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NASICON to Scandium Wolframate Transition in Li M Hf (PO ) (M5cr, Fe): Structure and Ionic Conductivity

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NASICON to Scandium Wolframate Transition in Li M Hf (PO ) (M5cr, Fe): Structure and Ionic Conductivity Solid State Ionics 112 (1998) 53±62 NASICON to scandium wolframate transition in Li11xx M Hf22x (PO43 ) (M 5 Cr, Fe): structure and ionic conductivity Enrique R. Losillaa,** , Sebastian Bruque a, , Miguel A.G. Aranda a , Laureano Moreno- Realab , E. Morin , M. Quarton b aDepartamento de Quõmica Inorganica, Cristalograf Âõa y Mineralogõa Â, Universidad de Malaga Â, Aptd. 59, 29071 Malaga Â, Spain bLaboratoire de Cristallochimie du Solide, Universite Pierre et Marie Curie,4Place Jussieu, 75252 Paris Cedex 05, France Received 6 February 1998; received in revised form 5 June 1998; accepted 5 June 1998 Abstract The Li11xx M Hf22x (PO43 ) (M 5 Cr, Fe, Bi) systems have been studied and single phases have been isolated for M 5 Cr and Fe. The samples have been characterized by X-ray powder diffraction, diffuse re¯ectance and impedance spectroscopy. There is a reconstructive transition between rombohedral NASICON and orthorhombic Sc243 (WO ) -type structures as a function of x, at very low values, 0.2 and 0.1 for Cr and Fe, respectively. For the Cr series, a further subtle structural change has been observed for x values higher than 1.7. These phases have the Sc243 (WO ) -type framework, but the symmetry is orthorhombic Pcnb at low values of x and monoclinic P21 /n at high values. The structural changes are discussed on the basis of the sizes of the cavities left by the two frameworks and the lithium order/disorder in these voids. These materials are ionic conductors and their electrical behaviours are also discussed. 1998 Elsevier Science B.V. All rights reserved. Keywords: NASICON-related materials; Scandium wolframate; Li ionic conductors 1. Introduction to four octahedra. A given stoichiometry may crys- tallize in several structure types such as Garnet [3], NASICON [1,2], Langbeinite [4] and Sc243 (WO ) Since the discovery of fast Na1 ion transport [5], these being not simple distortions of each other. properties in the NASICON system [1,2], numerous The structure adopted by Ax M243 (PO ) seems to studies on related phosphates have been carried out. depend on the size of the A and M cations and the IV Phosphates with the general formula Ax M243 (PO ) value of x. For example, NaM 2 (PO 43 ) adopts a x2 III IV consist in a [M243 (PO ) ] framework built up by NASICON-type structure and K243 M M (PO ) has corner-sharing MO64 octahedra and PO tetrahedra. Langbeinite-type structure [6]. In such frameworks, each octahedron is surrounded Jouanneaux et al. [7] pointed out that the x2 with six tetrahedra and each tetrahedron is connected [M243 (PO ) ] framework with Sc 2 (WO 43 ) -type structure is more suitable for small A cations than a * Corresponding authors. NASICON-type structure. The Sc243 (WO ) -type 0167-2738/98/$ ± see front matter 1998 Elsevier Science B.V. All rights reserved. PII: S0167-2738(98)00207-0 54 E.R. Losilla et al. / Solid State Ionics 112 (1998) 53 ±62 structure (SW) may adopt two symmetries. The 2. Experimental section highest symmetry is orthorhombic, space group 2.1. Synthesis Pcan. Primitive monoclinic symmetry also occurs (s.g. P21 /n) being pseudo-orthorhombic. A complete Li11xx M Hf22x (PO43 ) (M 5 Cr, Fe, Bi) composi- description of these structures (NASICON, SW, tions were prepared by conventional solid-state Garnet, Langbeinite, Bi0.5 Sb 1.5 (PO 4 ) 3 ) and the rela- reaction. Stoichiometric quantities of Li23 CO , HfO 2 , tionship between the unit cell symmetries and param- (NH42 ) HPO 4 and M 2 O 3 synthesized as described eters values has been already reported [7±10]. The below, were ground and heated in a Pt crucible to values of the unit cell parameters are sometimes very give the following overall reaction: similar and the way to distinguish between (11 x)/2Li CO 1 (22 x)HfO 1 (x/2)M O 1 NASICON and SW structures from powder diffrac- 23 2 23 tion data was smartly discussed [7]. →n 3(NH42 ) HPO 4Li 11xx M Hf22x (PO43 ) 1 (11 x)/ On the other hand, materials based on this stoi- ↑ ↑ ↑ chiometry (with Li cations) are promising candidates 2CO231 6NH 1 9/2H 2 O as solid electrolytes if the conductivity properties at room temperature are enhanced. In general, Cr23 O was obtained by thermal decomposition of LiM243 (PO ) (M5 Ge, Ti, Sn, Zr and Hf) com- (NH4227 ) Cr O . Fe 23 O was prepared by calcination at pounds crystallize in the NASICON structure and 4008C of iron acetohydroxide. This precursor was they are moderate lithium ion conductors with quite prepared dissolving Fe(NO33 ) ?9H 2 O and 2 31 different lithium mobility for different M(IV) cations NH43 CH COO (OAc :Fe molar ratio of 2.7) in [11±14]. An outstanding case is LiZr243 (PO ) as it water. NH3 aq. (25% w/w) was then added to obtain may crystallize in the NASICON or SW structures apHø9. After reaction, the brown solid was sepa- depending upon the synthetic temperature [15]. The rated by centrifugation, washed with deionized water conductivity may be increased by partial substitution up to a pHø7.5, and air-dried. Bi23 O (Panreac, 41 of M by trivalent cations as Al, Ga, In, Ti, Sc, Y, 99.5%), Li23 CO (Probus, 99.5%) and HfO 2 (Al- La, Cr, Fe [12,16,17]. The reason for this con- drich, 99.8%, microparticle size ,1 mm) were dried ductivity improvement is mainly due to a much at 2008C and used without further treatment; lower porosity of the pellets. Most works have been (NH42 ) HPO 4 (Panreac, 98%) was used as supplied. carried out in the zirconium and titanium systems The starting compounds were thoroughly mixed and there are very few studies on M 5 Sn and Hf. To and ground together with acetone in an agate mortar our knowledge, Aono et al. have carried out the only for one hour and heated at 0.58C?min21 to 4008C study about electrical properties and crystal structure and left at that temperature for one day to release of solid electrolytes based on LiHf243 (PO ) [18]. gases (NH32 , H O and CO 2 ). To avoid or minimize These authors suggested a NASICON-type structure the formation of by-products (LiMP27 O with M5Cr, for Li11xx M Hf22x (PO43 ) (M 5 Cr, Fe, Sc, In, Lu, Y) Fe and unreacted M23 O or HfO 2 ), the samples were series, although the samples were poorly character- heated at 0.58C?min21 with intermediate regrindings ized and sometimes multiphases. (with acetone for 30 min every 1508C) up to the ®nal LiHf243 (PO ) crystallizes in the NASICON struc- temperatures which depend upon the M metal. Tmax ture and it undergoes a topotactic and reversible for Bi, Fe and Cr were 750, 950 and 11008C, phase transition at low temperature that was char- respectively. These temperatures were maintained for acterized by variable temperature neutron powder 2 to 4 days until no changes were observed in the diffraction [19]. In this work, we have continued our X-ray powder patterns. studies on Li-containing NASICON materials. We have extended the study to the Li11xx M Hf22x (PO43 ) 2.2. X-ray powder diffraction characterization (M5 Cr, Fe, Bi) systems. The samples have been characterized by X-ray powder diffraction, diffuse X-ray powder diffraction patterns were recorded at re¯ectance and impedance spectroscopy. room temperature on a Siemens D5000 automated E.R. Losilla et al. / Solid State Ionics 112 (1998) 53 ±62 55 diffractometer using graphite-monochromated CuKa Rigaku Thermo¯ex TG 8110 apparatus from room radiation. The XRD patterns (128#2u #558) were temperature to 11008C at a heating rate of 108C/min autoindexed using the TREOR90 program [20]. A with calcined Al23 O as standard reference. high resolution synchrotron powder pattern for The diffuse±re¯ectance spectra, UV±VIS, were Li1.8 Fe 0.8 Hf 1.2 (PO 4 ) 3 was collected on the diffrac- obtained on a Shimadzu UV-3100 spectrophotometer tometer of BM16 line of ESRF (Grenoble, France). using an integrating sphere coated with BaSO4 and The sample, loaded in a borosilicate glass capillary the same substance as reference blank. f 50.5 mm, was rotated during data collection (l5 0.39989(2) A).Ê Data from the nine detectors were 2.5. Ionic conductivity characterization normalized and summed up to 0.0038 step size with local software. The powder pattern was re®ned by Pellets of 10 mm of diameter and a thickness of the Rietveld method [21] with the PC version of 1±2 mm were prepared for conductivity measure- GSAS [22] that has a pseudo-Voigt peak shape ments, by pressing ®ne powder at 200 MPa at room function [23] with the asymmetry correction included temperature. The pellets were sintered at 950± [24]. 11008Cfor2hinorder to increase their mechanical strength. Electrodes were made by coating opposite 2.3. Chemical analysis pellet faces with platinum lac and dried by heating at 2008C. Conductivity was determined by a.c. impe- The M/Hf, M/P and Hf/P molar ratios were dance measurements from 20 Hz to 1 MHz using a checked by Analytical Electron Microscopy (AEM) Hewlett-Packard 4284A impedance analyzer at 208C using a Philips CM 200 Supertwin-DX4 with an intervals on a heating cycle from 100 to 6008C in dry electron probe microanalyzer Edax (Si±Li detector). argon. The detector system has an ultra-thin window re- sulting in a resolution of 149 eV. Samples for the electron microscopy study were prepared as follows: 3. Results and discussion a small amount was ground in an agate mortar and dispersed in absolute ethanol, several drops of the Under the above reported synthetic conditions, resultant suspension were deposited onto a carbon Li11xx Bi Hf22x (PO43 ) series are multiphases.
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