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Oxygen Transport in Higher-Order Ruddlesden-Popper Phase Materials

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DOI: 10.1149/11106.2405ecst

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 ECS Transactions, 111 (6) 2405-2412 (2023)
10.1149/11106.2405ecst ©The Electrochemical Society

Oxygen Transport in Higher-Order Ruddlesden-Popper Phase Materials

Mudasir A. Yatooa,b and Stephen J. Skinnera,b

a
Imperial College London, Department of Materials, Faculty of Engineering,
Exhibition Road, London, SW7 2AZ, United Kingdom
b
EPSRC Centre for Doctoral Training in Advanced Characterisation of Materials,
Exhibition Road, London, SW7 2AZ, United Kingdom

A series of Ruddlesden-Popper phase materials – La3PrNi3O10-d, La2Pr2Ni3O10-d and

LaPr3Ni3O10-d – were synthesised and investigated by neutron powder diffraction to
understand the oxygen defect structure. The thermal expansion coefficient was
calculated for all compositions and was found to be in the range of 13.0 - 13.4 × 10-6
˚C-1, which is compatible with the commonly used electrolyte materials for solid
oxide fuel cells. A weak preference for Pr occupying the M(2) site in the rocksalt
layer was also observed. The majority of the oxygen vacancies were confined to the
perovskite layers with a particular preference for O(1) and O(5) sites at high
temperatures observed by neutron diffraction measurements. Further, a preference for
a curved oxygen transport pathway around the NiO6 octahedra was observed which
agrees with the published literature for these materials.

Introduction

Many electrochemical conversion and storage technologies such as batteries, fuel cells
and capacitors are being heavily investigated to decarbonise our environment(1–4). In
this regard, solid oxide cells (SOCs), a type of fuel cells, have shown promise. In
terms of materials development for these devices, mixed ionic-electronic conductivity
has been identified as one of the important properties of materials. As such ionic
conductivity plays an important role in determining the performance of oxygen ion
conductors as electrodes in SOCs. In oxygen ion conductors such as the Ruddlesden-
Popper (RP) phase materials where the composition is An+1BnO3n+1, A= Ln and B =
transition metals (n = 1-3), it is the oxygen defects which determine the ionic
conductivity because ionic conductivity of a material is directly proportional to the
concentration of lattice defects. In this context, the investigation of the oxygen defects
in these materials assumes importance.

Neutron powder diffraction (NPD) plays a crucial role because the neutron
scattering length of an oxygen atom is sizeable, 5.805±0.004 fm(5) and thus easily
detectable by neutron powder diffraction. Neutron diffraction is a reliable method to
determine the crystallographic positions of the oxide ions, their atomic displacement
parameters and their occupancies, while X-rays have a low sensitivity to oxygen,
particularly in a matrix of heavy atoms.

Ruddlesden-Popper phases were first synthesised by Ruddlesden and Popper in

1958(6). The lower-order (n=1) phases such as La2NiO4+ (LNO) are oxygen
overstoichiometric and have been studied extensively(7–10). Higher-order

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Ruddlesden-Popper phases, however, tend to be understoichiometric and, therefore,

oxygen vacancies are dominant defects. In comparison to lower-order Ruddlesden-
Popper phases, there are very few neutron diffraction studies of lanthanide-based
higher-order Ruddlesden-Popper phases such as La0.3Sr2.7CoFeO7-d (n = 2), and
LaSr3Co1.5Fe1.5O10-d (n = 3) available in the literature(11–13). This report will,
therefore, detail our recent neutron diffraction measurements of three n = 3
Ruddlesden-Popper compositions – La3PrNi3O10-d (L3P1N3), La2Pr2Ni3O10-d
(L2P2N3) and LaPr3Ni3O10-d (L1P3N3) – to provide a comprehensive study of oxygen
defect structure and transport properties in these materials. The higher-order phases
tend to be oxygen understoichiometric in nature and therefore oxygen vacancies are
predominant defects in these materials. The three phases under discussion too were
previously reported by our group to be oxygen deficient in nature (9,14–16).

Methods
Syntheses and characterisation:

All three compositions – L3P1N3, L2P2N3 and L1P3N3 – were synthesised using the
sol-gel route(17). The synthesised powders were characterised by X-ray powder
diffraction. The XRD patterns of the material were collected using a PANalytical
X’Pert Pro MPD (Cu K source) and Rietveld refinement of the XRD data, performed
with the GSAS/EXPGUI software package(18,19) was used to confirm the phase
identification.
Neutron powder diffraction of L2P2N3 at POLARIS:

In situ neutron powder diffraction data were collected on the high-flux medium
resolution POLARIS diffractometer at ISIS, the UK spallation source at the
Rutherford Appleton Laboratory, Oxfordshire, UK. Diffraction data were collected at
room temperature (25˚C) and 600˚C for 8 hours (150 µAmps), and every 50 degrees
from 100˚C to 550˚C for 2 hours (25 µAmps) after equilibrating the temperature at
each measurement. The sample was kept under a vacuum at all times. All the data
were collected in the d-spacing range of 0.40 - 4.50 Å and the data were corrected for
absorption before analysing by Rietveld refinement.
Neutron powder diffraction of L1P3N3 and L3P1N3 at POWGEN:

In situ neutron powder diffraction measurements were also collected for the other two
compositions, L1P3N3 and L3P1N3 at the POWGEN beamline, SNS, Oak Ridge
National Laboratory, USA. Powder samples were equilibrated under a continuous
flow of simulated air (20% O2) for at least one hour before measurement at each
temperature. Diffraction patterns were also collected every 100˚C from room
temperature to 800˚C in the d-spacing range of 0.45 – 5.35Å.

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3 Results and Discussion

Thermal Expansion Coefficients:

Figure 1 illustrates the variations of the a, b and c lattice parameters as a function of

temperature of representative L2P2N3 composition and shows the calculated thermal
expansion coefficients (TEC) for all three compositions. The unit cell parameters
show a linear increase throughout the temperature range with a close examination of
the data showing that the c parameter showed a significant increase when compared to
both the a and b parameters. This is because of the cumulative effect of stacking of
layers across the crystallographic c direction. Apart from the stacking effect, it was
observed that the c parameter was more responsive to the changes in temperature than
the a parameter because the expansion along the c axis is less restricted by the
expansion of the rock-salt layers(12,20). Also evident from Figure 1 is the relatively
higher increase in a lattice parameter compared with the b lattice parameter, which
points towards an increase in orthorhombic strain with increasing temperature.

The thermal expansion coefficients were calculated from the thermal variation
of the lattice parameters i.e., the slope of (λ-λ0/λ0) vs T (Figure 1b), where λ and λ0 are
the cubic roots of the volume at a particular temperature and room temperature
respectively. The calculated values of the TEC were found to be 13.0 × 10-6 ˚C-1 for
L1P3N3; 13.2 × 10-6 ˚C-1 for L2P2N3 and 13.4 × 10-6 ˚C-1 for L3P1N3, of the same
order of magnitude as those of the other components of SOFCs, and therefore
compatible with commonly used electrolytes such as Y2O3-stabilised ZrO2 (YSZ),
Ce0.8Gd0.2O2−δ (CGO) and La0.8Sr0.2Ga0.8Mg0.2O3-δ (LSGM)(21,22).

Figure 1. (a) Variation of the unit cell parameters with the increase in temperature for
representative L2P2N3 composition and (b) (λ-λ0/λ0) as a function of temperature for all the
three compositions showing the compatible TEC’s. (Note: standard deviations for the unit cell
parameters lie within the data markers).

La/Pr Ordering:

The Rietveld refinements of the neutron diffraction measurements revealed that the
fractional occupancy for the A-site cations, La and Pr, were slightly different, than the
nominal compositions; La3.26Pr0.74Ni3O9.76, La1.9Pr2.1Ni3O9.65 and La1.04Pr2.96Ni3O9.76.
Furthermore, the examination of the data for 50:50 composition (L2P2N3) in Table 1
shows that Pr preferentially orders into the 9-coordinated M(2) site in the rocksalt

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layer as compared to the 12-coordinated M(1) in the perovskite layer. However, the
neutron diffraction measurements of L1P3N3 and L3P1N3 compositions at elevated
temperatures showed that Pr has a weak preference for M(1) site.
Oxygen Defects and Transport:
Atomic displacement parameters and fractional occupancies obtained after refinement
of neutron diffraction data of the representative L2P2N3 composition, 2 and R
factors are illustrated in Table 1 below.

Table 1. Rietveld refinement parameters obtained for the L2P2N3 composition

recorded at 600˚C with an orthorhombic model (Bmab). (χ2= 3.6; Rp = 3.8% and Rwp
= 2.1%).

Atom Atomic displacement parameters (Å2) 100 Wyckoff

Fractional
U11/Uiso U22 U33 U12 U23 position
occupancy
La(1) 2.2(1) 8f
0.57(3)
Pr(1) 2.2(1) 8f
0.43(3)
La(2) 0.9(1) 8f
0.38(4)
Pr(2) 0.9(1) 8f
0.62(4)
Ni (1) 1.4(9) 4a 1.0
Ni(2) 1.2(6) 8f 1.0
O(1) 5.1(6) 4.1(6) 7.5(8) 5.4(4) 8e
0.92(2)
O(2) 2.9(4) 2.3(4) 3.6(4) 0.5(4) 8f
0.95(2)
O(3) 0.5(3) 1.7(4) 1.3(3) 0.3(2) 8e 1.0
O(4) 4.0(4) 4.8(7) 2.0(3) 1.8(6) 8f
0.99(1)
O(5) 3.0(6) 2.9(5) 0.6(4) 0.2(3) 8e
0.91(3)

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The occupancies of all the oxygen sites were refined and it was observed that
vacancies at low temperatures were confined to the O(1) site for the sample measured
at 25 ˚C. In cases where occupancies refined to 1.0, these were fixed in subsequent
refinement cycles. As was expected the total oxygen stoichiometry decreased with
increasing temperature, due to the reduction of the B-site cation, pointing towards the
expected decrease in the B-site cation average oxidation state. The oxygen
stoichiometry of 9.54 at 600 ˚C agrees well with previously published reports in

Figure 2. Ruddlesden-Popper unit cells for L2P3N3 structure. This derived from Rietveld
refinement of the neutron diffraction data collected at 600˚C. Oxygen positions are further
marked to guide the reader to visualise the oxygen transport pathways discussed.

related higher-order Ruddlesden-Popper materials by our group and others(12,14,15).

At 600 ˚C, the oxygen vacancies were observed in the O(1), O(2) and O(5) sites in the
order O(1) O(5) < O(2) ≪ O(3) O(4), meaning that the vacancies predominantly
prefer perovskite units of the structure. The atomic displacement parameters for the
oxygen atoms were best fit with an anisotropic model and the thermal parameters
expectedly show a considerable increase with the increase in temperature (Table 1).
The large ab plane anisotropy of the apical O(1) sites, particularly at high
temperatures, points towards faster oxygen diffusion in these materials. This apical
oxygen position is indeed known to exhibit an anisotropic Debye-Waller factor and
has been widely reported for lower-order Ruddlesden-Popper K2NiF4 materials(23–
25).

Taking into consideration the site occupancies, distances between these vacant
O sites and the atomic displacement parameters, it is possible to envision the possible
transport pathways in these materials (Figure 2). The distances between the oxygen
atoms at 600˚C for L2P2N3 were found to be: 2.72 Å between O(5) sites; 2.72 Å
between O(1) and O(2) sites and 2.77 Å between O(1) sites. This suggests
predominant participation of fractionally vacant sites via pathways such as
O(1)−O(2)−O(1), O(1)−O(1)−O(1) and O(5)−O(5)−O(2) with a possible preference to
the transport pathways involving O(1) and O(5) sites because of the relatively shorter
distances and high vacancy concentration at these sites. This preference for a curved

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 ECS Transactions, 111 (6) 2405-2412 (2023)

oxygen transport pathway such as O(1)−O(1)−O(1) around the NiO6 octahedra is

expected and in agreement with the published literature for materials such as
La0.3Sr2.7CoFeO7-d, LaSr3Co1.5Fe1.5O10-d, LaSrCo0.5Fe0.5O4-d and La1-xSrxBO3 (B = Cr,
Mn, Fe & Co.)(12,26,27).

Similarly, for the L3P1N3 and L1P3N3 compositions, it was observed that the
oxygen vacancies are spread over O(1), O(2) and O(3) sites and oxygen sites O(4) and
O(5) were fully occupied. This again suggests major transport pathways as
O(3)−O(3)−O(3) and O(1)−O(1)−O(1) in these materials.

Conclusions

Neutron diffraction measurements of three higher-order Ruddlesden-Popper

phases were discussed. Lattice parameters were shown to increase linearly with the
increase in temperature, with c parameter showing a significant increase than a and b
cell parameters because of the cumulative effect of stacking of layers along the c
crystallographic direction. A further observation of the b parameter showing only a
slight increase as compared to a parameter is interpreted in terms of an increase in
orthorhombic strain with the increase in temperature. The calculated TEC based on
neutron diffraction measurements was found to be around 13.0 × 10-6 ˚C-1, which is of
the same order as that of commonly used electrolyte materials in SOFC devices.

Furthermore, neutron diffraction results suggested that vacancies prefer the

perovskite block – O(1) and O(3) sites – and it, in fact, has been reported earlier that
majority of the oxygen vacancies in these materials are confined to the perovskite
layers, with a particular preference to equatorial oxygen sites. A further strong
preference for the curved oxygen transport pathways such as O(1)−O(1)−O(1) around
the NiO6 octahedra was recorded, in accord with the earlier reports in these materials.

Acknowledgements
M.A.Y and S.J.S would like to thank the Imperial College President’s PhD
Scholarships, EU Horizon 2020 (HERMES; Grant No. 952184) and EPSRC
Advanced Characterisation of Materials Centre for Doctoral Training for funding this
research. Thanks, are also due to ISIS (Ref#1710304) and Oak Ridge Laboratory
(Ref#20521) for beamtime and to Dr Helen Playford and Dr Cheng Li for their
assistance in recording the high temperature in situ data.

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