Full paper
Bifunctional Catalysts
Intrinsic Effects of Ruddlesden-Popper-Based Bifunctional
Catalysts for High-Temperature Oxygen Reduction
and Evolution
Yu Huan, Shouxiao Chen, Rui Zeng, Tao Wei,* Dehua Dong, Xun Hu,
and Yunhui Huang*
Unveiling the intrinsic effects of Ruddlesden-Popper (RP) series An+1BnO3n+1
(A = La, B = Ni, Co, Mn, Cu, n = 1, 2 and 3) catalysts is essential in order
to optimize the activity of oxygen reduction reaction (ORR) and evolution
reaction (OER). Here, it is demonstrated that the oxygen vacancy is not the
key point for RP to realize high ORR and OER activity at high temperature.
Instead, interstitial O2− with high concentration and fast migration, and
lattice oxygen with high activity are favorable for the high-temperature
catalytic activity. Aliovalent cation doping is an effective strategy to modify
the catalytic activity. For the RP catalysts, low-valence ion doping does not
introduce oxygen vacancies, which suppresses the activity of lattice oxygen
and decreases the interstitial O2− concentration; whereas high-valence ion
doping enhances the interstitial O2– concentration and the lattice oxygen
activity. The evaluations of six RP series (La2NiO4, La2CoO4, La3Co2O7,
La4Ni3O10, La2MnO4, and La2CuO4 based) and twenty samples as oxygen
electrodes for solid oxide fuel cells (SOFCs) and solid oxide electrolysis cells
(SOECs) demonstrate that this finding is applicable to all the selected RP
series.
1. Introduction
Driven by growing renewable energy demands, developing
alternative energy conversion and storage systems with high
efficiency, low cost, and environmental benignity represents a
major scientific challenge.[1] A critical element in the pursuit
of this challenge is the discovery of highly efficient and cost-
effective oxygen catalysts for electrochemical energy conversion
Dr. Y. Huan, S. Chen, Prof. T. Wei, Dr. D. Dong, X. Hu
School of Material Science and Engineering
University of Jinan
331 Nanxinzhuang West Road, Jinan, Shandong 250022, China
E-mail: mse_weit@ujn.edu.cn
R. Zeng, Prof. Y. Huang
State Key Laboratory of Material Processing and Die and Mould
Technology
School of Materials Science and Engineering
Huazhong University of Science and Technology
Wuhan, Hubei 430074, China
E-mail: huangyh@hust.edu.cn
The ORCID identification number(s) for the author(s) of this article
can be found under https://doi.org/10.1002/aenm.201901573.
DOI: 10.1002/aenm.201901573
Adv. Energy Mater. 2019, 1901573 1901573 (1 of 9)
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devices. There are two main types of
reverse electrochemical reactions occur-
ring on the surface of the oxygen catalysts,
oxygen reduction reaction (ORR)[2] and
oxygen evolution reaction (OER).[3] The
current bottleneck for many renewable
energy technologies with ORR (including
solid oxide fuel cells (SOFCs)) or OER
(such as solid oxide electrolysis cells
(SOECs)) lies in the low-oxygen kinetics.[4]
Many studies have demonstrated that
precious metals are excellent oxygen cata-
lysts. For example, Pt and its alloys have
been considered as the state-of-the-art
ORR catalysts while RuO2 and IrO2 as the
OER catalysts with fast kinetics.[5] How-
ever, their high cost and activity decay
prohibit the widespread use in practical
applications. The exploration of ORR and
OER catalysts with high efficiency and
low cost for accelerating the multistep
electron transfer is highly desirable.[1b,6] A
class of promising catalysts in the form of
binary oxides, such as Co3O4 or Mn3O4, have been used to cata-
lyze ORR and OER with moderate overpotentials.[7] Perovskite
metal oxides with high oxygen catalytic activities are considered
as alternative bifunctional catalysts for both ORR and OER.[8]
To enhance the activity and the stability of the perovskite elec-
trodes, strategies such as nanostructure engineering and surface
treatment have been successfully applied to tailor the physical
and chemical properties. Moreover, numerous independent
groups reported that the low-valence cation doping at A and/
or B sites is a rational strategy to introduce oxygen vacancies
in the perovskites.[9] For example, divalent Sr2+ doping at the
trivalent La3+ (A) site of La0.8Sr0.2MnO3[9a,10a,b] and Fe3+ doping
(or substituting) at the Mo6+ (B) site of Sr2Fe1.5Mo0.5O6−δ both
create high oxygen deficiencies and demonstrate excellent ORR
and OER performances for SOFCs and SOECs.[11] Thus low-
valence doping is applicable for the perovskite-type catalysts
to enhance the intrinsic oxygen catalytic ability by introducing
oxygen vacancies.
The Ruddlesden-Popper (RP) series exhibit mixed oxygen-
ionic and electronic conductivity, which have promising ORR
and OER applications for high-temperature SOFC/SOEC
electrodes,[12] ceramic membranes and low-temperature
Li-air battery electrodes, and sensors.[13] Substitution with
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high-valence Fe or Co ions at Ni sites in La2NiO4 can take effect
on the oxygen ionic transportation,[14] while low-valence Sr2+
doping at La3+ sites in La1.2Sr0.8MnO4+δ can monitor the oxygen
interstitial defects.[12a]
Although the aliovalent ion doping strategy (including dif-
ferent radii and electronegativities) has been widely employed
in the RPs, the intrinsic effects for ORR and OER are still
not very clear and should be verified. Here, we systematically
investigate the intrinsic effects of aliovalent ion doping on the
ORR/OER activities for the RP series An+1BnO3n+1 (n = 1, 2
and 3) electrodes. As high-temperature bifunctional catalysts,
the oxygen vacancy is not the key point for the RPs to realize
high ORR and OER activity; instead, the interstitial O2− (in the
AO layers) with high concentration and low activation energy,
and the lattice oxygen (in the perovskite-like layers) with high
activity are favorable to enhance both ORR and OER activity. In
our case, it is interesting that the aliovalent ion doping strategy
shows an opposite effect for the RPs as compared with the
perovskites, though they have some structural similarities.
2. Results
Crystal structures and lattice parameters of Ruddlesden-
Popper-type An+1BnO3n+1 are obtained by structural refine-
ments, as shown in Figure S1 (Supporting Information). For
n = 1, Figure 1A shows the XRD patterns of La2NiO4 and
La2CoO4 with tetragonal (I4/mmm) and orthorhombic (Abma)
symmetries. Figure 1B,C shows the obtained crystal structure,
Figure 1. A) The refined XRD data of La2NiO4 and La2CoO4. B,C) The schematic program of La2NiO4 and La2CoO4 structures with tetragonal and
orthorhombic symmetry. D,E) Possible transporting channels for oxygen ions in AO layers and electrons + oxygen ions in perovskite-like layers.
F,G) The schematic program of La3Ni2O7 and La4Ni3O10 crystal structure.
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which consists of alternating rock-salt AO (La2O2) layers and
perovskite-like (BO6) layers along the c-axis. Corner-shared
BO6 octahedrons build the perovskite-like layers and then are
sandwiched by two AO layers. Along the ab plane, the rock-salt
AO sheets are electron insulating and leave favorable trans-
porting pathways for interstitial O2− ions (Figure 1D). The BO6
octahedra are neatly arranged in La2NiO4 and have a slightly
twisted orientation in La2CoO4. Electronic transportation occurs
predominantly along the 2D perovskite-like sheets. Although
the perovskite-like layers do not allow for the existence of the
interstitial O2− ion,[10b] the alterable oxidation state of the B-site
cations accelerates the lattice oxygen diffusion via the MO6
octahedral structure, as shown in Figure 1E. Here, the O2−
transportation via the 3D channels is essentially determined by
the hopping mechanism in the perovskite-like layers and the
interstitial O2− migration mechanism in the rock-salt layers.
For n = 2, two-layer corner-shared BO6 octahedra build the
perovskite-like layers in typical La3Ni2O7, which are sandwiched
by two AO layers (Figure 1F). For n = 3, two-layer and three-
layer corner-shared BO6 octahedra build the perovskite-like
layers and arrange alternately in typical La4Ni3O10, and each of
the perovskite-like layers is also sandwiched by two AO layers
(Figure 1G).
The effects of oxygen vacancy, interstitial O2− concentration
and lattice oxygen on the ORR/OER activities were investi-
gated. Representative electrochemical impedance spectroscopy
(EIS) spectra performed on model cells are shown in Figure 2.
The oxygen diffusion mechanism was checked by examining
oxygen migration paths through the rock-salt layers and across
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Figure 2. A) Schematics of the model cell setup for LSCF, LNO110 and LNO001 film electrodes EIS measurement. B) SEM of smooth LNO110 surface.
C–F) Schematic and TEM characterizations for (110) and (001) crystal faces, respectively. G) Nyquist plot measured in air at 600 °C. H) Oxygen surface
exchange coefficient kq with temperature dependence. I) Oxygen partial pressure (ranges from 1 to 10−3 bar) dependence of the kq testing at 600 °C.

the perovskite-like layers. Here, the objective is to provide
critical insight into the mechanism how interstitial oxygen, lat-
tice oxygen and oxygen vacancies affect the ORR activity of RP
series oxides. La2NiO4 (compared with La0.6Sr0.4Co0.8Fe0.2O3
(LSCF)) thin films synthesized by pulsed laser deposition (PLD)
were used as the model electrodes. We compare the ORR activi-
ties of La2NiO4 with exposing (110) and (001) (in short, LNO110
and LNO001) crystal faces and LSCF electrodes working at dif-
ferent temperatures and oxygen partial pressures by evalu-
ating their EIS properties. The EIS was measured based on the
model cells with the thin-film electrode as working electrode,
YSZ as electrolyte substrate, porous Ag-YSZ as counter elec-
trode, and porous Au as current collector (see Figure 2A). The
as-prepared LNO110 film has very smooth surface (Figure 2B).
In Figure 2C,D, the local structure information determined by
TEM demonstrates the [110] orientation of La2NiO4 film. The
rock salt layer (diagram of [110] orientation) is exposed for
interstitial oxygen ions transportation. Particularly, in order
to understand the impact of oxygen vacancy on the overall
ORR performance, LNO001 film electrode was fabricated
(Figure 2E,F). We find that LNO110 exhibits much higher ORR
activity compared with LNO001 (Figure 2G), which is attrib-
uted to the interstitial oxygen in the rock-salt layer. For com-
parison, the oxygen exchange coefficients kq of the three film
electrodes in air at different temperatures were calculated from
the ORR area-specific resistance (ASR) (Figure 2H). LNO110
demonstrates a pronounced enhancement of kq value compared
to LNO001, indicative of the higher kinetic for oxygen reduction
reaction. The dependence of kq on oxygen partial pressure for
the LNO and LSCF is fitted using Equation (1)
k q ∝ POm2 (1)
in which PO2 is the oxygen partial pressure. The exponent m
can provide information about the rate-limiting step for ORR
kinetic. The reaction steps with the noticeable changes of cor-
responding exponent m can be described as follows[15]
O2,gas ↔ O2,ads ; m =1 (2)
O2,ads ↔ 2Oads ; m = 0.5 (3)
O2,ads + 4e − + 2Voxy
′′
↔ 2Ooxy
x
; m = 0.25 (4)
As shown in Figure 2I, the m values for LSCF and LNO001
film electrodes are close to 0.5, indicating that the dissociation
from molecular oxygen to atomic oxygen (Equation (3)) is likely
the rate-limiting step. The m value for LNO110 is 0.309 between
0.5 and 0.25, implying that the rate of ORR may be limited by
both oxygen dissociation and charge-transfer process. Herein,
our EIS results give the evidence that the (110) and (001)
crystal faces of LNO critically influence the kinetics of ORR
because of the different oxygen transporting mechanism. The
lower EIS for LNO110 film electrode confirms the importance

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Figure 3. A) Room temperature electron paramagnetic resonance analysis of RP electrodes, with Ba0.5Sr0.5Co0.8Fe0.2O3 as a reference. B) Schematic
of the {100}, {010}, and {110} surfaces (Line 1) in rock-salt layer, and the {001} surface across the perovskite-like layer (Line 2). C) Interstitial oxygen
and oxygen vacancy formation energies for oxygen ions transportation in bulk La2NiO4. D,E) Schematic of possible oxygen vacancies in perovskite-like
layer of LNO and in perovskite LSCF.
of interstitial oxygen ions for ORR reaction. As we know, the
perovskite LSCF can accommodate many oxygen vacancies in
the BO6 octahedra. The EIS value for LSCF film electrode is
higher than LNO110 but lower than LNO001, demonstrating the
positive role of oxygen vacancy in ORR reaction. The highest
EIS for LNO001 means that the oxygen vacancy in the perovs-
kite-like layer is not existent or can be ignored.
The electron paramagnetic resonance (EPR) spectra were
further used to evaluate the existence of oxygen vacancies in
the perovskite-like layers, as shown in Figure 3A. With Ba0.5S
r0.5Co0.8Fe0.2O3 as a reference, the main signal at g = 2.0 can
be assigned to the high content of oxygen vacancy. For the
Sr2+ (un)doped La2CoxNi1−xO4 samples, no apparent peaks
are observed, indicating the absence of oxygen vacancy. Theo-
retical computation (more details in supporting information)
was conducted for the formation energy Evac of oxygen vacancy
and interstitial oxygen in LNO. In LNO, interstitial oxygen ions
are tetrahedrally coordinated by La ions and located in the LaO
layers, and the paths for migration of the interstitial oxygen
ions are shown in Figure 3B. As previously discussed,[16] Line
1 shows the interstitial mechanism and Line 2 shows the trans-
port from an interstitial site occurring via displacement of
lattice oxygen (O2) to the next interstitial site. The activation
energies for interstitial oxygen migration via three directions
within the LaO plane are presented in Figure 3C. The energy
barriers for interstitial oxygen migration are 0.58 eV along the
[100] direction, 0.34 eV along the [010] direction, and 0.49 eV
along the [110] direction. Across the perovskite-like layer, the
activation energy of interstitial oxygen migration along [001]
direction (Line 2) is 1.85 eV, significantly higher than Line 1
(oxygen migration via a direct path between two interstitial
sites). For La2NiO4, the lattice oxygen O1 ions are coordinated
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to one Ni ion and three La ions, and the lattice oxygen O2 ions
are coordinated to two Ni ions and four La ions (Figure 3D).
The formation of an oxygen vacancy is found to be more ener-
getically favorable at an equatorial (O2) site than an apical (O1)
site, and the formation energy for both defects is very high
(Figure 3C). The formation energy of O1 vacancy is 5.07 eV,
corresponding to an extremely low oxygen chemical potential.
The oxygen vacancy formation energy at the O2 site is 4.33 eV,
lower than that at the O1 site, which is in good agreement
with previous reports.[17] The lower formation energy of the O2
vacancy may be due to the less distortion around the vacancy
compared to the O1 site. For comparison, the calculated oxygen
vacancy formation energy in LSCF is 3.47 eV, much lower than
that in LNO (Figure 3C,E). Interstitial oxygen formation is sig-
nificantly lower in energy than oxygen vacancy formation. In
conclusion, for the perovskite-like layer, the oxygen vacancies
are difficult formed due to the high formation energy; instead,
the interstitial oxygen ions possibly exist. All the analyses imply
that interstitial oxygen ions are likely to be the dominant for
oxygen transport in bulk LNO.
The iodometric method was used to examine the Cox+ and
Ni valences in Sr2+ (un)doped La2NiO4-based samples by oxi-
y+
dizing I− to I2. Subsequently, the interstitial O2- concentration
in the AO layers can be calculated according to the obtained
Cox+ and Niy+ valences. Table 1 lists the calculated B-site cation
valences, interstitial O2− concentration, and molecular formula
(obtained at room temperature). First, the low-valence Sr2+
doping at the La3+(A) sites does not create oxygen vacancies
in the perovskite-like layers; however, it decreases the intersti-
tial O2- concentration in the AO layers by reducing the B site
valence. For example, the average Cox+ valence in La2CoO4
is 2.961, while it reduces to 2.671 when Sr2+ is doped at the
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Table 1. The phase structure and the average bond length obtained by structural refinements; the average valence, B2+/B3+ ratio, and the interstitial
O2− concentration (δ) obtained by the iodometric method for Sr2+ (un)doped La2CoxNi1−xO4+δ samples. The average valence is for the B-site.

Sample Phase structure Average bond length Average valence M3+ [%] δ Value
<A-A> <A-B> <A-O> <B-O>
La2NiO4 Tetragonal 3.7700(2) 3.2519(6) 2.5917(1) 2.0537(1) 2.383(7) 38.37% 0.191(9)
La2Ni0.8Co0.2O4 Tetragonal 3.7673(1) 3.2552(3) 2.5860(2) 2.0574(6) 2.403(2) 40.32% 0.201(6)
La2Ni0.5Co0.5O4 Tetragonal 3.7604(5) 3.2398 2.5711(3) 2.0683(4) 2.661(4) 66.14% 0.330(7)
La2Ni0.3Co0.7O4 Tetragonal 3.7450(1) 3.209 2.5463(3) 2.0845(1) 2.723(6) 72.36% 0.361(8)
La2CoO4 Orthorhombic 3.8112(5) 3.2997(5) 2.6315(4) 2.0609(3) 2.961(1) 96.11% 0.480(6)
La1.5Sr0.5NiO4 Tetragonal 3.7532(1) 3.2219 2.5698 2.0692(1) 2.447(8) 44.78% -0.026(1)
La1.5Sr0.5Ni0.8Co0.2O4 Tetragonal 3.7422(1) 3.2191(3) 2.5840(3) 2.0246(4) 2.486(3) 48.63% -0.006(9)
La1.5Sr0.5Ni0.5Co0.5O4 Orthorhombic 3.7848(6) 3.2213(5) 2.5510(3) 1.9981(6) 2.507(3) 50.73% 0.003(7)
La1.5Sr0.5Ni0.3Co0.7O4 Orthorhombic 3.7840(4) 3.2212(2) 2.6398(4) 2.0302(1) 2.599 59.9% 0.049(5)
La1.5Sr0.5CoO4 Orthorhombic 3.7879(8) 3.2247(2) 2.6414(2) 2.0327(2) 2.671(5) 67.15% 0.085(8)

La3+ site in La1.5Sr0.5CoO4. The abnormal high B site valence
for La1.5Sr0.5NiO4 and La1.5Sr0.5Ni0.8Co0.2O4 (compared with
La2NiO4 and La2Ni0.8Co0.2O4) is mainly caused by the chemical
valence equilibrium, and their interstitial O2− concentration
in the AO layer is still much lower than that of the undoped
sample. Second, Cox+ ion doping (substitution) at B sites
shows a higher valence than Niy+. For example, the B site
valence increases from 2.383 for La2NiO4 to 2.961 for La2CoO4.
The increased B site valence in turn increases the intersti-
tial O2− concentration in the AO layers. In short, low-valence
Sr2+ doping at the high-valence La3+ site can suppress both of
the interstitial O2− concentration and the B site valence; Cox+
doping (substitution) at Niy+ site shows a higher B-site valence,
which benefits the interstitial O2− concentration and the lattice
oxygen activity. The crystal structures and the lattice parameters
obtained by structural refinement support the connection of
aliovalent cation doping (substitution) with the electrochemical
properties of the Sr2+ (un)doped La2NiO4-type electrodes, as
listed in Table 1 and Table S1 (Supporting Information).
The total conductivity and the oxygen permeation flux
with increasing testing temperature and corresponding
graphic analysis for the Sr2+ (un)doped La2NiO4-type sam-
ples are displayed in Figure 4. The M2+-O-M3+ small-polaron
model occurring in the MO6 octahedra of the perovskite-like
layers demonstrates the predominant electronic conduction
(Figure 4A). The Sr2+ (un)doped La2CoxNi1−xO4 with x = 0.2
exhibits the highest electronic conductivity (Figure 4B), which
is mainly caused by the balanced M2+/M3+ ratio. The conduc-
tivity decreases with further increasing high-valence Cox+ con-
tent, and the mismatched M2+/M3+ ratio is disadvantageous for
the electronic conductivity. For example, La2Co0.7Ni0.3O4 with
a B-site valence as high as 2.723 has a relatively low conduc-
tivity. Moreover, the Sr2+ (un)doped La2CoO4 with the highest
Co3+ content shows a high conductivity, which should be attrib-
uted to the phase transition (see Table 1). For An+1BnO3n+1 with
n = 2 and 3 (A = La, B = Ni, Co), the total conductivities have
the similar trend for the low-valence Sr2+ and/or high-valence
Cox+ doped La3Ni2O7 and La4Ni3O10 electrodes (Figure S2,
Supporting Information). Oxygen permeation flux was tested
to evaluate the high-temperature ORR/OER ability of the Sr2+
(un)doped La2CoxNi1−xO4 samples. The temperature-dependent
O2− migration was tested by gas separation technique. In
Figure 4D, the oxygen flux increases apparently with Cox+ con-
tent. For example, the La2CoO4 ceramic membrane achieves an
oxygen flux as high as 6.32 × 10−8 mol s−1 cm−2 at 900 °C, almost
two orders of magnitude higher than that of La1.5Sr0.5NiO4
(1.01 × 10−9 mol s−1 cm−2). For comparison, La2CoO4 demon-
strates a comparable oxygen flux to the LSCF cathode.[2a,b] The
obviously higher oxygen flux (between 400 and 800 °C) for
La2CoO4 than LSCF is ascribed to the easier migration of inter-
stitial O2− in the AO layer (Figure 4D1). On the other hand, the
Sr2+ doping also impedes the oxygen flux (Figure 4D1 vs 4D2).
Here, the bulk oxygen ionic conductivity is predominantly lim-
ited by the oxygen migration (porous platinum as a catalyst
deposited onto the 1.5 mm-thick ceramic surface). In addition,
the long-term stability of the oxygen flux for the An+1BnO3n+1
(n = 1) samples is excellent (Figure S3, Supporting Informa-
tion). For the La3Ni2O7-type and La4Ni3O10-type samples, the
oxygen permeation flux with increasing operating temperature
shows the similar trend with An+1BnO3n+1 (n = 1), as shown in
Figure S4 (Supporting Information).
The room-temperature electronic conductivity was tested, as
compared in Figure 4B. The low-temperature oxygen permea-
tion flux of bulk RP (with La2CoO4 as example) was estimated
by linear fitting method (the inset of Figure 4D). The fitted value
is around 10−17 mol s−1 cm−2, which means no O2− migration
or that the migration can be ignored. As schematically shown
in Figure 4C, the rock-salt AO layers can accommodate excess
oxygen. Taking La2CoO4 as an example, the highly concentrated
interstitial O2− ions with low activation energy are helpful for
accelerating the ORR and OER ability in the AO layers.[14,18] For
the perovskite-like layers, since there is no oxygen vacancy, the
ORR/OER ability may mainly come from the highly active lat-
tice oxygen.[19]
As shown in Figure 4E, the activity of lattice oxygen in the
perovskite-like layers is determined by the critical radius (rc)
of the opening size, which is built by two A-site ions and one
B-site ion.[14] However, the trivalent Co3+ with a smaller ionic
radius (than Ni2+) can enlarge rc by lattice relaxation, increasing
the lattice oxygen activity. Doping larger Sr2+ (1.44 Å) at the La3+

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Figure 4. The total conductivity, oxygen permeation flux, and the corresponding analysis with schematic program. Panel (A) presents the M2+-O-M3+
small-polaron mechanism in perovskite-like layer. B) The total conductivity tested with increased operating temperature. C) Interstitial O2− concentra-
tion in AO layer. D) The oxygen permeation flux (the inset estimates the low-temperature data by linear fitting method) tested with increased operating
temperature. E) The critical radius (rc) of opening size in octahedral structure.

(1.36 Å) site compresses rc. Interestingly, Naumovich’s com-
puter simulation revealed that the substitution of Ni2+ with
higher-valence cations tends to decrease the mobility of oxygen
anions by formation of a higher ionic charge-carrier concentra-
tion in the rock-salt and perovskite-like layers of La2NiO4,[19] but
it is not apt for our results.
A more direct comparison about the effects of aliovalent ion
doping on the high-temperature ORR and OER performances
of RP electrodes is given by SOFCs and SOECs. Although the
electrolyte-supported single cell prevents us from obtaining
the optimum performance due to its high ohmic drop, it is
useful to demonstrate the different ORR/OER abilities.[9b] First,
the Sr2+ (un)doped La2CoxNi1−xO4-type catalysts (n = 1) were
tested as electrodes in SOFCs and SOECs with a 300 µm thick
La0.9Sr0.1Ga0.8Mg0.2O3 (LSGM) as electrolyte and “NiO+SDC” as
the electrode (Figure S5, Supporting Information). The thermal
expansion coefficients (TECs) of the La2NiO4-type ceramics
were tested to match the LSGM electrolyte (Figure S6, Sup-
porting Information). The cell performance of a single cell in
both SOFC and SOEC modes measured at 800 °C is shown in
Figure 5. The positive and negative current densities refer to
the SOFC and SOEC operations, respectively. The high-tem-
perature OER ability of the An+1BnO3n+1-type electrodes during
the electrolysis can be predicted independently from the meas-
ured negative current densities. The cell voltage at a current
density of −0.9 A cm−2 is approximately 1.33 V for the La2CoO4
electrode and then increases to about 1.71 V for the La2NiO4
electrode. The cell voltages for Sr-doped La1.5Sr0.5CoO4 and
La1.5Sr0.5NiO4 are 1.5 and 1.74 V at −0.9 A cm−2, demonstrating
the negative effects of Sr2+ doping. The high-temperature ORR

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Figure 5. Electrochemical performances of SOFCs and SOECs operation at 800 °C and with a gas flow of 40 and 15 mL min−1 cm−2 H2/H2O at the
Ni-SDC electrode and ambient air at the An+1BnO3n+1-type electrodes. A) The cell voltage and power density as functions of current density. B) The
long-term stability of SOFCs for more than 100 h.
ability of the An+1BnO3n+1-type electrodes evaluated by SOFCs
shows a consistent trend with the OER results. The power den-
sity and cell voltage as functions of current density at 800 °C are
also shown in Figure 5A. La2CoO4 cathode exhibits a maximum
power density of 649 mW cm−2. The maximum power density
decreases apparently with increasing Niy+ content at B sites.
La2NiO4 cathode only shows a power density of 411 mW cm−2.
Moreover, with pure hydrogen as fuel, the power density of
the cell is 715 mW cm−2 with La2CoO4 cathode, but decreases
greatly to 428 mW cm−2 with La2NiO4 cathode (Figure S7, Sup-
porting Information). Figure 5B presents the results of 100 h
long-term durability test of SOFCs with An+1BnO3n+1 electrodes.
A constant operating voltage of 0.75 V was applied during the
long-term test to evaluate the effect of aliovalent ion doping.
The EIS of the full cell matches very well with the power
output (Figure S8, Supporting Information). The inferior per-
formance of the La2NiO4 cathode is due to the low interstitial
O2− concentration, slow lattice oxygen migration and low B-site
valence, which can be further confirmed by the poor cathodic
kinetics and high interfacial polarization resistance (Fig-
ures S9 and S10, Supporting Information). With La3Ni2O7- and
La4Ni3O10-type (n = 2 and 3) materials as cathodes, the SOFC
power outputs also demonstrate the similar trend to the Sr2+-
and Cox+-doped La2NiO4-type electrodes (n = 1) (Figure S11,
Supporting Information).
We conclude that the O2− transportation between the AO
layers and the perovskite-like layers is mainly ascribed to the
cooperative exchange mechanism, as schematized in Figures 1
and 3B. According to the charge-compensation mechanism,[20]
the high-valence Cox+ doping at B-sites enhances the interstitial
O2− concentration of the AO layers, while Sr2+ doping at the
Adv. Energy Mater. 2019, 1901573 1901573 (7 of 9)
www.advenergymat.de
La3+ site suppresses both the interstitial O2− concentration
and the B site valence (Table 1). Moreover, a validation pro-
cess with La2MnO4− (low-valence Ni doping at high-valence
Mn site) and La2CuO4− (high-valence Co doping at low-
valence Cu site) series as high-temperature SOFCs was oper-
ated. The obtained results are consistent with the trend of
above studied An+1BnO3n+1 (A = La, B = Ni, Co, n = 1, 2 and 3)
series (Figures S12 and S13, Supporting Information).
In conclusion, we have systematically investigated the
intrinsic effects on ORR and OER for the RP series high-tem-
perature oxygen catalysts. We find that the oxygen vacancy is
not the key point for the RPs to realize high-ORR and -OER
activity. The ORR and OER activity depend on the concentra-
tion of interstitial O2−, and the migration of the interstitial
O2− and lattice oxygen. The low-valence doping can decrease
the interstitial O2- concentration in the AO layers, and sup-
press the activity of lattice oxygen in perovskite-like layer by
reducing the B-site cation valence. The high-valence doping
gives rise to a higher interstitial O2− concentration in the AO
layers and enhances lattice oxygen activity in the perovskite-like
layers. Demonstrated by some joint electrochemical devices
such as model cells, oxygen permeation membranes, SOFCs
and SOECs, the RP electrodes with a rational aliovalent ion
doping strategy are available for most effective ORR and OER
catalysts, such as perovskites and noble metals.
3. Experimental Section
Ruddlesden-Popper-type An+1BnO3n+1 (n = 1): La2CoxNi1−xO4 and
La1.5Sr0.5CoxNi1−xO4 (x = 0, 0.2, 0.5, 0.7, 1), La2Mn1−xNixO4 (x = 0, 0.5),
© 2019 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.advancedsciencenews.com
La2Cu1−xCoxO4 (x = 0, 0.5); An+1BnO3n+1 (n = 2): La3Ni2O7, La2SrNi2O7,
and La3Co2O7; and An+1BnO3n+1 (n = 3): La4Ni3O10, La3SrNi3O10, and
La4Co3O10 solid solutions were synthesized by sol–gel method. LSCF
and Ce0.8Sm0.2O2 (SDC) were also synthesized by sol–gel method.
LSGM was attained via solid-state reaction. The powder X-ray
diffraction (XRD) data were collected to check the phase and conduct
the structural refinement by the GSAS software package. The total
conductivities were measured by the DC four-probe method. The O2
flux measurement was tested by an online microgas chromatography
(Varian 490-GC, Varian) from 600 to 900 °C. For the SOFC and SOEC
fabrication, 300 µm thick LSGM was used as the supporting electrolyte,
NiO+SDC (60: 40) composite as the electrode, and SDC as the buffer
layer at the anode side. The inlet gas (40 and 15 mL min−1 cm−2 H2/
H2O) was fed to the Ni/SDC electrode, while pure H2 was used as a
fuel and ambient air as the oxygen source. For the room-temperature
ORR and OER electrochemical testing, the working electrodes were
prepared by dip-coating the La2NiO4-based catalyst ink onto a glassy
carbon (GC) electrode. The working electrode was mounted to a
rotating disk with a Pt wire electrode as the counter electrode and a
Ag/AgCl electrode as the reference electrode. O2 or N2 saturated 0.1 m
KOH aqueous solution was used as the electrolyte. The ORR and OER
tests were carried out at 10 mV s−1 with a rotation rate of 1600 rpm. The
potential stair-step measurement for Tafel plots was performed with a
potentiostatic step of 20 mV for every 30 s. Li-air coin batteries with
lithium pellet as the anode, glass fiber as the separator, and 1 m LiPF6
in ethylene carbon (EC)/diethyl carbonate (DEC) as the electrolyte were
assembled in a glove box filled with pure argon as the protecting gas.
The air electrode was prepared by a spray method with nickel foam as
the substrate. The galvanostatic discharge–charge tests were conducted
with a multichannel battery testing system (LAND CT 2001A) in a dry
80 vol% pure N2 and 20 vol% pure O2 gas mixture within a voltage
window from 2.0 to 4.5 V (vs Li/Li+). The electrochemical properties
of ORR, OER, EIS, SOFCs, and Li–air batteries were tested on an
electrochemistry workstation (IM6). The EPR spectra were obtained by
using a Bruker A300 EPR spectrometer at X-band (≈9 GHz) at room
temperature. The LSCF, LNO110, and LNO001 powder were ground with
PVB–ethanol solution for fabricating PLD targets. The ceramic pellets
(25 mm in diameter) were fabricated by uniaxial press the powder and
then sintered at 1200 °C for 6h in air with a ramping rate of 3 °C min−1.
High-textured LSCF, LNO110, and LNO001 film electrodes with about
30 nm in thickness were fabricated by PLD technology on YSZ single-
crystal substrate electrolytes (CTM wafer, China) with Gd-doped CeO2
(GDC) as a buffer layer. The PLD growth was carried out at 600 °C
under an oxygen pressure of 10 mTorr. The (110) and (001) crystal
faces of LNO film electrodes were obtained by varying the operating
temperature, oxygen pressure, and cooling rate. The details (including
the DFT calculation) are described in the Supporting Information.
Supporting Information
Supporting Information is available from the Wiley Online Library or
from the author.
Acknowledgements
Y.H. and S.C. contributed equally. This work was supported by
the Natural Science Foundation of China (Grant Nos. 51702122,
51632001, and 51702119) and the Shandong Provincial Natural Science
Foundation, China (ZR2016EMQ07).
Conflict of Interest
The authors declare no conflict of interest.
Adv. Energy Mater. 2019, 1901573 1901573 (8 of 9)
www.advenergymat.de
Keywords
high ORR and OER, interstitial oxygen, lattice oxygen, Ruddlesden-
Popper series
Received: May 14, 2019
Published online:
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