SolidState

Ionics9 & 10(1983)851-858 851

Publishing Company
North-Holland

PHASE TRANSITIONS AND IONIC CONDUCTION IN 3D SKELETON PHOSPHATES

A3M2(PO4)3 : A = Li, Na, Ag, K ; M = Cr, Fe.

F. d'Yvoire, M. Pintard-ScrGpell, E. Bretey and M. de la Rochsre.

Laboratoire de Chimie AppliquGe, Universitg Paris-Sud, 91405 Orsay (France)

Phosphates A3M2(P04)3 (AMP) with A = Li, Na, Ag, K and M = Cr, Fe have been prepared
by direct synthesis, flux methods and cation exchange in molten salts. The Li, Na and
Ag-compounds are solid electrolytes structurally related to Nasicon (NaMP, AgMP and
I-LiMP) or to monoclinic Fe2(SO4)3 (II-L%'). Their conductivities are about l&?cm'
at 300°C. Below 35O"C, NaMP and II-LiMP undergo several reversible phase transitions
accompanied by slight changes of the crystal lattice and probably associated with a
disordering of the A+ ions. These transitions range from first order ones to transitions
spread over a wide range of temperature. Their effect upon conductivity is presented.
KFeP has a particular structure with a 3D network of linked P04, Fe06 and Fe05 poly-
hedra. The K+ ions occupy an interstitial space which presents too narrow bottlenecks
to allow a fast ion transport.

Since the discovery by Hong et al. (1, 2) of
fast Na+-ion transport properties in the "Nasi-
con" system Nal+xZr2SixP3_xOl2 with a maximum
conductivity for the composition Na3Zr2Si2PO12,
numerous studies on phosphates of similar compo-
sition, Na3M$11(P04)3, and similar structure
have been published (3 to 23). By replacing Na+
by another cation, different structures can be
formed (6). In order to better understand the
relationship between structure and ion transport,
a series of phosphates of the general formula
A3M2(P04)3 where A = Li, Na, Ag, K and M = Cr,
Fe has been investigated. These compounds will
be designated by AMP (e.g. NaFeP, LiCrP). The
present paper reports on their synthesis, crys-
tallographic data, phase transitions, ion
exchange properties and ionic conduction. Other
results concerning the detailed crystal struc-
tures and their modifications with temperature
are reported elsewhere (7, 24).
1. EXPERIMENTAL
1.1. Chemical syntheses
Two general methods were used : direct synthesis
(D.S.) and ion exchange reactions (I.E.).
1.1.1. Direct syntheses are achieved by heating
mixtures of phosphates, oxides and/or carbonates
with total molar ratios A/M and P/M equal to 3/2
(D.S.1 process) or superior to 3/2 (D.S.2 pro-
cess). For each compound, several starting
mixtures and heating temperatures can be
used (4, 5, 8). Those listed in table 1 have
been selected for giving the purest phases. The
general procedure is the following : the finely
ground mixture is placed in a Pt-crucible, pro-
gressively heated up to the temperature Tm and
then cooled in several hours by switching off
the furnace. Two or three successive heatings
separated by grinding operations are often neces-
sary to complete the reaction. In the D.S.2
process, the product is finally washed with water
and HCl 1M in order to eliminate the excess
alkali phosphates and other possible impurities.
In the case of LiCrP, some modifications were
brought to this general procedure in order to
improve the attack of Cr203 and minimize the
weight lost due to decomposition at high tempe-
rature : the starting mixture was slowly heated
up to 800°C then cooled, finely ground and pressed
at 300 MPa into cylindrical pellets. The pellets
were slowly heated up to llOO"C, then rapidly up

Table 1. Experimental conditions for the direct synthesis of the compounds

Compound Process Starting mixture Tm ("C)

D.S.2 Fe203 + 3.6 NaH2P04 + 2.2 Na4P207 1000

D.S.2 Cr203 + 3.7 NaH2P04 + Na4P207 1050
D.S.1 2 FeP04.2 H20 + 1.5 Li2C03 + NH4H2P04 950
D.S.1 Cr203 + 1.5 Li2C03 + 3 NH4H2P04 1310
D.S.1 Fe203 + 3 KH2P04 860
D.S.2 Fe203 + 4 KH2P04 + 0.4 KHC03 860

0 167-2738/83/0000~0000/$03.00 01983 North-Holland

to 131O"C, maintained for 5 mn at this temperature Table 2. Pellets thermal treatment for sinterini:
and air quenched. In these conditions, III-LiCrP
is formed (see § 2.3). II-LiCrP "as obtained by
Heating Time Cooling
annealing the pellets at 1060°C and I-LiCrP by Gas Tmax
Compound rate at Tmax rate
heating them at 1430°C for 2 mn and quenching. flow ("0
("C/mn) (mn) ("C/mn)
Except for KFeP, the above described methods do
not lead to single crystals of sufficient sizes NaFeP O2 IO 920 I 100
for an X-ray diffraction study ; in particular,
NaCrP IO 1245 5 1ou
NaFeP, which crystallizes as an eutectic compo- N2
nent, is obtained in a finely powdered form. II-LiFeP O2 3 930 IO 100
Sing& CC@&&& of NaFeP and NaCrP have been
AgFeP air 3 550 5 10
prepared by flux methods : (i) NaFeP, from a
mixture Na3Fe2(P0$)3 + 2.1 NaP03 + Na4Pz07 which KFeP O2 3 770 45 IO
"as melted at 870 C, cooled down to 775 C at a
rate of 150°C/h, maintained for 10 mn at 775°C
and then quenched, (ii) NaCrP, from a mixture
1.4. Conductivity measurements
Na3Cr2(P04)3 + 3 NaP03 + 3 Na4P207 which "as
heated at 115O'C by introduction In a preheated The conductivity was measured in the temperature
furnace and cooled at a rate of 150°C/h except range 50 % 35O'C on polycrystalline pellets by
in the range 900-68O'C where the cooling rate the complex impedance technique, using a Hewlett-
"as 15"C/h. In both cases, the product contained Packard 4800A vector impedance meter with R
a glass slowly soluble in water and square plate- frequency range of 5Hz to 5OOkHz.
lets or cube shaped crystals of NaMP (0.05 to
For I, II and III-LiCrP, the pellets were pre-
0.5 mm in edge length). Very few crystals were
pared as described above (I 1.1.1). For the
untwinned. Between crossed polars, the square
other compounds, the following procedure "as
sections of the crystals show symmetrical extinc-
used : the solids were finely ground for IOh in
tion with the higher index parallel to the [loo],
a ball mill in presence of ethanol then dried
[OlO] or [IlO] direction of the pseudohexagonal
and pressed at 300MPa to form cylindrical pellets
cell (see 5 2.1.2).
(bmm in diameter, 1 to 5mm thick) or rods (about
I x 1 x 5mm). The pellets and rods were sintered
1.1.2. Ion exchange reactions. Like Nasicon, the
according to the conditions reported in table 2
phosphates NaMP exhibit cation exchange properties
which has to be completed by the following
in molten salts. Therefore I-LiMP and AgMP have
remarks : (i) too long heating of the NaFeP
been prepared by reaction of NaMP with large
pellets at Tmax causes crystallite growth and
excess of molten LiN03 and AgN03 : mixtures
makes the pellets very brittle probably as a
Na3M2(P04)3 + n LiN03 (or AgN03) with n Q 100 consequence of the anisotropic contraction and
were heated for 2 h at 300 and 25O'C respectively,
phase transitions occuring on cooling ; (ii)
then cooled, washed with water and dried. Three
the heat treatment of NaCrP and KFeP may induce
successive treatments were carried out in order
a slight decomposition with the crystallisation
to shift the equilibrium toward the maximum
of Cr203 and Na3Cr3(P04)4 in the first case (see
exchange. Analysis of the final products led to I 2.1.1) and of an unknown phase, X, in the
compositions A,Na3_xM2(P04)3 with x = 2.96 for second case (see 5 2.4.2). An additional heating
A = Li, M = Fe or Cr and x = 2.90 for A = Ag,
of the pellets up to 1070 and 71O'C respectively
M = Fe. Thus, in all the cases the exchange "as re-forms the initial phase.
not quite complete. However, for simplicity, the
solids will be represented by their ideal formu- The bulk densities after sintering ranged from
lae : Li3M2(P04)3 and Ag3M2(P04)3 (or LiMP and 80 to 90 Z of the theoretical ones except for
AgMP). the AgFeP pellets (60 Z). The pellet faces and
rod ends were coated with gold by vacuum evapo-
1.2. X-ray diffraction ration or with platinum or silver paints. During
all the measurements, the conductivity cell "as
?owder diffraction photographs'were made using
kept under a dry gas flow.
a Guinier camera with CoKur radiation. For accu-
rate d-spacing measurements, aluminium tetraneta-. For each compound, dc conductivity measurements
phosphate (26) was added as an internal standard. were carried out with Au or Pt blocking elec-
Intensities were estimated visually or measured trodes. They showed the electronic conductivity
by diffractometry. A high temperature Guinier to be a negligible fraction (< 10-s) of the
camera with a Pt-Rh grid resistor as sample total one.
holder (27) "as used in some cases. Weissenberg
and precession photographs were made at room 2. RESULTS AND DISCUSSION
temperature and at controlled temperatures up to
180°C using a hot gas blower. The investigated compounds belong to three main
structural types :
1.3. Differential thermal analysis a) Nasicon (I),
b) monoclinic Fe2(S04)3 (28, 29),
The DTA curves were obtained with a B.D.L. appa-
c) K3Fe2(P04)3 (7).
ratus equipped with a semi-microprobe. The
transition enthalpies were determined using a These structures are made of a three-dimensional
Perkin Elmer DSC4. skeleton "'2(X04)3 (M' = Zr, Fe ; x = sit p, s)
 F. d’Yvoire et al. /Phase transitions and ionic conduction 853

and an interconnected interstitial space which

can contain A+ ions. The structural type adopted
by a given AMP phosphate depends chiefly on the
nature (apparently the size) of the A' ion as
shown in table 3.

Table 3. Structural types of the compounds

0.0, C
0 ; :-

-0.01 I R Y
)
50 100 I 50 T('C)

Fig. 1. DTA scan of a) NaFeP b) NaCrP c) AgFeP.

7%)Attempts to synthesize K3Cr2(P04)3 failed. Heating and cooling rate : IOO"C/h. Sample mass :
5mg. Note that the AT-scale of 6 and c is four
times that of U.

&I. A = Na (a-structural type)

DTA and X-ray diffraction experiments performed
at controlled temperature show that the compounds
NaMP undergo several reversible phase transitions
between room temperature and 180°C. If we call N
and y the room and high temperature forms respec-
tively, the transitions can be represented by :
M = Fe : ct+fi at 95'C ; Bey at 145°C
M = Cr : ~1s~' at 75"~ ; a’= R at s 138'C

,,:-,*
B=y at x 166OC. a

2.1.1. On DTA curves, the Fe-compound transitions

-0.02
appear as narrow peaks (fig. la and 2), typical Tf'C)
of first order transitions while the Cr-compound 92 Pb 96 98 " 144 146
a'=B and fi'+y transition peaks are not com-
pletely separate : they rather form a broad Fig. 2. DTA scan of NaFeP small crystals.
endo- (or exe-)thermic effect spreading from Heating and cooling rate : 20"C/h. Sample mass :
about 120 to 175'C with two maxima near 138 and 5mg. Average mass of each crystal : % IOe3mg.
166'C. Hysteresis between transition temperatures
observed on heating and cooling is very small in
all the cases except for the a&a' transition. monoclinic deformation while the B-forms are
The t~a&GLiurz cmtho..Lpi~ are : trigonal. Moreover, a-NaFeP is.a superstructure
of y : if we neglect the presence of some very
M ==Fe : Cx-bB : 3.0 + 0.2 kJmole-'
weak reflections (on both single crystal and
B+y : 0.7 + 0.1 "
powder photographs) ,+the_supersructure czn be
M=Cr: a-+a’ : 0.25 + 0.05 " described as G = 2ay ; b4 =_2bs ; $ = c
a'-+y : 2.0 + 0.4 " with possible space groups P3cl or P3cl. 1 t'is
similar to that reported by Tran Qui et al. (20)
For both compounds, the DTA curves do not show
for B-Na3Sc2(P04)3.
any other peak before melting is reached, i.e.
at 965'C for NaFeP and about 1230°C for NaCrP. (iii) The fioorn h~~pUtiu/r& IY.-~O~JT!A. The Fe and
The latter melts incongruently with the crystal- Cr a-forms present a weak monoclinic distortion
lization of Cr203 and Na3Cr3(P04)4 as previously and a superstructure. The superstructure reflec-
reported (5). tions are too weak to be observed on powder
diffractograms. These can be interpreted (4, 5)
2.1.2. X-ray diffraction experiments at room and with a monoclinic subcell (z, x;', G) similar
controlled temperatures show the a to y phase to the unit cell proposed by Hong (1) for
transitions to be associated with slight changes Na3Zr2Si2P012 : Z = 4, space group C2/c or Cc.
in the crystal lattice. The lattice distortion can be visualized by
choosing- a pseudohexagonal
. cell (a-. p. c-1
(i) The y-dutirnnare rhombohedral (see table 5),
similar to the y hexagonal cell and related to
isotypic with NaZr2(P04)3 (1).
(aY, z, c:) by 2 = (?l+i;;)/2,i? = (-z+G))/2 ,
(ii) The iti~.m~_diate fiahm4 CL’ and B : single cT= a1+3c?
- ; the parameters are listed in table
crystals investigations on these forms are made 4. The supercells (a',r, 3, determined from
difficult by frequent twinning. From powder dif- Weissenberg and precession photographs, are
fractograms, the Cr al-form presents a weak related to (2, rl;;,z) by the following
854 F. d’Yvoire et al. /Phase tramitiorrs arId ionic corrductiotr

--.++ t
Table 4. u-N~~M~(PO~)~ : monoclinic subcell (al, bl, cl) and pseudohexagonal cell (a , i7 , 2,
constants determined from powder diffractograms.

0 0
M a,(l) b,(i) Cl(i) Bl(“) a'=b'(A) c'(A) B'=n-u'(O) Y'(O)

Fe 15.127(3) 8.722(2) 8.793(l) 125.15(l) 8.731(Z) 21.569(3) 90.14(l) 120.07(2)

Cr 14.959(l) 8.655(l) 8.748(l) 124.53(l) 8.641(l) 21.621(3) 89.81(l) 119.89(l)

relations : of 0, attributable to the (L--J.' and (~'4 @ tran-

cl-NaFeP: ?= z i;‘=G,?=
-r +
a-NaCrP : a=z-c, ,c=i;: , ?= 2a7 + 4~7
The lattice constants aregiven in table 5. For
the iron compound, the systematic extinctions are
consistent with the space groups C2, Cm and C2/m.
However the ho1 reflections with L = 2n+l are
weak and most of them seem to be absent so that
the symmetry differs only slightly from CZ/c or
Cc. For the Cr-compound, the observed extinctions
or quasi extinctions lead to a symmetry close to
PZi/n. The above described superlattices strongly
suggest an oh&tiny CJ~the Nat ioti dt boom Xem-
~Q'Iu&ULQ, with a specific distribution for each
compound.
2.1.3. Conductivity. Variations of log (oT) vs.
l/T are presented in fig. 3. Compared with the
previously reported results (5), the present ones
are more complete and reliable, particularly in
the low conductivity region. For NaFeP, the ~--+a
transition is accompanied by a steep increase
of u, characteristic of a first order transition,
with an increase factor of about IO. Simul-
taneously, a decrease of the activation energy
EA is observed (table 7). The B-+y transition
is associated with a slight increase of o and a
further lowering of EA. A rather similar behaviour
has been described by Boehm et al. (18) for
Na3Sc2(P04)3. Concerning NaCrP, our conductivity
data on the whole agree with that of Delmas et
al. (12). In addition, they show, near 75'C, a
slope change and, near 14O"C, a slight increase
400, 300 200 100
- ciated with a small increase of conductivity.
sitions respectively. The &-+y transition is
Z+3cf
associated with a decrease of EA.
For both the iron andchrosium compounds, ; is
about 10-2R-'cm-' at 3OO'C. This value of -1100
is lower than that reported by Boehm (18) for
Na3Sc2(P04)3 (2.7 x 10-2Q-'cm-') and by Goode-
nough (2) for Na3Zr2Si2P012 (2.10-'fi-1cm-'). In
the series of these four compounds, ISvaries in
the same direction as the molar volume V,ell/Z.
An increase of this volume is probably accompa-
nied by an increase of the diameter of the
bottlenecks, which might favour the sodium ions
transport in the crystal.
2.2. A = Ag (n-structural type)
AgCrP and AgFeP were prepared from their sodium
analogues by ion exchange. Powder diffractograms
show NaCrP to be rhombohedral at r.t., isotypic
with y-NaMP (see table 5).
DTA of AgFeP (fig. lc) reveals a reversible phase
transition, c.+v, occuring at 73°C with an en-
thalpy of 0.22+0.06 kJmole-'. The y (high tempe-
rature) form is isotypic with y-NaMP and the 3
(r.t.) form is a superstructure of y ; although
the powder and single crystal diffractograms of
j are not completely interpreted, one can note
that many of the superstructure reflections are
consistent with ahex Q 8ahexy : in the recipro-
cal space, they appear as satellites of the
fundamental reflections located at a distance
3aq/8 in tile directions *- a* , 2 @and t ($-b*).
The conductivity of AgFeP (fig. 3 and table 7)
is much higher than that of the sodium analogue
near the room temperature and the activation
50 energy is lower. The 6-f transition is asso-

2.3. A = Li (n and b-structural types)

Three forms of LiMP were obtained : I, II and
III.

2.3.1. Form I is prepared by ion exchange from

NaMP (8 1.1.2) or, for LiCrP, by heating of the
forms II or III (§ 1.1.1 and table 6). It has a
Nasicon-type structure with a rhombohedral lat-
tice (table 5). The c parameter appears abnor-
-4
mally large compared with the other AMP compounds
(A = Na, Ag). A similar observation was made by
Hong (1) in the series A3Zr2Si2P012 and intcr-
103/T(K) preted as an indication that the Lit ions occupy
positions different from the other A+ ions.
Fig. 3. Temperature dependence of the conductivity
of phosphates AMP with a Nasicon type structure :
2.3.2. Form II is isotypic with the monoclinic
NaFeP ( ) ; NaCrP (------) modificationof F~z(SO~)~ (28, 29). This lacunar
AgFeP (-----------.);Iand III-LiCrP (----------.).
 F. d’Yvoire et al. /Phase transitions and ionic conduction 855

Table 5. Crystallographic data.

Structural Possible
Compound a& b(i) c(i) B(“) z
type space group

a y-Na3Fe2(P04)3 + P R?lc R3c 8.733(l) 21.798(2) 6 240.0

a Y-Na3Cr2(PO4)3 + P R?c, R3c 8.622(3) 21.720(8) 6 233.0

(I ENa3Fe2(PO4)3 x r P 8.729(l) 21.725(2) 6 238.9

a a-Na3Fe2 (PO4) 3 s C2, Cm, C2/m 15.127(3) 8.722(2) 21.569(3) 90.16(l) 12 237.1

a a-Na3Cr2 (PO4) 3 s P21/n(?) 21.181(2) 8.655(l) 30.540(3) 90.61(l) 24 233.3

a Ag3Cr2 (PO4) 3 P R?c, R3c 8.698(2) 22.009(4) 6 240.3

a B-Ag3Fe2 (PO4)3 r P 8.772(l) 22.113(2) 6 245.6

a I-Li3Fe2 (PO4) 3 P R~c, R3c 8.310(2) 22.506(5) 6 224.3

a I-Li3Cr2 (PO4) 3 P R%, R3c 8.272(2) 22.219(5) 6 219.4

b II-Li3Fe2 (PO4) 3 P P21/c 8.568(l) 8.613(l) 14.690(l) 125.16(l) 4 221.5

b II-Li3Cr2 (PO4) 3 P P2,/c 8.453(l) 8.547(l) 14.520(2) 125.15(l) 4 214.4

a KxNa3_xFe2 (PO4) 3 P Rgc, R3c 8.635(5) 22.78(l) 6 245.2

a KxNa3_xCr2 (PO4) 3 P Rjc, R3c 8.567(l) 22.654(6) 6 240.0

C K3Fe2 (PO4) 3 s c2/c 16.303(2) 9.463(l) 16.691(2) 118.39(l) 8 283.2

+ : at 200°C x : at 12O’C r : data for the rhombohedral sublattice

p : data obtained from powder s : data obtained from single crystal and powder

3D skeleton structure is made of SO4 tetrahedra have the following approximate values :
sharing corners with Fe06 octahedra. The tetra- II-LiFeP : AH(a-by) = 2.1 2 0.6 kJmole-’
hedra (T) and octahedra (0) form 0T30 units II-LiCrP : AH(c(Ac~‘) = 0.6 _+ 0.2 ”
similar to those found in Nasicon, but the arrsn- AH(ct’+y) = 1.0 : 0.4 ”
gement of the units is different. A close exami-
X-ray powder diffractograms of II-LiFeP perfor-
nation of the structure shows a three dimensio-
med below and above the transition temperatures
nally linked interstitial space in which the
bottlenecks have their shortest diameter close
showed no distinct modification , suggesting
that the transitions concern the Li cations dis-
to the sum 2r(Li+) + 2r(02-) = 3.9 d. In
tribution or ordering rather than the structure
Li3M2(P04)3, where S is replaced by P, a signi-
of the M2(PO4)3 anionic network. (Possible super-
ficant increase of the bottleneck diameters
structure reflections indicating an order in the
should be expected, enabling a 3D transport of
low temperature forms would surely be undiscer-
the Li+ ions (see I 2.3.4).
nible on powder photographs owing to the low
DTA of II-LiFeP and II-LiCrP (fig. 4) indicates scattering factor of Li+).
below 35O“C two and three reversible transitions
respectively as listed in table 6. As for NaCrP, 2.3.3. Form III is found only for M = Cr (see 5
the ~1’ (or a)-+B and 6 +y transitions take place 1.1.1 and table 6). Some similarities between
over a wide range of temperature and are not the powder diffractograms of I and III suggest
completely separate . The transition enthalpies

Table 6. Phase transitions in phosphates LiMP.

(The transition temperatures are given
in “C).

I-LiFeP 570911

II-LiFeP: .&6265,y (melt. p. : 1028)

L-LiCrP -.=+I1

II-LiCrP: a &a'262.~312,y_wIII&aI

III-LiCrP -@-@$I1
Fig. 4. DTA scan of a) II-LiFeP 6) II-LiCrP.
* exothermic transition Heating and cooling rate : 200°C/h. Sample
** very slow transformation at 1OOO’C. mass : 5mg.
856

Table 7. Activation energies of conduction and

conductivities.

I, ('.-'cm-')
HA ___--
Solid
(ev) at 5O'C at 300°C

NaFeP IX. 0.83 1.2 x lo-'

b 0.55
Y 0.41 9 x lo-'
NaCrP $1 0.68 1.7 x lo-7
(1' 0.91
-4 ‘..., s I .o
‘I., Y 0.36 7 x lo-'
AgFeP D 0.37 8 x 10-s
5 .,:,
\ Y 0.4
1 5.l 2 2,5 '3 II-LiFeP u (%) 0.54 5.6 x 10-s
lO'/T(K) 0.67 1.9 x IO--'
Y
I-LiCrP 0.8 2.5 x 10-a 3.5 x lo-'
Fig. 5. Temperature dependence of the conductivity II-LiCrP c( 0.49 1.2 x lo-'
of II-LiCrP ( ), II-LiFeP (------), CL' 0.69
KFeP (---------.-) and KFeP-XG (----------_). B 0.71 7 x lo-'
Y 0.50
III-LiCrP 0.8 4 x 10-s 6 x IO-'
that III might be derived fr:m I by a deformation KFeP 1.4 “u 5 x IO-'0
and perhaps a superstructure . KFeP-XG 0.6 3 x 1o-5
-__
2.3.4. Conductivity data are given in fig. 3 and (a) at T < IOO'C.
5 and in table 7. For I and III-LiCrP, which do
not exhibit any phase transition, the Arrhenius
law is observed in the whole investigated range 2.4. M = K
__-__
of temperature. For II-LiCrP, the a-+~' and
By iurl exchctnge in molten potassium nitrate,
u'+ 3 transitions are both associated with a
NaFeP and NaCrP lead to partially exchanged rhom-
rapid increase of 0, stretching over a certain
bohedral solids I:.J~a3_xM2(P04)3with x "J 0.95
range of temperature : (about 70 to 8O'C and 265
(see table 5). Hence, the compounds KMP cannot
to 285°C respectively). The 8-y transition is
be prepared by this method, probably as a conse-
marked only by a change of activation energy near
quence of the large size of the K+-ion. Attempts
33O'C. The II-LiFeP o-curve is a straight line
to obtain KMP by iti'&!& ~~$&he5in failed for M =
below 100°C. Beyond, the slope increases progres-
Cr but led to the wanted compound for M = Fe
sively up to 245'C, which is approximatively the
(see § 1.1.1 and table 5).
a--+fi transition-end temperature, and then de-
creases. The 0-y transition is accompanied by
2.4.1. The crystal structure of KFeP has been
a new slope increase. The y-form exhibits a
determined recently, (7).
., It consists of a 3D
constant activation energy.
network of linked P04, Fe06 and Fe05 polyhedra
and an interstitial space containing the K+ ions.
2.3.5. cumtnettis
The K+ sites are joined by passageways running be
(i) Both DTA and conductivity curves of II-LiMP
tween layers parallel to (101). However, the con--
show evidence for transitions (a or ct'-+B and
ditions for a fast ionic conduction are not ful-
B-y) stretching over substantial ranges oftem-
filledO: a) the passageways have bottlenecks of
peratures. Such transitions may be put into the
a 4.9 A minimum diameter distinc:ly shorter than
class III of O'Keefe (30).
the sum 2r(K+) + 2r(O*-) = 5.46 A ; b) no vacant
(ii) As well as NaFeP and NaCrP, which are
site having the I(+ size is present.
Nasicon-type, II-LiFeP and II-LiCrP, which are
structurally related to monoclinic Fe2(SO4)3,
2.4.2. A DTA curve of KFeP is shown in fig. 6.
undergo two or three reversible transitions below
The first peak which appears on heating is inter-
35O'C. On the contrary, the Nasicon-type I-LiFeP
preted as an incongruent melting occuring at
and I-LiCrP do not. Although these similarities
805°C : samples heated up to 815°C and quenched
and differences in behaviour are not well under-
are mixtures of a glass and an undetermined crys-
stood presently, they might be connected with
talline phase "X", while heating up to 860°C and
the relative sizes of the mobile ions and bottle-
quenching give a pure glass.
necks in the crystal : in NaMP and II-LiMP, the
sum of the A+ and 02- ionic diameters is probably
2.4.3. The conductivity data reported in table 7
close to the bottleneck diameter [see 5 2.1.3, §
and fig. 5 show that KFeP is a very poor conduc-
2.3.2 and (l)] w h'l
i e in I-LiMP (which has the
tor (0 = 3 x 10-RO-'cm-' at 400°C) as expected
same network as NaMP), this sum is smaller. The-
from structural data.
refore, the interaction between the mobile ions
and the network may be different. Previous mfasureclcnts (7) gave higher conducti-
 F. d’Yvoire et al. /Phase ttmrsitions and ionic conduction
(8) Delmas, C., Olazcuaga, R., Cherkaoui, F.,
(9)
(10)
(11)
(12)
Fig. 6. DTA scan of KFeP. Heating and cooling
rate : ZOO'C/h. Sample mass : 5mg. (13)
(14)
vities (IO-5R-'cm-' at 4OO'C). In fact, the ma-
terial which was used contained somes traces of
X phase, probably as a consequence of a too high (15)
sintering temperature (see § 1.4).
To explain these high values, pellets of KFeP
(16)
were completely transformed into a mixture of
phase X and glass by heating up to 815°C and
(17)
quenching. The conductivity of this material,
designated by KFeP-XG (fig. 5) was found to be
(18)
very high (1.5 x lo-'c?-'cm-' at 4OO'C) in compa-
rison with that of the undecomposed crystalline
KFeP, which explains our early results (7). But
(19)
it is distinctly lower than the values recently
reported for other potassium conductor glasses
such as "Kasicon" (25).
(20)
ACKNOWLEGEMENT
(21)
We are grateful to Professor L. Cot (E.N.s.c.,
Montpellier) and Professor M. Maurin (U.S.T.L.,
(22)
Montpellier) for providing DSC and conductivity
measurements facilities. We thank Dr J. Doucet
(23)
(Laboratoire de Physique des Solides, Orsay) for
the use of a high temperature Guinier camera.
REFERENCES
(24)
(1) Hong, H.Y-P., Mat. Res. Bull., 11 (1976)
173-182.
(25)
(2) Goodenough, J.B., Hong, H.Y-P. and Kafalas,
J.A., Mat. Res. Bull., 11 (1976) 203-220.
(26)
(3) Hong, H.Y-P., Proc. Int. Conf. on Fast Ion
Transport in Solids, Lake Geneva, U.S.A.,
(27)
May 1979, Vashishta, P. et al. (eds.), 431-
433, (Elsevier, 1979).
(28)
(4) Pintard-Scrgpel, M., d'Yvoire, F. and R&y,
F ., C.R. Acad. Sci., 286 C (1978) 381-383.
(29)
(5) d'Yvoire, F., Pintard-Scrcpel, M. and Bretey,
E ., C.R. Acad. Sci., 290 C (1980) 185-188.
(30)
(611Pintard-Scrgpel, M., d'Yvoire, F. and Bretey,
E ., Proceed. 2nd Europ. Conf. on Solid State
Chemistry, Veldhoven, The Netherlands, June
1982, Metselaar, R. et al. (eds.), Studies
Present address : Laboratoire de Chimie Minerale
in Inorg. Chem., 3, 215-218 (Elsevier, Ams-
Anpliq&e,
terdam, 1983).
34075 Montpellier Cgdex (France).
(7) Pintard-Scrgpel, M., Durand, J. and d'Yvoire,
Powder X-ray diffraction data will be sent by
F., Acta Cryst. (1933) C 39, 9-12.
the authors on request.
857
Brochu, R. and Le Flem, G., C.R. Acad. Sci.,
287 C (1978), 169-171.
BeltrAn-Porter, D., Olazcuaga, R., Fournes,
L., Menil, F. and Le Flem, G., Rev. Phys.
Appl., 15 (1980) 1155-1160.
Delmas, C., Viala, J.C., Olazcuaga, R., Le
Flem, G., Hagenmuller, P., Cherkaoui, F.
and Brochu, P., Mat. Res. Bull., 16 (1981)
83-90.
Delmas, C., Olazcuaga, R., Le Flem, G., Ha-
genmuller, P., Cherkaoui, F. and Brochu, P.,
Mat. Res. Bull., 16 (1981) 285-290.
Delmas, C., Viala, J.C., Olazcuaga, R., Le
Flem, G., Hagenmuller, P., Cherkaoui, F.
and Brochu, P., Sol. State Ionics (1981)
209-214.
Efremov, V.A. and Kalinin, V.B., Sov. Phys.
Crystallogr., 23 (1978) 393-396.
Okonenko, S.A., Stefanovich, S.Yu., Kalinin,
V.B. and Venevtsev, Yu.N., Sov. Phys. Sol.
State, 20 (1978) 1647-1648.
Lazoryak, B.I., Kalinin, V.B., Stefanovich,
S.Yu. and Efremov, V.A., Sov. Phys. Dokl.,
25 (1980) 67-68.
Stefanovich, S.Yu. and Kalinin, V.B., Sov.
Phys. Sol. State, 23 (1981) 2043-2044.
Delbecq, C.J., Marshall, S.A. and Susman,
S., Sol. State Ionics, 1 (1980) 145-149.
Boehm, L., Delbecq, C.J., Hutchinson, E.
and Susman, S., Sol. State Ionics, 5 (1981)
311-314.
Susman, S., Delbecq, C.J. and Brun, T.O.,
Proc. Electrochem. Sot., Spring Meet., May
1982, Montreal ; Ext. Abst., 1172-1173.
Tran Qui, D., Capponi, J.J., Gondrand, M.
and Joubert, J.C., Sol. State Lonics, 5
(1981) 305-306.
Boilot, J.P., Collin, G. and ComPs, R., Sol.
State Ionics, 5 (1981) 307-309.
Boilot, J.P., Collin, G. and Comgs, R., Sol.
State Comm., 45 (1983) 231-236.
Boilot, J.P., Collin, G. and Colomban, Ph.,
Nasicon and related Compounds : a review,
in Progress in Solid Electrolytes. Energy,
Mines and Resources, Canada. To be published.
de la RochPre, PI., d'Yvoire, F., Collin, G.,
ComPs, R. and Boilot, J.P., Proceedings of
this conference.
Lejeune, M., Colomban, Ph. and Boilot, J.P.,
J. non Cryst. Sol., 51 (1982) 273-276.
d'Yvoire, F., Bull. Sot. Chim. Fr., (1962)
1237-1243.
Doucet, J., Thesis, Paris-Sud University
(June 1978).
Moore, P.B. and Araki, T., N. Jb. Miner.
Abh., 121 (1974) 208-228.
Christidis, P.C. and Rentzeperis, P.J., Z.
Kristallogr., 141 (1975) 233-245.
O'Keefe, M., in Mahan, G.D. and Roth, W.L.,
Superionic conductors (Plenum Press, 1976)
101-114.
Chimie des Materiaux , E.N.S.C.,