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100 1 _ |a Merz, Steffen
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245 _ _ |a Dynamics of [Pyr 13 ][Tf 2 N] ionic liquid confined to carbon black
260 _ _ |a Cambridge
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520 _ _ |a The intrinsic ionic nature of room temperature ionic liquids (RTILs) bears the potential to replace classical aqueous electrolytes in electrochemical applications, for example in metal–air batteries. For a systematic adjustment of RTIL properties in porous cathodes, the ionic arrangement under confinement is of prime importance. Using spectrally resolved pulsed gradient stimulated echo nuclear magnetic resonance (PGSTE-NMR) and spin–lattice NMR relaxation time (T1) distributions, the dynamics of 1-methyl-1-propylpyrrolidiniumbis(trifluoromethylsulfonyl)imide ([Pyr13][Tf2N]) confined to carbon black were investigated. A considerable dependence of the [PYR13] mobility on the loading fraction of the carbon black pore space was found. There is evidence for a preferential layering of the RTIL adjacent to the carbon surface and a dependence of the ionic configuration on the local structure of the carbon surface. The inversion efficiency of inversion-recovery T1 data indicates a quasi-stationary layer at the carbon surface with solid-like properties, where the bulk-like properties of the RTIL are adopted as the distance to the surface increases. From the NMR diffusion data an intermediate layer between the quasi-stationary and the bulk-like RTIL is evident. This layer shows a particularly strong pore space loading dependence. While it has an anisotropic, two-dimensional mobility with reduced diffusion perpendicular to the surface at any loading, when it interfaces a gas phase at low loading its mobility is higher than bulk diffusion by up to an order of magnitude and chemical exchange with other layers is low. This layer appears to be of particular importance for the ion exchange between RTIL environments with different spacing from the carbon surface and hence crucial for the overall dynamics of RTILs in the investigated porous environment.
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700 1 _ |a Jakes, Peter
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700 1 _ |a Eichel, Rüdiger-A.
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700 1 _ |a Granwehr, Josef
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773 _ _ |a 10.1039/C9CP02651G
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