All-in-one improvement toward Li₆PS₅Br-Based solid electrolytes triggered by compositional tune

Sulfide solid electrolytes possess high ionic conductivity and moderate dendrite suppression capability, but rather poor compatibility against oxide cathodes and metallic Li. Here, we report O-doped Li6PS5Br as solid electrolyte synthesized by a facile solid-state sintering. Different from other O-incorporated sulfides, the O atoms in Li6PS5-xOxBr prefer to substitute the S atoms at free S2− sites rather than those at the PS4 tetrahedra. Remarkably, without deteriorating the ionic conductivity, this inorganic solid electrolyte with O doping exhibits comprehensively enhanced properties including excellent dendrite suppression capability, superior electrochemical and chemical stability against Li metal as well as high voltage oxide cathodes, and good air stability. Li(Ni0.8Co0.1Mn0.1)O2 and LiCoO2-based all-solid-state batteries with Li6PS4.7O0.3Br electrolyte deliver high specific capacity, superior rate capability, and outstanding cycling stability accompanied with low interfacial resistivity. This type of inorganic solid electrolytes is promising for all-solid-state batteries with high energy density.RST/Storage of Electrochemical EnergyRST/Neutron and Positron Methods in Material