Solid-state lithium ion electrolytes of lithium phosphate derivative compounds are provided which contain an anionic framework capable of conducting lithium ions. The activation energy of the lithium phosphate derivative compounds is from 0.2 to 0.45 eV and conductivities are from 0.01 to 10 mS/cm at 300K. Materials of specific formulae are provided and methods to alter the composite materials with inclusion of aliovalent ions shown. Lithium batteries containing the composite lithium ion electrolytes are also provided. Electrodes containing the lithium phosphate derivative materials and batteries with such electrodes are also provided.