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Correlating Li-Ion Solvation Structures and Electrode Potential Temperature Coefficients

Journal Article · · Journal of the American Chemical Society
DOI:https://doi.org/10.1021/jacs.0c10587· OSTI ID:1774640
 [1];  [1];  [2];  [1];  [1];  [3];  [3];  [2];  [4]
  1. Department of Materials Science and Engineering, Stanford University, Stanford, California 94305, United States
  2. Materials Science Division, Argonne National Laboratory, Lemont, Illinois 60439, United States; Department of Chemical Engineering, University of Illinois at Chicago, Chicago, Illinois 60607, United States
  3. Energy & Biotechnology Division, Sensors and Electron Devices Directorate, US Army Research Laboratory, Adelphi, Maryland 20783, United States
  4. Department of Materials Science and Engineering, Stanford University, Stanford, California 94305, United States; Stanford Institute for Materials and Energy Sciences, SLAC National Accelerator Laboratory, Menlo Park, California 94025, United States
+ Show Author Affiliations
Temperature coefficients (TCs) for either electrochemical cell voltages or potentials of individual electrodes have been widely utilized to study the thermal safety and cathode/anode phase changes of lithium (Li)-ion batteries. However, the fundamental significance of single electrode potential TCs is little known. Here, we discover that the Li-ion desolvation process during Li deposition/intercalation is accompanied by considerable entropy change, which significantly contributes to the measured Li/Li+ electrode potential TCs. To explore this phenomenon, we compare the Li/Li+ electrode potential TCs in a series of electrolyte formulations, where the interaction between Li-ion and solvent molecules occurs at varying strength as a function of both solvent and anion species as well as salt concentrations. As a result, we establish correlations between electrode potential TCs and Li-ion solvation structures and further verify them by ab initio molecular dynamics simulations. We show that measurements of Li/Li+ electrode potential TCs provide valuable knowledge regarding the Li-ion solvation environments and could serve as a screening tool when designing future electrolytes for Li-ion/Li metal batteries.
Research Organization:
Argonne National Laboratory (ANL), Argonne, IL (United States). Laboratory Computing Resource Center (LCRC); SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States)
Sponsoring Organization:
USDOE Office of Energy Efficiency and Renewable Energy (EERE), Transportation Office. Vehicle Technologies Office
Grant/Contract Number:
AC02-06CH11357; AC02-76SF00515
OSTI ID:
1774640
Alternate ID(s):
OSTI ID: 1777372
Journal Information:
Journal of the American Chemical Society, Journal Name: Journal of the American Chemical Society Journal Issue: 5 Vol. 143; ISSN 0002-7863
Publisher:
American Chemical Society (ACS)Copyright Statement
Country of Publication:
United States
Language:
English

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
electrodes
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solvents