Lithium Ion Solvation and Diffusion in Bulk Organic Electrolytes from First-Principles and Classical Reactive Molecular Dynamics

Ong, Mitchell T.; Verners, Osvalds; Draeger, Erik W.; Duin, Adri C. T. van; Lordi, Vincenzo; Pask, John E.

doi:10.1021/jp508184f

Cited by 170 publications

(237 citation statements)

References 56 publications

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“…The decrease in density, that is, the increase in the molar volume provides a more room for diffusion and a more chance to interrupt the solvation shell by solvents outside the shell. Solvents binding to a cation are usually one of main reasons to make the system viscous373839. Thus, the frequent reforming of the solvation shell will contribute to enhance the diffusivity.…”

Section: Discussionmentioning

confidence: 99%

A salient effect of density on the dynamics of nonaqueous electrolytes

Han

2017

Sci Rep

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The mobility and solvation of lithium ions in electrolytes are crucial for the performance and safety of lithium ion batteries. It has been known that a single type of solvent cannot satisfy the requirements of both mobility and solvation simultaneously for electrolytes. Therefore, complex solvent mixtures have been used to optimize both properties. Here we present the effects of density on the dynamics and solvation of organic liquid electrolytes via extensive molecular dynamics simulations. Our study finds that a small variation in density can induce a significant effect on the mobility of electrolytes but does not influence the solvation structure of a lithium ion. It turns out that an adjustment of the density of electrolytes could provide a more effective way to enhance mobility than a control of the solvent mixture ratio of electrolytes. Our study reveals that the density change of electrolytes mainly affects the residence time of solvents in the first solvation shell of a lithium ion rather than the structural change of the solvation sheath. Finally, our results suggest an intriguing point for understanding and designing electrolytes of lithium ion batteries for better performance and safety.

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Section: Discussionmentioning

confidence: 99%

A salient effect of density on the dynamics of nonaqueous electrolytes

Han

2017

Sci Rep

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“…Mater. [175] The much-reduced computational cost of ReaxFF as compared to that of AIMD simulations enables the study of size effects in Li-S systems. Of course, it is also possible that the parameters used are not optimal as it is almost impossible to include all possible species in the fitting.…”

Section: Size Effects and Reactive MD Simulationsmentioning

confidence: 99%

Computer Simulation of Cathode Materials for Lithium Ion and Lithium Batteries: A Review

2018

Energy & Environ Materials

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Driven by the increasing demand for electrochemical energy storage, lithium ion and lithium batteries have been the subject of tremendous scientific endeavors for decades. However, limited energy density, which is bottlenecked by available high-density cathode materials, has become a critical issue to be solved. Recently, computational studies have played an increasingly important role in the search for the next-generation high-density cathode materials. Not only important insights on the battery chemistry have been revealed, but also novel material systems have been proposed. This review highlights recent progresses in the computational studies of cathode materials for lithium ion and lithium batteries. It starts from a brief introduction of the scientific background of lithium ion and lithium batteries, followed by a brief discussion of the working principles of batteries. Different computer simulation techniques are shown to originate from the same quantum mechanical treatment of many-body systems with different levels of simplifications. Progresses in computational studies of different cathode materials, including intercalation electrode, conversion compounds, sulfur, and organosulfides, are then presented in detail. Finally, the capabilities of computational techniques in the study of cathode materials are summarized, and major challenges are discussed. REVIEW Lithium Ion Batteries

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“…[27] Two typical structures of such tetrahedrons in the thiophene and EDOT liquids obtained from our simulations are shown in Figure 3. tetrahedron structures formed by four oxygen atoms around the Li cation have been previously reported in bulk organic solvents ethylene carbonate, ethyl methyl carbonate, and their mixture.…”

Section: Resultsmentioning

confidence: 99%

“…Therefore, such investigations have far-reaching applications, for example in environmental chemistry, drug design, and energy materials. [22][23][24][25][26][27] However, due to possible change in the charge distribution in the vicinity of a solvated ion, the classical simulations may fall short of correct description of interactions at an atomistic level. [8][9][10][11] The field has also witnessed great strides towards more efficient Li-sulfur batteries, thanks to numerous theoretical and experimental studies aimed at enhancing their cycling performance.…”

Section: Introductionmentioning

confidence: 99%

Mechanism of Lithium Cation Hopping between Tetragonal Thiophene Cages

Partovi–Azar

Sebastiani

2019

Batteries & Supercaps

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We report on the atomistic mechanism of elementary hopping processes of Li + ions in liquid thiophene obtained from abinitio molecular dynamics simulations. We observe the formation of cage structures which solvate the cation. Besides the actual molecular solvation structure, we provide an analysis of the pathway and timescale of basic Li + diffusion steps in terms of coordination by sulfur atoms. We compare our results to the situation in a thiophene derivative, namely 3,4-ethylenedioxythiophene (EDOT). The calculations reveal that in both thiophene and EDOT liquids, a tetrahedral structure is formed around the Li + ion. While in the case of the former, the Li cation is coordinated by four sulfur atoms, in the latter case it is surrounded by four oxygens. The tetrahedrons act as cages, which accommodate the cation for a considerable duration (of the order of 100 ps). The elementary diffusion step occurs through a "permeable edge" of the tetrahedron formed by two sulfur (or oxygen) atoms at a characteristic distance. This finding indicates that Li + conduction in thiophene derivatives can be improved by rationally designing the compound in such a way that maximizes the occurrence of sulfur atoms at that particular distance from each other.[a] Dr.

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Lithium Ion Solvation and Diffusion in Bulk Organic Electrolytes from First-Principles and Classical Reactive Molecular Dynamics

Cited by 170 publications

References 56 publications

A salient effect of density on the dynamics of nonaqueous electrolytes

A salient effect of density on the dynamics of nonaqueous electrolytes

Computer Simulation of Cathode Materials for Lithium Ion and Lithium Batteries: A Review

Mechanism of Lithium Cation Hopping between Tetragonal Thiophene Cages

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