Hiroyuki Yoshida

1
, Toru Inagaki
1
, Koji Hashino
1
, Mitsunobu Kawano
1
, Hiroshi Ijichi
2
, Yoshiki Tatsuno
2
1 The Kansai Electric Power Company, Inc. 2 Kanden Power-tech Co., Ltd.
1. Introduction
Composite particles with NiO core and
ceria shell are synthesized by spray
pyrolysis technique.
The ceria parts on the surface of the particles connect at the early
step of the sintering, and there are no connections between Ni
parts.
The use of core-shell type composite anode materials with
higher Ni/ceria ratio may be one of solutions.
Ceria
NiO
Air
Aqueous solution
Ultrasonic vibrator
Furnaces
Filter
Air
H
2
O
H
2
O
H
2
O
H
2
O
Mists Metal nitrate Oxide
NO
x
NO
x
NO
x
NO
x
Drying Pyrolysis
Anode: Ni-GDC
High-resistance phases may
be formed during sintering.
Electrolyte: LSGM
Ni is used for the anode of SOFC.
High catalytic activity of the dissociation of H
2
High electron conductivity
Agglomeration during repeated reduction and
oxidation
Formation of high-resistance phases by
reaction with LSGM electrolyte
If Ni/ceria ratio is increased...
Strength of Ni network
Reaction between anode and electrolyte
In order to apply the cermet with higher
Ni/ceria ratio to the anode, preventing of
reaction between anode and electrolyte is
demanded.
Applying the composite particles prepared
by spray pyrolysis method
Spray pyrolysis technique
2. Experimental procedures
Conditions for spray pyrolysis
Raw materials Hydrates of Ni(CH
3
COO)
2
, Ce(NO
3
)
3
, and Gd(NO
3
)
3
, GDC Ce:Gd = 90:10 (by mol)
NiO:GDC70:3080:2090:10by weight 60:4072:2885:15 by volume
Reaction solutions Nickel concentration was fixed for all of solutions.
Synthesis conditionsMists of reaction solutions were flown into the reaction furnaces with 1 L/min air.
Temperatures of the furnaces: 200/400/800/1000
NiO/GDC (wt%) Ni (mol/L) GDC (mol/L)
70/30 0.54 0.100
80/20 0.54 0.058
90/10 0.54 0.026
NiO70-GDC
NiO80-GDC
NiO90-GDC
Cell performance test Cell: Ni-GDC/LSGM/SSC Thickness: 0.2 mmArea of electrode: 2 cm
2
Temperature: 750CH
2
flow: 7 ml/min/cm
2
Measurement: Current interruption method at the current density of 0.3 A/cm
2
.
SEM observation Pt-Pd was coated, and observed at the accelerated voltage of 15 keV.
TEM analysis Preparation: Eched by Ar
+
Observation: The accelerated voltage of 200 keV
EDSelement analysis: Mapping analysis of O, Ce, and Gd
Microstructure Analysis and Electrochemical Characterization of the Anode Using NiO-GDC
Composite Powders with Higher Ni Contents Prepared by Spray Pyrolysis Technique


NiO70-GDC 1200C NiO70-GDC 1240C NiO70-GDC 1280C
NiO80-GDC 1200C NiO80-GDC 1240C NiO80-GDC 1280C
NiO90-GDC 1200C NiO90-GDC 1240C NiO90-GDC 1280C
3. Results and discussion
2 mm 2 mm 2 mm
2 mm 2 mm 2 mm
2 mm 2 mm 2 mm
SEM
1150 1200 1240 1280
1150 1200 1240 1280
NiO80-
GDC
NiO90-
GDC
TEM-EDS mapping
0
0.2
0.4
0.6
0.8
1
1.2
1.4
0 0.2 0.4 0.6 0.8
Current density / A cm
-2
C
e
ll
v
o
lt
a
g
e
/
V
1150
1200
1240
1280
0
0.2
0.4
0.6
0.8
1
1.2
1.4
0 0.2 0.4 0.6 0.8
Current density / A cm
-2
C
e
ll v
o
lt
a
g
e
/

V
1150
1200
1240
1280
0
0.2
0.4
0.6
0.8
1
1.2
1.4
0 0.2 0.4 0.6 0.8
Current density / A cm
-2
C
e
ll v
o
lt
a
g
e
/
V
1150
1200
1240
1280
NiO70-GDC NiO80-GDC NiO90-GDC
I-V curves
0
0.05
0.1
0.15
0.2
0.25
0.3
0.35
0.4
0.45
0.5
1100 1150 1200 1250 1300
Sintering temperature /
IR
a

/

V
NiO70wt%
NiO80wt%
NiO90wt%
0
0.05
0.1
0.15
0.2
0.25
0.3
0.35
0.4
0.45
0.5
1100 1150 1200 1250 1300
Sintering temperature /
h
a
/
V
NiO70wt%
NiO80wt%
NiO90wt%
IR
a
vs. sintering temperature h
a
vs. sintering temperature
No remarkable tendency was observed. This tendency was corresponding to the
tendency of the cell performances.
< Microstructure analysis >
All samples showed that network structure formation started
at around 1200.
The connections between nickel parts of the neighboring
particles were observed at lower temperatures with higher
NiO/GDC ratios.
NiO90-GDC sintered at 1280had agglomerations of
nickel particles.
< Electrochemical performance >
Ni-GDC/LSGM/SSC cell with higher Ni contents were
operated.
NiO70-GDC cells (standard samples) indicated that cell
performance was drastically improved with sintering
temperatures.
NiO80-GDC and NiO90-GDC cells gave good performances
even at sintering temperatures.
Cermets with higher Ni contents prepared from NiO-
GDC composite particles were found to be promising
candidates for anodes of LSGM-based cells.