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Determination of the Volume Changes Occurring for Conversion/Alloying-Type Li-Ion Anodes upon Lithiation/Delithiation

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journal contribution
posted on 16.09.2020, 21:30 by Jakob Asenbauer, Matthias Kuenzel, Tobias Eisenmann, Adele Birrozzi, Jeng-Kuei Chang, Stefano Passerini, Dominic Bresser
High-capacity lithium-ion anodes such as alloying-, conversion-, and conversion/alloying-type materials are subjected to extensive volume variation upon lithiation/delithiation. However, a careful examination of these processes at the particle and electrode level as well as the impact of the kind of lithium-ion uptake mechanism is still missing. Herein, we investigated the volume variation upon lithiation/delithiation for a series of conversion/alloying materials with a varying relative contribution of the alloying and conversion reaction, i.e., carbon-coated ZnFe2O4, Zn0.9Fe0.1O, and Sn0.9Fe0.1O2 by operando dilatometry and ex situ scanning electron microscopy of the electrode cross section. While the theoretical estimation at the particle level indicates a rather large volume expansion of 113% (ZnFe2O4) and more, the true volume variation on the electrode level reveals very limited changes of only around 11% (ZnFe2O4). Combining the experimental findings with some theoretical considerations highlights the (to a certain extent unexpected) impact of the initial electrode porosity.

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