Search NASA⌕ Search

SEARCH · Search NASA

Results for “EUTECTICS”

Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.

At least 667 records · Page 37
All sourcesNASA NTRSDOE OSTI
DOE OSTI2026

Green pretreatment strategies for enhanced microbial lipid fermentation and synergistic high-quality lignin recovery for next-generation integrated biorefineries

Miscanthus × giganteus (Mxg) is a warm-season perennial grass being commercialized as a biomass feedstock for temperate farms. Three process strategies were compared for converting Mxg into single-cell oil and extracted lignin intermediates, as hydrothermal (HT) processing and two natural deep eutectic solvents (NADES), ChCl:LA (choline chloride:lactic acid) and ChCl:Gly (choline chloride:glycerol). Pretreatments were performed at 10% and 50% solids loading at 140 °C, 2 h; HT: 190 °C, 10 min. Enzymatic hydrolysates, generated at 10% solids using washed and unwashed biomass, were evaluated for microbial lipid production. Maximum glucose conversions from washed biomass reached 83.5% (ChCl:LA), 52.7% (ChCl:Gly), and 74.0% (HT). Remarkably, NADES-derived hydrolysates effectively replaced refined sugars for the cultivation of the oleaginous yeast Rhodotorula toruloides, achieving ∼51% higher biomass (OD 90.7) and lipid titers of 19.36 g/L within 45 h using a two-stage fermentation strategy. Lipid contents ranged from 34.5–44.5% dry weight, demonstrating reduced reliance on purified sugars. Beyond carbohydrate valorization, ChCl:LA pretreatment enabled high-purity lignin recovery (>89%) in a lignin-first strategy. Structural analyses (2D-HSQC and ³¹P NMR) showed syringyl (78.15%), guaiacyl (15.15%), and p-hydroxyphenyl (6.41%) units, with higher phenolic hydroxyl content (0.91 mmol/g) and a lower S/G ratio (0.19) than HT lignin (0.87 mmol/g, S/G 0.22). These attributes favor downstream lignin depolymerization into low-molecular-weight aromatics. Overall, NADES pretreatment simultaneously enhances microbial lipid yields and recovers high-quality lignin, advancing the economic feasibility of renewable diesel and sustainable aviation fuel (SAF) production from bioenergy crops within an integrated biorefinery framework.

2D HSQC↗
DOE OSTI2024

Physics-informed machine learning to predict solvatochromic parameters of designer solvents with case studies in CO 2 and lignin dissolution

The polarity of solvents plays a critical role in various research applications, particularly in their solubilities. Polarity is conveniently characterized by the Kamlet-Taft parameters that is, the hydrogen bonding acidity (α), the basicity (β), and the polarizability (π*). Obtaining Kamlet-Taft parameters is very important for designer solvents, namely ionic liquids (ILs) and deep eutectic solvents (DESs). However, given the unlimited theoretical number of combinations of ionic pairs in ILs and hydrogen-bond donor/acceptor pairs in DESs, experimental determination of their Kamlet-Taft parameters is impractical. To address this, the present study developed two different machine learning (ML) algorithms to predict Kamlet-Taft parameters for designer solvents using quantum chemically derived input features. The ML models developed in the present study showed accurate predictions with high R 2 and low RMSE values. Further, in the context of present interest in the circular bioeconomy, the relationship between the basicities and acidities of designer solvents and their ability to dissolve lignin and carbon dioxide (CO 2 ) is discussed. Our method thus guides the design of effective solvents with optimal Kamlet-Taft parameter values dissolving and converting biomass and CO 2 into valuable chemicals.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2019

Binder jet printed WC infiltrated with pre-made melt of WC and Co

WC-Co was made via binder jet additive manufacturing of tungsten carbide followed by melt infiltration with a Co-WC infiltrant. The goal of the study was to achieve fully densified parts in near-net shape with minimal shrinkage while keeping the Co content low. The exact amount of infiltrant was determined in order to fully densify with minimum shrinkage based on the actual volume taken up by WC powder in the preform based on theoretical density, the bounding volume of prints after shrinkage, and the volume from the infiltrant. The eutectic nature of the infiltrant enabled melting at much lower temperature compared to the melting temperature of pure Co. The density, microstructure, grain size, hardness, and fracture toughness were characterized. The shrinkage and net shaping were assessed with light scans. A detailed look at the fracture mechanics was assessed. Here, this approach achieved highly dense WC-Co parts in net-shape with Co vol% of near 29 (Co wt% ~19), density of 96.2% theoretical, hardness of 8.34 GPa, grain size of 7.7 μm, magnetic saturation of 0.5 T, room temperature thermal conductivity of 125 W/mK, and fracture toughness of 24.7 = MPa·m 1/2 .

36 MATERIALS SCIENCE↗
DOE OSTI2023

One-pot generation of lignin microspheres and digestible substrate with a polyol-DES pretreatment in high solid loading

Previous lignin microspheres (LMS) preparation needs multiple steps with very low yield and high cost. Herein, we developed a high-solid deep eutectic solvent (DES) pretreatment for an effective lignin fractionation and enzymatic saccharification of moso bamboo under mild temperature (110 °C) with high-solid loading. Lignin was significantly removed from the plant cell wall, and cellulose properties (e.g., crystallinity and degree of polymerization) were also altered during the pretreatment. As a result, the enzymatic digestibility of the pretreated bamboo was dramatically increased. Uniform micro-spherical lignin was directly produced from the pretreatment system, and its particle size could be regulated by controlling the solid loadings and pretreatment temperatures. The lignin microspheres formation mechanism was investigated by analyzing the lignin's size distribution, molecular weight distribution, chemical structure, and hydrophobicity. The DES showed excellent recyclability, and the recycled DES could still remove 42.78% lignin even after 7th circulation associated with 100% glucan saccharification. Further, the mass balance based on 1000 g biomass showed that 196.28 g LMS was directly recovered, which exhibited a high RhB adsorption. Besides, 404.91 g glucose and 36.67 g xylose were obtained after the enzymatic saccharification process. Specifically, GAPI analysis exhibited a near total green and yellow portions of the pictogram, indicating our DES process was green enough to make this biorefinery sustainable. Overall, the proposed DES generated synergistic productions of digestible solid and LMS which could contribute to establish a green and sustainable biorefinery sequence with diverse outputs in one pot.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2016

A{sub 5}RE{sub 4}X[TO{sub 4}]{sub 4} crystal growth: Fluoride flux synthesis of Na{sub 5}Ln{sub 4}F[GeO{sub 4}]{sub 4} (Ln=Pr, Nd), the first quaternary germanate oxyfluorides

Crystals of Na{sub 5}Pr{sub 4}F[GeO{sub 4}]{sub 4} and Na{sub 5}Nd{sub 4}F[GeO{sub 4}]{sub 4} were synthesized using a eutectic sodium fluoride, sodium chloride flux. Both compounds crystallize in the tetragonal space group I-4 with lattice parameters of a=12.1173(4) Å and c=5.6795(2) Å (Pr) and of a=12.0642(17) Å and c=5.6674(11) Å (Nd). The structure of the reported compounds is three-dimensional with face and corner sharing lanthanide polyhedra which edge and corner share with isolated germanium tetrahedra. These novel compositions represent the first example of quaternary germanium containing oxyfluorides. - Graphical abstract: Structural image of the first examples of quaternary germanate oxyfluorides. Display Omitted - Highlights: • Molten flux growth of crystals of two lanthanide germanate oxyfluorides. • Expansion of the A{sub 5}RE{sub 4}X[TO{sub 4}]{sub 4} family into germanate oxyfluorides. • Synthesis of Na{sub 5}Nd{sub 4}F[GeO{sub 4}]{sub 4} and Na{sub 5}Pr{sub 4}F[GeO{sub 4}]{sub 4}.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2015

Study of microstructure and silicon segregation in cast iron using color etching and electron microprobe analysis

An investigation on silicon segregation of lamellar, compacted and nodular graphite iron was carried out by applying a selective, immersion color etching and a modified electron microprobe to study the microstructure. The color etched micrographs of the investigated cast irons by revealing the austenite phase have provided data about the chronology and mechanism of microstructure formation. Moreover, electron microprobe has provided two dimensional segregation maps of silicon. A good agreement was found between the segregation profile of silicon in the color etched microstructure and the silicon maps achieved by electron microprobe analysis. However, quantitative silicon investigation was found to be more accurate than color etching results to study the size of the eutectic colonies. - Highlights: • Sensitivity of a color etchant to silicon segregation is quantitatively demonstrated. • Si segregation measurement by EMPA approved the results achieved by color etching. • Color etched micrographs provided data about solidification mechanism in cast irons. • Austenite grain boundaries were identified by measuring the local Si concentration.

36 MATERIALS SCIENCE↗
DOE OSTI2015

A pseudo-3D approach based on electron backscatter diffraction and backscatter electron imaging to study the character of phase boundaries between Mg and long period stacking ordered phase in a Mg–2Y–Zn alloy

In Mg–2 at.% Y–1 at.% Zn alloys, the LPSO (Long Period Stacking Ordered) phase is important to improve mechanical properties of the material. The aim of this paper is to present a study on the phase boundary character in these two-phase alloys. Using EBSD pattern analysis it was found that the 24R structure is the dominant LPSO phase structure in the current alloy. The phase boundary character between the Mg matrix and the LPSO phase was investigated using an improved pseudo-3D EBSD (electron backscatter diffraction) technique in combination with BSE or SE (backscatter or secondary electron) imaging. A large amount of very low-angle phase boundaries was detected. The (0 0 0 2) plane in the Mg matrix which is parallel to the (0 0 0 24) plane in the LPSO phase was found to be the most frequent plane for these phase boundaries. This plane is supposed to be the habit plane of the eutectic co-solidification of the Mg matrix and the LPSO phase. - Highlights: • It is shown that for the investigated alloy the LPSO phase has mainly 24R crystal structure. • A new method is presented which allows accurate determination of the 5-parameter grain or phase boundary character. • It is found that the low-angle phase boundaries appearing in the alloy all have basal phase boundary planes.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2015

Characterization of complex carbide–silicide precipitates in a Ni–Cr–Mo–Fe–Si alloy modified by welding

Nickel based alloys of the type Hastelloy-N™ are ideal candidate materials for molten salt reactors, as well as for applications such as pressure vessels, due to their excellent resistance to creep, oxidation and corrosion. In this work, the authors have attempted to understand the effects of welding on the morphology, chemistry and crystal structure of the precipitates in the heat affected zone (HAZ) and the weld zone of a Ni–Cr–Mo–Fe–Si alloy similar to Hastelloy-N™ in composition, by using characterization techniques such as scanning and transmission electron microscopy. Two plates of a Ni–Cr–Mo–Fe–Si alloy GH-3535 were welded together using a TiG welding process without filler material to achieve a joint with a curved molten zone with dendritic structure. It is evident that the primary precipitates have melted in the HAZ and re-solidified in a eutectic-like morphology, with a chemistry and crystal structure only slightly different from the pre-existing precipitates, while the surrounding matrix grains remained unmelted, except for the zones immediately adjacent to the precipitates. In the molten zone, the primary precipitates were fully melted and dissolved in the matrix, and there was enrichment of Mo and Si in the dendrite boundaries after solidification, and re-precipitation of the complex carbides/silicides at some grain boundaries and triple points. The nature of the precipitates in the molten zone varied according to the local chemical composition. - Graphical abstract: Display Omitted - Highlights: • Ni-based alloy with Cr, Mo, Si, Fe and C was welded, examined with SEM, EBSD, and TEM. • Original Ni{sub 2}(Mo,Cr){sub 4}(Si,C) carbides changed from equiaxed to lamellar shape in HAZ. • Composition and crystal structure remained almost unchanged in HAZ. • Original carbides changed to lamellar Ni{sub 3}(Mo,Cr){sub 3}(Si,C) in some cases in weld metal. • Precipitates were mostly incoherent, but semi-coherent in some cases in weld metal.

36 MATERIALS SCIENCE↗
DOE OSTI2016

Microstructure evolution in the fusion zone of laser-welded Mg–Gd–Y–Zr alloy during solution and aging treatment

The microstructure evolution in the fusion zone of laser-welded Mg-Gd-Y-Zr alloy during solution and aging treatment is investigated. The morphology of the Mg{sub 24}(Gd,Y){sub 5} in the divorced eutectic at the grain boundary transforms from a continuous network to disconnected and fragmentized islands and then to spheroidal particles before complete dissolution during the solution treatment at 430 °C. During the subsequent aging treatment at 225 °C, the precipitation sequence in the fusion zone follows the order of supersaturated solid solution (SSSS) → βʺ(D0{sub 19}) → βʹ(cbco) → β{sub 1}(fcc) → β(fcc). High-density precipitates are present at the original grain boundaries of the fusion zone from the welded structure but there are less precipitates in the interior of the original grains. The grain growth during the solution treatment at 430 °C comprises the slowly increasing stage, rapidly increasing stage, and stable stage. The network-distributed Mg{sub 24}(Gd,Y){sub 5} impedes migration of the grain boundaries, restricts grain growth in the first slowly increasing stage, and segregation of zirconium near the grain boundaries also affects migration of the grain boundaries. - Highlights: •Different quantities of precipitates are present at different location of grain. •The network-distributed Mg{sub 24}(Gd,Y){sub 5} restricts grain growth. •Segregation of Zr affects migration of grain boundaries.

36 MATERIALS SCIENCE↗
DOE OSTI2018

Evaluation of Zn-rich coatings for IMC reaction control in aluminum-magnesium dissimilar welds

Highlights: • Thermodynamic and diffusion simulations have estimated the Zn conc. required to change the IMC reaction in Al-Mg dissimilar welding. • The selected coating alloy was effective in changing the Al-Mg reaction path by forming τ-(Al,Zn){sub 49}Mg{sub 32} as a substitute for β-Al{sub 3}Mg{sub 2}. • Refill™ friction stir spot welds produced with the coating alloy exhibited a thinner reaction layer and an increase in lap shear strength. - Abstract: The dissimilar welding of Al to Mg is very challenging owing to the rapid formation of an intermetallic (IMC) reaction layer at the joint interface, typically comprised of the binary phases γ-Al{sub 12}Mg{sub 17} and β-Al{sub 3}Mg{sub 2}. A potential metallurgical solution has been explored that aimed to change the reaction path by using Al-Zn alloy coatings to promote alternative IMCs with a slower growth rate. To determine the optimum composition for the coating, combined CALPHAD thermodynamic calculations and diffusion simulations were used to estimate the minimum Zn concentration (20 at.%) required to suppress the formation of the faster growing Al{sub 3}Mg{sub 2} phase. This prediction was verified by both static diffusion and Refill™ friction stir spot welding (FSSW) experiments. In each case the selected coating alloy was effective in changing the Al-Mg reaction path by forming the τ-(Al,Zn){sub 49}Mg{sub 32} phase as a substitute for β-Al{sub 3}Mg{sub 2}. However, in static heat treatments there was no reduction in the IMC reaction layer thickness due to the new phase having similar growth kinetics to the β-Al{sub 3}Mg{sub 2} phase it replaced. Nevertheless, Refill™ friction stir spot welds prepared with the new AL-Zn coating alloy exhibited a thinner reaction layer and an increase in lap shear strength. This benefit was attributed to the Zn addition reducing the joint interface liquation temperature, which resulted in a lower peak weld temperature and less IMC reaction; although an increase in local eutectic melting limited the improvement observed.

36 MATERIALS SCIENCE↗
DOE OSTI2018

Microstructure, precipitates and hardness of selectively laser melted AlSi10Mg alloy before and after heat treatment

Highlights: • Microstructural characterization of SLM AlSi10Mg alloy and comparison with cast and powder AlSi10Mg • Effect of solution heat treatment and aging on the hardness change of SLM AlSi10Mg alloy • Evolution of strengthening precipitates and Fe-rich intermetallics in SLM AlSi10Mg during heat treatment - Abstract: The microstructure and precipitates within selectively laser melted (SLM) AlSi10Mg alloys in the as-built state and after T6 heat treatment were examined and correlated to the hardness evolution. The as-built alloy exhibited columnar patterns perpendicular to the build-direction and fish-scale pattern along the build-direction originating from the melt pool. The microstructure consisted of fine Al cells and eutectic structure with up to 4 μm in size. Tiny needle-like Si particles with highly faulted structure were identified within the Al cells and formed semi-coherent interface with the matrix. Nanoscale Si particles and π-Al{sub 8}Si{sub 6}Mg{sub 3}Fe phase were observed to segregate along the cell and grain boundary. Solution heat treatment (SHT) at 520 °C resulted in the dissolution of Al cellular microstructure. Precipitation and coarsening of the Si particles occurred, while the aspect ratio of Si particles remained nearly constant. The π-Al{sub 8}Si{sub 6}Mg{sub 3}Fe phase decomposed into plate-shaped β-Al{sub 5}SiFe. The artificial aging (AA) at 160 °C did not alter the microstructure but led to the formation of metastable Mg{sub 2}Si precipitates. The GP zones and β″ were identified through transmission electron microscopy after AA of 6 h, and β″ existed up to AA of 24 h. The hardness decreased after SHT due to the coarsening of the microstructure and reduced solid solution hardening. Hardness reached maximum magnitude after AA of 6–10 h due to the precipitation hardening, and remained relatively unchanged up to AA of 24 h. Microstructure and/or hardness of gas atomized powders and bulk cast AlSi10Mg alloys were also examined as references.

36 MATERIALS SCIENCE↗
DOE OSTI2016

The effect of phase interface on the synthesis of SnS{sub 2}-Cu{sub 2}S

Highlights: • Opto-crystalline character of the composition of Cu{sub 2}S and S{sub 2}Sn was considered. • The formation Cu{sub 2}SnS{sub 3} is strongly related to phase separation at interface. • The entanglement of phases is strongly due to the chemical bond competition. • The suggested fluctuation region is approved by PL spectra. • Reconstruction and cluster formation is evident by formation of flat-spiral flowers. - Abstract: Optical character of crystal structure of the composition of two different semiconducting metallic sulfides, Cu{sub 2}S and S{sub 2}Sn, in pure phase formation of the ternary chalcogenide Cu{sub 2}SnS{sub 3} was considered. Because of the difficulties related to the phase separation at the definite Eutectic temperature for the composite formation, which is evident in optical absorption fluctuations, solvothermal synthesis in the intermediate temperature range 180–220 °C seems convenient where tetragonal crystal structure is investigated by XRD. Absorption fluctuations below E = E{sub g} were more pronounced for the lower limit case (180 °C) reflected in a sharp peak located at 1.48 eV on S1 as seen in UV-PL measurement. The characteristic behavior of the interface, resulting in the reconstruction and cluster formation due to the offset of bond rupturing displacement of atomic positions, is in favor of aggregation instead of agglomeration, which is evident by formation of small flat-spiral flowers in SEM images.

36 MATERIALS SCIENCE↗
DOE OSTI2018

Grain boundary scavenging through reactive sintering of strontium and iron in samarium doped ceria electrolyte for ITSOFC applications

Highlights: • Addition of iron and strontium to Samarium doped ceria by combustion method and sintered at 1000 °C, 1200 °C, 1300 °C. • Viscous phase sintering of iron at 1200 °C modified to reactive sintering of iron and strontium at 1300 °C. • Grain boundary activation energy lowered without compensating the grain activation energy. • The highest scavenging factor of 10.52 with the lowest activation energy of 1.02eV was achieved. - Abstract: Lowering the operational temperature of ceria based electrolytes is important for commercialization of solid oxide fuel cells. Here, we report the effect of iron, strontium and iron/strontium co-addition in samarium (20 mol %) doped ceria (SDC) with respect to sintering, microstructural modifications and ionic conductivity. The nanoparticle synthesized through glycine-nitrate combustion method was sintered at 1000, 1200 and 1300 °C. An increase in density was observed in iron doped SDC due to viscous flow sintering while co-addition of strontium and iron lead to the reactive sintering at 1300 °C by forming a eutectic liquid phase which resulted in the density of 99%. The presence of iron and strontium generated a compensatory tensile strain in the lattice and an enhancement in oxygen vacancy concentration which resulted in higher ionic conductivity. Co-addition of strontium and iron in SDC, not only increases the density but also reduces the activation energy for grain boundary conductivity.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2023

Capturing the softening in T91 steel annealed with molten LBE through interfacial gradient plasticity

In order to study the effect of annealing with molten lead–bismuth eutectic alloy (mLBE) on the mechanical properties of T91 steel, micropillar compression tests were analyzed through the consideration of mechanical interface energy terms within gradient plasticity. The stress–strain curves of the micropillars showed significant stochastic effects, characterized by a different elastic and plastic behavior response for each pillar. Among the various pillars, some exhibited a similar trilinear behavior. Scanning electron microscopy (SEM) images of these specimens demonstrated localized slip deformation and slip planes after compression, while transmission electron microscopy (TEM) images showed the presence of a severe slip zone along the random grain boundaries (RGBs), indicating that the GBs played a dominant role in the deformation/slip. By employing interfacial gradient plasticity that can explicitly account for the presence of GBs, the trilinear response was captured, allowing for the determination of the mechanical interface parameter. As anticipated the pillars which underwent severe slip at the GBs had a lower value for the mechanical interface parameter. Finally, annealing with mLBE can, therefore, in some cases result in softening in the overall stress–strain, as it lowers the mechanical interface energy of GBs.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Electrodeposited nickel coatings for exceptional corrosion mitigation in industrial grade molten chloride salts for concentrating solar power

Molten chloride salt eutectics are attractive candidates for use as thermal energy storage media and heat transfer fluids in generation-three concentrating solar thermal power (Gen3 CSP) plants. However, corrosion of alloys in molten chloride salts, especially at high temperatures, is an extremely challenging problem that studies focus on lower temperatures, shorter durations, or analytical grade, and high-purity, salts. To date, there has been no study on corrosion or corrosion mitigation in an industrial-grade salt at a high temperature such as 750 °C. To alleviate this knowledge gap, the study presents new multiscale fractal-textured Ni coatings on various alloy surfaces for effective corrosion mitigation at 750 °C in molten chloride salts. Using the electrodeposition method, durable double-layer textured coatings were formed on stainless steel alloys (SS316, SS310, and SS347) and In800H. The corrosion performance of the coatings is investigated in both analytical-grade purity and, for the first time, practically relevant industrial-grade chloride salts. Ni-coated ferrous alloys showed an exceptionally reduced corrosion rate in the range of 350–480 μm/y in analytical-grade salts, and between 450 and 490 μm/y in purified industrial-grade salts at 750 °C. Ni coatings on ferrous alloys reduced corrosion rates by as much as 70% compared to uncoated surfaces and were comparable to the expensive Ha230 alloy with a high Ni content. As a result, by the use of innovative fractal corrosion mitigation coatings, for the first time, low-cost structural alloys are rendered viable for use with industrial-grade chloride salts, which is profoundly beneficial in practical systems.

14 SOLAR ENERGY↗
DOE OSTI2022

Promising Method of Sm–Co Magnet Reprocessing in Alkali Chloride Melts

Developing new, efficient methods for samarium and cobalt recovery from scraps/rejects and swarf at Sm–Co magnet manufacturing sites during shaping and finishing is an important task in terms of meeting their growing demand. In this work, the reaction of oxygen with a solution of samarium and cobalt chlorides in a LiCl–KCl eutectic melt was studied at 400–600 °C to explore possible methods for the separation and recovery of samarium and cobalt from these waste products. The pyrochemical reaction resulted in the formation and precipitation of samarium oxychloride, while the cobalt remained in the melt in a soluble chloride form. The effect of temperature and the amount of oxygen passed through the melt (oxygen-to-samarium molar ratio) on the course of the reaction were studied. Kinetic parameters of the oxygen with samarium chloride reaction were determined.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Dynamics of Glyceline and Interactions of Constituents: A Multitechnique NMR Study

In this work, the dynamics of the organic components of the deep eutectic solvent (DES) glyceline are analyzed using an array of complementary nuclear magnetic resonance (NMR) methods. Fast-Field Cycling 1 H relaxometry, Pulsed Field Gradient diffusion, Nuclear Overhauser Effect Spectroscopy (NOESY), 13 C NMR relaxation and pressure dependent NMR experiments are deployed to sample a range of frequencies and modes of motion of the glycerol and choline components of the DES. Generally, translational and rotational diffusion of glycerol are more rapid than those of choline while short range rotational motions observed from 13 C relaxation indicate slow local motion of glycerol at low choline chloride (ChCl) content. The rates of glycerol and choline local motions become more similar at higher ChCl. This result taken together with pressure dependent NMR studies show that the addition of ChCl makes it easier to disrupt glycerol packing. Finally, a relatively slow hydroxyl H-exchange process between glycerol and choline protons is deduced from the data. Consistent with this, NOESY results indicate relatively little direct H-bonding between glycerol and choline. These results suggest that the glycerol H-bonding network is disrupted as choline is added, but primarily in regions where there is intimate mixing of the two components. Thus, the local dynamics of most of the glycerol, resembles that of pure glycerol until substantial choline chloride is present.

13C NMR relaxation↗
DOE OSTI2022

Polymer-Stabilized Liquid Metal Nanoparticles as a Scalable Current Collector Engineering Approach Enabling Lithium Metal Anodes

Dendrites and dead lithium formation over prolonged cycling have long been challenges that hinder the safe implementation of metallic Li anodes. In this study, we employ polymer-stabilized liquid metal nanoparticles (LM-P NPs) of eutectic gallium indium (EGaIn) to create uniform Li nucleation sites enabling homogeneous lithium electrodeposition. Block copolymers of poly(ethylene oxide) and poly(acrylic acid) (PEO-b-PAA) were grafted onto the EGaIn surface, forming stabilized, well-dispersed NPs. Using a scalable spray coating approach, LM-P NPs were fabricated on copper current collectors, providing lithiophilic PEO sites and interactive carboxyl groups to guide Li deposition. The Li-EGaIn alloying process greatly reduced the Li + diffusion barrier, enabling fast Li transport through the coating layer, resulting in decreased nucleation overpotential. Therefore, about five times lower Li nucleation overpotential was obtained on the LM-P modified Cu with an optimal composition of the polymers than the bare Cu substrates. DFT computations was used to reveal the binding properties between the LM-P layer and Li. Due to the regulated Li plating/stripping process, as-obtained 30 μm Li anodes paired with LiNi 0.8 Co 0.1 Mn 0.1 O 2 (NCM8 11 ) with a negative/positive electrode capacity (N/P) ratio ~ 10 exhibited stable cycling performance at 0.5C for over 250 cycles, with an average Coulombic efficiency of 99.55%. Ultrathin Li (1 μm) anodes with an N/P ratio ~ 0.6 were also demonstrated in Li|LiFePO 4 cells, which examined the stabilization of Li by LM-P NPs and monitored practical loadings of Li anodes that are close to anode-free systems.

25 ENERGY STORAGE↗