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Materials Chemistry
Cite this: J. Mater. Chem., 2012, 22, 25388
www.rsc.org/materials PAPER
Structural and defect properties of the LaPO4 and LaP5O14-based proton
conductors
Satyajit Phadke,*a Juan C. Ninob and M. Saiful Islam*c
Published on 29 October 2012. Downloaded by CONRiCYT on 7/19/2018 6:14:19 AM.

Received 9th May 2012, Accepted 13th September 2012

DOI: 10.1039/c2jm32940a

Atomistic simulation techniques are used to perform a comparative study of intrinsic defects, dopant
incorporation and protonic groups in two lanthanum phosphate compounds, namely, the
orthophosphate (LaPO4) and the ultraphosphate (LaP5O14). The suitability of dopant incorporation
predicted from the dopant solution energies (with Ca and Sr the most favorable) is in excellent
agreement with trends in ionic conductivity from recent experimental investigations. The defect
chemistry of the phosphates related to protonic defects and oxygen vacancies created from extrinsic
doping is investigated. The results indicate favorable orientations for the protonic defect within the
structures. The binding energies for proton–dopant interactions indicate that defect association may
occur. In LaPO4 it was observed that the relaxed local atomic structure around an oxygen vacancy is
analogous to the formation of a P2O7 pyrophosphate anion.

1. Introduction Proton incorporation into these materials is accomplished by

Proton-conducting oxides have attracted considerable attention
owing to the potential electrochemical applications in fuel cells,
gas sensors, and ceramic membranes. In particular, proton-
conducting solid oxide fuel cells (SOFCs) or proton ceramic fuel
cells (PCFCs) can operate within an intermediate temperature
range (400–800
C).1–3
Several investigations (in the last decade or so) have focused
on ceramic based materials such as perovskite oxides (AMO3)
and phosphates (APO4).3–18 Within phosphates, the experi-
mental investigations have mainly focused on orthophosphates
such as LaPO4, Ba3Ce(PO4)3, CePO4, CsH2PO4, RbH2PO4,
CsH5(PO4)2, and some pyrophosphate materials.4,19–26 In
general, phosphates tend to form compounds of higher
complexity at higher phosphorus contents by corner sharing an
oxygen ion between adjacent PO4 tetrahedra. For example,
within the La2O3–P2O5 binary phase system, three different
phosphate compounds exist namely La2P4O13, La(PO3)3, and
LaP5O14 (in increasing order of structural complexity) in addi-
tion to LaPO4 which is a well investigated proton conducting
material.9,10,27–30 The conductivity of 1 mol% Sr doped LaPO4 is
about 106 S cm1 at 550
C while that of LaP5O14 is about
2  106 S cm1.31,32
a
Department of Materials Science and Engineering, Massachusetts
Institute of Technology, 77 Massachusetts Avenue, Cambridge, MA
02137, USA. E-mail: Phadke@mit.edu; Tel: +1 617 253 8468
b
Materials Science and Engineering Department, University of Florida, 172
Rhines Hall, Gainesville, FL 32611, USA. E-mail: jnino@mse.ufl.edu; Fax:
+1 352 846 3355; Tel: +1 352 846 3787
c
Department of Chemistry, University of Bath, Bath BA2 7AY, UK.
E-mail: m.s.islam@bath.ac.uk
acceptor doping on the cation site which leads to the formation
of charge compensating oxygen ion vacancies. The vacancies
can be readily filled to form mobile protonic defects in the
presence of ambient water vapor. Previous investigations on the
defect chemistry of proton conducting phosphate compounds
have been limited to orthophosphates (such as LaPO4) and
there is no reported study which discusses the defect chemistry
of more complex phosphate compounds at the microscopic
level.
Using contemporary computational techniques a compara-
tive study of orthophosphate LaPO4 and ultraphosphate
LaP5O14 has been performed in order to understand the defect
chemistry in complex phosphate compounds. These methods
are well suited to investigating the local defect structure in
materials at an atomic level which is crucial to develop a deeper
understanding of proton incorporation and proton dynamics
within the material. In particular, intrinsic defect formation
(such as Schottky and Frenkel), dopant incorporation, and
proton–dopant interactions in both LaPO4 and LaP5O14 have
been investigated.
2. Simulation methods
Comprehensive reviews of the atomistic simulation techniques
are available elsewhere.33–35 In general, the simulation involves
calculation of the potential energy of the system in terms of
atomic coordinates, with ion–ion interactions described as ionic
pairwise potentials. In accordance with the Born model, the
interatomic forces are separated into the long-range Coulombic
terms and short-range terms that correspond to electron
cloud overlap (Pauli repulsion) and attractive van der Waals

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interactions. The short range interactions are described by the Table 2 Parameters for the O–H interaction
following Buckingham interatomic potential:36
Morse potential Dc (eV)
1)
a (A

ro (A)

 Cij
Vij ðrÞ ¼ A exp  r=rij  6 (1) O/H 7.0525 2.1986 0.9485
r
where Aij, rij and Cij are potential parameters for each set of ion– Buckingham potential A (eV)

r (A)
6)
C (eV A
ion interactions in the material. In addition to the above short
O/H 311.97 0.25 0
range interactions, three-body interaction terms were also used
to account for the angle dependent nature of the O–P–O and P–
O–P bonds in the system. The P–O–P interaction term is required
only for LaP5O14 to maintain the angle between the corner
where D, b, and ro were obtained from ab initio quantum
sharing PO4 tetrahedra in the structure. In LaPO4, the tetrahedra
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mechanical cluster calculations (developed by Saul et al.44), with

are isolated from each other and hence there are no direct P–O–P
a point charge representation of the surrounding lattice. These
interactions between adjacent tetrahedra. Such three body
values are summarized in Table 2. The dipole of the hydroxyl
interaction terms have been widely employed previously in the
species was distributed across both ions with O assigned 1.4263
successful modeling of phosphates, apatite-materials, silicates
and H assigned +0.4263 to give an overall charge of 1 for the
and aluminosilicates.37,38,40,41 The three body term takes the
protonic defect. This charge distribution reproduces the correct
form of a harmonic angle-bending potential about the central ion
dipole moment of the O–H group. To describe the interaction
(P or O):
between the hydroxyl group and the lattice ions, an additional
1 Buckingham potential was included which was taken from
V3-body ¼ kðq  qo Þ2 (2)
2 previous studies of water incorporation into silicates.45 We note
where k is the force constant and qo is the equilibrium bond that such simulation techniques have been applied successfully to
angle. Ionic polarizability is accounted for through the shell the atomic-scale study of a wide variety of proton-conducting
model developed by Dick and Overhauser.42 The interatomic oxides for SOFCs including BaMO3 perovskites.46–49 As indi-
potential and shell model parameters used in this study of LaPO4 cated in the Introduction, the present work has focused on
and LaP5O14 are listed in Table 1. The parameters for La–O and structural, defect and dopant properties of these La-phosphate
O–O interactions have been transferred from previously pub- materials, which are not fully characterized. Nevertheless, this
lished work; those for P–O were derived for this study employing study is a valuable precursor to future work on the pathway of
empirical fitting procedures using observed structural data.36 proton migration which will require the use of ab initio simula-
The existence of a charged defect in a lattice can cause tion methods.
significant displacement or relaxation of the positions of the
surrounding lattice ions. Modeling of such effects is carried out 3. Results and discussion
using the two region Mott–Littleton approach, which partitions
the crystal into two spherical concentric regions.43 The inner 3.1 Structural modeling
region (consisting of >500 atoms) surrounding the defect is
The basic difference between the ultraphosphate (Fig. 1) and the
relaxed explicitly. However, the ions in the outer region are
orthophosphate (Fig. 2) lies in the condensed versus isolated
treated by more approximate quasi-continuum methods since the
nature of the phosphate anion in these materials. The structure of
defect forces are much weaker in this region.
LaPO4 consists of isolated PO4 tetrahedra that are corner sharing
For the protonic defect, the O–H interaction was modeled
only with LaO9 polyhedra as shown in Fig. 2. However, as we
using the following Morse potential:
move towards the phosphate rich compounds within the La2O3–
P2O5 phase diagram the materials become structurally more
V(r) ¼ D[1  exp(b(r  ro))]2 (3)
complex due to the condensation of the phosphate anion. In
LaP5O14 (which is structurally the most complex among the
Table 1 Interatomic potentials and shell model parameters for LaPO4 lanthanum phosphates), the anion consists of a three dimen-
and LaP5O14 sional network of corner sharing PO4 tetrahedra as shown in
Short-range Fig. 1(a). Although the basic building blocks comprising the
phosphate anion are still PO4 tetrahedra, they are arranged
Interaction A (eV)

r (A)
6)
C (eV A Ref. forming a regular ribbon-like morphology. A small segment of
the anion is shown in Fig. 1(a) and shows the manner in which
La /O
3+ 2
4579.23 0.3044 0.000 37 and 38
P5+/O2 1250.00 0.3240 0.000 — the tetrahedra are oriented.
O2/O2 22 764.30 0.1490 27.879 37 and 38 In LaP5O14 the P–O bonds can be classified as either bridging
(P–Ob) or terminal (P–Ot) oxygen bonds. If the oxygen ion is
Shell model
located at the vertex of two corner sharing PO4 tetrahedra then
Species Y (e)
2)
K (eV A Ref. the P–O bond is termed as a bridging oxygen bond. However, if
the oxygen ion is located at the vertex of a PO4 tetrahedron
La3+
0.25 145.0 37 and 38 which is corner sharing that particular oxygen ion with an LaO8
P5+ 5.00 99 999 39
O2 2.96 27.879 39 polyhedron, then the P–O bond is termed as a terminal oxygen
bond. In all the five different tetrahedra in LaP5O14, the

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Table 3 Experimental (Exp.) and calculated (Calc.) lattice parameters

for LaPO4 and LaP5O14. All values are in A

LaPO4 LaP5O14

Exp. Calc. D Exp. Calc. D

a 6.8313 6.8302 0.02 8.8206 8.8809 0.06

b 7.0705 6.9922 0.08 9.1196 9.0823 0.03
c 6.5034 6.6258 0.12 13.1714 12.9774 0.19
b 103.27 104.42 1.15 90.66 90.20 0.46
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Table 4 Experimental (Exp.) and calculated (Calc.) average bond

lengths for LaPO4 and LaP5O14

Bond length (A)
Difference
System Bond type Exp. Calc.

(A)

LaPO4 P–O 1.539 1.564 0.03

La–O 2.579 2.621 0.04
LaP5O14 P–Ot 1.474 1.519 0.02
P–Ob 1.593 1.615 0.02
La–O 2.423 2.503 0.08

Fig. 1 (a) View of LaP5O14 along the [001] direction. La3+ ions are
shown in orange (large spheres) and PO4 tetrahedra are shown in
green. (b) Segment of ribbon composed of PO4 tetrahedra as viewed
along the [010] direction. (O is the origin, A is the x-axis and B is the
y-axis).
In LaPO4 all the four P–O bonds in the PO4 tetrahedron are
equivalent and are of the terminal type due to the isolated
arrangement of the tetrahedra. From the experimental values
shown in Table 4 it can be seen that the average P–O bond length
in LaPO4 has an intermediate value between the terminal and
bridging P–O bond lengths in LaP5O14. The calculated structure
of LaPO4 is in excellent agreement with respect to the bond
lengths and the difference between the calculated and experi-
mental values is small (0.03 A).
The other difference in the
structures of LaPO4 and LaP5O14 is that in the former the
structure is composed of LaO9 polyhedra while the latter has
LaO8 polyhedra. The average experimental bond length for
La–O is longer for LaPO4 and matches well with the calculated
values (Table 4).

3.2 Intrinsic defects

Fig. 2 LaPO4 structure viewed along the c-axis. La3+ ions are shown in
orange (large spheres) and PO4 tetrahedra shown in green. (O is the
origin, A is the x-axis and B is the y-axis.)
terminal P–O bonds are considerably shorter than the bridging
P–O bonds.
The experimentally observed crystal structures of LaPO4 and
LaP5O14 were reproduced prior to carrying out the defect
calculations and the calculated lattice parameters are compared
with the experimental values in Table 3. The differences in the
observed and calculated lattice parameters are small indicating
that the potential model accurately represents these complex
structures, thus supporting the validity of the potentials used for
the subsequent defect calculations. Also, the differences in the
P–O terminal and bridging bond lengths in LaP5O14 are correctly
reproduced (listed in Table 4).
The energies of isolated point defects such as vacancies and
interstitials were calculated for all the anions and cations in the
LaPO4 and LaP5O14 structures. The calculated energies of the
isolated defects were then combined according to the defect
equations to evaluate the energy of formation of Frenkel and
Schottky defects that are summarized in Table 5. To evaluate the
partial Schottky defect energies (La-Schottky type and P-
Schottky type) the lattice energy for La2O3 and P2O5 was
obtained by modeling their respective crystal structure using
the same interatomic potentials that was employed to model the
lanthanum phosphates. The results in Table 5 indicate that the
energies of formation of Frenkel and Schottky defects are very
high suggesting that formation of such defects is highly unlikely
in the temperature range of stability of the materials.
The high defect formation energies can also be taken as an
indication of the structural integrity of the PO4 tetrahedra in the
phosphate materials. For example, the concentration of intrinsic
oxygen ion vacancies can be expected to be almost negligible.
This is consistent with experimental defect models in which there
is negligible ionic conductivity in the undoped materials. Thus

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Table 5 Energies of intrinsic defect formation in LaPO4 and LaP5O14. All values are shown in eV (S – Schottky and F – Frenkel)

Type Defect equilibrium LaPO4 LaP5O14

__
LaXLa + PP + 4OO / VLa + VP + 4VO + LaPO4
X X /// /////
(S) 46.09 114.46
__
LaXLa + 5PP + 14OO / VLa + 5VP + 14VO + LaP5O14
X X /// /////
_____
P (F) PX
P / V /////
P + P i 41.33 19.76
___
LaXLa / Lai + VLa
///
La (F) 17.06 14.69
__
O (F) OO / VO + Oi
X //
12.74 7.31
__
2LaX La + 3OO / 2VLa + 3VO + La2O3
X ///
La (S) 29.94 40.95
__
P (S) 2PXP + 5O X
O / 2V /////
P + 5V O + P2O5 74.51 34.23
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Table 6 Inter-ionic distances in the [P2O7]4 group compared with inter- According to Amezawa et al. 1 mol% alkali earth metal doped
ionic distances in [PO4]3 LaPO4 shows the following trend in decreasing order of
[P2O7]4 [PO4]3 [HPO4]2
conductivity Sr > Ca > Ba > Mg which is in agreement with the
dopant solution energy obtained for the various dopants in this
Distance Distance Distance study.31 We recognise, however, that the correlation between
Ion–ion

(A) Ion–ion

(A) Ion–ion

(A) dopant solution energetics and the proton conductivity may not
P1–P2 3.175 P–Padj 4.187 P–Padj 4.179 be straightforward since the low solubility or small amount of the
P1–Ob 1.719 P–O1 1.574 P–Oproton 1.882 dopants in the structure can simply relate to the low proton
P2–Ob 1.719 P–O2 1.576 P–O2 1.558 uptake. Another key factor is possible dopant trapping effects
P1–O2 1.550 P–O3 1.585 P–O3 1.542 which are addressed below.
P1–O3 1.564 P–O4 1.605 P–O4 1.541
P1–O4 1.552 Acceptor doping on the cation site produces oxygen vacancies,
P2–O2 1.547 which can then lead to the formation of protonic defects by the
P2–O3 1.553 dissociative absorption of ambient water as represented by the
P2–O4 1.572
following equation:
__ _
H2O + VO O / 2OHO
+ OX (5)
the extrinsic defects formed upon acceptor doping are likely to
dominate the defect chemistry of these phosphate materials, and Examination of the local relaxed structure around the oxygen
are considered in the next section. vacancy in LaPO4 revealed that the formation of an oxygen
vacancy is analogous to the generation of a [P2O7] pyrophos-
phate group in the structure. This is accomplished by corner
3.3 Dopant incorporation and vacancy defects sharing an oxygen ion between two neighboring PO4 tetrahedra,
and leads to a significant distortion of the tetrahedra involved
It is known that acceptor dopants (Ca and Sr) are used to arising from the stretching of the bridging P–Ob bonds
promote the observed proton incorporation and conduction in
as illustrated in Fig. 4(b). For comparison, the length
(1.718 A)
these phosphate materials. Although the prediction of the solu- of the remaining terminal P–Ot bonds of the pyrophosphate
bility limit of a particular dopant is a much more demanding group is listed in Table 6 where it can be seen that these bonds are
task, the relative energies of dopant incorporation provide useful much shorter (1.55 A).
In undoped LaPO4 the P–Ot bond
information about trends in dopant solubility between different

lengths (1.574–1.605 A) are also quite similar to the P–Ot bond
species. Here, the energetics of divalent dopant (D ¼ Mg2+, Ca2+, lengths in the pyrophosphate as shown in Fig. 4(a).
Sr2+, Ba2+) substitution on the La3+ site were investigated. The
defect equation for dopant incorporation for both lanthanum
phosphate materials can be denoted in the Kr€ oger–Vink notation
as shown below:

3OXO þ 2LaXLa ! 2D=La þ 2OXO þ V$$

2DO
O þ La2 O3 (4)

By combining the appropriate lattice energy and defect energy

terms the dopant solution reactions were then evaluated. In eqn
(4), ‘DO’ is the divalent dopant oxide substituting into the lattice
structure. The interatomic potentials for the dopant cations are
obtained from the respective metal oxides.50
The resulting dopant incorporation (or solution) energies for
LaPO4 and LaP5O14 are shown in Fig. 3 plotted as a function of
the dopant ionic radius. Of these four dopant ions, Ca2+ and Sr2+
are the most favorable while Ba2+ and Mg2+ seem to be unfa-
vorable. This result correlates well with experimental studies
reported by Norby and Christiansen who found proton
conductivity in 5 mol% Ca and 5 mol% Sr doped LaPO4.9 Fig. 3 Calculated solution energies as a function of dopant ionic radius.

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Fig. 4 (a) Orthophosphate group [PO4]3 and (b) pyrophosphate group [P2O7]4 in LaPO4 showing bridging oxygen ion (Ob) and P–Ob bond distances.
(c) Protonated orthophosphate group [HPO4]3 in LaPO4 also showing the P–O bond lengths.

The formation of a pyrophosphate group in LaPO4 upon the
introduction of an oxygen vacancy is in good agreement with the
experimental observation by Amezawa et al. using MAS-NMR
studies.10 Given the similarity of the double-tetrahedral units we
find here to those which form in the La1xBa1+xGaO4x/2 ionic
conductor we conjecture that oxide-ion transport in LaPO4 may
also involve the breaking and reforming of the [P2O7] units in a
cooperative ‘‘cogwheel-type’’ process, as in the gallate.37 Further
examination of the conduction process, for example, by molec-
ular dynamics methods, while beyond the scope of the present
study, needs to be undertaken.
3.4 O–H configuration and proton–dopant interactions
Atomistic simulations were used to probe the local environment
around a proton to determine the most favorable configuration
within the structure. For the doped LaPO4 system, upon addition
of a water molecule to the pyrophosphate group the oxygen
vacancy is filled by a hydroxyl ion and it leads to the formation of
two protonated orthophosphate groups as indicated by the
following equation proposed by Amezawa et al.10
[P2O7]4 + H2O / 2[HPO4]2
The above equation is analogous to eqn (5) which is relevant to
doped oxide materials. Analysis of the relaxed structure of a
protonated orthophosphate group indicates that there is
significant distortion of the tetrahedron due to the presence of an
additional proton. The presence of the proton on the oxygen ion
leads to stretching of the P–O bond (1.882 A)
as shown in
Fig. 4(c), whereas the other P–O bonds are much shorter as
summarized in Table 6.
Such O–H calculations were performed for all the 14 crystal-
lographically different oxygen ions in the structure of LaP5O14.
In the relaxed structure an equilibrium O–H distance of 0.98 A

was obtained for all the calculations. However, it was found that
in the relaxed structure the O–H bond was directed in such a way
that the equilibrium position of the proton was located in either
of the two hollow channels located either along the a-axis or the
c-axis. These hollow channels exist in the ultraphosphate due to
the open framework structure of the material. The equilibrium
positions for the protons bonded to oxygen ions O1 and O14 are
shown in Fig. 5(a) and (b) respectively. Along both crystallo-
graphic directions it can be seen that the proton is located within
the hollow channels (shown as dotted region in Fig. 5). The
existence of these channels may provide a low energy pathway
for proton conduction resulting in enhanced conductivity in the
ultraphosphate compared to the orthophosphate as experimen-
(6) tally observed previously.41
If there is dopant–OH association between the two oppositely
charged defects it can adversely affect the proton conductivity in
the material and hence it is of interest to calculate the energetics of

Fig. 5 View of LaP5O14 along (a) c-axis and (b) a-axis showing the location of hollow channels (dotted) in the structure. In the relaxed structure the
O–H bond is directed towards these channels and the proton preferentially tends to lie in these channels.

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Table 7 Proton–dopant interactions in LaPO4 and LaP5O14 1. High formation energies were found for all the types of
intrinsic Frenkel and Schottky defects suggesting that the degree
System D 2+
Ebinding (eV)

D–H (A)
of intrinsic disorder in both LaPO4 and LaP5O14 is negligible,
LaPO4 Mg 0.75 2.94 and confirms the structural integrity of the PO4 tetrahedra in the
Ca 0.59 3.04 undoped structures. Hence, extrinsic defects formed upon
Sr 0.57 3.19 acceptor doping are likely to dominate the defect chemistry in
Ba 0.56 3.37
LaP5O14 Mg 0.44 2.50 these phosphate materials, as observed. The trend for dopant
Ca 0.50 2.69 incorporation energetics (with oxygen vacancy compensation)
Sr 0.39 2.82 was as follows (Sr > Ca > Ba > Mg), which is in agreement with
Ba 0.45 3.30 experimental conductivity results for doped LaPO4 where Ca and
Sr are the most commonly used dopants.
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such an interaction. The cluster binding energy for such an
interaction can be calculated by considering the energy of the
cluster (Ecluster) and comparing it with the sum of the energies of
isolated individual defects as shown in the general equation below:
X  excellent agreement with previous experimental NMR observa-
Ebind ¼ Ecluster  Eisolated-defect (7)
A negative Ebind in such a case would indicate that dopant–OH
association is energetically favorable. In the case of the
lanthanum phosphate compounds the relevant equation would
be as follows:
Ebind ¼ E(OHO_ /D/La)  [E(OHO_ ) + E(D/La)] (8)
The calculated binding energies for the divalent dopant cations
for both phosphates are listed in Table 7. It is found that for all
the dopants the values are negative which implies that such defect
association is favorable. In LaPO4, the highest (strongest)
binding energy calculated was for the Mg dopant (0.75 eV)
while for all the other dopants the values were in the range of
about 0.55 eV. The lowest (weakest) energy calculated in
LaP5O14 was for the Sr dopant (0.39 eV) while Ca dopant
exhibited the highest binding energy (0.50 eV). The calculated
dopant ion–proton distances (D–H) are also listed in Table 7. It
can be seen that the D–H distance increases with increase of the
ionic radius of the dopant cation (RBa > RSr > RCa > RMg).
The high binding energy for the Ca dopant (in LaP5O14) and
Mg dopant (in LaPO4) suggests a greater change in the
conduction activation energy with an increase of dopant
concentration in these materials. Indeed, high binding energies
indicate strong proton trapping effects, which would be detri-
mental to proton conductivity. As already indicated, another
factor to be considered is the low Mg dopant incorporation into
both structures, which would affect the degree of proton uptake.
We note that a recent DFT study of Ba-doped LaPO4 has found
that Ba-doping stabilizes a proton at a distance of 2.7 angstrom
from the dopant by up to 0.2 eV relative to positions far from the
dopant.29,30
4. Conclusions
A comparative study of two lanthanum phosphate proton
conductors, namely the orthophosphate (LaPO4) and the ultra-
phosphate (LaP5O14), was performed using atomistic simulation
techniques. The defect chemistry of the phosphates was investi-
gated along with the examination of the local relaxed structures
around protonic defects and oxygen vacancies. The main
conclusions are as follows.
2. Examination of the local relaxed structure around the oxygen
vacancy in LaPO4 revealed the creation of a P2O7 pyrophosphate
group. This is accomplished by a significant relaxation of two
neighboring PO4 tetrahedra so as to share an oxygen ion, and is in
tion of the pyrophosphate anion in doped LaPO4.
3. The local environment around protonic defects in LaP5O14
was examined to predict the energetically favorable O–H
configuration. The calculations suggest that irrespective of the 14
crystallographically different oxygen sites, the O–H bond was
directed within either of the two hollow channels along the a- or
c-axes. For all the dopants examined, dopant–OH association
was found to be favorable in both materials. The weakest asso-
ciation is found for Sr in LaP5O14 and the strongest association
for Mg in LaPO4 indicating that local proton trapping effects
and proton mobility are sensitive to the type of acceptor dopant.
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