a ceramic material for the interconnect is favoured for
the tubular design and lanthanum chromite being the preferred
choice (its conductivity is further enhanced when some of the
lanthanum is substituted by magnesium or other alkaline earth
elements).
– However, the material needs to be sintered to quite high
temperature (1625ºC) to produce a dense phase and this makes
fabrication very difficult:
• All the cell components need to be compatible with respect to
chemical stability and mechanical compliance (i.e. similar thermal
expansion coefficients);
• The various layers need to be deposited in such a way that good
adherence is achieved without degrading the material due to the
use of too high sintering temperature;
• Many of the methods of fabrication are proprietary and lots of
research is being devoted in this area.
 SOFC components
• Sealing materials:
– Major issue with SOFCs is the method of sealing the ceramic
components to obtain gas tightness, particularly with planar
design. The wide temperature ranges pose significant
difficulties.
– Usual approach is to use glasses that have transition
temperature close to the operating temperature of the cell (these
materials soften when the cells are heated up and form a seal all
around the cell and this is particularly important for the planar
design in which a number of cell can be assembled in one layer).
– A particular problem is the migration of silica from such glasses
(especially onto the anodes) causing degradation in cell
performance.
– For all-ceramic stacks, glass ceramics have been used, but
migration of the silica component can still be a problem on both
the anode and cathode sides.
 Cell and stack designs
• Numerous designs od SOFCs emerged
since 1930s but since 1960s most
development was focused on:
– Planar SOFC
• Short stack planar (Julich)
• Integrated Planar (Rolls Royce)
– Tubular SOFC
• Siemens Westinghouse (relatively large diameter
>15 mm)
• Microtubular SOFC (Adelan) (diameter < 5 mm)
 Cell and stack designs
• Planar SOFC design
– Cell componets are configured as flat plates
which are connected in electrical series:
 Cell and stack designs
• Planar SOFC design – key requirements:
– Electrical performance:
• Minimise ohmic losses thus the current path in the components (especially those having
low electrical conductivity) must be designed to be as short as possible;
• There must be good electrical contact and sufficient contact area between the
components;
• The current collector must also be designed to facilitate current distribution and flow in
the stack.
– Electrochemical performance:
• Design must provide for full open circuit voltage and minimal polarisation losses thus
significant gass leakage or cross-leakage and electrical short must be avoided;
• Fuel and oxidant must be distributed uniformly not only across the area of each cell but
also to each cell of the stack;
• The gases must be able to quickly reach the reaction sites to reduce potential for mass
transport limitations.
– Thermal management:
• Means for stack cooling and more uniform temperature distribution during operation.
The design must permit the highest possible temperature gradient across the stack.
– Mechanical/structural integrity:
• Adequate mechanical strength for assembly and handling. Mechanical and thermal
stresses must be kept to minimum to prevent cracking, delamination or detachment of
the components under the variety of operating conditions the stack can experience.
 Cell and stack designs
The most important design feature of the Planar SOFC relates to gas flow
configuration and gas manifolding which can be arranged in several ways

Fuel and oxidants flows can be arranged as cross-flows, co-flows or counter-

flow with potentially significant effects on temperature and current distribution
within the stack depending on the stack precise configuration.
Cell and stack designs
• Flow channels are used to:
– Increase uniformity of gas
distribution and to promote
heat and mass transfer in
each cell;
– Often, the design takes care
of sufficient pressure drop
through the cell to promote
cell-to-cell flow uniformity
within the stack;
– The flow channels electrically
connect the interconnect and
the electrodes, thus the
contact area must be
considered in the design to
minimise contact resistance
losses.
Cell and stack designs
• Gas manifolds (external
and internal):
– Any stack design must
include gas manifold for
routing gas from a common
supply point to each cell and
removing; they often require
sealing to prevent gas
leakage or crossover;
– Manifolds should be design
to have a low pressure drop
in order to provide uniform
flow distribution to the stack.
 Planar Cell designs
• These can be broadly classified into two
categories:
– Self supporting where one of the cell components
(often the thickest layer) acts as the cell structural
support (thus the single cell can be design as
electrolyte, anode or cathode supported);
– In the external supporting configuration, the single cell
is configured as thin layers on the interconnect or a
porous substrate;
– Again, the most common cell materials are:
• Electrolyte: yttria-stabilised zirconia (YSZ);
• Anode: lanthanum strontium manganite (LSM);
• Cathode: nickel/zirconia cermet (Ni/YSZ).
Planar Cell designs

Micrograph of a planar cell

on porous metal structure
 Features of planar single cell
Cell configuration Advantage
Self-supporting
Electrolyte supported Relatively strong structural support
from dense electrolyte
Less susceptible to failure due to
anode re-oxidation
Anode supported Highly conductive anode
Lower operating temperature via
use of thin electrolyte
Cathode supported No oxidation issues
Lower operating temperature via
use of thin electrolyte
External supporting
Interconnect supported Thin cell components for lower
operating temperature
Stronger structures from metallic
interconnects
Porous substrate Thin cell components for lower
operating temperature
Potential for use of non-cell
material for support to improve
properties
Disadvantage
Higher resistance due to lower
electrolyte conductivity
Higher operating temperatures required
to minimise ohmic loses
Potential anode re-oxidation
Mass transport limitations due to thick
anodes
Lower conductivity
Mass transport limitation due to thick
cathodes
Interconnect oxidation
Flowfield design limitations due to cell
support requirement
Increased complexity due to addition of
new materials
Potential electrical shorts with porous
metallic substrate due to uneven surface
 Cell fabrication
– Based on deposition approach wide range of techniques have
been used focusing on the aim of making thin (5-20μm) YSZ
electrolytes:
• Sputtering - involving electrical discharge in argon/nitrogen mixtures
to deposit YSZ;
• Dip coating - porous substrates are immersed in YSZ slurries of
colloidal size particles. Deposited films are then dried and fired;
• Spin coating - YSZ films are produced on a dense or porous
substrate by spin coating a sol-gel precursor followed by heat
treatment at relatively low temperatures;
• Spray pyrolysis - a solution consisting of powder precursor and /or
particles of the final composition is sprayed onto a hot substrate
followed by a sintering step to densify the deposited layer;
• Other methods - electrophoretic deposition, slip casting, plasma
spraying, electrostatic assisted vapour deposition, vacuum
evaporation, lase spraying, transfer printing, sedimentation method,
and plasm metal organic chemical vapour deposition.
 Stack testing

Design will be shown and discussed at the laboratory session in the afternoon.
Stack testing
 Tubular SOFC design
• Two general types
are being pursued:
– Large diameter (> 15 microtubular

mm) (Siemens
Westinghouse Power
Corporation;
– Very small diameter
(< 5 mm) (Adelan, UK;
Adaptive Materials
Inc., USA).

This design will be discussed and its performance investigate/tested

further at the laboratory session this afternoon.
 Large tubular SOFC design

• The cell components are deposited in the form

of thin layers on a cylindrical tube.
– In the earlier designs the tube was made of calcia-
stabilised zirconia; this porous support tube (PST)
acted both as a structural member onto which the
active cell components were fabricated and as a
functional member to allow the passage of air to
the cathode during cell operation;
– This porous support tube was fabricated by
extrusion followed by sintering at an elevated
temperature (problems with air flow);
– The porous support tube was eliminated and
replaced by a doped LaMnO3 tube (air electrode- Eliminating the need for gas-tight seals
supported cell, AES) leading to significant
improvements in performance (see next figure)
 Chemical Engineering
• Group leader: Professor Kevin Kendall, FRS
“Development of solid oxide fuel cells (SOFC) using a range of existing
hydrocarbon fuels”

– The main work on fuel cells is emphasised on SOFC’s with projects on:

• Materials specification for electrolyte, electrode and interconnect;

• Operating conditions of the SOFC, especially with direct injection of various
fuels including methane, propane, butane, iso-octane, methanol, ethanol,
ethers, biodiesel and biogas;
• The potential of use of supercritical fluids for fuel processing to convert
biomass into syngas;
• Fuel cells operating on hydrogen from waste sugar (and also biogas –
mainly CH4) looking at flow and catalysis issues in collaboration with other
groups;
• There are 10 PhD students in the group at different stages of their research
advancement.

Dr W. Bujalski
Senior Research Fellow
 Chemical Engineering
• Since February 2004 we have been
involved in EU Project:

Sixth Framework Programme (Priority 6):

SUSTAINABLE ENERGY SYSTEMS
“Realising reliable, durable energy efficient
and cost effective SOFC systems”

Dr W. Bujalski
Senior Research Fellow
 Aims of the Project
Real-SOFC is an Integrated Project aimed at:
1. Solving the persisting generic problems of ageing with
planar Solid Oxide Fuel Cells (SOFC) in a concerted
action of the European fuel cell industry and research
institutions. This includes:
• gaining full understanding of degradation processes;
• finding solutions to reduce ageing;
• producing improved materials that then will be tested in stacks.

2. In this process further consideration will be given to:

• the design of cost effective materials;
• low cost components;
• optimised manufacturing process.

Dr W. Bujalski
Senior Research Fellow
 Structure of the Project
1. Overall, the project has been split into seven, so called, Working Packages (WP) in
order to cater for the strongly interdisciplinary character of SOFC technology. There
are 26 partners involved in the project from 13 European countries with four from
United Kingdom and Department of Chemical Engineering at The University of
Birmingham being one of them.

2. We are involved in WP 1 i.e. “Understanding the ageing of SOFC in industrial

applications”, which focuses on the identification of the mechanisms responsible for
the degradation of SOFC stacks (two different designs to be provided for testing by
Rolls Royce (UK) and Forschungszentrum Jülich GmbH (Germany) i.e. industrial
partners, respectively) and the determination of the sensitivity of these mechanisms
for the operational parameters relevant to those realistic systems.

3. This WP 1 is led by Energy Research Centre of the Netherlands and consists of

seven sub-tasks with The University of Birmingham responsible for Task 4 (WT 1.4)
i.e. “Cycled stack operation for 50 to 100 cycles at defined conditions”. This involves
both experimental testing and computer modelling for predicting reliability and
durability of cells and stacks.
.
Dr W. Bujalski
Senior Research Fellow
 Work Task 1.4

• Leader for Work Package 1 “Understanding of

aging of SOFC for industrial applications”

• Responsible partner for Work Task 1.4

“Cycled stack operation for 50 to 100 cycles at
defined conditions”

Framework 6 “Sustainable Energy Systems” Integrated Project

 University of Birmingham

Professor Kevin Kendall, FRS

Dr Waldemar Bujalski
Department of Chemical Engineering
University of Birmingham
Edgbaston
Birmingham B15 2TT, UK

k.kendall@bham.ac.uk; w.bujalski@bham.ac.uk

Framework 6 “Sustainable Energy Systems” Integrated Project

 Activities at UBHAM

The “state of art”

SOFC Test Station
from Advanced
Measurements Inc.
has been fully
operational now
with all the auxiliary
equipment in place
and all the “Health
and Safety” issues
related to working
with hydrogen
sorted out!

Framework 6 “Sustainable Energy Systems” Integrated Project

 Activities at Birmingham

• Experimental testing of R-R IP-SOFC tubes has been

carried out at different levels of “sophistication” as the
test facilities developed:
– Initially, temperature tests of the R-R tubes for a range of
controlled temperature ramps (from 1 deg C/min to 10 deg
C/min) and gas flow rates (from 0 to 10 l/min) with and without
air preheated in the process were carried out.
• General outcome:
– No signs of any damage to the cells was noticed. Even the
highest temperature ramps rates used did not cause any obvious
damage to the integrity of the tube!

“multi-cell membrane electrode assembly

(multi-cell MEA) module”

Framework 6 “Sustainable Energy Systems” Integrated Project

 Work with hydrogen at Birmingham

• Experimental runs were carried out using

hydrogen attempting achieving of 50 current
load cycles from 0 to the iDP=2.7 A (i.e.
current Design Point value) and back to OCV.
– Procedure provided by R-R for the run was
adhered to which conformed to general testing
procedures used in the programme;
– This procedure was unified/synchronised
across the manufactures/partners in order to
arrive at comparable results for different
makes of the fuel cells tested in the
programme;
– There were 16 thermocouples placed in the
box for monitoring the temperature in vicinity of
the tube.

Framework 6 “Sustainable Energy Systems” Integrated Project

 Conclusions

• The experimental rig enabled fully programmable/automated operation of the test

thus providing a regime for reproducible testing conditions in cycling tests;
• The conditions for the test itself were in accordance with the stack providers
requirements/limits and were specified for the programme of “standardisation” agreed
by the Real-SOFC participants;
• Temperature (16 thermocouples monitoring within the test box as well as air
preheater and furnace temperature) and electronic load control allowed detailed
monitoring of cyclic behaviour;
• First run consisted of 50 full cycles (up and down i.e. from open circuit to design
value of electronic load of 2.7 A). The nominal temperature for the cycling work was
set at 900ºC but the actual one experienced by the tube in the box was about 920ºC;
• The module has shown some increase in resistance at the end of the cycling
process. Initial visual inspection of the module in the test box identified a possible
defect in one of the cells, however, when the module was removed from the box after
completion of additional cycling tests leading to 93 cycles in total no physical damage
to its structure was identified;
• Overall, the tube performed very well. Even after reaching the limit for the allowed
minimum tube voltage of 9 V under full load (i.e. 2.7 A) the cut off point was reached
at the next load level of 2.6 A for all the remaining test points.

Framework 6 “Sustainable Energy Systems” Integrated Project

 Thermal Cycling with Second Generation

IV curves as a function of temperature cycles

for IP SOFC - RR_134W-40 10 cell tube (10 C/min)
Cycling results for 102 thermal cycles
at 10 C/min for Rolls Royce IP-SOFC
(blue arrows indicate re-starts)
11

11

10

10

U, [V]
9
OCV or U, [V]

Open Circuit Voltage [V]

2
9 Voltage at IDP of 2.5 A i.e. 0.278 A/cm [V]
8

IDP=2.5 A
8
7
0.00 0.05 0.10 0.15 0.20 0.25 0.30
2
Specific current load, i, [A/cm ]

7 Initial IV curve (1 C/min heating/cooling rate)

0 10 20 30 40 50 60 70 80 90 100 110 After 1 cycle (10 C/min up; 5 C/min down to 500 C & 2 C/min to 200 C)
After 10 cycles
Number of thermal cycles, [-] After 20 cycles
After 50 cycles
After 102 cycles

Framework 6 “Sustainable Energy Systems” Integrated Project

 Further work within the Real SOFC

• Further experimental work:

– To continue work with R-R tube to be followed by a bundle;

– Get a full “post mortem” info on the damaged tubes in order to
draw some sound conclusions on possible modes of failure;
– Also, to try to analyse the already acquired data fully (there is
lots of important, unravelled information there!);
– Carry out the thermal cycling (already done) and redox cycling
experiments with those tubes.

• Test with first generation of Jülich module using thermal

cycling, soon.

Framework 6 “Sustainable Energy Systems” Integrated Project

 Future work at Birmingham

• Substantial additional capital funds have been recently

secured from AWM (Advantage West Midlands i.e. the
regional development agency) for expanding our
activities in the following areas:

– CHP (testing production unit under the laboratory conditions and

in the field i.e. in a house in the Black Country housing estate);
– Further development of our testing facilities for variety of fuel
cells and their stacks;
– Fuel reforming and biofuels work in collaboration with
Biosciences;
– Modelling work in collaboration with Maths department.

Framework 6 “Sustainable Energy Systems” Integrated Project

 References

• “High temperature Solid Oxide Fuel Cells.

Fundamentals, design and applications”, (Edited
by: S.C. Singhal and K. Kendall), Elsevier Ltd.,
Oxford, UK (2003)

• “Fuel cell systems explained”, J. Larminie and A.

Dicks, John Wiley and Sons, Ltd., England
(Second Edition, 2003)