Transport anomalies emerging from strong correlation in ionic liquid electrolytes

Molinari, Nicola; Mailoa, Jonathan P.; Craig, Nathan; Christensen, Jake; Kozinsky, Boris

doi:10.1016/j.jpowsour.2019.04.085

Cited by 78 publications

(171 citation statements)

References 52 publications

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“…In a previous work, we extensively characterized the limitation of the dilute-limit approach to compute transport properties and predicted a negative transference number for a promising Na + -ion electrolyte system. 30 In this manuscript we study the transport properties of several Li + -salt/ionic liquid mixtures by combining molecular dynamics with fully-correlated multi-species concentrated solution theory, and we report following findings. First, we computationally confirm the measured negative t + Li , 28 and extend this surprising result to different chemistries and systems, suggesting this as a universal trend in Li + -salt/IL mixtures.…”

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confidence: 82%

“…Figure 2 reports t + Li , as computed using multi-component concentrated solution theory. 30,47 Strikingly,…”

Section: The Transference Number T +mentioning

confidence: 99%

“…We use a timestep of δt = 1.0 fs and a velocity-Verlet algorithm to evolve the equation of motions, while a Nosé-Hoover barostat (1000 δt coupling) and thermostat (100 δt coupling) enforce pressure and temperature, respectively. [42][43][44] The equilibration routine, used to over-come local energy barriers in search of lower energy minima, follows the structure generation and comprises a set of energy minimizations, compression/decompression, and annealing stages, broadly based on previous works 30,45,46 (full details in the Supplementary Information, Section 2).…”

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confidence: 99%

“…The adoption of fully correlated transport theory is a vital step to uncover transport anomalies such as a negative transference number, otherwise impossible to be found with the commonly-adopted dilute solution theory approach. 30 Our choice of the reference position is the center of mass of the entire system, as there is no single species that could be treated as a "solvent".…”

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confidence: 99%

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General Trend of Negative Transference Number in Li Salt/Ionic Liquid Mixtures

Molinari

Mailoa²,

Kozinsky³

2019

Preprint

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We show that strong cation-anion interactions in a wide range of lithium-salt/ionic liquid mixtures result in a negative lithium transference number, using molecular dynamics simulations and rigorous concentrated solution theory. This behavior fundamentally deviates from the one obtained using self-diffusion coefficient analysis and agrees well with experimental electrophoretic NMR measurements, which accounts for ion correlations. We extend these findings to several ionic liquid compositions. We investigate the degree of spatial ionic coordination employing single-linkage cluster analysis, unveiling asymmetrical anion-cation clusters. Additionally, we formulate a way to compute the effective lithium charge that corresponds to and agrees well with electrophoretic measurements and show that lithium effectively carries a negative charge in a remarkably wide range of chemistries and concentrations. The generality of our observation has significant implications for the energy storage community, emphasizing the need to reconsider the potential of these systems as next generation battery electrolytes.<br>

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confidence: 82%

“…Figure 2 reports t + Li , as computed using multi-component concentrated solution theory. 30,47 Strikingly,…”

Section: The Transference Number T +mentioning

confidence: 99%

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confidence: 99%

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confidence: 99%

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General Trend of Negative Transference Number in Li Salt/Ionic Liquid Mixtures

Molinari

Mailoa²,

Kozinsky³

2019

Preprint

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“…Molecular dynamics studies suggest strong correlation of the sodium ion with [FSI] − , [TFSI] − , [FTFSI] −[195] and [PF 6 ] −[197] ions on the timescale of the simulations. However such simulations are very dependent on the force fields employed .…”

Section: Transport Propertiesmentioning

confidence: 99%

Electrolytes for Lithium (Sodium) Batteries Based on Ionic Liquids: Highlighting the Key Role Played by the Anion

Rüther

Bhatt

Best

et al. 2020

Batteries & Supercaps

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Research since 2000 has clearly shown that ionic liquids (ILs) and their metal salt containing mixtures have good potential to be considered as electrolytes (ILELs) in lithium and other electropositive metal (ion) batteries. This outcome is particularly relevant for the operation of such devices in elevated temperature regimes where ILELs would have a significant advantage over the conventional organic carbonate solvent/LiPF6 electrolytes that, due to their limited thermal stability and flammability, cause concerns about the safety of current LIB technology. There is evidence from a number of review articles that physicochemical properties can be tailored such that ILELs could meet requirements for operating in batteries at lower temperature regimes. By drawing on a broad range of cation/anion combinations, there is further evidence from these papers that within a particular family of cations, the physicochemical properties of ILs and ILELs are largely defined by the anion component. Despite the key role of the anion there are few reviews that have sections dedicated to this aspect. This review surveys the physicochemical, transport and structural properties of ILs (mainly pyrrolidinium salts) and ILELs employing prominent and representative anion classes.

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Electrolytes for Sodium Ion Batteries: The Current Transition from Liquid to Solid and Hybrid systems

Darjazi,

Falco,

Colò

et al. 2024

Advanced Materials

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Sodium‐ion batteries (NIBs) have recently garnered significant interest in being employed alongside conventional lithium‐ion batteries, particularly in applications where cost and sustainability are particularly relevant. The rapid progress in NIBs will undoubtedly expedite the commercialization process. In this regard, tailoring and designing electrolyte formulation is a top priority, as they profoundly influence the overall electrochemical performance and thermal, mechanical, and dimensional stability. Moreover, electrolytes play a critical role in determining the system's safety level and overall lifespan. This review delves into recent electrolyte advancements from liquid (organic and ionic liquid) to solid and quasi‐solid electrolyte (dry, hybrid, and single ion conducting electrolyte) for NIBs, encompassing comprehensive strategies for electrolyte design across various materials, systems and their functional applications. Our objective is to offer strategic direction for the systematic production of safe electrolytes and to investigate the potential applications of these designs in real‐world scenarios while thoroughly assessing the current obstacles and forthcoming prospects within this rapidly evolving field.This article is protected by copyright. All rights reserved

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Transport anomalies emerging from strong correlation in ionic liquid electrolytes

Cited by 78 publications

References 52 publications

General Trend of Negative Transference Number in Li Salt/Ionic Liquid Mixtures

General Trend of Negative Transference Number in Li Salt/Ionic Liquid Mixtures

Electrolytes for Lithium (Sodium) Batteries Based on Ionic Liquids: Highlighting the Key Role Played by the Anion

Electrolytes for Sodium Ion Batteries: The Current Transition from Liquid to Solid and Hybrid systems

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