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Polyethylene oxide (PEO)/LiClO4 complexes usually are semi-crystalline.In this work, by using solid state NMR,we studied the two crystalline structures in such materials.By taking advantage of the various 13C T1 relaxations of different components,we selectively monitor the structure and dynamics present in the noncrystalline region.From the chemical shift and peak width,the structures present in the noncrystalline regions of different Li+ contents were distinguished and semi-quantified,which could deep our understanding of the ion transportation mechanism in the polymer electrolytes in general.