Numerical simulations of cyclic voltammetry for lithium-ion intercalation in nanosized systems: finiteness of diffusion
- PDF / 1,565,499 Bytes
- 9 Pages / 595.276 x 790.866 pts Page_size
- 69 Downloads / 201 Views
SHORT COMMUNICATION
Numerical simulations of cyclic voltammetry for lithium-ion intercalation in nanosized systems: finiteness of diffusion versus electrode kinetics E.M. Gavilán-Arriazu 1,2 & M.P. Mercer 3,4,5 & O.A. Pinto 2 & O.A. Oviedo 1 & D.E. Barraco 6 & H.E. Hoster 3,4,5 & E.P.M. Leiva 1 Received: 30 April 2020 / Revised: 5 June 2020 / Accepted: 7 June 2020 # Springer-Verlag GmbH Germany, part of Springer Nature 2020
Abstract The voltammetric behavior of Li+ intercalation/deintercalation in/from LiMn2O4 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 / LiMn2O4 (de)intercalation is also discussed in terms of preexisting modeling.
Introduction Lithium-ion batteries are widely used in small electronic devices and in the automotive industry. Proper design of the materials is a crucial stage for the operation of these types of batteries. In this sense, mathematical models play an important role. To simulate numerical cyclic voltammetry profiles for (de)intercalation of Li+ in LiMn2O4 and LiCoO2 cathodes, Vassiliev et al. [1] have designed a selfconsistent mathematical model, not only suitable for reproducing experimental data, but for predicting kinetic, thermodynamic and transport parameters. This model was
compared and fitted with multi-particle (bulk) experiments using LiMn2O4 and LiCoO2 cathodes in organic solvents and is used here, in the present work, to analyze the behavior of nanosystems. Planar and spherical geometries are approximations generally used to mimic lithium manganese oxide (LMO) thin films, porous electrodes and single particles [2, 3], which are the most common types of electrode material configuration [4–11]. LMO nanorods, which can be compared with a cylindrical geometry, have also been used [12, 13]. Furthermore, LiMn2O4 has the potential to be recycled in a simple way, and reused in layered form as cathode material for Sodium ion batteries [14].
This article is dedicated to Prof. Fritz Scholz on the occasion of his 65th birthday. Es ist ein Vergnügen, mit so einem Chefredakteur zusammenzuarbeiten. * E.M. Gavilán-Arriazu [email protected] * E.P.M. Leiva [email protected] 1
2
Departamento de Química Teórica y Computacional, Facultad de Ciencias Químicas, Universidad Nacional de Córdoba, INFIQC, Córdoba, Argentina Instituto de Bionanotecnología del NOA (INBIONATEC), Universidad Nacional de Santiago del Estero (UNSE), G4206XCP Santiago
Data Loading...
