SOLID

STATE
IONICS
Solid State Ionics 89 (1996) 179-196

Review

Oxide ion conducting solid electrolytes based on B&O,

P. Shuk”, H.-D. Wiemh6ferb, U. Guth”, W. Gijpeld, M. Greenblatt”‘”

*Department of Chemistry, Rutgers lJniver.siry, Piscutuway, NJ 088550939, USA
hInstifute of Inorganic Chemistry, University of Muenster, Wilhelm-Klemm-Str. 8, D-48149, Miinster, Germany
‘Institute of Physical Chemistry, University of Greifswald, Soldtmannsrr. 23, D- 17489, Greifswald, Germany
dInstitute ofPhysical and Theoretical Chemistry, University of Tuebingen, Auf der Morgenstelle 8, D-72076, Tuebingen, Germanq

Received 14 February 1996; accepted 21 February 1996

IN MEMORY OF PROFESSOR TAKEHIKO TAKAHASHI

Abstract

The high oxide ion conductivity of solid solutions of bismuth oxide was initially discovered by Takahashi and coworkers.
The bismuth oxide based compounds are much better solid electrolytes than the well-known stabilized zirconia. The only
difficulty which has prevented their use in high temperature fuel cells and gas sensors up to now is their instability against
reduction at low oxygen partial pressures. In this article, we review the structural properties, thermal expansion, electrical
conductivity, thermodynamic stability, and surface properties of bismuth oxide and solid solutions of bismuth oxide with
face centred cubic, rhombohedral, tetragonal or layer structures.

Keywords: Solid electrolyte; Oxide ion conductivity; Bismuth oxide; Crystal structure

1. Introduction ZrO, XT xM;L + 0: + XV,, (1)

Oxide ion conducting solid electrolytes play a where M.$: is a M2+-ion in a Zr4+ lattice site and 0;
decisive role in electrochemical cells for measuring is a 02--ion on a regular lattice site.
oxygen activities and thermodynamic data of solid, Yttria stabilized zirconia (Zr, _XYX02pX,2), the
liquid and gaseous phases. They have found wide most often applied solid electrolyte which exhibits
applications for gas monitoring and combustion high oxide ion conduction at elevated temperatures,
control, in metallurgy, petrology, chemical kinetics has a low dissociation pressure and is non-corrosive.
and in solid oxide electrolyte fuel cells [l-S]. However, compared to B&O,, solid electrolytes
Presently available solid electrolytes with high based on ZrO, have a relatively low oxide ion
oxide ion conductivity are mainly derived from solid conductivity at temperatures below 800 K and
solutions of zirconia. Relatively large concentrations require very high sintering temperatures (often high-
of oxide ion vacancies, Vi can be generated in the er than 2000 K).
crystal lattice of ZrO,, if lower valent metal ions are Although there have been some reports on B&O,
substituted for Zr4+ in ZrO,, e.g. Mgzf, Ca2+ and systems earlier [9,10], Takahashi and coworkers [l l]
Y 3+. . were the first to show that the face centered cubic
(fee) phase of Bi,O,, &B&O, stabilized by various
*Corresponding author. aliovalent metal ion substitutions, has the highest

0167-2738/96/$15.00 01996 Elsevier Science B.V. All rights reserved

PII SO167-2738(96)00348-7
 180 P. Shuk et ul. I Solid State Ionics 89 (1996) 179-196

oxide ion conductivity of all oxide ion conductors
known so far.
The conductivity of &Bi,O, is one to two orders
of magnitudes higher than that of stabilized zirconia
at corresponding temperatures. The highest values of
conductivities in the B&O, family of oxides are
observed in the high temperature &phase of B&O,
with defect fluorite structure. This high temperature
phase exhibits two vacant oxide ion sites per unit cell
which are statistically disordered. But this phase is
only stable in the temperature range 1003- 1097 K.
Fortunately, substitution of yttrium or rare earth
oxides stabilizes the &phase of B&O, down to room
temperature [ 12,131. Recently, several investigations
have been performed with the aim of combining the
advantages of stabilized B&O, (high conductivity
and low sintering temperature) with those of stabi-
lized ZrO, (low dissociation, non-corrosive) [ 14-
22].
The aim of this article is to review the properties
of oxide ion conductive solid electrolytes based on
B&O, with particular emphasis on structure, com-
position and conductivity.
2. Pure bismuth oxide
cooling, in the temperature range 773-923 K. The
structure of the various Bi,O, phases was investi-
gated systematically by Harwig [28-301. Table 1 and
Fig. 1 show the characteristic data and transforma-
tion temperatures for the different phases of B&O,.
The crystal structure of the monoclinic a-B&O,
was first determined by Sillen [23]. In the a-Bi,O,
structure, layers of bismuth ions, parallel to the (100)
plane of the monoclinic unit cell, are separated by
layers of oxide ions; the structure is an ordered
defect fluorite structure [29,30] with one quarter of
the oxygen sites vacant.
The (Y+S transition at 1002 K is accompanied by
an anomalously large transition enthalpy of 29.6
kJ/mole, which is 2.7 times the heat of fusion. The
relative entropy gain due to the o--G transition with
respect to the total entropy gain from the solid to the
liquid state is 75%. This result indicates a degree of
high disorder in the &phase and corresponds to the
melting of the sublattice [31]. Sillen [23] also
reported on a cubic phase obtained by quenching
Bi,O,, that has been fused for a long time in a
porcelain crucible. This cubic structure is related to
the fluorite structure but has ordered defects in the
oxygen sublattice in the (111) direction (Fig. 2).
Each Bi3+ ion has six oxygen neighbours arranged at

2.1. Structure Liquid

1097 K

The polymorphism of B&O, has been the subject

of a number of investigations [23-301. Levin and
6 phase S-pharcl
1002 K fee fee fee
Roth [26] reviewed the work prior to 1964. Four
polymorphs of Bi,O, have been reported in the
923 K _
literature. Some confusion about the stability or 912K -

metastability of the phases resulted from the high

tendency of bismuth oxide to incorporate other p - phase ‘{ phase

oxides as impurities. tetragonal bee

a - phase
The high temperature fluorite-related S-phase of
monoclinic
773 K -
B&O, was found to be an excellent oxide ion
(a - phase)
conductor. This phase exists between 1002 K and the
y- phase may
melting point of bismuth oxide at 1097 K. Below
persist to room
1002 K the S-phase transforms to the low-tempera- temperature

ture monoclinic a-phase. Large thermal hysteresis is 603 K -

usually observed on cooling the a-phase and one of a phase

two intermediate metastable phases may be formed: monoclinic

the tetragonal P-phase at 923 K or the body centred

cubic (bee) y-phase at 912 K. Usually these phases Fig. 1. Survey of the temperature regions of stable and metastable
transform to the monoclinic a-phase, on further phases encountered in Bi,O, [28].
 P. Shuk et al. I Solid State Ionics 89 (1996) 179-196 181

high level of disorder is clearly related to the

SILLEN model GATTOW model
Bi3r 0
0” 0 may also be observed at 902 K on cooling from the
WILLIS model
Fig. 2. Structure models for fluorite related &Bi,O,
six of the eight comers of a cube; two oxygens at
diagonally opposite corners of the cube are missing.
Gattow and Schroeder [32] showed by means of
high-temperature X-ray powder diffraction that the
S-phase of B&O, is fee. They rejected the model of
an ordered defect oxygen lattice and gave preference
to an oxygen sublattice with a statistical occupation
of the sites (occupancy factor of 75%). Willis [33-
35] replaced each anion site in the fluorite structure
by four equivalent sites displaced in the (111)
direction from the ideal position. The oxide ions
occupy these sites statistically with an occupancy
factor 3/16 (Fig. 2). Neutron diffraction studies of
Battle et al. [36] showed that S-Bi,O, has a defec-
tive-fluorite structure in which 43% of the regular
oxide ion sites are randomly occupied, the remaining
1.28 oxide ions per unit cell being displaced from
their ideal positions along the (111) directions. This
exceptionally high ion conductivity. The large anion
shifts and the high temperature factors observed for
oxygen and bismuth in S-Bi,O, are reasonable, since
the S-phase is stable only in a temperature range
close to the melting point [29].
The transition to the metastable tetragonal P-phase
may be observed at 923 K on cooling from the melt
or from the high temperature S-phase [31]. The
tetragonal fl-Bi,O, has a distorted defect-fluorite
structure with ordered vacant sites in the anion
sublattice [29]. The other metastable bee y-phase
melt or from the high temperature S-phase [31]. This
y-phase often persists to room temperature. It is
likely that the formation of the metastable phases is
[29]. affected by traces of impurities.
The unit cell parameters of all of the B&O, phases
are summarized in Table 1.
2.2. Electrical properties
The conductivities of the CY,p, y and S-phases
were systematically measured by Hat-wig [28,38].
Typical results which were obtained in repeated
heating and cooling runs are presented in Fig. 3 [28].
The electrical conductivity of Bi,O, increases by
three orders of magnitude at the cy+S transition at
1002 K. In the cooling direction, a hysteresis occurs
and the transition to the intermediate p- and y-
phases are observed by 80-90 K lower than 1002 K.
The transition from the metastable intermediate
phases to the stable a-phase is not reproducible and
does not occur at a finite temperature [28].
The total conductivity of the cr-phase of B&O, is
dominated by the electronic conduction (transference

Table 1
Structural data of the B&O, phases [29]

Phase (Y 6 a Y
Phase stability temperature range (K) <IO@2 1002-1097 603-923 773-912 *
Temperature (K) 298 1047 916 298
Structure monoclinic fee tetragonal bee
a (nm) 0.58496 0.56595 0.7738 1.0268
6 (nm) 0.81648
c (nm) 0.75101 0.5731
P’ (“) 112.977
* May persist to room temperature.
 182 P. Shuk et al. I Solid State Ionics 89 (1996) I79- 196

one out of every four oxygen sites is vacant in a

fluorite-type structure; (2) the electronic structure of
0
Bi3+ is characterized by the presence of 6s2 lone pair
electrons, leading to the very high polarizability of
the cation network which favours oxide ion mobility;
-1
(3) the particular ability of Bi3+ to accommodate
z
Y highly disordered oxygen surroundings. A further
m
g-2 advantage for electrochemical application is the
4 tendency of Bi3+ to promote the dissociation of
-3 oxygen molecule.
Although the S-phase of Bi,O, exhibits the high-
est oxide ion conductivities known so far, its use is
limited because it is only stable in the narrow
temperature range 1002-1097 K.

700 800 900 IO00 1100

2.3. Thermal expansion
T(K)

Fig. 3. Electrical conductivity, log u versus temperature of Bi,O, The thermal expansion coefficients of B&O, were
P81.
first determined by Gattow and Schroeder [32]. They
found very high thermal expansion coefficients for
number ti,,<0.002 [39]); holes are the mobile the a-phase of Bi,O, (Table 2). Levin and Roth
charge carriers. The electronic defect concentrations [26], however, found thermal expansion coefficients
are determined by impurities. These properties are that were a factor of two lower than those from
found in the entire temperature range up to the a+S high-temperature X-ray investigations. Typical val-
phase transition. In the temperature range 923-1002 ues of the thermal expansion coefficient of different
K a rapidly increasing concentration of oxygen phases of B&O, are summarized in Table 2. The
vacancies leads to an increase of the ionic con- transition from the 6- to the P-phase is accompanied
ductivity [28]. In the metastable p- and y-phases, the
conduction is predominantly ionic [28,39]. The Table 2
activation enthalpies as determined from the tem- The average thermal expansion coefficients (Y’ of the B&O,
perature dependence of the ionic conductivity are phases
132, 95 and 38.5 kJ/mol for the /3-, y- and S-phase, Temperature Middle thermal expansion Reference
respectively [28]. range (K) coefficients (Y’ (10-“/K)
According to Harwig [28,38], &B&O, exhibits a P Y 6
high ionic conductivity with mobile oxide ions as the
373-413 12.2
majority charge carriers. This is in agreement with 12.4
473-673
the results of electromotive force and transference 673-848 14.2 ~321
measurements by Takahashi et al. [ 11,401. The 848-948 14.8
conductivity of the a-phase is independent of the 948- IO23 43.6

oxygen partial pressure at least down to 10e3 Pa 298- 1003 11.0

[28]. The high intrinsic disorder and the high mobili- 1003- 1098 23.0 WI
ty of the oxide ions are consistent with the change in 913-298 20.0
923-773 24.0
entropy and the structure of the S-phase. High-
temperature neutron diffraction experiments con- 400-800 12.9 1371
940- 1020 20.0 99.0%
firmed that the oxygen sublattice is disordered and
liquid-like [29]. 400-800 10.6
Recently, Mairesse [41] summarized the reasons 949-1025 20.2 [371
930-840 19.2 99.9%
for the high oxide ion conductivity of &Bi,O,: (1)
 P. Shuk et al. I Solid State Ionics 89 (1996) 179- 196 183

by a large sudden volume change and a deterioration Table 3

The crystal phases observed in annealed and quenched specimens
of the mechanical properties of the material.
of (Bi,O,),-<(Ln,O,), (? unidentified phase) [49]

ho, Crystal phase observed

3. Solid electrolytes based on modified bismuth Ln x Annealed specimen Quenched specimen

oxide La 0.15-0.28 Rhomb Rhomb
0.30-0.40 Rhomb + LaOF-type
In their original work, Takahashi and coworkers 0.50 LaOF-type
Nd 0.10-0.30 Rhomb Rhomb + fee
demonstrated that the high temperature phase with
0.40 Rhomb + LaOF-type
high ionic conductivity can be stabilised to lower
0.50 LaOF-type
temperatures in a similar way as known for cubic Sm 0. IO-O.20 Rhomb + ? fee
zirconia, i.e. by substitution of aliovalent cations for 0.30 Rhomb fee
Bi. Bismuth oxide easily forms solid solutions with 0.35 Rhomb + fee fee
many other metal oxides. Different structures are 0.40 fee
0.50 LaOF-type
found including fee, rhombohedral and tetragonal

-
DY 0.20 Rhomb + ? fee
structures on the B&O,-rich side of the binary 0.30-0.40 fee
systems [42,43]. The stability region of the high Er 0.20 fee+? fee
ionic conductivity phases can be extended to room 0.25-0.30 fee
Yb 0.10 Tetragonal fee+?
temperature by incorporation of 22-27 mol% WO,
0.20 Tetragonal + ? fee
[44], 25-43 mol% Y,O, [45], 35-50 mol% Gd,O,
0.30 fee
[46], 17.5-45 mol% Er,O, [47], 28.5-50 mol% fee+?
Dy,O, [48], 30-40 mol% Sm,O, [49], 15-26 mol%
Nb,O, and 20-25 mol% Ta,O, [50], lo-35 mol%
Pr,O, 66 [51,52], and 30-50 mol% Tb203_5 [52,53]. La

3.1. Solid electrolytes based on solid solutions of

Bi,O,
- Nd

- Sm
3.1.1. Structure
Most of the ion conducting solid solutions of
- Gd
B&O, form with the fee structure of the high
temperature &B&O, phase. In addition, a rhom- -Y
bohedral structure corresponding to the rhombohedr- - Er
al Bi,O,-SrO structure (analysed by Sillen et al.
[54]) or a rhombohedral LaOF-structure were found
[55]. The type of structure that forms is largely
dependent on the ion radius of the substituted metal I I I I
cations and on their concentration. Some examples 0 0.2 0.4 0.6 0.8 1.0
of the relationship between the structure and the x

composition in solid solutions of Bi,O, with rare Fig. 4. Stability ranges of the rhombohedral and fee phases of
earth oxides are summarized in Table 3. Fig. 4 shows (Bi,O,),_,(Ln,O,)” in the ionic radius vs. composition diagram
the regions of fee and rhombohedral phases which [491.

are stable at room temperature as a function of the

ionic radius of Ln3+ and its content [49]. The thin
lines show the limits of accuracy due to the con-
centration measurement at relatively low and high
Ln,O, contents. Generally the rhombohedral phase
is formed in the systems doped with Ln,O, (Ln = La,
Nd, Sm, Gd), with relatively large rare earth ion radii
and relatively low x in (B&O,), _,(Ln,O,)x. The fee
phase of B&O, is stabilized by cations with smaller
cationic radii than Bi3+ and relatively high con-
centrations. Verkerk et al. [48,58] assumed that
 184 P. Shuk et al. I Solid State lonics 89 (1996) 179-196

stabilization of the relatively loose high temperature (B&O,), _JY203)+ oxide ion ordering occurs along
&phase structure occurs by a contraction of this the (111) and (110) directions. Subsequent neutron
structure due to the substituent. If the difference scattering and X-ray diffraction experiments on
between the ionic radius of Bi3+ (0.111 nm [59]) fluorite-type solid solutions (B&O,), _.,(Ln,O,),
and the substituted Ln3+ is large, the substitution (Ln=Y, Er, Yb) have revealed substantial short-
will result in a large distortion of the host lattice and range ordering, the extent of which increases with
only a small amount of substituent is necessary for increasing content of the substituent [65-671.
supplying the energy required to stabilize the fee A new phase, found by Watanabe et al. in the
phase of Bi,O,. Conversely, a small difference bismuth-rich region of the systems Bi,O,-Y,O,
between the ionic radii of Bi3+ and Ln3+ requires a [W and B&O,-Ho,O, [691 has a
large amount of substituent to stabilize the fee phase, Bi 0,765Sr0,2350,,383-tyPe layered structure with hexa-
as for example is the case for Gd3+ (Fig. 5). Too gonal symmetry and shows high oxide ion con-
large a difference between the ionic radii of the Ln3+ ductivity [70-721.
and Bi3+ ions makes the fee phase unstable [48].
A large number of ternary and quaternary Bi,O,- 3.1.2. Ionic conduction
based oxides have been synthesized and character- Verkerk et al. [48,58] studied the relationship of
ized [60-631. The substitution of two different metal the ionic radius of the Ln3+ substituent ion and the
oxides instead of only one favored the stabilization minimum amount of Ln,O, (xmin) required to stabi-
of the S-phase down to room temperature at distinct- lize the fee phase of Bi,O, and the affect of these
ly lower concentration of the oxides [62]. This factors on the conductivity. The correlation between
cooperative effect was attributed to the entropy the ionic radius and x,,,~” is given in Fig. 5. There are
increase in the quaternary systems, which is the main two opposing tendencies that must be optimized for
factor determining the defect properties of the fee maximal conductivity [48]: first, the ionic conduc-
phase. tivity increases with increasing ionic radius. Second,
It was shown by Battle et al. [64] that in x,,,~” increases with increasing ionic radius (Fig. 5),
however, a high x,,,~” value results in low oxide ion
conductivity. Nevertheless, the influence of the ionic
radius on the ionic conductivity is smaller than the
affect of the Ln,O, content. Therefore optimum
ionic conductivity is achieved by lowering x,,,~“. The
0.35 highest oxide ion conductivity occurs at the lowest
x,,,~” required to stabilize the fee phase for B&O,
0.30 stabilized by Er,O,, as shown in Fig. 6 [48].
In a highly defective structure a completely ran-
0.25
dom arrangement of oxygen vacancies is unfavour-
able and is only possible in small domains. A model
-2
of the short-range ordered units, or ordered microdo-
* 0.20
mains proposed for (Bi,O,),,,,(Ln,O,),,,, by Ver-
kerk et al. [73] is shown in Fig. 7. For this
0.15 composition every tetrahedron consists of three
Bi3+-ions and one Ln3+-ion, denoted as a (Bi,Ln)-
tetrahedron. Fig. 7 shows the oxide ions of a (001)
L
0.098 0.100 0.102 0.104 0.106 plane at z = 3 14. The cations above and below this
r ion @ml plane are indicated. The oxide ions are displaced in
Fig. 5. x,,,, the minimum value of x required to stabilize the fee
the direction of the lanthanide ions. It is clear from
phase in Bi,O,),_,(Ln,O,), vs. the ionic radius (r,,,,) of Ln’+ Fig. 7 that there are two different O-O distances.
[481. Indeed, from diffuse neutron scattering studies of
 P. Shuk et al. I Solid State Ionics 89 (1996) 179-196 185

B&O, solid solutions at lower temperatures (<870

/“--
K) two types of O-O distances have been identified:
0.268 nm and 0.290 nm respectively [73]. At about
the same temperature (870 K) a knee in the Ar-
rhenius plot of B&O, stabilized with Y,O, [45],
Gd,O, [46], Er,O, [47] or Dy,O, [48] was reported.

r-
The anomaly was ascribed to a change in the defect
713 K structure. The activation energy of the conductivity
is determined by the strength of the Ln-0 bond and
by the energy necessary for 02- ions to migrate
through the tetrahedral planes. In the low tempera-
ture region the effect of the Ln-0 bond strength is
predominant. Only oxide ions in the (Bi,Ln)-tetra-
hedron are mobile. Migration of an oxide ion from
3+ 3+ 3+
Yb3’ Er Y3+Dy Gd one tetrahedron to an empty site in the next one
involves breaking of the Ln-0 bond and passage
0.098 0.100 0.102 0.104 0.106 through (Ln,Bi)-, (Bi,Ln)- or (B&)-tetrahedral
r IO” (nm)
planes. At about 870 K the lattice disorders, resulting
Fig. 6. Electrical conductivity, log (T of (Bi,O,),_,(Ln,O,), for in a increase of the Ln-0 distance. In the high
x,,, vs. the ionic radius of the substituted Ln’+ [48]. temperature region all the oxide ions take part in the
conductivity process and there are no preferential
diffusion paths. Detailed calculations are necessary
to determine whether the strength of the Ln-0 bond
or the energy to migrate through a tetrahedral plane
is predominant at high temperatures [73].
Typical solid electrolytes based on Bi,O, are
summarized in Table 4. Most of them show fee or
rhombohedral crystal structure. Fig. 8 shows, that
solid electrolytes based on Bi,O, have one or two
orders of magnitude higher oxide ion conductivity
than stabilized zirconia. The y-type
B&V, _XMx05,5_y (M = Cu, Co, Ni) also present very
attractive conductivities, especially at low tempera-
tures and will be discussed separately.

3.1.3. Hole and electron conduction

The partial electronic conductivity of Bi,O,-based
oxide ion conductors was studied by cell voltage
(e.m.f.) and polarization measurements by Takahashi
et al. [75]. The hole (a,), electron (a,) and oxide ion
(ui) conductivities versus oxygen partial pressure
~(0,) in Bi,.,,Y,,,,O,,, are given in Fig. 9. The
partial pressure dependence of the electron and hole
conductivities correspond to aP -p( 0,)’ ‘4 and c,, -
l 02- 0 -oxygen vacancy n -Ln’+ 0 - Bi3+
P(O*)-“4, which indicate that the following defect
Fig. 7. A model of the ordered microdomain unit for equilibria are established in the presence of the large
(Bi,O,), ,,(Ln,W, 25 [731. and constant concentration of oxygen vacancies:
186 P. Shuk et al. I Solid State lonics 89 (1996) 179-196

Table 4
Typical solid electrolytes based on B&O, [12,13,41,47,48,52,56,57]

Composition Oxide ion conductivity q (S/cm) Structure

173 K 923 K 1153 K

% xssY,, &, 92 4.6. IO-’ 3.8. 1om2 0.02 fee
BiO 15 _ _ 2.3 (1073 K) fee
Bi,, &%, , ,O, 44T 6.0. IO-’ 5.0. IO_’ 0.27 rhomb
Bi,, ,,Ba,, , ,O 1.1.10-2 0.7 rhomb
lo-’ 1.1 _ fee
Bi,,.,,f’b,, &: :P’
Bi,,,,Y,, &, s 1.3. lo-2 0.11 0.35 fee
Bi,, &dO ,,O, 5 3.5.1o-J 0.056 0.26 fee
Bi,, ,,Tb,, ,,O ,4+fi 3.4. lo-’ 0.012 0.28 fee
Bi,, x,,Tb,, &, 5+fi 4.2.10-’ 0.28 0.75 fee
Bi,, ,,DY,~.,,O, 5 1.35.10-* 0.12 0.46 fee
Bi,, 71Ho,1.250 5 l.35~lo~2 0.17 0.40 fee
Bi,, 7&2501 J 1.27.10-’ 0.135 0.43 fee
Bi,,.J% #, 5 2.1. 1o-2 0.23 0.52 fee
Bi,, ,5Tml, &, 5 7.10-’ 0.08 0.40 fee
Bi,, 7 Yb,, 20, 5 8.0. IO-’ 0.074 0.40 fee
Bi 7&I ,sO, 3.3.10-’ 0.037 0.28 fee
0 5
Bi,, xoSmO 2,P1 5 2.3.10-1 0.02 0.15 fee
Bi,, x,$‘ro & Is+6 3.0.10+ 0.02 0.15 rhomb
Bi,,,,Nb,,,,O, hS 1.1.10-* 0.11 0.50 fee
Bi,, xc,Ta,,2,PI ,(, 5.0. lo-1 0.0 1 0.073 fee
Bi,, &o,, r201 hX 6.0. IO-’ 0.017 0.11 tetrag
Bi,,.,,W, ,,O I 6X l.o~lo-* 0.04 1 0.15 fee
B&V,, &r,, ,A 35 5.6. 1O-2 0.13 _ tetrag

T(K) o- 0 10” 973 K

1200 1100 1000 900 800
873 K

-2 - 773 I

-10 I I I I I
-5 -3 -I I 3 5 7

-log PCJ 2 ) (Pa)

Fig. 9. Oxygen partial pressure dependence of the hole and

electron conductivities of (Bi,O,),, ,,(Y,O,),, 27 solid electrolyte
8 9 10 II 12 13
[751.
F4 (K-I)
0, + 2V, H 200” + 4h’, (2)
Fig. 8. Oxide ion conductivity versus temperature for selected
solid electrolytes [28,47,74]. 20: tj 2V, + 4e’ + 0,. (3)
 I? Shuk et al. I Solid State Ionics 89 (1996) 179- 196 187

The hole and electron conductivity of Bi,,,,Y,,,,O,,, these crystals were twinned. Bi,VO,., is in fact the
can be expressed by the following equations [75]: upper limit of solid solution formation in B&O;
xVO,s with 0.86-(x< 1. On heating, the room-tem-
~~,/S*cm-’ = 5.0. 102[p(0,)lbar]“4 perature a-Bi,VO 5.s phase transforms through the
.exp[-106kJI(RT~mol)], (4) P-phase (stable at 720-840 K) to the tetragonal
y-Bi,VO,, phase [77]. a-Bi2V05,5 can be indexed
u,/S.cm-’ = 3.4. 105[p(02)lbar-“4 in a face-centered orthorhombic cell with a =
0.5533(l), b=0.5611(1) and c= 1.5288 nm. The
. exp[-213 kJI(RT. mol)]. (5)
mean cell parameters of the p form seems to be
tetragonal with a = b = 1.1285(S), and c = 1.542( 1)
Bouwmeester et al. [76] performed isothermal
nm at 775 K. The y-phase is tetragonal with a =
oxygen permeability experiments on sintered
0.3988(2), c = 1.542( 1) nm at 885 K and space group
Bi,.,,Er,.,,O,., and obtained a p-type electronic
14/mmm [78]. Thus the prototype y-cell is a subcell
conductivity similar to that of the Y substituted
of the (Y and the p cells according to the relationship
phase:
[77]:
a,/S.cm-’ = 3.0. 102[p(0,)lbar]“4
. exp[-91 kJI(RT. mol)]. (6)
These values of hole and electron conductivities of ap#2d2a,, b,#d2a,, cs#c,.
Bi,O, solid electrolytes are much lower than the
oxide ion conductivity in a broad oxygen partial The idealized structure of the y-phase, without
pressure range. Defect electron conductivity domi- oxygen vacancies, is presented in Fig. 10 with
nates oxide ion conductivity only at very low oxygen
partial pressures p(02)<10-‘6 Pa at 1000 K.

3.2. BIMEVOX solid electrolytes

The latest generation of attractive oxide ion con-

ducting solids is known under the short term
BIMEVOX (BI-bismuth, ME-dopant metal, V-vana-
dium, OX-oxygen). It denotes a family of multinary
oxides based on Bi2V0,,, [77-971. This phase is a
solid solution of Bi,O,*VO,,, whose compositions
covers the range -66.7 to 70.4% Bi,O,. The major
part of a recent review by Mairesse [41] focuses on
BIMEVOX, obtained from the parent compound
BiZV05,5 by substituting other cations for vanadium.

3.2.1. Structure
The structure of B&VO,., is of Aurivillius-type
[93] with [Bi20212+ layers sandwiched between
defect [VO,,,(V,),,,]*- perovskite-like slabs, with
the perovskite slab containing oxygen vacancies Vi
responsible for the high oxide ion conductivity
[77,78]. Bush et al. [94] first identified Bi,VO,,, as
an orthorhombic phase with unit cell parameters
a = 1.662, b = 1.684 and c = 1.55 nm. Owing to the
large unit cell volume, Mairesse [41] presumed that Fig. 10. The ideal structure of y-type Bi,VO, 5.
188 P. Shuk et al. I Solid State Ionics 89 (1996) I79- 196

typical alternating B&O, layers and VO, perovskite T (K)

like sheets. Compared with the ideal tetragonal 1000 900 800 700 600 500

structure, the structure of B&VO,,, exhibits a split-

ting of all the atomic positions except 0( 1). The
vanadium is in a highly distorted octahedral site. It is -1
assumed that the numerous oxygen vacancies in the
perovskite-like sheets, and the correlated shifts of the
cations from their ideal positions are responsible for
-2
the high oxide ion mobility and the low activation -z
energy in this phase. x
In the past it has been shown that the partial D

substitution of other metal ions for V suppresses the B

-3
r-+P or y+a transitions, allowing the highly
conducting y-structure to be stabilized to room
temperature. Recently Lazure et al. [97] reported
about possible substitution for vanadium with both
-4
Co and Bi.

3.2.2. Electrical conductivity 8 10 12 14 16 18 :

The compound Bi,VO,,, exhibits a relatively +4(K-l)
large oxide ion conductivity in the high-temperature
y-phase between 840 and 1050 K [77]. Many Fig. 11. Oxide ion conductivity of selected Bi2V,j,Mo,,0, 5-1
with M=Cu, Co, Ni and Zn [41].
elements can substitute for vanadium to form y-type
solid solutions. However, some of the y-type com-
pounds are metastable at room temperature [41]. In
order to achieve better conductivity at lower tem-
peratures, vanadium was partially substituted by ductivity value in BIMEVOX family ((r=4. 10e4
other elements including Cu, Ni or Zn [82-841, Pb S/cm at 500 K) in y-Bi,V,,ssTio,ls0,,4~~.
[86], MO [87], W [SS], Co [89,97], Ti, Zr, Sn and Pb
[90]. Depending on the chemical nature of the 3.2.3. Electrochemical properties
substituent M in Bi2V,_,M,0s.s_y, the critical con- Two compositions of the BIMEVOX family,
centration values x,,, limiting the y-solid solution %V,PO. IO,., -y
and Bi,V,,,Ni,,,O,,,_, were
domain differ considerably and have a maximum studied as solid electrolytes in electrochemical cells
value (x =0.5) with Nb and Sb [95,96]. However, the with various electrode materials such as gold and
minimum value of x is often around 0.10 indepen- strontium substituted lanthanum manganite [79].
dent of the formal valence of M [41]. Furthermore, Significant, about an order of a few percent, elec-
the best conductivities are always obtained with an x tronic contribution to the total conductivity was
value close to 0.10, whatever the dopant cation in evident, which plays a decisive role in the electrode
B&V, -xMxG5.5-1% All the BIMEVOX (M=Cu, polarization. In marked contrast with common con-
Ni, Zn and Co) exhibit the same temperature depen- ventional oxide ion conductors such as stabilized
dence of the conductivity with a more distinct zirconia, the electrode polarization decreases with
change of the slope in the case of Zn (Fig. 11). decreasing oxygen partial pressure, because of the
Double substitutions in Bi,VO,,S, either on the V site increasing electronic conductivity.
only, or simultaneously on both the Bi and V sites, The cathodic voltage limit of the stability range of
do not improve the oxide ion conductivity relative to Bi,V,.,(Cu/Ni),,,O,.,_, solid electrolytes was de-
the singly substituted phases [84]. Recently Yan and termined using the relaxation potential of a tip
Greenblatt [90] reported the highest oxide ion con- electrode after a reduction pulse and was found to be
 P. Shuk et al. I Solid State Ionics 89 (1996) 179- 196 189

below -300 mV with respect to air [79]. At 800 K

this value is equivalent to an oxygen partial pressure
of 5. 1O-4 Pa.

4. Mixed conductors based on bismuth oxide

solid electrolyte
Mixed conductors based on B&O, are of principal
interest as electrode materials and semipermeable v;;,o;
membranes for use in electro-catalysis and in gas solid electrolyte
separation. Solid solutions of B&O, with mixed- Fig. 12. Scheme of electrode reaction at the gas/solid electrolyte/
valent ions can lead to mixed electronic and ionic electrode interface for: (a) metal electrodes, (b) mixed-conducting
conduction. Studies of a number of B&O,-based electrodes.
mixed conductors e.g. Bi,03-Tb,O, [52,53,56,98-
1001, B&O,-Pr,O,, [51,52,98,99], B&O,-BiVO,
[101,102] and Bi,03-Y,03-TiO,_, [103] have
been reported. Some excellent mixed-conducting charge transfer reaction occurs over the whole
materials with high oxide ion conductivity, close to surface, because both oxide ions and electrons are
the conductivity of &Bi,O, and comparable p-type mobile, and so polarization losses are reduced
electronic conductivity, were found in solid solutions [99,108].
of Bi,O, with Tb,O,. The hole conductivity de- Mixed conductors based on B&O, are presented in
creases with decreasing Tb4+ concentration and Table 5 in comparison with some other mixed
oxygen pressure [ 1011. conductors.
Some molybdates, Bi,Mo,O,,, P-Bi,Mo,O,,,
Bi,Mo,O, and Bi,MoO, have shown very high
ionic-electronic conductivity even at temperatures as 5. Electronic surface properties of Bi,O, solid
low as 573 K [104-1061. electrolytes
A two-phase system consisting an intimate mix-
ture of an electronic conductor and an oxide ion Recently the electronic surface properties of
conducting phase is another approach to obtain a Bi,O,-based solid electrolytes have been studied by
mixed electron-ion conducting material. Both phases UV- and X-ray-photoelectron-spectroscopies (UPS,
should exhibit continuous conduction paths in the XPS) as well as electron-energy-loss-spectroscopy
mixture. Shen et al. [107] recently found promising (EELS) [109,110]. UPS yields information on the
results for mixed conduction in the ceramic two- work function of electrons and the ionisation energy
phase system consisting of oxide ion conducting of the surface. Using solid metal-metal oxide mix-
Bi ,,75Y,,250,.5 and the electronic conducting tetra- tures (such as Fe-FeO) as solid reference contacts
gonal phase Bi,CuO,_,. during the photoemission experiments, the position
Mixed-conducting oxides based on Bi,O, used as of the Fermi level was obtained with relation to the
electrode materials can have a number of advantages valence band edge and for the corresponding oxygen
in comparison with traditional noble metal elec- partial pressure (fixed by the metal-metal oxide
trodes. In the case of metal electrodes (e.g. Pt), system) [ill]. In addition EELS was used to de-
charge transfer between the electrode and the solid termine the energy difference between the highest
electrolyte occurs at or near the three-phase gas/ occupied and lowest unoccupied electronic levels,
electrode/solid electrolyte interface (Fig. 12). A i.e. the band gap between the valence band and the
potentially better electrode material is one for which conduction band. A band gap E, =2.8 eV was
oxygen exchange is not limited to the three-phase derived from the EEL spectrum [ 1 lo]. The data from
contact region. At a mixed-conducting electrode, the UPS and EELS suggest the band scheme in Fig. 13.
190 P. Shuk et al. I Solid State tonics 89 (1996) 179-196

Table 5
Properties of mixed-conducting oxides

Composition Ionic transport Ionicconductivity Temperature Reference

number (t,,,, ) u, (S/cm) T(K)

Bi,, KSPrO,$, s+8 0.93 0.91 973 WI

Bi,175%2501s+6 0.92 0.29 973 WI
Bi,,
d'rO,,O 0.88 0.2 1 973 [=I
Bi o w,Tb,, o,s:::+fi 0.9 1 1.2 973 1521
Bi,, ,,,Tb,, J’, s+8 0.85 0.38 973 [521
(Bit, 7sYI, J), A, v5 0.86 0.22 973 [2Il
(Pro, H31)“M
Ce,,.,,,Tb,,.&-, 0.18 0.0147 873 [IO61
La,, ,Sr,,.,,,Co,,,Fe,, A 0.007 1.8 1073 [IO61
Bi,, &o,,& 2s 0.51 0.00324 873 [I061

edge. This limits the electrolytic domain of the solid

N [cpsl
Fig. 13. Band scheme for cubic stabilized Bi,,,,Y,,,,O, s as
derived from UPS- and EELS results (at T=873 K). The energy
scale is referred to the energy E, of the valence band edge [I 101.
Electronic conductivity is predicted for such a
solid, if EF as a function of ~(0,) approaches the
conduction band edge to within of about 0.5 eV.
However, disordered solid compounds and in par-
ticular solid electrolytes often show additional elec-
tronic states in the band gap near the band edges
(band tailing). Such localized electronic states, due
to the high ionic disorder in the oxide lattice, were
found in bismuth oxide as well as in stabilized
zirconia [ 110,112,113], Therefore, electronic con-
ductivity can arise in these systems by electron
hopping through the localised electronic states near
the band edges. The Fermi level of bismuth oxide at
900 K is 0.7-0.9 eV below the conduction band
electrolyte towards low oxygen activities, i.e. under
reducing conditions. Potentials of -1 volt should
already lead to electronic conduction in the bismuth
oxide electrolyte at the cathode.
The electrolytic domain at low oxygen partial
pressure depends on the composition. The band gap,
being practically temperature independent in the
temperature range 700-900 K, increases with Y,O,
concentration and the position of the Fermi level E,
measured from the valence band edge E, shifts
slightly to higher values: for Bi,.,,Y,,,,O, ,5 E,= 2.8
eV and for Bi o,60Yo,400,,5 E,=3.2 eV. The position
of the Fermi level with Fe/Fe0 reference contacts
was E,-E,=2.1 eV for Bi,,75Y0,250,,5 and E,-
E,=2.3 eV for Bi0,60Y0,400,,5. These results are
comparable with energy gap data (E,=3.1 eV) for
&B&O, thin films deduced from optical adsorption
spectroscopy [ 1141.
XPS-spectra of the 01s level of Bi, _,YIO,,, (x=
0.25-0.40) samples at higher temperatures (700-
1000 K) can be deconvoluted into two contributions,
one with a maximum at Eb= 529.0eV and a second
at 531.4 eV. These two oxygen peaks are attributed to
lattice oxygen (lower binding energy) and adsorbed
oxygen or hydroxyl groups (higher binding energy),
respectively. Similar results have been obtained for
thin oxide layers on Bi-metal [115] or Bi containing
superconducting oxide phase [ 116,117]. If the tem-
perature increases above 673 K, the lattice oxygen
peak becomes more intense due to desorption of
adsorbed species.
 P. Shuk et al. I Solid Stare Ionics 89 (1996) 179-196 191

6. Electrochemical properties solid electrolytes was studied by Nagamoto and

The electrochemical behavior of the electrode/
solid electrolyte systems depends on many factors
such as oxygen partial pressure, temperature, micro-
structure of the electrode and composition of solid
electrolyte and electrode materials. Sputtered Pt and
Pt-gauze electrodes were investigated on ZrO,-
Y,O,, CeO,-Gd,O, and Bi,O,-Er,O, solid elec-
trolytes by Verkerk et al. [ 1181 by means of d-c
measurements as a function of temperature and
oxygen partial pressure. The electrode process was
found to be strongly influenced by the nature of the
solid electrolyte. The electrode resistance for Pt
electrodes on B&O,-Er,O, solid electrolytes was
found to be much lower than on ZrO,-Y,O, and
CeO*-Gd,O, solid electrolytes. With zirconia- and
ceria-based solid electrolyte materials, diffusion of
atomic oxygen on the Pt electrode was assumed to be
the rate-determining step in the electrode process,
whereas for bismuth oxide based materials diffusion
of adsorbed gas on the oxide surfaces was more
likely the rate-determining step [ 1181. A surface
control in the oxygen exchange kinetics has been
found by Boukamp et al. [ 119,120] from the direct
measurement of the gas-phase isotope ratios in “0
exchange experiments on solid solutions of B&O,
with Er,O, or Tb,O,.,. For Pt electrodes on Bi,O,-
Er,O, solid electrolytes frequency dispersion mea-
surements showed that two circuit elements are
sufficient to describe the impedance, a resistance R
and a Warburg impedance, W connected in parallel.
From a comparison with other solid electrolyte/
electrode combinations, it was concluded that R was
controlled by the diffusion of atomic oxygen along
the electrolyte surface to the electrode. A Warburg
impedance was typical for electrodes on B&O,-
based solid electrolytes and it was suggested that
bulk transport of electronic charge carriers in the
solid electrolytes was the rate determining process of
the Warburg coefficient. At high oxygen partial
pressure ~(0,) the d-c resistance of the electrode
process was determined by the resistance R (diffu-
sion on the surface of the solid electrolyte) and at
low ~(0,) by the Warburg impedance (diffusion
through the solid electrolyte) [ 1181.
The behavior of Ag, Pt and La, _,Sr,CoO, (x=0-
0.7) electrodes on Bi,_YEr,yO,,, (y=O.15, 0.20)
lnoue [ 1211 by means of a current interruption
method. The electrode resistance of noble metals was
found to be approximately proportional to ~(0,)~“*
suggesting that the rate-determining step is the
diffusion of dissociatively adsorbed oxygen. The
dependence of the resistance of cobaltite electrodes
on the oxygen partial pressure varied from - 1/4th
order at lower temperature to - 1/2th at higher
temperature. It was concluded that charge transfer as
well as diffusion are rate controlling, and that the
degree of contribution of each process changes with
temperature. The contribution of this diffusion to the
electrode impedance decreased with increasing Sr
concentration in lanthanum cobaltite [121]. It was
demonstrated by Tanabe and Fukushima 11221 that
the preparation method of the electrode material had
a great influence on its electrochemical properties. It
was shown that a thermal decomposition method for
cobaltite electrode preparation gave favorable polari-
zation properties of the electrode/electrolyte system.
The anodic and cathodic polarization behavior of
sputtered porous gold electrodes on Bi,,,,Er,,,,O,,,
solid electrolytes were studied by Vinke et al.
[ 123,124] as a function of temperature and oxygen
partial pressure using a three-electrode cell. Com-
parison with the polarization behavior of sputtered Pt
electrodes on the same solid electrolyte composition
showed little effect of the electrode material on the
exchange current densities. This result indicates that
the solid electrolyte surface was actively participat-
ing in the oxygen transfer process. The noble metal
electrode serves merely as an electron current collec-
tor. Analysis of the electrode impedance showed
strong influence of surface diffusion on the electrode
reaction [124].
The polarization resistance of doped cobaltite
electrodes on Bi,,,,Y,,,,O, .5 solid electrolytes was
determined from the steady-state current density
overpotential curves, which were measured in a three
electrode arrangement [ 125,126]. Cobaltites are ac-
tive mixed conducting electrodes, particularly at low
temperatures. At temperatures below 800 K the
polarization resistance of all investigated cobaltite
electrodes was below the value of active silver
electrodes (Fig. 14). This finding is connected with
relatively weakly bound oxygen species formed at
the surface of the perovskite-type oxide. These
 192 P. Shuk et al. I Solid State tonics 89 (1996) 179-196

Table 7
T W)
IO00 900 800 700 Fqrilibrium oxygen pressure of (B&O,), _,(Me,O,), solid elec-
trolytes from electrochemical measurements [ 1331

Composition Equilibrium oxygen pres-

sure
fog ~(0~) (Pa)
873 K 973 K

Bi@, 8.01+0.02 5.8OkO.04

(Bi,O,),_X(Y,O,)X x=0.25 8.45~0.10 6.09kO.08
0.30 8.8OkO.07 6.43 20.05
0.37 9.23kO.10 6.8OkO.08
(Bi,W-JDy,O,), x=0.30 860~0.07 6.18+0&l
0.35 8.90t0.10 6.44kO.08
0.40 9.31 kO.10 6.71 lrO.08
(Bi,W-X(Er,O,), x=0.27 8.63kO.10 6.30t0.08
0.32 9.01~0.10 6.56kO.08
0.37 9.55kO.10 6.92kO.08

IO 11 12 13 14 15

F4 (K-’ )
According to Takahashi et al. [ 1281 the overall
decomposition reaction of B&O, solid electrolytes is
Fig. 14. Temperature dependence of polarization resistivity rP of
various electrodes with Bi 0 7SY0250,.5 solid electrolyte [126]: Ag
described by:
(1h L%,% ,CoO, CV, Pr,,,% $00, (3), Nd, ,Sr,, $00, (4).
(B&O,),-,(Me,O,), ~(Bi,O,),-x~,(Me,O,), +
SrCo,,Pe,, $L (5).
2cuBi + 3a/2 0,. (7)

oxygen species are assumed to be active at low Thermodynamic data on S-B&O, and their solid
temperatures and to enhance the rate determining solution have been obtained by electrochemical
step of the electrode reaction corresponding to the measurements. Data shown in Table 6 indicates good
charge transfer step [ 1271. agreement between various investigators. Verkerk
and Burggraaf [132] showed that the range of ~(0,)
where (B&O,), _X(Ln,O,), solid electrolytes are
7. Stability range stable against reduction did not increase by addition
of Dy,O, or Er,O, with respect to pure S-Bi,O,.
At high temperatures, solid electrolytes based on However, later electrochemical investigations of
B&O, are unstable towards a reduction to metallic Berezovskaya et al. [133] showed a considerable
Bi under low oxygen pressure. For practical applica- increase of stability of (Bi,O,), _X(Ln,O,), solid
tions, it is very important to know the limiting electrolytes with increasing dopant concentration
oxygen partial pressure where reduction occurs. (Table 7).

Table 6
Temperature dependence of the standard Gibbs free energy for the formation of S-B&O, and solid electrolytes based on Bi,O, from
electrochemical measurements (referred to 1 mole B&O,)

Composition AG”=a+bT (kJ/mol) Reference

-a (kJ/mol) b.10” (kJ/(mol-K)) Validity range (K)

S-Bi,O, 561k2 26529 795-1095 [12gl

S-B&O, 558 272 991-1095 112%
&Bi,O, 56455 268+5 949- 1076 11301
Bi o @Y,.,, 0 15 561’5 271+10 750-950 [I311
Bi 0 &rO 4&I 5 55927 268213 750-950 [I321
 P. Shuk et al. I Solid State Ionics 89 (1996) I79- 196 193

Furthermore, in the rhombohedral Bi,O,-SrO p(O,)> 10-6-10-7 Pa at 973 K and p(O,)>lO-‘-

system, the stability in reducing atmospheres in-
creases with increasing Sr concentration. The oxygen
partial pressure for decomposition of Bi,O, deter-
mined from the known thermodynamic data were
compared with calculated values of decomposition
oxygen partial pressure of the (Bi,O,),,,,(SrO), 4X
rhombohedral phase (Table 8).
Further, the cubic phase in B&O,-Ln,O, systems
has been found to be unstable below about 970 K. It
undergoes a transformation to a mechanically un-
stable rhombohedral phase [ 1341. The phase trans-
formation can be suppressed by addition of alioval-
ent dopants (e.g. ZrO,), which is assumed to sup-
press the cation interdiffusion [ 1351.
Wang et al. [ 1361 obtained unexpectedly favorable
results on yttria stabilized bismuth oxide which
showed an extended stability interval for oxygen
partial pressures down to lOpI6 Pa at 973 K. These
data were confirmed by Jurado et al. [137].
The potential use of B&OX-based solid electrolytes
in solid oxide fuel cells was examined by Virkar et
al. [135,138] and very recently reviewed by Azad et
al. [139]. It was shown that by carefully optimising
the conduction properties in two-layer electrolytes
consisting of a thin layer of zirconia on B&O,-based
materials the interface partial pressure of oxygen can
be maintained high enough to prevent electrolyte
reduction.
The range of oxygen partial pressures over which
B&O, can be used as a solid electrolyte with
predominantly ionic conductivity is clearly more
limited in comparison to stabilized ZrO, due to its
smaller band gap (about 3 eV compared to 5.2 eV for
ZrO, solid electrolytes). Finally, solid electrolytes
based on Bi,O, are stable at oxygen partial pressure
10e9 Pa at 873 K.
8. Conclusions
Solid solutions with fluorite-type, fee, rhom-
bohedral, tetragonal and layer structures based on
Bi,O, are excellent candidates for use as solid
electrolytes and electrodes in electrochemical de-
vices. They are applicable at much lower tempera-
tures than devices with stabilized zirconia. Their
primary disadvantage at present is the instability
against reduction and the limited electrolytic domain.
However, development of solid solutions with appro-
priate composition and improved properties can be
expected. Due to the flexibility with which bismuth
oxide forms compounds with widely variable com-
positions and many different substitutions, there is a
large potential for further improvements in the
properties for medium and low temperature applica-
tions. Mixed conductors based on bismuth oxide
solid solutions represent an independent branch of
compounds which are potentially useful as a general
class of electrode materials.
Acknowledgments
This work was partially supported by the Alexan-
der von Humboldt Foundation (Germany).
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