SEARCH · Search NASA

Results for “Diffusion NMR”

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.

SourceResearch connectionFrom yearThrough year

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

At least 55 records · Page 3

All sources NASA NTRS DOE OSTI

DOE OSTI2025

Come for predictions, stay for complexity: synthesis and experimental probing of ionic conductivity in Li 9 B 19 S 33

Lithium thioborates, despite their potential cost-effectiveness and low density, have received considerably less attention as solid electrolytes compared to their thiophosphate counterparts. A primary obstacle to their widespread investigation has been the inherent challenge in synthesizing single-phase materials. Computational studies have predicted several lithium thioborate phases exhibiting high ionic conductivity, with Li 9 B 19 S 33 notably predicted to reach 80 mS cm −1 . However, experimental validation of these theoretical predictions remains absent. This work addresses this gap by detailing a successful synthesis of the previously elusive Li 9 B 19 S 33 phase, facilitated by in situ temperature dependent powder X-ray diffraction. Our findings reveal the peritectic nature of phase formation, necessitating an excess of boron sulfide in the reaction mixture. We further present a comprehensive structural characterization of Li 9 B 19 S 33 utilizing spectroscopic techniques like NMR, FT-IR, and diffuse reflectance and report on its ionic conductivity. Solid-state 6 Li NMR line narrowing experiments revealed an ion mobility activation energy of 0.26 eV whereas activation energies derived from impedance spectroscopy measurements were significantly higher, resulting in lower than theoretically predicted ionic conductivity.

Oppong, Richeal A. [Iowa State Univ., Ames, IA (Un↗

DOE OSTI2020

Mixtures of octanol and an ionic liquid: Structure and transport

Ionic liquids (ILs) with long alkyl substituents are amphiphilic, which leads to a bicontinuous liquid structure. The strongly interacting anionic and cationic head groups form a long range charge network, with the hydrocarbon tails forming a nonpolar domain. Such nonpolar domains have been shown to dissolve a variety of neutral organic solvents. In mixtures of ILs with solvents the neutral organic molecules residing in the nonpolar domains experience different environments and friction from the charged cations and anions. Thus, the neutral molecules diffuse much faster than predicted by hydrodynamic scaling using the average viscosity of the mixture. Here, we report studies on the structure and transport properties of mixtures of 1-octanol with the IL trihexyltetradecylphosphonium bis(trifluoromethylsulfonyl)imide (P 6,6,6,14 + /NTf 2 – ). The majority of the atom fraction in the P 6,6,6,14 + cation comprises four hydrocarbon substituents. The unique amphiphilic nature of ILs with the P 6,6,6,14 + cation makes 1-octanol fully miscible with the IL at ambient temperatures. X-ray scattering experiments show that the IL structure persists in the mixtures for 1-octanol mole fractions as large as x oct = 0.90. The self-diffusion coefficients of the three molecular species in the mixtures were measured by NMR experiments. The self-diffusion of the P 6,6,6,14 + cation is well described by the Stokes–Einstein equation, while the diffusivity of the NTf 2 – anion is slightly lower than the hydrodynamic prediction. The measured diffusivities of octanol in these mixtures are 1.3–4 times higher than the hydrodynamic predictions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2025

Probing the influence of ion-pairing on ligand-field excited-state dynamics

Exploration of the photophysical and photochemical properties of transition metal complexes has driven ground-breaking advancements in solar energy conversion technologies, including photoredox catalysis. While significant research has been devoted to understanding excited state properties of second- and third-row transition metal complexes, earth-abundant first-row metal complexes have received comparatively little attention in this context until very recently. In particular, the role of ion-pairing – which has been identified as a potentially significant factor for Ir(III)-based photosensitizers – has not been examined with regard to its influence on the ligand-field excited states that dominate much of first-row photophysics. A key challenge in studying ion-pair interactions lies in quantifying the extent and nature of ion-pairing, particularly in non-aqueous media where the vast majority of photophysical studies are performed. Cobalt(III) polypyridyl complexes provide an attractive platform to address such questions due to their demonstrated potential for applications in photoredox catalysis involving ligand-field excited states. In the present study, we prepared a cobalt(III) polypyridyl complex, [Co(4,4′-OMebpy) 3 ](BAr F 4 ) 3 (where 4,4′-OMebpy is 4,4′-dimethoxy-2,2′-bipyridine and BAr F 4 is tetrakis(3,5-bis(trifluoromethyl)-phenyl)borate) to probe ion-pairing in non-aqueous solutions. Specifically, analysis of data acquired from both variable-temperature diffusion ordered spectroscopy (DOSY) NMR and 1-D rotating-frame nuclear Overhauser effect (ROE) experiments allowed us to identify and differentiate between solvent-separated ion pairs in high-dielectric media and contact ion pairs in a low-dielectric solvent. Time-resolved absorption spectroscopy was then used to measure ground-state recovery dynamics under these varying conditions of ion-pairing, the results of which revealed an increase in excited-state lifetime for contact ion-pairs that we suggest arises from a reduction in outer-sphere reorganization energy relative to conditions which favored solvent-separated ion pairs. We believe this study demonstrates that one can leverage broadly available NMR-based methods to understand ion-pairing in non-aqueous solutions, which in turn can provide a microscopic picture of intermolecular interactions that can impact the photophysical properties of transition metal-based chromophores.

Ghosh, Atanu [Michigan State University, East Lans↗

DOE OSTI2020

Time-Domain Nuclear Magnetic Resonance Determination of Wettability Alteration: Analysis for Low-Salinity Water

Wettability has been shown to influence oil recovery. This property has become central to low-salinity (LSW) and smart (SWF) water flooding recovery mechanisms research. The challenge lies in the fact that oil recovery results from the combined effects of solid-liquid and liquid-liquid interactions. This demands methods that allow an independent interpretation of wettability alteration contributions. The primary objective of this work is to assess changes in wettability through the application of Time-Domain Nuclear Magnetic Resonance (TD-NMR) T 2 distribution and diffusion coefficient, starting with a well-controlled porous system, that is, glass beads, and then a model rock (Berea), in the presence of one phase, either oil or brine exclusively. Subsequently, two-phase fluid saturation was tested. For the glass beads, dimethyldichlorosilane was used to induce a hydrophobic response, as confirmed by contact angle experiments on slides of the same material. Sodium sulfate was used for its known positive influence on oil recovery during LSW and SWF. In cases where alteration of surface properties was expected, a leftward shift of the average T 2 distribution curve modes, accompanied by a reduction on the diffusion coefficient during the aging process was observed. The results of this work confirm that fluid-solid interactions during LSW and SWF, namely a shift in wettability, take place after the injection of low-salinity water.

42 ENGINEERING↗

DOE OSTI2021

A Study of Ferrocene Diffusion in Toluene/Tween 20/1-Butanol/Water Microemulsions for Redox Flow Battery Applications

Redox flow batteries (RFBs) possess multiple advantages as a flexible energy storage solution. However, RFB researchers are still facing many challenges in finding an appropriate electrolyte. Microemulsions have recently been proposed as a promising alternative RFB electrolyte because of their ability to accommodate organic redox species with fast electron transfer rates that are not soluble in aqueous phase, while still offering the high conductivity of an aqueous salt electrolyte. In this work, we focused on understanding the transport of ferrocene (Fc) in a toluene/Tween 20/1-butanol/water model microemulsion and studied the compositional influence on Fc diffusion. The results show that Fc redistributes among the oil, surfactant, and water microenvironments, and the corresponding diffusion and partition coefficients are quantified. Thus, a tortuous path diffusion model is proposed to describe the mass transport of Fc to an electrode surface. Diffusion coefficients are also obtained by pulsed-field gradient nuclear magnetic resonance (PFG NMR), while the values for Fc diffusion are substantially higher than those from electrochemical measurements, suggesting that they measure samples in different ways. The current contributions from each microenvironment indicate that the Fc permeability is much higher in the oil, even though the electron transfer reaction is likely occurring in the surfactant.

25 ENERGY STORAGE↗

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

Microsized Pore Structure Determination in EPDM Rubbers Using High-Pressure 129 Xe NMR Techniques

Microsized pore parameters, such as pore size and distance between pores in a series of model EPDM rubbers, were determined in situ under the pressure of 500 psi using 129 Xe nuclear magnetic resonance (NMR) techniques: spin–lattice (T 1 ) and spin–spin (T 2 ) relaxation measurements, pulsed-field gradient (PFG) NMR, and two-dimensional exchange spectroscopy (2D EXSY). The T 1 /T 2 (>>1) ratio for the xenon confined in the pores is larger than that for nonconfined free xenon. This suggests that almost the entire pore surface interacts with xenon atoms like a closed pore. While these pores still connect each other through very narrow diffusion/exchange channels, it is possible to observe the echo decay in PFG-NMR and cross-peaks in 2D EXSY. The results show that both diffusion (D pore ≈ 2.1 × 10 –10 m 2 /s) and exchange (exchange rate, τ exch = a few tens of milliseconds) of xenon between a pore within the material and outer surface are prolonged. The exchange distances (l), which correspond to the xenon gas penetration depth, were estimated to be 70–100 μm based on the measured diffusion coefficients and exchange rate (1/τ exch ). NMR diffraction analysis reveals that pore size (a) and pore distance (b) are on the order of magnitude of micrometers and tens of micrometers, while the diffusion coefficients of xenon gas in the diffusion channels (D eff ) are about 10 –8 m 2 /s. Overall, this study suggests that the pores with a few micrometers connected through very narrow flowing channels with the length of several tens of micrometers are developed 70 to 100 μm below the rubber surface. Furthermore, the overall steady-state diffusion of xenon is slower, approximately 2 orders of magnitudes, than the diffusion in the channel between the pores. Finally, the pore and exchange distances correlated with the composition of rubbers showed that the properties of EPDM rubber as a high-pressure gas barrier could be improved by reducing the size of cracks and the depth of gas penetration by the addition of both carbon black and silica fillers.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2020

Selective One-Dimensional 13 C– 13 C Spin-Diffusion Solid-State Nuclear Magnetic Resonance Methods to Probe Spatial Arrangements in Biopolymers Including Plant Cell Walls, Peptides, and Spider Silk

Two-dimensional (2D) and 3D through-space 13 C– 13 C homonuclear spin-diffusion techniques are powerful solid-state nuclear magnetic resonance (NMR) tools for extracting structural information from 13 C-enriched biomolecules, but necessarily long acquisition times restrict their applications. In this work, we explore the broad utility and underutilized power of a chemical shift-selective one-dimensional (1D) version of a 2D 13 C– 13 C spin-diffusion solid-state NMR technique. The method, which is called 1D dipolar-assisted rotational resonance (DARR) difference, is applied to a variety of biomaterials including lignocellulosic plant cell walls, microcrystalline peptide fMLF, and black widow dragline spider silk. 1D 13 C– 13 C spin-diffusion methods described here apply in select cases in which the 1D 13 C solid-state NMR spectrum displays chemical shift-resolved moieties. Furthermore, this is analogous to the selective 1D nuclear Overhauser effect spectroscopy (NOESY) experiment utilized in liquid-state NMR as a faster (1D instead of 2D) and often less ambiguous (direct sampling of the time domain data, coupled with increased signal averaging) alternative to 2D NOESY. Selective 1D 13 C– 13 C spin-diffusion methods are more time-efficient than their 2D counterparts such as proton-driven spin diffusion (PDSD) and dipolar-assisted rotational resonance. The additional time gained enables measurements of 13 C– 13 C spin-diffusion buildup curves and extraction of spin-diffusion time constants TSD, yielding detailed structural information. Specifically, selective 1D DARR difference buildup curves applied to 13 C-enriched hybrid poplar woody stems confirm strong spatial interaction between lignin and acetylated xylan polymers within poplar plant secondary cell walls, and an interpolymer distance of ~0.45–0.5 nm was estimated. Additionally, Tyr/Gly long-range correlations were observed on isotopically enriched black widow spider dragline silks.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2025

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↗

DOE OSTI2025

Extended molecular eigenmodes treatment of dipole–dipole NMR relaxation in real fluids

Traditional models of NMR relaxation fail to account for the complex, multi-exponential behavior of the autocorrelation function in realistic systems characterized by soft-interactions and molecules that are chemically and physically complex. Here, in this study, we describe the relative diffusion of the spin dipoles by means of a Fokker–Planck equation that includes an interaction potential of mean force to account for the response of the physical/chemical environment around the dipoles. By numerically solving the Fokker–Planck equation for the diffusion propagator, we estimate dipole–dipole NMR relaxation for like- and unlike-spin systems via its eigenmode solution. We test the model against molecular simulations of diffusing dipoles with harmonic potentials and also validate using experimental longitudinal relaxation data from real systems, including Gd(III)–aqua and Gd(III)–DO3A–butrol complexes, the latter being an important MRI contrast agent. Using this novel approach, we predict both the inner- and outer-shell contributions to the relaxivity rates with excellent accuracy at frequencies relevant to MRI. We also show that, under the appropriate assumptions, our framework naturally recovers the Bloembergen–Purcell–Pound, the Solomon–Bloembergen–Morgan, and the Hwang–Freed models. Our implementation is general and publicly available for application to a broad range of systems.

Pinheiro dos Santos, Thiago J. [Rice Univ., Housto↗

DOE OSTI2025

Solution‐Like Water Transport Across Molecular to Macroscopic Length Scales in Crosslinked Poly(Ethylene Glycol Diacrylate) Networks With Tailored Sidechains

Poly(ethylene glycol) (PEG)‐based materials, like PEG‐diacrylate (PEGDA), are prized for their hydrophilic, inert properties, and leveraged in hydrogels and as membrane mimics. While network chemistry is often tuned for selective transport and antifouling, fundamental understanding of water dynamics at the network surface and the impact on bulk transport is limited. We utilize Overhauser dynamic nuclear polarization (ODNP) to measure nanoscale water diffusivity near a tethered spin label at the water‐polymer surface and compare it to bulk water diffusivity from pulsed field gradient (PFG) NMR. Via active ester chemistry, spin labels and varied sidechain chemistries are introduced, modulating network hydrophilicity. Tuning network hydration through crosslinker content and functional groups further impacts water diffusivity. Results show rapid nanoscale water transport at the polymer surface, reflecting network volumetric water content, with further modulation by sidechain functionality. These findings demonstrate PEGDA's utility as a membrane mimic and the critical impact of network chemistry on water transport.

hydrogels↗

DOE OSTI2021

Effect of CO 2 -brine-rock reactions on pore architecture and permeability in dolostone: Implications for CO 2 storage and EOR

Geologic carbon sequestration (GCS) is considered a feasible technology for storing substantive volumes of greenhouse gases in subsurface geological formations. In the reservoir, far from carbon dioxide (CO 2 ) injection wells or in post-injection scenarios, diffusion dominates over advection. This condition conjoins with spatially distributed geochemical reactions to induce heterogeneous changes in pore architecture, i.e. pore body and throat sizes or surface roughness. These changes can affect CO 2 transport properties and storage capacity. In this work, we investigated mineral dissolution and precipitation in dolomite samples saturated with a CO 2 -saturated brine at 93 °C and 34.5 MPa, aged without flow. Two rock types samples, i.e. intergranular- and vuggy-dominant, were selected to investigate changes in pore size, porosity and permeability under reactive conditions. Mineral dissolution and precipitation were characterized using scanning electron microscopy. Changes in pore size were quantified via time-domain nuclear magnetic resonance (TD-NMR) transverse relaxation time (T 2 ) and diffusion coefficient (D) distributions. We show that mineral dissolution likely occurs in highly permeable pathways. These observations are confirmed through analysis of (T 2 ) and diffusion coefficient (D) distributions. In contrast to results during CO 2 -enriched brine continuous injection, mineral precipitation was observed in micropores. The leftward shift of the T 2 peaks, corresponding to micropores, also evidenced mineral precipitation in lowpermeability zones. However, microscale alterations resulted only in a subtle increase in porosity and permeability. Results in this study shed light on effects of geochemical reactions on alteration of rock properties in diffusion-dominated regions during CO 2 storage.

58 GEOSCIENCES↗

DOE OSTI2020

Relating Geometric Nanoconfinement and Local Molecular Environment to Diffusion in Ionic Polymer Membranes

Understanding structure-diffusion relationships in ionic polymer membranes not only illuminates fundamental mechanisms for membrane transport, but also informs further membrane development. In this study, we employ NMR diffusometry and molecular dynamics (MD) simulations to investigate diffusion coefficients and activation energies of diffusion (Ea) for both a lithium-form perfluorosulfonic acid membrane and aqueous solutions of lithium triflate. NMR shows that, at high water/ion molar ratio (?), Ea for water diffusion is slightly lower in the membrane than in solution. Conversely, membrane transport exhibits much higher Ea at low hydration as compared to solutions. MD simulations of a model system consisting of carbon nanotubes with varying diameter reveal that Ea of diffusion clearly relates to both the geometric nanoconfinement of the hydrophilic pathways in the membrane as well as the local molecular environment. These results demonstrate that Ea of diffusion can serve as a revelatory tool for the study of molecular transport processes and the coupling of morphology with transport at the nanoscale. This study thus provides new insights and new experimental and computational models for understanding transport in a wide range of polymer membranes, such as those used in molecular separations applications.

Zhang, Rui↗

DOE OSTI2022

Sodium diffusion in heterogeneous porous media: Connecting laboratory experiments and simulations

Sodium has been suggested as a tracer for brine in reservoir formations where a significant amount of sodium ion is found mainly in the aqueous phase. Fortunately, the most abundant sodium isotope, 23 Na, is Nuclear Magnetic Resonance (NMR) active, making it possible to study the structure and dynamical properties of both bulk and pore confined fluid systems. We investigated the diffusion of key dissolved sodium species in bulk solution and porous media as a function of composition, ionic strength, and permeability of the carbonate samples using NMR relaxometry and pulsed-field gradient (PFG) NMR techniques. We use Indiana limestone as an example of natural porous media and water as a freely diffusible tracer and carrier. We demonstrate apparent diffusion measurement of sodium based on changes in spin–spin relaxation time (T 2 ) signal in pore confinement. The diffusion rate of sodium decreases with increasing counter-ion size. This effect is greater at higher ionic strengths and lower chemical potentials in porous media. The reactive transport code, CrunchFlow, was used to complement the NMR experiments to simulate diffusion behavior in porous media. Combining these two methods provides a powerful approach to estimating effective diffusion coefficients in heterogeneous matrices. The modeling considers the influence of physical properties (porosity and tortuosity) and chemical properties (geochemical composition and chemical gradients). The results presented in this work highlight the advantage of measuring apparent diffusivity using NMR T 2 relaxometry in conjunction with numerical simulation to derive effective diffusivity and the corresponding matrix properties (i.e., tortuosity) of the system.

58 GEOSCIENCES↗

DOE OSTI2025

Water Dynamics of Superacid Aromatic Proton Exchange Membranes for Fuel Cell Applications

Proton exchange membranes (PEMs) with high conductivity are of critical importance for the development of fuel cells, electrolyzers, and other electrochemical technologies. In this research, poly(1,1,2,2-tetrafluoro-2-phenoxyethane-1-sulfonic acid) (PTPS) with an aromatic polymer main chain and a perfluorinated superacidic polymer side chain was synthesized. The water dynamics of PTPS were characterized across various length scales using a combination of Fourier-transform infrared spectroscopy (FTIR) and nuclear magnetic resonance (NMR) and compared with Nafion, a standard perfluorinated PEM, and sulfonated poly(ether sulfone) (SPES 40), an aromatic PEM without perfluorinated superacid side chains. The T 1 and T 2 relaxation times of water in the samples probed by NMR increase from SPES 40 to PTPS to Nafion, indicating that the local motion of the water molecules becomes faster. This trend corresponds well with the relative fraction of bulk-like water determined using FTIR. At larger length scales, the diffusion coefficient of water was characterized using pulsed-field gradient NMR (PFG-NMR). At a longer diffusion time (Δ = 100 ms), PTPS has a smaller diffusion coefficient compared with both Nafion and SPES 40, due to restricted diffusion, and this effect is also evident in the proton conductivity of the hydrated membranes. From this comparison, it is apparent that the aromatic backbone and side chain type greatly influence the water dynamics in PEMs at various length scales and the water dynamics significantly impact the bulk proton conductivity. These insights will lead to new designs for aromatic PEMs and help to identify bottlenecks in current materials.

25 ENERGY STORAGE↗

DOE OSTI2021

Concentration-Dependent Solvation Structure and Dynamics of Aqueous Sulfuric Acid Using Multinuclear NMR and DFT

Sulfuric acid is a ubiquitous compound for industrial processes and aqueous sulfate solutions also play a critical role in electrolytes for many prominent battery chemistries. While the thermodynamic literature for it is quite well-developed, comprehensive studies of the solvation structure, and particularly molecular-scale dynamical and transport properties, are less available. This study applies a multinuclear NMR approach to the elucidation of the solvation structure and dynamics over a wide temperature (-10 – 50?C) and concentration (0 – 18 M) range, combining 17O shift, linewidth, and T1 relaxation measurements, 33S shift and linewidth measurements, and 1H PFG-NMR measurements of the proton self-diffusivity. In conjunction, these results indicate a crossover between two regimes of solvation structure and dynamics, occurring above the concentration associated with the deep eutectic point (~ 4.5 M), with the high-concentration regime dominated by strong water-sulfate correlation. This description was borne out in detail by the activation energy trends with increasing concentration derived from the relaxation of both the H2O/H3O+ and H2SO4/HSO4-/SO42- 17O resonances and the 1H self-diffusivity. However, the 17O chemical shift difference between the H2O/H3O+ and H2SO4/HSO4-/SO42- resonances across the entire temperature range is nevertheless strikingly linear. A computational approach coupling MD simulations and DFT NMR shift calculations to reproduce this trend is presented, which will be the subject of further development. This combination of multinuclear, dynamical NMR and computational methods, and the results furnished by this study, will provide a platform for future studies on battery electrolytes where aqueous sulfate chemistry plays a central role in the solution structure.

Bazak, Jonathan D.↗

DOE OSTI2023

Structure and dynamics of ILs-based gel polymer electrolytes and its enhanced conductive properties with the incorporation of Al 2 O 3 nanofibers

Here, this work reports the enhanced mobility of ions in ionic liquid (IL)-based gel polymer electrolytes (GPEs) with the incorporation of Al 2 O 3 nanofibers. A combination of PVDF-HFP, EMIMTFSI and LiTFSI with 3 wt% Al 2 O 3 nanofibers has been prepared through solution casting technique. The room temperature ionic conductivity of PVDF-HFP: ILs electrolyte (45:55, weight ratio of 0.82) (GPE) is found to be 2.7 × 10 –5 S cm –1 , which increases up to 7.8 × 10 –5 S cm –1 in Al 2 O 3 containing GPE (Al-GPE). Pulsed field gradient (PFG) NMR results validate the increased ionic conductivity observed in Al-GPE. We found that the diffusivity of Li + , TFSI – and EMIM + increases when Al 2 O 3 nanofibers are well-distributed in the GPE matrix. The surface morphology and the amorphicity of GPEs are examined through SEM and XRD analyses. Lastly, the local structure of Al 2 O 3 fibers and the molecular-level interactions of ions with polymer, and their effect on the diffusivity of ions are established through solid-state NMR detecting 27 Al, 1 H, 13 C, 19 F nuclei including 2D 13 C{ 1 H} HETCOR NMR experiments. The 13 C DPMAS and CPMAS experiments highlight the dynamic heterogeneity associated with the ions that are embedded in the rigid and the mobile phase of GPEs. While some of the ionic species strongly interact with polymer chains in the rigid environment, the majority of them reside in the mobile phase and contribute to the overall increased conductivity. Most importantly, Al 2 O 3 nanofibers significantly affect the dynamics of ionic species that are present in the mobile phase between the polymer chains.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2024

Weakly solvating ester electrolyte for high voltage sodium-ion batteries

Ethyl acetate (EA) was identified as a promising electrolyte solvent for sodium-ion batteries (SIBs), exhibiting low viscosity, cost-effectiveness, and low toxicity. Despite a significant portion of aggregation being linked to the weak solvation of Na + /EA as revealed by molecular dynamics (MD) simulations, pulsed-field gradient nuclear magnetic resonance (pfg-NMR) analysis identified a noteworthy Na+ diffusion coefficient of 3.95×10 -10 m 2 s -1 at 25°C in the presence of 1 m NaPF 6 salt. Employing fluoroethylene carbonate (FEC) as a film-forming additive to create electrode-electrolyte interphase, this electrolyte surprisingly made ~210 mAh Na 0.97 Ca 0.03 [Mn 0.39 Fe 0.31 Ni 0.22 Zn 0.08 ]O 2 (NCMFNZO)/hard carbon (HC) pouch cells achieve a lengthy cycling lifetime of 250 cycles with ~80 % capacity retention, cycled up to 4.0 V at 40°C. X-ray photoelectron spectroscopy (XPS) revealed increasing interphasial organic species over cycling, augmenting charge transfer resistance on both cathode and anode, particularly during fast charging or low temperatures (<10°C), promoting Na plating. Finally, gas chromatography-mass spectrometry combined with density functional theory identified CO 2 as the major gas generated from charged cathode/electrolyte interactions, exhibiting temperature/voltage dependence.

25 ENERGY STORAGE↗