a high conductivity of 0.46 mS cm −1 at room temperature because the three-dimensional pathways in the open framework benefi t the diffusion of Na ions. [ 5 ] Further improvement (60%, 0.74 mS cm −1 ) has been obtained by substitution of Si on P sites in 94Na 3 PS 4 -6Na 4 SiS 4 . [ 6 ] However, the ionic conductivity is still low in comparison to liquid electrolytes, and therefore SEs with higher ionic conductivity need to be sought.Tatsumisago and co-workers found that an appropriate diffusion channel size is critical for fast ion diffusion and anion substitutions have a greater effect on ionic diffusivity than cation substitutions. [ 7 ] Moreover, Se-substituted lithium sulfi des demonstrate an enhanced ionic conductivity in comparison with their pristine compounds. [ 8 ] The advantages of Se-doping lie in two aspects. On one hand, the atomic radius of Se is bigger than that of S, so Se substitution on S sites may expand the lattice. On the other hand, the higher polarizability of Se 2− may weaken the binding energy between the moving ion and the anion framework. These modifi cations may be benefi cial for Na + diffusion because of the big ionic radius of sodium. It is therefore highly interesting to synthesize Na 3 PSe 4 and evaluate its electrochemical performance.In this study, cubic Na 3 PSe 4 was synthesized for the fi rst time and its crystal structure, spectra, and electrochemical performance were investigated. A ionic conductivity of 1.16 mS cm −1 was observed; to the best of our knowledge, this is one of the best values among sodium ion conductors and is the highest value reported for sulfi des to date. Figure 1 a shows the X-Ray Diffraction (XRD) pattern of Na 3 PSe 4 . The halo patterns in both cases refl ect the polyimide fi lm. The crystal structure of Na 3 PSe 4 has not been reported yet. Here, the integrated intensities from powder XRD data were extracted by the Le Bail method using the FullProf program. The crystal structure was solved by using the direct space method and was then refi ned by the Rietveld method. The crystal structure was determined to be cubic with the space group I -43 m (No. 217) and Z = 2. The plots of the observed, calculated, and difference patterns from the Rietveld refi nement (Figure 1 a) evidence the formation of single-phase Na 3 PSe 4 . The refi ned crystallographic data are listed in Table 1 . The cell has a lattice parameter a = 7.3094(2) Å, which is much larger than that of Si-doped Na 3 PS 4 ( a = 6.9978 Å). [ 6 ] A negative isotropic atomic displacement parameter ( U iso ) for P atoms and large U iso values for Na and Se atoms are obtained, indicating large disorders in the crystal structure. Comparison of the XRD patterns of Na 3 PSe 4 before and after ball milling ( Figure S1, Supporting Information) shows that only peak broadening is observed. This observation is in accordance with Differential scanning calorimetry (DSC) results ( Figure S2,The development of large-scale energy-storage system attracts worldwide attention because of the rapidly increasing de...

Low ionic conductivity of solid electrolytes is one of the key roadblocks for all-solid-state sodium ion batteries to be utilized to store peak-load energy from wind and solar power. In article number 1501294, Long Zhang and co-workers report fast sodium ion 3 D conduction pathways set up within the structure of a new selenide compound via reconstructing ion transport channels, thereby leading to a low activation energy and high ionic conductivity. SOLID ELECTROLYTES

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T 0 curves in the phase diagrams have been proven useful to understand thermodynamically glass formation in metallic alloys, emphasizing the importance of the metastable solid solutions crystallized partitionlessly. Here we focus on four typical binary eutectic alloys with distinct glassforming abilities and interatomic interactions, Ag 60 Cu 40 , Sb 17.5 Pb 82.5 , Au 81.4 Si 18.6 , and Ni 24 Zr 76 . The thermodynamics involved in the liquid-solid solution transition at T 0 temperatures for the alloys of eutectic compositions are quantified, and the validity of the thermodynamic properties is evaluated.The comparison of the melting entropies for the equilibrium and partitionless solidifications reveals a basic relation. Based on the thermodynamics of the equilibrium phases and the solid solutions, an understanding of the glass formation of metallic alloys is proposed.