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Title: Concentrated Electrolyte for the Sodium-Oxygen Battery: Solvation Structure and Improved Cycle Life

Alkali metal-oxygen batteries are of great interests for energy storage because of their unparalleled theoretical energy densities. Particularly attractive is the emerging Na-O 2 battery because of the formation of superoxide as the discharge product. Dimethyl sulfoxide (DMSO) is a promising solvent for this battery but its instability towards Na makes it impractical in the Na-O 2 battery. Here in this paper, we report the enhanced stability of Na in DMSO solutions containing concentrated sodium trifluoromethanesulfonimide (NaTFSI) salts (>3molkg -1). Raman spectra of NaTFSI/DMSO electrolytes and abinitio molecular dynamics simulation reveal the Na + solvation number in DMSO and the formation of Na(DMSO) 3(TFSI)-like solvation structure. The majority of DMSO molecules solvating Na + in concentrated solutions reduces the available free DMSO molecules that can react with Na and renders the TFSI anion decomposition, which protects Na from reacting with the electrolyte. Using these concentrated electrolytes, Na-O 2 batteries can be cycled forming sodium superoxide (NaO 2) as the sole discharge product with improved long cycle life, highlighting the beneficial role of concentrated electrolytes for Na-based batteries.
Authors:
ORCiD logo [1] ;  [2] ; ORCiD logo [1] ;  [1] ;  [1] ;  [3] ;  [1]
  1. The Ohio State Univ., Columbus, OH (United States). Dept of Chemistry & Biochemistry
  2. California State Univ. (CalState), Long Beach, CA (United States). Dept. of Physics and Astronomy
  3. Argonne National Lab. (ANL), Argonne, IL (United States). Materials Science Division
Publication Date:
Grant/Contract Number:
AC02-06CH11357
Type:
Accepted Manuscript
Journal Name:
Angewandte Chemie (International Edition)
Additional Journal Information:
Journal Name: Angewandte Chemie (International Edition); Journal Volume: 55; Journal Issue: 49; Journal ID: ISSN 1433-7851
Publisher:
Wiley
Research Org:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org:
National Science Foundation (NSF); USDOE Office of Energy Efficiency and Renewable Energy (EERE), Vehicle Technologies Office (EE-3V)
Country of Publication:
United States
Language:
English
Subject:
25 ENERGY STORAGE
OSTI Identifier:
1352612

He, Mingfu, Lau, Kah Chun, Ren, Xiaodi, Xiao, Neng, McCulloch, William D., Curtiss, Larry A., and Wu, Yiying. Concentrated Electrolyte for the Sodium-Oxygen Battery: Solvation Structure and Improved Cycle Life. United States: N. p., Web. doi:10.1002/anie.201608607.
He, Mingfu, Lau, Kah Chun, Ren, Xiaodi, Xiao, Neng, McCulloch, William D., Curtiss, Larry A., & Wu, Yiying. Concentrated Electrolyte for the Sodium-Oxygen Battery: Solvation Structure and Improved Cycle Life. United States. doi:10.1002/anie.201608607.
He, Mingfu, Lau, Kah Chun, Ren, Xiaodi, Xiao, Neng, McCulloch, William D., Curtiss, Larry A., and Wu, Yiying. 2016. "Concentrated Electrolyte for the Sodium-Oxygen Battery: Solvation Structure and Improved Cycle Life". United States. doi:10.1002/anie.201608607. https://www.osti.gov/servlets/purl/1352612.
@article{osti_1352612,
title = {Concentrated Electrolyte for the Sodium-Oxygen Battery: Solvation Structure and Improved Cycle Life},
author = {He, Mingfu and Lau, Kah Chun and Ren, Xiaodi and Xiao, Neng and McCulloch, William D. and Curtiss, Larry A. and Wu, Yiying},
abstractNote = {Alkali metal-oxygen batteries are of great interests for energy storage because of their unparalleled theoretical energy densities. Particularly attractive is the emerging Na-O2 battery because of the formation of superoxide as the discharge product. Dimethyl sulfoxide (DMSO) is a promising solvent for this battery but its instability towards Na makes it impractical in the Na-O2 battery. Here in this paper, we report the enhanced stability of Na in DMSO solutions containing concentrated sodium trifluoromethanesulfonimide (NaTFSI) salts (>3molkg-1). Raman spectra of NaTFSI/DMSO electrolytes and abinitio molecular dynamics simulation reveal the Na+ solvation number in DMSO and the formation of Na(DMSO)3(TFSI)-like solvation structure. The majority of DMSO molecules solvating Na+ in concentrated solutions reduces the available free DMSO molecules that can react with Na and renders the TFSI anion decomposition, which protects Na from reacting with the electrolyte. Using these concentrated electrolytes, Na-O2 batteries can be cycled forming sodium superoxide (NaO2) as the sole discharge product with improved long cycle life, highlighting the beneficial role of concentrated electrolytes for Na-based batteries.},
doi = {10.1002/anie.201608607},
journal = {Angewandte Chemie (International Edition)},
number = 49,
volume = 55,
place = {United States},
year = {2016},
month = {11}
}

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