Pseudocapacitive Storage in Nanolayered Ti2NTx MXene Using Mg-Ion Electrolyte

Djire, Abdoulaye; Bos, Andre; Liu, Jun; Zhang, Hanyu; Miller, Elisa M.; Neale, Nathan R.

doi:10.1021/acsanm.9b00289

Title: Pseudocapacitive Storage in Nanolayered Ti₂NT_x MXene Using Mg-Ion Electrolyte

Journal Article · Mon May 06 00:00:00 EDT 2019 · ACS Applied Nano Materials

DOI:https://doi.org/10.1021/acsanm.9b00289· OSTI ID:1527333

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National Renewable Energy Lab. (NREL), Golden, CO (United States)

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 Ti₂NT_x 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 Ti₂NT_x nitride MXene. Successful formation of nanolayered Ti₂NT_x MXene is characterized by XRD, SEM, and N₂ physisorption analyses. The identity of the surface terminating groups T_x are assigned to primarily O and/or OH based on Raman, FTIR, and STEM-EELS. When tested in various electrolytes, the nanolayered Ti₂NT_x 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 Ti₂NT_x 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 Ti₂NT_x 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 Ti₂NT_x MXene. Furthermore, these findings identify Ti₂NT_x MXene as a new pseudocapacitive material that possesses high capacitance and wide working voltage in a safe and environmentally friendly Mg-ion electrolyte.

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Research Organization:: National Renewable Energy Lab. (NREL), Golden, CO (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: AC36-08GO28308

OSTI ID:: 1527333

Report Number(s):: NREL/JA-5900-73444

Journal Information:: ACS Applied Nano Materials, Vol. 2, Issue 5; ISSN 2574-0970

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 66 works

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References (63)

Packing heat Neale, Nathan R. Nature Chemistry, Vol. 6, Issue 5 https://doi.org/10.1038/nchem.1933	journal	April 2014
Materials for electrochemical capacitors Simon, Patrice; Gogotsi, Yury Nature Materials, Vol. 7, Issue 11 https://doi.org/10.1038/nmat2297	journal	November 2008
Graphene, related two-dimensional crystals, and hybrid systems for energy conversion and storage Bonaccorso, Francesco; Colombo, Luigi; Yu, Guihua Science, Vol. 347, Issue 6217 https://doi.org/10.1126/science.1246501	journal	January 2015
Safety mechanisms in lithium-ion batteries Balakrishnan, P. G.; Ramesh, R.; Prem Kumar, T. Journal of Power Sources, Vol. 155, Issue 2 https://doi.org/10.1016/j.jpowsour.2005.12.002	journal	April 2006
Where Do Batteries End and Supercapacitors Begin? Simon, P.; Gogotsi, Y.; Dunn, B. Science, Vol. 343, Issue 6176 https://doi.org/10.1126/science.1249625	journal	March 2014
Ultracapacitors: why, how, and where is the technology Burke, Andrew Journal of Power Sources, Vol. 91, Issue 1, p. 37-50 https://doi.org/10.1016/S0378-7753(00)00485-7	journal	November 2000
Conducting-polymer-based supercapacitor devices and electrodes Snook, Graeme A.; Kao, Pon; Best, Adam S. Journal of Power Sources, Vol. 196, Issue 1 https://doi.org/10.1016/j.jpowsour.2010.06.084	journal	January 2011
Highly Flexible and All-Solid-State Paperlike Polymer Supercapacitors Meng, Chuizhou; Liu, Changhong; Chen, Luzhuo Nano Letters, Vol. 10, Issue 10 https://doi.org/10.1021/nl1019672	journal	October 2010
Conducting Polymer Nanowire Arrays for High Performance Supercapacitors Wang, Kai; Wu, Haiping; Meng, Yuena Small, Vol. 10, Issue 1 https://doi.org/10.1002/smll.201301991	journal	August 2013
Toward Flexible Polymer and Paper-Based Energy Storage Devices Nyholm, Leif; Nyström, Gustav; Mihranyan, Albert Advanced Materials https://doi.org/10.1002/adma.201004134	journal	February 2011
Design and Tailoring of the Nanotubular Arrayed Architecture of Hydrous RuO ₂ for Next Generation Supercapacitors Hu, Chi-Chang; Chang, Kuo-Hsin; Lin, Ming-Champ Nano Letters, Vol. 6, Issue 12 https://doi.org/10.1021/nl061576a	journal	December 2006
Anchoring Hydrous RuO2 on Graphene Sheets for High-Performance Electrochemical Capacitors Wu, Zhong-Shuai; Wang, Da-Wei; Ren, Wencai Advanced Functional Materials, Vol. 20, Issue 20 https://doi.org/10.1002/adfm.201001054	journal	August 2010
Graphene Oxide−MnO ₂ Nanocomposites for Supercapacitors Chen, Sheng; Zhu, Junwu; Wu, Xiaodong ACS Nano, Vol. 4, Issue 5 https://doi.org/10.1021/nn901311t	journal	March 2010
Effects of surface oxygen on charge storage in high surface area early transition-metal carbides and nitrides Djire, Abdoulaye; Ajenifujah, Olabode T.; Sleightholme, Alice E. S. Journal of Power Sources, Vol. 275 https://doi.org/10.1016/j.jpowsour.2014.10.161	journal	February 2015
2D metal carbides and nitrides (MXenes) for energy storage Anasori, Babak; Lukatskaya, Maria R.; Gogotsi, Yury Nature Reviews Materials, Vol. 2, Issue 2 https://doi.org/10.1038/natrevmats.2016.98	journal	January 2017
Cation Intercalation and High Volumetric Capacitance of Two-Dimensional Titanium Carbide Lukatskaya, M. R.; Mashtalir, O.; Ren, C. E. Science, Vol. 341, Issue 6153 https://doi.org/10.1126/science.1241488	journal	September 2013
Pseudocapacitance of MXene nanosheets for high-power sodium-ion hybrid capacitors Wang, Xianfen; Kajiyama, Satoshi; Iinuma, Hiroki Nature Communications, Vol. 6, Issue 1 https://doi.org/10.1038/ncomms7544	journal	April 2015
Pseudocapacitive storage via micropores in high-surface area molybdenum nitrides Djire, Abdoulaye; Siegel, Jason B.; Ajenifujah, Olabode Nano Energy, Vol. 51 https://doi.org/10.1016/j.nanoen.2018.06.045	journal	September 2018
Enhanced performance for early transition metal nitrides via pseudocapacitance in protic ionic liquid electrolytes Djire, Abdoulaye; Ishimwe, Jean Yves; Choi, Saemin Electrochemistry Communications, Vol. 77 https://doi.org/10.1016/j.elecom.2017.02.001	journal	April 2017
Unveiling the pseudocapacitive charge storage mechanisms of nanostructured vanadium nitrides using in-situ analyses Djire, Abdoulaye; Pande, Priyanka; Deb, Aniruddha Nano Energy, Vol. 60 https://doi.org/10.1016/j.nanoen.2019.03.003	journal	June 2019
The chemistry of two-dimensional layered transition metal dichalcogenide nanosheets Chhowalla, Manish; Shin, Hyeon Suk; Eda, Goki Nature Chemistry, Vol. 5, Issue 4, p. 263-275 https://doi.org/10.1038/nchem.1589	journal	April 2013
Formation of nickel cobalt sulfide ball-in-ball hollow spheres with enhanced electrochemical pseudocapacitive properties Shen, Laifa; Yu, Le; Wu, Hao Bin Nature Communications, Vol. 6, Issue 1 https://doi.org/10.1038/ncomms7694	journal	March 2015
Few layered MoS ₂ grown on pencil graphite: a unique single-step approach to fabricate economical, binder-free electrode for supercapacitor applications Sha, Rinky; Badhulika, Sushmee Nanotechnology, Vol. 30, Issue 3 https://doi.org/10.1088/1361-6528/aaed78	journal	November 2018
Effects of substrates on the capacitive performance of RuOx·nH2O and activated carbon–RuOx electrodes for supercapacitors Hu, Chi-Chang; Chen, Wei-Chun Electrochimica Acta, Vol. 49, Issue 21 https://doi.org/10.1016/j.electacta.2004.03.017	journal	September 2004
MXene: a promising transition metal carbide anode for lithium-ion batteries Naguib, Michael; Come, Jérémy; Dyatkin, Boris Electrochemistry Communications, Vol. 16, Issue 1, p. 61-64 https://doi.org/10.1016/j.elecom.2012.01.002	journal	March 2012
25th Anniversary Article: MXenes: A New Family of Two-Dimensional Materials Naguib, Michael; Mochalin, Vadym N.; Barsoum, Michel W. Advanced Materials, Vol. 26, Issue 7, p. 992-1005 https://doi.org/10.1002/adma.201304138	journal	December 2013
Ti ₃ C ₂ MXene as a High Capacity Electrode Material for Metal (Li, Na, K, Ca) Ion Batteries Er, Dequan; Li, Junwen; Naguib, Michael ACS Applied Materials & Interfaces, Vol. 6, Issue 14 https://doi.org/10.1021/am501144q	journal	June 2014
Two-Dimensional, Ordered, Double Transition Metals Carbides (MXenes) Anasori, Babak; Xie, Yu; Beidaghi, Majid ACS Nano, Vol. 9, Issue 10 https://doi.org/10.1021/acsnano.5b03591	journal	August 2015
Guidelines for Synthesis and Processing of Two-Dimensional Titanium Carbide (Ti ₃ C ₂ T _x MXene) Alhabeb, Mohamed; Maleski, Kathleen; Anasori, Babak Chemistry of Materials, Vol. 29, Issue 18 https://doi.org/10.1021/acs.chemmater.7b02847	journal	September 2017
Conductive two-dimensional titanium carbide ‘clay’ with high volumetric capacitance Ghidiu, Michael; Lukatskaya, Maria R.; Zhao, Meng-Qiang Nature, Vol. 516, Issue 7529 https://doi.org/10.1038/nature13970	journal	November 2014
Role of Surface Structure on Li-Ion Energy Storage Capacity of Two-Dimensional Transition-Metal Carbides Xie, Yu; Naguib, Michael; Mochalin, Vadym N. Journal of the American Chemical Society, Vol. 136, Issue 17 https://doi.org/10.1021/ja501520b	journal	April 2014
Understanding the MXene Pseudocapacitance Zhan, Cheng; Naguib, Michael; Lukatskaya, Maria The Journal of Physical Chemistry Letters, Vol. 9, Issue 6 https://doi.org/10.1021/acs.jpclett.8b00200	journal	February 2018
Synthesis of two-dimensional titanium nitride Ti ₄ N ₃ (MXene) Urbankowski, Patrick; Anasori, Babak; Makaryan, Taron Nanoscale, Vol. 8, Issue 22 https://doi.org/10.1039/C6NR02253G	journal	January 2016
Two-Dimensional Titanium Nitride (Ti ₂ N) MXene: Synthesis, Characterization, and Potential Application as Surface-Enhanced Raman Scattering Substrate Soundiraraju, Bhuvaneswari; George, Benny Kattikkanal ACS Nano, Vol. 11, Issue 9 https://doi.org/10.1021/acsnano.7b03129	journal	September 2017
Electrocatalytic and Optoelectronic Characteristics of the Two-Dimensional Titanium Nitride Ti ₄ N ₃ T _x MXene Djire, Abdoulaye; Zhang, Hanyu; Liu, Jun ACS Applied Materials & Interfaces, Vol. 11, Issue 12 https://doi.org/10.1021/acsami.9b01150	journal	March 2019
Influences from solvents on charge storage in titanium carbide MXenes Wang, Xuehang; Mathis, Tyler S.; Li, Ke Nature Energy, Vol. 4, Issue 3 https://doi.org/10.1038/s41560-019-0339-9	journal	March 2019
Understanding the Different Diffusion Mechanisms of Hydrated Protons and Potassium Ions in Titanium Carbide MXene Wen, Jing; Fu, Qishan; Wu, Wanying ACS Applied Materials & Interfaces, Vol. 11, Issue 7 https://doi.org/10.1021/acsami.8b21117	journal	January 2019
Multidimensional materials and device architectures for future hybrid energy storage Lukatskaya, Maria R.; Dunn, Bruce; Gogotsi, Yury Nature Communications, Vol. 7, Issue 1 https://doi.org/10.1038/ncomms12647	journal	September 2016
MXene-Conducting Polymer Asymmetric Pseudocapacitors Boota, Muhammad; Gogotsi, Yury Advanced Energy Materials, Vol. 9, Issue 7 https://doi.org/10.1002/aenm.201802917	journal	December 2018
Enhanced electrochemical performances of organ-like Ti3C2 MXenes/polypyrrole composites as supercapacitors electrode materials Wu, Wenling; Wei, Dan; Zhu, Jianfeng Ceramics International, Vol. 45, Issue 6 https://doi.org/10.1016/j.ceramint.2019.01.016	journal	April 2019
Hydrous RuO ₂ ‐Decorated MXene Coordinating with Silver Nanowire Inks Enabling Fully Printed Micro‐Supercapacitors with Extraordinary Volumetric Performance Li, Hongpeng; Li, Xiran; Liang, Jiajie Advanced Energy Materials, Vol. 9, Issue 15 https://doi.org/10.1002/aenm.201803987	journal	February 2019
All Pseudocapacitive MXene-RuO ₂ Asymmetric Supercapacitors Jiang, Qiu; Kurra, Narendra; Alhabeb, Mohamed Advanced Energy Materials, Vol. 8, Issue 13 https://doi.org/10.1002/aenm.201703043	journal	January 2018
MXene‐Based Composites: Synthesis and Applications in Rechargeable Batteries and Supercapacitors Yang, Jian; Bao, Weizhai; Jaumaux, Pauline Advanced Materials Interfaces, Vol. 6, Issue 8 https://doi.org/10.1002/admi.201802004	journal	February 2019
Computational Screening of MXene Electrodes for Pseudocapacitive Energy Storage Zhan, Cheng; Sun, Weiwei; Kent, Paul R. C. The Journal of Physical Chemistry C, Vol. 123, Issue 1 https://doi.org/10.1021/acs.jpcc.8b11608	journal	December 2018
Electronic and Optical Properties of 2D Transition Metal Carbides and Nitrides (MXenes) Hantanasirisakul, Kanit; Gogotsi, Yury Advanced Materials, Vol. 30, Issue 52 https://doi.org/10.1002/adma.201804779	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 Wang, Dashuai; Gao, Yu; Liu, Yanhui The Journal of Physical Chemistry C, Vol. 121, Issue 24 https://doi.org/10.1021/acs.jpcc.7b03057	journal	June 2017
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 Tang, Qing; Zhou, Zhen; Shen, Panwen Journal of the American Chemical Society, Vol. 134, Issue 40 https://doi.org/10.1021/ja308463r	journal	September 2012
Tunable Magnetism and Transport Properties in Nitride MXenes Kumar, Hemant; Frey, Nathan C.; Dong, Liang ACS Nano, Vol. 11, Issue 8 https://doi.org/10.1021/acsnano.7b02578	journal	June 2017
Synthesis of high-purity Ti2AlN ceramic by hot pressing Yan, Ming; Chen, Yan-lin; Mei, Bing-chu Transactions of Nonferrous Metals Society of China, Vol. 18, Issue 1 https://doi.org/10.1016/S1003-6326(08)60015-1	journal	February 2008
Fabrication of Ti 2 AlN ceramics with orientation growth behavior by the microwave sintering method Liu, Wulong; Qiu, Changjun; Zhou, Jie Journal of the European Ceramic Society, Vol. 35, Issue 5 https://doi.org/10.1016/j.jeurceramsoc.2014.11.020	journal	May 2015
Two-Dimensional Nanocrystals Produced by Exfoliation of Ti₃AlC₂ Naguib, Michael; Kurtoglu, Murat; Presser, Volker Advanced Materials, Vol. 23, Issue 37, p. 4248-4253 https://doi.org/10.1002/adma.201102306	journal	August 2011
Intercalation and delamination of layered carbides and carbonitrides Mashtalir, Olha; Naguib, Michael; Mochalin, Vadym N. Nature Communications, Vol. 4, Issue 1 https://doi.org/10.1038/ncomms2664	journal	April 2013
Structural and Electronic Properties and Stability of MX enes Ti ₂ C and Ti ₃ C ₂ Functionalized by Methoxy Groups Enyashin, Andrey N.; Ivanovskii, Alexander L. The Journal of Physical Chemistry C, Vol. 117, Issue 26 https://doi.org/10.1021/jp401820b	journal	June 2013
Pseudocapacitive charge storage via hydrogen insertion for molybdenum nitrides Pande, Priyanka; Deb, Aniruddha; Sleightholme, Alice E. S. Journal of Power Sources, Vol. 289 https://doi.org/10.1016/j.jpowsour.2015.03.171	journal	September 2015
Extent of Pseudocapacitance in High‐Surface Area Vanadium Nitrides Djire, Abdoulaye; Ajenifujah, Olabode; Thompson, Levi T. Batteries & Supercaps, Vol. 1, Issue 5 https://doi.org/10.1002/batt.201800050	journal	August 2018
First-order Raman scattering of the MAX phases Ta4AlC3, Nb4AlC3, Ti4AlN3, and Ta2AlC: First-order Raman scattering of ternary hexagonal carbides and nitrides Lane, Nina J.; Naguib, Michael; Presser, Volker Journal of Raman Spectroscopy, Vol. 43, Issue 7 https://doi.org/10.1002/jrs.3101	journal	December 2011
Interfacial processes involving electrocatalytic evolution and oxidation of H₂, and the role of chemisorbed H Conway, B. E.; Tilak, B. V. Electrochimica Acta, Vol. 47, Issue 22-23, p. 3571-3594 https://doi.org/10.1016/S0013-4686(02)00329-8	journal	August 2002
Titanium and vanadium oxynitride powders as pseudo-capacitive materials for electrochemical capacitors Porto, R. Lucio; Frappier, R.; Ducros, J. B. Electrochimica Acta, Vol. 82 https://doi.org/10.1016/j.electacta.2012.05.032	journal	November 2012
VN thin films as electrode materials for electrochemical capacitors Lucio-Porto, R.; Bouhtiyya, S.; Pierson, J. F. Electrochimica Acta, Vol. 141 https://doi.org/10.1016/j.electacta.2014.07.056	journal	September 2014
Pseudocapacitive Contributions to Electrochemical Energy Storage in TiO₂ (Anatase) Nanoparticles Wang, John; Polleux, Julien; Lim, James The Journal of Physical Chemistry C, Vol. 111, Issue 40, p. 14925-14931 https://doi.org/10.1021/jp074464w	journal	October 2007
Hydrolysis of 2D Transition-Metal Carbides (MXenes) in Colloidal Solutions Huang, Shuohan; Mochalin, Vadym N. Inorganic Chemistry, Vol. 58, Issue 3 https://doi.org/10.1021/acs.inorgchem.8b02890	journal	January 2019
Oxidation Stability of Colloidal Two-Dimensional Titanium Carbides (MXenes) Zhang, Chuanfang John; Pinilla, Sergio; McEvoy, Niall Chemistry of Materials, Vol. 29, Issue 11 https://doi.org/10.1021/acs.chemmater.7b00745	journal	May 2017
Electron transfer processes occurring on platinum neural stimulating electrodes: a tutorial on the i ( V _e ) profile Kumsa, Doe W.; Bhadra, Narendra; Hudak, Eric M. Journal of Neural Engineering, Vol. 13, Issue 5 https://doi.org/10.1088/1741-2560/13/5/052001	journal	August 2016

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

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Title: Pseudocapacitive Storage in Nanolayered Ti₂NT_x MXene Using Mg-Ion Electrolyte