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Multivalent Electrochemistry of Spinel MgxMn3–xO4 Nanocrystals

Journal Article · · Chemistry of Materials
 [1];  [2];  [2];  [3];  [3];  [2];  [3];  [4];  [2];  [2];  [2];  [5];  [4];  [3];  [3];  [2]
  1. Univ. of Illinois at Chicago, Chicago, IL (United States); Chungnam National Univ., Daejeon (South Korea); Argonne National Lab. (ANL), Lemont, IL (United States)
  2. Univ. of Illinois at Chicago, Chicago, IL (United States); Argonne National Lab. (ANL), Lemont, IL (United States)
  3. Argonne National Lab. (ANL), Lemont, IL (United States)
  4. Argonne National Lab. (ANL), Lemont, IL (United States); Univ. of Illinois at Chicago, Chicago, IL (United States)
  5. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
+ Show Author Affiliations
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 Mg0.5Mn2.5O4 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.
Research Organization:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
Grant/Contract Number:
AC02-06CH11357
OSTI ID:
1461417
Journal Information:
Chemistry of Materials, Journal Name: Chemistry of Materials Journal Issue: 5 Vol. 30; ISSN 0897-4756
Publisher:
American Chemical Society (ACS)Copyright Statement
Country of Publication:
United States
Language:
English

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Cited By (2)

Tailoring the electrochemical activity of magnesium chromium oxide towards Mg batteries through control of size and crystal structure journal January 2019
Hierarchical porosity via layer-tunnel conversion of macroporous δ-MnO 2 nanosheet assemblies journal January 2020

Figures / Tables (5)

Figure 1(p. 28)figure Figure 1
Figure 2(p. 29)figure Figure 2
Figure 3(p. 30)figure Figure 3
Figure 4(p. 31)figure Figure 4
Figure 5(p. 32)figure Figure 5

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Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Mg2+ intercalation
PDF
multivalent electrochemistry
nanocrystals
spinel-layered transition