Computational modeling for the development of next-generation lithium-ion battery electrodes

PhD thesis done at FAMAF (Universidad Nacional de Córdoba), working in the LAES computational area.

Advisors:

• Dr. Ezequiel Leiva (FCQ, Universidad Nacional de Córdoba)
• Dr. Daniel Barraco (FAMAF, Universidad Nacional de Córdoba)

Thesis committee:

• Dr. Roberto M. Torresi (IQ, Universidade de São Paulo)
• Dr. Alejandro A. Franco (LRCS, Université de Picardie Jules Verne)
• Dr. Fabián Vaca Chávez (FAMAF, Universidad Nacional de Córdoba)

Dissertation: Presented to the Faculty of Mathematics, Astronomy, Physics and Computer Science of the Universidad Nacional de Córdoba on April 5, 2024.

Abstract: Lithium-ion batteries are uniquely positioned for the energy transition needed to reduce carbon emissions into the atmosphere, due to the intermittent nature of renewable energy sources. In addition, there will be a high demand for them in the transportation sector. In this work, next-generation electrodes have been studied using computational techniques to address several critical challenges of the growing electric vehicle industry. The first one is related to fast battery charging, where a model was developed to predict the optimal particle size to reach a state of charge of 80% in 15 minutes of constant current charging. It was also used to propose a universal metric to standardize comparative evaluations between different materials to be considered in fast charging applications. Another aspect of great relevance in current research is the consideration of materials that allow storing a greater amount of energy than the current ones, among which silicon anodes stand out. In this field, atomic configurations of LiSi alloys have been obtained by a lithiation protocol and analyzed with nearest neighbor models to predict X-ray diffraction, Nuclear magnetic resonance and Mössbauer spectroscopy measurements.

Keywords: Lithium-ion batteries, fast-charging, heuristic model, benchmarking metric, Silicon anodes, nearest neighbor models, predictions of experimental results.

Instructions to compile the thesis

A Dockerfile is provided to compile the thesis in any OS. Linux example:

docker build -t <CONTAINER NAME> .
docker run <CONTAINER NAME>

and you can get the pdf of the thesis by running:

docker cp <CONTAINER ID>:/thesis/thesis.pdf .

Thesis figures comment

The figures of the thesis were generated using Python 3.11.6 with the specified versions of libraries that can be installed as follows:

pip install -r requirements.txt

The structures were inspected with VMD 1.9.4a57, Tcl configuration scripts are provided for the same purpose and can be run as

vmd -e src/Silicio/config.tcl <INPUT STRUCTURE>

PhD requirements fulfilled

Postgraduate courses

• Machine Learning School for Materials @ Ilum, CNPEM. 20 hrs, Sep 5-7, 2022.

• Machine learning for scarse data, ECI, DC, UBA. 15 hrs, Jul 26-30, 2021.

• Software design for scientific computing, FAMAF, UNC. 60 hrs, 2021. link.

• Python programming, ECyT, UNSAM. 96 hrs, 2021. link.

• Parallel computing, FAMAF, UNC. 120 hrs, 2020. link.

• Computational physics, FAMAF, UNC, 120 hrs, 2020. link.

• Nuclear magnetic resonance, FAMAF, UNC. 25 hrs, 2020.

• Computer simulations in condensed matter systems, FCQ, UNC. 40 hrs, 2019.

• Electrochemistry, FCQ, UNC. 80 hrs, 2019.

Seminars talks

• Fast-charging lithium batteries: from designing materials to optimizing charging protocols. Sep 14, 2023. Aula Magna, FAMAF.

• Machine learning interatomic potentials and their application to lithium batteries. Apr 22, 2022. Aula Magna, FAMAF.

Research activity

Scientific articles

• UMBEM: A Universal Metric for Benchmarking fast-charging Electrode Materials. F. Fernandez et al. Manuscript in preparation, 2023.

• Towards a fast-charging of LIBs electrode materials: a heuristic model based on galvanostatic simulations. F. Fernandez, E. M. Gavilán-Arriazu, D. E. Barraco, A. Visintín, Y. Ein-Eli, E. P. M. Leiva. Electrochimica Acta, 2023. https://doi.org/10.1016/j.electacta.2023.142951

• NMR, x-ray and Mössbauer results for amorphous Li-Si alloys using density functional tight-binding method. F. Fernandez, M. Otero, M. B. Oviedo, D. E. Barraco, S. A. Paz, E. P. M. Leiva. Physical Review B, 2023. https://doi.org/10.1103/PhysRevB.108.144201

• Density functional tight-binding model for Lithium-Silicon alloys. B. Oviedo, F. Fernandez, M. Otero, E. Leiva, A. Paz. The Journal of Physical Chemistry A, 2022. https://doi.org/10.1021/acs.jpca.3c00075

• Characterization of amorphous Li_xSi structures from ReaxFF via accelerated exploration of local minima. F. Fernandez, A. Paz, M. Otero, D. Barraco, E. Leiva. Physical Chemistry Chemical Physics, 2021. https://doi.org/10.1039/D1CP02216D

Conference presentations

• 2nd Renewable energy workshop: lithium batteries and hydrogen. Córdoba, Argentina. Oct, 2023. Poster: "A heuristic model based on galvanostatic simulations for fast charging of lithium-ion battery electrodes".

• Y-TEC PHD candidates exhibition. La Plata, Argentina. Sep, 2023. Poster: "Fast-charging lithium-ion batteries: A heuristic model to predict optimal particle size".

• 8th Meeting of Young Researchers in Materials Science and Technology. Córdoba, Argentina. Sep, 2023. Poster: "Nearest-neighbor model for predicting 7Li chemical shift spectra in Si anodes".

• 34th Topical Meeting of the International Society of Electrochemistry. Mar del Plata, Argentina. Mar 20-22, 2023.

  • Poster: "Study of electrochemical properties in the lithiation of an amorphous silicon structure using a DFTB potential".
  • Talk: "Galvanostatic maps for fast-charging diagnosis of active materials in LIBs", co-author.

• 107th Argentine Physics Association Meeting. Bariloche, Argentina. Sep 27-30, 2022.

  • Talk: "Development of lithium-ion battery materials: Computational physics applied to the optimization of silicon anodes".
  • Poster: "DFT study of amorphous and crystalline structures of LiSi and LiSn", co-author.

• XXI Meeting of surfaces and nanostructured materials. Río Cuarto, Argentina. Aug 9-11, 2022. Poster Flash: "Short range order of amorphous structures in silicon anodes using a semiempirical reactive potential". (Best poster flash award).

• 1st National Lithium Meeting. Argentina/Online. Dec 1-3, 2021. Poster: "Electrochemical and structural behavior of silicon anodes based on computational simulations".

• 8th International Workshop on Lithium, Industrial Minerals and Energy (IWLiME). Cochabamba, Bolivia/Online. Nov 8-10, 2021. Poster: "Amorphous Li-Si structures found via a novel simulation method using a reactive force field".

• 72nd Annual Meeting of the International Society of Electrochemistry. Jeju Island, Korea/Online. Aug 29-Sep 3, 2021. Talk: "Kinectic modeling on lithium-ion instertion in prototypical systems", co-autor.

• XII Argentina Congress of Physical Chemistry and Inorganic Chemistry. La Plata, Argentina/Online. Aug 19-29, 2021. Talk: "A journey through the nanoworld of Li batteries", co-author.

• 7th IWLiME. Antofagasta, Chile/Online. Nov 9-11, 2020. Poster: "First steps towards reproducing chemical shifts spectra of c-LiSi alloys using a semi-empirical force field".

• Workshop on scientific programming techniques. Córdoba, Argentina. Jul 15-26, 2019.

License

Modelado computacional para el desarrollo de electrodos de baterías de ion-litio de próxima generación © 2024 by Francisco Fernandez is licensed under Attribution-ShareAlike 4.0 International