Magnesium Insertion and Related Structural Changes in Spinel-Type Manganese Oxides

Crystals

Anna Randon-Vitanova¹  Ana Robba²  Robert Dominko²  Jan Bitenc²  Elena Tchernychova² 

[1] Honda R&D Europe (Deutschland) GmbH, Carl-Legien-Strasse 30, 63073 Offenbach, Germany;National Institute of Chemistry, Hajdrihova 19, 1000 Ljubljana, Slovenia;

关键词: spinel;    manganese;    lithium;    magnesium;    TEM;    electrochemistry;   

DOI  :  10.3390/cryst11080984

来源: DOAJ

【 摘 要 】

Commercial LiMn₂O₄ powder was used as the base material for probing magnesiation, cycling behavior, and structural stability/changes in (Mg_xLi_1-x)Mn₂O₄ spinel cathodes in aqueous Mg(NO₃)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.

【 授权许可】

Unknown