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Title: Pseudocapacitive Storage in Nanolayered Ti2NTx MXene Using Mg-Ion Electrolyte

Abstract

Electrochemical supercapacitors are hybrids of a capacitor and battery that rely on materials capable of storing charges via pseudocapacitive reactions in addition to conventional electrostatic double-layer charge storage. MXenes, a relatively new class of two-dimensional (2D) transition metal carbides and nitrides, are ideal candidates for supercapacitors due to their high electronic conductivity, high surface area, and ability to store charges via pseudocapacitive mechanisms. Nitride MXenes such as Ti2NTx are predicted to have higher pseudocapacitance than carbide MXenes but have not been explored experimentally. Here, we report on the synthesis, characterization, and pseudocapacitive charge storage mechanism in the Ti2NTx nitride MXene. Successful formation of nanolayered Ti2NTx MXene is characterized by XRD, SEM, and N2 physisorption analyses. The identity of the surface terminating groups Tx are assigned to primarily O and/or OH based on Raman, FTIR, and STEM-EELS. When tested in various electrolytes, the nanolayered Ti2NTx MXene exhibits pronounced reversible redox peaks and high areal capacitances (~1350 uF cm-2 in 1 M MgSO4 aqueous electrolyte) well exceeding that expected from a double-layer charge storage (~50 uF cm-2) showing that charge is stored in the Ti2NTx MXene via a pseudocapacitive mechanism. We report a trend in the capacitance as a function of cationmore » as follows: Mg2+ > Al3+ > H+ > Li+ > Na+ > K+, that matches theoretical predictions. Remarkably, nanolayered Ti2NTx MXene exhibits >200 F g-1 capacitance over a 1.0 V range in the Mg-ion electrolyte, and the capacitance increases to 160% of its initial value after 1000 cycles owing to the 2 e- process and the distinctive multilayer adsorption characteristic of the Mg2+ cation on the Ti2NTx MXene. Furthermore, these findings identify Ti2NTx MXene as a new pseudocapacitive material that possesses high capacitance and wide working voltage in a safe and environmentally friendly Mg-ion electrolyte.« less

Authors:
ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [1]
  1. National Renewable Energy Lab. (NREL), Golden, CO (United States)
Publication Date:
Research Org.:
National Renewable Energy Lab. (NREL), Golden, CO (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1527333
Report Number(s):
NREL/JA-5900-73444
Journal ID: ISSN 2574-0970
Grant/Contract Number:  
AC36-08GO28308
Resource Type:
Accepted Manuscript
Journal Name:
ACS Applied Nano Materials
Additional Journal Information:
Journal Volume: 2; Journal Issue: 5; Journal ID: ISSN 2574-0970
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; 77 NANOSCIENCE AND NANOTECHNOLOGY; energy storage; supercapacitor; 2D MXene; transition-metal nitride; pseudocapacitance

Citation Formats

Djire, Abdoulaye, Bos, Andre, Liu, Jun, Zhang, Hanyu, Miller, Elisa M., and Neale, Nathan R.. Pseudocapacitive Storage in Nanolayered Ti2NTx MXene Using Mg-Ion Electrolyte. United States: N. p., 2019. Web. https://doi.org/10.1021/acsanm.9b00289.
Djire, Abdoulaye, Bos, Andre, Liu, Jun, Zhang, Hanyu, Miller, Elisa M., & Neale, Nathan R.. Pseudocapacitive Storage in Nanolayered Ti2NTx MXene Using Mg-Ion Electrolyte. United States. https://doi.org/10.1021/acsanm.9b00289
Djire, Abdoulaye, Bos, Andre, Liu, Jun, Zhang, Hanyu, Miller, Elisa M., and Neale, Nathan R.. Mon . "Pseudocapacitive Storage in Nanolayered Ti2NTx MXene Using Mg-Ion Electrolyte". United States. https://doi.org/10.1021/acsanm.9b00289. https://www.osti.gov/servlets/purl/1527333.
@article{osti_1527333,
title = {Pseudocapacitive Storage in Nanolayered Ti2NTx MXene Using Mg-Ion Electrolyte},
author = {Djire, Abdoulaye and Bos, Andre and Liu, Jun and Zhang, Hanyu and Miller, Elisa M. and Neale, Nathan R.},
abstractNote = {Electrochemical supercapacitors are hybrids of a capacitor and battery that rely on materials capable of storing charges via pseudocapacitive reactions in addition to conventional electrostatic double-layer charge storage. MXenes, a relatively new class of two-dimensional (2D) transition metal carbides and nitrides, are ideal candidates for supercapacitors due to their high electronic conductivity, high surface area, and ability to store charges via pseudocapacitive mechanisms. Nitride MXenes such as Ti2NTx are predicted to have higher pseudocapacitance than carbide MXenes but have not been explored experimentally. Here, we report on the synthesis, characterization, and pseudocapacitive charge storage mechanism in the Ti2NTx nitride MXene. Successful formation of nanolayered Ti2NTx MXene is characterized by XRD, SEM, and N2 physisorption analyses. The identity of the surface terminating groups Tx are assigned to primarily O and/or OH based on Raman, FTIR, and STEM-EELS. When tested in various electrolytes, the nanolayered Ti2NTx MXene exhibits pronounced reversible redox peaks and high areal capacitances (~1350 uF cm-2 in 1 M MgSO4 aqueous electrolyte) well exceeding that expected from a double-layer charge storage (~50 uF cm-2) showing that charge is stored in the Ti2NTx MXene via a pseudocapacitive mechanism. We report a trend in the capacitance as a function of cation as follows: Mg2+ > Al3+ > H+ > Li+ > Na+ > K+, that matches theoretical predictions. Remarkably, nanolayered Ti2NTx MXene exhibits >200 F g-1 capacitance over a 1.0 V range in the Mg-ion electrolyte, and the capacitance increases to 160% of its initial value after 1000 cycles owing to the 2 e- process and the distinctive multilayer adsorption characteristic of the Mg2+ cation on the Ti2NTx MXene. Furthermore, these findings identify Ti2NTx MXene as a new pseudocapacitive material that possesses high capacitance and wide working voltage in a safe and environmentally friendly Mg-ion electrolyte.},
doi = {10.1021/acsanm.9b00289},
journal = {ACS Applied Nano Materials},
number = 5,
volume = 2,
place = {United States},
year = {2019},
month = {5}
}

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Works referenced in this record:

Packing heat
journal, April 2014


Materials for electrochemical capacitors
journal, November 2008

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

Graphene, related two-dimensional crystals, and hybrid systems for energy conversion and storage
journal, January 2015


Safety mechanisms in lithium-ion batteries
journal, April 2006


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


Ultracapacitors: why, how, and where is the technology
journal, November 2000


Conducting-polymer-based supercapacitor devices and electrodes
journal, January 2011


Highly Flexible and All-Solid-State Paperlike Polymer Supercapacitors
journal, October 2010

  • Meng, Chuizhou; Liu, Changhong; Chen, Luzhuo
  • Nano Letters, Vol. 10, Issue 10
  • DOI: 10.1021/nl1019672

Conducting Polymer Nanowire Arrays for High Performance Supercapacitors
journal, August 2013


Toward Flexible Polymer and Paper-Based Energy Storage Devices
journal, February 2011


Design and Tailoring of the Nanotubular Arrayed Architecture of Hydrous RuO 2 for Next Generation Supercapacitors
journal, December 2006

  • Hu, Chi-Chang; Chang, Kuo-Hsin; Lin, Ming-Champ
  • Nano Letters, Vol. 6, Issue 12
  • DOI: 10.1021/nl061576a

Anchoring Hydrous RuO2 on Graphene Sheets for High-Performance Electrochemical Capacitors
journal, August 2010

  • Wu, Zhong-Shuai; Wang, Da-Wei; Ren, Wencai
  • Advanced Functional Materials, Vol. 20, Issue 20
  • DOI: 10.1002/adfm.201001054

Graphene Oxide−MnO 2 Nanocomposites for Supercapacitors
journal, March 2010

  • Chen, Sheng; Zhu, Junwu; Wu, Xiaodong
  • ACS Nano, Vol. 4, Issue 5
  • DOI: 10.1021/nn901311t

Effects of surface oxygen on charge storage in high surface area early transition-metal carbides and nitrides
journal, February 2015


All-MXene (2D titanium carbide) solid-state microsupercapacitors for on-chip energy storage
journal, January 2016

  • Peng, You-Yu; Akuzum, Bilen; Kurra, Narendra
  • Energy & Environmental Science, Vol. 9, Issue 9
  • DOI: 10.1039/C6EE01717G

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


Cation Intercalation and High Volumetric Capacitance of Two-Dimensional Titanium Carbide
journal, September 2013


Pseudocapacitance of MXene nanosheets for high-power sodium-ion hybrid capacitors
journal, April 2015

  • Wang, Xianfen; Kajiyama, Satoshi; Iinuma, Hiroki
  • Nature Communications, Vol. 6, Issue 1
  • DOI: 10.1038/ncomms7544

Pseudocapacitive storage via micropores in high-surface area molybdenum nitrides
journal, September 2018


Recent advances in metal nitrides as high-performance electrode materials for energy storage devices
journal, January 2015

  • Balogun, Muhammad-Sadeeq; Qiu, Weitao; Wang, Wang
  • Journal of Materials Chemistry A, Vol. 3, Issue 4
  • DOI: 10.1039/C4TA05565A

Enhanced performance for early transition metal nitrides via pseudocapacitance in protic ionic liquid electrolytes
journal, April 2017


Unveiling the pseudocapacitive charge storage mechanisms of nanostructured vanadium nitrides using in-situ analyses
journal, June 2019


The chemistry of two-dimensional layered transition metal dichalcogenide nanosheets
journal, April 2013

  • Chhowalla, Manish; Shin, Hyeon Suk; Eda, Goki
  • Nature Chemistry, Vol. 5, Issue 4, p. 263-275
  • DOI: 10.1038/nchem.1589

Formation of nickel cobalt sulfide ball-in-ball hollow spheres with enhanced electrochemical pseudocapacitive properties
journal, March 2015

  • Shen, Laifa; Yu, Le; Wu, Hao Bin
  • Nature Communications, Vol. 6, Issue 1
  • DOI: 10.1038/ncomms7694

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
  • DOI: 10.1016/j.elecom.2012.01.002

25th Anniversary Article: MXenes: A New Family of Two-Dimensional Materials
journal, December 2013

  • Naguib, Michael; Mochalin, Vadym N.; Barsoum, Michel W.
  • Advanced Materials, Vol. 26, Issue 7, p. 992-1005
  • DOI: 10.1002/adma.201304138

Ti 3 C 2 MXene as a High Capacity Electrode Material for Metal (Li, Na, K, Ca) Ion Batteries
journal, June 2014

  • Er, Dequan; Li, Junwen; Naguib, Michael
  • ACS Applied Materials & Interfaces, Vol. 6, Issue 14
  • DOI: 10.1021/am501144q

Two-Dimensional, Ordered, Double Transition Metals Carbides (MXenes)
journal, August 2015


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

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
  • DOI: 10.1021/ja501520b

Understanding the MXene Pseudocapacitance
journal, February 2018

  • Zhan, Cheng; Naguib, Michael; Lukatskaya, Maria
  • The Journal of Physical Chemistry Letters, Vol. 9, Issue 6
  • DOI: 10.1021/acs.jpclett.8b00200

Synthesis of two-dimensional titanium nitride Ti 4 N 3 (MXene)
journal, January 2016

  • Urbankowski, Patrick; Anasori, Babak; Makaryan, Taron
  • Nanoscale, Vol. 8, Issue 22
  • DOI: 10.1039/C6NR02253G

Electrocatalytic and Optoelectronic Characteristics of the Two-Dimensional Titanium Nitride Ti 4 N 3 T x MXene
journal, March 2019

  • Djire, Abdoulaye; Zhang, Hanyu; Liu, Jun
  • ACS Applied Materials & Interfaces, Vol. 11, Issue 12
  • DOI: 10.1021/acsami.9b01150

Influences from solvents on charge storage in titanium carbide MXenes
journal, March 2019


Understanding the Different Diffusion Mechanisms of Hydrated Protons and Potassium Ions in Titanium Carbide MXene
journal, January 2019

  • Wen, Jing; Fu, Qishan; Wu, Wanying
  • ACS Applied Materials & Interfaces, Vol. 11, Issue 7
  • DOI: 10.1021/acsami.8b21117

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

MXene-Conducting Polymer Asymmetric Pseudocapacitors
journal, December 2018


Enhanced electrochemical performances of organ-like Ti3C2 MXenes/polypyrrole composites as supercapacitors electrode materials
journal, April 2019


All Pseudocapacitive MXene-RuO 2 Asymmetric Supercapacitors
journal, January 2018

  • Jiang, Qiu; Kurra, Narendra; Alhabeb, Mohamed
  • Advanced Energy Materials, Vol. 8, Issue 13
  • DOI: 10.1002/aenm.201703043

A facile method for synthesizing CuS decorated Ti 3 C 2 MXene with enhanced performance for asymmetric supercapacitors
journal, January 2019

  • Pan, Zhihu; Cao, Fa; Hu, Xing
  • Journal of Materials Chemistry A, Vol. 7, Issue 15
  • DOI: 10.1039/C9TA00085B

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
  • DOI: 10.1002/admi.201802004

Computational Screening of MXene Electrodes for Pseudocapacitive Energy Storage
journal, December 2018

  • Zhan, Cheng; Sun, Weiwei; Kent, Paul R. C.
  • The Journal of Physical Chemistry C, Vol. 123, Issue 1
  • DOI: 10.1021/acs.jpcc.8b11608

Electronic and Optical Properties of 2D Transition Metal Carbides and Nitrides (MXenes)
journal, November 2018


First-Principles Calculations of Ti 2 N and Ti 2 NT 2 (T = O, F, OH) Monolayers as Potential Anode Materials for Lithium-Ion Batteries and Beyond
journal, June 2017

  • Wang, Dashuai; Gao, Yu; Liu, Yanhui
  • The Journal of Physical Chemistry C, Vol. 121, Issue 24
  • DOI: 10.1021/acs.jpcc.7b03057

Tunable Magnetism and Transport Properties in Nitride MXenes
journal, June 2017


Synthesis of high-purity Ti2AlN ceramic by hot pressing
journal, February 2008

  • Yan, Ming; Chen, Yan-lin; Mei, Bing-chu
  • Transactions of Nonferrous Metals Society of China, Vol. 18, Issue 1
  • DOI: 10.1016/S1003-6326(08)60015-1

Fabrication of Ti 2 AlN ceramics with orientation growth behavior by the microwave sintering method
journal, May 2015


Two-Dimensional Nanocrystals Produced by Exfoliation of Ti3AlC2
journal, August 2011

  • Naguib, Michael; Kurtoglu, Murat; Presser, Volker
  • Advanced Materials, Vol. 23, Issue 37, p. 4248-4253
  • DOI: 10.1002/adma.201102306

Intercalation and delamination of layered carbides and carbonitrides
journal, April 2013

  • Mashtalir, Olha; Naguib, Michael; Mochalin, Vadym N.
  • Nature Communications, Vol. 4, Issue 1
  • DOI: 10.1038/ncomms2664

Structural and Electronic Properties and Stability of MX enes Ti 2 C and Ti 3 C 2 Functionalized by Methoxy Groups
journal, June 2013

  • Enyashin, Andrey N.; Ivanovskii, Alexander L.
  • The Journal of Physical Chemistry C, Vol. 117, Issue 26
  • DOI: 10.1021/jp401820b

Pseudocapacitive charge storage via hydrogen insertion for molybdenum nitrides
journal, September 2015


Extent of Pseudocapacitance in High‐Surface Area Vanadium Nitrides
journal, August 2018

  • Djire, Abdoulaye; Ajenifujah, Olabode; Thompson, Levi T.
  • Batteries & Supercaps, Vol. 1, Issue 5
  • DOI: 10.1002/batt.201800050

First-order Raman scattering of the MAX phases Ta4AlC3, Nb4AlC3, Ti4AlN3, and Ta2AlC: First-order Raman scattering of ternary hexagonal carbides and nitrides
journal, December 2011

  • Lane, Nina J.; Naguib, Michael; Presser, Volker
  • Journal of Raman Spectroscopy, Vol. 43, Issue 7
  • DOI: 10.1002/jrs.3101

Interfacial processes involving electrocatalytic evolution and oxidation of H2, and the role of chemisorbed H
journal, August 2002


Titanium and vanadium oxynitride powders as pseudo-capacitive materials for electrochemical capacitors
journal, November 2012


VN thin films as electrode materials for electrochemical capacitors
journal, September 2014


Pseudocapacitive Contributions to Electrochemical Energy Storage in TiO2 (Anatase) Nanoparticles
journal, October 2007

  • Wang, John; Polleux, Julien; Lim, James
  • The Journal of Physical Chemistry C, Vol. 111, Issue 40, p. 14925-14931
  • DOI: 10.1021/jp074464w

Hydrolysis of 2D Transition-Metal Carbides (MXenes) in Colloidal Solutions
journal, January 2019


Oxidation Stability of Colloidal Two-Dimensional Titanium Carbides (MXenes)
journal, May 2017


Electron transfer processes occurring on platinum neural stimulating electrodes: a tutorial on the i ( V e ) profile
journal, August 2016