Nonionic Research Articles

Electrocapacitive removal of Na and Cd ions from contaminated aqueous solution using Fe3O4-poly (3,4-ethylenedioxythiophene) poly(styrene sulfonate) modified chitosan nanosheets.

Chitosan nanosheets (NS) stabilized on poly (3,4-ethylenedioxythiophene): poly(styrene sulfonate) (PEDOT: PSS) was functionalized using Fe3O4 to capacitively remove chloride ions and toxic cadmium ions at optimized pH, concentration, and number of charging cycles. The synthesis procedure was investigated by Fourier transform infrared spectroscopy (FTIR), X-Ray Diffractometer (XRD), Transmission Electron Microscope (TEM), Scanning Electron Microscope - Energy Dispersive X-ray Spectroscopy (SEM-EDS), and Brunauer-Emmett-Teller (BET). The analyses confirms increase in surface area of the nanocomposite from 41 to 132 m2/g and a decrease in crystallinity from 75.3 to 66.9% after nanosheet formation. The highest sorption exchange capacity (SEC) for this work, 93% CdCO3 removal is achieved at 100 CDI cycles while 82% NaCl removal was achieved at 80 cycles. The SEC% increased with pH during Na ion deionization and decreased with pH during Cd removal. The works shows that chitosan is able to impart advanced structural properties to Fe3O4 and PEDOT and is able to reduce reverse migration of ions from electrodes to bulk solution, leading to higher SEC performance.

Designing Tin and Hard Carbon Architecture for Stable Sodium‐Ion Battery Anode

The lack of anodes stability is one among key barriers to the widespread commercialization of sodium‐ion batteries (SIBs). This is attributed to graphite, a well‐known common anode material for a range of commercial batteries including lithium‐ion batteries (LIBs), which limits the insertion of sodium (Na) ions due to their large ionic size. Tin (Sn) has shown its potential as a suitable anode material because it exhibits high capacities in conversion and alloying reactions. However, it endures significant volumetric expansion and slower reaction rates during sodiation. To overcome these challenges, this work presents a novel anode material for SIBs where a 2D layered architecture of Sn with a hard carbon (HC) buffer layer is engineered using physical vapor deposition technique. This novel anode (SnHT/HC) exhibits a high initial capacity of 470 mAhg−1 and an exceptional retention of 438 mAhg−1 after 3000 cycles at 0.2C, with 99 % Coulombic efficiency. SnHT/HC testing at varying fast charge and discharge C‐rate of 5C, 10C, 15C, and 50C has shown promising results. Better electron transport and reduced volumetric changes are perceived to enhance the overall performance of SnHT/HC electrodes.

Conduction channel creation by interstitial site engineering in otherwise insulating Na6ZnS4 for Na-conducting solid-state electrolytes

Na5.6Zn0.6Ga0.4S4, which retains the crystalline structure of its parent form Na6ZnS4, is described as a new class of Na-conducting solid-state electrolytes (SSEs) for all-solid-state batteries. We demonstrate that while Na6ZnS4 is ionically insulating (1.4 nS cm-1), Ga-substitution results in an astonishing improvement of ionic conductivity (σion) to 70.1 μS cm-1, making Na5.6Zn0.6Ga0.4S4 a practical SSE. This dramatic increase in σion (5 × 104 fold) is associated with an increased Na+ occupancy in interstitial sites as ‘x’ increases in Na6-xZn1-xGaxS4, where interstitial Na ions facilitate long-range Na+ conduction, which is otherwise immobile. Ga-substitution also results in phase-pure Na6-xZn1-xGaxS4, contributing at least partially to the enhancement of σion. Furthermore, Na6-xZn1-xGaxS4 exhibits neither releasing H2S gas nor compromising its crystalline structure for several hours under ambient conditions. Ga-substitution also enhances electrochemical stability. While the anodic limit remains largely unchanged, the cathodic limit is significantly lowered from 0.99 V vs. Na2Sn in Na6ZnS4 to 0.35 V in Na5.6Zn0.6Ga0.4S4, resulting in stable Na alloying/dealloying reactions in a symmetric Na2Sn ‖ Na2Sn cell. These findings are comprehensively supported by various experimental and theoretical methods. Finally, we construct a full cell (Na2Sn ‖ TiS2) and demonstrate the practicality of Na5.6Zn0.6Ga0.4S4 as a promising SSE in all solid-state Na ion batteries.

Enhancing strawberry resilience to saline, alkaline, and combined stresses with light spectra: impacts on growth, enzymatic activity, nutrient uptake, and osmotic regulation

BackgroundThis study examines the effects of various complementary light spectra on the growth, development, antioxidant activity, and nutrient absorption in strawberry plants under stress conditions. Light-emitting diodes (LEDs) were used to provide specific wavelengths, including monochromatic blue (460 nm), monochromatic red (660 nm), a dichromatic mix of blue and red (1:3 ratio), full-spectrum white light (400–700 nm), and ambient light as a control (no LED treatment). The stress treatments applied were: control (no stress), salinity (80 mM NaCl), alkalinity (40 mM NaHCO₃), and a combined salinity/alkalinity condition.ResultsOur results indicated that complementary light spectra, especially red and blue/red, helped mitigate the adverse effects of stress on plant growth and development. These spectra improved plant tolerance by enhancing the activity of polyphenol oxidase and peroxidase enzymes and increasing starch accumulation in the leaves. Furthermore, under stress conditions, red and blue-red light significantly boosted fruit anthocyanin levels. Although stress elevated antioxidant activity, supplementary light reduced this activity by alleviating stress compared to ambient light. While stress led to increased Na and Cl ion concentrations in leaves, treatments with blue, red, and blue-red light minimized these harmful effects and promoted the absorption of beneficial ions such as K, Mg, Fe, and Cu.ConclusionsAdjusting light quality significantly influences the morphology and physiology of strawberry plants, underscoring the role of specific light spectra in promoting optimal growth under stress conditions.Clinical trial numberNot applicable

XPS analysis of damp heat aged and fractured polymer/glass laminates

Essential for the durability of photovoltaic (PV) modules is the polymeric encapsulant. In addition to the well-established ethylene vinyl acetate copolymers (EVA), polyolefin elastomers (POE) are gaining market relevance. The main objective of this paper was to elucidate the ageing and degradation mechanisms of PV relevant glass laminates based on UV-transparent EVA and POE encapsulants by X-ray photoelectron spectroscopy (XPS).Special focus was given to the polymer/glass interfaces. Therefore, glass laminates were damp heat aged and debonded by monotonic compressive shear testing. Subsequently, the polymer side of the fractured surfaces was characterized by XPS and Fourier-transform infrared spectroscopy (FTIR). The polar EVA encapsulant revealed more pronounced deterioration than the less polar POE material.Significant differences were already discernible after 1kh of damp heat exposure. The diffusion of Na ions from the glass substrate into the polymer matrix and the formation of Na salts at the interface were ascertained for EVA and to a less extent also for POE. While EVA laminates failed primarily close to the interface, but still within the EVA material, glass residues were detected on the fractured POE surfaces indicating interface-near glass corrosion and a fracture path propagating back and forth within POE and glass.

Analysis of interlayer dependency of MoS2/g-C3N4 heterostructure as an anode material for sodium-ion batteries

In this present work, we explore the effectiveness of layered molybdenum disulfide (2H-MoS2) and graphitic carbon nitride (g-C3N4) heterostructure as anode for Sodium-Ion Batteries (SIBs) by using first principles analysis. To study the anode properties, we varied the interlayer distance between 2H-MoS2/g-C3N4 as 3Å, 6Å, 9Å,12 Å, and 14 Å between MoS2 as substrate and g-C3N4 as top layer. The fundamental properties, such as structural stability and electronic structure were analysed for the respective systems. The adsorption kinetics of Na ion on the g-C3N4 layer were analysed by performing molecular dynamics (MD) simulations to understand the adsorption mechanism better. Our results showed that the interlayer distance of 6 Å with formation energy of −4.31 eV, the theoretical specific capacity value of 765.32 mAhg−1, the average electrode potential is between 0.8 and 1.3 V and the adsorption energy of −2.16 eV is suitable for MoS2/g-C3N4 based anodes for Na ion batteries.

Occurrence and efficient removal of PFAS from landfill leachates using on-site DTRO systems: A comprehensive analysis across 11 Chinese cities

Per- and polyfluoroalkyl substances (PFAS), known for their persistent toxicity and mobility, pose significant environmental and human health risks. Here we explored the occurrence and efficacy of on-site Double-Pass Reverse Osmosis (DTRO) systems in removing 30 different PFAS from landfill leachates in 11 diverse cities across China. PFAS concentrations in landfill leachate ranged from 938 to 32,491 ng/L, averaging 6,486 ng/L, predominantly comprising short-chain PFAS, notably perfluorobutane sulfonate (PFBS). Notable emerging substitutes like 6:2 fluorotelomer sulfonate, fluorobutane sulfonamide, and 9-chlorohexadecafluoro-3-oxanone sulfonate were also identified. The PFAS levels correlated positively (r2 = 0.79, p < 0.01) with regional economic development, with coastal areas exhibiting higher concentrations than inland regions. The DTRO membrane filtration and ion exchange resin achieved an average removal efficiency of 94 % for ∑30PFAS and even 99.97 % for PFBS (the concentration of PFBS in the raw leachate ranged from 226.36 ng/L to 27,935.61 ng/L, with an average concentration of 4,506.88 ng/L). The Na ion exchange resin had a limited effect on further reducing the PFAS concentration. Our findings not only contribute to the theoretical understanding of PFAS behavior in landfill leachates but also offer a practical engineering applications for global waste management practices.

Na-doped cobalt spinel electrocatalysts prepared by programmed electrostatic spraying for improving OER activity and durability in acidic media

The daunting challenge to establish a trade-off among the activity, durability, and cost of electrocatalysts for oxygen evolution reaction (OER) with sluggish reaction kinetics impedes the practical green energy conversion. Hereby, a non-noble metal-based electrocatalyst (i.e., Na-doped Co3O4) was in-situ prepared by programmed electrostatic spraying as an advanced alternative to the costly and scarce state-of-the-art IrO2 and RuO2-based electrocatalysts. The utilization of this sprayer facilitates intimate contact with the substrate electrode and provides short ion diffusion paths, facilitating efficient electron transport. Additionally, the doping of Na ions into the Co3O4 structure results in structural distortion and charge redistribution, leading to the generation of oxygen vacancies (OVs). These OVs enhance the activity of lattice oxygen atoms, thus enabling rapid and durable oxygen evolution in an acidic media (0.5 M H2SO4). The optimal Na-Co3O4 (AA) exhibits a notably low overpotential of 360 mV@10 mA·cm−2 and at least 200 h stability. In addition, density functional theory (DFT) calculations confirm that the incorporation of Na ions significantly elevates electrical conductivity by decreasing the energy band gap and reduces the free energy barrier for the conversion of *O to *OOH, thereby improving the intrinsic OER activity. Finally, by implanting the catalyst in a single-cell proton exchange membrane water electrolyzer (PEMWE), the current density of 100 mA·cm−2 is achieved at a voltage of 1.62 V. This innovative non-noble metal catalyst holds great potential for scalable PEMWE anodes.

Cold Consolidation of Pharmaceutical Waste Glass Powders Through Alkali Activation and Binder Jet 3D Printing.

The recent COVID-19 emergency has led to an impressive increase in the production of pharmaceutical vials. This has led to a parallel increase in the amounts of waste glass; manufacturers typically recover material from faulty containers by crushing, giving origin to an unrecyclable fraction. Coarse fragments are effectively reused as feedstock for glass melting; on the contrary, fine powders (<100 microns), contaminated by metal and ceramic particles due to the same crushing operations, are landfilled. Landfilling is also suggested for pharmaceutical containers after medical use. This study aims at proposing new opportunities for the recycling of fine glass particles, according to recent findings concerning alkali activation of pharmaceutical glass, combined with novel processing, i.e., binder jetting printing. It has already been shown that pharmaceutical glass, immersed in low-molarity alkaline solution (not exceeding 2.5 M NaOH), undergoes surface dissolution and hydration; cold consolidation is later achieved, upon drying at 40-60 °C, by a condensation reaction occurring at hydrated layers of adjacent particles. Binder jetting printing does not realize a full liquid immersion of the glass powders, as the attacking solution is selectively sprayed on a powder bed. Here, we discuss the tuning of key parameters, such as the molarity of the attacking solution (from 2.5 to 10 M) and the granulometry of the waste glass, to obtain stable printed blocks. In particular, the stability depends on the formation of bridges between adjacent particles consisting of strong T-O bonds (Si-O-Si, Al-O-Si, B-O-Si), while degradation products (concentrating Na ions) remain as a secondary phase, solubilized by immersion in boiling water. Such stability is achieved by operating at 5 M NaOH.

Kinetic Study of NaF Gas Formation During Mold Flux Melting Based on Different Fluorides by Experimental and Computational Methods

Low‐basicity fluorine‐containing mold flux, which forms a porous slag film with NaF pores, is expected to solve the contradiction between heat transfer and lubrication in the continuous casting of peritectic steel. Herein, the kinetic mechanism and the influence of NaF gas formation based on the different fluorine raw materials (NaF, CaF2, and Na3AlF6) at 0.9 basicity and 6 wt% fluorine are investigated by the combination of experiments and calculations. The results show that CaF2 is the first to generate NaF gas at 1189 K, followed by Na3AlF6 (1238 K) and NaF (1328 K). NaF raw material produces the most NaF gas with the lowest activation energy in the three raw materials, due to high Na ion kinetic energy, the simple degree of polymerization, and Na‐F1 bonds. Correspondingly, NaF bubbles in the molten slag are the largest based on their aggregation. Na3AlF6 and CaF2 raw materials rank second and third, with F atoms primarily bonded as Al‐Fx and Ca‐Fx and the higher proportion of and structure. Notably, at 0.9 basicity and 6 wt% fluorine, Na3AlF6 as raw material generates a suitable amount of gas, making diffuse and fine NaF bubbles in the molten slag.

ABA deficiency and its impact on ion and metabolite profiles in tomato roots under single and combined stress conditions

Abscisic acid (ABA) plays a crucial role in the stress response of plants. Although the impact of ABA on individual stresses has been extensively studied, there is less research on its role in plants grown under stress combination, such as salinity and high temperature. This study analyzes the response at the ionomic and metabolomic levels of tomato roots to ABA deficiency under single salinity or heat stress, as well as under the combination of both stresses, using ABA-deficient (flacca, flc) tomato plants. ABA was found to be crucial in ionic regulation, particularly for Na, K, Ca, and other ions such as Cu, Mn, Zn, Mo, and Fe. However, its influence depended on the type of stress applied, indicating the complexity of plant responses to these adverse environmental factors. In our study, phenylpropanoids, terpenoids, and nitrogenous compounds were the metabolites most affected by endogenous ABA concentration and environmental treatment. On the other hand, the application of exogenous ABA to flc mutants did not fully restore root dry weight, although it did cause significant changes at the ionomic and metabolomic levels. Salinity and heat applied in combination aggravated the vulnerability of flc mutants compared to single stresses, making the application of exogenous ABA more effective under single stresses than under the combined stresses. Finally, a correlation analysis between the ionome and metabolome revealed that the accumulation or deficiency of some ions (i.e., Na, Zn, and Fe) was correlated with the abundance of important metabolites related to amino acid biosynthesis and terpenoid metabolism, among others.

Atomic-scale probing of ion migration dynamics in Na3Ni2SbO6 cathode for sodium ion batteries

Honeycomb-layered phases like Na3Ni2SbO6 have been extensively researched as high-voltage and high-rate capability cathode materials for sodium-ion batteries. However, our understanding of the structural stability and dynamic reaction mechanisms of Na3Ni2SbO6 cathode during cycling, especially at atomic-scale, remains limited. Here, we track the microstructure evolution during extraction of Na+ ions in Na3Ni2SbO6 cathode at atomic scale in an aberration-corrected transmission electron microscope. The electron beam irradiation that can provide a driving force for the Na+ ion migration, allows us to mimic the battery charge process. By controlling the electron beam dose, we study the structure evolution behavior to obtain insights into understanding the work principle and failure mechanism of Na3Ni2SbO6 cathode under different charge rate conditions. We find that the real-time structural evolution and ion migration pathways of Na3Ni2SbO6 cathode are distinct under different electron beam doses. High-dose irradiation reveals Na ion depletion, surface cracks, and phase transformations, mimicking rapid capacity decay. In contrast, low-dose irradiation shows slower ion migration, ordered Na vacancy formation, and maintaining structural integrity, which more closely resembles the electrochemical process of actual battery. This study provides an atomistic understanding of the structural stability and Na ions deintercalation mechanism in Na3Ni2SbO6 cathodes, offering new insights into optimizing electrode materials.

Environmentally sound geotechnologies for leaching metals from polymetallic ore processing wastes and wastewater

Global challenges (increased consumption of georesources, climatic changes, limited reserves) increase the relevance of the problems of growing waste accumulation and environmentally-sound modernization of mineral extraction. In this regard, the existing approaches to the design of geotechnologies for metal mining need to be improved based on a concept of so-called circulation waste management and ecologization of technological processes. The paper is devoted to the issue of formation of conceptual bases and directions of ecologization of geotechnologies at leaching metals from polymetallic ore processing wastes and wastewater. The study presents recommendations for improving in-situ leaching of ores in blocks, allowing to determine the optimal conditions for increasing the completeness of subsoil use and reducing environmental damage. It was revealed that at metal extraction with solution circulation through brine chambers the content of Na, Cl, SO4 and Ca ions in dialysate was low, while without circulation through brine, it significantly exceeded corresponding MPCs. This proves the fundamental feasibility of controlling natural leaching processes by enhancing the oxidizing potential of natural solvents through the addition of industrial oxidizing agents. It was found that increasing the duration of agitation leaching (both with and without mechanoactivation) leads to a uniform expansion of the local maximums of Pb yield from the pulp when the minimum NaCl concentration decreases from 11–12 to 7% at H2SO4 concentration of 0.6%. One of key results of the study is justifying the expansion of the use of disintegrators to realize targeted activation of tailings. The practical significance of the obtained results lies in the proved feasibility of optimizing the flow sheet of electrochemical extraction of metals from wastewater on the basis of the obtained regularities of the use of brine circulation through brine chambers. In addition, the totality of the obtained results of using a disintegrator for reextraction of lead from geomaterials will allow developing a methodology for calculating the parameters of mechanoactivation action to increase the degree of metal recovery from the tailings of North Ossetia-Alania’s (Zgidskoe, Sadonskoe, Arkhonskoe deposits) polymetallic ores beneficiation. The most promising way for further research is to substantiate methods of using underground space for complete removal of wastes (wastewater and tailings) after their multistage treatment.

Atomistic simulation of Na2Ti3O7: Defects, dopants, and diffusion properties

Na2Ti3O7 exhibits promise as a safe battery material for Na-ion batteries, currently undergoing extensive research. The atomistic simulation method is employed to scrutinize defects, dopant energies, and Na-ion migration in Na2Ti3O7. Notably, the Na-Frankel energy is the lowest, and the Na-anti-site cluster energy is lower than the Na-anti-site isolated energy. The migration of Na ions is observed to predominantly occur along the ab plane, where the activation energy is measured at 0.23 eV. K and Ge ions are identified as the most suitable isovalent and tetravalent dopants for Na and Ti sites, respectively. Furthermore, the introduction of the aliovalent dopant Al3+ ion on the Ti site can form additional Na+ ions. The electronic structures of the most favorable doped configurations are discussed.

Unveiling the Influence of Water Molecules on the Structural Dynamics of Prussian Blue Analogues.

3D-framework Prussian blue analogues (PBAs) are appealing as a cost-effective, sustainable cathodes for Na-ion batteries. However, the aqueous-based synthesis of PBAs inherently introduces three different forms of water molecules (surface, interstitial and crystal) into the structure. Removal of water molecules causes phase transformation from monoclinic (M) to rhombohedral (R). This work presents the effects of water molecules on the structure before the phase transformation temperature, employing two promising PBA cathodes, Na2Fe[Fe(CN)6]·1.69H2O and Na2Mn[Fe(CN)6]·1.76H2O. Specifically, the water molecules impact the molecular interactions at the local structure and the electrochemical properties. This work has performed calculations on low-vacancy Na2M[Fe(CN)6] PBAs (where M = Mn, Fe, Co, Ni and Cu) to understand the dehydration energy. Employing in situ high-temperature X-ray diffraction and Raman spectroscopy, this work observes that water removal induces negative thermal expansion and stronger interactions between C≡N and Na ions, resulting in biphasic reactions with sluggish kinetics. Additionally, water molecules play a role in maintaining the open 3D tunnels and facilitating a solid-solution like insertion of Na ions. Calculated phonon-Raman spectra provide insights into cyanide group deformations, revealing the interactions between water molecules, alkali-ions, and transition-metal ions. This study enhances the understanding of the relationship among electronic, vibrational, and electrochemical properties.

Influence of Wrinkle Structure on Properties of Na-doped ZnO Films

Un-doped ZnO and Na-doped ZnO (NZO) thin films with various Na doping concentrations were successfully fabricated on glass substrates by a sol-gel process. The effect of Na ions at concentrations of 0, 1, 2, 3, 4, and 5% on the crystalline structure, surface morphology, and optoelectronic properties of ZnO films was studied using appropriate measurement techniques. XRD analysis revealed a polycrystalline hexagonal wurtzite structure in the NZO films. The NZO films' average crystal size ranged from 17.7 nm to 19.6 nm. SEM micrographs showed that wrinkle network appeared in the pure and doped ZnO films due to solvent evaporation during the thermal annealing process. UV-Vis spectroscopy pointed out that the average transmittance of NZO films is as large as ca. 78%. The optical bandgap of the films varied slightly between 3.235 eV for the pure ZnO and 3.246 eV for the Na 5% doped NZO film. When Na ions were doped into the NZO films, the electrical conductivity improved. Moreover, the absorption figure of merit exhibited the largest value of 0.981 Ω-1cm-1 for the fabricated NZO films, which enables the use of these films for solar cells and for other optoelectronic applications.

Density Functional Investigations on 2D‐Be2C as an Anode for Alkali Metal‐Ion Batteries

ABSTRACTMetal‐ion batteries are in huge demand to cope with the increasing need for renewable energy, especially in automobiles. In this work, we apply first‐principle calculations to examine two‐dimensional beryllium carbide (2D‐Be2C) as a possible anode material for metal‐ion (Na and K) batteries. 2D‐Be2C is a semiconductor and becomes metallic by adsorbing metal ions. Negative adsorption energy indicates stable adsorption on the monolayer of Be2C. Alkali metal diffusion barrier and optimum path for minimum energy are studied within the framework of the climbing image nudged elastic band method. Here, six intermediate images are considered between the initial and final states. The lowest diffusion barriers for a single adsorbed Na and K atom are 0.016 and 0.026 eV, respectively. A maximum open circuit voltage of around 1 V is computed for K ions, whereas 0.5 V is for Na ions. Also, the maximum storage capacity of the Be2C monolayer is estimated at 1785 Ah/kg.

Functionalized MBene, Ti[formula omitted]BX[formula omitted] (X=Si, Ge, P, As) as potential excellent anode materials for lithium and sodium-ion batteries: A first-principles study

In the search for next-generation energy storage devices, superior-performance alternative electrode materials based on two-dimensional materials for rechargeable metal-ion batteries are essential. Here, we explored group III and IV functionalization of 2D Ti2B, Ti2BX2 (X=Si, Ge, P, As) as anode materials for Li and Na ion batteries using first-principles calculations. The structures had excellent metallic properties and demonstrated energetically favorable adsorptions for metal ions. Analyzing charge transfer and electronic band structures, silicon and phosphorous-functionalized Ti2B (Ti2BSi2 and Ti2BP2) showed the most potential. The energy band diagrams showed that both Ti2BSi2 and Ti2BP2 had metallic characteristics after Li and Na-ion adsorption, which offered considerable advantage for rechargeable-ion batteries. The structures exhibited low energy barriers for Li and Na-ion migration. The minimum energy barriers calculated for Na were 0.08 eV for Ti2BSi2 and 0.24 eV for Ti2BP2. Theoretical specific capacity and open circuit voltage were calculated using maximum layer adsorption. For both Li and Na, high values of specific capacity and low values of open circuit voltage (¡ 1 V) were found. Ti2BSi2 had the best performance, with a theoretical specific capacity of 1647.10 and 1317.68 mA h/g for Li and Na, respectively. Its open circuit voltages for Li and Na were 0.65 and 0.38 V. The insights of this study will be beneficial in fabricating high-performing Ti2BX2-based anodes for rechargeable Li and Na ion batteries.

Computational screening of sodium solid electrolytes through unsupervised learning

All-solid-state Na-ion batteries have emerged as alternatives to all-solid-state Li-ion batteries owing to the global abundance of Na element. However, finding a commercially viable Na-ion solid-state electrolyte (SSE) remains challenging due to the relatively poor understanding of the structures effective for conduction compared to those for Li-ion SSE. In this study, we develop a screening framework based on an unsupervised machine learning technique to characterize Na-ion SSEs according to their lattice structures. Specifically, we evaluate feature vectors encoding 180 structural properties for 12,670 materials containing Na ions. Subsequently, the resulting feature vectors are clustered using hierarchical density-based spatial clustering of applications with noise (HDBSCAN), leading to the discovery of 12 groups including those with experimentally proven Na-ion superionic conductors such as NASICONs and sodium chalcogenides. Post hoc analysis of these clusters reveals that the groups with high conductivity share similar characteristics, including the existence of ion channels for Na ions and the weak interactions between Na ions and the proximate atoms. Ab initio molecular dynamics simulations confirm that the promising groups exhibit exceptional ion diffusivity compared to other groups. By employing decision tree classifiers trained to screen promising groups, we demonstrate the rapid assessment of the potential of a given material. Finally, we offer perspectives and insights for the development of novel Na-ion SSEs for all-solid-state Na-ion batteries.

Na Vacancy-Driven Phase Transformation and Fast Ion Conduction in W-Doped Na3SbS4 from Machine Learning Force Fields.

Solid-state sodium batteries require effective electrolytes that conduct at room temperature. The Na3PnCh4 (Pn = P, Sb; Ch = S, Se) family has been studied for their high Na ion conductivity. The population of Na vacancies, which mediate ion diffusion in these materials, can be enhanced through aliovalent doping on the pnictogen site. To probe the microscopic role of extrinsic doping and its impact on diffusion and phase stability, we trained a machine learning force field for Na3-x W x Sb1-x S4 based on an equivariant graph neural network. Analysis of large-scale molecular dynamics trajectories shows that an increased Na vacancy population stabilizes the global cubic phase at lower temperatures with enhanced Na ion diffusion and that the explicit role of the substitutional W dopants is limited. In the global cubic phase, we observe large and long-lived deviations of atoms from the averaged symmetry, echoing recent experimental suggestions. Evidence of correlated Na ion diffusion is also presented that underpins the suggested superionic nature of these materials.