Uncovering the predictive pathways of lithium and sodium interchange in layered oxides.

Ion exchange is a powerful method to access metastable materials with advanced functionalities for energy storage applications. However, high concentrations and unfavourably large excesses of lithium are always used for synthesizing lithium cathodes from parent sodium material, and the reaction pathways remain elusive. Here, using layered oxides as model materials, we demonstrate that vacancy level and its corresponding lithium preference are critical in determining the accessible and inaccessible ion exchange pathways. Taking advantage of the strong lithium preference at the right vacancy level, we establish predictive compositional and structural evolution at extremely dilute and low excess lithium based on the phase equilibrium between Li0.94CoO2 and Na0.48CoO2. Such phase separation behaviour is general in both surface reaction-limited and diffusion-limited exchange conditions and is accomplished with the charge redistribution on transition metals. Guided by this understanding, we demonstrate the synthesis of NayCoO2 from the parent LixCoO2 and the synthesis of Li0.94CoO2 from NayCoO2 at 1-1,000 Li/Na (molar ratio) with an electrochemical assisted ion exchange method by mitigating the kinetic barriers. Our study opens new opportunities for ion exchange in predictive synthesis and separation applications.

Correction: Mechanisms of Electronic and Ionic Transport during Mg Intercalation in Mg-S Cathode Materials and Their Decomposition Products.

[This corrects the article DOI: 10.1021/acs.chemmater.2c03784.].

A database of computed Raman spectra of inorganic compounds with accurate hybrid functionals.

Raman spectroscopy is widely applied in identifying local structures in materials, but the interpretation of Raman spectra is non-trivial. An accurate computational database of reference spectra calculated with a consistent level of theory can significantly aid in interpreting measured Raman spectra. Here, we present a database of Raman spectra of inorganic compounds calculated with accurate hybrid functionals in density functional theory. Raman spectra were obtained by calculating dynamical matrices and polarizability tensors for structures from the Inorganic Crystal Structure Database. The calculated Raman spectra and other phonon properties (e.g., infrared spectra) are stored in a MongoDB database publicly shared through a web application. We assess the accuracy of our Raman calculations by statistically comparing ~80 calculated spectra with an existing experimental Raman database. To date, the database contains 161 compounds and is continuously growing as we add more materials computed with our automated workflow.

Pushing Forward Simulation Techniques of Ion Transport in Ion Conductors for Energy Materials.

Simulation techniques are crucial to establish a firm link between phenomena occurring at the atomic scale and macroscopic observations of functional materials. Importantly, extensive sampling of space and time scales is paramount to ensure good convergence of physically relevant quantities to describe ion transport in energy materials. Here, a number of simulation methods to address ion transport in energy materials are discussed, with the pros and cons of each methodology put forward. Emphasis is given to the stochastic nature of results produced by kinetic Monte Carlo, which can adequately account for compositional disorder across multiple sublattices in solids.

0D Pyramid-intercalated 2D Bimetallic Halides with Tunable Electronic Structures and Enhanced Emission under Pressure.

Hybrid metal halides are emerging semiconductors as promising candidates for optoelectronics. The pursuit of hybridizing various dimensions of metal halides remains a desirable yet highly complex endeavor. By utilizing dimension engineering, a diverse array of new materials with intrinsically different electronic and optical properties has been developed. Here, we report a new family of 2D-0D hybrid bimetallic halides, (C6 N2 H14 )2 SbCdCl9 ⋅ 2H2 O (SbCd) and (C6 N2 H14 )2 SbCuCl9 ⋅ 2H2 O (SbCu). These compounds adopt a new layered structure, consisting of alternating 0D square pyramidal [SbCl5 ] and 2D inorganic layers sandwiched by organic layers. SbCd and SbCu have optical band gaps of 3.3 and 2.3 eV, respectively. These compounds exhibit weak photoluminescence (PL) at room temperature, and the PL gradually enhances with decreasing temperature. Density functional theory (DFT) calculations reveal that SbCd and SbCu are direct gap semiconductors, where first-principles band gaps follow the experimental trend. Moreover, given the different pressure responses of 0D and 2D components, these materials exhibit highly tunable electronic structures during compression, where a remarkable 11 times enhancement in PL emission is observed for SbCd at 19 GPa. This work opens new avenues for designing new layered bimetallic halides and further manipulating their structures and optoelectronic properties via pressure.

Hydrogen Storage with Aluminum Formate, ALF: Experimental, Computational, and Technoeconomic Studies.

Long-duration storage of hydrogen is necessary for coupling renewable H2 with stationary fuel cell power applications. In this work, aluminum formate (ALF), which adopts the ReO3-type structure, is shown to have remarkable H2 storage performance at non-cryogenic (>120 K) temperatures and low pressures. The most promising performance of ALF is found between 120 K and 160 K and at 10 bar to 20 bar. The study illustrates H2 adsorption performance of ALF over the 77 K to 296 K temperature range using gas isotherms, in situ neutron powder diffraction, and DFT calculations, as well as technoeconomic analysis (TEA), illustrating ALF's competitive performance for long-duration storage versus compressed hydrogen and leading metal-organic frameworks. In the TEA, it is shown that ALF's storage capacity, when combined with a temperature/pressure swing process, has advantages versus compressed H2 at a fraction of the pressure (15 bar versus 350 bar). Given ALF's performance in the 10 bar to 20 bar regime under moderate cooling, it is particularly promising for use in safe storage systems serving fuel cells.

Exclusive Recognition of CO2 from Hydrocarbons by Aluminum Formate with Hydrogen-Confined Pore Cavities.

Exclusive capture of carbon dioxide (CO2) from hydrocarbons via adsorptive separation is an important technology in the petrochemical industry, especially for acetylene (C2H2) production. However, the physicochemical similarities between CO2 and C2H2 hamper the development of CO2-preferential sorbents, and CO2 is mainly discerned via C recognition with low efficiency. Here, we report that the ultramicroporous material Al(HCOO)3, ALF, can exclusively capture CO2 from hydrocarbon mixtures, including those containing C2H2 and CH4. ALF shows a remarkable CO2 capacity of 86.2 cm3 g-1 and record-high CO2/C2H2 and CO2/CH4 uptake ratios. The inverse CO2/C2H2 separation and exclusive CO2 capture performance from hydrocarbons are validated via adsorption isotherms and dynamic breakthrough experiments. Notably, the hydrogen-confined pore cavities with appropriate dimensional size provide an ideal pore chemistry to specifically match CO2 via a hydrogen bonding mechanism, with all hydrocarbons rejected. This molecular recognition mechanism is unveiled by in situ Fourier-transform infrared spectroscopy, X-ray diffraction studies, and molecular simulations.

As-Grown Miniaturized True Zero-Order Waveplates Based on Low-Dimensional Ferrocene Crystals.

As basic optical elements, waveplates with anisotropic electromagnetic responses are imperative for manipulating light polarization. Conventional waveplates are manufactured from bulk crystals (e.g., quartz and calcite) through a series of precision cutting and grinding steps, which typically result in large size, low yield, and high cost. In this study, a bottom-up method is used to grow ferrocene crystals with large anisotropy to demonstrate self-assembled ultrathin true zero-order waveplates without additional machining processing, which is particularly suited for nanophotonic integration. The van der Waals ferrocene crystals exhibit high birefringence (Δn (experiment) = 0.149  ±  0.002 at 636 nm), low dichroism Δκ (experiment) = -0.0007 at 636 nm), and a potentially broad operating range (550 nm to 20 µm) as suggested by Density Functional Theory (DFT) calculations. In addition, the grown waveplate's highest and the lowest principal axes (n1 and n3 , respectively) are in the a-c plane, where the fast axis is along one natural edge of the ferrocene crystal, rendering them readily usable. The as-grown, wavelength-scale-thick waveplate allows the development of further miniaturized systems via tandem integration.

Noncryogenic Air Separation Using Aluminum Formate Al(HCOO)3 (ALF).

Separating oxygen from air to create oxygen-enriched gas streams is a process that is significant in both industrial and medical fields. However, the prominent technologies for creating oxygen-enriched gas streams are both energy and infrastructure intensive as they use cryogenic temperatures or materials that adsorb N2 from air. The latter method is less efficient than the methods that adsorb O2 directly. Herein, we show, via a combination of gas adsorption isotherms, gas breakthrough experiments, neutron and synchrotron X-ray powder diffraction, Raman spectroscopy, and computational studies, that the metal-organic framework, Al(HCOO)3 (ALF), which is easily prepared at low cost from commodity chemicals, exhibits substantial O2 adsorption and excellent time-dependent O2/N2 selectivity in a range of 50-125 near dry ice/solvent (≈190 K) temperatures. The effective O2 adsorption with ALF at ≈190 K and ≈0.21 bar (the partial pressure of O2 in air) is ≈1.7 mmol/g, and at ice/salt temperatures (≈250 K), it is ≈0.3 mmol/g. Though the kinetics for full adsorption of O2 near 190 K are slower than at temperatures nearer 250 K, the kinetics for initial O2 adsorption are fast, suggesting that O2 separation using ALF with rapid temperature swings at ambient pressures is a potentially viable choice for low-cost air separation applications. We also present synthetic strategies for improving the kinetics of this family of compounds, namely, via Al/Fe solid solutions. To the best of our knowledge, ALF has the highest O2/N2 sorption selectivity among MOF adsorbents without open metal sites as verified by co-adsorption experiments..

Achieving Near-unity Photoluminescence Quantum Yields in Organic-Inorganic Hybrid Antimony (III) Chlorides with the [SbCl5 ] Geometry.

Hybrid organic-inorganic antimony halides have attracted increasing attention due to the non-toxicity, stability, and high photoluminescence quantum yield (PLQY). To shed light on the structural factors that contribute to the high PLQY, five pairs of antimony halides with general formula A2 SbCl5 and A2 Sb2 Cl8 are synthesized via two distinct methods and characterized. The A2 SbCl5 type adopts square pyramidal [SbCl5 ] geometry with near-unity PLQY, while the A2 Sb2 Cl8 adopts seesaw dimmer [Sb2 Cl8 ] geometry with PLQY≈0 %. Through combined data analysis with the literature, we have found that A2 SbCl5 series with square pyramidal geometry generally has much longer Sb⋅⋅⋅Sb distances, leading to more expressed lone pairs of SbIII . Additional factors including Sb-Cl distance and stability of antimony chlorides may also affect PLQY. Our targeted synthesis and correlated insights provide efficient tools to precisely form highly emissive materials for optoelectronic applications.

Aluminum formate, Al(HCOO)3: An earth-abundant, scalable, and highly selective material for CO2 capture.

A combination of gas adsorption and gas breakthrough measurements show that the metal-organic framework, Al(HCOO)3 (ALF), which can be made inexpensively from commodity chemicals, exhibits excellent CO2 adsorption capacities and outstanding CO2/N2 selectivity that enable it to remove CO2 from dried CO2-containing gas streams at elevated temperatures (323 kelvin). Notably, ALF is scalable, readily pelletized, stable to SO2 and NO, and simple to regenerate. Density functional theory calculations and in situ neutron diffraction studies reveal that the preferential adsorption of CO2 is a size-selective separation that depends on the subtle difference between the kinetic diameters of CO2 and N2. The findings are supported by additional measurements, including Fourier transform infrared spectroscopy, thermogravimetric analysis, and variable temperature powder and single-crystal x-ray diffraction.

Hybrid Germanium Bromide Perovskites with Tunable Second Harmonic Generation.

Ge-based hybrid perovskite materials have demonstrated great potential for second harmonic generation (SHG) due to the geometry and lone-pair induced non-centrosymmetric structures. Here, we report a new family of hybrid 3D Ge-based bromide perovskites AGeBr3 , A=CH3 NH3 (MA), CH(NH2 )2 (FA), Cs and FAGe0.5 Sn0.5 Br3 , crystallizing in polar space groups. These compounds exhibit tunable SHG responses, where MAGeBr3 shows the strongest SHG intensity (5×potassium dihydrogen phosphate, KDP). Structural and theoretical analysis indicate the high SHG efficiency is attributed to the displacement of Ge2+ along [111] direction and the relatively strong interactions between lone pair electrons of Ge2+ and polar MA cations along the c-axis. This work provides new structural insights for designing and fine-tuning the SHG properties in hybrid metal halide materials.

Fundamental investigations on the sodium-ion transport properties of mixed polyanion solid-state battery electrolytes.

Lithium and sodium (Na) mixed polyanion solid electrolytes for all-solid-state batteries display some of the highest ionic conductivities reported to date. However, the effect of polyanion mixing on the ion-transport properties is still not fully understood. Here, we focus on Na1+xZr2SixP3-xO12 (0 ≤ x ≤ 3) NASICON electrolyte to elucidate the role of polyanion mixing on the Na-ion transport properties. Although NASICON is a widely investigated system, transport properties derived from experiments or theory vary by orders of magnitude. We use more than 2000 distinct ab initio-based kinetic Monte Carlo simulations to map the compositional space of NASICON over various time ranges, spatial resolutions and temperatures. Via electrochemical impedance spectroscopy measurements on samples with different sodium content, we find that the highest ionic conductivity (i.e., about 0.165 S cm-1 at 473 K) is experimentally achieved in Na3.4Zr2Si2.4P0.6O12, in line with simulations (i.e., about 0.170 S cm-1 at 473 K). The theoretical studies indicate that doped NASICON compounds (especially those with a silicon content x ≥ 2.4) can improve the Na-ion mobility compared to undoped NASICON compositions.

Superionic Conduction in the Plastic Crystal Polymorph of Na4P2S6.

Sodium thiophosphates are promising materials for large-scale energy storage applications benefiting from high ionic conductivities and the geopolitical abundance of the elements. A representative of this class is Na4P2S6, which currently shows two known polymorphs-α and ß. This work describes a third polymorph of Na4P2S6, γ, that forms above 580 °C, exhibits fast-ion conduction with low activation energy, and is mechanically soft. Based on high-temperature diffraction, pair distribution function analysis, thermal analysis, impedance spectroscopy, and ab initio molecular dynamics calculations, the γ-Na4P2S6 phase is identified to be a plastic crystal characterized by dynamic orientational disorder of the P2S6 4- anions translationally fixed on a body-centered cubic lattice. The prospect of stabilizing plastic crystals at operating temperatures of solid-state batteries, with benefits from their high ionic conductivities and mechanical properties, could have a strong impact in the field of solid-state battery research.

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.

Insights into the Rich Polymorphism of the Na+ Ion Conductor Na3PS4 from the Perspective of Variable-Temperature Diffraction and Spectroscopy.

Solid electrolytes are crucial for next-generation solid-state batteries, and Na3PS4 is one of the most promising Na+ conductors for such applications, despite outstanding questions regarding its structural polymorphs. In this contribution, we present a detailed investigation of the evolution in structure and dynamics of Na3PS4 over a wide temperature range 30 < T < 600 °C through combined experimental-computational analysis. Although Bragg diffraction experiments indicate a second-order phase transition from the tetragonal ground state (α, P4̅21 c) to the cubic polymorph (ß, I4̅3m) above ∼250 °C, pair distribution function analysis in real space and Raman spectroscopy indicate remnants of a tetragonal character in the range 250 < T < 500 °C, which we attribute to dynamic local tetragonal distortions. The first-order phase transition to the mesophasic high-temperature polymorph (γ, Fddd) is associated with a sharp volume increase and the onset of liquid-like dynamics for sodium-cations (translational) and thiophosphate-polyanions (rotational) evident by inelastic neutron and Raman spectroscopies, as well as pair-distribution function and molecular dynamics analyses. These results shed light on the rich polymorphism of Na3PS4 and are relevant for a range host of high-performance materials deriving from the Na3PS4 structural archetype.

Under Pressure: Mechanochemical Effects on Structure and Ion Conduction in the Sodium-Ion Solid Electrolyte Na3PS4.

Fast-ion conductors are critical to the development of solid-state batteries. The effects of mechanochemical synthesis that lead to increased ionic conductivity in an archetypical sodium-ion conductor Na3PS4 are not fully understood. We present here a comprehensive analysis based on diffraction (Bragg and pair distribution function), spectroscopy (impedance, Raman, NMR and INS), and ab initio simulations aimed at elucidating the synthesis-property relationships in Na3PS4. We consolidate previously reported interpretations regarding the local structure of ball-milled samples, underlining the sodium disorder and showing that a local tetragonal framework more accurately describes the structure than the originally proposed cubic one. Through variable-pressure impedance spectroscopy measurements, we report for the first time the activation volume for Na+ migration in Na3PS4, which is ∼30% higher for the ball-milled samples. Moreover, we show that the effect of ball-milling on increasing the ionic conductivity of Na3PS4 to ∼10-4 S/cm can be reproduced by applying external pressure on a sample from conventional high-temperature ceramic synthesis. We conclude that the key effects of mechanochemical synthesis on the properties of solid electrolytes can be analyzed and understood in terms of pressure, strain, and activation volume.

Understanding the Structural and Electronic Properties of Bismuth Trihalides and Related Compounds.

Bismuth trihalides, BiX3 (X = F, Cl, Br, and I), have been thrust into prominence recently because of their close chemical relationship to the halide perovskites of lead, which exhibit remarkable performance as active layers in photovoltaic cells and other optoelectronic devices. In the present work, we have used calculations based on density functional theory to explore the energetics and electronic properties of BiX3 in a variety of known and hypothetical structure types. The results for BiX3 are compared with those obtained for the halides of the later rare earths, represented by YX3 and LuX3. The relative thermodynamic stabilities of the known and hypothetical structures are calculated, along with their band gaps. For the BiX3 systems, we have explored the role of lone-pair effects associated with bismuth(III), and for BiI3, we have compared the predicted structural behavior as a function of pressure with the available experimental data. We have also attempted to synthesize LuF3 in the perovskite-related ReO3-type structure, which is predicted to be only ∼7.7 kJ mol-1 above the convex hull. This attempt was unsuccessful but led to the discovery of a new hydrated phase, (H3O)Lu3F10H2O, which is isomorphous with the known ytterbium analogue.

Fundamentals of inorganic solid-state electrolytes for batteries.

In the critical area of sustainable energy storage, solid-state batteries have attracted considerable attention due to their potential safety, energy-density and cycle-life benefits. This Review describes recent progress in the fundamental understanding of inorganic solid electrolytes, which lie at the heart of the solid-state battery concept, by addressing key issues in the areas of multiscale ion transport, electrochemical and mechanical properties, and current processing routes. The main electrolyte-related challenges for practical solid-state devices include utilization of metal anodes, stabilization of interfaces and the maintenance of physical contact, the solutions to which hinge on gaining greater knowledge of the underlying properties of solid electrolyte materials.