Improved Parameterization of an Ethylene Carbonate Molecular Dynamics Model in Li-Air Batteries for Accurate Density and Transition Temperatures

Ward, Donald K.; Jones, Reese E.; Templeton, Jeremy Alan; Reyes, Karla Rosa; Kane, Marie

doi:10.1149/06127.0181ecst

Cited by 7 publications

(4 citation statements)

References 19 publications

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“…In EC, the density was measuredt ob e1 .32gcm À3 at 36 8Ca nd calculated to be 1.29 gcm À3 at 52 8C. [26] Assuming that the density of EC is 1.30 gcm À3 at 46 8C, then for an EC concentration of 14.8 mol dm À3 we find [Eq. (3)]:…”

Section: Resultsmentioning

confidence: 99%

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Degradation of an Ethylene Carbonate/Diethyl Carbonate Mixture by Using Ionizing Radiation

et al. 2017

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The reactivity of ethylene carbonate (EC) and of a EC/diethyl carbonate (DEC) mixture was studied under ionizing radiation to mimic the aging phenomena that occur in lithium‐ion batteries. Picosecond‐pulse radiolysis experiments showed that the attachment of the electron to the EC molecule is ultrafast (k(e−EC+EC)=1.3×109 L mol−1 s−1 at 46 °C). This reaction rate is accelerated by a factor of 5.7 compared with the electron attachment to propylene carbonate, which implies that the presence of the methyl group significantly slows the reaction. In a 50:50 EC/DEC mixture, just after the electron pulse the electron is solvated by a mixture of EC and DEC molecules, but its fast decay is attributed exclusively to electron attachment to the EC molecule. Stable products detected after steady‐state irradiation were mainly H2, CH4, CO, and CO2. The evolution of the radiolytic yields with the EC fraction shows that H2 and CH4 did not exhibit linear behavior, whereas CO and CO2 did. Indeed, H2 and CH4 mainly arise from the excited state of DEC, the formation of which is significantly affected by the evolution of the dielectric constant of the mixture and by the electron attachment to EC. CO formation is mainly due to the reactivity of the EC molecule, which is not affected in the mixture, as proven by pulse‐radiolysis experiments.

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Section: Resultsmentioning

confidence: 99%

“…[26] Assuming that the density of EC is 1.30 gcm À3 at 46 8C, then for an EC concentration of 14.8 mol dm À3 we find [Eq. (3)]:…”

mentioning

confidence: 99%

Degradation of an Ethylene Carbonate/Diethyl Carbonate Mixture by Using Ionizing Radiation

et al. 2017

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“…The size of the solvent box was considered to be 73 × 30 × 38 Å 3 which provides a correct density of EC (1.32 g cm −3 ) in the liquid phase. 27 This battery was coated with current collectors (Cu, Al, and SiO 2 ) to keep the battery components inside the simulation box. The current collectors are used to prevent leakage of electrolyte solution atoms and also to avoid shifting of the cathode and anode along the longitudinal direction (due to PBC conditions).…”

Section: Methodsmentioning

confidence: 99%

Toward efficient electrodes for a high-performance fast-charge Li-ion battery: molecular dynamics simulation and DFT calculations

Zaboli,

Raissi,

Hashemzadeh

et al. 2023

Phys. Chem. Chem. Phys.

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“…Since the parameters from SwissParam predicted the same glass transition temperature for EC and PC (EC is solid at room temperature, whereas PC is liquid), the inter-molecular Lennard-Jones energetic well-depth was modified so that transition temperature for pure EC was decreased to the experimentally measured temperature of 224 K. Full details are included Ref. 44 including the extensive thermalization procedures used to bring the complex mixture of long-chain molecules in the electrolyte to a thermodynamic equilibrium.…”

Section: Methodsmentioning

confidence: 99%

Assessing Electrolyte Transport Properties with Molecular Dynamics

Jones

Ward

Gittleson

et al. 2017

J. Electrochem. Soc.

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In this work we use estimates of ionic transport properties obtained from molecular dynamics to rank lithium electrolytes of different compositions. We develop linear response methods to obtain the Onsager diffusivity matrix for all chemical species, its Fickian counterpart, and the mobilities of the ionic species. We apply these methods to the well-studied propylene carbonate/ethylene carbonate solvent with dissolved LiBF 4 and O 2 . The results show that, over a range of lithium concentrations and carbonate mixtures, trends in the transport coefficients can be identified and optimal electrolytes can be selected for experimental focus; however, refinement of these estimation techniques is necessary for a reliable ranking of a large set of electrolytes. There is increasing interest in designing and manufacturing highperformance batteries for a wide variety of applications; 1 however, finding the best electrochemical system and configuration is a challenging task given all the possible combinations of electrodes and electrolyte components. In particular, choosing an electrolyte optimal for a given battery configuration and chemistry is daunting. Herein, we propose a computational approach to electrolyte screening and selection. Through a combination of techniques, e.g. ab initio calculations to provide fundamental parameters to molecular dynamics which, in turn, provides transport coefficients to a reaction-diffusion model of the full-scale battery, 2 we can predict battery performance. These predictions can be compared with limited experiments for validation before selecting the best candidates for intensive development. The concept of computational screening is not new, e.g. the work the Ceder group 3 and the battery-focused "Genome" efforts such as the Electrolyte Genome, 4 but here we focus on the selection of ideal electrolytes for Li batteries based on the transport properties which have been identified as critical to performance. 5,6 In order to effectively down-select from a large population of potential electrolytes, the parameters of a full-scale model of battery performance must come from more fundamental calculations. On a molecular level, the use of molecular dynamics (MD) to model diffusion, 7-15 ionic mobility, [16][17][18][19][20] and estimate the associated transport coefficients is wide-spread and has been shown to be predictive given representative interatomic potentials. In particular, Refs. 11,12,21 apply the techniques to measure the diffusivity of nonaqueous Li ion systems and Refs. 17,18 estimate the diffusivity and mobility of Li + in water.To address this big-data computational challenge, in the Theory section we introduce linear response methods to estimate the mutual diffusion and mobility coefficients of the species fluxes, using notation summarized in Table I. Generally speaking, linear response methods have many advantages over alternative methods that use large gradients/unphysical driving forces and large systems to estimate transport coefficients since they are equilibrium method...

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Improved Parameterization of an Ethylene Carbonate Molecular Dynamics Model in Li-Air Batteries for Accurate Density and Transition Temperatures

Cited by 7 publications

References 19 publications

Degradation of an Ethylene Carbonate/Diethyl Carbonate Mixture by Using Ionizing Radiation

Degradation of an Ethylene Carbonate/Diethyl Carbonate Mixture by Using Ionizing Radiation

Toward efficient electrodes for a high-performance fast-charge Li-ion battery: molecular dynamics simulation and DFT calculations

Assessing Electrolyte Transport Properties with Molecular Dynamics

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