Large Particles Research Articles

Novel pullulan-sodium alginate film incorporated with anthocyanin-loaded casein-carboxy methyl cellulose nanocomplex for real-time fish and shrimp freshness monitoring

This study fabricated novel smart colorimetric film from pullulan (P) and sodium alginate (SA) incorporated with anthocyanin (ACNs) loaded casein carboxymethylcellulose (CAS-CMC-ACNs) nanocomplex for the freshness monitoring of the fish and shrimp. The ACNs loaded nanocomplex exhibited large particle size (176.902 ± 4.641 nm) than CAS-CMC (155.454 ± 4.152 nm) nanocomplex without ACNs, and can be loaded in P/SA film with uniform distribution. The P/SA film incorporated with CAS-CMC-ACNs nanocomplex had a more compact structure, improved barrier properties, mechanical strength, and thermal stability than P/SA film incorporated with free ACNs, which could be attributed to hydrogen bonding among the components in the film matrix, as confirmed by SEM micrographs and FT-IR. Intriguingly, the composite film exhibited antibacterial effect against gram-negative bacteria E. coli (Escherichia coli) and gram-positive bacteria S. aureus (Staphylococcus aureus) with inhibition zone of 7 ± 0.283 mm and 8.6 ± 0.141 mm, and antioxidant effect. The composite film demonstrated a visible response to CO2 and pH buffer. Furthermore, the composite smart film demonstrated the potential to monitor the freshness of fish and shrimp stored at 25 °C for 24 h via a visual color change from pink to dark grey. The findings revealed that the fabricated film is an effective tool for evaluating the freshness of fish and shrimp.

Hazard evaluation of ignition sensitivity and explosion severity for aluminum and aluminum powder-petroleum ether mixtures

The safety implications of aluminum powder and petroleum ether have garnered significant attention as two typical materials in the production process of energetic materials. To investigate the effect of the common solvent petroleum ether on the ignition and explosion characteristics of aluminum powder, ignition energy, flame propagation characteristics, and explosion pressure of three aluminum powder sizes and their mixtures with petroleum ether through a Hartmann tube test device and a 20 L spherical explosion vessel test system. Findings show that the ignition energy of aluminum powder initially decreases and then increases with the increase of petroleum ether content. At the petroleum ether concentration of 5.5 % and 11 %, the minimum ignition energies of the mixed systems of Al-Flake, Al-T4, and Al-T2 are 1–20 mJ, 5–30 mJ, 450–485 mJ, and 1–20 mJ, 5–25 mJ, 440–480 mJ, respectively. Lower than the minimum ignition energy of the original sample (1–30 mJ, 10–40 mJ, 470–510 mJ), indicating that the aluminum powder dust containing low concentration solvent (5.5%, 11 %) is more sensitive to an electric spark. The ignition energy of the mixed system is rather increased when the content of petroleum ether is further increased to 16.5 %. On the contrary, the probability of ignition and the electric spark sensitivity are decreased. With the addition of petroleum ether to Al-Flake and Al-T4, the flame propagation speed slightly decreases and the phase duration lengthens. The flame propagation characteristics and combustion state of Al-T2 with large particles remained largely unchanged after the addition of petroleum ether. During the 20 L spherical explosion vessel test, the maximum explosion pressure and explosion index of the mixed samples initially increase and then decrease with the increase in petroleum ether concentration. A small quantity of petroleum ether intensifies the reaction intensity of aluminum dust. At an aluminum powder dust concentration of 250 g m-3, the explosion pressure and explosion index of Al-Flake and Al-T4 peak at a petroleum ether content of 5.5 %, while Al-T2 reaches its peak at 11 %.

The effect of surface modification strategies on biological activity of titanium implant

The surface morphology of titanium metal is an important factor affecting its hydrophilicity and biocompatibility, and exploring the surface treatment strategy of titanium metal is an important way to improve its biocompatibility . In this study , titanium (TA4) was firstly treated by large particle sand blasting and acid etching (SLA) technology, and then the obtained SLA-TA4 was treated by single surface treatments such as alkali-heat, ultraviolet light and plasma bombardment. According to the experimental results, alkali-heat treatment is the best treatment method to improve and maintain surface hydrophilicity of titanium. Then, the nanowire network morphology of titanium surface and its biological property, formed by further surface treatments on the basis of alkali-heat treatment, were investigated. Through the cell adhesion experiment of mouse embryonic osteoblast cells (MC3T3-E1), the ability of titanium material to support cell adhesion and cell spreading was investigated after different surface treatments. The mechanism of biological activity difference of titanium surface formed by different surface treatments was investigated according to the contact angle, pit depth and roughness of the titanium sheet surface. The results showed that the SLA-TA4 titanium sheet after a treatment of alkali heat for 10 h and ultraviolet irradiation for 1 h has the best biological activity and stability. From the perspective of improving surface bioactivity of medical devices, this study has important reference value for relevant researches on surface treatment of titanium implantable medical devices.

Aerosol fluidized bed coating: Exploring the impact of process conditions on process yield, coating coverage and thickness

Aerosol droplets are used to coat fluidized particles in this work. Coating experiments utilizing aerosol droplets (with a mean diameter of around 1μm) were performed under different process conditions to explore their impact on process yield, as well as on coating coverage. Core materials were glass and porous γ-Al2O3, which had mean diameters of 653μm and 610μm, respectively. Sodium benzoate (NaB) solution and silicon dioxide (SiO2) nanosuspension were used as the coating liquid. After sampling, particle pictures were taken by a scanning electron microscope and analyzed using image processing to determine the coating coverage. To simulate the coating process and determine, for each experiment, a factor for preferential deposition on already occupied positions, Monte Carlo simulations were used. Also, some particles were cut in the middle to measure coating layer thickness. Intraparticle coating thickness distribution from Monte Carlo simulations coarsely matches the measured thickness from cut particles. Results show that the process yield, coating coverage, and preference factor are affected by experimental conditions such as expanded bed height, fluidization air temperature, atomizing pressure, the number of aerosol inlets, as well as the surface potential of core particles. This study is first to examine the impact of surface charge of different core materials on droplet deposition. In an experiment with SiO2 nanosuspension, γ-Al2O3 cores could be coated quite uniformly with SiO2 nanoparticles with a layer thickness of ca. 1.1μm. This shows the potential of aerosol droplet deposition as a novel semi-wet method for coating large particles with nanoparticles without using any binders.

Soot oxidation activity and stability of NMxCe1-xO2-y nanoparticles (NM = Pd, Rh, Ru) supported on functionalized alumina

NMxCe1-xO2-y (NM = Pd, Rh, Ru) nanoparticles deposited on functionalized alumina were studied as catalysts of soot oxidation reaction. The activity and stability of ceria nanoparticles increased with the dopant content and adequate method of the alumina functionalization. Using the support functionalized with a decane layer increased the nanoparticles' dispersion and improved the catalyst stability. After the first run of the reaction, some deactivation occurred in all doped systems, while in the subsequent runs, the catalysts were stable. The deactivation was caused by the shape and structure changes (decrease in the number of oxygen defects, exposure of less active (111) planes, and formation of large NMOx particles). The catalyst containing ceria particles doped with x = 0.05 ruthenium was the most active in all three soot oxidation runs with T50% = 448, 480, and 483 °C.

EVALUATION OF THE GRAPHENE DISPERSIONS FOR KEVLAR FABRICS FUNCTIONALIZATION OBTAINED BY THE LIQUID-EXFOLIATION OF GRAPHITE

The process where pristine graphite is subjected to a solvent treatment seems simple and scalable and has attracted the attention of researchers over many years. However, for successful exfoliation, overcoming the van der Waals attractions between the adjacent layers of graphite is necessary. Over time, several methods have been created to overcome the attraction between layers. Graphene’s liquid phase exfoliation (LPE) occurs due to the strong interactions between the solvent molecules and the basal planes of graphite, overcoming the energetic resistance to exfoliation and subsequent dispersion. Ultra sonication used for exfoliation can produce single or few layered graphene flakes. During sonication the sound waves propagate through liquid medium in alternating high- and low-pressure cycles, strong mechanical and thermal energy released by acoustic cavitation results in splitting up large particles into fine ones and dispersing them. Simultaneous insertion of solvent and/or intercalation molecules in between the graphite layers takes place supporting graphite separation into graphene layers. ; The dispersion capacity of graphene flakes depends on how appropriate the solvent properties are to the corresponding properties of graphene, such as surface tension, Hildebrand, and Hansen solubility parameters. Only certain solvents can disperse graphene well and form a dispersion appropriate for specific future applications. In addition, after exfoliation by ultra sonication graphene flakes aggregation due to the van der Waals attractions must be overcome to prepare in long-term stable dispersions of nanometres-size graphene sheets. ; The research has focused on the preparation of stable dispersion ready for transfer without intermediate processes to the Kevlar fabrics. An experimental comparison of the potentials of the 4 solvents for the application resulted in three corresponding to the intended use, two of them examined in detail, supplementing the composition of the LPE liquid medium with triethanolamine to obtain sufficient performance graphene coverage on Kevlar textile fibres.

Experimental study of solid particles in thermal energy storage systems for shell and tube heat exchanger: Effect of particle size and flow direction

The solid particle thermal energy storage method offers cost-effective, simple, and high-temperature suitable solutions. It effectively resolves chemical compatibility and thermal stress issues in shell-and-tube heat exchangers. This work studies the quartz sands' particle sizes and flow direction's impact on heat exchanger performance. The results show that heat conduction and natural convection heat transfer mechanisms exist on the particle side. Flow direction minimally affects charge/discharge time and stored energy but significantly impacts delivered/recovered energy and exergy and energy and exergy efficiencies. Optimal performance is achieved when HTO enters from the top during charging and from the bottom during discharging, creating a transparent thermal gradient of “Top Temperature High, Bottom Temperature Low”. This distribution minimizes natural convection losses, resulting in a 15–17 % increase in energy efficiency and an 11–13 % increase in exergy efficiency compared to reverse flow. Smaller particles show slightly faster temperature rise due to lower energy storage density. Large and medium particles perform well, achieving energy efficiencies of 81.5 % and 81.0 % and exergy efficiencies of 62.1 % and 61.8 %, respectively. Small particles have an energy efficiency of 79.0 % and an exergy efficiency of 60.4 %, possibly due to higher porosity and increased heat losses.

Variation Law of Hybrid Explosion Characteristic Parameters of Gas and Coal Dust Coupled with Multiple Factors.

This study aims at extensively investigating the explosion characteristics of a hybrid mixture of gas and coal dust. Accordingly, the standard 20 L spherical explosion system was applied to measure parameters such as the lower explosion limit, maximum explosion pressure, and index of the hybrid mixture of different concentrations of gas and coal dust. Moreover, different coal dust particle sizes and components were measured. With regard to coal dust with different particle sizes and components, the obtained results revealed that, while the addition of gas significantly reduced the lower explosion limit, the maximum explosion pressure and index were increased; that is to say, the presence of gas will increase the explosion risk of coal dust. However, under conditions in which the particle size of the coal dust was large or the volatile content was low, the addition of gas was found to lead to a higher decrease of the lower explosion limit; this is, while the maximum explosion pressure and explosion index were increased. Consequently, gas can be argued to have a greater influence on the explosion risk of coal dust with a large particle size or low volatile content. Furthermore, regardless of the particle size or the volatile content of coal dust, the maximum explosion pressure and explosion index of the hybrid mixture were observed to be higher than that of the pure coal dust but lower than that of the pure gas. That is to say, the explosion intensity of the gas/coal dust composite system is higher than that of pure coal dust but less than that of pure gas. The research results can provide theoretical basis for coal mine explosion disaster prevention and control and have important significance.

Flow properties of single origin chocolates: Effect of product formulation and particle size.

The objective of this research was to evaluate changes in flow behavior of chocolate during chocolate grinding using a stone grinder as affected by chocolate formulation. Three different types of chocolates were evaluated. Two chocolates without milk added (70% chocolate) and two chocolates with milk added and with different amounts of cocoa nibs (30% chocolate and 14% chocolate) were tested. For the 70% chocolates, nibs of two different origins were used; therefore, a total of four samples were evaluated. Chocolates were processed in a stone grinder, and samples were taken as a function of grinding time. For each timepoint, the flow behavior of the samples was measured using a rotational rheometer and fitted to the Casson model. Particle size was measured using a laser scattering instrument. Results showed that yield stress increased linearly while the Casson plastic viscosity decreased exponentially with grinding time (smaller particles). Particle size distribution of the chocolates showed a prominent bimodal distribution for short grinding times (∼9 h) with small (∼15 µm) and large (∼100 µm) particles; with longer grinding time, the population of larger particles decreased. Yield stress values were higher for the 70% chocolate, but they were not very different between the two milk chocolates tested. The Casson plastic viscosity was greatest for the 70% chocolate, followed by the 30% chocolate. The 14% chocolate had the lowest Casson plastic viscosity. Changes of Casson plastic viscosity with particle size were more evident for the dark chocolates compared to the milk ones. These results are helpful to small chocolate producers who need better understanding of how the formulation and grinding of chocolate affect its flow behavior, which will ultimately affect chocolate handling during production.

Ultrasensitive and Wash-Free Detection of Tumor Extracellular Vesicles by Aptamer-Proximity-Ligation-Activated Rolling Circle Amplification Coupled to Single Particle ICP-MS.

Tumor-derived extracellular vesicles (TEVs) are rich in cellular information and hold great promise as a biomarker for noninvasive cancer diagnosis. However, accurate measurement of TEVs presents challenges due to their low abundance and potential interference from a high number of EVs derived from normal cells. Herein, an aptamer-proximity-ligation-activated rolling circle amplification (RCA) method for EV membrane recognition, coupled with single particle inductively coupled plasma mass spectrometry (sp-ICP-MS) for the quantification of TEVs, is developed. When DNA-labeled ultrasmall gold nanoparticle (AuNP) probes bind to the long chains formed by RCA, they aggregate to form large particles. Notably, small AuNPs scarcely produce pulse signals in sp-ICP-MS, thereby detecting TEVs in a wash-free manner. By leveraging the strong binding affinity of aptamers, dual aptamers for EpCAM and PD-L1 recognition, and the sp-ICP-MS technique, this method offers remarkable sensitivity and selectivity in tracing TEVs. Under optimized conditions, the present method shows a favorable linear relationship between the pulse signal frequency of sp-ICP-MS and TEV concentration within the range of 105-107 particles/mL, along with a detection limit of 1.1 × 104 particles/mL. The pulse signals from sp-ICP-MS combined with machine learning algorithms are used to discriminate cancer patients from healthy donors with 100% accuracy. Due to its simple and fast operation and excellent sensitivity and accuracy, this approach holds significant potential for diverse applications in life sciences and personalized medicine.

Narażenie dermalne – ważny aspekt bezpieczeństwa pracy z nanomateriałami

Dermal exposure – an important aspect of safety in working with nanomaterials Taking into account dermal exposure is an important aspect in ensuring safe working conditions with nanomaterials. Quantum dots and nanomaterials with a larger particle size, metallic or with a metallic component, have the highest probability of absorption through the skin. A crucial factor in the process of absorption of nanomaterials through the skin is the disruption of its protective function, which may result in an increased risk of penetration and permeation of nanomaterials into the dermis and the human bloodstream. Keywords: nanoparticles, nanomaterials, skin absorption, skin exposure

Fabrication and Stability Improvement of Monoglyceride Oleogel/Polyglycerol Polyricinoleate-Stabilized W/O High Internal Phase Pickering Emulsions.

To decrease the lipid content in water-in-oil (W/O) emulsions, high internal phase Pickering W/O emulsions (HIPPE) were fabricated using magnetic stirring using a combination of monoglyceride (MAG) oleogel and polyglycerol polyacrylate oleate (PGPR) as stabilizers. Effects of MAGs (glyceryl monostearate-GMS, glycerol monolaurate-GML and glycerol monocaprylate-GMC) and internal phase components on the formation and properties of HIPPEs were investigated. The results showed that milky-white stabilized W/O HIPPE with up to 85 wt% aqueous phase content was successfully prepared, and the droplet interfaces presented a network of MAG crystals, independent of the MAG type. All HIPPEs exhibited great stability under freeze-thaw cycles but were less plastic. Meanwhile, GML-oleogel-based HIPPEs had larger particle size and were less thermal stable than GMS and GMC-based HIPPEs. Compared to guar gum, the internal phase components of sodium chloride and sucrose were more effective in reducing the particle size of HIPPEs, improving their stability and plasticity, and stabilizing them during 100-day storage. HIPPEs presented great spreadability, ductility and plasticity after whipping treatment. This knowledge provides a new perspective on the use of oleogels as co-stabilizers for the formation of W/O HIPPEs, which can be used as a potential substitute for creams.

Investigation on microstructure and wear resistance of WC coated aluminum alloy using machine hammer peening

Due to the characteristic of low density and high strength, Aluminum alloy have been applied in various industries. However, poor surface properties, such as wear resistance, are the main reason for limiting its application. In this study, machine hammer peening (MHP) was used for embedding tungsten carbide (WC) particles in near-surface zone of aluminum alloy and the microstructure and wear resistance were investigated. The results show that WC particles can be embedded into aluminum alloy using MHP and WC coatings were generated with large and medium WC particles. The values of surface roughness were increased with increasing of WC particles sizes and XRD analysis indicated that no new compound was found during coating process. The significant increasing of wear resistance of WC coating has been obtained. MHP is a novel technique for obtaining WC coating and improving the tribological performance of aluminum alloy. Furthermore, it offers new possibilities to embedding hard particles in substrates of various materials.

A transformable and self-oxygenated smart probe for enhanced tumor sonodynamic therapy

Sonodynamic therapy (SDT) is emerging as a promising modality for cancer treatment. However, improving the tumor bioavailability and anti-hypoxia capability of sonosensitizers faces a big challenge. In this work, we present a tumor microenvironment (TME)-mediated nanomorphology transformation and oxygen (O2) self-production strategy to enhance the sonodynamic therapeutic efficacy of tumors. A smart probe Ce6-Leu@Mn2+ that consists of a glutathione (GSH) and leucine amino peptidase (LAP) dual-responsive unit, a 2-cyanobenzothiazole (CBT) group, and a Mn2+-chelated Ce6 as sonosensitizer for tumor SDT was synthesized, and its SDT potential for liver tumor HepG2 in living mice was systematically studied. It was found that the probes could self-assemble into large nanoparticles in physiological condition and spontaneously transformed into small particles under the dual stimulation of GSH and LAP in TME resulting in enhanced tumor accumulation and deep penetration. More notably, Ce6-Leu@Mn2+ could convert endogenous hydrogen peroxide to O2, thereby alleviating the hypoxia and achieving effective SDT against hypoxic tumors under the excitation of ultrasound. We thus believe this smart TME-responsive probe may provide a noninvasive and efficient means for malignant tumor treatment. Statement of significanceSonodynamic therapy (SDT) is emerging as a promising therapeutic modality for cancer treatment. However, how to improve the tumor bioavailability and anti-hypoxia capability of sonosensitizers remains a huge challenge. Herein, we rationally developed a theranostic probe Ce6-Leu@Mn2+ that can transform into small-size nanoparticles from initial large particles under the dual stimulation of LAP and GSH in tumor microenvironment (TME) resulting in enhanced tumor accumulation, deep tissue penetration as well as remarkable O2 self-production for enhanced sonodynamic therapy of human liver HepG2 tumor in living mice. This smart TME-responsive probe may provide a noninvasive and efficient means for hypoxic tumor treatment.

Magnetic Storm‐Time Red Aurora as Seen From Hokkaido, Japan on 1 December 2023 Associated With High‐Density Solar Wind

AbstractWe report a citizen science‐motivated study on the cause of an unusually bright red aurora as witnessed from Hokkaido, Japan during a magnetic storm on 1 December 2023. The auroral brightness of 5 kR is unusual for the Dst index peak of only −107 nT. In spite of the moderate storm amplitude, the extremely high solar wind density of >50/cc and dynamic pressure of >25 nPa caused the aurora oval extension to 53 magnetic latitudes (L = 2.8). We discuss that the drift loss of the ring current particles across the small‐size magnetopause is important, and Hokkaido was at the right position to see the direct effect of the large particle injection of the storm‐time substorm.

Study of the behavior of dust particles in helium turbines considering the effects of particle deposition and resuspension

The deposition of graphite dust poses significant challenges to the helium turbines in high-temperature gas-cooled reactors. In this study, FLUENT, a Computational Fluid Dynamics (CFD) program was used with a discrete-phase model and a random-walk model to calculate the trajectories of particles (assumed spherical). Considering the interactions between particles and the wall as well as the resuspension effect of the fluid, a particle-deposition model was established and coupled to the flow-field calculations of blades with film cooling using user-defined functions. The influence of different deposition models, particle diameters, and blowing ratios on deposition were investigated. The results show rebounding and resuspending particles significantly affect the particle-deposition rate and its distribution. With increasing particle diameter, the deposition rate initially increases and then decreases. The influence of blowing ratio on deposition is complex; as the blowing ratio is increased, the deposition rate of small particles increases, while that of large particles decreases.

Patterns of prokaryotic activity along the marine planktonic matter continuum

Prokaryotic abundance and activity are commonly assessed by dividing them into two size-fractions: free-living and attached to particles. Nevertheless, organic matter, essential for the growth of heterotrophic prokaryotes, is present in the environment in a continuum of sizes, from purely dissolved to large particles. Therefore, defining the activity of the prokaryotic community would be more accurate by considering all the distinct size fractions. To achieve this, we measured prokaryotic abundance (PA), heterotrophic prokaryotic activity (as leucine incorporation) and extracellular enzyme activities at a coastal site in the NW Mediterranean Sea. We conducted measurements in both bulk seawater and size fractionated samples sequentially passing through 5 different filter types: 0.2–0.8–3–5–10 μm pore size. Our results indicate that the fraction <0.8 μm contained the highest percentage of cells (91.6 ± 1.1 %) and leucine incorporation rates (72.2 ± 3.5 %). Most of the extracellular enzyme activity appeared in the dissolved fraction (<0.2 μm; 19.8–79.4 %), yet the specific activity of the enzymes (per cell activity) was 100–1000 times higher in the particulate (>0.8 μm) than in the free-living (0.2–0.8 μm) fraction. The size fraction with highest specific activities for leucine incorporation and most of the enzyme activities (β-glucosidase, esterase, Leu-aminopeptidase and alkaline phosphatase) was the 5–10 μm fraction. In contrast, the higher specific chitobiase activity in the >10 μm fraction, suggests that the prokaryotic community colonizing large particles might be more specialized in the hydrolysis of organic matter of zooplanktonic origin than the community colonizing smaller particles.

Internal Structure of Incipient Soot from Acetylene Pyrolysis Obtained via Molecular Dynamics Simulations.

A series of reactive molecular dynamics simulations is used to study the internal structure of incipient soot particles obtained from acetylene pyrolysis. The simulations were performed using the ReaxFF potential at four different temperatures. The resulting soot particles are cataloged and analyzed to obtain statistics of their mass, volume, density, C/H ratio, number of cyclic structures, and other features. A total of 3324 incipient soot particles were analyzed in this study. Based on their structural characteristics, the incipient soot particles are classified into two classes, termed type 1 and type 2 incipient soot particles in this work. The radial distribution of density, cyclic (5-, 6-, or 7-member rings) structures, and C/H ratio inside the particles revealed a clear difference in the internal structure between type 1 and type 2 particles. These classes were further found to be well represented by the size of the particles, with smaller particles in type 1 and larger particles in type 2. The radial distributions of ring structures, density, and the C/H ratio indicated the presence of a dense core region in type 2 particles. In contrast, no clear evidence of the presence of a core was found in type 1 particles. In type 2 incipient soot particles, the boundary between the core and shell was found to be around 50-60% of the particle's radius of gyration.

A Phenomenological Model for Estimating the Wear of Horizontally Straight Slurry Discharge Pipes: A Case Study

When a slurry TBM advances in pebble and rock strata, large rock particles are carried in pipelines out of a tunnel by moving slurry. To estimate the wear of horizontally straight slurry discharge pipes, a phenomenological model was proposed that was mainly based on knowledge gained by means of direct and indirect in situ observations. The proposed model applies an equation composed of three variables, namely, the wear rate (λ), the central angle (2α), and the excavated tunnel length (L), to estimate the wear distribution along a pipe’s internal surface. The results indicated that wear mainly occurred on the bottoms of pipes. In addition, linear relationships between the maximum pipe wear amount (δmax) and the excavated tunnel length (L) were found for specific pipes and specified types of ground. The observed wear rates of different pipes in different types of ground had varied constants. The wear rates were higher for pipes in rock ground than for those in a pebble layer. For horizontally straight pipes, the observed wear rates were 0.0045 mm/m in a pebble layer and 0.0212 mm/m in rock ground. Lastly, to improve the proposed model, more field monitoring will be necessary to determine the pipe wear rates in different types of ground in the future.

Mitigating kinetic hindrance of single-crystal Ni-rich cathodes through morphology modulation, nickel reduction, and lithium vacancy generation achieved by terbium doping

Single crystallization has proven to be effective in enhancing the capacity and stability of Ni-rich LiNi1−x−yCoxMnyO2 (SNCM) cathode materials, particularly at high cut-off voltages. Nevertheless, the synthesis of high-quality single-crystal particles remains challenging because of severe particle agglomeration and irregular morphologies. Moreover, the limited kinetics of solid-phase Li+ diffusion pose a significant concern because of the extended diffusion path in large single-crystal particles. To address these challenges, we developed a Tb-doped single-crystal LiNi0.83Co0.11Mn0.06O2 (SNCM-Tb) cathode material using a straightforward mixed molten salt sintering process. The Tb-doped Ni-rich single crystals presented a quasi-spherical morphology, which is markedly different from those reported in previous studies. Tb4+ doping significantly enhanced the dynamic transport of Li+ ions in the layered oxide phase by reducing the Ni valence state and creating Li vacancies. A SNCM-Tb material with 1 at% Tb doping shows a Li+ diffusion coefficient up to more than 9 times higher than pristine SNCM in the non-diluted state. In situ X-ray diffraction analysis demonstrated a significantly facilitated H1-H2-H3 phase transition in the SNCM-Tb materials, thereby enhancing their rate capacity and structural stability. SNCM-Tb exhibited a reversible capacity of 186.9 mA h g−1 at 5 C, retaining 94.6% capacity after 100 cycles at 0.5 C under a 4.5 V cut-off. Our study elucidates the Tb4+ doping mechanisms and proposes a scalable method for enhancing the performance of single-crystal Ni-rich NCM materials.