A Simple Halogen-Free Magnesium Electrolyte for Reversible Magnesium Deposition through Cosolvent Assistance

Fan, Shengqi; Asselin, Genevieve M.; Pan, Baofei; Wang, Hao; Ren, Yang; Vaughey, John T.; Sa, Niya

doi:10.1021/acsami.9b18833

Title: A Simple Halogen-Free Magnesium Electrolyte for Reversible Magnesium Deposition through Cosolvent Assistance

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Abstract

Rechargeable Mg batteries are one of the most investigated polyvalent-metal storage batteries owing to the increased safety associated with the nondendritic nature of Mg electrodeposition, high volumetric capacity, and low cost. To realize the commercial applications of Mg batteries, there are still a number of challenges remaining unsolved, in particular, the lack of halogen free Mg electrolytes, as the use of the halogens remains a major limiting factor to achieving high voltage cathodes. The research presented here introduces an innovative approach to prepare a halogen-free Mg-based electrolyte in a simple, nonsynthetic method that can plate and strip Mg reversibly. Results suggest that by introducing a secondary amine cosolvent the magnesium bis(trifluoromethanesulfonyl)imide (Mg(TFSI)₂) salt can be easily dissolved into a wide array of polar but aprotic ether solvents. A systematic structural investigation of a representative Mg(TFSI)₂ electrolyte in the cosolvent systems with the secondary amine was performed using pair distribution function (PDF) analysis, single crystal diffraction analysis, and NMR. The experimental atomic scale understanding reveals an ion pair structure of Mg²⁺ coordinated with six oxygen donors from the bis(trifluoromethanesulfonyl)imide (TFSI) anions and the THF solvent located in the first solvation shell. The as-formed neutral ion pair structure acts as the activemore »« less

Authors:

Fan, Shengqi ^[1]; Asselin, Genevieve M. ^[1]; Pan, Baofei ^[2];

^[2];

^[3];

^[2];

^[1]

Univ. of Massachusetts, Boston, MA (United States)
Argonne National Lab. (ANL), Argonne, IL (United States). Chemical Sciences and Engineering Division
Argonne National Lab. (ANL), Argonne, IL (United States). Advanced Photon Source (APS)

Publication Date:: Thu Jan 30 00:00:00 EST 2020

Research Org.:: Argonne National Lab. (ANL), Argonne, IL (United States)

Sponsoring Org.:: USDOE Office of Science (SC), Basic Energy Sciences (BES); National Science Foundation (NSF)

OSTI Identifier:: 1632168

Grant/Contract Number:: AC02-06CH11357; 1919919

Resource Type:: Accepted Manuscript

Journal Name:: ACS Applied Materials and Interfaces

Additional Journal Information:: Journal Volume: 12; Journal Issue: 9; Journal ID: ISSN 1944-8244

Publisher:: American Chemical Society (ACS)

Country of Publication:: United States

Language:: English

Subject:: 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; electrolyte; magnesium; energy storage; rechargeable Mg battery; Mg electrolyte; reversible Mg deposition; non-halogen Mg electrolyte

Citation Formats


                    Fan, Shengqi, Asselin, Genevieve M., Pan, Baofei, Wang, Hao, Ren, Yang, Vaughey, John T., and Sa, Niya. A Simple Halogen-Free Magnesium Electrolyte for Reversible Magnesium Deposition through Cosolvent Assistance.  United States: N. p., 2020. 
Web.  doi:10.1021/acsami.9b18833.

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                    Fan, Shengqi, Asselin, Genevieve M., Pan, Baofei, Wang, Hao, Ren, Yang, Vaughey, John T., & Sa, Niya. A Simple Halogen-Free Magnesium Electrolyte for Reversible Magnesium Deposition through Cosolvent Assistance.  United States.  https://doi.org/10.1021/acsami.9b18833

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                    Fan, Shengqi, Asselin, Genevieve M., Pan, Baofei, Wang, Hao, Ren, Yang, Vaughey, John T., and Sa, Niya. Thu .  
"A Simple Halogen-Free Magnesium Electrolyte for Reversible Magnesium Deposition through Cosolvent Assistance".  United States.  https://doi.org/10.1021/acsami.9b18833.  https://www.osti.gov/servlets/purl/1632168.

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@article{osti_1632168,

  title        = {A Simple Halogen-Free Magnesium Electrolyte for Reversible Magnesium Deposition through Cosolvent Assistance},

  author       = {Fan, Shengqi and Asselin, Genevieve M. and Pan, Baofei and Wang, Hao and Ren, Yang and Vaughey, John T. and Sa, Niya},

  abstractNote = {Rechargeable Mg batteries are one of the most investigated polyvalent-metal storage batteries owing to the increased safety associated with the nondendritic nature of Mg electrodeposition, high volumetric capacity, and low cost. To realize the commercial applications of Mg batteries, there are still a number of challenges remaining unsolved, in particular, the lack of halogen free Mg electrolytes, as the use of the halogens remains a major limiting factor to achieving high voltage cathodes. The research presented here introduces an innovative approach to prepare a halogen-free Mg-based electrolyte in a simple, nonsynthetic method that can plate and strip Mg reversibly. Results suggest that by introducing a secondary amine cosolvent the magnesium bis(trifluoromethanesulfonyl)imide (Mg(TFSI)2) salt can be easily dissolved into a wide array of polar but aprotic ether solvents. A systematic structural investigation of a representative Mg(TFSI)2 electrolyte in the cosolvent systems with the secondary amine was performed using pair distribution function (PDF) analysis, single crystal diffraction analysis, and NMR. The experimental atomic scale understanding reveals an ion pair structure of Mg2+ coordinated with six oxygen donors from the bis(trifluoromethanesulfonyl)imide (TFSI) anions and the THF solvent located in the first solvation shell. The as-formed neutral ion pair structure acts as the active component for reversible Mg deposition. We believe this new route of preparing Mg electrolytes can extend the current understanding of Mg electrolyte functionality for rechargeable Mg batteries and offers more guidance for the future electrolyte design.},

  doi          = {10.1021/acsami.9b18833},

  journal      = {ACS Applied Materials and Interfaces},

  number       = 9,

  volume       = 12,

  place        = {United States},

  year         = {Thu Jan 30 00:00:00 EST 2020},

  month        = {Thu Jan 30 00:00:00 EST 2020}

}

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