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

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

Journal Article · Mon Jan 05 00:00:00 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.

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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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Cited by: 43 works

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References (24)

Building better batteries Armand, M.; Tarascon, J.-M. Nature, Vol. 451, Issue 7179, p. 652-657 https://doi.org/10.1038/451652a	journal	February 2008
Materials Science and Materials Chemistry for Large Scale Electrochemical Energy Storage: From Transportation to Electrical Grid Liu, Jun; Zhang, Ji-Guang; Yang, Zhenguo Advanced Functional Materials, Vol. 23, Issue 8 https://doi.org/10.1002/adfm.201200690	journal	June 2012
Electrochemical Energy Storage for Green Grid Yang, Zhenguo; Zhang, Jianlu; Kintner-Meyer, Michael C. W. Chemical Reviews, Vol. 111, Issue 5, p. 3577-3613 https://doi.org/10.1021/cr100290v	journal	May 2011
The Li-Ion Rechargeable Battery: A Perspective Goodenough, John B.; Park, Kyu-Sung Journal of the American Chemical Society, Vol. 135, Issue 4 https://doi.org/10.1021/ja3091438	journal	January 2013
Electrolyte roadblocks to a magnesium rechargeable battery Muldoon, John; Bucur, Claudiu B.; Oliver, Allen G. Energy & Environmental Science, Vol. 5, Issue 3, p. 5941-5950 https://doi.org/10.1039/c2ee03029b	journal	January 2012
Mg rechargeable batteries: an on-going challenge Yoo, Hyun Deog; Shterenberg, Ivgeni; Gofer, Yosef Energy & Environmental Science, Vol. 6, Issue 8, p. 2265-2279 https://doi.org/10.1039/c3ee40871j	journal	January 2013
Metallic anodes for next generation secondary batteries Kim, Hansu; Jeong, Goojin; Kim, Young-Ugk Chemical Society Reviews, Vol. 42, Issue 23 https://doi.org/10.1039/c3cs60177c	journal	January 2013
Nonaqueous Electrochemistry of Magnesium Gregory, Thomas D.; Hoffman, Ronald J.; Winterton, Richard C. Journal of The Electrochemical Society, Vol. 137, Issue 3, p. 775-780 https://doi.org/10.1149/1.2086553	journal	January 1990
Prototype systems for rechargeable magnesium batteries Aurbach, D.; Lu, Z.; Schechter, A. Nature, Vol. 407, Issue 6805, p. 724-727 https://doi.org/10.1038/35037553	journal	October 2000
Structural Analysis of Electrolyte Solutions for Rechargeable Mg Batteries by Stereoscopic Means and DFT Calculations Pour, Nir; Gofer, Yossi; Major, Dan T. Journal of the American Chemical Society, Vol. 133, Issue 16 https://doi.org/10.1021/ja1098512	journal	April 2011
Boron-based electrolyte solutions with wide electrochemical windows for rechargeable magnesium batteries Guo, Yong-sheng; Zhang, Fan; Yang, Jun Energy & Environmental Science, Vol. 5, Issue 10, p. 9100-9106 https://doi.org/10.1039/c2ee22509c	journal	August 2012
Magnesium Borohydride: From Hydrogen Storage to Magnesium Battery Mohtadi, Rana; Matsui, Masaki; Arthur, Timothy S. Angewandte Chemie International Edition, Vol. 51, Issue 39, p. 9780-9783 https://doi.org/10.1002/anie.201204913	journal	August 2012
A Scientific Study of Current Collectors for Mg Batteries in Mg(AlCl ₂ EtBu) ₂ /THF Electrolyte Lv, Dongping; Xu, Terrence; Saha, Partha Journal of The Electrochemical Society, Vol. 160, Issue 2 https://doi.org/10.1149/2.085302jes	journal	December 2012
A study of a fluorine substituted phenyl based complex as a 3 V electrolyte for Mg batteries Lv, Dongping; Tang, Duihai; Duan, Yuhua J. Mater. Chem. A, Vol. 2, Issue 37 https://doi.org/10.1039/C4TA02686A	journal	January 2014
A facile approach using MgCl2 to formulate high performance Mg2+ electrolytes for rechargeable Mg batteries Liu, Tianbiao; Shao, Yuyan; Li, Guosheng Journal of Materials Chemistry A, Vol. 2, Issue 10 https://doi.org/10.1039/c3ta14825d	journal	January 2014
Constitution of Grignard Reagent RMgCl in Tetrahydrofuran Sakamoto, Shigeru; Imamoto, Tsuneo; Yamaguchi, Kentaro Organic Letters, Vol. 3, Issue 12 https://doi.org/10.1021/ol010048x	journal	June 2001
Subambient Pressure Ionization with Nanoelectrospray Source and Interface for Improved Sensitivity in Mass Spectrometry Page, Jason S.; Tang, Keqi; Kelly, Ryan T. Analytical Chemistry, Vol. 80, Issue 5 https://doi.org/10.1021/ac702354b	journal	March 2008
Achieving 50% Ionization Efficiency in Subambient Pressure Ionization with Nanoelectrospray Marginean, Ioan; Page, Jason S.; Tolmachev, Aleksey V. Analytical Chemistry, Vol. 82, Issue 22 https://doi.org/10.1021/ac1019123	journal	November 2010
Improving N -Glycan Coverage using HPLC-MS with Electrospray Ionization at Subambient Pressure Marginean, Ioan; Kronewitter, Scott R.; Moore, Ronald J. Analytical Chemistry, Vol. 84, Issue 21 https://doi.org/10.1021/ac301961u	journal	September 2012
The Solvation Structure of Mg Ions in Dichloro Complex Solutions from First-Principles Molecular Dynamics and Simulated X-ray Absorption Spectra Wan, Liwen F.; Prendergast, David Journal of the American Chemical Society, Vol. 136, Issue 41 https://doi.org/10.1021/ja505967u	journal	October 2014
Improved Electrolyte Solutions for Rechargeable Magnesium Batteries Gofer, Yosef; Chusid, Orit; Gizbar, Haim Electrochemical and Solid-State Letters, Vol. 9, Issue 5 https://doi.org/10.1149/1.2186003	journal	January 2006
Electrolytic Conditioning of a Magnesium Aluminum Chloride Complex for Reversible Magnesium Deposition Barile, Christopher J.; Barile, Elizabeth C.; Zavadil, Kevin R. The Journal of Physical Chemistry C, Vol. 118, Issue 48 https://doi.org/10.1021/jp506951b	journal	November 2014
Highly soluble alkoxide magnesium salts for rechargeable magnesium batteries Liao, Chen; Guo, Bingkun; Jiang, De-en J. Mater. Chem. A, Vol. 2, Issue 3 https://doi.org/10.1039/C3TA13691D	journal	January 2014
Coordination Chemistry in magnesium battery electrolytes: how ligands affect their performance Shao, Yuyan; Liu, Tianbiao; Li, Guosheng Scientific Reports, Vol. 3, Issue 1 https://doi.org/10.1038/srep03130	journal	November 2013

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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
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

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