No abstract

In the search for novel solid electrolytes for solid-state batteries, thiophosphate ionic conductors have been in recent focus owing to their high ionic conductivities, which are believed to stem from a softer, more polarizable anion framework. Inspired by the oft-cited connection between a soft anion lattice and ionic transport, this work aims to provide evidence on how changing the polarizability of the anion sublattice in one structure affects ionic transport. Here, we systematically alter the anion framework polarizability of the superionic argyrodites LiPSX by controlling the fractional occupancy of the halide anions (X = Cl, Br, I). Ultrasonic speed of sound measurements are used to quantify the variation in the lattice stiffness and Debye frequencies. In combination with electrochemical impedance spectroscopy and neutron diffraction, these results show that the lattice softness has a striking influence on the ionic transport: the softer bonds lower the activation barrier and simultaneously decrease the prefactor of the moving ion. Due to the contradicting influence of these parameters on ionic conductivity, we find that it is necessary to tailor the lattice stiffness of materials in order to obtain an optimum ionic conductivity.

This critical review presents the state of the art research progress, proposes strategies to improve the conductivity of solid electrolytes, discusses the chemical and electrochemical stabilities, and uncovers future perspectives for solid state batteries.

In the search for room-temperature batteries with high energy densities, rechargeable metal-air (more precisely metal-oxygen) batteries are considered as particularly attractive owing to the simplicity of the underlying cell reaction at first glance. Atmospheric oxygen is used to form oxides during discharging, which-ideally-decompose reversibly during charging. Much work has been focused on aprotic Li-O(2) cells (mostly with carbonate-based electrolytes and Li(2)O(2) as a potential discharge product), where large overpotentials are observed and a complex cell chemistry is found. In fact, recent studies evidence that Li-O(2) cells suffer from irreversible electrolyte decomposition during cycling. Here we report on a Na-O(2) cell reversibly discharging/charging at very low overpotentials (< 200 mV) and current densities as high as 0.2 mA cm(-2) using a pure carbon cathode without an added catalyst. Crystalline sodium superoxide (NaO(2)) forms in a one-electron transfer step as a solid discharge product. This work demonstrates that substitution of lithium by sodium may offer an unexpected route towards rechargeable metal-air batteries.