Direct observation of MgO formation at cathode electrolyte interface of a spinel MgCo2O4 cathode upon electrochemical Mg removal and insertion

Sa, Niya; Mukherjee, Arijita; Han, Binghong; Ren, Yang; Klie, Robert F.; Key, Baris; Vaughey, John T.

doi:10.1016/j.jpowsour.2019.03.102

Title: Direct observation of MgO formation at cathode electrolyte interface of a spinel MgCo₂O₄ cathode upon electrochemical Mg removal and insertion

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Abstract

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.

Authors:

Sa, Niya ^[1]; Mukherjee, Arijita ^[2];

^[3]; Ren, Yang ^[4]; Klie, Robert F. ^[2]; Key, Baris ^[5]; Vaughey, John T. ^[5]

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
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
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)
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:: 2019-06-01

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

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

OSTI Identifier:: 1524066

Alternate Identifier(s):: OSTI ID: 1547571

Grant/Contract Number:: AC02-06CH11357

Resource Type:: 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.

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                    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.  https://doi.org/10.1016/j.jpowsour.2019.03.102

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                    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.  https://doi.org/10.1016/j.jpowsour.2019.03.102.  https://www.osti.gov/servlets/purl/1524066.

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@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},

  number       = C,

  volume       = 424,

  place        = {United States},

  year         = {2019},

  month        = {6}

}

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Title: Direct observation of MgO formation at cathode electrolyte interface of a spinel MgCo2O4 cathode upon electrochemical Mg removal and insertion

Abstract

Citation Formats

Title: Direct observation of MgO formation at cathode electrolyte interface of a spinel MgCo₂O₄ cathode upon electrochemical Mg removal and insertion