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Title: Direct observation of MgO formation at cathode electrolyte interface of a spinel MgCo 2O 4 cathode upon electrochemical Mg removal and insertion

Abstract

Identifying a Mg 2+ insertion mechanism into Mg cathode is one crucial challenge of designing Mg batteries that own comparable specific energy to the lithium ion systems. Spinel Mg cathodes are attractive candidates mainly attributed to its high intercalation voltage and theoretical capacity, however, electrochemically removing Mg from its solid structure with identified capacity dedicated to actual reversible Mg intercalation introduce complications. Work presented here applies Scanning/Transmission Electron Microscopy with Energy Loss Spectroscopy and diffraction method to investigate the cathode electrolyte interface for a spinel MgCo 2O 4 material electrochemically cycled in the presence of a non-aqueous, low water content Mg electrolyte. Findings at an atomic scale suggest a complete de-magnesiation is occurring for thin MgCo 2O 4 particles upon electrochemical charging, but a vast majority of MgCo 2O 4 shows formation of an amorphous MgO layer with a thickness of similar to ~10 nm at the cathode electrolyte interface. The amorphous MgO layer is directly jointed with the crystalline MgCo 2O 4 at the outer edge of the cathode. Formation of MgO at the cathode electrolyte interface is believed to be the detrimental factor preventing further electrochemical cell cycling of MgCo 2O 4. A possible reaction pathway of intercalation-initiatedmore » surface conversion is proposed to explain reversible Mg insertion with MgCo 2O 4.« less

Authors:
 [1];  [2]; ORCiD logo [3];  [4];  [2];  [5];  [5]
  1. Univ. of Massachusetts, Boston, MA (United States); Argonne National Lab. (ANL), Argonne, IL (United States). Joint Center for Energy Storage Research (JCESR); Argonne National Lab. (ANL), Argonne, IL (United States). Chemical Sciences and Engineering Division
  2. Argonne National Lab. (ANL), Argonne, IL (United States). Joint Center for Energy Storage Research (JCESR); Univ. of Illinois, Chicago, IL (United States). Dept. of Physics
  3. Argonne National Lab. (ANL), Argonne, IL (United States). Chemical Sciences and Engineering Division
  4. Argonne National Lab. (ANL), Argonne, IL (United States). Advanced Photon Source (APS)
  5. Argonne National Lab. (ANL), Argonne, IL (United States). Joint Center for Energy Storage Research (JCESR); Argonne National Lab. (ANL), Argonne, IL (United States). Chemical Sciences and Engineering Division
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1524066
Alternate Identifier(s):
OSTI ID: 1547571
Grant/Contract Number:  
AC02-06CH11357
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Journal of Power Sources
Additional Journal Information:
Journal Volume: 424; Journal Issue: C; Journal ID: ISSN 0378-7753
Publisher:
Elsevier
Country of Publication:
United States
Language:
English
Subject:
25 ENERGY STORAGE; magnesium; spinel; cathode; STEM

Citation Formats

Sa, Niya, Mukherjee, Arijita, Han, Binghong, Ren, Yang, Klie, Robert F., Key, Baris, and Vaughey, John T. Direct observation of MgO formation at cathode electrolyte interface of a spinel MgCo2O4 cathode upon electrochemical Mg removal and insertion. United States: N. p., 2019. Web. doi:10.1016/j.jpowsour.2019.03.102.
Sa, Niya, Mukherjee, Arijita, Han, Binghong, Ren, Yang, Klie, Robert F., Key, Baris, & Vaughey, John T. Direct observation of MgO formation at cathode electrolyte interface of a spinel MgCo2O4 cathode upon electrochemical Mg removal and insertion. United States. doi:10.1016/j.jpowsour.2019.03.102.
Sa, Niya, Mukherjee, Arijita, Han, Binghong, Ren, Yang, Klie, Robert F., Key, Baris, and Vaughey, John T. Sat . "Direct observation of MgO formation at cathode electrolyte interface of a spinel MgCo2O4 cathode upon electrochemical Mg removal and insertion". United States. doi:10.1016/j.jpowsour.2019.03.102. https://www.osti.gov/servlets/purl/1524066.
@article{osti_1524066,
title = {Direct observation of MgO formation at cathode electrolyte interface of a spinel MgCo2O4 cathode upon electrochemical Mg removal and insertion},
author = {Sa, Niya and Mukherjee, Arijita and Han, Binghong and Ren, Yang and Klie, Robert F. and Key, Baris and Vaughey, John T.},
abstractNote = {Identifying a Mg2+ insertion mechanism into Mg cathode is one crucial challenge of designing Mg batteries that own comparable specific energy to the lithium ion systems. Spinel Mg cathodes are attractive candidates mainly attributed to its high intercalation voltage and theoretical capacity, however, electrochemically removing Mg from its solid structure with identified capacity dedicated to actual reversible Mg intercalation introduce complications. Work presented here applies Scanning/Transmission Electron Microscopy with Energy Loss Spectroscopy and diffraction method to investigate the cathode electrolyte interface for a spinel MgCo2O4 material electrochemically cycled in the presence of a non-aqueous, low water content Mg electrolyte. Findings at an atomic scale suggest a complete de-magnesiation is occurring for thin MgCo2O4 particles upon electrochemical charging, but a vast majority of MgCo2O4 shows formation of an amorphous MgO layer with a thickness of similar to ~10 nm at the cathode electrolyte interface. The amorphous MgO layer is directly jointed with the crystalline MgCo2O4 at the outer edge of the cathode. Formation of MgO at the cathode electrolyte interface is believed to be the detrimental factor preventing further electrochemical cell cycling of MgCo2O4. A possible reaction pathway of intercalation-initiated surface conversion is proposed to explain reversible Mg insertion with MgCo2O4.},
doi = {10.1016/j.jpowsour.2019.03.102},
journal = {Journal of Power Sources},
issn = {0378-7753},
number = C,
volume = 424,
place = {United States},
year = {2019},
month = {6}
}

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