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

10.26434/chemrxiv.9943961 ◽

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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(Rare Earth/Li) Titanates and Niobates as Ionic Conductors

MRS Proceedings ◽

10.1557/proc-658-gg2.3 ◽

2000 ◽

Vol 658 ◽

Author(s):

A. Morata-Orrantia ◽

S. García-Martín ◽

E. Morán ◽

U. Amador ◽

M. A. Alario-Franco

Keyword(s):

Rare Earth ◽

Ionic Conductivity ◽

Lithium Ion ◽

Related Structure ◽

Ionic Conductors ◽

X Ray Diffraction ◽

X Ray ◽

Properties Of Materials ◽

Ion Conducting ◽

Diffraction Patterns

ABSTRACTThe lithium ion conducting properties of materials of composition La0.58Li0.26TiO3, Nd0.58Li0.26TiO3, La0.67Li0.25Ti0.75Al0.25O3 and La0.29Li0.12NbO3 have been compared in relation with their microstructure. All the oxides have powder X-ray diffraction patterns characteristic of a perovskite-related structure with lattice parameters a∼√2ap, b∼√2ap, c∼2ap (p refers to cubic perovskite). However, some important differences are observed in their microstructure by SAED and HRTEM. Ordering between vacancies, Li+ and La3+ or Nd3+ and twinning of the NbO6 or TiO6 octahedra tilting system are shown in La0.29Li0.12NbO3 and Nd0.58Li0.26TiO3, which are the materials having a lower ionic conductivity. The La0.58Li0.26TiO3 and La0.67Li0.25Ti0.75Al0.25O3 oxides do not show ordering between cations.

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

10.26434/chemrxiv.9807770.v1 ◽

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

The lithium argyrodites Li6PS5X (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 Li6PS5I (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.Here we explore the influence of isoelectronic substitution of sulfur with selenium in Li6PS5-xSexI. 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 S2-with Se2- 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.

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Phase-locked constructing dynamic supramolecular ionic conductive elastomers with superior toughness, autonomous self-healing and recyclability

10.21203/rs.3.rs-1131433/v1 ◽

2021 ◽

Author(s):

Jing Chen ◽

Yiyang Gao ◽

Lei Shi ◽

Wei Yu ◽

Zongjie Sun ◽

...

Keyword(s):

Ionic Conductivity ◽

Lithium Ion ◽

High Ionic Conductivity ◽

Self Healing ◽

Ionic Conductors ◽

Soft Phase ◽

New Strategy ◽

Solid State Batteries ◽

Conductive Elastomers ◽

Phase Design

Abstract Stretchable ionic conductors are considerable to be the most attractive candidate for next-generation flexible ionotronic devices. Nevertheless, high ionic conductivity, excellent mechanical properties, good self-healing capacity and recyclability are necessary but can be rarely satisfied in one material. Herein, we demonstrate a novel ionic conductor design, dynamic supramolecular ionic conductive elastomers (DSICE), via “phase-locked” strategy, wherein “locking soft phase” polyether backbone conducts lithium-ion (Li+) transport and the combination of dynamic disulfide metathesis and stronger supramolecular quadruple hydrogen bonds in the hard domains contributes to the self-healing capacity and mechanical versatility. The dual-phase design performs its own functions and the conflict among ionic conductivity, self-healing capability, and mechanical compatibility can be thus defeated. The well-designed DSICE exhibits high ionic conductivity (3.77×10−3 S m−1 at 30°C), high transparency (92.3%), superior stretchability (2615.17% elongation), strength (27.83 MPa) and toughness (164.36 MJ m−3), excellent self-healing capability (~99% at room temperature) and favorable recyclability. This work provides a new strategy for designing the advanced ionic conductors and offers promise for flexible iontronic devices or solid-state batteries.

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

10.26434/chemrxiv.9807770.v2 ◽

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

The lithium argyrodites Li6PS5X (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 Li6PS5I (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.Here we explore the influence of isoelectronic substitution of sulfur with selenium in Li6PS5-xSexI. 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 S2-with Se2- 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.

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X-ray characterization of the new nasicon compositions Na3Zr2−x/4Si2−xP1+xO12 with x=0.333, 0.667, 1.000, 1.333, 1.667

Powder Diffraction ◽

10.1017/s0885715600009660 ◽

1997 ◽

Vol 12 (3) ◽

pp. 171-174 ◽

Cited By ~ 5

Author(s):

M. Lucco-Borlera ◽

D. Mazza ◽

L. Montanaro ◽

A. Negro ◽

S. Ronchetti

Keyword(s):

Ionic Conductivity ◽

Solid Electrolytes ◽

High Ionic Conductivity ◽

Constant Number ◽

Nasicon Structure ◽

Ionic Conductors ◽

X Ray ◽

Octahedral Sites ◽

First Time

It is known that solids with composition Na3Zr2Si2PO12 heated at 1200 °C crystallize in the nasicon structure. This material shows a high ionic conductivity that represents an interesting improvement in the field of solid electrolytes. Our experimental results allow to establish for the first time that nasicon structures are stable along the compositional join Na3Zr2−x/4Si2−xP1+xO12 with x extending from 0 to 1.667. These structures are characterized by a Zr underoccupation of octahedral sites and a constant number of Na+ ions. This fact envisages a possible application of these materials in the field of ceramic sensors and ionic conductors.

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

10.26434/chemrxiv.9807770 ◽

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

The lithium argyrodites Li6PS5X (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 Li6PS5I (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.Here we explore the influence of isoelectronic substitution of sulfur with selenium in Li6PS5-xSexI. 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 S2-with Se2- 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.

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High ion-conducting solid polymer electrolytes based on blending hybrids derived from monoamine and diamine polyethers for lithium solid-state batteries

RSC Advances ◽

10.1039/c7ra01542a ◽

2017 ◽

Vol 7 (33) ◽

pp. 20373-20383 ◽

Cited By ~ 6

Author(s):

Ta-Ming Liu ◽

Diganta Saikia ◽

Sze-Yuan Ho ◽

Ming-Chou Chen ◽

Hsien-Ming Kao

Keyword(s):

Solid State ◽

Ionic Conductivity ◽

Polymer Electrolyte ◽

Polymer Electrolytes ◽

Solid Polymer Electrolyte ◽

Solid Polymer Electrolytes ◽

High Ionic Conductivity ◽

Solid Polymer ◽

Solid State Batteries ◽

Ion Conducting

The blended hybrid solid polymer electrolyte possessed a high ionic conductivity value of 1.2 × 10−4 S cm−1 at 30 °C.

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On the Properties of an Ion Conductive System Incorporated in Hybrid Films

MRS Proceedings ◽

10.1557/proc-628-cc6.19 ◽

2000 ◽

Vol 628 ◽

Author(s):

G. González ◽

P. J. Retuert ◽

S. Fuentes

Keyword(s):

Electrochemical Impedance ◽

Ternary Phase Diagram ◽

Lithium Perchlorate ◽

Molar Ratio ◽

Ionic Conductors ◽

X Ray Diffraction ◽

Poly Ethylene Oxide ◽

Ion Conducting ◽

Poly Ethylene ◽

High Degree

ABSTRACTBlending the biopolymer chitosan (CHI) with poly (aminopropilsiloxane) oligomers (pAPS), and poly (ethylene oxide) (PEO) in the presence of lithium perchlorate lead to ion conducting products whose conductivity depends on the composition of the mixture. A ternary phase diagram for mixtures containing 0.2 M LiClO4 shows a zone in which the physical properties of the products - transparent, flexible, mechanically robust films - indicate a high degree of molecular compatibilization of the components. Comparison of these films with binary CHI-pAPS nanocomposites as well as the microscopic aspect, thermal behavior, and X-ray diffraction pattern of the product with the composition PEO/CHI/pAPS/LiClO4 1:0.5:0.6:0.2 molar ratio indicates that these films may be described as a layered nanocomposite. In this composite, lithium species coordinated by PEO and pAPS should be inserted into chitosan layers. Electrochemical impedance spectroscopy measurements indicate the films are pure ionic conductors with a maximal bulk conductivity of 1.7*10-5 Scm-1 at 40 °C and a sample-electrode interface capacitance of about 1.2*10-9 F.

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