Dual-ion Li–Mg batteries offer a potential route to cells that combine desirable properties of both single-ion species. To maximize the energy density of a dual-ion battery, we propose a strategy for achieving simultaneous intercalation of both ionic species, by chemically modifying the intercalation host material to produce a second, complementary, class of insertion sites. We show that donor-doping of anatase TiO2 to form large numbers of cationic vacancies allows the complementary insertion of Li+ and Mg2+ in a dual-ion cell with a net increase in cell energy density, due to a combination of an increased reversible capacity, an increased operating voltage, and a reduced polarization. By tuning the lithium concentration in the electrolyte, we achieve full utilization of the Ti4+/Ti3+ redox couple with excellent cyclability and rate capability. We conclude that native interstitial sites preferentially accommodate Li+ ions, while Mg2+ ions occupy single-vacancy sites. We also predict a narrow range of electrochemical conditions where adjacent vacancy pairs preferentially accommodate one ion of each species, i.e., a [LiTi+MgTi] configuration. These results demonstrate the implementation of additional host sites such as cationic sites as an effective approach to increase the energy density in dual-ion batteries.
Koketsu, T., Ma, J., Morgan, B., Body, M., Legein, C., Goddard, P., Borkiewicz, O., Strasser, P., & Dambournet, D. (2020). Exploiting Cationic Vacancies for Increased Energy Densities in Dual-Ion Batteries. Energy Storage Materials, 25, 154-163. https://doi.org/10.1016/j.ensm.2019.10.019