Owing to their high conductivity, crystalline Li 7-3x Ga x La 3 Zr 2 O 12 garnets are promising electrolytes for allsolid-state lithium-ion batteries. Herein, the influence of Ga doping on the phase, lithium-ion distribution, and conductivity of Li 7-3x Ga x La 3 Zr 2 O 12 garnets is investigated, with the determined concentration and mobility of lithium ions shedding light on the origin of the high conductivity of Li 7-3x Ga x La 3 Zr 2 O 12 . When the Ga concentration exceeds 0.20 Ga per formula unit, the garnet-type material is found to assume a cubic structure, but lower Ga concentrations result in the coexistence of cubic and tetragonal phases. Most lithium within Li 7-3x Ga x La 3 Zr 2 O 12 is found to reside at the octahedral 96h site, away from the central octahedral 48g site, while the remaining lithium resides at the tetrahedral 24d site. Such kind of lithium distribution leads to high lithium-ion mobility, which is the origin of the high conductivity; the highest lithium-ion conductivity of 1.46 mS/cm at 25 °C is found to be achieved for Li 7-3x Ga x La 3 Zr 2 O 12 at x = 0.25. Additionally, there are two lithium-ion migration pathways in the Li 7-3x Ga x La 3 Zr 2 O 12 garnets: 96h-96h and 24d-96h-24d, but the lithium ions transporting through the 96h-96h pathway determine the overall conductivity. Disciplines Engineering | Physical Sciences and Mathematics

Here, a P2-type layered Na Zn TeO (NZTO) is reported with a high Na ion conductivity ≈0.6×10 S cm at room temperature (RT), which is comparable to the currently best Na Zr Si P O NASICON structure. As small amounts of Ga substitutes for Zn , more Na vacancies are introduced in the interlayer gaps, which greatly reduces strong Na -Na coulomb interactions. Ga-substituted NZTO exhibits a superionic conductivity of ≈1.1×10 S cm at RT, and excellent phase and electrochemical stability. All solid-state batteries have been successfully assembled with a capacity of ≈70 mAh g over 10 cycles with a rate of 0.2 C at 80 °C. Na nuclear magnetic resonance (NMR) studies on powder samples show intra-grain (bulk) diffusion coefficients D on the order of 12.35×10 m s at 65 °C that corresponds to a conductivity σ of 8.16×10 S cm , assuming the Nernst-Einstein equation, which thus suggests a new perspective of fast Na ion conductor for advanced sodium ion batteries.

A novel solid sodium-ion conductor, NaMgTeO (NMTO) with a P2-type honeycomb-layered structure, has been synthesized for the first time by a simple solid-state synthetic route. The conductor of NMTO exhibits high conductivity of 2.3 × 10 S cm at room temperature (RT) and a large electrochemical window of ∼4.2 V (versus Na/Na). The conductor is remarkably stable, both in the ambient environment and within its metallic Na anode. This facile sodium-ion conductor displays potential for use in all-solid-state sodium-ion batteries (SS-SIBs).

Thermodynamic and kinetic properties of molecular adsorption and transport in metal–organic frameworks (MOFs) are crucially important for many applications, including gas adsorption, filtration, and remediation of harmful chemicals. Using the in situ 1H nuclear magnetic resonance (NMR) isotherm technique, we measured macroscopic thermodynamic and kinetic properties such as isotherms and rates of mass transfer while simultaneously obtaining microscopic information revealed by adsorbed molecules via NMR. Upon investigating isopropyl alcohol adsorption in MOF UiO-66 by in situ NMR, we obtained separate isotherms for molecules adsorbed at distinct environments exhibiting distinct NMR characteristics. A mechanistic view of the adsorption process is obtained by correlating such resolved isotherms with the cage structure effect on the nucleus-independent chemical shift, molecular dynamics such as the crowding effect at high loading levels, and the loading level dependence of the mass transfer rate as measured by NMR and elucidated by classical Monte Carlo simulations.

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Liquid–liquid transition (LLT) refers to the phase transition among thermodynamically distinct liquid states with identical composition in analogy to the polymorphic transition in solid. The growing awareness of its significance to understanding the nature of liquid also provokes curiosity about its potential impact on crystallization. Here, we report a first-order liquid–liquid transition above liquidus temperature in the melt of sodium acetate trihydrate using nuclear magnetic resonance, differential scanning calorimetry, and high-precision density measurements, which show negligible change in density associated with the observed LLT. Further, the kinetics and products of crystallization are significantly influenced by LLT, providing a new way for the controlling crystallization pathway and realizing crystal polymorph selection.

Defect engineering leads to an effective manipulation of the physical and chemical properties of metal–organic frameworks (MOFs). Taking the common missing linker defect as an example, the defective MOF generally possesses larger pores and a greater surface area/volume ratio, both of which favor an increased amount of adsorption. When it comes to the self-diffusion of adsorbates in MOFs, however, the missing linker is a double-edged sword: the unsaturated metal sites, due to missing linkers, could interact more strongly with adsorbates and result in a slower self-diffusion. Therefore, it is of fundamental importance to evaluate the two competing factors and reveal which one is dominating, a faster self-diffusion due to larger volume or a slower self-diffusion owing to strong interactions at unsaturated sites. In this work, via Monte Carlo and molecular dynamics simulations, we investigate the behavior of isopropyl alcohol (IPA) in the Zr-based UiO-66 MOFs, with a specific focus on the missing linker effects. The results reveal that unsaturated Zr sites bind strongly with IPA molecules, which in return would significantly reduce the self-diffusion coefficient of IPA. Besides this, for the same level of missing linkers, the location of defective sites also makes a difference. We expect such a theoretical study will provide an in-depth understanding of self-diffusion under confinement, inspire better defect engineering strategics, and promote MOF based materials toward challenging real-life applications.