Film strains enhance the reversible cycling of intercalation electrodes

Abstract: A key cause of chemo-mechanical degradation in battery electrodes is that they undergo abrupt phase transformation during the charging/discharging cycle. This phase transformation is accompanied by lattice misfit strains that nucleate microcracks, induce fracture and, in extreme cases, amorphize the intercalation electrode. In this work, we propose a strategy to prevent the chemo-mechanical degradation of intercalation electrodes: we show that by engineering suitable film strains we can regulate the phase transformations in thin-film intercalation electrodes and circumvent the large volume changes. We test this strategy using a combination of theory and experiment: we first analytically derive the effect of film strain on the electrochemical response of a thin-film intercalation electrode and next apply our analytical model to a representative example (LixV2O5 with multiple phase transformations). We then test our theoretical predictions experimentally. Specifically, we electrochemically cycle thin-film V2O5 electrodes with different film strains and measure their structure, voltage, and stress responses. Our findings show that tensile film strains lower the voltage for phase transformations in thin-film V2O5 electrodes and facilitate their reversible cycling across a wider voltage window without chemo-mechanical degradation. These results suggest that film strain engineering is an alternative approach to preventing chemo-mechanical degradation in intercalation electrodes. Beyond thin-film electrodes, our findings from this study are applicable to the study of stress-induced phase transformations in particle-based electrodes and the thin surface layers forming on cathode particles.