Thomas Maxisch | Searcharxiv

arXiv2006

Configurational electronic entropy and the phase diagram of mixed-valence oxides: the case of Li$_x$FePO$_4$

We demonstrate that configurational electronic entropy, previously neglected, in {\it ab initio} thermodynamics of materials can qualitatively modify the finite-temperature phase stability of mixed-valence oxides. While transformations from low-T ordered or immiscible states are almost always driven by configurational disorder (i.e. random occupation of lattice sites by multiple species), in FePO$_4$--LiFePO$_4$ the formation of a solid solution is almost entirely driven by electronic, rather than ionic configurational entropy. We argue that such an electronic entropic mechanism may be relevant to most other mixed-valence systems.

cond-mat.mtrl-sci↗

arXiv2005

The electronic structure and band gap of LiFePO4 and LiMnPO4

Materials with the olivine LixMPO4 structure form an important new class of materials for rechargeable Li batteries. There is significant interest in their electronic properties because of the importance of electronic conductivity in batteries for high rate applications. The density of states of LixMPO4 (x = 0, 1 and M = Fe, Mn) has been determined with the ab initio GGA+U method, appropriate for these correlated electron systems. Computed results are compared with the optical gap of LiFePO4, as measured using UV-Vis-NIR diffuse reflectance spectroscopy. The results obtained from experiment (3.8-4.0 eV) and GGA+U computations (3.7 eV) are in very good agreement. However, standard GGA, without the same level of treatment of electron correlation, is shown to make large errors in predicting the electronic structure. It is argued that olivines are likely to be polaronic conductors with extrinsically determined carrier levels and that their electronic conductivity is therefore not simply related to the band gap.

cond-mat.mtrl-sci↗