Journal of Alloys and Compounds 931 (2023) 167557

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Journal of Alloys and Compounds

journal homepage: www.elsevier.com/locate/jalcom

Mo doped Ruddlesden-Popper Pr1.2Sr0.8NiO4+δ oxide as a novel cathode

for solid oxide fuel cells ]]
]]]]]]
]]

⁎ ⁎
Yihui Liu a, , Zhuofei Pan a, Xiyong Chen b, Chao Wang a, Haizhao Li c,
a
Hubei Key Laboratory of Advanced Technology for Automotive Components & Hubei Collaborative Innovation Center for Automotive Components Technology,
Wuhan University of Technology, Wuhan 430070, Hubei, China
b
Guangxi Key Laboratory of Processing for Non-ferrous Metals and Featured Materials, School of Resources, Environment and Materials, Guangxi University,
Nanning 530004, Guangxi, China
c
School of Vehicle & Transportation Engineering, Henan University of Science and Technology, Luoyang 471003, Henan, China

a r t i cl e i nfo a bstr ac t

Article history: A new type of Ruddlesden-Popper Pr1.2Sr0.8Ni1−xMoxO4+δ (PSNMO) cathode with x = 0, 0.025, 0.050, 0.075
Received 5 March 2022 was prepared by the sol-gel method. The conductivity of Pr1.2Sr0.8NiO4+δ cathodes reaches the max values
Received in revised form 9 October 2022 and then decreases the continuous increase of Mo amount in all the Mo doped cathodes. Results of elec­
Accepted 10 October 2022
trochemical impedance spectroscopy show that the Pr1.2Sr0.8Ni0.950Mo0.050O4+δ has the lowest polarization
Available online 13 October 2022
resistance of 0.110 Ω cm2 at 750 °C among PSNMO cathodes. And results of electrical conductivity relaxation
and X-ray photoelectron spectroscopy indicate that Mo-doping improves the oxygen surface exchange
Keywords:
Solid oxide fuel cell properties of PSNMO cathodes, which can be mainly ascribed to co-interaction of oxygen vacancy and
Pr1.2Sr0.8NiO4+δ interstitial oxygen in PSNO cathodes after Mo-doping.
Mo-doping © 2022 Elsevier B.V. All rights reserved.
Oxygen reduction activity
Electrical conductivity relaxation

1. Introduction
As a power generation device that can efficiently convert fuel
chemical energy into electrical energy, solid oxide fuel cell (SOFC) is
cleaner and more reliable than traditional power generation devices
[1,2]. However, the processes of oxygen reduction reaction (ORR)
that occurred on the cathode side have great impacts on the overall
performance of the cells [3]. Ruddlesden-Popper A2BO4 oxides are
kinds of mixed ion-electron conductor (MIEC), in which perovskite
layers and rock salt layers are alternately arranged [4]. Due to the
special structure, the rock salt layer needs more non-stoichiometric
oxygen for coordination, and the holes formed in this layer are also
more conducive to the transport of electrons [5,6]. Therefore, it has
higher oxygen surface exchange properties compared with tradi­
tional perovskite materials. Common Ruddlesden-Popper structure
crystals such as Ln2NiO4 (Ln]La, Pr, Nd) generally have a relatively
low thermal expansion coefficient (TEC), which can match well with
the electrolyte [7]. However, Ruddlesden-Popper oxides have lower
electrical conductivity than perovskite materials since electron
conductor holes are mainly transported between NiO6 octahedrons
⁎
Corresponding authors.
E-mail addresses: liuyihui@whut.edu.cn (Y. Liu), lihaizhao@haust.edu.cn (H. Li).
in the perovskite layers and the rock salt layer hinders the move­
ment of holes, which results in lower overall catalytic performance
than that of perovskite materials [8,9].
Doping is a commonly used modification and optimization
methods for SOFC cathode materials [10]. Ghorbani-Moghadam et al.
found that the increase of Fe substitution in Co sites led to the de­
crease of the electrical conductivity but the improvement of ORR
activity of La0.7Sr1.3Co1−xFexO4 symmetrical cells [11]. A Sr and Ni co-
doped Ruddlesden-Popper perovskite oxide La1.6Sr0.4Cu0.6Ni0.4O4+δ
has been investigated as cathode materials and results showed that a
maximum powder output of 1020 mW cm−2 and a polarization re­
sistance (Rp) of 0.062 Ω cm2 at 750 °C were obtained in protonic
ceramic fuel cells [12]. Effects of bismuth-doping on electrochemical
performance of La2−xBixNiO4+δ (x = 0, 0.02 and 0.04) were evaluated
and results indicated that the obtained Rp for La1.96Bi0.04NiO4+δ was
0.18 Ω cm2, which was 56% lower than that of the La2NiO4+δ sample
at 750 °C [13]. La2−xCu1−y-zNiyMzO4-δ (M=Sc, Ga, In) cathodes were
investigated by Zhang, et al. and results showed that M-doping had a
great influence on the conductivity and transmission performance of
cathodes and was also beneficial to the stability and thermal ex­
pansion performance [14]. Shen et al. prepared the Mo doped
Ba0.5Sr0.5Co0.8Fe0.2O3-δ (BSCF) cathodes as cathode and anode and
results showed that Mo not only stabilized the structure of BSCF to
improve the redox stability, but also dramatically enhanced the

https://doi.org/10.1016/j.jallcom.2022.167557
0925-8388/© 2022 Elsevier B.V. All rights reserved.
Y. Liu, Z. Pan, X. Chen et al.
electrochemical performance and thermal expansion compatibility
of BSCF cathodes [15]. Nb-doping greatly improved the catalytic
performance and also the structure and chemical stability of
SrCo0.2Fe0.8O3-δ by suppressing the formation of impurity particles
on the cathode surface [16]. The optimization of the electrochemical
performance of Pr1.2Sr0.8NiO4+δ (PSNO) was mainly focused on the
co-doping of Ln elements on A-site, or the doping of transition
metals at the B site, while the doping with high valence and large
radius is still less [4,17,18]. For instance, the effects of Mo-doping on
the performance of PSNO as SOFC cathode are still unclear for the
complicated Pr valence state and conductive mechanism [19,20]. The
Ruddlesden-Popper composites with high catalytic performance and
high conductivity need to be further explored.
Here a type of perovskite-like cathode materials
Pr1.2Sr0.8Ni1−xMoxO4+δ (x = 0, 0.025, 0.050, 0.075) (PSNMO) were
prepared based on the sol-gel method. X-ray photoelectron spec­
troscopy (XPS), electrical conductivity relaxation (ECR), electro­
chemical impedance spectroscopy (EIS) tests were performed to
identify the interaction mechanism of Mo-doping to electrochemical
performance of PSNMO cathodes. Results show that the appropriate
amount of Mo-doping can significantly improve oxygen surface ex­
change properties of PSNMO cathodes.
2. Experiment
2.1. Preparation of samples and cells
The cathode powder was synthesized by a sol-gel method.
Stoichiometric amount of Pr(NO3)30.6 H2O, Sr(NO3)2, Ni
(NO3)20.6 H2O (Sinopharm Chemical Reagent Co. Ltd.) and
C4H4NNbO9.xH2O were dissolved simultaneously in deionized water.
Then an amount of citric acid (CA) (the molar ratio of CA to metal
ions is 1.5:1) was added to obtain a blue-green solution. A stoi­
chiometric amount of ethylene diamine tetraacetic acid (EDTA) (the
ratio of EDTA to metal ions is 1:1) was dissolved in an appropriate
amount of ammonia and poured into the blue-green nitrate solution.
The ammonia was used to adjust the pH value of the mixed solution
to 7. The obtained solution was heated and stirred at 80 °C for 5 h to
obtain a blue-green gel. Then the gel was placed in a blast drying
oven and heated up to 180 °C for 6 h to obtain the fluffy and porous
black precursors. These precursors were sintered in a muffle furnace
at 1050 ℃ for 3 h to obtain the Pr1.2Sr0.8NiO4+δ (PSNO),
Pr1.2Sr0.8Ni0.975Mo0.025O4+δ (PSNMO-25), Pr1.2Sr0.8Ni0.950Mo0.050O4+δ
(PSNMO-50), Pr1.2Sr0.8Ni0.925Mo0.075O4+δ (PSNMO-75) powders.
Finally, these powders mixed with the same quality of ethanol were
ball-milled separately for 24 h with a rotation speed of 460 r/min.
Commercial Gd0.1Ce0.9O2-δ (GDC) powders (Ningbo SOFCMAN
Energy Technology Co. Ltd, China) were placed in a round mold after
ball-milling under a pressure of 20 MPa for 3 min to obtain a GDC
green body, which was sintered at 1550 °C for 5 h to obtain dense
GDC electrolytes. The cathode powders and the binder (terpineol
solution mixed with ethylcellulose) were fully ground and mixed to
obtain cathode slurry. The mass ratio of powder and binder is 1:1.
The cathode slurry was coated on the center of the GDC electrolytes
and then calcined in a muffle furnace at 1000 °C for 2 h. The cathode
materials were fully consolidated as the work cathodes. The counter
cathode, reference cathode and current collector were all prepared
with Pt slurry on the opposite side of the work cathode after calci­
nation at 900 ℃ for 2 h.
1 g of cathode powder was placed in a rectangular dry pressing
mold and held at 20 MPa for 3 min provided by a hydraulic press.
And it was then calcined at 1350 °C for 5 h to obtain a size of
20 × 6 × 0.6 mm dense spline, which was used for subsequent
conductivity and ECR tests.
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Journal of Alloys and Compounds 931 (2023) 167557
2.2. Characterization methods
The composition and crystal structure of the cathode powders
were characterized by an X-ray diffractometer (XRD, D8 Advance)
with Cu Kα radiation source. The diffraction patterns were recorded
at a 2θ range of 20º-80º. The microstructures of the cathode, elec­
trolyte and contact surface were observed by scanning electron
microscopy (SEM, JSM-IT300). The thermal expansion properties of
PSNO, PSNMO-50 from 25° to 1000°C were measured by a thermal
analyzer (DIL402C) with a heating rate of 10 °C s−1. X-ray photo­
electron spectroscopy (XPS, AXIS-ULTRA DLD-600 W) was used at
room temperature to detect the surface chemistry of PSNO and
PSNMO-50 cathodes with monochromated Al Kα X-rays and a pass
energy of 25 eV. The obtained binding energies were calibrated with
the binding energy of C 1 s as 284.6 eV.
EIS tests with different cathodes were carried out by using an
electrochemical workstation (Gamry Interface 1000). The test tem­
perature range is 650–800 °C with a temperature interval of 50 °C.
The test parameters adopt 10 mV signal amplitude and the fre­
quency range of the open circuit is 0.1 Hz to 100 kHz.
The conductivities of different samples were measured by the
four-terminal method in the temperature range of 200–850 °C with
a temperature interval of 50 °C. The resistance measurements were
carried out using the multifunctional digital meter (Keithley Model
2000). The four-terminal method was also employed for the ECR
tests to characterize the oxygen surface exchange performance of
different samples at 750 °C. When the atmosphere of the sample
switched from air to pure oxygen, the oxygen content in the sample
will gradually change and reach a new balance. The changing curve
was recorded and fitted through a set program. The oxygen surface
exchange coefficient (Kchem) of the sample can be obtained using the
principle of Fick's second law. For the dense spline sample with the
thickness of 2d, the chemical diffusion coefficient (Dchem) and the
Kchem can be calculated by the following equation:
2
n DChem t
2L 2exp 2
(t ) (0)
=1 2 2
( ) (0) n=1
n( n + d2 + d) (1)
Where σ(0), σ(t) and σ(∞) denote the initial, time dependent and
final conductivities, respectively.
L = ntan n = d × Kchem/ Dchem (2)
The detailed information about the calculation processes of
oxygen surface exchange coefficients can be found in the previous
literatures [21].
3. Results and discussion
3.1. Phase composition and microstructure
Fig. 1a shows that clear peaks of Ruddlesden-Popper crystal
structure can be observed without other impure peaks in XRD pat­
terns of PSNO, PSNMO-25 and PSNMO-50 powders. When the
amount of Mo-doping increases to 0.075, the impurity SrMoO4 phase
generates because of the high valence state and large ionic radius of
Mo, which was also confirmed in previous study [22]. Fig. 1a shows
that the peaks of XRD tested with PSNMO cathodes shift towards
lower 2θ angles with the increase of Mo-doping amounts because
the ionic radii of Mo4+ (0.65 Å) and Mo5+ (0.61 Å) are larger than that
of Ni 2+ (0.49 Å) and Ni 3+ (0.56 Å). After calculation by Bragg's
equation using the peaks at 2θ about 33.3º, lattice parameters of
PSNO, PSNMO-25, PSNMO-50, PSNMO-75 are 3.793, 3.803, 3.796
and 3.799 Å, respectively. Results show that Mo-doping leads to the
lattice expansion. Fig. 1b shows XRD patterns of PSNO and GDC
Y. Liu, Z. Pan, X. Chen et al.
Fig. 1. XRD patterns of (a) PSNO, PSNMO-25, PSNMO-50, PSNMO-75 powders prepared by sol-gel method and (b) the GDC, PSNO and PSNO+GDC powders.
powder co-fired at 1000 °C for 3 h. Results show that all peak posi­
tions correspond well and no other impurity peaks appear compared
with the standard card of GDC (01–075–0161).
The microstructures of the cross-section of the PSNO cathode are
shown Fig. 2a. And results indicate that the cross-section of the GDC
electrolyte is in a dense state and has no defects, such as small holes
and pores. The PSNMO cathodes on the top of the electrolyte are in a
loose and porous state, which enlarges the specific surface area of
the cathodes. The expansion of the contact area between the cathode
and oxygen can increase the number of catalytic sites. At the same
time, the tight connection between the porous cathode and GDC
electrolyte ensures that the O2- passes efficiently through the three
phases boundary (TPB) into the electrolyte [23]. Fig. 2b shows the
low magnification microstructure of the cathode and electrolyte. The
uniform cathode thickness and relatively flat cathode surface are
obtained and the pore sizes of the cathode skeleton structure are
consistent with the density distribution, which ensures the uni­
formity of the current collector. Also, the contact surfaces between
the electrolyte and the cathode are relatively flat, which is beneficial
to the increase of the transmission rate of oxygen ions.
3.2. Electrochemical characterizations
Fig. 3 shows the measured EIS of the prepared half-cells with
different cathodes in the temperature range of 650–800 °C at a
temperature interval of 50 °C. Fig. 3a, b, c and d correspond to the EIS
of PSNO, PSNMO-25, PSNMO-50 and PSNMO-75 cathodes,
Fig. 2. Cross-section morphologies of PSNO cathodes: (a) High multiple, (b) Low multiple.
3
Journal of Alloys and Compounds 931 (2023) 167557
respectively. The high-frequency intercept of each semicircle curve
with the real axis represents the ohmic resistance (RΩ). The differ­
ence between the high and low frequency intercepts is the Rp. Rp
values at different temperatures are listed in Table 1. The Rp values of
PSNO, PSNMO-25, PSNMO-50 and PSNMO-75 are 0.318, 0.215, 0.110,
0.208 Ω at 750 °C, respectively. Rp values of Mo-doped cathodes are
reduced compared the PSNO cathode, which means that Mo-doping
improves the catalytic performance of the original cathode. Also, the
Rp of the cathodes shows a trend of decreasing at first stage and then
increasing with the increase of Mo-doping. The low doping amount
of Mo may lead to the stabilization of the 3D-perovskite structure of
cathodes. While the continuous increase of doped Mo causes the
partial disruption of the electronic pathway [24]. The more formed
SrMoO4 may be another reason for the Mo-doped the decrease. The
PSNMO-50 cathode reaches the best electrochemical performance.
Fig. 4a shows the equivalent circuit of the EIS fitting of Nyquist
plots. The actual test curves of the EIS are fitted through this circuit
to obtain the values of the high-frequency polarization resistance
(RH), the low-frequency polarization resistance (RL). The RH corre­
sponds to the processes of oxygen ions migration in cathodes and
the RL represents the processes of oxygen adsorption, dissociation
and diffusion [25]. Fig. 4b and c show the RH and RL values of each
cathode at different temperatures. RH and RL show the similar trend
with the increase of Mo-doping. RL decreases when Mo-doping
amount are 0.025 and 0.050, indicating that the dissociation and
adsorption processes of oxygen are accelerated. Similarly, Mo-
doping also improves oxygen ions migration property, which can be
Y. Liu, Z. Pan, X. Chen et al. Journal of Alloys and Compounds 931 (2023) 167557

Fig. 3. Electrochemical impedance spectra of (a) PSNO, (b) PSNMO-25, (c) PSNMO-50 and (d) PSNMO-75 cathodes under open circuit at 650–800 °C.

Table 1
3.3. Surface chemistry
Polarization resistance of PSNO and PSNMO cathodes at 650–800 °C under open
circuit. As PSNMO-50 has the lowest Rp among the PSNMO cathodes,
Cathodes Rp (Ω cm2) here PSNO and PSNMO-50 cathodes are selected for further analysis
to explain the improvement mechanism of Mo-doping. The XPS
650 °C 700 °C 750 °C 800 °C
diagrams of the O 1 s on the surface of PSNO and PSNMO-50 are
PSNO 2.115 0.756 0.318 0.107 shown in Fig. 5a and b, respectively. The XPS spectrum for O 1 s of
PSNMO-25 1.873 0.438 0.215 0.091
PSNO can be decomposed into 528.88, 530.97, 531.70 and 532.67 eV.
PSNMO-50 1.010 0.393 0.110 0.036
PSNMO-75 1.122 0.416 0.208 0.087 The O 1 s spectrum of PSNMO-50 contains peaks located at 528.82,
530.80, 531.62 and 532.54 eV. The higher binding energies at
531.70–532.67 eV and 531.62–532.54 eV represent the adsorbed
concluded from the variation trend of RH. But the excess Mo-doping oxygen and the surface oxygen [26,27]. The peaks at 530.97 and
causes the decrease of catalytic performance of the cathode. This can 530.80 eV correspond to the lattice oxygen of Pr-O and Sr-O bonds in
be found by the higher RH and RL values of PSNMO-75 than that of the perovskite layer. The peaks at 528.88 and 528.82 eV correspond
PSNMO-50 cathode. Also, the values of RL decrease greatly compared to the lattice oxygen combined in the rock salt layer. Table 2 shows
to those of RH, indicating that the improved electrochemical per­ the surface oxygen proportions of different types of oxygen calcu­
formance of PSNO cathodes are mainly ascribed to the promotion of lated from the peak area of XPS spectra. After Mo-doping, the pro­
oxygen surface exchange property by Mo-doping. portion of lattice oxygen in the rock salt layer increases from 10.34%

4
Y. Liu, Z. Pan, X. Chen et al. Journal of Alloys and Compounds 931 (2023) 167557

Fig. 4. (a) The equivalent circuit diagram, (b) the curve of the RL and (c) RH values of PSNO, PSNMO series cathodes at 650–800 °C obtained by fitting the equivalent circuit
diagram.

Fig. 5. XPS spectra for O 1 s of (a) PSNO, (b) PSNMO-50 cathodes; Pr 3d5/2 in (c) PSNO and (d) PSNMO-50 cathodes.

5
Y. Liu, Z. Pan, X. Chen et al.
Table 2
Detailed data of the O 1 s peaks on the surface of PSNO and PSNMO-50 cathodes.
Cathodes Rock salt layer Perovskite layer Surface adsorbed oxygen
Binding energy（eV）
PSNO 528.88 530.97 531.70 532.67
(10.34%) (28.19%) (39.46%) (22.01%)
PSNMO-50 528.82 530.80 531.62 532.54
(12.03%) (31.22%) (29.27%) (27.48%)
to 12.03%, and the proportion of lattice oxygen in the perovskite
layer increases from 28.19% to 31.22%. Meanwhile, to regulate the
charge mismatch in PSNMO cathodes caused by Mo-doping, the
concentration of interstitial O will increase to some extent, which is
beneficial to the conduction of oxygen ion [28]. All these improve the
electrochemical performance of PSNMO cathodes.
Fig. 5c and d show the XPS spectra for Pr 3d5/2 orbitals of PSNO
and PSNMO-50, respectively. The peaks of the PSNO cathode at
binding energy of 929.98 and 934.34 eV represent Pr3+, and the peak
at 932.60 eV represents Pr4+ [29,30], of which the area corre­
sponding to the Pr4+ peaks accounts for 27.01%. The peaks of the
PSNMO-50 cathode at the binding energy of 929.01 and 933.41 eV
represent Pr3+, and the peak at 931.71 eV represents Pr4+ [31], of
which the area corresponding to the Pr4+ peaks accounts for 25.24%.
These results show that Mo-doping reduces the proportion of Pr4+
ions, leading to the decrease of the overall valence of Pr element and
the possible increase of free electrons from A-site atoms. Also, all the
peaks for Pr 3d5/2 in PSNMO-50 migrate to the lower binding energy
regions compared to that of PSNMO, implying that the interaction
between O and Pr atoms is weakened and the oxygen ions migrate
more easily.
Fig. 6 shows XPS spectra for Ni 2p3/2 and Mo 3d5/2 of PSNMO-50
cathodes. The peak at binding energy of 853.42 eV corresponds to
Ni2+, while the peak at 854.57 eV is assigned to Ni3+ (Fig. 6a). The
peaks at 230.76 and 231.19 eV are attributed to Mo4+ and Mo5+, re­
spectively. This proves that Ni in PSNMO-50 exists as mixed valence
of Ni2+ and Ni3+. The doping of Mo with higher valence Mo4+ and
Mo5+ into PSNO could reduce the Ni3+ to Ni2+ because of the elec­
troneutrality compensation. Therefore, Mo-doping is beneficial to
keeping Ni ions in a lower valence state.
3.4. Oxygen exchange property, electrical conductivity and thermal
expansion behaviors
The oxygen surface exchange properties include the adsorption
and dissociation processes of oxygen on the cathode surface, which
Fig. 6. XPS spectra for (a) Ni 2p3/2 and (b) Mo 3d5/2 of PSNMO-50 cathodes.
6
Journal of Alloys and Compounds 931 (2023) 167557
plays a vital role in the reaction rate of oxygen. The conductivity
change curves of the spline are recorded during ECR tests when the
atmosphere is switched from air to pure oxygen. Since the thickness
of the spline is thin, the transport of oxygen ions in bulk is negligible
[32–34]. Fig. 7a, b, c and d show the scatter plots of the ECR results of
PSNO, PSNMO-25, PSNMO-50, PSNMO-75 at 750 °C, respectively. The
fitting curves corresponding to different plots and Kchem obtained
through the normalized fitting are shown in Fig. 7e. The Kchem of
PSNO, PSNMO-25, PSNMO-50, PSNMO-75 are 4.0 × 10−4, 4.7 × 10−4,
5.3 × 10−4, 4.9 × 10−4 cm s−1, respectively. The Kchem increases with
the of Mo-doping amount increasing to 0.025 (PSNMO-25) and 0.050
(PSNMO-50). Generally, the oxygen vacancy concentration has great
effects on the surface exchange process and oxygen dissociation
takes place at the surface oxygen vacancies [35]. As mentioned
above, high valence Mo4+/Mo5+ doping results in less oxygen va­
cancies but more interstitial oxygen in PSNO, and improves the
stability of PSNO and oxygen surface exchange properties. When
Mo-doping amount increases to 0.075 (PSNMO-75), Kchem decreases
conversely compared to PSNMO-50. The continuous increase of
doped Mo may cause the partial disruption of the electronic
pathway and the formed second phase SrMoO4 thus the decrease of
the oxygen surface exchange properties [24].
The influence of the amount of Mo-doping on the thermal ex­
pansion behaviors of the cathodes are also investigated with PSNO
and PSNMO-50 cathode bars. Fig. 8a shows the thermal expansion
curve of PSNO and PSNMO-50 at 25–1000 °C. The TECs of PSNO and
PSNMO-50 are shown in Table 3. In the temperature range of
25–900 °C, the TECs of PSNO and PSNMO-50 are 14.39 × 10−6 and
12.55 × 10−6 K−1, respectively. The change in the low-temperature
range may be related to the dissociation of oxygen in the cathode
surface. Results show that the TEC of the PSNO material is sig­
nificantly reduced after Mo-doping, which is very close to the TEC of
the GDC electrolyte (12.23 ×10−6 K−1) [36]. The decrease of TEC of
PSNMO-50 may be due to the stronger electronegativity caused by
the higher valence of the doped Mo, which reduces the oxygen ions
loss in the crystal lattice at high temperatures.
Curves shown in Fig. 8b reflect the changes of the conductivity of
PSNO, PSNMO-25, PSNMO-50, PSNMO-75 in the temperature range
of 200–800 °C. The conductivities of all PSNMO cathodes increase
first and then decrease with the increase of Mo-doping amounts. The
conductivities of PSNMO-25, PSNMO-50 are higher than that of
PSNO at the corresponding temperatures. When the Mo-doping
reaches the highest concentration, the electrical conductivity of
PSNMO-75 is lower than that of PSNO. High valence Mo-doping into
PSNO can reduce the Ni3+ to Ni2+ based on the electroneutrality
principle and the new second phase was formed, such as SrMoO4
Y. Liu, Z. Pan, X. Chen et al. Journal of Alloys and Compounds 931 (2023) 167557

Fig. 7. ECR experimental data and fitting curve of (a) PSNO, (b) PSNMO-25, (c) PSNMO-50, (d) PSNMO-75, (e) Oxygen surface exchange coefficient corresponding to all fitting
curves.

[37]. The oxygen vacancies will increase by reducing Ni3+ to Ni2+ as at about 550 °C. The peak conductivity of the PSNMO-25 material
described as the following equation: reaches 200 S cm−1. While the measured conductivity of
La1.5Pr0.5NiO4 and La1.5Pr0.5Ni0.9Cu0.1O4 did not exceed 100 S cm−1
× + O× 1
NiNi O NiNi + VO·· + O2 [38]. PSNMO series materials show better electrical conductivity
2 (3)
than conventional perovskite-like materials, reaching the standard
where O×O is the lattice oxygen and VO··
is the oxygen vacancy. and ×
NiNi (100 S cm−1) required as oxygen cathodes [39]. Generally, there are
NiNi represent Ni3+ and Ni2+, respectively. Therefore, a continuous two opposite types of effects of Mo-doping on the conductivity. Mo-
increase of Mo-doping content results in less oxygen vacancies, doping enlarges the volume of the unit cell, which is beneficial to the
which decreases the conductivity of the material. Each conductivity bulk transport process of oxygen ions, thereby increasing its elec­
curve increases first and then decreases and reaches the peak value trical conductivity. On the other hand, Mo-doping results in less

7
Y. Liu, Z. Pan, X. Chen et al.
Fig. 8. (a) Thermal expansion curves of PSNO and PSNMO-50 at 25–1000 °C. (b) Electrical conductivity of PSNO, PSNMO-25, PSNMO-50, PSNMO-75 at 200–800 °C.
Table 3
TEC data of PSNO and PSNMO-50 cathodes.
Samples Temperature range
30–750 °C 750–900 °C 30–900 °C
TEC (×10−6 K−1) PSNO 14.28 14.93 14.39
PSNMO-50 12.50 12.76 12.55
oxygen vacancies, which decreases the conductivity of the material.
In summary, Mo-doping increases the conductivities of PSNO while
excess Mo amounts cause to the decrease of conductivities. Similar
phenomenon has been reported in niobium doped SrCo0.2Fe0.8O3-δ
cathodes [16]. All results above show that the Mo-doped PSNO
cathodes can be the promising cathode materials for SOFCs.
4. Conclusion
In this paper, effects of Mo-doping on electrochemical perfor­
mance of Pr1.2Sr0.8Ni1−xMoxO4+δ (x = 0, 0.025, 0.050, 0.075) oxides are
investigated as potential cathode materials by EIS, XPS, ECR tests,
et al. Results show that the electrical conductivity of PSNMO cath­
odes was greatly improved with Mo-doping compared to PSNO
cathodes with x = 0.025 and 0.050, whch is benefical to the elec­
trochemical performance of cathodes. The Rp values of PSNMO
reaches the lowest with x = 0.05 and then increases by analysing the
EIS data (0.110 Ω cm2 at 750 °C). And ECR results indicate that the
promoted performance of PSNMO was mainly ascribed to the im­
proved oxygen surface exchange properties. Combined with results
of EIS, XPS and ECR tsets, the performance improvement results
from the co-interaction of surface oxygen vacancy and interstitial
oxygen after Mo-doping. Our work suggests that Mo-doped
Pr1.2Sr0.8NiO4+δ oxides could be potential applications as cathode
materials for SOFCs.
CRediT authorship contribution statement
Yihui Liu: Conceptualization, Methodology, Resources,
Investigation, Writing – review & editing, Supervision, Funding ac­
quisition. Zhuofei Pan: Methodology, Investigation, Data curation,
Writing – original draft. Xiyong Chen: Validation, Supervision,
Project administration, Funding acquisition. Chao Wang: Validation,
Supervision, Project administration. Haizhao Li: Methodology,
Resources, Writing – review & editing, Supervision.
8
Journal of Alloys and Compounds 931 (2023) 167557
Data availability
Data will be made available on request.
Declaration of Competing Interest
The authors declare that they have no known competing fi­
nancial interests or personal relationships that could have appeared
to influence the work reported in this paper.
Acknowledgments
The project was supported by Open Foundation of Guangxi Key
Laboratory of Processing for Non-ferrous Metals and Featured
Materials, Guangxi University (2022GXYSOF26, 2021GXYSOF01), the
National Natural Science Foundation of China (52062002), Open
project of Hubei Key Laboratory of Power System Design and Test for
Electrical Vehicle (ZDSYS202212), 111 Project (B17034) and
Innovative Research Team Development Program of Ministry of
Education of China (IRT_17R83). XRD, TEC, SEM and XPS examina­
tions were assisted by the Center of Material Research and Analysis
of Wuhan University of Technology.
References
[1] S. Dwivedi, Solid oxide fuel cell: materials for anode, cathode and electrolyte, Int.
J. Hydrog. Energy 45 (2020) 23988–24013.
[2] J. Zhou, Z. Wang, M. Han, Z. Sun, K. Sun, Optimization of a 30 kW SOFC combined
heat and power system with different cycles and hydrocarbon fuels, Int. J.
Hydrog. Energy 47 (2022) 4109–4119.
[3] A. Ndubuisi, S. Abouali, K. Singh, V. Thangadurai, Recent advances, practical
challenges, and perspectives of intermediate temperature solid oxide fuel cell
cathodes, J. Mater. Chem. A 10 (2022) 2196–2227.
[4] M.A. Yatoo, S.J. Skinner, Ruddlesden-popper phase materials for solid oxide fuel
cell cathodes: a short review, Mater. Today.: Proc. 56 (2022) 3747–3754.
[5] P. Ding, W. Li, H. Zhao, C. Wu, L. Zhao, B. Dong, S. Wang, Review on ruddlesden-
popper perovskites as cathode for solid oxide fuel cells, J. Phys. -Mater. 4 (2)
(2021) 022002.
[6] T. Ma, T. Xia, Q. Li, L. Sun, L. Huo, H. Zhao, Highly electrocatalytic activity
Ruddlesden_Popper type electrode materials for solid oxide fuel cells, J. Eur.
Ceram. Soc. 42 (2022) 490–498.
[7] B. Philippeau, F. Mauvy, C. Mazataud, S. Fourcade, J.C. Grenier, Comparative
study of electrochemical properties of mixed conducting Ln2NiO4+δ (Ln = La, Pr
and Nd) and La0.6Sr0.4Fe0.8Co0.2O3-δ as SOFC cathodes associated to Ce0.9Gd0.1O2-
δ, La0.8Sr0.2Ga0.8Mg0.2O3-δ and La9Sr1Si6O26.5 electrolytes, Solid State Ion. 249
(2013) 17–25.
[8] G. Amow, I.J. Davidson, S.J. Skinner, A comparative study of the Ruddlesden-
Popper series, Lan+1NinO3n+1 (n=1, 2 and 3), for solid-oxide fuel-cell cathode
applications, Solid State Ion. 177 (2006) 1205–1210.
[9] T.W. Chiu, Y.T. Lin, I.F. Yen, H.H. Hsieh, S.F. Wang, Properties and performance of
La2NiO4+δ-LaNiO3 composite cathodes for intermediate-temperature solid oxide
fuel cells, Ferroelectrics 457 (2013) 105–110.
Y. Liu, Z. Pan, X. Chen et al.
[10] M. Bilal Hanif, M. Motola, S. qayyum, S. Rauf, A. Khalid, C.J. Li, C.X. Li, Recent
advancements, doping strategies and the future perspective of perovskite-based
solid oxide fuel cells for energy conversion, Chem. Eng. J. 428 (2022) 132603.
[11] T. Ghorbani-Moghadam, A. Kompany, M. Golmohammad, Study of structural,
electrical and electrochemical properties of La0.7Sr1.3Co1−xFexO4 (x = 0, 0.1, 0.3,
0.5) Ruddlesden-Popper oxides as promising cathode for intermediate solid
oxide fuel cells, J. Alloy. Compd. 900 (2022) 163382.
[12] J. Ma, Y. Pan, Y. Wang, Y. Chen, A Sr and Ni doped Ruddlesden−Popper perovskite
oxide La1.6Sr0.4Cu0.6Ni0.4O4+δ as a promising cathode for protonic ceramic fuel
cells, J. Power Sources 509 (2021) 230369.
[13] C. Yao, J. Yang, H. Zhang, S. Chen, J. Meng, K. Cai, Evaluation of bismuth doped
La2−xBixNiO4+δ (x = 0, 0.02 and 0.04) as cathode materials for solid oxide fuel
cells, Ceram. Int. 47 (2021) 24589–24596.
[14] Z. Zhang, Z. Du, A. Niemczyk, K. Li, H. Zhao, K. Swierczek, A-site non­
stoichiometry and B-site doping with selected M3+ cations in La2−xCu1−y-
zNiyMzO4-δ layered oxides, Solid State Ion. 317 (2018) 26–31.
[15] Y. Shen, Y. Song, Y. Zhao, J. Zhao, M. Yan, Q. Lu, Y. Bu, Mo-doped
Ba0.5Sr0.5Co0.8Fe0.2O3-δ as a high-performance symmetric electrode for solid
oxide fuel cells, J. Alloy. Compd. 928 (2022) 167029.
[16] Y. Qiu, H. Li, Y. Liu, B. Chi, J. Pu, J. Li, Effects of niobium doping on the stability of
SrCo0.2Fe0.8O3-δ cathodes for intermediate temperature solid oxide fuel cells, J.
Alloy. Compd. 829 (2020) 154503.
[17] R.K. Sharma, S.K. Cheah, M. Burriel, L. Dessemond, J.M. Bassat, E. Djurado, Design
of La2−xPrxNiO4+δ SOFC cathodes: a compromise between electrochemical per­
formance and thermodynamic stability, J. Mater. Chem. A 5 (2017) 1120–1132.
[18] N.I. Khamidy, J. Laurencin, D. Ferreira Sanchez, F. Monaco, F. Charlot, E. Djurado,
Durability of nanostructured LaPrNiO4+δ electrode for solid oxide cells:
Electrochemical, microstructural, and structural investigation, J. Power Sources
450 (2020) 227724.
[19] J. Cheng, S. Zhang, B. Meng, J. Ding, X. Tan, Preparation and the superior oxygen
permeability of a new CO2-resistant Ruddlesden-Popper composite oxide
Pr2Ni0.9Mo0.1O4+δ, J. Alloy. Compd. 742 (2018) 966–976.
[20] D. Li, X. Zhang, Y. Jin, X. Zong, Y. Xiong, Suppression of Sr surface segregation in
La0.8Sr0.2Co0.2Fe0.8O3-δ via Nb doping in B-site, Ceram. Int. 48 (2022) 2161–2168.
[21] D. Chen, Z. Shao, Surface exchange and bulk diffusion properties of
Ba0.5Sr0.5Co0.8Fe0.2O3-δ mixed conductor, Int. J. Hydrog. Energy 36 (2011)
6948–6956.
[22] P.B. de Sousa, I.C. Nogueira, G.O.M. Gusmão, S.B.S. Gusmão, F.H.P. Lopes,
B.S. Sousa, J.C. Sczancoski, A.F. Gouveia, L.S. Cavalcante, Structural investigation
and sonophotocatalytic properties of the solid solutions Sr(Mo1−xWx)O4 crystals
synthesized by the sonochemical method, J. Mater. Sci.: Mater. Electron. 33
(2022) 22127–22152.
[23] G. Chasta, Himanshu, M.S. Dhaka, A review on materials, advantages, and
challenges in thin film based solid oxide fuel cells, Int. J. Energy Res. 46 (2022)
14627–14658.
[24] A. Aguadero, D. Pérez-Coll, J.A. Alonso, S.J. Skinner, J. Kilner, A new family of Mo-
doped SrCoO3-δ perovskites for application in reversible solid state electro­
chemical cells, Chem. Mater. 24 (2012) 2655–2663.
Journal of Alloys and Compounds 931 (2023) 167557
[25] H. Li, M. Wei, Y. Liu, X. Chen, G. Guo, F. Liu, C. Fan, D. Zhang, Enhanced me­
chanisms of oxygen reduction on Pr0.4Sr0.6Co0.2Fe0.8O3-δ impregnated
La1−xSrxCo1−yFeyO3-δ cathodes for solid oxide fuel cells, J. Alloy. Compd. 927
(2022) 167033.
[26] S. Wang, Y. Wu, Y. Gao, H. Chen, A.M. Abdalla, A.K. Azad, Z. Lü, B. Wei, A highly
stable of tungsten doped Pr0.6Sr0.4Fe0.9W0.1O3-δ electrode for symmetric solid
oxide fuel cells, Int. J. Hydrog. Energy 47 (2022) 34205–34215.
[27] B. Zhang, Y. Wan, Z. Hua, K. Tang, C. Xia, Tungsten-doped PrBaFe2O5+δ double
perovskite as a high-performance electrode material for symmetrical solid oxide
fuel cells, ACS Appl. Energy Mater. 4 (2021) 8401–8409.
[28] Y. Huan, S. Chen, R. Zeng, T. Wei, D. Dong, X. Hu, Y. Huang, Intrinsic effects of
Ruddlesden-Popper-based bifunctional catalysts for high-temperature oxygen
reduction and evolution, Adv. Energy Mater. 9 (2019) 1901573.
[29] F. Jin, Y. Shen, R. Wang, T. He, Double-perovskite PrBaCo2/3Fe2/3Cu2/3O5+δ as
cathode material for intermediate-temperature solid-oxide fuel cells, J. Power
Sources 234 (2013) 244–251.
[30] C. Lu, B. Niu, W. Yi, Y. Ji, B. Xu, Efficient symmetrical electrodes of
PrBaFe2−xCoxO5+δ (x=0, 0.2,0.4) for solid oxide fuel cells and solid oxide elec­
trolysis cells, Electrochim. Acta 358 (2020) 136916.
[31] Y. Gou, G. Li, R. Ren, C. Xu, J. Qiao, W. Sun, K. Sun, Z. Wang, Pr-doping motivating
the phase transformation of the BaFeO3-δ perovskite as a high-performance solid
oxide fuel cell cathode, ACS Appl. Mater. Interfaces 13 (2021) 20174–20184.
[32] T. Hong, K. Brinkman, C. Xia, Copper oxide as a synergistic catalyst for the oxygen
reduction reaction on La0.6Sr0.4Co0.2Fe0.8O3-δ perovskite structured electro­
catalyst, J. Power Sources 329 (2016) 281–289.
[33] V. Thoreton, Y. Hu, C. Pirovano, E. Capoen, N. Nuns, A.S. Mamede, G. Dezanneau,
C.Y. Yoo, H.J.M. Bouwmeester, R.N. Vannier, Oxygen transport kinetics of the
misfit layered oxide Ca3Co4O9+δ, J. Mater. Chem. A 2 (2014) 19717–19725.
[34] B. Hu, Y. Wang, Z. Zhu, C. Xia, H.J.M. Bouwmeester, Measuring oxygen surface
exchange kinetics on mixed-conducting composites by electrical conductivity
relaxation, J. Mater. Chem. A 3 (2015) 10296–10302.
[35] D. Huan, L. Zhang, K. Zhu, X. Li, N. Shi, Y. Yang, C. Xia, Y. Xie, R. Peng, Oxygen
vacancy-engineered cobalt-free Ruddlesden-Popper cathode with excellent CO2
tolerance for solid oxide fuel cells, J. Power Sources 497 (2021) 229872.
[36] J. Zhou, P. Tang, J.H. Bai, Y.X. Chen, Y. Meng, X.F. Zhu, N. Wang, D.F. Zhou, W. Yan,
A new type of Gd0.2Ce0.8O3-δ fuel cell electrolyte containing Er0.2Bi0.8O1.5 with
highly improved performance, J. Alloy. Compd. 901 (2022) 163654.
[37] P. Zhang, G. Guan, D.S. Khaerudini, X. Hao, C. Xue, M. Han, Y. Kasai, A. Abudula, B-
site Mo-doped perovskite Pr0.4Sr0.6(Co0.2Fe0.8)1−xMoxO3-σ (x = 0, 0.05, 0.1 and
0.2) as electrode for symmetrical solid oxide fuel cell, J. Power Sources 276
(2015) 347–356.
[38] C. Zhao, Q. Zhou, T. Zhang, L. Qu, X. Yang, T. Wei, Preparation and electrochemical
properties of La1.5Pr0.5NiO4 and La1.5Pr0.5Ni0.9Cu0.1O4 cathode materials for in­
termediate-temperature solid oxide fuel cells, Mater. Res. Bull. 113 (2019) 25–30.
[39] Y. Chen, W. Zhou, D. Ding, M. Liu, F. Ciucci, M. Tade, Z. Shao, Advances in cathode
materials for solid oxide fuel cells: complex oxides without alkaline earth metal
elements, Adv. Energy Mater. 5 (2015) 1500537.