Advancing Guidelines for Compositional Selection and Processing Conditions for Solid-State Battery Materials

Conventional liquid electrolyte batteries are nearing their practical energy density limits despite the intensifying demand for greater energy and power densities. Solid-state batteries (SSBs), enabled by ion-conducting solid electrolytes (SEs), offer promise for meeting these needs while simultaneously providing improved safety, but still face challenges in high voltage cathode incorporation and economic competitiveness against liquid counterparts.Chloride SEs, which are subject to complex structure-property relationships, show promise as catholyte candidates in dual SE high-voltage SSBs when paired with another SE. Taking a joint computational-experimental approach, we reveal the presence of a high concentration of planar and nonstoichiometric defects in mechanochemically-synthesized Li3YCl6 that facilitate Li-ion conduction and present a method of controlling its Li+ conductivity by tuning the defect concentration with synthesis and heat treatments. By carefully modulating the synthetic conditions in the Na-Y-Zr-Cl family of SEs, we demonstrate control of polymorphism and conduction properties in Na2ZrCl6 and Na3YCl6. Transition metal orderings in the Na2.25Y0.25Zr0.75Cl6 composition are shown to strongly impact Na-ion transport, providing a new way to optimize conductivity in aliovalently-doped SEs. Motivated by our improved understanding of chloride SE processing, we develop a reaction temperature-based approach to identify SE candidates chemically compatible with chlorides. We demonstrate that the Li2ZrCl6 and Li6PS5Cl pairing is a conductive, scalable, and kinetically stabilized system with high potential for implementation in dual SE SSBs.Finally, we focus on facilitating manufacturing of air-sensitive sulfide SEs and Li-Si anodes. First, we propose a reversible 1-undecanethiol coating for sulfide SEs (LPSC), enabling handling in humid ambient air. Leveraging solid state NMR, we reveal that the thiol chain end anchors to the LPSC surface with S-S bonds while the hydrocarbon tail repels water, preserving the LPSC structure and conductivity after two days of air exposure. Next, we outline a prelithiation strategy for Si anodes designed to decrease first cycle losses, quantifying the phase fraction of Li-Si alloy formed with 7Li NMR.The guidelines for materials selection and improved processing parameters in SSBs outlined herein represent important advancements towards elevating energy storage technologies beyond the limitations of conventional Li and Na-ion batteries

Removal of Na+ and Ca2+ with Prussian blue analogue electrodes for brackish water desalination

Desalination of brackish water sources is critical to addressing the growing global freshwater demand. One promising approach is electrically driven desalination using intercalation electrodes. While intercalation electrodes have been widely researched for energy storage applications, only a small subset of those materials is suitable for desalination. Here we report the synthesis, characterization, and in-device testing of three Prussian blue analogue intercalation compounds: copper, manganese, and zinc hexacyanoferrate with formulas KxM[Fe(CN)6]z·nH2O (M = Cu, Mn, Zn). The desalination performance for each of these materials against carbon electrodes is reported for Na+ intercalation and for Ca2+ intercalation using 1000 ppm NaCl and 1000 ppm CaCl2 feed solutions, respectively. While the copper and manganese analogs showed promising performance for Na+ and Ca2+ intercalation, the zinc compound was unstable and underwent rapid dissolution. Manganese hexacyanoferrate showed the best desalination performance in terms of salt removal capacities and salt removal rates with NaCl while copper hexacyanoferrate performed the best with CaCl2. The manganese analog proved to be the most stable intercalation material, retaining 83% and 72% of its salt removal capacity after 280 cycles in NaCl and CaCl2 feed solutions respectively

Les usages politiques du passé

Que le passé se prête à des usages politiques, toute l’histoire de l’historiographie l’atteste. D’où vient alors que le souci d’une manipulation du passé se fasse toujours plus insistant, comme en témoignent la récente querelle des historiens allemands sur la signification du nazisme ou celle, en cours, sur le communisme ? Autour de quelques dossiers actuels, cet ouvrage s’attache à réfléchir sur notre présent historiographique et ses multiples usages politiques

Synthetic control of structure and conduction properties in Na–Y–Zr–Cl solid electrolytes

In the development of low cost, sustainable, and energy-dense batteries, chloride-based compounds are promising catholyte materials for solid-state batteries owing to their high Na-ion conductivities and oxidative stabilities. The ability to further improve Na-ion conduction, however, requires an understanding of the impact of long-range and local structural features on transport in these systems. In this study, we leverage different synthesis methods to control polymorphism and cation disorder in Na-Y-Zr-Cl solid electrolytes and interrogate the impact on Na-ion conduction. We demonstrate the existence of a more conductive P21/n polymorph of Na2ZrCl6 formed upon ball milling. In Na3YCl6, the R3̄ polymorph is shown to be more conductive than its P21/n counterpart owing to the presence of intrinsic vacancies and disorder on the Y sublattice. Transition metal ordering in the Na2.25Y0.25Zr0.75Cl6 composition strongly impacts Na-ion transport, where a greater mixing of Y3+ and Zr4+ on the transition metal sublattice facilitates ion migration through partial activation of Cl rotations at relevant temperatures. Overall, Na-ion transport sensitively depends on the phases and transition metal distributions stabilized during synthesis. These results are likely generalizable to other halide compositions and indicate that achieving control over the synthetic protocol and resultant structure is key in the pursuit of improved catholytes for high voltage solid-state sodium-ion batteries

Development of o-Chlorophenyl Substituted Pyrimidines as Exceptionally Potent Aurora Kinase Inhibitors

The o-carboxylic acid substituted bisanilinopyrimidine 1 was identified as a potent hit (Aurora A IC50 = 6.1 ± 1.0 nM) from in-house screening. Detailed structure–activity relationship (SAR) studies indicated that polar substituents at the para position of the B-ring are critical for potent activity. X-ray crystallography studies revealed that compound 1 is a type I inhibitor that binds the Aurora kinase active site in a DFG-in conformation. Structure–activity guided replacement of the A-ring carboxylic acid with halogens and incorporation of fluorine at the pyrimidine 5-position led to highly potent inhibitors of Aurora A that bind in a DFG-out conformation. B-Ring modifications were undertaken to improve the solubility and cell permeability. Compounds such as 9m with water-solubilizing moieties at the para position of the B-ring inhibited the autophosphorylation of Aurora A in MDA-MB-468 breast cancer cells

Development of o-Chlorophenyl Substituted Pyrimidines as Exceptionally Potent Aurora Kinase Inhibitors

The o-carboxylic acid substituted bisanilinopyrimidine 1 was identified as a potent hit (Aurora A IC50 = 6.1 ± 1.0 nM) from in-house screening. Detailed structure–activity relationship (SAR) studies indicated that polar substituents at the para position of the B-ring are critical for potent activity. X-ray crystallography studies revealed that compound 1 is a type I inhibitor that binds the Aurora kinase active site in a DFG-in conformation. Structure–activity guided replacement of the A-ring carboxylic acid with halogens and incorporation of fluorine at the pyrimidine 5-position led to highly potent inhibitors of Aurora A that bind in a DFG-out conformation. B-Ring modifications were undertaken to improve the solubility and cell permeability. Compounds such as 9m with water-solubilizing moieties at the para position of the B-ring inhibited the autophosphorylation of Aurora A in MDA-MB-468 breast cancer cells

Stacking Faults Assist Lithium-Ion Conduction in a Halide-Based Superionic Conductor.

In the pursuit of urgently needed, energy dense solid-state batteries for electric vehicle and portable electronics applications, halide solid electrolytes offer a promising path forward with exceptional compatibility against high-voltage oxide electrodes, tunable ionic conductivities, and facile processing. For this family of compounds, synthesis protocols strongly affect cation site disorder and modulate Li+ mobility. In this work, we reveal the presence of a high concentration of stacking faults in the superionic conductor Li3YCl6 and demonstrate a method of controlling its Li+ conductivity by tuning the defect concentration with synthesis and heat treatments at select temperatures. Leveraging complementary insights from variable temperature synchrotron X-ray diffraction, neutron diffraction, cryogenic transmission electron microscopy, solid-state nuclear magnetic resonance, density functional theory, and electrochemical impedance spectroscopy, we identify the nature of planar defects and the role of nonstoichiometry in lowering Li+ migration barriers and increasing Li site connectivity in mechanochemically synthesized Li3YCl6. We harness paramagnetic relaxation enhancement to enable 89Y solid-state NMR and directly contrast the Y cation site disorder resulting from different preparation methods, demonstrating a potent tool for other researchers studying Y-containing compositions. With heat treatments at temperatures as low as 333 K (60 °C), we decrease the concentration of planar defects, demonstrating a simple method for tuning the Li+ conductivity. Findings from this work are expected to be generalizable to other halide solid electrolyte candidates and provide an improved understanding of defect-enabled Li+ conduction in this class of Li-ion conductors