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Infiltration of La

n+1
Ni
n
O
3n+1
and La
0.6
Sr
0.4
Co
0.2
Fe
0.8
in LSGM Cathodes for
Intermediate Temperature SOFCs

Timothy V. Flavin

Northwestern University, Materials Science and Engineering

Mentor: Justin G. Railsback

Advisor: Scott A. Barnett

June 11, 2014
LNO and LSCF in Solid Oxide Fuel Cells
2



Infiltration of La
n+1
Ni
n
O
3n+1
and La
0.6
Sr
0.4
Co
0.2
Fe
0.8
in LSGM Cathodes for
Intermediate Temperature SOFCS




Timothy Flavin
Materials Science & Engineering
Northwestern University
June 11, 2014



Abstract

Solid oxide fuel cells with infiltrated La
0.9
Sr
0.1
Ga
0.8
Mg
0.2
O
3-!
(LSGM) cathodes have the
potential to provide low polarization resistances at intermediate temperatures between 500-650
C. The present study examines LSGM cathodes infiltrated with La
n+1
Ni
n
O
3n+1
(LNO) and
La
0.6
Sr
0.4
Co
0.2
Fe
0.8
O
3-!
(LSCF). Symmetrical LSGM cathodes were loaded with varying ratios of
LNO and LSCF infiltrates on both sides of bulk LSGM electrolytes. Each infiltration was fired at
900 C to evaporate the infiltrate solution and allow LNO to form Ruddlesden-Popper phases. X-
ray diffraction determined this temperature ideal for formation of the La
2
Ni
1
O
4
and a La
8
Ni
4
O
17

ordered secondary phase. Cathode polarization resistance R
p
, tested using impedance
spectroscopy, was highest in the cells with an even ratio of LNO:LSCF, whereas the R
p
was
lowest in the cells primarily loaded with LSCF. At 650 C, cells infiltrated only with LSCF had a
polarization resistance as low as 0.21 "cm
2
, which compares well to a previous LSCF/LSGM
cathode study that found R
p
of 0.18 "cm
2
. Cells infiltrated only with LNO had a polarization
resistance as low as 0.33 "cm
2
, which is the lowest recorded R
p
for LNO any LNO based
electrode. The temperature dependence of R
p
yielded an activation energy of #1.5 eV for all cells
infiltrated with LSCF, and an activation energy of #1.2 eV for cells infiltrated with LNO only.
LNO and LSCF in Solid Oxide Fuel Cells
3

Table of Contents
1. Introduction ............................................................................................................................... 4
1.1 Solid Oxide Fuel Cell Operation ........................................................................................... 4
1.2 Cathode Oxygen Reduction Reaction ................................................................................... 5
1.3 Cell Infiltration ...................................................................................................................... 5
2. Experimental ............................................................................................................................. 7
2.1 Fabrication of LSGM Electrolytes ........................................................................................ 7
2.2 Preparation of Symmetrical Cells ......................................................................................... 7
2.3 Experimental Design ............................................................................................................. 9
2.4 SOFC Test Preparation ......................................................................................................... 9
2.5 Cathode Characterization Methods ..................................................................................... 10
3. Results and Discussion ............................................................................................................ 10
3.1 Composite Cathode Microstructure ................................................................................. 10
3.2 Impedance Spectra .......................................................................................................... 12
3.3 Polarization Resistance: Infiltrate Composition Effect ................................................... 13
3.4 Activation Energy Calculation ........................................................................................ 14
4. Conclusions .............................................................................................................................. 15
Acknowledgements ..................................................................................................................... 15
References .................................................................................................................................... 16




LNO and LSCF in Solid Oxide Fuel Cells
4
1. Introduction

Solid oxide fuel cells (SOFC) are an emerging alternative energy device capable of achieving
very high efficiency, high power densities, and low emissions
[1]
. SOFCs convert chemical energy
to electricity directly, by separating a combustion reaction into two half reactions mediated by an
oxygen conducting electrolyte and electrocatalytic electrodes. Due to their fuel flexibility,
SOFCs can use commonly available fuels, which could reduce fossil fuel use for electricity
production and mitigate global climate change
[2]
.

As fuel cell technology continues to grow, improvements in cost, power density, and efficiency
can also prove to make SOFCs a very cost-effective energy source. However, despite the
numerous benefits of SOFCs, their high temperature demands limit them and prohibit fuel cells
from becoming a viable option for widespread energy production.

High operating temperatures in SOFCs can lead to material incompatibilities, and degradation
[3]
.
Additionally, higher temperatures lead to higher operating and balance of plant costs, limiting
the financial feasibility of fuel cell use. In order to reduce operating costs and improve cell
longevity, it is advantageous to create cells that can function at lower temperatures (500-650 C)
called intermediate-temperature solid oxide fuel cells (IT-SOFCs).

1.1 Solid Oxide Fuel Cell Operation

SOFCs are comprised of three principle components: the anode, cathode, and electrolyte. At the
anode, hydrogen fuel is oxidized by O
2-
ions coming from the electrolyte layer. The electrolyte
serves to electrically insulate the anode from the cathode while conducting O
2-
ions from the
cathode to the anode. At the cathode, oxygen is reduced using current flowing from the anode,
which completes the cycle of oxygen ions and electrons through the cell to produce electricity as
shown in fig. 1.


Figure 1: Solid oxide fuel cell schematic
[1]
LNO and LSCF in Solid Oxide Fuel Cells
5
1.2 Cathode Oxygen Reduction Reaction

At the cathode, oxygen is reduced according to the following Kroger-Vink reaction (equation1)
in perovskite materials
[5]
:

(Eq. 1)


Whereas in Ruddlesden-Popper materials such as LNO that conduct oxygen ions interstitially,
the ORR proceeds overall as:

(Eq. 2)
[5]

Due to the slow ORR kinetics, overpotentials, and corresponding polarization resistances arise
during operation. These exponentially grow in magnitude as temperature decreases
[5]
. By
minimizing this resistance to the oxygen reduction reaction (ORR) within the fuel cell cathode, it
is possible to operate the cell even at intermediate temperatures. ORR polarization resistance is a
prime contributor to loss of efficiency in SOFCs, particularly at lower temperatures
[4]
. One way
to reduce this resistance is through cathode infiltration. An infiltrate solution can be absorbed
into a porous cathode scaffold to modify the surface of the cathode particles. The nanostructuring
and large surface area resultant from infiltration corresponds to a higher volumetric density of
active sites, leading to a smaller polarization resistance
[4]
. Catalysts in the infiltrate such as
Sm
0.5
Sr
0.5
CoO
3-! (SSC), La
0.6
Sr
0.4
Co
0.2
Fe
0.8
O
2-!
(LSCF), and La
2
NiO
4
(LNO) have been proven to
improve fuel cell performance when combined with mixed ionic-electronic conductor (MIEC)
cathode materials
[4,5,1]
. Because the scaffold material of the cathode is an MIEC material, the
cathode has excellent ionic and electric conductivity, while the infiltrated particles on the surface
of the scaffold allow for high catalytic activity and minimal ORR resistance
[4]
. This combination
of properties indicate that infiltrated cathodes can help to lower cell polarization resistance and
make IT-SOFCs a realistic option for power application.

1.3 Cell Infiltration

The method of infiltrating catalytically active particles onto the surface of SOFC cathode has
been proven to improve polarization resistance at low temperatures
[4]
. The process is sometimes
referred to as impregnation, during which a liquid solution containing the stoichiometric metal
salt precursors of the chosen infiltrate is dropped onto a porous cathode scaffold. After soaking
into the cathode, the cell is then fired at high temperatures at which the precursors can combine
and bond to the surface of the cathode. Fig. 2 provides a schematic for the typical infiltration
process, taken from Dong Dings Enhancing SOFC cathode performance by surface
modification through infiltration
[4]
.

During infiltration, the cathode backbone material is soaked in infiltrate solution. When it is
treated at high temperatures, the infiltrate material bonds to the cathode as a distribution of
particles or a thin film coating. When the infiltrate is distributed throughout the cathode, the cell
is considered to a composite cathode material cell, which consists of the original scaffold
material as well as any particles infiltrated into the cell.
LNO and LSCF in Solid Oxide Fuel Cells
6

Figure 2: Schematic of infiltration process
[4]

In the present study, both La
n+1
Ni
n
O
3n+1
(LNO) and La
0.6
Sr
0.4
Co
0.2
Fe
0.8
O
3- !
(LSCF) were
infiltrated into a La
0.9
Sr
0.1
Ga
0.8
Mg
0.2
O
3-!
(LSGM) cathode scaffold. LSGM is the base scaffold
due to its high ionic conductivity at low temperatures
[6,7]
. LNO has very high oxygen self-
diffusion and surface exchange values, but is limited in performance by its low electrical
conductivity
[1]
. LSCF is an excellent electronic conductor with good oxygen surface exchange
and ionic conductivity
[8]
.

At processing temperature, the LSCF infiltrated nanoparticles will be of standard perovskite
structure
[9]
. At elevated temperatures, LNO takes on an ordered Ruddlesden-Popper (RP) phase,
in which perovskite units layer with rock salt layers, shown in fig. 3
[1]
. In this Ruddlesden-
Popper phase, LNO takes on the general form La
n+1
Ni
n
O
3n+1
, with n representative of the number
of perovskite layers that lie between each rock salt layer in the unit cell. Higher n values
correspond to higher order Ruddlesden-Popper LNO molecules. In the present study the n=1
phase is the primary focus, as it has the best oxygen exchange and self-diffusion properties of the
LNO RP series
[10]
.

Figure 3: Ruddlesden-Popper structure, with n = 1, 2, and 3 shown left to right
[1]

LNO and LSCF in Solid Oxide Fuel Cells
7
2. Experimental
2.1 Fabrication of LSGM Electrolytes
La
0.9
Sr
0.1
Ga
0.8
Mg
0.2
O
3-!
(LSGM) powder was ground and die-pressed at 120 MPa into 0.5g
pellets, 1.9 cm in diameter. The resulting thickness was #0.5 mm. The pellets were sintered at
1450 C for four hours to allow them to achieve dense structure.
2.2 Preparation of Symmetrical Cells
To fabricate the cathode scaffold, LSGM ink was screen printed in 3 layers onto the dense
LSGM electrolyte. Each layer was a circle 0.8 cm in diameter, and the pellets were dried at 150
C after each layer was printed. After all layers were printed, the pellets were sintered at 1425 C
for 4 hours. Next, a single layer of LSCF ink was printed atop the LSGM layers to serve as a
current collector, and was fired at 1100 C for 1 hours. At the end of the printing/sintering
process, each cell had 3 LSGM layers and 1 LSCF current collector layer symmetrically sintered
on each side, as shown in fig. 4.

Figure 4: The LSGM cathode (black) sintered upon the dense LSGM electrolyte
To prepare the infiltrate solutions, stoichiometric quantities of nitrate salt precursors were
measured and dissolved in water as follows:
La
n+1
Ni
n
O
3n+1
(LNO): 2La(NO
3
)
3
+ Ni(NO
3
)
2

La
0.6
Sr
0.4
Co
0.2
Fe
0.8
O
3- !
(LSCF): 3La(NO
3
)
3
+ 2Sr(NO
3
)
2
+ Co(NO
3
)
2
+ 4Fe(NO
3
)
3

The cathode scaffold on both sides of each cell was dropped with 7 L of infiltrate solution for
each step, as shown in fig. 5. After each infiltration step, the cells were dried of any excess
solution and fired at 900 C for 4 hours to burn out the nitrate solutions and to allow the
precursors to form the ordered perovskite phases mentioned previously. After 12 full infiltration
steps, the cathodes were loaded with 30-50% infiltrate mass by weight.
LNO and LSCF in Solid Oxide Fuel Cells
8

Figure 5: Cell infiltration process
In order to ensure the LNO precursors combined to form the proper Ruddlesden-Popper phase,
the three samples of the solution was fired at 800, 900, and 950 C for 4 hours and tested using x-
ray diffraction to find which phase is present. As shown in fig. 6, a pronounced peak of La
2
NiO
4

at ~31 did not form at 800 C. At both 900 and 950 C, peaks for La
2
NiO
4
and an ordered
Ruddlesden-Popper phase (La
8
Ni
4
O
17
) were observed. However, at 950 C, a strong peak of the
La
3
O
3
rock salt structure appeared in the sample. Thus, in order to achieve the ORR catalytic
properties of LNO, it was concluded that 900 C was the ideal firing temperature for the
infiltration steps.

Figure 6: Verification of 900 C as optimum firing temperature for infiltrates. Lanthanum oxide
(non perovskite) peak disappears above 800 C, but reappears at 950 C.
LNO and LSCF in Solid Oxide Fuel Cells
9
2.3 Experimental Design
Prior to infiltration, each cell is identical. Then cells were each infiltrated 12 times with varying
ratios of LNO to LSCF. Group A, a control group, was infiltrated 12 times only with LNO.
Group B was infiltrated 11 times with LNO and once with LSCF. Group C was infiltrated evenly,
with 6 infiltrations of LNO and LSCF each. Group E was infiltrated 11 times with LSCF and
once with LNO. Group F, another control, was infiltrated with only LSCF. This infiltration
scheme can be more clearly visualized in table 1. Each of the 5 test groups consisted of 3
replicate cells.

Table 1: Cathode infiltration scheme

Group A Group B Group C Group D Group E
LNO infiltrations 12 11 6 1 0
LSCF infiltrations 0 1 6 11 12
2.4 SOFC Test Preparation
After all infiltrations were complete, each cell was printed with silver ink grids to serve as
current collectors, and silver paste was used to connect silver wire to the grid (shown in fig. 7).
All silver was dried and cured at 150 C.

Figure 7: Silver grid printed (left) and silver wire with silver paste to wire the cell (right)
After the cells were wired, they were connected in parallel to a testing rig (shown in fig. 8) and
inserted in into a testing furnace for electrochemical impedance spectroscopy (EIS).

LNO and LSCF in Solid Oxide Fuel Cells
10

Figure 8: Cells wired and connected to test rig.
2.5 Cathode Characterization Methods
The cathode microstructure was observed after testing using scanning electron microscopy
(SEM) and analyzed using energy dispersive spectroscopy (EDS) in a Hitachi 8030 microscope.
Samples were coated with osmium to limit charging during imaging. X-ray diffraction was done
in a Scintag powder diffractometer using a Cu K! source (1.54 ).
The electrochemical impedance spectra (EIS) were taken with an electrochemical workstation
(IM6, ZAHNER) from 500 to 650 C over the frequency range from 0.1 Hz to 1 MHz with signal
amplitude of 5mV.
3. Results and Discussion
3.1 Composite Cathode Microstructure
Fig. 9(a) and (b) are fracture cross-sectional SEM images of a Group E cell, infiltrated only with
LSCF. At 800x the interface between the dense LSGM electrolyte (top) and the porous
composite cathode (bottom) is clear. When magnification is intensified to 5000k, the LSGM
porosity of the scaffold is evident, as well as apparent surface modifications from the infiltrates.
LNO and LSCF in Solid Oxide Fuel Cells
11



Figure 9: Group F cathode infiltrated with LSCF at (a) 800x and (b) 5000x.

In order to ensure complete penetration of the infiltrate solutions into the cathode, an EDS line
scan was completed across a Group A cathode infiltrated with only LNO. The scan shown in fig.
10 illustrates the presence of nickel as a function of position in the cell. In the dense LSGM
electrolyte which is void of nickel, EDS detected negligible traces of Ni. However, at the
electrolyte/cathode interface, detected nickel spikes. This verifies that infiltrate particles
infiltrated completely though the cathode, rather than remaining at the surface.
(a)
(b)
LNO and LSCF in Solid Oxide Fuel Cells
12

Figure 10: EDS line scan across a Group A cell infiltrated with LNO only.
3.2 Impedance Spectra
Fig. 11 shows the results of electrochemical impedance spectra (EIS) of the composite cathodes
at 650 C. When imaginary impedance is plotted vs. real resistance at a range of discrete
frequencies in the form of a Nyquist plot, the arc-like plots can be used to calculate R
p
, which is
the distance on the real axis between each arcs two intersections with the real axis. A wider arc
is indicative of higher R
p
, and smaller indicates a low R
p
.


Figure 11: Nyquist plot of each cell type, plotting imaginary impedance (y-axis) vs. real
impedance (x-axis)
LNO and LSCF in Solid Oxide Fuel Cells
13
Fig. 12 shows the EIS data in terms of imaginary impedance as a function of frequency in the
form of a Bode plot. These plots can be indicative of the mechanisms at work in the cathode (i.e.
electron scattering, ORR resistance, kinetics, etc.) depending on the position of each curves
peak in relation to frequency. It is interesting to note that the evenly mixed 6:6 ratio of
LNO:LSCF observed its peak imaginary impedance around 24 Hz, whereas the other cells saw
peak imaginary impedance near 40 Hz. Unfortunately, further investigations of the mechanisms
at work are currently beyond the scope of this project.

Figure 12: Bode plot of each cell type, plotting imaginary impedance (y-axis) vs. frequency
3.3 Polarization Resistance: Infiltrate Composition Effect
Table 2 shows the total area-specific polarization resistances (i.e., the difference between the real
axis intercepts of the impedance arcs) from EIS data in fig. 11 for cathodes of each infiltrate
composition. R
p
values were markedly higher in samples with maximum infiltrate mixing (i.e.
LNO:LSCF ratio 6:6). The lowest R
p
was observed in the cells loaded only with LSCF, and cells
loaded with a 1:11 ratio of LNO:LSCF varied little from those of a 12:0 ratio. This data can be
more clearly visualized in fig. 13.
Table 2: Average polarization resistance values of each cell group obtained for fits to the
impedance spectra in fig. 11
Measurement
temperature
LNO:LSCF Ratio
12:0 (Group A) 11:1 (Group B) 6:6 (Group C) 1:11 (Group D) 0:12 (Group E)
650 C 0.401 "cm
2
0.565 "cm
2
0.817 "cm
2
0.240 "cm
2
0.220 "cm
2

600 C 0.985 "cm
2
1.36 "cm
2
3.83 "cm
2
0.681 "cm
2
0.653 "cm
2

550 C 2.68 "cm
2
4.27 "cm
2
12.0 "cm
2
2.24 "cm
2
2.27 "cm
2

500 C 9.47 "cm
2
9.98 "cm
2
40.4 "cm
2
8.46 "cm
2
9.13 "cm
2

LNO and LSCF in Solid Oxide Fuel Cells
14


Figure 13: Polarization resistance as a function of LSCF composition at varied temperature
The best R
p
was found in a cell in Group E which achieved an R
p
= 0.21 "cm
2
at 650 C. This
resistance is comparable to that of previous LSCF-LSGM composite cathodes, which have
reached R
p
as low as 0.19 "cm
2 [8]
. The best performing cell infiltrated primarily with LNO was
found in group A and achieved a polarization resistance R
p
= 0.33 "cm
2
. This resistance is
significantly lower than that of previous LNO-based composite cathodes, which reached R
p
no
lower than 1.37 "cm
2
at 650 C
[10]
.
3.4 Activation Energy Calculation
Table 3 shows the activation energy calculated for the different LNO:LSCF ratios. The cells
containing significant amounts of LSCF (Groups C, D, and E) showed activation energies
ranging from 1.47-1.58 eV, comparable to previous LSCF-LSGM composite cells which showed
activation energies ranging from 1.63-1.71 eV
[8]
. Cells primarily infiltrated with LNO saw
activation energies significantly lower, ranging from 1.20-1.26 eV.
Table 3: Activation energy
LNO: LSCF Ratio Activation Energy (eV)
12:0 1.26
11:1 1.20
6:6 1.58
1:11 1.47
0:12 1.54
LNO and LSCF in Solid Oxide Fuel Cells
15

Figure 14: log R
p
vs. 1/T for each cathode composition

In fig. 14, the slopes of the log R
p
vs. 1/T data (fig. 14) yield the activation energies of each
cathode composition. Cells containing 6, 11, and 12 infiltrations of LSCF appear parallel.
However, cells containing primarily LNO (i.e. 0 or 1 infiltrations of LSCF) had smaller slopes,
indicating lower activation energy.

4. Conclusions

LNO-LSCF infiltrated LSGM cathodes were investigated. LSGM cathodes were loaded between
30 and 50 wt.% LNO and LSCF, and cells loaded only with LSCF yielded the best
electrochemical performance. The cells loaded with a 50% ratio of LNO-LSCF showed
markedly worse performance. The composite cathode polarization resistance showed an
Arrhenius dependence on temperature with activation energy of #1.5 eV for cells loaded
primarily with LSCF, and #1.2 eV for cells loaded primarily with LNO.

Acknowledgements

I sincerely thank Dr. Scott Barnett and Dr. Kathleen Stair for making this research and this
project possible. I also thank my mentor Justin Railsback for his careful guidance and tireless
enthusiasm, as well as the entire Barnett group for making my past three years of research
memorable.
LNO and LSCF in Solid Oxide Fuel Cells
16
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n+1
Ni
n
O
3n+1
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9. Qiang, F., Sun, K., Zhang, N., Zhu, X., Le, S., Zhou, D. Characterization of electrical
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10. Woolley, R., Skinner, S. Novel La
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