Mechanical Strength Improvement of NiO-YSZ Anode for Solid

Oxide Fuel Cell

Final Year Design Project Report

Submitted by
Qasim Yar Muhammad 2017375
Muhammad Usama Hakeem 2017334
Muhammad Nawaz Khan 2017301

Advisor
« Dr Shirjeel Khan » « Assistant Professor FMSE GIKI »
Co-Advisor
«Dr Ramzan Abdul Karim » « Assistant Professor FMSE GIKI»

Faculty of Material Science and Engineering

Ghulam Ishaq Khan Institute of Engineering Sciences and Technology.
July 2021
 Certificate of approval

Certificated that the work contained in this thesis entitled " Mechanical Strength

Improvement of NiO-YSZ Anode for Solid Oxide Fuel Cell " was carried out by (Qasim Yar

Muhammad, Muhammad Usama Hakeem, and Muhammad Nawaz Khan), under the supervision of (Dr

Shirjeel Khan) for the partial fulfillment of the

degree requirement of Bachelor of Science in Material Science and Engineering.

Approved by

Name and signature Name and signature

Advisor Dean FMSE
ACKNOWLEDGEMENT:
This project completion would have not been possible without the rigorous support of our parents,

and the supervision of our advisor and co-advisor. We are grateful to the faculty for providing us

with the state-of-art facilities.

 ABSTRACT

The strength and durability of the porous cermet support during long-term cell operation is

important for the reliability of the cells and stacks in anode supported solid oxide fuel cells

(SOFCs). This study analyzed the effect of adding cubic-BN to improve the mechanical strength of

nickel-yttria stabilised zirconia (Ni-YSZ) based SOFC anode supports over time. The flexural

strength, phase, and microstructural variations of the SOFC anode support materials, Ni-3YSZ (3

mol percent YSZ), Ni-8YSZ (8 mol percent YSZ), and Cubic-BN added Ni-YSZ composites, were

sintered and exposed to various circumstances before being evaluated.The research suggests that

adding cubic-BN to Ni-3YSZ increases the cermet's long-term strength and durability, however

adding it to Ni-8YSZ cermet had no significant effect on the strength degradation behaviour of the

Ni-8YSZ based anode support. The tetragonal to monoclinic phase transformation in partially

stabilised zirconia was examined using SEM and XRD, and its effect was seen following the

addition of cubic-BN to Ni-3YSZ, resulting in increased long-term stability and mechanical

strength. By replacing the Ni-8YSZ anode support with cubic-BN added Ni-3YSZ, the material

cost of SOFCs could be greatly reduced without sacrificing long-term strong durability, bringing

SOFCs closer to commercialization.

Table of Contents
Final Year Design Project Report....................................................................................................................1
Advisor............................................................................................................................................................1
Certificate of approval.....................................................................................................................................2
Approved by....................................................................................................................................................2
Chapter 1: Introduction.......................................................................................................................................6
1.1 PROJECT DEFINITION.....................................................................................................................6
1.2 PROJECT OBJECTIVES..........................................................................................................................6
Chapter 2: Literature Review..............................................................................................................................8
2.1 PROJECT BACKGROUND.....................................................................................................................8
2.2 PREVIOUS WORK..................................................................................................................................8
2.3 COMPARATIVE STUDY........................................................................................................................9
Chapter 3: Design Methodology........................................................................................................................11
3.1 METHODS INVOLVED........................................................................................................................11
3.2 RATIOS INVOLVED.............................................................................................................................11
3.3 SINTERING AND ITS EFFECT............................................................................................................12
Chapter 4: Mechanical Testing and Analysis....................................................................................................14
4.1 Results and Discussions:..........................................................................................................................14
Mechanical Testing Results...............................................................................................................................15
Weibull Strength and Distribution.....................................................................................................................17
Conclusion.........................................................................................................................................................19
Further Research...............................................................................................................................................19
REFERENCES..................................................................................................................................................20
SDG GOALS MAP...........................................................................................................................................20
Chapter 1: Introduction

1.1 PROJECT DEFINITION

A solid-state electrochemical cell that transforms chemical energy into electrical energy is known as a

solid oxide fuel cell (SOFC). As compared to other types of fuel cells, SOFCs have a high efficiency

of over 80% when it comes to absorbing the heat produced during the conversion ( Alaswad et al .,

2020). Fuels used in SOFCs reform within the fuel cell itself without the need for external reforming

or a metal catalyst because they operate at very high temperatures (800–1000°C). On the other hand,

using such a high temperature environment makes selection materials for fuel cell parts challenging

( Alaswad et al ., 2020).

SOFCs, which use various electroceramics as cathodes, electrolytes, and anodes, can be used for a

wide range of applications, including large-scale power plants, small-scale power plants, and portable

or emergency power generators (Bharadwaj et al., 2012). SOFCs can convert waste gases (methanol

from biomass) to electricity and heat with minimal environmental impact when biological waste

gases are available from waste treatment plants. SOFCs are a revolutionary energy conversion

technology for producing clean and efficient power (Mehran et al.,2018)

1.2 PROJECT OBJECTIVES

The term "electrode-supported" was introduced to reflect that the mechanical stability of such fuel

cells is transferred from the thick, dense electrolyte layer to an even thicker, porous electrode (0.5–1.5

m). Fuel cells could be supported on the anode,cathode or

electrolyte(Alessandra Sanson, Angela Gondolini). Despite the fact that the cathode-supported

configuration has greater structural stability and uses less expensive cathode material (Gondolini et
al., 2012; Su et al., 2015), the anode-supported configuration is preferred because it is simpler to

manufacture.

The anode is made of nickel and YSZ cermet. Tubular or planar SOFCs have advantages in terms of

thermal shock resistance and ease of sealing, whereas planar SOFCs have advantages in terms of

power density and ease of cell manufacturing (Brandon et al.,2016). In both the single cell and the

SOFC stack, the porous Ni-YSZ anode support cermet acts as the mechanical backbone (Mehran et

al.,2018). The mechanical reliability of the Ni-YSZ anode support determines the SOFC stack's

integrity during long-term operation.

However long-term anode operation at high temperatures and humidity, in SOFC causes the anode

support to be subjected to sustained thermal and mechanical stresses. The anode support cermet's

durability and strength deteriorate, potentially causing the SOFC stack to collapse (Wachsman & Lee,

2011).

Many researchers have shown that adding a small amount of materials in the Ni-YSZ anode cermet

yields improved electrical mechanical and microstructural properties of the anode cermet.Those

materials will be briefly discussed in the literature review.This study will highlight the addition of

different materials and their effects on the electrical,mechanical and microstructural properties of the

Ni-YSZ.However the focus of this study is to investigate the effect on properties of Ni-YSZ

especially flexural strength by the addition of cubic Boron Nitride.

 Chapter 2: Literature Review

2.1 PROJECT BACKGROUND

This section will discuss past and current research on SOFC and SOFC anode materials. It is

necessary to investigate electrode materials such as composites and cermets at higher temperatures in

SOFC to increase thermal, mechanical, and chemical compatibility in cell reactions.High catalytic

activity, high performance, and high conductivities with relatively significant porosity are required

for SOFC electrodes(Bharadwaj et al., 2012). The greater working temperature of SOFC, on the other

hand, remains a challenge. Highly conductive materials, for example, are unreliable and incapable of

performing at high temperatures. Aside from that, the electrode materials utilised in SOFCs must be

compatible and have strong cyclability during starting and shutdown( Alaswad et al ., 2020). The

following are the main characteristics of any SOFC electrode material:

• Optimum catalytic activity and electrical conductivity

• Efficient thermal expansion stability

• Electrode and electrolyte compatibility at working temperature

• Must be durable at higher temperatures

• Must be fuel flexible

•Low coking resistance and cheap cost

2.2 PREVIOUS WORK

Ni-3YSZ and NI-8YSZ are state of the art anode materials for SOFC.Previously research has been

done to improve the mechanical properties of these materials by adding al203 nanopowders (Mehran

et al.,2018).Based on the thermal and mechanical properties we came up with the following materials

that could be added to NiO-YSZ.Boron nitride,Aluminum nitride, Tungsten carbide, Tungsten

alloy(W–Ni–Fe) YSZ composite potentially suitable materials for high strength applications. These

materials show high strength and are chemically inert to some extent. Already research has been

conducted for Tungsten YSZ composites for high strength applications.

2.3 COMPARATIVE STUDY

Boron nitride is one of the hardest materials after diamond. It has very high chemical resistance. It

can withstand high temperatures above 1000 degree centigrade depending on its allotropic form(Li, Y

et al.,2018). It has very high thermal conductivity i.e. half of diamond and strength that make this

material very suitable for SOFC. It would improve the mechanical properties on NiO-YSZ anode as

well as improving its thermal stability.There are many allotropic forms of BN among which cubic

BN, hexagonal BN, amorphous BN and Wurtzite BN are popular ones. This project will focus on

adding c-BN to NiO-YSZ anode powders. The reason why we have chosen c-BN is due to its high

strength, better mechanical properties and high thermal conductivity than other forms. C-BN

structural and thermal stability is below 1500 degree Celsius while h-BN is stable above 1500 -1600

degree centigrade (Cahill et al., 2020). BN due to high hardness shows exceptional wear resistance in

a frictional environment. Hence SOFC operating temperature range is 500-1000 degree Celsius.

Therefore, c-BN would be a suitable addition to NiO-YSZ powders .

Cubic BN is the second hardest material next to diamond. It has been used in wear resistance and the

abrasive environment’s micro hardness ranges from 75-90.Its young modulus or elastic modulus

ranges from 630-770 Gpa. Bulk modulus is approximately 400 Gpa. It can absorb a high amount of

energy before cracking and rupturing (Solozhenko, Bushlya and Zhou, 2019).

From consulting multiple research papers, we have inferred that Bi2O3, SiO2, TiO2, Fe2O3 and

Al2O3 were advised as sintering aids for NiO-YSZ. Resistivity of YSZ is greatly enhanced at low

temperature by incorporating Silica, titania, iron and Bismuth oxide, hence incorporating such
additives is out of question. In contrast, alumina seems to be a good candidate as a sintering additive.

Additionally, boron nitride (BN) is identified as a novel sintering aid (Angewandten et al., 2006).

Although no practical research work has been done on boron nitride and YSZ composites.

The percentage of addition of c-BN depend on the batch of samples.Manly 3 batches will be

produced that will have percentage varying from 0.1 to 2 % by weight.The reason for adding such a

low percentage of c-BN is due to its high strength and even a minute amount can have significant

effect on improving the mechanical strength of Ni-YSZ anode.Further more,the percentage of c-BN is

so minute that it might not have any effect on the electrical conductivity of Ni-YSZ anode material.

The purpose of this research is to see how adding cubic Boron Nitride to Ni-YSZ affects its

properties, particularly flexural strength.

 Chapter 3: Design Methodology

3.1 METHODS INVOLVED

Ball Milling is a process which is really vital to the progress of this project. Before delving deep why

Ball milling is vital, let’s look at what ball milling is initially. Ball milling is the breakdown of

particles from large agglomerates into small particles, even in Nano range. Using centrifugal force

initiated because of the rotation of the jar and ball bearings hitting the powder, it causes uniform

decrease in its size due to this. Centrifugal force depends upon rotations occurring in specific time,

and the radius of the jar. Greater the rotations, and greater the radius of the jar; the force will increase

causing an instantaneous decrease in the size of the powder. The ball hitting the powder frequency

decides the amount of time it will cause the decrease in size. It is a vital part of the project as powders

having different compositions need to be broken down so that pellet making can occur. Pellet making

and baking will be discussed later in this report.

3.2 RATIOS INVOLVED

Ball milling isn’t just breakdown of particles but promotes cohesion among particles, plus resulting in

a uniform product in the end. The ball milling facility was installed in the Material Science faculty,

which is currently present in the ceramics lab. Ball milling was performed for a period of twenty-four

hours continuously, after the ball milling process pellets were made from a customized die making

model produced on the CAD software. Including the tolerances and respective clearances. Five

samples were used in this project with different ratios of NiO and 3YSZ, plus additions of additives

such as Boron Nitride to check whether the strength enhances or not, and if strength enhances at

which particular ratios does it improve. Carbon Black is also added to make sure porosity is present

in the pellets, if porosity isn’t present in the pellets being made then oxidation at the anode will not be

occurring, and in the end causing hindrance in the solid oxide fuel cell.
 Table 1ratios of elements and materials used for ball milling mixture

3.3 SINTERING AND ITS EFFECT

Boron Nitride is used in the formation of pellets because it is considered one of the hardest materials

present, with high energy absorption capability. Sintering is considered a forming process in which

binding of particles with each other is brought into account, with the help of binding additives. The

process of sintering. The process of sintering can be visualized in the figure given below.

As stated earlier it promotes cohesion amongst each other, can be seen in the figure. Porosity is

removed and one uniform structure is formed, if this uniformity is not present then under influence of

heat treatment cycles the pellet formed will collapse, resulting in no results as mechanical testing will
be impossible. Carbon Black is added to enforce porosity, but sintering helps us to avoid excessive

porosity in the pellet.

 Chapter 4: Mechanical Testing and Analysis

4.1 Results and Discussions:

Initial observations recorded the characterization of NiO-3YSZ powder with different composition

additions of boron nitride powder.1%,1.5%, 0.5% Off boron nitride was added to NiO-3YSZ powder

and their initial XRD peaks Were observed in the following graph.

Figure 1 Initial XRD Peaks of powders (unmixed) before ball Milling

The above graph shows the XRD peaks of powders before ball milling process. The powders are not

yet mixed and are shown as separate Materials. The peaks of these powder give clear indication when

matched with expert high score that these peaks match with the given database.

Similarly. And XRD characterization was carried out after ball milling process of the mixed samples

containing 1.5%, 1 % and 0.5% boron nitride in NiO-3YSZ samples. The graph plotted below shows

the mixed powder XRD peaks after ball milling process.

Figure 2 XRD Peaks after mixing and ball milling.

The figure above shows. The variation of intensities of different percentages of boron nitride added in

the NiO-3YSZ sample. The variation of angles. And the. Existence of. Powders in the mixed form

after boiling Is evident from this expert High score search and match database.

Mechanical Testing Results

Mechanical testing was carried out for 6 samples that included three 4gm samples of 0.5BN and three

6gm samples of 1.5 BN in NiO-3YSZ. Flexural testing was the basis of our mechanical test which

included the result from a 3 point bend test. The Graphs below shows the bending stresses of

compression. As it can be clearly noticed that sample 1 and 2 had fairly similar failure stresses that

gave us an average value to draw a Weibull distribution graph for it. Sample no 3 underwent critical

stresses and failure before reaching the desired point. Hence giving us deviation from the normal

range.
 Figure 3 Flexural Strength of 1.5 BN in NiO-3YSZ sample 2 Figure 4 Flexural Strength of 1.5 BN in NiO-3YSZ

sample 1

Figure 5 Flexural Strength of 1.5 BN in NiO-3YSZ sample 3

The flexural bend test was also carried out for the remaining three gm 0.5 BN samples. The results

showed a better result than the 1.5 BN samples with more strain and increased failure stress. This

helps us choose the 0.5 BN sample over the 1.5 BN samples. It is because of the failure stress is much

higher and gives us better strength. This is a salient feature in determining better mechanical strength

for SOFC anodes.

Figure 6 Flexural strength of 0.5 BN in NiO-3YSZ sample 1 Figure 7 Flexural strength of 0.5

BN in NiO-3YSZ sample 2

Figure 8 Flexural strength of 0.5 BN in NiO-3YSZ sample 3

Weibull Strength and Distribution

Weibull distribution is a prominent technique for pdf analysis that accurately describes the physics of

failure in samples. It is commonly used for procedures with less than 20 samples (Lazzari, 2017).

In our experiments the samples underwent mechanical flexural testing , the results of which were

plotted via the equation:

j−0.3
S j=1− …….. Equation 1
N + 0.4

No prior conditions or environment was used to conduct the mechanical testing. The figures shown

below represent the Weibull plot which was calculated using the distribution table in the table. As it
is evident from the graph that 1.5 BN has much higher Weibull strength i.e. 1.85-2.20 in comparison

with 0.5 BN i.e. 1.1-1.6.

Figure 9 0.5 BN Weibull logarithmic graph Figure 10 1.5 BN Weibull logarithmic graph

Table 2 Weibull Distribution for BN 0.5 and 1.5 in NiO-3YSZ

Table 1. Weibull distribution for NiO-3YSZ 0.5% BN

Rank j Sj σf lnσf (-ln ln(1/Sj)

1 0.794117647 3.14 1.1442228 1.467401781

2 0.50000000 3.86 1.350667183 0.366512921
3 0.205882353 4.85 1.578978705 -0.457709854

The above distribution shows the values calculated from eqn 1. Where σf represents failure stress at

which the cermet broke. Similarly the natural logarithm of the values were taken in order to graph the

Weibull plot to determine how much strength has improved in the cermet sample by adding BN.
 Conclusion

In determining a suitable ration for improving the mechanical strength of SOFC Anode of NiO-3YSZ

we used BN as a fitting nano-powder. The process was rigorous, and many attempts were made to

determine the right ratio to improve mechanical strength and improve the long-term durability. The

ball Milling machine provided the means to crush the nano powders to an appropriate range where

the thermomechanical reaction took place and the sample powder pellets were sintered. The strengths

that we achieved through mechanical testing were unique since no literature has ever reported this

process with BN as the nano-powder which is why a comparison was not made. The results however

can be interpreted for further research use in the long term durability of SOFC anodes.

Further Research

The process doesn’t end at mechanical results and BN nano powders but can also be extended to

several mixing ration that can provide better strength modulus. There are other elements such as SiC

which are being experimented on to improve SOFC anode, similarly this process can be repeated

again with different ratios and heat treatment cycle to determine better strength modulus. The

degradation test however wasn’t possible due to the COVid-19 Scenario and can be implemented for

this research to accurately predict its failure strength.

 REFERENCES

Lazzari, L. (2017). Statistical Analysis of Corrosion Data. In Engineering Tools for Corrosion (pp.
131–148). Elsevier. https://doi.org/10.1016/b978-0-08-102424-9.00008-2
Bharadwaj, S. R., Varma, S., & Wani, B. N. (2012). Electroceramics for Fuel Cells, Batteries and
Sensors. Functional Materials, 639–674. https://doi.org/10.1016/b978-0-12-385142-0.00016-7

Angewandten, F. Der et al. (2006) ‘(12) United States Patent’, 2(12).

Cahill, J. T. et al. (2020) ‘Transformation of boron nitride from cubic to hexagonal under 1-atm
helium’, Diamond and Related Materials, 109, p. 108078. doi:
https://doi.org/10.1016/j.diamond.2020.108078.
Li, R. et al. (2020) ‘Thermal cycling stability of novel hexagonal boron nitride (h-BN)/glass
compressive seals for planar intermediate temperature solid oxide fuel cells’, Journal of Alloys
and Compounds. Elsevier B.V., 843, p. 155620. doi: 10.1016/j.jallcom.2020.155620.
Li, Y. et al. (2018) ‘Synthesis and characterization of boron nitride powder’, AIP Conference
Proceedings, 1971. doi: 10.1063/1.5041102.
Menzler, N. H. (2003) ‘Densification of SOFC Yttria-Stabilized Zirconia Electrolytes Through
Addition of Sintering Additives’, ECS Proceedings Volumes, 2003–07(1), pp. 238–245. doi:
10.1149/200307.0238pv.
Solozhenko, V. L., Bushlya, V. and Zhou, J. (2019) ‘Mechanical properties of ultra-hard
nanocrystalline cubic boron nitride’, arXiv, 85(3), pp. 1–13.
Abed Alaswad, Ahmad Baroutaji, Ahmed Rezk, Mohamad Ramadan, Abdul G Olabi,Advances in
Solid Oxide Fuel Cell Materials,Reference Module in Materials Science and Materials
Engineering,Elsevier,2020,
Mehran, M. T., Khan, M. Z., Lim, T. H., Lee, S. B., & Song, R. H. (2018). Effect of nano-Al2O3
addition on mechanical durability of nickel-yttria stabilized zirconia anode support of solid
oxide fuel cells. Ceramics International, 44(12), 14824–14833.
https://doi.org/10.1016/j.ceramint.2018.05.114
Goutianos, S., Frandsen, H. L., & Sørensen, B. F. (2010). Fracture properties of nickel-based anodes
for solid oxide fuel cells. Journal of the European Ceramic Society, 30(15), 3173–3179.
https://doi.org/10.1016/j.jeurceramsoc.2010.07.028
Pećanac, G., Wei, J., & Malzbender, J. (2016). Fracture toughness of solid oxide fuel cell anode
substrates determined by a double-torsion technique. Journal of Power Sources, 327, 629–637.
https://doi.org/10.1016/j.jpowsour.2016.07.103
Monzon, H., & Laguna-Bercero, M. A. (2015). The Influence of Reduction Conditions on a Ni-YSZ
SOFC Anode Microstructure and Evolution. ECS Transactions, 68(1), 1229–1235.
https://doi.org/10.1149/06801.1229ecst
Cubero, A., Peña, J. I., & Laguna-Bercero, M. A. (2015). Optimization of Ni-YSZ solid oxide fuel
cell anodes by surface laser melting. Applied Surface Science, 335, 39–43.
https://doi.org/10.1016/j.apsusc.2015.01.230

SDG GOALS MAP

S. No SUSTAINABLE DEVELOPMENT GOALS Please Tick
()

1. GOAL 1: NO POVERTY

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7.