Dataset Information

Understanding Ionic Diffusion Mechanisms in Li₂S Coatings for Solid-State Batteries: Development of a Tailored Reactive Force Field for Multiscale Simulations.

ABSTRACT: In order to investigate Li₂S as a potential protective coating for lithium anode batteries using superionic electrolytes, we need to describe reactions and transport for systems at scales of >10,000 atoms for time scales beyond nanoseconds, which is most impractical for quantum mechanics (QM) calculations. To overcome this issue, here, we first report the development of the reactive analytical force field (ReaxFF) based on density functional theory (DFT) calculations on model systems at the PBE0/TZVP and M062X/TZVP levels. Then, we carry out reactive molecular dynamics simulations (RMD) for up to 20 ns to investigate the diffusion mechanisms in bulk Li₂S as a function of vacancy density, determining the activation barrier for diffusion and conductivity. We show that RMD predictions for diffusion and conductivity are comparable to experiments, while results on model systems are consistent with and validated by short (10-100 ps) ab initio molecular dynamics (AIMD). This new ReaxFF for Li₂S systems enables practical RMD on spatial scales of 10-100 nm (10,000 to 10 million atoms) for the time scales of 20 ns required to investigate predictively the interfaces between electrodes and electrolytes, electrodes and coatings, and coatings and electrolytes during the charging and discharging processes.

SUBMITTER: D'Amore M

PROVIDER: S-EPMC10694816 | biostudies-literature | 2023 Nov

REPOSITORIES: biostudies-literature

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Understanding Ionic Diffusion Mechanisms in Li<sub>2</sub>S Coatings for Solid-State Batteries: Development of a Tailored Reactive Force Field for Multiscale Simulations.

D'Amore Maddalena M Yang Moon Young MY Das Tridip T Ferrari Anna Maria AM Kim Minho M MM Rocca Riccardo R Sgroi Mauro M Fortunelli Alessandro A Goddard William A WA

The journal of physical chemistry. C, Nanomaterials and interfaces 20231115 47

In order to investigate Li<sub>2</sub>S as a potential protective coating for lithium anode batteries using superionic electrolytes, we need to describe reactions and transport for systems at scales of >10,000 atoms for time scales beyond nanoseconds, which is most impractical for quantum mechanics (QM) calculations. To overcome this issue, here, we first report the development of the reactive analytical force field (ReaxFF) based on density functional theory (DFT) calculations on model systems ...[more]

PMID: 38053625

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Project description:A theoretical framework to explain how interactions between redox mediators (RMs) and electrolyte components impact electron transfer kinetics, thermodynamics, and catalytic efficiency is presented. Specifically focusing on ionic association, 2,5-di-tert-butyl-1,4-benzoquinone (DBBQ) is used as a case study to demonstrate these effects. Our analytical equations reveal how the observed redox couple's potential and electron transfer rate constants evolve with Li+ concentration, resulting from different redox activity mechanisms. Experimental validation by cyclic voltammetry measurements shows that DBBQ binds to three Li+ ions in its reduced state and one Li+ ion in its neutral form, leading to a maximum in the electron transfer kinetic constant at around 0.25 M. The framework is extended to account for other phenomena that can play an important role in the redox reaction mechanisms of RMs. The effect of Li+ ion solvation and its association with the supporting salt counteranion on the redox processes is considered, and the role of "free Li+" concentration in determining the electrochemical behaviour is emphasized. The impact of Li+ concentration on oxygen reduction reaction (ORR) catalysis was then explored, again using DBBQ and modelling the effects of the Li+ concentration on electron transfer and catalytic kinetics. We show that even though the observed catalytic rate constant increases with Li+ concentration, the overall catalysis can become more sluggish depending on the electron transfer pathway. Cyclic voltammograms are presented as illustrative examples. The strength of the proposed theoretical framework lies in its adaptability to a wider range of redox mediators and their interactions with the various electrolyte components and redox active molecules such as oxygen. By understanding these effects, we open up new avenues to tune electron transfer and catalytic kinetics and thus improve the energy efficiency and rate capability of Li-O2 batteries. Although exact results may not transfer to different solvents, the predictions of our model will provide a starting point for future studies of similar systems, and the model itself is easily extensible to new chemistries.

Dataset Information

Understanding Ionic Diffusion Mechanisms in Li₂S Coatings for Solid-State Batteries: Development of a Tailored Reactive Force Field for Multiscale Simulations.

Publications

Understanding Ionic Diffusion Mechanisms in Li<sub>2</sub>S Coatings for Solid-State Batteries: Development of a Tailored Reactive Force Field for Multiscale Simulations.

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Dataset Information

Understanding Ionic Diffusion Mechanisms in Li2S Coatings for Solid-State Batteries: Development of a Tailored Reactive Force Field for Multiscale Simulations.

Publications

Understanding Ionic Diffusion Mechanisms in Li<sub>2</sub>S Coatings for Solid-State Batteries: Development of a Tailored Reactive Force Field for Multiscale Simulations.

Similar Datasets

OmicsDI is part of the ELIXIR infrastructure

Tweets

Understanding Ionic Diffusion Mechanisms in Li₂S Coatings for Solid-State Batteries: Development of a Tailored Reactive Force Field for Multiscale Simulations.