Publications
High-throughput ab initio screening of binary solid solutions in olivine phosphates for Li-ion battery cathodes
H. R. Hajiyani, U. Preiss, R. Drautz, T. Hammerschmidt.
Modelling and Simulation in Materials Science and Engineering, 21, 074004, (2013)
Abstract
A promising approach to improving the performance of iron-phosphate FePO4
cathode materials for Li-ion batteries is to partly or fully substitute Fe with
other metals. Here, we use high-throughput density-functional theory (DFT)
calculations to investigate binary mixtures of metal atoms M and M` in (Li)MyM`1-yPO4 olivine phosphates. We determine the formation energy for
various stoichiometries of different binary combinations of metals for the cases
of full lithiation and delithiation. Systematic screening of all combinations of
Fe and Mn with elements of the 3d transition-metal (TM) series allows us to
identify trends with average band filling and atomic size. We also included
compounds that verify the observed relations or that were discussed as cathode
materials, particularly Ni–Co, V–Cu and V–Ni, as well as combinations with 4d
TMs (Fe–Zr, Fe–Mo, Fe–Ag) and with Mg (Fe–Mg and Ni–Mg). Based on our
DFT calculations for each compound, we estimate the volume change during
intercalation, the intercalation voltage, the energy density and the thermal
stability with respect to reaction with oxygen. Our calculations indicate that the
energy density of the binary TM phosphates increases with average band filling
while the thermal stability of the compounds decreases.
DOI: 10.1088/0965-0393/21/7/074004
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