A fundamental study on the [(μ-Cl)3 Mg2 (THF)6 ]+ dimer electrolytes for rechargeable Mg batteries
Abstract
We present a fundamental study on [(μ-Cl)3 Mg2 (THF)6 ]+ dimer electrolytes using various physical methods including Subambient Pressure Ionization with Nanoelectrospray Mass spectrometry (SPIN-MS), Raman spectroscopy, 25Mg{1H} NMR, 27Al{1H} NMR and electrochemical analysis. For the first time, long time sought THF solvated [MgCl]+ species was experimentally characterized by SPIN mass spectrometry in the solution of the Mgdimer containing electrolyte, confirming the mono-Cl- abstraction reaction between MgCl2 and an Al Lewis acid. Solvated MgCl2 in the electrolyte was confirmed by Raman spectroscopy. The experimental results establish the previously proposed dimerization equilibrium of solvated [MgCl]+ and MgCl2 with [(μ-Cl)3Mg2(THF)6]+. 25Mg{1H} NMR, 27Al{1H} NMR and electrochemical analysis on chloration reaction of [(μ-Cl)3Mg2(THF)6]AlPh3Cl with external Cl- led to further insights on the coordination chemistry of the dimer electrolyte. Finally, a comprehensive mechanism is proposed for the reversible electrochemical Mg deposition and stripping and Mg2+ and Cl- ion transports of the Mg dimer electrolytes in rechargeable Mg batteries.
- Authors:
-
- Pacific Northwest National Lab. (PNNL), Richland, WA (United States). Energy Process and Materials Division
- Pacific Northwest National Lab. (PNNL), Richland, WA (United States). Biological Sciences Division
- Pacific Northwest National Lab. (PNNL), Richland, WA (United States). William R. Wiley Environmental Molecular Science Lab.
- Publication Date:
- Research Org.:
- Pacific Northwest National Lab. (PNNL), Richland, WA (United States). Environmental Molecular Sciences Lab. (EMSL)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES); USDOE Office of Science (SC), Biological and Environmental Research (BER); National Institutes of Health (NIH)
- OSTI Identifier:
- 1170046
- Report Number(s):
- PNNL-SA-104532
Journal ID: ISSN 1359-7345; CHCOFS; 47301; 48135; KC0208010
- Grant/Contract Number:
- AC05-76RL01830; 1R33CA155252; GM103491-12
- Resource Type:
- Accepted Manuscript
- Journal Name:
- ChemComm
- Additional Journal Information:
- Journal Volume: 51; Journal Issue: 12; Journal ID: ISSN 1359-7345
- Publisher:
- Royal Society of Chemistry
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 25 ENERGY STORAGE; Environmental Molecular Sciences Laboratory
Citation Formats
Liu, Tianbiao, Cox, Jonathan T., Hu, Dehong, Deng, Xuchu, Hu, Jianzhi, Hu, Mary Y., Xiao, Jie, Shao, Yuyan, Tang, Keqi, and Liu, Jun. A fundamental study on the [(μ-Cl)3 Mg2 (THF)6 ]+ dimer electrolytes for rechargeable Mg batteries. United States: N. p., 2015.
Web. doi:10.1039/c4cc07621d.
Liu, Tianbiao, Cox, Jonathan T., Hu, Dehong, Deng, Xuchu, Hu, Jianzhi, Hu, Mary Y., Xiao, Jie, Shao, Yuyan, Tang, Keqi, & Liu, Jun. A fundamental study on the [(μ-Cl)3 Mg2 (THF)6 ]+ dimer electrolytes for rechargeable Mg batteries. United States. https://doi.org/10.1039/c4cc07621d
Liu, Tianbiao, Cox, Jonathan T., Hu, Dehong, Deng, Xuchu, Hu, Jianzhi, Hu, Mary Y., Xiao, Jie, Shao, Yuyan, Tang, Keqi, and Liu, Jun. Mon .
"A fundamental study on the [(μ-Cl)3 Mg2 (THF)6 ]+ dimer electrolytes for rechargeable Mg batteries". United States. https://doi.org/10.1039/c4cc07621d. https://www.osti.gov/servlets/purl/1170046.
@article{osti_1170046,
title = {A fundamental study on the [(μ-Cl)3 Mg2 (THF)6 ]+ dimer electrolytes for rechargeable Mg batteries},
author = {Liu, Tianbiao and Cox, Jonathan T. and Hu, Dehong and Deng, Xuchu and Hu, Jianzhi and Hu, Mary Y. and Xiao, Jie and Shao, Yuyan and Tang, Keqi and Liu, Jun},
abstractNote = {We present a fundamental study on [(μ-Cl)3 Mg2 (THF)6 ]+ dimer electrolytes using various physical methods including Subambient Pressure Ionization with Nanoelectrospray Mass spectrometry (SPIN-MS), Raman spectroscopy, 25Mg{1H} NMR, 27Al{1H} NMR and electrochemical analysis. For the first time, long time sought THF solvated [MgCl]+ species was experimentally characterized by SPIN mass spectrometry in the solution of the Mgdimer containing electrolyte, confirming the mono-Cl- abstraction reaction between MgCl2 and an Al Lewis acid. Solvated MgCl2 in the electrolyte was confirmed by Raman spectroscopy. The experimental results establish the previously proposed dimerization equilibrium of solvated [MgCl]+ and MgCl2 with [(μ-Cl)3Mg2(THF)6]+. 25Mg{1H} NMR, 27Al{1H} NMR and electrochemical analysis on chloration reaction of [(μ-Cl)3Mg2(THF)6]AlPh3Cl with external Cl- led to further insights on the coordination chemistry of the dimer electrolyte. Finally, a comprehensive mechanism is proposed for the reversible electrochemical Mg deposition and stripping and Mg2+ and Cl- ion transports of the Mg dimer electrolytes in rechargeable Mg batteries.},
doi = {10.1039/c4cc07621d},
journal = {ChemComm},
number = 12,
volume = 51,
place = {United States},
year = {Mon Jan 05 00:00:00 EST 2015},
month = {Mon Jan 05 00:00:00 EST 2015}
}
Web of Science
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