High Li-ionic conductivity of Li29Zr9Nb3O40 ceramic sintered in oxygen-deficient atmosphere

2022 ◽  
Vol 896 ◽  
pp. 163082
Author(s):  
Jiahao Chen ◽  
Hong Zhang ◽  
Lin Yang ◽  
Hongzhu Chen ◽  
Junming Shao ◽  
...  
Keyword(s):  
Ionic Conductivity

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

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

<p>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 <i>interlaboratory reproducibility</i> 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<sup>-1</sup> in the measured total ionic conductivity (1.3 – 5.8 mScm<sup>-1</sup> 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.</p>

Under Pressure: Mechanochemical Effects on Structure and Ion Conduction in the Sodium-Ion Solid Electrolyte Na3PS4

2020 ◽  
Author(s):  
Theodosios Famprikis ◽  
O. Ulas Kudu ◽  
James Dawson ◽  
Pieremanuele Canepa ◽  
François Fauth ◽  
...  
Keyword(s):  
Ionic Conductivity ◽  
Mechanochemical Synthesis ◽  
Activation Volume ◽  
External Pressure ◽  
Sodium Ion ◽  
Variable Pressure ◽  
Ion Conductor ◽  
Ceramic Synthesis ◽  
Solid State Batteries ◽  
Fast Ion

<div> <p>Fast-ion conductors are critical to the development of solid-state batteries. The effects of mechanochemical synthesis that lead to increased ionic conductivity in an archetypical sodium-ion conductor Na<sub>3</sub>PS<sub>4</sub> are not fully understood. We present here a comprehensive analysis based on diffraction (Bragg, pair distribution function), spectroscopy (impedance, Raman, NMR, INS) and <i>ab-initio</i> simulations aimed at elucidating the synthesis-property relationships in Na<sub>3</sub>PS<sub>4</sub>. We consolidate previously reported interpretations about the local structure of ball-milled samples, underlining the sodium disorder and showing that a local tetragonal framework more accurately describes the structure than the originally proposed cubic one. Through variable-pressure impedance spectroscopy measurements, we report for the first time the activation volume for Na<sup>+</sup> migration in Na<sub>3</sub>PS<sub>4</sub>, which is ~30% higher for the ball-milled samples. Moreover, we show that the effect of ball-milling on increasing the ionic conductivity of Na<sub>3</sub>PS<sub>4</sub> to ~10<sup>-4</sup> S/cm can be reproduced by applying external pressure on a sample from conventional high temperature ceramic synthesis. We conclude that the key effects of mechanochemical synthesis on the properties of solid electrolytes can be analyzed and understood in terms of pressure, strain and activation volume.</p> </div>

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

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

<p>The sodium-ion conducting family of Na<sub>3</sub><i>Pn</i>S<sub>4</sub>, with <i>Pn</i> = 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 Na<sub>3</sub><i>Pn</i>S<sub>4</sub>, the solid solutions with WS<sub>4</sub><sup>2-</sup> introduction are explored. The influence of the substitution with WS<sub>4</sub><sup>2-</sup> for PS<sub>4</sub><sup>3-</sup> and SbS<sub>4</sub><sup>3-</sup>, 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<sup>-1</sup> for Na<sub>2.9</sub>P<sub>0.9</sub>W<sub>0.1</sub>S<sub>4</sub> and 41 ± 8 mS·cm<sup>-1</sup> for Na<sub>2.9</sub>Sb<sub>0.9</sub>W<sub>0.1</sub>S<sub>4</sub> can be observed. This work acts as a stepping-stone towards further engineering of ionic conductors using vacancy-injection via aliovalent substituents.</p>

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

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

<p>The sodium-ion conducting family of Na<sub>3</sub><i>Pn</i>S<sub>4</sub>, with <i>Pn</i> = 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 Na<sub>3</sub><i>Pn</i>S<sub>4</sub>, the solid solutions with WS<sub>4</sub><sup>2-</sup> introduction are explored. The influence of the substitution with WS<sub>4</sub><sup>2-</sup> for PS<sub>4</sub><sup>3-</sup> and SbS<sub>4</sub><sup>3-</sup>, 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<sup>-1</sup> for Na<sub>2.9</sub>P<sub>0.9</sub>W<sub>0.1</sub>S<sub>4</sub> and 41 ± 8 mS·cm<sup>-1</sup> for Na<sub>2.9</sub>Sb<sub>0.9</sub>W<sub>0.1</sub>S<sub>4</sub> can be observed. This work acts as a stepping-stone towards further engineering of ionic conductors using vacancy-injection via aliovalent substituents.</p>

Changing the Static and Dynamic Lattice Effects for the Improvement of the Ionic Transport Properties Within the Argyrodite Li6PS5-xSexI

2019 ◽  
Author(s):  
Roman Schlem ◽  
Michael Ghidiu ◽  
Sean Culver ◽  
Anna-Lena Hansen ◽  
Wolfgang Zeier
Keyword(s):  
Ionic Conductivity ◽  
Activation Barrier ◽  
Parent Compound ◽  
Ionic Transport ◽  
X Ray Diffraction ◽  
X Ray ◽  
Lattice Effects ◽  
Solid State Batteries ◽  
All Solid State Batteries ◽  
Pulse Echo

<p>The lithium argyrodites Li<sub>6</sub>PS<sub>5</sub>X (X = Cl, Br, I) have been gaining momentum as candidates for electrolytes in all-solid-state batteries. While these materials have been well-characterized structurally, the influences of the static and dynamic lattice properties are not fully understood. Recent improvements to the ionic conductivity of Li<sub>6</sub>PS<sub>5</sub>I (which as a parent compound is a poor ionic conductor) via elemental substitutions have shown that a multitude of influences affect the ionic transport in the lithium argyrodites, and that even poor conductors in this class have room left for improvement.</p><p>Here we explore the influence of isoelectronic substitution of sulfur with selenium in Li<sub>6</sub>PS<sub>5-<i>x</i></sub>Se<i><sub>x</sub></i>I. Using a combination of X-ray diffraction, impedance spectroscopy, Raman spectroscopy, and pulse-echo speed of sound measurements,we explore the influence of the static and dynamic lattice on the ionic transport. The substitution of S<sup>2-</sup>with Se<sup>2- </sup>broadens the diffusion pathways and structural bottlenecks, as well as leading to a softer more polarizable lattice, all of which lower the activation barrier and lead to an increase in the ionic conductivity. This work sheds light on ways to systematically understand and improve the functional properties of this exciting material family. </p>

Characterizations of Synthetic 8mol% YSZ with Comparison to 3mol %YSZ for HT-SOFC

2020 ◽  
Vol 38 (4A) ◽  
pp. 491-500
Author(s):  
Abeer F. Al-Attar ◽  
Saad B. H. Farid ◽  
Fadhil A. Hashim
Keyword(s):  
Ionic Conductivity ◽  
Electrochemical Impedance ◽  
Structural Information ◽  
Impedance Analysis ◽  
High Energy ◽  
Yttria Stabilized Zirconia ◽  
X Ray Diffraction ◽  
Stabilized Zirconia ◽  
Powder Morphology ◽  
X Ray

In this work, Yttria (Y2O3) was successfully doped into tetragonal 3mol% yttria stabilized Zirconia (3YSZ) by high energy-mechanical milling to synthesize 8mol% yttria stabilized Zirconia (8YSZ) used as an electrolyte for high temperature solid oxide fuel cells (HT-SOFC). This work aims to evaluate the densification and ionic conductivity of the sintered electrolytes at 1650°C. The bulk density was measured according to ASTM C373-17. The powder morphology and the microstructure of the sintered electrolytes were analyzed via Field Emission Scanning Electron Microscopy (FESEM). The chemical analysis was obtained with Energy-dispersive X-ray spectroscopy (EDS). Also, X-ray diffraction (XRD) was used to obtain structural information of the starting materials and the sintered electrolytes. The ionic conductivity was obtained through electrochemical impedance spectroscopy (EIS) in the air as a function of temperatures at a frequency range of 100(mHz)-100(kHz). It is found that the 3YSZ has a higher density than the 8YSZ. The impedance analysis showed that the ionic conductivity of the prepared 8YSZ at 800°C is0.906 (S.cm) and it was 0.214(S.cm) of the 3YSZ. Besides, 8YSZ has a lower activation energy 0.774(eV) than that of the 3YSZ 0.901(eV). Thus, the prepared 8YSZ can be nominated as an electrolyte for the HT-SOFC.

Solid Polymer Electrolytes from Crosslinked PEG and Dilithium N,N'-Bis(trifluoromethanesulfonyl)perfluoroalkane-1,ω-disulfonamide and Lithium Bis(trifluoromethanesulfonyl)imide Salts

2008 ◽  
Vol 73 (12) ◽  
pp. 1777-1798 ◽  
Author(s):  
Olt E. Geiculescu ◽  
Rama V. Rajagopal ◽  
Emilia C. Mladin ◽  
Stephen E. Creager ◽  
Darryl D. Desmarteau
Keyword(s):  
Ionic Conductivity ◽  
Polymer Electrolytes ◽  
Minimum Energy ◽  
Ionic Conductivities ◽  
Solid Polymer Electrolytes ◽  
Solid Polymer ◽  
Segmental Motion ◽  
Concentrated Electrolytes ◽  
Two Factors ◽  
Poly Ethylene

The present work consists of a series of studies with regard to the structure and charge transport in solid polymer electrolytes (SPE) prepared using various new bis(trifluoromethanesulfonyl)imide (TFSI)-based dianionic dilithium salts in crosslinked low-molecular-weight poly(ethylene glycol). Some of the thermal properties (glass transition temperature, differential molar heat capacity) and ionic conductivities were determined for both diluted (EO/Li = 30:1) and concentrated (EO/Li = 10:1) SPEs. Trends in ionic conductivity of the new SPEs with respect to anion structure revealed that while for the dilute electrolytes ionic conductivity is generally rising with increased length of the perfluoroalkylene linking group in the dianions, for the concentrated electrolytes the trend is reversed with respect to dianion length. This behavior could be the result of a combination of two factors: on one hand a decrease in dianion basicity that results in diminished ion pairing and an enhancement in the number of charge carriers with increasing fluorine anion content, thereby increasing ionic conductivity while on the other hand the increasing anion size and concentration produce an increase in the friction/entanglements of the polymeric segments which lowers even more the reduced segmental motion of the crosslinked polymer and decrease the dianion contribution to the overall ionic conductivity. DFT modeling of the same TFSI-based dianionic dilithium salts reveals that the reason for the trend observed is due to the variation in ion dissociation enthalpy, derived from minimum-energy structures, with respect to perfluoroalkylene chain length.

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