The lithium‐conducting, rare‐earth halides, Li3MX6 (M = Y, Er; X = Cl, Br), have garnered significantly rising interest recently, as they have been reported to have oxidative stability and high ionic conductivities. However, while a multitude of materials exhibit a superionic conductivity close to 1 mS cm−1, the exact design strategies to further improve the ionic transport properties have not been established yet. Here, the influence of the employed synthesis method of mechanochemical milling, compared to subsequent crystallization routines as well as classic solid‐state syntheses on the structure and resulting transport behavior of Li3ErCl6 and Li3YCl6 are explored. Using a combination of X‐ray diffraction, pair distribution function analysis, density functional theory, and impedance spectroscopy, insights into the average and local structural features that influence the underlying transport are provided. The existence of a cation defect within the structure in which Er/Y are disordered to a new position strongly benefits the transport properties. A synthetically tuned, increasing degree of this disordering leads to a decreasing activation energy and increasing ionic conductivity. This work sheds light on the possible synthesis strategies and helps to systematically understand and further improve the properties of this class of materials.
Lithium argyrodite superionic conductors are currently being investigated as solid electrolytes for all-solid-state batteries. Recently, in the lithium argyrodite Li6PS5X (X = Cl, Br, and I), a site-disorder between the anions S2– and X– has been observed, which strongly affects the ionic transport and appears to be a function of the halide present. In this work, we show how such a disorder in Li6PS5Br can be engineered via the synthesis method. By comparing fast cooling (i.e., quenching) to more slowly cooled samples, we find that the anion site-disorder is higher at elevated temperatures, and that fast cooling can be used to kinetically trap the desired disorder, leading to higher ionic conductivities as shown by impedance spectroscopy in combination with ab initio molecular dynamics. Furthermore, we observe that after milling, a crystalline lithium argyrodite can be obtained within 1 min of heat treatment. This rapid crystallization highlights the reactive nature of mechanical milling and shows that long reaction times with high energy consumption are not needed in this class of materials. The fact that site-disorder induced via quenching is beneficial for ionic transport provides an additional approach for the optimization and design of lithium superionic conductors.
Over the last decade, some studies with laboratory pair distribution function (PDF) data emerged. Yet, limited Qmax or instrumental resolution impeded in-depth structural refinements. With more advanced detector technologies, the question arose how to design novel PDF equipment for laboratories that will allow decent PDF refinements over r = 1–70 Å. It is crucial to reflect the essential requirements, namely, monochromatic X-rays, suppression of air scattering, instrumental resolution, and overall measurement times. The result is a novel PDF setup based on a STOE STADI P powder diffractometer in transmission-/Debye-Scherrer geometry with monochromatic Ag Kα1 radiation, featuring a MYTHEN2 4K detector covering a Q range of 0.3–20.5 Å−1. PDF data are collected in a moving PDF mode within 6 h. Structural signatures of liquids can be satisfactorily resolved in the PDF as shown for the ionic liquid hmimPF6. The high instrumental resolution is mirrored in low qdamp values determined from LaB6 measurements. PDF data from a powder sample of ca. 7 nm TiO2 nanoparticles were successfully refined over up to 70 Å with goodness-of-fit values Rw < 0.22 (respectively Rw = 0.18 over 30 Å), thanks to the low background and high instrumental resolution, hereby enlarging the accessible r range by several tens of Angstroms compared to previous laboratory PDF studies.
We investigate the structure-activity correlations of methanation catalysts obtained by thermal decomposition of a Ni-based metal-organic framework, using pair distribution function, X-ray absorption spectroscopy and X-ray diffraction.
This publication is part of a joint Special Collection with ChemElectroChem on "Catalysts and Reactors under Dynamic Conditions for Energy Storage and Conversion (DynaKat)".Please check ourhomepage for more articles in the collection.
<p>Lithium argyrodite superionic conductors are currently being investigated as solid electrolytes for all-solid-state batteries. Recently, in the lithium argyrodite Li<sub>6</sub>PS<sub>5</sub>X (X = Cl, Br, I), a site-disorder between the anionsS<sup>2–</sup>and X<sup>–</sup>has been observed, which strongly affects the ionic transport and appears to be a function of the halide present. In this work, we show how such disorder in Li<sub>6</sub>PS<sub>5</sub>Br can be engineered <i>via</i>the synthesis method. By comparing fast cooling (<i>i.e. </i>quenching) to more slowly cooled samples, we find that anion site-disorder is higher at elevated temperatures, and that fast cooling can be used to kinetically trap the desired disorder, leading to higher ionic conductivities as shown by impedance spectroscopy in combination with <i>ab-initio</i>molecular dynamics. Furthermore, we observe that after milling, a crystalline lithium argyrodite can be obtained within one minute of heat treatment. This rapid crystallization highlights the reactive nature of mechanical milling and shows that long reaction times with high energy consumption are not needed in this class of materials. The fact that site-disorder induced <i>via</i>quenching is beneficial for ionic transport provides an additional approach for the optimization and design of lithium superionic conductors.</p>
<p>Lithium argyrodite superionic conductors are currently being investigated as solid electrolytes for all-solid-state batteries. Recently, in the lithium argyrodite Li<sub>6</sub>PS<sub>5</sub>X (X = Cl, Br, I), a site-disorder between the anionsS<sup>2–</sup>and X<sup>–</sup>has been observed, which strongly affects the ionic transport and appears to be a function of the halide present. In this work, we show how such disorder in Li<sub>6</sub>PS<sub>5</sub>Br can be engineered <i>via</i>the synthesis method. By comparing fast cooling (<i>i.e. </i>quenching) to more slowly cooled samples, we find that anion site-disorder is higher at elevated temperatures, and that fast cooling can be used to kinetically trap the desired disorder, leading to higher ionic conductivities as shown by impedance spectroscopy in combination with <i>ab-initio</i>molecular dynamics. Furthermore, we observe that after milling, a crystalline lithium argyrodite can be obtained within one minute of heat treatment. This rapid crystallization highlights the reactive nature of mechanical milling and shows that long reaction times with high energy consumption are not needed in this class of materials. The fact that site-disorder induced <i>via</i>quenching is beneficial for ionic transport provides an additional approach for the optimization and design of lithium superionic conductors.</p>
The synthesis of Mg-substituted copper hydroxycarbonates by constant-pH co-precipitation with subsequent ageing of the precipitate has been studied in detail. This allowed the retrieval of crystalline magnesian malachite samples, which showed a "radical-sign-shaped" pH drop and the blue/green color change during ageing that is well-known from the analogous Cu/Zn system. The crystallization of Cu-rich samples has been studied elaborately by means of powder diffraction, pair distribution function (PDF), and infrared spectroscopy, thus elucidating the ageing chemistry of Cu,Mg hydroxycarbonates in general. It was found that up to 17 % Mg can be incorporated into the crystalline malachite using a synthesis route comparable to that established for Cu/ZnO catalysts, but with drastically elongated precipitate ageing times. For higher Mg contents, a step-like pH drop was observed instead, and an amorphous variant of the hydroxycarbonate, referred to as "magnesian georgeite", could be isolated. From such a Mg-rich sample (Cu/Mg 70 : 30 at. %), a Cu/MgO catalyst has been prepared that shows high activity and good stability in CO hydrogenation to methanol over 800 hrs. time on stream.
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