A composite electrolyte tri-layer structure, including: a first layer comprising a first ceramic electrolyte, which first electrolyte is stable against contact with lithium metal; a second layer comprising a second ceramic electrolyte, which second electrolyte is stable against aqueous contact; and a third layer comprising a third non-aqueous electrolyte interposed between the first layer and second layer, wherein the first electrolyte, the second electrolyte, and the third electrolyte each have a different relative chemical stability. Also disclosed is a method of making and using the tri-layer structure, and an energy storage article or device incorporating at least one of the tri-layer structures.