Lithium Insertion Mechanism in Iron-Based Oxyfluorides with Anionic Vacancies Probed by PDF Analysis

The mechanism of lithium insertion that occurs in an iron oxyfluoride sample with a hexagonal–tungsten–bronze (HTB)-type structure was investigated by the pair distribution function. This study reveals that upon lithiation, the HTB framework collapses to yield disordered rutile and rock salt phases followed by a conversion reaction of the fluoride phase toward lithium fluoride and nanometer-sized metallic iron. The occurrence of anionic vacancies in the pristine framework was shown to strongly impact the electrochemical activity, that is, the reversible capacity scales with the content of anionic vacancies. Similar to FeOF-type electrodes, upon de-lithiation, a disordered rutile phase forms, showing that the anionic chemistry dictates the atomic arrangement of the re-oxidized phase. Finally, it was shown that the nanoscaling and structural rearrangement induced by the conversion reaction allow the in situ formation of new electrode materials with enhanced electrochemical properties.     

Generalized Born scattering in anisotropic media

The Born scattering approximation has been widely used in seismology to study scattered waves, and to linearize the propagation problem for inversion. The standard Born theory requires the model be separated into a smooth, reference model and a perturbation. Scattering occurs from the pertubation. In the distorted Born approximation, when the reference model is inhomogeneous, the reference Green's functions are normally not known exactly, but the error in these Green's functions is rarely quantified. In this paper, we generalize Born scattering theory to include the errors in the Green's functions explicitly, and obtain scattering integrals from these errors. For forward modelling, there is no need to separate the model into a reference and perturbation part - approximate Green's functions in the true model can be used to calculate the scattered signals.

The theory is developed for inhomogeneous, anisotropic media. Asymptotic ray theory results are suitable approximate Green's functions for the generalized Born scattering theory. The error terms are simple, easily calculated and included in the scattering integrals. Various applications of generalized Born scattering theory have already appeared in the literature, e.g. quasi-shear ray coupling, and this paper is restricted to an improved and more complete theoretical development. Further applications will appear elsewhere.     

Generalized Rotation numbers

A rooted graph is a pair (G,x), where G is a simple undirected graph and x ∈ V(G). If G is rooted at x, its kth rotation number h_k (G,x) is the minimum number of edges in a graph F of order |G| + k such that for every v ∈ V(F) we can find a copy of G in F with the root vertex x at v. When k = 0, this definition reduces to that of the rotation number h(G,x), which was introduced in [“On Rotation Numbers for Complete Bipartite Graphs,” University of Victoria, Department of Mathematics Report No. DM-186-IR (1979)] by E.J. Cockayne and P.J. Lorimer and subsequently calculated for complete multipartite graphs. In this paper, we estimate the kth rotation number for complete bipartite graphs G with root x in the larger vertex class, thereby generalizing results of B. Bollobás and E.J. Cockayne [“More Rotation Numbers for Complete Bipartite Graphs,” Journal of Graph Theory, Vol. 6 (1982), pp. 403–411], J. Haviland [“Cliques and Independent Sets,” Ph. D. thesis, University of Cambridge (1989)], and J. Haviland and A. Thomason [“Rotation Numbers for Complete Bipartite Graphs,” Journal of Graph Theory, Vol. 16 (1992), pp. 61–71]. © 1993 John Wiley & Sons, Inc.