Fast ion transport in the NASICON analog Na3Sc2(PO4)3: Structure and conductivity

Susman, S.; Delbecq, C. J.; Brun, T. O.; Prince, E.

doi:10.1016/0167-2738(83)90099-1

Cited by 52 publications

(26 citation statements)

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“…The number of scandium phosphates is comparatively small, although they attracted attention as ionic conductors [1][2][3][4]. Also complex scandium phosphate frameworks have been reported recently [5,6].…”

Section: Discussionmentioning

confidence: 99%

Crystal structure of sodium scandium bis(monohydrogenphosphate), NaSc(HPO4)2

Ewald¹,

Prots²,

Zhang³

et al. 2004

Zeitschrift Für Kristallographie - New Crystal Structures

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P205(-H20). Specimens could be isolated from suspensions with a typical composition of 0.500 g (3.626 mmol) SC2O3 (ABCR, 99.9 %), 1.383 g (3.626 mmol) Na4B 4 (>7 • 10H 2 0 (Aldrich, A.C.S.) and 6.688 g (58.008 mmol) phosphoric acid (85 %, Merck, p.a.) in 5 ml of water. Filled in 20 ml Teflon autoclaves (degree of filling: 30-40 %), the reaction mixture was kept at 443 K for six days. The raw product was filtrated and washed with water and acetone and finally dried in air at 333 K. AbstractH2NaOgP2Sc, monoclinic, Clcl (no. 9), a = 10.4446(9) A, b = 16.371(2) A, c = 9.0553(7) A, ß= 122.420(3)°, V= 1307.1 Ä 3 ,Z= 8, R gl (F) = 0.023, wRrerfF 2 ) = 0.054, T= 293 K. Source of materialSingle crystals of NaSc(HPC>4)2 were obtained as minority phase during hydrothermal investigations in the system Na20-Sc2Qj-B20j- DiscussionThe number of scandium phosphates is comparatively small, although they attracted attention as ionic conductors [1 [ 12]). All these structures comprise complex partial structures of alternating A^Oi octahedra and HPO4 tetrahedra that, connected via common comers, build fourmembered rings of polyhedra. Only the crystal structure of LiIn(HP0 4 )2 [10] contains an anionic arrangement which is identical to that of the title compound (in terms of topology), but not isotypic. The crystal structure of NaSc(HP0 4 )2 was solved in the acentric space group Clcl [Flack parameter x = 0.02(2)]. It comprises scandium in sixfold coordination by oxygen with Sc-O distances ranging from 1.996(2) A to 2.146(2) A. Each corner of these distorted octahedra (¿O-Sc-O = 82.80(6)° -96.30(6)° for adjacent oxygen atoms) is shared by a HP0 4 group. The hydrogenphosphate tetrahedra (d(P-O = 1.506(2) A -1.594(2) A, ¿O-P-O = 103.15(9)° -113.49(9)°) themselves share the three unprotonated oxygen atoms with adjacent Sc06 polyhedra. In this manner six-and four-membered rings of alternating octahedra and tetrahedra are formed. As a linear arrangement of the fourmembered rings is found (equatorial positions of the Sc06 octahedra), it is possible to describe the structure by a ladder motif (figure, top) which is a common structural feature in many phosphates. These polyhedral ladders can either be isolated or connected to sheets or 3D networks [13,14]. The title compound comprises waved ladders running along [100] that are connected to adjacent ladders (perpendicular in latitudinal direction) via the apical oxygen atoms of the ScC>6 octahedra forming a 3D network. Sodium is located in the cavities of the network (figure, bottom) and is six-to sevenfold coordinated by oxygen in the Na-O distance range between 2.3 A and 3.0 A.

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Section: Discussionmentioning

confidence: 99%

Crystal structure of sodium scandium bis(monohydrogenphosphate), NaSc(HPO4)2

Ewald¹,

Prots²,

Zhang³

et al. 2004

Zeitschrift Für Kristallographie - New Crystal Structures

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“…In the 1980s, rare earth metal scandium substituted NASICONs were obtained by using a solid-state reaction (4). Simultaneously, a mild hydrothermal method was also applied and resulted in an open-framework NASI-CON-type Na Sc''' (PO ) (10). Recently, hydrothermal synthesis of M Ce'4(PO ) H O (M"NH , Na, K) powders under alkaline conditions were reported, but the structures of them were not clari"ed (11).…”

Section: Introductionmentioning

confidence: 99%

A Novel Open-Framework Cerium Phosphate Fluoride: (NH4)[CeIVF2(PO4)]

Wang

Takei

et al. 2001

Journal of Solid State Chemistry

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“…5,22 In contrast, Winand et al, Delmas et al, and Sorokin et al observed an α → β or β → γ phase transition. 20,23,24 The E a values from literature and this study are summarized in Table 2.…”

Section: Resultsmentioning

confidence: 94%

Arrhenius Behavior of the Bulk Na-Ion Conductivity in Na₃Sc₂(PO₄)₃ Single Crystals Observed by Microcontact Impedance Spectroscopy

et al. 2018

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NASICON-based solid electrolytes with exceptionally high Na-ion conductivities are considered to enable future all solid-state Na-ion battery technologies. Despite 40 years of research the interrelation between crystal structure and Na-ion conduction is still controversially discussed and far from being fully understood. In this study, microcontact impedance spectroscopy combined with single crystal X-ray diffraction, and differential scanning calorimetry is applied to tackle the question how bulk Na-ion conductivity σbulk of sub-mm-sized flux grown Na3Sc2(PO4)3 (NSP) single crystals is influenced by supposed phase changes (α, β, and γ phase) discussed in literature. Although we found a smooth structural change at around 140 °C, which we assign to the β → γ phase transition, our conductivity data follow a single Arrhenius law from room temperature (RT) up to 220 °C. Obviously, the structural change, being mainly related to decreasing Na-ion ordering with increasing temperature, does not cause any jumps in Na-ion conductivity or any discontinuities in activation energies Ea. Bulk ion dynamics in NSP have so far rarely been documented; here, under ambient conditions, σbulk turned out to be as high as 3 × 10–4 S cm–1 at RT (Ea, bulk = 0.39 eV) when directly measured with microcontacts for individual small single crystals.

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Fast ion transport in the NASICON analog Na3Sc2(PO4)3: Structure and conductivity

Cited by 52 publications

References 10 publications

Crystal structure of sodium scandium bis(monohydrogenphosphate), NaSc(HPO4)2

Crystal structure of sodium scandium bis(monohydrogenphosphate), NaSc(HPO4)2

A Novel Open-Framework Cerium Phosphate Fluoride: (NH4)[CeIVF2(PO4)]

Arrhenius Behavior of the Bulk Na-Ion Conductivity in Na₃Sc₂(PO₄)₃ Single Crystals Observed by Microcontact Impedance Spectroscopy

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Fast ion transport in the NASICON analog Na3Sc2(PO4)3: Structure and conductivity

Cited by 52 publications

References 10 publications

Crystal structure of sodium scandium bis(monohydrogenphosphate), NaSc(HPO4)2

Crystal structure of sodium scandium bis(monohydrogenphosphate), NaSc(HPO4)2

A Novel Open-Framework Cerium Phosphate Fluoride: (NH4)[CeIVF2(PO4)]

Arrhenius Behavior of the Bulk Na-Ion Conductivity in Na3Sc2(PO4)3 Single Crystals Observed by Microcontact Impedance Spectroscopy

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Arrhenius Behavior of the Bulk Na-Ion Conductivity in Na₃Sc₂(PO₄)₃ Single Crystals Observed by Microcontact Impedance Spectroscopy