TY - JOUR
T1 - Mapping Structural Changes in Electrode Materials
T2 - Application of the Hybrid Eigenvector-Following Density Functional Theory (DFT) Method to Layered Li0.5MnO2
AU - Seymour, Ieuan D.
AU - Chakraborty, Sudip
AU - Middlemiss, Derek S.
AU - Wales, David J.
AU - Grey, Clare P.
N1 - Publisher Copyright:
© 2015 American Chemical Society.
Acknowledgement: Via our membership of the U.K.'s HPC Materials Chemistry Consortium, which is funded by EPSRC (No. EP/L000202), this work made use of the facilities of HECToR and ARCHER, the U.K.'s national high-performance computing service, which is funded by the Office of Science and Technology through EPSRC's High End Computing Programme. Research was also carried out at the Center for Functional Nanomaterials, Brookhaven National Laboratory, which is supported by the U.S. Department of Energy, Office of Basic Energy Sciences, under Contract No. DE-AC02-98CH10886. C.P.G acknowledges the NorthEast Center for Chemical Energy Storage (NECCES), an Energy Frontier Research Center funded by the U.S. Department of Energy, Office of Science, Basic Energy Sciences under Award #DE-SC0012583. I.D.S. would like to acknowledge funding from the Geoffrey Moorhouse Gibson Studentship in Chemistry from Trinity College Cambridge. S.C. would like to acknowledge Carl Tryggers Stiftelse for Vetenskaplig Forskning (CTS) and Rajeev Ahuja.
PY - 2015/8/3
Y1 - 2015/8/3
N2 - The migration mechanism associated with the initial layered-to-spinel transformation of partially delithiated layered LiMnO2 was studied using hybrid eigenvector-following coupled with density functional theory. The initial part of the transformation mechanism of Li0.5MnO2 involves the migration of Li into both octahedral and tetrahedral local minima within the layered structure. The next stage of the transformation process involves the migration of Mn and was found to occur through several local minima, including an intermediate square pyramidal MnO5 configuration and an independent Mn3+ to Mn2+ charge-transfer process. The migration pathways were found to be significantly affected by the size of the supercell used and the inclusion of a Hubbard U parameter in the DFT functional. The transition state searching methodology described should be useful for studying the structural rearrangements that can occur in electrode materials during battery cycling, and more generally, ionic and electronic transport phenomena in a wide range of energy materials.
AB - The migration mechanism associated with the initial layered-to-spinel transformation of partially delithiated layered LiMnO2 was studied using hybrid eigenvector-following coupled with density functional theory. The initial part of the transformation mechanism of Li0.5MnO2 involves the migration of Li into both octahedral and tetrahedral local minima within the layered structure. The next stage of the transformation process involves the migration of Mn and was found to occur through several local minima, including an intermediate square pyramidal MnO5 configuration and an independent Mn3+ to Mn2+ charge-transfer process. The migration pathways were found to be significantly affected by the size of the supercell used and the inclusion of a Hubbard U parameter in the DFT functional. The transition state searching methodology described should be useful for studying the structural rearrangements that can occur in electrode materials during battery cycling, and more generally, ionic and electronic transport phenomena in a wide range of energy materials.
UR - http://www.scopus.com/inward/record.url?scp=84940100190&partnerID=8YFLogxK
U2 - 10.1021/acs.chemmater.5b01674
DO - 10.1021/acs.chemmater.5b01674
M3 - Article
AN - SCOPUS:84940100190
VL - 27
SP - 5550
EP - 5561
JO - Chemistry of Materials
JF - Chemistry of Materials
SN - 0897-4756
IS - 16
ER -