Solid State Ionics 159 (2003) 159 – 165

www.elsevier.com/locate/ssi

Electrical properties in La2Sr4Ti6O19
d: a potential anode

for high temperature fuel cells
J. Canales-Vázquez, S.W. Tao, J.T.S. Irvine *
School of Chemistry, University of St. Andrews, Fife KY16 9ST, UK

Received 2 September 2002; received in revised form 25 November 2002; accepted 20 December 2002

Abstract

La2Sr4Ti6O19
d has been investigated as a potential anode for fuel cells due to the high total conductivity found under
reducing conditions. This mixed oxide is the n = 6 member of the excess oxygen perovskite-related family La2Srn
2TinO3n + 1.
The structure of this family of compounds can be described as perovskite slabs joined by crystallographic shears where the
characteristic excess oxygen of these mixed oxides is accommodated. Phases such as La2Sr4Ti6O19
d could be considered as a
potential oxygen ion or proton conductor due to the significant amount of interstitial oxygen found in both reduced and oxidised
forms. Partial removal of the excess oxygen by reduction of Ti4 + might lead to an enhancement of the ionic conductivity together
with electronic conductivity due to the presence of Ti3 +. The electrical properties of this material have been studied in a range of
oxygen and water partial pressure revealing the important role played by d, i.e. the amount of Ti3 +, on these phases. Under the
most reducing conditions, metallic conductivity, e.g. 60 S cm
1, is observed and under slightly higher P(O2), e.g. wet hydrogen,
a metal to insulator transition is observed. In addition, initial fuel cell tests were carried out to check the performance of
La2Sr4Ti6O19
d as an anode for fuel cells. Using La2Sr4Ti6O19
d as an anode, the polarisation resistance (Rp) varies from 2.97
V cm2 at 900 jC in wet H2 to 8.93 V cm2 at 900 jC operating in wet CH4. A current value of 119 mA cm
2 at 600 mV was
found, whereas the maximum power density was 76 mW cm
2 both measured in wet H2 at 900 jC.
D 2003 Elsevier Science B.V. All rights reserved.

Keywords: La2Sr4Ti6O19
d; Temperature; Anode

1. Introduction problems associated with the use of this cermet how-

Ni-YSZ cermets are currently used as anodes in fuel
cells because they meet most of the requirements:
mixed conductivity, thermal and chemical stability at
operating conditions and also catalytic activity to
promote the oxidation of the fuel. There exist several
* Corresponding author. Tel.: +44-1334-463817; fax: +44-1334-
463808.
E-mail address: jtsi@st-andrews.ac.uk (J.T.S. Irvine).
ever, such as carbon build-up when operating with
natural gas, sulphur poisoning and long-term degrada-
tion related to the agglomeration of Ni particles [1,2].
Mixed oxide materials offer a potential improve-
ment over YSZ cermets, especially due to the ability of
transition metals to present multiple oxidation states.
The possibility of multiple oxidation states might
enhance the electronic conductivity and also facilitates
catalytic activity. In addition, mixed oxides are less
likely to suffer from carbon build-up or sulphur
poisoning than YSZ cermets [3].

0167-2738/03/$ - see front matter D 2003 Elsevier Science B.V. All rights reserved.
doi:10.1016/S0167-2738(03)00002-X
160 J. Canales-Vázquez et al. / Solid State Ionics 159 (2003) 159–165
Characteristics such as high electronic conductivity,
high ionic conductivity and good catalytic activity, as
well as mixed protonic and electronic conduction have
been reported in many perovskite-mixed metal oxides
[4– 7]. Such characteristics are an essential require-
ment for high performance fuel cell anode materials.
Some of these properties may open up possibilities
with respect to fuel cells operating at lower temper-
ature (600 jC) than in current technologies.
La2Srn
2TinO3n + 1 is the general formula for a
family of layered perovskites, whose main feature is
their ability to accommodate excess oxygen in compa-
rison to the parent primitive perovskite [8]. La2Ti2O7 is
one of the end members (the n = 2 member) of this
family whereas the archetype of the perovskite struc-
ture, SrTiO3, is the other end member. The structure of
La2Ti2O7 has been widely investigated previously by
several authors [9 – 12] and it can be described as
perovskite slabs joined by crystallographic shears
where the excess oxygen is accommodated (Fig. 1).
As n increases, the perovskite slabs become bigger
until for n = l (SrTiO3), the structure is just a per-
ovskite framework. According to the structural model
proposed by Bowden et al. [13] for La-doped SrTiO3,
the structure of La2Sr4Ti6O19
d could be described as
La2Ti2O7-like planes randomly distributed within a
perovskite framework. Perovskite phases of stoichi-
ometry LaxSr1
xTiO3 have frequently been reported
as being prepared in air in the literature [14,15,17,18].
Such compositions are chemically counterintuitive as
they necessitate significant Ti3 + formation especially
for larger values of x, and this is unlikely in air. In our
Fig. 1. Schematic representation of the structures of La2Ti2O7 (a) and SrTiO3 (b).
experience, the colour of the samples, thermal analysis
and the frequent presence of extra diffraction peaks in
XRD and especially electron diffraction do not support
this stoichiometry. Instead, we suggest that usually
such phases contain some excess oxygen as described
herein.
Reduction of Ti4 + to Ti3 + on these mixed oxides
will lead to an improvement in the electronic conduc-
tivity together with a loss of oxygen in order to
maintain the electroneutrality. Removal of the excess
oxygen is likely to occur and it could be considered as
a way to enhance oxide ionic or, perhaps, protonic
conductivity.
In the present work, the electrical characterisation
of the n = 6 member (La2Sr4Ti6O19
d) of the La2
Srn
2TinO3n + 1 family was performed by means of
ac impedance spectroscopy and dc conductivity meas-
urements in a range of oxygen and water partial
pressures. Initial fuel cell tests were also carried out
in order to check the performance of the La2Sr4
Ti6O19
d phases as anodes for fuel cells.
2. Experimental
La2Sr4Ti6O19
d was synthesized by solid state
reaction, grinding stoichiometric amounts of pre-dried
powders of >99% purity of La2O3, SrCO3 and TiO2
from Aldrich. This mixture was then calcined at
1300 – 1400 jC for 24 h. The resulting powder was
ground and pressed uniaxially at 3.5 –4 tons pressure.
These pellets were then fired in air at 1400 –1600 jC
 J. Canales-Vázquez et al. / Solid State Ionics 159 (2003) 159–165
for 48 h. The resultant pellets were ground and pressed
again and then fired for further 48 h yielding yellow
pellets. Reduced phases were achieved by reduction at
1000 jC in 5% H2/Ar for 48 h yielding black pellets.
Phase purity was controlled by X-ray diffraction
(XRD) using a Stoe StadiP Transmission X-ray dif-
fractometer, using CuKa1 radiation. Energy dispersive
X-ray spectroscopy (EDS) microanalysis using an
Oxford Link ISIS system was performed to check
the homogeneity of the samples.
Ac impedance data were acquired using a 1260
Solartron impedance analyser over the frequency
range 0.1 Hz – 6.6 MHz. Measurements were per-
formed on pellets (75% dense) coated with organo-
platinum paste on each face and fired afterwards at 900
jC for 1 h. The samples were mounted in a compres-
sion jig with Pt wire electrodes. The measurements
were performed in a range of water and oxygen partial
pressures (static air, wet Ar and dry Ar). Total con-
ductivity was measured over a range of temperatures
from 25 to 900 jC in reducing conditions (wet and dry
5% H2/Ar), using the four terminal dc technique also in
75% dense pellets.
For fuel cell tests, La2Sr4Ti6O19
d powders ob-
tained at 1500 jC that had been subsequently reduced
at 1000 jC for 48 h were used. An ethanol-based slurry
formed with the reduced powder was coated onto YSZ
pellets and fired at 1300 jC for 4 h to form a thin layer
of anode for the fuel cell test. To investigate anode
polarisation, a three-probe cell was prepared for ac
impedance measurements. The arrangement of work-
ing, counter and reference electrode is schematised in
Fig. 2. The electrolyte is 20 mm in diameter and 2 mm
in thickness. The active area of working electrode
(anode) is 1 cm2. A gold current collector was applied
Fig. 2. Schematic drawing of the three-electrode arrangement of the
electrochemical cell.
161
onto the working electrode using an Au mesh with a
thin partially covering layer of Au paste between the
oxide and the mesh to ensure adherence. The fuel cell
performance was measured in a normal two-electrode
configuration cell. The electrolyte for cell performance
measurements is YSZ with 17% alumina addition of
0.3 mm thickness (CeramTec) chosen due to its supe-
rior mechanical properties. The cathode used was
commercial La0.8Sr0.2MnO3 (Praxair, USA). Platinum
paste was used as cathode current collector. For both
types of cells, the thickness of anode was about 50 Am,
a thickness that has been found to be fairly optimum in
previous studies of oxides in our laboratory.
The impedance of the electrochemical cell was
recorded at 900 jC at open circuit voltage (OCV)
and at different atmospheres with a 20-mV ac signal
amplitude by which stable and reproducible spectra
were observed. Measurements were carried out in the
1  105 – 0.01 Hz frequency domain.
Humidified 5% H2 in Ar, 100% H2 and 100% CH4
were used as the fuel at the working electrode, O2 being
supplied at the counter electrode. The fuel cell perform-
ance was recorded by cyclic-voltammetry at a scan rate
of 1 mV s
1. All electrochemical tests were performed
after reducing the La2Sr4Ti6O19
d anode in 5% H2 at
850 jC for 2 days to achieve the highest conductivity
due to the slow kinetic process of reduction.
3. Results and discussion
In order to investigate conductivity as a function of
oxygen partial pressure, a series of impedance spec-
troscopic measurements were performed. In each
atmosphere studied, samples were first annealed at
800 jC until equilibrium was achieved, then measure-
ments performed at lower temperatures. A pronounced
dependence of the total conductivity (i.e. grain and
grain boundary) with the oxygen partial pressure was
found, showing features typical of an n-type conduc-
tor, i.e. higher conductivity at lower oxygen partial
pressure. The activation energy calculated from the
corresponding Arrhenius plots (Fig. 3) revealed the
same tendency, and it decreased as the P(O2) de-
creased, from 1.3 eV for the sample measured in air
to 0.3 eV for the sample measured in dry argon. The
decrease in the activation energy in addition to the
increase in conductivity at lower P(O2) must be ex-
162 J. Canales-Vázquez et al. / Solid State Ionics 159 (2003) 159–165

Fig. 5. Complex impedance plots for La2Sr4Ti6O19-d measured in

dry Ar.
Fig. 3. Arrhenius plots for La2Sr4Ti6O19-d in air, wet Ar and dry Ar.

(capacitance f 10
8 F) and the other was assigned

4+
plained by Ti being reduced to Ti . The more 3+
reduced the conditions, the more Ti3 + is present in
the sample, which leads to an enhancement of the
electronic conductivity. Nyquist plots were studied to
analyse the different contributions to the conductivity
due to bulk, grain boundary and electrode responses.
In the sample measured in dry Ar at room temperature,
it is possible to clearly observe two semicircles: one
corresponds to a typical grain boundary response
to an electrode response (capacitance f 10
4 F),
possibly related to a Schottky barrier (Fig. 4). At
higher temperatures, the electrode response is less
important (Fig. 5) and above 300 jC only the grain
boundary can be observed. Other atmospheres (wet Ar,
static air) gave similar responses and sometimes it was
possible to distinguish between the responses for the
bulk and the grain boundary as can be observed in the
ZU and MU = jxZVvs. frequency plots (Fig. 6). The very

Fig. 4. Nyquist plot corresponding to La2Sr4Ti6O19-d measured in dry Ar at room temperature.

 J. Canales-Vázquez et al. / Solid State Ionics 159 (2003) 159–165
Fig. 6. Imaginary impedance (a) and imaginary modulus (b) vs.
frequency for La2Sr4Ti6O19-d measured in wet Ar at 631 K.
small value of grain boundary capacitance indicates
that narrow, well-ordered grain boundaries are formed,
despite the fairly large porosity (25%) of the sample.
There is some depression of the semicircle which may
relate to porosity; however, the most important role of
the porosity is to facilitate gas diffusion and hence
reduction of the grain boundaries.
Conductivity was also studied in different reducing
conditions by the four terminal dc techniques (Fig. 7),
again initially annealing at high temperature (950 jC)
until equilibrium was achieved. A reduced sample was
measured in dry and wet flowing H2/Ar atmospheres.
In dry H2/Ar, a metallic behaviour was found with
conductivity dropping from 60 S cm
1 at room
temperature to 40 S cm
1 at 950 jC. In addition,
magnetic measurements on the same sample per-
formed from 4 K to room temperature revealed Pauli
paramagnetism which is a typical feature in metals.
These conductivity values are somewhat higher than
the values reported for the A-site-deficient perovskites
Sr1
3x/2LaxTiO3
d [16]. The interstitial oxygen in
La2Sr4Ti6O19
d might be easily removed under re-
ducing conditions and therefore the reduction of Ti4 +
163
to Ti3 + is favoured. As a consequence, there is more
Ti3 + for the same P(O2), which explains the higher
values in conductivity found. These results also
revealed a discrepancy with recent studies by Marina
et al. [17] that have reported a semiconducting behav-
iour in similar compositions prepared in air, probably
due to the longer time under reducing conditions used
to achieve the complete reduction of the sample in our
experiments. In addition, our results agree with those
reported in previous studies in the La1
xSrxTiO3
system [18]. Furthermore, the sample measured in
wet H2/Ar showed the presence of an insulator-metal
transition at around 400 jC. This metal-insulator
transition could have a number of origins, i.e. that
the distribution of Ti3 + changes in a similar fashion as
occurs in Ti4O7 (Magnéli phases) [19]. At temper-
atures below 400 jC, Ti3 + is distributed forming long-
distance couples (Ti3 + – O – Ti3 +) that disappear at
higher temperatures leading to Ti3 + randomly distrib-
uted in the structure. Ordering in couples leads to a
partial localisation of electrons avoiding in this way the
formation of a metallic band due to the presence of
some discrete levels of energy. At temperatures above
400 jC, the Ti3 + are not in couples anymore, facilitat-
ing in this way the formation of the metallic band.
Alternatively, this metal-insulator transition could be
understood in terms of a change from dominant met-
allic to dominant semiconductor on cooling. The two
components could be both in the bulk or it could be a
semiconducting grain boundary and a metallic grain.
The lower conductivity observed in wet H2/Ar might
be explained by the fact of partial oxidation decreasing
the amount of Ti3 + leading to a lower conductivity due
to the smaller number of charge carriers.
Fig. 7. Plot of conductivity vs. temperature for La2Sr4Ti6O19-d in
dry and wet 5% H2/Ar.
164 J. Canales-Vázquez et al. / Solid State Ionics 159 (2003) 159–165
As stated before, the presence of interstitial oxygen
within the perovskite framework might possibly
enhance the ionic transport. Nevertheless, no evidence
of ionic conduction was found by means of ac impe-
dance or dc measurements due to the fact that the
conductivity in these phases is mainly via electrons.
Thermogravimetric analysis can be used in order to
estimate the concentration of protonic defects, because
their creation is mainly caused by dissociative water
uptake. However, no evidence of water uptake was
observed for La2Sr4Ti6O19
d in any of the atmos-
pheres used. The use of techniques such as electro-
chemical permeability or studies of Faradaic efficiency
could help in determining the existence of ionic trans-
port in La2Sr4Ti6O19
d and this will be investigated in
the future.
4. Fuel cell tests
The polarisation resistance (Rp) of the La2Sr4Ti6
O19
d anode measured using three electrode config-
uration in wet 5% H2/Ar is 6.59 V cm2 at 850 jC (Fig.
8). It has been recently reported that the polarisation
Fig. 8. Impedance measurements obtained at OCV and at 850 jC in
4.9% H2 + 2.3% H2O + 92.8% Ar (5), at 900 jC in 97% CH4 + 3%
H2O (5), 4.9% H2 + 2.3% H2O + 92.8% Ar (o) and 97% H2 + 3%
H2O (4), respectively. Rp = 8.93 V cm2 (CH4), 4.56 V cm2 (5%
H2), 2.97 V cm2 (H2) at 900 jC, 6.59 V cm2 (5% H2) at 850 jC.
Fig. 9. Fuel cell performance using La2Sr4Ti6O19-d as anode and
La0.8Sr0.2MnO3 as cathode. (a) 97% H2 + 3% H2O at 850 jC; (b)
97% H2 + 3% H2O at 900 jC and (c) 97% CH4 + 3% H2O at 900
jC. Note: current densities at 600 mV are 75, 119, 30 mA cm
2 for
(a), (b) and (c), respectively. Maximum power densities are 50 mW
cm
2 at 0.45 V, 76 mW cm
2 at 0.47 V and 21 mW cm
2 at 0.45
V for (a), (b) and (c), respectively.
resistance of La0.35Sr0.65TiO3 is 52 V cm2 in wet H2 at
850 jC [20]. This large difference in polarisation
resistance may be attributed to the long-time reduction
before our tests in order to achieve the highest elec-
trical conductivity or the preparation of materials and
anode, as the true chemical composition of the two
materials is not significantly different. The Rp de-
creases with the increase in temperature. It dropped
to 4.56 V cm2 at 900 jC in wet 5% H2/Ar. The Rp is
also sensitive to hydrogen concentration. A polarisa-
tion of 2.97 V cm2 was obtained at 900 jC in wet H2.
The relatively high Rp value may be due to the low
ionic conductivity, which might be further improved
by optimisation of the electrode microstructure and
also by modification of the composition. At 900 jC,
the polarisation resistance in wet CH4 is almost three
times larger than in wet H2 indicating that La2Sr4Ti6
O19
d itself is not a suitable anode material for direct
methane fuel cells.
The fuel cell performance with La2Sr4Ti6O19
d
anode and La0.8Sr0.2MnO3 cathode is shown in Fig. 9.
Current densities of 75 and 119 mA cm
2 at 600 mV
were achieved at 850 and 900 jC, respectively, when
wet H2 was applied as the fuel. The performance of the
cell is limited by the anode polarisation. A maximum
power density of 76 mW cm
2 is obtained in wet H2 at
a potential of 0.47 V. The maximum current density is
about 78 mA cm
2 at 900 jC when wet methane was
 J. Canales-Vázquez et al. / Solid State Ionics 159 (2003) 159–165
used as the fuel indicating again that La2Sr4Ti6O19
d
itself is not a good anode material for a direct methane
fuel cell, which is consistent with the anode polar-
isation test shown in Fig. 8. In addition, no carbon was
observed after the tests, indicating that cracking did
not occur.
5. Conclusions
The electrical properties of La2Sr4Ti6O19
d were
studied by ac impedance spectroscopy and dc con-
ductivity measurements, revealing the potential of this
mixed oxide as an anode for fuel cells. The total
conductivity revealed a strong dependence on oxygen
stoichiometry, i.e. the amount of Ti3 +, showing the
typical behaviour of an n-type conductor.
High total conductivity (60 S cm
1), mainly elec-
tronic, was found for the reduced phases measured
under 5% H2/Ar atmospheres, revealing metallic
behaviour. A metal-insulator transition was observed
when measuring in wet 5% H2/Ar, enhancing the effect
of oxygen stoichiometry in the band structure of this
material.
An anode polarisation resistance of 2.97 V cm2 is
achieved in wet H2 at 900 jC using pure La2Sr4Ti6
O19
d as anode. Accordingly, the maximum current
and power densities are 321 mA cm
2 and 76 mW
cm
2, respectively, in wet H2 at 900 jC. The perform-
ance in wet CH4 is not good compared to that in wet
H2. With modification of both chemical composition
and electrode microstructure, La2Sr4Ti6O19
d could
be considered a potential anode material or anode
constituent material for SOFCs. Indeed, recent data
have shown excellent anode performance for a very
similar material composited with ceria [20].
Acknowledgements
The authors would like to thank the HiT Proton
Project and EPSRC for funding and Martin Smith at
165
St. Andrews for his assistance with magnetic measure-
ments.
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