Simulation of the surface structure of lithium manganese oxide spinel.
- Chemical Sciences and Engineering Division
Simulations of the surface structure of low-index surfaces of LiMn{sub 2}O{sub 4} (LMO), a candidate Li-ion battery electrode material, have been performed within the GGA+U approximation, using the VASP code. Surfaces of (001), (110), and (111) orientation were considered, with at least two terminations treated in each case. A slab geometry was employed, with termination-layer vacancies introduced to remove the bulk dipole moment while maintaining ideal stoichiometry. To complement static-structure relaxation calculations, molecular-dynamics simulations were performed to explore the phase space of possible surface reconstructions. A reconstruction is predicted for the Mn-terminated (111) surface, in which the top layers mix in stoichiometric proportions to form an LMO termination layer with square-planar-coordinated Mn. Average surface Mn oxidation states are reduced, relative to the bulk, for all surfaces considered, as a consequence of the lower-energy cost of Jahn-Teller distortion at the surface. Threefold-coordinated surface Mn, found for two terminations, is divalent, which may enhance its vulnerability to dissolution. The Li-terminated (001) surface is lowest in energy, consistent with previous classical-potential simulations for MgAl{sub 2}O{sub 4} that showed the Mg-terminated (001) surface to be lowest in energy.
- Research Organization:
- Argonne National Lab. (ANL), Argonne, IL (United States)
- Sponsoring Organization:
- EE
- DOE Contract Number:
- DE-AC02-06CH11357
- OSTI ID:
- 1018504
- Report Number(s):
- ANL/CSE/JA-69811; TRN: US201114%%35
- Journal Information:
- Phys. Rev. B, Vol. 83, Issue 19 ; May 31, 2011
- Country of Publication:
- United States
- Language:
- ENGLISH
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