Facile Electrochemical Mg-Ion Transport in a Defect-Free Spinel Oxide

Kwon, Bob Jin; Yin, Liang; Roy, Indrani; Leon, Noel J.; Kumar, Khagesh; Kim, Jae Jin; Han, Jinhyup; Gim, Jihyeon; Liao, Chen; Lapidus, Saul H.; Cabana, Jordi; Key, Baris

doi:10.1021/acs.chemmater.2c00237

Facile Electrochemical Mg-Ion Transport in a Defect-Free Spinel Oxide

Journal Article · Thu Apr 07 00:00:00 EDT 2022 · Chemistry of Materials

DOI:https://doi.org/10.1021/acs.chemmater.2c00237· OSTI ID:1879893

^[1]; Yin, Liang ^[1]; Roy, Indrani ^[2]; Leon, Noel J. ^[1]; Kumar, Khagesh ^[2]; ^[1]; Han, Jinhyup ^[1]; Gim, Jihyeon ^[1]; ^[1]; ^[1]; ^[3]; ^[1]

Argonne National Lab. (ANL), Lemont, IL (United States)
Univ. of Illinois, Chicago, IL (United States)
Argonne National Lab. (ANL), Lemont, IL (United States); Univ. of Illinois, Chicago, IL (United States)

Inversion, i.e. Mg/Mn antisite disorder, in a spinel oxide simultaneously causes blockage of favorable Mg²⁺ migration paths, raising activation barriers for diffusion, and it reduces the number of redox-active metals, limiting the maximum capacity in the spinel. Here, an inversion-free spinel, MgCr_1.5Mn_0.5O₄, was synthesized by exploiting the different intrinsic crystal field stabilization of redox-active Cr and Mn in the form of a solid-solution. The capability of the tailored spinel to reversibly (de)intercalate Mg²⁺ at high redox potentials was investigated. The decrease in inversion dramatically lowered the electrochemical overpotential and hysteresis, and enabled utilization of high potentials at ~2.9 V (vs. Mg/Mg²⁺) upon re-intercalation of Mg²⁺. A combination of characterization techniques reveals that the structural, compositional, and redox changes within the spinel oxide were consistent with the observed electrochemical Mg²⁺ activity. Quantification of selective solely to lattice Mg²⁺ upon the electrochemical reaction was investigated by monitoring NMR signals in isotope ²⁵Mg-enriched spinel oxides. Our findings enhance the understanding of Mg²⁺ transport within spinel oxide frameworks and provide conclusive evidence for bulk Mg migration in oxide lattices at high redox potentials with minimized electrochemical hysteresis.

View Accepted Manuscript (DOE)

Research Organization:: Argonne National Laboratory (ANL), Argonne, IL (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Joint Center for Energy Storage Research (JCESR); National Science Foundation (NSF); Brookhaven National Laboratory (BNL)

Grant/Contract Number:: AC02-06CH11357; SC0012704

OSTI ID:: 1879893

Journal Information:: Chemistry of Materials, Journal Name: Chemistry of Materials Journal Issue: 8 Vol. 34; ISSN 0897-4756

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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