Fast Ion Transport In Solids Research Articles

Solid-state ionics: The key to the discovery and domination of lithium batteries: some learnings from β-alumina and titanium disulfide

Solid-state ionics, the study of fast ion transport in solids, expanded explosively after the discovery of sodium ion transport in β-alumina 50 years ago and has revolutionized energy storage. Lithium-ion batteries have come from a dream with titanium disulfide to enabling the communications revolution and are enabling renewable energy. Much can be learned from these early studies that will allow the attainment of a fossil-free society and a sustainable environment.

Rapid Low-Dimensional Li+ Ion Hopping Processes in Synthetic Hectorite-Type Li0.5[Mg2.5Li0.5]Si4O10F2.

Understanding the origins of fast ion transport in solids is important to develop new ionic conductors for batteries and sensors. Nature offers a rich assortment of rather inspiring structures to elucidate these origins. In particular, layer-structured materials are prone to show facile Li+ transport along their inner surfaces. Here, synthetic hectorite-type Li0.5[Mg2.5Li0.5]Si4O10F2, being a phyllosilicate, served as a model substance to investigate Li+ translational ion dynamics by both broadband conductivity spectroscopy and diffusion-induced 7Li nuclear magnetic resonance (NMR) spin–lattice relaxation experiments. It turned out that conductivity spectroscopy, electric modulus data, and NMR are indeed able to detect a rapid 2D Li+ exchange process governed by an activation energy as low as 0.35 eV. At room temperature, the bulk conductivity turned out to be in the order of 0.1 mS cm–1. Thus, the silicate represents a promising starting point for further improvements by crystal chemical engineering. To the best of our knowledge, such a high Li+ ionic conductivity has not been observed for any silicate yet.

Solid Polymer Electrolytes Based on Chitosan and Europium Triflate

The solid polymer electrolytes (SPEs) have been extensively studied since the pioneering work of Wright and Armand et al[1, 2]. Previous studies were focused on poly(ethylene oxide) (PEO) and lithium salts [3]. However recent research aimed at developing SPE based on natural polymers, which are interesting due to their natural abundance, low price and environmentally friendly nature [4]. Chitosan is a natural polymer obtained from chitin and it has been largely investigated due to its biodegradability, non-toxicity, absorption properties and biocompatibility. In this presentation are described the preparation and characterization of novel systems from chitosan and europium (III) trifluoromethanesulfonate salt. The transparent samples were characterized by thermal analysis (DSC and TGA), impedance spectroscopy and electron paramagnetic resonance (EPR). The Chitosan55.04%Eu(Trif)3 sample showed the best ionic conductivity of 1.52×10-6 and 7.66×10-5 S∙cm-1 at 25ºC and 80ºC, respectively. The thermal analysis revealed that the degradation started at around 120 - 145ºC and the weight loss ranged from 15 to 40%. The EPR analysis showed a broadening of the EPR resonance lines with increasing europium contents in the chitosan membranes due to the magnetic dipole–dipole coupling and spin-spin exchange between the Eu2+ions. ACKNOWLEDGEMENTS We are grateful to the Fundação para a Ciência e Tecnologia (PestC/QUI/UI0686/2013, POPH/FSE for a grant SFRH/BD/97232/2013 (R. Alves)) for financial support of this work. The authors are also grateful to, FAPESP, CNPq and CAPES for financial support. M. M. Silva acknowledges CNPq, for the mobility grant provided by this institution. REFERENCES [1] P. V. Wright, British Polymer Journal 7 (1975) 319. [2] M. B. Armand. J. M. Chabagno, M. J. Duclot, In Fast Ion Transport in Solids; Vashishta, P., Mundy, J. N., Shenoy, G. K., Eds.; North-Holland: Amsterdam, The Netherlands, 1979, p 131. [3] P. K. Varshney, S. Gupta, Ionics 17 (2011) 479-483. [4] I. S. M. Noor, S. R. Majid, A. K. Arof, D. Djurado, S. C. Neto, A. Pawlicka, Solid State Ionics 225 (2012) 649-653.

Influence of Si/P ordering on Na+ transport in NASICONs

The influence of Si/P ordering on Na(+) transport in the high conducting NASICON composition, Na3Zr2Si2PO12, is investigated using molecular dynamics simulation. The study demonstrates that the Na(+) conductivity in the system changes by more than an order of magnitude depending on the Si/P order in the structure. This rather surprising observation is attributed to the modulations in the electrostatic potential energy landscape along the conduction channel originating out of the increased coulombic repulsion of Na(+) with P(5+) ions compared to Si(4+). The study reveals the significance of the order of framework cations in fast ion transport in solids with aliovalent substitutions.

Fast Ion Transport in Solids

Fast Ion Transport in Solids

Superionicity as a local fluctuation of the chemical bond

A microscopic model is proposed for the fast ion transport in solids. It is suggested that the change of bonding which occurs locally and fluctuates in time is the key mechanism responsible for the superionicity. The change of bonding is considered to be driven by the lattice vibration. In order to corroborate the idea, the bonding nature of binary compounds have been studied by using a pseudopotential theory. It is concluded that the real space pseudopotential which reflects the valence electron distribution, provides useful information to understand the link between the ion transport and the electronic structure of the materials.

ChemInform Abstract: How to Study Fast Ion Transport in Solids by NMR

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A chemical approach for the microscopic mechanism of fast ion transport in solids

A microscopic mechanism that explains the various behaviors observed in superionic conductors is proposed. It is suggested that the local change of chemical bond which fluctuates in time is responsible for the fast ion transport in solids. Criteria which decide if a certain material can behave as superionic conductor or not are also given, and it is suggested that compounds based on cadmium and mercury chalcogenides are strong candidates to be superionics.

How to Study Fast Ion Transport in Solids by Nuclear Magnetic Resonance (NMR)

How to Study Fast Ion Transport in Solids by Nuclear Magnetic Resonance (NMR)

Fast ion transport in solids induced by an electric field

A theoretical model is suggested to describe the abrupt transition, induced by an electric field, of a cation sublattice in the ionic crystal bulk, as a result of which the crystal passes into the superionic conductivity state. The concepts which underlie the model are that the Frenkel defect interactions play an essential part in crystal, and the electric field greatly influences the defect formation energy. Expressions for the free energy of disordering, for the interstitial population in the crystal as a function of the strength of the electric field applied and for the critical value of the electric field which induces phase transitions have been obtained in terms of the mean field approximation. The first experimental data on the discovery and analysis of the jump in the ionic conductivity induced by an electric field, described previously, are discussed.

Fast ion transport in oxide glasses

The discovery of fast ion transport in solids has in recent years stimulated much interest in the scientific community both with regard to obtaining improved understanding of the phenomenon and applying such materials in advanced battery systems. More recently the phenomenon of fast ion transport has also been observed to occur in increasing numbers of amorphous systems. In this paper we review recent transport data obtained in over 100 glasses which appear to exhibit exceptionally high Ag, Li, Na and F ion conductivities at temperatures far from the melting points. We also include results recently obtained in our laboratory for glasses in the lithium borate system. Common characteristics of these glasses are summarized and are compared with predictions of classical diffusion theory. Relatively low and composition-independent values of σ 0 indicate poor agreement with a simple isolated-ion diffusion model, while composition-dependent activation energies are related to structural changes. Some glasses share similar properties with their crystalline counterparts while others do not. This is discussed in terms of the relative disorder already existing within the crystals. The need for improved characterization of glasses is also discussed.

21–25 May 1979 Fast ion transport in solids—Electrolytes and electrodes, Lake Geneva, Wisconsin, U.S.A.

21–25 May 1979 Fast ion transport in solids—Electrolytes and electrodes, Lake Geneva, Wisconsin, U.S.A.

21–25 May 1979 Fast ion transport in solids- Electrolytes and electrodes, Lake Geneva, Wisconsin, U.S.A.

21–25 May 1979 Fast ion transport in solids- Electrolytes and electrodes, Lake Geneva, Wisconsin, U.S.A.

Fast ion transport in solids — electrolytes and electrodes

Fast ion transport in solids — electrolytes and electrodes

Mechanism of fast ion transport in solids

The mechanism of fast ionic diffusion in solids is discussed in terms of isolated defects and domains for stoichiometric and non-stoichiometric compounds such as silver iodide and sodium β-alumina. The structural criteria for finding fast motion and some recent data on tunnel and layer materials are described.

Fast Ion Transport in Solids, Solid State Batteries and Devices, Proceedings of the NATO sponsored Advanced Study Institute at Belgirate, Italy, September, 1972 edited by W. van Gool, North Holland, Amsterdam, 1973. xvi+728 pages, Dfl. 100 (about$35.10)

Fast Ion Transport in Solids, Solid State Batteries and Devices, Proceedings of the NATO sponsored Advanced Study Institute at Belgirate, Italy, September, 1972 edited by W. van Gool, North Holland, Amsterdam, 1973. xvi+728 pages, Dfl. 100 (about$35.10)

Fast Ion Transport in Solids, Solid State Batteries and Devices

not Available.