The importance of nonlinear fluid response in joint density-functional theory studies of battery systems
By Deniz Gunceler, Kendra Letchworth-Weaver, Ravishankar Sundararaman, Kathleen A. Schwarz, T. Arias. 2013
198 citations recorded by the source corpus.
Delivering the full benefits of first-principles calculations to battery materials demands the development of accurate and computationally efficient electronic structure methods that incorporate the effects of the electrolyte environment and electrode potential. Realistic electrochemical interfaces containing polar surfaces are beyond the regime of validity of existing continuum solvation theories developed for molecules, due to the presence of significantly stronger electric fields. We present an ab initio theory of the nonlinear dielectric and ionic response of solvent environments within the framework of joint density-functional theory, with precisely the same optimizable parameters as conventional polarizable continuum models. We demonstrate that the resulting nonlinear theory agrees with the standard linear models for organic molecules and metallic surfaces under typical operating conditions. However, we find that the saturation effects in the rotational response of polar solvent molecules, inherent to our nonlinear theory, are crucial for a qualitatively correct description of the ionic surfaces typical of the solid electrolyte interface.
Subfields: Atomic and Molecular Physics, and Optics, Catalysis, Electrical and Electronic Engineering
View Paper: https://www.semanticscholar.org/paper/e5656e06c5178fc5b6c320c395a6b468829e1fca
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In Atomic and Molecular Physics, and Optics
In Catalysis
In Electrical and Electronic Engineering
Citations in the corpus
- Highly Fluorinated Interphases Enable High-Voltage Li-Metal Batteries (2018, background): “13 eV in the activation energy barrier for Li diffusion at the electrolyte/Li-metal electrode interface.(43) Thus, the surface diffusivity should be increased by more than two orders of magnitude, which facilitates Li transport along the interface and promotes the formation of a uniform morphology o”