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Title: Fluorinated Aryl Sulfonimide Tagged (FAST) salts: modular synthesis and structure–property relationships for battery applications

Abstract

Solid-state electrolytes are attracting great interest for their applications in potentially safe and stable high-capacity energy storage technologies. Lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) is widely used as a lithium ion source, especially in solid-state polymer electrolytes, due to its solubility and excellent chemical and electrochemical stability. Unfortunately, chemically inert LiTFSI cannot be easily modified to optimize its properties or allow for conjugation to other molecules, polymers, or substrates to prepare single-ion conducting polymer electrolytes. Chemical modifications of TFSI often erode its advantageous properties. Herein, we introduce Fluorinated Aryl Sulfonimide Tagged (FAST) salts, which are derived from successive nucleophilic aromatic substitution (SNAr) reactions. Experimental studies and density functional theory calculations were used to assess the electrochemical oxidative stabilities, chemical stabilities, and degrees of ion dissociation of FAST salts as a function of their structures. FAST salts offer a platform for accessing functional sulfonimides without sacrificing many of the advantageous properties of TFSI.

Authors:
ORCiD logo [1]; ORCiD logo [2]; ORCiD logo [1]; ORCiD logo [3]; ORCiD logo [1];  [2]; ORCiD logo [4]; ORCiD logo [3]; ORCiD logo [1]
  1. Department of Chemistry, Massachusetts Institute of Technology, Cambridge, USA
  2. Department of Chemical Engineering, Massachusetts Institute of Technology, Cambridge, USA
  3. Department of Mechanical Engineering, Massachusetts Institute of Technology, Cambridge, USA
  4. Samsung Advanced Institute of Technology (SAIT), Burlington, USA
Publication Date:
Research Org.:
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). National Energy Research Scientific Computing Center (NERSC)
Sponsoring Org.:
USDOE Office of Science (SC)
OSTI Identifier:
1483900
Alternate Identifier(s):
OSTI ID: 1434114; OSTI ID: 1543790
Grant/Contract Number:  
AC02-5CH11231; AC02-05CH11231
Resource Type:
Journal Article: Published Article
Journal Name:
Energy & Environmental Science
Additional Journal Information:
Journal Name: Energy & Environmental Science Journal Volume: 11 Journal Issue: 5; Journal ID: ISSN 1754-5692
Publisher:
Royal Society of Chemistry (RSC)
Country of Publication:
United Kingdom
Language:
English
Subject:
25 ENERGY STORAGE; Chemistry; Energy & Fuels; Engineering; Environmental Sciences & Ecology

Citation Formats

Huang, Mingjun, Feng, Shuting, Zhang, Wenxu, Giordano, Livia, Chen, Mao, Amanchukwu, Chibueze V., Anandakathir, Robinson, Shao-Horn, Yang, and Johnson, Jeremiah A. Fluorinated Aryl Sulfonimide Tagged (FAST) salts: modular synthesis and structure–property relationships for battery applications. United Kingdom: N. p., 2018. Web. doi:10.1039/C7EE03509H.
Huang, Mingjun, Feng, Shuting, Zhang, Wenxu, Giordano, Livia, Chen, Mao, Amanchukwu, Chibueze V., Anandakathir, Robinson, Shao-Horn, Yang, & Johnson, Jeremiah A. Fluorinated Aryl Sulfonimide Tagged (FAST) salts: modular synthesis and structure–property relationships for battery applications. United Kingdom. https://doi.org/10.1039/C7EE03509H
Huang, Mingjun, Feng, Shuting, Zhang, Wenxu, Giordano, Livia, Chen, Mao, Amanchukwu, Chibueze V., Anandakathir, Robinson, Shao-Horn, Yang, and Johnson, Jeremiah A. 2018. "Fluorinated Aryl Sulfonimide Tagged (FAST) salts: modular synthesis and structure–property relationships for battery applications". United Kingdom. https://doi.org/10.1039/C7EE03509H.
@article{osti_1483900,
title = {Fluorinated Aryl Sulfonimide Tagged (FAST) salts: modular synthesis and structure–property relationships for battery applications},
author = {Huang, Mingjun and Feng, Shuting and Zhang, Wenxu and Giordano, Livia and Chen, Mao and Amanchukwu, Chibueze V. and Anandakathir, Robinson and Shao-Horn, Yang and Johnson, Jeremiah A.},
abstractNote = {Solid-state electrolytes are attracting great interest for their applications in potentially safe and stable high-capacity energy storage technologies. Lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) is widely used as a lithium ion source, especially in solid-state polymer electrolytes, due to its solubility and excellent chemical and electrochemical stability. Unfortunately, chemically inert LiTFSI cannot be easily modified to optimize its properties or allow for conjugation to other molecules, polymers, or substrates to prepare single-ion conducting polymer electrolytes. Chemical modifications of TFSI often erode its advantageous properties. Herein, we introduce Fluorinated Aryl Sulfonimide Tagged (FAST) salts, which are derived from successive nucleophilic aromatic substitution (SNAr) reactions. Experimental studies and density functional theory calculations were used to assess the electrochemical oxidative stabilities, chemical stabilities, and degrees of ion dissociation of FAST salts as a function of their structures. FAST salts offer a platform for accessing functional sulfonimides without sacrificing many of the advantageous properties of TFSI.},
doi = {10.1039/C7EE03509H},
url = {https://www.osti.gov/biblio/1483900}, journal = {Energy & Environmental Science},
issn = {1754-5692},
number = 5,
volume = 11,
place = {United Kingdom},
year = {Wed May 16 00:00:00 EDT 2018},
month = {Wed May 16 00:00:00 EDT 2018}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record at https://doi.org/10.1039/C7EE03509H

Citation Metrics:
Cited by: 20 works
Citation information provided by
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Works referenced in this record:

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Single-Ion Conducting Polymer Electrolytes for Lithium Metal Polymer Batteries that Operate at Ambient Temperature
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Single Lithium-Ion Conducting Polymer Electrolytes Based on a Super-Delocalized Polyanion
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Single-ion BAB triblock copolymers as highly efficient electrolytes for lithium-metal batteries
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New aromatic polymer electrolytes for application in lithium metal batteries
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Electrochemical Properties of Quaternary Ammonium Salts for Electrochemical Capacitors
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Density Functional Theory Study of the Role of Anions on the Oxidative Decomposition Reaction of Propylene Carbonate
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"Water-in-salt" electrolyte enables high-voltage aqueous lithium-ion chemistries
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Li-ion battery materials: present and future
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Electrolytes and Interphases in Li-Ion Batteries and Beyond
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“Water-in-Salt” electrolytes enable green and safe Li-ion batteries for large scale electric energy storage applications
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The future cost of electrical energy storage based on experience rates
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Lithium-Sulfur Batteries: Progress and Prospects
journal, February 2015


Effect of Molecular Weight and Salt Concentration on Ion Transport and the Transference Number in Polymer Electrolytes
journal, October 2015


Natural hybrid orbitals
journal, September 1980


Lithium salts for advanced lithium batteries: Li–metal, Li–O 2 , and Li–S
journal, January 2015


Recent Advances in Electrolytes for Lithium-Sulfur Batteries
journal, April 2015


Understanding the Chemical Stability of Polymers for Lithium–Air Batteries
journal, January 2015


Computational Design of New Magnesium Electrolytes with Improved Properties
journal, July 2017


Synthesis and characterization of a new family of aryl-trifluoromethanesulfonylimide Li-Salts for Li-ion batteries and beyond
journal, October 2015


Lithium–oxygen batteries: bridging mechanistic understanding and battery performance
journal, January 2013


Towards greener and more sustainable batteries for electrical energy storage
journal, November 2014


Polymer Electrolytes for Lithium-Ion Batteries
journal, April 1998


Materials challenges in rechargeable lithium-air batteries
journal, May 2014


Novel lithium and sodium salts of sulfonamides and bis(sulfonyl)imides: synthesis and electrical conductivity
journal, January 2014


A novel and efficient method for the synthesis of polyfluoroarenesulfonyl bromides from polyfluoroarenethiols
journal, January 2010


Electrolytes for solid-state lithium rechargeable batteries: recent advances and perspectives
journal, January 2011


Instability of Poly(ethylene oxide) upon Oxidation in Lithium–Air Batteries
journal, March 2015


The electrochemistry of noble metal electrodes in aprotic organic solvents containing lithium salts
journal, January 1991


Lithium battery chemistries enabled by solid-state electrolytes
journal, February 2017


Enhancing electrochemical intermediate solvation through electrolyte anion selection to increase nonaqueous Li–O 2 battery capacity
journal, July 2015


Single Lithium-Ion Conducting Polymer Electrolytes Based on a Super-Delocalized Polyanion
journal, January 2016


Works referencing / citing this record:

CCDC 1590310: Experimental Crystal Structure Determination
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CCDC 1590311: Experimental Crystal Structure Determination
dataset, January 2018


CCDC 1590312: Experimental Crystal Structure Determination
dataset, January 2018


Lithium-Sulfur Batteries: Progress and Prospects
journal, February 2015


Recent Advances in Electrolytes for Lithium-Sulfur Batteries
journal, April 2015


Lithium-Sulfur Batteries: Electrochemistry, Materials, and Prospects
journal, November 2013


Single Lithium-Ion Conducting Polymer Electrolytes Based on a Super-Delocalized Polyanion
journal, January 2016


Concentrated Electrolyte for the Sodium-Oxygen Battery: Solvation Structure and Improved Cycle Life
journal, November 2016


Gutmann Donor and Acceptor Numbers for Ionic Liquids
journal, July 2012


The electrochemistry of noble metal electrodes in aprotic organic solvents containing lithium salts
journal, January 1991


A novel and efficient method for the synthesis of polyfluoroarenesulfonyl bromides from polyfluoroarenethiols
journal, January 2010


Synthesis and characterization of a new family of aryl-trifluoromethanesulfonylimide Li-Salts for Li-ion batteries and beyond
journal, October 2015


Li-ion battery materials: present and future
journal, June 2015


Computational Design of New Magnesium Electrolytes with Improved Properties
journal, July 2017


Effect of Molecular Weight and Salt Concentration on Ion Transport and the Transference Number in Polymer Electrolytes
journal, October 2015


Single-Ion Conducting Polymer Electrolytes for Lithium Metal Polymer Batteries that Operate at Ambient Temperature
journal, September 2016


Promising Routes to a High Li + Transference Number Electrolyte for Lithium Ion Batteries
journal, October 2017


Understanding the Chemical Stability of Polymers for Lithium–Air Batteries
journal, January 2015


Nonaqueous Liquid Electrolytes for Lithium-Based Rechargeable Batteries
journal, October 2004


Electrolytes and Interphases in Li-Ion Batteries and Beyond
journal, October 2014


Nonaqueous Li–Air Batteries: A Status Report
journal, October 2014


Natural hybrid orbitals
journal, September 1980


Spectroscopic studies of ionic solvation. X. Study of the solvation of sodium ions in nonaqueous solvents by sodium-23 nuclear magnetic resonance
journal, November 1971


Reactions in the Rechargeable Lithium–O 2 Battery with Alkyl Carbonate Electrolytes
journal, May 2011


Density Functional Theory Study of the Role of Anions on the Oxidative Decomposition Reaction of Propylene Carbonate
journal, December 2011


Instability of Poly(ethylene oxide) upon Oxidation in Lithium–Air Batteries
journal, March 2015


Issues and challenges facing rechargeable lithium batteries
journal, November 2001


Lithium battery chemistries enabled by solid-state electrolytes
journal, February 2017


Opportunities and challenges for a sustainable energy future
journal, August 2012


Towards greener and more sustainable batteries for electrical energy storage
journal, November 2014


Advances in understanding mechanisms underpinning lithium–air batteries
journal, September 2016


Advances in lithium–sulfur batteries based on multifunctional cathodes and electrolytes
journal, September 2016


The future cost of electrical energy storage based on experience rates
journal, July 2017


Single-ion BAB triblock copolymers as highly efficient electrolytes for lithium-metal batteries
journal, March 2013


Electrolytes for solid-state lithium rechargeable batteries: recent advances and perspectives
journal, January 2011


Lithium–oxygen batteries: bridging mechanistic understanding and battery performance
journal, January 2013


Natural population analysis
journal, July 1985


Enhancing electrochemical intermediate solvation through electrolyte anion selection to increase nonaqueous Li–O 2 battery capacity
journal, July 2015


"Water-in-salt" electrolyte enables high-voltage aqueous lithium-ion chemistries
journal, November 2015


Electrochemical Properties of Quaternary Ammonium Salts for Electrochemical Capacitors
journal, January 1997


The absolute electrode potential: an explanatory note (Recommendations 1986)
journal, January 1986


Materials challenges in rechargeable lithium-air batteries
journal, May 2014