Synthesis and Mg2+ deintercalation in manganese spinel nanocrystals

Hu, Linhua; Kim, Soojeong; Jokisaari, Jacob R.; Nolis, Gene M.; Yoo, Hyun Deog; Freeland, John W.; Klie, Robert F.; Fister, Tim T.; Cabana, Jordi

doi:10.1016/j.jssc.2022.123464

Title: Synthesis and Mg²⁺ deintercalation in manganese spinel nanocrystals

Journal Article · Tue Aug 02 00:00:00 EDT 2022 · Journal of Solid State Chemistry

DOI:https://doi.org/10.1016/j.jssc.2022.123464· OSTI ID:1961407

Hu, Linhua ^[1]; Kim, Soojeong ^[2]; Jokisaari, Jacob R. ^[3];

^[1];

^[4]; Freeland, John W. ^[5];

^[3]; Fister, Tim T. ^[2];

^[1]

Univ. of Illinois, Chicago, IL (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). Joint Center for Energy Storage Research (JCESR)
Argonne National Lab. (ANL), Argonne, IL (United States). Joint Center for Energy Storage Research (JCESR); Univ. of Illinois, Chicago, IL (United States)
Univ. of Illinois, Chicago, IL (United States); Argonne National Lab. (ANL), Argonne, IL (United States). Joint Center for Energy Storage Research (JCESR); Pusan National Univ., Busan (Korea, Republic of)
Argonne National Lab. (ANL), Argonne, IL (United States). Advanced Photon Source (APS)

Transition metal oxides are promising materials as cathodes for divalent batteries with high capacity under high voltage. A major challenge is the sluggish kinetics of intercalation of divalent cations into the oxide host. Tailoring of the size, composition and crystal structure of oxides is a necessary strategy to alleviate these barriers, which challenges our control of their synthesis. In this work, we selectively synthesize spinel-type Mg_xMn_3-xO₄ nanocrystals with different Mg/Mn ratios and investigate their ability to electrochemically shuttle Mg²⁺ ions. Crystal-chemical characterization of the reaction outcomes was conducted with X-ray diffraction, X-ray absorption spectroscopy, electron microscopy, and elemental analysis. Both 5 nm thick MgMn₂O₄ nanosheets and 10 nm Mg_0.41Mn_2.59O₄ nanocubes underwent reversible Mg²⁺ deintercalation, yet no obvious reaction was observed in 60 nm Mg_1.2Mn_1.8O₄ nanocubes. Our results suggest that both the size of the spinel nanocrystals and the Mg/Mn ratios play a role in the observed behaviour. The advances in the synthesis of spinel oxide nanocrystals achieved, and their correlation with Mg²⁺ deintercalation, pave the way toward the precise synthesis of multivalent cathode materials that fundamentally overcome barriers to practical application.

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

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES); National Research Foundation of Korea (NRF); National Science Foundation (NSF)

Grant/Contract Number:: AC02-06CH11357; NRF-2021R1C1C1005446; NRF-2018R1A5A1025594; DMR-0959470

OSTI ID:: 1961407

Journal Information:: Journal of Solid State Chemistry, Vol. 315; ISSN 0022-4596

Publisher:: ElsevierCopyright Statement

Country of Publication:: United States

Language:: English

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Manganese spinel nanocrystals
Synthesis
Reversible intercalation
High capacity
X-ray absorption spectroscopy

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