Room-temperature Na-ion batteries currently attract increasing interest in research and industry, and could have the potential to replace the widely applied Li-ion batteries . However, the energy density of Na-ion batteries is inherently reduced when compared to their respective Li-analogues and extensive research on novel high capacity anode and cathode materials is carried out to compensate for these disadvantages of the sodium chemistry .
Electrochemical alkali-ion exchange techniques are powerful tools to synthesize novel active materials for secondary batteries or to study Li/Na/K analogous intercalation compounds . Herein, we report comprehensive investigations on the electrochemically conducted exchange of Li-ions by Na-ions within the host lattice of layered LiCoO2. Linear sweep and cyclic voltammetry experiments are applied to analyze the Li-Na-substitution behavior and any impact on the electrochemical properties in sodium-ion batteries. The electrochemical measurements are complemented by in-operando X-ray diffraction (XRD) analysis and comprehensive ex-situ material characterization including scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDS), and electron backscatter diffraction (EBSD). We discuss the mechanisms of Li-Na-substitution in LiCoO2 with respect to the different properties of Li and Na-ions and their interactions with the host lattice.
The combination of electrochemical investigations and in-operando materials characterization reveals that the 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 with the formal stoichiometry Li0.5Na0.4CoO2. The different ionic radii of Li and Na-ions 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 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.
 V. Palomares, M. Casas-Cabanas, E. Castillo-Martinez, M.H. Han, T. Rojo, Update on Na-based battery materials. A growing research path, Energy Environ. Sci. 6 (2013) 2312–2337.
 P.K. Nayak, L. Yang, W. Brehm, P. Adelhelm, From Lithium-Ion to Sodium-Ion Batteries: Advantages, Challenges, and Surprises, Angewandte Chemie (International ed. in English) 57 (2018) 102–120.
 C. Heubner, S. Heiden, M. Schneider, A. Michaelis, In-situ preparation and electrochemical characterization of submicron sized NaFePO4 cathode material for sodium-ion batteries, Electrochim. Acta 233 (2017) 78–84.