Understanding the MXene Pseudocapacitance
Abstract
MXenes have attracted great attention as next-generation capacitive energy-storage materials, but the mechanisms underlying their pseudocapacitive behavior are not well understood. Here we provide a theoretical description of the surface redox process of Ti3C2Tx (T = O, OH), a prototypical MXene, in 1 M H2SO4 electrolyte, based on joint density functional theory with an implicit solvation model and the analysis of Gibbs free energy under a constant-electrode potential. From the dependence of the O/OH ratio (or the surface H coverage) and the surface charge on the applied potential, we obtain a clear picture of the capacitive energy-storage mechanism of Ti3C2Tx that shows good agreement with previous experimental findings in terms of the integral capacitance and Ti valence change. We find a voltage-dependent redox/double-layer co-charging behavior: the capacitive mechanism is dominated by the redox process, but the electric double-layer charge works against the redox process. This new insight may be useful in improving the capacitance of MXenes.
- Authors:
-
[2];
[4];
[3];
[1]
- Univ. of California, Riverside, CA (United States)
- Tulane Univ., New Orleans, LA (United States)
- Drexel Univ., Philadelphia, PA (United States)
- Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
- Publication Date:
- Research Org.:
- Energy Frontier Research Centers (EFRC) (United States). Fluid Interface Reactions, Structures and Transport Center (FIRST); Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States); Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States). National Energy Research Scientific Computing Center (NERSC)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES)
- OSTI Identifier:
- 1493989
- Alternate Identifier(s):
- OSTI ID: 1484259
- Grant/Contract Number:
- AC05-00OR22725; AC02-05CH11231
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Journal of Physical Chemistry Letters
- Additional Journal Information:
- Journal Volume: 9; Journal Issue: 6; Journal ID: ISSN 1948-7185
- Publisher:
- American Chemical Society
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Citation Formats
Zhan, Cheng, Naguib, Michael, Lukatskaya, Maria, Kent, Paul R. C., Gogotsi, Yury, and Jiang, De-en. Understanding the MXene Pseudocapacitance. United States: N. p., 2018.
Web. doi:10.1021/acs.jpclett.8b00200.
Zhan, Cheng, Naguib, Michael, Lukatskaya, Maria, Kent, Paul R. C., Gogotsi, Yury, & Jiang, De-en. Understanding the MXene Pseudocapacitance. United States. https://doi.org/10.1021/acs.jpclett.8b00200
Zhan, Cheng, Naguib, Michael, Lukatskaya, Maria, Kent, Paul R. C., Gogotsi, Yury, and Jiang, De-en. Tue .
"Understanding the MXene Pseudocapacitance". United States. https://doi.org/10.1021/acs.jpclett.8b00200. https://www.osti.gov/servlets/purl/1493989.
@article{osti_1493989,
title = {Understanding the MXene Pseudocapacitance},
author = {Zhan, Cheng and Naguib, Michael and Lukatskaya, Maria and Kent, Paul R. C. and Gogotsi, Yury and Jiang, De-en},
abstractNote = {MXenes have attracted great attention as next-generation capacitive energy-storage materials, but the mechanisms underlying their pseudocapacitive behavior are not well understood. Here we provide a theoretical description of the surface redox process of Ti3C2Tx (T = O, OH), a prototypical MXene, in 1 M H2SO4 electrolyte, based on joint density functional theory with an implicit solvation model and the analysis of Gibbs free energy under a constant-electrode potential. From the dependence of the O/OH ratio (or the surface H coverage) and the surface charge on the applied potential, we obtain a clear picture of the capacitive energy-storage mechanism of Ti3C2Tx that shows good agreement with previous experimental findings in terms of the integral capacitance and Ti valence change. We find a voltage-dependent redox/double-layer co-charging behavior: the capacitive mechanism is dominated by the redox process, but the electric double-layer charge works against the redox process. This new insight may be useful in improving the capacitance of MXenes.},
doi = {10.1021/acs.jpclett.8b00200},
journal = {Journal of Physical Chemistry Letters},
number = 6,
volume = 9,
place = {United States},
year = {2018},
month = {2}
}
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Figures / Tables:
Figure 1: Partially protonated Ti3C2O2 as a prototypical MXene electrode in an acidic electrolyte: side view (left) and top view (right). The 2D material has an ideal surface area (counting two sides) of ∼479 m2/g.
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Works referenced in this record:
Role of Surface Structure on Li-Ion Energy Storage Capacity of Two-Dimensional Transition-Metal Carbides
journal, April 2014
- Xie, Yu; Naguib, Michael; Mochalin, Vadym N.
- Journal of the American Chemical Society, Vol. 136, Issue 17
Cation Intercalation and High Volumetric Capacitance of Two-Dimensional Titanium Carbide
journal, September 2013
- Lukatskaya, M. R.; Mashtalir, O.; Ren, C. E.
- Science, Vol. 341, Issue 6153
Ion Intercalation into Two-Dimensional Transition-Metal Carbides: Global Screening for New High-Capacity Battery Materials
journal, October 2014
- Eames, Christopher; Islam, M. Saiful
- Journal of the American Chemical Society, Vol. 136, Issue 46
MXene-based materials for electrochemical energy storage
journal, January 2018
- Zhang, Xu; Zhang, Zihe; Zhou, Zhen
- Journal of Energy Chemistry, Vol. 27, Issue 1
MXene: a promising transition metal carbide anode for lithium-ion batteries
journal, March 2012
- Naguib, Michael; Come, Jérémy; Dyatkin, Boris
- Electrochemistry Communications, Vol. 16, Issue 1, p. 61-64
Sulfur Cathodes Based on Conductive MXene Nanosheets for High-Performance Lithium-Sulfur Batteries
journal, February 2015
- Liang, Xiao; Garsuch, Arnd; Nazar, Linda F.
- Angewandte Chemie International Edition, Vol. 54, Issue 13
Are MXenes Promising Anode Materials for Li Ion Batteries? Computational Studies on Electronic Properties and Li Storage Capability of Ti 3 C 2 and Ti 3 C 2 X 2 (X = F, OH) Monolayer
journal, September 2012
- Tang, Qing; Zhou, Zhen; Shen, Panwen
- Journal of the American Chemical Society, Vol. 134, Issue 40
Two-Dimensional Molybdenum Carbide (MXene) as an Efficient Electrocatalyst for Hydrogen Evolution
journal, August 2016
- Seh, Zhi Wei; Fredrickson, Kurt D.; Anasori, Babak
- ACS Energy Letters, Vol. 1, Issue 3
Electrochemical and in-situ X-ray diffraction studies of Ti 3 C 2 T x MXene in ionic liquid electrolyte
journal, November 2016
- Lin, Zifeng; Rozier, Patrick; Duployer, Benjamin
- Electrochemistry Communications, Vol. 72
Effect of Postetch Annealing Gas Composition on the Structural and Electrochemical Properties of Ti 2 CT x MXene Electrodes for Supercapacitor Applications
journal, July 2015
- Rakhi, R. B.; Ahmed, Bilal; Hedhili, M. N.
- Chemistry of Materials, Vol. 27, Issue 15
Flexible and conductive MXene films and nanocomposites with high capacitance
journal, November 2014
- Ling, Zheng; Ren, Chang E.; Zhao, Meng-Qiang
- Proceedings of the National Academy of Sciences, Vol. 111, Issue 47
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
High-Capacitance Mechanism for Ti 3 C 2 T x MXene by in Situ Electrochemical Raman Spectroscopy Investigation
journal, November 2016
- Hu, Minmin; Li, Zhaojin; Hu, Tao
- ACS Nano, Vol. 10, Issue 12
Probing the Mechanism of High Capacitance in 2D Titanium Carbide Using In Situ X-Ray Absorption Spectroscopy
journal, May 2015
- Lukatskaya, Maria R.; Bak, Seong-Min; Yu, Xiqian
- Advanced Energy Materials, Vol. 5, Issue 15
Ultra-high-rate pseudocapacitive energy storage in two-dimensional transition metal carbides
journal, July 2017
- Lukatskaya, Maria R.; Kota, Sankalp; Lin, Zifeng
- Nature Energy, Vol. 2, Issue 8
Atomic Defects in Monolayer Titanium Carbide (Ti 3 C 2 T x ) MXene
journal, September 2016
- Sang, Xiahan; Xie, Yu; Lin, Ming-Wei
- ACS Nano, Vol. 10, Issue 10
Nanoscale Elastic Changes in 2D Ti 3 C 2 T x (MXene) Pseudocapacitive Electrodes
journal, March 2016
- Come, Jeremy; Xie, Yu; Naguib, Michael
- Advanced Energy Materials, Vol. 6, Issue 9
NMR reveals the surface functionalisation of Ti 3 C 2 MXene
journal, January 2016
- Hope, Michael A.; Forse, Alexander C.; Griffith, Kent J.
- Physical Chemistry Chemical Physics, Vol. 18, Issue 7
Probing the electrochemical capacitance of MXene nanosheets for high-performance pseudocapacitors
journal, January 2016
- Ji, Xiao; Xu, Kui; Chen, Chi
- Physical Chemistry Chemical Physics, Vol. 18, Issue 6
Atomic-Scale Analysis of the RuO 2 /Water Interface under Electrochemical Conditions
journal, April 2016
- Watanabe, Eriko; Rossmeisl, Jan; Björketun, Mårten E.
- The Journal of Physical Chemistry C, Vol. 120, Issue 15
Ab Initio Study of the Charge-Storage Mechanisms in RuO 2 -Based Electrochemical Ultracapacitors
journal, December 2011
- Liu, Yongduo; Zhou, Fei; Ozolins, Vidvuds
- The Journal of Physical Chemistry C, Vol. 116, Issue 1
Charge Storage Mechanism of RuO 2 /Water Interfaces
journal, August 2017
- Watanabe, Eriko; Ushiyama, Hiroshi; Yamashita, Koichi
- The Journal of Physical Chemistry C, Vol. 121, Issue 35
Understanding the pseudocapacitance of RuO 2 from joint density functional theory
journal, September 2016
- Zhan, Cheng; Jiang, De-en
- Journal of Physics: Condensed Matter, Vol. 28, Issue 46
Impacts of electrode potentials and solvents on the electroreduction of CO 2 : a comparison of theoretical approaches
journal, January 2015
- Steinmann, Stephan N.; Michel, Carine; Schwiedernoch, Renate
- Physical Chemistry Chemical Physics, Vol. 17, Issue 21
Atomistic Mechanisms Underlying Selectivities in C 1 and C 2 Products from Electrochemical Reduction of CO on Cu(111)
journal, December 2016
- Xiao, Hai; Cheng, Tao; Goddard, William A.
- Journal of the American Chemical Society, Vol. 139, Issue 1
Partial oxidation of step-bound water leads to anomalous pH effects on metal electrode step-edges
journal, January 2016
- Schwarz, Kathleen; Xu, Bingjun; Yan, Yushan
- Physical Chemistry Chemical Physics, Vol. 18, Issue 24
Joint Density-Functional Theory: Ab Initio Study of Cr 2 O 3 Surface Chemistry in Solution
journal, August 2005
- Petrosyan, S. A.; Rigos, A. A.; Arias, T. A.
- The Journal of Physical Chemistry B, Vol. 109, Issue 32
Joint density-functional theory for electronic structure of solvated systems
journal, May 2007
- Petrosyan, S. A.; Briere, Jean-Francois; Roundy, David
- Physical Review B, Vol. 75, Issue 20
Grand canonical electronic density-functional theory: Algorithms and applications to electrochemistry
journal, March 2017
- Sundararaman, Ravishankar; Goddard, William A.; Arias, Tomas A.
- The Journal of Chemical Physics, Vol. 146, Issue 11
Joint density functional theory of the electrode-electrolyte interface: Application to fixed electrode potentials, interfacial capacitances, and potentials of zero charge
journal, August 2012
- Letchworth-Weaver, Kendra; Arias, T. A.
- Physical Review B, Vol. 86, Issue 7
The importance of nonlinear fluid response in joint density-functional theory studies of battery systems
journal, October 2013
- Gunceler, Deniz; Letchworth-Weaver, Kendra; Sundararaman, Ravishankar
- Modelling and Simulation in Materials Science and Engineering, Vol. 21, Issue 7
The charge-asymmetric nonlocally determined local-electric (CANDLE) solvation model
journal, February 2015
- Sundararaman, Ravishankar; Goddard, William A.
- The Journal of Chemical Physics, Vol. 142, Issue 6
Generalized Gradient Approximation Made Simple
journal, October 1996
- Perdew, John P.; Burke, Kieron; Ernzerhof, Matthias
- Physical Review Letters, Vol. 77, Issue 18, p. 3865-3868
Pseudopotentials for high-throughput DFT calculations
journal, January 2014
- Garrity, Kevin F.; Bennett, Joseph W.; Rabe, Karin M.
- Computational Materials Science, Vol. 81
Dependence of elastic and optical properties on surface terminated groups in two-dimensional MXene monolayers: a first-principles study
journal, January 2016
- Bai, Yuelei; Zhou, Kun; Srikanth, Narasimalu
- RSC Advances, Vol. 6, Issue 42
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
A grid-based Bader analysis algorithm without lattice bias
journal, January 2009
- Tang, W.; Sanville, E.; Henkelman, G.
- Journal of Physics: Condensed Matter, Vol. 21, Issue 8
Accurate and efficient algorithm for Bader charge integration
journal, February 2011
- Yu, Min; Trinkle, Dallas R.
- The Journal of Chemical Physics, Vol. 134, Issue 6
Works referencing / citing this record:
Electrochromic Effect in Titanium Carbide MXene Thin Films Produced by Dip‐Coating
journal, February 2019
- Salles, Pol; Pinto, David; Hantanasirisakul, Kanit
- Advanced Functional Materials, Vol. 29, Issue 17
Revealing the Pseudo‐Intercalation Charge Storage Mechanism of MXenes in Acidic Electrolyte
journal, May 2019
- Mu, Xinpeng; Wang, Dashuai; Du, Fei
- Advanced Functional Materials, Vol. 29, Issue 29
MXene‐Based Composites: Synthesis and Applications in Rechargeable Batteries and Supercapacitors
journal, February 2019
- Yang, Jian; Bao, Weizhai; Jaumaux, Pauline
- Advanced Materials Interfaces, Vol. 6, Issue 8
MXene-Conducting Polymer Asymmetric Pseudocapacitors
journal, December 2018
- Boota, Muhammad; Gogotsi, Yury
- Advanced Energy Materials, Vol. 9, Issue 7
Electrochemical Behavior of Ti 3 C 2 T x MXene in Environmentally Friendly Methanesulfonic Acid Electrolyte
journal, August 2019
- Zhao, Xin; Dall'Agnese, Chunxiang; Chu, Xue‐Feng
- ChemSusChem, Vol. 12, Issue 19
Automated Scalpel Patterning of Solution Processed Thin Films for Fabrication of Transparent MXene Microsupercapacitors
journal, October 2018
- Salles, Pol; Quain, Evan; Kurra, Narendra
- Small, Vol. 14, Issue 44
Highly Conductive Ti 3 C 2 T x MXene Hybrid Fibers for Flexible and Elastic Fiber-Shaped Supercapacitors
journal, January 2019
- Zhang, Jizhen; Seyedin, Shayan; Qin, Si
- Small, Vol. 15, Issue 8
Highly Enhanced Pseudocapacitive Performance of Vanadium‐Doped MXenes in Neutral Electrolytes
journal, August 2019
- Gao, Zhi‐Wen; Zheng, Weiran; Lee, Lawrence Yoon Suk
- Small, Vol. 15, Issue 40
Delaminating Vanadium Carbides for Zinc‐Ion Storage: Hydrate Precipitation and H + /Zn 2+ Co‐Action Mechanism
journal, August 2019
- Wang, Changda; Wei, Shiqiang; Chen, Shuangming
- Small Methods, Vol. 3, Issue 12
Layer-by-layer self-assembly of pillared two-dimensional multilayers
journal, June 2019
- Tian, Weiqian; VahidMohammadi, Armin; Wang, Zhen
- Nature Communications, Vol. 10, Issue 1
High-capacitance Ti 3 C 2 T x MXene obtained by etching submicron Ti 3 AlC 2 grains grown in molten salt
journal, January 2018
- Cui, Cong; Hu, Minmin; Zhang, Chao
- Chemical Communications, Vol. 54, Issue 58
Applications of 2D MXenes in energy conversion and storage systems
journal, January 2019
- Pang, Jinbo; Mendes, Rafael G.; Bachmatiuk, Alicja
- Chemical Society Reviews, Vol. 48, Issue 1
Two-dimensional transitional metal dihydride crystals with anisotropic and spin-polarized Fermi Dirac cones
journal, January 2018
- Lv, Haifeng; Wu, Daoxiong; Li, Xiuling
- Journal of Materials Chemistry C, Vol. 6, Issue 42
A first-principles roadmap and limits to design efficient supercapacitor electrode materials
journal, January 2019
- Ali, Basant A.; Allam, Nageh K.
- Physical Chemistry Chemical Physics, Vol. 21, Issue 32
Origin of theoretical pseudocapacitance of two-dimensional supercapacitor electrodes Ti 3 C 2 T 2 (T = bare, O, S)
journal, January 2019
- Wang, Lijing; Wang, Jin; Zhang, Zhenzhou
- Journal of Materials Chemistry A, Vol. 7, Issue 27
Superfast high-energy storage hybrid device composed of MXene and Chevrel-phase electrodes operated in saturated LiCl electrolyte solution
journal, January 2019
- Malchik, Fyodor; Shpigel, Netanel; Levi, Mikhael D.
- Journal of Materials Chemistry A, Vol. 7, Issue 34
The development of 2D materials for electrochemical energy applications: A mechanistic approach
journal, March 2019
- Hynek, David J.; Pondick, Joshua V.; Cha, Judy J.
- APL Materials, Vol. 7, Issue 3
Distinguishing electronic contributions of surface and sub-surface transition metal atoms in Ti-based MXenes
journal, February 2020
- Yang, Yizhou; Hantanasirisakul, Kanit; Frey, Nathan C.
- 2D Materials, Vol. 7, Issue 2
Interfacial and electronic properties of heterostructures of MXene and graphene
journal, February 2019
- Li, Rui; Sun, Weiwei; Zhan, Cheng
- Physical Review B, Vol. 99, Issue 8
Probing the pseudocapacitance and energy-storage performance of facets from first principles
journal, August 2019
- Keilbart, Nathan; Okada, Yasuaki; Dabo, Ismaila
- Physical Review Materials, Vol. 3, Issue 8
Review on Carbon/Polyaniline Hybrids: Design and Synthesis for Supercapacitor
journal, June 2019
- Wang, Xiaoning; Wu, Dan; Song, Xinhui
- Molecules, Vol. 24, Issue 12
Great Enhancement of Carbon Energy Storage through Narrow Pores and Hydrogen-Containing Functional Groups for Aqueous Zn-Ion Hybrid Supercapacitor
journal, July 2019
- Liu,
- Molecules, Vol. 24, Issue 14
pH-Dependent Distribution of Functional Groups on Titanium-Based MXenes
journal, July 2019
- Ibragimova, Rina; Puska, Martti J.; Komsa, Hannu-Pekka
- ACS Nano, Vol. 13, Issue 8
Great Enhancement of Carbon Energy Storage through Narrow Pores and Hydrogen-Containing Functional Groups for Aqueous Zn-Ion Hybrid Supercapacitor
journal, July 2019
- Liu,
- Molecules, Vol. 24, Issue 14
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