Journal
ACTA MATERIALIA
Volume 56, Issue 7, Pages 1539-1545Publisher
PERGAMON-ELSEVIER SCIENCE LTD
DOI: 10.1016/j.actamat.2007.12.002
Keywords
Li-ion battery; Sn electrode; alpha-Sn; strain energy; electrode potential
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Sn and Sn-based compounds have attracted great interest as candidates for anode materials in lithium-ion batteries. Despite the great deal of attention focused on the effects of the volume change of the Sri anode during the lithiation/delithiation process on the cyclic property of the batteries, its influence on the electrode potential is still not well understood. In this study, by constructing a simple Sn-Li battery system, we have investigated the effects of the volume change associated with the formation of Li-Sn compounds on the electrode potential from the viewpoint of the Gibbs free energy and associated elastic-strain energy. Our experimental results show that (i) alpha-Sn, which is a low-temperature phase and in thermodynamic non-equilibrium at around 298 K (our experimental temperature), is also formed together with usual beta-Sn after several cycles of the lithiation and delithiation processes and (ii) when a Sri plate-shape electrode is lithiated, the experimental electrode potential underruns the value expected thermodynamically. These experimental results can be consistently explained by considering the contribution of the elastic-strain energy to the chemical free energy of formation. (C) 2007 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.
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