Jump to main content
Jump to site search

Issue 47, 2010
Previous Article Next Article

LiMSO4F (M = Fe, Co and Ni): promising new positive electrode materials through the DFT microscope

Author affiliations

Abstract

A theoretical study of the lithium intercalated LiMSO4F and deintercalated MSO4F systems, where M = Fe, Co and Ni has been performed within the framework of density functional theory. Beyond predictions of structural evolution and average voltages versus a lithium electrode, we have applied partial density of states and Bader's topological analysis of the electron density to the study of lithium deintercalation. Upon lithium extraction, charge rearrangement occurs for nickel between different d-orbitals, but with little net positive charge gain, while cobalt and iron atoms end up with a clear oxidized state. The participation of oxygen ions in accepting the electron of the lithium is thus enhanced for LiNiSO4F. However, this effect does not affect the long-range electrostatic interactions a lot in the lithiated phase, since the valence of all transition metals is very close due to initial lower oxidized state for the Ni atom in the host. It is found that this is not essentially a long-range electrostatic interaction within the lithiated phase but within the host which explains, at least partly, the increase in voltage by passing from Fe to Ni. Our results also shed light upon the possibility of getting an approximate evaluation of the local strain associated with delithiation from the atomic volume evolutions, which are also likely to affect the electrochemical potential.

Graphical abstract: LiMSO4F (M = Fe, Co and Ni): promising new positive electrode materials through the DFT microscope

Back to tab navigation

Publication details

The article was received on 10 May 2010, accepted on 27 Aug 2010 and first published on 26 Oct 2010


Article type: Paper
DOI: 10.1039/C0CP00517G
Citation: Phys. Chem. Chem. Phys., 2010,12, 15512-15522
  •   Request permissions

    LiMSO4F (M = Fe, Co and Ni): promising new positive electrode materials through the DFT microscope

    C. Frayret, A. Villesuzanne, N. Spaldin, E. Bousquet, J. Chotard, N. Recham and J. Tarascon, Phys. Chem. Chem. Phys., 2010, 12, 15512
    DOI: 10.1039/C0CP00517G

Search articles by author

Spotlight

Advertisements