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Title: Reversible Electrochemical Interface of Mg Metal and Conventional Electrolyte Enabled by Intermediate Adsorption

Abstract

Conventional electrolytes made by mixing simple Mg salts and aprotic solvents, analogous to those in Li-ion batteries, are incompatible with Mg anodes because Mg metal readily reacts with such electrolytes, producing a passivation layer that blocks Mg transport. Here, we report that, through tuning a conventional electrolyte - Mg(TFSI) (TFSI is N(SO CF ) ) - with an Mg(BH ) cosalt, highly reversible Mg plating/stripping with a high Coulombic efficiency is achieved by neutralizing the first solvation shell of Mg cationic clusters between Mg and TFSI and enhanced reductive stability of free TFSI . A critical adsorption step between Mg atoms and active Mg cation clusters involving BH anions is identified to be the key enabler for reversible Mg plating/stripping through analysis of the distribution of relaxation times (DRT) from operando electrochemical impedance spectroscopy (EIS), operando electrochemical X-ray absorption spectroscopy (XAS), nuclear magnetic resonance (NMR), and density functional theory (DFT) calculations. 2+ 2+ - - 2+ - - 0 - 2 2 3 2 4 2 4

Authors:
ORCiD logo [1];  [2];  [1]; ORCiD logo [2]; ORCiD logo [1]; ORCiD logo [3]; ORCiD logo [4]; ORCiD logo [1]; ORCiD logo [3];  [5];  [5];  [5];  [4]; ORCiD logo [5]; ORCiD logo [4];  [6]; ORCiD logo [5]; ORCiD logo [5]; ORCiD logo [7]; ORCiD logo [2] more »; ORCiD logo [8]; ORCiD logo [1]; ORCiD logo [5] « less
  1. Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Joint Center for Energy Storage Research (JCESR), Lemont, IL (United States)
  2. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Advanced Light Source (ALS); Joint Center for Energy Storage Research (JCESR), Lemont, IL (United States)
  3. Argonne National Lab. (ANL), Lemont, IL (United States); Joint Center for Energy Storage Research (JCESR), Lemont, IL (United States)
  4. Pacific Northwest National Lab. (PNNL), Richland, WA (United States). Environmental Molecular Sciences Lab. (EMSL)
  5. Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
  6. Joint Center for Energy Storage Research (JCESR), Lemont, IL (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Univ. of California, Berkeley, CA (United States)
  7. Joint Center for Energy Storage Research (JCESR), Lemont, IL (United States); Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
  8. Sandia National Lab. (SNL-NM), Albuquerque, NM (United States); Joint Center for Energy Storage Research (JCESR), Lemont, IL (United States)
Publication Date:
Research Org.:
Sandia National Lab. (SNL-NM), Albuquerque, NM (United States); Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Argonne National Lab. (ANL), Argonne, IL (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1639082
Alternate Identifier(s):
OSTI ID: 1638713; OSTI ID: 1780735
Report Number(s):
SAND-2020-6649J; PNNL-SA-144809
Journal ID: ISSN 2380-8195; 687020
Grant/Contract Number:  
AC04-94AL85000; AC05-76RL01830; AC02-06CH11357; AC02-05CH11231
Resource Type:
Accepted Manuscript
Journal Name:
ACS Energy Letters
Additional Journal Information:
Journal Volume: 5; Journal Issue: 1; Journal ID: ISSN 2380-8195
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Interfaces; adsorption; electrodeposition; cluster chemistry; electrolytes

Citation Formats

Wang, Hui, Feng, Xuefei, Chen, Ying, Liu, Yi-Sheng, Han, Kee Sung, Zhou, Mingxia, Engelhard, Mark H., Murugesan, Vijayakumar, Assary, Rajeev S., Liu, Tianbiao Leo, Henderson, Wesley, Nie, Zimin, Gu, Meng, Xiao, Jie, Wang, Chongmin, Persson, Kristin, Mei, Donghai, Zhang, Ji-Guang, Mueller, Karl T., Guo, Jinghua, Zavadil, Kevin, Shao, Yuyan, and Liu, Jun. Reversible Electrochemical Interface of Mg Metal and Conventional Electrolyte Enabled by Intermediate Adsorption. United States: N. p., 2019. Web. https://doi.org/10.1021/acsenergylett.9b02211.
Wang, Hui, Feng, Xuefei, Chen, Ying, Liu, Yi-Sheng, Han, Kee Sung, Zhou, Mingxia, Engelhard, Mark H., Murugesan, Vijayakumar, Assary, Rajeev S., Liu, Tianbiao Leo, Henderson, Wesley, Nie, Zimin, Gu, Meng, Xiao, Jie, Wang, Chongmin, Persson, Kristin, Mei, Donghai, Zhang, Ji-Guang, Mueller, Karl T., Guo, Jinghua, Zavadil, Kevin, Shao, Yuyan, & Liu, Jun. Reversible Electrochemical Interface of Mg Metal and Conventional Electrolyte Enabled by Intermediate Adsorption. United States. https://doi.org/10.1021/acsenergylett.9b02211
Wang, Hui, Feng, Xuefei, Chen, Ying, Liu, Yi-Sheng, Han, Kee Sung, Zhou, Mingxia, Engelhard, Mark H., Murugesan, Vijayakumar, Assary, Rajeev S., Liu, Tianbiao Leo, Henderson, Wesley, Nie, Zimin, Gu, Meng, Xiao, Jie, Wang, Chongmin, Persson, Kristin, Mei, Donghai, Zhang, Ji-Guang, Mueller, Karl T., Guo, Jinghua, Zavadil, Kevin, Shao, Yuyan, and Liu, Jun. Wed . "Reversible Electrochemical Interface of Mg Metal and Conventional Electrolyte Enabled by Intermediate Adsorption". United States. https://doi.org/10.1021/acsenergylett.9b02211. https://www.osti.gov/servlets/purl/1639082.
@article{osti_1639082,
title = {Reversible Electrochemical Interface of Mg Metal and Conventional Electrolyte Enabled by Intermediate Adsorption},
author = {Wang, Hui and Feng, Xuefei and Chen, Ying and Liu, Yi-Sheng and Han, Kee Sung and Zhou, Mingxia and Engelhard, Mark H. and Murugesan, Vijayakumar and Assary, Rajeev S. and Liu, Tianbiao Leo and Henderson, Wesley and Nie, Zimin and Gu, Meng and Xiao, Jie and Wang, Chongmin and Persson, Kristin and Mei, Donghai and Zhang, Ji-Guang and Mueller, Karl T. and Guo, Jinghua and Zavadil, Kevin and Shao, Yuyan and Liu, Jun},
abstractNote = {Conventional electrolytes made by mixing simple Mg salts and aprotic solvents, analogous to those in Li-ion batteries, are incompatible with Mg anodes because Mg metal readily reacts with such electrolytes, producing a passivation layer that blocks Mg transport. Here, we report that, through tuning a conventional electrolyte - Mg(TFSI) (TFSI is N(SO CF ) ) - with an Mg(BH ) cosalt, highly reversible Mg plating/stripping with a high Coulombic efficiency is achieved by neutralizing the first solvation shell of Mg cationic clusters between Mg and TFSI and enhanced reductive stability of free TFSI . A critical adsorption step between Mg atoms and active Mg cation clusters involving BH anions is identified to be the key enabler for reversible Mg plating/stripping through analysis of the distribution of relaxation times (DRT) from operando electrochemical impedance spectroscopy (EIS), operando electrochemical X-ray absorption spectroscopy (XAS), nuclear magnetic resonance (NMR), and density functional theory (DFT) calculations. 2+ 2+ - - 2+ - - 0 - 2 2 3 2 4 2 4},
doi = {10.1021/acsenergylett.9b02211},
journal = {ACS Energy Letters},
number = 1,
volume = 5,
place = {United States},
year = {2019},
month = {12}
}

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