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Title: Engineering the Interlayer Spacing by Pre-Intercalation for High Performance Supercapacitor MXene Electrodes in Room Temperature Ionic Liquid

Abstract

MXenes exhibit excellent capacitance at high scan rates in sulfuric acid aqueous electrolytes, but the narrow potential window of aqueous electrolytes limits the energy density. Organic electrolytes and room-temperature ionic liquids (RTILs) can provide higher potential windows, leading to higher energy density. The large cation size of RTIL hinders its intercalation in-between the layers of MXene limiting the specific capacitance in comparison to aqueous electrolytes. In this work, different chain lengths alkylammonium (AA) cations are intercalated into Ti3C2Tx, producing variation of MXene interlayer spacings (d-spacing). AA-cation-intercalated Ti3C2Tx (AA-Ti3C2), exhibits higher specific capacitances, and cycling stabilities than pristine Ti3C2Tx in 1 m 1-ethly-3-methylimidazolium bis-(trifluoromethylsulfonyl)-imide (EMIMTFSI) in acetonitrile and neat EMIMTFSI RTIL electrolytes. Pre-intercalated MXene with an interlayer spacing of ≈2.2 nm, can deliver a large specific capacitance of 257 F g–1 (1428 mF cm–2 and 492 F cm–3) in neat EMIMTFSI electrolyte leading to high energy density. Quasi elastic neutron scattering and electrochemical impedance spectroscopy are used to study the dynamics of confined RTIL in pre-intercalated MXene. Furthermore, molecular dynamics simulations suggest significant differences in the structures of RTIL ions and AA cations inside the Ti3C2Tx interlayer, providing insights into the differences in the observed electrochemical behavior.

Authors:
ORCiD logo [1];  [2];  [2]; ORCiD logo [3]; ORCiD logo [3];  [4];  [5]; ORCiD logo [3];  [1];  [6]; ORCiD logo [3];  [5]; ORCiD logo [3]; ORCiD logo [4]; ORCiD logo [4];  [2]; ORCiD logo [1]
  1. Tulane Univ., New Orleans, LA (United States)
  2. Vanderbilt Univ., Nashville, TN (United States)
  3. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
  4. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Univ. of Tennessee, Knoxville, TN (United States)
  5. North Carolina State Univ., Raleigh, NC (United States)
  6. National Inst. of Standards and Technology (NIST), Gaithersburg, MD (United States); Univ. of Maryland, College Park, MD (United States)
Publication Date:
Research Org.:
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1817386
Alternate Identifier(s):
OSTI ID: 1797598
Grant/Contract Number:  
AC05-00OR22725
Resource Type:
Accepted Manuscript
Journal Name:
Advanced Functional Materials
Additional Journal Information:
Journal Volume: 31; Journal Issue: 33; Journal ID: ISSN 1616-301X
Publisher:
Wiley
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE

Citation Formats

Liang, Kun, Matsumoto, Ray A., Zhao, Wei, Osti, Naresh C., Popov, Ivan, Thapaliya, Bishnu P., Fleischmann, Simon, Misra, Sudhajit, Prenger, Kaitlyn, Tyagi, Madhusudan, Mamontov, Eugene, Augustyn, Veronica, Unocic, Raymond R., Sokolov, Alexei P., Dai, Sheng, Cummings, Peter T., and Naguib, Michael. Engineering the Interlayer Spacing by Pre-Intercalation for High Performance Supercapacitor MXene Electrodes in Room Temperature Ionic Liquid. United States: N. p., 2021. Web. https://doi.org/10.1002/adfm.202104007.
Liang, Kun, Matsumoto, Ray A., Zhao, Wei, Osti, Naresh C., Popov, Ivan, Thapaliya, Bishnu P., Fleischmann, Simon, Misra, Sudhajit, Prenger, Kaitlyn, Tyagi, Madhusudan, Mamontov, Eugene, Augustyn, Veronica, Unocic, Raymond R., Sokolov, Alexei P., Dai, Sheng, Cummings, Peter T., & Naguib, Michael. Engineering the Interlayer Spacing by Pre-Intercalation for High Performance Supercapacitor MXene Electrodes in Room Temperature Ionic Liquid. United States. https://doi.org/10.1002/adfm.202104007
Liang, Kun, Matsumoto, Ray A., Zhao, Wei, Osti, Naresh C., Popov, Ivan, Thapaliya, Bishnu P., Fleischmann, Simon, Misra, Sudhajit, Prenger, Kaitlyn, Tyagi, Madhusudan, Mamontov, Eugene, Augustyn, Veronica, Unocic, Raymond R., Sokolov, Alexei P., Dai, Sheng, Cummings, Peter T., and Naguib, Michael. Fri . "Engineering the Interlayer Spacing by Pre-Intercalation for High Performance Supercapacitor MXene Electrodes in Room Temperature Ionic Liquid". United States. https://doi.org/10.1002/adfm.202104007.
@article{osti_1817386,
title = {Engineering the Interlayer Spacing by Pre-Intercalation for High Performance Supercapacitor MXene Electrodes in Room Temperature Ionic Liquid},
author = {Liang, Kun and Matsumoto, Ray A. and Zhao, Wei and Osti, Naresh C. and Popov, Ivan and Thapaliya, Bishnu P. and Fleischmann, Simon and Misra, Sudhajit and Prenger, Kaitlyn and Tyagi, Madhusudan and Mamontov, Eugene and Augustyn, Veronica and Unocic, Raymond R. and Sokolov, Alexei P. and Dai, Sheng and Cummings, Peter T. and Naguib, Michael},
abstractNote = {MXenes exhibit excellent capacitance at high scan rates in sulfuric acid aqueous electrolytes, but the narrow potential window of aqueous electrolytes limits the energy density. Organic electrolytes and room-temperature ionic liquids (RTILs) can provide higher potential windows, leading to higher energy density. The large cation size of RTIL hinders its intercalation in-between the layers of MXene limiting the specific capacitance in comparison to aqueous electrolytes. In this work, different chain lengths alkylammonium (AA) cations are intercalated into Ti3C2Tx, producing variation of MXene interlayer spacings (d-spacing). AA-cation-intercalated Ti3C2Tx (AA-Ti3C2), exhibits higher specific capacitances, and cycling stabilities than pristine Ti3C2Tx in 1 m 1-ethly-3-methylimidazolium bis-(trifluoromethylsulfonyl)-imide (EMIMTFSI) in acetonitrile and neat EMIMTFSI RTIL electrolytes. Pre-intercalated MXene with an interlayer spacing of ≈2.2 nm, can deliver a large specific capacitance of 257 F g–1 (1428 mF cm–2 and 492 F cm–3) in neat EMIMTFSI electrolyte leading to high energy density. Quasi elastic neutron scattering and electrochemical impedance spectroscopy are used to study the dynamics of confined RTIL in pre-intercalated MXene. Furthermore, molecular dynamics simulations suggest significant differences in the structures of RTIL ions and AA cations inside the Ti3C2Tx interlayer, providing insights into the differences in the observed electrochemical behavior.},
doi = {10.1002/adfm.202104007},
journal = {Advanced Functional Materials},
number = 33,
volume = 31,
place = {United States},
year = {2021},
month = {6}
}

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