Pulsed Field Gradient Research Articles

Destabilization of water-in-crude oil emulsions using naphthenic acids

Naphthenic Acids (NAs) are widely believed to universally act in a stabilizing capacity during the formation of water-in-crude oil emulsions. This work provides evidence to the contrary wherein differences between commercially acquired NAs and those extracted from crude exhibit opposing effects on emulsion stability. Addition of the commercial NAs to a crude oil prior to water-in-oil emulsion formation resulted in an increase in emulsion destabilization rate. This was demonstrated via quantification of water droplet coalescence using pulsed field gradient nuclear magnetic resonance (NMR) and, over long timescales in the visual observation of the disengagement of a free water phase. The efficacy of the commercial NAs to act in such a demulsification capacity was shown to be effective at concentrations as low as 0.5v/v% and in the presence of saline water of up to 3.5 wt% NaCl. Differences in NA demulsifying ability was observed between three crude oils of various origins with some demonstrating clear visual phase separation whilst others remained in an emulsified state. Conversely, addition of NAs extracted from a crude oil at similar concentrations had negligible effect on the rate of emulsion destabilization. Comparative characterization of the commercial and indigenous NAs was performed using 1H NMR, Diffusion Ordered Spectroscopy (DOSY), Rheometry, Pendant Drop Tensiometry, and Gas Chromatography–Mass Spectrometry. The results of this characterization indicated that differences in emulsion stability were governed not by differences in the reduction of emulsion droplet interfacial tension (IFT) but by the kinetics of molecular diffusion of the NAs during both the emulsification and destabilization phases.

Combining Experiments and Simulations to Examine the Temperature-Dependent Behavior of a Disordered Protein.

Intrinsically disordered proteins are a class of proteins that lack stable folded conformations and instead adopt a range of conformations that determine their biochemical functions. The temperature-dependent behavior of such disordered proteins is complex and can vary depending on the specific protein and environment. Here, we have used molecular dynamics simulations and previously published experimental data to investigate the temperature-dependent behavior of histatin 5, a 24-residue-long polypeptide. We examined the hypothesis that histatin 5 undergoes a loss of polyproline II (PPII) structure with increasing temperature, leading to more compact conformations. We found that the conformational ensembles generated by the simulations generally agree with small-angle X-ray scattering data for histatin 5, but show some discrepancies with the hydrodynamic radius as probed by pulsed-field gradient NMR spectroscopy, and with the secondary structure information derived from circular dichroism. We attempted to reconcile these differences by reweighting the conformational ensembles against the scattering and NMR data. By doing so, we were in part able to capture the temperature-dependent behavior of histatin 5 and to link the observed decrease in hydrodynamic radius with increasing temperature to a loss of PPII structure. We were, however, unable to achieve agreement with both the scattering and NMR data within experimental errors. We discuss different possible reasons for this including inaccuracies in the force field, differences in conditions of the NMR and scattering experiments, and issues related to the calculation of the hydrodynamic radius from conformational ensembles. Our study highlights the importance of integrating multiple types of experimental data when modeling conformational ensembles of disordered proteins and how environmental factors such as the temperature influence them.

Effects of Homogeneous and Heterogeneous Crowding on Translational Diffusion of Rigid Bovine Serum Albumin and Disordered Alfa-Casein.

Intracellular environment includes proteins, sugars, and nucleic acids interacting in restricted media. In the cytoplasm, the excluded volume effect takes up to 40% of the volume available for occupation by macromolecules. In this work, we tested several approaches modeling crowded solutions for protein diffusion. We experimentally showed how the protein diffusion deviates from conventional Brownian motion in artificial conditions modeling the alteration of medium viscosity and rigid spatial obstacles. The studied tracer proteins were globular bovine serum albumin and intrinsically disordered α-casein. Using the pulsed field gradient NMR, we investigated the translational diffusion of protein probes of different structures in homogeneous (glycerol) and heterogeneous (PEG 300/PEG 6000/PEG 40,000) solutions as a function of crowder concentration. Our results showed fundamentally different effects of homogeneous and heterogeneous crowded environments on protein self-diffusion. In addition, the applied "tracer on lattice" model showed that smaller crowding obstacles (PEG 300 and PEG 6000) create a dense net of restrictions noticeably hindering diffusing protein probes, whereas the large-sized PEG 40,000 creates a "less restricted" environment for the diffusive motion of protein molecules.

A dual-core NMR system for field-cycling singlet assisted diffusion NMR.

Long-lived singlet spin order offers the possibility to extend the spin memory by more than an order of magnitude. This enhancement can be used, among other applications, to assist NMR diffusion experiments in porous media where the extended lifetime of singlet spin order can be used to gain information about structural features of the medium as well as the dynamics of the imbibed phase. Other than offering the possibility to explore longer diffusion times of the order of many minutes that, for example, gives unprecedented access to tortuosity in structures with interconnected pores, singlet order has the important advantage to be immune to the internal field gradients generated by magnetic susceptibility inhomogeneities. These inhomogeneities, however, are responsible for very short T2 decay constants in high magnetic field and this precludes access to the singlet order in the first instance. To overcome this difficulty and take advantage of singlet order in diffusion experiments in porous media, we have here developed a dual-core system with radiofrequency and 3-axis pulsed field gradients facilities in low magnetic field, for preparation and manipulation of singlet order and a probe, in high magnetic field, for polarisation and detection. The system operates in field-cycling and can be used for a variety of NMR experiments including diffusion tensor imaging (both singlet assisted and not). In this paper we present and discuss the new hardware and its calibration, and demonstrate its capabilities through a variety of examples.

Double pulsed field gradient diffusion MRI to assess skeletal muscle microstructure.

Preliminary study to determine whether double pulsed field gradient (PFG) diffusion MRI is sensitive to key features of muscle microstructure related to function. The restricted diffusion profile of molecules in models of muscle microstructure derived from histology were systematically simulated using a numerical simulation approach. Diffusion tensor subspace imaging analysis of the diffusion signal was performed, and spherical anisotropy (SA) was calculated for each model. Linear regression was used to determine the predictive capacity of SA on the fiber area, fiber diameter, and surface area to volume ratio of the models. Additionally, a rat model of muscle hypertrophy was scanned using a single PFG and a double PFG pulse sequence, and the restricted diffusion measurements were compared with histological measurements of microstructure. Excellent agreement between SA and muscle fiber area (r2 = 0.71; p < 0.0001), fiber diameter (r2 = 0.83; p < 0.0001), and surface area to volume ratio (r2 = 0.97; p < 0.0001) in simulated models was found. In a scanned rat leg, the distribution of these microstructural features measured from histology was broad and demonstrated that there is a wide variance in the microstructural features observed, similar to the SA distributions. However, the distribution of fractional anisotropy measurements in the same tissue was narrow. This study demonstrates that SA-a scalar value from diffusion tensor subspace imaging analysis-is highly sensitive to muscle microstructural features predictive of function. Furthermore, these techniques and analysis tools can be translated to real experiments in skeletal muscle. The increased dynamic range of SA compared with fractional anisotropy in the same tissue suggests increased sensitivity to detecting changes in tissue microstructure.

A second order asymptotic model for diffusion MRI in permeable media

Starting from a reference partial differential equation model of the complex transverse water proton magnetization in a voxel due to diffusion-encoding magnetic field gradient pulses, one can use periodic homogenization theory to establish macroscopic models. A previous work introduced an asymptotic model that accounted for permeable interfaces in the imaging medium. In this paper we formulate a higher order asymptotic model to treat higher values of permeability. We explicitly solved this new asymptotic model to obtain a system of ordinary differential equations that can model the diffusion MRI signal and we present numerical results showing the improved accuracy of the new model in the regime of higher permeability.

Structure and Ionic Conductivity of Li-Disordered Bismuth o-Thiophosphate Li60-3xBi16+x(PS4)36.

The structure of the first lithium-containing bismuth ortho (o)-thiophosphate was determined using a combination of powder X-ray, neutron, and electron diffraction. Li60-3xBi16+x(PS4)36 with x in the range of 4.1-6.5 possesses a complex monoclinic structure [space group C2/c (No. 15)] and a large unit cell with the lattice parameters a = 15.4866 Å, b = 10.3232 Å, c = 33.8046 Å, and β = 85.395° for Li44.4Bi21.2(PS4)36, in agreement with the structure as observed by X-ray and neutron pair distribution function analysis. The disordered distribution of lithium ions within the interstices of the dense host structure and the Li ion dynamics and diffusion pathways have been investigated by solid-state nuclear magnetic resonance (NMR) spectroscopy, pulsed field gradient NMR diffusion measurements, and bond valence sum calculations. The total lithium ion conductivities range from 2.6 × 10-7 to 2.8 × 10-6 S cm-1 at 20 °C with activation energies between 0.29 and 0.32 eV, depending on the bismuth content. Despite the highly disordered nature of lithium ions in Li60-3xBi16+x(PS4)36, the underlying dense host framework appears to limit the dimensionality of the lithium diffusion pathways and emphasizes once more the necessity of a close inspection of the structure-property relationships in solid electrolytes.

Structure and dynamics of ILs-based gel polymer electrolytes and its enhanced conductive properties with the incorporation of Al2O3 nanofibers

This work reports the enhanced mobility of ions in ionic liquid (IL)-based gel polymer electrolytes (GPEs) with the incorporation of Al2O3 nanofibers. A combination of PVDF-HFP, EMIMTFSI and LiTFSI with 3 wt% Al2O3 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 Al2O3 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 Al2O3 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 Al2O3 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 27Al, 1H, 13C, 19F nuclei including 2D 13C{1H} HETCOR NMR experiments. The 13C 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, Al2O3 nanofibers significantly affect the dynamics of ionic species that are present in the mobile phase between the polymer chains.

Nuclear Magnetic Resonance Studies of Bicontinuous Liquid Crystalline Phases of Cubic Symmetry: Transport Properties from 2H Nuclear Magnetic Resonance Relaxation Rates.

The ternary system didodecyltrimethylammonium bromide, 1-decanol, and water forms an extended reversed continuous phase of cubic symmetry at 25 °C. The cubic phase belongs to the space group Im3m, as shown by small-angle X-ray experiments. We present extensive deuterium NMR relaxation data from this cubic phase for 1-decanol, deuterated at the carbon adjacent to the hydroxyl carbon position. 2H spin-lattice (R1) and spin-spin (R2) relaxation rates were measured over the existence region of the cubic phase, which extends from 0.2 to 0.6 in volume fraction of the dividing bilayer surface of the cubic phase. The data are interpreted with an existing theoretical framework for NMR spin relaxation in bicontinuous cubic phases, which takes its starting point in the description of bicontinuous phases using periodic minimal surfaces. Specifically, we obtain the self-diffusion coefficient over the minimal surface in one unit cell for 1-decanol. We also present pulsed field gradient NMR-derived self-diffusion data for didodecyltrimethylammonium bromide and compare the two sets of data. The diffusion data for both components show a mild, if any, dependence on the volume fraction of the bilayer surface. Furthermore, we present diffusion data for the water component in the cubic phase. Finally, we discuss the influences of the choice of the value of the product of the deuterium quadrupole constant and the order parameter S. Within the framework of the model used to analyze the relaxation data, a value for this parameter is required. As an initial value, we rely on measurements of deuterium quadrupolar splittings from deuterated decanol in an anisotropic phase.

Cations impact radical reaction dynamics in concentrated multicomponent aqueous solutions.

Ultraviolet (UV) photolysis of nitrite ions (NO2-) in aqueous solutions produces a suite of radicals, viz., NO·, O-, ·OH, and ·NO2. The O- and NO· radicals are initially formed from the dissociation of photoexcited NO2-. The O- radical undergoes reversible proton transfer with water to generate ·OH. Both ·OH and O- oxidize the NO2- to ·NO2 radicals. The reactions of ·OH occur at solution diffusion limits, which are influenced by the nature of the dissolved cations and anions. Here, we systematically varied the alkali metal cation, spanning the range from strongly to weakly hydrating ions, and measured the production of NO·, ·OH, and ·NO2 radicals during UV photolysis of alkaline nitrite solutions using electron paramagnetic resonance spectroscopy with nitromethane spin trapping. Comparing the data for the different alkali cations revealed that the nature of the cation had a significant effect on production of all three radical species. Radical production was inhibited in solutions with high charge density cations, e.g., lithium, and promoted in solutions containing low charge density cations, e.g., cesium. Through complementary investigations with multinuclear single pulse direct excitation nuclear magnetic resonance (NMR) spectroscopy and pulsed field gradient NMR diffusometry, cation-controlled solution structures and extent of NO2- solvation were determined to alter the initial yields of ·NO and ·OH radicals as well as alter the reactivity of NO2- toward ·OH, impacting the production of ·NO2. The implications of these results for the retrieval and processing of low-water, highly alkaline solutions that comprise legacy radioactive waste are discussed.

Study of Speciation and Transport Properties for Different Compositions of Carbonates in Li2CO3–Na2CO3 and Li2CO3–K2CO3 Binary Systems at High Temperature in Molten State

Molten alkali carbonates play a central role in carbon-capture technologies. To characterize the structural and transport properties, we used NMR, pulse field gradient (PFG) NMR, electrical impedancemetry, and molecular dynamics simulation. Different compositions in Li2CO3–Na2CO3 and Li2CO3–K2CO3 binary systems at 1003 K have been studied. The NMR measurements confirmed only the presence of anionic species CO32– whatever the composition. Some structural evolution of K+ and Li+ cations around the oxygen was detected in the composition Li2CO3–K2CO3. With the addition of K2CO3 in the carbonate mixture, the interaction between the charge carriers present in the liquid increases and results in a decrease of electrical conductivity.

Water and Molecular Exchange in Biological Cells Studied Using 1H Pulsed Field Gradient NMR.

This review presents the results of studies of molecular exchange processes in various biological systems (erythrocytes, yeast, liposomes, etc.) performed using pulsed field gradient NMR (PFG NMR). The main theory of processing necessary for the analysis of experimental data is briefly presented: the extraction of self-diffusion coefficients, calculation of cell sizes, and permeability of cell membranes. Attention is paid to the results of assessing the permeability of biological membranes for water molecules and biologically active compounds. The results for other systems are also presented: yeast, chlorella, and plant cells. The results of studies of the lateral diffusion of lipid and cholesterol molecules in model bilayers are also presented.

PAP(248-286) Conformational Changes during the Lag Phase of Amyloid Fibril Formation.

The initial stage of fibril formation of C-terminal region PAP(248-286) of human seminal plasma protein prostatic acid phosphatase was considered. Amyloid fibrils from the peptide PAP(248-286) are termed as a semen-derived enhancer of viral infection (SEVI) found in abundant quantities in semen. The kinetics of the amyloid fibril formation process consists of two characteristic phases (lag phase/nucleation phase and growth phase/elongation phase). The lag phase can be caused by the presence of mature amyloid fibrils (seeds) in protein solution, so-called secondary nucleation. The secondary nucleation includes interaction of protein monomers with the mature fibril surface that leads to protein spatial structural changes for further amyloid fibril formation. In this work, changes of the PAP(248-286) spatial structure were obtained during the secondary nucleation phase. Pulsed-field gradient (PFG) NMR was used to characterize the behavior of monomeric PAP(248-286) in water solution after PAP(248-286) seed addition. The self-diffusion coefficient showed compactization of the peptide monomer due to fibril-monomer interactions. PAP(248-286) spatial structural changes were detected with the help of high-resolution NMR spectroscopy and molecular dynamics (MD) simulation. The folding of PAP(248-286) occurs due to backbone chain bending in the region of H270 and T275 amino acid residues. Obtained folded conformation of PAP(248-286) emerging in the secondary nucleation process is energetically favorable and retains after monomer-amyloid interaction. The structural changes are associated with localization of PAP(248-286) hydrophobic surface regions, which are probably responsible for peptide monomer-amyloid interactions.

Water Diffusion and Uptake in Injectable ETTMP/PEGDA Hydrogels.

Differential scanning calorimetry (DSC) and pulsed field gradient spin echo nuclear magnetic resonance (PFGSE NMR) were used to characterize water in hydrogels of ethoxylated trimethylolpropane tri-3-mercaptopropionate (ETTMP) and poly(ethylene glycol) diacrylate (PEGDA). Freezable and nonfreezable water were quantified using DSC; water diffusion coefficients were measured using PFGSE NMR. No freezable water (free or intermediate) was detected from DSC for hydrogels of 0.68 and greater polymer mass fractions. Water diffusion coefficients, from NMR, decreased with increasing polymer content and were assumed to be weighted averages of free and bound water contributions. Both techniques showed decreasing ratios of bound or nonfreezable water mass per polymer mass with increasing polymer content. Swelling studies were used to quantify the equilibrium water content (EWC) to determine which compositions would swell or deswell when placed in the body. At 30 and 37 °C, fully cured, non-degraded ETTMP/PEGDA hydrogels at polymer mass fractions of 0.25 and 0.375, respectively, were shown to be at EWC.

New Network Polymer Electrolytes Based on Ionic Liquid and SiO2 Nanoparticles for Energy Storage Systems.

Elementary processes of electro mass transfer in the nanocomposite polymer electrolyte system by pulse field gradient, spin echo NMR spectroscopy and the high-resolution NMR method together with electrochemical impedance spectroscopy are examined. The new nanocomposite polymer gel electrolytes consisted of polyethylene glycol diacrylate (PEGDA), salt LiBF4 and 1-ethyl-3-methylimidazolium tetrafluoroborate (EMIBF4) and SiO2 nanoparticles. Kinetics of the PEGDA matrix formation was studied by isothermal calorimetry. The flexible polymer-ionic liquid films were studied by IRFT spectroscopy, differential scanning calorimetry and temperature gravimetric analysis. The total conductivity in these systems was about 10-4 S cm-1 (-40 °C), 10-3 S cm-1 (25 °C) and 10-2 S cm-1 (100 °C). The method of quantum-chemical modeling of the interaction of SiO2 nanoparticles with ions showed the advantage of the mixed adsorption process, in which a negatively charged surface layer is formed from Li+ BF4- ions on silicon dioxide particles and then from ions of the ionic liquid EMI+ BF4-. These electrolytes are promising for use both in lithium power sources and in supercapacitors. The paper shows preliminary tests of a lithium cell with an organic electrode based on a pentaazapentacene derivative for 110 charge-discharge cycles.

Influence of polymer modification on intra-MOF self-diffusion in MOF-based mixed matrix membranes

Mixed-matrix membranes (MMMs) represent a promising membrane type for gas and liquid separations. Such membranes can be formed by dispersing crystals of metal–organic frameworks (MOFs) in polymers. For liquid separations, crosslinked polymers are desirable because crosslinking reduces polymer dilation and plasticization effects by liquid sorbates. However, polymer crosslinking processes can unfavorably change transport and related structural properties of MOF fillers. In this work, 13C pulsed field gradient (PFG) NMR was used to investigate possible changes in intra-MOF self-diffusion of p-xylene and o-xylene after MMM polymer crosslinking. The studied MMMs were formed by dispersing MOF crystals of the type ZIF-71 in Torlon (a poly(amide-imide)) or Matrimid (a polyimide) polymers. The reported PFG NMR data indicate that the polymer crosslinking process used does not influence the intra-ZIF diffusivities when all effects on these diffusivities that are related to diffusing molecules crossing over the crystal boundaries or reflected away from these boundaries are removed. In contrast, these data show that the crosslinking process resulted in a significant decrease of the effective size of ZIF-71 crystals inside the studied MMMs, especially in the ZIF-71/Matrimid MMM. This crystal size decrease is attributed to a partial degradation of the ZIF-71 crystals inside the MMMs due to the crosslinking process. This conclusion was found to be in agreement with the results of electron microscopy analysis. PFG NMR studies and data analysis similar to those presented here can be used for quantifying any types of MOF crystal degradation inside MOF-based MMMs.

Hydration and Mobility of Alkaline Metal Cations in Sulfonic Cation Exchange Membranes.

The interconnection of ionogenic channel structure, cation hydration, water and ionic translational mobility was revealed in Nafion and MSC membranes based on polyethylene and grafted sulfonated polystyrene. A local mobility of Li+, Na+ and Cs+ cations and water molecules was estimated via the 1H, 7Li, 23Na and 133Cs spin relaxation technique. The calculated cation and water molecule self-diffusion coefficients were compared with experimental values measured using pulsed field gradient NMR. It was shown that macroscopic mass transfer is controlled by molecule and ion motion near sulfonate groups. Lithium and sodium cations whose hydrated energy is higher than water hydrogen bond energy move together with water molecules. Cesium cations in possession of low hydrated energy are directly jumping between neighboring sulfonate groups. Cation Li+, Na+ and Cs+ hydration numbers (h) in membranes were calculated from 1H chemical shift water molecule temperature dependences. The values calculated from the Nernst-Einstein equation and the experimental conductivity values were close to each other in Nafion membranes. In MSC membranes, calculated conductivities were one order of magnitude more compared to the experimental ones, which is explained by the heterogeneity of the membrane pore and channel system.

Effect of Poloxamer Binding on the Elasticity and Toughness of Model Lipid Bilayers.

Poloxamers, also known by their trade name, Pluronics, are known to mitigate damage to cellular membranes. However, the mechanism underlying this protection is still unclear. We investigated the effect of poloxamer molar mass, hydrophobicity, and concentration on the mechanical properties of giant unilamellar vesicles, composed of 1-palmitoyl-2-oleoyl-glycero-3-phosphocholine, using micropipette aspiration (MPA). Properties including the membrane bending modulus (κ), stretching modulus (K), and toughness are reported. We found that poloxamers tend to decrease K, with an impact largely dictated by their membrane affinity, i.e., both a high molar mass and less hydrophilic poloxamers depress K at lower concentrations. However, a statistically significant effect on κ was not observed. Several poloxamers studied here showed evidence of membrane toughening. Additional pulsed-field gradient NMR measurements provided insight into how polymer binding affinity connects to the trends observed by MPA. This model study provides important insights into how poloxamers interact with lipid membranes to further understanding of how they protect cells from various types of stress. Furthermore, this information may prove useful for the modification of lipid vesicles for other applications, including use in drug delivery or as nanoreactors.

Nuclear magnetic resonance signal decay in the presence of a background gradient: Normal and anomalous diffusion.

A novel way for calculating the diffusion-weighted nuclear magnetic resonance (NMR) attenuation signal expression in the presence of a background gradient is developed. This method is easily applicable to NMR-attenuated signals arising from any pulse field gradient sequence experiments. Here, we provide detailed calculations for the classical pulsed gradient stimulated echo and the pulsed gradient spin echo, as the particular cases. Within this general theoretical framework, devised for Gaussian processes with stationary increments, we recover and extend the previous Stejskal-Tanner results in the case of normal diffusion and we furnish a new expression in the case of anomalous diffusion.

Lithium Aluminate Nanoflakes as an Additive to Sulfur Cathodes for Enhanced Mass Transport in High-Energy-Density Lithium-Sulfur Pouch Cells Utilizing Sparingly Solvating Electrolytes.

The utilization of sparingly solvating electrolytes has been reckoned as a promising approach to realizing high-energy-density lithium-sulfur batteries under lean electrolyte conditions through decoupling the electrolyte amount from sulfur utilization. However, the inferior wettability of high-concentration sparingly solvating electrolytes compromises mass transport, thereby impeding the maximum utilization of active material in sulfur cathodes. To address this issue, in this study, we incorporate lithium aluminate (LiAlO2) nanoflakes as an additive to sulfur cathodes to enhance the mass transport by improving the percolation and accessibility of sparingly solvating electrolytes to the bulk of the electrodes. The electrochemical kinetics of LiAlO2-containing sulfur cathodes are investigated using the galvanostatic intermittent titration technique. The Li+ self-diffusion coefficients of electrode materials were estimated through pulsed-field gradient nuclear magnetic resonance (PFG-NMR) spectroscopy. Finally, a 193 Wh kg-1 Li-S pouch cell (excluding the mass of the laminated Al pouch) is demonstrated by utilizing the LiAlO2-incorporated sulfur cathode with a high S-loading of 4.3 mg cm-2 in a low electrolyte/sulfur (E/S) ratio of 3 μL mg-1. The Li-S pouch cell retains 80% of its initial specific cell capacity after 50 cycles. Our comprehensive understanding of the role of LiAlO2 additives in enhancing the mass transport and Li+ self-diffusion coefficient of sulfur cathodes will contribute immensely toward the development of high-energy-density Li-S batteries under lean electrolyte conditions.