Alkali-glass behavior in honeycomb-type layered Li3-xNaxNi2SbO6 solid solution

Coélio Vallée (1) , Matthieu Saubanère (2, 1) , Paula Sanz Camacho (3, 2) , Yohan Biecher (3, 2) , Bernard Fraisse (1) , Emmanuelle Suard (4) , Gwenaelle Rousse (5, 2) , Dany Carlier (3, 2) , Romain Berthelot (1, 2)

1 ICGM - Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier
2 RS2E - Réseau sur le stockage électrochimique de l'énergie
3 ICMCB - Institut de Chimie de la Matière Condensée de Bordeaux
4 ILL - Institut Laue-Langevin
5 CSE - Chimie du solide et de l'énergie

Layered oxide compositions Li3–xNaxNi2SbO6 have been prepared by solid-state synthesis. A complete solid solution is evidenced and characterized by X-ray and neutron diffraction as well as 7Li and 23Na solid-state nuclear magnetic resonance spectroscopy. The transition-metal layer is characterized by the classic honeycomb Ni2+/Sb5+ ordering, whereas a more uncommon randomly mixed occupancy of lithium and sodium is evidenced within the alkali interslab space. In situ X-ray diffraction and density functional theory calculations show that this alkali disordered feature is entropically driven. Fast cooling then appears as a synthesis root to confine bidimensional alkali glass within crystalline layered oxides.

Mots clés: alkali mixed occupancy; solid-solution; honeycomb ordering; Layered oxides

Domaines: Chimie inorganique; Matériaux

Coélio Vallée, Matthieu Saubanère, Paula Sanz Camacho, Yohan Biecher, Bernard Fraisse, et al.. Alkali-glass behavior in honeycomb-type layered Li3-xNaxNi2SbO6 solid solution. Inorganic Chemistry, 2019, 58 (17), pp.11546-11552. ⟨10.1021/acs.inorgchem.9b01385⟩. ⟨hal-02289822⟩