Highly decoupled ionic and protonic solid electrolyte systems, in relation to other relaxing systems and their energy landscapes

Mizuno, Fuminori; Bélières, Jean-Philippe; Kuwata, Naoaki; Pradel, Annie; Ribes, M.; Angell, C. Austen

doi:10.1016/j.jnoncrysol.2006.06.006

Cited by 78 publications

(97 citation statements)

References 52 publications

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“…According to the latest reports on protic ionic conductors, the observed crossover is a manifestation of the liquid− glass transition of the ionic glass former. 13,17,20 In this context, it is crucial to note that the glass transition (Tg) is usually defined as the temperature at which the structural relaxation time (τα) reaches 1000 s. 36 However, for the hemisuccinate salt the conductivity relaxation time at the Tg point is even 100-fold faster than τα , τσ ∼ 5 s. This result suggests that in this case of the protic conductor there is a distinctive separation (decoupling) between the time-scale of ionic transport and structural relaxation in the vicinity of the glass transition temperature, that is, the charge transfer is continued when the host dynamics became arrested. Nevertheless, to investigate this phenomenon in more detail it is necessary to obtain information on the temperature behavior of structural relaxation times of the studied ionic materials.…”

Section: Generalmentioning

confidence: 99%

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Molecular Origin of Enhanced Proton Conductivity in Anhydrous Ionic Systems

et al. 2015

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Ionic systems with enhanced proton conductivity are widely viewed as promising electrolytes in fuel cells and batteries. Nevertheless, a major challenge toward their commercial applications is determination of the factors controlling the fast proton hopping in anhydrous conditions. To address this issue, we have studied novel proton-conducting materials formed via a chemical reaction of lidocaine base with a series of acids characterized by a various number of proton-active sites. From ambient and high pressure experimental data, we have found that there are fundamental differences in the conducting properties of the examined salts.On the other hand, DFT calculations revealed that the internal proton hopping within the cation structure strongly affects the pathways of mobility of the charge carrier. These findings offer a 2 fresh look on the Grotthuss-type mechanism in protic ionic glasses as well as provide new ideas for the design of anhydrous materials with exceptionally high proton conductivity.

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Section: Generalmentioning

confidence: 99%

“…13,25,26 Surprisingly, in the case of conventional imidazolium-based protic ionic liquids (ILs) the charge transfer is mostly coupled to structural relaxation. 14,27 The reason lies in the complete ionization of these systems combined with a low value of self-dissociation coefficient of the cation with both nitrogen atoms protonated.…”

Section: Introductionmentioning

confidence: 99%

Molecular Origin of Enhanced Proton Conductivity in Anhydrous Ionic Systems

et al. 2015

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“…In contrast to pure succinonitrile, this mixture remains in the orientationally disordered state down to low temperatures and crosses over to a glassy-crystal state at an orientational glass temperature of T g = 144 K. 20,21 . Most plastic crystals (including cyclo-octanol 22 ) can be characterized as rather "strong" glass formers 17,23 within the strong/fragile classification scheme used to account for the different degrees of deviations from Arrhenius behavior of the -relaxation time. 24 Thus 60SN-40GN is an especially Electronic mail: peter.lunkenheimer@physik.uni-augsburg.de interesting system as it represents one of the rare examples 25 of a relatively fragile plastic crystal.…”

Section: Introductionmentioning

confidence: 99%

“…24 Thus 60SN-40GN is an especially Electronic mail: peter.lunkenheimer@physik.uni-augsburg.de interesting system as it represents one of the rare examples 25 of a relatively fragile plastic crystal. 20,23,26 Thus it is well suited to check if the relation between apparent energy barrier and N corr , suggested for structural glass formers, 6 holds in plastic crystals, too: For a fragile material this relation should lead to a significantly stronger variation of N corr than the relatively weak temperature dependence observed in cyclo-octanol. 8 In addition, we study the fieldinduced peak broadening, which is also found in 60SN-40GN, however with some deviations from the behavior reported in the other plastic crystals.…”

Section: Introductionmentioning

confidence: 99%

Nonlinear dielectric spectroscopy in a fragile plastic crystal

Michl

Bauer

Lunkenheimer

et al. 2016

The Journal of Chemical Physics

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In this work we provide a thorough examination of the nonlinear dielectric properties of a succinonitrileglutaronitrile mixture, representing one of the rare example of a plastic crystal with fragile glassy dynamics. The detected alteration of the complex dielectric permittivity under high fields can be explained considering the heterogeneous nature of glassy dynamics and a field-induced variation of entropy. While the first mechanism was also found in structural glass formers, the latter effect seems to be typical for plastic crystals. Morover, the third harmonic component of the dielectric susceptibility is reported, revealing a spectral shape as predicted for cooperative molecular dynamics. In accord with the fragile nature of the glass transition in this plastic crystal, we deduce a relatively strong temperature dependence of the number of correlated molecules, in contrast to the much weaker temperature dependence in plasticcrystalline cyclo-octanol, whose glass transition is of strong nature.

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“…R τ gives a physical idea of the relation between the conductivity and the structural relaxation processes (Mizuno, et al, 2006). This index describes the extent to which the charge carrier conducting motions in a given glass can be considered decoupled/coupled from the polymeric chains motions of the glassy matrix (Merino, et al, 2011).…”

Section: Dielectric Measurementsmentioning

confidence: 99%

A contribution to the study of the molecular mobility in polymeric materials by Thermal and Dielectric Analysis

Foj¹,

Belén²

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T h e s i s S u p e r v i s o r : P R O F . D r . M a r í a J e s ú s S a n c h i s S á n c h e z t o o b t a i n t h e d e g r e e o f D o c t o r o f P h i l o s o p h y a t t h e U n i v e r s i t a t P o l i t è c n i c a d e V a l è n c i a Prof. Dr. María Jesús Sanchis SánchezThe work presented in this thesis was carried out at the Universitat Politècnica de València and was financially supported by the Spanish Ministry of Economy and Competitiveness (Projects Nos. MAT2008-06725-C03-03 and MAT2012-33483)."Cuando quieres algo, todo el Universo conspira para que ACKNOWLEDGEMENTSTras estos años de trabajo, llega el momento de mostrar mi agradecimiento a todas las personas que me han acompañado y apoyado durante el desarrollo de mi tesis doctoral.En primer lugar, me gustaría expresar mi gratitud a mi directora de tesis María J.Sanchis por su inestimable ayuda durante todos estos años. Muchas gracias por confiar en mí, por darme esta oportunidad y por las incalculables horas invertidas tanto para el desarrollo de esta tesis como al mío propio.También me gustaría agradecer a mis estimadas compañeras Marta Carsí y Pilar Ortiz su ayuda y amistad en este largo recorrido que suponer realizar una tesis doctoral. He aprendido mucho de vosotras tanto científica como personalmente. En este punto, no puedo olvidarme de mi querida Aurora Alonso, que pese a no formar parte de nuestro grupo de investigación, me ha apoyado, aconsejado y dado su amistad durante todos estos años.Quiero mostrar mi agradecimiento a los profesores José M. García y Félix C. García ABSTRACTThe development of new and more complex polymeric materials involves challenging problems to basic sciences. The relationship between structure and molecular dynamics assumes great importance for the future development of novel technologies based on such polymers. Thus, the understanding of how small changes in the chemical structure affect the properties of the material is essential to progress in the technological and scientific area. An in-depth analysis of the molecular mobility leads to establish the structure-properties relationships. On this basis, the main aim of the present work is to study the molecular mobility of two different families of polymeric materials. For this purpose, the experimental techniques mainly used were Differential Scanning Calorimetry (DSC) and Dielectric Relaxation Spectroscopy (DRS) (Chapter 3).The first family of polymers characterized was a series of chemically cross-linked copolymers composed by Vinylpyrrolidone (VP) and Butyl Acrylate (BA) monomers. The study was divided in two parts, which are collected in Chapter 4 and 5.In the first place, Chapter 4 contains the influence of the monomer molar ratio (XVP/YBA) on the copolymer properties. Thus, a Fourier Transform Infrared Spectroscopy (FTIR) analysis verified dipole-dipole interactions between amide groups. The influence of these interactions on several parameters related to the molecular mobility was evidenced by the DSC, DRS and Dynamic Mechanical Analysis (DMA) techni...

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Highly decoupled ionic and protonic solid electrolyte systems, in relation to other relaxing systems and their energy landscapes

Cited by 78 publications

References 52 publications

Molecular Origin of Enhanced Proton Conductivity in Anhydrous Ionic Systems

Molecular Origin of Enhanced Proton Conductivity in Anhydrous Ionic Systems

Nonlinear dielectric spectroscopy in a fragile plastic crystal

A contribution to the study of the molecular mobility in polymeric materials by Thermal and Dielectric Analysis

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