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Title: A fundamental study on the [(μ-Cl) 3 Mg 2 (THF) 6 ] + dimer electrolytes for rechargeable Mg batteries

Abstract

We present a fundamental study on [(μ-Cl) 3 Mg 2 (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 MgCl 2 and an Al Lewis acid. Solvated MgCl 2 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) 3Mg 2(THF)6] +. 25Mg{ 1H} NMR, 27Al{ 1H} NMR and electrochemical analysis on chloration reaction of [(μ-Cl) 3Mg 2(THF) 6]AlPh 3Cl 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 Mg 2+ and Cl- ion transports of the Mg dimer electrolytes in rechargeable Mg batteries.

Authors:
 [1];  [2];  [3];  [3];  [3];  [3];  [1];  [1];  [2];  [1]
  1. Pacific Northwest National Lab. (PNNL), Richland, WA (United States). Energy Process and Materials Division
  2. Pacific Northwest National Lab. (PNNL), Richland, WA (United States). Biological Sciences Division
  3. Pacific Northwest National Lab. (PNNL), Richland, WA (United States). William R. Wiley Environmental Molecular Science Lab.
Publication Date:
Research Org.:
Pacific Northwest National Laboratory (PNNL), Richland, WA (US), Environmental Molecular Sciences Laboratory (EMSL)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22); USDOE Office of Science (SC), Biological and Environmental Research (BER) (SC-23); 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. doi: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. doi: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 = {2015},
month = {1}
}

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