Exploiting cationic vacancies for increased energy densities in dual-ion batteries
journal contributionposted on 2019-12-10, 13:23 authored by Toshinari Koketsu, Jiwei Ma, Benjamin J Morgan, Monique Body, Christophe Legein, Pooja GoddardPooja Goddard, Olaf J Borkiewicz, Peter Strasser, Damien Dambournet
© 2019 Elsevier B.V. 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.
French National Research Agency under Idex@Sorbonne University for the Future Investments program (No. ANR-11-IDEX-0004-02)
Sino German TU9 network for electromobility” under the grant reference number 16N11929.
U.S. DOE under Contract No. DE-AC02-06CH11357
Royal Society (Grant No. UF130329)
Faraday Institution (faraday.ac.uk; EP/S003053/1, grant number FIRG003).