Modelling, Simulation and Control of A Solid Oxide Fuel Cell System: A Bond Graph Approach

MODELLING, SIMULATION AND CONTROL OF A
SOLID OXIDE FUEL CELL SYSTEM: A BOND GRAPH

APPROACH
P. Vijay
MODELLING, SIMULATION AND CONTROL OF A
SOLID OXIDE FUEL CELL SYSTEM: A BOND GRAPH
APPROACH
Thesis submitted to
Indian Institute of Technology, Kharagpur
For the award of the degree
of
Doctor of Philosophy
by
P. Vijay
Under the guidance of
Dr. Arun Kumar Samantaray

and
Dr. Amalendu Mukherjee
DEPARTMENT OF MECHANICAL ENGINEERING

INDIAN INSTITUTE OF TECHNOLOGY, KHARAGPUR
DECEMBER 2009
© 2009, P. Vijay. All rights reserved.
This thesis is dedicated to
My Parents
CERTIFICATE OF APPROVAL
Date: / /
Certified that the thesis entitled Modelling, Simulation and Control of a Solid
Oxide Fuel Cell System: A Bond Graph Approach submitted by P.Vijay to Indian
Institute of Technology, Kharagpur, for the award of the degree of Doctor of
Philosophy has been accepted by the external examiners and that the student has
successfully defended the thesis in the viva-voce examination held today.
Signature Signature Signature
Name Name Name
(Member of the DSC) (Member of the DSC) (Member of the DSC)
Signature Signature
Name Name
(Supervisor) (Supervisor)
Signature Signature
Name Name
(External Examiner) (Chairman)

DECLARATION
I certify that
a. the work contained in this thesis is original and has been done by me under the
guidance of my supervisor(s).
b. the work has not been submitted to any other Institute for any degree or
diploma.
c. I have followed the guidelines provided by the Institute in preparing the thesis.
d. I have conformed to the norms and guidelines given in the Ethical Code of
Conduct of the Institute.
e. whenever I have used materials (data, theoretical analysis, figures, and text)
from other sources, I have given due credit to them by citing them in the text
of the thesis and giving their details in the references. Further, I have taken
permission from the copyright owners of the sources, whenever necessary.
(P. Vijay)
CERTIFICATE
This is to certify that the thesis entitled Modelling, Simulation and Control of a
Solid Oxide Fuel Cell System: A Bond Graph Approach, submitted by Mr. P.
Vijay to Indian Institute of Technology, Kharagpur, is a record of bona fide research
work carried under our supervision and is worthy of consideration for the award of
the degree of Doctor of Philosophy of the Institute.
Dr. Arun Kumar Samantaray Dr. Amalendu Mukherjee

Associate Professor Professor
Mechanical Engineering Department Mechanical Engineering Department
I.I.T. Kharagpur, India, 721 302 I.I.T. Kharagpur, India, 721 302
Email: samantaray@mech.iitkgp.ernet.in Email: amalendu@mech.iitkgp.ernet.in
Date: Date:
Acknowledgement
Foremost, I would like to express my sincere gratitude to my supervisors Dr. Arun Kumar
Samantaray and Prof. Amalendu Mukherjee. Dr. Samantaray with his seemingly inexhaustible
energy and enthusiasm, his amazing intellect and a keen eye for detail, gave excellent guidance to
me throughout the course of the work. He urged me to communicate my work to the scientific
community which ensured that the work was properly recognised. The freedom that he gave me to
pursue my own way of work helped me to gain confidence in my abilities. My independent research
works, which are not included in this thesis, have been communicated to different journals. Prof.
Mukherjee with his immense knowledge, excellent intellect and great intuitive prowess gave
direction to the work and is a person whom I would always look up to and wish to emulate. He
gave the initial momentum to the work, which was high enough to carry it through to completion,
overcoming all the resistances it had to encounter. His uncompromising intellectual rigour and his
insistence on thorough understanding of the basic physical concepts instilled in me values which
will guide me throughout my career.
I would like to express my gratitude to Prof. Ranjit Karmakar, Prof. Ranjan Bhattacharyya,
and Prof. Kingshook Bhattacharyya, who as members of the Doctoral Scrutiny Committee
provided constructive criticism and advice during various stages of the work. Prof. Ranjan
Bhattacharyya as the research coordinator took care to accommodate me into the lab environment
and encouraged me by keeping a tab on my progress. Prof. Ranjit Karmakar taught the bond graph
modelling course with such lucidity that it left a lasting impression on me.
I am thankful to Prof. Ajay Kumar Chattopadhayya, Head of Mechanical Engg.

Department, for providing a congenial environment in the Department leading to smooth
completion of my research work.
I would also like to make special mention of the research scholars of this department and my
fellow colleagues Dr. Nilotpal Banerjee, Dr. Karali Patra, Dr. Sanjoy Kumar Ghosal, Dr.
Sharifuddin Mondal, Dr. Sukhamoy Pal, Mr. Sovan Sundar DasGupta, Dr. Somnath Sarangi,
and Mr. Tarun Kumar Bera who helped me in a lot of ways and maintained a lab environment
conducive for research. I am also thankful to Mr. Birendra Nath Ghosh and Mr. D.K.
Chakraborty for their good housekeeping of the machine dynamics laboratory.
I would like to express my sincere gratitude to all who directly or indirectly helped me for the
successful completion of my thesis work.
Finally I will always remember the best wishes and blessings of my parents concerning this
venture. Without their encouragement and moral support it would not have been possible for me
to complete my Ph.D.
Campus of I I T, Kharagpur (P. Vijay)

July, 2009
Abstract
A non-linear bond graph model of a Solid Oxide Fuel Cell (SOFC) is developed in
this work by using the concepts of network thermodynamics, which features several
improvements over the models of electrochemical reaction systems available in the
literature. The constitutive relations of a C-field for modelling the energy storage in a
mixture of two gas species are formulated and an existing R-field model is extended
to represent the entropy convection in multi species gas flows. The developed model
is energetically consistent and it clearly illustrates the physical structure of the system.
Moreover, this model is useful in designing integrated model-based control strategies
for the SOFC system.
The relationship between the partial pressures of the gas species in the channel
and the fuel and oxygen utilisations (FU and OU, respectively) are established for a
given set of input parameters and used for plotting the characteristic curves of the
SOFC for various operating conditions. From the dynamic response studies, it is
found that the developed model captures all the essential features of SOFC’s
dynamics. A physical model-based control strategy is then formulated and it is found
from the closed loop system simulations that all the control objectives are achieved at
the same time by the proposed control strategy.
Finally, an algorithm has been developed to optimise the operational efficiency of

the SOFC system (consisting of a cell, an after-burner and two recuperators) under
varying load conditions. For this purpose, a comprehensive steady state model of the
SOFC is derived and used inside the optimisation loop. The results indicate that
constant FU operation of the fuel cell at a particular value of FU (which depends upon
the specific system) can closely approximate the maximum efficiency operation of the
fuel cell in terms of the cell operating conditions as well as the energy and exergy
efficiencies. It is concluded from the dynamic response studies that the constant FU
and constant temperature operating strategy (achieved through a secondary control
loop) is suitable for the SOFC system because it gives good system efficiency and
lower temperature transients, which leads to longer cell life.
Keywords: Solid Oxide Fuel Cell, Bond graph, Network thermodynamics, Electro-
chemical reaction, Fuel Utilisation, SOFC control strategy, Operational efficiency
optimisation.
Abstract
ii
List of Acronyms
AC Alternating Current
AFC Alkaline Fuel Cell
DC Direct Current
FU Fuel Utilisation
LHV Lower Heating Value
LSM Lanthanum Strontium Manganite
MCFC Molten Carbonate Fuel Cell
MEA Membrane Electrode Assembly
NTU Number of Transfer Units
OU Oxygen Utilisation
PAFC Phosphoric Acid Fuel Cell
PEMFC Proton Exchange Membrane Fuel Cell
PI Proportional Integral
PID Proportional, Integral and Derivative
SOFC Solid Oxide Fuel Cell
TPB Triple Phase Boundary
YSZ Yttria Stabilised Zirconia
1D One Dimensional
2D Two Dimensional
List of Acronyms
iv
Nomenclature
A Area (m2)
Ac Effective cell area (m2)
AF Forward affinity (J mol-1 )
AR Reverse affinity (J mol-1)
cp , cv Specific heat capacity at constant pressure and volume (J kg-1 K-1)
D Diffusion coefficient (m2 s-1)
E Activation energy (J mol-1)
F Faraday’s constant (C mol-1)
G Gibbs free energy (J)
h Specific enthalpy (J kg-1)
H Enthalpy (J)
i Current (A)
j Current density (A cm-2)
k Thermal conductivity (J m-1 s-1 K-1)
K Valve coefficient (m s)
m Mass (kg)
m Mass flow rate (kg s-1)
M Molar mass (g)
n Number of moles (mol)
ne Number of electrons participating in the reaction
p Pressure (N m-2)
Nomenclature
q Heat flow rate (J s-1)

R Specific gas constant (J kg-1 K-1)
R Universal gas constant (J mol-1 K-1)
s Specific entropy (J kg-1 K-1)
S Entropy (J K-1)
S Entropy flow rate (J K-1 s-1)
T Temperature (K)
U Internal energy (J)
u Specific internal energy (J kg-1)
v Specific volume (m3 kg-1)
V Volume (m3)
V Volume flow rate (m3 s-1)
w Mass fraction
x Valve stem position (m)
ν Stoichiometric coefficient
η Over-voltage (V)
μ Chemical potential (J kg-1)
σ Stefan-Boltzmann constant (J m-2 s-1K-4)
ε Emissivity
τ Thickness (m)
ψ Pre-exponential coefficient (A m-2)
ξ Reaction advancement coordinate (mol)
ζ f ,ζ o Fuel and oxygen utilisations
β Charge transfer coefficient

λ Convection heat transfer coefficient (J m-2 s-1 K-1)
γ Adiabatic index
ηen Energy efficiency
ηex Exergy efficiency
vi
Nomenclature
Subscripts
ai Anode side inlet
an Anode
ao Anode side outlet
act Activation
amb Ambient state
ABO After -burner outlet
AS Air source
b Bulk
c Cell
ca Cathode
ci Cathode side inlet
co Cathode side outlet
conc Concentration
d Downstream side
eq Equilibrium
ENV Environment
FCO Fuel cell outlet
gen Generated
HT Heat transfer
H Hydrogen gas
HS Hydrogen source
I1 Interconnect on the anode side
I2 Interconnect on the cathode side
L Limiting
M Membrane electrode assembly
N Nitrogen gas
ohm Ohmic
O Oxygen gas
PL Polarisation losses
r Reaction
vii
Nomenclature
TPB Triple phase boundary

u Upstream side
W Water Vapour
0,a Anode exchange
0,c Cathode exchange
1 Gas species #1
2 Gas species #2
Superscripts
abi After-burner inlet
abo After-burner outlet
fco Fuel cell outlet
HX1 Hydrogen inlet pre-heater
HX2 Air inlet pre-heater
i Inlet
o Outlet
r Reaction
ref Reference state
0 Initial state
viii
Table of Contents
Abstract i
List of Acronyms iii
Nomenclature v
Chapter 1: Introduction 1
1.1. Background and Motivation 1
1.2. Contributions of the Thesis 6
1.3. Organisation of the Thesis 7
Chapter 2: Literature Review and Fundamental Concepts 9
2.1. Introduction 9
2.2. Concept of Chemical Equilibrium 13
2.3. Bond Graph Formulation of Chemical Reaction Kinetics 15
2.4. Bond Graph Modelling of Electrochemical Systems 20
2.5. Simulation and Control of the SOFC System 25
2.6. Objectives of the Present Work 28
Chapter 3: Bond Graph Model of a Solid Oxide Fuel Cell 29
3.1. Introduction 29
3.2. A Preliminary Bond Graph Model of the Hydrogen Oxidation
31
Electrochemical Reaction
3.3. A Bond Graph Model of the SOFC Using a C-field for the
41
Mixture of Two Gas Species
3.3.1. Process Description and Modelling Approach 42
3.3.2. Modelling Assumptions 44
3.3.3. Word Bond Graph 44
3.3.4. Storage of a Two Species Gas Mixture Represented in a
46
C-Field
3.3.5. Bond Graph Model of the SOFC 51
3.4. Formulation of the True Bond Graph Model of the SOFC 61
3.4.1. Convection of a Two Species Gas Mixture Represented in
61
an R-Field
3.4.2. True Bond Graph Model of the SOFC 65
3.5. Conclusions 71
Chapter 4: Simulation of the Open and Closed Loop
73
Dynamics of SOFC
4.2. Model Initialization and Open Loop System Simulations 75
4.2.1. Static Characteristics 81
4.2.2. Selection of the Operating Regime 86
4.2.3 Dynamic Response 86
4.3. Detailed Bond Graph Model for Dynamic Simulation 88
4.4. Model Validation and Control Strategy Formulation 94
4.5. Open and Closed Loop Dynamic Responses 100
4.6. Conclusions 104
Chapter 5: Optimisation of Operational Efficiency Under
107
Varying Loads
5.2. Steady State Model of the SOFC System 110
5.2.1. The Dynamic Equations of the SOFC Bond Graph Model 110
5.2.2. The Steady State Model of the SOFC 121
5.2.3. Validation of the Steady State Model of the SOFC 127
5.2.4. Steady State Models of the After-burner and the Heat
129
Exchangers
5.3. Optimisation of the SOFC Operating Conditions 131
5.3.1. Optimisation Algorithm 134
5.3.2. Discussions on the Results of the Efficiency Optimisation
136
Study
5.4. Simulation of the Dynamic Responses 140
x
5.5. Conclusions 146
Chapter 6: Conclusions 149
References 153
Appendices 163
Appendix A Bond Graph Notations Revisited 163
A.1. Introduction 163
A.2. Causality 165
A.3. Activation 167
A.4. Sensors, Actuators and Instrumentation Circuits 167
A.5. Systems with Differential Causality 169
A.6. Field Elements 172
Appendix B Derivations of Some Important Relations 174
B.1. Chemical Potential of a Constituent in an Ideal Gas
174
Mixture
B.2. Gibbs-Duhem Equation 176
B.3. Isentropic Nozzle Flow Equation 177
B.4. Nernst Equation 179
B.5. Butler-Volmer Equation 182
Appendix C The Nelder-Mead Simplex Algorithm 187
Appendix D List of Files and Programs Given in the Compact Disc 191
Curriculum Vitae 193
xi
xii
Chapter 1
Introduction
1.1. Background and Motivation
The ever increasing energy requirements of mankind and rapidly depleting natural
resources combined with the detrimental effects of increased atmospheric pollution
have motivated scientists and engineers to develop cleaner and more efficient energy
conversion mechanisms. The efficiency of the heat engine, which is predominantly
employed today to convert energy to a useful form, is limited by the Carnot efficiency.
The heat engine is also highly polluting and responsible for effects such as ozone
layer depletion and green house effect. In this context, fuel cells, which are efficient
and environmentally friendly power-generating systems that produce electrical energy
by combining fuel and oxygen electro-chemically, are alternatives worthy of
consideration. Fuel cell research is attracting much greater effort and attention today
than ever before in its long history.
Chapter 1
A battery is an energy storage device, which contains the reactant chemicals. The
electrodes in a battery take part in the chemical reaction. A battery must be discarded
once the reactants are depleted (unless the battery is rechargeable). On the other hand,
a fuel cell is an energy conversion device where the reactants are continuously
supplied and the products are continuously removed. The electrodes and electrolyte
do not participate in the chemical reaction but they provide the surfaces on which the
reactions take place and they also serve as conductors for the electrons and ions.
Therefore, a fuel cell can be defined as a thermo-electrochemical device, which
converts chemical energy from the reaction of a fuel with an oxidant directly and
continuously into electrical energy.
The basic components of a general fuel cell are two porous electrodes, i.e. anode
and cathode, which are separated by a solid or liquid electrolyte. The electrolyte is
impervious to gases. Fuel is supplied to the anode side and air is supplied to the
cathode side. The oxidation reaction is made possible by conduction of ions through
the electrolyte. Although the basic principle behind the operation of a fuel cell is quite
simple, many challenges have to be overcome before its successful implementation.
Many issues regarding suitable materials for the electrolyte, interconnects, gas seals
and electrodes have to be addressed. There are also issues regarding cell stack design
and life span improvement that warrant immediate attention.
Once the above issues have been taken care of, the remaining big challenges are
computer controlling of fuel cell stack for load variation with minimum response time,
better stack design (improved heat integration, less fuel flow resistance, by-products
removal), lowering of stack mass per unit volume and cyclic endurance. Other
challenges related to successful implementation of fuel cell technology are: DC-to-DC
conversion through electronic transformer and power conditioner, i.e. DC to AC
conversion, for utility services and domestic appliances [Basu, 2007]. Developing
robust controls for integrated fuel cell systems is also a major challenge.
There are many types of fuel cells currently under research and development. Fuel
cells are classified according to the electrolyte used. Among many types, the major
ones are:
2
Introduction
Molten carbonate fuel cells (MCFCs): Electrolyte is a mixture of molten alkali

carbonates that conducts carbonate ions. Operate at 600 – 700 oC.
Proton exchange membrane fuel cells (PEMFCs): A polymer membrane that conducts
protons (or hydrogen ions) is used as an electrolyte. Operate at 80 – 100 oC.
Phosphoric acid fuel cells (PAFCs): Phosphoric acid is used as electrolyte and it
conducts protons. Operate at 180 – 210 oC.
Alkaline fuel cells (AFCs): Electrolyte is an aqueous solution of alkaline hydroxide

o
(e.g. KOH), which readily conducts hydroxyl ions. Operate at 50 – 100 C.
Solid oxide fuel cells (SOFCs): Electrolyte is a ceramic that conducts ions at high
temperatures. Operate at 800 – 1000 oC.
SOFC is of considerable interest since it has considerably high system efficiency

in comparison to other fuel cell systems with cogeneration. The high efficiency of
SOFC systems is a result of high operating temperatures and negligible deterioration
in performance over several years. This is the type of fuel cell that is considered in
this work. Expensive catalysts, which are needed in the case of proton-exchange fuel
cells (platinum) and most other types of low temperature fuel cells, are not needed in
SOFCs due to the high operating temperatures. Moreover, light hydrocarbon fuels,
such as methane, propane and butane, can be internally reformed within the anode
because of the high operating temperature.
An SOFC is made up of four layers, three of which are ceramics (refer to Fig. 1.1).
A single cell consisting of these four layers stacked together is typically only a few
millimeters thick. Hundreds of these cells are then stacked together in series to form a
stack. The ceramics used in SOFCs do not become electrically and ionically active
until they reach very high temperature.
The electrolyte represents the media through which ions migrate from one
electrode to the other; thus causing a voltage difference between the anode and the
cathode, and consequently an electric current through an external load. For this
3
Chapter 1
reason, the electrolyte must meet the requirements such as high ionic conductivity,
high electronic resistivity, thermal expansion compatible with those of the other cell
components, chemical stability in contact with the two electrodes, resistance to
thermal cycling and low cost. It must also be fully dense to prevent short circuiting of
reacting gases through it and it should also be as thin as possible to minimize resistive
losses in the cell. Yttria stabilized zirconia (YSZ), which is a ceramic material, is
usually used as the electrolyte material [Singhal, 1994].
Fig. 1.1: Schematic representation of an SOFC
The requirements of physical properties of the anode are high electronic

conductivity and ionic conductivity, porous structure optimized for the mass transport
of the gas species, thermal expansion compatible with those of the other cell
components, chemical stability in contact with the two electrodes, resistance to
thermal cycling and high catalytic activity. The reaction takes place at the so-called
triple phase boundary (TPB), where electrons, ions and gas phase coexist. The typical
material of the anode is Nickel-Yttria stabilized Zirconia cermet [Singhal, 1994].
The requirements of physical properties of the cathode are similar to those of the
anode. The cathode must be porous in order to allow oxygen molecules to reach the
electrode/electrolyte interface. The most commonly used cathode material is
4
Introduction
lanthanum manganite. It is often doped with strontium and referred to as lanthanum

strontium manganite (LSM). The interconnect serves the purpose of connecting cells
together to form a stack and it also acts as a collector of the electrical current. It
functions as the electrical contact to the cathode while protecting it from the reducing
atmosphere of the anode.
The design and handling of complex SOFC systems require efficient control
strategies to promote safe and reliable operation. The development of powerful
control algorithms is based on an exact knowledge of the operating behaviour, which
can be obtained from dynamic system models. The fuel cell system involves multiple
energy domains such as chemical, thermal, electrical, hydraulic, mechanical etc.
Furthermore, it involves several phenomena with radically different time scales.
The reactions at the basis of the fuel cell operation are in the domain of
electrochemistry. The energy and mass balances implied in continuously feeding
reactants to the cell and pre-treating of reactants belong to chemical engineering
domain. The need to maintain the SOFC’s temperature during operation by means of
taking away the heat energy released due to the exothermic reaction falls into the
domain of thermal engineering. Electrical engineering is involved in the conversion
and transmission of the cell’s power output. Modelling and applying control theory to
such a multidisciplinary system is a challenging task. The bond graph technique is
ideally suited for modelling such systems that involve multiple energy domains. The
bond graph model of the fuel cell system can also be easily coupled to the dynamic
model of the system it is intended to power, i.e. to construct hardware in the loop
simulation system for design of efficient control strategies. Bond graph modelling of
SOFC systems ensures that the models are energetically consistent as the conservation
laws are built into the bond graph junction structure. Moreover, subsequent
modifications to the model can be easily incorporated and the causal structure of the
bond graph aids in computer simulation of the system. Causal studies on the bond
graph model show directly how element constitutive relations should be combined to
produce computer simulation of the system [Karnopp, 1990]. The simulations are
valuable in helping to understand the competing physical processes that are
5
Chapter 1
responsible for controlling the cell performance. Such understanding can assist in the
cell design and optimization as well as interpreting the experimental observations.
SOFCs have a wide variety of applications from use as auxiliary power units in
vehicles to stationary power generation with outputs ranging from 100 W to 2 MW.
SOFCs are also coupled with gas turbines in order to improve their efficiencies by
means of utilising the heat energy released due to the exothermic reaction. The SOFC
is also expected to be applied for combined heat and power systems, which produce
electricity and heat energy in a single integrated unit, and for certain other military
applications. In all these applications, the SOFC has to undergo transient operation
during start-up, shutdown and even during load fluctuations. Therefore, the study of
the transient operation of the SOFC is very important and so is the need to develop
suitable operating and control strategies to improve its dynamic performance.
One of the important advantages of the SOFC system over the heat engine is its
improved fuel efficiency. Attaining high efficiency from a power source is necessary
to achieve the goals of sustainable energy production in the future. Due to operational
constraints, the maximum possible efficiency may not be achieved under different
operating conditions of an SOFC system. Hence, the optimum energy efficient
operating conditions of the SOFC system have to be studied under varying load and
other inputs. This knowledge will help us in developing suitable operating strategies
for the SOFC system so as to achieve maximum fuel efficiency and minimum harm to
the environment.
1.2. Contributions of the Thesis
The main contributions of this work are summarised as follows.
• A true bond graph model of an SOFC has been developed for the first time.
For this purpose, the constitutive relations of a C-field for energy storage by
two species of gases in a control volume are formulated and an existing R-
field model has been extended for modelling of forced convection of a mixture
6
Introduction
of two gas species. The developed true bond graph model represents the
couplings between the various energy domains in a unified manner and
captures all the essential dynamics of the SOFC.
• A physical model-based control strategy for the SOFC is developed, which
satisfies the common SOFC control objectives.
• A comprehensive steady state model of the SOFC has been derived from the
bond graph model. A cascaded optimization algorithm has been developed,
which utilizes the steady state SOFC model and steady state models of the
after-burner and heat exchangers in order to investigate the implication of the
common SOFC control strategies on the energy and exergy efficiency of the
system. Based on this investigation, a suitable operating strategy that
maximises the efficiency of the SOFC system has been suggested.
1.3. Organisation of the Thesis
This thesis is organised into five other chapters other than this chapter. Overviews
of the contributions made in those chapters are given in the following.
A comprehensive survey of the literature pertaining to dynamic modelling of the

SOFC and the bond graph modelling of electrochemical reaction systems are
presented in Chapter 2. Literature on the simulation and control aspects of the SOFC
systems are also discussed in the same chapter.
Chapter 3 details the development of the true bond graph model of an SOFC. The
ideas involved in advancing the already available bond graph models of
electrochemical systems to model the SOFC are presented in a gradual manner before
finally presenting a true bond graph model.
The simulation studies based on the developed bond graph model of the SOFC are
presented in Chapter 4. A control strategy to improve the dynamic performance of the
SOFC is also presented therein.
In Chapter 5, a comprehensive steady state model is derived from the previously

developed bond graph model. This model, along with the steady state models of the
7
Chapter 1
after-burner and the heat exchangers, is used to optimise the operational efficiency of
the SOFC system under varying load conditions. Three different operating strategies
are simulated to compare their dynamic performances.
The conclusions drawn from this thesis and the scope for future research work are
given in Chapter 6.
Thereafter, a list of relevant references is presented. All these references are cited
in the main chapters and appendices of this thesis.
Finally, the thesis ends with appendices, which describe the basic bond graph
theory and alternative forms of the models given in the thesis by following
international convention, derivations of some important relations and the Nelder-
Mead simplex algorithm used for the optimisation studies.
8
Chapter 2
Literature Review and Fundamental Concepts
2.1. Introduction
The history of the fuel cell starts with William Grove who discovered it in 1839
[Grove 1839; Grove 1842]. Grove found that by arranging two platinum electrodes
with one end of each immersed in a container of sulphuric acid and the other ends
separately sealed in containers of oxygen and hydrogen, constant current flowed
between the electrodes. The sealed containers held water as well as the gases, and he
noted that the water level rose in both the tubes as the current flowed. By combining
several sets of such electrodes in a series circuit, he created the first fuel cell. Detailed
discussions on the history of fuel cells can be found in [Liebhafsky & Cairns, 1968].
The first SOFC’s emerged in 1930’s due to Emil Baur and H. Preis. The materials
they used were zirconium, yttrium, cerium, lanthanum, and tungsten oxide [Stambouli
& Traversa, 2002]. More recently, rising energy prices and advances in materials
technology have contributed to extensive research work on SOFCs.
Chapter 2
A number of dynamic models of SOFC are available in the literature [Aguiar et al.,
2004; Aguiar et al., 2005; Mueller et al., 2006; Qi et al., 2005; Singhal, 2000a;
Singhal, 2000b; Wang et al., 2007]. Most of them are distributed parameter, cell level,
multidimensional models [Fahrenthold & Venkataraman, 1997; Franco et al., 2005a;
Franco et al., 2005b; Franco et al., 2006]. Some other models excessively simplify the
system by representing them as equivalent electrical circuits [Choi et al., 2006]. The
physical processes that contribute to the local phenomena, or the occurrence of
concentration over-voltage at anode-cathode interface, are mainly due to the diffusion
of the reactants/products through the electrolyte to/from the reaction sites [Aguiar et
al., 2004]. The characteristic time constant of the diffusion process is in the order of
several milliseconds to a few tenths of a second [Singhal & Kendall, 2003]; whereas
the time constant of the thermal dynamics is of the order of a few minutes, which
necessitate a multi-scale simulation approach for the solution of detailed distributed
parameter models [Franco et al., 2005a; Franco et al., 2005b; Franco et al., 2006].
Though detailed models are suitable for configuration design and performance
evaluation, they are unsuitable for real time control applications as the computational
load is high. On the other hand, the equivalent circuit models use empirical relations
and cannot provide sufficient information (instantaneous pressures, temperatures,
mass flow rates etc.) for control strategy design. There is a need for a control oriented
model which captures all the necessary dynamics of the fuel cell system and, at the
same time, is not computationally too intensive. As the fast dynamics are irrelevant
from control perspective, they can be neglected in a control oriented model.
There is abundant literature on the bond graph modelling of thermo-fluid systems.

Applications of bond graph modelling to hydraulic systems can be found in [Borutzky,
1999; Borutzky et al., 2000, Mukherjee et al., 2006; Thoma & Bouamama, 2000], to
thermo-fluid systems in [Bouamama, 2003; Bouamama et al., 2006; Brown, 2002a;
Brown, 2002b; Hubbard & Brewer, 1981; Karnopp, 1979; Shoureshi & McLaughlin,
1984] and to 1D and 2D heat conduction in [Gawthrop 1999; Granda & Tang, 1989;
Nakrachi & Dauphin-Tanguy, 2003].
Works on the bond graph modelling of chemical reactions and electrochemical

reaction systems such as batteries and fuel cells are also available in the literature
10
[Auslander, et al., 1973; Bruun & Pedersen, 2007; Karnopp, 1990; Oster et al., 1971;
Oster et al., 1973; Thoma & Bouamama, 2000; Wyatt, 1978]. Some ideas from the
models presented in those works are adopted in the present work. Therefore, the
salient features of the models presented in them are discussed in the following and
their advantages and drawbacks are pointed out.
Network or bond graph modelling of the kinetics of the isothermal and isobaric
chemical reactions were discussed in [Auslander, et al., 1973; Oster et al., 1971; Oster
et al., 1973; Wyatt, 1978]. It was indicated that the energy storage in a volume of
matter can be represented by a C-field element having three ports: a heat port, a
mechanical port and a chemical port. The constitutive relations of this capacitive field
element represented the thermo-statics or the equilibrium thermodynamics of that
volume. Assuming that all changes occur slowly enough so that the gas is
approximately at internal equilibrium at each moment, the change in the internal
energy of that volume of matter was given by
∂U ∂U ∂U
dU = dV + dS + dm , (2.1)
∂V ∂S ∂m
where V, S and m are the volume, entropy and mass respectively. Using
thermodynamic relations, the partial derivative terms on the right hand side of Eq.
(2.1) are given by the intensive variables pressure, temperature and chemical potential
as ∂U ∂V = − p , ∂U ∂S = T and ∂U ∂m = μ , respectively. Therefore, Eq. (2.1)

becomes
dU = p dV + T dS + μ dm . (2.2)
From Eq. (2.2), we can see that the change in the internal energy of the volume
can be represented as a sum of three distinct energy exchanges. The Equation (2.2)
can be written in terms of time derivatives as
U = pV + TS + μ m . (2.3)
11
Chapter 2
From Eq. (2.3), it is evident that the internal energy of the volume changes due to
three distinct power exchanges which can be represented by the products of the
corresponding effort and flow variables. Therefore, the energy storage in the volume
can be represented as a 3 port C-field as shown in Fig. 2.1. This C-field has three
power ports: the flow and effort variables for the mechanical port are V and p,
respectively; those for the thermal port are S and T, respectively; and those for the
material transport port are m and μ, respectively.
Fig. 2.1: Thermodynamic C-field With Three Power Ports
A thermodynamic capacitor by itself gives no information about rates, available

energy loss, entropy production or any other non-equilibrium phenomenon. As in
most cases in experimental and biological chemistry, only isothermal and isobaric
chemical reaction kinetics was considered in [Wyatt, 1978] by keeping the
temperature and pressure constant through contact with large reservoirs. Therefore,
the thermal ( T – S ) and the mechanical ports ( p – V ) were not included in the model.
The development of the network model of the chemical reactions requires formulation
of a thermodynamic force that drives the reaction flux. Such a force can be derived
from the reaction thermodynamics and it is called the affinity.
The non-equilibrium part of the chemical reaction was represented by a resistive

field element in [Wyatt, 1978]. Non-equilibrium thermodynamics represents the
relations between forces (intensive variables) and flows (the rate of change of
extensive variables). The first and second laws of thermodynamics impose restrictions
on the possible constitutive relations of the resistive element. The first law requires
that the power flow through the omitted T – S port will be exactly the sum of the
12
power flows into the other ports. In an isothermal situation the second law says
roughly that other forms of energy can be converted to heat, but that conversion in the
other direction is impossible. In terms of the resistors without explicit T – S ports, the
second law manifests itself as the requirement that the sum of the power flows into
the remaining ports be always positive.
2.2. Concept of Chemical Equilibrium
For any isolated thermodynamic system undergoing a general process which does not
have any particular restrictions, the sign of the change in entropy of the universe
(system plus its surroundings), given by the second law of thermodynamics, is a
convenient criterion for determining its spontaneity [Callen, 1985; Holman, 1988;
Zemansky & Dittman, 1997]. But, many practical processes occur under the
conditions of constant temperature and pressure. For reactions occurring at isothermal
and isobaric conditions, the sign of the change in Gibbs function of the reaction gives
the information about the spontaneity of the reaction.
A derivation illustrating the relation between the sign of the Gibbs free energy
change and the spontaneity of the process [Zemansky & Dittman, 1997] is given in
the following. Consider a hydrostatic system in mechanical and thermal equilibrium
but not in chemical equilibrium. Suppose that the system is in contact with a reservoir
at temperature T and undergoes an infinitesimal irreversible process involving an
exchange of heat δQ from the reservoir. The process may involve a chemical reaction.
Therefore, the entropy change of the universe is dS0 + dS , where the entropy change
of the reservoir is dS0 and the entropy change of the system is dS . According to the
second law of thermodynamics, an irreversible process leads to the increase in the
entropy of the universe. Thus, we may write dS0 + dS > 0 .
Since dS0 = −δQ T , we have
13
Chapter 2
dQ
− + dS > 0 or dQ − TdS < 0 . (2.4)
T
During the infinitesimal irreversible process, the internal energy of the system
changes by an amount dU , and an amount of work pdV is performed by the system.
Therefore, according to the first law,
dQ = dU + pdV . (2.5)
Substituting Eq. (2.5) into the inequality (2.4), we get
dU + pdV − TdS < 0 . (2.6)
By definition, the Gibbs function G is given as
G = U + pV − TS , (2.7)
which on differentiation gives
dG = dU + pdV + Vdp − TdS − SdT . (2.8)
When the conditions of constant temperature and pressure are imposed on Eq.
(2.8), it becomes
dG = dU + pdV − TdS . (2.9)
From Eq. (2.6) and Eq. (2.9), it is clear that the condition for the process to be
irreversible and occur spontaneously is dG < 0 . Conversely, the non-spontaneity of an
isothermal and isobaric process can be identified by the condition dG > 0 . Therefore,
if dG for a isothermal and isobaric chemical reaction system is negative, it means
that the process will occur irreversibly until the equilibrium is reached at which, the
Gibbs function G will become minimum, i.e. dG = 0 (refer to Fig. 2.2).
14
Fig. 2.2: Variation of the Gibbs Function of the Reaction with the Reaction Advancement
2.3. Bond Graph Formulation of Chemical Reaction Kinetics
The network formulation of the chemical reaction kinetics [Wyatt, 1978] is described
here with respect to the following example reaction.
k
ZZZ
2A+B YZZ+
X
Z 2C , (2.10)
k −
where k+ is the forward reaction rate coefficient and k− is the reverse reaction rate
coefficient. The progress or advancement of a reaction can be represented in terms of
mole numbers as
ni ( t ) = ni ( 0 ) + ν iξ ( t ) , (2.11)
where ξ ( t ) is the reaction advancement coordinate with ξ ( 0 ) = 0 and ν i is the
stoichiometric coefficient of the i th species. The stoichiometric coefficients of the

species in this example reaction (refer to Eq. (2.10)) are ν A = 2 , ν B = 1 and ν C = 2 .
The time variation of the number of moles of the three species are related as
dnA = −ν A dξ , dnB = −ν Bdξ and dnC = ν C dξ . As these quantities are perfect
differentials, their integrations give the following:
15
Chapter 2
nA (t ) = nA (0) −ν Aξ ( t ) , (2.12)
nB (t ) = nB (0) −ν Bξ ( t ) , (2.13)
and nC (t ) = nC (0) + ν Cξ ( t ) , (2.14)
where ξ ( 0 ) = 0 .
The reaction advancement coordinate may be thought of as a generalized

displacement whose time derivative defines the reaction rate. The corresponding
effort, which drives the reaction, is called affinity. The Gibbs free energy is the
maximum amount of non-expansion work that can be extracted from a closed system
through a completely reversible process. The change in Gibbs free energy of a system
which is maintained at constant temperature and pressure is given as [Wyatt, 1978;
Zemansky & Dittman, 1997]
∂G ∂G ∂G
dG = dnC − dnA − dnB , (2.15)
∂nC ∂nA ∂nB
which gives
dG = ( μCν C − μAν A − μ Bν B ) dξ . (2.16)
In a general form, Eq. (2.16) is given as
⎛ ⎞
dG = ⎜ ∑ μνi i − ∑ μνi i ⎟ dξ , (2.17)
⎝ i∈P i∈R ⎠
where subscript i is used to represent the sums over the product and the reactant
components. In this example, P= [ A B] and R= [ C ] .
The affinity of the reaction is given by [Thoma & Bouamama, 2000; Wyatt, 1978]
A = ∑ μν
i i − ∑ μν
i i , (2.18)
i∈R i∈P
16
where the quantity AF = ∑ μν

i i is defined as the forward affinity and the quantity
i∈R
AR = ∑ μν
i i is defined as the reverse affinity.
i∈P
Therefore, Eq. (2.17) can be written as
dG
= −A . (2.19)
dξ
This affinity may be defined as a generalized effort. At the equilibrium, the

affinity of the reaction is zero, i.e. dG dξ = 0 , which implies that the Gibbs free
energy G is minimum as shown in Fig. 2.2. Thus, at the equilibrium, A = 0 and
AF = AR .
The reaction rates are defined by the law of mass action. The law of mass action
states that the rate of an elementary reaction (a reaction that proceeds through only
one mechanistic step) is proportional to the product of the concentrations of the
participating molecules. In modern chemistry, this is derived using statistical
mechanics [Benson, 1960]. However, the concentration dependence of the rate can be
qualitatively understood from the collision theory of chemical reactions [Benson,
1960; Butt, 2000; Houston, 2001; Pannetier & Souchay, 1967; Wright, 2004],
according to which, molecules must collide in order to react together. As the
concentration of the reactants increases, the frequency of the molecules colliding
increases, striking each other more frequently by being in closer contact at any given
point in time. Therefore, according to this law [Butt, 2000], the net rate of the
reversible chemical reaction considered in Eq. (2.10) is given as
ξ = k+ cA2 cB − k− cC2 , (2.20)
where c refers to the concentration of the species ‘i’. The concentration of a specific
component is defined as the ratio of the number of moles of that component to the
total number of moles of products and reactants.
17
Chapter 2
The bond graph model for the kinetics of the reaction (refer to Eq. (2.10)) is
shown in Fig. 2.3. Note that the transformer elements shown in Fig. 2.3 have arrows
above them. This notation, used in [Mukherjee et al., 2006] is also used in this thesis.
It is used because it makes the constitutive relation of the transformer very clear. The
constitutive relations do not depend on the power direction but only on the direction
of the arrow above the transformers (refer to Appendix A).
In true bond graph representation, the effort and flow variables are chemical
potential and mole flow rate, respectively. As the model represents isothermal and
isobaric reactions, the T – S port and the P – V ports are omitted.
The chemical potential of the component ‘i’ is given as (refer to Appendix B)
⎛ ci ⎞
μi = μi ,0 (T , p ) + RT ln ⎜ ⎟, (2.21)
⎝ cΣ ⎠
where ci is the concentration of the component ‘i’, cΣ is the reference concentration
(it is usually taken as unity) and μi ,0 is the standard chemical potential. Equation
(2.21) can be written in terms of number of moles ‘n’ as
⎛ ni ⎞
μi = μi ,0 (T , p ) + RT ln ⎜ ⎟, (2.22)
⎝ nΣ ⎠
which forms the constitutive relation for the capacitive element of the bond graph
model in Fig. 2.3.
From Eq. (2.21), the concentrations of the reacting species can be represented in
terms of their chemical potentials as
⎛ μ − μi ,0 (T , p ) ⎞
ci = exp ⎜ i ⎟. (2.23)
⎝ RT ⎠
18
The effort in the bond number 7 shown in Fig. 2.3 denotes the forward affinity of
the reaction and is given by e7 = AF = 2μA + μB . Similarly, the effort in bond number
8 denotes the reverse affinity of the reaction and is given by e8 = AR = 2μC .
Fig. 2.3: The Bond Graph Model of an Isothermal and Isobaric Chemical Reaction
The non-equilibrium part of the chemical reaction kinetics is represented as an R-

field whose inputs are the forward and reverse affinities and the output is the reaction
rate. The constitutive relation of the R-field is formulated using the mass action law.
However, other more complex rate laws can also be used for some reactions. From
Eqs. (2.20) and (2.23), the flows in the bonds numbered 7 and 8 are given as
⎛ 2 μ − 2 μA,0 ⎞ ⎛ μB − μB,0 ⎞ ⎛ 2μC − 2μC,0 ⎞

f 7 = f8 = ξ = k+ exp ⎜ A ⎟ exp ⎜ ⎟ − k− exp ⎜ ⎟ , (2.24)
⎝ RT ⎠ ⎝ RT ⎠ ⎝ RT ⎠
where, ξ has the unit of mol s-1. The constitutive relation of the R-field element can
also be written in terms of the forward and reverse affinities, which are the efforts in
the bonds numbered 7 and 8, respectively, as
⎛ −2μA,0 − μB,0 ⎞ ⎛ AF ⎞ ⎛ −2μC,0 ⎞ ⎛ AR ⎞

ξ = k+ exp ⎜ ⎟ exp ⎜ ⎟ − k− exp ⎜ ⎟ exp ⎜ ⎟. (2.25)
⎝ RT ⎠ ⎝ RT ⎠ ⎝ RT ⎠ ⎝ RT ⎠
19
Chapter 2
The direction of the two flows are opposite as denoted by the power directions of
the bonds numbered 7 and 8 in Fig. 2.3. This resistance field satisfies the Onsager
reciprocity requirements [Onsager, 1931a; Onsager, 1931b]. The network
representation of the chemical reactions helps in integrating the kinetic (rate laws
defined by Eq. (2.20)) and thermodynamic (affinities as defined in Eq. (2.18) as
driving forces) points of view.
2.4. Bond Graph Modelling of Electrochemical Systems
Bond graph models for chemical kinetics were extended to electrochemical systems
such as electrical vehicle batteries including the electrical, chemical and thermal
effects in [Karnopp, 1990]. Such energy storage systems undergo drastic change in
temperature during operation. In [Karnopp, 1990], it was assumed that the
temperatures and pressures were imposed on the phases representing the reactants and
the products. Under such conditions, the Gibbs function was found to be an
appropriate thermodynamic potential for representing the energy storage in the system.
A C-field with the Gibbs function as the thermodynamic potential is shown in Fig. 2.4.
Note that the thermal and the mechanical ports of the C-field are in differential
causality. Even if the temperature imposed on the system is not constant, the entropy
flow rate in the thermal bond of the C-field can be calculated as
∂S ∂S ∂S
S = T+ p + ni . (2.26)
∂T ∂p ∂ni
Fig. 2.4: The C-field with the Gibbs Function as the Thermodynamic Potential
20
In [Karnopp, 1990], the bond graph model for a Daniell cell consisting of a copper
electrode in a copper sulphate solution and a zinc electrode in a zinc sulphate solution
with the two solutions separated by a diaphragm was given. The reactions at the
anode, the cathode and the total reaction, respectively, are
→ Cu 2+ + 2e −
Cu ⎯⎯ (2.27)
Zn 2+ + 2e− ⎯⎯
→ Zn (2.28)
−
Zn 2+ + Cu ⎯⎯→
2e
Cu 2+ + Zn (2.29)
In an electrochemical reaction, the reaction rate is proportional to the current or

the charge flow rate in the external circuit. The current (i) and the reaction flux (J) are
related as
i = ne Fξ , (2.30)
where ne is the number of electrons participating in the reaction and F is the Faradays
constant. As the temperature and pressure are imposed on the system, the change in
the Gibbs free energy of the reaction is given by ∑ μ n . Under reversible operation
i i
of the cell, the change in the Gibbs free energy of the reaction is converted into
electrical energy. Equating these two energies, the relation between the change in the
Gibbs free energy of the reaction and the reversible cell voltage is obtained as
ΔG
Vr = . (2.31)
ne F
If some useful current has to be drawn from the cell, it is accompanied by several
irreversibilities due to the rate limiting or loss elements in the system. Therefore, the
actual cell voltage, V , is less than the reversible cell voltage, Vr . The over-voltage is
defined as
η = Vr − V . (2.32)
21
Chapter 2
With these considerations, the bond graph model for the electrochemical reaction
mechanism of the Daniell cell (Fig. 2.5) was given in [Karnopp, 1990]. The thermal
and the mechanical bonds of the C-field are in differential causality, which means that
the temperature and the pressure are imposed on the C-field. If the model represents
an isothermal system, then there is no necessity to include the thermal and the
mechanical ports. For including the thermal effects, an anonymous compliance
element was introduced in [Karnopp, 1990] as shown in Fig. 2.5, which imposes the
temperature of the system. The resistance field element models the entropy generated
due to the polarisation losses. This generated entropy was given by the power balance
as
ηi
Sgen = . (2.33)
T
Fig. 2.5: The Bond Graph Model of a Daniell Cell
The entropy flow rate output of the C-field element is given according to Eq.
(2.26). This gives rise to numerical problems in simulation due to the differential
causality unless the first and the second terms in Eq. (2.26) are neglected [Karnopp,
1990]. The second term in Eq. (2.26) could be neglected if the reaction is assumed to
occur at constant pressure. However, for neglecting the first term, we must assume
that the temperature does not change much, in which case an isothermal model may
22
be good enough. We would still get a non-isothermal model by neglecting the first
and the second terms in the Eq. (2.26), as the entropy change due to the reaction is
accounted for in the third term. But even then there is the problem of the unknown
parameter of the C-element.
The problem of differential causality for the thermodynamic C-field with the
Gibbs function as the potential may be avoided by considering the temperature and
the pressure of the system as state variables. In this case, the change in the Gibbs free
energy of the matter represented by the C-field is given as follows. The Gibbs
function G is defined as
G = U + pV − TS . (3.34)
Differentiating Eq. (3.34) and substituting the expression for dU , which is given as
dU = TdS − pdV + μ dm , (3.35)
we get
dG = Vdp − SdT + μ dm . (3.36)
By using Eq. (3.36), an integrally causalled C-field may be constructed as shown

in Fig. 2.6, for which, the Gibbs function would be the thermodynamic potential.
However, such usage of the extensive variables as efforts and intensive variables as
flows will not be convenient for constructing the other parts of the model and
therefore not followed in this work.
Fig. 2.6: An Integrally Causalled C-field with the Gibbs Function as the Thermodynamic Potential
23
Chapter 2
Though the bond graph model of the electrochemical cell proposed in [Karnopp,
1990] is a significant improvement over the isothermal models given earlier, it suffers
from the problem of differential causality and the lack of knowledge of the parameter
of the compliance element. Moreover, in a fuel cell, the reactants are continuously
replenished and the products are continuously removed so as to produce electrical
energy continuously. In the case of high temperature fuel cells like the SOFC, the
temperatures of the reactants are raised by pre-heating before being supplied to the
cell. This requires the inclusion of the phenomena of convection in the model wherein
the flowing masses carry energy along with them. Though the model given in
[Karnopp, 1990] can represent the non-isothermal electrochemical reaction dynamics
of a Daniell cell, it is unsuitable for modelling fuel cells.
Bond graph model of electric batteries and fuel cells were given in [Thoma 1999],
where some newly defined elements were used. Bond graph modelling of chemical
reactions were also discussed in [Thoma & Bouamama, 2000]. These models also
suffer from the problem of differential causality and do not include the convection
processes which are essential for modelling fuel cells.
A bond graph model of a high temperature fuel cell was presented in [Bruun &
Pedersen, 2007]. In that work, a mixed approach was taken, where the electrical and
the electrochemical parts were modelled using true bond graphs whereas all other
parts were modelled by using pseudo bond graphs. The coupling between the pseudo
bond graph and the true bond graph parts can only be done using ad hoc elements that
do not obey the rules of normal bond graph elements [Heny et al., 2000]. Therefore,
that approach was not adopted for this work.
Bond graph models of lead acid batteries were also given by [Esperilla et al.,
2003; Esperilla et al., 2005; Esperilla et al., 2007a; Esperilla et al., 2007b]. The
isothermal models given by them were merely bond graph equivalents of electrical
circuits and the chemical reaction dynamics were not modelled. They also proposed
simple non-isothermal models that included the thermal effects. The bond graph
model of a polymer electrolyte membrane (PEM) fuel cell was developed in [Saisset
24
et al., 2006]. They used a mixture of pseudo and true bond graphs with block diagram
components for performing the thermo-chemical calculations.
The primary aim of this work is to develop a true bond graph model of the high
temperature fuel cell (SOFC) based on the concepts of network thermodynamics,
which will be an improvement over the existing bond graph models of the
electrochemical cell. The developed model should be able to capture all the essential
dynamics of the cell so as to give a comparable performance with other detailed
SOFC models available in the literature.
2.5. Simulation and Control of the SOFC System
Many emerging applications of the SOFC will require their ability to follow very fast
load transients [Mueller et al., 2006]. The transients in SOFC dynamics occur during
load changes (due to variable power demand) and also during start-up and shut down.
Dynamic response studies are important for analysing the SOFC transient operation
and its interactions with the distributed energy network. SOFC stack dynamics are
identified to have three characteristic response times governed by different
mechanisms. One of these is due to power electronics and the electrochemical
dynamics with characteristic response time in the order of milliseconds; another is due
to hydrogen composition changes within the cell with characteristic response time in
the order of seconds, and the third is due to the cell temperature change with
characteristic response time in the order of minutes to hours [Dicks & Martin, 1998].
A one dimensional model of an anode supported intermediate temperature, direct

internal reforming SOFC was presented in [Aguiar et al., 2004]. The model was
obtained by applying mass and energy balances to the air channel, the fuel channel
and the solid structures. The steady state characteristic curves and the spatial
distribution of several important variables such as temperatures, voltage and mass
fractions were plotted. The dynamic characteristics of this model were studied in
[Aguiar et al., 2005] by subjecting it to step disturbances. A control strategy was also
25
Chapter 2
formulated and tested for achieving the control objectives of constant temperature and
constant fuel utilisation (FU) operation of the fuel cell.
The fuel utilisation and air utilisation are two of the most important control
variables of the fuel cell [Aguiar et al., 2005]. Fuel utilisation ( ζ f ) is defined as the
ratio of the mass flow rate of the fuel taking part in the reaction to the mass flow rate
of the fuel supplied to the cell. Air Utilisation is defined as the ratio of mass flow rate
of oxygen consumed by the reaction to the mass flow rate of oxygen supplied to the
cell. As it is the oxygen in the air that is being utilised, oxygen utilisation (OU) will
be a more appropriate term than air utilisation and is used in some works [Zhang et al.,
2006]. Therefore, in this work it will be referred to as OU ( ζ o ). Some common
objectives of the SOFC control system include: Controlling the average stack
temperature; maintaining constant fuel utilisation (FU) for all power outputs; and
ensuring that the OU is always less than a maximum specified value. Stack
temperature control is normally provided by varying the air ratio, i.e., the supply of
the air for cooling [Aguiar et al., 2005]. Another requirement for the operation of the
SOFC, which is often neglected by most researchers, is that the difference of pressure
between the anode and the cathode channels has to be small [Serra et al., 2005;
Wachter et al., 2006]; the adequate value being dependent on the membrane electrode
assembly (consisting of the electrodes and the electrolyte, abbreviated as MEA)
support (allowable stress) and on the age of the fuel cell (fatigue considerations).
Some authors [He, 1998; Wang et al., 2007; Zhu & Tomsovic, 2002] state that the
pressure difference between the hydrogen and oxygen must be kept below 8kPa under
transient conditions and below 4kPa during steady state conditions in order to prevent
damage to the electrolyte. Therefore, formulation of a suitable physical model-based
control strategy for the SOFC, which satisfies all the above-mentioned control
objectives, is considered as an objective of the present work.
The aim of the last part of this work is to formulate a suitable operating strategy of
the SOFC system (including the heat exchangers and the after-burners), which
maximises the energy efficiency of the overall system. Literature on the energy and
exergy analysis based optimisation of the fuel cell system is abundant. In [Kazim,
2004], exergy analysis is performed on a Polymer Electrolyte Membrane (PEM) fuel
26
cell at variable operating conditions. Energy and exergy analyses are performed on
simple hydrogen fed SOFC power system in [Chan et al., 2002] and it was reported
that the second law efficiency is higher than the first law efficiency. Exergy analysis
was performed in [Saidi et al., 2005] in order to optimize the operating conditions of a
PEM fuel cell. Other studies on exergy analysis of fuel cell systems can be consulted
in [Akkaya et al., 2007; Calise et al., 2006; Monanteras & Frangopoulos, 1999; Song
et al., 2005]. Several works in the literature deal with various aspects of the
optimization of the fuel cell system. In some works, a very detailed and specialized
model of the fuel cell is adopted for such optimization studies [Lin et al., 2006; Wu et
al., 2006], whereas in others the model is over-simplified [Chen et al., 2006; Cownden
et al., 2001; Douvartzides et al., 2003; Frangopoulos & Nakos, 2006; Hussain et al.,
2005; Na & Gou, 2007; Palazzi et al., 2007; Saidi et al., 2005; Subramanyan &
Diwekar, 2007; Yeh & Chen, 2008]. The former is computationally expensive, while
the latter does not sufficiently represent the fuel cell system dynamics for
development of control laws. There is a need for a comprehensive static model of the
fuel cell system that can calculate the states of the system given the inputs so that it
can be used for studying the optimum operating conditions of an SOFC system.
In [Aguiar et al., 2005; Mueller et al., 2006; Singhal & Kendall, 2003; Stiller et al.,
2006], maintaining constant FU and constant cell temperature is advocated as the
desirable operating condition for an SOFC. Constant FU operation of the fuel cell is
recommended because it minimises the dynamics during load changes [Mueller et al.,
2006] and also avoids uneven distribution of voltage and temperature within the cell
[Stiller et al., 2006]. The constant temperature operation is recommended in order to
avoid thermal cracking [Stiller et al., 2006]. However, the implications of maintaining
these operating conditions on the efficiency of the SOFC system have not been
investigated in any work. In this work, the influence of cell operating conditions on
the efficiency and dynamic performance are studied.
27
Chapter 2
2.6. Objectives of the Present Work
Based on these discussions, it is found that bond graph method is ideally suited for
modelling the multi-disciplinary SOFC system. Clearly, there is a lack of a
comprehensive bond graph model of the fuel cell system in the literature, which
includes the chemical, electrical, thermal and pneumatic dynamics of the system. The
availability of such a comprehensive bond graph model will aid in the analysis and
design of the SOFC system and will also be useful in designing integrated model-
based control strategies for the overall system. There is also a lack of suitable physical
model-based control strategies for achieving the control objectives of the SOFC
system and improving its dynamic performance.
Although constant FU and constant temperature operation is advocated as the

desirable operating condition of an SOFC for several reasons, the implications of such
an operation of the cell on the system efficiency and transient dynamics have not been
investigated so far. Also, there is a lack of a comprehensive steady state model of the
SOFC system, which can be utilised in an optimisation algorithm for investigating the
optimal efficient operating condition of the SOFC system. Such a static model, if
available, can be used to investigate the implications of various operating strategies
on the SOFC system’s efficiency.
Therefore, the objectives of the present work are summarised as follows:
1. To develop a true bond graph model of an SOFC from the principles of network
thermodynamics.
2. To validate the model by comparing its static characteristics and dynamic
responses with other models from literature and to develop a physical model-
based control strategy to achieve the common SOFC control objectives.
3. To develop a comprehensive steady state model of the SOFC system and use it to
investigate the implications of various operating strategies on the energetic and
exergetic efficiencies of the SOFC system.
28
Chapter 3
Bond Graph Model of a Solid Oxide Fuel Cell
3.1. Introduction
Many of the applications of SOFC systems require their ability to follow very fast
load transients. Therefore, static models of SOFC systems are unsuitable for their
design. The choice of a proper modelling method, which is suitable for the analysis of
the multidisciplinary system's behaviour, controller synthesis and at the same time,
clearly exposes the interplay between various subsystems, is very important because it
can greatly reduce the further development time. The purpose of the work presented
in this chapter is to develop a non-linear model of an SOFC using the bond graph
approach [Gawthrop, 1991; Granda, 2002; Karnopp et al., 2006; Mukherjee et al.,
2006; Thoma & Bouamama, 2000], which can be utilised for system dynamic studies.
Chapter 3
As fuel cell system is inherently multidisciplinary, being composed of interacting

subsystems or parts from different engineering disciplines, it requires an integration of
chemical engineering, process engineering, mechanical engineering, electrical
engineering, and control engineering. Bond graphs provide a unified approach to the
modelling and analysis of dynamic systems and are ideally suited for modelling fuel
cell systems because the coupling between different domains can be easily modelled.
Moreover, a fundamental property of a bond graph model relates to power
conservation in the junction structure, which in the context of a fuel cell system
ensures that the various constraints, e.g. conservation of mass and energy, are always
correctly represented. Moreover, subsequent modifications to the model can be easily
incorporated and the causal structure of the bond graph aids in computer simulation of
the system.
Although a number of control relevant models of SOFC are available in the

literature, only few deal with bond graph modelling of fuel cells. An early effort in
this direction was made in [Karnopp, 1990] where a bond graph model for
electrochemical energy storage in batteries including the electrical, chemical and
thermal effects was given and a C-field for multiple gas species was suggested. Bond
graph modelling of lead acid batteries and fuel cells was discussed in [Bruun &
Pedersen, 2007; Esperilla et al., 2003; Esperilla et al., 2005; Saisset et al., 2006;
Thoma, 1999]. In those works, pseudo bond graph approach was used. This is because
chemical processes are usually described by using a control volume in which matter
flows across boundaries carrying energy with it in several forms, which is considered
to be difficult to represent in true bond graphs [Heny et al., 2000]. However, pseudo
bond graphs suffer from the disadvantage that they cannot be readily coupled to other
energy domains, except by means of some ad hoc elements that do not obey the rules
of normal bond graph elements [Heny et al., 2000]. In the work presented in this
chapter, a true bond graph approach has been taken in order to model the fuel cell.
This is because, a true bond graph representation assures that the model is
energetically consistent and it depicts the couplings between the energy variables in
the system clearly. The entropies generated due to various processes in the system are
taken into consideration in a true bond graph model, whereas these are neglected in a
pseudo bond graph representation. The contributions of the cell irreversibilities to the
30
transient responses are included in a true bond graph representation. Thus, a true bond
graph model not only gives more accurate results, but also helps to calculate the
exergetic efficiency of the system.
In this chapter, a true bond graph model of the SOFC is systematically developed
starting from the previous ideas about electrochemical reaction dynamics modelling
from literature, which were presented in Chapter 2. A preliminary model of the
hydrogen oxidation electrochemical reaction is first developed which is an
improvement over the earlier model by [Karnopp, 1990]. This model uses a C-field
with the internal energy as the thermodynamic potential for representing the energy
storage in the reactants and the products, thereby avoiding the problem of differential
causality present in the model proposed by [Karnopp, 1990].
This model is then improved to represent a fuel cell by formulating and using C-
fields capable of representing energy storage in two species gas mixtures. These C-
fields are used for modelling the anode and the cathode channel control volumes of
the fuel cell. This results in a model in which some parts of are constructed by using
pseudo bonds and entropy convection processes are not sufficiently represented in the
model.
In order to rectify these deficiencies, a true bond graph model of the SOFC is
finally presented, which uses an extended R-field for representing the convection of
mixture of two gas species.
3.2. A Preliminary Bond Graph Model of the Hydrogen

Oxidation Electrochemical Reaction
The bond graph models of electrochemical reaction systems given in the literature
[Karnopp, 1990; Thoma & Bouamama, 2000] model the energy storage in the
reacting species using a C-field, in which the Gibbs free energy serves as the
thermodynamic potential. These models suffer from the drawback that two of the
three power ports of the energy storing C-field are differentially causalled (refer to
31
Chapter 3
Section 2.4 of Chapter 2). A preliminary bond graph model of the electrochemical
hydrogen oxidation reaction is developed in this section, which avoids the problem of
differential causality. This is achieved by using a C-field [Breedveld, 1984;
Mukherjee et al., 2006] in which the internal energy serves as the thermodynamic
potential for modelling the energy storage in the reactant and product gas species. In
this representation, the C-field element is integrally causalled and hence the
differential causality is avoided.
The electrochemical reaction of hydrogen oxidation is the basic reaction in any

fuel cell. In an SOFC, hydrocarbons such as methane may also be used as fuel instead
of pure hydrogen. In such a case, the hydrocarbons must undergo a reforming reaction
resulting in the formation of hydrogen, which then undergoes the oxidation reaction
with oxygen. In this work, only pure hydrogen is considered as the fuel. The hydrogen
oxidation reaction is given as follows.
Ο 2 + 4e − → 2Ο 2 − . (3.1)
2H 2 + 2Ο 2− → 2H 2 Ο + 4e − . (3.2)
2H 2 + Ο 2 → 2H 2 Ο . (3.3)
The formulation of the thermodynamic C-field is given in the following. This C-

field represents a volume of ideal gas contained in a collapsible chamber. This
chamber allows heat and mass transfer with the surroundings. Mechanical work can
also be done on the system or extracted from the system. The change in the internal
energy of the gas volume represented by the C-field is given by
∂U ∂U ∂U
dU = dV + dS + dm , (3.4)
∂V ∂S ∂m
which can be written in terms of time derivatives as
∂U ∂U ∂U
U= V+ S+ m. (3.5)
∂V ∂S ∂m
32
From well-known thermodynamic relations ∂U ∂V = − p , ∂U ∂S = T
and ∂U ∂m = μ , it is evident that the internal energy of the volume of the gases
change due to three distinct power exchanges which can be represented by the
products of the corresponding effort and flow variables.
Therefore, the energy storage in the gas mixture can be represented as a 3 port C-
field as shown in Fig. 3.1. This C-field has three power ports: the flow and effort
variables for the mechanical port are V and p, respectively; those for the thermal port
are S and T, respectively; and those for the material transport port are m and μ,
respectively. The entropy flow into the control volume is due to two kinds of
phenomena: heat transfer and mass transfer. Therefore, if S = ms then the entropy
flow rate is given by
S = ms + ms = ms + SHT . (3.6)
Fig. 3.1: A Thermodynamic C-field with Internal Energy as the Thermodynamic Potential
In Eq. (3.6), the component ms is the convected entropy due to mass transfer and
S HT = ms is the entropy growth due to heat transfer to/from the gas volume.
The enthalpy of the gas volume is given as
h = μ + Ts . (3.7)
33
Chapter 3
An outer layer is added to the C-field as shown in Fig. 3.1 which simultaneously
enforces the thermodynamic relationships given in Eqs. (3.6) and (3.7).
Thermodynamic relations or constitutive relations for the C-field can be derived

as follows by assuming that ideal gas law applies. Using the first law of
thermodynamics and the definition of entropy, we get for a particular mass of gas in a
control volume,
du = Tds − pdv , (3.8)
which using the ideal gas law and the definition of internal energy becomes
RT
cv dT = Tds − dv . (3.9)
v
Integration of Eq. (3.9) by assuming constant cv leads to
S0 ⎧⎪⎛ T ⎞cv ⎛ Vm0 ⎞R ⎫⎪

s − 0 = ln ⎨⎜ 0 ⎟ ⎜ 0 ⎟ ⎬ . (3.10)
m ⎪⎩⎝ T ⎠ ⎝ V m ⎠ ⎪⎭
Multiplying Eq. (3.10) with m we get
S 0m ⎧⎪⎛ T ⎞mcv ⎛ Vm0 ⎞mR ⎫⎪

S − 0 = ln ⎨⎜ 0 ⎟ ⎜ 0 ⎟ ⎬ , (3.11)
m ⎪⎩⎝ T ⎠ ⎝ V m ⎠ ⎪⎭
which can be rearranged to obtain the expression for temperature as a function of the
three state variables (S, V and m, which are integrations of the flow variables in bonds
connected to the three port C-field) as
R
−
⎛ Vm0 ⎞ cv ⎛ S S0 ⎞
T = To ⎜ 0 ⎟ exp ⎜ − 0 ⎟. (3.12)
⎝V m ⎠ ⎝ mcv m cv ⎠
The expression for internal energy of the gas volume may now be obtained as
34
R
−
⎛ Vm 0 ⎞ cv ⎛ S S0 ⎞
U = mCvTo ⎜ 0 ⎟ exp ⎜ − 0 ⎟. (3.13)
⎝V m ⎠ ⎝ mcv m cv ⎠
The expression for pressure is obtained making use of the ideal gas law
( p = mRT / V ) or alternatively by taking the partial derivative of Eq. (3.13) with
respect to the volume ( p = − ∂U ∂V ). In its final form, the pressure is expressed as
−γ −γ
m0 RT 0 ⎛ V ⎞ ⎛ m ⎞ ⎛ S S0 ⎞
p= ⎜ ⎟ ⎜ ⎟ exp ⎜ − ⎟. (3.14)
V 0 ⎝ V 0 ⎠ ⎝ m0 ⎠ 0
⎝ mcv m cv ⎠
The chemical potential of the gas volume is the partial derivative of internal
energy with respect to the mass. This leads to a very cumbersome formula. An
alternative derivation which leads to a simple expression is presented in the following.
The chemical potential of the gas volume is also given as
μ = u + pv − Ts = cvT + RT − Ts . (3.15)
By substituting the expressions for specific entropy and temperature given,

respectively, in Eq. (3.10) and Eq. (3.12), into Eq. (3.15), we get the expression for
chemical potential in terms of the three state variables. However, due to the
assumption of constant specific heat capacities, the chemical potential obtained is not
very accurate. In order to get a more accurate expression for chemical potential, the
standard procedure given in [Zemansky & Dittman, 1997] is followed. From Eq.
(3.15), we obtain
μ = h − Ts . (3.16)
Substituting h = h0 + ∫ cp dT and s = s 0 + ∫ ( cp T ) dT − R ln ( p p 0 ) in Eq. (3.16),
we get
⎛ p⎞
μ = μ 0 (T ) + RT ln ⎜ 0 ⎟, (3.17)
⎝p ⎠
35
Chapter 3
where μ 0 (T ) is purely a function of temperature only. The values of μ 0 (T ) for the
individual gases are calculated using the following relation [Benson, 1977]:
⎡ ⎛ a3T 2 a4T 3 a5T 4 ⎞ ⎤

μ 0 (T ) = RT ⎢ a1 − a1 ln (T ) − ⎜ a2T + + + ⎟ − a6 ⎥ + μo , (3.18)
⎣ ⎝ 2 3 4 ⎠ ⎦
where the values of experimentally obtained coefficients a1 … a6 and μo for various

gases are given in [Benson, 1977]. The pressure and the temperature in Eq. (3.17) are
written in terms of the state variables by using the earlier expressions (refer Eqs.
(3.12) and (3.14)). The Equations (3.12), (3.14) and (3.17) are the constitutive
relations of the 3 port C-field as they give the effort variables ( T , p and μ ) in terms
of the three state variables ( m, V and S ), which are obtained by integrating the flow
variables. An alternative way of deriving the expression for the chemical potential of
a constituent gas in an ideal gas mixture (Eq. (3.17)) is given in Appendix B.
A preliminary bond graph model of the electrochemical hydrogen oxidation

reaction is shown in Fig. 3.2. The mechanical ports are not shown for the C-fields in
Fig. 3.2 because the volume is considered to be constant. The two R-field elements
shown in Fig. 3.2 are included to facilitate the temperature equilibration of the
reactant and product gas species as they occupy the same volume.
The transformation of energy from the chemical to the electrical domain is given
in the following. The change in the Gibbs free energy of the system is given as (refer
to Section 2.4 in Chapter 2)
dG = Vdp − SdT + μ dm . (3.19)
Using Eq. (3.19) and the assumption of constant temperature and pressure, the
change in the Gibbs free energy of the reaction is obtained as
∂G ∂G ∂G
dG = dnW − dnH − dnO . (3.20)
∂nW ∂nH ∂nO
36
Fig. 3.2: A Preliminary Bond Graph Model of the Hydrogen Oxidation Electrochemical Reaction
Note that the temperature and the pressure of the system may changes during the
system’s dynamics. However, Eq. (3.20) is assumed to be valid for each instantaneous
values of pressure and temperature of the system.
A quantity called the reaction coordinate ( ξ ) is defined such that dnH = −ν H dξ ,
dnO = −ν O dξ and dnW = ν W dξ . Using these relations and the definition of the
chemical potential, Eq. (3.20) becomes
dG = ( μ Wν W − μHν H − μOν O ) dξ . (3.21)
37
Chapter 3
As the quantities in Eq. (3.21) are state functions, the equation can be written as
ΔG = ( μ Wν W − μHν H − μOν O ) Δξ . (3.22)
If unit mole of fuel (hydrogen) is considered then Δξ = 1 . Therefore, the change

in the Gibbs free energy per mole of fuel is given by
ΔG = μ Wν W − μHν H − μOν O , (3.23)
Note that the chemical potentials are in J.mol-1 in Eq. (3.23). Under reversible
conditions, this change in the Gibbs free energy is converted entirely into electrical
energy. Therefore, from the energy balance, the reversible cell voltage can be
obtained as
ΔG
Vr = − , (3.24)
ne F
where the denominator gives the charge of the total number of electrons participating
in the reaction per mole of the fuel. The Equation (3.24) can further be written in
terms of the partial pressures of the reactant and the product gases and is called the
Nernst equation (refer to Appendix B). The Nernst equation is used to calculate the
effect of the change in the partial pressures of the reacting species on the reversible
cell voltage. Note that the minus sign in Eq. (3.24) is required to obtain a positive
value of voltage because the change in the Gibbs free energy per mol as defined in Eq.
(3.23) is negative (as the free energy of the products is less than the free energy of the
reactants).
The chemical potentials are calculated in J.kg-1 in the anode and cathode channel
C-fields of the model. The three transformers shown in the effort activated bonds
around the 1ξ junction have factors of ‘1000/Mi’ in order to convert the chemical
potentials to J.mol-1. The 1ξ junction shown in the Fig. 3.2 enforces the following
relationship, which defines the negative of the change in Gibbs free energy per mol of
fuel for the reaction.
38
ν H M H μ H + ν O M O μO −ν W M W μ W
−ΔG = . (3.25)
1000
The reversible cell voltage, which is defined by the Nernst equation [Liebhafsky
& Cairns, 1968], is realised by means of a transformer element (with modulus ne F )
in Fig. 3.2. When the reaction system is in equilibrium, the change in the molar Gibbs
free energy ( ΔG ) is zero. Therefore, the reversible voltage as predicted by the Nernst
equation is also zero. When the reaction system is forced out of equilibrium (i.e.,
when the concentrations of the reactants and the products differ from the equilibrium
concentrations), the reversible open circuit voltage (Vr) can be calculated by using the
Nernst equation (refer to Appendix B). However, the reaction cannot proceed as the
circuit is not closed. But once the circuit is closed (as we try to draw current from the
cell), the irreversibilities come into play and result in voltage losses.
The mole flow rate of the reaction ( ξ ), which can be considered as the reaction
rate, is related to the mole flow rates of consumption and production of the reactants
and products, respectively, as
r
nW nHr nOr
ξ= =− =− . (3.26)
νW νH νO
The reaction mole flow rate and the current (i) are related as
i = ξ ne F . (3.27)
Therefore, the relations between the mass-flow rates (in kg.s-1) of hydrogen,
oxygen and water vapour taking part in the reaction and the current drawn by the load
are given as
r
1000ne FmW 1000ne FmHr 1000ne FmOr
i= =− =− (3.28)
νWMW ν HMH ν OM O
39
Chapter 3
and they are realised through the 1ξ junction and the set of transformers in the flow
activated bonds surrounding it as shown in Fig. 3.2. The current, i , drawn by an un-
modelled external load is represented by a source of flow.
Note that in Fig. 3.2, transformers have been used in between two activated bonds
(signal ports). They simply act as a gain which amplifies the effort or the flow signal.
This kind of usage is adopted from [Mukherjee et al., 2006]. This convention is
followed here because it clearly reveals the structure of the electrochemical process.
Note that the bond graph model in Fig. 3.2 is also given using the conventional
representation in Appendix A.
The theoretical open-circuit voltage ( Vr ) is the maximum voltage that can be

achieved by an electrochemical cell under specific operating conditions. However, the
voltage of an operating cell, which is equal to the voltage difference between the
cathode and the anode, is generally lower than this. As current is drawn from a fuel
cell, the cell voltage falls due to internal resistances and over-voltage losses. The
actual cell voltage is generally obtained by subtracting all the voltage losses from the
open circuit voltage. The field element RPL shown in Fig. 3.2 models these voltage
losses or over-voltages (η). The entropy generated due to these irreversible processes
are obtained from the power balance as
ηi
S PL = , (3.29)
TW
and it is introduced into the zero junction representing the water vapour temperature
as shown in Fig. 3.2.
This bond graph model redresses several shortcomings of the previously proposed
bond graph models of electrochemical reactions in the literature. The use of internal
energy as the thermodynamic potential for the energy storing C-fields helps to avoid
the problem of differential causality encountered in the earlier models. In the model
given in Fig. 3.2, the temperature is not imposed on the system. Rather the system
temperature is decided by the exothermic reaction and the irreversible polarization
40
phenomena. This is very relevant for modelling fuel cell systems as the temperature of
such systems are dependant on the heat released due to the reactions and the over-
voltage phenomena. Further, the relations between the enthalpies of the gas species
and their entropies are clearly represented in the bond graph. This facilitates the direct
measurement of the enthalpy of the reaction, which is given by the difference between
the enthalpy of the products and the enthalpy of the reactants, from the bond graph
model. Note that the enthalpy of the considered reaction is positive because it is an
exothermic reaction (the enthalpy of the products is more than the enthalpy of the
reactants). This results in the increase of the temperature in the reaction system.
However, some more issues have to be addressed so as to obtain a bond graph

model which adequately represents the process dynamics of the fuel cell. One of the
problems faced while using the model shown in Fig. 3.2 concerns the two R-fields
which are added to facilitate temperature equilibration between the gas species. As
this process of temperature equilibration is extremely fast, the resistance needs to be
made very small, which makes the model very stiff (the simulation time is too large).
Another drawback of this model is that the thermal part and the electrochemical part
of the model are not connected by true bonds carrying powers but rather by activated
bonds or signal bonds which are signal carriers. Further, in the SOFC, the hydrogen
and the water vapour are present in the anode channel and are separated from the
oxygen in the cathode channel by the electrolyte. The model presented in Fig. 3.2
does not correctly represent this situation and hence cannot as such be used to
represent the SOFC dynamics. Therefore, further improvements are needed which are
made to the model in the subsequent sections.
3.3. A Bond Graph Model of the SOFC Using a C-field for

the Mixture of Two Gas Species
In the SOFC, a mixture of hydrogen and water vapour is present in the anode side and
a mixture of oxygen and nitrogen (which are considered to be the constituents of air)
is present in the cathode side. Therefore, it is justified to assume constant
41
Chapter 3
temperatures for each of these two mixtures. In this section, the basic process
occurring in an SOFC is described, the modelling assumptions are stated and the word
bond graph model of the SOFC is given. Later, the formulation of a C-field for
representing the energy storage in a mixture of two gas species is given. Finally, the
developed C-field is used to construct a bond graph model of the SOFC. The various
over-voltages or voltage losses and the entropy generation due to those over-voltages
are also represented in the bond graph model.
3.3.1. Process Description and Modelling Approach
The basic components of the SOFC are the anode, the cathode and the electrolyte, as
are shown in Fig. 3.3. They are together referred to as the MEA.
Fuel (hydrogen) is supplied to the anode side and air is supplied to the cathode
side. At the cathode–electrolyte interface, oxygen molecules accept electrons coming
from the external circuit to form oxide ions as given in Eq. (3.1).
The solid electrolyte allows only oxide ions to pass through. At the anode–
electrolyte interface, hydrogen molecules present in the fuel react with oxide ions to
form steam, and electrons get released as given in Eq. (3.2). As a result of the
potential difference set up between anode and cathode due to the resultant excess and
scarcity of electrons at anode and cathode respectively, electric current flows in the
external circuit through which they are connected and thus the circuit is closed.
Because the reaction is exothermic, heat is evolved as a by-product. The overall
reaction is given in Eq. (3.3).
The current drawn from the fuel cell and the temperatures of the anode and cathode
channel exhaust gases are the variables that are measured for controlling the valves
shown in Fig. 3.3. The pressures in the inlet and the outlet sides are assumed to be
known constants and the inlet side temperature is also assumed to be a known constant.
42
The model developed in this work is physics based zero-dimensional bond graph
model of a single cell, which is suitable for system dynamics studies and will be
helpful in developing control strategies. In line with [Aguiar et al., 2005], the cell is
considered to be at the centre of the stack such that no edge effects are present. The
anode channel volume, through which the supplied hydrogen and the produced water
vapour flow, is represented as a single volume and is referred to as the anode channel
volume. Similarly the cathode channel volume through which the air flows is
represented as a single volume and is referred to as the cathode channel volume. The
intensive variables; temperature, pressure and chemical potential, for each gas are
assumed to be uniform throughout the control volume. The interconnect plates form
the interface between the cells in a stack and also form the channels through which
the gases flow. The thermal capacitances of the solids (anode, cathode, electrolyte and
interconnect) are lumped. The convective heat transfer taking place between the gases
and the MEA and also between the gases and the interconnect plates are modelled.
The radiation heat transfer between the MEA and the interconnect plates and the
convection of heat energy due to the gas flow are also considered in the model. The
supply and the removal of gases to and from the channel volumes are through four
different controlled valves as shown in Fig. 3.3.
Fig. 3.3: Schematic of an SOFC
43
Chapter 3
3.3.2. Modelling Assumptions
The following assumptions are made in order to create a bond graph model of the
system.
1. The water formed due to the reaction is in the vapour form. All the gases
involved are assumed to be ideal. This assumption is valid because of the low
pressure and high operating temperatures.
2. Because it is a zero-dimensional model, the spatial variation of intensive
variables such as temperature, pressure and chemical potential are neglected.
3. The fuel considered in this model is pure hydrogen. The oxidant is air with
oxygen and nitrogen as its primary constituents.
4. The pressures of the gases are assumed to be governed by the Dalton’s law of
partial pressures.
5. As the pressure difference across the valves is small, the flows through the
valves are assumed to be governed by linear nozzle flow equations [Thomas,
1999].
6. As the cell is well insulated, the heat loss to the surrounding is neglected.
7. As the fast dynamics are irrelevant from control perspective, the diffusion
process is modelled through an approximation.
3.3.3. Word Bond Graph
A word bond graph represents the technological level of the model where the global
system is decomposed into its subsystems. It is the first step towards building a bond
graph model in which words define the components. The word bond graph for the
open-loop SOFC system is given in Fig. 3.4, which shows its various components.
The interaction between various subsystems is through the exchange of power. The
power variables for different domains are labelled in Fig. 3.4.
44
Fig. 3.4: Word Bond Graph Model of the SOFC
The gases in the anode and the cathode channel volumes interact with other
components of the system by exchanging energy in thermal, chemical and mechanical
domains. The power variables for the thermal domain are the temperature and the
entropy flow rate. The power variables for the chemical domain are the chemical
potential and the mass flow rate and those for the mechanical domain are the pressure
and the volume flow rate. The MEA heat transfer part models the thermal phenomena
due to heat transfer between the two control volumes (channels) and also accounts for
the heat generated due to chemical reactions and current flow through the MEA. The
interaction between the electro-chemical part and the two control volumes are through
the exchange of chemical energies. The exchange of electrical energy takes place
45
Chapter 3
between the electro-chemical and the electrical parts. The voltage and the current are
the power variables for the electrical domain. The thermal energy is also exchanged
between the channel volumes and the interconnects. The inlet and exhaust gases flow
through the valves which are initially modeled using pseudo bonds ( p and m as
power variables) but later they are represented using true bonds ( μ and m as power
variables) in a refined true bond graph model.
3.3.4. Storage of a Two Species Gas Mixture Represented in

a C-Field
In this section, the constitutive relations for a bond graph C-field representing the
energy storage by two species of gases in a control volume are derived. The relations
for a C-field representing a single gas species already exists in the literature
[Breedveld, 1984; Breedveld & Beaman, 1985; Feenstra, 2000; Mukherjee et al.,
2006] and were presented in Section 3.2. Although the constitutive relations are given
by considering a mixture of two gas species, it can be extended for a mixture of any
number of gas species. The two gas species are represented by subscripts 1 and 2. The
C-field for the two species gas mixture proposed here models the following scenario.
A mixture of two gases is contained in a collapsible chamber, which allows heat
transfer from and to the surroundings. In the general scenario modelled here, it is
assumed that individual gases can independently flow either into or out of the
chamber. Allowing the individual gas mass flow rates in proportion to their mass
fractions in the mixture can also incorporate the mass flow of the mixture as a whole.
The change of internal energy of the two gases in the mixture is given by
∂U ∂U ∂U ∂U
dU = dV + dS + dm1 + dm2 . (3.30)
∂V ∂S ∂m1 ∂m2
The above equation may be written in terms time derivatives as
∂U ∂U ∂U ∂U
U= V+ S+ m1 + m2 . (3.31)
∂V ∂S ∂m1 ∂m2
46
From well-known thermodynamic relations ∂U ∂V = − p , ∂U ∂S = T ,
∂U ∂m1 = μ1 and ∂U ∂m2 = μ2 , it is evident that the internal energy of the volume
of the gases change due to four distinct power exchanges which can be represented by
the products of the corresponding effort and flow variables.
The energy storage in the gas mixture can be represented as a 4 port C-field as
shown in Fig. 3.5. This C-field has four power ports: the flow and effort variables for
the mechanical port are V and p, respectively; those for the thermal port are S and T,
respectively; and those for the material ports are m 's and μ’s, respectively.
The growth of entropy inside the control volume can be given as
S = m1s1 + m2 s2 + S HT , (3.32)
where the first two terms are due to the mass transfers of the two species and the third
term is due to the heat transfer through the chamber walls.
By making use of the relations, h1 = μ1 + Ts1 and h2 = μ2 + Ts2 , an outer layer can
be added to the C-field as shown in the Fig. 3.5. The thermodynamic relationships
required for constructing the C-field are derived by assuming that both the species of
gases in the chamber are in thermal equilibrium, i.e., they have a common
temperature (T), and that they occupy a common volume (V).
Fig. 3.5: Two Species of Gases Represented in a C-field
47
Chapter 3
Note that SOFC systems operate at near atmospheric pressure and high
temperature. This is why one can assume ideal gas model. According to the
fundamental thermodynamic relation [Zemansky & Dittman, 1997], the change in the
specific entropy of an ideal gas (gas species #1) in terms of the specific internal
energy, the specific volume, the partial pressure and the equilibrium temperature is
given by,
du1 p1dv1
ds1 = + . (3.33)
T T
Using the ideal gas equation of state ( pv = RT ) and the definition of specific heat
capacity at constant volume ( du = cv dT ), Eq. (3.33) may be rewritten as
cv1dT R1dv1
ds1 = + . (3.34)
T v1
Integrating Eq. (3.34) from an initial state (indicated by superscript 0) to a final

state with the assumption of constant specific heat capacities and then writing the
specific quantities in terms of the absolute quantities ( s = S m and v = V m , where S,
V and m are state variables) gives
S10 ⎧⎪⎛ T ⎞cv1 ⎛ Vm0 ⎞ R1 ⎫⎪

s1 = 0 + ln ⎨⎜ 0 ⎟ ⎜ 0 1 ⎟ ⎬ . (3.35)
m1 ⎪⎩⎝ T ⎠ ⎝ V m1 ⎠ ⎪⎭
Similarly, for gas species #2, which occupies the same volume and is at same
temperature, we obtain
S20 ⎧⎪⎛ T ⎞cv2 ⎛ Vm0 ⎞ R2 ⎫⎪

s2 = 0 + ln ⎨⎜ 0 ⎟ ⎜ 0 2 ⎟ ⎬ . (3.36)
m2 ⎪⎩⎝ T ⎠ ⎝ V m2 ⎠ ⎪⎭
Multiplying Eq. (3.35) with m1 and Eq. (3.36) with m2 , we get the following
expressions for the entropies of the gas species #1 and #2.
48
⎧ mc 0 m1R1 ⎫
S10 m1 ⎪⎛ T ⎞ 1 v1 ⎛ Vm1 ⎞ ⎪
S1 − = ln ⎨⎜ 0 ⎟ ⎜⎜ 0 ⎟⎟ ⎬ (3.37)
m10 ⎪⎩⎝ T ⎠ ⎝ V m1 ⎠ ⎭⎪
⎧ mc 0 m2 R2 ⎫
S 20 m2 ⎪⎛ T ⎞ 2 v2 ⎛ Vm2 ⎞ ⎪
and S2 − = ln ⎨⎜ 0 ⎟ ⎜⎜ 0 ⎟⎟ ⎬. (3.38)
m20 ⎝ T ⎠ V m
⎩⎪ ⎝ 2⎠
⎭⎪
The total entropy of a mixture of gases is given by the sum of the entropies of the
individual gases:
⎧ m R +m R m c +m c 0 m1R1 ⎛ 0 ⎞m2 R2 ⎫
S10 m1 S20 m2 ⎪⎛ V ⎞ 1 1 2 2 ⎛ T ⎞ 1 v1 2 v2 ⎛ m1 ⎞ m ⎪
S− − = ln ⎨⎜ 0 ⎟ ⎜ 0⎟ ⎜⎜ ⎟⎟ ⎜⎜ 2 ⎟⎟ ⎬ (3.39)
m10 m20 ⎪⎩⎝ V ⎠ ⎝T ⎠ ⎝ m1 ⎠ ⎝ m2 ⎠ ⎪⎭
where S = ( S1 + S 2 ) .
From Eq. (3.39), the temperature of the gases is given as a function of the four
state variables ( m1 , m2 , V and S ):
⎛ S m1S10 m2 S20 ⎞
T = T 0 exp ⎜ − − ⎟
⎜ m1cv1 + m2cv2 m1m10cv1 + m10 m2cv2 m1m20cv1 + m20 m2cv2 ⎟⎠
⎝
⎛ m1R1 ⎞ ⎛ m2 R2 ⎞ (3.40)
⎛ m R +m R ⎞
−⎜ 1 1 2 2 ⎟ ⎜ ⎟ ⎜ ⎟
⎛V ⎞ ⎝ m1cv1 + m2cv2 ⎠ ⎛ m ⎞⎝ m1cv1 + m2cv2 ⎠ ⎛ m2 ⎞⎝ m1cv1 + m2cv2 ⎠
×⎜ 0 ⎟ ⎜⎜ 10 ⎟⎟ ⎜⎜ 0 ⎟⎟ .
⎝V ⎠ ⎝ m1 ⎠ ⎝ m2 ⎠
The internal energy of the gas mixture is obtained as the sum of the internal
energies of both the gases in the chamber, i.e. U = m1cv1T + m2 cv2T , or
⎛ m R +m R ⎞ ⎛ m1R1 ⎞ ⎛ m2 R2 ⎞
−⎜ 1 1 2 2 ⎟ ⎜ ⎟ ⎜ ⎟
⎛V ⎞ ⎝ m1cv1 + m2cv2 ⎠ ⎛ m ⎞⎝ m1cv1 + m2cv2 ⎠ ⎛ m2 ⎞⎝ m1cv1 + m2cv2 ⎠
U = ( m1cv1 + m2cv2 ) T 0 ⎜ 0 ⎟ ⎜⎜ 10 ⎟⎟ ⎜⎜ 0 ⎟⎟
⎝V ⎠ ⎝ m1 ⎠ ⎝ m2 ⎠ (3.41)
⎛ S m1S10 ⎞ m2 S20
× exp ⎜ − − ⎟ .
⎜ m1cv1 + m2cv2 m m 0
c + m 0
m c m m 0
c + m 0
m c ⎟
⎝ 1 1 v1 1 2 v2 1 2 v1 2 2 v2 ⎠
49
Chapter 3
The total pressure in the chamber is then obtained by summing the partial
pressures, i.e. p = m1 R1T / V + m2 R2T / V , where T is given by Eq. (3.40). The same
result can also be obtained by taking the partial derivative of the total internal energy
in Eq. (3.41) with respect to the total volume.
⎛ m R + m2 R2 ⎞ ⎛ S m1S10 m2 S20 ⎞
p =T0 ⎜ 1 1 ⎟ exp ⎜ − − ⎟⎟
⎜
⎝ m1cv1 + m2cv2
V 0 0 0 0
⎝ ⎠ m1m1 cv1 + m1 m2cv2 m1m2 cv1 + m2 m2cv2 ⎠
(3.42)
⎛ m R +m R ⎞ ⎛ m1R1 ⎞ ⎛ m2 R2 ⎞
− 1 1 2 2 ⎜ ⎟ ⎜ ⎟
⎛V ⎞ ⎜⎝ m1cv1 + m2cv2 ⎟⎠ ⎛ ⎞ m c + m c ⎛ ⎞ m c
m1 ⎝ 1 v1 2 v2 ⎠ m2 ⎝ 1 v1 2 v2 ⎠ + m c
×⎜ 0 ⎟ ⎜⎜ 0 ⎟⎟ ⎜⎜ 0 ⎟⎟ .
⎝V ⎠ ⎝ m1 ⎠ ⎝ m2 ⎠
Likewise, the chemical potentials of the gases can be obtained by taking the
partial derivative of U with respect to their corresponding masses. That leads to a
cumbersome formula. Alternatively, the chemical potential of gas #1 can be given as
μ1 = u1 + p1v1 − Ts1 = cv1T + R1T − Ts1 . (3.43)
Equation (3.43) can be written as
μ1 = h1 − Ts1 . (3.44)
Substituting h1 = h10 + ∫ cp dT and s1 = s10 + ∫ ( cp T ) dT − R1 ln ( p1 p10 ) in Eq.
(3.44), we get
⎛ p1 ⎞
μ1 = μ10 (T ) + R1T ln ⎜ 0 ⎟, (3.45)
⎝ p1 ⎠
where μ10 (T ) is purely a function of the temperature. The values of μ10 (T ) for the
individual gas molecules are calculated using the relation given in Eq. (3.18). The
partial pressure of the gas species #1 and the temperature of the mixture in Eq. (3.45)
are written in terms of the state variables by using the earlier expressions (refer to Eqs.
(3.40) and (3.42)). The chemical potential of gas #2 is calculated in a similar fashion:
50
⎛ p2 ⎞
μ2 = μ20 (T ) + R2T ln ⎜ 0 ⎟. (3.46)
⎝ p2 ⎠
The Equations (3.40), (3.42), (3.45) and (3.46) are the constitutive relations of the
four port C-field as they give the effort variables ( μ1 , μ 2 , p and T ) in terms of the
four state variables ( m1 , m2 , V and S ), which are obtained by integrating the flow
variables in the bonds connected to the four port C-field.
3.3.5. Bond Graph Model of the SOFC
The bond graph model of the SOFC, which utilises the C-fields presented in Section
3.3.4 for representing the energy storage in the gas mixtures in the anode and the
cathode channels, is shown in Fig. 3.6. The same bond graph in the conventional
representation may be referred to in Appendix A.
The electrochemical part of the bond graph (i.e., the calculation of the voltage and
the current) is the same as described in Section 3.2 (refer to Eqs. (3.24), (3.27) and
(3.28)). The theoretical open-circuit voltage ( Vr ) is the maximum voltage that can be
achieved by a fuel cell under specific operating conditions. However, the voltage of
an operating cell, which is equal to the voltage difference between the cathode and the
anode, is generally lower than this. As current is drawn from a fuel cell, the cell
voltage falls due to the internal resistances and over-voltage losses. The electrode
over-voltage losses are associated with the electrochemical reactions taking place at
the electrode/electrolyte interfaces and can be divided into concentration and
activation over-voltages. These losses are common to all types of fuel cells and cannot
be eliminated; although temperature, pressure, gas flow rate and composition,
electrode and electrolyte materials, and cell design, all influence their magnitude. The
actual cell voltage is generally obtained by subtracting all the voltage losses from the
open circuit voltage.
51
Chapter 3
Fig. 3.6: Bond Graph Model of the SOFC by Using the 4 Port C-fields
52
There are different kinds of voltage losses or over-voltages contributing to the cell
irreversibility. Activation over-voltage refers to the over potential required to exceed
the activation energy barrier so that the electrode reactions proceed at the desired rate.
The anodic and the cathodic activation over-voltages are governed by the Butler-
Volmer equation [Bockris et al., 1998; Campanari & Iora, 2004; Qi et al., 2005]
which in its general form (refer to Appendix B for derivation) is given as
⎧⎪ ⎛ β n Fη ⎞ ⎛ − (1 − β ) ne Fηact ⎞ ⎫⎪
i = i0 ⎨exp ⎜ e act ⎟ − exp ⎜ ⎟⎬ . (3.47)
⎪⎩ ⎝ RT ⎠ ⎝ RT ⎠ ⎪⎭
If the transfer coefficient ( β ) is 0.5 (refer to Eq. (B.47) in Appendix B), which is
normally the case [Qi et al., 2005], the anodic and cathodic activation over-voltages
can be obtained from Eq. (3.47) as
2RTM ⎛ 0.5i ⎞
ηact,an = sinh −1 ⎜
⎜ i ⎟⎟
(3.48)
ne F ⎝ 0,an ⎠
2RTM ⎛ 0.5i ⎞
and ηact,ca = sinh −1 ⎜
⎜ i ⎟⎟
, (3.49)
ne F ⎝ 0,c ⎠
where the anodic and the cathodic exchange currents are given as
⎛ p ⎞⎛ p ⎞ ⎛ −E ⎞
i0,an = ψ an Ac ⎜ H ⎟ ⎜ W ⎟ exp ⎜ an ⎟
⎝ pamb ⎠ ⎝ pamb ⎠ ⎝ RTM ⎠
0.25
⎛ p ⎞ ⎛ −E ⎞
and i0,ca = ψ ca Ac ⎜ O ⎟ exp ⎜ ca ⎟.
⎝ pamb ⎠ ⎝ RTM ⎠
It is clear from Eqs. (3.48) and (3.49) that the contribution of the activation over-
voltage to the overall voltage loss is significant at low currents.
The Ohmic over-voltage (ηohm ) is due to the resistance to the transport of ions in
the electrolyte and to the flow of electrons through the electrodes and current
collectors. It is governed by the Ohm’s law:
53
Chapter 3
ηohm = iRohm , (3.50)
where Rohm is the resistance per unit area. The ohmic over-voltage comes into play
typically at the middle range of current densities within which the fuel cell is usually
designed to operate. However, due to load fluctuations during operation, the fuel cell
may have to be operated at low and high current density conditions, where other kinds
of over-voltages are predominant.
The reactants, i.e. hydrogen and oxygen, in the flow channels have to diffuse
through the porous anode and cathode, respectively, to reach the electrode electrolyte
interface where the reaction occurs. Similarly, the product of the reaction, i.e., water
vapour, which is formed at the anode electrolyte interface, has to diffuse through the
porous anode so as to reach the flow bulk in the anode channel. If the cell is
functioning reversibly, the partial pressures of the reactant and the product gas species
are same at the flow bulk in the gas channels and at the TPB where the actual reaction
takes place (called so because of the presence of three phases, viz. the solid nickel or
lanthium strontium manganite of the electrodes, the solid yttria stabilized zirconium
oxide phase of the ceramic electrolyte and the gas phase of either the reactants or the
products). But when current is drawn from the cell, the partial pressures of the gas
species at the TPB differ from their corresponding partial pressures in the bulk due to
limitations imposed by the diffusion process (refer to Fig. 3.7). The voltage lost due to
this pressure difference between the bulk and the TPB is called as the concentration
over-voltage.
Fig. 3.7: Schematic Showing the Variation of the Partial Pressures of Hydrogen and Water Vapour
Through the Anode, and Oxygen Through the Cathode
54
The physical processes that contribute to the occurrence of the concentration over-
voltage include gas species molecular transport in the electrode pores, solution of
reactants into the electrolyte, dissolution of products out of the electrolyte and
diffusion of the reactants/products through the electrolyte to/from the reaction sites.
By assuming that the pressure loss of one of the reactants, say hydrogen, determines
the concentration over-voltage and that the pressure drop between the bulk and the
TPB region is linear, a simple expression for the concentration over-voltage can be
derived as follows. If the system is at steady state, then the absolute rate of diffusion
of the gas for a unit of geometric area must be equal to the current. Therefore
i = k ( pH,b − pH,TPB ) . (3.51)
Moreover, pH,TPB tends to zero as the current ‘i’ tends to a limiting value ‘ iL ’. So
we can write
iL
pH,b = . (3.52)
k
Substituting Eq. (3.52) into Eq. (3.51), we get
pH,TPB =
( iL − i ) . (3.53)
k
The difference in the Nernst voltages calculated by using the partial pressures of
the reacting gas species at the bulk and the TPB gives the concentration over-voltage.
A simplified model for the concentration over-voltage in terms of the partial pressures
can be derives as follows.
By using Eqs. (3.23), (3.24) and (3.45), and taking the reference pressure as unity,
the reversible Nernst voltage of the cell is represented in terms of the species partial
pressures and temperature as (refer to Appendix B)
ΔG 0 ⎛ pν W ⎞
Vr = − − RT ln ⎜ ν HW ν O ⎟ , (3.54)
ne F ⎝ pH pO ⎠
55
Chapter 3
where ΔG 0 = μ W0 ν W − μH0ν H − μO0ν O , which is the change in the Gibbs free energy of
the reaction at the reference state.
The concentration over-voltage is obtained by subtracting the Nernst voltage (Eq.

(3.54)) obtained by using the partial pressures at the flow bulk and those at the TPB as
⎛ pνW,b
W
⎞ ⎛ pνW,TPB
W
⎞
ηconc = − RT ln ⎜ ν H ν O
⎜p p ⎟⎟ + RT ln ⎜⎜ ν H νO ⎟⎟ . (3.55)
⎝ H,b O,b ⎠ p p
⎝ H,TPB O,TPB ⎠
It is assumed that the pressure loss of hydrogen alone is significant and is

responsible for the concentration over-voltage. Imposing this assumption on Eq.
(3.55) results in
RTM ⎛ pH,b ⎞
ηconc = ln ⎜ ⎟. (3.56)
ne F ⎜⎝ pH,TPB ⎟⎠
Substitution of Eq. (3.52) and Eq. (3.53) into Eq. (3.56) yields [Mueller et al.,
2006]
RTM ⎛ iL ⎞ RTM ⎛ i ⎞
ηconc = ln ⎜ ⎟=− ln ⎜ 1 − ⎟ . (3.57)
ne F ⎝ iL − i ⎠ ne F ⎝ iL ⎠
The concentration over-voltage is significant only at high currents. From Eq.

(3.57), it can be understood that the concentration over-voltage is very less when
i << iL . It becomes significantly high when the value of the current approaches the
limiting current. Note that Eq. (3.57) is not valid for i = iL .
All these over-voltages are modelled by the RS-field shown in Fig. 3.6. The effort
output (for the port with current as the flow input) of the RS-field is given as
RTM ⎛ ⎛ 0.5i ⎞ ⎛ 0.5i ⎞ ⎛ i ⎞⎞

η= ⎜ 2sinh −1 ⎜⎜ ⎟
⎟
+ 2sinh −1 ⎜
⎜ i ⎟ ⎟ − ln ⎜1 − ⎟ ⎟ + iRohm (3.58)
ne F ⎜ ⎝ iL ⎠ ⎟⎠
⎝ ⎝ i0,a ⎠ ⎝ 0,c ⎠
56
and the flow output (for the port with temperature as the effort input), i.e. the entropy
flow rate which goes to the heat transfer part of the model, is given as
iR ⎛ ⎛ 0.5i ⎞ ⎛ 0.5i ⎞ ⎛ i ⎞ ⎞ i 2 Rohm

S PL = ⎜ 2sinh −1 ⎜⎜ ⎟
⎟
+ 2sinh −1 ⎜
⎜ ⎟⎟ − ln ⎜1 − ⎟ ⎟⎟ + . (3.59)
⎜
ne F ⎝ ⎝ i0,a ⎠ ⎝ i0,c ⎠ ⎝ iL ⎠⎠ TM
The 0TM junction shown in Fig. 3.6 represents the temperature of the MEA solid.
Convection is an important means of heat transfer in an SOFC as the gases flow

through the anode and the cathode channels. Due to the ideal gas assumption and the
low velocities, the flow in a fuel cell is usually laminar. The bond graph model shown
in Fig. 3.6 includes the convective heat transfers between the anode and cathode
channel gases, the MEA and the interconnects. The R-fields, Rcv2 and Rcv4, model the
convective heat transfers between the gases and the MEA and the R-fields, Rcv1 and
Rcv3, model the convective heat transfers between the gases and the interconnects
denoted by I1 and I2, respectively, in Fig. 3.6. As the solid parts of the SOFC have
high thermal capacities and the cell is well insulated from the surroundings, the
temperatures of the interconnects are represented by the two sources of effort shown
in Fig. 3.6. The constitutive relations of the R-field, Rcv1, is given as [Mukherjee et al.,
2006; Thoma & Ould Bouamama, 2000]
λan Ac (TI1 − Tan )

S3 = (3.60)
Tan
λan Ac (TI1 − Tan )

and S4 = . (3.61)
TI1
The constitutive relations for the other R-field elements defining the convection
heat transfer (Rcv2, Rcv3 and Rcv4) are defined in a similar fashion. The thermal
capacity of the MEA is represented by the compliance element CM in Fig. 3.6. The
constitutive relation of thermal capacity [Karnopp et al., 2006; Thoma & Ould
Bouamama, 2000] of CM element is given as:
57
Chapter 3
⎛ S − S M0 ⎞
TM = TM0 exp ⎜ M ⎟. (3.62)
⎝ mM cM ⎠
The supply of fuel and air to the cell and the rejection of excess gases are through
four valves. Hydrogen gas is supplied to the anode channel through the anode channel
inlet valve and hydrogen-water vapour mixture goes out through the anode channel
outlet valve. The air is supplied to the cathode channel through the cathode channel
inlet valve and the depleted air exits through the cathode channel outlet valve. As the
pressure difference across the valves is small, a linearised nozzle flow equation is
used to calculate the mass flow rate through the valves [Thomas, 1999].
The models of these valves are shown separately in Fig. 3.8 and the connections
with the main bond graph in Fig. 3.6 are indicated by the numbered interface ports.
The pseudo bond graph models of the anode channel inlet valve, the anode channel
outlet valve, the cathode channel inlet valve and the cathode channel outlet valve are
shown in Fig. 3.8. The constitutive relations of the R-elements, which represent the
valve resistances in Fig. 3.8, are given as
m = K ( pu − pd ) . (3.63)
The values of the pressure variables are obtained from the main model in Fig. 3.6
through signal ports. Likewise, the calculated mass flow rates are exported through
signal ports to be used in the main model. The total mass flow rates, which are
represented by 1-junctions in Fig. 3.8 are converted into individual species mass flow
rates by multiplication with the upstream mass fractions. The mass fractions of the gas
species in the air source and those of the anode and cathode channels are represented
as gains in Fig. 3.8. The models of anode channel and the cathode channel outlet
valves need the information of the contemporary values of the mass fractions of the
individual gas species in the anode and the cathode channels. These mass fractions are
calculated from the state variables in the main model shown in Fig. 3.6 and used to
modulate the corresponding gains in the outlet valve models given in Fig. 3.8.
58
(a) (b)
(c) (d)
Fig. 3.8: Sub-models for (a) Anode Channel Inlet Valve, (b) Anode Channel Outlet Valve, (c)
Cathode Channel Inlet Valve and (d) Cathode Channel Outlet Valve
The entropy of the reaction is accounted in the following way. The entropy
balance for the anode channel control volume is given by
S an = mH sH + mW sW + S1 , (3.64)
where the quantities mH and mW are given respectively (refer to Fig. 3.6) as follows.
mH = mHi − mHo − mHr . (3.65)
mW = mW
i
− mW
o
+ mW
r
. (3.66)
Substituting Eqs. (3.65) and (3.66) into Eq. (3.64), we get
S an = sH mHi − sH mHo − sH mHr + sW mW

i
− sW mW
o
+ sW mW
r
+ S1 , (3.67)
which can further be written as
59
Chapter 3
S an = S Hi − S Ho − S Hr + S Wi − S Wo + S Wr + S1 . (3.68)
Similarly the entropy balance equation for the cathode channel control volume
may be written as
S ca = SOi − SOo − SOr + S Ni − S No + S8 . (3.69)
From Eqs. (3.68) and (3.69), it is apparent that this model accounts for the entropy
change of the reaction. This entropy change results in the enthalpy change of the
reaction which is positive for this case (the enthalpy of the products being more than
the enthalpy of the reactants). Note that the enthalpies of all the gas species can be
directly read from the bond graph model.
The bond graph model presented in this section avoids the stiff differential
equations of the system resulting from the earlier model presented in Section 3.2 (due
to the presence of the R-fields for temperature equilibration) by means of using a C-
field which assumes a constant temperature for two species gas mixtures. However,
some parts of the model are constructed by using pseudo bond graphs (the valves) and
the electrochemical part of the model is constructed by using activated or signal bonds.
This is not desirable because energy consistency of the system is not very clear from
the bond graph. Also, the entropy convection phenomena are not clearly represented
in this bond graph model. For example, in Eq. (3.67), the specific entropies of the
inlet side and outlet side must be used, respectively, for calculating the inlet and outlet
entropy flow rates, while the channel volume specific entropy must be used for
calculating the entropy flow due to the reaction. Due to the improper representation of
the entropy convection in the model, the heat released due to the exothermic reaction
is insufficiently removed. During simulations, the sources of efforts representing the
interconnect temperatures ( TI1 and TI2 ) act as heat sinks. If the sources of efforts are
replaced by capacitive elements representing the thermal capacitance of the
interconnect solids then the temperature of the cell will go on increasing as the
reaction proceeds. This restricts the usage of the model only for cases in which the
temperature of the cell does not vary much. All these deficiencies are rectified in the
true bond graph model of the SOFC presented in the next section in which the entropy
60
convection is represented in an R field element and the pseudo and activated parts of
the model are replaced with true bonds.
3.4. Formulation of the True Bond Graph Model of the

SOFC
In this section, a true bond graph model of the SOFC is formulated to rectify the
deficiencies of the preliminary models developed in the previous sections. The C-
fields for energy storage in the two species gas mixtures developed in Section 3.3.4
are used in this model. Further, an R-field element is formulated (based on the model
given in [Breedveld, 1984]) for modelling the entropy convection of a two species gas
mixture.
3.4.1. Convection of a Two Species Gas Mixture Represented

in an R-Field
Models for the irreversible convective flow of compressible fluids are available in the
literature. In [Brown, 2007], they are modelled by using convection bonds and the HS
element. A true bond graph formulation for the forced convection of a compressible
ideal gas was given in [Feenstra, 2000]. The energy storage in a control volume was
modelled as a C-field element and the gas enters and leaves the control volume
through two R-field elements. However, the formulation in [Feenstra, 2000] assumed
convection of a single gas species. In this work, the resistive field is extended to
handle the flow of a gas mixture, which will be used to represent the convection of
fluids between different control volumes in the SOFC model.
The details of the sub-model for modelling the convection of a two-component

gas mixture are given in Fig. 3.9. The most important element in the expanded model
of the MR element is the RS-field element (see Fig. 3.9). This element is modelled by
following the same true bond graph representation given in Breedveld’s original work
[Breedveld, 1984]. This element receives the downstream side temperature and the
61
Chapter 3
information of the valve position (x), the upstream side chemical potentials and
temperature, and the downstream side chemical potentials to calculate the mass and
entropy flow rates. Note that all these variables are inputs to the MR element. To
maintain the clarity of the figure, the connections needed to explicitly show these
modulations are not drawn.
From the causal analysis, this sub-model receives six effort variables and
computes six flow variables without the use of integration and/or differentiation.
Therefore, this sub-model can be represented as an encapsulated R-field (a six port
element MR in Fig. 3.9). From the continuity equation, the mass flow rate of a
particular gas is the same for the inlet and the outlet side. This reduces the total
number of independent flow variables to four (see Fig. 3.9). Then the constitutive
relation of the non-linear resistive field element is given as
(S , S ,m ,m ) { },
T
= Φ R (Tu , Td , μ1u , μ1d , μ2u , μ2d )
T
u d 1 2 (3.70)
where, Φ R is a vector-valued function. The individual relations between the input and
the output variables are derived as follows.
Fig. 3.9: Bond Graph Representation For Convection of a Two-Component Gas Mixture
62
The overall mass flow rate ( m ) of the mixture is imposed at the 1m junction by
the modulated RS-field element in Fig. 3.9 and it is given by the linear nozzle
equation:
m = K ( pu − pd ) . (3.71)
Note that although Eq. (3.71) needs the total upstream and downstream side
pressures, they can indeed be calculated from the chemical potentials and
temperatures. These calculations are given later in this section (see Eqs. (3.76–3.79)).
The individual mass flow rates of the two gases are then realized through the
modulated transformer elements shown in Fig. 3.9 as m1 = mw1u and m2 = mw2u . The
upstream mass fractions w1u and w2u are obtained from the upstream side storage
element, i.e. w1u = m1u ( m1u + m2u ) , w2u = m2u ( m1u + m2u ) and w1u + w2u = 1 , where
m1u and m2u are the contemporary masses (state variables) in the upstream side
control volume.
The entropy flow rate due to the mass flow rate is calculated by means of a
transformer element (between junctions 1S and 1m ), which is modulated by the
specific entropy of the upstream side gases. This information of the upstream side
specific entropy can either be obtained directly from the upstream side storage
element or if a standalone scheme is required, it can be calculated from the upstream
side μ ’s and T ’s (which are inputs of the MR element) as
su = cp1w1u + cp2 w2u −

( μ1u w1u + μ2u w2u ) . (3.72)
Tu
The entropy flow rate from the upstream side is given as S u = msu . The R-field
represents the change in the intensive variables between the upstream and the
downstream sides. The temperatures, pressures and the chemical potentials of the gas
mixture in the upstream and the downstream sides are imposed by the storage
elements on the corresponding sides. Due to this, there is an enthalpy difference
63
Chapter 3
between the upstream and the downstream sides. This enthalpy difference can be
represented as the relation between the changes in the intensive variables by using the
Gibbs-Duhem equation [Callen, 1985; Denbigh, 1955] as (refer to Appendix B)
v ( pu − pd ) = su (Tu − Td ) + w1u ( μ1u − μ1d ) + w2u ( μ2u − μ2d ) . (3.73)
This relation is enforced by the 1m -junction in Fig. 3.9. Due to the enthalpy
difference between the upstream and the downstream side gases, entropy is generated
in the resistive field. Using the principle of power conservation, the irreversible
entropy generated Sgen can be given as
mv ( Pu − Pd )
Sgen = . (3.74)
Td
Substitution of Eq. (3.73) into Eq. (3.74) gives
m ( su (Tu − Td ) + w1u ( μ1u − μ1d ) + w2u ( μ2u − μ2d ) )

Sgen = , (3.75)
Td
where su (Tu − Td ) + w1u ( μ1u − μ1d ) + w2u ( μ 2u − μ 2d ) and Td are effort inputs to the RS-
element and m is calculated internally from the constitutive relation of the RS-
element (see Eq. (3.71)).
The downstream side entropy flow rate is the sum of the upstream side entropy
flow rate ( Su imposed at 1S -junction by the MTF element) and the irreversible
entropy generated ( Sgen in Eq. (3.75)). This sum is realized by means of the zero-
junction shown in Fig. 3.9.
The upstream and downstream pressures, which are needed in Eq. (3.71), can
either be read directly from the upstream and downstream side storage elements or
can be calculated as functions of μ ’s and T ’s (the input variables to the MR element)
as follows. The change in the upstream side specific entropy of a given mass of gas
species #1 is given by
64
⎛ ⎛ T ⎞cv1 ⎛ v ⎞ R1 ⎞
s1u − s = ln ⎜ ⎜ u0 ⎟ ⎜ u1
0
0 ⎟
⎟. (3.76)
1u
⎜ ⎝ Tu ⎠ ⎝ vu1 ⎠ ⎟
⎝ ⎠
Substitution of s1u = Cp1 − μ1u Tu in Eq. (3.76) and rearrangement gives
cv1
−
⎛ μ μ ⎞⎛ Tu ⎞
0 R1
vu1 = vu1
0
exp ⎜ − 1u + 0
1u
⎟⎜ 0 ⎟ . (3.77)
⎝ Tu R1 T R ⎠⎝ Tu ⎠
u 1
The upstream side partial pressure of gas species #1 is given as
cv1
RT ⎛ μ μ 0 ⎞ ⎛ T ⎞ R1
p1u = 1 u = pu1
0
exp ⎜ 1u − 01u ⎟ ⎜ u0 ⎟ . (3.78)
vu1 ⎝ Tu R1 Tu R1 ⎠ ⎝ Tu ⎠
Similarly, the upstream partial pressure of gas #2 is
cv2
RT ⎛ μ μ 0 ⎞⎛ T ⎞ R2
p2u = 2 u = pu2
0
exp ⎜ 2u − 02u ⎟⎜ u0 ⎟ . (3.79)
vu2 ⎝ Tu R2 Tu R2 ⎠⎝ Tu ⎠
The total upstream side pressure is pu = p1u + p2u . The total downstream side
pressure can also be expressed similarly.
3.4.2. True Bond Graph Model of the SOFC
The true bond graph model of the SOFC system is given in Fig. 3.10. The same bond
graph model in the conventional representation may be referred to in Appendix A.
This model uses the 4-port C-field (presented in Section 3.3.4) for representing the
storage of the gases inside the anode and the cathode flow channels. It also uses the
R-field representation discussed in Section 3.4.1 for modelling the entropy convection
at the inlet and the outlet of the SOFC channels.
65
Chapter 3
Representing a thermodynamic system in terms of true bond graph involves the

concepts of network thermodynamics, which depend on the following three postulates
[Perelson, 1975]:
1. The assumption of local phase equilibrium is made. That is, even though the
system as a whole may be far from the equilibrium, locally one can still
describe the state of the system by thermodynamic variables, such as the
temperature, the pressure, and the chemical potential.
2. The physical space is viewed as discrete rather than as a continuum. This will
generate finite dimensional models described by ordinary differential
equations as opposed to the partial differential equation description of
continuum theories.
3. Although complex processes are occurring on every volume element of the
physical system, we assume that one can conceptually separate these processes
into dissipative and non-dissipative parts.
The true bond graph model of the SOFC, shown in Fig. 3.10, is constructed by
using the concepts of network thermodynamics. As the volumes of both the channels
remain constant, the mechanical ports of the C-fields are not shown in Fig. 3.10. The
constitutive relations for the two C-fields shown in Fig. 3.10 were given in Section
3.3.4 (Eqs. (3.40), (3.42), (3.45) and (3.46)), where the subscripts 1 and 2 represent
the gas species in the anode and cathode channels. Note that the outer layer of the C-
field presented in Section 3.3.4 imposing the entropy balance (Eq. (3.32) and the
enthalpy-entropy relations) is not used in the model given in Fig. 3.10. Rather, in this
model the mass and entropy balances of the anode and cathode channel control
volumes are given by the corresponding zero junctions in Fig. 3.10. The 0Tan and the
0Tca junctions give the entropy balances for the anode channel and the cathode
channel control volumes, respectively. The 0 μH , 0μW , 0 μO and 0 μN junctions give the
mass balances for the hydrogen, water vapour, oxygen and nitrogen gases,
respectively, in the control volumes. The 0TM junction gives the entropy balance at the
MEA solid control volume.
66
The capacitive elements and fields in the model represent equilibrium

thermodynamics part of the model. As the simulation proceeds, the matter inside the
control volume represented by these elements change reversibly from one equilibrium
state to the next, which means that the process is assumed to be quasi-static. The R-
fields represent the non-equilibrium parts of the model, i.e. they introduce the
irreversibilities into the system. The R-field elements represented by ‘MR’ in Fig.
3.10 introduce the irreversibility due to mass convection into the system (refer to
Section 3.4.1). The R-field element represented by ‘RS’ in Fig. 3.10 introduces the
irreversibility due to the over-voltage phenomena (ohmic, concentration and
activation losses). The other R-field elements introduce the irreversibilities due to the
heat transfer phenomena.
The inlet and outlet valve resistances are modelled by the MR-fields described in
the previous section where subscripts mentioned in the nomenclature identify them.
The valve resistances in the MR-fields may be controlled by modifying the variables
for the stem positions. Note that although only hydrogen gas flows through the anode
side inlet valve, the information of chemical potential of water vapour ( μ W ) inside
the anode channel is required for computing the downstream side pressure, which is
supplied by an information bond in Fig. 3.10. Similarly, the additional information of
the chemical potentials of nitrogen and oxygen in the atmosphere are required in the
anode channel outlet valve model to calculate the downstream side pressure, which is
provided by the source of efforts as shown in Fig. 3.10. The downstream side entropy
flow is the sum of the upstream side entropy flow and the entropy generated due to
the enthalpy difference between the upstream and the downstream sides (Eq. (3.75)).
In this model, the chemical potentials of the gases not only drive the electro-
chemical reaction but also, along with temperatures, determine the flow of the gases
in and out of the channels. This is because, though the mass flow through the MR-
field element is determined from the upstream and downstream side pressures (Eq.
(3.71)), the individual pressures can be written as functions of the chemical potential
and the temperature (Eqs. (3.78–3.79)). Thus, the coupling between the chemical,
thermal, mechanical and the hydraulic domains, which is encountered in a fuel cell
system, is effectively represented here in a unified manner by using true bond graphs.
67
Chapter 3
Fig. 3.10: True Bond Graph Model of the SOFC
The transformation of power from the chemical domain into the electrical domain
is elegantly represented by means of true bonds, as shown in Fig. 3.10, instead of the
activated bonds in the preliminary models presented in Sections 3.2 and 3.3.5. This
transformation is implemented by the 1ξ junction and the transformers surrounding it.
The electrochemical relations are the same as those given in Section 3.2. The
reversible cell voltage is given by Eq. (3.24) and the relation between the reaction rate
and the current is given by Eq. (3.27). The relation between the current and the
reaction mass flow rates of the reactants and the product (in kg.s-1) is also given by Eq.
(3.28).
The transformation between the electrical and the thermal domains is due to the
RS field element shown in Fig. 3.10, which models the different polarisation losses
(activation concentration and ohmic) and the entropy generation due to them. The
68
constitutive relations of the RS-field element were developed in Section 3.3.5 (refer to
Eqs. (3.47–3.59)).
The constitutive relations of the convective heat transfer resistances Rcv1, Rcv2,
Rcv3 and Rcv4 are the same as those that were given in Section 3.3.5. The constitutive
relations for the convective heat transfer resistance were given in Eqs. (3.60) and
(3.63). The constitutive relations for the other heat transfer resistances are similar.
Note that the same bond numbering for the thermal part is used both in Fig. 3.6 and
Fig. 3.10. The constitutive relation of the CM element representing the thermal
capacity of the MEA solid is the same as given in Section 3.3.5 (refer to Eq. (3.62)).
The unmodelled load is represented by the flow source as shown in Fig. 3.10.
The thermal capacitance of the interconnect plates are represented by the two
capacitive elements CI1 and CI2 and their constitutive relations are given, respectively,
as
⎛ S − S0 ⎞
TI1 = TI10 exp ⎜ I1 I1 ⎟ . (3.80)
⎝ mI1cI1 ⎠
⎛ S − S I20 ⎞
and TI2 = TI20 exp ⎜ I2 ⎟. (3.81)
⎝ mI2 cI2 ⎠
The enthalpy of the reaction is given as
ΔH = ΔG + T ΔS , (3.82)
where the part T ΔS is released as heat when the fuel cell operates reversibly. Under
irreversible operation (under all realistic circumstances), the change in the Gibbs free
energy of the reaction ( ΔG ) is not completely converted into useful electrical work.
Rather, some of it ends up as heat energy. These irreversibilities, which are called
over-voltages, give rise to entropy generation and are taken care by the RS-field
element in the model. In order to account for the entropy change of the reaction, the
following entropy flow rate is added to the MEA by means of a modulated source of
flow in Fig. 3.10:
69
Chapter 3
mHr ( hH − μH ) mOr ( hO − μO ) mWr ( hW − μ W )

Sr = + − , (3.83)
Tan Tca Tan
where the specific enthalpies are expressed as follows [Benson, 1977]:
h = R ( a1T + a2T 2 + a3T 3 + a4T 4 + a5T 5 ) + h0 . (3.84)
The values of the coefficients a1 a6 and h0 for the different gases are taken
from [Benson, 1977]. The source of flow MSf: S r is modulated with signals i (to
calculate mHr , mOr and mWr according to Eq. (3.83)), μ W , μH , μO , Tan and Tca (the
later five are calculable from state variables). Note that these modulating signals are
not shown in Fig. 3.10 to maintain the visual clarity of the figure.
Unlike the pseudo bond graphs, the energetic consistency of the true bond graph
presented in Fig. 3.10 is apparent. The continuity of energy flows across different
domains and across different interfaces is ensured because the effort and the flow
variables correspond to the power variables in the corresponding energy domains
throughout the bond graph model. The interface between the chemical and the
electrical domain is provided by the transformer element with ne F as the modulus.
The hydraulic and the thermal domains are coupled via the entropy generation due to
the gas enthalpy difference between the cell interior and the exterior, which is called
as the entropy of mixing. These entropy generations are represented in the four MR-
field elements in Fig. 3.10. The coupling between the electrical and the thermal
energy domains is provided by the RS-field element in Fig. 3.10. The entropy
generated in the RS-field element is due to the charge transport in the electrodes,
electrolyte and interconnect plates, the charge transfer taking place at the electrode
electrolyte interface and also due to the mass diffusion through the porous electrodes.
The entropy generation due to the convective heat transfer between the gas and solid
phases are represented by the R-fields, Rcv1, Rcv2, Rcv3 and Rcv4. The expressions for
these entropy generation terms were already discussed in Sections 3.3.5 and 3.4.1.
Further, all the storage elements in the developed global model given in Fig. 3.10
are in integral causality. There is no causality violation at any place in the junction
70
structure. This ensures the energy consistency in the model. Moreover, this integrally
causalled model does not have algebraic or causal loops, which ensures that this
model is well computable.
3.5. Conclusions
The systematic development of a zero dimensional true bond graph model of an

SOFC system by using the concepts of network thermodynamics is discussed in this
chapter. A preliminary bond graph model of the hydrogen oxidation electrochemical
reaction is developed. This preliminary model makes use of a C-field in which the
internal energy serves as the thermodynamic potential. The preliminary model avoids
the differential causality problem present in the models proposed earlier in the
literature and gives a clear insight into the dynamics of the electrochemical hydrogen
oxidation reaction. Moreover, the relations between the enthalpies and the entropies
of the reacting gas species which are clearly represented in the bond graph model
facilitate the measurement of the reaction enthalpies. In order to enhance this model to
represent fuel cells, a C-field for representing the energy storage in a two species gas
mixture is formulated. This C-field is used in the construction of a bond graph model
of an SOFC. In this model, the two species C-fields are used to represent the
capacitance of the gas mixtures in the flow channels. Various over-voltages
encountered in an SOFC are also included. Some parts of this model are constructed
as pseudo bond graphs, which is not desirable. Also, the entropy convection processes
are not clearly represented in this model. In order to rectify these deficiencies, a true
bond graph model of the SOFC is developed by using the concepts of network
thermodynamics. For this purpose, an already available R-field formulation for single
species gas is extended to represent the convection of two component gas mixtures.
The formulations developed in this chapter can be extended to mixtures of more than
two gas species.
The true bond graph model offers significant improvements over the previous
bond graph models of the electrochemical reaction systems available in the literature.
71
Chapter 3
They include, the use of internal energy as the thermodynamic potential of the C-field
used in modelling the chemical reaction systems, the formulation and use of a C-field
to model the energy storage in two species gas mixtures encountered in an SOFC, the
extension and the use of an R-field [Breedveld, 1984] element to represent the entropy
convection in the SOFC inlet and outlet gas streams. The couplings between the
various energy domains in a fuel cell system have been represented in a unified
manner by using the true bond graphs. The developed model ensures energy balance
at all physical process interfaces, e.g. entropy generation due to mixing, entropy
generation due to heat transfer, charge transport and diffusion phenomena. The true
bond graph model developed in this work clearly exposes the physical structure and
process dynamics of the SOFC. Causal analysis shows that model is energetically
consistent and, at the same time, it is well computable.
The developed model will be useful in designing integrated model-based control

strategies for the overall system by including the load and power conditioning
components. Moreover, various other control theoretic tools, fault detection
algorithms, and fault tolerant and robust control algorithms can be readily applied to
the bond graph model. Because this model is based on the second law of
thermodynamics of the system and the principles of network thermodynamics [Oster
et al., 1971; Perelson, 1975], it can be used for performing exergy based system
optimisation studies [Saidi et al., 2005]. Some of these possibilities are explored in
the later chapters of this thesis.
72
Chapter 4
Simulation of the Open and Closed Loop

Dynamics of SOFC
4.1. Introduction
The static characteristic curves of the SOFC are useful for obtaining the voltages and
power densities for various values of current densities (j’s) and varying operating
conditions, e.g. FU’s, temperatures and pressures. They are also useful in identifying
the operating regime of the SOFC. Given the SOFC geometric and design
specifications, the static characteristic curves are extremely useful in characterizing
the stable operation of the cell under different operating conditions.
For the given values of system operating pressure, the air source and hydrogen
source pressures, the outlet pressures, the cell temperature and the inlet gas
compositions, the FU and the OU (also referred to as the air utilisation in some works)
may be interpreted in terms of the partial pressures of the gases in the anode channel
Chapter 4
and the cathode channel. This knowledge is useful for obtaining the various static
characteristic curves of the SOFC.
Many emerging applications of SOFC require it to follow very fast load transients
[Mueller et al., 2006]. A detailed true bond graph model (with heat transfer,
hydraulics and the diffusion phenomena), which complies with other advanced
models available the literature [Aguiar et al., 2004], was developed in the previous
chapter. That model is used in this chapter to obtain the static characteristic curves of
the SOFC and to analyse the dynamic responses through simulations. Note that
various static characteristic curves of the SOFC given in this chapter are plotted with
current densities (j’s) rather than currents on the x-axis so as to comply with the
conventions followed in the literature. The current density is the current passing
through unit cell area, i.e. j=i/Ac.
In order to investigate the dynamic properties of a system, step response tests are
usually used. These tests can reveal key process dynamic parameters such as time
constant, overshoot, gain, etc. Therefore, in this work, the SOFC model is subjected to
step load current changes and the transient response characteristics are investigated.
Controlling average stack temperature, maintaining constant FU for all power

outputs, and ensuring that the air ratio always exceeds a minimum specified value are
some common control objectives of the SOFC. Stack temperature control is normally
provided by varying the air ratio, i.e., the supply of air for cooling [Aguiar et al.,
2005]. In [Aguiar et al., 2005], two main control loops were implemented in order to
achieve the control objectives. A master controller sets the fuel and air flow rates
proportional to the current and a typical feedback PID temperature controller which,
given the outlet fuel gas temperature, responds by changing the air flow around the
default air flow set by the master controller.
The FU is usually maintained constant by controlling the fuel flow rate into the
system [Mueller et al., 2006]. Another requirement for the operation of the SOFC,
which is often neglected by most researchers, is that the difference of the pressure
between the anode and the cathode channels has to be small [Serra et al., 2005;
Wachter et al., 2006]; the adequate value being dependent on the membrane support
74
Open and Closed Loop SOFC Dynamics
(allowable stress) and on the age of the fuel cell (fatigue considerations). Some
authors [He, 1998; Wang et al., 2007; Zhu & Tomsovic, 2002] state that the pressure
difference between the anode and cathode channels must be kept below 8kPa under
transient conditions and below 4kPa during steady state conditions in order to prevent
damage to the electrolyte. In this chapter, a physical model-based control strategy for
the SOFC system is developed. It is based on manipulating the flows through four
inlet and outlet valves. The developed control laws satisfy all the above-mentioned
operational constraints and the control objectives.
4.2. Model Initialization and Open Loop System Simulations
In this section, the true bond graph model of the SOFC described in Section 3.4.2 of
the previous chapter is simulated to obtain the static characteristic curves and dynamic
responses to a step change in the load current. In order to simulate the steady state
operation of the SOFC, the single port C-elements in the true bond graph model
described in the previous chapter have to be initialized with the values of generalized
displacements (initial entropies in this case). Similarly, the two C-field elements have
to be initialized with the values of the initial masses of the constituent gases and their
entropies.
According to the operational requirement of the SOFC, FU must be maintained

constant. Normally, FU of 0.8–0.9 is desired [Wang et al., 2007]. In this work, a value
of 0.8 is chosen for the FU and a value of 0.125 is chosen for the OU.
The static characteristic curves of the SOFC give the behaviour of the voltage and
the current under varying operating conditions, i.e. temperatures, pressures, FU and
OU. They basically give us an idea of the contributions of the various over-voltages to
the overall voltage loss in the cell under different operating conditions. For obtaining
the static performance curves of the SOFC, the variables such as the operating
temperature, the desired current density, the desired total anode and cathode channel
pressures ( pan0 , pca0 ), the FU ( ζ f ), the OU ( ζ o ), the source and the sink pressures (pHS,
pAS, pENV) and the species mass fractions at the air source ( wO,AS and wN,AS ) are
75
Chapter 4
considered as the known variables. We need to establish relationships between the

steady state values of these known variables and the steady state partial pressures of
the individual gas species in the channels. This is necessary because it is evident from
the Nernst equation that the open circuit voltage (reversible voltage) of the cell
depends on these partial pressures. Moreover, the activation and the concentration
over-voltages also depend on the species partial pressures.
In order to establish the desired relations, the steady state mass balances for the
anode and the cathode channels are written. From those mass balance equations, the
valve coefficients (which are unknown variables) which will lead to the desired steady
state operation are obtained. In the following discussions, the superscript ‘0’ refers to
the desired steady state value of the variable which needs to be set for obtaining the
desired static characteristic curves.
The steady state mass balance in the anode channel by taking into consideration
the required value of FU is given as
m Hi = m Hr + m Ho , (4.1)
m Wr = m W
o
(4.2)
and m Hr = ζ f m Hi , (4.3)
where the hydrogen inlet and outlet mass flow rates and the water vapour outlet mass
flow rate are given by the linear nozzle flow equations:
m Hi = K ai ( pHS − pan0 ) , (4.4)
m Ho = K ao wH,an
0
( pan0 − pENV ) , (4.5)
and o
m W = K ao wW,an
0
( pan0 − pENV ) . (4.6)
76
0
Note that in the Eqs. (4.1–4.6), the unknown variables are K ai , K ao , wH,an and
0
wW,an . However, the total steady state mass in the anode channel can be calculated
using the ideal gas law because the desired anode channel pressure, temperature and
the volume are known. Therefore, the three equations (Eqs. (4.1–4.3)) are solved for
the two valve coefficients ( K ai and K ao ) and for the ratio of the mass fractions, i.e.,
0 0 0
wW,an mW,an nW,an MW
0
= 0
= 0
. (4.7)
wH,an mH,an nH,an MH
Solving the Eqs. (4.1–4.3), we get the expressions for the inlet and outlet valve
coefficients as
m Hr
K ai = (4.8)
ζ f pHS − ζ f pan0
m Wr
and K ao = , (4.9)
0
wW,an pan0 − wW,an
0
pENV
and the ratio of the partial pressures of the two gas species in the anode channel is
found to be
0
nH,an pH0 1 − ζ f
= = . (4.10)
0
nW,an 0
pW ζf
As we know the total pressure in the anode channel, we can calculate the
individual partial pressures of hydrogen and water vapour; thus establishing the
relationship between the FU and the partial pressures of individual species.
The mass balance in the cathode channel along with the required OU is given as
m Oi = m Or + m Oo , (4.11)
m Ni = m No (4.12)
77
Chapter 4
and m Or = ζ o m Oi , (4.13)
where the oxygen and nitrogen inlet and outlet mass flow rates are given by the linear
nozzle flow equations:
m Oi = K ci wO,AS ( pAS − pca0 ) (4.14)
m Ni = K ci wN,AS ( pAS − pca0 ) (4.15)
m Oo = K co wO,ca
0
( pca0 − pENV ) (4.16)
and m No = K co wN,ca
0
( pca0 − pENV ) . (4.17)
0 0
Solving Eqs. (4.11–4.13) for the variables K ci , K co and nN,ca nO,ca (refer to the
discussion for the anode channel case), we get the expressions for the cathode channel
inlet and outlet valve coefficients as
m Or
K ci = (4.18)
ζ o ( wO,AS pAS − wO,AS pca0 )
m Or (1 − ξ o )
and K co = , (4.19)
ζ o ( wO,ca
0
pca0 − wO,ca
0
pENV )
and also the ratio of the partial pressures of the two gas species as
0 0
nN,AS nN,ca pN0
= = . (4.20)
0
nO,AS (1 − ζ o ) 0
nO,ca pO0
By assuming that nN,AS nO,AS is fixed and equal to that of the normal atmospheric
air at sea level (i.e., 3.76), the partial pressures of nitrogen and oxygen in the cathode
channel can be obtained from the known total pressure of the cathode channel.
Thus, the steady state values of the partial pressures of the gas species at the anode
and the cathode gas channels are derived as functions of the SOFC operating
78
conditions such as the temperature, the anodic and cathodic pressures, the load current,
the FU and the OU. Therefore, for any set of desired operating conditions of the
SOFC, the cell voltage can be obtained by using the Nernst equation (refer to
Appendix B) and the over-voltage relations (refer to Section 3.3.5 of Chapter 3).
Static characteristics of a fuel cell system are used to determine its operating
regime. The partial pressures of the hydrogen and water vapour in the anode channel
are set to obtain desired FU, i.e. pH pW = (1 − ζ f ) ζ f . The OU is set to zero (i.e.,
there is sufficient air flow such that the rate of oxygen consumption in the reactions
can be neglected). This is achieved by setting the partial pressures of nitrogen and
oxygen in the cathode channel in such a way that pN pO is equal to the ratio
0.79 0.21 , which is the same ratio as in the normally available atmospheric air.
We can also get an idea of the values of the inlet and the outlet valve coefficients
which have to be used in the dynamic model for simulating the desired steady state
operation of the SOFC. These can be obtained by substituting the relations for the
reaction mass flow rates of the gas species into Eqs. (4.8–4.9, 4.18–4.19). The
reaction mass flow rates of the gas species are (refer to Section 3.2 in Chapter 3)
iν W M W
r
m W = , (4.21)
1000ne F
iν H M H
m Hr = , (4.22)
1000ne F
iν O M O
and m Or = . (4.23)
1000ne F
The initial partial pressures of the constituent gases, the initial temperatures of the
mixture and the volume of the channels are the input parameters of the C-fields. The
initial masses of the constituent gases are calculated from these inputs by using the
ideal gas law. The initial mass of hydrogen and water vapour in the anode channel and
that of oxygen and nitrogen in the cathode channel are calculated by using the ideal
gas law. For example, the initial mass of hydrogen in the anode channel is given by
79
Chapter 4
pH0 Van
mH0 = , (4.24)
RHTan0
where the value of pH0 is known from the calculations discussed earlier (refer to Eq.
(4.10)) and Tan0 is the desired steady state temperature. The initial masses of other gas
species are similarly calculated.
The initial entropy of the anode channel gas mixture (hydrogen and water vapour)
is calculated as
⎧⎛ T 0 ⎞ mH cv,H + mH RH + mW cv,W + mW RW ⎛ p ref ⎞ mH RH ⎛ p ref ⎞mW RW ⎫

0 0 0 0 0 0
⎪ ⎪
San0 = SHref + S Wref + ln ⎨⎜ an ref ⎟
H
⎜ 0 ⎟
W
⎜ 0 ⎟ ⎬
⎪⎩⎝ Tan ⎠ ⎝ pH ⎠ ⎝ pW ⎠ ⎭⎪
(4.25)
and the initial entropy of the cathode channel gas mixture (oxygen and nitrogen) is
calculated as
⎧⎛ T 0 ⎞mOcv,O + mO RO + mN cv,N + mN RN ⎛ p ref ⎞ mO RO ⎛ p ref ⎞ mN RN ⎫

0 0 0 0 0 0
⎪ ⎪
Sca0 = SOref + S Nref + ln ⎨⎜ caref ⎟ O
⎜ 0 ⎟
N
⎜ 0 ⎟ ⎬ ,(4.26)
⎪⎩⎝ Tca ⎠ ⎝ pO ⎠ ⎝ pN ⎠ ⎪⎭
where the values of all entropies at reference states are obtained from tables [Benson,
1977].
The initial entropy of the element CM representing the thermal capacity of the
MEA is given as
⎛ T0 ⎞
SM0 = SMref + mM cM ln ⎜ Mref ⎟
(4.27)
⎝ TM ⎠
and the initial entropies of the capacitance elements CI1 and CI2 are, respectively,
given as
80
⎛ TI10 ⎞
SI10 = SI1ref + mI1cI1 ln ⎜ ref ⎟ (4.28)
⎝ TI1 ⎠
⎛ TI20 ⎞
and SI20 = SI2ref + mI2cI2 ln ⎜ ref ⎟. (4.29)
⎝ TI2 ⎠
Use of the values of the valve coefficients calculated from Eqs. (4.8–4.9, 4.18–
4.19) in the dynamic model will not result in the exact desired steady state conditions
at the beginning of the simulation due to the influence of unaccounted thermal
dynamics. Therefore, a first phase simulation is run until the transients phase is over,
and the final values of the states are taken as the initial values for the next phase of the
simulation. This next phase simulation is run at a steady state operating mode with the
desired values of the FU and the OU. A step change in the load current is then
imposed in order to study the dynamic response.
4.2.1. Static Characteristics
The simulations were performed using the software SYMBOLS Shakti [Samantaray
& Mukherjee, 2006]. The parameter values used in the simulation are given in Table
4.1. In Fig. 4.1, the polarization and current density curves obtained from the model
are compared with the data from [Aguiar et al., 2004] in which the fuel considered
was CH4 and the fuel composition for obtaining the static characteristic curves was
fully reformed steam and methane mixture. It can be seen that that the difference
between the results is small because the principal gaseous species in the anode
channel are still H2 and H2O, which is a valid assumption used in [Aguiar et al., 2004].
A part of the small difference between the results can also be attributed to the
difference in the calculations of the activation over-voltage between this model and
[Aguiar et al., 2004].
81
Chapter 4
Fig. 4.1: Polarisation and Power Density Curves of the SOFC
Fig. 4.2 shows the reversible cell voltage as a function of the FU with the system
pressure as the parameter. From these curves, it is evident that the reversible cell
voltage decreases with the increase in the FU and also that increasing system pressure
results in increased Nernst voltage. However, this increase is quite small. Moreover,
high-pressure operation may lead to other complications. Therefore, the cell pressure
is kept slightly above the atmospheric pressure. It can also be seen that the reversible
cell voltage drops significantly for FU’s near the value of unity. That is why; a FU of
more than 0.9 is normally not desired [Wang et al., 2007]. On the other hand, a low
FU is economically unviable. These curves agree with similar curves given in
[Singhal & Kendall, 2003].
82
Table 4.1: Parameters Used in the Simulations

Data Description Value Unit
Van Volume of the anode chamber 0.0001 m3
Vca Volume of the cathode chamber 0.0001 m3
Tan0 Initial temperature of anode chamber gases 1073 K
Tca0 Initial temperature of cathode chamber gases 1073 K
0
pH Initial partial pressure of hydrogen 22000 Pa
0
pW Initial partial pressure of water vapour 88000 Pa
0
p N Initial partial pressure of nitrogen 89242.62 Pa
0
pO Initial partial pressure of oxygen 20757.38 Pa
pENV Pressure of environment 100000 Pa
pAS Pressure at air source 120000 Pa
pHS Pressure at hydrogen source 120000 Pa
TENV Temperature of environment 300 K
TAS Temperature of air source 745 K
THS Temperature of hydrogen source 745 K
Ean Activation energy per mole of the anode 110000 J mol-1
Eca Activation energy per mole of the cathode 120000 J mol-1
ψ an Pre-exponential co-efficient for anode 7x109 A m-2
ψ ca Pre-exponential co-efficient for cathode 7x109 A m-2
Rohm Ohmic resistance per unit area 0.2 Ωcm2
R Universal gas constant 8.314 J mol-1 K-1
ne Number of electrons involved in the reaction 4 -
F Faraday’s constant 96493 C mol-1
Ac Cell effective area 0.01 m2
iL Limiting current 1000 A
man Mass of anode solid 0.02950 kg
mca Mass of cathode solid 0.00295 kg
mel Mass of electrolyte solid 0.00118 kg
min Mass of interconnect solid 0.04 kg
can, cca, cel , cI1 Common specific heat capacity of anode, cathode,
500 J kg-1 K-1
& cI2 electrolyte and interconnect
λa Convection heat transfer coefficient in anode channel 2987 J m-2 s-1 K-1
λc Convection heat transfer coefficient in cathode channel 1322.8 J m-2 s-1 K-1
83
Chapter 4
Fig. 4.2: Characteristic Curves Showing the Variation of Nernst Voltage as a Function of FU
The power density and the polarisation curves for a cell operating at 1073K and
1bar with undepleted air (zero OU) and FU of 0.03 are shown in Fig. 4.3, where the
various internal cell voltage losses are also indicated. For the cell under consideration,
it can be seen from Fig. 4.3 that the ohmic and the activation losses are the major
losses while the concentration voltage loss is minimum. Concentration losses cause
the cell potential to drop to zero sharply with a concave curvature at a current density
called the limiting current density [Aguiar et al., 2004]. For the cell and the operating
conditions chosen in this work, no concave curvature is observed as high ohmic and
activation losses cause the cell voltage to drop to zero much before the limiting
current density ( jL = 10 A/cm 2 ) is reached.
Fig. 4.3: The Polarisation Curve Showing the Contribution of Various Voltage Losses
84
The power density and polarisation curves for a cell operating at 1bar with
undepleted air and FU of 0.03 and with the operating temperature as a parameter are
shown in Fig. 4.4a. At very low current densities, the cell voltage is almost equal to
the reversible Nernst voltage. Thus at zero current density, the cell potential is higher
for lower operating temperatures. At about 0.05 Acm-2, the curves cross and the trend
is reversed (refer to Fig. 4.4b). This trend is also reported in [Petruzzi et al., 2003].
This is because of the fact that at higher current densities, the polarisation losses are
significant and they decrease with increase in the cell operating temperature. Thus,
higher operating temperatures for the cell are preferred. It can also be seen that the
power densities increase with the increase in the cell operating temperature.
(a) (b)
Fig. 4.4: (a) Polarisation and Power Density Curves for Different Cell Operating Temperatures and (b)
an Enlarged Version Showing the Voltage Curves at Lower Current Densities
The power density and polarisation curves for a cell operating at 1bar and 1073K,
with undepleted air and with the FU as a parameter, are shown in Fig. 4.5. It can be
concluded from Fig. 4.5 that increase in the FU results in decrease in the cell voltage
and power density. This is primarily due to the fall in the Nernst voltage caused by the
decrease in the hydrogen partial pressure. These curves (Figs. 4.3, 4.4 and 4.5) are in
agreement with those given in [Aguiar et al., 2004].
85
Chapter 4
Fig. 4.5: Polarisation and Power Density Curves for Different values of FU
4.2.2. Selection of the Operating Regime
Fuel cells are normally designed to operate at a cell voltage between 0.6 V and 0.7 V
because this operating range gives a good compromise between the cell efficiency, the
power density, the operating cost (FU) and stable operation. It further avoids possible
anode oxidation at low cell voltage [Chan et al., 2001]. It may not be beneficial to
operate the fuel cell at the operating point corresponding to maximum power density
as the cell voltage becomes low (about 0.5V). With reference to Fig. 4.3, the ideal
operating range of the current densities is from 1.2 Acm-2 (at 0.7V) to 1.6 Acm-2 (at
0.6V) and the corresponding range of power densities is from 0.8 Wcm-2 to 0.92
Wcm-2.
4.2.3. Dynamic Response
The dynamic response of the fuel cell to a step change in the load current is shown in
Fig. 4.6. The dynamic response study helps us in understanding the various physical
processes involved in the functioning of the fuel cell and ultimately guides us in
developing efficient control strategies to the improve SOFC system’s load following
capability.
86
The valve coefficients for the four valves are fixed at the values given by Eqs.
(4.8–4.9, 4.18–4.19) to obtain the open-loop dynamic response of the SOFC. Step
changes are made in the load current from 100A to 80A at 500s and from 80A to 90A
at 2000s. The dynamic responses of the cell voltage, current, FU and OU to the step
changes of load current, the data being normalised with respect to the initial steady
state conditions (Voltage = 0.609036 V, Current = 100 A, FU = 0.8 and OU = 0.125),
are shown in Fig. 4.6a.
When the current is decreased, the combined effect of the changes in the partial
pressures and the polarization losses results in the increase of the cell voltage. It is
observed that the cell voltage initially overshoots before settling to a steady state
value. This overshoot in the cell voltage was also reported in [Achenbach, 1995; Qi et
al., 2006]. The FU and the OU, which are proportional to the current, also decrease.
The reverse phenomena are observed with the increase in the external load current.
The sudden decrease in the load current results in the decrease in the rate of
hydrogen and oxygen consumption and the rate of water vapour formation. In other
words, the reaction rate decreases. This results in the accumulation of hydrogen and
oxygen in the chambers and hence their partial pressures increase almost abruptly. At
the same time, the partial pressure of water vapour falls, as shown in Fig. 4.6b. The
decrease in the current also results in the decrease in the polarization losses and the
decrease in the reaction entropy flow rate ( Sr ) (due to reduced mass flow rates) and
thereby results in the fall of the system temperature. The reverse phenomena are
observed (at t = 2000 s in Fig. 4.6) when the load current density is increased.
It can be seen from Fig. 4.6b that the hydraulic (pressure) dynamics is much faster
than the thermal (temperature) dynamics. This was also observed in the results of
[Murshed et al., 2007; Qi et al., 2006]. Although the entropy flow due to the ohmic
losses and the reaction are directly proportional to the current, the entropy flow due to
the activation and concentration losses depend upon the gas species partial pressures.
Therefore, the change in the heat production does not happen instantaneously with the
change in the current. Further, the solid components of the SOFC have high thermal
capacities. Due to these reasons, it usually takes a long time (in the order of several
87
Chapter 4
minutes [Achenbach, 1995; Mueller et al., 2006; Murshed et al., 2007; Qi et al.,
2006]) for the cell temperature to settle down to a steady state value after a
disturbance. On the other hand, the pressure dynamics is faster due to the reason that
the changes in the inlet and outlet mass flow rates are fast (only the small time delay
associated with valve actuation, which is not modelled in this work, can affect it).
(a) (b)
Fig. 4.6: Dynamic Response Curves for (a) Voltage, Current, FU and OU Normalised to their Initial
Values and (b) Species Partial Pressures and Cell Temperature
Note that the dynamic characteristics are useful in the feedback control of the fuel
cell. The static and dynamic characteristics presented in this section show that the
model produces comparable results to various published researches [Achenbach,
1995; Aguiar et al., 2004; Chan et al., 2001; Mueller et al., 2006; Petruzzi et al.,
2003; Qi et al., 2006; Singhal & Kendall, 2003] and it captures all the essential
dynamics of the SOFC system.
4.3. Detailed Bond Graph Model for Dynamic Simulation
The true bond graph model discussed in Chapter 3 is further improved in this section
to account for certain un-modelled dynamics. These improvements shown in Fig. 4.7
include more detailed representation of the concentration over-voltage, inclusion of
88
the conduction and radiation heat transfer effects in the cell and representation of the
flow resistance by isentropic nozzle flow equation rather than a linear flow relation.
Fig. 4.7: True Bond Graph Model of the Closed-Loop SOFC System
The MEA solid is represented by three control volumes; one each for the anode,
the cathode and the electrolyte. The temperatures of the solid anode, cathode and
electrolyte control volumes are represented by the junctions ‘0an,s’, ‘0ca,s’ and ‘0el’,
respectively.
It is assumed that the entropy generated due to the ohmic resistance is added to the
solid electrolyte. The ohmic resistance is modelled by the resistive field RSO between
the 1i junction and the 0el-junction in Fig. 4.7. The inputs to this field are the current
( i ) and the electrolyte temperature ( Tel ). The outputs are the over-voltage ( ηohm ) and
the entropy flow rate ( Sel ), which are calculated as
89
Chapter 4
ηohm = iRohm (4.30)
i 2 Rohm
and Sel = . (4.31)
Tel
The concentration over-voltage is represented in more detail in the improved

model as follows. The concentration over-voltage is given in terms of the partial
pressures of the gas species at the flow bulk and at the TPB as (refer to Section 3.3.5
in Chapter 3)
⎛ pνW,b
W
⎞ ⎛ pνW,TPB
W
⎞
ηconc = − RT ln ⎜ ν H ν O
⎜p p ⎟⎟ + RT ln ⎜⎜ ν H νO ⎟⎟ , (4.32)
⎝ H,b O,b ⎠ ⎝ pH,TPB pO,TPB ⎠
which can be rearranged to separate out the anodic and cathodic contributions as
⎛ pνO,b
O
⎞ ⎛ pνH,b
H
pνW,TPB
W
⎞
ηconc = ηconc,an + ηconc,ca = RT ln ⎜⎜ νO ⎟⎟ + R T ln ⎜⎜ ν W ν H ⎟⎟ . (4.33)
⎝ pO,TPB ⎠ ⎝ pW,b pH,TPB ⎠
The values of the stoichiometric coefficients and ne are substituted in Eq. (4.33) to
yield [Aguiar et al., 2004],
RTan ⎛ pW,TPB pH,b ⎞

ηconc,an = ln ⎜ ⎟, (4.34)
2 F ⎜⎝ pW,b pH,TPB ⎟⎠
RTca ⎛ pO,b ⎞
and ηconc,ca = ln ⎜ ⎟. (4.35)
4 F ⎜⎝ pO,TPB ⎟⎠
The partial pressures of the gas species at the TPB are calculated as follows [Chan
et al., 2001; Kim et al., 1999; Virkar et al., 2000; Zhu & Kee, 2003]. At steady state,
the fluxes (J) of the reactants (hydrogen and oxygen) and the product (water vapour)
through the electrodes are related to the current (refer to Section 3.2 of Chapter 3) as
follows.
i
−JH = 2JO = − J W = . (4.36)
2F
90
Equimolar counter current diffusion of hydrogen and water vapour takes place in
the anode. For one dimensional diffusion, the hydrogen flux is given by [Chan et al.,
2001]
dcH
J H = − Deff,an . (4.37)
dx
As dcH = dp H RTan , Eq. (4.37) becomes
i dp H
= Deff,an . (4.38)
2F RTan dx
Integration of Eq. (4.38) yields
RTanτ an i
pH,TPB = pH,b − . (4.39)
2 FDeff,an
Therefore the partial pressure of hydrogen at the TPB can be calculated by using
Eq. (4.39). The second term on the right hand side of Eq. (4.39) represents the
pressure loss due to the limitations imposed by the diffusion process and is
responsible for the loss in the cell voltage. Similarly, the partial pressure of water
vapour at the TPB can be obtained as
RTanτ an i
pW,TPB = pW,b − . (4.40)
2 FDeff,an
On the cathode side, the nitrogen flux is zero. The oxygen flux is given by [Chan
et al., 2000]
dcO pO,TPBδ O J O
J O = − Deff,ca + . (4.41)
dx pca
As dcO = dpO RTca , Eq. (4.41) becomes
i dpO p δ i
= − Deff,ca + O,TPB O . (4.42)
4F RTca dx 4 Fpca
91
Chapter 4
Integration of Eq. (4.42) and substitution of δ O = 1 gives the expression for the
partial pressure of oxygen at the TPB as
⎛ RTcaτ ca i ⎞
pO,TPB = pca − ( pca − pO,b ) exp ⎜ ⎟⎟ . (4.43)
⎜ 4 FD p
⎝ eff,ca ca ⎠
The activation and the concentration over-voltages at the anode are modelled by
the resistive field element RSan
A,C between the 1i-junction and the 0an,s-junction in Fig.
4.7. The inputs to the resistive field are the current and the anode temperature. In
addition, this element is modulated with the signals of gas species partial pressures.
These signal bonds are not shown in the figure for maintaining the visual clarity. The
outputs of the field are the total anodic over-voltage (ηan ) and the entropy generated
( Sact,conc,an ) due to the anodic over-voltages. The anodic over-voltage is given as
ηan = ηact,an + ηconc,an . (4.44)
The entropy flow rate is obtained from the energy balance by assuming that all the
energy dissipated by the activation and the concentration losses is converted into heat.
From the energy balance, we get
Sact,conc,anTan,s = ηact,an i + ηconc,an i . (4.45)
Substitution of the expressions for ηact,an and ηconc,an from Eq. (3.48) and Eq.
(4.34), respectively, into Eq. (4.45) yields
2iR ⎛ i ⎞ iRTan ⎛p p ⎞
Sact,conc,an = sinh -1 ⎜ ⎟⎟ + ln ⎜ W,TPB H,b ⎟ . (4.46)
⎜ 2i ⎜ ⎟
ne F ⎝ 0,a ⎠ 2 FTan,s ⎝ pW,b pH,TPB ⎠
Similarly, the activation and the concentration over-voltages at the cathode are
modelled by the resistive field element between the 1i-junction and the 0ca,s-junction
in Fig. 4.7, where the 0ca,s-junction represents the common temperature of the cathode
solid. The constitutive relations of this field are given as
92
ηca = ηact,ca + ηconc,ca , (4.47)
2iR ⎛ i ⎞ iRTca ⎛ p ⎞
and Sact,conc,ca = sinh -1 ⎜ ⎟ + ln ⎜ O,b ⎟ . (4.48)
ne F ⎜ 2i ⎟ 4 FT ⎜p ⎟
⎝ 0,c ⎠ ca,s ⎝ O,TPB ⎠
The conduction heat transfers inside the MEA are included in the improved model
and are represented by the two-port field elements Rcd1 and Rcd2 as shown in Fig. 4.7.
The constitutive relations of the R-field element Rcd1 are given as
kM Ac (Tel − Tan,s )
Scd1,el = (4.49)
τ MTel
kM Ac (Tel − Tan,s )
and Scd1,an,s = , (4.50)
τ MTan,s
where Scd1,el and Scd1,an,s are the entropy flow rates at the electrolyte and the solid
anode sides, respectively. The constitutive relations of the R-field element Rcd2 are
similar.
As the SOFC operates at high temperatures, thermal radiation is a significant

mode of heat transfer [Murshed et al., 2007]. The radiation heat transfer between the
solid anode and the interconnect is modelled by the field element Rrd1 and that
between the solid cathode and the interconnect is modelled in Fig. 4.7 by the field
element Rrd2. The constitutive relations of the field element Rrd1 are given as
( σ Ac Tan,s ) (Tan,s
4
− TI14 )
Srd1,an,s = (4.51)
( (1/ ε ) + (1/ ε ) − 1)
an in
(σ Ac TI1 ) (Tan,s4
− TI14 )
and Srd1,I1 = , (4.52)
( (1/ ε an ) + (1/ ε in ) − 1)
where Srd1,an,s and Srd1,I1 are the entropy flow rates at the solid anode and the
interconnect sides, respectively. The constitutive relations of the R-field element Rrd2
are similar.
93
Chapter 4
The mass flow rates through the valve resistances are given by the isentropic
nozzle flow equations. The overall mass flow rate of the gas mixture is given by the
formulae for the mass flow through an isentropic nozzle [Karnopp et al., 2006] as
2γ (γ +1) γ
pu 2γ ⎛ pd ⎞ ⎛p ⎞
m = A ( x ) ⎜ ⎟ −⎜ d ⎟ . (4.53)
Tu R (γ − 1) ⎝ pu ⎠ ⎝ pu ⎠
where the valve areas are given by A ( x ) = Ax by assuming linear valve characteristic,
i.e. the coefficient of discharge varies linearly with the valve stem displacement. Such
a relation has been used for modelling flow through valves in a fuel cell system and in
other process engineering systems in the literature [Caux et al., 2005; Pukrushpan et
al., 2002; Thomas, 1999; Yu et al., 2005].
4.4. Model Validation and Control Strategy Formulation
In this section, the true bond graph model of the SOFC, to which the changes detailed
in Section 4.3 are incorporated, is validated by comparing its characteristic curves
with those of [Aguiar et al., 2004]. Also, a physical model-based control strategy is
formulated for improving the dynamic performance of the SOFC during a load change.
The parameters used for simulating the detailed model shown in Fig. 4.7, other than
those given in Table 4.1, are given in Table 4.2.
Table 4.2: Parameters Used in the Simulations of the Detailed Model

Data Description Value Unit
σ Boltzman constant 5.6704x10-8 J m-2 s-1K-4
ε an , ε ca , ε in Emissivity constants of anode, cathode and interconnect 0.9 -
Deff,an Anode diffusion coefficient 3.66x10-5 m2 s-1
Deff,ca Cathode diffusion coefficient 1.37x10-5 m2 s-1
KP PI controller proportional gain -3.44e-7 K-1
KI PI controller integral gain -1e-8 K-1 s-1
kM MEA thermal conductivity 2 J m-1 s-1 K-1
τ an Anode thickness 500 x10-6 m
τ ca Cathode thickness 50 x10-6 m
τ el Electrolyte thickness 20 x10-6 m
τ in Interconnect thickness 500 x10-6 m
94
The comparison between the polarization and the power density curves from the
developed model and from the literature [Aguiar et al., 2004] is shown in Fig. 4.8. It
is evident from the Fig. 4.8 that there is good agreement between the characteristic
curves obtained from the improved bond graph model and those from [Aguiar et al.,
2004]. This agreement is better than the one shown in Fig. 4.1, which can be
attributed to the more detailed representation of the concentration over-voltage in the
improved model.
Fig. 4.8: Comparison of characteristic Curves of the Improved Model with Data from Literature
The compliance elements and the compliance fields in the improved model of the
SOFC are also initialized in the same manner as was discussed in Section 4.2. The
mass balances for individual gas species are written so as to obtain the values of the
valve displacements which will give desired steady state operation of the SOFC. The
steady state mass balances in the anode channel are given by the Eqs. (4.1–4.3). The
gas species inlet and outlet mass flow rates are given by the isentropic nozzle flow
equations as
2 γH ( γ H +1) γ H
xai Aai pHS 2γ H ⎛ pan0 ⎞ ⎛ pan0 ⎞
m =
i
⎜ ⎟ −⎜ ⎟ , (4.54)
R (γ H − 1) ⎝ pHS ⎠
H
THS ⎝ pHS ⎠
95
Chapter 4
2 γ an ( γ an +1) γ an
0
wH,an Aao xao pan0 2γ an ⎛ pENV ⎞ ⎛p ⎞
m =
0
⎜ ⎟ − ⎜ ENV
0 ⎟
, (4.55)
R (γ an − 1) ⎝ pan0 ⎠
H
Tan0 ⎝ pan ⎠
0
wW,an Aao xao pan0 2γ an ⎛ pENV ⎞ ⎛p ⎞
and m =
0
⎜ ⎟ − ⎜ ENV
0 ⎟
. (4.56)
R(γ an − 1) ⎝ pan0 ⎠
W
Tan0 ⎝ pan ⎠
In a procedure similar to that followed in Section 4.2, the anode chamber inlet and
outlet valve displacements required for obtaining a steady state operation with the
desired FU and OU are obtained from the mass balance equations, respectively, as
m Hr
xai = (4.57)
2 γH ( γ H +1) γ H
ζ f Aai pHS 2γ H ⎛ p ⎞ 0
⎛ p ⎞ 0
⎜ ⎟
an
−⎜ ⎟
an
THS R (γ H − 1) ⎝ pHS ⎠ ⎝ pHS ⎠
m Wr
and xao = , (4.58)
w 0
Aao p 0
2γ an ⎛ pENV ⎞ ⎛p ⎞
W,an an
⎜ ⎟ − ⎜ ENV
0 ⎟
Tan0 R(γ an − 1) ⎝ pan0 ⎠ ⎝ pan ⎠
subject to the condition that
0
nH,an pH0 1 − ζ f
= = . (4.59)
0
nW,an 0
pW ζf
The steady state mass balances in the cathode channel are given by the Eqs. (4.11–
4.13). The gas species inlet and outlet mass flow rates are given by the isentropic
nozzle flow equations as
2 γ air ( γ air +1) γ air

wO,AS Aci xci pAS 2γ air ⎛ pca0 ⎞ ⎛ p0 ⎞
m = i
⎜ ⎟ − ⎜ ca ⎟ , (4.60)
R(γ air − 1) ⎝ pAS ⎠
O
TAS ⎝ pAS ⎠

wN,AS Aci xci pAS 2γ air ⎛ pca0 ⎞ ⎛ p0 ⎞
m =i
⎜ ⎟ − ⎜ ca ⎟ , (4.61)
R(γ air − 1) ⎝ pAS ⎠
N
TAS ⎝ pAS ⎠
96

0
wO,ca Aco xco pca0 2γ air ⎛ pENV ⎞ ⎛p ⎞
m =o
⎜ ⎟ − ⎜ ENV
0 ⎟
, (4.62)
R(γ air − 1) ⎝ pca0 ⎠
O
Tca0 ⎝ pca ⎠

0
wN,ca Aco xco pca0 2γ air ⎛ pENV ⎞ ⎛p ⎞
and m =
o
⎜ ⎟ − ⎜ ENV
0 ⎟
. (4.63)
R(γ air − 1) ⎝ pca0 ⎠
N
Tca0 ⎝ pca ⎠
The cathode chamber inlet and outlet valve displacements required for obtaining a
steady state operation with the desired FU and OU are obtained from the cathode
channel mass balance equations as
m Or
xci = (4.64)
ζ o wO,AS Aci pAS 2γ air ⎛ p ⎞ 0
⎛ p ⎞
0
⎜ ⎟
ca
−⎜ ca
⎟
TAS R(γ air − 1) ⎝ pAS ⎠ ⎝ pAS ⎠
and xco =
(1 − ζ o ) × m Or , (4.65)
ζ o wO,ca
0
Aco pca0 2γ air ⎛ pENV ⎞ ⎛p ⎞
⎜ ⎟ − ⎜ ENV
0 ⎟
Tca0 R(γ air − 1) ⎝ pca0 ⎠ ⎝ pca ⎠
subject to the condition that
0 0
nN,AS nN,ca pN0
= = . (4.66)
0
nO,AS (1 − ζ o ) 0
nO,ca pO0
The valve displacements of the two inlet and the two outlet valves are set
according to the Eqs. (4.57–4.58, 4.64–4.65) and the C-fields are initialized by using
the partial pressures of the gas species in the anode and the cathode channel according
to Eqs. (4.59) and (4.66) so as to obtain a steady state operation of the SOFC with the
desired FU and OU. Also, the compliance elements representing the capacities of the
solids are initialized properly. Even with these initializations, the system response will
exhibit small transients due to the thermal dynamics. A first phase simulation is run
until the transients phase is over, and the final values of the states are taken as the
initial values for the next phase of the simulation. This next phase simulation is run at
97
Chapter 4
a steady state operating mode with the desired values of the FU and the OU. A step
change in the load current is then imposed in order to study the dynamic response.
The motivation for the proposed control strategy in order to achieve the control
objectives comes from Eqs. (4.57–4.58) and Eqs. (4.64–4.65). If the temperature is
assumed to be constant, it is evident that the valve displacements given in these
equations are only functions of the current density. This means that if all the valve
displacements are varied proportionally to the current (in the case of a change in load
current) then the steady state operation with the desired values of OU, FU and channel
pressures will be maintained. Note that the reaction mass flow rates are functions of
current only. But the temperature of the gases in the channels will not remain constant,
i.e., they would vary from their initial steady state values when the load current
changes. Hence, it is necessary to measure both the chamber gas temperatures. The
control strategy proposed in this work consists of a primary controller, which
simultaneously controls the four valves by varying their valve displacements in order
to maintain constant FU and OU.
However, the above-mentioned control action does not ensure constant cell
temperature. The usual method followed in literature [Aguiar et al., 2005] for
controlling the SOFC temperature is the manipulation of the excess air supplied to the
cell. This method is also adopted in this work to maintain a constant temperature of
the SOFC despite load changes. For this purpose, a secondary PI temperature
controller, which manipulates the air ratio around the value set by the primary
controller, is added. According to [Aguiar et al., 2005], the maximum and minimum
limits of the OU are set as 0.5 and 0.07, respectively. The cathode chamber gas
temperature is compared with the set point value of the temperature and the objective
of the PI controller is to reduce the temperature error signal by manipulating the flow
through cathode chamber inlet and outlet valves by means of varying their valve
displacements. It is assumed that the economic cost of increased airflow is
insignificant with respect to other operational costs.
The outputs of the primary controller are the four valve displacements, which are
given as
98
iν H M H
xai = , (4.67)
2 γH ( γ H +1) γ H
ζ f Aai ne FpHS 2γ H ⎛ pan0 ⎞ ⎛ p0 ⎞
⎜ ⎟ − ⎜ an ⎟
THS R(γ H − 1) ⎝ pHS ⎠ ⎝ pHS ⎠
iν W M W
xao = , (4.68)
0
1000wW,an Aao ne Fpan0 2γ an ⎛ pENV ⎞ ⎛p ⎞
⎜ ⎟ − ⎜ ENV
0 ⎟
Tan R(γ an − 1) ⎝ pan0 ⎠ ⎝ pan ⎠
iν O M O
xci1 = (4.69)
1000ζ o wO,AS Aci ne FpAS 2γ air ⎛ p ⎞ 0
⎛ p ⎞0
⎜ ⎟
ca
−⎜ ca
⎟
TAS R (γ air − 1) ⎝ pAS ⎠ ⎝ pAS ⎠
and 1
xco =
(1 − ζ o ) iν O M O . (4.70)
1000w 0
ζ o Aco ne Fp 0
2γ air ⎛ pENV ⎞ ⎛p ⎞
O,ca ca
⎜ ⎟ − ⎜ ENV
0 ⎟
Tca R(γ air − 1) ⎝ pca0 ⎠ ⎝ pca ⎠
The secondary controller acts only on the cathode inlet and outlet valves by means
of manipulating their valve displacements ( xci and xco ) in order to vary the OU. The
modified expression for the cathode inlet valve displacement is given by the sum of
the displacements due to the primary controller ( xci1 given by Eq. (4.69)) and the
output of the PI controller. Note that the PI controller proportional and the integral
gains are negative values in Table 4.2. This is because the error input of the PI
controller is defined as the difference between the reference or set point temperature
and the cathode channel gas temperature (refer to Fig. 4.7). Therefore, a positive
value for the error means that the cell temperature is less than the controller set point
temperature. In order to increase the temperature of the cell, the air flow rate should
be decreased which requires that the cathode inlet valve displacement should also be
reduced. The negative values of the proportional and the integral gains make the
output of the PI controller denoted by xci2 (refer to Fig. 4.7) negative thereby
decreasing the overall cathode channel inlet valve displacement ( xci ). The controller
works in the opposite way when the cell temperature becomes more than the set point
temperature.
99
Chapter 4
Once the cathode inlet valve displacement has been changed, the cathode outlet
valve displacement given by Eq. (4.70) is no longer valid. It becomes necessary to
obtain a modified expression for the cathode outlet valve displacement, which along
with the modified cathode inlet valve displacement will satisfy the mass balance
equations given in Eqs. (4.1–4.3) and (4.11–4.13), thereby giving the desired pressure
and OU. The relation between xci and xco , subject to the constraints of the mass
balance equations, can be obtained by equating the ζ o ’s in Eq. (4.64) and Eq. (4.65).
From this relation, the modified formulae to calculate the cathode outlet valve
displacement is given by

Aci pAS 2γ air ⎛ pca0 ⎞ ⎛ p0 ⎞ iν O M O r
xci wO,AS ⎜ ⎟ − ⎜ ca ⎟ − m O
TAS R(γ air − 1) ⎝ pAS ⎠ ⎝ pAS ⎠ 1000ne F
xco = .(4.71)
0
Aco p 2γ air ⎛ pENV ⎞ ⎛p ⎞
0
wO,ca ca
⎜ ⎟ − ⎜ ENV
0 ⎟
Tca R (γ air − 1) ⎝ pca0 ⎠ ⎝ pca ⎠
Note that the measured value of xci must be used in the above expression (i.e., the
total valve displacement of the primary and the secondary controllers). The block
diagram of the above control strategy, with both the primary and secondary
controllers, is shown in the model given earlier in Fig. 4.7, where the outputs of the
blocks FC1, FC2, FC3 and FC4 are given by Eqs. (4.67), (4.68), (4.69) and (4.71),
respectively.
4.5. Open and Closed Loop Dynamic Responses
The dynamic response of the fuel cell to a step change in the load current with and
without the control system is discussed in this section. The open loop dynamic
responses of the gas species partial pressures, the pressure difference between the
cathode and the anode gas chambers and the temperature to the step changes in load
current are shown in Fig. 4.9a. In order to show the details of the transients, the same
curves are shown with a smaller time scale in Fig. 4.9b. The dynamic responses of the
cell voltage, current, the FU and the OU to the step changes of load current are shown
100
in Fig. 4.10, the data being normalized with respect to the initial steady state
conditions (Voltage = 0.602663 V, Current = 100 A, FU = 0.8 and OU = 0.125).
All the dynamic system responses are very similar to the ones given in Section
4.2.3 with small changes in the steady state values. The transient thermal response is
similar for both the cases with nearly the same time constants. The voltage responses
are also similar with both cases exhibiting the characteristic over-shoot. However, the
dynamic pressure responses of the improved model shown in Fig. 4.9 has a larger
time constant as compared to that shown in Fig. 4.6b. This is due to the nonlinear
relation used to model the valve flow resistance in the improved model. Because of
this pressure dynamics, the FU and OU responses also exhibit increased response
times as shown in Fig. 4.10. The simulation time requirement (computational cost) for
the improved model is much larger than that of the model described in Section 3.4.2
of Chapter 3.
(a) (b)
Fig. 4.9: Dynamic Pressure and Temperature Responses of the Open-Loop SOFC System
Comparing the temperature response in Fig. 4.6b and Fig. 4.9, it can be concluded
that there is negligible change in both the steady state values and the response times.
The inclusion of the radiation heat transfer effects has only resulted in many fold
increase in the simulation time (computational load) without significantly changing
the dynamic response. Therefore, in future analyses, the radiation heat transfer is not
considered.
101
Chapter 4
Fig. 4.10: Dynamic Voltage, OU and FU Responses of the Open-Loop SOFC System
The dynamic responses of the fuel cell with only the primary controller (i.e.,
without the PI temperature controller) to the same step changes in the load current are
shown Fig. 4.11. As the load current changes from 100A to 80A, the increase in the
cell voltage is less than that observed in the previous case. The FU and the OU are
maintained at their steady state values as the fuel flow and the airflow are manipulated
by the controller. There is a very little change in the partial pressures of the reactants
and the product as shown in Fig. 4.11b. The temperature of the cathode chamber
gases decreases from 1073K to 1056K. The voltage increase in this case can be
attributed partly to the temperature change (however, this part is very small) and
partly to the decrease in the cell losses due to the lower current density. It can be seen
that the pressure difference between the anode and the cathode chambers is
maintained at zero. The reverse phenomena are observed with an increase in the
external load current.
102
(a) (b)
Fig. 4.11: Dynamic Closed Loop Responses of the SOFC with Only the Primary Controller
The dynamic response of the fully controlled fuel cell (i.e. with the primary and
the secondary controllers) to the same step changes in the load is shown in Fig. 4.12.
As the load current changes from 100A to 80A, there is an increase in the cell voltage.
The FU is maintained at its initial steady state value. The OU is varied by the
controller so as to bring back the cell temperature to the initial steady state value.
There is a very little change in the partial pressures of the reactants and the product, as
can be seen from Fig. 4.12b. The voltage increase in this case can be attributed to the
decrease in the cell losses due to the lower current density. However, the pressure
difference between the anode and the cathode chambers is not zero (62 Pa). The
0 0
reason for this increase can be understood from Eq. (4.66). The term nN,AS nO,AS is
constant and pN pO varies with the variation in the OU ( ζ o ). The reverse
phenomena are observed with an increase in the external load current.
From these results, it is evident that the temperature and the pressure control
requirements are conflicting and some trade off between them may be required. The
maximum allowable pressure difference value depends on the membrane support and
the age of the fuel cell [Serra et al., 2005]. In the considered design, the pressure
difference, obtained from the simulations (62 Pa) is small. If, in some case, the
pressure difference turns out to be large enough then a third controller which resets
the temperature set point of the PI controller when the chamber pressure crosses a
certain limit may be added in order to retain the pressure difference within the
103
Chapter 4
allowable limits. Additionally, the temperature control can also be accomplished by

varying the temperature of the input fuel and the air by means of external heat
exchangers. However, these aspects are not studied in this work.
(a) (b)
Fig. 4.12. Dynamic Closed Loop Responses of the SOFC with both the Primary and the Secondary Controllers
The computer simulation results show that the proposed control strategy satisfies
the control objectives and can be treated as a promising candidate for online
implementation.
4.6. Conclusions
In this chapter, the true bond graph model presented in the last chapter is properly
initialized and simulations are performed to obtain the static and the dynamic
characteristics of the SOFC. For obtaining the static characteristic curves of the
SOFC, the FU and the OU have been interpreted in terms of the partial pressures of
the gas species in the channels, for a given set of known and input parameters. In
order to study the transient response characteristics, the model is subjected to step
changes in the load current. A number of static characteristic curves for the SOFC
104
have been obtained. These curves are used to determine the operating regime of the
SOFC. The polarisation and power density curves obtained from the model are found
to agree with the data from the literature. From the results, it is found that the
developed model satisfactorily captures all the essential dynamics of the SOFC. The
physical explanations for the behaviour of the various dynamic responses are given.
Certain further improvements relating to the conduction and radiation effects in

the cell, the flow of the reactants and products, and the diffusion of the reactants and
the products through the electrodes are incorporated into the model. This revised
model is then used for control system synthesis. A physical model-based control
strategy for the SOFC which requires simultaneous control of all the four valves (two
inlet and two exhaust valves) is developed. From the simulations it is concluded that
all the control objectives involving the constraints on the FU, the OU, the cell
operating temperature and the pressure difference between the anode and the cathode
channels are achieved by the proposed control system. It is also shown that the
temperature and the pressure control objectives are conflicting requirements and some
trade off may be required between them in practice.
105
Chapter 4
106
Chapter 5
Optimisation of Operational Efficiency
Under Varying Loads
5.1. Introduction
One of the main advantages of a fuel cell system is its high-energy conversion
efficiency as compared to other conventional power sources. The efficiency of the
fuel cell system depends upon the operating conditions of the cell, which is
determined by the inputs to the system. The models of the SOFC system available in
the literature are either too simple or too detailed and hence cannot be satisfactorily
used for optimization purposes. There is a lack of a comprehensive static model of the
fuel cell system that can calculate the states of the system given the inputs so that it
can be used for system optimization studies.
Chapter 5
An SOFC system is expected to operate under varying load conditions. This raises
a question as to how to control the operating conditions of the cell to achieve
maximum efficiency for all load current densities. This work aims to investigate the
optimal operating conditions of an SOFC system that will result in the maximum
energy and exergy efficiencies. For this purpose, a comprehensive steady state model
of the fuel cell is derived in this chapter from the true bond graph model of the SOFC
presented in Section 3.4.2 of Chapter 3. This steady state model can be used to
calculate the steady state values of variables such as voltage, partial pressures of the
gas species in the anode and cathode channels, temperatures of the solids and the
gases, the reaction and the outlet mass flow rates of the gas species, the fuel and the
oxygen utilizations, power and the energy and exergy efficiencies from the inputs
specified in terms of the cathode and anode inlet mass flow rates and the current
drawn by the load. The cell stack, which has the highest irreversibility as compared to
other system components, makes the prime contribution to the overall exergetic cost
in a fuel cell system. Moreover, unlike other system components, the irreversibilities
of the stack are highly dependent on the current density because the activation and the
ohmic over-voltages increase with the current density. As the true bond graph model
given in Chapter 3 (from which the steady state model of the SOFC is derived) is
developed from the second law analysis, it includes the contributions of the cell
irreversibilities to the system’s dynamics.
In a hydrogen-fed SOFC system, the anode and the cathode outlet gases go to an
after-burner, where all the remaining hydrogen is combusted, from where they pass
through two pre-heaters which are used for heating the inlet hydrogen and air streams.
Thus, the temperatures of the anode and the cathode inlet streams are not independent
variables in a fuel cell system; they depend upon the fuel cell outlet gas temperatures
and mass flow rates. In order to introduce this dependency, the after-burner and the
pre-heater models have to be included in the efficiency analysis.
A schematic representation of the SOFC system considered for this study is shown
in Fig. 5.1. The exhaust gases from the anode and the cathode sides are fed to an after-
burner where all the remaining hydrogen is combusted. The exhaust gases from the
after-burner first pass through a hydrogen heat exchanger, HX1, where they lose some
108
Optimisation of Operational Efficiency Under Varying Loads
of their heat energy to the fuel cell inlet hydrogen stream and then they enter an air
heat exchanger, HX2, where they heat up the fuel cell inlet air and are then released
into the atmosphere.
Fig. 5.1: A Schematic of the SOFC System Considered in This Work
Commercializing the SOFC requires efficient control systems for maximizing the
fuel efficiency of the system. Maximizing the operating efficiency of the SOFC under
varying load conditions and achieving smooth operation during load changes are
important issues in SOFC system control. Research on such issues is being actively
pursued ( [Aguiar et al., 2005; Golbert & Lewin, 2007; Hasikos et al., 2009; Mueller
et al., 2006; Stiller et al., 2006]). The former is achieved through complex control
methods like model predictive control whereas the latter is usually achieved by
maintaining a constant fuel concentration within the cell. However, the implications
of maintaining constant FU on the efficiency of the SOFC system have not been
investigated so far.
In this work, an algorithm, which uses the comprehensive steady state model of
the SOFC system in order to determine the cell operating conditions and control laws
corresponding to the maximum system efficiency, is developed. In the literature
[Aguiar et al., 2005; Mueller et al., 2006; Singhal & Kendall, 2003; Stiller et al.,
2006], maintaining constant FU and constant cell temperature is advocated as the
109
Chapter 5
desirable operating condition for an SOFC. Constant FU operation of the fuel cell is
recommended because it minimises the dynamics during load changes [Mueller et al.,
2006] and also avoids uneven distribution of voltage and temperature within the cell
[Stiller et al., 2006]. The constant temperature operation is recommended in order to
avoid thermal cracking [Stiller et al., 2006]. However, the implications of maintaining
these operating conditions on the efficiency of the SOFC system have not been
investigated in any work. This analysis is carried out in this chapter by comparing the
dynamic responses of the SOFC system operated with three different control
strategies: (1) maximum efficiency operation, (2) a suitably chosen constant FU
operation, which approximates the maximum efficiency operation and (3) constant
FU and constant cell-temperature operation.
5.2. Steady State Model of the SOFC System
In this section, the steady state model of the SOFC is obtained from the previously
developed true bond graph model. The differential equations representing the SOFC
are written down from the bond graph. The steady state model which is derived from
the dynamic model is discussed in detail. The formulations of the steady state models
of the after-burner and the heat exchangers are also given.
5.2.1. The Dynamic Equations of the SOFC Bond Graph

Model
The differential equations obtained from the previously developed true bond graph
model, which represent the dynamics of the SOFC system, will be used in this section.
The improvements incorporated into the model in chapter 4 produce only small
changes in the system steady states and in the transient responses, but they also make
the simulation very slow. Therefore, those modifications are not considered in the
110
present analysis. However, some modifications to the SOFC model, which are
described below, are required so as to incorporate it into the circuit shown in Fig. 5.1.
For the study detailed in this chapter, the anode and the cathode inlet mass flow
rates are considered as the input variables which are to be imposed on the system. On
the other hand, the anode and the cathode channel outlet mass flow rates are decided
by the pressure differences between the cell and the after-burner and are given by
linear nozzle flow equations. This is why the inlet flow resistances are represented by
MR-field elements whereas the outlet flow resistances are represented by R-field
elements in Fig. 5.2. Also, the intensive variables at the channel inlets and outlets are
not constants but are variables corresponding to the heat exchanger outlets and the
after-burner inlet, respectively. Therefore, these are represented by modulated effort
sources in Fig. 5.2.
Fig. 5.2: True Bond Graph Model of the SOFC
111
Chapter 5
The mass balances for the two gas species at the anode channel gases control
volume, which are given by the zero junctions 0 μH and 0μW in the Fig. 5.2, are
m H = m Hi − m Hr − m Ho (5.1)
and m W = m Wr − m W
o
, (5.2)
where the inlet mass flow rate of hydrogen is a controlled and measured input to the
system.
The entropy balance at the anode channel gases control volume, which is
modelled by the 0Tan junction in Fig. 5.2, is
San = Sani − Sano − S1 . (5.3)
The expansions for the various terms in the Eqs. (5.1–5.3) are discussed in the
following.
The total outlet mass flow rate from the anode channel that is calculated in the
R ao -field in Fig. 5.2 is given by the linearised nozzle flow equation as
m ano = K ao ( pan − pAB ) , (5.4)
from which, the outlet mass flow rates of the two constituent gases can be obtained as
m Ho = wH,an K ao ( pan − pAB ) (5.5)
and o
m W = wW,an K ao ( pan − pAB ) . (5.6)
The total pressure of the gases at the anode channel is represented as a function of
the temperatures and the chemical potentials of the two gas species (refer to Eqs.
(3.80–3.81) in Section 3.4.1 of Chapter 3) as
112
cvH cvW
⎛ μ μ ⎞⎛ T ⎞
0 RH ⎛ μ μ ⎞ ⎛ Tan ⎞0 RW
pan = pH0 exp ⎜ H − 0 ⎟ ⎜ an0 ⎟
H
+ pW
0
exp ⎜ W − 0 W
⎟⎜ 0 ⎟ . (5.7)
⎝ Tan RH Tan RH ⎠ ⎝ Tan ⎠ ⎝ Tan RW Tan RW ⎠ ⎝ Tan ⎠
The mass flow rates of the hydrogen consumed in the reaction and that of the
water vapour produced due to the reaction are functions of the current drawn from the
cell, which is a system input (i.e., measured), and are given (in kg/s) by (refer to the
1n junction and the transformer structure in Fig. 5.2) the charge balance equations
(refer to Section 3.2 of Chapter 3):
iν H M H
m Hr = (5.8)
1000ne F
iν W M W
and r
m W = . (5.9)
1000ne F
Note that the molar masses are given in grams per mole and thus the factor 1000
appears in the denominator of Eqs. (5.8–5.9) for conversion of mass flow rates from
grams per second to kilograms per second. The same factor appears in some other
equations (e.g., Eq. (5.27) and Eq. (5.48)) in this work precisely due to the same
reason.
The entropy flow rate into the anode channel control volume, Sani , which is
calculated in the MRai field shown in Fig. 5.2, is given by the sum of the convective
entropy flow due to the inlet mass flow and the entropy generated due to the enthalpy
difference between the inlet and the anode channel gases as (refer to Section 3.4.1 of
Chapter 3)
Sani = m Hi sai + Sgen,ai , (5.10)
where the entropy generated at the anode inlet is given by
m Hi ( μ H,ai − μ H,an + sai (Tai − Tan ) )

Sgen,ai = (5.11)
Tan
113
Chapter 5
and the specific entropy of the anode side upstream gas is
cpH − μH,ai
sai = . (5.12)
Tai
The entropy flow out of the anode channel volume, which is calculated in the Rao
field shown in Fig. 5.2, is
m o S
Sano = m ano san = an an . (5.13)
mH + mW
From the effort balance at the 0Tan junction in Fig. 5.2, it can be seen that the
entropy flow rate due to the convective heat transfer with the solids (MEA and the
interconnect) is
S1 = S2 + S3 , (5.14)
where S2 and S3 are given by the constitutive relations of Rcv2 and Rcv1, respectively,
in Fig. 5.2 as (refer to Section 3.3.5 of Chapter 3)
λ (T − T )
S2 = an an M (5.15)
Tan
λ (T − T )
and S3 = an an I1 . (5.16)
Tan
The temperature and the chemical potentials of the anode channel gases are given
by the constitutive relations for the anode channel C-field in terms of the state
variables as (refer to Section 3.3.4 of Chapter 3)
⎛ mH RH ⎞ ⎛ mW RW ⎞
⎜ ⎟ ⎜ ⎟
⎛ m ⎞⎝ mHc Hv + mW c Wv
⎜ ⎟⎛m ⎞⎝ mHc Hv + mW c Wv
⎜ ⎟
⎠ ⎠
Tan = Tan0 X1 ⎜ H0 ⎟ ⎜⎜ W ⎟⎟ , (5.17)
⎜m ⎟ 0
⎝ H⎠ ⎝ mW ⎠
114
⎛ San mH SH0 mW SW 0 ⎞
⎜ − − ⎟
⎜ mHcvH + mW c W 0 H 0 W
mH mHc v + mH mW c v 0 H 0 W ⎟
mH mW c v + mW mWc v ⎠
where X1 =e⎝ v
,
⎛ pH,an ⎞
μH,an = μH0 (Tan , pH,an
0
) + RHTan ln ⎜⎜ 0 ⎟⎟ (5.18)
⎝ pH,an ⎠
⎛ pW,an ⎞
and μW,an = μW0 (Tan , pW,an
0
) + RWTan ln ⎜⎜ 0 ⎟⎟ . (5.19)
⎝ pW,an ⎠
Similarly, the mass balances at the cathode channel gases control volume, given
by the zero junctions 0 μO and 0 μN in the Fig. 5.2, are
m O = m Oi − m Or − m Oo (5.20)
and m N = m Ni − m No , (5.21)
where the inlet mass flow rate of the air is an controlled and measured input to the
system from which, the inlet mass flow rates of oxygen and nitrogen are obtained as
m Oi = wO,AS m cai and m Ni = wN,AS m cai .
The entropy balance at the cathode channel gases control volume, which is
represented by the 0Tca junction in Fig. 5.2, is
Sca = Scai − Scao − S8 . (5.22)
The expansions for the various terms in the Eqs. (5.20–5.22) are discussed in the
following.
The total outlet mass flow rate from the cathode channel which is calculated in
the Rco-field element in Fig. 5.2 is given by the linearized nozzle flow equation as
m cao = K co ( pca − pAB ) , (5.23)
115
Chapter 5
from which, the outlet mass flow rate of the two constituent gases can be obtained as
m Oo = wO,ca K co ( pca − pAB ) (5.24)
and m No = wN,ca K co ( pca − pAB ) . (5.25)
The total pressure of the gases at the cathode is represented as a function of the
temperatures and the chemical potentials of the two cathode gas species (refer to
Section 3.4.1 of Chapter 3) as
cvO cvN
⎛ μ μ 0 ⎞ ⎛ T ⎞ RO ⎛ μ μ 0 ⎞⎛ T ⎞ RN
pca = pO0 exp ⎜ O − 0 O ⎟ ⎜ ca0 ⎟ + pN0 exp ⎜ N − 0 N ⎟⎜ ca0 ⎟ . (5.26)
⎝ Tca RO Tca RO ⎠ ⎝ Tca ⎠ ⎝ Tca RN Tca RN ⎠⎝ Tca ⎠
The mass flow rate of oxygen consumed in the reaction (refer to the 1n junction
and the transformer structure in Fig. 5.2) is given (in kg/s) by (refer to Section 3.2 of
Chapter 3)
iν O M O
m Or = . (5.27)
1000ne F
The entropy flow rate into the cathode channel control volume, which is given by
the MRci field element in Fig. 5.2, is (refer to Section 3.4.1 in Chapter 3)
Scai = m cai sci + Sgen,ci , (5.28)
where the entropy generated at the cathode inlet is
Sgen,ci =
(
m cai wO,ci ( μO,ci − μO,ca ) + wN,ci ( μ N,ci − μ N,ca ) + sci (Tci − Tca ) ), (5.29)
Tca
and the specific entropy of the cathode side upstream gas mixture is
μO,ci wO,ci + μ N,ci wN,ci

sci = cpO wO,ci + cpN wN,ci − . (5.30)
Tci
116
The entropy flow out of the cathode channel volume, which is calculated in the
Rco field in Fig. 5.2, is
m o S
Scao = m cao sca = ca ca . (5.31)
mO + mN
From the effort balance at the 0Tca junction in Fig. 5.2, the entropy flow rate due
to the convective heat transfer with the solids (the MEA and the interconnect) is
S8 = S9 − S7 , (5.32)
where S9 and S7 are given by the constitutive relations of Rcv3 and Rcv4, respectively,
in Fig. 5.2 as (refer to Section 3.3.5 of Chapter 3)
λ (T − T )
S9 = ca ca I2 (5.33)
Tca
λ (T − T )
and S7 = ca ca M . (5.34)
Tca
The temperature and the chemical potentials of the cathode channel gases are
given in terms of the state variables by the constitutive relations for the cathode
channel C-field as (refer to Section 3.3.4 of Chapter 3)
⎛ mO RO ⎞ ⎛ mN RN ⎞
( ) ( )
⎜ ⎟ ⎜ ⎟
Tca = Tca0 X 2 mO mO0 ⎜⎝ mOc v + mNc v ⎟⎠ 0 ⎜ m c +m c ⎟
O N O N
mN mN ⎝ O v N v ⎠, (5.35)
⎛ Sca mO SO0 mN S N0 ⎞
⎜ − − ⎟
⎜ mOcv + mN c
O N 0 O 0 N
mO mOc v + mO mN c v mO mN c v + mN mN c v ⎟⎠
0 O 0 N
where X 2 =e ⎝ v
,
⎛ pO,ca ⎞
μO,ca = μO0 (Tca , pO,ca
0
) + ROTca ln ⎜⎜ 0 ⎟⎟ (5.36)
⎝ pO,ca ⎠
117
Chapter 5
⎛ pN,ca ⎞
and μN,ca = μN0 (Tca , pN,ca
0
) + RNTca ln ⎜⎜ 0 ⎟⎟ . (5.37)
⎝ pN,ca ⎠
The entropy balance for the solid (MEA and the interconnects) control volumes
gives rise to three more differential equations as follows. The flow balance at the 0TI1
and 0TI2 junctions (refer to Fig. 5.2) give (refer to Section 3.3.5 of Chapter 3)
λ (T − T )
SI1 = S4 = an an I1 (5.38)
TI1
λ (T − T )
and SI2 = S10 = ca ca I2 . (5.39)
TI2
The flow balance at the 0TM junction (refer to Fig. 5.2) gives
SM = SPL + S5 − S6 + Sr , (5.40)
where S5 and S6 are the entropy flow rates due to the convection heat transfer with
the gases and are given by the constitutive relations of the Rcv2 and Rcv4 fields,
respectively, as (refer to Section 3.3.5 of Chapter 3)
λ (T − T )
S5 = an an M (5.41)
TM
λ (T − T )
and S6 = ca ca M . (5.42)
TM
The expansions for the various terms in the Eq. (5.40) are discussed in the
following. The entropy flow rate due to the reaction, which is applied to the 0TM
junction in Fig. 5.2, is (refer to Section 3.4.2 of Chapter 3)

Sr =
r
m W ( hW − μ W ) m Hr ( hH − μH ) m Or ( hO − μO )
− − . (5.43)
Tan Tan Tca
118
The temperature of solids are given in terms of the state variables by the
constitutive relations of the compliance elements CM , CI1 and CI2 , respectively, as
⎛ S − S M0 ⎞
TM = TM0 exp ⎜ M ⎟, (5.44)
⎝ mM cM ⎠
⎛ S − S0 ⎞
TI1 = TI10 exp ⎜ I1 I1 ⎟ , (5.45)
⎝ mI1cI1 ⎠
⎛ S I2 − S I20 ⎞
and TI2 = T exp ⎜
0
I2 ⎟. (5.46)
⎝ mI2 cI2 ⎠
The reversible cell voltage is given by the Nernst equation [Singhal & Kendall,
2003] as
ΔG
Vr = − , (5.47)
ne F
where ΔG is the change in the Gibbs free energy [Singhal & Kendall, 2003]:
ν W M W μ W −ν H M H μ H −ν O M O μ O
ΔG = . (5.48)
1000
The calculation of ΔG is realised through the 1n junction in Fig. 5.2.
The actual cell voltage is less than the reversible voltage due to the irreversibilities
in the system. The irreversibilities cause voltage losses called over-voltages (refer to
Section 3.3.5 of Chapter 3). The actual cell voltage is obtained by subtracting the
over-voltages from the reversible voltage (refer to 1i junction in Fig. 5.2) as
V = Vr − η , (5.49)
119
Chapter 5
where, η = ηconc + ηo + ηact,a + ηact,c . The sum of all the over-voltages, η , is calculated
in the RS field in Fig. 5.2, where the various types of over-voltages are calculated as
described in the following.
The ohmic over-voltage is given by the Ohm’s law: ηo = iRohm . Activation over-
voltage, which refers to the over potential required to exceed the activation energy
barrier so that the electrode reactions proceed at the desired rate are governed by the
Butler-Volmer equation [Qi et al., 2005], which in its general form is given as
⎧⎪ ⎛ β n Fη ⎞ ⎛ − (1 − β ) ne Fηact ⎞ ⎪⎫
i = i0 ⎨exp ⎜ e act ⎟ − exp ⎜ ⎟⎬ . (5.50)
⎪⎩ ⎝ RT ⎠ ⎝ RT ⎠ ⎪⎭
If the transfer coefficient ( β ) is 0.5, which is normally the case [Qi et al., 2005],
then the anodic and cathodic activation over-voltages can be obtained from Eq. (5.50)
as
2RTM ⎛ 0.5i ⎞
ηact,a = sinh −1 ⎜
⎜ i ⎟⎟
(5.51)
ne F ⎝ 0,a ⎠
2RTM ⎛ 0.5i ⎞
and ηact,c = sinh −1 ⎜
⎜ i ⎟⎟
, (5.52)
ne F ⎝ 0,c ⎠
⎛ p ⎞⎛ p ⎞ ⎛ − Ean ⎞
where, i0,a = ψ an Ac ⎜ H ⎟ ⎜ W ⎟ exp ⎜ ⎟
⎝ pamb ⎠ ⎝ pamb ⎠ ⎝ RTM ⎠
0.25
⎛ p ⎞ ⎛ −E ⎞
and i0,c = ψ ca Ac ⎜ O ⎟ exp ⎜ ca ⎟.
⎝ pamb ⎠ ⎝ RTM ⎠
Concentration over-voltage results due to the difference between the concentration

of the gases at the electrode-electrolyte interface, where the reaction occurs, and those
in the bulk. The physical processes that contribute to its occurrence include gas
species molecular transport in the electrode pores, solution of reactants into the
electrolyte, dissolution of the products out of the electrolyte and diffusion of the
120
reactants/products through the electrolyte to/from the reaction sites. The concentration
over-voltage is given as [Mueller et al., 2006]
RTM ⎛ i ⎞
ηconc = − ln ⎜ 1 − ⎟. (5.53)
ne F ⎝ iL ⎠
The entropy flow rate due to the polarisation losses (over-voltage losses), which is
calculated from energy balance in the RS-field in Fig. 5.2, is given as
iR ⎛ ⎛ 0.5i ⎞ ⎛ 0.5i ⎞ ⎛ i ⎞ ⎞ i 2 Rohm

SPL = ⎜ 2sinh −1 ⎜⎜ ⎟ + 2sinh −1 ⎜ ⎟ − ln ⎜1 − ⎟ ⎟⎟ + . (5.54)
ne F ⎜⎝ ⎟ ⎜ i ⎟
⎝ i0,a ⎠ ⎝ 0,c ⎠ ⎝ iL ⎠⎠ TM
The nine differential equations (Eqs. (5.1–5.3, 5.20–5.22, 5.38–5.40)), after

relevant substitutions, represent the state equations of the SOFC system consisting of
nine state variables: mO , mH , mW , mN , San , Sca , S I1 , S I2 and SM . This model is
based upon the second law of thermodynamics analysis of the fuel cell system and
therefore, it is suitable for exergy calculations.
5.2.2. The Steady State Model of the SOFC
In this work, the optimum operating conditions of the SOFC are investigated. In order
to perform the optimisation process we need a model that should be comprehensive
(i.e., able to predict all the required variables of the system) and at the same time
should also be computationally efficient. The use of the dynamic model in the
optimisation algorithm is computationally expensive. For this purpose, it is desired to
formulate a comprehensive steady state model of the fuel cell system which can be
solved to find the steady state values of variables such as temperatures, pressures,
outlet mass flow rates, voltage, the fuel and the oxygen utilizations, power and
efficiency, given the inputs such as the anode and the cathode inlet mass flow rates
and the current drawn from the fuel cell. This model could then be used to study the
optimum operating conditions of the SOFC system.
121
Chapter 5
The steady state model of the SOFC system can be obtained from the dynamic
model by means of omitting the dynamic (derivative) terms from its system equations.
It results in a set of algebraic equations, which can be solved to obtain the steady state
values of the state variables, using which, the steady state values of other variables of
interest can be calculated. In a bond graph model, this procedure translates to
assignment of derivative causalities to storage elements (C and I-elements) and
replacement of the differentially causalled storage elements by appropriate null
sources. The resulting model has a junction structure determined solely by the
resistive elements and sources. However, this procedure sets up a set of algebraic
loops between the resistive elements in the model. The objective is to assign
causalities in such a way that the junction structure becomes explicitly solvable.
However, it is impossible to assign such causalities in our case due to the complex
non-linearities involved in the SOFC model. The other approach is to directly write
down the constraints and solve them implicitly. When this procedure is applied to the
fuel cell dynamic model described earlier, the resulting algebraic equations became
too complicated. Moreover, they could not be solved by sophisticated numerical
methods such as those available in Matlab software. This is the reason why a steady-
state model of a fuel cell unit has not been developed so far. It is found in the
literature that either a full model is recursively simulated or an over-simplified steady
state model is used in all fuel cell optimisation problems [Chen et al., 2006; Cownden
et al., 2001; Douvartzides et al., 2003; Frangopoulos & Nakos, 2006; Hussain et al.,
2005; Na & Gou, 2007; Palazzi et al., 2007; Saidi et al., 2005; Subramanyan &
Diwekar, 2007; Yeh & Chen, 2008].
This is the motivation to develop an alternative simpler formulation of a steady

state SOFC model. In this work, first, the partial pressures are calculated and the
chemical potentials and various specific quantities are expressed as empirical
functions of the known partial pressures and the unknown temperatures. Then the
resulting implicit equations for unknown temperatures are solved. Later, it is
shown/validated that the steady state model obtained through this simplification
approach indeed gives good predictions.
122
It is possible to calculate the anode and the cathode channel mass fractions and the
partial pressures directly from the system inputs and known parameters as follows.
At steady state, Eq. (5.1) becomes
m Hi − m Hr − m Ho = 0 . (5.55)
Use of the expression for the outlet mass flow rate of hydrogen in the above
equation gives
m Ho = m Hi − m Hr = wH,an K ao ( pan − pAB ) . (5.56)
From Eq. (5.2) and the expression for the water vapour outlet mass flow rate, we
get
o
m W = wW,an K ao ( pan − pAB ) . (5.57)
Because of the fact that wH,an + wW,an = 1 , Eq. (5.57) may be written as
m Wr = (1 − wH,an ) K ao ( pan − pAB ) . (5.58)
By eliminating wH,an from Eqs. (5.56) and (5.58), we obtain an expression for pan
as
K ao pAB + m W
r
+ m Hi − m Hr
pan = . (5.59)
K ao
By substituting Eq. (5.59) into Eq. (5.56), and noting that wH,an + wW,an = 1 , we
arrive at
m Hi − m Hr
wH,an = (5.60)
r
m W + m Hi − m Hr
123
Chapter 5
r
m W
and wW,an = . (5.61)
r
m W + m Hi − m Hr
The partial pressures of hydrogen and water vapour inside the anode channel are
then calculated as
wH,an M W pan
pH = (5.62)
M W wH,an + M H wW,an
wW,an M H pan
and pW = . (5.63)
M W wH,an + M H wW,an
Similarly, at steady state, Eq. (5.20) becomes
m Oi − m Or − m Oo = 0 . (5.64)
Using the expression for the outlet mass flow rate of oxygen in the above equation
gives
m Oo = m Oi − m Or = wO,ca K co ( pca − pAB ) . (5.65)
From Eq. (5.21) and the expression for the nitrogen outlet mass flow rate, we get
m No = wN,ca K co ( pca − pAB ) . (5.66)
From wH,an + wW,an = 1 , Eq. (5.66) may be written as
m No = (1 − wO,ca ) K co ( pca − pAB ) . (5.67)
Eliminating wO,ca from Eqs. (5.65) and (5.67), we obtain an expression for pca as
K co pAB + m Ni + m Oi − m Or
pca = . (5.68)
K co
By substituting Eq. (5.68) into Eq. (5.67), and noting that wO,ca + wN,ca = 1 , we get
124
m Oi − m Or
wO,ca = (5.69)
m Ni − m Oi − m Or
m Ni
and wN,ca = . (5.70)
m Ni − m Oi − m Or
The partial pressures of the oxygen and the nitrogen inside the cathode channel
are then calculated as
wO,ca M N pca
pO = (5.71)
M N wO,ca + M O wN,ca
wN,ca M O pca
and pN = . (5.72)
M N wO,ca + M O wN,ca
Now that the steady state values of the partial pressures of the gas species are
known, we just need to calculate the steady state temperatures so that the values of all
the variables of interest can be computed. To find the temperatures, Tan , Tca and TM ,
the steady state forms of the state equations (Eqs. (5.3, 5.22 and 5.40)) are used.
The entropy balance equations (Eqs. (5.3, 5.22 and 5.40)) are written in terms of
the temperatures and the pressures instead of the dynamic model’s state variables. The
chemical potentials and the specific enthalpies and entropies encountered in the
expressions are represented as polynomial functions of the temperatures and the
pressures [Benson, 1977], whose coefficients are calculated from the spectroscopic
data.
The chemical potential is calculated from
⎛ p⎞
μ = μ0 (T ) + RT ln ⎜ ⎟, (5.73)
⎝ p0 ⎠
where μ0 (T ) is purely a function of the temperature. The values of μ0 (T ) for the
individual gas species are calculated as:
125
Chapter 5
⎡ ⎛ a3T 2 a4T 3 a5T 4 ⎞ ⎤

μ0 (T ) = RT ⎢ a1 − a1 ln (T ) − ⎜ a2T + + + ⎟ − a6 ⎥ + μo . (5.74)
⎣ ⎝ 2 3 4 ⎠ ⎦
The specific enthalpies of the gases are calculated as
h = R ( a1T + a2T 2 + a3T 3 + a4T 4 + a5T 5 ) + h0 (5.75)
and the specific entropies of all the gas species are calculated as
⎛ ⎛ 3⎞ ⎛ 4⎞ ⎛5⎞ ⎛ p ⎞⎞
s = R ⎜ 2a1 + 2a2T + ⎜ ⎟ a3T 2 + ⎜ ⎟ a4T 3 + ⎜ ⎟ a5T 4 − a1 ln T − a6 − ln ⎜ ⎟ ⎟ + s0 ,(5.76)
⎜ ⎝ 2⎠ ⎝ 3⎠ ⎝ 4⎠ ⎟
⎝ ⎝ p0 ⎠ ⎠
where the coefficients a1,…,a6 are taken from [Benson, 1977].
Note that the temperatures TI1 and TI2 become equal to Tan and Tca , respectively,
at steady state and hence the unknowns in Eqs. (5.3, 5.22 and 5.40) are the three
temperatures Tan , Tca and TM . Thus, we arrive at a set of three algebraic equations in
three unknown variables Tan , Tca and TM , which is lot simpler to solve than the
original set of nine equations (Eqs. (5.1–5.3, 5.20–5.22, 5.38–5.40)) given in terms of
nine state variables. The new set of equations can now be solved numerically in order
to find the fuel cell temperatures. Using these, the other variables of interest such as
the voltage, power, OU, FU, system efficiencies etc. can be calculated.
The cell voltage is calculated by using the Eqs. (5.49–5.53) given in the last
section. In the literature, the FU and the OU are considered to be the most important
variables that have to be controlled during the operation of the fuel cell [Aguiar et al.,
2005]. The FU may be given as
m Hr iν H M H
ζf = = . (5.77)
m H 1000ne Fm Hi
i
The OU of the fuel cell may be quantitatively given as
126
m Or iν O M O
ζo = = . (5.78)
m O 1000ne Fm Oi
i
5.2.3. Validation of the Steady State Model of the SOFC
In this section, the developed steady state model of the SOFC is validated by
comparing the steady state model results with the simulation results from the dynamic
model. The dynamic model of the SOFC, which was described in Section 5.2.1, is
used to perform the simulations. The relevant parameter values are given in Table 5.1.
The input variables have been arbitrarily selected as follows: m ani = 1.30781 ×10−6
kg/s; m cai = 2.84754 ×10−4 kg/s; Tai = 700 K; Tci = 700 K; i = 80 A and 100 A (two
cases). Corresponding to these input variables, the steady-state model predicts the
following steady-state values for case 1 ( i = 80 A): Tan = 926.622 K, Tca = 929.202 K,
TM = 928.015 K, pO = 21247.5 Pa, pN = 88812.4 Pa, pH = 39085.5 Pa,
pW = 69188.7 Pa and V = 0.63888 V. For case 2 ( i = 100 A), the predicted steady-
state values are Tan = 1017.251 K, Tca = 1020.733 K, TM = 1019.019 K,
pO = 20757.4 Pa, pN = 89242.6 Pa, pH = 22136.1 Pa, pW = 87866.1 Pa and
V = 0.59161 V.
The objective of the validation step is to verify whether the dynamic responses
converge to the predicted steady-state values for any arbitrarily chosen initial
conditions. Two different initial condition sets were tried out to check the
independence of the steady state response to the initial values. In the first scenario, the
following arbitrary initial conditions were chosen: San0 = 0.272576 J/K,
Sca0 = 0.285695 J/K, S M0 = 20 J/K, S I10 = 20 J/K, SI20 = 20 J/K, mN0 = 2.73347 ×10−5 kg,
mO0 = 7.2627 × 10−6 kg, mH0 = 4.84941× 10−7 kg and mW

0
= 1.73338 ×10−5 kg. These
values correspond to the following initial partial pressures and temperatures:
pO0 = 20757.38 Pa, pN0 = 89242.62 Pa, pH0 = 22000 Pa, pW
0
= 88000 Pa, Tan0 = 1100 K,
127
Chapter 5
Tca0 = 1100 K and TM0 = 1100 K. The second set of initial conditions was chosen as
follows: San0 = 0.321541 J/K, Sca0 = 0.339347 J/K, S M0 = 20 J/K, S I10 = 20 J/K,
S I20 = 20 J/K, mN0 = 3.34091×10−5 kg, mO0 = 8.87664 × 10−6 kg, mH0 = 5.92706 ×10−7 kg
0
and mW = 2.11858 × 10−5 kg, which correspond to the following initial partial
pressures and temperatures: pO0 = 20757.38 Pa, pN0 = 89242.62 Pa, pH0 = 22000 Pa,
0
pW = 88000 Pa, Tan0 = 900 K, Tca0 = 900 K and TM0 = 900 K.
Comparison between the results of the dynamic and the steady state models are
shown in Fig. 5.3. In the Fig. 5.3a, the cathode temperatures obtained from the steady
state and the dynamic model are plotted for the two different values of the current.
The corresponding voltage responses of the dynamic and the steady state models are
shown in Fig. 5.3b. It can be seen from Fig. 5.3 that the results of the steady state
model agree with that of the dynamic model with very small differences and that the
steady state values are independent of the initial conditions. The small differences
may be attributed to the approximations we have used to derive the steady state model,
namely the use of the polynomial functions of the temperatures and the pressures
[Benson, 1977] (as obtained from the spectroscopic data) to calculate the chemical
potentials, the specific enthalpies and entropies.
(a) (b)
Fig. 5.3: Comparison of the (a) Cathode Temperature and the (b) Voltage of the SOFC Between the
Dynamic and the Steady state Models
128
5.2.4. Steady State Models of the After-burner and the Heat

Exchangers
A simple steady state model of the after-burner is used in this work. This model
assumes complete combustion of hydrogen at constant pressure [Murshed et al.,
2007]. Moreover, as the pressure loss in the after-burner volume is very small, it has
negligible effect on the after-burner outlet temperature [Kandepu, 2007]. Hence the
pressure at the after-burner (pAB) is assumed to be constant and equal to 1 bar. Also,
ideal gas mixing inside the after-burner channel is assumed so that the exit gas
temperature is same as the inside temperature. By assuming that the after-burner is
well insulated so that the energy losses to the environment are negligible, the energy
balance for the after-burner control volume is
hHabi m Hfco + hOabi m Ofco + hNabi m Nfco +

. (5.79)
hWabi m W
fco
+ m Hfco ( LHV )H = hOabo m Oabo + hNabo m Nabo + hWabo m W
abo
In Eq. (5.79), ( LHV )H means the Lower Heating Value of the reaction, which is a
synonym for the enthalpy of the combustion reactions when all the water in the
products is in the gaseous state. The lower heating values for various reactions at
atmospheric pressure and at various temperatures are taken from the tables of
experimental data [Benson, 1977].
Further assuming that all the hydrogen remaining in the fuel cell exhaust is
combusted in the after-burner, the after-burner outlet mass flow rates of oxygen
( m Oabo ), nitrogen ( m Nabo ) and water vapour ( m W
abo
) can be calculated by using the
principle of mass conservation as
M O m Hfco
m Oabo = m Ofco − , (5.80)
2M H
M W m Hfco
abo
m W = m W
fco
+ (5.81)
MH
129
Chapter 5
and m Nabo = m Nfco . (5.82)
The inlet specific enthalpies of the gas species in Eq. (5.79) can be calculated by
using the previously discussed polynomial equation [Benson, 1977], where the
temperature is equal to the fuel cell outlet temperature ( TFCO ), which is assumed to be
equal to the cathode gas temperature ( Tca ). The after-burner outlet specific enthalpies
are expressed in terms of the polynomial equations given in Eq. (5.75) and then Eq.
(5.79) is solved numerically in order to find the after-burner outlet temperature ( TABO ).
The SOFC system consists of two counter-current heat exchangers, HX1 and HX2,
as shown in Fig. 5.1. Because the outlet temperatures of the cold and the hot fluids of
the heat exchangers need to be calculated from the inlet temperatures and mass flow
rates, the effectiveness-number of transfer units ( ε -NTU ) method [Incropera &
Dewitt, 1996] is used to model the heat exchangers. The heat capacity rates of the
cold and hot fluids are calculated as
Cc = ∑ m c cp,c and Ch = ∑ m h cp,h . (5.83)
By comparing their values, the lower and higher values are assigned as Cmin and
Cmax , respectively. The ratio of the heat capacity rates is calculated as Cr = Cmin Cmax .
The effectiveness of the counter-current heat exchangers can be calculated as
1 − exp ( − NTU (1 − Cr ) )
ε= for Cr < 1 (5.84)
1 − Cr exp ( − NTU (1 − Cr ) )
NTU
or ε= for Cr = 1 , (5.85)
1 + NTU
where, NTU = UA Cmin , U is the overall heat transfer coefficient and A is the
effective heat transfer area of the heat exchanger.
The heat exchange rate between the hot and the cold gas streams is q = ε qmax ,
where the theoretical maximum heat transfer rate is
130
qmax = Cmin (Th,i − Tc,i ) , (5.86)
Th,i refers to the inlet temperature of the hot fluid, which is equal to the after-burner
outlet temperature in the case of HX1 and the hot fluid outlet temperature of HX1
HX1
( Th,o ) in the case of HX2, and Tc,i refers to the inlet temperature of the cold fluid to
the heat exchangers, which is 298K for both the heat exchangers HX1 and HX2.
From the energy balance, the exit temperatures of the hot and the cold fluids can
be calculated as
q q
Th,o = Th,i − and Tc,o = Tc,i − . (5.87)
Ch Cc
Given the anode and cathode inlet mass flow rates, the temperatures and the
current drawn by the load, the steady state values of the fuel cell outlet mass flow
rates and the temperatures of the gases can be obtained from the steady state fuel cell
model described earlier. By using the fuel cell outlet mass flow rates and the
temperatures as the inputs to the models of the after-burner and the heat exchangers
described by Eqs. (5.79–5.87), the temperatures of the cathode and the anode inlet
streams can be calculated, which will further be used for the calculation of the fuel
cell outlet stream temperatures. This forms an algebraic loop, which is why the
calculations are repeated iteratively until the difference between the fuel cell inlet
stream temperatures and the heat exchanger cold fluid outlet temperatures converges
to within a specified small value. Such recursive methods have been adopted in
various studies on exergy analysis and optimisation of fuel cell systems [Akkaya et al.,
2007; Calise et al., 2006; Chan et al., 2002; Douvartzides et al., 2003; Saidi et al.,
2005].
5.3. Optimisation of the SOFC Operating Conditions
The aim of this work is to find the optimal working conditions of the SOFC system in
terms of the first and the second law efficiencies, and to investigate the optimal
131
Chapter 5
operating strategies of the SOFC system. A design problem is not considered here, i.e.,
it will be assumed that the fuel cell system components are available and their
parameters are fixed. The inputs to the fuel cell system model are the anode and the
cathode inlet mass flow rates and the current drawn by the load. The question that
motivated this study is, “For a given value of current drawn from the fuel cell by the
load, what values of anodic and cathodic inlet mass flow rates will result in maximum
system efficiency?”
For the SOFC system under consideration, the operating conditions solely depend
upon the current drawn by the load and the anodic and the cathodic inlet mass flow
rates. In this investigation, the current drawn from the fuel cell is considered as a
disturbance (i.e., it is not a variable that can be manipulated) as the load usually
decides it. The anode and the cathode inlet mass flow rates are considered as the
design variables, which can be manipulated in order to optimise the objective function.
The objective of this optimization study is to maximise the system efficiency, which
is defined as [Rosen, 1990]
Vi
ηen = . (5.88)
m ( LHV )H
i
H
Because our model accounts for the various irreversibilities in the fuel cell, the
exergetic efficiency of the system can also be calculated as [Cownden et al., 2001;
Hussain et al., 2005; Rosen, 1990; Rosen & Scott, 1988]
Vi
ηex = . (5.89)
m ΔGT0
i
H
where ΔGT0 is the standard free enthalpy of reaction at temperature T and pressure p0
= 1bar (also known as the standard Gibbs function change).
Exergy efficiency (also known as the second-law efficiency or rational efficiency)

computes the efficiency of a process by taking the second law of thermodynamics into
account. According to the second law of thermodynamics, no system can be 100%
energy efficient. Therefore, the energy efficiency does not give any indication of how
132
the system compares to a thermodynamically perfect one operating under the same
conditions. In comparison, the exergy efficiency or the rational efficiency of a system
can reach 100% because the work output is compared to the potential of the input to
do work. As for all fuels, ΔG o < ΔH o , the exergy efficiency must always be greater
than the energy efficiency.
The destruction of exergy is closely related to the creation of entropy and any
system containing highly irreversible processes will have low exergy efficiency.
Modelling the thermodynamics of the system by using the second law analysis of the
system helps in identifying the causes of entropy generation in the system. This
knowledge could be utilised to modify the system (operating conditions, geometry,
material properties, etc.) so that the irreversibilities in the system are minimised and it
operates at maximum exergy efficiency. Note that, in recent years, the second law
based modelling methods for thermodynamic optimisation known as entropy
generation minimisation (also called thermodynamic optimisation or finite time
thermodynamics) is being widely used for engineering design of thermal systems
[Balaji et al., 2007; Bejan, 1996; Bejan, 2002; Krane, 1987; Maximov, 2006; Ogulata
& Doba, 1998]. In this method, the models incorporate basic principles of
thermodynamics and heat transfer, and the optimization is subjected to finite-size and
finite-time constraints. The parameters required for the system optimization and the
simulations, excluding the ones given in the Table 4.1 in Chapter 4, are given in Table
5.1.
Table 5.1: Parameters used in the Efficiency Optimisation and Simulation

Parameter Description Value Unit
Ch,HX1 Hot fluid thermal capacitance of HX1 0.04224 J K-1
Cc,HX1 Cold fluid thermal capacitance of HX1 0.41919 J K-1
Ch,HX2 Hot fluid thermal capacitance of HX2 0.62083 J K-1
Cc,HX2 Cold fluid thermal capacitance of HX2 0.73702 J K-1
CAB Thermal capacitance of after-burner gases 0.1919 J K-1
UHX1 Overall heat transfer coefficient of HX1 10 J m-2 s-1 K-1
UHX2 Overall heat transfer coefficient of HX2 10 J m-2 s-1 K-1
AHX1 Area of HX1 0.0038525 m2
AHX2 Area of HX2 0.0452986 m2
TAS , THS Temperatures of air and hydrogen sources 298 K
133
Chapter 5
5.3.1. Optimisation Algorithm
A program is written in Matlab for maximizing the system efficiency at a given value
i
of the load current by taking man and mcai as the design variables. This program also
calculates the corresponding steady state values of the variables of interest such as the
temperatures, pressures, mass flow rates, voltage, FU, OU and power. The Matlab
function ‘fminsearch’, which finds the minimum of a scalar function of several
variables, starting at an initial estimate and using the Nelder-Mead Simplex algorithm
(refer to Appendix C), is used in this routine. In this program a cascaded optimization
is used wherein another optimization loop runs inside the main optimization loop.
The main optimization loop of the algorithm searches for the optimum values of
i
man and mcai which maximize the system efficiency for a given value of the load
current. The initial guess values of the design variables ( mani and mcai ) are passed on
to the function ‘fminsearch’ along with the function ‘Func 1’ which describes the
negative value of system efficiency (the objective function to be minimized). The
algorithm for the function ‘Func1’ is given in the form of a flow chart in Fig. 5.4. This
algorithm is executed every time the objective function evaluation is required for the
test points generated by the main loop (according to the Nelder-Mead Simplex
algorithm).
There are two more instances of the usage of the unconstrained multivariable
optimization function ‘fminserch’ within the function ‘Func 1’. In the first instance,
shown as the predefined process ‘Func 2’ in Fig. 5.4, it is used to solve the nonlinear
algebraic equations obtained from the steady state forms of the equations (Eqs. (5.3,
5.22 & 5.40)) in order obtain the steady state fuel cell temperatures Tan , Tca and TM .
The objective function to be minimized therein is given as
( ) + ( S ) + ( S )
2 2 2
F2 = Sani − Sano − S1 i
ca − Scao − S8 PL + S5 − S6 + Sr . (5.90)
134
Start
Ho , m W
Calculate m o
Oo , m No , pH , pW , pO , pN , wH,an , wW,an ,
, m
wO,an & wN,an using Eqs. (5.55–5.72)
HX1 HX2
Assign initial guess values to Tai , Tci , Tc,o & Tc,o
Is Tai − Tc,o
HX1
< 0.1 Yes
and Tci − Tc,o
HX2
< 0.1
No
Set Tai = Tc,o

HX1
and Tci = Tc,o
HX2
Calculate V , ζ f , ζ o & ηex
using Eqs. (5.47–5.53, 5.77–
5.78, 5.89)
Assign initial guess values to
Tan , Tca & TM
Define F1 = −Vi ( m Hi ( LHV )H )
Func 2
Stop
Set TFCO = Tca
Oabo , m W
Calculate m abo
Nabo using Eqs. (5.80–5.82)
& m
Assign initial guess values to TABO
Func 3
Calculate Tc,oHX1 & Tc,oHX2 using Eqs. (5.83–5.87)
Fig. 5.4: Flow Chart of the Function ‘Func 1’ Used in the Optimization Routine
The second instance of its use is shown as the predefined process ‘Func 3’ in Fig.
5.4, where it is used for obtaining the after-burner outlet stream temperature ( TABO ) by
135
Chapter 5
solving Eq. (5.79). The objective function to be minimized therein is given in least
squares form as
⎛ m Hfco ( LHV )H + hHabi m Hfco + hOabi m Ofco + hNabi m Nfco ⎞

2
F3 = ⎜ ⎟ . (5.91)
⎜ + habi m fco − h abo m abo − h abo m abo − habo m abo ⎟
⎝ W W O O N N W W ⎠
For a specific value of the current density (e.g., 1 A/cm2), the initial estimates for
the optimisation routine were obtained through trial and error. In this trial and error
approach, both the above-mentioned optimisation routines and a dynamic simulation
model described later were used. Once an optimal solution was obtained for that
specific value of the current density, in the next step, i.e., for the next value of the
current density (e.g., 0.99 A/cm2 and 1.01 A/cm2), the initial guess values were taken
to be the solutions obtained from the previous step. This way of successive
approximation of initial guess values reduced the convergence time of further
optimisations by many folds.
5.3.2. Discussions on the Results of the Efficiency

Optimization Study
The results obtained from the efficiency optimization study are summarised in the
following. The cathode and the anode inlet mass flow rates that give the maximum
system efficiency for various current densities are shown in Fig. 5.5a. At low current
densities, lower inlet mass flow rates give maximum efficiency; whereas, at higher
current densities, higher inlet mass flow rates are required. This is expected because at
higher current densities, the reaction rate is higher and hence more amounts of
reactants are consumed, which have to be replenished by the inlet flow. Several
publications in the literature [Aguiar et al., 2005; Mueller et al., 2006] recommend
constant FU operating strategy for the SOFC in order to minimise the transients
during the load changes. An interesting observation from Fig. 5.5a is that the anode
inlet mass flow rate that gives maximum system efficiency has an almost linear
relationship with the current density. This observation served as a motivation for
136
investigating whether the constant FU operation of the SOFC could closely

approximate the operation with maximum efficiency operating conditions. This is
because the FU of an SOFC can be maintained constant if the anode inlet mass flow
rate is varied proportionally to the current (this can be seen from Eq. (5.77)).
(a) (b)
(c) (d)
Fig. 5.5: SOFC System Operating Conditions for Maximum Efficiency and Constant FU Operations
Showing (a) the Anode and the Cathode Inlet Mass Flow Rates, (b) the FU and the OU, (c) Voltages and
Power Densities and (d) the Pressures and the Temperatures
Fuel cells are normally designed to operate at a cell voltage between 0.6V and
0.7V, as this range of operation is found to be a good compromise between the cell
efficiency, the power density, capital cost, stability of the operation and avoids
137
Chapter 5
possible anode oxidation at low cell voltage [Aguiar et al., 2005]. This operating
voltage range also offers a compromise between the cell efficiency and the power
density for the case of maximum efficiency operation also(this can be verified from
Fig. 5.5c and Fig. 5.6). From Fig. 5.5c, it can be seen that the above-mentioned
voltage range corresponds to the current densities between 0.45 to 0.88 A/cm2.
In order to compare the maximum efficiency operation and constant FU operation

of the SOFC, it is desired to obtain the linear relation between the anode inlet mass
flow rate and the current density, which will closely approximate the anode inlet mass
flow rate curve corresponding to the maximum efficiency operation within the desired
operating range (0.45 to 0.88 A/cm2). This is done by performing a least squares fit of
the data ( m ani and i ) corresponding to maximum efficiency in Fig. 5.5a within the
operating range (0.45 to 0.88 A/cm2) to a straight line passing through the origin
( m ani = ci ). Thus, the constant FU value which is expected to approximate the
maximum efficiency operation can be calculated as
ν HMH
ζf = . (5.92)
1000ne Fc
It is found to be equal to 0.891 for the considered system. Note that the FU value
0.891 is specific for the data considered here and this value would change for
different cell and heat exchanger parameter values. The cathode inlet mass flow rate
corresponding to the maximum efficiency in Fig. 5.5a within the operating range is
fitted (least squares fit of m cai vs. i ) to a cubic polynomial ( m cai = ai 3 + bi 2 + ci + d ).
By using these linear and the cubic polynomial relations for the inlet mass flow rates
as inputs to the steady state SOFC system model, the operating conditions
corresponding to the constant FU operation are calculated for various current densities.
The constant FU operation imposed by the polynomials for the inlet mass flow rates is
expected to be a close enough approximation to the maximum efficiency operation in
terms of the system efficiencies and the operating conditions.
The FU and the OU for constant FU operation and the maximum efficiency
operation are compared in Fig. 5.5b. The value of the constant FU (for the system
138
considered) at which the efficiencies of both the strategies are nearly equal is equal to
0.891, whereas the FU for the maximum efficiency operation reduces gradually with
the increase in the current density. Note that the FU value 0.891 is specific for the
data considered here and this value would change for different cell and heat
exchanger parameter values. The OU curves for both the operating strategies coincide
within the operating current density range as shown in Fig. 5.5b.
The cell voltage and the power density curves for the maximum efficiency
operation and the constant FU operation are shown in Fig. 5.5c. At low current
densities, the over-voltages are less and hence the cell voltage is large. This is also the
reason for high efficiencies observed in the low current density range. It can be seen
from Fig. 5.5c that the difference in the cell voltages and the power densities between
the maximum efficiency operation and the constant FU operation is small, more so in
the operating range. As per the definition of efficiency in Eq. (5.88), the maximum
possible power density at a particular value of the current density will result in the
maximum efficiency. At low current densities, the maximum power density is less
and at high current densities, the power density is more, which is mainly due to the
fact that the power density depends more on the current density than the voltage.
The anode pressures for both the operating strategies and the cell temperatures for
both the operating strategies are shown in Fig. 5.5d. Although the pressures are nearly
the same for both the operating strategies, the temperatures show slight deviations in
the operating range. The energy and the exergy efficiencies for the maximum
efficiency and the constant FU operating strategies are plotted in Fig. 5.6.
The exergy efficiency is higher than the energy efficiency as can be seen in Fig.
5.6, which is also reported in other literature [Chan et al., 2002; Cownden et al., 2001;
Hussain et al., 2005] for hydrogen fed SOFC systems. Within the operating range of
the fuel cell, the energy and exergy efficiencies for both the cases almost coincide.
This result is important because it establishes that if the SOFC is operated at a
particular value of FU (which depends upon the system), the efficiency of the system
remains very near to the maximum despite the changes in the load current density.
139
Chapter 5
However, it is to be noted that this applies only when the cathode inlet mass flow rate
is equal to that required for the maximum efficiency operation.
Fig. 5.6: The Energy and Exergy Efficiencies of the SOFC System for Maximum Efficiency and
Constant FU Operations
5.4. Simulation of the Dynamic Responses
Comparison of the closed loop dynamic response of the SOFC system, which is
operated by using different control strategies during a step change in the load current,
is given in this section. The true bond graph model of the SOFC shown in Fig. 5.2
along with the pseudo bond graph models of the after-burner and the heat exchangers
are used to perform the dynamic simulations of the SOFC system. The after-burner
and the heat exchangers are modelled by using the pseudo bond graph approach
[Karnopp, 1978; Thoma & Ould Bouamama, 2000] (the effort and flow variables are
T and H , respectively) as shown in Fig. 5.7. As a usual assumption, the hydraulic
storage is neglected in heat-exchanger design [Incropera & Dewitt, 1996]. It may be
assumed that the hydraulic resistance has been already modelled at the fuel cell exit.
As the after burner and the heat exchanger models are obtained from the first law
analysis, it is convenient to represent their dynamics in terms of pseudo bond graphs.
Note that there is no convenient way of deriving the after-burner model using second
140
law of thermodynamics. Therefore, the energy balance equations used in the after-
burner modelling are represented in a pseudo-bond graph. To maintain compatibility,
the heat exchanger is also modelled as a pseudo-bond graph.
The CAB element in the after-burner section marked in Fig. 5.7 represents the
thermal capacitance of the after-burner gases. The two modulated sources of flows to
the left of the CAB element give the after-burner inlet enthalpy flow rate ( H abi ) and
the enthalpy flow rate due to the hydrogen combustion reaction in the after-burner
( H r ). These flow sources are modulated by the signals of the fuel cell outlet gas
species mass flow rates and the cathode gas temperature (which come from the true
bond graph model of the fuel cell shown in Fig. 5.2). All the hydrogen gas coming out
of the fuel cell is consumed in the instantaneous combustion reaction taking place at
the after-burner, which is justified from the fact that the combustion reaction time
constant is sufficiently small as compared to the other dynamics in the system.
Fig. 5.7: Pseudo Bond Graph Models of the After-burner and the Heat Exchangers
The coupling element for thermo-fluid (CETF) systems, described in [Bouamama

et al., 2006], is extended here for multi-component gas mixture as shown in Fig. 5.8.
The after-burner outlet enthalpy flow rate, which is also the hot fluid inlet enthalpy
141
Chapter 5
flow rate of the hydrogen heat exchanger (HX1), is given by the CETF element. The
CETF element is modulated by the after-burner outlet species mass flow rates given
by Eqs. (5.80–5.82). The heat exchanger is assumed to be an ideal one in which the
pressure and the mass flow rates do not change between the inlet and the outlet sides.
This is justified from the point that SOFC systems operate at a little above the
atmospheric pressure and thus the pressure difference across the heat exchangers is
negligible. The thermal capacitances of the hot and the cold fluids of the heat
exchanger, HX1, are represented by Ch and Cc elements, respectively, in Fig. 5.7. The
capacitance of the solid wall separating the two fluids is neglected [Chantre et al.,
1994] because we are not interested in the start-up dynamics. The cold fluid inlet
enthalpy flow rate is given by the CETF element which is modulated by the anode
i
inlet mass flow rate signal ( m an ), whereas the cold fluid outlet mass flow rate is given
by the MSf element which is modulated by the signals of the anode inlet mass flow
i
rate ( m an ) and the temperature of the cold fluid. The heat transfer rate between the hot
and the cold fluids of the hydrogen heat exchanger (HX1) is modelled by the MR
element (modulated with mass flow rate signals) using the NTU formulation given in
Eqs. (5.83–5.86) as the constitutive relations. The air heat exchanger (HX2) is also
modelled in a similar fashion. The temperatures defined by the cold fluid thermal
capacitances (Cc) of the heat exchangers HX1 and HX2 are given as those of the
anode and the cathode inlet temperatures (Tai and Tci, respectively) to the SOFC bond
graph model shown in Fig. 5.2. The chemical potentials of the gas species at the
channel inlets ( μH,ai , μ N,ci and μO,ci ) are also represented as functions of these
temperatures by using Eqs. (5.73 and 5.74).
The simulations are performed with the same parameters (given in Table 5.1),
which were used in the optimisation algorithm. The aim of the simulations is to
compare the dynamic responses of the SOFC system, operated by using three
different control strategies, subjected to a step change in the load current. The first
control strategy, referred to as ‘Strategy 1’, consists of operating the fuel cell system
under the maximum efficiency conditions. This is achieved by manipulating the anode
and the cathode inlet mass flow rates according to the polynomial relations in terms of
the current, which are obtained by fitting the data (within the operating current density
142
range) resulting from the optimization program. The second control strategy, referred
to as ‘Strategy 2’, consists of operating the fuel cell under constant FU and variable
OU conditions. This is achieved by the manipulation of the inlet mass flow rates
according to the polynomial relations discussed in the Section 5.3.2.
Fig. 5.8: Expanded Form of CETF Element for Multi-component Gas Mixtures
In addition to the constant FU requirement, another requirement for the fuel cell
operation is to maintain constant cell temperature despite the changes in the load
[Stiller et al., 2006]. This is usually achieved by manipulating the cathode inlet mass
flow rate [Aguiar et al., 2005; Mueller et al., 2006; Stiller et al., 2006] (i.e.,
manipulating the OU). In this work, the constant cell temperature requirement is
achieved by means of introducing a PI controller, which manipulates the cathode inlet
mass flow rate around the value, set by using the cubic polynomial relation mentioned
earlier. Doing so will cause the cathode inlet mass flow rate to deviate from the value
corresponding to that of the maximum efficiency operation. Naturally, this will also
result in decrease of the system efficiency. The absolute values of the proportional
and the integral gains used for the PI controller are 1e-4 and 1e-10, respectively. The
constant FU and the constant temperature operation of the SOFC system, referred to
as ‘Strategy 3’, is simulated in order to investigate the effect of maintaining constant
cell temperature on the system efficiency. The parameter values used in the
simulation are the same as those given in Table 5.1.
In the simulation, the load current density is changed from 0.8 A/cm2 to 0.6 A/cm2
at 500s. The closed loop dynamic responses of the cell voltage, the temperature and
143
Chapter 5
the energy and the exergy efficiencies of the SOFC system operated by using the three
above mentioned three operating strategies are given in Figs. 5.9 and 5.10,
respectively.
The dynamic responses of the cell voltage due to the step change in the current
density for the SOFC system operated by using the three operating strategies are
given in Fig. 5.9a. It can be seen from the Fig. 5.9a that the difference in the cell
voltage between the three operating strategies is very less. The initial steady state
voltages of the cell operating using ‘Strategy 2’ and ‘Strategy 3’ coincide because the
temperature set-point for the PI controller is given as the initial steady state
temperature. The cell operation by using ‘Strategy2’ gives the highest voltage and is
closely followed by ‘Strategy 3’. Maximum efficiency operation of the fuel cell gives
the minimum voltage. Overshoot in the voltage response is observed in all three cases.
The highest overshoot is observed in the case of ‘Strategy 1’ followed by ‘Strategy 2’.
Operating the cell using ‘Strategy 3’ gives rise to very little overshoot, which means a
good transient response. From the dynamic voltage response, it can be concluded that
operating the fuel cell using ‘Strategy 3’ is better than the other two strategies as it
results in high voltage and a good transient response.
(a) (b)
Fig. 5.9: Dynamic Response Curves of (a) Voltage and (b) Temperature of the SOFC System Operated
by Using Three Different Control Strategies
144
The temperature dynamic response is given in Fig. 5.9b. Here too it is found that
‘Strategy 3’ is the best operating strategy for the fuel cell, as the temperature is
maintained constant, while ‘Strategy 1’ is the worst as it gives rise to a large change
in cell temperature.
The energy and exergy efficiencies of the fuel cell system operated using the three
operating strategies are shown in Fig. 5.10 for comparison. It can be seen that the
difference in the system efficiencies (energy and exergy) between the three operating
strategies is very less. Operating the fuel cell by using ‘Strategy 1’ gives the
maximum system efficiencies (both energy and exergy), whereas ‘Strategy 3’ gives
the lowest system efficiencies (both energy and exergy). From the results, we
conclude that for obtaining a constant FU operation, some system efficiency has to be
sacrificed. A further sacrifice of system efficiency is necessary if the cell temperature
is to be maintained constant.
Fig. 5.10: Energy and Exergy Efficiencies of the SOFC System Operated by Using Three Different
Control Strategies
‘Strategy 3’ gives the most favourable operating conditions (constant FU and

temperature) although it results in slightly decreased system efficiency (both energy
and exergy). However, this decrease in the system efficiency is very small. Thus, it
145
Chapter 5
can be concluded that ‘Strategy 3’ closely approximates the maximum efficiency

operation of the fuel cell in terms of the system efficiencies, in addition to providing
the most favourable operating conditions, i.e. constant FU and cell temperature.
5.5. Conclusions
An algorithm has been developed in this chapter to find the optimal operating
conditions of a hydrogen fed SOFC system. This algorithm makes use of a steady
state model of the SOFC and also the steady state models of the after-burner and the
heat exchangers. For this purpose, a comprehensive steady state model of the SOFC
has been developed for the first time from the previously developed true bond graph
model. This steady state model can be solved to find the steady state values of the
variables of interest such as the temperatures, pressures, outlet mass flow rates,
voltage, fuel and oxygen utilizations, power and efficiency from the given inputs: the
anode and the cathode inlet mass flow rates and the current drawn from the fuel cell.
For a particular value of the current density, the developed algorithm maximises the
system efficiency by considering the anodic and the cathodic inlet mass flow rates as
the design variables and it also gives the values of the corresponding cell operating
conditions.
It is observed from the results of the optimization study that the anode inlet mass
flow rate corresponding to the maximum system efficiency has an approximately
linear relationship with the current density. This implies that the constant FU
operation of the fuel cell at a particular value of the FU (which depends upon the
system) can closely approximate the maximum efficiency operation of the fuel cell in
terms of the cell operating conditions as well as the energy and the exergy efficiencies.
The comparison between constant FU operation and the maximum efficiency
operation curves shows that the operating conditions of the cell are nearly the same
for both the cases. These results indicate that within the operating range of the SOFC
system, the sensitivity of the system efficiency to the variation in the FU is small.
146
The closed loop responses of the SOFC system operated by using three different
control strategies (maximum efficiency, constant FU, constant FU and temperature;
referred to as ‘Strategy 1’, ‘Strategy 2’ and ‘Strategy 3’, respectively), during a step
change in the load current are compared. It is found from the simulations that the
differences in the operating conditions between the fuel cell operated using the three
control strategies is small. It is also found that some system efficiency has to be
sacrificed to operate the fuel cell under constant FU and constant temperature
conditions. However, this decrease in the system efficiency is very small to be of any
significance. Thus, it can be concluded that ‘Strategy 3’ operation of the SOFC
closely approximates the maximum efficiency operation in terms of the system
efficiencies, in addition to providing the most favourable operating conditions, i.e.
constant FU and cell temperature. However, the constant FU value for the specific
fuel cell system has to be designed from the optimization studies and it may change
due to gradual changes to the system, e.g., degradation of the heat transfer coefficients
of the heat exchangers over long periods of operation.
Moreover, it is of interest to note that if an MEA material that has good capacity
to endure cyclic temperature stresses were developed in the future then ‘Strategy 2’
would be the preferred control law because it would give near maximum efficiency
with a very simple control law.
147
Chapter 5
148
Chapter 6
Conclusions
This dissertation deals with modelling the dynamics of the multi disciplinary SOFC
system through bond graphs. Control strategies for improving the SOFC’s dynamic
performance and for optimising its operational efficiency under varying loads have
also been investigated.
A zero-dimensional true bond graph model of the SOFC is developed in Chapter 3

by using the concepts of network thermodynamics. This model incorporates several
corrective modifications over the previous bond graph models of the electrochemical
reaction systems available in the literature. They include the use of internal energy as
the thermodynamic potential of the C-field used in modelling the chemical reaction
systems, the formulation and use of a C-field to model the energy storage in two
species gas mixtures encountered in an SOFC, and the extension and use of an R-field
to represent the entropy convection in the SOFC inlet and outlet gas streams. The
Chapter 6
problem of differential causality, which was present in the earlier models given in the
literature, is eliminated by using the internal energy as the thermodynamic potential
for the C-field in the developed bond graph model.
This is the first time a completely true bond graph model of a fuel cell has been
developed. This model ensures the thermodynamic consistency of the system and it
clearly illustrates the physical structure of the system. The couplings between the
various energy domains in a fuel cell system have been represented in a unified
manner by using true bond graphs. The developed model is useful for designing
integrated model-based control strategies for the SOFC system.
The true bond graph model is simulated after proper initialisation and the
simulation results are given in Chapter 4. For a given set of input parameters, the
partial pressures of the gas species in the channels are related to the FU and the OU of
the SOFC by solving the steady state mass balance equations. Using these relations,
the static characteristic curves of the SOFC have been obtained for various operating
conditions. SOFC’s transient response to step changes in the load current have been
studied through simulations. It is concluded from the transient response results that
the true bond graph model developed in this work captures all the essential dynamics
of the SOFC.
Thereafter, the radiation heat transfer effects within the cell and an improved
representation of the concentration polarisation (considering diffusion of gases
through the electrodes) are included in the bond graph model. Then the improved
model is used to test a physical model-based control strategy developed in this work
to achieve the common SOFC control objectives. It is concluded from the simulations
that all the control objectives involving the constraints on the FU, the OU, the cell
operating temperature and the pressure difference between the anode and the cathode
channels are achieved by the proposed control system. It is also shown that the
temperature and the pressure control objectives are conflicting requirements and some
trade off may be required between them in practice.
In the last part of the work, a comprehensive steady state model of the SOFC has
been developed from the true bond graph model. An algorithm has been developed to
150
Conclusions
optimise the operational efficiency of the SOFC system (consisting of the cell, the
after-burner and two recuperators) under varying load conditions. This algorithm
utilises the developed steady state model of the SOFC and also the steady state
models of the after-burner and the heat exchangers. From the optimisation results, it is
found that the constant FU operation of the fuel cell at a particular value of FU (which
depends upon the system) can closely approximate the maximum efficiency (both the
energy and the exergy efficiencies) operation of the fuel cell and at the same time it
can maintain favourable cell operating conditions, i.e. satisfy the constraints on the
temperatures and the difference between the anode and the cathode channel pressures.
Dynamic responses of the SOFC system which was operated using three different
control strategies have been compared. It is concluded that the constant FU and
constant temperature operating strategy is best for the SOFC system in terms of both
the system efficiency and the cell life. However, if an MEA material that has good
capacity to endure cyclic temperature stresses is developed in the future then the
constant FU operation would be the preferred control strategy because it would give
the near maximum efficiency with a very simple control law.
Based on this work, the following areas are suggested for further exploration.
• A one or two dimensional model of the SOFC may be constructed by

considering more lumps of the cell control volume, each lump being
represented by the model developed in this work. Such a higher dimensional
model may be used for studying the spatial distribution of the intensive
variables such as the temperature, pressure, voltage etc. under different
operating conditions.
• In this work, the electrical load part is represented by a flow source. In future
work, the electrical domain model may be extended by including the models
of the power conditioning components and various kinds of loads. Such an
extended model may be used for designing integrated model based control
strategies for the overall system.
151
Chapter 6
• The non-linear bond graph model of the SOFC developed in this work may
be used for state estimation so as to implement advanced control methods such
as the model predictive control for the SOFC system.
• Pure hydrogen has been considered in this work as the fuel for the SOFC.
However, the SOFC is capable of operating with other hydrocarbon fuels such
as methane. In the future, the model may be extended to include such fuels.
This will involve modelling the reforming and the shift reactions (reactions
through which the hydrocarbons are broken down to hydrogen). The
reforming reactions are endothermic reactions and when they occur inside the
SOFC, they take up the heat released due to the exothermic hydrogen
oxidation reaction. Sometimes, these reforming and shift reactions are
designed to occur at a reformer so that pure hydrogen is supplied to the cell.
Models of the reforming and the shift reactions may be included, either in the
cell or in an upstream side reformer so as to study their effect on the SOFC
system’s dynamics.
• SOFCs are sometimes coupled with gas turbines to improve the efficiency of
the system by utilising the energy in the exhaust gases. The model of a gas
turbine may be integrated with the SOFC model developed in this work to
study the dynamics of such hybrid power generation systems.
• In this work, the activation and the concentration polarisations are modelled
as voltage losses and they are represented in the electrical side of the system.
However, the activation polarisation losses can be modelled by including the
models of the charge transfer phenomena at the electrode electrolyte
interfaces, the charge transport through the electrolyte and the micro kinetics
of the electrode surface reactions. The time scales of such processes are very
small when compared to the thermal and hydraulic dynamics of the SOFC.
Therefore, coupling them with the model developed in this work and
simulating them together is a challenging task. Such multi-scale simulations
may be performed in the future. Also, detailed models of the diffusion
processes leading to the concentration over-voltage may be incorporated into
the model developed in this work.
152
References
[1] Achenbach E. Response of a Solid Oxide Fuel Cell to Load Change. J. Power
Sources, 1995, 57,105–109.
[2] Aguiar, P., Adjiman, C. S., and Brandon, N. P. Anode-supported intermediate-

temperature direct internal reforming solid oxide fuel cell I. Model-based
steady-state performance. J. Power Sources, 2004, 138, 120–136.
[3] Aguiar, P., Adjiman, C. S., and Brandon, N. P. Anode-supported intermediate-

temperature direct internal reforming solid oxide fuel cell II. Model-based
dynamic performance and control. J. Power Sources, 2005, 147, 136–147.
[4] Akkaya, A. V., Sahin, B., and Erdem, H. H. Exergetic performance coefficient
analysis of a simple fuel cell system. Int. J. Hydrogen Energy, 2007, 32, 4600
– 4609.
[5] Auslander, D. M., Oster, G. F., Perelson A., and Clifford, G. On systems with
coupled chemical reaction and diffusion. Trans. ASME, J. Dyn. Syst. Meas.
Control, 1973, 94, 239–248.
References
[6] Balaji, C., Hölling, M., and Herwig, H. Entropy generation minimization in
turbulent mixed convection flows. Int. Commns. Heat and Mass Transfer,
2007, 34, 544–552.
[7] Basu, S. Recent Trends in Fuel Cell Science and Technology, 2007 (Anamaya
Publishers, New Delhi).
[8] Bejan, A. Fundamentals of exergy analysis, entropy generation minimization,

and the generation of flow architecture. Int. J. Energy Res., 2002, 26, 545–565.
[9] Bejan, A. Method of entropy generation minimization, or modeling and

optimization based on combined heat transfer and thermodynamics. Rev Ge’n
Therm, 1996, 35, 637–646.
[10] Benson, R. S. Advanced Engineering Thermodynamics. 2nd ed., 1977

(Pergamon Press Limited).
[11] Benson, S. W. The foundations of chemical kinetics, 1960 (McGraw-Hill book

company, New York).
[12] Bockris, J. O'M., Reddy, A. K. N. and Gamboa-Aldeco, M. Modern

Electrochemistry: Fundamentals of Electrodics, 2nd edition, 1998, (Kluwer
Academic/Plenum Publishers).
[13] Borutzky, W. Bond graph modeling from an object oriented modeling point of
view. Simulation Practice and Theory, 1999, 7 (5), 439–461.
[14] Borutzky, W., Barnard, B., and Thoma, J. U. Describing bond graph models of
hydraulic components in Modelica. Mathematics and Computers in Simulation,
2000, 53 (4–6), 381–387.
[15] Bouamama, B. O. Bond graph approach as analysis tool in thermofluid model

library conception. J. Franklin Institute, 2003, 340 (1), 1–25.
[16] Bouamama, B. O., Medjaher, K., Samantaray, A. K., and Staroswiecki, M.

Supervision of an industrial steam generator. Part I: Bond graph modeling.
Control Engineering Practice, 2006, 14 (1), 71–83.
[17] Breedveld P. C., and Dauphin-Tanguy, G. Bond Graphs for Engineers, 1992
(North-Holland, Amsterdam).
[18] Breedveld, P. C. Physical Systems Theory in terms of Bond Graphs. Ph.D.

Thesis, Twente University, Enschede, 1984.
[19] Breedveld, P. C., and Beaman, J. J. Physical systems modelling with Eulerian
frames and bondgraphs. Proc. ASME winter meeting, Miami, USA, 1985.
[20] Brown, F. T. Engineering System Dynamics – A Unified Graph Centered

Approach, 2007 (Taylor & Francis Group, FL).
154
References
[21] Brown, F. T. Non-iterative evaluation of multiphase thermal compliances in

bond graphs. Proc. IMechE, Part I: J. Systems and Control Engineering,
2002a, 216 (1), 13–19.
[22] Brown, F. T. Simulating distributed-parameter multiphase thermodynamic

systems using bond graphs. ASME Dynamic Systems and Control, 2002b, 71,
545–553.
[23] Bruun, K., and Pedersen, E. Bond Graph Model of a High Temperature Fuel
Cell. Proc. ICBGM'07, 2007, 39 (1), 256–263.
[24] Butt, J. B. Reaction Kinetics and reactor design, 2000 (Marcel Dekker Inc.,
New York).
[25] Calise, F., Palombo, A., and Vanoli, L. Design and partial load exergy analysis
of hybrid SOFC–GT power plant. J. Power Sources, 2006, 158, 225–244.
[26] Callen, H. B. Thermodynamics and an introduction to thermostatistics, 1985

(John .Wiley & Sons, Inc.).
[27] Campanari, S., and Iora, P. Definition and sensitivity analysis of a finite
volume SOFC model for a tubular cell geometry. J. Power Sources, 2004,
132, 113–126.
[28] Caux, S., Lachaize, J., Fadel, M., Shott, P., and Nicod, L. Modelling and
control of a Fuel Cell System and Storage Elements in transport applications. J.
Process Control, 2005, 15, 481–491.
[29] Cellier, F. E., Continuous System Modeling, 1991 (Springer-Verlag, New

York).
[30] Chan, S. H., Khor, K. A., and Xia, Z. T. A complete polarization model of a
solid oxide fuel cell and its sensitivity to the change of cell component
thickness. J. Power Sources, 2001, 93, 130–140.
[31] Chan, S. H., Low, C. F., and Ding, O. L. Energy and exergy analysis of simple
solid-oxide fuel-cell power systems. J. Power Sources, 2002, 103, 188–200.
[32] Chantre, P., Maschke, B.M., and Barthelemy, B. Physical modeling and
parameter identification of a heat exchanger, Industrial Electronics, Control
and Instrumentation, IECON '94, Bologna, Italy, 1994, 3, 1965–1970.
[33] Chen, K. I., Winnick, J., and Manousiouthakis, V. I. Global optimization of a

simple mathematical model for a proton exchange membrane fuel cell.
Computers and Chemical Engineering, 2006, 30, 1226–1234.
[34] Choi, W. Howze, Jo. W., and Enjeti, P. Development of an equivalent circuit
model of a fuel cell to evaluate the effects of inverter ripple current. J. Power
Sources, 2006, 158, 1324–1332.
155
References
[35] Cownden, R., Nahon, M., and Rosen, M. A. Exergy analysis of a fuel cell
power system for transportation applications. Exergy Int. J., 2001, 1 (2), 112–
121.
[36] Denbigh, K. The principles of chemical equilibrium, 1955 (Cambridge

university press).
[37] Dicks, A. L., and Martin, P. A. A Fuel Cell Balance of Plant Test Facility. J.
Power Sources, 1998, 71, 321–327.
[38] Douvartzides, S. L., Coutelieris, F. A., and Tsiakaras, P.E. On the systematic
optimization of ethanol fed SOFC-based electricity generating systems in
terms of energy and exergy. J. Power Sources, 2003, 114, 203–212.
[39] Esperilla, J. J., Felez, J., and Vera, C. Thermal model for lead-acid batteries.
Proc. ICBGM’03, 2003, 35, 293–299.
[40] Esperilla, J. J., Félez, J., Romero, G., and Carretero, A. A full model for
simulation of electrochemical cells including complex behavior. J. Power
Sources, 2007a, 165, 436–445.
[41] Esperilla, J. J., Félez, J., Romero, G., and Carretero, A. A model for
simulating a lead-acid battery using bond graphs. Simulation Modelling
Practice and Theory, 2007b, 15, 82–97.
[42] Esperilla, J. J., Vera, C., Felez, J., and Mera, J. M. Electrochemical cells
modeling by means of the bond graph technique: Application of lead-acid
batteries using the bond graph technique. Proc. ICBGM’05, 2005, 255–261.
[43] Fahrenthold, E. P., and Venkataraman, M. System Dynamics Modeling of

Porous Media. J. Dynamic systems, Measurement and Control, 1997, 119,
251–259.
[44] Feenstra, P. J. A Library of Port-based Thermo-Fluid Submodels. M.Sc.Thesis.

University of Twente, 2000.
[45] Franco, A. A., Schott, P., Jallut, C. and Maschke, B. A dynamic mechanistic
model of an electrochemical interface. J. The Electrochemical Society, 2006,
153 (6), A1053–A1061.
[46] Franco, A. A., Schott, P., Jallut, C. and Maschke, B. Multi-scale Bond Graph
Model of the electrochemical dynamics in a fuel cell. In Proc. 3rd European
PEFC Forum, Lucerne, Switzerland, 2005a, Paper no. B063.
[47] Franco, A. A., Schott, P., Jallut, C. and Maschke, B. Multi-scale Bond Graph
Model of the electrochemical dynamics in a fuel cell. In Proc. 5th MATHMOD
Conference, Vienna, Austria, 2005b, ISBN 3-901608-25-7.
156
References
[48] Frangopoulos, C. A., and Nakos, L. G. Development of a model for

thermoeconomic design and operation optimization of a PEM fuel cell system.
Energy, 2006, 31, 1501–1519.
[49] Gawthrop P., and Smith, L. MetaModeling: Bond graphs and Dynamic
Systems, 1996 (Prentice-Hall).
[50] Gawthrop, P. J. Bond graphs: A representation for mechatronic systems.

Mechatronics, 1991, 1 (2), 127–156.
[51] Gawthrop, P. J. Thermal modelling using mixed energy and pseudo bond
graphs. Proc. IMechE, Part I: J. Systems and Control Engineering, 1999, 213
(3), 201–216.
[52] Golbert, J., and Lewin, D. R. Model-based control of fuel cells (2): Optimal
efficiency. J. Power Sources, 2007, 173, 298–309.
[53] Granda J. J. The role of bond graph modelling and simulation in mechatronics
systems–An integrated software tool: CAMP-G, MATLAB-SIMULINK.
Mechatronics, 2002, 12, 1271–1295.
[54] Granda, J. J., and Tang, S. Computer simulation of heat transfer models using
a pseudo bond graph network. Transactions of the Society for Computer
Simulation International, 1989, 5 (4), 265–283.
[55] Grove, W. R. On Gaseous Voltaic Battery. Phil. Mag., S.3, 1842, 21, 417.
[56] Grove, W. R. On Voltaic Series and the Combination of Gases by Platinum.

Phil. Mag., S.3, 1839, 14, 127.
[57] Hasikos, J., Sarimveis, H., Zervas, P.L., and Markatos, N.C. Operational
optimization and real-time control of fuel-cell systems. J. Power Sources,
2009, doi:10.1016/j.jpowsour.2009.01.048.
[58] He, W. Dynamic model for molten carbonate fuel cell power generation
systems. Energy Conversion and Management, 1998, 39 (8), 775–783.
[59] Heny, C., Simanca, D., and Delgado, M. Pseudo-bond graph model and
simulation of a continuous stirred tank reactor. J. Franklin Institute, 2000, 337,
21–42.
[60] Holman, J. P. Thermodynamics. 4th edition, 1988 (McGraw-Hill, Inc,

Singapore).
[61] Houston, P. L. Chemical kinetics and reaction dynamics, 2001 (McGraw Hill
book company, Singapore).
[62] Hubbard, M., and Brewer, J. W. Pseudo bond graphs of circulating fluids with
application to solar heating design. J. Franklin Institute, 1981, 311 (6), 339–
354.
157
References
[63] Hussain, M. M., Baschuk, J. J., Li, X., and Dincer, I. Thermodynamic analysis
of a PEM fuel cell power system. Int. J. Thermal Sciences, 2005, 44, 903–911.
[64] Incropera, F. P., and Dewitt, D. P. Fundamentals of Heat and Mass transfer,
1996, (4th edition, Wiley, New York).
[65] Kandepu, R., Imsland, L., Foss, B. A., Stiller, C., Thorud, B., and Bolland, O.
Modeling and control of SOFC-GT-based autonomous power system. Energy,
2007, 32, 406–417.
[66] Karnopp, D. Bond graph models for electrochemical energy storage: Electrical,
Chemical and Thermal effects. J. Franklin institute, 1990, 327 (6), 983–992.
[67] Karnopp, D. C. State variables and pseudo-bond graphs for compressible

thermo-fluid systems. J. Dynamic Systems, Measurement and Control, 1979,
101, 201–204.
[68] Karnopp, D. C., Margolis, D. L., and Rosenberg, R. C. System Dynamics:

Modeling and Simulation of Mechatronic Systems. 4th ed. 2006, (John Wiley
& Sons Inc., New Jersey).
[69] Karnopp, D. C., Margolis, D. L., and Rosenberg, R. C. System Dynamics: A

Unified Approach, 2nd ed., 1990b (Wiley, New York).
[70] Karnopp, D. Pseudo bond graphs for thermal energy transport. J. Dynamic
Systems, Measurement and Control, Transactions of the ASME, 1978, 100 (3),
165–169.
[71] Kazim, A. Exergy analysis of a PEM fuel cell at variable operating conditions.
Energy Conversion and Management, 2004, 45, 1949–1961.
[72] Kim, J., Virkar, A. V., Fung, K., Mehta, K., and Singhal, S. C. Polarization
Effects in Intermediate Temperature, Anode-Supported Solid Oxide Fuel
Cells. J. The Electrochemical Society, 1999, 146 (1), 69–78.
[73] Krane, R. J. A Second Law analysis of the optimum design and operation of
thermal energy storage systems, Int. J. Hear Mass Transfer. 1987, 30 (1), 43–
57.
[74] Lagarias, J.C., Reeds, J. A., Wright, M. H., and Wright, P. E. Convergence
Properties of the Nelder-Mead Simplex Method in Low Dimensions. SIAM J.
Optimization, 1998, 9 (1), 112–147.
[75] Liebhafsky, H. A., and Cairns, E. J. Fuel Cells and Fuel Batteries: A guide to
their research and development, 1968 (John Wiley and Sons, New York).
[76] Lin, H. H., Cheng, C. H., Soong, C. Y., Chen, F., and Yan, W. M.
Optimization of key parameters in the proton exchange membrane fuel cell. J.
Power Sources, 2006, 162, 246–254.
158
References
[77] Maximov, J. T. Thermodynamic optimization of mechanical systems with

dissipative processes. Int. J. Mechanical Sciences, 2006, 48, 62–74.
[78] Monanteras, N. C., and Frangopoulos, C. A. Towards synthesis optimization

of a fuel-cell based plant. Energy Conversion & Management, 1999, 40,
1733–1742.
[79] Mueller, F., Brouwer, J., Jabbari, F., and Samuelsen, S. Dynamic Simulation
of an Integrated Solid Oxide Fuel Cell System Including Current-Based Fuel
Flow Control. J. Fuel Cell Science and Technology, 2006, 3, 144–154.
[80] Mukherjee, A., Karmakar, R., and Samantaray, A. K. Bond Graph in

Modeling, Simulation and Fault Identification. 2006 (CRC Press, Florida,
ISBN: 9781420058659).
[81] Murshed, AKM. M., Huang, B., and Nandakumar, K. Control relevant
modeling of planar solid oxide fuel cell system. J. Power Sources, 2007, 163,
830–845.
[82] Na, W., and Gou, B. The efficient and economic design of PEM fuel cell
systems by multi-objective optimization. J. Power Sources, 2007, 166, 411–
418.
[83] Nakrachi, A., and Dauphin-Tanguy G. A distributed parameter pseudo bond

graph for heat conduction modeling: Notion of cellular bond graph. ASME,
Dynamic Systems and Control Division, 2003, DSC 72 (2), 911–916.
[84] Nelder, J. A., and Mead, R. A simplex method for function minimization.
Computer Journal, 1965, 7, 308–313.
[85] Ogulata, R. T., and Doba, F. Experiments and entropy generation

minimization analysis of a cross-flow heat exchanger Int. J. Heat and Mass
Transfer. 1998, 41 (2), 373–381.
[86] Onsager, L. Reciprocal Relations in Irreversible Processes I. Physical Review,

1931, 37, 405–426.
[87] Onsager, L. Reciprocal Relations in Irreversible Processes II. Physical Review,

1931, 38, 2265–2279.
[88] Oster, G. F., Perelson, A. S., and Katchalski, A. Network thermodynamics :

dynamic modeling of biophysical systems. Q. Rev. Biophysics, 1973, 6 (1), 1–
134.
[89] Oster, G., Perelson, A., and Katchalsky, A. Network Thermodynamics. Nature,
1971, 234, 393–399.
[90] Palazzi, F., Autissier, N., Marechal, F. M. A., and Favrat, D. A methodology
for thermo-economic modeling and optimization of solid oxide fuel cell
systems. Applied Thermal Engineering, 2007, 27, 2703–2712.
159
References
[91] Pannetier, G., and Souchay, P. Chemical Kinetics, 1967 (Elsevier Publishing
Co. Ltd., Essex, England).
[92] Paynter, H. M. Analysis and Design of Engineering Systems, 1961 (M. I. T.

Press, Cambridge).
[93] Perelson, A. S., Network Thermodynamics, An Overview, Biophysical

Journal, 1975, 15, 667–685.
[94] Petruzzi, L., Cocchi, S., and Fineschi, F. A global thermo-electrochemical

model for SOFC systems design and engineering. J. Power Sources, 2003, 118,
96–107.
[95] Pukrushpan, J. T., Peng, H., and Stefanopoulou, A. G. Simulation and analysis
of transient fuel cell system performance based on a dynamic reactant flow
model. In Proc. ASME International Mechanical Engineering Congress &
Exposition, IMECE, 2002.
[96] Qi, Y., Huang, B., and Chuang, K. T. Dynamic modeling of solid oxide fuel
cell: The effect of diffusion and inherent impedance. J. Power Sources, 2005,
150, 32–47.
[97] Qi, Y., Huang, B., and Luo, J. Dynamic modeling of a finite volume of solid
oxide fuel cell:The effect of transport dynamics. Chemical Engineering
Science, 2006, 61, 6057–6076.
[98] Rosen, M. A. Comparison based on energy and exergy analyses of the

potential cogeneration efficiencies for fuel cells and other electricity
generation devices. Int. J. Hydrogen Energy, 1990, 15 (4), 267–274.
[99] Rosen, M. A., and Scott, D. S. A Thermodynamic investigation of the

potential for cogeneration for fuel cells. Int. J. Hydrogen Energy, 1988, 13
(12), 775–782.
[100] Rosenberg R.C., and Karnopp, D.C. Introduction to Physical System

Dynamics, 1983 (Mc Graw Hill, New York).
[101] Sabersky, R. H., Acosta, A. J., and Hauptmann, E. Fluid Flour, 1971
(Macmillan, New York).
[102] Saidi, M. H., Ehyaei, M. A., and Abbasi, A. Optimization of a combined heat
and power PEFC by exergy analysis. J. Power Sources, 2005, 143, 179–184.
[103] Saisset, R., Fontes, G., Turpin, C., and Astier, S. Bond Graph model of a PEM
fuel cell. J. Power Sources, 2006, 156, 100–107.
[104] Samantaray, A. K., and Mukherjee, A. Users Manual of SYMBOLS Shakti,

2006 (High-Tech Consultants, STEP, Indian Institute of Technology,
Kharagpur, <http://www.htcinfo.com/>).
160
References
[105] Serra, M., Aguado, J., Ansede, X., and Riera, J., Controllability analysis of
decentralized linear controllers for polymeric fuel cells. J. Power Sources,
2005, 151, 93–102.
[106] Shoureshi, R., and McLaughlin, K. Modeling and dynamics of two-phase flow
heat exchangers using temperature–entropy bond graphs. Proc. American
Control Conference, 1984, 1, 93–98.
[107] Singhal S. C. Advances in solid oxide fuel cell technology. Solid State Ionics,
2000a, 135, 305–313.
[108] Singhal, S. C. Science and Technology of Solid-Oxide Fuel Cells. MRS Bull.
2000b, 25 (3), 16–21.
[109] Singhal, S. C., and Kendall, K. High Temperature Solid Oxide Fuel Cells:
Fundamentals, Design and Applications, 2003 (Elsevier Ltd).
[110] Song, S., Douvartzides, S., and Tsiakaras, P. Exergy analysis of an ethanol
fuelled proton exchange membrane (PEM) fuel cell system for automobile
applications. J. Power Sources, 2005, 145, 502–514.
[111] Stambouli, A. B., and Traversa, E. Solid oxide fuel cells (SOFCs): a review of
an environmentally clean and efficient source of energy, Renewable &
Sustainable Energy Reviews, 2002, 6, 433–455.
[112] Stiller, C., Thorud, B., Bolland, O., Kandepu, R., and Imsland, L. Control
strategy for a solid oxide fuel cell and gas turbine hybrid system. J. Power
Sources, 2006, 158, 303–315.
[113] Subramanyan, K., and Diwekar, U. M. Optimizing model complexity with

application to fuel cell based power systems. Chemical Engineering and
Processing, 2007, 46, 1116–1128.
[114] Thoma J. Electric batteries and fuel cells modeled by bond graphs. Simulation
Practice and Theory, 1999, 7 (5-6), 613–622.
[115] Thoma, J. U. Simulation by Bondgraphs: Introduction to a Graphical Method,

1990 (Springer Verlag, Berlin).
[116] Thoma, J., and Bouamama, B. O. Modelling and Simulation in Thermal and
Chemical Engineering, 2000 (Springer-Verlag, New York).
[117] Thomas, P. Simulation of Industrial Processes for Control Engineer, 1999

(Butterworth Heinemann, London).
[118] Virkar, A. V., Chen, J., Tanner, C. W., and Kim, J. The role of electrode
microstructure on activation and concentration polarizations in solid oxide
fuel cells. Solid State Ionics, 2000, 131, 189–198.
161
References
[119] Wachter, C., Lunderstadt, R., and Joos, F. Dynamic model of a pressurized
SOFC/Gas turbine hybrid power plant for the development of control concepts.
J. Fuel Cell Science and Technology, 2006, 3, 271–279.
[120] Wang, X., Huang, B., and Chen, T. Data driven predictive control of solid
oxide fuel cells. J. Power Sources, 2007, 17, 103–114.
[121] Wright, M. R. Introduction to chemical kinetics, 2004 (John Wiley and sons
Ltd., West Sussex, England).
[122] Wu, J., Liu, Q., and Fang, H. Toward the optimization of operating conditions
for hydrogen polymer electrolyte fuel cells. J. Power Sources, 2006, 156, 388–
399.
[123] Wyatt, J. L. jr. Network Representation of Reaction–Diffusion Systems far

from Equilibrium, Computer Programs in Biomedicine, 1978, 8, 180–195.
[124] Yeh, T. K., and Chen, C. H. Modeling and optimizing the performance of a
passive direct methanol fuel cell. J. Power Sources, 2008, 175, 353–362.
[125] Yu, Q., Choe, S., Srivastava, A. K., and Gao, W. Improved Modeling and
Control of a PEM Fuel Cell Power System for Vehicles. In Proc. IEEE
SoutheastCon, 2005, 331–336.
[126] Zemansky, M. W., and Dittman, D. H. Heat and Thermodynamics, 1997,

(McGraw-Hill, Singapore).
[127] Zhang, X., Li, J., Li, G., and Feng, Z. Cycle analysis of an integrated solid
oxide fuel cell and recuperative gas turbine with an air reheating system. J.
Power Sources, 2007, 164 (2), 752–760.
[128] Zhu, H., and Kee, R. J. A general mathematical model for analyzing the
performance of fuel-cell membrane-electrode assemblies, J. Power Sources,
2003, 117, 61–74.
[129] Zhu, Y., and Tomsovic, K. Development of models for analyzing the load-
following performance of microturbines and fuel cells. Electric Power Systems
Research, 2002, 62, 1–11.
162
Appendices
Appendix A
Bond graph Notations Revisited
A.1. Introduction
In this appendix, a concise introduction to the bond graph modelling method is given.
Bond graph is a graphical tool based on the power exchanges between different
dynamical parts in a system. A bond graph model is capable of providing physical
insight into the dynamic behaviour of a system. Moreover, the notation of causality
provides a tool not only for formulation of system equations but also for qualitative
analysis of the system behaviour, viz. controllability, observability, fault diagnosis, etc.
Appendices
In 1959, Paynter [Paynter, 1961] gave the revolutionary idea of portraying

systems in terms of power bonds, connecting the elements of the physical system to
the so called junction structures which were manifestations of the constraints. Later
on, bond graph theory has been developed further by many researchers [Breedveld &
Dauphin-Tanguy, 1992; Brown, 2007; Cellier, 1991; Gawthrop & Smith, 1996;
Karnopp et al., 1990; Karnopp & Rosenberg, 1983; Mukherjee et al., 2006; Thoma,
1990] who have worked on extending this modelling technique to power hydraulics,
mechatronics, general thermodynamic systems and recently to electronics and non-
energetic systems like economics and queuing theory.
Through bond graph approach, a physical system can be represented by symbols

and lines, identifying the power flow paths. The lumped parameter elements of
resistance, capacitance and inertance are interconnected in an energy conserving way
by bonds and junctions resulting in a network structure. From the pictorial
representation of the bond graph, the derivation of system equations is so systematic
that a computer can be programmed to do it. The whole procedure of modelling and
simulation of the system may be performed by some of the existing software, e.g.
ENPORT, Camp-G, SYMBOLS, 20Sim, Dymola, etc.
The factors of power, i.e. Effort and Flow, have different interpretations in
different physical domains. Yet, power can always be used as a generalized co-
ordinate to model coupled systems residing in several energy domains. Table A.1
gives the interpretations of the effort and the flow variables in different energy
domains. In bond graphs, one needs to recognize only four groups of basic symbols,
i.e., three basic one port passive elements: inertance (I), capacitance (C), and
resistance (R); two basic active source elements: source of effort (Se or SE) and
source of flow (Sf or SF); two basic two port elements: gyrator (GY) and transformer
(TF); and two basic junctions: constant effort junction (0) and constant flow junction
(1). The basic variables are the effort (e), the flow (f), the time integral of effort (p)
and the time integral of flow (Q). In a bond graph, the assignment of power directions
may be as arbitrary as fixing the co-ordinate systems in classical analysis. The
reference power direction is shown by a half-arrow at one end of the bond. The
assignment of bond numbers fixes the names of the elements or junctions. This is a
164
Appendices
bookkeeping technique adopted by most of the existing bond graph modelling

software. Table A.2 gives definition of Bond graph elements with integral causality.
Note that in Table. A.2, the representation of the transformer elements are different
from that of the ones used in some other works. This notation (followed in
[Mukherjee et al., 2006]) has the advantage that it removes the dependence of the
transformer constitutive relation on the power direction as was the case in other
notations [Karnopp et al., 1990]. Rather, the constitutive relations of the transformer
only depend on the arrow placed over it but not on the power directions. When
causalities are assigned to the model, the causal forms of the two-port element’s
equations are derived from the acausal constitutive relations. The two-port’s relations
in the two possible causalled forms are given in Table A.2. This is the notation that
has been followed throughout this work.
Table A.1: Effort and Flow Variables in Different Energy Domains

Domain Effort Flow
Electrical Voltage (V) Current (A)
Translational mechanics Force (N) Velocity (m s-1)
Rotational mechanics Torque (N m) Angular velocity (rad s-1)
Hydraulics Pressure (N m-2) Volume flow (m3 s-1)
Thermal Temperature (K) Entropy flow (W K-1)
Chemical Chemical potential (N m mol-1) Molar flow (mol s-1)
A.2. Causality
Causality establishes the cause and effect relationships between the factors of power.
In bond graphs, the inputs and the outputs are characterized by the causal stroke
which is shown by a short line perpendicular to the bond at one of its ends. The causal
stroke indicates the direction in which the effort signal is directed. The end of the
bond that does not have a causal stroke is the end towards which the flow signal is
directed. The proper causality for a storage element (I or C) is called integral
causality, where the cause is integrated to generate the effect. Sometimes the causal
165
Appendices
stroke for a storage element has to be inverted, which means the constitutive
relationship for the corresponding element is to be written in a differential form. At an
1 junction, only one bond should bring the information of flow. This uniquely
causalled bond at a junction is termed as the strong bond. Similarly, at a 0 junction,
only one bond can be stroked at the junction side; this strong bond determines the
effort at the junction. The weak bonds are the bonds other than the strong bond.
Table A.2: Definition of Bond Graph Elements

Definition
Type Name Symbol
Linear Nonlinear
f=
1
I∫
edt f =ψ I ( ∫ edt )
Inertance
df ⎛ df ⎞
e=I e = φI ⎜ ⎟
dt ⎝ dt ⎠
Storages
e=
1
C∫
fdt e = φC ( ∫ fdt )
Capacitance
de ⎛ de ⎞
f =C f =ψC ⎜ ⎟
dt ⎝ dt ⎠
f =e/ R f = ψ R (e)
Dissipation Resistance
e=R f e = φR ( f )
e2 = r f1 e2 = r ( x) f1
Gyrator I
e1 = r f 2 e1 = r ( x) f 2
f 2 = (1 / r )e1 f 2 = (1/ r ( x) ) e1
Gyrator II
f1 = (1 / r )e2 f1 = (1/ r ( x) ) e2
Transducers
(ideal) f 2 = μ f1 f 2 = μ ( x) f1
Transformer I
e1 = μ e2 e1 = μ ( x) e2
e2 = (1 / μ )e1 e2 = (1/ μ ( x) ) e1
Transformer II
f1 = (1 / μ ) f 2 f1 = (1/ μ ( x) ) f 2
Effort (Source of
e = e (t )
effort)
Sources
Flow (Source of f = f (t )
flow)
e1 = e2 = e3
Zero (0) f1e1 + f 2 e2 − f3 e3 = 0
f 2 = f3 − f1
Junctions
f 2 = f3 = f1
One (1) f1e1 + f 2 e2 − f3e3 = 0
e1 = e3 − e2
166
Appendices
A.3. Activation
Some bonds in a bond graph may be only information carriers. These bonds are not
power bonds. Such bonds, where one of the factors of the power is masked are called
activated bonds. For example, in a bond representing the velocity pick-up, the
information of force must be masked and in a bond representing a force sensor, the
information of the flow must be masked. A full arrow somewhere on the bond shows
that some information is allowed to pass and some information is masked. The
information which is allowed to pass may be written near that full arrow (refer to
Table A.3). The concept of activation is very significant to depict feedback control
systems.
The term activation initially seems a misnomer. However, Paynter's idea was
based on the fact that though the information of a factor of power is masked on one
end, an activated bond on the other end can impart infinite power which is derived
from a tank circuit used for both the measurement or actuation device (for instance,
the pick-up, the amplifier and the exciter, all have external power sources).
A.4. Sensors, Actuators and Instrumentation Circuits
Additional pseudo-states can be added for measurement of any factor of power on a

bond graph model by using pseudo-storage elements. A flow activated integrally
causalled C-element would observe the flow (and consequently time integral of flow),
whereas an effort activated integrally causalled I-element would observe the effort
(and consequently generalized momentum). Activated storage elements are perceived
as conceptual instrumentation on a model. They do not interfere in the dynamics of
the system.
The flow activated integrally causalled C-element and the effort activated
integrally causalled I-element are also referred to as detector of flow (Df element) and
detector of effort (De element), respectively, in some bond graph literature. The
symbols for the effort and the flow detectors are shown in Table. A.3. Detectors are
167
Appendices
usually weak bonds at the connected junctions. Therefore, the flow detector is usually
connected to an 1-junction whereas the effort detector is usually connected to a 0-
junction.
Table A.3: Definition of Activated Bonds and Sensors
Name Type Symbol Definition
e = e (t )
Effort
Activated f =0
Bond f = f (t )
Flow
e=0
e = e (t )
Sensors Effort
f =0
(Detectors)
f = f (t )
flow
e=0
Activated bonds are used to implement modulated sources, and non-linear

constitutive relations of two-port and one-port elements. These are called modulated
sources, elements or two-ports and their bond graph notations are given by prefixing
‘M’ to their respective normal symbolic names. The modulating signal(s) may come
from a real sensor (De or Df, if the modulation is due to control action) or through an
activated bond emanating from a junction (if the modulation is a natural physical
phenomena, e.g., the modulated source of effort representing the torque due to gravity
in a vertical pendulum is a function of the pendulum’s angle with the vertical axis).
In order to illustrate the use of activated bonds and detectors in instrumentation

circuits, an example consisting of two articulated vehicles shown in Fig. A.1 is
considered. The vehicles are connected by means of a spring. The motions of the cars
are sustained by applying force on the second car. It is proposed to control the
velocity of the two cars by picking up the velocity of the first car and applying an
effort which is proportional to the error in velocity to the second car. The bond graph
for the system using the conventions followed in this work is shown in the Fig. A.2a.
Note that the transformer element used in between the two flow activated bonds is not
168
Appendices
power conserving. In fact it is just a gain that is to be multiplied with the input signal
to give the output signal. The corresponding bond graph of the same system using the
alternative convention being used by other researchers (the so-called international
convention) is shown in Fig. A.2b. The later model, which is a hybrid bond graph and
block diagram representation, explicitly shows the sensors (Df) and actuators (MSe)
in the model. The bond graph models which were given in the Figs. 3.2, 3.6 and 3.10
in Chapter 3 are redrawn using the international conventions in Figs. A.3, A.4 and A.5,
respectively.
Fig. A.1: Example System Considered for Illustrating the Use of Activated Bonds
(a) (b)
Fig. A.2: Bond Graph of the Example System in (a) the Convention Used in this Work and (b) the
International Convention Being Followed Now-a-days
A.5. Systems with Differential Causality
The situation of differential causality arises for system models in which some storage
elements are not dynamically independent. This, however, does not mean that the
parameters of these storage elements do not appear in the equations. In such cases,
169
Appendices
these parameters get associated with the parameters of other storage elements which
have achieved integral causality. The occurrence of differential causalities in a system
may indicate serious violations of principles of conservation of energy. Any storage
element with differential causality does not contribute state variables. The
constitutive relation of a differentially causalled element is written in the derivative
form. Therefore, initial conditions for such storage elements cannot be independently
specified. For example, the constitutive relation for a differentially causalled C-
element is given as
de
f =C . (A.1)
dt
Fig. A.3: Preliminary Bond Graph Model of the Hydrogen Oxidation Electrochemical Reaction
(Original Fig. 3.2) in International Convention
170
Appendices
Fig. A.4: Bond Graph Model of the SOFC (Original Fig. 3.6) Using the 4 Port C-fields in International
Convention
171
Appendices
Fig. A.5: True Bond Graph Model of the SOFC (Original Fig. 3.10) in International Convention
A.6. Field Elements
The single port C, I and R elements can also be generalized for multiple ports. Such
multi-port storage and dissipative elements are called field elements. Let us consider
the C-field for example. The efforts in a set of bonds are determined by displacements
in the bonds of the same set as
n
ei = ∑ K ij Q j , (A.2)
j =1
where, i = 1, 2,..., n and Kij’s are the stiffness influence coefficients and
t
Q j = ∫ f j dt + Q0 .
0
172
Appendices
Such a relation may be represented by a multiport C element called C-field. C-

fields are a common feature in modelling of thermodynamic systems. For instance, a
collapsible chamber in an engine or a compressor chamber can store energy through
interaction of three modes, viz. the mechanical port associated with the piston motion,
the thermal port for the heat transfer and the chemical work done by mass transfer and
combustion.
The constitutive relations for an integrally causalled nonlinear C-field (with n

bonds, all of which have causal strokes placed away from the C-field) are given by
⎛ t t t
⎞
e1 = φC1 ( Q1 , Q2 ," , Qn , θ ) = φC1 ⎜ ∫ f1dt , ∫ f 2 dt ," , ∫ f n dt ,θ ⎟ ,
⎝ −∞ −∞ −∞ ⎠
⎛ t t t
⎞
e2 = φC2 ( Q1 , Q2 ," , Qn ,θ ) = φC2 ⎜ ∫ f1dt , ∫ f 2 dt ," , ∫ f n dt , θ ⎟ ,
⎝ −∞ −∞ −∞ ⎠ (A.2)
#
⎛ t t t
⎞
en = φCn ( Q1 , Q2 ," , Qn ,θ ) = φCn ⎜ ∫ f1dt , ∫ f 2 dt ," , ∫ f n dt ,θ ⎟ ,
⎝ −∞ −∞ −∞ ⎠
where φC1 , φC2 , " , φCn are scalar valued non-linear functions written in terms of the
state variables and a set of parameters ( θ ) associated with the field element.
Similar relationships can be established for linear and non-linear I and R field
elements. The parameters associated with linear fields are always referred enclosed
within square braces ([K], [I] and [R]) as matrices.
173
Appendices
Appendix B
Derivations of Some Important Relations
B.1. Chemical Potential of a Constituent in an Ideal Gas

Mixture
A brief derivation of the expression for the chemical potential of a constituent in an

ideal gas mixture [Liebhafsky & Cairns, 1968] is given in this section.
The Gibbs function G is defined as
G = U + pV − TS . (B.1)
Differentiating Eq. (B.1) and substituting the expression for dU , which is given
as
dU = TdS − pdV + μ dm , (B.2)
we get
dG = Vdp − SdT + μ dm , (B.3)
which implies
⎛ ∂G ⎞
⎜ ⎟ =V . (B.4)
⎝ ∂p ⎠T , n
174
Appendices
Substituting the equation of state for ideal gas in Eq. (B.4), we get
⎛ ∂G ⎞ mRT
⎜ ⎟ = , (B.5)
⎝ ∂p ⎠T ,n p
integration of which yields
⎛ p ⎞
ΔG = G − G 0 = mRT ln ⎜ 0 ⎟ , (B.6)
⎝p ⎠
which further leads to
⎛ p ⎞
μ − μ 0 = RT ln ⎜ 0 ⎟
. (B.7)
⎝p ⎠
Since any ideal gas in a mixture of ideal gases behaves as though it were present
alone at its partial pressure, Eq. (B.7) also applies to every constituent in the mixture
of ideal gases, provided that the partial pressure of that constituent is used in Eq. (B.7).
Equation (B.7) can also be written in terms of the mole fraction (xi) as
μi − μio = RT ln ( xi ) , (B.8)
where μio is the chemical potential of the i-th constituent at xi =1.
The chemical potential for a solute in a dilute solution is generally given in terms
of the concentrations, which can be obtained as follows. Dilute solutions can be
considered like ideal gases with regard to their state properties, i.e., the solute
molecules may be considered to occupy the whole volume with negligible interaction
with the solvent molecules. Therefore, Eq. (B.8) is valid for dilute solutions. Also, as
ni nsolvent ,
ni ni
xi = . (B.9)
ni + nsolvent nsolvent
175
Appendices
where ni is the number of moles of the i-th solute and nsolvent is the number of moles of
the solvent.
Substituting nsolvent = 1000 ρsolventVsolvent M solvent into Eq. (B.9) and noting that
Vsolvent Vtotal , we get
ni M solvent
xi = . (B.10)
1000Vtotal ρsolvent
As ( ni Vtotal ) = ci and (1000 ρsolvent M solvent ) = csolvent ,
ci
xi = . (B.11)
csolvent
Therefore, the chemical potential for a solvent in a dilute solution is given as
μi − μio = RT ln ( ci ) , (B.12)
where the concentration of the solvent has been taken as unity.
B.2. Gibbs-Duhem Equation
The Gibbs-Duhem equation [Callen, 1985; Denbigh, 1955] gives the relationship
between the intensive thermodynamic variables, the pressure, the temperature and the
chemical potential. The derivation of the Gibbs-Duhem equation from other standard
thermodynamic relations is given in the following.
The Gibbs function is defined as
G = U + PV − TS , (B.13)
which may be written as
176
Appendices
U = μ n − PV + TS . (B.14)
In differential form, Eq. (B.14) can be written as
dU = μ dn + ndμ − PdV − VdP + TdS + SdT . (B.15)
The change in the internal energy may be given as
∂U ∂U ∂U
dU = dV + dS + dn . (B.16)
∂V ∂S ∂n
From well-known thermodynamic relations ∂U ∂V = − p , ∂U ∂S = T
and ∂U ∂m = μ , Eq. (B.16) can be expressed as
dU = TdS − PdV + μ dn . (B.17)
Subtracting Eq. (B.17) from Eq. (B.15), we arrive at the Gibbs-Duhem equation as
nd μ − VdP + SdT = 0 . (B.18)
This equation can also be generalized for multi-species mixtures as
∑n dμ
i i − VdP + SdT = 0 . (B.19)
B.3. Isentropic Nozzle Flow Equation
The derivation of the mass flow relation for an isentropic nozzle [Sabersky et al.,
1971] is presented in this section. The energy equation for the nozzle may be written
as
uu2 u2
hu + = hd + d , (B.20)
2 2
177
Appendices
where h is the specific enthalpy and u is the velocity. The subscripts ‘u’ and ‘d’
represent the upstream and the downstream sides, respectively. The outlet mass flow
rate from the nozzle may be given as
Aud
m = ρ Aud = , (B.21)
vd
where ρ is the density of the fluid, A is the throat area of the nozzle and vd is the
specific volume of the downstream side fluid. Substituting the expression for ud
obtained from Eq. (B.20) into Eq. (B.21), we obtain
A 2 ( hu − hd ) + uu2
m = . (B.22)
vd
In most of the practical applications, the velocity at the inlet of the nozzle (i.e., the
upstream side) is negligibly small when compared to the outlet velocity (i.e., the
velocity at the throat of the nozzle). Therefore, Eq. (B.22) becomes
A 2 ( hu − hd )
m = . (B.23)
vd
For an ideal gas, the specific enthalpy is given as h = cpT and the specific volume
is given according to the ideal gas law as vd = RTd p d . Therefore, considering
constant cp, Eq. (B.23) becomes
pd A 2cp (Tu − Td )
m = . (B.24)
RTd
If the flow through the nozzle is assumed to be adiabatic and reversible then the
process is isentropic and is governed by the following relation:
( γ −1) γ
Td ⎛ pd ⎞
=⎜ ⎟ , (B.25)
Tu ⎝ pu ⎠
178
Appendices
where γ = cp cv .
Substituting Eq. (B.25) into Eq. (B.24), we obtain the relation for the mass flow
rate through an isentropic nozzle as
2γ (γ +1) γ
pu 2γ ⎛ pd ⎞ ⎛p ⎞
m = A ( x ) ⎜ ⎟ −⎜ d ⎟ . (B.26)
Tu R (γ − 1) ⎝ pu ⎠ ⎝ pu ⎠
B.4. Nernst Equation
The reversible voltage of an electrochemical cell is given by the Nernst equation

[Liebhafsky & Cairns, 1968]. A brief derivation of the Nernst equation is given in this
section.
The change in Gibbs free energy per mole for an electrochemical reaction is given
as
ΔG = ∑ μν
i i − ∑ μν
i i , (B.32)
i∈P i∈R
where i refers to a particular reactant or product species and P and R are the set of
products and reactants participating in the reaction, respectively.
For the reversible operation of the cell, this change in the Gibbs free energy is
completely converted into electrical energy. Therefore,
ΔG = − ne FVr . (B.33)
The reversible voltage Vr can be interpreted as being equal and opposite to the
electromotive force needed to establish virtual chemical equilibrium in an ideal
electrochemical cell; no matter how far removed the state of the reactants and
products are from the actual chemical equilibrium.
179
Appendices
For ideal gas mixture, the chemical potentials of the constituents are given by
(refer to Section B.1)
μi = μi ,0 + RT ln ( pi ) , (B.34)
where the reference pressure is taken as unity.
Substituting the chemical potentials of the reactants and the products in the form
given in Eq. (B.34) into Eq. (B.32) gives
⎛ ∏ pi ⎞
ΔG = ∑ μi ,0ν i − ∑ μi ,0ν i + RT ln ⎜⎜ i∈P ⎟,
⎟ (B.35)
i∈P i∈R ⎜ ∏ pi ⎟
⎝ i∈R ⎠
where ∑μ
i∈P
ν − ∑ μi ,0ν i = ΔG 0 , which is the Gibbs free energy of the reaction at the
i ,0 i
i∈R
standard state.
From Eqs. (B.33) and (B.35), we get
⎛ ∏ pi ⎞
− ne FVr = ΔG + RT ln ⎜⎜ i∈P
0 ⎟.
⎟ (B.36)
⎜ ∏ pi ⎟
⎝ i∈R ⎠
This equation is called the Nernst equation. The Nernst equation is widely used in
electrochemistry to calculate the effect of changes in the partial pressure and the
concentration of the substances, which participate in the cell reaction, on the cell
voltage.
At equilibrium, ΔG = 0 and then Eq. (B.35) becomes
⎛ ∏ pi ,eq ⎞
ΔG = − RT ln ⎜⎜ i∈P
0 ⎟.
⎟ (B.37)
⎜ ∏ pi ,eq ⎟
⎝ i∈R ⎠
180
Appendices
Defining a constant K eq = ∏ pi ,eq ∏p i ,eq , known as the equilibrium constant

i∈P i∈R
for the reaction, Eq. (B.37) may be written as
⎛ ΔG 0 ⎞
K eq = exp ⎜ − ⎟. (B.38)
⎝ RT ⎠
This equilibrium constant is a constant for a particular reaction at a particular

temperature. It depends on the equilibrium values of the partial pressures of the
reactants and the products of the reaction at that temperature and it denotes the
equilibrium composition of the mixture. However, it varies with change in the
temperature.
Using Eq. (B.38), the Nernst equation given in Eq. (B.36) can also be written as
⎛ ∏ pi ⎞
− ne FVr = −RT ln K eq + RT ln ⎜⎜ i∈P ⎟.
⎟ (B.39)
⎜ ∏ pi ⎟
⎝ i∈R ⎠
This equation may also be written in terms of the concentrations of the reacting
species by using the following form for the chemical potentials instead of Eq. (B.34).
μi = μi,0 + RT ln ( ci ) . (B.40)
Note that in Eq. (B.40), the reference concentration has been taken as unity. Using
Eq. (B.40) and following the same procedure, the Nernst equation may be derived as
⎛ ∏ ci ⎞
− ne FVr = −RT ln K eq + RT ln ⎜⎜ i∈P ⎟.
⎟ (B.41)
⎜ ∏ ci ⎟
⎝ i∈R ⎠
181
Appendices
B.5. Butler-Volmer Equation
The Butler-Volmer equation [Bockris et al., 1998] describes how the electrical current
on an electrode depends on the electrode potential. A charge double layer usually
forms at the interface between the electrode and the electrolyte. Many models have
been put forward to explain the double layer phenomenon. The simplest one is the
Helmholtz model according to which, the charge accumulation at the two sides of the
interface forms an ideal electrical capacitor. The charge densities on the two sheets
are equal in magnitude but opposite in sign. Therefore, the drop in potential between
these two layers of charge is linear. Charge transfer across this double layer is
essential for the electrochemical reaction to proceed. This process of charge transfer
across the potential difference created due to the double layer is described by the
Butler-Volmer equation. This charge transfer can be considered as a rate process.
In any rate process such as the charge transfer process, the initial condition of the
system is characterised by a certain configuration of involved entities (ions, atoms,
sites etc.). Similarly, the final state is characterised by a different configuration of
those entities. During the transfer of the ion from the initial to the final site, the
configuration of the system keeps on changing. There is a critical configuration
beyond which the configuration of the ion and the sites more closely resembles the
final state. This critical configuration is known as the activated complex. Each
configuration during the process of charge transfer corresponds to a particular energy
for the system. Hence, this phenomenon can be represented by the motion of a point
along the potential energy curve shown in Fig. B.1. The peak of the potential energy
curve corresponds to the configuration of the system known as the activated complex.
As the system has to climb a potential energy barrier, it has to be activated with
critical activation energy ΔH ≠ for the process to occur. If the entropy change ΔS ≠ in
going from the initial to this activated state is taken into account then the rate process
needs a critical free energy of activation ΔG ≠ = ΔH ≠ − T ΔS ≠ .
The system in the activated state (i.e., the activated complex) has a property that it
will break down to the final state if there are specific vibrations of the configurations.
The vibration leading to the breakdown of the activated complex, given by the
182
Appendices
Planck’s law, takes place with a certain vibration frequency ν which has an energy E
associated with it:
E = hv , (B.42)
where h is the Planck’s constant.
According to the kinetic theory, the translation of the entities is associated with a
translational energy, which is given as kT 2 per entity and kT for a pair of entities,
where k is the Boltzmann constant. Hence, if the vibrations of the configurations are
viewed as translations, the associated energy is given by
E = kT . (B.43)
Fig. B.1: The Free Energy of Activation and the Electrical Potential Across the Double Layer
Equating Eq. (B.42) and Eq. (B.43), we get
183
Appendices
kT
ν= . (B.44)
h
The important assumption in the rate process theory is that the activated
complexes are in equilibrium with the reactants. Therefore, the mass action law can
be used to give
cAC o≠
= K eq = e −ΔG RT , (B.45)
cR
where cAC and cR are the concentrations of the activated complex and the reactants,
o≠
respectively, K eq is the equilibrium constant and ΔG is the standard free energy of
activation.
The number of times the rate process occurs per second ( ν e ) is equal to the
concentration of the activated complexes ( cAC ) times the frequency (ν ). Therefore,
kT o≠
νe = cR e −ΔG RT , (B.46)
h
o≠
where ΔG is the free energy of activation of the reaction. This represents the
chemical energy barrier that has to be overcome by the charged particles. This
chemical energy barrier has a peak at some distance across the interface which also
corresponds to a particular configuration of the reaction system known as activated
complex, i.e. the critical configuration that must be attained before the charge transfer
process can occur.
The above formulations do not account for the electric field created by the double
layer. The double layer results in a linearly varying potential difference across the
interface as shown in Fig. B.1. Let Δφe be the equilibrium potential difference across
the interface. We define a factor β , which is called as the symmetry factor or the
transfer coefficient, such that
184
Appendices
Distance across the double layer to the summit

β= . (B.47)
Distance across the whole double layer
This electrical field lowers the energy barrier by the amount β F Δφe for one mole
of charged particles to move in one direction and raises the energy barrier by the
amount (1 − β ) F Δφe for one mole of charged particles to move in the opposite
direction. Let us consider here that the movement of the charged particle is in such a
direction that it is aided by the electrical field. The ΔG o ≠ in Eq. (B.46) can be
considered to consist of two parts, a chemical energy part and an electrical energy part.
ΔG o ≠ = ΔGchem
o≠
+ β F Δ φe . (B.48)
Substituting Eq. (B.48) into Eq. (B.46), the rate of charge transfer is given as
kT −ΔGchem
o≠
νe = ci e RT
e − β F Δφe RT
. (B.49)
h
The current is obtained by multiplying Eq. (B.49) by the Faraday’s constant as
G kT −ΔGchem
o≠
i =F ci e RT
e − β F Δφe RT
. (B.50)
h
According to the principle of microscopic reversibility, there must also be a

current in the opposite direction at equilibrium. In this case, the potential difference
across the interface raises the energy barrier by the amount (1 − β ) F Δφe and hence
ΔG o ≠ = ΔGchem
o≠
− (1 − β ) F Δφe . (B.51)
Therefore, the current in the opposite direction is given as
H kT −ΔGchem
e(
o≠
1− β ) F Δφe RT
i =F ci e RT
. (B.52)
h
At equilibrium, the currents in both the directions must be equal and this
equilibrium current is known as the exchange current:
185
Appendices
= kchem ci e(
1− β ) F Δφe RT
i0 = kchem ci e − β F Δφe RT
, (B.53)
where kchem is the chemical part given by
kT −ΔGchem
o≠
kchem = e RT
. (B.54)
h
Let Δφ be the interface potential of the system when it is driven out of

equilibrium. The deviation of the interface potential from its equilibrium value is
termed as the over-potential ( η ). In a fuel cell, this over-potential is actually the
voltage loss as the cell is taken out of equilibrium by means of drawing current from it.
Thus, the interface potential is given as
Δφ = Δφe − η . (B.55)
Away from equilibrium, the net current at the electrode-electrolyte interface is

non-zero and it is given by
− (1− β ) F Δφ RT
i = kchem ci e β F Δφ RT
− kchem ci e . (B.56)
Substituting Eq. (B.55) into Eq. (B.56), we get
β F ( Δφe −η ) RT − (1− β ) F ( Δφe −η ) RT

i = kchem ci e − kchem ci e , (B.57)
which can be written as
(
i = i0 e β Fη RT
− e −(1− β ) Fη RT
). (B.58)
This equation is called the Butler-Volmer equation. This formula holds good for
both the electrode electrolyte interfaces as the same charge transfer phenomena occurs
at both the places.
186
Appendices
Appendix C
The Nelder-Mead Simplex Algorithm
The Nelder and Mead simplex method [Lagarias, 1998; Nelder and Mead, 1965] is
implemented for solving n-dimensional unconstrained minimization problem to find
X = ( x1 , x2 ,..., xn ) which minimizes f ( X ) . The geometric figure formed by a set of
n+1 points in an n-dimensional space is called a simplex. The basic idea in the
simplex method is to compare the value of the objective function f ( X ) at the n+1
vertices {Xj} of a simplex and move the simplex gradually toward the optimum point
during the iterative process. Starting from an initial simplex with n+1 known vertices
{Xj}, a new vertex will be computed to define a new simplex using reflection,
expansion, or contraction.
One iteration of the Nelder-Mead method consists of the following three steps.
1. Ordering: Determine the worst (Xh), second worst (Xsh) and the best
vertex (Xl), in the current working simplex by evaluating the objective
function f ( X j ) . These evaluations are called trials and denoted by T j ,
i.e., Th = f ( X h ) , Tsh = f ( Xsh ) and Tl = f ( X l ) .
2. Centroid: Calculate the centroid X0 of the best side, i.e., the one opposite
n +1
1
the worst vertex X h as X0 =
n
∑
j =1, j ≠ h
Xj .
187
Appendices
3. Transformation: Compute the new working simplex from the current one.
First, try to replace only the worst vertex Xh with a better point by using
reflection, expansion or contraction with respect to the best side. All test
points lie on the line defined by Xh and X0 , and at the most two of them
are computed in one iteration. If this succeeds, the accepted point becomes
the new vertex of the working simplex. If this fails, reduce the simplex
towards the best vertex Xl. In this case, n new vertices are computed. The
different transformations are illustrated in Fig. C.1.
Simplex transformations in the Nelder-Mead method are controlled by four

parameters: α for reflection, β for contraction, γ for expansion and δ for
reduction. They should satisfy the constraints: α > 0 , 0 < β < 1 , γ > 1 , γ > α and
0 < δ < 1 . The standard values used in most implementations are α = 1 , β = 1/ 2 ,
γ = 2 and δ = 1/ 2 .
Fig. C.1: Different Transformations of a Two-dimensional Simplex
The flow chart of the Simplex algorithm is shown in Fig. C.2. The working of
simplex transformations in step 3 is described in the following:
• Reflect: Compute the reflection point X r = α ( X o − X h ) + X o and Tr = f ( X r ) .
If Tl ≤ Tr < Tsh then accept X r and terminate the iteration.
188
Appendices
• Expand: If Tr < Tl then compute the expansion point Xe = γ ( X r − X o ) + X o
and Te = f ( Xe ) . If Te < Tr then accept Xe and terminate the iteration.
Otherwise (if Te ≥ Tr ), accept X r and terminate the iteration.
• Contract: If Tr ≥ Tsh then compute the contraction point X c by using the better
of the two points X h and X r .
o Outside: If Tsh ≤ Tr < Th then compute Xc+ = Xo + β ( X r − Xo ) and
Tc+ = f ( Xc+ ) . If Tc+ ≤ Tr then accept Xc+ and terminate the iteration.
Otherwise, perform a reduction transformation.

o Inside: If Tr ≥ Th then compute Xc- = Xo + β ( X h − X o ) and
Tc- = f ( Xc- ) . If Tc- < Th then accept Xc- and terminate the iteration.
Otherwise, perform a reduction transformation.
• Reduce: Compute n new vertices X j = Xl + δ ( X j − Xl ) and T j = f ( X j ) , for
j = 0,..., n , with j ≠ l .
189
Appendices
Start Optimization
Calculate first simplex vertices

Yes
Rank trials in order: (Tl, …, Tsh, Th) No
Make reflection to get Xr
Tr<Tl Tr<Tsh Tr<Th
Make expansion to get Xe Make +ve contraction Make -ve contraction

to get Xc+ to get Xc-
Te<Tr
Xh=Xc+ Tc+≤Tr Tc-<Th Xh=Xc-
Xh=Xe Xh=Xr
Make reduction
to get ‘n’ new
vertices Xj
Convergence
criteria
Stop Optimization
Fig. C.2: Flow Chart of the Nelder-Mead Simplex Algorithm
190
Appendices
Appendix D
List of Files and Programs Given in the

Compact Disc
Compatibility
S. Location/
File Name Description (OS & Remarks
No. Directory
Software)
1 Thesis.pdf Root\Thesis\ Full thesis Adobe
Acrobat 5.0+
2 Basic_model.bgp, Root\Models\ Bondpad Windows XP, Use Runge-
Detailed_model_no_c Bondpad files (*.bgp) files of Symbols Kutta Gill
ontrol.bgp, the SOFC Shakti method with
Detailed_model_with_ models 1000 steps,
control.bgp, described in the 16384 records
SOFC_system thesis and an error
.bgp limit of 5e-5 for
simulation
3 ANODE.cap, Root\Models\ Symbols Windows XP,
CATHODE.cap, Capsule files capsules used in Symbols
convres.cap, the bond graph Shakti
convresmulti.cap, models
CR.cap, HEEX.cap,
MCR.cap, OCR.cap,
OMCR.cap, TC.cap,
TR.cap, TRad.cap
4 Optimisation_code.m, Root\Matlab\ Matlab code for Windows XP, To be run for
ConstFU_operation.m, the optimisation Matlab 7.0 different values
routine and for of current
finding density within
operating the cell
conditions operating range
corresponding
to constant FU
operation
191
Appendices
192
Curriculum Vitae
P. Vijay did his graduation, Bachelor of Mechanical Engineering, from K.S.

Rangasamy College of Technology, Madras University, Tamil Nadu in the year 2000.
He obtained his Master of Engineering (M. E) degree from Government College of
Engineering, Salem in the year 2002. After that he served as faculty in the mechanical
engineering department of Sethu Institute of Technology, Madurai and in the school
of mechanical engineering of SASTRA deemed university, Tanjavur. In the year
2006, he joined in the Ph.D. Programme at IIT, Kharagpur as a regular scholar to
pursue his research work in the area of fuel cell modelling and control. Following are
the list of papers published and communicated, from the present research work.
In Journals
1. Vijay, P., Samantaray, A. K., and Mukherjee, A. Bond graph model of a
solid oxide fuel cell with a C-field for mixture of two gas species.
Proceedings of the Institution of Mechanical Engineers, Part I: J. Systems
and Control Engineering, 2008, 222 (4), 247–259.
2. Vijay, P., Samantaray, A. K., and Mukherjee, A. On the rationale behind
constant fuel utilization control of solid oxide fuel cells. Proceedings of
the Institution of Mechanical Engineers, Part I: J. Systems and Control
Engineering, 2009, 223 (2), 229–252.
3. Vijay, P., Samantaray, A. K., and Mukherjee, A. A Bond Graph Model-
based Evaluation of a Control Scheme to Improve the Dynamic
Performance of a Solid Oxide Fuel Cell. Mechatronics, 2009, 19 (4), 489–
502.
4. Vijay, P., Samantaray, A. K., and Mukherjee, A. Constant Fuel Utilization
Operation of a SOFC System: An Efficiency Viewpoint. Accepted for
publication in ASME Journal of Fuel Cell Science and Technology.
In Proceedings of Conferences
1. Vijay, P., Mukherjee, A., and Samantaray, A. K. Bond Graph Model of a
Solid Oxide Fuel Cell. Millennium Energy Summit, Central Glass and
Ceramic Research Institute, Kolkata, September 27–29, 2007.
194

Modelling, Simulation and Control of A Solid Oxide Fuel Cell System: A Bond Graph Approach

Uploaded by

Document Information

Original Title

Copyright

Available Formats

Share this document

Share or Embed Document

Sharing Options

Did you find this document useful?

Is this content inappropriate?

Copyright:

Available Formats

Modelling, Simulation and Control of A Solid Oxide Fuel Cell System: A Bond Graph Approach

Uploaded by

Copyright:

Available Formats

MODELLING, SIMULATION AND CONTROL OF A

SOLID OXIDE FUEL CELL SYSTEM: A BOND GRAPH

Under the guidance of

Dr. Arun Kumar Samantaray

DEPARTMENT OF MECHANICAL ENGINEERING

Signature Signature Signature

Name Name Name

(Member of the DSC) (Member of the DSC) (Member of the DSC)

(External Examiner) (Chairman)

Dr. Arun Kumar Samantaray Dr. Amalendu Mukherjee

I am thankful to Prof. Ajay Kumar Chattopadhayya, Head of Mechanical Engg.

Campus of I I T, Kharagpur (P. Vijay)

Finally, an algorithm has been developed to optimise the operational efficiency of

q Heat flow rate (J s-1)

β Charge transfer coefficient

ηex Exergy efficiency

TPB Triple phase boundary

1.1. Background and Motivation

Molten carbonate fuel cells (MCFCs): Electrolyte is a mixture of molten alkali

Alkaline fuel cells (AFCs): Electrolyte is an aqueous solution of alkaline hydroxide

SOFC is of considerable interest since it has considerably high system efficiency

Fig. 1.1: Schematic representation of an SOFC

The requirements of physical properties of the anode are high electronic

lanthanum manganite. It is often doped with strontium and referred to as lanthanum

1.2. Contributions of the Thesis

The main contributions of this work are summarised as follows.

1.3. Organisation of the Thesis

A comprehensive survey of the literature pertaining to dynamic modelling of the

In Chapter 5, a comprehensive steady state model is derived from the previously

Literature Review and Fundamental Concepts

There is abundant literature on the bond graph modelling of thermo-fluid systems.

Works on the bond graph modelling of chemical reactions and electrochemical

as ∂U ∂V = − p , ∂U ∂S = T and ∂U ∂m = μ , respectively. Therefore, Eq. (2.1)

U = pV + TS + μ m . (2.3)

Fig. 2.1: Thermodynamic C-field With Three Power Ports

A thermodynamic capacitor by itself gives no information about rates, available

The non-equilibrium part of the chemical reaction was represented by a resistive

2.2. Concept of Chemical Equilibrium

Since dS0 = −δQ T , we have

Substituting Eq. (2.5) into the inequality (2.4), we get

dU + pdV − TdS < 0 . (2.6)

By definition, the Gibbs function G is given as

which on differentiation gives

dG = dU + pdV + Vdp − TdS − SdT . (2.8)

dG = dU + pdV − TdS . (2.9)

2.3. Bond Graph Formulation of Chemical Reaction Kinetics

where ξ ( t ) is the reaction advancement coordinate with ξ ( 0 ) = 0 and ν i is the

stoichiometric coefficient of the i th species. The stoichiometric coefficients of the

differentials, their integrations give the following:

and nC (t ) = nC (0) + ν Cξ ( t ) , (2.14)

The reaction advancement coordinate may be thought of as a generalized

dG = ( μCν C − μAν A − μ Bν B ) dξ . (2.16)

In a general form, Eq. (2.16) is given as

where the quantity AF = ∑ μν

Therefore, Eq. (2.17) can be written as

This affinity may be defined as a generalized effort. At the equilibrium, the

ξ = k+ cA2 cB − k− cC2 , (2.20)

The chemical potential of the component ‘i’ is given as (refer to Appendix B)

where ci is the concentration of the component ‘i’, cΣ is the reference concentration

(2.21) can be written in terms of number of moles ‘n’ as

8 denotes the reverse affinity of the reaction and is given by e8 = AR = 2μC .

The non-equilibrium part of the chemical reaction kinetics is represented as an R-

⎛ 2 μ − 2 μA,0 ⎞ ⎛ μB − μB,0 ⎞ ⎛ 2μC − 2μC,0 ⎞

U = pV + TS + μ m . (2.3)

ξ = k+ cA2 cB − k− cC2 , (2.20)