NMR studies of Li mobility in NASICON-type glass-ceramic ionic conductors with optimized microstructure

AbstractThe glass-ceramics of the phosphorus containing Na5RSi4O12type (R=rare earth) Na+-superionic conductors (Narpsio-V) in the system Na2O-Sm2O3-P2O5-SiO2 were prepared by crystallization of glasses with the composition Na3+3x-ySm1-xPySi3-yO9. The optimum conditions for crystallization were discussed with reference to the conduction properties and the preparation of uncracked bulky glass-ceramic Narpsio-V. The ionic conductivity of the glass-ceramic Na3.9Sm0.6P0.3Si2.7O9 at 300°C was drastically enhanced from 2.38×10-2 S/cm to 7.15×10-2 S/cm upon implantation of 200 keV Na+ ions to a fluence of 1 × 1015 cm-2.

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Effect of simultaneous addition of aluminum and chromium on the lithium ionic conductivity of LiGe2(PO4)3 NASICON-type glass–ceramics

Solid State Ionics ◽

10.1016/j.ssi.2016.03.012 ◽

2016 ◽

Vol 289 ◽

pp. 180-187 ◽

Cited By ~ 22

Author(s):

Mohammad Illbeigi ◽

Alireza Fazlali ◽

Mahdi Kazazi ◽

Amir H. Mohammadi

Keyword(s):

Ionic Conductivity ◽

Glass Ceramics ◽

Simultaneous Addition ◽

Nasicon Type

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Copper-Conducting Nasicon-Type CuTi2(PO4)3 Glass-Ceramics for Application to a Novel O2 Sensor

MRS Proceedings ◽

10.1557/proc-548-641 ◽

1998 ◽

Vol 548 ◽

Cited By ~ 2

Author(s):

K. Yamamoto ◽

T. Kasuga ◽

M. NOGAMI

Keyword(s):

Electrical Conductivity ◽

Low Temperature ◽

Glass Ceramic ◽

Redox Reaction ◽

Electromotive Force ◽

Glass Ceramics ◽

Concentration Cell ◽

Nasicon Type ◽

Controlled Crystallization ◽

Crystallization Of Glass

ABSTRACTFast Cu+-conducting ceramics containing NASICON-type CuTi2(PO4)3 and Cu3 (PO4)2 phases, which three-dimensionally interlock with each other, has been successfully prepared by the controlled crystallization of glass in the Cu-Ti-P-O system. The electrical conductivity of the glass-ceramic was ∼3×10−4Scm−1 at 300°C. The obtained glass-ceramics was applied to an oxygen-concentration cell operating at low temperature such as 100°C. The electromotive force (EMF) of the sensor showed good Nemstian response. The mechanism for O2 sensing is discussed in terms of the redox reaction between Cu+ ion in the dense glass-ceramic and O2 gas.

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How Certain Are the Reported Ionic Conductivities of Thiophosphate-Based Solid Electrolytes? an Interlaboratory Study

10.26434/chemrxiv.11316497.v2 ◽

2020 ◽

Author(s):

Saneyuki Ohno ◽

Tim Bernges ◽

Johannes Buchheim ◽

Marc Duchardt ◽

Anna-Katharina Hatz ◽

...

Keyword(s):

Standard Deviation ◽

Ionic Conductivity ◽

Relative Standard Deviation ◽

Solid Electrolytes ◽

Ionic Conductivities ◽

Ionic Conductors ◽

Energy Storage Devices ◽

Activation Barriers ◽

Storage Devices ◽

Relative Standard

Owing to highly conductive solid ionic conductors, all-solid-state batteries attract significant attention as promising next-generation energy storage devices. A lot of research is invested in the search and optimization of solid electrolytes with higher ionic conductivity. However, a systematic study of an interlaboratory reproducibility of measured ionic conductivities and activation energies is missing, making the comparison of absolute values in literature challenging. In this study, we perform an uncertainty evaluation via a Round Robin approach using different Li-argyrodites exhibiting orders of magnitude different ionic conductivities as reference materials. Identical samples are distributed to different research laboratories and the conductivities and activation barriers are measured by impedance spectroscopy. The results show large ranges of up to 4.5 mScm-1 in the measured total ionic conductivity (1.3 – 5.8 mScm-1 for the highest conducting sample, relative standard deviation 35 – 50% across all samples) and up to 128 meV for the activation barriers (198 – 326 meV, relative standard deviation 5 – 15%, across all samples), presenting the necessity of a more rigorous methodology including further collaborations within the community and multiplicate measurements.

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Defect-Mediated Conductivity Enhancements in Na3-xPn1-xWxS4 (Pn = P, Sb) using Aliovalent Substitutions

10.26434/chemrxiv.9943961.v2 ◽

2019 ◽

Author(s):

Till Fuchs ◽

Sean Culver ◽

Paul Till ◽

Wolfgang Zeier

Keyword(s):

Ionic Conductivity ◽

Vacancy Concentration ◽

Sodium Ion ◽

High Ionic Conductivity ◽

Ionic Conductors ◽

X Ray Diffraction ◽

X Ray ◽

Solid State Batteries ◽

Ion Conducting ◽

Very High

The sodium-ion conducting family of Na3PnS4, with Pn = P, Sb, have gained interest for the use in solid-state batteries due to their high ionic conductivity. However, significant improvements to the conductivity have been hampered by the lack of aliovalent dopants that can introduce vacancies into the structure. Inspired by the need for vacancy introduction into Na3PnS4, the solid solutions with WS42- introduction are explored. The influence of the substitution with WS42- for PS43- and SbS43-, respectively, is monitored using a combination of X-ray diffraction, Raman and impedance spectroscopy. With increasing vacancy concentration improvements resulting in a very high ionic conductivity of 13 ± 3 mS·cm-1 for Na2.9P0.9W0.1S4 and 41 ± 8 mS·cm-1 for Na2.9Sb0.9W0.1S4 can be observed. This work acts as a stepping-stone towards further engineering of ionic conductors using vacancy-injection via aliovalent substituents.

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Defect-Mediated Conductivity Enhancements in Na3-xPn1-xWxS4 (Pn = P, Sb) using Aliovalent Substitutions

10.26434/chemrxiv.9943961.v1 ◽

2019 ◽

Author(s):

Till Fuchs ◽

Sean Culver ◽

Paul Till ◽

Wolfgang Zeier

Keyword(s):

Ionic Conductivity ◽

Vacancy Concentration ◽

Sodium Ion ◽

High Ionic Conductivity ◽

Ionic Conductors ◽

X Ray Diffraction ◽

X Ray ◽

Solid State Batteries ◽

Ion Conducting ◽

Very High

The sodium-ion conducting family of Na3PnS4, with Pn = P, Sb, have gained interest for the use in solid-state batteries due to their high ionic conductivity. However, significant improvements to the conductivity have been hampered by the lack of aliovalent dopants that can introduce vacancies into the structure. Inspired by the need for vacancy introduction into Na3PnS4, the solid solutions with WS42- introduction are explored. The influence of the substitution with WS42- for PS43- and SbS43-, respectively, is monitored using a combination of X-ray diffraction, Raman and impedance spectroscopy. With increasing vacancy concentration improvements resulting in a very high ionic conductivity of 13 ± 3 mS·cm-1 for Na2.9P0.9W0.1S4 and 41 ± 8 mS·cm-1 for Na2.9Sb0.9W0.1S4 can be observed. This work acts as a stepping-stone towards further engineering of ionic conductors using vacancy-injection via aliovalent substituents.

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Factors Affecting the Wear Behavior of Monolithic Zirconia and the Antagonists: Literature Review

Current Dentistry ◽

10.2174/2542579x02666200206111259 ◽

2020 ◽

Vol 2 (1) ◽

pp. 4-11

Author(s):

Marcia Borba ◽

Paula Benetti ◽

Giordana P. Furini ◽

Kátia R. Weber ◽

Tábata M. da Silva

Keyword(s):

Literature Review ◽

Glass Ceramic ◽

Wear Behavior ◽

Glass Ceramics ◽

Surface Treatments ◽

Human Tooth ◽

Initial Surface ◽

Monolithic Zirconia ◽

Feldspathic Porcelain

Background: The use of zirconia-based ceramics to produce monolithic restorations has increased due to improvements in the optical properties of the materials. Traditionally, zirconiabased ceramics were veneered with porcelain or glass-ceramic and were not directly exposed to the oral environment. Therefore, there are several doubts regarding the wear of the monolithic zirconia restoration and their antagonists. Additionally, different surface treatments are recommended to promote a smooth surface, including glaze and several polishing protocols. To support the correct clinical application, it is important to understand the advantages and limitations of each surface treatment. Objective: The aim of this short literature review is to investigate the factors that may affect the wear of monolithic zirconia restorations in service and their antagonists. Methods: Pubmed/Medline database was accessed to review the literature from a 10-year period using the keywords: zirconia, monolithic, prosthesis, wear. Both clinical and in vitro studies were included in the review. Results: Studies investigated the effect of several surface treatments, including grinding with diamond- burs, polishing and glazing, on the surface roughness, phase transformation and wear capacity of monolithic zirconia. The wear behavior of monolithic zirconia was frequently compared to the wear behavior of other ceramics, such as feldspathic porcelain, lithium disilicate-based glassceramic and leucite-reinforced glass-ceramic. Human tooth, ceramics and resin composites were used as antagonist in the investigations. Only short-term clinical studies are available (up to 2 years). Conclusion: Literature findings suggest that zirconia monolithic restorations are wear resistant and unlikely to cause excessive wear to the antagonist, especially when compared to feldspathic porcelain and glass-ceramics. Monolithic zirconia should be polished rather than glazed. Yet, none of the polishing systems studied was able to completely restore the initial surface conditions of zirconia after being adjusted with burs. More clinical evidence of the antagonist tooth wear potential of monolithic zirconia is needed.

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Towards Higher Electric Conductivity and Wider Phase Stability Range via Nanostructured Glass-Ceramics Processing

Nanomaterials ◽

10.3390/nano11051321 ◽

2021 ◽

Vol 11 (5) ◽

pp. 1321

Author(s):

Tomasz K. Pietrzak ◽

Marek Wasiucionek ◽

Jerzy E. Garbarczyk

Keyword(s):

Glass Ceramic ◽

Electronic Conductivity ◽

Glass Ceramics ◽

Temperature Stability ◽

Ceramic Materials ◽

Glassy Matrix ◽

Oxide Glasses ◽

Thermal Transitions ◽

Stability Range ◽

Conductivity Enhancement

This review article presents recent studies on nanostructured glass-ceramic materials with substantially improved electrical (ionic or electronic) conductivity or with an extended temperature stability range of highly conducting high-temperature crystalline phases. Such materials were synthesized by the thermal nanocrystallization of selected electrically conducting oxide glasses. Various nanostructured systems have been described, including glass-ceramics based on ion conductive glasses (silver iodate and bismuth oxide ones) and electronic conductive glasses (vanadate-phosphate and olivine-like ones). Most systems under consideration have been studied with the practical aim of using them as electrode or solid electrolyte materials for rechargeable Li-ion, Na-ion, all-solid batteries, or solid oxide fuel cells. It has been shown that the conductivity enhancement of glass-ceramics is closely correlated with their dual microstructure, consisting of nanocrystallites (5–100 nm) confined in the glassy matrix. The disordered interfacial regions in those materials form “easy conduction” paths. It has also been shown that the glassy matrices may be a suitable environment for phases, which in bulk form are stable at high temperatures, and may exist when confined in nanograins embedded in the glassy matrix even at room temperature. Many complementary experimental techniques probing the electrical conductivity, long- and short-range structure, microstructure at the nanometer scale, or thermal transitions have been used to characterize the glass-ceramic systems under consideration. Their results have helped to explain the correlations between the microstructure and the properties of these systems.

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Microstructural Effects on Conduction Properties of Na5YSi4 O 12‐Type Glass‐Ceramic Na + ‐Fast Ionic Conductors

Journal of The Electrochemical Society ◽

10.1149/1.1836978 ◽

1996 ◽

Vol 143 (7) ◽

pp. 2180-2186 ◽

Cited By ~ 16

Author(s):

Kimihiro Yamashita ◽

Takao Umegaki ◽

Masashi Tanaka ◽

Toshiya Kakuta ◽

Takeshi Nojiri

Keyword(s):

Glass Ceramic ◽

Ionic Conductors ◽

Fast Ionic Conductors ◽

Microstructural Effects ◽

Conduction Properties

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Anion ordering enables fast H− conduction at low temperatures

Science Advances ◽

10.1126/sciadv.abf7883 ◽

2021 ◽

Vol 7 (23) ◽

pp. eabf7883

Author(s):

Hiroki Ubukata ◽

Fumitaka Takeiri ◽

Kazuki Shitara ◽

Cédric Tassel ◽

Takashi Saito ◽

...

Keyword(s):

Ionic Conductivity ◽

Room Temperature ◽

Structural Transition ◽

Hexagonal Lattice ◽

Ionic Conductors ◽

Activation Barriers ◽

Energy Devices ◽

Energy Applications ◽

Chemical Disorder ◽

New Energy

The introduction of chemical disorder by substitutional chemistry into ionic conductors is the most commonly used strategy to stabilize high-symmetric phases while maintaining ionic conductivity at lower temperatures. In recent years, hydride materials have received much attention owing to their potential for new energy applications, but there remains room for development in ionic conductivity below 300°C. Here, we show that layered anion-ordered Ba2−δH3−2δX (X = Cl, Br, and I) exhibit a remarkable conductivity, reaching 1 mS cm−1 at 200°C, with low activation barriers allowing H− conduction even at room temperature. In contrast to structurally related BaH2 (i.e., Ba2H4), the layered anion order in Ba2−δH3−2δX, along with Schottky defects, likely suppresses a structural transition, rather than the traditional chemical disorder, while retaining a highly symmetric hexagonal lattice. This discovery could open a new direction in electrochemical use of hydrogen in synthetic processes and energy devices.

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