Three types of next generation batteries are currently being envisaged among the international community: metal-air batteries, multivalent cation batteries and all-solid-state batteries. These battery designs require high-performance, safe and cost effective electrolytes that are compatible with optimized electrode materials. Solid electrolytes have not yet been extensively employed in commercial batteries as they suffer from poor ionic conduction at acceptable temperatures and insufficient stability with respect to lithium-metal. Here we show a novel type of glasses, which evolve from an antiperovskite structure and that show the highest ionic conductivity ever reported for the Li-ion (25 mS cm À1 at 25 C). These glassy electrolytes for lithium batteries are inexpensive, light, recyclable, non-flammable and non-toxic.Moreover, they present a wide electrochemical window (higher than 8 V) and thermal stability within the application range of temperatures.

The advent of a Li+ or Na+ glass electrolyte with a cation conductivity σi > 10−2 S cm−1 at 25 °C and a motional enthalpy ΔHm = 0.06 eV that is wet by a metallic lithium or sodium anode is used to develop a new strategy for an all-solid-state, rechargeable, metal-plating battery.