Toward First Principles Prediction of Voltage Dependences of Electrolyte/Electrolyte Interfacial Processes in Lithium Ion Batteries

In lithium ion batteries, Li+ intercalation into electrodes is induced by applied voltages, which are in turn associated with free energy changes of Li+ transfer (ΔG t ) between the solid and liquid phases. Using ab initio molecular dynamics (AIMD) and thermodynamic integration techniques, we comput...

Full description

Saved in:
Bibliographic Details
Published in:Journal of physical chemistry. C 2013-11, Vol.117 (46), p.24224-24235
Main Authors: Leung, Kevin, Tenney, Craig M
Format: Article
Language:English
Subjects:
Applied sciences
Chemistry
Direct energy conversion and energy accumulation
Electrical engineering. Electrical power engineering
Electrical power engineering
Electrochemical conversion: primary and secondary batteries, fuel cells
Electrochemistry
ENERGY STORAGE
Exact sciences and technology
General and physical chemistry
Properties of electrolytes: conductivity
Citations: Items that this one cites
Items that cite this one
Online Access:Get full text
Tags: Add Tag
No Tags, Be the first to tag this record!
Description
Summary:In lithium ion batteries, Li+ intercalation into electrodes is induced by applied voltages, which are in turn associated with free energy changes of Li+ transfer (ΔG t ) between the solid and liquid phases. Using ab initio molecular dynamics (AIMD) and thermodynamic integration techniques, we compute ΔG t for the virtual transfer of a Li+ from a LiC6 anode slab, with pristine basal planes exposed, to liquid ethylene carbonate confined in a nanogap. The onset of delithiation, at ΔG t = 0, is found to occur on LiC6 anodes with negatively charged basal surfaces. These negative surface charges are evidently needed to retain Li+ inside the electrode and should affect passivation (“SEI”) film formation processes. Fast electrolyte decomposition is observed at even larger electron surface densities. By assigning the experimentally known voltage (0.1 V vs Li+/Li metal) to the predicted delithiation onset, an absolute potential scale is obtained. This enables voltage calibrations in simulation cells used in AIMD studies and paves the way for future prediction of voltage dependences in interfacial processes in batteries.
ISSN:1932-7447
1932-7455
DOI:10.1021/jp408974k