This invention provides lithium-based batteries that include one or more inorganic barrier layers disposed between the anode and the cathode. The inorganic barrier layer is a lithium-ion conductor and is non-permeable to lithium-containing compounds, such as lithium polysulfides or lithium dendrites. The inorganic barrier layer may be in direct contact with the anode or cathode, or electrically isolated from the anode and cathode. The principles disclosed herein solve the problem of maintaining electrical isolation of the anode and cathode, while providing efficient lithium-ion conduction without crossover of other lithium species that would otherwise limit the power performance of the battery.