Multivalent Electrochemistry of Spinel MgxMn3–xO4 Nanocrystals

Kim, Chunjoong; Adil, Abdullah A.; Bayliss, Ryan D.; Kinnibrugh, Tiffany L.; Lapidus, Saul H.; Nolis, Gene M.; Freeland, John W.; Phillips, Patrick J.; Yi, Tanghong; Yoo, Hyun Deog; Kwon, Bob Jin; Yu, Young -Sang; Klie, Robert; Chupas, Peter J.; Chapman, Karena W.; Cabana, Jordi

doi:10.1021/acs.chemmater.7b03640

Title: Multivalent Electrochemistry of Spinel Mg_xMn_3–xO₄ Nanocrystals

Journal Article · 20 February 2018 · Chemistry of Materials

DOI: https://doi.org/10.1021/acs.chemmater.7b03640 · OSTI ID:1461417

Kim, Chunjoong ^[1]; Adil, Abdullah A. ^[2]; Bayliss, Ryan D. ^[2]; Kinnibrugh, Tiffany L. ^[3]; Lapidus, Saul H. ^[3]; Nolis, Gene M. ^[2]; Freeland, John W. ^[3]; Phillips, Patrick J. ^[4]; Yi, Tanghong ^[2];

^[2]; Kwon, Bob Jin ^[2]; Yu, Young -Sang ^[5]; Klie, Robert ^[4]; Chupas, Peter J. ^[3];

^[3];

^[2]

Univ. of Illinois at Chicago, Chicago, IL (United States); Chungnam National Univ., Daejeon (South Korea); Argonne National Lab. (ANL), Lemont, IL (United States)
Univ. of Illinois at Chicago, Chicago, IL (United States); Argonne National Lab. (ANL), Lemont, IL (United States)
Argonne National Lab. (ANL), Lemont, IL (United States)
Argonne National Lab. (ANL), Lemont, IL (United States); Univ. of Illinois at Chicago, Chicago, IL (United States)
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)

Oxides undergoing reversible electrochemical cycling of Mg²⁺ ions would enable novel battery concepts beyond Li⁺, capable of storing large amounts of energy. However, materials showing this chemical reactivity are scarce. Suitable candidates require small particles to shorten transport lengths, together with chemically complex structures that promote cation mobility, such as spinel. These goals pose a challenge for materials chemists. Here, nanocrystals of spinel-type Mg_0.5Mn_2.5O₄ were prepared using colloidal synthesis, and their electrochemical activity is presented. Cycling in an aqueous Mg²⁺ electrolyte led to a reversible transformation between a reduced spinel and an oxidized layered framework. This reaction involves large amounts of capacity because of the full oxidation to Mn⁴⁺, through the extraction of both Mg²⁺ and, in the first cycle, Mn²⁺ ions. Re-formation of the spinel upon reduction resulted in enrichment with Mg²⁺, indicating that its insertion is more favorable than that of Mn²⁺. Incorporation of water into the structure was not indispensable for the transformation, as revealed by experiments in non-aqueous electrolytes and infrared spectroscopy. Lastly, the findings open the door for the use of similar nanocrystals in Mg batteries provided that electrolytes with suitable anodic stability are discovered, thereby identifying novel routes toward electrode materials for batteries with high energy.

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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)

Grant/Contract Number:: AC02-06CH11357

OSTI ID:: 1461417

Journal Information:: Chemistry of Materials, Vol. 30, Issue 5; ISSN 0897-4756

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 21 works

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