RT Journal Article
T1 A joint computational and experimental evaluation of CaMn_2 O_4 polymorphs as cathode materials for Ca Ion batteries
A1 Arroyo De Dompablo, María Elena
A1 Krich, Christopher
A1 Nava Avendano, Jessica
A1 Biskup Zaja, Nevenko
A1 Palacin, M. Rosa
A1 Barde, Fanny
AB The identification of potential cathode materials is a must for the development of a new calcium-ion based battery technology. In this work, we have first explored the electrochemical behavior of marokite-CaMn2O4 but the experimental attempts to deinsert Ca ion from this compound failed. First-principles calculations indicate that in terms of voltage and capacity, marokite-CaMn2O4 could sustain reversible Ca deinsertion reactions; half decalciation is predicted at an average voltage of 3.7 V with a volume variation of 6%. However, the calculated barriers for Ca diffusion are too high (1 eV), in agreement with the observed difficulty to deinsert Ca ion from the marokite structure. We have extended the computational investigation to two other CaMn2O4 polymorphs, the spinel and the CaFe2O4 structural types. Full Ca extraction from these CaMn2O4 polymorphs is predicted at an average voltage of 3.1 V, but with a large volume variation of around 20%. Structural factors limiting Ca diffusion in the three polymorphs are discussed and confronted with a previous computational investigation of the virtual-spinel [Ca](T)[Mn-2](O)O-4. Regardless the potential interest of [Ca](T)[Mn-2](O)O-4 as cathode for Ca ion batteries, calculations suggests that the synthesis of this compound would hardly be feasible. The present results unravel the bottlenecks associated with the design of feasible intercalation Ca electrode materials, and allow proposing guidelines for future research.
PB American Chemical Society
SN 0897-4756
YR 2016
FD 2016-09-28
LK https://hdl.handle.net/20.500.14352/104745
UL https://hdl.handle.net/20.500.14352/104745
LA eng
NO A Joint Computational and Experimental Evaluation of CaMn2O4 Polymorphs as Cathode Materials for Ca Ion Batteries M. Elena Arroyo-de Dompablo, Christopher Krich, Jessica Nava-Avendaño, Neven Biškup, M. Rosa Palacín, and Fanny Bardé Chemistry of Materials 2016 28 (19), 6886-6893 DOI: 10.1021/acs.chemmater.6b02146
NO Toyota Battery Research division at Higashi Fuji
NO Ministerio de Economia y Competitividad (España)
DS Docta Complutense
RD 7 abr 2025