Dynamics of [Pyr<sub>13</sub>][Tf<sub>2</sub>N] ionic liquid confined to carbon black

Merz, Steffen; Jakes, Peter; Taranenko, Svitlana; Eichel, Rüdiger‐A.; Granwehr, Josef

doi:10.1039/c9cp02651g

Cited by 12 publications

(23 citation statements)

References 78 publications

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“…If the ILs are preferably located on the CB surface due to its high ionophilicity, a higher degree of pore space filling leads, on average, to a reduced pathway length for exchange between different sample environments. An analogous hypothesis was phrased previously based on NMR experiments on static samples [59].…”

Section: H-t 2app Time Distributionsmentioning

confidence: 67%

“…The weighted residuals did not show systematic features, yet this may have been reinforced by the approximation procedure used here, where the weighting matrix was determined iteratively. While underregularization was avoided with this procedure, overregularization may occur in situations where systematic residuals are present due to the unsuitability of the exponential kernel for certain exchange features or oscillations in the echo amplitude evolution [59]. A more accurate method that provides more faithful results would be an independent noise determination based on multiple repetitions of the experiment, followed by a noise analysis for each data point [59].…”

Section: H-t 2app Time Distributionsmentioning

confidence: 99%

“…In an earlier study, we investigated the dynamics of 1-Methyl-1-propylpyrrolidiniumbis (trifluoromethylsulfonyl)imide ([Pyr 13 ][Tf 2 N]) confined to CB using PGSTE-NMR in combination with T 1 relaxation time measurements [59]. We found evidence for a quasi-stationary IL film coating the carbon surface with a lubricating effect on the layer directly above.…”

Section: Introductionmentioning

confidence: 99%

“…We found evidence for a quasi-stationary IL film coating the carbon surface with a lubricating effect on the layer directly above. This layer showed an increased long-range mobility, causing an increased overall motion along the carbon surface [59]. However, identification of different environments using variations of their spectral signature was impeded by low resolution due to susceptibility variations inside the porous carbon environment or by incompletely averaged anisotropic interactions [60].…”

Section: Introductionmentioning

confidence: 99%

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MAS-NMR of [Pyr13][Tf2N] and [Pyr16][Tf2N] Ionic Liquids Confined to Carbon Black: Insights and Pitfalls

et al. 2021

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Electrolytes based on ionic liquids (IL) are promising candidates to replace traditional liquid electrolytes in electrochemical systems, particularly in combination with carbon-based porous electrodes. Insight into the dynamics of such systems is imperative for tailoring electrochemical performance. In this work, 1-Methyl-1-propylpyrrolidinium bis(trifluoromethylsulfonyl)imide and 1-Hexyl-1-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide were studied in a carbon black (CB) host using spectrally resolved Carr-Purcell-Meiboom-Gill (CPMG) and 13-interval Pulsed Field Gradient Stimulated Echo (PFGSTE) Magic Angle Spinning Nuclear Magnetic Resonance (MAS-NMR). Data were processed using a sensitivity weighted Laplace inversion algorithm without non-negativity constraint. Previously found relations between the alkyl length and the aggregation behavior of pyrrolidinium-based cations were confirmed and characterized in more detail. For the IL in CB, a different aggregation behavior was found compared to the neat IL, adding the surface of a porous electrode as an additional parameter for the optimization of IL-based electrolytes. Finally, the suitability of MAS was assessed and critically discussed for investigations of this class of samples.

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Section: H-t 2app Time Distributionsmentioning

confidence: 67%

Section: H-t 2app Time Distributionsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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MAS-NMR of [Pyr13][Tf2N] and [Pyr16][Tf2N] Ionic Liquids Confined to Carbon Black: Insights and Pitfalls

et al. 2021

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“…Thereby, the residuals of the fit should be consistent with Gaussian white noise without any systematic features, thus the obtained distribution represents the full information available in the data. [21] In battery materials, the ionic mobility is of central importance and often represents a performance-limiting property. [22] Solid electrolytes are of particular interest.…”

Section: Introductionmentioning

confidence: 99%

Independent component analysis combined with Laplace inversion of spectrally resolved spin-alignment echo/T ₁ 3D ⁷Li NMR of superionic Li₁₀GeP₂S₁₂

Paulus

Eichel

et al. 2021

Zeitschrift Für Physikalische Chemie

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The use of independent component analysis (ICA) for the analysis of two-dimensional (2D) spin-alignment echo–T 1 7Li NMR correlation data with transient echo detection as a third dimension is demonstrated for the superionic conductor Li10GeP2S12 (LGPS). ICA was combined with Laplace inversion, or discrete inverse Laplace transform (ILT), to obtain spectrally resolved 2D correlation maps. Robust results were obtained with the spectra as well as the vectorized correlation maps as independent components. It was also shown that the order of ICA and ILT steps can be swapped. While performing the ILT step before ICA provided better contrast, a substantial data compression can be achieved if ICA is executed first. Thereby the overall computation time could be reduced by one to two orders of magnitude, since the number of computationally expensive ILT steps is limited to the number of retained independent components. For LGPS, it was demonstrated that physically meaningful independent components and mixing matrices are obtained, which could be correlated with previously investigated material properties yet provided a clearer, better separation of features in the data. LGPS from two different batches was investigated, which showed substantial differences in their spectral and relaxation behavior. While in both cases this could be attributed to ionic mobility, the presented analysis may also clear the way for a more in-depth theoretical analysis based on numerical simulations. The presented method appears to be particularly suitable for samples with at least partially resolved static quadrupolar spectra, such as alkali metal ions in superionic conductors. The good stability of the ICA analysis makes this a prospect algorithm for preprocessing of data for a subsequent automatized analysis using machine learning concepts.

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Polysiloxane‐Based Single‐Ion Conducting Polymer Blend Electrolyte Comprising Small‐Molecule Organic Carbonates for High‐Energy and High‐Power Lithium‐Metal Batteries

Liang

Zarrabeitia

Chen

et al. 2022

Advanced Energy Materials

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devices and electric vehicles. [1][2][3][4] To achieve even higher energy densities, the use of lithium metal as the negative electrode is considered the next big step. However, the continuous electrolyte decomposition at the electrode|electrolyte interface, owing to the lack of a stable solid electrolyte interphase (SEI), results in low Coulombic efficiency (CE) and, potentially, dendritic lithium deposition. Thus eventually cause rapid cell failure and, in a worst case, accidental short-circuiting, posing severe safety issues and hindering commercialization. [5][6][7] Nonetheless, there has been a revitalized interest in lithiummetal anodes, encouraged by recent advances towards the stabilization of the anode|electrolyte interface. These advances were achieved by different strategies, including the formulation of beneficial electrolyte compositions, [8] the application of artificial interphases, [9] the use of 3D host matrices, [10] and the replacement of conventional liquid electrolytes by solidstate electrolytes. [11] Among these strategies, the utilization of solid-state electrolytes -inorganic and/or polymeric -potentially provides great advantages concerning the safe operation of lithium-metal anodes. [12,13] The first report on polymer electrolytes, characterized by high flexibility and light weight, dated back to the late 1970s with poly(ethylene oxide) (PEO) serving as the lithium salt dissolving medium. [14,15] Later, gel-type polymer electrolytes were developed by swelling a polymer matrix, such as poly(vinylidene fluoride-co-hexafluoropropylene) (PVdF-HFP), polyacrylonitrile (PAN), or poly(vinyl alcohol) (PVA) with a lithium salt-containing liquid electrolyte. [16] In such systems, the polymer essentially takes over the role of the separator and is not actively involved in the charge transport. Differently, the lithium salt anions substantially contribute to the charge transport, resulting in a lithium transference number (t Li + ) well below 0.5. This leads to a large concentration gradient and reversed electric field in the cell, which in turn results in large overpotentials, limited dis-/charge rates, and fast dendrite growth. [17][18][19][20] Accordingly, increasing the t Li + , ideally to a value close to unity, provides a solution to overcome the above mentioned challenges. The most straightforward approach to realize this is the covalent tethering of the anionic function to the polymer to immobilize the negative charge, yielding single-ion Single-ion conducting polymer electrolytes are considered particularly attractive for realizing high-performance solid-state lithium-metal batteries. Herein, a polysiloxane-based single-ion conductor (PSiO) is investigated. The synthesis is performed via a simple thiol-ene reaction, yielding flexible and self-standing polymer electrolyte membranes (PSiOM) when blended with poly(vinylidene fluoride-co-hexafluoropropylene) (PVdF-HFP). When incorporating 57 wt% of organic carbonates, these polymer membranes provide a Li + conductivity of >0.4 mS cm −1 at 20 °C ...

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Dynamics of [Pyr₁₃][Tf₂N] ionic liquid confined to carbon black

Abstract: Spectrally resolved PGSTE and T1 NMR revealed the dynamics of [Pyr13][Tf2N] confined to carbon black. Pore space loading has the potential to qualitatively change the RTIL dynamics in environments relevant for electrochemical applications.

Cited by 12 publications

References 78 publications

MAS-NMR of [Pyr13][Tf2N] and [Pyr16][Tf2N] Ionic Liquids Confined to Carbon Black: Insights and Pitfalls

MAS-NMR of [Pyr13][Tf2N] and [Pyr16][Tf2N] Ionic Liquids Confined to Carbon Black: Insights and Pitfalls

Independent component analysis combined with Laplace inversion of spectrally resolved spin-alignment echo/T ₁ 3D ⁷Li NMR of superionic Li₁₀GeP₂S₁₂

Polysiloxane‐Based Single‐Ion Conducting Polymer Blend Electrolyte Comprising Small‐Molecule Organic Carbonates for High‐Energy and High‐Power Lithium‐Metal Batteries

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Dynamics of [Pyr13][Tf2N] ionic liquid confined to carbon black

Abstract: Spectrally resolved PGSTE and T1 NMR revealed the dynamics of [Pyr13][Tf2N] confined to carbon black. Pore space loading has the potential to qualitatively change the RTIL dynamics in environments relevant for electrochemical applications.

Cited by 12 publications

References 78 publications

MAS-NMR of [Pyr13][Tf2N] and [Pyr16][Tf2N] Ionic Liquids Confined to Carbon Black: Insights and Pitfalls

MAS-NMR of [Pyr13][Tf2N] and [Pyr16][Tf2N] Ionic Liquids Confined to Carbon Black: Insights and Pitfalls

Independent component analysis combined with Laplace inversion of spectrally resolved spin-alignment echo/T 1 3D 7Li NMR of superionic Li10GeP2S12

Polysiloxane‐Based Single‐Ion Conducting Polymer Blend Electrolyte Comprising Small‐Molecule Organic Carbonates for High‐Energy and High‐Power Lithium‐Metal Batteries

Contact Info

Product

Resources

About

Dynamics of [Pyr₁₃][Tf₂N] ionic liquid confined to carbon black

Independent component analysis combined with Laplace inversion of spectrally resolved spin-alignment echo/T ₁ 3D ⁷Li NMR of superionic Li₁₀GeP₂S₁₂