Research Article

Cite This: ACS Appl. Mater. Interfaces 2019, 11, 27924−27933 www.acsami.org

Approaching Durable Single-Layer Fuel Cells: Promotion of

Electroactivity and Charge Separation via Nanoalloy Redox
Exsolution
Kang Shao,†,‡ Fengjiao Li,†,‡ Guanghong Zhang,†,‡ Qianling Zhang,†,‡ Kristina Maliutina,†,‡
and Liangdong Fan*,†,‡
†
College of Chemistry and Environmental Engineering, Shenzhen University, Shenzhen 518060, Guangdong Province, P. R. China
‡
Shenzhen Key Laboratory of New Lithium-ion Batteries and Mesoporous Materials, Shenzhen University, Shenzhen 518060,
Guangdong, PR China
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*
S Supporting Information
Downloaded via UNIV OF GOTHENBURG on October 22, 2019 at 12:57:25 (UTC).

ABSTRACT: Single-layer fuel cells (SLFCs) based on mixed

semiconductors and ionic conductors demonstrate simplified
material preparation and fabrication procedure and possess high
performance potentially. However, the operational stability and
principle of SLFCs have not yet been convinced of either
commercialization or fundamental interests. We hereby report on
the employment of a perovskite oxide-based phase-structured
redox-stable semiconductor prior to determining a possible
solution that improves the durability of the SLFC. Feasible
working principles are established and an in-depth understanding
of the short-circuit-free phenomenon in SLFCs with the mixed
ionic and electronic conductors is provided. Additionally, a smart
material design and cell structure processing are also proposed. An
extended nonstop testing period of up to 2 days confirms the
project feasibility and improved durability of the SLFCs, achieved by replacing the unstable lithiated oxide phase with redox-
stable perovskite oxide, though the electrochemical performance is sacrificed. The precipitated metal/alloy nanoparticle on
perovskite oxide not only improves the electrode reaction kinetics but also facilitates the charge separation and ionic conduction
in SLFCs, consequently enhancing the fuel cell performance and electrical efficiency. The results confirmed the potential of
stable operation for future practical deployment of SLFCs via appropriate selection of material and cell structure design. It is
greatly believed that the physical junction plays a crucial role in overcoming the internal short-circuit issue of SLFCs.
KEYWORDS: single-layer fuel cell, solid oxide fuel cell, semiconductor, metal/alloy nanoparticle exsolution, p−n junction,
Schottky junction

1. INTRODUCTION favored characteristics attract increasing attention. However,

The development of highly efficient energy conversion
technologies has been extensively pursued in the last two
decades because of the boosted energy crisis and the concerns
of environmental impact. Fuel cells attracted the colossal
interest of researchers nowadays because of the high efficiency
and environmental compliance. The low-temperature-operat-
ing proton exchange membrane fuel cells (PEMFCs) have the
capabilities of higher reversible electrical efficiency and close
daily life application, which make them competitive to that of
conventional energy conversion devices like combustion
engines and so on. Notwithstanding, the present drawbacks,
such as the high cost of precious benchmark electrocatalysts
(Pt/C) and sluggish electrode reaction kinetics in PEMFCs,
hinder the ultimate efficiency, which is lower than that when
operating at high temperatures, and suppress the world-
spanning commercialization. Substantially, the solid oxide fuel
cells (SOFCs) operated at higher than 700 °C with kinetic-
the typical intermediate and high-temperature-operated
SOFCs suffer from severe cell material incompatibility issue
and large capital input.1,2 The reduction of the SOFC running
temperature that simplifies the sealing and slows down
degradation has been highly desirable and becomes the
worldwide tendency.3−5 Versatile approaches were developed
in the last several years with enormous progress by seeking for
active cell components to replace the current electrolyte and
electrode material system or by optimizing the fuel cell
microstructure/cell configuration via using nanomaterials and
nanotechnology.5−9 Nevertheless, there are often competitive
tensions among fuel cell performance, durability, and system
cost. The remarkable electrochemical efficiency is often at the
Received: May 15, 2019
Accepted: July 10, 2019
Published: July 10, 2019

© 2019 American Chemical Society 27924 DOI: 10.1021/acsami.9b08448

ACS Appl. Mater. Interfaces 2019, 11, 27924−27933
ACS Applied Materials & Interfaces
Figure 1. Electrochemical performance of SLFCs using NCAL as the semielectrocatalyst and LNSDC as the ionic conductor at 550 °C: (a) steady-
state polarization curve, (b) EIS under OCV condition, and (c) current response under a constant voltage of 0.7 V in H2/air atmosphere.
expense of the diminishing durability.10,11 Generally, the classic
three-layer structure, that is, the porous anode, cathode, and
the sandwiched dense electrolyte layer together called the
membrane electrode assembly, is the center of the fuel cells.
The electrolyte layer is the key to realize fuel cell functionality,
which, however, causes the intrinsic interfacial chemical−
thermal−mechanical compatibility issues as well as huge
interfacial reaction/charge-transfer energy loss, not to mention
the insufficient ionic conductivity of the current typical
electrolyte materials.12 These, in turn, suppress the industrial
demonstration to still the state-of-the-art material system: Ni-
cermet anode, yttria-stabilized zirconia electrolyte, and perov-
skite (La,Sr)MnO3 cathode, which were used since the invent
of SOFCs, more than one century ago. Therefore, a
breakthrough on highly efficient energy conversion system/
technology at high temperature with similar/surpassing
functionality as that of SOFCs is decidedly required.
A recent development in the novel high-temperature energy
conversion technology, the single-component/single-layer fuel
cell (SLFC) or electrolyte-free fuel cell device, has attracted
profound attention of researchers worldwide because of the
simplified cell structure and superior performance compared
with that of the traditional three-layer SOFCs.13−19 In the
SLFC configuration, the typical three-layer structure of anode/
electrolyte/catode has been replaced with a single homoge-
neous composite of ionic and semiconducting materials or
semi-ionic conductors. No electrode/electrolyte interfacial
chemical/thermomechanical compatibility issue and much
reduced interfacial polarization resistance appear in such a
novel device. Moreover, fuel cell peak power outputs up to
1000 mW cm−2 were demonstrated in the literature by using
hydrogen as a fuel and air as an oxidant at 550 °C,20−22 which
are clearly superior to those of the three-layer SOFCs with
classic electrolyte layer. Consequently, the electrolyte layer in
the SOFC devices was removed or replaced with a semi-
conducting layer, whereas the fuel cell functionalities were
maintained or even extended. Accompanying with the quick
material evolution and subsequent cell performance enhance-
ments, some other analogous works like the correlated
perovskite fuel cells23 and transition of electronic conductors
to pure proton conductors in layered lithiated transition metal
oxides24 were reported, which jointly contributed to the
understanding of the working principle or the science behind
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SLFCs for efficient energy conversion.13,16,20,21,25−27 Simplified
materials and straightforward device fabrication technology,
harmonious work environments, and electrical properties are,
on the one hand, stimulating large interests both in the
fundamental study and in the commercialization growth. On
the other hand, the large-scale industrialization and scalability
of SLFCs are still suppressed by the difficulties in the
understanding of the novel fuel cell working principles and
detailed reaction pathways. Considerable efforts have been
applied to digging out the working principle as the electric
short-circuiting problem is avoided in SLFCs using a
semiconducting layer instead of an electronic insulating layer
as the separator. Currently, the p−n junction,13 Schottky
junction (SJ),16 bulk heterojunctions20,25 as well as the
semiconductor energy band alignment similar to perovskite
solar cell principle21 creating by intentionally constructing or
in situ formation under fuel cell atmosphere have been
proposed based on the usage of semiconducting oxides with a
wide band gap,28,29 while the direct evidence or believable/
consensus principle/mechanism is still missing. From the
technical aspect, simple procedures of co-pressing and low-
temperature sintering are generally adopted fabricating the
single-cell unit. The resulting porous structure, which is
required for the formation of a triple-phase boundary, that is,
an active site for the electrochemical reaction, is detrimental to
the fuel cell voltage and energy efficiency because of the fuel
and oxidant crossover. In addition, though proposed as a single
layer, a vital lithiated transition oxide precursor is generally
presented on both sides of the composite layer as a current
collector and electrocatalysts which can enhance the efficiency
of the fuel cell,20,28,30 however, bring the suspicion of
traditional three-layer SOFC configuration. Moreover, the
gradual reduction of the active phase to the metal phase and an
intrinsic porosity may lead to the deterioration of performance
and limitation of the durability of a single cell. Only a few
limited cases reported on the durability under open-circuit
voltage (OCV) conditions and not the actual fuel cell
operational conditions.30−32 In response to this, an initial
attempt was performed to verify the electrochemical perform-
ance and stability of SLFC by using Ni0.8Co0.15Al0.05LiO2
(NCAL) as the semiconducting electrocatalyst, (Li/
Na)2CO3-Sm0.2Ce0.8O2 as the ionic conductor composite,
and NCAL-coated nickel foam as a current collector and
DOI: 10.1021/acsami.9b08448
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electrode. Although it represented an acceptable OCV (∼1.00
V), a promising fuel cell peak power density (428.8 mW
cm−2), and low polarization losses at 550 °C (Figure 1a,b), it
degraded quickly within a few hours, as shown in Figure 1c.
Tremendous efforts have also been established prior to
creating the standardized procedures for SLFC fabrication
and performance testing.33 The issues of the time dependence
of the fuel cell performance and subsequent degradation are
still the barriers to the further implementation of such a
promising technology for energy conversion.27,31,34
Thereby, in the present study, we aim to verify the
operational stability of SLFCs in an extended time. Redox-
stable materials, Pr0.4Sr0.6Co0.2Fe0.7Nb0.1O3−δ (PSCFN)-based
perovskite oxides,35,36 as a proof of concept, are employed to
replace the commonly used, reducing atmosphere phase-
instable lithiated transition metal oxides. The effect of current
collection and enhanced electrode catalytic activity by using
such a lithiated transition-metal oxide functional layer is also
excluded. For further verification of the working principles and
acceleration of the electrochemical reaction, a strategy of in
situ-/ex situ-exsolved metal/alloy nanoparticles socketed on a
perovskite oxide matrix surface10,37,38 is first employed in
SLFCs. The integration of the enhanced electrochemical
performance and extended stability under the real fuel cell
conditions confirm the positive junction role for charge
separation in SLFCs and verify the effective method to
improve fuel cell performance through a simple but effective
material and cell structural design.
2. EXPERIMENTAL SECTION
2.1. Material Fabrication. Pr0.4Sr0.6Co0.2Fe0.7Nb0.1O3−δ (P-
PSCFN) and Pr0.8Sr1.2(Co,Fe)0.8Nb0.2O4+δ (K-PSCFN) were synthe-
sized by using the solid-state reaction (SSR) method and calcinated
under 1050 °C for 5 h based on the procedure provided elsewhere.35
Co−Fe alloy-deposited K-PSCFN (H-PSCFN) was fabricated by
reducing P-PSCFN in 10% hydrogen gas balanced with nitrogen at
900 °C for 10 h. Ni0.8Co0.15Al0.05LiO2 (NCAL) was also obtained by
the SSR technique with hydroxide or nitrate chemical precursors and
annealed in air at 800 °C for 5 h. The required ionic conductor of
Sm0.2Ce0.8O2-(Li/Na)2CO3 (LNSDC) was achieved by mechanical
mixing and subsequent heat-treatment procedures in accordance with
our previous work.39
2.2. Single-Cell Fabrications and Electrochemical Perform-
ance Measures. Five sets of fuel cells in a single-layer or three-layer
configuration were fabricated, as shown in Table 1. All fuel cells were
Table 1. Fuel Cells and Their Compositions Used in This
Work
Cell
number Cell configuration and composition
I nickel foam−NACL/3NCAL−7LNSDC/nickel foam−NACL
II nickel foam−NACL/3(P-PSCFN)−7LNSDC/nickel foam−
NACL
III 3(P-PSCFN)−7LNSDC
IV 3(K-PSCFN)−7LNSDC
V 3(H-PSCFN)−7LNSDC
VI 3NCAL−7LNSDC
as-prepared by a one-step method using a dry-pressing technique in
stainless steel die at 300 MPa for 1 min. Green pellets except the H-
PSCFN-based single cells were sintered in air at 700 °C for 2 h to
reduce porosity and to achieve sufficient mechanical strength. The
total thickness of the single cells was around 1 mm. Both sides were
coated with a silver paste as a current collector (DAD-87, Shanghai
Research Institute of Synthetic Resin, China). The single cells were
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then mounted at one end of an aluminum oxide ceramic tube with a
high-temperature ceramic glue and then heat-treated in a tube furnace
from room temperature to the desired temperature at a ramp rate of 5
°C min−1 in air before being subjected to an H2/air atmosphere,
whereas the H-PSCFN cells were directly subjected to an H2/air
atmosphere from the room temperature to stabilize the exsolved
metal−oxide nanocomposite. Fuel cell electrochemical performance
studies were performed on an electrochemical workstation (Solartron
potentiostat 1260A plus impedance analyzer 1470E, England). The
voltage−current density curves, which are the polarization curves,
were recorded from OCV to 0 V at a ramp rate of 50 mV s−1. The
current responses under a constant voltage of 0.7 V were obtained to
identify the operational durability under the actual fuel cell
atmosphere. Electrochemical impedance spectroscopy (EIS) was
also performed under an OCV with an amplitude of 50 mV and a
frequency range of 100 kHz to 0.01 Hz. The obtained EIS curves were
fitted with an empirical equivalent circuit model to obtain the detailed
electrode reaction and ionic transport polarization resistances. The
current responses under the voltage bias (−2 to ∼2 V) of NCAL and
H/K-PSCFN-based SLFC components in different gas atmospheres
were also recorded to identify the possible rectification effect of the
resultant physical junction and to conclude with a possible working
principle.
2.3. Other Physical and Chemical Characterizations. Powder
X-ray diffraction (XRD) analysis of all samples was carried out on a
Rigaku Dmax/Ultima IV diffractometer (Bruker D8 ADVANCE,
Germany) with monochromatized Cu Kα radiation (λ = 1.54056 Å)
to investigate the changes in the physical phase structure. To check
the compatibility of perovskite oxide with LNSDC ionic conductors,
mechanical mixing of perovskite oxide and LNSDC and then
calcination at 700 °C for 2 h were carried out. The microstructures
and morphologies were observed by using a field emission scanning
electron microscope (SEM, JSM-7800F & TEAM Octane Plus) with
an accelerating voltage of 15 kV. The texture and lattice parameters of
the obtained perovskite oxide and composites were investigated by
using a transmission electron microscope (TEM, JEM-2100 & X-
Max80) with an accelerating voltage of 200 kV. X-ray photoelectron
spectroscopy (XPS) measurements were performed using an
ESCALAB 250Xi spectrometer under an ultrahigh vacuum,with Al
Kα radiation, (1486.6 eV) and a multichannel detector to study the
surface oxygen vacancy content and other elements’ valence
information. All the collected binding energies were calibrated by
using the C 1s peak at 284.6 eV as the reference with an uncertainty
of ±0.2 eV.
3. RESULTS
In terms of the insufficient stability of NCAL-based SLFCs
because of the gradual reduction of the metal oxide to the
metal phase, the redox-stable p-type perovskite PSCFN−
LNSDC is used to replace NCAL−LNSDC in the middle of
the SLFC to construct a non-conventional three-layer fuel cell
NCAL/p-PSCFN−LNSDC/NCAL (cell II). The fuel cell
performance at 550 °C is shown in Figure 2. An OCV of 0.98
V and a peak power density up to 238 mW cm−2 are achieved
at 550 °C, suggesting the functionality of the P-PSCFN
semiconductor and an acceptable electrocatalytic activity for
SLFC, though the maximum power output is lower compared
to the NCAL-based cells (cell I). The latter is possibly owing
to the inferior catalytic activity and ionic conductivity of
perovskite oxide compared with the NCAL materials, as
reflected by the EIS study. Cell II gives an ohmic and electrode
polarization resistance of 0.55 and 0.57 Ω cm2, respectively,
based on the EIS study and fitting results (Figure 2b).
Notwithstanding, it is interesting to see that cell II gives a
relatively stable performance up to 24 h around 170 mA cm−2
under a constant operational voltage of 0.7 V (Figure 3c),
making P-PSCFN as an attractive semiconductor to replace
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Figure 2. (a) I−V and I−P polarization curves, (b) impedance curves of fuel cells with a configuration of NCAL/PSCFN−LNSDC/NCAL cells at
550 °C, and (c) chronopotentiometric stability test of the corresponding cells at 0.7 V.

NCAL for durable SLFCs, also suggesting the feasibility for
future applications.
Figure 3. (a) Cell voltage and power density as functions of current
density, (b) impedance spectra under OCV condition, and (c) short-
term stability under a constant voltage of 0.7 V of SLFCs (cell III to
V) with the P/K/H-PSCFN semiconducting electrocatalyst and
LNSDC ionic conductor under fuel cell atmosphere at 600 °C.
In spite of the positive role of NCAL for SLFC, the easy
reduction characteristics under the real fuel cell conditions still
query the chemical/thermal compatibility and long-term
stability. In addition, similar to the conventional Ni-based
cermet anode in SOFC, the redox problem and possible
carbon deposition issue with the hydrocarbon fuel remain.
Therefore, real SLFCs (cell III−V) with P-PSCFN, K-PSCFN,
and surface alloy-precipitated K2NiF4-type structured H-
PSCFN semiconductors combined with the ionic conductor
LNSDC respectively, which are free from the nickel foam-
supported NCAL functional layers, are then built. All fuel cells
give OCVs higher than 0.90 V at 600 °C under an H2/air
atmosphere (Figure 3a); the value is even higher than that of
the benchmarked SOFCs with mixed ionic and electronic
conducting doped ceria electrolytes whose OCV values are
never larger than 0.90 V when the temperature is above 450
°C,40 suggesting the realizing of fuel cell functionality with the
semi-ionic conducting core materials in true SLFCs. Moreover,
it is worthy to mention that SLFCs with H-PSCFN show the
highest electrochemical performance, in terms of both the
OCV value and peak power output, among all fuel cell samples
under identical operational conditions. The fuel cell peak
output of SLFCs has the following sequence: cell V (161.80
mW cm−2) > cell IV (130.47 mW cm−2) > cell III (77.60 mW
cm−2) at 600 °C, though they are lower than the initial
performance of NCAL-based cell (cell I) and pseudo-SOFC
with the NCAL current collector or catalytic layers (cell II).
Irrespective of the enhanced OCV value, the improved
electrode activities of K-PSCFN and H-PSCFN could explain
the increased peak fuel cell performance, as reflected by the
much reduced electrochemical impedance (Figure 3b), which
were fitted by using the empirical equivalent circuit (LR0(R1/
CPE1)(R2/CPE2)) model (Figure S1), and the results are
summarized in Tables 2 and S1. The cell V with H-PSCFN
semiconductor gives the lowest Ohmic and electrode polar-
ization resistances, followed by the cell IV with K-PSCFN,
whereas cell III using P-PSCFN shows the largest polarization

Table 2. Summary of the Electrochemical Performances (OCV, Peak Power Density/Pmax, Ohmic and Electrode Polarization
Resistance, and Fuel Cell Short-Term Stability) of SLFCs with Various Semiconducting Materials at 600 °C

Cell Semiconductor OCV (V) Pmax (mW cm−2) Ro (Ω cm2) Rp (Ω cm2) Rtotal (Ω cm2) Durability (h)
III P-PSCFN 0.93 77.60 1.10 1.19 2.29 45/52
IV K-PSCFN 0.95 130.47 0.71 1.22 1.93 7.5
V H-PSCFN 0.97 161.80 0.62 0.95 1.57 24.5

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loss under OCV condition. Notably, no metal exsolution

appears below 700 °C, as reflected by the H2 temperature-
programmed reduction (H2-TPR) analysis (Figure S2), and
the morphology of Co−Fe nanoalloy-socketed PSCFN oxide is
preserved after a heat treatment under an oxidizing atmosphere
(in air) at 600 °C for 3 h (Figure S3), which leads to different
reaction activities and fuel cell performance between P-PSCFN
and H-PSCFN and their cells in this study. An extended period
stability testing of SLFCs with different semiconducting
materials and the LNSDC composite under an identical
operational potential of 0.7 V was also performed, and the
results are shown in Figure 3c. All of the tested samples
showed a relatively stable current response under a constant
voltage of 0.7 V/600 °C and a real fuel cell condition for a
short-term period. In particular, SLFCs with P-PSCFN present
a stable current up to 45 h (totally 52 h) before a fluctuation
takes place because of the hydrogen gas pressure drop caused
by the technical issue of the on-site hydrogen gas supplier. This
is evidently better than the SLFCs with NCAL core materials,
as shown in Figure 1b. The significantly improved operational
stability can be attributed to the redox-stable phase structure,
at least the well-maintained oxide phases of the applied
perovskite oxide semiconducting materials. These initial results
Figure 4. Temperature dependence of the SLFC cell V’s electro-
demonstrate once again the strong potential of using the
chemical performances: (a) polarization curves and (b) correspond-
redox-stable perovskite phase as an alternative to the ing impedance spectra response.
commonly used phase-unstable materials and expanding the
choice of material for the newly developed SLFC technology.
In fact, besides the good material redox properties, sufficient
chemical compatibility between versatile PSCFN semiconduc-
tors and LNSDC ionic conductors heat-treated at 700 °C for 2
h in air based on the XRD pattern investigations, as shown in
Figure S4, also ensures the stable performance. In addition,
typical Co−Fe alloy diffraction peaks that appeared around
44.8° and 65° (JPCDS 00-049-1568) are observed in the XRD
pattern of H-PSCFN, which agrees with the previous study.35
The formed alloy nanoparticles can elucidate the improved
electrocatalytic activity and subsequently the improved fuel cell
efficiency over P-PSCFN. Moreover, the exsolved metal on the
parental PSCFN semiconductors could form metal/semi-
conductor interface or junction in situ and can contribute to
charge separation and transfer capability, which will be
provided in detail in the Discussion section.
The effect of operating temperature on the electrochemical
performance of SLFCs based on the H-PSCFN semiconductor
(cell V) is shown in Figure 4. The corresponding OCVs and
peak power outputs are attributed to 0.95, 0.97, and 1.02 V and
247.85, 161.80, and 136.38 mW cm−2 at 650, 600, and 550 °C,
respectively (Figure 4a). As expected, both the Ohmic and
reaction polarization resistances reduce as the operating
temperature increases, leading to improvement in the
characteristics of the fuel cell at elevated temperatures (Figure
4b). After a short time operation, porous anodic and cathodic
zones and a relatively dense middle layer could be found
(Figure S5), which allow rapid gas diffusion and good physical
gas separation for the functionality of fuel cell. Figure 5. (a) SEM and (b) high-resolution TEM images of the H-
A deep look into the morphology and texture of the PSCFN material. Inset is the EDX element analysis.
nanometal/alloy-exsolved H-PSCFN by scanning electron
microscopy (SEM) and transmission electron microscopy those of P-PSCFN and K-PSCFN with a smooth particle
(TEM) confirms that well-distributed nanoparticles with a surface, as shown in Figure S6a,b, agreeing with previous
diameter of 30−40 nm are thermodynamically exsolved on the work.35 The tiny nanoparticles are indexed to the Co−Fe alloy
surface of the perovskite oxide matrix after being treated in a according to the high-resolution energy-dispersive X-ray
reducing atmosphere at a temperature of 900 °C, as shown in spectroscopy (EDX) mapping elemental analysis, and Co−Fe
Figure 5. This surface morphology is clearly different from alloy nanoparticles with the calculated atomic ratio of Co to Fe
27928 DOI: 10.1021/acsami.9b08448
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Figure 6. High-resolution XPS spectra of the O 1s spectrum: (a) P-PSCFN, (b) K-PSCFN, (c) H-PSCFN, and (d) ratio of the deconvoluted
surface oxygen vacancy to lattice oxygen concentration and of (e) Co 2p and (f) Fe 2p spectra of the H-PSCFN sample.
of about 1:1 upon intentional reduction are generated as in the
inset of Figure 5b. The high-resolution TEM image of H-
PSCFN showed a distinct fringe with an interplanar lattice
spacing of ∼0.202 nm, corresponding to the (110) plane of the
Co−Fe alloy (inset of Figure 5), again confirming the
formation of Co−Fe alloy in H-PSCFN. Furthermore, the
homogeneous distribution of the elements is confirmed by the
EDX elemental mapping analysis for H-PSCFN (Figure S7a−
h).
4. DISCUSSION
In this work, we propose using redox-stable materials based on
perovskite oxide as semiconductor materials and its composite
with high ionic conductors as key materials for SLFCs. The
phase-stable structure clearly improves the durability of the
electrochemical characteristics under real fuel cell condition
compared to the easily reducible NCAL materials, although the
fuel cell performance is sacrificed. The initial results
demonstrated a promising direction for the development of a
facile but reliable SLFC for future deployment.
We can also conclude that the application of a higher
electrocatalytically active K2NiF4-type and surface alloy-
deposited oxides enhance the performance of the SLFCs
(cells IV and V) under identical operating conditions
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compared to the fuel cell using ABO3 simple oxide (cell III).
This phenomenon can be elucidated by the following aspects:
(1) the increased ratio between the surface oxygen vacancy/
adsorbed oxygen content and the lattice oxygen concentration
in K-PSCFN and H-PSCFN complex oxides over the single
perovskite P-PSCFN oxide, as clarified in Figure 6a−d.
Generally, two oxygen peaks are observed in the XPS spectra
of the O 1s spectrum for all of the PSCFN samples, attributed
to 528.7 and 531.0 eV. The former corresponded to the lattice
oxygen, also known as β-oxygen; the latter is indexed to the
oxygen species adsorbed or loosely bonded oxygen (normally
correlated with the surface oxygen vacancies), known as α-
oxygen, which is believed to be the active site for the surface-
adsorbing oxygen molecule.41,42 The ratio between the
cumulative amount of α-oxygen peak and β-oxygen peak,
reflecting the relative oxygen vacancy concentration in the
sample, increases from 0.88 in P-PSCFN to 0.94 in K-PSCFN
and then to 1.37 for the H-PSCFN sample. The higher the
ratio, the better the oxygen surface exchange efficiency or
oxygen reduction activity is expected.43,44 In particular, the
reduction of P-PSCFN to H-PSCFN leads to a significant
increase in the concentration of oxygen vacancies on the oxide
surface (Figure 6d), which reinforces the gas exchange
coefficient between the gas and the oxide surface,42,45,46 and
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consequently reduces the electrode polarization resistances, as

reflected in Figure 3b; (2) the electrical conductivities of H-
PSCFN and K-PSCFN are reduced35 compared to that of P-
PSCFN, which accidentally makes a good balance of the
electronic and ionic conductivities in the composite and helps
to improve the voltage efficiency and the SLFC perform-
ance;47,48 (3) possible proton intercalation/conduction in the
layer-structured oxide under fuel cell conditions increases the
additional ionic conductivity and length of the triple-phase
boundary of the electrode and subsequently improves the
reaction kinetics and fuel cell performance.49−51 Furthermore,
the presence of Co−Fe metal/alloy nanoparticles in the range
of 30−40 nm on the surface of the perovskite oxide matrix, as
shown in Figure 5, also reflected by the presence of the metal
state/zero valence state in the Fe 2p and Co 2p XPS spectra of
the H-PSCFN (Figure 6e,f) whereas absence in the
corresponding spectra of P/K-PSCFN samples (Figure S8),
significantly improves the anodic activity of hydrogen
oxidation. This approach, in fact, has been demonstrated as a
promising strategy for improving the electrochemical activity
of perovskite oxide while maintaining/obtaining the nano-
structures at elevated temperatures under extremely harsh fuel
cell condition. The research topic recently has been the focus
of the SOFC community10,38,44,46,52 and other related
fields53,54. Consequently, these factors co-contribute to
enhancing the efficiency of fuel cells. Integrating with the
intrinsic chemical and structural stabilities of the oxide Figure 7. (a) Response current as a function of voltage bias for the H-
structure, SLFCs based on the aforementioned redox-stable PSCFN-based SLFCs (cell V) in air, H2/N2, and H2/air atmospheres,
perovskite oxides show promising applications toward the next respectively and (b) proposed SLFC working principle from the
deployment phase. physical junction aspect, including bulk p−n junction (right) formed
Another possible role of the precipitated metal/alloy on the under H2/air fuel cell atmosphere and metal−semiconductor Schottky
semiconducting perovskite oxide matrix is to form the physical barrier by in-situ surface exsolved metal nanoparticle on perovskite
metal−semiconductor interaction, that is schottky junction oxide (left).
(SJ) or internal built-in electric field, to help block the electron
transport through the SLFC bulk, in the meanwhile, to based on the p−n junction working principle.18,25 The linear
improve the ionic transport capability through the composite response of cell V (not cell IV) under negative bias and H2/air
bulk.16,55,56 The former effect, in turn, enhances the OCV of condition may be caused by the dissolution of the alloy
SLFCs instead of causing the internal short-circuit problem, as nanoparticle in H-PSCFN upon the negative voltage bias,10
shown in Figure 3a. To identify the SJ formation instead of an which reduces the junction effect. Furthermore, the rectifica-
Ohmic contact, ex situ checks of the voltage bias (−2 to 2 V)− tion response appears under the N2/air atmosphere, which
current responses for cell IV with the K-PSCFN−LNSDC might be caused by another physical junction effect, the metal/
composite, cell V using the H-PSCFN−LNSDC composite, semiconductor contact or SJ (Figure 7b, left). Similar to the
and cell VI with the NCAL−LNSDC composite in N2/air, H2/ p−n junction, a built-in electric field is also formed in SJ
N2, and H2/air (fuel cell) atmospheres at 600 °C were because of the different work functions between metal and
performed. For cell VI, the rectification response can only be semiconductor. The presence of the oxygen partial pressure
observed in H2/air condition; a nearly linear response of difference and the remaining surface Co−Fe alloy nano-
current to voltage is observed in the air (Figure S9a), which particles/semiconducting K-PSCFN in air at less than 600
clearly follows the Ohmic law, reflecting no junction response. °C58 (also see Figure S3) promote the generation of SJ at fuel
However, for cell IV and cell V, a clear rectification response in side which may help relievethe electronic conducting short-
the I−V characteristics appears as shown in Figures 7a and circuit issue of SLFC.
S9b, respectively, regardless of the applied atmospheres. In The distinct response of cell V with the alloy nanoparticle-
other words, the current increases exponentially with a forward deposited H-PSCFN over cell III and VI, even in the air
voltage bias, whereas the current increases first and is then atmosphere, supports the formation of Schottky contact rather
stably maintained with an increased negative voltage bias. In than Ohmic contact at the alloy nanoparticle−semiconductor
fact, PSCFN has been employed as a symmetrical electrode in interface16,59, which joins with the bulk p−n junction formed
SOFC;57 it possesses both the electron- and hole-conducting under a specific atmosphere reinforcing the charge separation
properties which are strongly sensitive to the applied gas to prevent the electronic conduction through the bulk.
atmosphere. In this context, under certain specific conditions Integrating the advantages of the improved electrode reaction
of H2/air or H2/N2 and even in an atmosphere with oxygen activity or kinetics and charge separation capability, the cell V
concentration (N2/air), a bulk heterojunction (p−n) can be obtains the best OCV and electrical efficiency among all
formed in situ, as illustrated in the right part of Figure 7b, to samples. On the basis of the experimental observations and
build the fuel cell electric field, and consequently to relieve the analyses, an illustration of a possible working principle of SLFC
internal short circuit issue, similar to the photovoltaic effect is therefore proposed in Figure 7b. A gas-responded metal−
27930 DOI: 10.1021/acsami.9b08448
ACS Appl. Mater. Interfaces 2019, 11, 27924−27933
ACS Applied Materials & Interfaces
semiconductor interface or SJ is in situ formed on the fuel side,
which combines with the formed bulk p (PSCFN in oxygen
atmosphere)/n (PSCFN under hydrogen gas) junction in a
specific H2/air fuel cell atmosphere to block the electronic
transport through the composite bulk or the internal SLFC,
leading to an enhanced OCV or providing a solution to the
electronic short-circuit problem. Consequently, SLFCs based
on mixed ionic and electronic conductors exhibit the same
functionality as that of conventional fuel cells with an
electronic insulating electrolyte layer.
5. CONCLUSIONS
In this work, phase-structured redox-stable perovskite oxides
and their derivatives are employed to replace conventional
lithiated metal oxides as key semiconducting materials
designed for reliable SLFCs. Though their fuel cell perform-
ances are lower than that in the latter case, the stability is
significantly improved. In particular, cell III with the P-PSCFN
semiconductor and electrocatalyst showed a durable perform-
ance for more than 2 days of constant voltage testing, which
takes the first step toward durable SLFC technology. Improved
electrochemical performances are also achieved via regulating
oxygen vacancies and metal/alloy nanoparticle exsolution. The
generated SJ, that is the metal/semiconductor contact,
combining with the in situ formed p−n junction, not only
promotes the anode hydrogen oxidation reaction kinetics but
also benefits the charge separation to improve the voltage
efficiency and the ionic transport through the internal built-in
electric fields. These reduce the ohmic loss and electrode
reaction polarization resistance simultaneously, consequently
enabling the best electrical efficiency. This work also acts as the
first attempt focusing on the stability of the SLFCs for practical
application. Further development of phase-structured stable
higher electroactive semiconductors and ionic conductors and
study of the impact of the precipitated nanoalloys/metal
contents on the fuel cell performance for higher electro-
chemical efficiency and extended durability are highly desired.
These issues as well as the elucidation of the underlying
mechanism of their potential degradation in SLFCs under real
fuel cell conditions will be investigated and introduced in the
future work.
■ ASSOCIATED CONTENT
* Supporting Information
S
The Supporting Information is available free of charge on the
ACS Publications website at DOI: 10.1021/acsami.9b08448.
Material characterization: RT-XRD patterns of P-
PSCFN, K-PSCFN, H-PSCFN, and their composites
with LNSDC after being treated at 700 °C for 2 h in air;
SEM images of P-PSCFN, K-PSCFN, H-PSCFN,
LNSDC, NACL, and reoxidized H-PSCFN in air at
600 °C for 3 h, and the cross section of SLFC after
testing; EDX elemental (survey, O, Pr, Sr, Co, Fe, and
Nb) mapping of H-PSCFN; XPS high-resolution spectra
of Co 2p and Fe 2p of K-PSCFN and P-PSCFN; H2-
TPR of P-PSCFN (0−1000 °C); applied equivalent
circuit model for EIS fitting; voltage−current curves of
NCAL−LNSDC and K-PSCFN−LNSDC single layers
under different atmospheres to identify the possible
metal−semiconductor junctions; and EIS fitting results
using the equivalent circuit model of Ro/R1(CPE1)/
R2(CPE2) with the assistance of ZView software (PDF)
27931
Research Article
■ AUTHOR INFORMATION
Corresponding Author
*E-mail: fanld@szu.edu.cn.
ORCID
Liangdong Fan: 0000-0002-5485-9553
Author Contributions
The manuscript was written through the contributions of all
authors. All authors have given approval to the final version of
the manuscript.
Notes
The authors declare no competing financial interest.
■ ACKNOWLEDGMENTS
Financial support from the Natural Science Foundation of
Guangdong Province (2017A030313289), Shenzhen Govern-
ment’s Plan of Science and Technology (nos.
JCYJ20170302141158010 and JCYJ20180305125247308),
and National Natural Science Foundation of China (nos.
21706162 and 51402093) are acknowledged. The authors also
thank the Instrumental Analysis Center of Shenzhen University
(Xili Campus) for help.
■
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27933 DOI: 10.1021/acsami.9b08448

ACS Appl. Mater. Interfaces 2019, 11, 27924−27933