Ana Robba (Author), Elena Tchernychova (Author), Jan Bitenc (Author), Anna Randon-Vitanova (Author), Robert Dominko (Author)

Abstract

Commercial LiMn$_2$O$_4$ powder was used as the base material for probing magnesiation, cycling behavior, and structural stability/changes in (Mg$_x$Li$_{1-x}$)Mn$_2$O$_4$ spinel cathodes in aqueous Mg(NO$_3$)$_2$ and non-aqueous Mg(TFSI)$_2$/diglyme and Mg(Mg(HFIP)$_2$ − 2Al(HFIP)$_3$/diglyme electrolytes. Each of the samples was delithiated and, then, magnesiated electrochemically in the corresponding electrolyte. The electrochemical activity of the cathode cycled in aqueous electrolyte showed high reversibility during the oxidation process; however, large polarization and a relatively fast capacity fading were the culprits of the system. Cycling in Mg(TFSI)2/diglyme electrolyte solution resulted in much lower initial specific capacity compared to an aqueous counterpart, as well as a much faster failure. On the other hand, cycling in Mg(HFIP)$_2$ − 2Al(HFIP)$_3$/diglyme electrolyte solution demonstrated excellent cycling performance with very low polarization in the first cycles. The observed voltages for this system were near theoretical values for the Mg insertion. Although the electrochemical measurements suggest reversible magnesiation, detailed structural and analytical STEM investigation revealed the differences in the atomic structure and Mn valence of all three cathode samples upon cycling. The electrolytes’ influence on the structural rearrangement during Mg insertion is discussed for each of the three systems.

Keywords

spinel;mangan;litij;magnezij;TEM;elektrokemija;manganese;lithium;magnesium;electrochemistry;

Data

Language: English
Year of publishing:
Typology: 1.01 - Original Scientific Article
Organization: UL FKKT - Faculty of Chemistry and Chemical Technology
UDC: 544.1:544.6
COBISS: 78444291 Link will open in a new window
ISSN: 2073-4352
Views: 92
Downloads: 30
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Other data

Secondary language: Slovenian
Secondary keywords: spinel;mangan;litij;magnezij;TEM;elektrokemija;
Type (COBISS): Article
Pages: str. 1-12
Volume: ǂVol. ǂ11
Issue: ǂiss. ǂ8
Chronology: Aug. 2021
DOI: 10.3390/cryst11080984
ID: 14956870