Calorimetric Study of Alkali Metal Ion (K+, Na+, Li+) Exchange in a Clay-Like MXene
Abstract
Intercalation of ions in layered materials has been explored to improve the rate capability in Li-ion batteries and supercapacitors. Here, this work investigates the energetics of alkali ion exchange in a clay-like MXene, Ti3C2Tx, where Tx stands for anionic surface moieties, by immersion calorimetry in aqueous solutions. The measured immersion enthalpies of clay-like Ti3C2Tx, ΔHimm, at 25 °C in 1 M KCl, 1 M NaCl, 1 M LiCl, and nanopure water are -9.19 (±0.56), -5.90 (±0.31), -1.31 (±0.20), and -1.29 (±0.13) kJ/mol of MXene, respectively. Inductively coupled plasma mass spectrometry is used to obtain the concentrations of alkali ions in the solid and aqueous phases. Using these concentrations, the enthalpies of exchange of alkali metal ions (Li+, Na+, and K+) are calculated; ΔHex in 1 M KCl, 1 M NaCl, 1 M LiCl, and nanopure water are -9.3 (±2.2), 21.0 (±0.9), -1.3 (±0.2), and 302.4 (±0.6) kJ/mol of MXene, respectively. Both immersion and exchange enthalpies are most exothermic for potassium. This suggests that K+ ions interact more strongly with anions present in the interlayers of this MXene than Na+ and Li+ ions. Lastly, water vapor adsorption calorimetry indicates very weak interaction of water with the MXene, while immersion calorimetry suggestsmore »
- Authors:
-
[3];
[1];
[4]
- Univ. of California, Davis, CA (United States). Peter A. Rock Thermochemistry Lab.
- Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
- Drexel Univ., Philadelphia, PA (United States)
- Univ. of California, Davis, CA (United States). Peter A. Rock Thermochemistry Lab.; Washington State Univ., Pullman, WA (United States)
- Publication Date:
- Research Org.:
- Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Energy Frontier Research Centers (EFRC) (United States). Fluid Interface Reactions, Structures and Transport Center (FIRST)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES)
- OSTI Identifier:
- 1394415
- Alternate Identifier(s):
- OSTI ID: 1488731
- Grant/Contract Number:
- AC05-00OR22725
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Journal of Physical Chemistry. C
- Additional Journal Information:
- Journal Volume: 121; Journal Issue: 28; Journal ID: ISSN 1932-7447
- Publisher:
- American Chemical Society
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Citation Formats
Sharma, Geetu, Muthuswamy, Elayaraja, Naguib, Michael, Gogotsi, Yury, Navrotsky, Alexandra, and Wu, Di. Calorimetric Study of Alkali Metal Ion (K+, Na+, Li+) Exchange in a Clay-Like MXene. United States: N. p., 2017.
Web. doi:10.1021/acs.jpcc.7b02419.
Sharma, Geetu, Muthuswamy, Elayaraja, Naguib, Michael, Gogotsi, Yury, Navrotsky, Alexandra, & Wu, Di. Calorimetric Study of Alkali Metal Ion (K+, Na+, Li+) Exchange in a Clay-Like MXene. United States. https://doi.org/10.1021/acs.jpcc.7b02419
Sharma, Geetu, Muthuswamy, Elayaraja, Naguib, Michael, Gogotsi, Yury, Navrotsky, Alexandra, and Wu, Di. Wed .
"Calorimetric Study of Alkali Metal Ion (K+, Na+, Li+) Exchange in a Clay-Like MXene". United States. https://doi.org/10.1021/acs.jpcc.7b02419. https://www.osti.gov/servlets/purl/1394415.
@article{osti_1394415,
title = {Calorimetric Study of Alkali Metal Ion (K+, Na+, Li+) Exchange in a Clay-Like MXene},
author = {Sharma, Geetu and Muthuswamy, Elayaraja and Naguib, Michael and Gogotsi, Yury and Navrotsky, Alexandra and Wu, Di},
abstractNote = {Intercalation of ions in layered materials has been explored to improve the rate capability in Li-ion batteries and supercapacitors. Here, this work investigates the energetics of alkali ion exchange in a clay-like MXene, Ti3C2Tx, where Tx stands for anionic surface moieties, by immersion calorimetry in aqueous solutions. The measured immersion enthalpies of clay-like Ti3C2Tx, ΔHimm, at 25 °C in 1 M KCl, 1 M NaCl, 1 M LiCl, and nanopure water are -9.19 (±0.56), -5.90 (±0.31), -1.31 (±0.20), and -1.29 (±0.13) kJ/mol of MXene, respectively. Inductively coupled plasma mass spectrometry is used to obtain the concentrations of alkali ions in the solid and aqueous phases. Using these concentrations, the enthalpies of exchange of alkali metal ions (Li+, Na+, and K+) are calculated; ΔHex in 1 M KCl, 1 M NaCl, 1 M LiCl, and nanopure water are -9.3 (±2.2), 21.0 (±0.9), -1.3 (±0.2), and 302.4 (±0.6) kJ/mol of MXene, respectively. Both immersion and exchange enthalpies are most exothermic for potassium. This suggests that K+ ions interact more strongly with anions present in the interlayers of this MXene than Na+ and Li+ ions. Lastly, water vapor adsorption calorimetry indicates very weak interaction of water with the MXene, while immersion calorimetry suggests a weakly hydrophilic nature of the MXene surface.},
doi = {10.1021/acs.jpcc.7b02419},
journal = {Journal of Physical Chemistry. C},
number = 28,
volume = 121,
place = {United States},
year = {Wed Jun 21 00:00:00 EDT 2017},
month = {Wed Jun 21 00:00:00 EDT 2017}
}
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Figures / Tables:
Figure 1.: a) Water vapor adsorption isotherms and (b) Differential heat of adsorption as a function of the amount of water adsorbed. The degas temperatures are given in the brackets. Red and black traces correspond to MXene obtained by HCl-LiF treatment and the blue trace corresponds to that obtained bymore »
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