Ab initio study of stability and quadrupole coupling constants in borophosphates.

The DFT method was used to predict the formation energies and quadrupole coupling constants CQ in a series of borophosphates: Li3BP2O8, Li2NaBP2O8, Na3BP2O8, Li2B3PO8, Na5B2P3O13, LiNa2B5P2O14 and Na3B6PO13 composed of different networks and different amounts of borate and phosphate units. The change in formation energies with increasing number of B atoms in this series is attributed to the multiplicity of boron sites and is explained by density of states calculations. The calculated CQ values of 7Li, 23Na and 11B are correlated with the coordination and distortion of polyhedra to elucidate the influence of local and more distant environments. As for the CQ of 11B, it should be in the ranges of 0.26-0.36, 0.48-0.84 and ∼1 MHz for boron tetrahedral distortion indices of 0.004-0.013, 0.015-0.019 and 0.033, respectively, whereas CQ ∼3.0 MHz corresponds to boron in a triangular site. The obtained numerical relationships make it possible to predict the quadrupole frequencies for these nuclei based only on their local environment, and vice versa, to propose structural models from NMR data. These results provide guidance for studying similar characteristics of other borophosphates, the structure of which varies depending on the initial reaction, composition and temperature.

NaGaPO4F - a KTiOPO4-structured solid sodium-ion conductor.

Advanced ionic conductors are crucial for a large variety of contemporary technologies spanning solid state ion batteries, fuel cells, gas sensors, water desalination, etc. In this work, we report on a new member of KTiOPO4-structured materials, NaGaPO4F, with sodium-ion conductivity. NaGaPO4F has been obtained for the first time via a facile two-step synthesis consisting of a hydrothermal preparation of an ammonia-based precursor, NH4GaPO4F, followed by an ion exchange reaction with NaNO3. Its crystal structure was precisely refined using a combination of synchrotron X-ray powder diffraction and electron diffraction tomography. The material is thermally stable upon 450 °C showing no significant structural transformations or degradation but only a ∼1% cell volume expansion. Na-ion mobility in NaGaPO4F was investigated by a joint experimental and computational approach comprising solid-state nuclear magnetic resonance (NMR) and density functional theory (DFT). DFT and bond-valence site energy (BVSE) calculations reveal 3D diffusion of sodium in the [GaPO4F] framework with migration barriers amounting to 0.22 and 0.44 eV, respectively, while NMR yields 0.3-0.5 eV that, being coupled with a calculated bandgap of ∼4.25 eV, makes NaGaPO4F a promising fast Na-ion conductor.

Electronic structure, sodium diffusion and redox potentials of low-symmetry NaMFe(MoO4 )3 (M = Mg, Ni).

Sodium polyanionic compounds with transition metals are of considerable research interest for the search of new cathode materials for sodium-ion batteries. In this work, we employed ab initio calculations to evaluate three key battery properties: phase stability, diffusion barriers and redox voltage of low-symmetry molybdates NaMFe(MoO4 )3 (M = Mg, Ni) with α- and ß-NaFe2 (MoO4 )3 structures. First, we showed that the Hubbard Ucorrection within the GGA + Uapproach is necessary to correctly refer these molybdates to semiconductors. The sodium diffusion along various pathways was thoroughly examined, which allowed us to establish the most probable pathways with the lowest migration barriers. These compounds have different directions of sodium diffusion with twice different barriers that was associated to the peculiarities of their crystal structure. The high potentials and structural stability during sodium extraction, along with low-diffusion barriers predicted for NaMFe(MoO4 )3 (M = Mg, Ni) indicate that these molybdates may be promising high-voltage cathode materials for sodium-ion batteries.

Coexistence of three types of sodium motion in double molybdate Na9Sc(MoO4)6: 23Na and 45Sc NMR data and ab initio calculations.

The rechargeable Na-ion batteries attract much attention as an alternative to the widely used but expensive Li-ion batteries. The search for materials with high sodium diffusion is important for the development of solid state electrolytes. We present the results of experimental and ab initio studies of the Na-ion diffusion mechanism in Na9Sc(MoO4)6. The ion conductivity reaches the value of 3.6 × 10-2 S cm-1 at T ∼ 850 K. The 23Na and 45Sc NMR data reveal the coexistence of three different types of Na-ion motion in the temperature range from 300 to 750 K. They are activated at different temperatures and are characterized by substantially different dynamics parameters. These features are confirmed by ab initio calculations of activation barriers for sodium diffusion along various paths.