Studies of Si[sub 1−x]C[sub x] Electrode Materials Prepared by High-Energy Mechanical Milling and Combinatorial Sputter Deposition

Abstract

A review of recent literature on composite and nanocomposite electrode materials is first presented emphasizing that most authors do not compare the experimental specific capacity of the composite with that expected based on the phases present. We provide such a comparison and suggest that much of the apparent confusion in the literature, when taken as a whole, can be understood if nanocomposites prepared by "aggressive" methods like high energy milling and high temperature heat-treatment contain significant amounts of amorphous or nanocrystalline . In order to help resolve the confusion, samples of were prepared by high-energy mechanical milling for and by combinatorial co-sputtering for . X-ray diffraction shows the mechanically milled samples to be a mixture of nanocrystalline and Si. Electrochemical studies of the mechanically milled samples show that the attained specific capacity can be described accurately assuming that the Si is active and can reversibly react with 3.75 Li atoms per Si atom , while the is inactive. The co-sputtered samples are amorphous or extremely nanostructured for all x. For , the specific capacity decreases with increasing , from about at , to about at , presumably due to the formation of inactive regions of . The capacity of the co-sputtered samples does not reach small values at , unlike the ballmilled samples, because there are presumably some regions of and among the inactive regions due to the high quenching rate of the sputtering process. Commercially relevant compositions are identified.