Effects of intermetallic phases on the electrochemical properties of rapidly-solidified Si-Cr alloys for rechargeable Li-ion batteries

摘要

The microstructures and the electrochemical properties of rapidly-solidified Si-Cr alloys of various compositions were investigated in order to elucidate the effects of intermetallic phases on the cyclic energy capacity of the materials. Rapidly-solidified ribbons of the alloys were prepared by using a melt-spinning process, which is one of the most efficient rapid-solidification processes. The ribbons were fragmented by using a ball-milling process to produce powders of the alloys. To examine the electrochemical characteristics of the alloys, we mixed each of the alloy powders with Ketjenblack(A (R)), a conductive material, and a binder dissolved in deionized water and used it to form electrodes. The electrolyte used was 1.5-M LiPF6 dissolved in ethyl carbonate/dimethyl carbonate/fluoroethylene carbonate. The microstructures and the phases of the alloys were analyzed by using scanning electron microscopy, transmission electron microscopy, and X-ray diffraction analyses. The obtained results showed that the microstructures of the rapidly-solidified Si-Cr alloys were composed of Si and CrSi2 phases. Fine Si particles with diameters of 50 - 100 nm were observed in an eutectic constituent while the sizes of the primary Si and CrSi2 phases were relatively larger at 500 - 900 nm. The specific energy capacities (C) of the Si-Cr alloys decreased linearly with increasing volume fraction (f) of the CrSi2 phase as follows: C = -1,667f + 1,978 after the 50th cycle. The Columbic efficiency after the 3rd cycle increased slightly with increasing volume fraction of the CrSi2 phase; this was effective in improving the cycling capacity of the Si particles.