An Elementary Picture of Dielectric Spectroscopy in Solids: Physical Basis

Delgado, Adolfo; García-Sánchez, M.F.; M’Peko, Jean-Claude; Ruiz‐Salvador, A. Rabdel; Rodríguez‐Gattorno, Geonel; Echevarría, Yuri; Fernandez-Gutierrez, F.

doi:10.1021/ed080p1062

Cited by 79 publications

(38 citation statements)

References 44 publications

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“…In practice, accordingly, the value of resistance basically reduces to the diameter of the corresponding impedance semicircle. 13,15 As expected from conductive processes in dielectric-like materials, the resistance-related semicircle diameter in Fig. 3 decreases with the increasing temperature.…”

Section: Resultssupporting

confidence: 55%

“…This suggests that glycerol, used as plasticizer, should in some way participate in the dissociation of the salt ions that are finally accumulated at the sample-electrode interface, as it was proposed also elsewhere. 16 In any case, as generally found in literature, 13,15 the dielectric characterization of the inner response from these DNA-based membranes should absolutely concentrate on the high-frequency region.…”

Section: Resultsmentioning

confidence: 77%

“…4(a) and (b), and following the criteria on the order of magnitude of capacitance; established in literature, 13,15 the above capacitance plateau-related C 0 values on the order of 10 À11 and 10 À5 F can be here associated, respectively, with the high-frequency bulk DNA matrix behavior and the low-frequency materialelectrode interface polarization processes. In particular, the low-frequency C 0 values for the LiClO 4 -containing membranes were mostly, in average, somewhat higher than those for the LiClO 4 -free ones (with comparable geometrical factor), especially toward the lower measurement temperatures.…”

Section: Resultsmentioning

confidence: 86%

“…The order magnitude of the capacitance elements, involved in the whole equivalent circuit representing the material, irrespective of its physico-chemical nature, may be used to identify the origin (e.g., bulk matrix or interface) of the observed dielectric response. 13,15 Alternatively, in theory, such an analysis may be also performed when looking directly at the frequency spectra of capacitance of the material under study. The mathematical relationship between the complex capacitance and the impedance is well known to follow the expression…”

Section: Resultsmentioning

confidence: 99%

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DNA-based ionic conducting membranes

Firmino¹,

Grote²,

Kajzar³

et al. 2011

Journal of Applied Physics

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Deoxyribonucleic acid based gel solid electrolytes were prepared and their electric properties were characterized. Their ionic conductivity is in the range of 10 À4-10 À5 S/cm at room temperature and increases linearly in function of temperature, obeying an Arrhenius-like relationship. The present study, combined with the literature data, suggests that the electrical conduction mechanism in these membranes involve ion motion and/or charge hopping, promoted most likely by a significant interaction between the membrane components. The good conductivity results, as found here, together with the good transparency and good adhesion to the electrodes show that the DNA-based gel polymer electrolytes are very promising materials for application in various electrochromic devices.

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Section: Resultssupporting

confidence: 55%

Section: Resultsmentioning

confidence: 77%

Section: Resultsmentioning

confidence: 86%

Section: Resultsmentioning

confidence: 99%

See 2 more Smart Citations

DNA-based ionic conducting membranes

Firmino¹,

Grote²,

Kajzar³

et al. 2011

Journal of Applied Physics

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“…11,25−28 In the case of solid-state ion conductors, electric modulus spectroscopy often provides more-instructive spectra, as the modulus is inversely related to capacitance (M* = 1/C*) and the bulk microregions of the material typically have the smallest capacitance by 2−3 orders of magnitude, when compared with the grain boundaries. [19][20][21]29 For this analysis, M″ vs f was plotted and the critical frequency of the loss peak corresponding to the bulk response was followed over the temperature sweeps. Figure 5a shows selected data points recorded for LGP that demonstrate the temperature dependence of the imaginary modulus loss peak position.…”

Section: Chemistry Of Materialsmentioning

confidence: 99%

Lithium-Ion Trapping from Local Structural Distortions in Sodium Super Ionic Conductor (NASICON) Electrolytes

2014

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Herein, we report a study on the structural and thermodynamic effects that cation size disparity may have in NASICONtype solid solutions. A sol−gel procedure was used to synthesize two new NASICON-type lithium-ion conductors with nominal compositions LiGe 2−y Sn y (PO 4 ) 3 and Li 1+x Al x Ge 2−y−(1/2)x Sn y−(1/2)x (PO 4 ) 3 . The effect of tin substitution on structure and lithium-ion conductivity was studied with powder X-ray diffraction, Raman spectroscopy, and dielectric spectroscopy. It is found that, although increased unit-cell dimensions derived from X-ray data suggest that tin incorporation should open the conduction bottleneck regions and improve conductivity, a decrease in conductivity is observed. Analysis of the electrical data shows that the conduction activation energy is comprised of contributions from carrier motion and generation, the latter accounting for up to 20% of the total activation energy. This result, currently unreported for NASICON-type materials, is correlated with local structural distortions observed in Raman spectra. It is deduced that the bottleneck regions suffer distortions due to the large ionic radius disparity among cationic constituents, which results in the "trapping" of charge carriers. Data estimated for the entropy of motion are also presented and discussed, considering the most probable thermodynamic equilibrium states.

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Elucidation of Enhanced Lithium Conductivity in Nanoporous Ionogel Using Solid State NMR

Weijers

Karanth

Ganapathy

et al. 2022

Adv Materials Inter

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Hybrid electrolytes may have synergistic properties enhancing mechanical strength, ionic conductivity and/or mechanical, or thermal stability. [3,4] The of sol-gel processed ionogels form composites in situ, which is a different approach than physical mixture composites in example. [3][4][5][6][7] Recently Sagara et al. found synergistic properties of the lithium-bis((fluorosulfonyl) imide/1-ethyl-3-methylimidazolium bis(fluorosulfonyl)imide (Li-FSI/EMI-FSI) and lithium-bis((trifluoromethylsulfonyl) imide 1-butyl-1-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide (Li-TFSI/BMP-TFSI) ILEs combined with a silicon network in which the obtained gel showed better lithium ion conductivities than the bulk ionic liquid. [8,9] In this work the ionogel shows similar rate performance compared to conventional liquid electrolyte LiPF 6 in EC:DMC in Li-LFP battery cells. Chen et al. [10] proposed that the origin of this behavior that is, increase in lithium conductivity in nano-SCE is facilitated by the de-solvation of the lithium ions. In this work lithium-bis((trifluoromethyl)sulfonyl)imide/1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide (Li-TFSI/EMI-TFSI) ILE is used (Figure 1). Previously it has been shown that porous silica networks show several mechanisms which lead to a change in the diffusivity of the various mobile species. Guyomard-Lack et al. show that lithium diffusivity is an interplay between surface and bulk associated lithium concentrations. [11] The two environments are further elucidated by Jayakody et al. who show two diffusion regimes by varying pore sizes, restrictive diffusion at the surface and long ranged diffusion in the bulk. [12] For nano-SCE comprising of SiO 2 , ILE and water, the silanol hydroxyl bonds are thought to be (partially) covered by water molecules. [10] In this structure, the TFSI anion hydrogen bonds through their OSO group with these immobilized water molecules. The EMI cations would show increased affinity compared to lithium cations with the formed TFSI layer through hydrogen bonding. As a result, with the proper number of water molecules, an immobile "glacial" layer is formed on the silicon backbone and charge layers emerge of which the layer next to water molecules consists predominantly of hydrogen bond making EMI cations. The charge layers form a dipole of which the TFSI associated to lithium is drawn, which leads to a lower net activation energy of lithium mobility. As this type of diffusion Nanostructured solid composite electrolyte or nano-SCE, which is composed of an ionic liquid, nanoporous silica, and residuals of immobilized precursor components, shows promising synergistic properties. The ionic conductivity of nano-SCE is in the range of 2-5 mS cm −1 , which exceeds the bulk ionic liquid conductivity at ambient temperature, while maintaining characteristics of a solid electrolyte such as having no leakage issues as the ionic liquid is confined, and lower flammability compared to conventional liquid electrolytes. In this study, the underlying mechanism...

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An Elementary Picture of Dielectric Spectroscopy in Solids: Physical Basis

Cited by 79 publications

References 44 publications

DNA-based ionic conducting membranes

DNA-based ionic conducting membranes

Lithium-Ion Trapping from Local Structural Distortions in Sodium Super Ionic Conductor (NASICON) Electrolytes

Elucidation of Enhanced Lithium Conductivity in Nanoporous Ionogel Using Solid State NMR

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