Peculiarities of Phase Formation in Mn-Based Na SuperIonic Conductor (NaSICon) Systems: The Case of Na1+2 xMnxTi2- x(PO4)3(0.0 ≤ x ≤ 1.5)

This project has received funding from the European Regional Development Fund (Project no. 01.2.2-LMT-K-718-02–0005) under grant agreement with the Research Council of Lithuania (LMTLT). We thank the High Performance Computing Center “HPC Saulėtekis” at the Faculty of Physics, Vilnius University, for the use of computational resources.NAtrium SuperIonic CONductor (NASICON) structured phosphate framework compounds are attracting a great deal of interest as suitable electrode materials for "rocking chair"type batteries. Manganese-based electrode materials are among the most favored due to their superior stability, resource non-criticality, and high electrode potentials. Although a large share of research was devoted to Mn-based oxides for Li- and Na-ion batteries, the understanding of thermodynamics and phase formation in Mn-rich polyanions is still generally lacking. In this study, we investigate a bifunctional Na-ion battery electrode system based on NASICON-structured Na1+2xMnxTi2-x(PO4)3 (0.0 ≤ x ≤ 1.5). In order to analyze the thermodynamic and phase formation properties, we construct a composition-temperature phase diagram using a computational sampling by density functional theory, cluster expansion, and semi-grand canonical Monte Carlo methods. The results indicate finite thermodynamic limits of possible Mn concentrations in this system, which are primarily determined by the phase separation into stoichiometric Na3MnTi(PO4)3 (x = 1.0) and NaTi2(PO4)3 for x 1.0. The theoretical predictions are corroborated by experiments obtained using X-ray diffraction and Raman spectroscopy on solid-state and sol-gel prepared samples. The results confirm that this system does not show a solid solution type behavior but phase-separates into thermodynamically more stable sodium ordered monoclinic α-Na3MnTi(PO4)3 (space group C2) and other phases. In addition to sodium ordering, the anti-bonding character of the Mn-O bond as compared to Ti-O is suggested as another important factor governing the stability of Mn-based NASICONs. We believe that these results will not only clarify some important questions regarding the thermodynamic properties of NASICON frameworks but will also be helpful for a more general understanding of polyanionic systems. ©ERDF (Project no. 01.2.2-LMT-K-718-02–0005); The Institute of Solid State Physics, University of Latvia (Latvia), as the Centre of Excellence has received funding from the European Union’s Horizon 2020 Framework Programme H2020-WIDESPREAD-01-2016-2017-Teaming Phase2 under grant agreement No. 739508, project CAMART2

Molecular origin of enhanced proton conductivity in anhydrous ionic systems

YesIonic systems with enhanced proton conductivity are widely viewed as promising electrolytes in fuel cells and batteries. Nevertheless, a major challenge toward their commercial applications is determination of the factors controlling the fast proton hopping in anhydrous conditions. To address this issue, we have studied novel proton-conducting materials formed via a chemical reaction of lidocaine base with a series of acids characterized by a various number of proton-active sites. From ambient and high pressure experimental data, we have found that there are fundamental differences in the conducting properties of the examined salts. On the other hand, DFT calculations revealed that the internal proton hopping within the cation structure strongly affects the pathways of mobility of the charge carrier. These findings offer a fresh look on the Grotthuss-type mechanism in protic ionic glasses as well as provide new ideas for the design of anhydrous materials with exceptionally high proton conductivity

On the Symmetry, Electronic Properties, and Possible Metallic States in NASICON-Structured A₄V₂(PO₄)₃ (A = Li, Na, K) Phosphates

In this work, the electronic structure and properties of NASICON-structured A4V2(PO4)3, where A = Li, Na, K were studied using hybrid density functional theory calculations. The symmetries were analyzed using a group theoretical approach, and the band structures were examined by the atom and orbital projected density of states analyses. Li4V2(PO4)3 and Na4V2(PO4)3 adopted monoclinic structures with the C2 space group and averaged vanadium oxidation states of V+2.5 in the ground state, whereas K4V2(PO4)3 adopted a monoclinic structure with the C2 space group and mixed vanadium oxidation states V+2/V+3 in the ground state. The mixed oxidation state is the least stable state in Na4V2(PO4)3 and Li4V2(PO4)3. Symmetry increases in Li4V2(PO4)3 and Na4V2(PO4)3 led to the appearance of a metallic state that was independent of the vanadium oxidation states (except for the averaged oxidation state R32 Na4V2(PO4)3). On the other hand, K4V2(PO4)3 retained a small band gap in all studied configurations. These results might provide valuable guidance for crystallography and electronic structure investigations for this important class of materials

A Comparative Study of Mixed Phosphate-Pyrophosphate Materials for Aqueous and Non-Aqueous Na-ion Batteries

Na-ion batteries based on abundant and sustainable materials might become one of the leading alternative technologies especially suitable for large-scale stationary storage. Various (mixed)phosphate framework materials are attracting much interest mainly due to their high structural stability and diversity. In this study, we report on the successful synthesis of mixed phosphate-pyrophosphate Na7V4(PO4)(P2O7)4, Na4Fe3(PO4)2P2O7, and Na4Mn3(PO4)2P2O7. The electrochemical properties of these materials are comprehensively characterized in different organic and aqueous electrolytes. The findings reveal that Na7V4(PO4)(P2O7)4 and Na4Fe3(PO4)2P2O7 exhibit very good cycling performance and rate capability in organic solvent-based electrolytes. However, their performance deteriorates significantly even in ‘water-in-salt’ aqueous electrolytes due to the rapid electrochemical degradation. Na4Mn3(PO4)2P2O7 demonstrates limited electrochemical activity in organic electrolytes and virtually no activity in ‘water-in-salt’ electrolytes, likely due to degradation processes resulting in blocking interphasial layers on electrode particles. These results underscore the need for further research to optimize the performance of these materials and identify potential strategies for enhancing their stability and activity in different electrolytes

Engineering of conformal electrode coatings by atomic layer deposition for aqueous Na-Ion battery electrodes

The application of atomic layer deposition on active material particles or as conformal layers directly on electrodes is an effective and viable approach for protecting the battery materials from degradation. Al2O3, TiO2, and HfO2 coatings are applied on NaTi2(PO4)3, which is among the most studied negative electrode materials for aqueous Na-ion batteries. The coated electrodes are characterized in terms of electrochemical kinetics, charge capacity retention, and electrochemical impedance spectra. Al2O3, a widely used protective coating in non-aqueous batteries, is shown to be insufficient to suppress parasitic processes and is eventually dissolved by reaction with hydroxide during extended cycling in aqueous Na2SO4. However, this process provides a local buffering effect making the protective action of this coating mainly of chemical nature. TiO2 is found to be very resistant to increase in pH and remains almost intact during electrochemical cycling. However, we provide strong evidence that TiO2 itself is electrochemically active in aqueous electrolytes at negative potentials. The protonation of TiO2 leads to an additional increase in local pH which is detrimental to NaTi2(PO4)3 and results in even faster capacity loss than in uncoated electrodes. Only HfO2 is found to be sufficiently stable and electrochemically inert ALD coating for negative NaTi2(PO4)3 electrodes operating in aqueous electrolytes

Mechanism of Efficient Proton Conduction in Diphosphoric Acid Elucidated via First-Principles Simulation and NMR

Diphosphoric acid (H_4P_2O_7) is the first condensation product of phosphoric acid (H_3PO_4), the compound with the highest intrinsic proton conductivity in the liquid state. It exists at higher temperature (T > 200 °C) and lower relative humidity (RH ≈ 0.01%) and shows significant ionic conductivity under these conditions. In this work, ab initio molecular dynamics simulations of a pure H_4P_2O_7 model system and NMR spectroscopy on nominal H_4P_2O_7 (which contains significant amounts of ortho- and triphosphoric acid in thermodynamic equilibrium) were performed to reveal the nature and underlying mechanisms of the ionic conductivity. The central oxygen of the molecule is found to be excluded from any hydrogen bonding, which has two interesting consequences: (i) compared to H_3PO_4, the acidity of H_4P_2O_7 is severely increased, and (ii) the condensation reaction only leads to a minor decrease in hydrogen bond network frustration, which is thought to be one of the features enabling high proton conductivity. A topological analysis of diphosphoric acid’s hydrogen bond network shows remarkable similarities to that of phosphonic acid (H_3PO_3). The hydrogen bonding facilitates protonic polarization fluctuations (Zundel polarization) extending over several molecules (Grotthuss chains), the other important ingredient for efficient structural diffusion of protons. At T = 160 °C, this is estimated to make a conductivity contribution of about 0.1 S/cm, which accounts for half of the total ionic conductivity (σ ≈ 0.2 S/cm). The other half is suggested to result from diffusion of charged phosphate species (vehicle mechanism) that are present in high concentration, resembling conduction in ionic liquids