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Title: Computational Studies of Solubilities of LiO 2 and Li 2O 2 in Aprotic Solvents

Knowledge of the solubilities of Li 2O 2 and LiO 2 in aprotic solvents is important for insight into the discharge and charge processes of Li-O 2 batteries, but these quantities are not well known. In this contribution, the solvation free energies of molecular LiO 2 and Li 2O 2 in various organic solvents were calculated using various explicit and implicit solvent models, as well as ab initio molecular dynamics (AIMD) methods. Best estimates for the solvation energies from these calculations along with calculated lattice energies of Li 2O 2 and LiO 2 were used to determine the solubility of bulk LiO 2 and Li 2O 2. The computed solubility of LiO 2 (1.8 × 10 -2 M) is about 15 orders higher than that of Li 2O 2 (2.0 × 10 -17 M) due to a much less negative lattice energy of bulk LiO 2 compared to that of Li 2O 2. The difference in solubilities between LiO 2 and Li 2O 2 likely will affect the nucleation and growth mechanisms and resulting morphologies of the products formed during battery discharge, influencing the performance of the battery cell. In conclusion, the calculated LiO 2 and Li 2O 2 solubilitiesmore » provide important information for fundamental studies of discharge and charge chemistries in Li-O 2 batteries.« less
Authors:
 [1] ;  [1] ;  [2] ;  [1] ;  [1] ;  [1]
  1. Argonne National Lab. (ANL), Argonne, IL (United States)
  2. Argonne National Lab. (ANL), Argonne, IL (United States); California State Univ., Northridge, CA (United States)
Publication Date:
Grant/Contract Number:
AC02-06CH11357
Type:
Accepted Manuscript
Journal Name:
Journal of the Electrochemical Society
Additional Journal Information:
Journal Volume: 164; Journal Issue: 11; Journal ID: ISSN 0013-4651
Publisher:
The Electrochemical Society
Research Org:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22), Joint Center for Energy Storage Research (JCESR); USDOE Office of Science (SC), National Energy Research Scientific Computing Center (NERSC); Argonne National Laboratory, Laboratory Computing Resource Center
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 25 ENERGY STORAGE; DFT; solubility; battery; Li air
OSTI Identifier:
1393255

Cheng, Lei, Redfern, Paul, Lau, Kah Chun, Assary, Rajeev S., Narayanan, Badri, and Curtiss, Larry A.. Computational Studies of Solubilities of LiO2 and Li2O2 in Aprotic Solvents. United States: N. p., Web. doi:10.1149/2.0721711jes.
Cheng, Lei, Redfern, Paul, Lau, Kah Chun, Assary, Rajeev S., Narayanan, Badri, & Curtiss, Larry A.. Computational Studies of Solubilities of LiO2 and Li2O2 in Aprotic Solvents. United States. doi:10.1149/2.0721711jes.
Cheng, Lei, Redfern, Paul, Lau, Kah Chun, Assary, Rajeev S., Narayanan, Badri, and Curtiss, Larry A.. 2017. "Computational Studies of Solubilities of LiO2 and Li2O2 in Aprotic Solvents". United States. doi:10.1149/2.0721711jes. https://www.osti.gov/servlets/purl/1393255.
@article{osti_1393255,
title = {Computational Studies of Solubilities of LiO2 and Li2O2 in Aprotic Solvents},
author = {Cheng, Lei and Redfern, Paul and Lau, Kah Chun and Assary, Rajeev S. and Narayanan, Badri and Curtiss, Larry A.},
abstractNote = {Knowledge of the solubilities of Li2O2 and LiO2 in aprotic solvents is important for insight into the discharge and charge processes of Li-O2 batteries, but these quantities are not well known. In this contribution, the solvation free energies of molecular LiO2 and Li2O2 in various organic solvents were calculated using various explicit and implicit solvent models, as well as ab initio molecular dynamics (AIMD) methods. Best estimates for the solvation energies from these calculations along with calculated lattice energies of Li2O2 and LiO2 were used to determine the solubility of bulk LiO2 and Li2O2. The computed solubility of LiO2 (1.8 × 10-2 M) is about 15 orders higher than that of Li2O2 (2.0 × 10-17 M) due to a much less negative lattice energy of bulk LiO2 compared to that of Li2O2. The difference in solubilities between LiO2 and Li2O2 likely will affect the nucleation and growth mechanisms and resulting morphologies of the products formed during battery discharge, influencing the performance of the battery cell. In conclusion, the calculated LiO2 and Li2O2 solubilities provide important information for fundamental studies of discharge and charge chemistries in Li-O2 batteries.},
doi = {10.1149/2.0721711jes},
journal = {Journal of the Electrochemical Society},
number = 11,
volume = 164,
place = {United States},
year = {2017},
month = {8}
}

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