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Background

Materials and Methods

Results and Analysis

Conclusions

References

Acknowledgement

Department of Chemical and Materials Engineering, University of Alberta, Edmonton, Alberta, Canada, T6G 2G6

Guangya Wang, Jingli Luo*

Promoting Influence of Doping Indium into BaCe0.5Zr0.3Y0.2O3- δ on

the Chemical Stability, Sinterbility and Electrical Properties

Enhance the chemical stability of BCZY

Ensure high electrical conductivity

Improve the sinterbility of BCZY

Solid oxide fuel cells (SOFCs) can directly and high efficiently convert chemical energy of hydrocarbon gases to electricity [1].

Proton conducting SOFCs (PC-SOFCs) is suitable to work at intermediate temperature (500-700 oC), not only reducing operating cost but also expanding space for selecting potential materials [2].

Proton conducting electrolyte domains ohmic resistance and significantly affect cell performance [3].

BaCe0.5Zr0.3Y0.2O3-δ (BCZY) have excellent electrical conductivity, but is prone to decompose in acid gas [4].

Indium is an ideal dopant to enhance chemical stability and sinterbility of BCZY [1,2].

Objectives

Process routine

Characterization methods

Results and Analysis

Phase purity and crystal structure

Enhanced chemical stability

Desirable electrical properties

Improved sinterbility

SOFC application

Fig. 6 Shrinkage plots of different indium content BCZIY samples.

Porous anode support substrate

Thin electrolyte membrane

Porous cathode

Indium content Lattice parameters [Å] Unit cell volume

[Å3]

x a b c V

0 6.009 8.543 6.121 303.24

0.05 5.961 8.325 6.005 291.20

0.1 5.442 7.935 5.878 247.67

0.2 5.228 7.632 5.668 216.36

𝛔 =𝐀

𝐓𝐞−𝐄𝐚𝐊𝐓

Indium content Electrical conductivity [Scm-1]

Ea [eV] 600 oC 650 oC 700 oC

0 7.7*10-3 8.3*10-3 1.4*10-2 0.57

0.05 3.7*10-3 4.8*10-3 6.2*10-3 0.84

0.1 9.1*10-3 1.2*10-2 1.6*10-2 0.48

0.2 0.4*10-3 1.3*10-3 2.1*10-3 0.89

Fig. 1 XRD spectra of powder calcined at (I) 850 oC for 6 h and (II) 1100 oC for 6 h

Table 1 Crystal structure parameters of samples with different indium content

Fig. 3 XRD spectra of BCZIY (In=0.1) after chemical stability test, showing details between 20-60 o.

Fig. 4 Ahrrenius plots of different samples

Table 2 Conductivities and activation energy of different samples tested at each temperature under humid H2 (H2O 3 vol%)

Fig. 5 SEM images of different indium content pellets sintered at 1500 oC for 8 h. Fig. 2 XRD spectra of pellets before and after treatment under pure CO2 (+ H2O 3 vol%)

at 700 oC for 15 h, before: a 0, c 0.05, e 0.1, g 0.2; after: b 0, d 0.05, f 0.1, h 0.2. The dense pellets were obtained by sintering at 1500 oC for 8 h.

Fig. 7 Configuration of anode support fuel cell with BCZIY (In=0.1) as electrolyte material

Fig. 8 (a) I-V cure and power density variation with current density; (b) result

of electrochemical impedance spectra (EIS) test; (c) stability test of fuel cell under 650 oC fed by H2 (H2O 3 vol%)

Chemical stability and sinterbility of BCZY can be increasingly enhanced by

doping increasing amount of indium.

BCZIY with molar ratio of In at 0.1 showed the best electrical conductivity

(1.6*10-2 S/cm, 700 oC, H2 with H2O 3 vol%), compared with other doping

amount (0, 0.05, 0.2).

BCZIY (In=0.1) exhibited promising potentials as electrolyte materials used in

PC-SOFC.

1. Fabbri, E., D. Pergolesi, and E. Traversa, Materials challenges toward proton-conducting oxide fuel cells: a critical review. Chemical Society Reviews, 2010. 39(11): p. 4355-4369.

2. Magraso, A., et al., Development of Proton Conducting SOFCs Based on LaNbO4 Electrolyte - Status in Norway. Fuel Cells, 2011. 11(1): p. 17-25.

3. Ishihara, T., H. Matsuda, and Y. Takita, DOPED LAGAO3 PEROVSKITE-TYPE OXIDE AS A NEW OXIDE IONIC CONDUCTOR. Journal of the American Chemical Society, 1994. 116(9): p. 3801-3803.

4. Giannici, F., et al., Indium Doping in Barium Cerate:  the Relation between Local Symmetry and the Formation and Mobility of Protonic Defects. Chemistry of Materials, 2007. 19(23): p. 5714-5720.

Ba(NO3)2

Ce (NO3)3.6H2O

ZrO(NO3)2.xH2O

In(NO3)3.yH2O

Y(NO3)3.6H2O

H2O

Glycine

Heat + stirring

Homogeneous

solution

H2O

evaporation

Combustion

BCZIxY

nano-

powder

X=0, 0.05,

0.1, 0.2

Calcine at 850 oC for 6 h

BCZIxY

powders

with

perovskite

structure

Spin

coating Anode

support

fuel cells

Phase structure was identified using a Rigaku

Rotaflex X-ray diffractometer with Co Kα and the

data was analyzed with Jade software.

The morphologies, microstructures and grain size

were investigated by JEOL scanning electron

microscope (SEM).

Thermal expansion properties were measured by

dilatometer, LINSIE Premium L750, Germany.

Power density, open circuit voltage, and stability

of fuel cells were characterized by Solartron 1287.

(I) (II)

(a)

(c)

(b)