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At least 469 records · Page 26

Carbon-sequestration gradient insulation composites

The massive use of carbon-sequestration building materials promises a potential global carbon sink in decarbonizing the building industry. Renewable biogenic materials from abundant agriculture waste for building practice have been around over thousands of years. However, in addition to their flammability and moisture problems, addressing their low thermal and structural performance is also becoming indispensable and urgent when it comes to environmentally sustainable and energy-efficient buildings. Here, we report a nature-inspired biogenic gradient insulation composite with an optimized silica concentration of 30 wt %, a density of 0.246 g/cm 3 , and a porosity of 86%. The gradient hybrid composite exhibits a thermal conductivity of 28.2 mW m -1 K -1 , which is the lowest achieved under optimal preparation conditions. Here, it also shows a flexural modulus of 590 MPa for the aerogel-rich layer without surface modification, and it demonstrates superior fire retardancy and superhydrophobicity after surface treatment.

36 MATERIALS SCIENCE↗

Review on Preprocessing Strategies, Deactivation, Thermal Safety, and Future Perspectives in Lithium-Ion Battery Recycling

The rapid growth in the use of lithium-ion batteries (LIBs) in electric vehicles, consumer electronics, and renewable energy storage has made effective end-of-life management essential. Recycling LIBs is critical not only for resource recovery and environmental protection but also for ensuring safety and economic viability. This review focuses on the preprocessing technologies that precede typical recovery processes, including disassembly, sorting, discharging, electrolyte removal, dismantling, thermal treatment, separation, and flotation. These steps play a foundational role in determining the efficiency, safety, and environmental impact of LIB recycling. LIBs pose substantial fire and explosion risks due to residual charge, flammable electrolytes, and reactive materials. The conditions and successive progression of the exothermic reactions which lead to thermal runaway has been discussed. It also explores secure deactivation techniques such as external circuit discharge, saline immersion, and thermomechanical methods, alongside fire prevention strategies including the use of flame retardants, elimination of oxidants, and reduction of heat generation and accumulation. Challenges and future directions are outlined, highlighting the need for standardized designs, automation, and safer, more sustainable recycling infrastructure. Furthermore, this review is distinguished by its focused analysis of preprocessing and deactivation steps, with particular attention to the thermal safety engineering aspects of LIB recycling.

Battery deactivation↗

Li 2 GeS 3 : Lithium Ionic Conductor with an Unprecedented Structural Type

Lithium-ion batteries (LIBs) are widely used in electric vehicles, mobile electronic devices, and large-scale stationary energy storage systems. However, their liquid electrolytes present significant safety concerns due to their inherent flammability. To address this, the focus has shifted toward all-solid-state batteries (ASSBs) utilizing inorganic solid electrolytes that promise enhanced safety. In this work, we report the discovery of a new crystal structural type of Li-ion conductor, Li 2 GeS 3 , with a unique structure, synthesized by a solid-state reaction from Li 2 S and GeS 2 . It was first reported in 2000 with an orthorhombic unit cell, but its detailed crystal structure remains veiled. Here, we have unveiled its structure for the first time, employing an ab initio structure determination technique from powder X-ray and time-of-flight neutron diffraction data. The compound has an unprecedented crystal structural type with a hexagonal $P6_1$ symmetry and a unit cell of α = 6.79364(4) Å and c = 17.90724(14) Å. Its structure is comprised of a distorted hexagonal close-packed arrangement of sulfur anions with three asymmetric metal atoms: Li1, Li2, and Ge are in tetrahedral cavities surrounded by sulfur atoms. The ionic conductivity of Li 2 GeS 3 was measured to be 1.63 × 10 –8 S cm –1 at 303 K and 2.45 × 10 –7 S cm –1 at 383 K. Bond valence energy landscape calculations revealed three-dimensional lithium diffusion pathways within the structure. This novel crystal structure in Li 2 GeS 3 holds the potential for developing high-performance ionic conductors through suitable chemical substitution and offers valuable insights into designing new ionic conductors for ASSBs.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Halide Substitution Effects on Lithium-Ion Diffusion in Protonated Antiperovskites

Solid-state electrolytes (SSEs) for all-solid-state lithium-ion batteries are generating intense interest because these batteries can improve the safety and performance compared with devices fabricated with conventional, flammable liquid electrolytes. In these SSEs, it has been suggested that Li + ion diffusion in the grain boundaries is hindered and is a critical determinant of the overall ionic conductivity (σ). However, Li + ion diffusivities in the grain (D G ) and the grain boundary (D GB ) are difficult to determine experimentally, with few techniques capable of distinguishing the individual contributions. Here, we distinguished the D G and D GB for the protonated lithium antiperovskites (pLiAPs) SSEs: Li 2 OHCl, Li 2 OHBr, Li 2 OHF 0.1 Cl 0.9 , Li 2 OHF 0.1 Br 0.9 , and Li 2 OHCl 0.3 7Br 0.63 . The measurements were obtained directly from 7 Li pulsed-field gradient nuclear magnetic resonance (PFG-NMR) at 353 K. The 7 Li PFG-NMR echo profiles were composed of two primary components with additional secondary oscillatory components – the so-called NMR diffraction phenomenon. The length scale separating the two main components corresponds to a diffusion length of ~1.7 µm, which is thought to be the average grain size (by diameter). The short-range (≤ 1.7 µm) diffusion component associated with D G (≈10 -11 m 2 /s) varied minimally with halide substitution, while the long-range (≥ 1.7 µm) component D GB (≈10 -12 to 10 -15 m 2 /s) was highly sensitive to the substitution of halides and closely correlated with s. In addition, from the comparison of the ratio D GB /D G to D t (the Li + ion diffusion coefficient estimated from the rotational correlation time, t c ), it was determined that the contribution of D G to σ is negligible; 0.01 ~ 0.04 in the pLiAPs studied here. Finally, these insights provide fundamental understanding of the halide substitution effects on Li + ion grain versus grain boundary diffusion, and suggest that careful engineering of the grain boundaries at the microscopic level is necessary to achieve high-performance pLiAP SSEs.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Influence of Ether-Functionalized Pyrrolidinium Ionic Liquids on Properties and Li + Cation Solvation in Solvate Ionic Liquids

Ionic liquids are tunable solvents composed entirely of ions that have properties desirable as electrolytes for lithium batteries such as non-flammability and a large electrochemical stability window. Solvate ionic liquids are a subclass of ionic liquids that consist of a glyme-based solvent and lithium salt in an equimolar ratio, where Li + cation-glyme solvation interactions result in ionic liquid-like properties. LiG4TFSi is a well-studied solvate ionic liquid consisting of equimolar amounts of lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) and tetraglyme (G4). In this work, pyrrolidinium ionic liquids with ether-functionalized side chains were synthesized containing either one ether (EO1) moiety or three ether (EO3) moieties and mixed with LiG4TFSI to form a new class of electrolyte mixtures. Their physical and transport properties, as well as ion solvation structures, were characterized by electrochemical, thermal, rheological, and spectroscopic measurements. The conductivity of the electrolyte mixture composed of EO1:LiTFSI:G4 in a 1:1:1 molar ratio is 2.54 mS/cm at 30 °C, compared to 1.53 mS/cm for LiG4TFSI, an increase of 67%. A significant decrease in the conductivity to 0.279 mS/cm is observed for the EO3:LiTFSI:G4 mixture in a 1:1:0.4 molar ratio. Pulsed-field gradient nuclear magnetic resonance (PFG-NMR) measurements revealed that the EO1 cation diffuses significantly faster than the EO3 cation in their respective mixtures. Liquid-state 13 C NMR experiments indicate that Li + cations preferentially coordinate with tetraglyme. Li + cations do not coordinate with the EO1 cation and only coordinate with EO3 ether side chains at lower concentrations of tetraglyme. We hypothesize that the oligoether EO3 cation competes with G4 and TFSI - for lithium cation solvation in G4 deficient compositions, leading to a largely adverse effect on the mass transport properties of the electrolyte.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

High-Temperature-Performance Cyanate Ester Composites with Carboranes

Cyanate ester (CE) is an important class of materials among high-temperature performance thermosets. It is used in aerospace launch vehicles, heat sinks, booms, and trusses of satellites etc. due to its high glass transition temperatures (>220°C), excellent thermal stability, and low flammability. Current approaches to improve the thermal stability of CE include incorporation of siloxanes or phosphorus- based flame retardants (PFRs). In this work, we have explored boron-based hydroxy (PD) and epoxy (EP) functionalized carborane additives to improve the thermal properties of CE. Carborane fillers were solvent blended at various mass loadings in the resin and cured to study their effect on thermal properties. PD and EP carboranes react with CE to form iminocarbonate and oxazolidinone linkages respectively. Cure kinetics studies at different wt% loadings explained that carboranes catalyze the curing reaction by reducing curing activation energy by about 54% and 26% for 10 wt% loadings of PD and EP carboranes respectively. In addition, carborane-filled cyanate ester (CE) nanocomposites demonstrate an exceptionally high thermal stability as compared to the pristine resin in air and inert environment. Our thermogravimetric analysis (TGA) experiments show that the ultimate char yield of the resin can be increased from 0% to as high as 76% and 82% with 30 wt% PD and EP carborane loading respectively at 1000 °C in air. The initial degradation temperature T d;5 of the composites decreased with increasing carborane loadings in both air and argon. For instance, T d;5 for CE was 465 and 471.6 °C in argon and air while that for P20 was 437.4 and 452.1 °C. Modulated TGA studies gave evidence of the effect of carboranes on degradation kinetics and the mechanism of the resin in air and inert environment. The effect of bonding between carboranes and CE at various loadings on the thermal expansion of the matrix was also studied using Thermomechanical Analyzer (TMA). PD carborane reduced the T g for P20 to about 225 °C while CE had T g >350 °C.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Selecting the Optimal Fluorinated Ether Co-Solvent for Lithium Metal Batteries

To guide the selection of a suitable fluorinated ether (FE) co -solvent for lithium metal batteries, it is crucial to understand the relationship between the organic structures of the FEs and the electrochemical performance of an FE-containing electrolyte. In this work, 1,1,2,2-tetrafluoro-1-(2,2,2-trifluoroethoxy)ethane (FEE), 1,1,2,2-tetrafluoro-3-(1,1,2,2-tetrafluoroethoxy)-propane (TTE), and 1,2-bis(1,1,2,2-tetrafluoroethoxy)ethane (OFDEE) were chosen as representative FE co-solvents because of their distinct structural properties. The structure-activity relationship between the FEs and the electrochemical performance of Li||LiNi 0.6 Mn 0.2 Co 0.2 O 2 (Li||NMC622) cells was correlated and quantified by Fourier-transform infrared and multi-dimensional nuclear magnetic resonance techniques. Sand's model was also employed to assess the extent of lithium dendrite formation in the cells using various FE electrolytes. The cycling performance of Li||NMC622 cells using different FE co-solvents follows the order FEE > TTE > OFDEE. Further, since the direct measurement of Sand's time is difficult, we introduced relative Sand's time to probe the diffusion behavior of each electrolyte, and the results showed that the best performance was obtained in the electrolyte with the longest relative Sand's time. Moreover, the lithium metal cell using the electrolyte with FEE co-solvent showed similar capacity retention compared with the baseline electrolyte at room temperature, but it demonstrated significantly improved low-temperature performance. The results indicate that FEE is a promising co-solvent candidate for improving the low-temperature performance of lithium metal batteries because it possesses not only non-solvating behavior but also very low viscosity and non-flammability. The advanced electrolyte LiPF 6 -FEC-DMC-FEE enables very stable cycling of lithium metal batteries at various temperatures.

25 ENERGY STORAGE↗

Rational Electrolyte Design for Elevated-Temperature and Thermally Stable Lithium-Ion Batteries with Nickel-Rich Cathodes

As the energy density of lithium-ion batteries (LIBs) increases, the shortened cycle life and the increased safety hazard of LIBs are drawing increasing concerns. To address such challenges, a series of localized high-concentration electrolytes (LHCEs) based on a solvating-solvent mixture of tetramethylene sulfone and trimethyl phosphate and a high flash-point diluent 1H,1H,5H-octafluoropentyl 1,1,2,2-tetrafluoroethyl ether were designed. The LHCEs exhibited non-flammability and greatly suppressed heat release at high temperatures, which would potentially improve the safety performance of the LIBs. Moreover, the optimal LHCE achieved capacity retentions of 87.1% and 81.7% in graphite||LiNi 0.8 Mn 0.1 Co 0.1 O 2 cells after 500 cycles at 25 °C and 45 °C, respectively, which were significantly better than the conventional electrolyte, whose capacity retentions were only 75.2% and 38.5% under the same condition. Mechanistic studies revealed that the LHCE not only formed a more robust solid electrolyte interphase, but also exhibited improved anodic stability, compared with the conventional electrolyte. Further, this work sheds light in rational electrolyte design for high energy density LIBs with high battery performance and low safety concerns.

25 ENERGY STORAGE↗

Improved Li + Transport in Polyacetal Electrolytes: Conductivity and Current Fraction in a Series of Polymers

Polymer electrolytes mitigate safety concerns surrounding flammable liquid electrolytes in lithium-ion batteries. Poly(ethylene oxide) (PEO) electrolytes demonstrate viable conductivity values (~1 × 10 -3 S/cm) at elevated temperatures (>70 °C) but a relatively low Li + current fraction (≤0.2) because strong Li + coordination inhibits cation mobility. We have developed a series of polyacetal electrolytes by systematically varying methylene oxide (MO) and ethylene oxide (EO) units in the polymer backbone. These materials maintain high oxygen-to-carbon ratios like PEO but offer improved ion transport, revealing trends of decreasing conductivity and increasing current fraction with respect to polymer composition. In particular, the increasing current fraction measured via the Bruce-Vincent method suggests that MO units improve Li+ mobility relative to anion mobility. Here, we calculate an overall efficacy (product of conductivity and current fraction) for each polymer/salt composition and identify two polymers - P(EO-MO) and P(EO-2MO) - that outperform PEO at high and low salt concentrations, respectively.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Gas Generation in Lithium Cells with High-Nickel Cathodes and Localized High-Concentration Electrolytes

High-nickel layered-oxide cathodes (LiNi x Mn y Co 1-x-y O 2 , x ≥ 0.8) exhibit high capacities, but also experience rapid capacity fade during cycling, and are susceptible to heat generation and gas release. Advanced electrolytes, such as localized high-concentration electrolytes (LHCE), substantially stabilize the cathode during cycling and have lower flammability than conventional electrolytes, but gas generation with these electrolytes is yet to be assessed. We demonstrate here that gas generation from a high-nickel cathode in an LHCE is half as much as in a conventional electrolyte at 4.4 V. The gas generation in LHCE is further reduced at 4.3 V, but the LHCE generates a similar amount of gas as the conventional electrolyte at 4.6 V. Neither electrolyte can prevent gas generation after cycling; cathodes after 200 cycles generate similar amounts of gas as pristine cathodes during high-voltage hold. Finally, it is shown that in both electrolytes, oxygen from the cathode lattice plays a critical role in gas generation.

25 ENERGY STORAGE↗

Chemo-Mechanical Behavior and Stability of High-Loading Cathodes in Solid-State Batteries

Solid-state batteries can offer higher energy density and improved safety compared to lithium ion batteries, which use flammable liquid electrolytes. Increasing the ratio of cathode active materials in composite cathodes enhances the energy density and reduces manufacturing costs. Changes in the ratio of cathode active materials alter the microstructure and chemo-mechanical response of a cathode during operation. Understanding the relationship between composition, microstructure, and chemo-mechanical interactions is critical for optimizing solid-state cathodes. Here, in this study, we engineered composite cathodes with varying ratios of LiNi 0.8 Co 0.1 Mn 0.1 O 2 and Li 6 PS 5 Cl to systematically investigate the role of microstructural evolution in long-term chemo-mechanical transformations. Chemo-mechanical stresses resulting from the volume changes of the cathode active materials led to degradation mechanisms, such as fracture and interfacial delamination. Active material fracture and delamination led to underutilization of active material and significant capacity decay during cycling. Coatings that suppress active material-active material interactions during cycling may aid in suppressing the generation of local stress hotspots.

36 MATERIALS SCIENCE↗

Nanoscopic Plugs Block Hydrogen Crossover in Submicron Thick Proton-Conducting SiO 2 Membranes for Water Electrolysis

Zero-gap electrolyzers based on submicron thick proton-conducting oxide membranes (POMs) represent a promising approach to increasing the efficiency of H 2 production from water electrolysis while moving away from conventional perfluorosulfonic acid (PFSA) membranes. A critical barrier to the commercialization of such electrolyzers is that the ultrathin nature of POMs, which is necessary to achieve low cell resistance, makes them more susceptible to defects that can lead to unacceptably high rates of H 2 crossover. Herein, we demonstrate an approach to mitigate this problem through selective deposition of carbon-containing silicon oxide (SiO x C y ) “nanoplugs” into the defects of submicron thick SiO 2 membranes using a facile electrochemically mediated deposition process. Selective deposition of nanoplugs within the defects was verified by multiple characterization techniques, while scanning electrochemical microscopy (SECM) was used to confirm selective plugging of H 2 -crossover hotspots associated with defects at identical locations. Thanks to the use of nanoplugs, the H 2 permeance of 250 nm thick SiO 2 membranes was reduced by 5 to 6 orders of magnitude compared to the unmodified atomic layer deposition (ALD) SiO 2 membranes while having negligible impact on the ionic resistance of the membrane. These plug-modified membranes also enabled safe and stable operation of a zero-gap full cell electrolysis cell, in contrast to cells lacking nanoplugs that produced anode effluent streams having H 2 concentrations near or exceeding the lower flammability limit (LFL) of H 2 . Furthermore, beyond water electrolysis, this defect-sealing strategy has the potential to be broadly implemented in other applications, such as fuel cells and flow batteries, offering a versatile solution to mitigate crossover-related performance losses.

ALD SiO2↗

Techno-Economic Analysis of Recycled Ionic Liquid Solvent Used in a Model Colloidal Platinum Nanoparticle Synthesis

Ionic liquids have garnered significant attention over the past 20 years as alternatives to conventional volatile organic solvents because they are non-flammable, have negligible vapor pressures, possess high thermal and chemical stabilities, and can potentially be recycled. A more recent use of ionic liquids is their application as a solvent in the synthesis of colloidal inorganic nanoparticles; however, a major challenge in the adoption of ionic liquids is that they are generally more expensive than their traditional organic solvent counterparts. Herein, we provide insight into how recycling an ionic liquid solvent affects the product characteristics in a model colloidal platinum nanoparticle synthesis, the structure of the ionic liquid through each recycle, and the overall cost of nanoparticle fabrication using a techno-economic analysis. Using a standard ionic liquid, 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide (BMIM-NTf2), as the solvent for a Pt nanoparticle synthesis, we demonstrate that the ionic liquid can be recovered and reused through multiple successive reactions following the initial reaction with virgin, or as-purchased, ionic liquid. The use of recycled ionic liquid does not cause any degradation in the product quality or change in nanoparticle morphology. Techno-economic analysis of this synthesis method revealed that, through ionic liquid recycling, nanoparticle preparation using BMIM-NTf2 can achieve a cost that is not only competitive but also potentially lower than that of the conventional organic solvent, 1-octadecene.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Projecting Large Fires in the Western US With an Interpretable and Accurate Hybrid Machine Learning Method

More frequent and widespread large fires are occurring in the western United States (US), yet reliable methods for predicting these fires, particularly with extended lead times and a high spatial resolution, remain challenging. In this study, we proposed an interpretable and accurate hybrid machine learning (ML) model, that explicitly represented the controls of fuel flammability, fuel availability, and human suppression effects on fires. The model demonstrated notable accuracy with a F 1 -score of 0.846 ± 0.012, surpassing process-driven fire danger indices and four commonly used ML models by up to 40% and 9%, respectively. More importantly, the ML model showed remarkably higher interpretability relative to other ML models. Specifically, by demystifying the “black box” of each ML model using the explainable AI techniques, we identified substantial structural differences across ML fire models, even among those with similar accuracy. The relationships between fires and their drivers, identified by our model, were aligned closer with established fire physical principles. The ML structural discrepancy led to diverse fire predictions and our model predictions exhibited greater consistency with actual fire occurrence. With the highly interpretable and accurate model, we revealed the strong compound effects from multiple climate variables related to evaporative demand, energy release component, temperature, and wind speed, on the dynamics of large fires and megafires in the western US. Our findings highlight the importance of assessing the structural integrity of models in addition to their accuracy. They also underscore the critical need to address the rise in compound climate extremes linked to large wildfires.

54 ENVIRONMENTAL SCIENCES↗

Enabling safe aqueous lithium ion open batteries by suppressing oxygen reduction reaction

Abstract Due to the non-flammable nature of water-based electrolytes, aqueous lithium-ion batteries are resistant to catching fire. However, they are not immune to the risk of explosion, since the sealing structure adopted by current batteries limits the dissipation of heat and pressure within the cells. Here, we report a safe aqueous lithium-ion battery with an open configuration using water-in-salt electrolytes and aluminum oxide coated anodes. The design can inhibit the self-discharge by substantially suppressing the oxygen reduction reaction on lithiated anodes and enable good cycle performance over 1000 times. Our study may open a pathway towards safer lithium-ion battery designs.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Sub-second and ppm-level optical sensing of hydrogen using templated control of nano-hydride geometry and composition

Abstract The use of hydrogen as a clean and renewable alternative to fossil fuels requires a suite of flammability mitigating technologies, particularly robust sensors for hydrogen leak detection and concentration monitoring. To this end, we have developed a class of lightweight optical hydrogen sensors based on a metasurface of Pd nano-patchy particle arrays, which fulfills the increasing requirements of a safe hydrogen fuel sensing system with no risk of sparking. The structure of the optical sensor is readily nano-engineered to yield extraordinarily rapid response to hydrogen gas (<3 s at 1 mbar H 2 ) with a high degree of accuracy (<5%). By incorporating 20% Ag, Au or Co, the sensing performances of the Pd-alloy sensor are significantly enhanced, especially for the Pd 80 Co 20 sensor whose optical response time at 1 mbar of H 2 is just ~0.85 s, while preserving the excellent accuracy (<2.5%), limit of detection (2.5 ppm), and robustness against aging, temperature, and interfering gases. The superior performance of our sensor places it among the fastest and most sensitive optical hydrogen sensors.

36 MATERIALS SCIENCE↗

Enabling selective zinc-ion intercalation by a eutectic electrolyte for practical anodeless zinc batteries

Abstract Two major challenges hinder the advance of aqueous zinc metal batteries for sustainable stationary storage: (1) achieving predominant Zn-ion (de)intercalation at the oxide cathode by suppressing adventitious proton co-intercalation and dissolution, and (2) simultaneously overcoming Zn dendrite growth at the anode that triggers parasitic electrolyte reactions. Here, we reveal the competition between Zn 2+ vs proton intercalation chemistry of a typical oxide cathode using ex-situ/ operando techniques, and alleviate side reactions by developing a cost-effective and non-flammable hybrid eutectic electrolyte. A fully hydrated Zn 2+ solvation structure facilitates fast charge transfer at the solid/electrolyte interface, enabling dendrite-free Zn plating/stripping with a remarkably high average coulombic efficiency of 99.8% at commercially relevant areal capacities of 4 mAh cm −2 and function up to 1600 h at 8 mAh cm −2 . By concurrently stabilizing Zn redox at both electrodes, we achieve a new benchmark in Zn-ion battery performance of 4 mAh cm −2 anode-free cells that retain 85% capacity over 100 cycles at 25 °C. Using this eutectic-design electrolyte, Zn | |Iodine full cells are further realized with 86% capacity retention over 2500 cycles. The approach represents a new avenue for long-duration energy storage.

25 ENERGY STORAGE↗