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Si alloy anodes were produced by mechanical milling in this study. They were prepared by ball milling the pieces of pre-alloyed melt spun ribbon. Our study was focused on the effect of a milling time on the electrochemical performance of Si alloys and microstructural evolution. As a result, it appears that the longer milling time, more cycle stability, the finer crystal size. In addition, we performed XRD, TEM analysis to characterize microstructure and intermetallic phases. This study leads to the best understanding to date of the electrochemistry of a Si alloy anode with an inactive matrix