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Insights into the electrochemical Li/Na-exchange in layered LiCoO2 cathode material

 
: Heubner, Christian; Matthey, Björn; Lein, Tobias; Wolke, Florian; Liebmann, Tobias; Lämmel, Christoph; Schneider, Michael; Herrmann, Mathias; Michaelis, Alexander

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Energy storage materials 27 (2020), S.377-386
ISSN: 2405-8297
Sächsische Aufbaubank - Förderbank SAB
EFRE; 100345904; NaKaSub
Englisch
Zeitschriftenaufsatz
Fraunhofer IKTS ()
sodium-ion; battery; Lithium Ion; exchange; substitution; cathode

Abstract
The electrochemical alkali ion exchange is a powerful technique to synthesize novel active materials for secondary batteries or to study Li/Na/K analogous intercalation compounds. Herein, we report for the first time the electrochemically conducted exchange of Li-ions by Na-ions within the host lattice of LiCoO2. Li-Na substitution in a potential range of 2.0 – 4.0 V vs Na/Na+ leads to the formation of a Li-Na-mixed intercalation compound. In-operando XRD measurements and ex-situ EDS-mappings indicate that the different ionic radii and the corresponding CoO2-layer distances forbid Li-Na mixing in the lattice, resulting in the emergence of Na- and Li-rich domains during Na-ion insertion. Charging and discharging of the resulting Li-Na-mixed intercalation compound is dominated by Na-insertion and extraction, while Li-ions remain in the lattice until it is completely depleted of Na-ions. These novel insights concerning competitive kinetics, thermodynamics and phase evolution behavior can be highly useful to understand similarities and differences of Na- and Li-insertion chemistries to develop materials for future Na-ion batteries based on the comprehensive scientific knowledge in Li-ion technology.

: http://publica.fraunhofer.de/dokumente/N-582137.html