Local and Translational Motion of the 6Li and 7Li Ions in the Li3Sc2(PO4)3 and Li3In2(PO4)3 Compounds

1990 ◽  
Vol 210 ◽  
Author(s):  
Igor S. Pronin ◽  
Sergei E. Sigaryov ◽  
Andrei A. Vashman
Keyword(s):  
Solid Electrolytes ◽  
Translational Motion ◽  
Ion Pairs ◽  
Lithium Ion ◽  
Spectroscopy Data ◽  
Ionic Radii ◽  
Ion Motion ◽  
Mixed Alkali ◽  
Mixed Alkali Effect ◽  
Li Ion

AbstractBasing on impedance and NMR spectroscopy data it is shown that there are two types of lithium ion motion in the each polymorhic modification of the Li3 Sc2 (P04)3 and Li3 In2 (P04)3 solid electrolytes. First type is a translational motion of these ions which determines the a values, while the second one is Li ion motion within the lithium ion—ion pairs at the distance about the sum of two lithium ionic radii. Substitution of 7Li by 6Li leads to the mixed alkali effect—type behaviour of σ.

scholarly journals Lithium-ion conductivity in Li6Y(BO3)3: a thermally and electrochemically robust solid electrolyte

2016 ◽  
Vol 4 (18) ◽  
pp. 6972-6979 ◽  
Author(s):  
Beatriz Lopez-Bermudez ◽  
Wolfgang G. Zeier ◽  
Shiliang Zhou ◽  
Anna J. Lehner ◽  
Jerry Hu ◽  
...  
Keyword(s):  
Energy Storage ◽  
Solid Electrolyte ◽  
Solid Electrolytes ◽  
Lithium Ion ◽  
Ion Conductivity ◽  
Ion Diffusion ◽  
New Energy ◽  
Li Ion ◽  
Lithium Ion Conductivity ◽  
Storage Technologies

The development of new frameworks for solid electrolytes exhibiting fast Li-ion diffusion is critical for enabling new energy storage technologies.

Cationic covalent organic framework based all-solid-state electrolytes

2020 ◽  
Vol 4 (4) ◽  
pp. 1164-1173 ◽  
Author(s):  
Zhen Li ◽  
Zhi-Wei Liu ◽  
Zhen-Jie Mu ◽  
Chen Cao ◽  
Zeyu Li ◽  
...  
Keyword(s):  
High Temperature ◽  
Solid State ◽  
Solid Electrolytes ◽  
Lithium Ion ◽  
Ion Conductivity ◽  
Li Ion Battery ◽  
Covalent Organic Framework ◽  
Li Ion ◽  
Lithium Ion Conductivity ◽  
Organic Framework

Two new imidazolium-based cationic COFs were synthesized and employed as all-solid electrolytes, and exhibited high lithium ion conductivity at high temperature. The assembled Li-ion battery displays preferable battery performance at 353 K.

scholarly journals Blend Hybrid Solid Electrolytes Based on LiTFSI Doped Silica-Polyethylene Oxide for Lithium-Ion Batteries

Membranes ◽  
2019 ◽  
Vol 9 (9) ◽  
pp. 109 ◽  
Author(s):  
Jadra Mosa ◽  
Jonh Fredy Vélez ◽  
Mario Aparicio
Keyword(s):  
Ionic Conductivity ◽  
Solid Electrolytes ◽  
Room Temperature ◽  
Sol Gel ◽  
Lithium Ion ◽  
Hybrid Structure ◽  
Hybrid Network ◽  
Li Ion Batteries ◽  
Li Ion ◽  
Sol Gel Synthesis

Organic/inorganic hybrid membranes that are based on GTT (GPTMS-TMES-TPTE) system while using 3-Glycidoxypropyl-trimethoxysilane (GPTMS), Trimethyletoxisilane (TMES), and Trimethylolpropane triglycidyl ether (TPTE) as precursors have been obtained while using a combination of organic polymerization and sol-gel synthesis to be used as electrolytes in Li-ion batteries. Self-supported materials and thin-films solid hybrid electrolytes that were doped with Lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) were prepared. The hybrid network is based on highly cross-linked structures with high ionic conductivity. The dependency of the crosslinked hybrid structure and polymerization grade on ionic conductivity is studied. Ionic conductivity depends on triepoxy precursor (TPTE) and the accessibility of Li ions in the organic network, reaching a maximum ionic conductivity of 1.3 × 10−4 and 1.4 × 10−3 S cm−1 at room temperature and 60 °C, respectively. A wide electrochemical stability window in the range of 1.5–5 V facilitates its use as solid electrolytes in next-generation of Li-ion batteries.

scholarly journals Evidence for a Solid-Electrolyte Inductive Effect in Superionic Conductors

2020 ◽  
Author(s):  
Sean Culver ◽  
Alex Squires ◽  
Nicolo Minafra ◽  
Callum Armstrong ◽  
Thorben Krauskopf ◽  
...  
Keyword(s):  
Solid Electrolyte ◽  
Solid Electrolytes ◽  
Density Functional ◽  
Inductive Effect ◽  
Ionic Conductivities ◽  
Lithium Ion ◽  
Density Functional Theory Calculations ◽  
Ion Diffusion ◽  
Functional Theory ◽  
Li Ion

<p>Identifying and optimizing highly-conducting lithium-ion solid electrolytes is a critical step towards the realization of commercial all–solid-state lithium-ion batteries. Strategies to enhance ionic conductivities in solid electrolytes typically focus on the effects of modifying their crystal structures or of tuning mobile-ion stoichiometries. A less-explored approach is to modulate the chemical-bonding interactions within a material to promote fast lithium-ion diffusion. Recently, the idea of a solid-electrolyte inductive effect was proposed, whereby changes in bonding within the solid-electrolyte host-framework modify the potential-energy landscape for the mobile ions, resulting in an enhanced ionic conductivity. This concept has since been invoked to explain anomalous conductivity trends in a number of solid electrolytes. Direct evidence for a solid-electrolyte inductive effect, however, is lacking—in part because of the challenge of quantifying changes in local bonding interactions within a solid-electrolyte host-framework. <a></a><a>Here, we consider the evidence for a solid-electrolyte inductive effect in the archetypal superionic lithium-ion conductor Li<sub>10</sub>Ge<sub>1−<i>x</i></sub>Sn<i><sub>x</sub></i>P<sub>2</sub>S<sub>12</sub>, using Rietveld refinements against high-resolution temperature-dependent neutron-diffraction data, Raman spectroscopy, and density functional theory calculations.</a> Substituting Ge for Sn weakens the {Ge,Sn}–S bonding interactions and increases the charge-density associated with the S<sup>2-</sup> ions. This charge redistribution modifies the Li<sup>+</sup> substructure causing Li<sup>+</sup> ions to bind more strongly to the host-framework S anions; which in turn modulates the Li-ion potential-energy surface, increasing local barriers for Li-ion diffusion. Each of these effects is consistent with the predictions of the solid-electrolyte inductive effect model. Density functional theory calculations further predict that this inductive effect occurs even in the absence of changes to the host-framework geometry due to Ge → Sn substitution. These results provide direct evidence in support of a measurable solid-electrolyte inductive effect and demonstrate its application as a practical strategy for tuning ionic conductivities in superionic lithium-ion conductors.</p>

scholarly journals Correlation of Mechanical and Electrical Behavior of Polyethylene Oxide-Based Solid Electrolytes for All-Solid State Lithium-Ion Batteries

Batteries ◽  
2019 ◽  
Vol 5 (1) ◽  
pp. 26 ◽  
Author(s):  
Fabian Peters ◽  
Frederieke Langer ◽  
Nikolai Hillen ◽  
Katharina Koschek ◽  
Ingo Bardenhagen ◽  
...  
Keyword(s):  
Solid State ◽  
Ionic Conductivity ◽  
Mechanical Strength ◽  
Solid Electrolytes ◽  
Large Scale ◽  
Lithium Ion ◽  
Scale Production ◽  
Li Ion Batteries ◽  
Scanning Calorimetry ◽  
Li Ion

Mechanical and electrochemical stability are key issues for large-scale production of solid state Li-ion batteries. Polymer electrolytes can provide good ionic conductivity, but mechanical strength needs to be improved. In this study, we investigate the correlation of mechanical and electrical properties of poly (ethylene oxide) (PEO)-based solid electrolytes for Li-ion batteries. The influence of alumina and LiClO4 addition are investigated. Differential scanning calorimetry (DSC) is used to study the thermal behavior of salt-free and salt-containing samples and to identify the melting temperature. Dynamic mechanical analysis reveals the elastic properties as a function of temperature. Electrochemical properties are investigated using impedance spectroscopy. It is found that addition of alumina increases mechanical strength, while LiClO4 decreases it. Addition of LiClO4 and Al2O3 increases ionic conductivity and improves mechanical properties. However, there is no overlapping window of high mechanical strength and high ionic conductivity.

scholarly journals Sodium-free mixed alkali bioactive glasses

2016 ◽  
Vol 2 (1) ◽  
Author(s):  
Delia S. Brauer ◽  
Raika Brückner ◽  
Maxi Tylkowski ◽  
Leena Hupa
Keyword(s):  
Coefficient Of Thermal Expansion ◽  
Release Rates ◽  
Ion Release ◽  
Bioactive Glasses ◽  
Ionic Radii ◽  
Alkali Ions ◽  
Processing Window ◽  
Mixed Alkali ◽  
Mixed Alkali Effect ◽  
High Temperature Processing

AbstractTwo sodium-free mixed alkali series of bioactive glasses based on compositions Bioglass 45S5 and ICIE1, containing lithium and/or potassium as alkali ions, were prepared by a melt-quench route. Thermal properties showed the well-known mixed alkali effect, with glass transition and crystallisation temperatures and the coefficient of thermal expansion going either through a minimum or a maximum for the mixed alkali composition, resulting in a wider processing window. Ion release, by contrast, was controlled by the modifier ionic radius, with ion release rates in dynamic and static dissolution studies increasing for potassium-substituted glasses compared to the composition containing lithium as the only alkali ion. This was caused by pronounced changes in oxygen packing density and molar volume of the glasses owing to the differences in ionic radii (76 pm for Li+ and 138 pm for K+). Partially substituting one alkali for another therefore helps to improve high temperature processing of bioactive glasses and can also be used to control or tailor ion release.

scholarly journals Компьютерное моделирование структуры и механических свойств слоев силицена на графите при движении иона лития

2019 ◽  
Vol 61 (2) ◽  
pp. 365
Author(s):  
А.Е. Галашев ◽  
К.А. Иваничкина
Keyword(s):  
Lithium Ion ◽  
Structural Features ◽  
Graphite Substrate ◽  
Planar Channel ◽  
Ion Motion ◽  
Voronoi Polyhedra ◽  
Dc Electric Field ◽  
Li Ion ◽  
The Times ◽  
Dynamics Method

AbstractThe molecular dynamics method is applied to study structural and mechanical effects appearing during the lithium ion motion in a dc electric field along a planar channel formed by perfect silicene sheets and sheets containing vacancy-type defects. Mono-, di-, tri-, and hexavacancies of rather densely and uniformly filled silicene sheets are arranged one above the other on a graphite substrate. The times of Li^+ ion passage through silicene channels with various gaps are determined. The construction of Voronoi polyhedra and truncated polyhedrons, whose centers coincide with the moving ion position allowed revealing the structural features inherent to the two-dimensional layered structure. The nature of stresses appearing in silicene sheets most critical to ion motion over the channel is determined.

scholarly journals Evidence for a Solid-Electrolyte Inductive Effect in Superionic Conductors

2020 ◽  
Author(s):  
Sean Culver ◽  
Alex Squires ◽  
Nicolo Minafra ◽  
Callum Armstrong ◽  
Thorben Krauskopf ◽  
...  
Keyword(s):  
Solid Electrolyte ◽  
Solid Electrolytes ◽  
Density Functional ◽  
Inductive Effect ◽  
Ionic Conductivities ◽  
Lithium Ion ◽  
Density Functional Theory Calculations ◽  
Ion Diffusion ◽  
Functional Theory ◽  
Li Ion

<p>Identifying and optimizing highly-conducting lithium-ion solid electrolytes is a critical step towards the realization of commercial all–solid-state lithium-ion batteries. Strategies to enhance ionic conductivities in solid electrolytes typically focus on the effects of modifying their crystal structures or of tuning mobile-ion stoichiometries. A less-explored approach is to modulate the chemical-bonding interactions within a material to promote fast lithium-ion diffusion. Recently, the idea of a solid-electrolyte inductive effect was proposed, whereby changes in bonding within the solid-electrolyte host-framework modify the potential-energy landscape for the mobile ions, resulting in an enhanced ionic conductivity. This concept has since been invoked to explain anomalous conductivity trends in a number of solid electrolytes. Direct evidence for a solid-electrolyte inductive effect, however, is lacking—in part because of the challenge of quantifying changes in local bonding interactions within a solid-electrolyte host-framework. <a></a><a>Here, we consider the evidence for a solid-electrolyte inductive effect in the archetypal superionic lithium-ion conductor Li<sub>10</sub>Ge<sub>1−<i>x</i></sub>Sn<i><sub>x</sub></i>P<sub>2</sub>S<sub>12</sub>, using Rietveld refinements against high-resolution temperature-dependent neutron-diffraction data, Raman spectroscopy, and density functional theory calculations.</a> Substituting Ge for Sn weakens the {Ge,Sn}–S bonding interactions and increases the charge-density associated with the S<sup>2-</sup> ions. This charge redistribution modifies the Li<sup>+</sup> substructure causing Li<sup>+</sup> ions to bind more strongly to the host-framework S anions; which in turn modulates the Li-ion potential-energy surface, increasing local barriers for Li-ion diffusion. Each of these effects is consistent with the predictions of the solid-electrolyte inductive effect model. Density functional theory calculations further predict that this inductive effect occurs even in the absence of changes to the host-framework geometry due to Ge → Sn substitution. These results provide direct evidence in support of a measurable solid-electrolyte inductive effect and demonstrate its application as a practical strategy for tuning ionic conductivities in superionic lithium-ion conductors.</p>

Relaxation Processes and the Mixed Alkali Effect in Alkali Metasilicate Glasses

1996 ◽  
Vol 455 ◽  
Author(s):  
J. Habasaki ◽  
I. Okada ◽  
Y. Hiwatari
Keyword(s):  
Boson Peak ◽  
Dynamics Simulation ◽  
Relaxation Processes ◽  
Lithium Metasilicate ◽  
Mixed Alkali ◽  
Mean Squared Displacement ◽  
Mixed Alkali Effect ◽  
Li Ion ◽  
The Mean ◽  
Β Relaxation

ABSTRACTA molecular dynamics simulation (MD) of lithium metasilicate (Li2SiO3) and related mixed alkali system (LiKSiO3) has been performed. Changes in the mean squared displacement and the corresponding clear two-step (β and α1) relaxations in a density correlation function have been observed at 700 K (self-part) for each ion in Li2SiO3 following an exponential decay by vibrational motion in a simulation up to 300 ps (run I). The mean squared displacement of the atoms shows the change in the slope at ca. 300 ps when the simulation is extended up to 1 ns (run II). Here we call the slowest relaxation (ca. 300 ps∼) the α2 region.Oscillation, which is clearer for O and Si than for Li, is found in the second (β-relaxation) region of the function, which is attributed to the so called “boson peak”. Both the β-relaxation and the boson peak are found to be due to the correlated motion.The slower relaxation (α1-relaxation) can be fitted to a stretched exponential form and the origin of this type of decay is confirmed to be waiting time distribution of jump motions. The back-correlated jumps also decrease the decay rate.Components A and B in α1 and α2 regions for Li ion are analyzed, where the Li ion of component A is located within the first neighboring sites and that of component B moves longer than the nearest neighbor distances by cooperative jump motion. The component B shows accelerated dynamics larger than t-linear ones (∼ t1.77) in the region 50–300 ps, and the dynamics can be characterized as Lévy flight.We have found that the contribution of the cooperative jumps decreases in the mixed alkali glass. This explains the maximum of the Haven ratio accompanied with the mixed alkali effect.

Dynamics of Ion Locking in Doubly Polymerized Ionic Liquids

2020 ◽  
Author(s):  
Swati Arora ◽  
Julisa Rozon ◽  
Jennifer Laaser
Keyword(s):  
Dielectric Constant ◽  
Ionic Liquid ◽  
Ionic Liquids ◽  
Ion Pairs ◽  
Polymer Chains ◽  
Ion Motion ◽  
Charged Species ◽  
Broadband Dielectric Spectroscopy ◽  
Covalently Linked ◽  
Insight Into

<div>In this work, we investigate the dynamics of ion motion in “doubly-polymerized” ionic liquids (DPILs) in which both charged species of an ionic liquid are covalently linked to the same polymer chains. Broadband dielectric spectroscopy is used to characterize these materials over a broad frequency and temperature range, and their behavior is compared to that of conventional “singly-polymerized” ionic liquids (SPILs) in which only one of the charged species is attached to the polymer chains. Polymerization of the DPIL decreases the bulk ionic conductivity by four orders of magnitude relative to both SPILs. The timescales for local ionic rearrangement are similarly found to be approximately four orders of magnitude slower in the DPILs than in the SPILs, and the DPILs also have a lower static dielectric constant. These results suggest that copolymerization of the ionic monomers affects ion motion on both the bulk and the local scales, with ion pairs serving to form strong physical crosslinks between the polymer chains. This study provides quantitative insight into the energetics and timescales of ion motion that drive the phenomenon of “ion locking” currently under investigation for new classes of organic electronics.</div>

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