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Title: Li + Defects in a Solid-State Li Ion Battery: Theoretical Insights with a Li 3 OCl Electrolyte

Abstract

In a solid-state Li ion battery, the solid-state electrolyte exits principally in regions of high externally applied potentials, and this varies rapidly at the interfaces with electrodes due to the formation of electrochemical double layers. Here, we investigate the implications of these for a model solid-state Li ion battery Li|Li 3OCl|C, where C is simply a metallic intercalation cathode. We use DFT to calculate the potential dependence of the formation energies of the Li + charge carriers in superionic Li 3OCl. We find that Li+ vacancies are the dominant species at the cathode while Li+ interstitials dominate at the anode. With typical Mg aliovalent doping of Li 3OCl, Li + vacancies dominate the bulk of the electrolyte as well, with freely mobile vacancies only ~ 10 -4 of the Mg doping density at room temperature. We study the repulsive interaction between Li+ vacancies and find that this is extremely short range, typically only one lattice constant due to local structural relaxation around the vacancy and this is significantly shorter than pure electrostatic screening. We model a Li 3OCl- cathode interface by treating the cathode as a nearly ideal metal using a polarizable continuum model with an ε r = 1000.more » There is a large interface segregation free energy of ~ - 1 eV per Li + vacancy. Combined with the short range for repulsive interactions of the vacancies, this means that very large vacancy concentrations will build up in a single layer of Li 3OCl at the cathode interface to form a compact double layer. The calculated potential drop across the interface is ~ 3 V for a nearly full concentration of vacancies at the surface. This suggests that nearly all the cathode potential drop in Li 3OCl occurs at the Helmholtz plane rather than in a diffuse space-charge region. We suggest that the conclusions found here will be general to other superionic conductors as well.« less

Authors:
 [1];  [2];  [3]; ORCiD logo [2]
  1. Stanford Univ., CA (United States). SUNCAT Center for Interface Science and Catalysis, Dept. of Chemical Engineering
  2. SLAC National Accelerator Lab., Menlo Park, CA (United States). SUNCAT Center for Interface Science and Catalysis
  3. Technische Univ. Munchen, Garching (Germany). Chair for Theoretical Chemistry and Catalysis Research Center
Publication Date:
Research Org.:
SLAC National Accelerator Lab., Menlo Park, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1369455
Grant/Contract Number:
AC02-76SF00515
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Chemistry of Materials
Additional Journal Information:
Journal Volume: 29; Journal Issue: 10; Journal ID: ISSN 0897-4756
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
25 ENERGY STORAGE; 36 MATERIALS SCIENCE

Citation Formats

Stegmaier, Saskia, Voss, Johannes, Reuter, Karsten, and Luntz, Alan C. Li+ Defects in a Solid-State Li Ion Battery: Theoretical Insights with a Li3 OCl Electrolyte. United States: N. p., 2017. Web. doi:10.1021/acs.chemmater.7b00659.
Stegmaier, Saskia, Voss, Johannes, Reuter, Karsten, & Luntz, Alan C. Li+ Defects in a Solid-State Li Ion Battery: Theoretical Insights with a Li3 OCl Electrolyte. United States. doi:10.1021/acs.chemmater.7b00659.
Stegmaier, Saskia, Voss, Johannes, Reuter, Karsten, and Luntz, Alan C. Wed . "Li+ Defects in a Solid-State Li Ion Battery: Theoretical Insights with a Li3 OCl Electrolyte". United States. doi:10.1021/acs.chemmater.7b00659. https://www.osti.gov/servlets/purl/1369455.
@article{osti_1369455,
title = {Li+ Defects in a Solid-State Li Ion Battery: Theoretical Insights with a Li3 OCl Electrolyte},
author = {Stegmaier, Saskia and Voss, Johannes and Reuter, Karsten and Luntz, Alan C.},
abstractNote = {In a solid-state Li ion battery, the solid-state electrolyte exits principally in regions of high externally applied potentials, and this varies rapidly at the interfaces with electrodes due to the formation of electrochemical double layers. Here, we investigate the implications of these for a model solid-state Li ion battery Li|Li3OCl|C, where C is simply a metallic intercalation cathode. We use DFT to calculate the potential dependence of the formation energies of the Li+ charge carriers in superionic Li3OCl. We find that Li+ vacancies are the dominant species at the cathode while Li+ interstitials dominate at the anode. With typical Mg aliovalent doping of Li3OCl, Li+ vacancies dominate the bulk of the electrolyte as well, with freely mobile vacancies only ~ 10-4 of the Mg doping density at room temperature. We study the repulsive interaction between Li+ vacancies and find that this is extremely short range, typically only one lattice constant due to local structural relaxation around the vacancy and this is significantly shorter than pure electrostatic screening. We model a Li3OCl- cathode interface by treating the cathode as a nearly ideal metal using a polarizable continuum model with an εr = 1000. There is a large interface segregation free energy of ~ - 1 eV per Li+ vacancy. Combined with the short range for repulsive interactions of the vacancies, this means that very large vacancy concentrations will build up in a single layer of Li3OCl at the cathode interface to form a compact double layer. The calculated potential drop across the interface is ~ 3 V for a nearly full concentration of vacancies at the surface. This suggests that nearly all the cathode potential drop in Li3OCl occurs at the Helmholtz plane rather than in a diffuse space-charge region. We suggest that the conclusions found here will be general to other superionic conductors as well.},
doi = {10.1021/acs.chemmater.7b00659},
journal = {Chemistry of Materials},
number = 10,
volume = 29,
place = {United States},
year = {Wed Apr 26 00:00:00 EDT 2017},
month = {Wed Apr 26 00:00:00 EDT 2017}
}

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