A fundamental study on the [(μ-Cl)3 Mg2 (THF)6 ]+ dimer electrolytes for rechargeable Mg batteries
- 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.
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.
- Research Organization:
- Pacific Northwest National Lab. (PNNL), Richland, WA (United States). Environmental Molecular Sciences Lab. (EMSL)
- Sponsoring Organization:
- USDOE Office of Science (SC), Basic Energy Sciences (BES); USDOE Office of Science (SC), Biological and Environmental Research (BER); National Institutes of Health (NIH)
- Grant/Contract Number:
- AC05-76RL01830; 1R33CA155252; GM103491-12
- OSTI ID:
- 1170046
- Report Number(s):
- PNNL-SA-104532; CHCOFS; 47301; 48135; KC0208010
- Journal Information:
- ChemComm, Vol. 51, Issue 12; ISSN 1359-7345
- Publisher:
- Royal Society of ChemistryCopyright Statement
- Country of Publication:
- United States
- Language:
- English
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