A fundamental study on the [(μ-Cl)3 Mg2 (THF)6 ]+ dimer electrolytes for rechargeable Mg batteries

Liu, Tianbiao; Cox, Jonathan T.; Hu, Dehong; Deng, Xuchu; Hu, Jianzhi; Hu, Mary Y.; Xiao, Jie; Shao, Yuyan; Tang, Keqi; Liu, Jun

doi:10.1039/c4cc07621d

A fundamental study on the [(μ-Cl)₃ Mg₂ (THF)₆ ]⁺ dimer electrolytes for rechargeable Mg batteries

Journal Article · Sun Jan 04 23:00:00 EST 2015 · ChemComm

DOI:https://doi.org/10.1039/c4cc07621d· OSTI ID:1170046

Liu, Tianbiao ^[1]; Cox, Jonathan T. ^[2]; Hu, Dehong ^[3]; Deng, Xuchu ^[3]; Hu, Jianzhi ^[3]; Hu, Mary Y. ^[3]; Xiao, Jie ^[1]; Shao, Yuyan ^[1]; Tang, Keqi ^[2]; Liu, Jun ^[1]

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.

View Accepted Manuscript (DOE)

Research Organization:: Pacific Northwest National Laboratory (PNNL), Richland, WA (US), Environmental Molecular Sciences Laboratory (EMSL)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22); USDOE Office of Science (SC), Biological and Environmental Research (BER) (SC-23); National Inst. of Health (NIH)

Grant/Contract Number:: AC05-76RL01830

OSTI ID:: 1170046

Report Number(s):: PNNL-SA--104532; 47301; 48135; KC0208010

Journal Information:: ChemComm, Journal Name: ChemComm Journal Issue: 12 Vol. 51; ISSN CHCOFS; ISSN 1359-7345

Publisher:: Royal Society of ChemistryCopyright Statement

Country of Publication:: United States

Language:: English

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Cited By (6)

Computational Insights into Mg‐Cl Complex Electrolytes for Rechargeable Magnesium Batteries Moss, Jared B.; Zhang, Liping; Nielson, Kevin V. Batteries & Supercaps, Vol. 2, Issue 9 https://doi.org/10.1002/batt.201900029	journal	June 2019
The Role of MgCl ₂ as a Lewis Base in ROMgCl-MgCl ₂ Electrolytes for Magnesium-Ion Batteries Pan, Baofei; Huang, Jinhua; He, Meinan ChemSusChem, Vol. 9, Issue 6 https://doi.org/10.1002/cssc.201501557	journal	February 2016
Fast kinetics of magnesium monochloride cations in interlayer-expanded titanium disulfide for magnesium rechargeable batteries Yoo, Hyun Deog; Liang, Yanliang; Dong, Hui Nature Communications, Vol. 8, Issue 1 https://doi.org/10.1038/s41467-017-00431-9	journal	August 2017
Exposing elusive cationic magnesium–chloro aggregates in aluminate complexes through donor control Brouillet, Etienne V.; Kennedy, Alan R.; Koszinowski, Konrad Dalton Transactions, Vol. 45, Issue 13 https://doi.org/10.1039/c6dt00531d	journal	January 2016
A key concept of utilization of both non-Grignard magnesium chloride and imide salts for rechargeable Mg battery electrolytes Mandai, Toshihiko; Akita, Yasuhiro; Yagi, Shunsuke Journal of Materials Chemistry A, Vol. 5, Issue 7 https://doi.org/10.1039/c6ta10194a	journal	January 2017
A new class of non-corrosive, highly efficient electrolytes for rechargeable magnesium batteries Zhao-Karger, Zhirong; Gil Bardaji, Maria Elisa; Fuhr, Olaf Journal of Materials Chemistry A, Vol. 5, Issue 22 https://doi.org/10.1039/c7ta02237a	journal	January 2017

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