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

Kun Liang; Ray A. Matsumoto; Wei Zhao; Naresh C. Osti; Ivan Popov; Bishnu P. Thapaliya; Simon Fleischmann; Sudhajit Misra; Kaitlyn Prenger; Madhusudan Tyagi; Eugene Mamontov; Veronica Augustyn; Raymond R. Unocic; Alexei P. Sokolov; Sheng Dai; Peter T. Cummings; Michael Naguib

doi:10.1002/adfm.202104007

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

Kun Liang, Ray A. Matsumoto, Wei Zhao, Naresh C. Osti, Ivan Popov, Bishnu P. Thapaliya, Simon Fleischmann, Sudhajit Misra, Kaitlyn Prenger, Madhusudan Tyagi, Eugene Mamontov, Veronica Augustyn, Raymond R. Unocic, Alexei P. Sokolov, Sheng Dai, Peter T. Cummings, Michael Naguib

Research output: Contribution to journal › Article › peer-review

124 Scopus citations

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 Ti₃C₂T_x, producing variation of MXene interlayer spacings (d-spacing). AA-cation-intercalated Ti₃C₂T_x (AA-Ti₃C₂), exhibits higher specific capacitances, and cycling stabilities than pristine Ti₃C₂T_x 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. Molecular dynamics simulations suggest significant differences in the structures of RTIL ions and AA cations inside the Ti₃C₂T_x interlayer, providing insights into the differences in the observed electrochemical behavior.

Original language	English
Article number	2104007
Journal	Advanced Functional Materials
Volume	31
Issue number	33
DOIs	https://doi.org/10.1002/adfm.202104007
State	Published - Aug 16 2021

Funding

This work was supported as part of the Fluid Interface Reactions, Structures, and Transport (FIRST) Center, an Energy Frontier Research Center funded by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences. This research at ORNL's Spallation Neutron Source was sponsored by the Scientific User Facilities Division, Office of Basic Energy Sciences, U.S. Department of Energy. STEM imaging was conducted at the Center for Nanophase Materials Sciences, which is a DOE Office of Science User Facility. Access to the HFBS was provided by the Center for High‐Resolution Neutron Scattering, a partnership between the NIST and the NSF under agreement no. DMR‐1508249. Certain commercial material suppliers are identified in this article to foster understanding. Such identification does not imply recommendation or endorsement by the National Institute of Standards and Technology, nor does it imply that the materials or equipment identified are necessarily the best available for the purpose.

Funders	Funder number
Scientific User Facilities Division
National Science Foundation	DMR‐1508249
U.S. Department of Energy
National Institute of Standards and Technology
Office of Science
Basic Energy Sciences

Keywords

MXenes
Ti C
intercalation
interlayer spacing
room temperature ionic liquid
supercapacitor

Access to Document

10.1002/adfm.202104007

Cite this

Liang, K., Matsumoto, R. A., Zhao, W., Osti, N. C., Popov, I., Thapaliya, B. P., Fleischmann, S., Misra, S., Prenger, K., Tyagi, M., Mamontov, E., Augustyn, V., Unocic, R. R., Sokolov, A. P., Dai, S., Cummings, P. T., & Naguib, M. (2021). Engineering the Interlayer Spacing by Pre-Intercalation for High Performance Supercapacitor MXene Electrodes in Room Temperature Ionic Liquid. Advanced Functional Materials, 31(33), Article 2104007. https://doi.org/10.1002/adfm.202104007

@article{21c36858ac2541a68d3c272cc919c935,

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. 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.",

keywords = "MXenes, Ti C, intercalation, interlayer spacing, room temperature ionic liquid, supercapacitor",

author = "Kun Liang and Matsumoto, {Ray A.} and Wei Zhao and Osti, {Naresh C.} and Ivan Popov and Thapaliya, {Bishnu P.} and Simon Fleischmann and Sudhajit Misra and Kaitlyn Prenger and Madhusudan Tyagi and Eugene Mamontov and Veronica Augustyn and Unocic, {Raymond R.} and Sokolov, {Alexei P.} and Sheng Dai and Cummings, {Peter T.} and Michael Naguib",

note = "Publisher Copyright: {\textcopyright} 2021 Wiley-VCH GmbH.",

year = "2021",

month = aug,

day = "16",

doi = "10.1002/adfm.202104007",

language = "English",

volume = "31",

journal = "Advanced Functional Materials",

issn = "1616-301X",

publisher = "wiley",

number = "33",

}

Liang, K, Matsumoto, RA, Zhao, W, Osti, NC, Popov, I, Thapaliya, BP, Fleischmann, S, Misra, S, Prenger, K, Tyagi, M, Mamontov, E, Augustyn, V, Unocic, RR, Sokolov, AP , Dai, S, Cummings, PT & Naguib, M 2021, 'Engineering the Interlayer Spacing by Pre-Intercalation for High Performance Supercapacitor MXene Electrodes in Room Temperature Ionic Liquid', Advanced Functional Materials, vol. 31, no. 33, 2104007. https://doi.org/10.1002/adfm.202104007

TY - JOUR

T1 - Engineering the Interlayer Spacing by Pre-Intercalation for High Performance Supercapacitor MXene Electrodes in Room Temperature Ionic Liquid

AU - Liang, Kun

AU - Matsumoto, Ray A.

AU - Zhao, Wei

AU - Osti, Naresh C.

AU - Popov, Ivan

AU - Thapaliya, Bishnu P.

AU - Fleischmann, Simon

AU - Misra, Sudhajit

AU - Prenger, Kaitlyn

AU - Tyagi, Madhusudan

AU - Mamontov, Eugene

AU - Augustyn, Veronica

AU - Unocic, Raymond R.

AU - Sokolov, Alexei P.

AU - Dai, Sheng

AU - Cummings, Peter T.

AU - Naguib, Michael

PY - 2021/8/16

Y1 - 2021/8/16

N2 - 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. 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.

AB - 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. 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.

KW - MXenes

KW - Ti C

KW - intercalation

KW - interlayer spacing

KW - room temperature ionic liquid

KW - supercapacitor

UR - http://www.scopus.com/inward/record.url?scp=85107923564&partnerID=8YFLogxK

U2 - 10.1002/adfm.202104007

DO - 10.1002/adfm.202104007

M3 - Article

AN - SCOPUS:85107923564

SN - 1616-301X

VL - 31

JO - Advanced Functional Materials

JF - Advanced Functional Materials

IS - 33

M1 - 2104007

ER -

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

Abstract

Funding

Keywords

Access to Document

Other files and links

Fingerprint

Cite this