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All solid state lithium-ion batteries have the advantages of high safety, long cycle life and high energy density, as compared with the conventional lithium-ion batteries, and have been attracting more and more research interest. Solid electrolyte is a crucial component of all solid state lithium-ion batteries, which largely determine the performance of the batteries. In this work, a polymer-lithium-ceramics complex was designed and synthesized. The structure and dynamics of the polymer-ceramic interface was studied with solid-state NMR techniques.