Ceramics International 43 (2017) 11642–11647

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Ceramics International
journal homepage: www.elsevier.com/locate/ceramint

Effects of mixing state of composite powders on sintering behavior of MARK

cathode for solid oxide fuel cells
Mansoo Park, Hwa Young Jung, Jeong Yun Kim, Hyoungchul Kim, Kyung Joong Yoon, Ji-
⁎
Won Son, Jong-Ho Lee, Byung-Kook Kim, Hae-Weon Lee
High-Temperature Energy Materials Research Center, Korea Institute of Science and Technology, 5 Hwarangno 14-gil, Seongbuk-gu, Seoul 02792, Republic
of Korea

A R T I C L E I N F O A BS T RAC T

Keywords: For efficient development of high-performance composite electrodes for solid oxide fuel cells (SOFCs), it is
Composites (B) crucial to precisely tailor the microstructural features of the electrodes, such as their grain size, phase
Sintering (A) connectivity, and pore structure. Herein, we report the effects of the mixing state of component powders of a
LSM-YSZ (D) composite cathode composed of Sr-doped LaMnO3 (LSM) and yttria-stabilized zirconia (YSZ) on its sintering
Fuel cells (E)
behavior. LSM-YSZ composite powders were synthesized by a particle-dispersed glycine-nitrate process using
YSZ particles as inclusions in the LSM precursor solution. The dispersion state of the YSZ particles in the
solution was varied from a well-dispersed state to a highly flocculated state through adjustment of the amount of
adsorbed polyethylene glycol. The dispersion state of the component powders was found to strongly impact the
densification behavior of the composite, which was explained by the formation of a continuous network of the
“slow-sintering” inclusion particles. A highly porous structure with phase connectivity and sufficient triple phase
boundaries could be achieved by enhancing the mixing homogeneity and optimizing the mixing scale. The
proposed concept provides new insights into the microstructural evolution of composites in constrained
sintering, and it could potentially enable development of the ideal electrode structure for SOFCs.

1. Introduction influences the microstructures and properties of the composite com-

Various composite cathodes of solid oxide fuel cells (SOFCs), which
consist of ion- and electron-conducting phases, have been widely
employed for enhancing the electrochemical activity of a cathode
functional layer [1–24]. In general, composites of strontium-doped
lanthanum manganite and yttria-stabilized zirconia (LSM-YSZ) have
been employed in high-temperature SOFCs operating at 750–1000 °C
[1–12], whereas composites of lanthanum strontium cobalt ferrite and
gadolinium doped ceria (LSCF-GDC) have been used for intermediate-
temperature operation of SOFCs at 600–750 °C [13–24]. There has
been a great deal of interest in the development of advanced composite
microstructure to improve performance; most of such research efforts
have been focused on the optimization of the composition and sintering
conditions of composite cathodes [6,7,9,10,18–20,22,23]. The values
of the optimal composition of the ion-conducting phase as reported in
the literature are in a wide range: 35–65 vol% [18–20,22]. This wide
range is attributed to the variation in the powder mixing state on
account of the differences in the powder characteristics and packing
structure; this powder packing structure of a green body strongly
pact after the sintering process [25–28].
Mixing homogeneity is the most critical parameter in the develop-
ment of composite cathodes since it maximizes particles’ contacts,
which, in turn, increases the length of the triple phase boundary.
Mixing homogeneity is affected by the intrinsic characteristics of
starting powders, dispersion quality, and packing structure. Once the
dispersion quality and packing structure are optimized, the character-
istics of the starting component powders become the most important
parameter governing the mixing state. However, the physical char-
acteristics of starting powders have not been defined clearly in most
previous studies, and thus, it is difficult to trace back the correlations
among the mixing state, packing structure, and sintered microstruc-
ture. Therefore, a lack of definition of powder characteristics makes it
extremely difficult to establish a correlation between the processing
variables and the cathode performance.
In many cases, in-house developed powders have been used in
cathode processing, but detailed information on the powder character-
istics and packing structure is not available [18,19]. In particular, when
the in-house powders were highly aggregated, the optimal composition

⁎
Corresponding author.
E-mail address: hwlee@kist.re.kr (H.-W. Lee).

http://dx.doi.org/10.1016/j.ceramint.2017.05.347
Received 20 March 2017; Received in revised form 26 May 2017; Accepted 30 May 2017
Available online 31 May 2017
0272-8842/ © 2017 Published by Elsevier Ltd.
M. Park et al.
was found to lie in a highly unusual range, indicating a possibly
undesirable mixing state of the composite system in terms of the
mixing homogeneity and mixing scale [22]. For achieving good mixing
homogeneity, it is crucial to achieve a homogeneous dispersion state to
ensure the maximum number of contacts between the component
particles. If one component particles were to be highly aggregated, the
mixture would lose a substantial number of particle contacts between
different components.
In addition, good mixing homogeneity itself is not the only
condition for obtaining an ideal composite cathode; an optimum pore
structure, e.g., optimum pore size and optimum porosity, is also crucial
for efficient gas transport. In order to control the pore structure of
composite cathodes, it is necessary to understand the constrained
sintering that is caused by the different sintering rates of the
component phases [28–30]. In general, a composite comprises matrix
and dispersed phases, which have continuous and discontinuous
distributions, respectively. Regardless of their different sintering rate,
the initial stage of composite sintering is controlled mainly by the
continuous matrix phase until the dispersed particles come into direct
contact to form a continuous network. Once the dispersed particles
form a three-dimensionally continuous network throughout the matrix,
the composite sintering proceeds through the competition of the two
phases. If the dispersed particles are a slower-sintering element than
the matrix phase or if they do not sinter at all, the composite sintering
rate reduces considerably [28–34]. In other words, the spatial dis-
tribution of the component particles as well as the difference in their
sintering rates play decisive roles in cathode processing and micro-
structure development.
In the present study, LSM-YSZ composite powder was synthesized
by the particle-dispersed glycine-nitrate process (PD-GNP). In PD-
GNP, YSZ particles were dispersed in the LSM precursor solution, and
a composite powder composed of the dispersed YSZ phase and the LSM
matrix was formed via self-combustion. The dispersion state of the YSZ
particles in the precursor solutions was controlled by adjusting the
adsorbed amount of polyethylene glycol (PEG), and various distribu-
tions of the dispersed phases in an identical matrix packing structure
were achieved with the aim of systematically evaluating the effects of
the spatial distribution of the dispersed particles on the composite
sintering. We show that the densification of the LSM-YSZ composite is
directly affected by the dispersion state of the YSZ particles at a given
composition, which suggests that the packing structure in a green body
is a critical parameter determining the performance of composite
cathodes.
2. Experimental procedures
The step of dispersion of inclusion particles in PD-GNP is crucial
for the control of nanocomposite cathode powders with the aim of
meeting the requirement of intermediate-temperature SOFC cathodes.
In this study, the polymer adsorption isotherm curve, which provides
information on the dispersion state of the dispersant and inclusion, was
obtained for the LSM-YSZ systems. The YSZ (inclusion) particles were
dispersed in the LSM-GNP solution by using a polymer dispersant.
Here, 8 mol% YSZ (8YSZ, d50: 0.2 µm, Tosho, Japan) with a surface
area of ~15 m2/g was used as the inclusion and PEG (Aldrich, USA)
with a molecular weight of 20,000 ( ± 5000) g/mol was used as the
dispersant for the 8YSZ powder. For this adsorption isotherm study,
the amount of PEG was varied. PEG was sufficiently dissolved in
distilled water at room temperature, and the YSZ aqueous solution was
prepared by adding 8YSZ powder to the PEG-dissolved solutions and
subsequently sonicating the mixture. The supernatant and cake of the
YSZ aqueous solution were separated by centrifugation, sufficiently
dried at 80 °C in an oven, and weighed for measuring the amount of
residual adsorbed PEG. For calculating the amount of adsorbed PEG,
thermal gravimetric analysis (TGA, STA 409, Netzsch, Germany) of the
cakes was performed at a heating rate of 10 °C/min by using air as a
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Ceramics International 43 (2017) 11642–11647
purge gas flowing at 50 ml/min. The PEG adsorption isotherm curve
was obtained from the weight results of each supernatant and TGA data
of the cake.
The LSM-YSZ composite powders were synthesized by the PD-GNP,
which involves three basic steps. In the first step, La2O3 (99.9% purity),
SrCO3 (99.9% purity), and MnO2 (99% purity) precursors were used to
prepare LSM ((La0.7Sr0.3)0.95MnO3-δ)-GNP solution and dissolved in
distilled water and H2O2 (99.9% purity) as a solvent. HNO3 (60%
purity) was employed as both a solvent and an oxidizing agent, and
glycine (NH2CH2COOH, 99.5% purity) was added as a combustion
fuel; all these materials were sourced from Aldrich (USA).
Stoichiometric amounts of the precursors were calculated to prepare
the LSM-GNP solution with a concentration of 1 M, and the glycine/
nitrate and glycine/cation molar ratios were 0.75 and 2.52, respec-
tively, which were modified ratios. The general principle and applica-
tions of the GNP have been summarized elsewhere [35–37]. The
second step involved powder dispersion. The YSZ powders were
dispersed into the LSM-GNP solution by using 2–3 wt% PEG with
YSZ powder weight, and they were mixed by ball milling to ensure
homogeneous mixing. The last step involved the process of self-
combustion. The mixture solution was heated on a hot plate to remove
about 30% water. While the mixture solution was still hot, it was added
drop by drop to a ceramic reactor that was preheated to between
350 °C and 400 °C. The water in the mixture solution evaporated
rapidly, and the resulting viscous liquid swelled, auto-ignited, and
initiated a highly exothermic self-contained combustion process; this
resulted in conversion of the mixed powder and precursor materials
into nanocomposite powders.
Finally, after spontaneous ignition, the as-received LSM-YSZ com-
posite powders were dry-ball-milled using zirconia grinding media for
24 h. After sieving of the powders, they were calcined at 800 °C to
obtain the desired product. Thermal gravimetric-differential thermal
analysis (TG-DTA, STA 409, Netzsch, Germany) of the as-received
powders was performed at a heating rate of 10 °C/min by using air
flowing at 50 ml/min.
X-ray diffraction (XRD) patterns were obtained using an X-ray
diffractometer (PW3830, PANalytical, Netherlands) with Cu-Kα radia-
tion (step size of 0.02° and time per step of 1 s). Before measurement,
angular correction was performed using a high-quality silicon stan-
dard.
The particle size and distribution were measured using a particle
size analyzer (UPA-150, Microtrac, USA). In addition, a scanning
electron microscopy (SEM, FEI XL30 FEG, Philips, Netherlands) and
a transmission electron microscopy (TEM, FEI CM-30, Philips,
Netherlands) were used to confirm the morphology and size of the
obtained nanocomposite powder particles.
The green bodies of all synthesized powders were compacted by
cold uniaxial pressing at 100 MPa for measurement of the sintering
behavior. Linear shrinkages of the green bodies with increasing
temperature were measured at a heating rate of 5 °C/min by using a
dilatometer (DIL 402 C, Netzsch, Germany). The porosity and relative
density of the samples were measured by the Archimedes method.
3. Results and discussion
The dispersion state of the YSZ particles in the suspension was
preserved throughout the powder synthesis, which, in turn, directly
affected the mixing state of the composite powders. However, it would
be rather difficult to achieve dispersion stability of the YSZ particles
against reflocculation, especially in an electrostatically stabilized
suspension, since the precursor solutions for the GNP contain extre-
mely high concentrations of ionic species, e.g., nitrates and constituent
cations. Thus, steric stabilization for the dispersion of YSZ particles
should first be achieved in the precursor solution. In this study, the
steric barrier was developed using PEG with a molecular weight of ~
20000 g/mol that was adsorbed on the YSZ particle surface. Since PEG
M. Park et al. Ceramics International 43 (2017) 11642–11647

Fig. 1. Adsorption isotherm of PEG on YSZ powder.

molecules are nonionic, they are relatively insensitive to the ionic

environment similar to GNP precursor solutions. Fig. 1 shows the
amount of PEG adsorbed on the surface of YSZ powder dispersed in
deionized water as a function of the PEG concentration. The amount of Fig. 2. TEM micrograph of LSM nanoparticle matrix after PD-GNP.
adsorbed PEG was measured by the solution depletion method and
calculated on the basis of the dry weight of the YSZ powder. The
amount of adsorbed PEG continuously increased up to the saturated
state, at which point the YSZ particle surfaces were fully covered with
PEG molecules. As shown in Fig. 1, the saturated coverage of the YSZ
particles was achieved above the PEG concentration of 0.5 wt%, at
which point the suspension achieved dispersion stability against
reflocculation. Below this point, the YSZ particles were expected to
be highly or partially flocculated. The results in this figure demonstrate
that the degree of flocculation of the YSZ powder could be controlled by
adjusting the amount of PEG.
LSM-YSZ composites were synthesized by the PD-GNP by using
YSZ particles with various dispersion states. YSZ particles in highly,
partially, and well-dispersed states were employed to synthesize LSM-
YSZ composites by using PEG concentrations of 0.1, 0.4, and 0.7 wt%,
respectively. The resultant powders were expected to have different
powder pecking structures according to the different dispersion states
of the YSZ particles; this is schematized in the inset of Fig. 1. In the
LSM-YSZ composite with well-dispersed YSZ particles, the YSZ particle
has smaller interparticle spacing and a higher coordination number
with LSM particles than those of the highly and partially dispersed YSZ Fig. 3. Weight losses of LSM-YSZ composite powders prepared with YSZ particles
particles in the composite. After the PD-GNP, TEM investigations were having different dispersed states.
performed to confirm successful synthesis of the nanoscale LSM
particles. The TEM image shown in Fig. 3 reveals that extremely fine
LSM matrix particles with a primary particle size of about 15–20 nm
were synthesized.
TGA analysis was conducted during calcination; Fig. 2 shows the
weight loss of the LSM-YSZ composites with various dispersion states
as a function of temperature. The data in this figure indicate that the
weight loss is greatly affected by the dispersion state of the YSZ
particles in the LSM precursor solutions. The composite powder with
well-dispersed YSZ particles exhibits a weight loss of about 5.08% up to
900 °C, which is much lower than that of the composite powder with
highly flocculated YSZ particles (22.7%). Weight loss is closely related
to the amount of residual carbon and unreacted precursor chemicals.
The composite powders with highly flocculated YSZ particles have
substantially larger amounts of residues, thusly leading to higher
weight loss as compared with the other composites. Therefore, the
TGA analysis of the as-synthesized composite powders demonstrates
that LSM-YSZ composites were properly synthesized in terms of Fig. 4. Particle size distribution of LSM-YSZ composite powders.
containing YSZ powder particles flocculated to different degrees.
The particle size distribution was measured as shown in Fig. 4. It
in the size range of 50–500 nm whereas that with well-dispersed YSZ
can be seen from this figure that the dispersion state of the YSZ
particles showed a narrower distribution range of 50–300 nm. The
particles affected the aggregate size distribution, and the composite
GNP enabled acquisition of composite powders in which LSM nano-
powder prepared with flocculated YSZ particles was highly aggregated

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M. Park et al.
Fig. 5. Plot of relative density versus sintering temperature for LSM-YSZ composite
powders.
particles act as a common matrix phase, and the spatial distribution of
the YSZ particles varied with their dispersion state in the LSM
precursor solutions. These composite powders were evaluated to
understand the effects of the dispersion state of the YSZ particles on
the sintering of the LSM-YSZ composites.
The change in the relative density with increasing temperature for
the LSM-YSZ composite compacts with different YSZ dispersion states
is shown in Fig. 5. It can be seen from this figure that the dispersion
state of the YSZ particles strongly influences the densification behavior
of the LSM-YSZ composites. This figure also illustrates that the LSM-
YSZ composites with highly flocculated YSZ particles have a higher
relative density than do the LSM-YSZ composites with YSZ particles in
the other two dispersed states.
In general, the LSM matrix exhibits considerably retarded densifi-
cation in the presence of dispersed “slow-sintering” YSZ particles
owing to the constraining effect. Because all the composite powders
have an almost identical LSM matrix regardless of the dispersion state,
content, and size of the YSZ particles, the densification of the
composite is dependent solely on the spatial distribution of “slow-
Fig. 6. Schematic drawings of difference in constrained sintering in terms of YSZ network development as a function of interparticle spacing.
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Ceramics International 43 (2017) 11642–11647
sintering” YSZ particles dispersed throughout the fine LSM matrix. As
the LSM matrix undergoes sintering shrinkage, the interparticle
spacing between the YSZ particles decreases, and local clusters form
subsequently. Further matrix shrinkage results in the formation of a
global cluster containing a majority of the YSZ particles, and such
global clusters interconnect throughout the LSM matrix, which results
in the formation of the so-called percolation cluster. Once developed,
“slow-sintering” YSZ clusters severely retard densification. Therefore,
the difference in the limiting density at high temperatures is a result of
the formation of the globally developed YSZ network structure, and the
dispersion state of the YSZ particles predominantly determines the
critical shrinkage point for the formation of the three-dimensionally
interconnected YSZ network structure because of different interparticle
spacings in different dispersed states. In particular, the transition of
local clusters to a global cluster is a critical factor for developing a high-
performance LSM-YSZ composite cathode because the total length of
the triple phase boundary is maximized at this transition point; this, in
turn, provides complete three-dimensional connectivity of all the
constituent phases, including LSM, YSZ, and the pores.
The situation that prevails during the densification of the LSM-YSZ
composite is schematized in Fig. 6; this figure shows the clustering
behavior of the YSZ particles and the consequent composite shrinkage
in two composites with different YSZ dispersion states. The interpar-
ticle spacing of YSZ particles is closely related to their dispersion state
structure of YSZ particles, and it increases in proportion to the floc size.
In the composite with the small interparticle spacing of the YSZ
particles, its continuous network structure develops easily even with
the small LSM matrix shrinkage, as shown in Fig. 6a. Upon the
formation of a continuous network, the densification of the composite
is retarded due to the “slow-sintering” YSZ skeleton. Thus, the sintered
density of the LSM-YSZ composite is affected primarily by the global
constraint imposed by the continuous network of YSZ particles. This
suggests that high mixing homogeneity is required in order to realize a
high-porosity composite cathode due to the rapid development of a
continuous YSZ network structure as shown in Fig. 6b; this also helps
to maximize the length of the triple phase boundary. The LSM-YSZ
composite powder prepared with well-dispersed YSZ particles was
compacted by cold press. This cold-pressed compact was then heated
up to 1250 °C and held for 3 h in air. Fig. 7 shows its cross section after
a sintering cycle. This figure illustrates high mixing homogeneity and a
M. Park et al.
Fig. 7. Cross-sectional SEM micrograph of LSM-YSZ composite powders sintered at
1250 °C.
continuous network structure of the YSZ phase; this interpenetration
microstructure supports aforementioned discussions. A forthcoming
paper will address the development of an improved composite cathode
electrode of SOFCs via a precise control of the mixing homogeneity and
mixing scale of the constituent particles, and corresponding data of
electrochemical impedance spectroscopy as well.
Now, it is instructive to review the results reported in previous
works that addressed the composition optimization of composite
cathodes in terms of the packing structure and its effect on constrained
sintering. Barnett [38] pointed out that approximately one-third of the
triple phase boundary was inactive owing to LSM grains that are
isolated because of the underdevelopment of the LSM network
structure. In this case, the fine YSZ matrix was not sintered to the
critical shrinkage point required for the formation of a continuous
network of LSM grains.
Similar examples can be found in the literature on LSCF-GDC
composite cathodes [18,19]. Despite the starting powders being the
same, these two studies reported completely different compositions
required for minimizing the cathode polarization loss. A more careful
comparison reveals that there appears to be a substantial difference in
the composite packing structure due to different deposition methods.
One of the studies employed slurry painting and subsequent cold
isostatic pressing, whereas the other used spin coating of the composite
slurry. Even though neither study specified the details of the film
deposition conditions, the optimum compositions determined by both
studies showed a significant discrepancy of almost 14%, i.e., 36 vol%
vs. 50 vol% of GDC. Under the assumption that the packing structures
are similarly uniform, the difference in the optimal compositions can
be explained by the packing density, which is responsible for the
interparticle spacing of coarse GDC particles dispersed in the fine LSCF
matrix. Another possible reason for the different optimum composi-
tions is shear-induced flocculation of coarse GDC particles, which is
likely to occur during spin coating of the composite slurry [19]. If the
composite suspension has a suitable dispersion quality, the consider-
ably high shear rate during spin coating would force the large GDC
particles to hydrodynamically interact with each other to form shear-
induced homo-floccules. Because the spin coating process under high
shear inevitably forces rapid drying of the coating layer due to the
counter air flow that is proportional to the rotational speed, these close
contacts of coarse GDC particles are likely to persist in the composite
cathode films even after the drying process. This is extremely similar to
what we observed in the LSM-YSZ composite cathode prepared with
flocculated YSZ particles which possesses large interparticle spacing
and consequently high critical matrix shrinkage for the network
formation of the dispersed particles.
One of the most extreme examples is found in the LSCF-GDC
composite cathode developed by Liu et al., in which substantially
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Ceramics International 43 (2017) 11642–11647
aggregated LSCF powder synthesized by the GNP was used with
commercially available nanosized GDC powder [22]. On the basis of
measurement of polarization loss, they concluded that the optimum
composite composition was LSCF/GDC ~ 40/60 by weight. This GDC
content is far higher than that reported in any other studies, even
though Liu et al. used nanometer-sized GDC powder. Despite the
uniform packing structure, the highly aggregated LSCF powder
obtained by the GNP led to poor packing density, thus substantially
increasing the critical matrix shrinkage for the development of the GDC
network structure. In turn, it is inevitable to increase the GDC content
in order to compensate for the increased matrix shrinkage. Finally, the
composite cathode should be designed in consideration of not only by a
simple particle size ratio but also the powder packing structure in order
to systematically control the composite microstructure to achieve the
desired performance.
4. Conclusions
In this study, we prepared LSM-YSZ composite powders by the PD-
GNP of LSM precursor solutions containing YSZ particles with different
dispersion states. The sintered density of the LSM-YSZ composites
shows a strong dependence on the dispersion state of the YSZ particles
owing to constrained sintering. The formation of the global YSZ
network structure severely retards the densification of the LSM-YSZ
composite. The dispersion state of the YSZ particles directly affects the
interparticle spacing between the dispersed YSZ particles and deter-
mines the critical matrix shrinkage for the development of the YSZ
network structure. Thus, the composition of composite cathodes should
be optimized according to the packing structure and packing efficiency
of individual component powders.
Acknowledgements
This work was financially supported by the institutional research
program of the Korea Institute of Science and Technology and the
Energy Technology Development Program of the Korea Institute of
Technology Evaluation and Planning (KETEP) granted financial re-
source from the Ministry of Trade, Industry & Energy, Republic of
Korea (No. 20143010031810).
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