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Title: Probing Electrochemical Mg-Ion Activity in MgCr2–xVxO4 Spinel Oxides

Abstract

Mg migration in oxide spinels is impeded by strong affinity between divalent Mg and oxygen, suggesting a necessity of exploring new chemistry of solid lattices for functional Mg-ion electrode materials. Cationic mobility with a suitable activation energy in Cr spinels is Tn. evidenced by theoretical and experimental results, while redox potentials of V are appropriate to operate with currently limited candidates of '''c" nonaqueous electrolytes. By controlling the structure, composition, and complexity, a largely solid-solution MgCrVO4 spinel was synthesized, which, unlike nanocornposites, can bring together the advantages of each transition metal in the lattice. The spinel was successfully synthesized by a simple solid-state reaction with minor inactive Cr- or V-rich components, which was confirmed via 25Mg MAS NMR and high-resolution X-ray diffraction analyses. A thermally and anodically stable Mg(TPFA)2/triglyme electrolyte was utilized for high-temperature electrochemistry and lowering kinetic barriers at and across interfaces so as to observe intercalation behavior of Mg in the designed lattice. Multimodal characterization confirmed an apparent bulk demagnesiation from MgCrVO4 with partial reversibility by probing evolution of the local and long-range structure as well as vanadium and chromium electronic states within the lattice. Furthermore, characterization experiments also provided a direct evidence for (de)intercalation reactions that occurredmore » without any major competitive conversion reactions or insertion of protons into the lattice, except for the formation of a surface rock salt phase upon charge. These findings in Mg-ion activity expand opportunities to design Mg spinel oxide materials while highlighting the need to identify the origins of reversibility challenges due to, but not limited to, phase stability, particularly for the charged states, barriers at the interface, electrolyte stabilities, and desolvation phenomena, collectively hindering practical use as cathode materials.« less

Authors:
 [1];  [1]; ORCiD logo [1];  [1];  [1];  [2];  [1];  [2]; ORCiD logo [1]; ORCiD logo [1];  [3]; ORCiD logo [3]; ORCiD logo [1];  [1]; ORCiD logo [1]; ORCiD logo [1]
  1. Argonne National Lab. (ANL), Lemont, IL (United States)
  2. Univ. of Illinois at Chicago, IL (United States)
  3. Argonne National Lab. (ANL), Lemont, IL (United States); Univ. of Illinois at Chicago, IL (United States)
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States). Advanced Photon Source (APS)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1604980
Grant/Contract Number:  
AC02-06CH11357
Resource Type:
Accepted Manuscript
Journal Name:
Chemistry of Materials
Additional Journal Information:
Journal Volume: 32; Journal Issue: 3; Journal ID: ISSN 0897-4756
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Spinel; Oxides; Lattices; Electrodes; Electrochemical cells

Citation Formats

Kwon, Bob Jin, Lau, Ka-Cheong, Park, Haesun, Wu, Yimin A., Hawthorne, Krista L., Li, Haifeng, Kim, Soojeong, Bolotin, Igor L., Fister, Timothy T., Zapol, Peter, Klie, Robert F., Cabana, Jordi, Liao, Chen, Lapidus, Saul H., Key, Baris, and Vaughey, John T.. Probing Electrochemical Mg-Ion Activity in MgCr2–xVxO4 Spinel Oxides. United States: N. p., 2019. Web. https://doi.org/10.1021/acs.chemmater.9b04206.
Kwon, Bob Jin, Lau, Ka-Cheong, Park, Haesun, Wu, Yimin A., Hawthorne, Krista L., Li, Haifeng, Kim, Soojeong, Bolotin, Igor L., Fister, Timothy T., Zapol, Peter, Klie, Robert F., Cabana, Jordi, Liao, Chen, Lapidus, Saul H., Key, Baris, & Vaughey, John T.. Probing Electrochemical Mg-Ion Activity in MgCr2–xVxO4 Spinel Oxides. United States. https://doi.org/10.1021/acs.chemmater.9b04206
Kwon, Bob Jin, Lau, Ka-Cheong, Park, Haesun, Wu, Yimin A., Hawthorne, Krista L., Li, Haifeng, Kim, Soojeong, Bolotin, Igor L., Fister, Timothy T., Zapol, Peter, Klie, Robert F., Cabana, Jordi, Liao, Chen, Lapidus, Saul H., Key, Baris, and Vaughey, John T.. Fri . "Probing Electrochemical Mg-Ion Activity in MgCr2–xVxO4 Spinel Oxides". United States. https://doi.org/10.1021/acs.chemmater.9b04206. https://www.osti.gov/servlets/purl/1604980.
@article{osti_1604980,
title = {Probing Electrochemical Mg-Ion Activity in MgCr2–xVxO4 Spinel Oxides},
author = {Kwon, Bob Jin and Lau, Ka-Cheong and Park, Haesun and Wu, Yimin A. and Hawthorne, Krista L. and Li, Haifeng and Kim, Soojeong and Bolotin, Igor L. and Fister, Timothy T. and Zapol, Peter and Klie, Robert F. and Cabana, Jordi and Liao, Chen and Lapidus, Saul H. and Key, Baris and Vaughey, John T.},
abstractNote = {Mg migration in oxide spinels is impeded by strong affinity between divalent Mg and oxygen, suggesting a necessity of exploring new chemistry of solid lattices for functional Mg-ion electrode materials. Cationic mobility with a suitable activation energy in Cr spinels is Tn. evidenced by theoretical and experimental results, while redox potentials of V are appropriate to operate with currently limited candidates of '''c" nonaqueous electrolytes. By controlling the structure, composition, and complexity, a largely solid-solution MgCrVO4 spinel was synthesized, which, unlike nanocornposites, can bring together the advantages of each transition metal in the lattice. The spinel was successfully synthesized by a simple solid-state reaction with minor inactive Cr- or V-rich components, which was confirmed via 25Mg MAS NMR and high-resolution X-ray diffraction analyses. A thermally and anodically stable Mg(TPFA)2/triglyme electrolyte was utilized for high-temperature electrochemistry and lowering kinetic barriers at and across interfaces so as to observe intercalation behavior of Mg in the designed lattice. Multimodal characterization confirmed an apparent bulk demagnesiation from MgCrVO4 with partial reversibility by probing evolution of the local and long-range structure as well as vanadium and chromium electronic states within the lattice. Furthermore, characterization experiments also provided a direct evidence for (de)intercalation reactions that occurred without any major competitive conversion reactions or insertion of protons into the lattice, except for the formation of a surface rock salt phase upon charge. These findings in Mg-ion activity expand opportunities to design Mg spinel oxide materials while highlighting the need to identify the origins of reversibility challenges due to, but not limited to, phase stability, particularly for the charged states, barriers at the interface, electrolyte stabilities, and desolvation phenomena, collectively hindering practical use as cathode materials.},
doi = {10.1021/acs.chemmater.9b04206},
journal = {Chemistry of Materials},
number = 3,
volume = 32,
place = {United States},
year = {2019},
month = {12}
}

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