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

Sharma, Geetu; Muthuswamy, Elayaraja; Naguib, Michael; Gogotsi, Yury; Navrotsky, Alexandra; Wu, Di

doi:10.1021/acs.jpcc.7b02419

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

Journal Article · Wed Jun 21 00:00:00 EDT 2017 · Journal of Physical Chemistry. C

DOI:https://doi.org/10.1021/acs.jpcc.7b02419· OSTI ID:1394415

Sharma, Geetu ^[1]; Muthuswamy, Elayaraja ^[1]; Naguib, Michael ^[2];

^[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)

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, Ti₃C₂T_x, where T_x stands for anionic surface moieties, by immersion calorimetry in aqueous solutions. The measured immersion enthalpies of clay-like Ti₃C₂T_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. 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.

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

Grant/Contract Number:: AC05-00OR22725

OSTI ID:: 1394415

Alternate ID(s):: OSTI ID: 1488731

Journal Information:: Journal of Physical Chemistry. C, Vol. 121, Issue 28; ISSN 1932-7447

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 28 works

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