On how interactions influence kinetic limitations in alkali-ion batteries. Application to Li-ion intercalation into graphite through voltammetric experiments

Here, we report on a novel study for battery application regarding the impact of interactions in charge transfer and diffusional features in finite-size systems. An easy way to represent these features is the construction of a map called zone diagram for voltammetry simulations, where different doma...

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Bibliographic Details
Published in:Journal of solid state electrochemistry 2021-12, Vol.25 (12), p.2793-2806
Main Authors: Gavilán-Arriazu, E. M., Barraco, D. E., Leiva, E. P. M.
Format: Article
Language:English
Subjects:
Analytical Chemistry
Characterization and Evaluation of Materials
Charge transfer
Chemistry
Chemistry and Materials Science
Condensed Matter Physics
Electrochemical analysis
Electrochemistry
Energy Storage
Experiments
Film thickness
Graphite
Intercalation
Lithium ions
Metal ions
Original Paper
Physical Chemistry
Rechargeable batteries
Surface waves
Voltammetry
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Summary:Here, we report on a novel study for battery application regarding the impact of interactions in charge transfer and diffusional features in finite-size systems. An easy way to represent these features is the construction of a map called zone diagram for voltammetry simulations, where different domains are related with a characteristic charge transfer-diffusional limitation. This is particularly relevant for alkali-ion intercalation into hosts, since interactions between inserted ions have demonstrated to have a strong influence on the electrochemical behaviour of these systems. The Frumkin isotherm is used here as a general model to understand the simplest scenarios, which introduces interactions between inserted particles in their thermodynamic descriptions. We show how the impact of these interactions becomes more evident for systems that present a reversible charge transfer. On the contrary, for irreversible reactions, features tend to become independent of interactions. Finally, we apply the methodology to understand some features of Li-ion intercalation in graphite films. It comes out that for this system, a surface wave (adsorption like) behaviour could only be reached in experiments lasting more than a year. This explains the large hysteresis found in experiments. We also constructed a sweep rate-film thickness zone diagram, to present the results in a more straightforward fashion to experimentalists.
ISSN:1432-8488
1433-0768
DOI:10.1007/s10008-021-05079-6