Електрохімія літій-манганової шпінелі, модифікованої церієм, в апротонному та водному електролітах

Yu. V. Shmatok; N. I. Globa; V. A. Sirosh; I. V. Romanova

doi:10.15407/hftp16.02.222

Authors

Yu. V. Shmatok V.I. Vernadsky Institute of General and Inorganic Chemistry of National Academy of Sciences of Ukraine / Institute for Sorption and Problems of Endoecology of National Academy of Sciences of Ukraine
N. I. Globa V.I. Vernadsky Institute of General and Inorganic Chemistry of National Academy of Sciences of Ukraine / Institute for Sorption and Problems of Endoecology of National Academy of Sciences of Ukraine
V. A. Sirosh V.I. Vernadsky Institute of General and Inorganic Chemistry of National Academy of Sciences of Ukraine / Institute for Sorption and Problems of Endoecology of National Academy of Sciences of Ukraine
I. V. Romanova Institute for Sorption and Problems of Endoecology of National Academy of Sciences of Ukraine

DOI:

https://doi.org/10.15407/hftp16.02.222

Keywords:

lithium-manganese spinel, doping, surface modification, aprotic electrolyte, aqueous electrolyte, specific capacity, kinetics, electrochemical extraction of lithium

Abstract

Modification of the structure and surface of spinel LiMn₂O₄ with metal ions is an effective way to improve its electrochemical characteristics. The paper examines the effect of doping with cerium ions on the structural and surface characteristics of spinels LiCe_xMn_2-xO₄ (х = 0, 0.01, 0.05 and 0.1), as well as their capacitive and cyclic characteristics in systems with aprotic and aqueous electrolytes. Using the X-ray diffraction method, it has been found that only a small part of cerium ions is incorporated into the spinel structure, and the excess cerium crystallizes in the form of a separate CeO₂ phase. According to the data of scanning electron microscopy, the CeO₂ phase exists in the form of individual non-agglomerated particles with a size of several tens of nanometers, which are in direct contact with spinel particles of 100–300 nm in size. Cyclic voltammetry and galvanostatic cycling methods were used to determine the specific, cyclic and kinetic characteristics of the synthesized materials in aprotic (1M LiPF₆ in a mixture of ethylene carbonate:dimethyl carbonate:diethyl carbonate) and aqueous (5M LiNO₃ in H₂O) electrolytes. It is shown that the specific capacity of spinels depends on both the composition of the spinel itself and the type of electrochemical system. Depending on the spinel composition, the initial specific capacity in the aprotic system is 100–121 mA·h/g and 81–103 mA·h/g in the aqueous system. The obtained results demonstrate the overall positive effect of the structural and surface modification of spinel by cerium ions on its electrochemical behavior. Based on cyclic voltammetry data, a comparison of the kinetic characteristics of the studied spinel samples in aprotic and aqueous electrochemical systems was carried out, for which the lithium diffusion coefficient was calculated and the controlling mechanism of the electrochemical reaction was determined. A possibility of using synthesized spinel samples as materials for the electrochemical extraction of lithium from aqueous solutions is shown.

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