Integrated Circular Economy Model System for Direct Lithium Extraction: From Minerals to Batteries Utilizing Aluminum Hydroxide.

Aluminum hydroxide, an abundant mineral found in nature, exists in four polymorphs: gibbsite, bayerite, nordstrandite, and doyleite. Among these polymorphs gibbsite, bayerite, and commercially synthesized amorphous aluminum hydroxide have been investigated as sorbent materials for lithium extraction from sulfate solutions. The amorphous form of Al(OH)3 exhibits a reactivity higher than that of the naturally occurring crystalline polymorphs in terms of extracting Li+ ions. This study employed high-temperature oxide melt solution calorimetry to explore the energetics of the sorbent polymorphs. The enthalpic stability order was measured to be gibbsite > bayerite > amorphous Al(OH)3. The least stable form, amorphous Al(OH)3, undergoes a spontaneous reaction with lithium, resulting in the formation of a stable layered double hydroxide phase. Consequently, amorphous Al(OH)3 shows promise as a sorbent material for selectively extracting lithium from clay mineral leachate solutions. This research demonstrates the selective direct extraction of Li+ ions using amorphous aluminum hydroxide through a liquid-solid lithiation reaction, followed by acid-free delithiation and relithiation processes, achieving an extraction efficiency of 86%, and the maximum capacity was 37.86 mg·g-1 in a single step during lithiation. With high selectivity during lithiation and nearly complete recoverability of the sorbent material during delithiation, this method presents a circular economy model. Furthermore, a life cycle analysis was conducted to illustrate the environmental advantages of replacing the conventional soda ash-based precipitation process with this method, along with a simple operational cost analysis to evaluate reagent and fuel expenses.

Separation of Lithium from Aluminum-Containing Clay Mineral Leachate Solution Using Energy-Efficient Membrane Solvent Extraction.

This study investigated a novel membrane solvent extraction (MSX) process for the recovery and separation of lithium (Li) from clay minerals using a cation exchange organic extractant [di-(2-ethylhexyl)phosphoric acid] (DEHPA). The Li is selectively extracted from clay mineral leachate solution using highly efficient aluminum hydroxide sorbents to form lithium aluminum double hydroxide sulfate (LDH sulfate) as the precipitate. Several delithiation methods have been explored to separate Li from aluminum (Al). LDH sulfate is dissolved in dilute H2SO4 and used as the feed solution, and DEHPA is used to selectively separate Li and Al from the feed solution. The MSX process immobilizes DEHPA in the microporous membrane pores and continuously removes Al from the feed solution to obtain pure Li. The efficiency of DEHPA for the selective separation of Li from Al is determined by measuring its distribution coefficient. This study used the optimum feed solution pH of 3, strip solution concentration of 2 mol/L H2SO4, and an organic phase composition of 30% v/v DEHPA in Isopar-L. The MSX process achieved a Li yield of about 92% and a purity of ⩾ 94%. The results suggest that the innovative MSX technology is a time- and energy-efficient approach for the recovery and separation of high-purity Li for application in Li-ion batteries and other clean energy technologies.

Packing bimodal magnetic particles to fabricate highly dense anisotropic rare earth bonded permanent magnets.

Highly dense and magnetically anisotropic rare earth bonded magnets have been fabricated via packing bimodal magnetic particles using a batch extrusion process followed by compression molding technology. The bimodal feedstock was a 96 wt% magnet powder mixture, with 40% being anisotropic Sm-Fe-N (3 µm) and 60% being anisotropic Nd-Fe-B (100 µm) as fine and coarse particles, respectively; these were blended with a 4 wt% polyphenylene sulfide (PPS) polymer binder to fabricate the bonded magnets. The hybrid bonded magnet with an 81 vol% magnet loading yielded a density of 6.15 g cm-3 and a maximum energy product (BH)m of 20.0 MGOe at 300 K. Scanning electron microscopy (SEM) indicated that the fine-sized Sm-Fe-N particles filled the gap between the large Nd-Fe-B particles. Rietveld analysis of the X-ray diffraction data showed that the relative contents of the Nd2Fe14B and Sm2Fe17N3 phases were 61% and 39%, respectively, in the hybrid bonded magnet. The PPS binder coated most of the magnetic particles homogeneously. Compared with the magnetic properties of the initial Nd-Fe-B and Sm-Fe-N powders, the reduction in the remanence, from the demagnetization curve, is ascribed to the dilution effect of the binder, the non-perfect alignment, and the internal magnetic stray field.

Slug Flow Coprecipitation Synthesis of Uniformly-Sized Oxalate Precursor Microparticles for Improved Reproducibility and Tap Density of Li(Ni0.8Co0.1Mn0.1)O2 Cathode Materials.

The microparticle quality and reproducibility of Li(Ni0.8Co0.1Mn0.1)O2 (NCM811) cathode materials are important for Li-ion battery performance but can be challenging to control directly from synthesis. Here, a scalable reproducible synthesis process is designed based on slug flow to rapidly generate uniform micron-size spherical-shape NCM oxalate precursor microparticles at 25-34 °C. The whole process takes only 10 min, from solution mixing to precursor microparticle generation, without needing aging that typically takes hours. These oxalate precursors are convertible to spherical-shape NCM811 oxide microparticles, through a preliminary design of low heating rates (e.g., 0.1 and 0.8 °C/min) for calcination and lithiation. The outcome oxide cathode particles also demonstrate improved tap density (e.g., 2.4 g mL-1 for NCM811) and good specific capacity (202 mAh g-1 at 0.1 C) in coin cells and reasonably good cycling performance with LiF coating.

Scalable Advanced Li(Ni0.8Co0.1Mn0.1)O2 Cathode Materials from a Slug Flow Continuous Process.

Li[Ni0.8Co0.1Mn0.1]O2 (LNCMO811) is the most studied cathode material for next-generation lithium-ion batteries with high energy density. However, available synthesis methods are time-consuming and complex, restricting their mass production. A scalable manufacturing process for producing NCM811 hydroxide precursors is vital for commercialization of the material. In this work, a three-phase slug flow reactor, which has been demonstrated for its ease of scale-up, better synthetic control, and excellent uniform mixing, was developed to control the initial stage of the coprecipitation of NCM811 hydroxide. Furthermore, an equilibrium model was established to predict the yield and composition of the final product. The homogeneous slurry from the slug flow system was obtained and then transferred into a ripening vessel for the necessary ripening process. Finally, the lithium-nickel-cobalt-manganese oxide was obtained through the calcination of the slug flow-derived precursor with lithium hydroxide, having a tap density of 1.3 g cm-3 with a well-layered structure. As-synthesized LNCMO811 shows a high specific capacity of 169.5 mAh g-1 at a current rate of 0.1C and a long cycling stability of 1000 cycling with good capacity retention. This demonstration provides a pathway toward scaling up the cathode synthesis process for large-scale battery applications.

Effective antiviral coatings for deactivating SARS-CoV-2 virus on N95 respirator masks or filters.

The application of antiviral coatings to masks and respirators is a potential mitigating step toward reducing viral transmission during the SARS-CoV-2 (severe acute respiratory syndrome coronavirus 2) pandemic. The use of appropriate masks, social distancing, and vaccines is the immediate solution for limiting the viral spread and protecting people from this virus. N95 respirator masks are effective in filtering the virus particles, but they cannot kill or deactivate the virus. We report a possible approach to deactivating SARS-CoV-2 by applying an antimicrobial coating (Goldshield 75) to masks and respirators, rendering them suitable for repeated use. Masks coated with Goldshield 75 demonstrated continuous inactivation of the Alpha and Beta variants of the SARS-CoV-2 over a 3-day period and no loss of inactivation when stored at temperatures at 50 °C.

Additively Manufactured NdFeB Polyphenylene Sulfide Halbach Magnets to Generate Variable Magnetic Fields for Neutron Reflectometry.

Halbach arrays are the most efficient closed structures for generating directed magnetic fields and gradients, and are widely used in various electric machines. We utilized fused deposition modeling-based Big Area Additive Manufacturing technology to print customized, compensated concentric Halbach array rings, using polyphenylene sulfide-bonded NdFeB permanent magnets for polarized neutron reflectometry. The Halbach rings could generate a 0 ≤ B ≤ 0.30 T field, while preserving 90% polarization of an axial neutron beam. Polarized neutron beams are used to study a wide range of structural and magnetic phenomena spanning physics, chemistry, and biology. In this study, we demonstrate the effectiveness of additive manufacturing for producing prototype Halbach arrays, characterize their magnetic properties, and generated magnetic fields, and discuss the conservation of neutron beam polarization as a function of magnetic field.

Polymer, Additives, and Processing Effects on N95 Filter Performance.

The current severe acute respiratory syndrome coronavirus 2 (SARS-COV-2) pandemic has highlighted the need for personal protective equipment, specifically filtering facepiece respirators like N95 masks. While it is common knowledge that polypropylene (PP) is the industry standard material for filtration media, trial and error is often required to identify suitable commercial precursors for filtration media production. This work aims to identify differences between several commercial grades of PP and demonstrate the development of N95 filtration media with the intent that the industry partners can pivot and help address N95 shortages. Three commercial grades of high melt flow index PP were melt blown at Oak Ridge National Laboratory and broadly characterized by several methods including differential scanning calorimetry (DSC), X-ray diffraction (XRD), and neutron scattering. Despite the apparent similarities (high melt flow and isotacticity) between PP feedstocks, the application of corona charging and charge enhancing additives improve each material to widely varying degrees. From the analysis performed here, the most differentiating factor appears to be related to crystallization of the polymer and the resulting electret formation. Materials with higher crystallization onset temperatures, slower crystallization rates, and larger number of crystallites form a stronger electret and are more effective at filtration.

Recovery of Lithium from Geothermal Brine with Lithium-Aluminum Layered Double Hydroxide Chloride Sorbents.

We report a three-stage bench-scale column extraction process to selectively extract lithium chloride from geothermal brine. The goal of this research is to develop materials and processing technologies to improve the economics of lithium extraction and production from naturally occurring geothermal and other brines for energy storage applications. A novel sorbent, lithium aluminum layered double hydroxide chloride (LDH), is synthesized and characterized with X-ray powder diffraction, scanning electron microscopy, inductively coupled plasma optical emission spectrometry (ICP-OES), and thermogravimetric analysis. Each cycle of the column extraction process consists of three steps: (1) loading the sorbent with lithium chloride from brine; (2) intermediate washing to remove unwanted ions; (3) final washing for unloading the lithium chloride ions. Our experimental analysis of eluate vs feed concentrations of Li and competing ions demonstrates that our optimized sorbents can achieve a recovery efficiency of ∼91% and possess excellent Li apparent selectivity of 47.8 compared to Na ions and 212 compared to K ions, respectively in the brine. The present work demonstrates that LDH is an effective sorbent for selective extraction of lithium from brines, thus offering the possibility of effective application of lithium salts in lithium-ion batteries leading to a fundamental shift in the lithium supply chain.

Neutron vibrational spectroscopic studies of novel tire-derived carbon materials.

Sulfonated tire-derived carbons have been demonstrated to be high value-added carbon products of tire recycling in several energy storage system applications including lithium, sodium, potassium ion batteries and supercapacitors. In this communication, we compared different temperature pyrolyzed sulfonated tire-derived carbons with commercial graphite and unmodified/non-functionalized tire-derived carbon by studying the surface chemistry and properties, vibrational spectroscopy of the molecular structure, chemical bonding such as C-H bonding, and intermolecular interactions of the carbon materials. The nitrogen adsorption-desorption studies revealed the tailored micro and meso pore size distribution of the carbon during the sulfonation process. XPS and neutron vibrational spectra showed that the sulfonation of the initial raw tire powders could remove the aliphatic hydrogen containing groups ([double bond splayed left]CH2 and -CH3 groups) and reduce the number of heteroatoms that connect to carbon. The absence of these functional groups could effectively improve the first cycle efficiency of the material in rechargeable batteries. Meanwhile, the introduced -SO3H functional group helped in producing terminal H at the edge of the sp2 bonded graphite-like layers. This study reveals the influence of the sulfonation process on the recovered hard carbon from used tires and provides a pathway to develop and improve advanced energy storage materials.

Membrane-Based Gas Separation Accelerated by Hollow Nanosphere Architectures.

The coupling of hollow carbon nanospheres with triblock copolymers is a promising strategy to fabricate mixed-matrix membranes. This is because the symmetric microporous shells combine with the hollow space to promote gas transport, and the unique soft-rigid molecular structure of triblock copolymers can accommodate a high loading of fillers without a significant loss of mechanical strength.

Thermoreversible Morphology and Conductivity of a Conjugated Polymer Network Embedded in Block Copolymer Self-Assemblies.

Self-assembly of block copolymers provides numerous opportunities to create functional materials, utilizing self-assembled microdomains with a variety of morphology and periodic architectures as templates for functional nanofillers. Here new progress is reported toward the fabrication of thermally responsive and electrically conductive polymeric self-assemblies made from a water-soluble poly(thiophene) derivative with short poly(ethylene oxide) side chains and Pluronic L62 block copolymer solution in water. The structural and electrical properties of conjugated polymer-embedded self-assembled architectures are investigated by combining small-angle neutron and X-ray scattering, coarse-grained molecular dynamics simulations, and impedance spectroscopy. The L62 solution template organizes the conjugated polymers by stably incorporating them into the hydrophilic domains thus inhibiting aggregation. The changing morphology of L62 during the micellar-to-lamellar phase transition defines the embedded conjugated polymer network. As a result, the conductivity is strongly coupled to the structural change of the templating L62 phase and exhibits thermally reversible behavior with no signs of quenching of the conductivity at high temperature. This study shows promise for enabling more flexibility in processing and utilizing water-soluble conjugated polymers in aqueous solutions for self-assembly based fabrication of stimuli-responsive nanostructures and sensory materials.

Nanoparticle Shape Evolution and Proximity Effects During Tip-Induced Electrochemical Processes.

Voltage spectroscopies in scanning probe microscopy (SPM) techniques are widely used to investigate the electrochemical processes in nanoscale volumes, which are important for current key applications, such as batteries, fuel cells, catalysts, and memristors. The spectroscopic measurements are commonly performed on a grid of multiple points to yield spatially resolved maps of reversible and irreversible electrochemical functionalities. Hence, the spacing between measurement points is an important parameter to be considered, especially for irreversible electrochemical processes. Here, we report nonlocal electrochemical dynamics in chains of Ag particles fabricated by the SPM tip on a silver ion solid electrolyte. When the grid spacing is small compared with the size of the formed Ag particles, anomalous chains of unequally sized particles with double periodicity evolve. This behavior is ascribed to a proximity effect during the tip-induced electrochemical process, specifically, size-dependent silver particle growth following the contact between the particles. In addition, fractal shape evolution of the formed Ag structures indicates that the growth-limiting process changes from Ag(+)/Ag redox reaction to Ag(+)-ion diffusion with the increase in the applied voltage and pulse duration. This study shows that characteristic shapes of the electrochemical products are good indicators for determining the underlying growth-limiting process, and emergence of complex phenomena during spectroscopic mapping of electrochemical functionalities.

Superior Conductive Solid-like Electrolytes: Nanoconfining Liquids within the Hollow Structures.

The growth and proliferation of lithium (Li) dendrites during cell recharge are currently unavoidable, which seriously hinders the development and application of rechargeable Li metal batteries. Solid electrolytes with robust mechanical modulus are regarded as a promising approach to overcome the dendrite problems. However, their room-temperature ionic conductivities are usually too low to reach the level required for normal battery operation. Here, a class of novel solid electrolytes with liquid-like room-temperature ionic conductivities (>1 mS cm(-1)) has been successfully synthesized by taking advantage of the unique nanoarchitectures of hollow silica (HS) spheres to confine liquid electrolytes in hollow space to afford high conductivities (2.5 mS cm(-1)). In a symmetric lithium/lithium cell, the solid-like electrolytes demonstrate a robust performance against the Li dendrite problem, preventing the cell from short circuiting at current densities ranging from 0.16 to 0.32 mA cm(-2) over an extended period of time. Moreover, the high flexibility and compatibility of HS nanoarchitectures, in principle, enables broad tunability to choose desired liquids for the fabrication of other kinds of solid-like electrolytes, such as those containing Na(+), Mg(2+), or Al(3+) as conductive media, providing a useful alternative strategy for the development of next generation rechargeable batteries.

Far-infrared optical conductivity gap in superconducting MgB2 films.

We report the first study of the optical conductivity of MgB2 covering the range of its lowest-energy superconducting gap. Terahertz time-domain spectroscopy is utilized to determine the complex, frequency-dependent conductivity sigma(omega) of thin films. The imaginary part reveals an inductive response due to the emergence of the superconducting condensate. The real part exhibits a strong depletion of oscillator strength near 5 meV resulting from the opening of a superconducting energy gap. The gap ratio of 2Delta0/k(B)TC approximately 1.9 is well below the weak-coupling value, pointing to complex behavior in this novel superconductor.