Atomistic Mechanisms Underlying the Maximum in Diffusivity in Doped Li₇La₃Zr₂O₁₂

Abstract

Doped lithium lanthanum zirconium oxide (LLZO) is a promising class of solid electrolytes for lithium-ion batteries due to their good electrochemical stability and compatibility with Li metal anodes. Ionic diffusivity in these ceramics is known to occur via correlated, vacancy-mediated jumps of Li + between alternating tetrahedral and octahedral sites. Aliovalent doping at the Zr site increases the concentration of vacancies in the Li + sublattice and cation diffusivity, but such an increase is universally followed by a decrease for Li + concentration lower than 6.3−6.5 Li molar content. Molecular dynamics simulations based on density functional theory show that the maximum in diffusivity originates from competing effects between the increased vacancy concentration and the increasing occupancy of the low-energy tetrahedral sites by Li + , which increases the overall activation energy associated with diffusion. For the relatively high temperatures of our simulations, Li + concentration plays a dominant role in transport as compared to dopant chemistry.

A Workflow for Identifying Viable Crystal Structures with Partially Occupied Sites Applied to the Solid Electrolyte Cubic Li7La3Zr2O12

“…O and La atoms are represented by red and green spheres, respectively, and Zr atoms are represented by blue polyhedra. (c) Experimental and theoretical site assignments and/or starting structures in the literature: a, b, c, d, e, f, g, h, i, j, k, l, m, n, − ,− o, p, , q, r, s, t, and u . Asterisks (*) indicate that the experimental assignments used neutron diffraction; the rest of the structures were solved with X-ray diffraction.…”

“…To further reduce our large data set to unique conformations, we constructed the upper triangular connectivity matrix of the Li sublattice for each structure. First, we defined a connectivity matrix as the distances between each Li atom to every other Li 18 e, 19 f, 20 g, 21 h, 22 i, 22 j, 22 k, 23 l, 24 m, 21 n, 7−9,25−29 o, 30 p, 31,32 q, 33 r, 34 s, 35 t, 35 and u. 36 Asterisks (*) indicate that the experimental assignments used neutron diffraction; the rest of the structures were solved with X-ray diffraction.…”