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

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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.

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Acknowledgments

E.P.M. Leiva acknowledges grants PIP CONICET 11220150100624CO, PUE/2017 CONICET, FONCYT PICT-2015-1605 and SECyT of the Universidad Nacional de Córdoba. Support by CCAD-UNC and GPGPU Computing Group, Y-TEC and an IPAC grant from SNCAD-MinCyT, Argentina, are also gratefully acknowledged. M.P. Mercer and H.E. Hoster thank the Faraday Institution (faraday.ac.uk; EP/S003053/1), grant number FIRG003, for funding.

Author information

Authors and Affiliations

  1. Departamento de Química Teórica y Computacional, Facultad de Ciencias Químicas, Universidad Nacional de Córdoba, INFIQC, Córdoba, Argentina

    E.M. Gavilán-Arriazu, O.A. Oviedo & E.P.M. Leiva

  2. Instituto de Bionanotecnología del NOA (INBIONATEC), Universidad Nacional de Santiago del Estero (UNSE), G4206XCP, Santiago del Estero, Argentina

    E.M. Gavilán-Arriazu & O.A. Pinto

  3. Department of Chemistry, Lancaster University, Bailrigg, Lancaster, UK

    M.P. Mercer & H.E. Hoster

  4. ALISTORE European Research Institute CNRS FR 3104, Hub de l’Energie, 80039, Amiens, France

    M.P. Mercer & H.E. Hoster

  5. The Faraday Institution, Harwell Science and Innovation Campus, Didcot, UK

    M.P. Mercer & H.E. Hoster

  6. Facultad de Matemática, Astronomía y Física, IFEG-CONICET, Universidad Nacional de Córdoba, Córdoba, Argentina

    D.E. Barraco

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  1. E.M. Gavilán-Arriazu
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  2. M.P. Mercer
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  3. O.A. Pinto
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  4. O.A. Oviedo
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  5. D.E. Barraco
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  6. H.E. Hoster
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  7. E.P.M. Leiva
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Correspondence to E.M. Gavilán-Arriazu or E.P.M. Leiva.

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This article is dedicated to Prof. Fritz Scholz on the occasion of his 65th birthday. Es ist ein Vergnügen, mit so einem Chefredakteur zusammenzuarbeiten.

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Gavilán-Arriazu, E., Mercer, M., Pinto, O. et al. Numerical simulations of cyclic voltammetry for lithium-ion intercalation in nanosized systems: finiteness of diffusion versus electrode kinetics. J Solid State Electrochem 24, 3279–3287 (2020). https://doi.org/10.1007/s10008-020-04717-9

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