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Various embodiments relate to a method comprising forming a template from a template precursor, wherein the template contains an entrapped ceramic precursor, which can be further processed to form a ceramic solid, such as an oxide ceramic solid. In one embodiment, the template precursor is a hydrogel precursor and the template is a hydrogel template. The hydrogel template can include, for example, agarose, chitosan, alginate or a photo-initiating receptive hydrogel template such as a functionalized poly (ethylene glycol). Various devices, including electrolyte interfaces and energy storage devices, as well as thermoelectric devices are also provided. In one embodiment, the oxide ceramic solid is a cubic garnet having a nominal formula of Li7La3Zr2O12 (LLZO).