D UAL D EGREE P ROJECT - S TAGE 0

Structure property relationships for

fuel cell and flow battery electrodes

Author: Supervisor:
Aadarsh Parashar Dayadeep Monder

Department of Energy Science and Engineering

I NDIAN I NSTITUTE OF T ECHNOLOGY

B OMBAY

July 17, 2019

 iii

Abstract
The performance of solid oxide fuel cells (SOFCs) and vanadium redox flow
batteries (VRFBs) depend largely on the structure properties of their elec-
trodes. These electrodes are made up of roughly spherical particles for SOFCs
and long cylindrical fibers for VRFBs, hence, packing algorithms can be used
to numerically reconstruct the electrodes to predict their morphological prop-
erties. The initial work done in this regard is discussed in the report and
the intended plans and goals are listed further. These include modeling the
SOFC electrodes with functionally graded properties and then modeling the
performance of the device on the cell level; also, using the cell-level models
of VRFB to test the performance with the morphological properties obtained
by the earlier simulations.
 v

Contents

Abstract iii

1 Introduction 1
1.1 Fuel cells . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1
1.2 Vanadium redox flow batteries . . . . . . . . . . . . . . . . . . 2
1.3 Modeling micro-structures of electrodes . . . . . . . . . . . . . 3
1.3.1 Numerical methods . . . . . . . . . . . . . . . . . . . . 3

2 Outline of Dual Degree Project 5

2.1 Stage zero . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
2.1.1 Methodology for the structure generation . . . . . . . 5
2.1.2 Three phase boundary length calculation . . . . . . . . 7
2.1.3 Results of the simulations . . . . . . . . . . . . . . . . . 7
2.2 Proposal for stages I and II . . . . . . . . . . . . . . . . . . . . . 9
2.2.1 SOFC . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10
2.2.2 VRFB . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10

Bibliography 11
 vii

List of Figures

1.1 Schematic model of an SOFC . . . . . . . . . . . . . . . . . . . 2

1.2 Schematic model of a redox flow battery . . . . . . . . . . . . . 3

2.1 Flow chart for the drop-and-roll algorithm implemented for

the structure generation . . . . . . . . . . . . . . . . . . . . . . 6
2.2 Illustrations of the various kinds of overlaps possible between
particles in the structure . . . . . . . . . . . . . . . . . . . . . . 7
2.3 Projection of the 3-particle overlapping particles as shown in
Figure 2.2(b) to the intersecting plane (the yz plane). The solid
lines are the pair of particles of our interest and the dashed line
depict the third intersecting particle . . . . . . . . . . . . . . . 8
2.4 The variation of the connected TPBL with the solid fraction of
phase a . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8
2.5 Variation of active TPBL with the solid fraction of phase a for
mono-dispersed and poly-dispersed cases . . . . . . . . . . . . 9
2.6 Variation of total vs active TPBL with the solid fraction of a
type particles . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9
 ix

List of Abbreviations

SOFC Solid Oxide Fuel Cell

VRFB Vanadium Redox Flow Battery
YSZ Yttria Stabilized Zirconia
LSM Lanthanum Strontium Manganite
FIB-SEM Focused Ion Beam Scanning Electron Microscopy
XRT X-ray Tomography
TPB Three Phase Boundary
TPBL Three Phase Boundary Length
 xi

List of Symbols

r mean radius of a type of particle µm

r radius of a type of particle µm
σ standard deviation of the normal distribution µm
ψ solid volume fraction of a particle
θ contact angle rad
λvTPB three phase boundary length per unit volume m−2

Superscripts
as after sintering

Subscripts
a a type particles
b b type particles
f f type particles
i particle of type i (with i = a, b or f if not otherwise specified)
ni number of particle sizes for i type particle
 1

Chapter 1

Introduction

In the age when renewable energy resources are becoming a necessity for
the humans to survive, it becomes of prime importance to develop devices
which can efficiently convert and store energy. One of the most promising
devices for conversion happens to be fuel cell, the solid oxide (SOFC) type in
particular. Moving on to the storage devices, if we consider a long term and
large scale storage device option, the flow battery check the most of the boxes
required for an optimum system. In particular, vanadium redox flow battery
(VRFB) promises the best performances amongst all the different types de-
scribed in the literature. The following two sections talk in some detail about
the basics and working of these two devices.

1.1 Fuel cells

Fuel cells are electrochemical devices which convert the chemical energy
stored in fuels (theoretically hydrogen and short hydrocarbons for high tem-
perature versions) into useful electrical energy. In this process, it bypasses the
thermal route taken by the most conventional energy conversion devices – IC
engines, and hence can achieve higher efficiencies than the limits set by the
second law of thermodynamics, and can theoretically achieve an efficiency
of 40-60 % (O’Hayre et al., 2016). This makes it one of the most promising
energy conversion devices in the upcoming future.

Cathode : O2 + 4 e− −−→ 2 O2− (1.1a)

2− −
Anode : 2 H2 + 2 O −−→ 2 H2 O + 4 e (1.1b)
Fuel cells are made up of two electrodes separated by a membrane which
only allows transporting ions to pass through. In the case of SOFCs, the
electrodes and membranes are made of composite ceramics which require
higher temperatures to operate efficiently. Anodes are typically made of Ni
and yttria-stabilized-zirconia (YSZ), cathodes are made of lanthanum stron-
tium manganite (LSM) and the electrolyte membrane is also usually made of
YSZ. Figure 1.1 shows a typical fuel cell manufactured with traditional ma-
terials. Usually, the cell is supported on the anode layer, this means that the
anode layer is thick enough to maintain structural integrity of the cell.
2 Chapter 1. Introduction

e-
Air Cathode gas channel Excess
in air out
LSM based cathode

YSZ based electrolyte

Ni-YSZ anode

H2 Excess
Anode gas channel
in H2 out
e-
F IGURE 1.1: Schematic model of an SOFC

The basic reaction driving the fuel cell is given in Equations 1.1a and 1.1b.
These two reactions happen at two different electrodes separated by an elec-
trolyte which allows ion exchange. Now, since for both of the reactions, three
different species – ion, electron and gas, are needed at one place, hence the
electrodes need to be porous and a good conductor of both electrons and
ions. Also, it easily follows that the reaction could only happen at an inter-
face where all the three phases meet – three phase boundary. This, in addi-
tion to some other structure properties of the electrode such as the effective
conductivity of electrons and ions in their respective media and the effective
diffusivity of the gaseous phase help determine the performance of the cell.

1.2 Vanadium redox flow batteries

Flow batteries are a type of electrochemical cell where chemical energy is
provided by two chemical compounds dissolved in liquids contained within
the system and separated by a selectively permeable membrane. In several
kinds of flow batteries available, the most promising one is the all-vanadium
type, where both the anolyte and the catholyte are solutions of vanadium
salts in different oxidation states. This ensures that even if there is crossover
of ions across the membrane, there won’t be any parasitic reactions; it would
only result in a decrease in the cell voltage.

Charging
Positive electrode : VO2+ + H2 O −−−−−−* VO2 + + e−
)−−−−−− (1.2a)
Discharging
Charging
Negative electrode : V3+ + e− )−−−−−−
−−−−−−* V2+ (1.2b)
Discharging

In Figure 1.2, a schematic diagram of a redox flow battery is shown. Both the
electrodes have solutions, of different vanadium salts in case of all VRFBs,
1.3. Modeling micro-structures of electrodes 3

F IGURE 1.2: Schematic model of a redox flow battery (Qi and

Koenig, 2017)

flowed through them. The electrodes are made of highly porous carbon felt
which provide a high surface area for the reactions described in equations
1.2a and 1.2b to happen.

1.3 Modeling micro-structures of electrodes

It has been established in the introductory sections for both of the technolo-
gies that the structure properties play a vital role in determining the perfor-
mances of both the devices. Hence, optimizing the conditions which lead
to the best working conditions becomes paramount. Modeling the micro-
structure of the electrodes would help us extract the structure properties
which could in turn be plugged into a cell level model to predict the per-
formances. There are other ways to predict or measure the structure prop-
erties available in literature as well which include use of percolation theory
(Bertei and Nicolella, 2011) and use of experimental techniques such as fo-
cused ion beam scanning electron microscopy (FIB-SEM) in SOFCs (Choi et
al., 2011) and X-ray tomography (XRT) in VRFBs (Kok et al., 2019). Each
method has its own demerits. Percolation theory fails to agree with experi-
mental results after a certain degree of compactness of the structure, hence,
the level of accuracy is compromised. In the experimental techniques, one
has to physically make the electrodes, which can prove to be costly, specially
in the FIB-SEM method, where the electrode is destroyed in the process of
extraction of the structure properties. Hence, computational recreation of the
electrodes through numerical methods prove to be the optimum solution.

1.3.1 Numerical methods

The electrodes of both SOFCs and VRFBs can be constructed as a collection
of spherical and long-cylindrical particles, respectively. Hence, the recon-
struction of one of the electrodes generally means that the other one can be
simulated as well with some extra efforts. There are significant amounts of
4 Chapter 1. Introduction

studies done for reconstructing SOFC electrodes like Bertei et al., 2013 and
modeling structures with non-spherical starting particles like Bertei et al.,
2014, but there is a dearth of studies for predicting properties of VRFBs. This
can turn out to be a useful contribution from this dual degree project.
 5

Chapter 2

Outline of Dual Degree Project

This chapter would list down the work done during the stage zero of the dual
degree project and also lay down an intended work-plan for the upcoming
two semesters.

2.1 Stage zero

During stage zero, the code for extraction of one of the required morpho-
logical property, namely the total three phase boundary length (TPBL) of a
structure was written and the results were compared with the data given in
the literature by Bertei et al., 2012 and Kenney et al., 2009.

2.1.1 Methodology for the structure generation

In the simulations, three kinds of particles, namely a, b and f are used. They
can represent the composite materials forming a typical SOFC electrode with
an addition with a “pore-former” which decomposes on sintering and is ab-
sent from the final structure. These are added to provide additional porosity
to the structure. The particles are characterized by a mean particle radius, i.e.,
r a , r b and r f and a standard deviation from the mean in case of poly-disperse
mixture of the particles – σa , σb and σ f . Since these particles are discrete and
hence they cannot have a continuous distribution of the radii, instead they
would have some discrete values as their radius only, they are characterized
by the distribution of particle sizes ni , i.e., for any given type of particle i, the
radii would be ri1 , ri2 , . . . , rin .
i

The code for generation of the structures was borrowed from the original
writers and used directly. It implemented the drop-and-roll algorithm to
generate the structure. The flow chart for the same is illustrated in Figure
2.1. The main inputs to the algorithm include the mean radii of the parti-
cles of each phases (ri ), their variance (σi ), the number of different radii to
use in the poly-disperse case (ni ) and the required volume fraction of phase
a in the final structure (ψaas ). Other auxiliary inputs include parameters like
the domain size of the structure, periodicity and maximum numbers of iter-
ations. The algorithm starts with a particle of type a or b in accordance with
the current and final solid fraction required of the phases in the structure.
6 Chapter 2. Outline of Dual Degree Project

Then it choses a random ( x, y) for that particle to start falling from. The par-
ticle is then allowed to fall from the maximum allowed height of the domain
until it reaches the floor or a stable position. Stable positions are attained
if the falling particle sits on top of three already fixed particles or two fixed
particles and the walls. This process is repeated until the domain is full of
particles. A slice of preset thickness is sliced off from the top and bottom to
eliminate edge effects.

F IGURE 2.1: Flow chart for the drop-and-roll algorithm imple-

mented for the structure generation (Bertei et al., 2012)
2.1. Stage zero 7

2.1.2 Three phase boundary length calculation

The logic for calculating the active and total three phase boundary length
concerns with calculating the arc lengths of the circles formed by the overlap
of two particles of different type, i.e., we are interested in the a-b type overlap.
There can be two cases for the overlaps shown in Figure 2.2; first case which is
relatively simple to analyze where only two particles overlap and the whole
circle qualifies as three phase boundary. Here, the radius of the intersecting
plane is calculated and the total circumference is added to the total TPBL and
the active TPBL if both the particles are percolating. The second case in which
there is at least another particle simultaneously intersecting the concerned
pair of particles, the part where there are more than two particle overlap has
to be neglected. Figure 2.3 illustrates how this is done - each intersecting
plane which is identified is divided into smaller arcs (usually 360 divisions)
and the distance between the center of the arc and center of the third particle
in contact is compared with the radius of the third particle in contact. If this
distance comes out to be more than the radius, then the arc is a valid TPB,
otherwise not.

a Intersecting plane b

a particle b particle a particle b particle

a/b particle
y y
zx zx

F IGURE 2.2: Illustrations of the various kinds of overlaps pos-

sible between particles in the structure

2.1.3 Results of the simulations

Figure 2.4 shows the results of the simulation for two different contact angles,
i.e., for two different degrees of sintering of the particles. The radii of both
the particles were taken to be the same and equal to 0.25 µm and the variance
was kept zero to simulate the mono-disperse case. The results closely follow
the trend as reported by Bertei et al., 2012 for both the contact angles. There
is considerable amount of variance in the results which could be attributed
to the regular failure of the structure generation code, which led to a zero
output from the TPB calculation code. This is one of the things to be rectified
in the due course of the project.

Figure 2.5 illustrates the effect of dispersion on the TPBL in the structure.
Moving from mono-dispersed to poly-dispersed starting particles results in
8 Chapter 2. Outline of Dual Degree Project

u(θ )

u(θ 0 )

y x
z
F IGURE 2.3: Projection of the 3-particle overlapping particles as
shown in Figure 2.2(b) to the intersecting plane (the yz plane).
The solid lines are the pair of particles of our interest and the
dashed line depict the third intersecting particle

·1012 θ = 15◦ ·1013 θ = 23◦

Reported 1 Reported
5
TPBL density, λvTPB (m−2 )

Calculated r a = rb = 0.25 µm Calculated

σa = σb = 0
4 0.8

3 0.6

2 0.4
r a = rb = 0.25 µm
σa = σb = 0
1 0.2

0 0
20 40 60 80 20 40 60 80
as
Solid fraction of phase a, ψa as
Solid fraction of phase a, ψa

F IGURE 2.4: The variation of the connected TPBL with the solid
fraction of phase a (Bertei et al., 2012)

a reduction of TPBL. Also, the maxima of the TPBL shifts slightly towards
the higher volume fraction of the poly-dispersed particle type, i.e. if only a
type particles are poly-dispersed, the maxima of the TPBL would occur at a
slightly higher solid fraction of a type particles than 50 %. This horizontal
shift can be attributed to the shift in percolating thresholds of the particles.

In Figure 2.6, the difference in total and active TPBL is illustrated. As we

move away from the 50 % mark of the solid fraction, the ratio of active TPBL
to the total TPBL decreases. This happens because at lower solid fractions,
the particles are not able to percolate, hence the TPB is not active.
2.2. Proposal for stages I and II 9

·1012

Active TPBL density, λvTPB (m−2 )

r a = rb = 0.25 µm
4 σa = σb = 0.2 µm
θ = 15◦

2
Monodispersed
Polydispersed
1 Polydispersed phase a
Polydispersed phase b

0
20 30 40 50 60 70 80
as
Solid fraction of phase a, ψa

F IGURE 2.5: Variation of active TPBL with the solid fraction of

phase a for mono-dispersed and poly-dispersed cases

1
θ = 15◦
Ratio of active to total TPBL

θ = 23◦
0.8

0.6 r a = rb = 0.25 µm
σa = σb = 0

0.4

0.2

0
20 30 40 50 60 70 80
as
Solid fraction of phase a, ψa

F IGURE 2.6: Variation of total vs active TPBL with the solid

fraction of a type particles

2.2 Proposal for stages I and II

The designated work for the dual degree project can be divided into two
parts – first part dealing with modeling the structures made up of spherical
particles for simulating electrodes of SOFCs. The other part deals with the
simulation of non-spherical particles to generate properties for VRFB elec-
trodes. The following sections would elucidate the problem statement.
10 Chapter 2. Outline of Dual Degree Project

2.2.1 SOFC
The problem for SOFCs would include re-coding the structure generation
code so that the errors induced by it as evident in Figure 2.4 gets mini-
mized. Following that, the code for extracting all the morphological prop-
erties, viz. two phase surface area, effective conductivities and effective dif-
fusivity would be developed. These results would be validated by the results
already published in the literature by Bertei et al., 2013.

The problem that comes after the initial work would be to model function-
ally graded electrodes. The motivation for the same comes from the fact that
SOFCs can potentially have both the fuel reforming as well as the main reac-
tion inside the cell while operation. But, the reforming reaction is endother-
mic and the the main reaction is exothermic. In addition to that, one would
ideally want the reforming reaction to be slow at the inlet of the cell and faster
at the end of the cell such that there is an even distribution of fuel across the
length and there are no areas of starvation. All of this can potentially be
achieved with functionally graded electrodes. Hence, modeling those and
testing the performance of the cell would follow after the aforesaid work.
The reference for this part would be Saied et al., 2017.

2.2.2 VRFB
Simultaneously with the modeling for SOFC electrodes, development of code
for modeling structures with non-spherical (specifically long fibers) would
be done referring to Bertei et al., 2014. This would then be followed by the
extraction of structure properties and cell level modeling. The verification of
the results would be done by the data from Kok et al., 2019.
 11

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