New insights in the mechanism of cation migration induced by cation-anion dynamic coupling in superionic conductors

This review focuses on fundamental understanding, various synthesis routes, chemical/electrochemical stability of halide-based lithium superionic conductors, and their potential applications in energy storage as well as related challenges.

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Magnetism and ion diffusion in honeycomb layered oxide $${\hbox {K}_2\hbox {Ni}_2\hbox {TeO}_6}$$

Scientific Reports ◽

10.1038/s41598-020-75251-x ◽

2020 ◽

Vol 10 (1) ◽

Cited By ~ 1

Author(s):

Nami Matsubara ◽

Elisabetta Nocerino ◽

Ola Kenji Forslund ◽

Anton Zubayer ◽

Konstantinos Papadopoulos ◽

...

Keyword(s):

Low Temperature ◽

Muon Spin ◽

Diffusion Mechanism ◽

Diffusion Constant ◽

Muon Spin Rotation ◽

Oxide Material ◽

Ion Diffusion ◽

Energy Materials ◽

Layered Oxide ◽

Energy Devices

Abstract In the quest for developing novel and efficient batteries, a great interest has been raised for sustainable K-based honeycomb layer oxide materials, both for their application in energy devices as well as for their fundamental material properties. A key issue in the realization of efficient batteries based on such compounds, is to understand the K-ion diffusion mechanism. However, investigation of potassium-ion (K$$^+$$ + ) dynamics in materials using e.g. NMR and related techniques has so far been very challenging, due to its inherently weak nuclear magnetic moment, in contrast to other alkali ions such as lithium and sodium. Spin-polarised muons, having a high gyromagnetic ratio, make the muon spin rotation and relaxation ($$\mu ^+$$ μ + SR) technique ideal for probing ions dynamics in these types of energy materials. Here we present a study of the low-temperature magnetic properties as well as K$$^+$$ + dynamics in honeycomb layered oxide material $${\hbox {K}_2\hbox {Ni}_2\hbox {TeO}_6}$$ K 2 Ni 2 TeO 6 using mainly the $$\mu ^+$$ μ + SR technique. Our low-temperature $$\mu ^+$$ μ + SR results together with complementary magnetic susceptibility measurements find an antiferromagnetic transition at $$T_{\mathrm{N}}\approx 27$$ T N ≈ 27 K. Further $${\mu}^{+}$$ μ + SR studies performed at higher temperatures reveal that potassium ions (K$$^+$$ + ) become mobile above 200 K and the activation energy for the diffusion process is obtained as $$E_{\mathrm{a}}=121 (13)$$ E a = 121 ( 13 ) meV. This is the first time that K$$^+$$ + dynamics in potassium-based battery materials has been measured using $$\mu ^+$$ μ + SR. Assisted by high-resolution neutron diffraction, the temperature dependence of the K-ion self diffusion constant is also extracted. Finally our results also reveal that K-ion diffusion occurs predominantly at the surface of the powder particles. This opens future possibilities for potentially improving ion diffusion as well as K-ion battery device performance using nano-structuring and surface coatings of the particles.

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Recent Progress in the Fundamental Understanding of Garnet-Based Superionic Conductors and Fabrication of Solid-State Cells for Advanced Lithium Batteries

ECS Meeting Abstracts ◽

10.1149/ma2015-02/3/236 ◽

2015 ◽

Keyword(s):

Solid State ◽

Lithium Batteries ◽

Recent Progress ◽

Superionic Conductors ◽

Fundamental Understanding

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Lithium ion diffusion mechanism in covalent organic framework based solid state electrolyte

Physical Chemistry Chemical Physics ◽

10.1039/c9cp02117e ◽

2019 ◽

Vol 21 (19) ◽

pp. 9883-9888 ◽

Cited By ~ 1

Author(s):

Kecheng Zhang ◽

Bingkai Zhang ◽

Mouyi Weng ◽

Jiaxin Zheng ◽

Shunning Li ◽

...

Keyword(s):

Solid State ◽

Diffusion Mechanism ◽

Lithium Ion ◽

One Dimension ◽

Ion Diffusion ◽

Solid State Electrolyte ◽

Covalent Organic Framework ◽

System P ◽

Lithium Ion Diffusion ◽

Organic Framework

Mechanism of Li-ions diffusion in a one-dimension tunnel of COF-5 and structure of the COF-5@LiClO4@THF system.

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1D to 2D Na-Ion Diffusion Linked to Structural Transitions in Na0.7CoO2

Acta Crystallographica Section A Foundations and Advances ◽

10.1107/s2053273314096363 ◽

2014 ◽

Vol 70 (a1) ◽

pp. C363-C363

Author(s):

Marisa Medarde ◽

Mattia Mena ◽

Jorge Gavilano ◽

Ekaterina Pomjakushina ◽

Jun Sugiyama ◽

...

Keyword(s):

Solid State ◽

Structural Similarity ◽

Clean Energy ◽

Rechargeable Batteries ◽

Atomic Scale ◽

Structural Transitions ◽

Ion Diffusion ◽

Energy Materials ◽

Energy Devices ◽

Neutron Powder Diffraction Data

One of the most important scientific problems faced by our society is how to convert and store clean energy. In order to achieve a significant progress in this field we need to understand the fundamental dynamical processes that govern the transfer of energy on an atomic scale. For many energy devices such as solid-state batteries and solid-oxide fuel cells, this means understanding and controlling the complex mechanisms of ion diffusion in solid matter. Because of the unusual evolution of correlated electronic properties (frustrated magnetism and superconductivity), the layered Co-oxide family NaxCoO2 (0<x<1), object of this work, has been extensively studied during the last decade. More recently it has also attracted the attention of applied sciences, mainly because of its structural similarity with LixCoO2, one of the most common Li-ion battery electrodes. In view of the larger abundance of Na in the earth crust with respect to Li, Na-ion batteries enjoy an increased attention. Hence we decided to investigate the Na-ion diffusion in this material, whose possible use as cathode for solid-state rechargeable batteries has recently been proposed [1]. The present study reports the observation of a crossover from quasi-1D to 2D Na-ion diffusion in Na0.7CoO2. High resolution neutron powder diffraction data indicate the existence of two structural transitions at T1=290K and T2=400K [2]. We present here evidence indicating that both transitions are closely related to changes in the Na-ion mobility. Analysis of the anomalies in the Na-Na distances, the Debye-Waller factors and the scattering density in the paths connecting neighbouring Na sites strongly suggest that Na-ion diffusion starts at T1, although for T1<T<T2 it occurs preferentially along quasi-1D paths. A fully isotropic diffusion is only observed for T>T2, coinciding with the equalization of all first-neighbor Na-Na distances in the structure [2]. These findings provide new insight on the subtle mechanisms controlling the Na-ion diffusion in the NaxCoO2 family and could be used for the design of related energy materials with improved functional properties. Fig. 1. Fourier difference maps of the z = 0.25 Na planes at T = 50, 320 and 450 K showing the evolution of the residual scattering density in the paths connecting the Na1 and Na2 sites (from ref.[2]).

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The Li-Ion and Na-Ion Diffusion Mechanism in Halogen Substituted Solid Sulfide Electrolytes Studied by Solid State NMR and DFT Based Molecular Dynamics Simulations

ECS Meeting Abstracts ◽

10.1149/ma2016-03/2/710 ◽

2016 ◽

Keyword(s):

Molecular Dynamics ◽

Solid State ◽

Molecular Dynamics Simulations ◽

Solid State Nmr ◽

Diffusion Mechanism ◽

Ion Diffusion ◽

Li Ion ◽

Dynamics Simulations

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New Series of Ternary Metal Chloride Superionic Conductors for High Performance All-Solid-State Lithium Batteries

10.21203/rs.3.rs-150360/v1 ◽

2021 ◽

Author(s):

Jianwen Liang ◽

Eveline van der Maas ◽

Jing Luo ◽

Xiaona Li ◽

Ning Chen ◽

...

Keyword(s):

Solid State ◽

Ionic Conductivity ◽

Lithium Batteries ◽

Solid Electrolytes ◽

Room Temperature ◽

Ionic Conductivities ◽

Orthorhombic Phase ◽

Superionic Conductors ◽

Orthorhombic Structure ◽

Trigonal Structure

Abstract Understanding the relationship between structure, ionic conductivity, and synthesis is the key to the development of solid electrolytes for all-solid-state Lithium batteries. Here, we investigate chloride solid electrolytes with compositions Li3 − 3xM1+xCl6 (-0.14 < x ≤ 0.5, M = Tb, Dy, Ho, Y, Er, Tm). When x > 0.04, a trigonal to orthorhombic phase transition occurs in the isostructural Li-Dy-Cl, Li-Ho-Cl, Li-Y-Cl, Li-Er-Cl and Li-Tm-Cl solid electrolytes. The new orthorhombic phase shows a four-fold increase in ionic conductivity up to 1.3×10− 3 S cm− 1 at room temperature for Li2.73Ho1.09Cl6 (x = 0.09) when compared to the trigonal Li3HoCl6. For isostructural Li-Dy-Cl, Li-Y-Cl, Li-Er-Cl and Li-Tm-Cl solid electrolytes, about one order of magnitude increase in ionic conductivities are observed for the orthorhombic structure compared to the trigonal structure. Using the Li-Ho-Cl components as an example, detailed studies of its structure, phase transition, ionic conductivity, air stability and electrochemical stability have been made. Molecular dynamics simulations based on density functional theory reveal that the different cations arrangement in the orthorhombic structure leads to a higher lithium diffusivity as compared to the trigonal structure, rationalizing the improved ionic conductivities of the new Li-M-Cl electrolytes. All-solid-state batteries of In/Li2.73Ho1.09Cl6/NMC811 demonstrate excellent electrochemical performance at both room temperature and − 10°C. As relevant to the vast number of isostructural halide electrolytes, the present structure control strategy provides guidance for the design of novel halide superionic conductors.

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