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Conductivity Enhancement in Lanthanum Phosphates
Satyajit R. Phadkew and Juan C. Nino
Materials Science and Engineering Department, University of Florida, Gainesville, Florida 32611
Current proton exchange membranes (PEM) are based on poly- As such, the mechanism of proton conduction in these materials
meric materials such as perfluorosulfonic acid (Nafiont), which is much less understood.
have an upper limit to their temperature of operation (o1001C). In the phosphate-rich region of the La2O3–P2O5 binary-phase
To overcome this limitation, ceramic PEM materials are being diagram, four stoichiometrically different lanthanum phosphate
investigated for transportation applications, where operating materials exist, namely LaPO4 (orthophosphate), La2P4O13
temperatures in the range of 2001–6001C are desired. In this (tetraphosphate), La(PO3)3 (metaphosphate/polyphosphate),
study, the conductivity behavior of lanthanum orthophosphate and LaP5O14 (ultraphosphate).21 The difference in stoichiome-
(LaPO4) has been compared and contrasted with lanthanum ul- try in the above compounds is accommodated crystallochemi-
traphosphate (LaP5O14) in order to better understand crystal cally by changes in the degree of interlinking or condensation
structure—proton conduction relationships in ceramic materi- (trend shown in Fig. 1) of the phosphate anion. This leads to a
als. The conductivity of the lanthanum phosphates (doped and different yet closely related crystallochemical arrangement. For
undoped) was measured using impedance spectroscopy in the example, in LaPO4, the phosphate anion consists of isolated
temperature range 3001–6001C. The conductivity of 5 mol% tetrahedra of PO4 but in LaP5O14, the phosphate anion consists
Sr21-doped LaP5O14 (1.01 104 S/cm, 6001C) was found to of condensed corner sharing PO4 tetrahedra arranged in a rib-
be an order of magnitude higher than similarly doped LaPO4 bon-like morphology.
(7.00 106 S/cm, 6001C), which is a well-investigated proton Owing to the nature of bonding and marked structural differ-
conducting material. In addition, it was observed that the acti- ences in the arrangement of PO4 tetrahedra, both LaPO4 and
vation energy for protonic conduction was much lower for doped LaP5O14 present quite different avenues and prospects for pro-
LaP5O14 (0.8070.01 eV) as compared with LaPO4 (1.0970.01 ton conduction in the material, which will be discussed in detail
eV). A hypothesis relating the oxygen-to-oxygen ion distance in later in the text.
a material to the activation energy for proton conduction is pre- It is well known that in LaPO4 acceptor, doping leads to the
sented and the experimental results obtained have been critically formation of charge compensating oxygen ion vacancies, which
examined on the basis of the hypothesis and other relevant lit- is equivalent to formation of a pyrophosphate group.18 The
erature. From this analysis, it is shown that the condensed pyrophosphate is formed by the local condensation of two ad-
nature of the phosphate anion in LaP5O14 can provide low- jacent PO4 tetrahedra, one of which is missing is an oxygen ion.
energy avenues for proton transport within the material leading In the presence of ambient water vapor, the hydrolysis of the
to enhanced conductivity in the material. Limitations of the cur- pyrophosphate leads to the formation of protonic defects as
rently proposed model for proton conduction along with some represented by the equation below:
other plausible explanations for the conductivity enhancement
have also been discussed. H2 O þ ½P2 O7 4 ! 2½HPO4 2 (1)
could have been sticking to the surface sample because the crys-
tals were grown from a phosphoric acid melt. Initial samples
that were not subjected to this heat treatment showed a very
high P:La ratio as compared with the expected value in EDS
analysis.
SEM and EDS were performed on a JEOL 6400 microscope,
(JEOL, Peabody, MA) on samples that were sputter coated with
gold. An accelerating voltage of 10 kV was used during analysis.
Activation
Material energy (eV) Material Activation energy (eV)
Fig. 7. View of LaPO4 along the c-axis. La31 ions shown in orange and
PO4 tetrahedra shown in green.32
IV. Conclusion
Synthesis of lanthanum ultraphosphate (LaP5O14) single crystals
of three different compositions (undoped, 1 and 5 mol% Sr21
doped) was carried out by precipitation from concentrated
phosphoric acid solutions. Phase purity of the prepared crystals
was established by comparing the experimental powder diffrac-
tion pattern with the theoretical pattern and also from quan-
titative EDS analysis. Conductivity measurements were per-
formed on crystal samples of all the above-prepared composi-
tions along the [100] direction in the temperature range of 3001–
6001C using EIS. Within the 1 mol% Sr-doped LaP5O14 sam-
ples, conductivity was also measured along the transverse direc-
tion. The obtained results were critically compared and
contrasted with the measured conductivity of identically doped
lanthanum orthophosphate (LaPO4) samples to better under-
stand crystal structure–property relationships in lanthanum
phosphate materials. For all the compositions characterized,
the LaP5O14 samples showed a higher conductivity and lower
activation energy as compared with the respective LaPO4
samples. The conductivity of 5 mol% Sr21-doped LaP5O14
Fig. 9. Proton jump distances in (a) LaPO4 and (b) LaP5O14. (1.01 104 S/cm, 6001C) was an order of magnitude higher
than identically doped LaPO4 (7.00 106 S/cm, 6001C), while
comparatively much lower (0.15 eV). Such low-energy values for the activation energy for protonic conduction was lower
rotational motion are consistent with other computational (0.8070.01 eV) as compared with (1.0970.01 eV). To explain
investigations on perovskite oxides.35–37 The rotational motion the differences in observed conduction behavior of the two ma-
of a proton does not contribute to proton transport directly but terials, a hypothesis relating the proton jump distance in a ma-
can substantially assist in the process in LaP5O14. Essentially, terial to the activation energy was presented. Such a correlation
this means that an intertetrahedral proton jump, which has a has been reported previously in the perovskite-type oxide mate-
high-energy barrier in LaPO4, can be substituted for by an rials, which was extended to phosphate materials. The obtained
energetically inexpensive low-barrier rotation around an oxygen results were critically analyzed on the basis of the proposed
ion in LaP5O14, thus leading to an overall lower activation hypothesis and other relevant literature available. From the anal-
energy in LaP5O14. ysis it was shown that the condensed nature of the phosphate
Because the corner-sharing PO4 tetrahedra in LaP5O14 form a anion, which forms a three-dimensional networked structure in
three-dimensional networked structure (as seen in Figs. 8(a) and LaP5O14 renders, is more favorable for achieving enhanced pro-
(b)), multiple paths are available for the protons to travel along ton conduction. Some other plausible explanations for the same
different directions in the material. This can probably explain have also been discussed along with possible limitations of the
the similar activation energy calculated for protonic conduction currently proposed model for proton conduction.
along two different directions in 1 mol% Sr-doped LaP5O14
(0.7670.02 and 0.8970.02 eV).
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