Enhanced ionic liquid mobility induced by confinement in 1D CNT membranes

Berrod, Quentin; Ferdeghini, Filippo; Judeinstein, Patrick; Genevaz, Nicolas; Ramos, R.; Fournier, A.; Dijon, Jean; Ollivier, Jacques; Rols, S.; Yu, Dehong; Mole, Richard A.; Zanotti, Jean-Marc

doi:10.1039/c6nr01445c

Cited by 56 publications

(58 citation statements)

References 22 publications

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“…At around l p ≃ l d , D starts to increase and assumes values higher than in the bulk, at all T. This effect is not surprising as it has already been reported in experiments (see, for instance, Ref. [43] for ½C 8 mim½BF 4 confined in carbon nanotubes), and in the simulation work of Ref. [22] for ½C 1 mim½Cl, where it has been justified in terms of purely geometric arguments [44].…”

Section: A the Diffusion Coefficientssupporting

confidence: 66%

Re-entrant Phase Transitions and Dynamics of a Nanoconfined Ionic Liquid

Mossa

2018

Phys. Rev. X

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Ionic liquids constrained at interfaces or restricted in subnanometric pores are increasingly employed in modern technologies, including energy applications. Understanding the details of their behavior in these conditions is therefore critical. By using molecular dynamics simulation, we clarify theoretically and numerically the effect of confinement at the nanoscale on the static and dynamic properties of an ionic liquid. In particular, we focus on the interplay among the size of the ions, the slit pore width, and the length scale associated to the long-range organization of polar and apolar domains present in the bulk material. By modulating both the temperature and the extent of the confinement, we demonstrate the existence of a complex reentrant phase behavior, including isotropic liquid and liquid-crystal-like phases with different symmetries. We show how these changes impact the relative organization of the ions, with substantial modifications of the Coulombic ordering, and their dynamical state. In this respect, we reveal a remarkable decoupling of the dynamics of the counterions, pointing to very different roles played by these in charge transport under confinement. We finally discuss our findings in connection with very recent experimental and theoretical work.

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Section: A the Diffusion Coefficientssupporting

confidence: 66%

Re-entrant Phase Transitions and Dynamics of a Nanoconfined Ionic Liquid

Mossa

2018

Phys. Rev. X

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“…A direct way to circumvent the spontaneous formation of aggregates within the ILs would be to confine the liquid in a porous material with pores smaller than the characteristic size of the aggregates. Following experimental data 23 , recent MD results indicate 24 that imposing confinement of ILs in Carbon NanoTubes (CNT) with diameter under 2 nm exalts the transport properties by several orders of magnitude. To date, no evidence shows that such gigantic transport properties are solely due to the frustration of the spontaneous nano-aggregates formation.…”

Section: Discussionmentioning

confidence: 83%

Ionic Liquids: evidence of the viscosity scale-dependence

Berrod

Ferdeghini

Zanotti

et al. 2017

Sci Rep

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Ionic Liquids (ILs) are a specific class of molecular electrolytes characterized by the total absence of co-solvent. Due to their remarkable chemical and electrochemical stability, they are prime candidates for the development of safe and sustainable energy storage systems. The competition between electrostatic and van der Waals interactions leads to a property original for pure liquids: they self-organize in fluctuating nanometric aggregates. So far, this transient structuration has escaped to direct clear-cut experimental assessment. Here, we focus on a imidazolium based IL and use particle-probe rheology to (i) catch this phenomenon and (ii) highlight an unexpected consequence: the self-diffusion coefficient of the cation shows a one order of magnitude difference depending whether it is inferred at the nanometric or at the microscopic scale. As this quantity partly drives the ionic conductivity, such a peculiar property represents a strong limiting factor to the performances of ILs-based batteries.

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“…Currently, the entropic ratchet mechanism is the only able to account for them. Also, the entropic ratchet mechanism is possibly relevant for the understanding of facilitated or jammed-like transport observed for ionic-liquids confined in conical nanopores26, with likely outcomes for the improvement of electric batteries and cells that use confined geometries30.…”

Section: Discussionmentioning

confidence: 99%

The concept of entropic rectifier facing experiments

Lairez

Clochard

Wegrowe

2016

Sci Rep

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The transport of molecules in confined media is subject to entropic barriers. So theoretically, asymmetry of the confinement length may lead to molecular ratchets with entropy as the only driving force for the biased transport. We address experimentally this question by performing alternative ionic current measurements on electrolytes confined in neutral conical nanopores. In case anions and cations widely differ in size, we show that rectification of ionic current can be obtained that depends on ions size and cycle frequency, consistently with the entropic ratchet mechanism.

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Enhanced ionic liquid mobility induced by confinement in 1D CNT membranes

Cited by 56 publications

References 22 publications

Re-entrant Phase Transitions and Dynamics of a Nanoconfined Ionic Liquid

Re-entrant Phase Transitions and Dynamics of a Nanoconfined Ionic Liquid

Ionic Liquids: evidence of the viscosity scale-dependence

The concept of entropic rectifier facing experiments

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