Results for “Solid additives” — Page 9

DOE OSTI2025

Investigation of MgO additives on microstructure and properties of thin LLZO electrolytes for all-solid-state batteries

To realize high-energy density lithium lanthanum zirconate (LLZO)-based solid-state batteries (SSB), LLZO electrolytes should be fabricated with low thickness and high mechanical strength. An effective strategy for strengthening ceramic materials is to use additives. Here, we employed MgO nanopowders and fibers as additives for the thin LLZO electrolyte in order to improve the mechanical strength. The microstructure, mechanical properties, and electrochemical properties are characterized to investigate the effects of adding MgO and sintering time. The MgO remains at grain boundaries after sintering, making the microstructure of LLZO fine and uniform. The mechanical strength of the MgO-added LLZO was enhanced by more than 60% while maintaining high ionic conductivity (1 × 10 -4 S cm -1 ) at room temperature. Li symmetric cells using the MgO fiber–LLZO and MgO powder–LLZO exhibit 2 and 3 times higher critical current density (CCD) than those of pure LLZO, and a solid-state full cell exhibits stable cycling performance. Further, these results demonstrate that the use of MgO nanopowder or fiber as an additive for thin LLZO is beneficial for high-current density cycling, by improving mechanical properties and microstructure.

25 ENERGY STORAGE↗

DOE OSTI2024

Cellulose Nanofibers as Rheological Modifiers to Improve Biomass Slurry Processing and Fermentation

This study investigates the enhancement of biomass slurry processability through the addition of rheological modifiers, focusing on carboxymethyl cellulose (CMC) and TEMPO-mediated oxidized cellulose nanofibrils (TCNF). Three sets of experiments were conducted to assess the effects of these additives on slurry processing and fermentation. Initial experiments evaluated the slurry extrudability, concluding that TCNF aids extrusion similarly to CMC. Subsequent experiments explored slurry viscosity reduction mechanisms, revealing that while CMC significantly reduced the viscosity, TCNF’s impact is negligible. Additionally, TCNF performed comparably to CMC in water retention tests across different conditions, which suggests that TCNF have potential as an effective additive for maintaining slurry fluidity at high solid concentrations through enhanced water retention. Lastly, both additives were investigated to ensure that they did not impact hydrolyzed biomass fermentation. The findings suggest that TCNF’s mechanisms differ from those of traditional water-soluble polymers like CMC, offering insights into novel approaches to improve the biomass processing efficiency and subsequent fermentation.

Jamieson, Zachary↗

NASA NTRS1972

Normal freezing of ideal ternary systems of the pseudobinary type

Perfect liquid mixing but no solid diffusion is assumed in normal freezing. In addition, the molar compositions of the freezing solid and remaining liquid, respectively, follow the solidus and liquidus curves of the constitutional diagram. For the linear case, in which both the liquidus and solidus are perfectly straight lines, the normal freezing equation giving the fraction solidified at each melt temperature and the solute concentration profile in the frozen solid was determined as early as 1902, and has since been repeatedly published. Corresponding equations for quadratic, cubic or higher-degree liquidus and solidus lines have also been obtained. The equation of normal freezing for ideal ternary liquid solutions solidified into ideal solid solutions of the pseudobinary type is given. Sample computations with the use of this new equation were made and are given for the Ga-Al-As system.

Li, C. H.↗

NASA NTRSDate not supplied

Recommendations For Developing Space Suit Integrated Food Systems and Delivering Nutrition Before, During, and After Lunar Eva

INTRODUCTION Artemis missions will include a higher tempo and frequency of extravehicular activities (EVAs) than any previous space program. Because of the physical demands expected from the crew, future space suit designs are required to incorporate nutritional support to the astronauts during lunar surface EVAs lasting longer than 4 hours. The purpose of this project was to provide recommendations to aid the development of an in-suit system that can adequately, safely, and acceptably deliver nutrition to a crewmember while confined to a space suit during EVA. METHODS Physiological, logistical, and engineering aspects of potential in-suit nutrition approaches were assessed through literature reviews, assessments of commercial off the shelf (COTS) foods, suit volumetric modeling, and feedback from subject matter experts and crewmembers. Key driving factors in the development of in-suit nutrition requirements included how much and what type of nutrition should be included, what food formulations are appropriate and safe, what are inherent limitations of space suits, what are the potential risks to the crewmember in the suit, and what practices and preferences from astronauts should be considered. Design references were conceptualized and assessed for strengths and limitations as potential in-suit nutrition systems for surface EVA. RESULTS Acute exogenous energy demands vary greatly depending on activity intensity and duration, and partial energy replenishment (i.e., 60–80 kcal∙hr-1 of EVA, or 460–680 kcal for EVAs lasting up to 8 hours) during activities could improve performance, safety, and recovery. COTS foods capable of providing these energy requirements exist; however, no COTS foods have been identified that pass NASA flight standards for microbiological safety and stability. In-suit nutrition delivery design references that were considered included in-suit concepts for a prefilled drink bag, a hydratable drink bag, and a solid food stick. In addition, a helmet feed port concept was considered for use with drink bags external to the suit. Volumetric models of the in-suit drink bag concepts, based on xEMU dimensions, indicate challenges of fitting formulations > 200 ml (equating to approximately 200 kcal). Astronaut feedback on the four concepts indicated that despite some individual preferences for inclusion of solid foods and helmet port designs, the prefilled drink bag concept was the most preferred. A prefilled drink bag can only be used if food safety and stability can be ensured, possibly requiring advancements in food delivery hardware. CONCLUSION The ability to meet the increased need for nutrition during surface EVAs through provision of nutrients in the suited configuration would benefit overall crew health, performance, and morale, and thus increase the likelihood of mission success. It is recommended that in-suit nutrition capabilities provide at least 400–600 kcal within the suit during EVAs lasting > 4 hours and that suit designs include a dedicated volume for food grade nutrition systems. The developed food system should either allow for 1) installation of prefilled (sealed sterile) liquid nutrition in the suit and provide a mechanism to break the seal at the time that consumption is desired or 2) demonstrate that the unsealed food product shelf life allows for safe consumption after at least 12 hours of EVA.

E L Dillon↗

NASA NTRSDate not supplied

Recommendations for Developing Space Suit Integrated Food Systems and Delivering Nutrition Before, During, and After Lunar EVA

INTRODUCTION Artemis missions will include a higher tempo and frequency of extravehicular activities (EVAs) than any previous space program. Because of the physical demands expected from the crew, future space suit designs are required to incorporate nutritional support to the astronauts during lunar surface EVAs lasting longer than 4 hours. The purpose of this project was to provide recommendations to aid the development of an in-suit system that can adequately, safely, and acceptably deliver nutrition to a crewmember while confined to a space suit during EVA. METHODS Physiological, logistical, and engineering aspects of potential in-suit nutrition approaches were assessed through literature reviews, assessments of commercial off the shelf (COTS) foods, suit volumetric modeling, and feedback from subject matter experts and crewmembers. Key driving factors in the development of in-suit nutrition requirements included how much and what type of nutrition should be included, what food formulations are appropriate and safe, what are inherent limitations of space suits, what are the potential risks to the crewmember in the suit, and what practices and preferences from astronauts should be considered. Design references were conceptualized and assessed for strengths and limitations as potential in-suit nutrition systems for surface EVA. RESULTS Acute exogenous energy demands vary greatly depending on activity intensity and duration, and partial energy replenishment (i.e., 60–80 kcal∙hr-1 of EVA, or 460–680 kcal for EVAs lasting up to 8 hours) during activities could improve performance, safety, and recovery. COTS foods capable of providing these energy requirements exist; however, no COTS foods have been identified that pass NASA flight standards for microbiological safety and stability. In-suit nutrition delivery design references that were considered included in-suit concepts for a prefilled drink bag, a hydratable drink bag, and a solid food stick. In addition, a helmet feed port concept was considered for use with drink bags external to the suit. Volumetric models of the in-suit drink bag concepts, based on xEMU dimensions, indicate challenges of fitting formulations > 200 ml (equating to approximately 200 kcal). Astronaut feedback on the four concepts indicated that despite some individual preferences for inclusion of solid foods and helmet port designs, the prefilled drink bag concept was the most preferred. A prefilled drink bag can only be used if food safety and stability can be ensured, possibly requiring advancements in food delivery hardware. CONCLUSION The ability to meet the increased need for nutrition during surface EVAs through provision of nutrients in the suited configuration would benefit overall crew health, performance, and morale, and thus increase the likelihood of mission success. It is recommended that in-suit nutrition capabilities provide at least 400–600 kcal within the suit during EVAs lasting > 4 hours and that suit designs include a dedicated volume for food grade nutrition systems. The developed food system should either allow for 1) installation of prefilled (sealed sterile) liquid nutrition in the suit and provide a mechanism to break the seal at the time that consumption is desired or 2) demonstrate that the unsealed food product shelf life allows for safe consumption after at least 12 hours of EVA.

space suit↗

DOE OSTI2025

Volumetric Additive Manufacturing of Dormant Catalytic Chemistries to Generate Silicone Micro‐ and Millifluidic Devices and Instant Molds

Tomographic volumetric additive manufacturing (T‐VAM) rapidly prints solid objects within minutes, accessing photochemistries that are traditionally challenging for layer‐based additive manufacturing methods. This includes high‐viscosity materials, air‐free chemistries, and solid‐state systems. Catalytic chemistries are appealing as a pathway to engineering advanced materials, including tough thermosets, silicone elastomers, and complex block copolymers. However, photoactivated dormant catalytic chemistries, where the catalyst irreversibly activates upon exposure to light, are incompatible with typical tomographic VAM approaches. To address this limitation, a zero‐dose optimization strategy is devised to preserve dormant catalysts in desired regions by keeping them unexposed to light. VAM printed micro‐ and millifluidic devices and instant molds are successfully produced within minutes in silicones polymerized using photoactivated dormant platinum photohydrosilylation catalysts. The printed channels are programmed to be 500 and 2500 µm for the micro‐ and millifluidic devices, and print fidelity is assessed by X‐ray computed tomography. This work demonstrates the potential of zero‐dose optimization to expand the range of chemistries accessible for VAM, enabling the rapid fabrication of complex devices.

Additive Manufacturing↗

NASA NTRS2008

C3 Performance of the Ares-I Launch Vehicle and its Capabilities for Lunar and Interplanetary Science Missions

NASA s Ares-I launch vehicle will be built to deliver the Orion spacecraft to Low-Earth orbit, servicing the International Space Station with crew-transfer and helping humans begin longer voyages in conjunction with the larger Ares-V. While there are no planned missions for Ares-I beyond these, the vehicle itself offers an additional capability for robotic exploration. Here we present an analysis of the capability of the Ares-I rocket for robotic missions to a variety of destinations, including lunar and planetary exploration, should such missions become viable in the future. Preliminary payload capabilities using both single and dual launch architectures are presented. Masses delivered to the lunar surface are computed along with throw capabilities to various Earth departure energies (i.e. C3s). The use of commercially available solid rocket motors as additional payload stages were analyzed and will also be discussed.

Thomas, H. Dan↗

NASA NTRSDate not supplied

Overview of the High Reynolds Number Ascent Wind Tunnel Test of the Space Launch System at the National Transonic Facility

Transonic, high Reynolds number wind tunnel testing for the Space Launch System (SLS) ascent flight environment was conducted in the National Transonic Facility (NTF) at the NASA Langley Research Center from December 2019 to April 2021. The test was sponsored by the SLS Program and the NASA Engineering & Safety Center with the ob- jective of assessing and characterizing Reynolds number effects on the ascent aerodynamics of the SLS launch vehicle. The cryogenic test article was a 1.75%-scale representation of the SLS Block 1 Cargo configuration that was fabricated mostly out of stainless steel, but with several additive-manufactured components including the Solid Rocket Booster (SRB) attach brackets and the SRB nozzles. This was the first use of additive manufacturing on structural components of a cryogenic model in the NTF, therefore post-fabrication material testing and inspections were performed to satisfy safety requirements. Force & moment and surface pressure data were acquired for Mach numbers between 0.50 and 0.95 over a range of Reynolds numbers based on core stage diameter between 2x10^6 and a maximum of 40x10^6 corresponding to 45% of flight Reynolds number. Additionally, flow visualization data using Pressure Sensitive Paint were acquired with a focus on the SRB forward attach area, which is susceptible to Reynolds number sensitivity at transonic speeds. This pa- per provides an overview of the test campaign including details on the unique test article and the experimental setup and test execution. General test findings and observations are also presented, but the majority of the test results and data analyses are provided in a companion paper.

Space Launch System↗

NASA NTRSDate not supplied

Overview of the High Reynolds Number Ascent Wind Tunnel Test of the Space Launch System at the National Transonic Facility

Transonic, high Reynolds number wind tunnel testing for the Space Launch System (SLS) ascent flight environment was conducted in the National Transonic Facility (NTF) at the NASA Langley Research Center from December 2019 to April 2021. The test was sponsored by the SLS Program and the NASA Engineering & Safety Center with the ob- jective of assessing and characterizing Reynolds number effects on the ascent aerodynamics of the SLS launch vehicle. The cryogenic test article was a 1.75%-scale representation of the SLS Block 1 Cargo configuration that was fabricated mostly out of stainless steel, but with several additive-manufactured components including the Solid Rocket Booster (SRB) attach brackets and the SRB nozzles. This was the first use of additive manufacturing on structural components of a cryogenic model in the NTF, therefore post-fabrication material testing and inspections were performed to satisfy safety requirements. Force & moment and surface pressure data were acquired for Mach numbers between 0.50 and 0.95 over a range of Reynolds numbers based on core stage diameter between 2x10^6 and a maximum of 40x10^6 corresponding to 45% of flight Reynolds number. Additionally, flow visualization data using Pressure Sensitive Paint were acquired with a focus on the SRB forward attach area, which is susceptible to Reynolds number sensitivity at transonic speeds. This paper provides an overview of the test campaign including details on the unique test article and the experimental setup and test execution. General test findings and observations are also presented, but the majority of the test results and data analyses are provided in a companion paper.

Space Launch System↗

DOE OSTI2024

A non-melting additive approach to structural repair of aluminum aircraft fastener holes

The damage to fastener holes in aerospace aluminum structures presents significant challenges for aircraft durability, and conventional bushing methods for repairing oversized holes often fall short due to the lack of metallurgical bonding and limited edge distance availability. This study investigates additive friction stir deposition, a non-melting additive process, as a viable alternative for the structural repair of aerospace fastener holes. The repair process, demonstrated on AA7050 (Al-Zn-Mg-Cu-Zr) hole structures, involves filling oversized holes with new material and machining to restore the original hole size. The repaired hole coupons are defect-free and exhibit good fatigue performance under fully reversed tension-compression loading (R = -1). At a nominal stress amplitude of 123.5 MPa, the average number of cycles to failure is 12,666 for unrepaired baseline coupons and 17,372 for effectively repaired coupons. Restoring complex geometries without compromising fatigue performance has been difficult in aerospace applications; this study marks the first demonstration of additive repair that consistently outperforms the unrepaired baseline coupons. Notably, the result is achieved through a low-energy, cost-effective solution without the need for post-repair heat treatment. Except for a few outliers, the post-repair fatigue performance generally remains inferior to that of undamaged, pristine coupons, likely due to precipitate evolution in AA7050 caused by the thermomechanical processing nature of additive friction stir deposition. This evolution weakens the repair region and the adjacent base material, leading to faster crack initiation and growth compared to the properly aged base material, AA7050-T7451.

36 MATERIALS SCIENCE↗

DOE OSTI2025

Plasmon-enhanced ultralow-threshold solid-state triplet fusion upconversion

Triplet fusion upconversion has potential applications in solar cells, photoredox catalysis, additive manufacturing and bioimaging. However, solid-state upconversion systems have struggled to measure up to their solution-phase counterparts, often requiring enormous optical power densities to operate at the maximum efficiency. Here we substantially improve the performance of upconversion films through excitation with surface plasmons that propagate along a planar silver-film interface, leading to an absorption enhancement that reduces the intensity threshold I th by a factor of 19 and enhances the external quantum efficiency by a factor of 17. From this, we achieve I th values as low as 3.4 mW cm −2 and an external quantum efficiency up to 0.094%. To demonstrate real-world viability, we couple the upconversion film to plasmons generated by the near-field of excitons in an organic light-emitting diode. As a result, this scheme is then used to fabricate a white-emitting organic light-emitting diode where blue emission sources from plasmon-excited upconversion, achieving a high colour rendering index of 86.2 and setting precedent for blue emission in the absence of high-energy polarons or triplets.

36 MATERIALS SCIENCE↗

DOE OSTI2025

Mechanochemical Solid Form Screening of Zeolitic Imidazolate Frameworks Using Structure-Directing Liquid Additives

We demonstrate a systematic application of the mechanochemical liquid-assisted grinding (LAG) methodology to screen for forms of zinc imidazolate (ZnIm 2 ), of fundamental importance as the simplest member of the zeolitic imidazolate framework materials family. The exploration of 45 different liquid additives, selected based on their molecular structure and physicochemical properties has resulted in eight different ZnIm 2 topological forms, appearing in 13 crystallographically distinct solid forms (including two previously unknown forms of the crb (BCT) topology), amorphous phases, and the interrupted moc-Zn 4 Im 8 HIm. All prepared topological forms were also explored computationally, using dispersion-corrected periodic density functional theory (DFT) calculations, enabling the rationalization of screening outcomes, and setting the stage for future prediction of additive-directed metal–organic framework (MOF) synthesis. This first systematic exploration of LAG in screening for three-dimensional MOFs demonstrates the potential of the liquid additive to not only accelerate materials synthesis, but also to direct it toward topologically different MOFs. The discovery of novel forms of a material that already exhibits at least 21 crystallographically and functionally different forms provides a strong testimony on the power of mechanochemistry in metal–organic materials discovery.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2024

Theoretical design and performance of three-dimensional, pillared FeS 2 cathodes

Three-dimensional (3D) electrode design can provide improved capacities and rate capabilities over conventional two-dimensional electrodes by enhancing electrical and ionic transport. Here, expanding upon our previous modeling efforts for conversion chemistry lithium-ion batteries, we develop a pseudo-four-dimensional (P4D) approach that is subsequently used to investigate the design of a pillared FeS 2 electrode. The model considers transport in three dimensions with an additional “fourth” dimension corresponding to the solid-state lithium transport within the active material particles. Additionally, we allow for expansion of the active material during the conversion reaction to understand how internal stresses impact the electrochemical performance of the cell. By optimizing the model with respect to areal capacity, we are able to predict areal capacities up to 16.8 mAh/cm 2 for an areal current density of 1.78 mA/cm 2 and a 103% improvement for the three-dimensional electrodes over planar electrodes of equal volume. Despite the promising results, our simulations suggest that 3D design may be difficult for conversion cathode materials due to the large internal stresses that arise during conversion. Nevertheless, the model is robust and adaptable to other materials that may be more suitable for 3D electrodes due to a lesser change in volume during discharge.

Conversion cathode materials↗

DOE OSTI2026

Uncovering hidden bias in neutron diffraction residual strain measurements

When calculating residual strain via neutron or X-ray diffraction, uncertainties propagated from the peak fit are often inadequate to describe the true scatter of measurements about a singular strain state, such as one that should describe a macroscopic continuum. Because diffraction is inherently a selective process, orientation-dependent scatter arises from the sub-sampling of strong microstructure and strain gradients. This paper investigates the appropriateness of propagated uncertainties with reference to their original intention, i.e. noise about a mean value. Thirty-six unique orientations of strain measurements are taken at multiple locations within an additive friction-stir deposition component with fine-scale gradients (∼200 µm) of plastic strain, texture and residual elastic strain. Multiple strain and stress calculation pathways are compared: direct substitution of three measurements into Hooke's law, direct inversion of any six unique orientations into the strain state tensor and thirty-six measurement least-squares estimation. For the last two cases, the appropriateness of the uncertainty interval is statistically evaluated on the basis of a physical constraint: common agreement under the strain transformation law. For this sample, the direct inversion of six measurements retains a conservative estimate of the uncertainty. However, propagated uncertainties in the least-squares solution greatly underestimate the true experimental scatter. A simple pathway to estimate appropriate uncertainty intervals is suggested. These results demonstrate that the interpretation of uncertainty in residual strain is strongly dependent on intrinsic sample-dependent effects, and that oversampling orientations and statistical analysis can give more accurate results with realistic uncertainties.

36 MATERIALS SCIENCE↗

DOE OSTI2025

Evaluating Autoxidation Radical Scavengers and Additives to Enhance Aminopolymer Sorbent Stability

Solid amine sorbents have shown promise in the removal of ultradilute CO 2 from the atmosphere. Despite being a promising candidate material type for this application, these sorbents are prone to degradation during long-term exposure to environmental components such as CO 2 , O 2 , and H 2 O, with amine oxidation being a particularly challenging problem. In this study, we investigate the potency of different radical scavengers and additives in mitigating the degradation of a model poly- (ethylenimine) (PEI)/Al 2 O 3 sorbent under direct air capture (DAC)-relevant conditions. The results reveal that a 4,4′-bis(α,α- dimethylbenzyl)diphenylamine (BDDPA)-incorporated PEI/Al 2 O 3 sorbent showed the most resistance toward oxidative degradation at varying exposure times and BDDPA loadings under CO 2 -free air (21% O 2 /balance N 2 ) at 120 °C. Interestingly, under humid (∼43% relative humidity (RH) at 26 °C) and dry 0.04% CO 2 -air, the BDDPA/PEI/Al 2 O 3 sorbent showed enhanced sorbent stability both at 70 and 120 °C after 4.5 h of exposure. Under humid CO 2 -free air, at 120 °C, the antioxidant performance slightly declined (in comparison to the dry CO 2 -free air condition) but displayed a much higher stability than the pristine sorbent. Overall, the ability of BDDPA to inhibit sorbent degradation under dry and humid, CO 2 -free and CO 2 -containing (0.04%) air at intermediate (70 °C) and elevated (120 °C) temperatures is promising in prolonging sorbent stability and underscores the importance of performing accelerated oxidation studies in the presence of all species that are expected to be present in DAC processes to identify suitable stabilization treatments for sorbent materials.

36 MATERIALS SCIENCE↗

NASA NTRS2019

Evaluation Studies of Solid Oxide-Based Fuel Cells for Light-Weight Electrical Power in Aviation: Concepts and Opportunities for the Application of Additive Manufacturing

Currently NASA is investigating the feasibility of hybrid-electric, solid oxide fuel cell power (SOFC) systems for generating electrical power for airborne propulsion and secondary/auxiliary power. As part of this project, researchers are investigating the performance of SOFC hardware in aviation-like environments, to establish the barriers, and potential suitability, of this technology. Immediate findings indicate the unsuitability of current SOFC stack architectures with regards to ease of manufacture, specific energy, as well as environmental and mechanical durability. One possible solution is to create light-weight high specific energy density solid oxide fuel cells. The possibility may be achievable by the use of modern processing techniques such as additive manufacturing. Here I discuss the use additive manufacturing to fabricate ceramic anode, electrolytes, and cathode cells supported on various metal foams with predicted performance based upon variable porosities

Goldsby, Jon C.↗

DOE OSTI2026

Anion-dependent phase behavior of methylimidazolium-based ionic liquids mixed with water: Correlation between local molecular structure and mesoscale behaviors

The mesoscopic phase behavior of decylmethylimidazolium (C 10 mim) ionic liquids (ILs) bearing three monovalent anions—thiocyanate (SCN − ), nitrate (NO 3 − ), and chloride (Cl − )—mixed with water at relatively high IL contents (50–95 wt%) was investigated. Small-angle and wide-angle X-ray scattering (SAXS/WAXS) were employed to follow the evolution of both local and mesoscale structures across this composition range. In the absence of water, C 10 mimSCN and C 10 mimCl behaved as disordered liquids, whereas C 10 mimNO 3 spontaneously formed a hexagonally ordered cylindrical mesophase and displayed a sticky-solid macroscopic appearance. Upon addition of water, C 10 mimSCN remained a viscous liquid and only weakly ordered lamellar domains were observed. This limited ordering is attributed to the lack of hydrogen bonding and weak interaction energy between SCN − anions and C 10 mim + cations. In contrast, the trigonal-planar NO 3 − and point-like Cl − anions promoted the formation of well-defined hexagonal mesophases up to 35–45 wt% water. The formation of hydrogen bonding of the two anions with imidazolium ring protons likely enabled the creation of compact ion clusters that effectively exclude water molecules from the immediate vicinity of the IL aggregates. These findings demonstrate that the interaction energy between ion pairs dictate IL-water interactions and therefore control the transition from disordered liquids to ordered mesophases in IL/water mixtures with high IL contents. In conclusion, the combined SAXS/WAXS analysis reveals a correlation between local intermolecular structure and the emergence of mesoscopic order, providing a systematic framework for tailoring mesoscale structures in alkylimidazolium-based IL/water systems.

36 MATERIALS SCIENCE↗

DOE OSTI2024

Chemically Driven Multistep Crystallization in the Synthesis of Sodium Yttrium Fluoride Via a Porous, Electrochemically Active Intermediate

Two-step crystallization mechanisms based on liquid–liquid phase separations followed by crystallization are commonly observed both in the laboratory and in nature. While this pathway quite often occurs as a result of a chemical reaction, the subsequent nucleation and growth are often considered as separate, discrete events from the reaction itself. We show this mechanism in the aqueous synthesis sodium yttrium fluoride, but by using a combination of experimental techniques and computational modeling, we show an additional step of solid-state chemical diffusion that is essential to the nucleation mechanism. In this system, we observe at least four distinct steps in the crystallization process, including (1) the segregation of aqueous ions into a dense liquid phase, (2) the formation of a metastable amorphous aggregate, (3) the continuous, gradual solid-state diffusion of sodium and fluoride ions into the amorphous aggregate toward a NaYF4 stoichiometry, and (4) the crystallization of a stable cubic sodium yttrium fluoride phase. Unlike previous descriptions of nucleation and growth, we find that the stoichiometry of the final solid phase evolves throughout the crystallization process rather than being determined at the time of the initial separation from solution. Further, this emphasizes that the chemical reaction cannot be assumed to be a separate event from the phase separation and growth, especially in compounds with variable stoichiometry. We also find that the amorphous aggregate that forms prior to the ion incorporation step adopts a porous, gel-like structure, which we isolated and showed to be electrochemically active, allowing for its potential use as a battery anode in lithium and sodium ion batteries, among other potential applications.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗