J Mater Sci

Ceramics
CERAMICS

Effect of nonequivalent substitution of Pr3+/4+ with Ca2+

in PrBaCoFeO5+d as cathodes for IT-SOFC
Fangjun Jin1,* , Xianglin Liu1, Xueying Chu1, Yu Shen2, and Jinhua Li1,*

1
International Joint Research Center for Nanophotonics and Biophotonics, Nanophotonics and Biophotonics Key Laboratory of
Jilin Province, School of Science, Changchun University of Science and Technology, Changchun 130022, People’s Republic of China
2
School of Materials Science and Engineering, Changchun University of Science and Technology, Changchun 130022, People’s
Republic of China

Received: 6 July 2020 ABSTRACT

Accepted: 19 September 2020
Ó Springer Science+Business
Media, LLC, part of Springer
Nature 2020
We used a Ca doping strategy with PrBaCoFeO5?d (PBCF) to prepare a novel
double-perovskite Pr1–xCaxBaCoFeO5?d (PCBCF). x = 0.05 and x = 0.1 samples
exhibited a single phase with layered double-perovskite structure, combined
with good chemical compatibility with common electrolyte materials. X-ray
photoelectron spectroscopy profiles of PCBCF were compared to that of PBCF to
detect differences in oxidation states. The substitution of Ca2? for Pr ions in
PCBCF effectively reduces the thermal expansion coefficient and material costs.
Though the introduction of Ca2? reduced the electrical conductivity, it
improved the oxygen catalytic activity. The improved electrochemical perfor-
mance was attributed to the increased oxygen vacancy concentration in the
lattice. The optimal composition x = 0.1 cathode exhibited the best catalytic
activity and durability. The polarization impedance and maximum power
density of the 0.1 cathode were 0.027 X cm2 and 728 mW cm-2 at 800 °C,
respectively. Distribution of relaxation time analysis demonstrated that the 0.1
cathode electrochemical reactions under oxygen partial pressures involved at
least three processes and confirmed that the transfer process of oxide ions and
charge transfer process are the major rate-determining steps of the oxygen
reduction reaction. The combination of experimental and analysis results indi-
cated that the 0.1 sample has considerable potential as part of a cathode for
application in intermediate-temperature solid oxide fuel cells.

Handling Editor: David Cann.

Address correspondence to E-mail: tsly2006@foxmail.com; jinfj@cust.edu.cn; lijh@cust.edu.cn

https://doi.org/10.1007/s10853-020-05375-y

GRAPHIC ABSTRACT
Introduction
The solid oxide fuel cell (SOFC) is one of the all-solid-
state power generation devices of critical importance
for future power generation technology because of its
low pollution and high energy conversion efficiency.
The traditional commercial SOFC uses La0.9Sr0.1
MnO3–d (LSM) as the cathode operating temperature
of approximately 800–1000 °C. This high operating
temperature has specific drawbacks not conducive to
the commercial application and stable operation of
the cell stacks. Therefore, it is crucial to develop
suitable cathode materials with a good electrochem-
ical activity at lower temperatures [1–3].
Recently, many new cathode materials have been
found to exhibit reasonable catalytic activity in an
intermediate-temperature (IT) range (600–800 °C)
[4–8]. Among these materials, the layered perovskite-
type oxide LnBaCo2O5?d (Ln = Pr, Nd, Sm, Gd, and
Y) have attracted considerable attention as cathodes
for IT-SOFC [6–8]. LnBaCo2O5?d oxides have excel-
lent oxygen diffusion and surface exchange capacity
owing to its special layered structure, with alternative
stacking of CoO||BaO||CoO||LnO||CoO (Ln
is lanthanide metal) along the c-axis. This orderly
J Mater Sci
layer structure effectively reduces the oxygen-bond-
ing strength and promotes oxygen ion diffusivity.
Among the LnBaCo2O5?d series double perovskite
oxides, PrBaCo2O5?d (PBC) has the best electrical
conductivity and electrochemical properties. Kim
et al. [9] found that PBC has the intensive oxygen
transport capacity and kinetics and high conductiv-
ity, implying that this material is promising for use in
SOFC cathodes and oxygen separation membranes.
For example, the surface exchange (kchem) and bulk
diffusion (Dchem) coefficient values of PBC are much
higher than those of GdBaCo2O5?d (GBC). Zhang
et al. [6] and Zhou et al. [7] further confirmed that
PBC has the best electrochemical properties among
LnBaCo2O5?d series cathode materials. The area-
specific resistance (ASR) of the PBC cathode at 700 °C
is 0.070 and 0.213 X cm2 on the La0.9Sr0.1Ga0.8Mg0.2
O3–d (LSGM) and Sm0.2Ce0.8O1.9 (SDC) electrolytes,
respectively [6, 7]. The maximum power density
(MPD) and ASR of PBC on the thin-film SDC elec-
trolyte were 620 mW cm-2 and 0.4 X cm2 at 600 °C,
respectively [10]. In addition, the presence of Pr in the
perovskite oxides is also beneficial for reducing the
overpotential loss of the cathode [11].
However, the practical application of the PBC
cathode is severely restricted by its high thermal
J Mater Sci
expansion coefficient (TEC) (21.5 9 10-6 K-1) [7],
hindering its matching with conventional electrolytes
and sealing materials. For example, the respective
average TECs of the LaGaO3-based electrolyte and
the alkaline-earth–doped LnCrO3 are * 11.5 9
10-6 K-1 and * 10 9 10-6 K-1 [12, 13]. These high
TECs are mainly attributed to the thermal reduction
(Co4? ? Co3? ? Co2?) and the associated oxygen
loss and continuous lattice expansion [7, 8]. In addi-
tion, it also includes the influence of the spin-state
transition of Co3? at lower temperatures [14].
Therefore, it is necessary to adopt effective methods
to reduce the TEC of PBC cathode materials. One of
the effective ways is to add an electrolyte (such as
CeO2-based electrolytes) into the cathode to form a
composite cathode. Introducing low-TEC electrolytes
lowers the TEC of cathodes and also enhances oxy-
gen ion diffusion capacity, leading to an improve-
ment in the electrochemical properties of cathodes
[15]. Researchers investigating PBC–SDC composite
cathodes suggested that adopting a 70 wt% PBC ?
30 wt% SDC composite electrode leads to superior
electrochemical performance [16, 17]. The MPD and
ASR of a PBC–30SDC composite cathode are
875 mW cm-2 and 0.25 X cm2 at 600 °C, respectively
[17]. However, introducing the second phase into
cathode cannot efficiently overcome the shortcom-
ings of the parent cathode material, such as instabil-
ity, oxygen reduction reaction (ORR) activity, and
high cobalt cost. To overcome these problems, proper
ion doping strategies have been used to tailor the
properties of PBC. Partial replacement of cobalt with
transition metal in PBC has been extensively studied
as cathodes by research groups [18–20]. For example,
Zhao et al. [18] demonstrated that the TECs of
PrBaCo2–xFexO5–d cathodes gradually decrease with
increasing Fe content, while it showed good tolerance
against carbon dioxide and chemical compatibility
with CeO2-based electrolytes. Our group investigated
Fe- and Cu-co-doped PBC cathode (PrBaCo2/3Fe2/3
Cu2/3O5?d) as well and found that the ASR on
Gd0.1Ce0.9O1.95 electrolyte at 700 °C and average
TECs between 30 and 850 °C were 0.144 X cm2 and
16.6 9 10-6 K-1 [20].
Another widely used method is alkaline earth
metal ion doping at the A-site of double perovskites
[21–29]. For example, Ca doping at the Ba-site of
double perovskites was proposed; it exhibited excel-
lent electrochemical properties and durability in air
containing CO2, while also reducing TEC and
maintaining high electrical conductivity [21, 24, 25].
Chen et al. [21] evaluated the Ca doping at Ba-site of
PrBa0.8Ca0.2Co2O5?d as a potential cathode IT-SOFC,
suggesting that it showed excellent ORR activity and
extended stability in both normal air and an atmo-
sphere with more CO2. Partial substitution of Sr for
Ba was also proved to improve conductivity and
electrochemical performance [26, 27]. The ASR and
MPD (anode-supported SDC electrolyte film) of
PrBa0.5Sr0.5Co2O5?d reached 0.05 X cm2 and
-2
1045 mW cm , respectively [26]. However, it was
observed that surface segregation of SrO and BaO
contains Sr and Ba perovskites, leading to a gradual
degradation of the catalysis [30, 31]. Choi et al. [28]
reported a co-doping strategy (Sr and Fe co-doping)
in PBC. The synergistic effect of co-doping in the PBC
lattice facilitated the generation of oxygen ions
through the pore channels that effectively enhanced
oxygen diffusion capacity, while keeping good ther-
mal stability and chemical compatibility at high
temperatures.
We investigated the properties of PrBaCoFeO5?d
(PBCF) double perovskite as a cathode for IT-SOFC
[32]. The doping of Fe ions has not been expected in
terms of decreasing the TEC, but the electrochemical
performance deteriorated. Based on these studies, we
used a Ca doping strategy in PBCF to prepare a novel
double-perovskite Pr1–xCaxBaCoFeO5?d (PCBCF). By
tailoring A-site and B-site compositions in the Co-
based double perovskites, we identified enhanced
electrochemical activity. The synergistic effects of Ca
and Fe co-doping on the crystal structure, electrical
conductivity, oxidation, and electrochemical perfor-
mances were investigated in detail. In addition, the
Ca ion replacement of Pr ion is advantageous in
reducing the cost of the cells. Preliminary results
indicated that co-doping in PrBaCo2O5?d double
perovskite oxides was an effective means of modu-
lating properties and obtaining a reliable cathode for
the IT-SOFC.
Experimental
Materials and cell preparation
Pr1–xCaxBaCoFeO5?d (PCBCF; x = 0.05, PCBCF005;
x = 0.1, PCBCF01; x = 0.15, PCBCF015) powders
were obtained via a sol–gel method. Pr6O11,
Ca(NO3)2, Ba(NO3)2, Fe(NO3)39H2O, and

Co(NO3)26H2O were weighed as reaction precursors,
according to the stoichiometric ratio of chemical
molecules. The Pr6O11 was first dissolved in dilute
nitric acid to form nitrates. The complexing agents
(EDTA and citric acid) and metal nitrate were mixed
in deionized water, and the pH was adjusted with
ammonia. The mixed solution was heated and stirred
on a magnetic agitator, and the water evaporated
until it formed a homogeneous gel. Subsequently, the
gel was heated at 180 °C to form a dry gel. The dry gel
was pretreated at 600 °C for 4 h and at 900 °C for 10 h.
Finally, the required phase structure PCBCF samples
were obtained by sintering at 1000 °C for 10 h. In
order to measure the electrical conductivity and ther-
mal expansion behavior of PCBCF samples more
accurately, dense samples were obtained by sintering
at 1100 °C for 10 h. La0.9Sr0.1Ga0.8Mg0.2O3–d (LSGM)
powders were prepared via a solid-state reaction.
Dense LSGM electrolyte pellets were obtained by
sintering at 1400 °C for 10 h. NiO, Gd0.1Ce0.9O1.95
(GDC), and Sm0.2Ce0.8O1.9 (SDC) were prepared by a
combustion method. The required powders were
obtained after 800 °C for 2 h. Anode powder was
obtained by fine mixing of 65 wt%NiO and 35 wt%
SDC (NiO–SDC). The electrolyte-supported (0.3 mm)
symmetrical cells (PCBCF|LSGM|PCBCF) and single
cells (PCBCF|LSGM|SDC|NiO-SDC) were fabricated
to investigate the electrochemical performance. The
electrodes layer and buffer layer were prepared by a
screen printing (SP) technique. The detailed prepara-
tion process was reported in our previous works
[32, 33].
Characterization
The phase structure and compatibility were detected
by an X-ray diffractometer (XRD, Rigaku D/Max–
2550) using Cu Ka radiation; 2h was recorded in the
20°–80° range with a step size of 0.02°. Oxygen con-
tent in the PCBCF samples was determined using the
iodometric titration technique under a nitrogen
atmosphere at room temperature. The surface
microstructure of samples was observed by a scan-
ning electron microscopy (SEM, JEOL, JSM–6010LA).
The oxidation state of transition metal ions was
determined by X-ray photoelectron spectrometer
(XPS, VG Scientific ESCALAB MK II). The expansion
behavior of samples was obtained by a dilatometer
(Netzsch DIL 402C); the flow rate of air as a purging
gas was 60 mL min-1. The electrical conductivity
J Mater Sci
was measured by the van der Pauw method, using a
DC current voltage source (Shanghai Qianfeng,
SB118). The electrochemical impedance spectrum
(EIS) and cell performance were measured by an
electrochemical analyzer (Corrtest, CS350).
Results and discussion
Phase structure and morphology
The XRD patterns of PCBCF samples after sintering
at 1000 °C for 10 h are shown in Fig. 1. For compar-
ison, the XRD pattern of PBCF is also included. Ca-
doped PCBCF005 and PCBCF01 have a pure phase
double-perovskite structure. The XRD pattern of
PBCF sample showed distinct doublet in the
2h = 45°–50° and 65°–70° ranges, typical of the
tetragonal structure of layered double perovskite
with the space group P4/mmm [32]. With the
increasing amount of Ca dopant, the double peaks
became less apparent, because the structure of
PCBCF samples was changed from tetragonal to
cubic (with the space group Pm-3 m), showing only
singlet in the 2h range. Similar phenomena were
reported in some double-perovskite structured fer-
rocobaltites and ferrocuprates [34–36]. Diffraction
peaks shift to higher angles with an increase in Ca
doping concentration, which indicates that Ca doping
causes lattice shrinkage. The effective ionic radius of
Ca2? (1.34 Å) is similar to that of Pr3? (* 1.30 Å)
[23, 37]; accordingly, the lattice shrinkage of PCBCF
samples may be attributed to the change of Pr4?
Figure 1 XRD patterns of samples sintered at 1000 °C for 10 h
in air: (a) PBCF; (b) PCBCF005; (c) PCBCF01; and
(d) PCBCF015.
J Mater Sci

concentration. This is demonstrated by the XPS data

in ‘‘XPS analysis’’ section. An evident impure phase
was found in nominal compositions of the PCBCF015
sample, indicating that the Ca doping reached the
upper limit in the PBCF sample. The impurities
marked with 5 and . may belong to the phases of
Pr2O3 (JCPDS#6–410) and BaCoO3–x (JCPDS#52–
429)/BaFeO3–x (JCPDS#23–1024), respectively. The
oxygen content of the PCBCF samples is determined
by iodometric titration. The oxygen content values
(5 ? d) of PCBCF005 and PCBCF01 samples are 5.72
and 5.65 at room temperature, respectively. The
oxygen content values of PCBCF are lower than those
of PBCF [32] because of the introduction of low-va-
lence Ca2?, which decreases the average oxidation
state of cations. A decrease in oxygen content is
suggested as an increase in oxygen vacancy in the
lattice, which contributed to improving the electro-
chemical properties.
The microstructures of the PCBCF samples after
sintering at 1000 °C in air are shown in Fig. 2. The
results show that doping significantly influenced a
grain size and sintered densities. Grain size and
compactness decreased with increased doping con-
centration. With the doping of calcium ions, the grain
size of samples became more uniform. The grain size
of PCBCF005 ranged from 0.5 to 2 lm, of PCBCF01
ranged from 0.5 to 1 lm, and of PCBCF015 was
* 0.5 lm. The grain size and compactness decrease
with an increase in Ca doping concentration indi-
cating faster nucleation than the grain growth, which
might have occurred due to oxygen vacancies created
after replacing Pr3?/4? ions with Ca2? ions to
decrease further the mobility of ions resulting in
slower lower grain growth.
The chemical compatibility was studied by calcin-
ing the PCBCF01 with common electrolytes (1:1) in
mixed powders at 1000 °C for 10 h. Figure 3 shows
the XRD patterns of PCBCF01–electrolyte mixture Figure 2 SEM image of PCBCF samples sintered at 1000 °C for
powders. The PCBCF01 sample and the electrolytes 10 h in air: a PCBCF005; b PCBCF01; and c PCBCF015.
had their own diffraction peaks; no new diffraction
peaks and no peak displacement were detected. This XPS analysis
finding suggests that PCBCF01 has good chemical
compatibility with LaGaO3-based and CeO2-based Surface properties (especially the cationic oxidation
electrolytes below 1000 °C. This temperature is also state) are essential factors for understanding the cat-
much higher than the operating temperature of IT- alytic activity of the cathode. Figure 4 shows the
SOFC. deconvoluted XPS profiles for Pr 3d, Ba 3d, Co 2p, and
Fe 2p in the PCBCF samples. For comparison, the XPS
profiles of PBCF are also included in Fig. 4. The Pr
3d5/2 and 3d 3/2 peaks in Fig. 4a were fitted by a
 J Mater Sci

Figure 3 XRD patterns of PCBCF01–LSGM, PCBCF01–SDC,

and PCBCF01–GDC mixtures after calcining at 1000 °C for 10 h.

standard Gaussian–Lorentzian deconvolution to

attain two different Pr species, which could be
assigned to Pr3? and Pr4? of the samples. The bind-
ing energy (BE) values of 927.4–927.8 eV|932.7–
933.0 eV at 3d5/2 and 948.0–948.3 eV|953.1–953.6 eV
at 3d3/2 are characteristic of surface Pr3? species,
while the BE values of 931.0–931.3 eV at 3d5/2 and
952.0–952.4 eV at 3d3/2 are representative of Pr4?
species. This finding agrees with those reported
previously [19, 38]. The investigation of the XPS Co
2p spectra determined the Co valence state. It is
known that the XPS core-level profiles of a transition
metal offer information about the electronic configu-
ration/valence state of the transition metal ion and
the electronic structure. Importantly, for (Ba, Co)-
containing perovskites, the XPS Co 2p and Ba
3d emission occur in the same energy range (* 770 to
* 810 eV) and the spin–orbit splittings of the Co 2p1/2,
2p3/2 and Ba 3d3/2, 3d5/2 doublets were very similar
(* 15 eV) [39]. Therefore, Co 2p and Ba 3d spectra in
PCBCF samples are required to be deconvolved
simultaneously. The indirect information about Co
2p states can be obtained by extracting the Ba
3d contribution from the total spectrum. In order to
better distinguish Co signals from the Ba component,
the Ba2? 3d5/2 and 3d3/2 peak were positioned at BE
of 779.7 and 795.0 eV in the PCBCF samples, as
shown in Fig. 4b, respectively [40]. However, the
Ba2? 3d5/2 and 3d3/2 peak were fitted at BE of 780.6 Figure 4 XPS profiles of a Pr 3d, b Co 2p and Ba 3d, and c Fe
and 795.9 eV in the PBCF samples. We attributed this 2p3/2 in samples.
difference to the doping of calcium and the formation
of small amounts of carbonate on the surface. No
J Mater Sci
satellite peaks for any samples were detected at the
binding energy levels of 785.0–790.0 eV in Fig. 4b,
suggesting the absence of Co2? species in PCBCF and
PBCF samples [20, 41]. The Co 2p3/2 and 2p1/2 peaks
can be deconvoluted into two different Co species,
which could be assigned to Co3? and Co4?. The
binding BE values of 777.6–777.8 eV and
793.0–793.1 eV are characteristic of surface Co3?
species, while the BE values of 778.8–779.2 eV and
794.1–794.5 eV are representative of Co4? species.
This finding agrees with those reported previously
[20, 42]. Figure 4c shows the XPS spectrum of Fe 2p3/2
of PCBCF and PBCF samples. Two different Fe 2p3/2
peaks were detected, where the fitted peaks were at
* 709.0 eV and 710.4 eV. These peaks may be
attributed to the presence of Fe3? and Fe4?. This
result is similar to that reported in the literature
[20, 32, 43].
It shows that the coexistence of [Pr1–xCoFe]3? and
[Pr1–xCoFe]4? cations at the surface of PCBCF and
PBCF samples contributes to the good electrochemi-
cal performance described below. The integrated
intensity ratios of the Pr4?/Pr3?, Co3?/Co4?, and
Fe3?/Fe4? were calculated from the XPS profiles and
presented in Fig. 5. After substitution by Ca2?, the
samples possessed a higher percentage of Pr4? spe-
cies. According to the principle of electroneutrality,
the reduced positive charge caused by the Ca2?
nonequivalent substitution of Pr3?/4? in PCBCF
samples can be offset by promoting the Pr ions from
low to high valence states. The high ratio of Pr4? in
the PCBCF samples may be beneficial to charge
Figure 5 Percentage contributions of core electrons of (a) Pr3?/4?,
(b) Co3?/4?, and (c) Fe3?/4?.
compensation in cathodic atmospheres. Moreover,
the concentration of Co3? ions increased with the
doping of calcium, while the ratio of Fe3? to Fe4? did
not change considerably. The results indicated that
the activity cathodic ORR was closely related to the
oxidation state of transition metal ions [35, 44]. In the
cobalt-containing perovskite oxides, the presence of
more Co3? may imply better ORR activity, while
more Co4? may have better electronic conductivity.
Therefore, more Co4? in lattice increases the carrier
concentration. More Co3? results in more oxygen
vacancy in the lattice, which facilitates the O2
adsorption. This result will be confirmed further in
the section on electrical conductivity and electro-
chemical properties.
Thermal expansion behavior
The thermal matching between the components
(cathode, anode, electrolyte, and interconnect)
directly influences the durability of cells. Figure 6
shows thermal expansion and differential curves for
PCBCF and PBCF samples. The thermal expansion
and differential curve of the PCBCF had a weak
mutation at * 400 °C, ascribed to thermal reduction
of Co4?/Fe4? ? Co3?/Fe3? and corresponding to
the generation of oxygen vacancies [35]. The defect
equation of the process can be expressed as (M
denotes Fe or Co):
1
2MM þ O  
O , 2MM þ VO þ O2 ð1Þ
2
In addition, no other fluctuations were detected
within the test temperature range, indicating that no
Figure 6 Thermal expansion curves of PBC, PBCF, and PCBCF
samples between 30 and 1000 °C.
 J Mater Sci

other oxidation state and structural phase transition

occurred. However, a distinct shrinkage peak (Co3?/
Fe3??Co2?/Fe2?) was found in the thermal expan-
sion coefficient curve of the PBCF and PCBCF005
samples [32, 45]. The defect equation of the process
can be expressed as:
  1
2M 0
M þ OO , 2MM þ VO þ O2 ð2Þ
2

This result indicates that the introduction of the

appropriate Ca ions in PCBCF could inhibit thermal
reduction of transition metal ions, thus improving
stability.
The average TECs of PCBCF005 and PCBCF01
were 19.5 and 19.0 9 10-6 K-1 between 30 and
1000 °C. This value was lower than those of PBCF
(21.0 9 10-6 K-1) and PBC (21.5 9 10-6 K-1) sam-
ples. It is well known that the high TEC of cobalt-
based materials is mainly attributed to the transition
of the spin state of Co3? from a low-spin to an
intermediate- and high-spin state [14], which leads to
lattice expansion. For the PCBCF samples, Fe doping
reduced the content of Co and the stronger bond
energy of Fe–O compared with Co–O resulted in the
reduction of the TEC [35]. The relatively low TEC of
PCBCF was also closely related to the doping of Ca2?
because the Ca2? in the lattice can stabilize Co3? in
the intermediate-spin state [46]. The presence of Co3?
in the intermediate-spin state could reduce the ion-
icity and increase the covalence of Co–O [23, 46]. In
general, ionic bonds exhibited higher thermal
expansion behavior relative to covalent bonds, which
is another cause of a decline in the TEC [35].
Although the introduction of Ca and Fe reduced the
TEC, it was still larger compared with common
electrolyte materials. Therefore, the preparation of
composite cathodes in the latter is helpful in reducing
TEC and improving electrochemical properties.
Electrical conductivity
The conductivity of cathode material is directly
related to the charge collection efficiency, ohm loss,
and charge compensation rate in the ORR process.
The mixed ionic–electronic conducting (MIEC) oxides
can transport oxygen ion and electron simultaneously
at high temperatures. However, considering that
electronic conductivity is much higher than ion con-
ductivity in MIEC oxides, total conductivity usually
refers to electronic conductivity. Figure 7 shows the
Figure 7 Electrical conductivity curves of PBC, PBCF, and
PCBCF samples.
electrical conductivity of PCBCF01 and PCBCF015
after sintering at 1100 °C for 10 h. For comparison,
the conductivity curves of PBC and PBCF samples
are also shown in Fig. 7. Electrical conductivity of the
samples increased with temperature and reached a
maximum value at * 450 °C (PCBCF01) and
* 325 °C (PCBCF015), showing a semiconductor-like
behavior. Electrical conductivity began to gradually
decrease beyond * 450 °C and * 325 °C, exhibiting
a metallic behavior. The conductivity is closely rela-
ted to the variability of cobalt and iron oxidation state
within the oxides. For cobalt- and iron-based per-
ovskite-related oxides, the oxygen desorption a-peak
(200–600 °C) is typically associated with the reduc-
tion of Co4?/Fe4? to Co3?/Fe3?, while the b-peak
([ 800 °C) is usually related to the reduction of Co3?
to Co2? [6, 45]. Therefore, for PCBCF samples, semi-
conductor–metal transition is attributed to the
reduction of Co4?/Fe4? to Co3?/Fe3?. The conduc-
tion mechanism of PCBCF samples belongs to the
hopping p-type small polaron conduction mode
(Co4?/Fe4?–O2––Co3?/Fe3?). Similar conductive
behavior was found in other perovskite oxides
[6, 7, 20, 47]. As the test temperature increases, the
localized electronic carriers are thermally activated,
resulting in an increase in conductivity. However,
when the temperature reaches a certain level
(* 450 °C for PCBCF01 and * 325 °C for
PCBCF015), thermal reduction of Co4?/Fe4? to
Co3?/Fe3? begins to affect the carrier concentration
and the corresponding formation of oxygen vacancy
hinders the path of electron transport, leading to a
decrease in conductivity. The maximum conductivity
J Mater Sci

Figure 8 SEM images of a cross-sectional view of a PCBCF005, c

b PCBCF005|LSGM, c PCBCF01, and d PCBCF01|LSGM.

values of PCBCF01 and PCBCF015 samples are

173 S cm-1 at 450 °C and 177 S cm-1 at 325 °C,
respectively. Compared with the PBCF cathode, the
maximum conductivity values of the PCBCF samples
are lower. The conductivity of LnBaCo2O5?d-based
materials is closely related to rare earth and transition
metal elements [6, 34, 35]. The reason for the
decreased conductivity of PCBCF samples may be
derived from: (1) The increased concentration of Co3?
decreases the carrier concentration and introduces
carrier localization and (2) the formation of oxygen
vacancies perturbs the (Co, Fe)3?–O2-–(Co, Fe)4?
periodic potential. Compared with other similar
materials, such as PrBaCo2/3Fe2/3Cu2/3O5?d and
NdBaCoFeO5?d, the conductivity values of PBCFC
cathodes are still higher. Moreover, for the PCBCF01
sample, notably, the conductivity phase transition
(semiconductor ? metal) temperature tended to be
higher and the conductivity decayed relatively
slowly as the temperature increased (to [ 450 °C)
compared with those of the PBCF cathode, as shown
in Fig. 7. This result is attributed to the introduction
of Ca2?, which inhibits thermal reduction of Co3?/4?
and Fe3?/4? in the lattice and mitigates the effect of
carrier concentration reduction, leading to the
improvement of the phase stability above 450 °C.
Compared with the PCBCF01 sample, the different
conductive behavior of PCBCF015 (its semiconduc-
tor–metal transition temperature) may be related to
the impure phase inside the material.

Electrochemical performance

To evaluate the electrochemical activity of PCBCF

cathodes, symmetrical cells were fabricated using
LSGM as an electrolyte. The cross-sectional
microstructure of symmetrical cell is shown in Fig. 8.
The cathodes exhibited uniform porosity and a
thickness of * 30 lm. Besides, the LSGM electrolyte
is very dense and has good adhesion with the cath-
ode. The cathode electrochemical process can be
investigated by the electrochemical impedance spec-
trum (EIS) measured in symmetrical cells under
realistic operating conditions. Figure 9a–c represents
the EIS of PCBCF cathodes tested at 600–800 °C in
ambient air. The ohmic resistances of cells were
 J Mater Sci

Figure 9 Typical impedance of a PCBCF005, b PCBCF01, and c

c PCBCF015 cathodes on LSGM electrolyte; d ASR of PBCF and
PCBCF cathodes; inset shows the Arrhenius plots.

normalized in EIS. The ASR is equal to the intercept

of the arcs on the x-axis. Figure 9d shows ASR values
of PCBCF cathodes, and the inset shows corre-
sponding Arrhenius plots. As shown in Fig. 9, the
doping concentration of calcium ions has a remark-
able influence on the ORR activity. The ASRs of
cathodes on LSGM electrolyte are 0.211, 0.107, 0.077,
and 0.194 X cm2 for PBCF, PCBCF005, PCBCF01, and
PCBCF015 cathodes at 700 °C, respectively. The
activation energy values are 124.40, 105.59, 101.43,
and 100.60 kJ mol-1 for PBCF, PCBCF005, PCBCF01,
and PCBCF015 cathodes, respectively. The ASRs
(except PCBCF015) are lower than that of PBCF
cathodes at the same condition. The good catalytic
activity may be attributed to the introduction of Ca2?
into Pr3?/4? that effectively increases the oxygen
nonstoichiometry, which is conducive to the O2
adsorption and succeeding electron transfer to gen-
erate O- in the ORR. In addition, doping of Ca into
an A-site contributes to lowering the TEC, which
improves the thermal stability of the components
(confirmed by thermal expansion analysis). Among
the PCBCF cathode materials, PCBCF01 has the best
catalytic activity. The deterioration of catalytic per-
formance of the PCBCF15 cathode is due to the
influence of the impure phase, which was confirmed
by XRD results. Compared with the desirable target
value of cathodes for application in IT-SOFC, the ASR
of PCBCF01 cathodes is lower [48]. Besides, the ASR
values of PCBCF01 are also lower than those of pre-
viously studied similar cathodes. For example, at
700 °C, the ASR of PrBaCo2/3Fe2/3Cu2/3O5?d on GDC
electrolytes was 0.144 X cm2 [2]; the ASRs of
PrBaCo2/3Fe2/3Mn1/2O5?d [33], Pr0.9Ca0.1BaCo2O5?d
[23], and PrBaCo1.6Fe0.4O5?d [34] on SDC electrolytes
were 0.149, 0.081, and 0.130 X cm2, respectively.
To identify the process of influencing the electro-
chemical reaction and to understand the kinetics of
the redox reaction, the EIS of PCBCF01 cathode was
measured under different oxygen partial pressures
(Po2), as shown in Fig. 10. The plots were fitted by
equivalent circuits, shown in the inset of Fig. 9a.
According to the variation of Po2, two different
equivalent circuits were adapted to fit EIS data. Rohm
was the ohmic resistance of the cell. (R1–CPE1), (R2–
J Mater Sci
Figure 10 a Typical impedance of PBCFC01 cathode at 700 °C
under various PO2 (inset is the equivalent circuit model); b DRT
plots; c curves of polarization resistances versus PO2.
CPE2), and (R3–CPE3) corresponded to the high,
intermediate, and low arcs, respectively. The solid
lines in Fig. 9a are the fitted curves using the equiv-
alent circuits, while the points indicate experimental
data. The distribution of relaxation times (DRTs)
computing revealed several distinct processes in
redox reactions without an a priori choice of an
equivalent circuit. Using this method, the process of
polarization loss can be identified and targeted to
improve the catalytic performance of the cathode.
Characteristic frequency is the reciprocal of relax-
ation time in electrode processes. As shown in
Fig. 10a, three distinct peaks were detected in the
DRT curves, corresponding to high-frequency (HF),
intermediate-frequency (IF), and low-frequency (LF)
regions. According to the DRT analysis results, cor-
responding equivalent circuit fitting is shown in
Fig. 10. In this equivalent circuit model, R1, R2, and
R3 correspond to the electrode processes at HF, IF,
and LF, respectively. In general, the dependence of
polarization resistance (Rp) on Po2 can be represented
by:.
Rp ¼ kðPO2 Þn ð3Þ
According to n value, the electrochemical process
can be observed in the electrode reaction [49, 50]. The
dependence of Rp on Po2 is shown in Fig. 10c. The
results of linear fitting show that the n value for R1 is
0.07, which is close to 0. The insensitivity of the HF
region has little dependence on pO2, implying that the
HF process likely represents the transfer process of
O- from TPB/cathode to electrolyte. n of 0.4 for the
R2 indicates that IF region may be associated with the
charge transfer reaction of Oad to O-1ad , while n of 0.99
for R3 indicates that LF region likely subordinates to
mass transfer near the interface (including oxygen
adsorption, dissociation, and diffusion). The catalytic
activity is significantly enhanced with increasing
content of oxygen; the corresponding characteristic
peak for a specific process also shifts. For example,
when the PO2 is higher than 60%, it is difficult to
distinguish the LF region arc. In this case, the EIS is
fitted with two R-CPE elements. In this work, the
reaction rate limiting step is the transport process of
oxide ions and charge transfer process for PCBCF01.
In addition to good electro-catalytic activity and
stability, the ideal cathode material should have cer-
tain anti-carbon dioxide poisoning capability. Many
studies have shown that perovskite cathode-con-
taining alkaline earth element is susceptible to sur-
rounding CO2, even in small amounts [51, 52]. The
poor durability in a containing CO2 atmosphere is
due to the resulting surface cationic segregation and
the formation of carbonates, which may cause the

Figure 11 a Durability of PCBCF01 cathode in air with 1%, 3%,
and 5% CO2 at 700 °C; b typical impedance of PCBCF01 cathode
at 800 °C with different CO2 concentrations.
structural distortion and generation of an insulation
phase on the surface. The EIS of PCBCF01 cathode
with different concentrations of CO2 at 800 °C is also
shown in Fig. 11b. Apparently, the ASR of the
PCBCF01 cathode is sensitive to containing CO2
atmosphere; an increase in CO2 concentration inhibits
the reaction of oxygen catalytic at TPB significantly.
The ASR increased from 0.027 to 0.112 X cm2, * four
times, with the concentration of CO2 level up to 5% in
air. This is due to a decrease in the concentration of
oxygen molecules, and accordingly, CO2 replaces
oxygen to occupy part of vacancy sites in the cathode,
thus hindering the exchange of oxygen between the
lattice oxygen and free oxygen [52]. The time-de-
pendent ASR plots of PCBCF01 cathode displayed
good stability at 700 and 800 °C. Figure 11a shows
the durability of PCBCF01 cathode in the air with
different concentrations of CO2 at 700 °C. The ASR of
the PCBCF01 cathode remained relatively constant
when the concentration of CO2 was approximately
1%. After the flow witched to 3% and 5% CO2, ASR
began to increase with time. The ASR increased at an
early stage, but then the increasing rate of ASR
gradually slowed as it became stable. The CO2 con-
centration plays an important role in the competitive
adsorption/desorption process between O2 and CO2,
and the ability of PCBCF01 to incorporate CO2 is
more favorable at a CO2 concentration [ 1%. In
addition, after a relatively long-term operation, the
ASR of PCBCF01 cathode is likely to maintain
stable after the adsorption of CO2 is saturation. The
results show that the PCBCF01 cathode has better
J Mater Sci
Figure 12 I–V and I–P curves of Ni–SDC/SDC/LSGM/
PCBCF01 cell with H2 as fuel and ambient air as oxidant.
durability in the realistic working environment
because the concentration of CO2 in the air is only
0.04%, which is much lower than the current level.
Single performance
The cell performance of PCBCF01 as a cathode was
measured in a single cell with LSGM (0.3 mm) elec-
trolyte-supported PCBCF01|LSGM|SDC|NiO-SDC
configuration. The SDC buffer was introduced to
prevent the chemical reaction between NiO anode
and LSGM electrolyte. Figure 12 shows the I–V and
I–P curves of the single cell with H2 as fuel and static
air as an oxidant. The power density increases with
increasing operating temperature. The MPD values
are 728, 517, and 347 mW cm-2 for PCBCF01 cath-
odes at 800, 750, and 700 °C, respectively. Impor-
tantly, the MPD of the PCBCF01 cathode at 800 °C is
comparable to double-perovskite PBCF
(749 mW cm-2) and higher than that of the
NdBaCoFeO5?d cathode (669 mW cm-2) [32]. Com-
bined with electrochemical impedance analysis,
favorable electrochemical results indicate that the
PCBCF01 has the potential to be used as a cathode for
IT-SOFCs.
Conclusions
Pr1–xCaxBaCoFeO5?d samples were prepared and
evaluated as cathodes for IT-SOFC. Results show that
PCBCF005 and PCBCF01 have a pure phase double-
perovskite structure. PCBCF samples have excellent
chemical compatibility with LaGaO3-based and
J Mater Sci
CeO2-based electrolytes below 1000 °C. XPS analysis
revealed that Co and Fe ions coexisted in PCBCF
samples in the form of ? 3 and ? 4. The Ca2?
nonequivalent substitution of Pr3?/4? in PCBCF
samples promoted the formation of oxygen vacancy,
which contributed to improve electrochemical per-
formance. The average TEC of PCBCF01 was
19.0 9 10-6 K-1. The electrical conductivity value of
PCBCF01 was 173 S cm-1 at 450 °C. DRT analysis
showed that PBCFC cathode electrochemical reac-
tions under oxygen partial pressures involved at least
three processes. The ASRs of PCBCF cathodes on
LSGM electrolytes were 0.107, 0.077, and 0.194 X cm2
for PCBCF005, PCBCF01, and PCBCF015 cathodes at
700 °C, respectively. PCBCF01 exhibited a good cat-
alytic activity and durability under the CO2-contain-
ing test atmosphere. The results concerning PCBCF
cathodes indicate that PCBCF01 is promising as a
cathode for use in IT-SOFCs.
Acknowledgements
This work is supported by the National Natural Sci-
ence Foundation of China (21,703,017, 51702021), the
‘‘111’’ Project of China (D17017), the Developing
Project of Science and Technology of Jilin Province
(20180519017JH, 202002040JC, 20200201060JC) and
the International Science and Technology Coopera-
tion Project of Jilin Province (20190701029GH).
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