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Title: Designer interphases for the lithium-oxygen electrochemical cell

Abstract

An electrochemical cell based on the reversible oxygen reduction reaction: 2Li+ + 2e- + O2 ↔ Li2O2, provides among the most energy dense platforms for portable electrical energy storage. Such Lithium-Oxygen (Li-O2) cells offer specific energies competitive with fossil fuels and are considered promising for electrified transportation. Multiple, fundamental challenges with the cathode, anode, and electrolyte have limited practical interest in Li-O2 cells because these problems lead to as many practical shortcomings, including poor rechargeability, high overpotentials, and specific energies well below theoretical expectations. We create and study in-situ formation of solid-electrolyte interphases (SEIs) based on bromide ionomers tethered to a Li anode that take advantage of three powerful processes for overcoming the most stubborn of these challenges. The ionomer SEIs are shown to protect the Li anode against parasitic reactions and also stabilize Li electrodeposition during cell recharge. Bromine species liberated during the anchoring reaction also function as redox mediators at the cathode, reducing the charge overpotential. Finally, the ionomer SEI forms a stable interphase with Li, which protects the metal in high Gutmann donor number liquid electrolytes. Such electrolytes have been reported to exhibit rare stability against nucleophilic attack by Li2O2 and other cathode reaction intermediates, but alsomore » react spontaneously with Li metal anodes. We conclude that rationally designed SEIs able to regulate transport of matter and ions at the electrolyte/anode interface provide a promising platform for addressing three major technical barriers to practical Li-O2 cells.« less

Authors:
ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [1];  [2]; ORCiD logo [1]; ORCiD logo [3]; ORCiD logo [3];  [1]
  1. Cornell Univ., Ithaca, NY (United States). School of Chemical and Biomolecular Engineering
  2. Cornell Univ., Ithaca, NY (United States). Dept. of Materials Science and Engineering
  3. Cornell Univ., Ithaca, NY (United States). School of Applied and Engineering Physics; Cornell Univ., Ithaca, NY (United States). Kavli Inst. at Cornell for Nanoscale Science
Publication Date:
Research Org.:
Cornell Univ., Ithaca, NY (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Engineering & Technology
OSTI Identifier:
1625969
Grant/Contract Number:  
SC0001086
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Science Advances
Additional Journal Information:
Journal Volume: 3; Journal Issue: 4; Journal ID: ISSN 2375-2548
Publisher:
AAAS
Country of Publication:
United States
Language:
English
Subject:
25 ENERGY STORAGE; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Science & Technology - Other Topics

Citation Formats

Choudhury, Snehashis, Wan, Charles Tai-Chieh, Al Sadat, Wajdi I., Tu, Zhengyuan, Lau, Sampson, Zachman, Michael J., Kourkoutis, Lena F., and Archer, Lynden A. Designer interphases for the lithium-oxygen electrochemical cell. United States: N. p., 2017. Web. doi:10.1126/sciadv.1602809.
Choudhury, Snehashis, Wan, Charles Tai-Chieh, Al Sadat, Wajdi I., Tu, Zhengyuan, Lau, Sampson, Zachman, Michael J., Kourkoutis, Lena F., & Archer, Lynden A. Designer interphases for the lithium-oxygen electrochemical cell. United States. https://doi.org/10.1126/sciadv.1602809
Choudhury, Snehashis, Wan, Charles Tai-Chieh, Al Sadat, Wajdi I., Tu, Zhengyuan, Lau, Sampson, Zachman, Michael J., Kourkoutis, Lena F., and Archer, Lynden A. Sat . "Designer interphases for the lithium-oxygen electrochemical cell". United States. https://doi.org/10.1126/sciadv.1602809. https://www.osti.gov/servlets/purl/1625969.
@article{osti_1625969,
title = {Designer interphases for the lithium-oxygen electrochemical cell},
author = {Choudhury, Snehashis and Wan, Charles Tai-Chieh and Al Sadat, Wajdi I. and Tu, Zhengyuan and Lau, Sampson and Zachman, Michael J. and Kourkoutis, Lena F. and Archer, Lynden A.},
abstractNote = {An electrochemical cell based on the reversible oxygen reduction reaction: 2Li+ + 2e- + O2 ↔ Li2O2, provides among the most energy dense platforms for portable electrical energy storage. Such Lithium-Oxygen (Li-O2) cells offer specific energies competitive with fossil fuels and are considered promising for electrified transportation. Multiple, fundamental challenges with the cathode, anode, and electrolyte have limited practical interest in Li-O2 cells because these problems lead to as many practical shortcomings, including poor rechargeability, high overpotentials, and specific energies well below theoretical expectations. We create and study in-situ formation of solid-electrolyte interphases (SEIs) based on bromide ionomers tethered to a Li anode that take advantage of three powerful processes for overcoming the most stubborn of these challenges. The ionomer SEIs are shown to protect the Li anode against parasitic reactions and also stabilize Li electrodeposition during cell recharge. Bromine species liberated during the anchoring reaction also function as redox mediators at the cathode, reducing the charge overpotential. Finally, the ionomer SEI forms a stable interphase with Li, which protects the metal in high Gutmann donor number liquid electrolytes. Such electrolytes have been reported to exhibit rare stability against nucleophilic attack by Li2O2 and other cathode reaction intermediates, but also react spontaneously with Li metal anodes. We conclude that rationally designed SEIs able to regulate transport of matter and ions at the electrolyte/anode interface provide a promising platform for addressing three major technical barriers to practical Li-O2 cells.},
doi = {10.1126/sciadv.1602809},
url = {https://www.osti.gov/biblio/1625969}, journal = {Science Advances},
issn = {2375-2548},
number = 4,
volume = 3,
place = {United States},
year = {2017},
month = {4}
}

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