An In Situ X-Ray Diffraction Study of the Reaction of Li with Crystalline Si
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- 1 January 2007
- journal article
- Published by The Electrochemical Society in Journal of the Electrochemical Society
- Vol. 154 (3), A156-A161
- https://doi.org/10.1149/1.2409862
Abstract
The electrochemical reaction of lithium with a crystalline Si composite electrode at room temperature was investigated using in situ X-ray diffraction (XRD) techniques. The study confirmed that crystalline Si becomes amorphous during the first lithiation. The range of the coexistence region between crystalline Si and amorphous lithiated Si is 3350±200mAh∕g3350±200mAh∕g . The highly lithiated amorphous LixSiLixSi phase was found to crystallize into Li15Si4Li15Si4 rapidly at about 60mV60mV (vs Li∕Li+Li∕Li+ ) and this Li15Si4Li15Si4 phase exists over a relatively narrow range of capacity. During delithiation, the Li15Si4Li15Si4 phase coexists with amorphous LizSiLizSi with z=2.0−1+0z=2.0−1+0 . Once all the Li15Si4Li15Si4 phase disappears, the amorphous phase persists as the remaining Li is extracted. The formation of the Li15Si4Li15Si4 phase can be avoided if the potential of the Si electrode is controlled above 70mV70mV during cycling. Based on the electrochemical and XRD data, a “phase diagram” was constructed to show the phase changes and regions of phase stability that occur during the lithiation and delithiation of the Si electrode.Keywords
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