Fabrication and characterization

of 5 % Zn doped
BaCe0.7Zr0.1Y0.15Zn0.05O3-δ industrial
based thin film proton conducting
minerals for IT-SOFC
Ahmed Afif Bin Abedin
Faculty of Integrated Technologies
Universiti Brunei Darussalam
AUTHORS

• Ahmed Afif ¹, Abul K. Azad ¹, Mridula Biswas ², Juliana Zaini ¹.

¹ Universiti Brunei Darussalam, Faculty of integrated Technologies, Jalan

Tungku Link, Gadong BE1410, Brunei Darussalam.
² Defiant Renewables Pvt. Ltd. Pune, India.
OUTLINE

• Overview
• Experimental & results
• Future work
• Conclusion
Overview
 A novel method for the preparation of a thin film proton-conducting electrolyte is
presented.

 The present work deals with the fabrication of 5 % Zn doped BaCe0.7Zr0.1Y0.15 Zn0.05O3-δ
(BCZYZn15) thin film electrolyte. Electrolyte materials were prepared by an acetate-
methoxyethanol solution method and examined by multilayer (4, 6, 8 times) coating on
silicon and anode (NiO- BaCe0.7Zr0.1Y0.15 Zn0.05O3-δ ) substrate at different temperatures.

 A thin, dense, crack free BCZYZn15 electrolyte film was successfully obtained on a
dense anode by spin coating. Postmortem analysis by scanning electron microscope
(SEM) revels that no crack on 6 layers coating at 1100°C. Furthermore, this work shows
that, Zn doped BaCe0.7Zr0.1Y0.15 Zn0.05O3-δ dense thin film could be good industrial mineral
for IT-SOFC.
Samples
 BaCe0.7Z0.1Y0.15Zn0.05O3-δ (BCZYZn15)-NiO, Where x = 0.15
electrolyte supported anode

 BaCe0.7Z0.15Y0.15O3-δ (BCZY) electrolyte solutions are 1, 2,

3 & 4 = 0.31, 0.62, 1.75 & 3.5 ml of Acetylacetone.

 BaCe0.7Z0.1Y0.15Zn0.05O3-δ (BCZY with 5% Zn) electrolyte

Experimental & results

• Sample Preparation
• XRD
• SEM
 Preparation of solution:
 Barium, Cerium, Zirconium acetate, Yttrium nitrate hexahydrate, Zinc Nitrate
Sample Preparation hexahydrate, Acetylacetone, polyvinylpyrrolidone, polyethylene glycol,
acetic acid, ammonium hydroxide and 2-Methoxyethanol were used to
prepare the BCZYZn solution.
Powders preparation:
o BaCe0.7Zr0.1Y0.15 Zn0.05O3-δ powders were
 First, Ba-Ac and Ce-Ac powders was dissolved in acetic acid two separate
synthesized by Solid state reaction (SSR) method.
beaker at 230-250 ℃ and then cooled down to the room temperature.
Next, Zr-Ac, Y(NO3)3. 6H2O, Zn(NO3)2.6H2O, Acac, PVP, and PEG were added to
o Stoichiometric amount of BaCO3, CeO2, ZrO2, Y2O3 the solution and dissolved with stirring.
and ZnO were mixed by ball milling with acetone.
 The pH of the solution was then adjusted to 4 with the addition of
o The finely ground dried materials were fired at
ammonium hydroxide. 2-Methoxyethanol was added to improve the
1000°C for 8 h and pellet sintered at 1200°C for 8
h. The final sintering temperature was 1400°C for wettability of the solution.
10 h. Thin film electrolyte preparation:
o NiO and BaCe0.7Zr0.1Y0.15 Zn0.05O3-δ powders with • First single crystal silicon were used as substrates for BCZYZn15 thin film
the 6:4 weight ratio and sintered at 1400°C for 10 deposition.
h. • The substrates were spin coated with chemical solution at the speed of
3000 rpm for 60 s using a Laurell spin-coater. After that, the coated substrates
were dried on a hot plate at 300 °C for 10 min.
• Subsequently, the samples were rapidly sintered in a pre-heated tube furnace.
Processing time and temperature were varied for parameter optimization. For
comparison, conventional sintering with ramping rate of 10 °C/min was also
carried out.
• After silicon substrate, NiO-BCZYZn15 anode substrate was used for final
characterization.
XRD

The phase structure, purity, identity and

homogeneity of the mixed oxide was examined
by at ambient temperature using Shimadzu-7000
diffractometer (CuK1=1.5406 Å) in the 2 range
from 10o to 90o. The data were collected with a
0.01o step size and a count time of 60 s/step. The
obtained data were refined by the Rietveld
method using the FullProf software.
Rietveld analysis of X-ray diffraction
data for BaCe0.7Zr0.1Y0.15Zr0.05O3-δ (BCZYZn15)
 Rietveld analysis of X-ray diffraction
data for BaCe0.7Z0.25-xYxZn0.05O3 (BCZYZn)
Sample Parameters BCZYZn15
Space group PBNM
χ2 1.58
Cell parameter a 6.163(3)
(Å) b 6.154(4)
c 8.814(2)
Calculated Density (g/cm3) 6.161
Vol. (Å) 334.369
No. of fitted parameter 26
Rp/Exp Ratio 1.36
R- factor 9.41
Rf - factor 12.4
Rp 18.8
Rwp 27.6
SEM
 The microscopic features of the
prepared electrolytes were characterized
using Scanning Electron Microscope
(JSM-7610F).
 The SEM data were collected with
voltage range of 2 kV to 5 kV and with
magnification of 1700 to 60000 times in
range.
 SEM images of electrolyte and anode
• The surface was smooth and free of
(a) (b)
cracks.
• The grains were well grown and BCZY
connected to each other making high
density materials. These suggest non
porous high density feature.
• No trace of liquid or secondary phases
was found at the grain boundary region
in the investigated samples. The NiO
images also show that the grain sizes
are large and completely compact
which give high density as the required
aspect of electrolyte. (a) BCZYZ15 & (b) BCZYZ15-NiO
• Temp at 1400 ℃.
 Electrolyte solution in Silicon substrate
(a) (b) (c)
• BCZY solutions are 1,
2, 3 & 4 = 0.31, 0.62,
1.75 & 3.5 ml of
Acetylacetone.
• Cluster of pores were
found to form. Each
cluster does not go much
beyond 100nm.
• Individual pores are also
present. Each cluster also
contains many smaller
pores.
• Crack is visible
(a) BCZY1, (b) BCZY2 & (c) BCZY3 solution in Silicon substrate.
 Electrolyte solution in anode substrate
(a) (b)
 Solution 2 and solution 4 are
producing uniform microstructure.
 Solution 1 and solution 3 show phase
separation: one phase contains more
crack while the other one contains
more pores.
 Sinter ability of any solution is not bad (c) (d)

although all the film contains pore.

 Temp at 1000 ℃ most of the pores, it
was observed that they are not
penetrating film from one end to the
other.
 Pores are mainly visible at the side of 4 layers of coating of (a) BCZY1, (b) BCZY2, (c)
larger grains. BCZY3 & (d) BCZY4 solution on anode
substrate
 Electrolyte solution in anode substrate
 Solution 1 and solution 3 have produced (a) (b)
more porous film while solution 2 and
solution 4 has generated less porous.
 The pores observed are neither associated
with organics /network formation in the
solution/film during processing nor
associated with processing defects
 The pores are associated with de-sintering/ (c) (d)

exaggerated grain growth because they are

observed beside bigger grains.
 Some kind of planes are also observed over
the films, which indicates directional
growth. Sintering is excellent except
overgrowth of grains.
4 layers of coating of (a) BCZY1, (b) BCZY2, (c) BCZY3 &
(d) BCZY4 solution with 5 mol% ZnO on anode substrate
 Electrolyte solution in anode substrate
(a) (b)
(a) BCZY2 and (b) BCZY3 with 5 mol% ZnO on
anode substrate with 6 layer coating
• solution 2 is better than others.
• The sintering is good. Grain compositions
distribute properly. No secondary phase.
Sintering is excellent except overgrowth of
grains.
• Crack is visible.
(c) (d)
BCZY4 with 5 mol% ZnO on anode substrate (c) 6
layer & (d) 8 layer coaing
• solution 4 is comparatively better solution and
that coating 6 is better than 4 and 8. All images
show phase separation: one phase contains more
crack while the other one contains more pores.
• Temp at 1100 ℃.
Conclusion
• In this study, 5% Zn doped BaCe0.7Z0.1Y0.15Zn0.05O3 proton conducting
thin film electrolyte was successfully fabricated at relatively low
sintering temperature. It could be good industrial mineral for IT-SOFC
Next steps and future work
• To test power density & current density.
• To compare with other samples in same series.
THANK YOU