Numerical simulations of cyclic voltammetry for lithium-ion intercalation in nanosized systems: finiteness of diffusion versus electrode kinetics

• Published in: Journal of solid state electrochemistry Vol. 24; no. 11-12; pp. 3279 - 3287
• Main Authors: Gavilán-Arriazu, E.M., Mercer, M.P., Pinto, O.A., Oviedo, O.A., Barraco, D.E., Hoster, H.E., Leiva, E.P.M.
• Format: Journal Article
• Language: English
• Published: Berlin/Heidelberg Springer Berlin Heidelberg 01-11-2020; Springer Nature B.V
• Subjects: Analytical Chemistry; Characterization and Evaluation of Materials; Chemistry; Chemistry and Materials Science; Computer simulation; Condensed Matter Physics; Diffusion; Electrochemistry; Electrodes; Energy Storage; Intercalation; Kinetics; Lithium ions; Lithium manganese oxides; Mathematical models; Nanoparticles; Physical Chemistry; Short Communication; Thin films; Voltammetry
• ISSN: 1432-8488; 1433-0768
• DOI: 10.1007/s10008-020-04717-9

The voltammetric behavior of Li
+
intercalation/deintercalation in/from LiMn
2
O
4
thin films and single particles is simulated, supporting very recent experimental results. Experiments and calculations both show that particle size and geometry are crucial for the electrochemical response. A remarkable outcome of this research is that higher potential sweep rates, of the order of several millivolts per second, may be used to characterize nanoparticles by voltammetry sweeps, as compared with macroscopic systems. This is in line with previous conclusions drawn for related single particle systems using kinetic Monte Carlo simulations. The impact of electrode kinetics and finite space diffusion on the reversibility of the process and the finiteness of the diffusion in ion Li / LiMn
2
O
4
(de)intercalation is also discussed in terms of preexisting modeling.