Understanding the ionic conduction in solid electrolytes in contact with electrodes is vitally important to many applications, such as lithium ion batteries. The problem is complex because both the internal properties of the materials (e.g., electronic structure) and the characteristics of the externally contacting phases (e.g., voltage of the electrode) affect defect formation and transport. In this paper, we developed a method based on density functional theory to study the physics of defects in a solid electrolyte in equilibrium with an external environment. This method was then applied to predict the ionic conduction in lithium fluoride (LiF), in contact with different electrodes which serve as reservoirs with adjustable Li chemical potential (μLi) for defect formation. LiF was chosen because it is a major component in the solid electrolyte interphase (SEI) formed on lithium ion battery electrodes. Seventeen possible native defects with their relevant charge states in LiF were investigated to determine the dominant defect types on various electrodes. The diffusion barrier of dominant defects was calculated by the climbed nudged elastic band method. The ionic conductivity was then obtained from the concentration and mobility of defects using the Nernst-Einstein relationship. Three regions for defect formation were identified as a function of μLi: (1) intrinsic, (2) transitional, and (3) p-type region. In the intrinsic region (high μLi, typical for LiF on the negative electrode), the main defects are Schottky pairs and in the p-type region (low μLi, typical for LiF on the positive electrode) are Li ion vacancies. The ionic conductivity is calculated to be approximately 10−31 S cm−1 when LiF is in contact with a negative electrode but it can increase to 10−12 S cm−1 on a positive electrode. This insight suggests that divalent cation (e.g., Mg2+) doping is necessary to improve Li ion transport through the engineered LiF coating, especially for LiF on negative electrodes. Our results provide an understanding of the influence of the environment on defect formation and demonstrate a linkage between defect concentration in a solid electrolyte and the voltage of the electrode.

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Published in Physical Review B: Condensed Matter and Materials Physics, v. 91, no. 13, article 134116, p. 1-9.

©2015 American Physical Society

The copyright holder has granted permission for posting the article here.

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Funding Information

J.P., Y.T.C., and Y.Q. gratefully acknowledge the support by Department of Energy and the Assistant Secretary for Energy Efficiency and Renewable Energy (Office of Vehicle Technologies of the U.S. Department of Energy under Contract No. DE-AC02-05CH11231, Subcontract No. 7056410) under the Advanced Battery Materials Research (BMR) Program. J.P. and Y.T.C. acknowledge the support from National Science Foundation Grant No. 1355438 (Powering the Kentucky Bioeconomy for a Sustainable Future) and the Center for Computational Sciences at University of Kentucky.

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