Journalartikel
Autorenliste: House, Robert A.; Maitra, Urmimala; Jin, Liyu; Lozano, Juan G.; Somerville, James W.; Rees, Nicholas H.; Naylor, Andrew J.; Duda, Laurent C.; Massel, Felix; Chadwick, Alan V.; Ramos, Silvia; Pickup, David M.; McNally, Daniel E.; Lu, Xingye; Schmitt, Thorsten; Roberts, Matthew R.; Bruce, Peter G.
Jahr der Veröffentlichung: 2019
Seiten: 3293-3300
Zeitschrift: Chemistry of Materials
Bandnummer: 31
Heftnummer: 9
ISSN: 0897-4756
eISSN: 1520-5002
Open Access Status: Hybrid
DOI Link: https://doi.org/10.1021/acs.chemmater.9b00227
Verlag: American Chemical Society
Abstract:
It is possible to increase the charge capacity of transition metal (TM) oxide cathodes in alkali-ion batteries by invoking redox reactions on the oxygen. However, oxygen loss often occurs. To explore what affects oxygen loss in oxygen redox materials, we have compared two analogous Na-ion cathodes, P2-Na0.67Mg0.28Mn0.72O2 and P2-Na0.78Li0.25Mn0.75O2. On charging to 4.5 V, >0.4e(-) are removed from the oxide ions of these materials, but neither compound exhibits oxygen loss. Li is retained in P2-Na0.78Li0.25Mn0.25O2 but displaced from the TM to the alkali metal layers, showing that vacancies in the TM layers, which also occur in other oxygen redox compounds that exhibit oxygen loss such as Li[Li0.2Ni0.2Mn0.6]O-2, are not a trigger for oxygen loss. On charging at 5 V, P2-Na0.78Li0.25Mn0.75O2 exhibits oxygen loss, whereas P2-Na0.67Mg0.28Mn0.72O2 does not. Under these conditions, both Na+ and Li+ are removed from P2-Na0.78Li0.25Mn0.75O2, resulting in underbonded oxygen (fewer than 3 cations coordinating oxygen) and surface-localized O loss. In contrast, for P2-Na0.67Mg0.28Mn0.72O2, oxygen remains coordinated by at least 2 Mn4+ and 1 Mg2+ ions, stabilizing the oxygen and avoiding oxygen loss.
Zitierstile
Harvard-Zitierstil: House, R., Maitra, U., Jin, L., Lozano, J., Somerville, J., Rees, N., et al. (2019) What Triggers Oxygen Loss in Oxygen Redox Cathode Materials?, Chemistry of Materials, 31(9), pp. 3293-3300. https://doi.org/10.1021/acs.chemmater.9b00227
APA-Zitierstil: House, R., Maitra, U., Jin, L., Lozano, J., Somerville, J., Rees, N., Naylor, A., Duda, L., Massel, F., Chadwick, A., Ramos, S., Pickup, D., McNally, D., Lu, X., Schmitt, T., Roberts, M., & Bruce, P. (2019). What Triggers Oxygen Loss in Oxygen Redox Cathode Materials?. Chemistry of Materials. 31(9), 3293-3300. https://doi.org/10.1021/acs.chemmater.9b00227
Schlagwörter
CHARGE-COMPENSATION; HIGH-VOLTAGE; LITHIUM BATTERIES; POSITIVE ELECTRODE MATERIAL
