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Li3+xln 1 _xMxBr6 (M=Zn, Co, Fe) was synthesized by nano-grinding. No peak of source materials was observed for all the compounds in XRD measurements. With an increase of x for M=Fe compounds, the lattice constants decreased, because the ionic radius ofFe 2 + ion are much smaller than that of ln 3 + ion. In the high temperature phase for Li 3 +xln 1 _xMxBr 6 (M=Zn, Co), the conductivity decreased with x. In Zn compound, a new phase transition was observed at about 345 K and the conductivity became higher than that of the medium temperature phase. In Li 3 +xln 1 _xFexBr 6 , the conductivity of high temperature phase was almost equal to that for LhlnBr 6 . In 7 Li NMR measurement, the spectra in high temperature phase for Li 3 +xln 1 _xFexBr 6 was narrowed to be less than 1 kHz. It is indicated that Li+ ion diffuse fast in the crystal and these compounds are good Li ion conductors.

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