Probing Electrochemical Mg-Ion Activity in MgCr_2–xV_xO₄ Spinel Oxides

Journal Article · Fri Dec 27 00:00:00 EST 2019 · Chemistry of Materials

DOI:https://doi.org/10.1021/acs.chemmater.9b04206· OSTI ID:1604980

Kwon, Bob Jin ^[1]; Lau, Ka-Cheong ^[1]; Park, Haesun  ^[1]; Wu, Yimin A. ^[1]; Hawthorne, Krista L. ^[1]; Li, Haifeng ^[2]; Kim, Soojeong ^[1]; Bolotin, Igor L. ^[2]; Fister, Timothy T.  ^[1]; Zapol, Peter  ^[1]; Klie, Robert F. ^[3]; Cabana, Jordi  ^[3]; Liao, Chen  ^[1]; Lapidus, Saul H. ^[1]; Key, Baris  ^[1]; Vaughey, John T.  ^[1]

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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)

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.

• Research Organization: Argonne National Lab. (ANL), Argonne, IL (United States). Advanced Photon Source (APS)
• Sponsoring Organization: USDOE Office of Science (SC), Basic Energy Sciences (BES)
• Grant/Contract Number: AC02-06CH11357
• OSTI ID: 1604980
• Journal Information: Chemistry of Materials, Vol. 32, Issue 3; ISSN 0897-4756
• Publisher: American Chemical Society (ACS)
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Spinel
Oxides
Lattices
Electrodes
Electrochemical cells