Solid State lonics 40/41 (1990) 934-937
North-Holland
THE BIMEVOX SERIES: A NEW FAMILY OF
HIGH PERFORMANCES OXIDE ION CONDUCTORS
F. ABRAHAM, J.C. BOIVIN, G. M A I R E S S E and G. NOWOGROCKI
LCPS (Laboratoire de Cristallochimie et Physicochirnie du Sohde), U.R.A. C.N.R.S. 452, E.N.S.C.L.. U.S. ZL.F.A.,
BP 108. 59652 Villeneuve d'Ascq Cedex. France
A new family of oxygen anionic conductors, exhibiting high performances at low temperature, has been prepared and charac-
terized. They derive from Bi4V20~ by partial substitution of vanadium by other metallic ions (BIMEVOX). Results dealing with
the copper substituant (BICUVOX) are detailed.
1. Introduction
Recently, we have synthesized Bi4V2Oll, a new
c o m p o u n d exhibiting several phase transitions on
heating, before melting at 1160 K [ 1 ]. The structure
o f the different phases can be described as alternat-
ing B i 2 0 2+ a n d V O 2 ~ layers. All these structures can
be derived from that o f "/-Bi2MoO6 (Bi20~ + and
M o O ] - layers) by f o r m a t i o n o f oxygen vacancies in
the metal oxygen layers; thus the c o m p o u n d can be
f o r m u l a t e d (Bi202) 2+ (VO3.5l~o.5) 2-. Disorder, at
least in the high-temperature phase (y f o r m ) , leads
to high anionic conductivity. At lower t e m p e r a t u r e
(c~ and 13 f o r m s ) , the structure becomes ordered, the
unit cells larger, and the conductivity appreciably
lower.
To stabilize the high temperature disordered phase,
we have imagined to prevent o r d e r by partial sub-
stitution o f v a n a d i u m by other metallic ions. These
substitutions were successfully realized with numer-
ous metallic ions and led to a new family o f materials
designated by the a c r o n y m BIMEVOX. In the pres-
ent paper, we report the results o b t a i n e d with copper
in the B I C U V O X series. The i m p r o v e m e n t o f the
conductivity at l o w - t e m p e r a t u r e is related with the
r o o m - t e m p e r a t u r e crystal structure o f the substi-
tuted c o m p o u n d which is c o m p a r e d with the high-
t e m p e r a t u r e ~, structure.
0167-2738/90/$ 03.50 © Elsevier Science Publishers B.V.
( North-Holland )
Experimental
Polycrystalline B I C U V O X samples were prepared
by heating the a p p r o p r i a t e oxides, according to the
reaction Bi203+ ( 1 - x ) / 2 V205 + x C u O - ,
Bi2VI xCu,Os.5-3~/: to 875 K, regrinding and cal-
cination at 1120 K for 20 h in gold crucibles in air.
Single crystals o f Bi4V2Oli and Bi2V0.gCuo.lO 535
( B I C U V O X . 10) were obtained by slow cooling (3
K / h ) of the fused c o m p o u n d s from 1225 K to room-
temperature. The shapes o f BiaV20~ single crystals
were sufficiently well defined to realize rigorous ab-
sorption corrections during X-ray structure investi-
gation. On the other hand, B I C U V O X single crystals
were ground to a spherical shape using the Nonius
device.
B1CUNOX. 10 single crystal data were collected at
295 K using a CAD-4 N O N I U S diffractometer.
Bi4V2011 X-ray data were recorded at 885 K with a
four-circle. Philips P W I I 0 0 diffractometer. The
crystal was enclosed in a slightly narrowed quartz
capillary. The t e m p e r a t u r e was m a i n t a i n e d using a
heating device consisting o f a gas blower which sup-
plies a t e m p e r a t u r e regulated flow of air on the crys-
tal (A.E.T., Grenoble, F r a n c e ) .
The conductivity and oxygen transport measure-
ments were carried out using the technics previously
described [ 1 ].
 F. Abraham et al. I B I M E V O X - - high performances oxide ion conductors 935

3. Results Table 1
Experimental data and structure refinement parameters.
A solid solution Bi2V~_xCuxOs.s_3x/2 was formed 7-BiAV2OIj BICUVOX.
10
for 0~<x~<0.12. In the range 0~<x~<0.07, the com-
p o u n d is orthorhombic a n d isotypic with the a-form diffractometer Philips PW 1100 Nonius CAD-4
temperature 885 K 295 K
of Bi4V20~ t. O n the contrary, for 0.07 ~<x ~ 0.12, the
unit-cell parameters (A) a=3.988(2) a=3.907(1 )
room-temperature unit cell is tetragonal a n d of the c=15.42(1) c=15.41(1)
y-BiAV20~ ~ type. space group 14/mmm I4/mmm
Fig. 1 shows variations of conductivity versus in- 0-range ( ° ) 2-27 2-45
verse temperature for one composition in the ortho- h, k, / ranges O <~h,k ~ 5 -7~<h,k~7
0~<l~<18 -30~</~<30
rhombic d o m a i n ( B I C U V O X . 0 5 ) and for one in the
tetragonal phase (B1CUVOX. 10). The last one pre- no. of measured reflections 168 3864
sents a slight change of slope at about 645 K and the no. of independent 99 304
reflections with I> 3a(I )
experimental points are on the same Arrhenius plots ~t(cm-J ) for 734 729
on heating and cooling. O n the contrary, the first one Mo Kot-.7107 ,~
exhibits a drop of conductivity at about 795 K, more R factor 0,046 0.037
i m p o r t a n t during the heating than during the cooling Rwfactor 0.056 0.032
and which occurs with a notable hysteresis. The ox- (w= 1 for all reflections)
ygen-transport n u m b e r m e a s u r e m e n t s clearly indi-
cate that O 2- anions are the only charge carriers. Table 2
Atomic coordinates.
Io9o,~t
,,,Z~m- ! szco',s, o'~ Atom Site Occu- x y z B (A~)
t n !6 17 I 8 19 2,0 pancy
IO"T
"/-Bi4V2Ol j and BIMEVOX.10 "ideal" positions
I ~ 6 o

2 * Bi 4e 1 0 0 0.1690(1) 1.99(3)
V 2b 1 0 0 1/2 4.1(3)
O
O(1) 4d 1 0 1/2 1/2 1.9(4)

4 ~ 7-Bi4V2Oll with splitting of metallic positions

Bi(1) 16m 1/8 0.053(2) 0,053 0.1640(6) 3.0(3)

~r Bi(2) 4e 1/2 0 0 0.1731(6) 2.1(I)
i V 8h 1/4 0.041(5) 0.041 1/2 3.3(4)
logo,, O(1) 4d 1 0 1/2 1/4 3.1(4)
¢l:'rC r , ~ 1 BICUVOX tO 0(2) 4e 1 0 0 0.414(5) 14(2)
12
I 1 13 I ~ 15 16 17 ! 8 i ~ 20 0(3) 8g 0.375 0 1/2 0.027(5) 9(3)

BICUVOX. 10 with splitting of metallic positions

b
i × _
Bi(1) 16m 1/8 0.0430(9) 0.0430 0.1659(3) 3.4(1)
Bi(2) 4e 1/2 0 0 0.1705(1) 1.23(2)
3 ~ V,Cu 8h 1/4 0.0524(8) 0.0524 1/2 1.14(8)
[ O(1) 4d 1 0 1/2 1/4 2.5(2)
4
0(2) 16m 1/4 0.084(7) 0.084 0.400(2) 6.1(1)
0(3) 8g 0.3375 0 1/2 0.037(2) 5.8(9)

For BICUVOX. 10, preliminary Weissenberg pho-

Fig. 1. Arrhenius plots for two BICUVOX compositions: ( X ) on tographs revealed a tetragonal cell with I 4 / m m m
heating, (O) on cooling. symmetry. Moreover, satellite reflections appear and
936 F. Abraham et al. / B I M E V O X - - high performances oxide ion conductors

are located in incommensurable positions at about While in a- and ~ - B i 4 V 2 0 1 l , ordering of the me-
h+0.3, k+0.3, 1; they were not taken into account tallic positions and of oxygen vacancies lead to a drop
in the structure refinement. in conductivity, partial substitution of vanadium by
Both single crystal structures were solved in the copper (0.07 ~<x ~<0.12 ) prevents this ordering and
I 4 / m m m space group (table 1). Introduction of allows stabilization of the high-symmetry 7-Bi4V20, t
atomic coordinates representing "ideal" positions for structural type. The slightly higher slope of the Ar-
the metal atoms led to a poor agreement and did not rhenius plot in the low-temperature range (fig. 1b)
allow location of oxygen atoms (apart O( 1 ) ). Split- is probably associated with the incommensurable
ting of metallic positions gave a good convergence modulation of the structure mentioned above.
and permitted location of all atoms. The final co-
ordinates are reported in table 2. In both structures
only O(1) atoms, belonging to Bi2022÷ layers, re-
5. Conclusions
main ordered and the splitting of the others are of
the same order of magnitude.
Comparison of several high performances anionic
conductors is reported on fig. 3. The most striking
feature is the high value of a in the 500-700 K tem-
4. Discussion
perature range: for example, at 510 K, the conduc-
tivity of BICUVOX.10 reaches 1 × 10 -3 f~-' cm -~,
Schematic view of these structures is represented
which is about two orders of magnitude higher than
on fig. 2. For reason of clarity, the splitting of the
metallic sites is not drawn. It is quite evident that
complete Bi20] + layers are interleaved with per-
ovskite-like sheets. The numerous oxygen vacancies 0 lJ 1;Z 1~3 1,4- 1~5 1,-6 1-7 I;B t,3 2,~ 2;1 2~2'1~
and the displacement of the metallic ions from the
more symmetrical positions are responsible for the
high anionic conductivity observed.

Bi

~ 0(3)

.3

_4
'\
\

6o0 ~oo 4oo - - ~2'oo {°c)

Fig. 3. Comparative Arrhenius plots for: ( • ) YSZ:

Fig. 2. Schematic representation of the structure of 7-Bi4VzO~j (ZrO2)o.9(Y203)oj; ( O ) (BieO3)o.s(Er203)o:; (*) Bi4VzOl,;
and BICUVOX. 10. ( ¥ ) BICUVOX.050; ( A ) BICUVOX.0.75; ( V ) BICUVOX. 10.
 F. Abraham et al. / B I M E V O X - - high performances oxide ion conductors 937

the best oxide ion conductors known up to now [2,3 ]. References

Further characterizations of B I C U V O X are pres-
ently in progress: electrochemical stability versus ox- [ 1] F. Abraham, M.F. Debreuille-Gresse, G. Mairesse and G.
ygen partial pressure a n d temperature, single crystal Nowogrocki, Solid State lonics 28-30 (1988) 529.
[2] R.M. Dell and A. Hoper, in: Solid electrolytes, eds. P.
neutron diffraction and conductivity Hagenmullerand W. Van Gool (Academic Press, New York,
measurements,... 1978), p. 291.
These results will be compared with those ob- [3] M.J. Verker, K. Keizer and A.J. Burggraaf, J. Appl.
tained from others substituted B I M E V O X exhibit- Electrochem. 10 ( 1981 ) 81.
ing a similar e n h a n c e m e n t of a n i o n i c conductivity at
low temperature.