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Title: Calorimetric Study of Alkali Metal Ion (K +, Na +, Li +) Exchange in a Clay-Like MXene

Intercalation of ions in layered materials has been explored to improve the rate capability in Li-ion batteries and supercapacitors. This work investigates the energetics of alkali ion exchange in a clay-like MXene, Ti 3C 2T x, where T x stands for anionic surface moieties, by immersion calorimetry in aqueous solutions. The measured immersion enthalpies of clay-like Ti 3C 2T x, ΔH imm, 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. Water vapor adsorption calorimetry indicates very weak interaction ofmore » water with the MXene, while immersion calorimetry suggests a weakly hydrophilic nature of the MXene surface.« less
Authors:
 [1] ;  [1] ;  [2] ; ORCiD logo [3] ; ORCiD logo [1] ; ORCiD logo [4]
  1. Univ. of California, Davis, CA (United States). Peter A. Rock Thermochemistry Lab.
  2. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
  3. Drexel Univ., Philadelphia, PA (United States)
  4. Univ. of California, Davis, CA (United States). Peter A. Rock Thermochemistry Lab.; Washington State Univ., Pullman, WA (United States)
Publication Date:
Grant/Contract Number:
AC05-00OR22725
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
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) (SC-22)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
OSTI Identifier:
1394415

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., 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. doi:10.1021/acs.jpcc.7b02419.
Sharma, Geetu, Muthuswamy, Elayaraja, Naguib, Michael, Gogotsi, Yury, Navrotsky, Alexandra, and Wu, Di. 2017. "Calorimetric Study of Alkali Metal Ion (K+, Na+, Li+) Exchange in a Clay-Like MXene". United States. doi: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. 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. 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 = {2017},
month = {6}
}