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Title: Influences from solvents on charge storage in titanium carbide MXenes

Abstract

We report that pseudocapacitive energy storage in supercapacitor electrodes differs significantly from the electrical double-layer mechanism of porous carbon materials, which requires a change from conventional thinking when choosing appropriate electrolytes. Here we show how simply changing the solvent of an electrolyte system can drastically influence the pseudocapacitive charge storage of the two-dimensional titanium carbide, Ti 3C 2 (a representative member of the MXene family). Measurements of the charge stored by Ti 3C 2 in lithium-containing electrolytes with nitrile-, carbonate- and sulfoxide-based solvents show that the use of a carbonate solvent doubles the charge stored by Ti 3C 2 when compared with the other solvent systems. We find that the chemical nature of the electrolyte solvent has a profound effect on the arrangement of molecules/ions in Ti 3C 2, which correlates directly to the total charge being stored. Finally, having nearly completely desolvated lithium ions in Ti 3C 2 for the carbonate-based electrolyte leads to high volumetric capacitance at high charge–discharge rates, demonstrating the importance of considering all aspects of an electrochemical system during development.

Authors:
ORCiD logo [1];  [1];  [1];  [2];  [3];  [4]; ORCiD logo [5];  [1];  [1];  [1];  [6]; ORCiD logo [5]; ORCiD logo [7]; ORCiD logo [1]
  1. Drexel Univ., Philadelphia, PA (United States)
  2. Université Paul Sabatier, Toulouse (France); Sichuan University, Chengdu (China)
  3. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Univ. of Tennessee, Knoxville, TN (United States)
  4. Murata Manufacturing Co., Ltd, Nagaokakyo-shi, Kyoto (Japan)
  5. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
  6. National Inst. of Standards and Technology (NIST), Gaithersburg, MD (United States); Univ. of Maryland, College Park, MD (United States)
  7. Université Paul Sabatier, Toulouse (France); Réseau sur le Stockage Electrochimique de l’Energie (RS2E), Amiens (France)
Publication Date:
Research Org.:
Energy Frontier Research Centers (EFRC) (United States). Fluid Interface Reactions, Structures and Transport Center (FIRST); Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1502529
Grant/Contract Number:  
AC05-00OR22725
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Nature Energy
Additional Journal Information:
Journal Volume: 4; Journal Issue: 3; Journal ID: ISSN 2058-7546
Publisher:
Nature Publishing Group
Country of Publication:
United States
Language:
English
Subject:
25 ENERGY STORAGE; 36 MATERIALS SCIENCE

Citation Formats

Wang, Xuehang, Mathis, Tyler S., Li, Ke, Lin, Zifeng, Vlcek, Lukas, Torita, Takeshi, Osti, Naresh C., Hatter, Christine, Urbankowski, Patrick, Sarycheva, Asia, Tyagi, Madhusudan, Mamontov, Eugene, Simon, Patrice, and Gogotsi, Yury. Influences from solvents on charge storage in titanium carbide MXenes. United States: N. p., 2019. Web. doi:10.1038/s41560-019-0339-9.
Wang, Xuehang, Mathis, Tyler S., Li, Ke, Lin, Zifeng, Vlcek, Lukas, Torita, Takeshi, Osti, Naresh C., Hatter, Christine, Urbankowski, Patrick, Sarycheva, Asia, Tyagi, Madhusudan, Mamontov, Eugene, Simon, Patrice, & Gogotsi, Yury. Influences from solvents on charge storage in titanium carbide MXenes. United States. doi:10.1038/s41560-019-0339-9.
Wang, Xuehang, Mathis, Tyler S., Li, Ke, Lin, Zifeng, Vlcek, Lukas, Torita, Takeshi, Osti, Naresh C., Hatter, Christine, Urbankowski, Patrick, Sarycheva, Asia, Tyagi, Madhusudan, Mamontov, Eugene, Simon, Patrice, and Gogotsi, Yury. Mon . "Influences from solvents on charge storage in titanium carbide MXenes". United States. doi:10.1038/s41560-019-0339-9. https://www.osti.gov/servlets/purl/1502529.
@article{osti_1502529,
title = {Influences from solvents on charge storage in titanium carbide MXenes},
author = {Wang, Xuehang and Mathis, Tyler S. and Li, Ke and Lin, Zifeng and Vlcek, Lukas and Torita, Takeshi and Osti, Naresh C. and Hatter, Christine and Urbankowski, Patrick and Sarycheva, Asia and Tyagi, Madhusudan and Mamontov, Eugene and Simon, Patrice and Gogotsi, Yury},
abstractNote = {We report that pseudocapacitive energy storage in supercapacitor electrodes differs significantly from the electrical double-layer mechanism of porous carbon materials, which requires a change from conventional thinking when choosing appropriate electrolytes. Here we show how simply changing the solvent of an electrolyte system can drastically influence the pseudocapacitive charge storage of the two-dimensional titanium carbide, Ti3C2 (a representative member of the MXene family). Measurements of the charge stored by Ti3C2 in lithium-containing electrolytes with nitrile-, carbonate- and sulfoxide-based solvents show that the use of a carbonate solvent doubles the charge stored by Ti3C2 when compared with the other solvent systems. We find that the chemical nature of the electrolyte solvent has a profound effect on the arrangement of molecules/ions in Ti3C2, which correlates directly to the total charge being stored. Finally, having nearly completely desolvated lithium ions in Ti3C2 for the carbonate-based electrolyte leads to high volumetric capacitance at high charge–discharge rates, demonstrating the importance of considering all aspects of an electrochemical system during development.},
doi = {10.1038/s41560-019-0339-9},
journal = {Nature Energy},
issn = {2058-7546},
number = 3,
volume = 4,
place = {United States},
year = {2019},
month = {3}
}

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Cited by: 18 works
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Works referenced in this record:

Effect of viscosity and volume on the specific conductivity of lithium salts in solvent mixtures
journal, September 1999


Electrochemical in Situ Tracking of Volumetric Changes in Two-Dimensional Metal Carbides (MXenes) in Ionic Liquids
journal, November 2016

  • Jäckel, Nicolas; Krüner, Benjamin; Van Aken, Katherine L.
  • ACS Applied Materials & Interfaces, Vol. 8, Issue 47
  • DOI: 10.1021/acsami.6b11744

Lithium solvation in dimethyl sulfoxide-acetonitrile mixtures
journal, December 2014

  • Semino, Rocío; Zaldívar, Gervasio; Calvo, Ernesto J.
  • The Journal of Chemical Physics, Vol. 141, Issue 21
  • DOI: 10.1063/1.4902837

Anomalous Increase in Carbon Capacitance at Pore Sizes Less Than 1 Nanometer
journal, September 2006


Biredox ionic liquids with solid-like redox density in the liquid state for high-energy supercapacitors
journal, November 2016

  • Mourad, Eléonore; Coustan, Laura; Lannelongue, Pierre
  • Nature Materials, Vol. 16, Issue 4
  • DOI: 10.1038/nmat4808

A review of electrode materials for electrochemical supercapacitors
journal, January 2012

  • Wang, Guoping; Zhang, Lei; Zhang, Jiujun
  • Chemical Society Reviews, Vol. 41, Issue 2, p. 797-828
  • DOI: 10.1039/C1CS15060J

Controlling the actuation properties of MXene paper electrodes upon cation intercalation
journal, October 2015


Pseudocapacitive oxide materials for high-rate electrochemical energy storage
journal, January 2014

  • Augustyn, Veronica; Simon, Patrice; Dunn, Bruce
  • Energy & Environmental Science, Vol. 7, Issue 5
  • DOI: 10.1039/c3ee44164d

Beyond Intercalation-Based Li-Ion Batteries: The State of the Art and Challenges of Electrode Materials Reacting Through Conversion Reactions
journal, August 2010

  • Cabana, Jordi; Monconduit, Laure; Larcher, Dominique
  • Advanced Materials, Vol. 22, Issue 35
  • DOI: 10.1002/adma.201000717

Geometrically confined favourable ion packing for high gravimetric capacitance in carbon–ionic liquid supercapacitors
journal, January 2016

  • Wang, Xuehang; Zhou, Haitao; Sheridan, Edel
  • Energy & Environmental Science, Vol. 9, Issue 1
  • DOI: 10.1039/C5EE02702K

Guidelines for Synthesis and Processing of Two-Dimensional Titanium Carbide (Ti 3 C 2 T x MXene)
journal, September 2017


One-Step Synthesis of Hollow Dimpled Polystyrene Microparticles by Dispersion Polymerization
journal, February 2017


Transition from Battery to Pseudocapacitor Behavior via Structural Water in Tungsten Oxide
journal, April 2017


MXene as a Charge Storage Host
journal, February 2018


Solving the Capacitive Paradox of 2D MXene using Electrochemical Quartz-Crystal Admittance and In Situ Electronic Conductance Measurements
journal, August 2014

  • Levi, Mikhael D.; Lukatskaya, Maria R.; Sigalov, Sergey
  • Advanced Energy Materials, Vol. 5, Issue 1
  • DOI: 10.1002/aenm.201400815

Fast and Reversible Surface Redox Reaction in Nanocrystalline Vanadium Nitride Supercapacitors
journal, May 2006

  • Choi, D.; Blomgren, G. E.; Kumta, P. N.
  • Advanced Materials, Vol. 18, Issue 9
  • DOI: 10.1002/adma.200502471

The high-flux backscattering spectrometer at the NIST Center for Neutron Research
journal, May 2003

  • Meyer, A.; Dimeo, R. M.; Gehring, P. M.
  • Review of Scientific Instruments, Vol. 74, Issue 5
  • DOI: 10.1063/1.1568557

Carbon-Based Supercapacitors Produced by Activation of Graphene
journal, May 2011


Materials for electrochemical capacitors
journal, November 2008

  • Simon, Patrice; Gogotsi, Yury
  • Nature Materials, Vol. 7, Issue 11
  • DOI: 10.1038/nmat2297

To Be or Not To Be Pseudocapacitive?
journal, January 2015

  • Brousse, Thierry; Bélanger, Daniel; Long, Jeffrey W.
  • Journal of The Electrochemical Society, Vol. 162, Issue 5
  • DOI: 10.1149/2.0201505jes

Energy Storage in Nanomaterials – Capacitive, Pseudocapacitive, or Battery-like?
journal, March 2018


Where Do Batteries End and Supercapacitors Begin?
journal, March 2014


Efficient storage mechanisms for building better supercapacitors
journal, May 2016


Electrochemical Characteristics and Impedance Spectroscopy Studies of Carbon-Carbon Supercapacitors
journal, January 2003

  • Taberna, P. L.; Simon, P.; Fauvarque, J. F.
  • Journal of The Electrochemical Society, Vol. 150, Issue 3, p. A292-A300
  • DOI: 10.1149/1.1543948

Partial breaking of the Coulombic ordering of ionic liquids confined in carbon nanopores
journal, September 2017

  • Futamura, Ryusuke; Iiyama, Taku; Takasaki, Yuma
  • Nature Materials, Vol. 16, Issue 12
  • DOI: 10.1038/nmat4974

New Perspectives on the Charging Mechanisms of Supercapacitors
journal, April 2016

  • Forse, Alexander C.; Merlet, Céline; Griffin, John M.
  • Journal of the American Chemical Society, Vol. 138, Issue 18
  • DOI: 10.1021/jacs.6b02115

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


Capacitance of Ti3C2Tx MXene in ionic liquid electrolyte
journal, September 2016


Direct observation of ion dynamics in supercapacitor electrodes using in situ diffusion NMR spectroscopy
journal, February 2017


A review of electrolyte materials and compositions for electrochemical supercapacitors
journal, January 2015

  • Zhong, Cheng; Deng, Yida; Hu, Wenbin
  • Chemical Society Reviews, Vol. 44, Issue 21
  • DOI: 10.1039/C5CS00303B

Enhanced Li-Ion Accessibility in MXene Titanium Carbide by Steric Chloride Termination
journal, January 2017

  • Kajiyama, Satoshi; Szabova, Lucie; Iinuma, Hiroki
  • Advanced Energy Materials, Vol. 7, Issue 9
  • DOI: 10.1002/aenm.201601873

Resolving the Structure of Ti 3 C 2 T x MXenes through Multilevel Structural Modeling of the Atomic Pair Distribution Function
journal, December 2015


Multidimensional materials and device architectures for future hybrid energy storage
journal, September 2016

  • Lukatskaya, Maria R.; Dunn, Bruce; Gogotsi, Yury
  • Nature Communications, Vol. 7, Issue 1
  • DOI: 10.1038/ncomms12647

Capacitance of two-dimensional titanium carbide (MXene) and MXene/carbon nanotube composites in organic electrolytes
journal, February 2016


Ultra-high-rate pseudocapacitive energy storage in two-dimensional transition metal carbides
journal, July 2017


2D metal carbides and nitrides (MXenes) for energy storage
journal, January 2017


Conductive two-dimensional titanium carbide ‘clay’ with high volumetric capacitance
journal, November 2014

  • Ghidiu, Michael; Lukatskaya, Maria R.; Zhao, Meng-Qiang
  • Nature, Vol. 516, Issue 7529
  • DOI: 10.1038/nature13970