Solid State Ionics 125 (1999) 285–302

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Aspects of the formation and mobility of protonic charge carriers

and the stability of perovskite-type oxides

K.D. Kreuer
¨ Festkorperforschung
Max-Planck-Institut f ur ¨ , Heisenbergstr. 1, D-70569, Stuttgart, Germany

Abstract

Proton conducting acceptor-doped perovskite-type alkaline earth cerates, zirconates, niobates and titanates have been
investigated experimentally and by numerical simulations. For all cubic perovskites the concentration of protonic defects
almost reaches the acceptor dopant concentration under appropriate conditions, and the mobility of protonic defects fall into
a narrow range. Any symmetry reduction, however, leads to a reduction of the concentration and mobility of protonic
defects. For all oxides, dynamical hydrogen bonding is suggested to lead to a local lattice softening, which provides an
advantageous environment for high proton-mobility. This effect may explain the very high proton conductivity in covalent
acceptor-doped BaZrO 3 , which has been found experimentally for the first time. Since this oxide also shows good
thermodynamic phase stability, it is an interesting candidate as separator material in high-drain electrochemical applications
such as fuel-cells.  1999 Elsevier Science B.V. All rights reserved.

Keywords: Perovskite-type oxides; Protonic charge carriers; BaZrO 3 ; Electrochemical applications

1. Introduction but prevents them from being used in high-drain

Although high proton conductivity has been re-
ported for many perovskite-type oxides in humid
atmosphere [1] the combination of high proton
conductivity and stability, which is a prerequisite for
the application of such compounds as a separator
material in electrochemical cells, is generally consid-
ered to be a key problem [2]. Oxides with high
conductivity (e.g. BaCeO 3 -based compounds) gener-
ally show very low phase stability (e.g. with respect
to carbonate or hydroxide formation [2]), while more
stable oxides (e.g. In-doped CaZrO 3 ) show very low
conductivity, which only permits their use in low-
drain applications (e.g. potentiometric sensors [3])
E-mail address: kreuer@chemix.mpi-stuttgart.mpg.de (K.D.
Kreuer)
applications such as fuel cells.
This paper is a report on our recent progress in the
search for perovskite-type oxides with high proton
conductivity and high thermodynamic phase stabili-
ty. The research strategy is based on a few relation-
ships between chemistry and structure on one side
and the above addressed properties on the other side,
which have been worked out for some well-known
proton conducting perovskite-type oxides. Since the
quality of the data is critical to this approach, some
initial comments on the acquisition of experimental
and simulation data are necessary.
2. Acquisition of experimental and numerical
data
IR-spectroscopy in the diffuse back scattering

0167-2738 / 99 / $ – see front matter  1999 Elsevier Science B.V. All rights reserved.
PII: S0167-2738( 99 )00188-5
286 K.D. Kreuer / Solid State Ionics 125 (1999) 285 – 302
mode [4,5], 1 H-pulsed-field-gradient NMR [4–6] and
X-ray diffraction including Rietveld refinement [7]
have been described elsewhere. Some critical aspects
of the sample preparation, thermogravimetry, impe-
dance spectroscopy and MD-simulations are dis-
cussed in what follows.
2.1. Samples
In the present work, acceptor-doped perovskites of
the type ABO 3 (A 5 Ba, Sr; B 5 Ce, Zr, Ti) and the
complex perovskite Ba(Ca 0.39 Nb 0.61 )O 32d
(Ca:Ba 3 CaNb 2 O 9 ) have been prepared as dense
ceramics. The preparation procedure described in
Ref. [8] has been adopted for each composition.
Especially for the zirconates, high final sintering
temperatures ( . 17008C) were required to obtain the
desired densities ( . 98% of theoretical) and to
minimise grain boundary resistances. Two ‘single-
crystalline’ specimens prepared by induction melting
[6], Y-doped BaCeO 3 and BaZrO 3 , (Y:BaCeO 3 ,
Y:SrCeO 3 ) are also included in this study. The
experimental results are discussed together with
those obtained for a series of BaCeO 3 ceramics
doped with 2–20 mol.% Y [4] and for solid solutions
of Ba 2 YSnO 5.5 and BaSnO 3 [9].
2.2. Hydration isobars
Since the dominant reaction leading to the forma-
tion of protonic defects is the dissociative uptake of
water, the concentration of protonic defects can
readily be determined by thermogravimetric analysis
(TGA) where the temperature T and the water-partial
pressure pH 2 O are the experimental parameters. Con-
ventionally, pH 2 O is varied for a given temperature,
which yields the equilibrium constant K of the
hydration reaction for that temperature (e.g. Ref.
[6]). Since K(T ) generally shows Arrhenius behav-
iour, i.e. temperature-independent standard hydration
enthalpies and entropies, the thermodynamic parame-
ters may also be obtained from the hydration isobars.
Recording the weight at a constant water partial-
pressure, pH 2 O 523 hPa, as a function of temperature
has two advantages: (i) the sample may be slowly
hydrated (with decreasing T ) or dehydrated (with
increasing T ) only once, and (ii), for a given
measuring time, the samples more closely approach
equilibrium. The equilibration rate is generally de-
termined by the chemical diffusion of water (am-
bipolar diffusion of V ??O and 2 OH ?O ) which is written
[8]:
(2 2 X)DOH ?O DV ??O
D˜ H 2 O 5 ]]]]]]]
XDOH ?O 1 2(1 2 X)DV ??O
where the degree of hydration X 5 [OH ?O ] /S and S is
the hydration limit.
Fig. 1 shows this diffusion coefficient as a func-
tion of the degree of hydration for two perovskites.
For completely dehydrated samples, DH 2 O equals the
self diffusion coefficient of protonic defects, which is
high for the compounds under consideration. But for
compounds with low self diffusion coefficients of
oxygen ion vacancies, this initially decreases rapidly
upon hydration (see curve for Ba 2 YSnO 5.5 ) and
eventually approaches the diffusion coefficient of
oxygen ion vacancies. The concentration of protonic
defects in compounds with high oxygen ion con-
ductivity (e.g. BaCeO 3 based compositions) therefore
equilibrates much faster. The self diffusion coeffi-
cient of oxygen ion vacancies of the compounds
considered, obtained from the ionic conductivities
under high vacuum ( p,10 21 Pa), are shown in Fig.
2. The approximate maximum grain sizes for
equilibration within 1 day are indicated. While a 10
mm powder of Y:BaCeO 3 may be equilibrated within
1 day even at room temperature, for Ba 2 YSnO 5.5 this
is only possible at 3708C. Accordingly, we have
adjusted the cooling and heating runs in the TGA
experiments for each compound and grain size
(typically 10 mm after 2 h ballmilling). The absence
of any visible hysteresis provides additional con-
firmation that the thermodynamic equilibria were
achieved.
The concentration of protonic defects among
titanates does not saturate at low water partial
pressures. Overnight treatments in an autoclave at
T54508C and pH 2 O 53.5 MPa allows one to de-
termine the saturation concentration of protonic
defects for these compounds.
2.3. Impedance spectroscopy
The protonic conductivity is commonly deter-
mined by impedance spectroscopy which allows one
 K.D. Kreuer / Solid State Ionics 125 (1999) 285 – 302 287

Fig. 1. The hydration rate is frequently controlled by the chemical diffusion coefficient of water. This is shown as a function of the degree
of hydration X for both an oxide with a high and a low diffusion coefficient of oxygen ion vacancies.

Fig. 2. Oxygen ion vacancy diffusion coefficients as obtained from conductivities under high vacuum ( ptotal ,10 23 Pa). The maximum grain
size for equilibration within 1 day is indicated on the right axis (see text).
288 K.D. Kreuer / Solid State Ionics 125 (1999) 285 – 302
to extract bulk resistances from the complex impe-
dance as a function of frequency. In Cole–Cole
representations the bulk response shows up as a high
frequency arc corresponding to a specific capacitance
of about 1–10 pF cm 21 (´¯10–100). Particularly in
the presence of high grain-boundary impedances,
which often respond at only slightly lower fre-
quency, the bulk arc may easily be overlooked either
because of the limited frequency range or because of
poor resolution between bulk and grain boundary
responses. As can be seen in the spectra shown in
Fig. 3, for zirconates, titanates and stannates the bulk
arc may be resolved at lower temperatures. Of
course, the availability of single crystals makes this
problem obsolete (Fig. 3b). The very low impedance
of the Y-doped BaZrO 3 crystal supports the assump-
tion that the high frequency arc in the spectrum of
the polycrystalline Y-doped BaZrO 3 indeed origi-
nates from bulk proton conductivity.
2.4. Quantum molecular dynamics simulations
Important tools to attack the problem of the
underlying proton conduction mechanism are quan-
tum-MD simulations which have been described
elsewhere [10]. But still there is a gap between
typical diffusion rates for protonic defects in oxides
(1 /t ¯10 210 –10 29 s 21 at T51000 K) and the time
increments accessible by such techniques (a few ps).
Since no long range diffusion is observed during
such simulations, transition state energies may be
estimated by extrapolating Helmholtz potential
curves, obtained for example from pair correlation
functions, to a point in phase space which is assumed
to correspond to the transition state. In order to avoid
such model assumptions, we have carried out MD-
runs at extremely high temperatures (T .2000 K)
which produce a number of successful proton jumps
(Fig. 4) and therefore allows the identification of the
transition state in phase space [5]. As will be pointed
out below (Section 4.1), this allows one to determine
the diffusion paths and some relevant interactions
determining the transition state energy.
3. Formation of protonic defects
Assuming ideal behaviour of all species involved
in the hydration reaction, which leads to the forma-
tion of two protonic defects, the equilibrium con-
dition is written [4]:
K 5 [OH ?O ] 2 /([V ??O ][O Ox ] pH 2 O ).
Together with the site restriction (because of high
defect concentration):
[O xO ] 1 [V ??O ] 1 [OH O? ] 5 3
and the electroneutrality condition:
2[V ??O ] 1 [OH ?O ] 1 [Y Ba
?
9 ]50
] 2 [Y Ce
the concentration of protonic defects as a function of
pH 2 O and K is written:
[OH ?O ] 5
]]]]]]]]]]
3KpH 2 O 2 KpH 2 O (9KpH 2 O 2 6KpH 2 O S 1 KpH 2 O S 2 1 24S 2 4S 2 )
]]]]]]]]]]]]]
œ
KpH 2 O 2 4
where kT ln K 5 TDS8 2 DH8 and S is the effective
dopant concentration (water solubility limit).
For cubic perovskites, which exhibit only one kind
of oxygen site, this expression fits the hydration
isobars (Fig. 5) quite well. Despite the slight ortho-
rhombic distortion of Y:BaCeO 3 [7] the fit with
single standard chemical potential differences for the
different species occupying the two oxygen sites is
still surprisingly good. Only for Y:SrZrO 3 and
Y:SrCeO 3 , which deviate highly from an ideal cubic
perovskite, the hydration isobars cannot be fitted
with this simple expression. In particular, the exist-
ence of different oxygen sites seems to reduce the
water uptake [7]. Additionally Y:SrCeO 3 slowly
starts to decompose into hydroxides below T¯4008C
(as confirmed by X-ray diffraction and IR-spectros-
copy). For the cubic cases, however, the good fit
with single standard chemical potentials indicates the
absence of discrete associates, typically between
protonic defects and the negatively charged acceptor
dopants.
Fig. 5 also shows the thermodynamic parameters
of the hydration reaction for the cubic perovskites
except for the titanates, which do not take up
sufficient water under the experimental conditions to
allow a fit of sufficient significance. The data support
the general observation that the hydration enthalpy
for perovskite-type oxides become more negative in
the order: titanates → niobates → zirconates →
stannates → cerates, indicating that basicity is a
 K.D. Kreuer / Solid State Ionics 125 (1999) 285 – 302 289

Fig. 3. Impedance spectra for representative polycrystalline (a) and single crystal samples (b) (see text).
290 K.D. Kreuer / Solid State Ionics 125 (1999) 285 – 302
Fig. 4. The evolution of the mean square displacement with time for three protons in a box of 33333 unit cells of BaZrO 3 as obtained
from a quantum-MD-simulation [25].
major parameter. This is also supported by the
evolution of the hydration enthalpy for the solid
solutions Ba(Ce 12xY x )O 32d and Ba 2 Sn 22xY x O 32d
(Fig. 6) where the increasing basicity with increasing
Y-content is accompanied by a more negative hydra-
tion enthalpy.
Since hydration enthalpy and entropy are not
found to be related, the hydration entropy has to be
considered as a separate parameter determining the
equilibrium constant of the hydration reaction. This
is demonstrated in Fig. 7 which shows the normal-
ised hydration isobars of a 2% Y-doped BaCeO 3 [4]
and a 10% Y-doped BaZrO 3 compared to that of a
10% Y-doped BaCeO 3 . Despite the less negative
hydration enthalpy of BaCeO 3 with the lower dopant
level, the dehydration temperature is distinctly high-
er, reflecting the considerably less negative hydration
entropy. The low hydration entropy of Y:BaZrO 3 is
also the reason for the stabilisation of protonic
defects up to quite high temperature despite the
relatively less negative hydration enthalpy. To what
extent the hydration entropy is determined by con-
figurational or vibrational terms (e.g. degrees of
freedom related to the local rotational diffusion of
the protonic defect (see also Section 4)) is not yet
clear.
Apart from the equilibrium constant K of the
hydration reaction, the saturation limit S determines
the concentration of protonic defects. Determinations
of S are often found irreproducible and significantly
lower than the acceptor dopant concentration. The
hydration isobars normalised with respect to the total
dopant level S0 , obtained in this work (Fig. 8),
however, show saturation limits well above 80% for
all cubic perovskites in accordance with recent
observations [4,11]. Even for 5% Sc-doped SrTiO 3 a
proton defect concentration of 3.7% has been found
gravimetrically after hydrothermal treatment. The
remaining reduction of the saturation limit with
respect to the dopant concentration may then simply
be the consequence of a slight substitution of the
dopant on the A-site, where it acts as a donor [6].
This is obviously a minor effect for ceramics pre-
pared at relatively low temperatures (1400–17208C).
For single crystals prepared well above 20008C,
however, this effect may drastically reduce the water
solubility [6]. The low saturation limits of the two
orthorhombic perovskites (Y:SrCeO 3 and Y:SrZrO 3 )
 K.D. Kreuer / Solid State Ionics 125 (1999) 285 – 302 291

Fig. 5. Hydration isobars for different perovskite-type oxides. The decomposition of Sr(Ce 0.9 Y 0.1 )O 32d below |5008C (see text) is indicated
by the dashed line. The experimental data shown as rough curves are fit with the smooth curves from the model detailed in the text.

have already been explained by the decay of the
oxygen site into two sites with different affinities
towards hydration [7].
4. Mobility of protonic defects
It has been frequently suggested that the mobility
of protonic defects involves proton transfer between
neighbouring oxygen ions and reorientation of the
hydroxide ion on the oxygen site [12]. For a few
perovskites (BaCeO 3 - and Ba 3 CaNb 2 O 9 -based) sev-
eral independent experiments [13–15] and numerical
simulations [5,16,17] provide evidence for the
reorientation step being brought about by rapid
rotational diffusion of the protonic defect, supporting
the assumption that proton transfer is the rate
limiting step. In such Grotthuss-type mechanisms the
proton is the only mobile species while the oxygen is
localised in the vicinity of its crystallographic posi-
tion. Nevertheless, proton transfer in oxides is fre-
quently believed to be coupled to the local oxygen
dynamics, because of the large separations between
nearest neighbour oxygen ions (e.g. 320 pm in
BaCeO 3 [12]) and the strong localisation of the
proton within the valence electron density of the
oxygen. (It should, however, be noted, that from
INS-studies especially Colomban and Filleaux claim
the existence of ‘free protons’ [18–20].) In a first
attempt to model proton transfer [21] thermally
292 K.D. Kreuer / Solid State Ionics 125 (1999) 285 – 302
Fig. 6. The hydration enthalpy of two perovskite-type oxides as
functions of the basic Y-dopant concentration [4,9].
activated compression of the OH–O separation has
been assumed to assist the proton transfer event.
Based on this concept, results of quantum molecular
dynamics simulations have been interpreted. While
the obtained activation enthalpy for proton diffusion
was in good agreement with the experimental results
for BaCeO 3 (0.41 and 0.46 eV, respectively [5]), the
model could not explain the decreasing proton
mobility under pressure and the high activation
enthalpy of proton diffusion in SrCeO 3 (0.63 eV).
The model suggests extremely low activation en-
thalpies for perovskites with low lattice constants,
that are not confirmed experimentally. This concept
and the experimental results are also controversial
with respect to the identification of the rate-limiting
step and the role of hydrogen bonding [5].
In the following a closer view of the MD-simula-
tion data will be presented that is consistent with the
available experimental results (see Ref. [22]). Then
our recent proton mobility data for simple cubic
perovskites will be discussed followed by the effects
of symmetry breaking.
4.1. Proton conduction mechanism
As opposed to earlier simulations [16,17], our
recent quantum MD-simulations of protons in
BaCeO 3 produced a few successful proton transfer
events for a very high temperature (2500 K) [5].
Although the poor statistics do not allow for a
quantitative determination of the proton diffusion
coefficient (see Fig. 4), details of the diffusion
mechanism are identified by analysing the evolution
of the system with time instead of interpreting pair
correlation functions with respect to a given model
of the diffusion mechanism [5]. This leads to two
surprising observations.
1. Even for configurations with OH–O separations
well below 240 pm, proton transfer occurs with a
very low probability because of a wrong orienta-
tion of the OH. This rather points with its proton
to one of the other seven O-neighbours.
2. With this the OH forms a transient but very
strong bent hydrogen bond reducing the OH–O
separation from 312 pm (cubic case) to an average
of 281 pm, where the transient OH–O pair
correlation function shows a very broad maxi-
mum [22].
From this transient pair correlation function the
Helmholtz energy of the system as a function of the
OH–O separation coordinate is obtained (Fig. 9).
This shows a very shallow minimum reflecting the
extended fluctuations of the OH–O separation. The
energy the system gains by strong hydrogen bonding,
which is indicated in the OH-stretching regime of the
IR-spectra (Fig. 10), tentatively compensates for the
energy required to deform the CeO 6 -octahedron over
a wide range of OH–O separations. This ‘softening’
of the proton environment does not only allow for
the extended OH–O fluctuations but also for the easy
breaking of such strong hydrogen bonds. This may
explain the high rates of both proton transfer and
rotational diffusion.
To give some background to these novel observa-
 K.D. Kreuer / Solid State Ionics 125 (1999) 285 – 302 293

Fig. 7. Hydration isobars (fitted curves) for three perovskite-type oxides with similar dehydration temperatures but distinctly different
hydration enthalpies (see text).

Fig. 8. Hydration isobars (smoothened data from Fig. 5) normalised with respect to the acceptor dopant concentration. The curves for the
cubic perovskites are bold.

tions, some features of the thermodynamics of proton may be small (65 meV in the case of BaCeO 3
diffusion are identified (Fig. 11). [7]).
2. The proton prefers an OH orientation off of the
1. Even for strong hydrogen bonding the activation octahedral diagonal, probably because of the
energy for rotational diffusion of protonic defects strong H 1 –Ce 41 repulsion. Thus the transient
294 K.D. Kreuer / Solid State Ionics 125 (1999) 285 – 302

Fig. 9. Helmholtz energy of BaCeO 3 as a function of the O–O separation (obtained from the O–O pair correlation function) and the OH–O
separation (obtained from the transient OH–O pair correlation function [5,22]) indicating the ‘softening’ of the proton environment.

hydrogen bonds are not linear and additional
energy is required to bring the hydrogen bonded
complex close to linear, which favours proton
transfer. This is brought about by an elongation of
the B–O bonds [5], which explains the increase of
the activation enthalpy under pressure.
3. Since the protonic defect may form transient
hydrogen bonds with eight oxygen neighbours
and OH orientation and OH–O separation have to
match in the transition state, there may be signifi-
cant negative contributions to the proton diffusion
entropy, which becomes apparent in reduced pre-
exponential factors.
should indeed have major contributions from com-
pressing the separation of proton donor and acceptor
(Fig. 11). The instability of intra-octahedron hydro-
gen bonds is also indicated in the OH-stretching
absorption region for the perovskites with the highest
lattice constants, i.e. the highest structural oxygen
separations (Fig. 10). For these a small but distinct
absorption at an unusually high frequency of ¯4250
cm 21 is observed which may be assigned to non-
hydrogen bonded OH in this type of oxides.
4.2. Mobility of protonic defects in cubic
perovskites

The second feature actually also explains why the
diffusion path changes for perovskites with reduced
lattice constants, such as SrTiO 3 or CaTiO 3 [22]. For
these, proton transfer between the vertices of neigh-
bouring octahedra is favoured over intra octahedron
transfer. The latter is probably suppressed because of
the strong H 1 –Ti 41 repulsion preventing the forma-
tion of a linear hydrogen bond, which may rather be
formed between oxygens of neighbouring octahedra.
In this case the activation enthalpy of proton transfer
Fig. 12a shows the proton conductivities in the
temperature ranges where impedance spectroscopy
allows a reliable separation of the bulk response (see
Section 2.3). With the concentration of protonic
defects taken from the hydration isobars (Fig. 5)
proton mobilities have been obtained via the Nernst–
Einstein relationship (Fig. 12b). Except for Sc-doped
BaTiO 3 all cubic perovskites show similar proton
mobilities, although, with some variation in the
activation enthalpy. A plot of the pre-exponential
 K.D. Kreuer / Solid State Ionics 125 (1999) 285 – 302 295

Fig. 10. Infrared spectra in the OH-stretching regime for hydrated perovskite-type oxides in the order of decreasing unit cell volume. The
spectra have been obtained in the diffuse back scattering mode which has been found to produce similar spectra as in transmission [4]. The
spectra of the cubic oxides are shown bold and the lattice constants are indicated. Note the absorption around 4250 cm 21 for the perovskites
with large unit cell volume, which may originate from non-hydrogen bonded OH (see text).
296 K.D. Kreuer / Solid State Ionics 125 (1999) 285 – 302
Fig. 11. Schematic illustration of intra- and inter-octahedra proton
transfer. While the activation enthalpy of the first, which is
suggested to occur in perovskites with large lattice constants (e.g.
BaZrO 3 ), has major contributions from the elongation of the B–O
bonds, the rate of the latter, which is proposed to occur in
perovskites with small lattice constants (e.g. SrTiO 3 , CaTiO 3 ), is
strongly dependent on fluctuations of the separation of oxygens of
adjacent octahedra. Transient hydrogen bonds are indicated by
dashed lines.
factors versus the activation enthalpies (Fig. 13)
exhibits a slope of ¯1 / 630 K. Since the order of this
temperature is reminiscent of typical dehydration
temperatures of these oxides, the proton mobilities at
the dehydration temperatures (K5l) for two water
partial pressures are plotted in Fig. 14. The sort of
‘universal’ curves with activation enthalpies of about
0.6 eV may be considered to correspond to the
maximum conductivity achievable for a given water
partial pressure. Since the activation enthalpy of
these curves only slightly differs from the activation
enthalpy of the proton mobilities in these oxides
(0.42–0.58 eV), there is obviously no significant
correlation between the chemical potential (activity)
of water in the perovskite and the proton mobility.
This has important implications for the development
of stable oxides with high proton conductivity (see
Section 5).
4.3. Effects of symmetry reduction
This ‘universal’ behaviour is restricted to cubic
perovskites. As can be seen already from the trans-
port data presented in Fig. 12, the mobilities of
protonic defects in perovskites with structures
strongly deviating from cubic (mostly orthorhombic)
are significantly lower. This effect has recently been
investigated in detail by comparing structural and
dynamical features of protonic defects in Y:BaCeO 3
and Y:SrCeO 3 [7]. The large orthorhombic distortion
of Y:SrCeO 3 has tremendous effects on the arrange-
ment of the lattice oxygen. The cubic oxygen site
degenerates into two sites with probabilities of 1 / 3
and 2 / 3. Due to different chemical interactions with
the cations, especially the strontium on the A-site,
the oxygens on these sites show distinctly different
electron densities (basicities) and therefore different
binding energies for the proton. The different site
binding energies and the biased rotational diffusion
in this environment is thought to increase the activa-
tion energy of proton mobility. Additionally, the
diffusion paths are restricted to one dimension with
high energy barriers separating the different paths.
But the mobilities of protonic defects may also be
reduced by a local symmetry reduction, due to the
presence of the acceptor dopant. From the results of
quasi elastic neutron scattering (QNS) experiments it
has been suggested that acceptor dopants may act as
discrete trap sites for protons. The QNS spectra have
been fitted by the rates for proton liberation from
these trap sites and the mobility of the ‘free’ proton
[23]. Conceptionally, such a two state model leads to
the general behaviour shown in Fig. 15a. At low
temperature (strong association limit) the activation
enthalpy is expected to be the sum of association and
migration enthalpy and the absolute value of the
proton mobility is expected to be inversely propor-
tional to the concentration of trap sites. A recent
study of the transport properties of BaCeO 3 with
different levels of Y-dopant indeed showed a drastic
reduction of the proton mobility with the acceptor
dopant concentration [4], but this was not the result
of a reduction of the pre-exponential factor as
 K.D. Kreuer / Solid State Ionics 125 (1999) 285 – 302 297

Fig. 12. Proton conductivities (a) and diffusivities of protonic defects (b) of different perovskite-type oxides. The curves of the cubic
perovskites are shown bold.
298 K.D. Kreuer / Solid State Ionics 125 (1999) 285 – 302

Fig. 13. Pre-exponential factor versus activation enthalpy for the diffusivities of protonic defects among various perovskite-type oxides.

Fig. 14. The diffusivities of protonic defects at the dehydration temperature (K51) of different cubic perovskite-type oxides for two
different water partial pressures.
 K.D. Kreuer / Solid State Ionics 125 (1999) 285 – 302 299

Fig. 15. (a) The diffusivity of protonic defects for different acceptor dopant (trap) concentration, as anticipated by the ‘two-state-model’
[23]. (b) Experimentally determined proton diffusivities for BaCeO 3 doped with different acceptor dopant concentrations [4].
300 K.D. Kreuer / Solid State Ionics 125 (1999) 285 – 302
anticipated by the two-state model. The proton
mobility was instead reduced by an increase of the
activation enthalpy with the pre-exponential being
almost unchanged (Fig. 15b). This behaviour sug-
gests a more delocalised effect of the acceptor
dopant on the proton mobility. In this particular case,
the introduction of Y apparently leads to an increase
of the basicity of all oxygens in the lattice and
therefore to a stronger binding of the protons to the
oxygens in general. Nevertheless, not only a good
size matching but also acid / base matching is re-
quired in the choice of the acceptor dopant with
respect to an optimisation of proton mobility.
The relatively low mobility of protonic defects in
Sc:BaTiO 3 (Fig. 12) may be due to the symmetry
reduction of the proton environment as a conse-
quence of the high dielectric polarisation leading to
an increase of the proton self-localisation [12]. But
since the data have been obtained with metastable
cubic BaTiO 3 ceramics of very low grain size,
transport measurements on more defined materials
with high dielectric constants are planned.
5. Stable oxides with high proton conductivity
Empirically high thermodynamic stability and high
proton conductivity still seem to exclude one
another. Cerates, for example, show high proton
conductivity for a given water partial pressure up to
quite high temperatures, but below |7008C they
react even with air to form carbonates. On the other
hand, rather stable zirconates are reported to either
dissolve very little water or show high activation
enthalpies for proton conductivity. A first attempt to
understand the available data, which are summarised
in Ref. [1], is based on a simple ionic model for the
estimation of the perovskite stability and acid / base
considerations to estimate the energetic stabilisation
of protonic defects [2]. But especially the novel data
on Y:BaZrO 3 presented in this paper, may be better
understood by including effects of the oxide lattice
covalency and entropic stabilisation effects.
Since Y:BaZrO 3 shows an ideal cubic perovskite
structure (as opposed to Y:SrZrO 3 ), it is not surpris-
ing that the concentration of protonic defects ap-
proaches that of the acceptor dopant under appro-
priate conditions (Fig. 8). The rather high dehydra-
tion temperature is, however, somewhat unexpected
considering the relatively less negative hydration
enthalpy of 276 kJ mol 21 , which is in accordance
with the amphoteric character of the zirconate.
Correspondingly, the hydration entropy is also found
to be significantly less negative than that for other
perovskites. This behaviour may qualitatively be
explained by the directional character of the Zr–O
bond and the strength of the hydrogen bond inter-
action, which are both estimated by a quantum
chemical calculation [5]. Compared to BaCeO 3 , both
interactions are stronger but compensate over a wider
range of oxygen separations, which leads to a more
effective local ‘softening’ of the lattice in the proton
environment. (Note, that the average contraction of
the oxygen sublattice around the protonic defect is,
however, smaller than in BaCeO 3 [5].) This may not
only explain the surprisingly low activation enthalpy
of proton mobility but also the high entropy of the
protonic defect that leads to the relatively less
negative formation entropy. The covalency of the
Zr–O bond also corresponds to a less positive charge
on the Zr compared to Ce in more ionic BaCeO 3 ,
which reduces the repulsion between Zr and the
proton, and therefore also the activation enthalpy of
proton mobility (see also Fig. 11).
Fig. 16 shows the H 2 O pressure of dehydration
(K51 for the formation reaction) and the CO 2 partial
pressure at which decomposition into ZrO 2 and
BaCO 3 occurs. For applications in air ( pCO 2 538 Pa)
and a maximum humidification of pH 2 O 5100 hPa,
these data indicate phase stability and stability of
protonic defects in the temperature range 330 to
4708C. At the dehydration temperature the bulk
proton conductivity clearly exceeds a value of 10 22
S cm 21 , which makes the material an interesting
candidate for high drain applications. But this re-
quires a reduction of the grain boundary resistance,
which is comparable to the bulk resistance at 4708C
for our samples. On the other hand optimisation of
the acid / base matching and concentration of the
acceptor dopant still leaves some room for a further
increase of the proton conductivity.
On the background of these surprising findings, it
also appears attractive to look for other covalent
perovskites with strong hydrogen bonding of
protonic defects. Apart from further optimising more
ionic complex perovskites, as described in Ref.
 K.D. Kreuer / Solid State Ionics 125 (1999) 285 – 302 301

Fig. 16. The water partial pressure of dehydration (K51) and the partial pressure of carbon dioxide, where decomposition into carbonates
occurs [26], as a function of temperature for BaZrO 3 . The potential application range is indicated (see text).

[2,24] this should be another fruitful strategy in the
development of stable oxides with high proton
conductivity.
6. Conclusions
Experimental and numerical investigations re-
vealed a few new aspects of the formation and
mobility of protonic defects in perovskite-type ox-
ides.
1. For cubic perovskites, the concentration of
protonic defects approaches the acceptor dopant
concentration under appropriate conditions. Sym-
metry reduction leads to a reduction of the
saturation limit of protonic defects S0 .
2. Apart from S0 , the standard hydration enthalpy
DH8 and entropy DS8 determine the concentration
of protonic defects. In particular, the entropic
stabilisation of protonic defects is not found to be
related to the enthalpic stabilisation, i.e. perov-
skite-type oxides with less negative hydration
enthalpy may still exhibit a high concentration of
protonic defects.
3. The mobilities of protonic defects at the dehydra-
tion temperatures of cubic perovskites are empiri-
cally found to fall close to universal curves for
given water partial pressures.
4. Strong, dynamical hydrogen bonding of the
protonic defect with its eight nearest or four next
nearest neighbour oxygen atoms are found. This
results in transient reductions of the separation
between corresponding oxygens and a local sof-
302 K.D. Kreuer / Solid State Ionics 125 (1999) 285 – 302

tening of the proton environment. High proton ¨

[8] K.D. Kreuer, E. Schonherr, J. Maier, Solid State Ionics
70–71 (1994) 278.
mobility as a typical phenomenon between the
[9] K. Eberman, P. Murugaraj, K.D. Kreuer, J. Maier, in
solid and the liquid state [27] is favoured in this preparation.
environment. ¨
[10] W. Munch, G. Seifert, K.D. Kreuer, J. Maier, Solid State
5. The formation of fast proton conduction paths by Ionics 97 (1997) 39.
this local lattice softening and the entropic stabili- [11] F. Krug, T. Schober, Solid State Ionics 92 (1996) 297.
[12] K.D. Kreuer, Chem. Mater. 8 (1996) 610.
sation of protonic defects allows even hard,
[13] M. Pionke, T. Mono, W. Schweika, T. Springer, H. Schober,
covalent, stable, less basic perovskite-type oxides, Solid State Ionics 97 (1997) 497.
such as BaZrO 3 -based materials, to show high [14] Th. Matzke, U. Stimming, Ch. Karmonik, M. Soetramo, R.
proton conductivity. ¨
Hempelmann, F. Guthoff, Solid State Ionics 86–88 (1996)
621.
¨
[15] R. Hempelmann, M. Soetratmo, O. Hartmann, R. Wappling,
Solid State Ionics 107 (1998) 269.
Acknowledgements ¨
[16] W. Munch, G. Seifert, K.D. Kreuer, J. Maier, Solid State
Ionics 86–88 (1996) 647.
The author wishes to thank Yu. Baikov (St. [17] F. Shimojo, K. Hashino, H. Okazaki, J. Phys. Soc. Jpn. 66
Petersburg) for supplying a Y:BaZrO 3 single crystal, (1997) 8.
[18] Ph. Colomban, J. Tomkinson, Solid State Ionics 97 (1997)
A. Fuchs and P. Senk for technical assistance, W.
123.
¨
Munch and J. Maier for discussion and K. Eberman [19] G.J. Kearley, F. Fillaux, M.H. Baron, J. Tomkinson, S.M.
for reading the proofs. Bennington, Science 264 (1994) 1285.
[20] F. Fillaux, N. Leygue, R. Baddour-Hadjean, S. Parker, Ph.
Colomban, A. Gruger, Chem. Phys. 216 (1997) 281.
[21] K.D. Kreuer, A. Fuchs, J. Maier, Solid State Ionics 77
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