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Effect of particle size in Li4Ti5O12 (LTO)-LiMn2O4 (LMO) batteries: a numerical simulation study

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Abstract

Multiscale numerical simulations based on the porous-electrode theory developed by Newman et al. have been carried out in COMSOL 5.4 environment for different particle sizes (PS) of LiMn2O4 cathode material in Li4Ti5O12 (LTO)-LiMn2O4 (LMO) batteries. The electrolyte used in the simulations was 1.2 M LiPF6 in a 3:7 wt % mixture of ethyl carbonate (EC) and ethyl methyl carbonate (EMC). The model has been validated against experimental data from the literature for half cells (LTO-Li and LMO-Li) and full LTO-LMO cells. A multiple-material model has been adapted to describe an LMO cathode as a material blend with two PS (100 and 1000 nm radii), representing a binary PS distribution (PSD) within the material. The simulation results show that larger populations of small particles at constant cathode material load and constant current density over the electroactive area can effectively allow for larger currents to be applied due to the compensating larger active surface area per unit volume, which decreased the local current density at the LMO crystal interface with the electrolyte. However, higher overpotentials were obtained for cells with higher proportions of small particles, meaning that there is a compromise between electrical work output and C-rate. These findings highlight the importance of microstructure and PS in battery design, particularly in the LTO-LMO system

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taken from reference [37]) and the simulated curve obtained in this work (solid line)

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Abbreviations

\({\mathrm{A}}_{\mathrm{c}}\) :

Cell cross-sectional area

\({a}\)  :

Electrode interfacial specific surface area (per unit volume)

\({{\alpha }}_{{a}}\)  :

Anodic transfer coefficient

\({\alpha }_{c}\)  :

Cathodic transfer coefficient

\({\upbeta }_{pos}\)  :

Bruggeman coefficient for tortuosity in positive electrode

\({\upbeta }_{sep}\)  :

Bruggeman coefficient for tortuosity in separator

\({{c}}_{{l}{ref}}\)  :

Reference lithium salt concentration

\({{c}}_{{l}}\)  :

Lithium salt concentration in the electrolyte

\({{c}}_{{l}}^{0}\)  :

Initial electrolyte salt concentration

\({{c}}_{{s},{max}}\)  :

Maximum possible lithium concentration in the solid matrix

\({{c}}_{{s}}\)  :

Lithium concentration in the solid matrix

\({D}_{l}\)  :

Lithium’s diffusion coefficient in the electrolyte

\({D}_{s}\)  :

Lithium’s diffusion coefficient in the solid active material

\({D}_{{s}}^{{neg}}\)  :

Lithium’s diffusion coefficient in the negative electrode material

\({D}_{{s}}^{{pos}}\)  :

Lithium’s diffusion coefficient in the positive electrode material

\({E}_{{eq}}\)  :

Equilibrium potential

\({\upepsilon }_{{l},{neg}}\)  :

Electrolyte phase volume fraction negative electrode

\({\upepsilon }_{{l},{pos}}\)  :

Electrolyte phase volume fraction positive electrode

\({\upepsilon }_{\mathrm{l},\mathrm{pos}}\) :

Electrolyte phase volume fraction positive electrode

\({\upepsilon }_{{l}}\)  :

Electrolyte-phase volume fraction

\({\upepsilon }_{{s},{pos},{LMO}}\)  :

Solid phase volume fraction LMO positive electrode

\({\upepsilon }_{{s},{pos},{lmo}}\)  :

Solid phase volume-fraction lmo positive electrode

\({\upepsilon }_{{s},{pos}}\)  :

Solid phase volume fraction of active material mix, positive electrode

\({\upepsilon }_{{s}}\)  :

Solid-phase volume fraction

\({\upepsilon }_{{sep}}\)  :

Electrolyte phase volume fraction separator

\(\mathrm{F}\) :

Faraday’s constant

\({{fr}}_{{pos},{lmo}}\)  :

Mass fraction of lmo in lmo/LMO mix

\({\upphi }_{{l}}\)  :

Electrolyte electric potential

\({\upphi }_{{s}}\)  :

Solid-phase electric potential

\({{i}}_{{l}}\)  :

Current in the electrolyte

\({{i}}_{{s}}\)  :

Current in the solid phase

\({{j}}_{{n}}\)  :

Pore-wall current density across the active material/electrolyte interface, averaged over the interfacial area

\(k_{a}\)  :

Anodic reaction rate constant

\({k}_{c}\)  :

Cathodic reaction rate constant

\(k_{neg}\)  :

Reaction rate coefficient active material negative electrode

\({{k}}_{{pos},{LMO}}\)  :

Reaction rate coefficient LMO positive electrode

\({{k}}_{{pos},{lmo}}\)  :

Reaction rate coefficient lmo positive electrode

\({\mathrm{k}}_{\mathrm{pos}}\)  :

Reaction rate coefficient LMO positive electrode

\({\mathrm{L}}_{\mathrm{neg}}\) :

Thickness of negative electrode

\({\mathrm{L}}_{\mathrm{pos}}\) :

Thickness of positive electrode

\({\mathrm{L}}_{\mathrm{sep}}\) :

Thickness of separator

\(\mathrm{R}\) :

Universal gas constant

\({\mathrm{r}}_{\mathrm{p}}\) :

Active material particle radius

\(\mathrm{r}\) :

Radial distance measured from the center of the particle

\({\mathrm{rp}}_{\mathrm{neg}}\) :

Particle radius active material negative electrode

\({\mathrm{rp}}_{\mathrm{pos},\mathrm{LMO}}\) :

Particle radius LMO positive electrode

\({\mathrm{rp}}_{\mathrm{pos},\mathrm{lmo}}\) :

Particle radius lmo positive electrode

\({\mathrm{rp}}_{\mathrm{pos}}\) :

Particle radius LMO positive electrode

\({\uprho }_{{p}}\)  :

Positive electrode density

\({{SOC}}_{{cell}0}\)  :

Initial cell state-of-charge

\({\upsigma }_{{l}}\)  :

Electrolyte ionic conductivity

\({\upsigma }_{{l}}^{{eff}}\)  :

Electrolyte effective ionic conductivity

\({\upsigma }_{{s}}\)  :

Solid-phase electric conductivity

\({\upsigma }_{{s}}^{{neg}}\)  :

Negative electrode electric conductivity

\({\upsigma }_{{s}}^{{pos}}\)  :

Positive electrode electric conductivity

\({{t}}_{+}^{0}\)  :

Lithium ion transport number

\(t\)  :

Time

\(T\)  :

Temperature

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Acknowledgements

W.R.T, A.Y.T, and E.J.C. are Permanent Research Fellows of Consejo Nacional de Investigaciones Científicas y Técnicas (CONICET). A.R. acknowledges a Peruilh doctoral fellowship. Funding from Agencia Nacional de Promoción Científica y Tecnológica (ANPCyT) and Universidad de Buenos Aires are gratefully acknowledged.

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Authors and Affiliations

  1. Instituto de Química de Los Materiales, Ambiente y Energía (INQUIMAE), UBA-CONICET, Pabellón II, Ciudad Universitaria 1428, Ciudad Autónoma de Buenos Aires, Argentina

    A. Rozenblit & E. J. Calvo

  2. Departamento Ingeniería Química, Facultad de Ingeniería, UBA, Pabellón de Industrias, Ciudad Universitaria 1428, Ciudad Autónoma de Buenos Aires, Argentina

    A. Rozenblit

  3. Centro de Investigación y Desarrollo de Materiales Avanzados y Almacenamiento de Energía de Jujuy (CIDMEJU), Centro de Desarrollo, Tecnológico General Manuel Savio, Av. Martijena S/N, Y4612, Palpalá, Jujuy, Argentina

    W. R. Torres & A. Y. Tesio

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Rozenblit, A., Torres, W.R., Tesio, A.Y. et al. Effect of particle size in Li4Ti5O12 (LTO)-LiMn2O4 (LMO) batteries: a numerical simulation study. J Solid State Electrochem 25, 2395–2408 (2021). https://doi.org/10.1007/s10008-021-05020-x

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