Influences from solvents on charge storage in titanium carbide MXenes

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

doi:10.1038/s41560-019-0339-9

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

Journal Article · Mon Mar 04 00:00:00 EST 2019 · Nature Energy

DOI:https://doi.org/10.1038/s41560-019-0339-9· OSTI ID:1502529

^[1]; Mathis, Tyler S. ^[1]; Li, Ke ^[1]; Lin, Zifeng ^[2]; Vlcek, Lukas ^[3]; Torita, Takeshi ^[4];

^[5]; Hatter, Christine ^[1]; Urbankowski, Patrick ^[1]; Sarycheva, Asia ^[1]; Tyagi, Madhusudan ^[6];

^[5];

^[7];

^[1]

Drexel Univ., Philadelphia, PA (United States)
Université Paul Sabatier, Toulouse (France); Sichuan University, Chengdu (China)
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Univ. of Tennessee, Knoxville, TN (United States)
Murata Manufacturing Co., Ltd, Nagaokakyo-shi, Kyoto (Japan)
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
National Inst. of Standards and Technology (NIST), Gaithersburg, MD (United States); Univ. of Maryland, College Park, MD (United States)
Université Paul Sabatier, Toulouse (France); Réseau sur le Stockage Electrochimique de l’Energie (RS2E), Amiens (France)

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.

View Accepted Manuscript (DOE)

Cite

Export

Save

Research Organization:: 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)

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

Grant/Contract Number:: AC05-00OR22725

OSTI ID:: 1502529

Journal Information:: Nature Energy, Vol. 4, Issue 3; ISSN 2058-7546

Publisher:: Nature Publishing GroupCopyright Statement

Country of Publication:: United States

Language:: English

Citation Metrics:

Cited by: 263 works

Citation information provided by
Web of Science

References (42)

Effect of viscosity and volume on the specific conductivity of lithium salts in solvent mixtures Brouillette, Dany; Perron, Gérald; Desnoyers, Jacques E. Electrochimica Acta, Vol. 44, Issue 26 https://doi.org/10.1016/S0013-4686(99)00267-4	journal	September 1999
Electrochemical in Situ Tracking of Volumetric Changes in Two-Dimensional Metal Carbides (MXenes) in Ionic Liquids Jäckel, Nicolas; Krüner, Benjamin; Van Aken, Katherine L. ACS Applied Materials & Interfaces, Vol. 8, Issue 47 https://doi.org/10.1021/acsami.6b11744	journal	November 2016
Lithium solvation in dimethyl sulfoxide-acetonitrile mixtures Semino, Rocío; Zaldívar, Gervasio; Calvo, Ernesto J. The Journal of Chemical Physics, Vol. 141, Issue 21 https://doi.org/10.1063/1.4902837	journal	December 2014
Integration of ultrathin graphene/polyaniline composite nanosheets with a robust 3D graphene framework for highly flexible all-solid-state supercapacitors with superior energy density and exceptional cycling stability Li, Ke; Liu, Jingjing; Huang, Yanshan Journal of Materials Chemistry A, Vol. 5, Issue 11 https://doi.org/10.1039/C6TA11224B	journal	January 2017
Anomalous Increase in Carbon Capacitance at Pore Sizes Less Than 1 Nanometer Chmiola, J. Science, Vol. 313, Issue 5794 https://doi.org/10.1126/science.1132195	journal	September 2006
Biredox ionic liquids with solid-like redox density in the liquid state for high-energy supercapacitors Mourad, Eléonore; Coustan, Laura; Lannelongue, Pierre Nature Materials, Vol. 16, Issue 4 https://doi.org/10.1038/nmat4808	journal	November 2016
A review of electrode materials for electrochemical supercapacitors Wang, Guoping; Zhang, Lei; Zhang, Jiujun Chemical Society Reviews, Vol. 41, Issue 2, p. 797-828 https://doi.org/10.1039/C1CS15060J	journal	January 2012
Controlling the actuation properties of MXene paper electrodes upon cation intercalation Come, Jeremy; Black, Jennifer M.; Lukatskaya, Maria R. Nano Energy, Vol. 17 https://doi.org/10.1016/j.nanoen.2015.07.028	journal	October 2015
Pseudocapacitive oxide materials for high-rate electrochemical energy storage Augustyn, Veronica; Simon, Patrice; Dunn, Bruce Energy & Environmental Science, Vol. 7, Issue 5 https://doi.org/10.1039/c3ee44164d	journal	January 2014
Beyond Intercalation-Based Li-Ion Batteries: The State of the Art and Challenges of Electrode Materials Reacting Through Conversion Reactions Cabana, Jordi; Monconduit, Laure; Larcher, Dominique Advanced Materials, Vol. 22, Issue 35 https://doi.org/10.1002/adma.201000717	journal	August 2010
Geometrically confined favourable ion packing for high gravimetric capacitance in carbon–ionic liquid supercapacitors Wang, Xuehang; Zhou, Haitao; Sheridan, Edel Energy & Environmental Science, Vol. 9, Issue 1 https://doi.org/10.1039/C5EE02702K	journal	January 2016
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
One-Step Synthesis of Hollow Dimpled Polystyrene Microparticles by Dispersion Polymerization Park, Sung Hwan; Kim, Jinwoo; Lee, Wang-Eun Langmuir, Vol. 33, Issue 9 https://doi.org/10.1021/acs.langmuir.6b04428	journal	February 2017
Transition from Battery to Pseudocapacitor Behavior via Structural Water in Tungsten Oxide Mitchell, James B.; Lo, William C.; Genc, Arda Chemistry of Materials, Vol. 29, Issue 9 https://doi.org/10.1021/acs.chemmater.6b05485	journal	April 2017
MXene as a Charge Storage Host Okubo, Masashi; Sugahara, Akira; Kajiyama, Satoshi Accounts of Chemical Research, Vol. 51, Issue 3 https://doi.org/10.1021/acs.accounts.7b00481	journal	February 2018
Solving the Capacitive Paradox of 2D MXene using Electrochemical Quartz-Crystal Admittance and In Situ Electronic Conductance Measurements Levi, Mikhael D.; Lukatskaya, Maria R.; Sigalov, Sergey Advanced Energy Materials, Vol. 5, Issue 1 https://doi.org/10.1002/aenm.201400815	journal	August 2014
Fast and Reversible Surface Redox Reaction in Nanocrystalline Vanadium Nitride Supercapacitors Choi, D.; Blomgren, G. E.; Kumta, P. N. Advanced Materials, Vol. 18, Issue 9 https://doi.org/10.1002/adma.200502471	journal	May 2006
The high-flux backscattering spectrometer at the NIST Center for Neutron Research Meyer, A.; Dimeo, R. M.; Gehring, P. M. Review of Scientific Instruments, Vol. 74, Issue 5 https://doi.org/10.1063/1.1568557	journal	May 2003
Carbon-Based Supercapacitors Produced by Activation of Graphene Zhu, Y.; Murali, S.; Stoller, M. D. Science, Vol. 332, Issue 6037, p. 1537-1541 https://doi.org/10.1126/science.1200770	journal	May 2011
Materials for electrochemical capacitors Simon, Patrice; Gogotsi, Yury Nature Materials, Vol. 7, Issue 11 https://doi.org/10.1038/nmat2297	journal	November 2008
To Be or Not To Be Pseudocapacitive? Brousse, Thierry; Bélanger, Daniel; Long, Jeffrey W. Journal of The Electrochemical Society, Vol. 162, Issue 5 https://doi.org/10.1149/2.0201505jes	journal	January 2015
Energy Storage in Nanomaterials – Capacitive, Pseudocapacitive, or Battery-like? Gogotsi, Yury; Penner, Reginald M. ACS Nano, Vol. 12, Issue 3 https://doi.org/10.1021/acsnano.8b01914	journal	March 2018
Qualitative Electrochemical Impedance Spectroscopy study of ion transport into sub-nanometer carbon pores in Electrochemical Double Layer Capacitor electrodes Segalini, J.; Daffos, B.; Taberna, P. L. Electrochimica Acta, Vol. 55, Issue 25 https://doi.org/10.1016/j.electacta.2010.01.003	journal	October 2010
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
Efficient storage mechanisms for building better supercapacitors Salanne, M.; Rotenberg, B.; Naoi, K. Nature Energy, Vol. 1, Issue 6 https://doi.org/10.1038/nenergy.2016.70	journal	May 2016
Electrochemical Characteristics and Impedance Spectroscopy Studies of Carbon-Carbon Supercapacitors Taberna, P. L.; Simon, P.; Fauvarque, J. F. Journal of The Electrochemical Society, Vol. 150, Issue 3, p. A292-A300 https://doi.org/10.1149/1.1543948	journal	January 2003
Partial breaking of the Coulombic ordering of ionic liquids confined in carbon nanopores Futamura, Ryusuke; Iiyama, Taku; Takasaki, Yuma Nature Materials, Vol. 16, Issue 12 https://doi.org/10.1038/nmat4974	journal	September 2017
New Perspectives on the Charging Mechanisms of Supercapacitors Forse, Alexander C.; Merlet, Céline; Griffin, John M. Journal of the American Chemical Society, Vol. 138, Issue 18 https://doi.org/10.1021/jacs.6b02115	journal	April 2016
Li-ion battery materials: present and future Nitta, Naoki; Wu, Feixiang; Lee, Jung Tae Materials Today, Vol. 18, Issue 5 https://doi.org/10.1016/j.mattod.2014.10.040	journal	June 2015
Capacitance of Ti3C2Tx MXene in ionic liquid electrolyte Lin, Zifeng; Barbara, Daffos; Taberna, Pierre-Louis Journal of Power Sources, Vol. 326 https://doi.org/10.1016/j.jpowsour.2016.04.035	journal	September 2016
Direct observation of ion dynamics in supercapacitor electrodes using in situ diffusion NMR spectroscopy Forse, Alexander C.; Griffin, John M.; Merlet, Céline Nature Energy, Vol. 2, Issue 3 https://doi.org/10.1038/nenergy.2016.216	journal	February 2017
A review of electrolyte materials and compositions for electrochemical supercapacitors Zhong, Cheng; Deng, Yida; Hu, Wenbin Chemical Society Reviews, Vol. 44, Issue 21 https://doi.org/10.1039/C5CS00303B	journal	January 2015
Enhanced Li-Ion Accessibility in MXene Titanium Carbide by Steric Chloride Termination Kajiyama, Satoshi; Szabova, Lucie; Iinuma, Hiroki Advanced Energy Materials, Vol. 7, Issue 9 https://doi.org/10.1002/aenm.201601873	journal	January 2017
Resolving the Structure of Ti ₃ C ₂ T _x MXenes through Multilevel Structural Modeling of the Atomic Pair Distribution Function Wang, Hsiu-Wen; Naguib, Michael; Page, Katharine Chemistry of Materials, Vol. 28, Issue 1 https://doi.org/10.1021/acs.chemmater.5b04250	journal	December 2015
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
Capacitance of two-dimensional titanium carbide (MXene) and MXene/carbon nanotube composites in organic electrolytes Dall’Agnese, Yohan; Rozier, Patrick; Taberna, Pierre-Louis Journal of Power Sources, Vol. 306 https://doi.org/10.1016/j.jpowsour.2015.12.036	journal	February 2016
Ultra-high-rate pseudocapacitive energy storage in two-dimensional transition metal carbides Lukatskaya, Maria R.; Kota, Sankalp; Lin, Zifeng Nature Energy, Vol. 2, Issue 8 https://doi.org/10.1038/nenergy.2017.105	journal	July 2017
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
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
Biredox ionic liquids with solid-like redox density in the liquid state for high-energy supercapacitors Mourad, Eléonore; Coustan, Laura; Lannelongue, Pierre arXiv https://doi.org/10.48550/arxiv.1711.11518	text	January 2017
The High-Flux Backscattering Spectrometer at the NIST Center for Neutron Research Meyer, A.; Dimeo, R. M.; Gehring, P. M. arXiv https://doi.org/10.48550/arxiv.cond-mat/0209153	text	January 2002
Beyond Intercalation-Based Li-Ion Batteries: The State of the Art and Challenges of Electrode Materials Reacting Through Conversion Reactions (Adv. Mater. 35/2010) Cabana, Jordi; Monconduit, Laure; Larcher, Dominique Advanced Materials, Vol. 22, Issue 35 https://doi.org/10.1002/adma.201090116	journal	September 2010

Cited By (19)

Knittable and Washable Multifunctional MXene‐Coated Cellulose Yarns Uzun, Simge; Seyedin, Shayan; Stoltzfus, Amy L. Advanced Functional Materials, Vol. 29, Issue 45 https://doi.org/10.1002/adfm.201905015	journal	September 2019
Solvation‐Involved Nanoionics: New Opportunities from 2D Nanomaterial Laminar Membranes Zhan, Hualin; Xiong, Zhiyuan; Cheng, Chi Advanced Materials, Vol. 32, Issue 18 https://doi.org/10.1002/adma.201904562	journal	December 2019
Porous g‐C ₃ N ₄ and MXene Dual‐Confined FeOOH Quantum Dots for Superior Energy Storage in an Ionic Liquid Shi, Minjie; Xiao, Peng; Lang, Junwei Advanced Science, Vol. 7, Issue 2 https://doi.org/10.1002/advs.201901975	journal	November 2019
Electrochemical Behavior of Ti ₃ C ₂ T _x MXene in Environmentally Friendly Methanesulfonic Acid Electrolyte Zhao, Xin; Dall'Agnese, Chunxiang; Chu, Xue‐Feng ChemSusChem, Vol. 12, Issue 19 https://doi.org/10.1002/cssc.201901746	journal	August 2019
Advances on three‐dimensional electrodes for micro‐supercapacitors: A mini‐review Liu, Long; Zhao, Huaping; Lei, Yong InfoMat, Vol. 1, Issue 1 https://doi.org/10.1002/inf2.12007	journal	March 2019
Ti ₂ CT _x MXene‐based all‐optical modulator Yi, Jun; Li, Jie; Huang, Shuohan InfoMat, Vol. 2, Issue 3 https://doi.org/10.1002/inf2.12052	journal	December 2019
“HOT” Alkaline Hydrolysis of Amorphous MOF Microspheres to Produce Ultrastable Bimetal Hydroxide Electrode with Boosted Cycling Stability Zhang, Haobing; Xu, Ben; Mei, Hao Small, Vol. 15, Issue 49 https://doi.org/10.1002/smll.201904663	journal	October 2019
An Ultrafast Conducting Polymer@MXene Positive Electrode with High Volumetric Capacitance for Advanced Asymmetric Supercapacitors Li, Ke; Wang, Xuehang; Li, Shuo Small, Vol. 16, Issue 4 https://doi.org/10.1002/smll.201906851	journal	December 2019
Plate-to-Layer Bi2MoO6/MXene-Heterostructured Anode for Lithium-Ion Batteries Zhang, Peng; Wang, Danjun; Zhu, Qizhen Nano-Micro Letters, Vol. 11, Issue 1 https://doi.org/10.1007/s40820-019-0312-y	journal	September 2019
Achieving high energy density and high power density with pseudocapacitive materials Choi, Christopher; Ashby, David S.; Butts, Danielle M. Nature Reviews Materials, Vol. 5, Issue 1 https://doi.org/10.1038/s41578-019-0142-z	journal	October 2019
La ³⁺ :Ni–Cl oxyhydroxide gels with enhanced electroactivity as positive materials for hybrid supercapacitors Chen, Kunfeng; Liang, Feng; Xue, Dongfeng Dalton Transactions, Vol. 49, Issue 4 https://doi.org/10.1039/c9dt04410h	journal	January 2020
Microscopic dynamics in room-temperature ionic liquids confined in materials for supercapacitor applications Osti, Naresh C.; Mamontov, Eugene Sustainable Energy & Fuels, Vol. 4, Issue 4 https://doi.org/10.1039/c9se00829b	journal	January 2020
Low electronegativity Mn bulk doping intensifies charge storage of Ni ₂ P redox shuttle for membrane-free water electrolysis Liu, Zichen; Zhang, Gong; Zhang, Kai Journal of Materials Chemistry A, Vol. 8, Issue 7 https://doi.org/10.1039/c9ta10213b	journal	January 2020
Energy storage: The future enabled by nanomaterials Pomerantseva, Ekaterina; Bonaccorso, Francesco; Feng, Xinliang Science, Vol. 366, Issue 6468 https://doi.org/10.1126/science.aan8285	journal	November 2019
Interfacial Dissociation of Contact-Ion-Pair on MXene Electrodes in Concentrated Aqueous Electrolytes Kim, Kijae; Okubo, Masashi; Yamada, Atsuo Journal of The Electrochemical Society, Vol. 166, Issue 15 https://doi.org/10.1149/2.0931915jes	journal	January 2019
MXenes as High-Rate Electrodes for Energy Storage Lin, Zifeng; Shao, Hui; Xu, Kui Trends in Chemistry, Vol. 2, Issue 7 https://doi.org/10.1016/j.trechm.2020.04.010	journal	July 2020
Stumbling through the Research Wilderness, Standard Methods To Shine Light on Electrically Conductive Nanocomposites for Future Healthcare Monitoring Boland, Conor S. ACS Nano, Vol. 13, Issue 12 https://doi.org/10.1021/acsnano.9b06847	journal	November 2019
Interlayer gap widened α-phase molybdenum trioxide as high-rate anodes for dual-ion-intercalation energy storage devices Yu, Minghao; Shao, Hui; Wang, Gang Nature Communications, Vol. 11, Issue 1 https://doi.org/10.1038/s41467-020-15216-w	journal	March 2020
Predicting the pseudocapacitive windows for MXene electrodes with voltage-dependent cluster expansion models Goff, James M.; Vieira, Francisco Marques dos Santos; Keilbart, Nathan D. arXiv https://doi.org/10.48550/arxiv.2102.11863	preprint	January 2021

Similar Records

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 · OSTI ID:1502529

Djire, Abdoulaye; Bos, Andre; Liu, Jun; +3 more

Superfast high-energy storage hybrid device composed of MXene and Chevrel-phase electrodes operated in saturated LiCl electrolyte solution

Journal Article · Tue Aug 06 00:00:00 EDT 2019 · Journal of Materials Chemistry. A · OSTI ID:1502529

Malchik, Fyodor; Shpigel, Netanel; Levi, Mikhael D.; +4 more

Ultra-high-rate pseudocapacitive energy storage in two-dimensional transition metal carbides

Journal Article · Mon Jul 10 00:00:00 EDT 2017 · Nature Energy · OSTI ID:1502529

Lukatskaya, Maria R.; Kota, Sankalp; Lin, Zifeng; +8 more

Related Subjects

25 ENERGY STORAGE
36 MATERIALS SCIENCE

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

Citation Formats

References (42)

Cited By (19)

Similar Records

Related Subjects