Primary Particle Size Research Articles

Large eddy simulation-bivariate sectional model for non-spherical TiO2 nanoparticle synthesis in flame

Numerical simulation of nanoparticle synthesis in flame necessitates a high level of fidelity for turbulent flame, as well as delivers more detail insight into the evolution of structure and size distribution of particles undergoing various dynamic events. In the present work, a new simulation approach coupling large-eddy simulation (LES) and bivariate sectional model is proposed to explore the synthesis of nanoparticles in turbulent flame. More specifically, the nonlinear LES-partially stirred reactor model (NLES-PaSR) is utilized to simulate the turbulent flame, wherein the gradient-type structural subgrid-scale (SGS) model for turbulent flow and partially stirred reactor (PaSR) model for turbulent combustion are considered. In addition, the volume-based bivariate sectional model is thoroughly coupled with the LES model for the first time to describe the spatiotemporally resolved formation and growth of nanoparticles using particle number concentration and surface area concentration as two sets of variables. Compared directly with the LES-monodisperse (LES-Mono) and LES-univariate sectional (LES-UniSe) models, the LES-bivariate sectional (LES-BiSe) model has significant advantages in its ability to analyze and predict the size, morphology, as well as polydispersed particle size distribution (PSD) evolution of nanoparticles at a moderate computational cost simultaneously. In the LES framework, the proposed model successfully simulates the spatiotemporally resolved formation and growth of non-spherical TiO2 nanoparticle in turbulent diffusion burner. The predicted results derived from the LES-BiSe model are in good agreement with the experimental measurements. Also, the aggregate and primary particle size distribution shows highly temporal fluctuation, which mainly results from the continuous variations of particle path induced by the unsteady turbulent combustion. Furthermore, the present work demonstrates the profound dependence of particle morphological on both spatiotemporal evolution and their intrinsic size distribution. In particular, the large aggregates in the higher sections are commonly found as irregular structure with fractal-like dimensions.

Effect of strontium addition, cooling rate and T6 heat treatment on the corrosion behaviour of Al-20%Mg2Si composite

Mg2Si reinforced AMCs are considered a promising structural material as the in-situ formation of Mg2Si particle offers excellent matrix/reinforcement stability that allow effective load transfer. Addition of Strontium (Sr) could minimize sharp edges shape of Mg2Si particles in as-cast condition improving the mechanical properties. Incorporating Strontium (Sr) can reduce the sharp-edged morphology of Mg2Si particles in their initial cast state, leading to enhanced mechanical properties. However, existing research on Mg2Si reinforced AMCs does not show sufficient data on corrosion behavior. This research aims to investigate the microstructural changes and corrosion performance of as-cast Al-20 %Mg2Si under various influencing factors including varying solidification rate, addition of Sr and post- fabrication metalwork such as T6 heat treatment. The composite materials were prepared using in-situ casting procedure with high purity of the elements. Microstructure characterization was carried out by optical microscopy, in which the primary Mg2Si particle sizes were measured by image analyser. Corrosion behaviour of the fabricated composite was analysed using electrochemical test. Optical microscopic images reveals that the primary Mg2Si was refined and transform to polyhedron upon addition of 0.01w.t. % Sr into Al-20 %Mg2Si and resulted in improved corrosion resistance upon immersion testing and potentiodynamic polarization testing in 3.5 % NaCl with decreasing the Icorr from 0.80 to 0.41 μA/cm2.The Al-20 %Mg2Si which solidified under lower cooling rate have coarser dendritic primary Mg2Si which results in higher corrosion rate (Icorr = 4.98 μA/cm2). T6 heat treatment transformed the primary Mg2Si to fine dendrites with spherical secondary Mg2Si phase and consequently enhancing the corrosion resistance by decreasing the Icorr to 2.93 μA/cm2.

Nanoparticles of the Perovskite-Structure CaTiO3 System: The Synthesis, Characterization, and Evaluation of Its Photocatalytic Capacity to Degrade Emerging Pollutants.

In this research work, the photocatalytic capacity shown by the nanoparticles of the CaTiO3 system was evaluated to degrade two pollutants of emerging concern, namely methyl orange (MO)-considered an organic contaminating substance of the textile industry that is non-biodegradable when dissolved in water-and levofloxacin (LVF), an antibiotic widely used in the treatment of infectious diseases that is released mostly to the environment in its original chemical form. The synthesis process used to obtain these powders was the polymeric precursor method (Pechini), at a temperature of 700 °C for 6 h. The characterization of the obtained oxide nanoparticles of interest revealed the presence of a majority perovskite-type phase with an orthorhombic Pbnm structure and a minority rutile-type TiO2 phase, with a P42/mnm structure and a primary particle size <100nm. The adsorption-desorption isotherms of the synthesized solids had H3-type hysteresis loops, characteristic of mesoporous solids, with a BET surface area of 10.01m2/g. The Raman and FTIR spectroscopy results made it possible to identify the characteristic vibrations of the synthesized system and the characteristic deformations of the perovskite structure, reiterating the results obtained from the XRD analysis. Furthermore, a bandgap energy of ~3.4eV and characteristic emissions in the violet (437 nm/2.8 eV) and orange (611 nm/2.03 eV) were determined for excitation lengths of 250 nm and 325 nm, respectively, showing that these systems have a strong emission in the visible light region and allowing their use in photocatalytic activity to be potentialized. The powders obtained were studied for their photocatalytic capacity to degrade methyl orange (MO) and levofloxacin (LVF), dissolved in water. To quantify the coloring concentration, UV-visible spectroscopy was used considering the variation in the intensity of the characteristic of the greatest absorption, which correlated with the change in the concentration of the contaminant in the solution. The results showed that after irradiation with ultraviolet light, the degradation of the contaminants MO and LVF was 79.4% and 98.1% with concentrations of 5 g/L and 10 g/L, respectively.

Electric sampling of soot particles in spreading non-premixed flames: methodology and influence of gravity

Finer strategies of spacecraft fire mitigation require more experimental data related to fire detection. Fire detection systems developed on Earth rely massively on the optical detection of soot particles, which are present in the smoke. To detect the fire correctly, it is thus important to know how the optical properties of these particles are affected in reduced gravity. With different transport processes and increased residence time, soot in reduced gravity can be different from those produced at normal gravity. As their optical properties are related to their morphological properties, a better understanding about the evolution of soot particle morphology in flames under microgravity conditions is required. Within this context, a novel technique of soot sampling using electric field is applied to a spreading non-premixed flame at normal and micro-gravity. The soot particles sampled are observed subsequently under Transmission Electron Microscopy (TEM). Density, soot particle projected area, radius of gyration, fractal dimension, and primary particle size are extracted and the influence of gravity is investigated with the evolution of these morphological properties within the flame. Though the present study cannot be conclusive in itself, the similarity between the evolution of the optical density measured throughout the flame just before the electric perturbation required by the sampling technique and the evolution of the amount of soot deposited due to the electric perturbation along the sampling plates supports the future works that need to be devoted to further assess the consistency of the technique.

Co–Fe–oxide nanoparticles supported on the various highly dispersed matrices: the effect of the carrier on structural and magnetic properties

sA series of mixed oxides was synthesized by deposition of the guest phase on the highly dispersed oxide matrix. Fumed nanooxides SiO2, Al2O3, SiO2/Al2O3, and SiO2/Al2O3/TiO2 with the specific surface area of 65–91 m2/g were selected as highly dispersed matrices. Co–Fe mixed oxides with the general formula Co4xFexOy (Co: Fe = 4: 1) were deposited as the guest oxides using the two-step method: (i) solvate-stimulated modification of the surface of fumed nanocarriers with the mixture of cobalt nitrate (II) and iron (III) formate and (ii) subsequent heat treatment up to 600 °C to form Co4xFexOy. The aim of this paper was to study the influence of the composition and structure of fumed oxide matrices and deposited guest phase on the morphology of the resulting composites in the gaseous and aqueous media using the XRD, XPS, FTIR, nitrogen adsorption and SEM/EDX, as well as quasi-elastic light scattering (QELS) methods. The low-temperature nitrogen adsorption isotherms have a sigmoidal shape with a narrow hysteresis loop characteristic of mesoporous materials. The specific surface area (SBET) of the composites varies from 48 to 82 m2/g, showing a tendency towards a decrease in the SBET values by 10–26% in comparison with the initial nanocarriers. The SEM data show the denser aggregate structure of nanocomposites compared to the initial carriers. The primary particle size was in the 30–60 nm range and the EDX data confirm the formation of a guest phase on the mixed aluminosilicate carriers, mainly in the surface patches corresponding to the alumina structure. According to the QELS data, there is a tendency to form aggregates of 100–10 μm in size in the aqueous media. The XRD method shows that the deposited metal oxides are in the form of crystalline phases of Co3O4 with the crystallites of 25–26 nm in size for the individual SiO2 and Al2O3 nanocarriers and 34–37 for the mixed ones, but the iron oxide reflections were not identified for the composites. XPS observation demonstrates the signal of Fe 2p electrons as the form of Fe2O3 oxide in the surface layer of nanocomposites as well as Co 2p as the Co3O4 and Co(OH)2.

Regeneration behavior of FePO4·2H2O from spent LiFePO4 under extremely acidic condition (pH < 0.8): Mechanism study and the properties of regenerated LiFePO4

With the large-scale application of LiFePO4 batteries in electric vehicles and energy storage, the recycling of spent LiFePO4 cathode materials is receiving increasing attention. Hydrometallurgical derived full-component separation strategy has been verified as the most capable recycling process for LiFePO4 cathode. During which, complete elements (i.e., Li, Fe and P) are dissolved into a solution of excessive acidic leachate, and subsequently separated to obtain battery-grade FePO4·2H2O and lithium salt, enabling high element recovery rates of up to 100 %. However, the use of excessive leaching agent leads to high acidity of the leaching solution (pH < 0.8), which brings a necessary of pH regulation prior to the regeneration of FePO4·2H2O, markedly complicating the succedent separation and purification. In this investigation, a practical method for directly regenerating FePO4·2H2O from H2SO4-based full-component leaching solution is proposed. In this process, H2SO4 as leaching agent is used to digest LiFePO4 completely, and then Fe and P are premeditatedly recovered from the extremely acidic filtrate (pH < 0.8) as FePO4·2H2O via direct precipitation without any pH regulator. Consequently, there are no extra impurities affecting the recovery of Fe and P during regeneration. The regeneration behavior of FePO4·2H2O under extremely acidic condition are investigated and the growth mechanism is also clarified by monitoring the overall microstructure and phase evolutions. The results demonstrate that the above regeneration is found to be an exponential growth process driven by the quantity of nucleation site, and meanwhile influenced by the dissolution-reprecipitation equilibrium of amorphous iron phosphate. Specifically, the process can be accelerated by introducing FePO4·2H2O or amorphous iron phosphate to increase the nucleation sites. Additionally, the primary nanosheet size of regenerated FePO4·2H2O causes a smaller primary particle size of the corresponding LiFePO4/C material, contributing to its better physical and electrochemical properties. This work provides a guidance for the direct regeneration of FePO4·2H2O from excessive acidic leachate and has potential industrial applications.

Exploring Cohesive Sediment Flocculation With Surface Heterogeneity: A Theoretical Lagrangian‐Type Flocculation Model

AbstractThe flocculation of cohesive sediments significantly influences the particle size, concentration, and settling velocity and further influences sediment transport and pollutant transformation in the natural environment. The population balance equation (PBE) was used to model flocculation processes, including aggregation and floc breakup. This paper presents a theoretical Lagrangian‐type flocculation dynamic model established by solving the PBE using moment methodology and similarity transformation. The influence of surface heterogeneities (F2a) of the particles was incorporated. Sensitivity tests revealed that the model performance was significantly related to the aggregation and breakup parameters, which varied with ambient conditions. Furthermore, the effects of the shear rate, sediment concentration, particle size, and surface heterogeneity were analyzed theoretically. A critical shear rate distinguishes two cases: an increasing shear rate tends to increase the equilibrium floc size (Dfe) under low‐shear conditions, whereas a negative correlation exists at high‐shear levels. The dependence of Dfe on sediment concentration is complex, and increasing the initial concentration can enhance or limit the propensity to flocculate at different shear levels. Additionally, the enlargement of the primary particle size and surface heterogeneity reduces the propensity for flocculation. This study proposes a preliminary theoretical analysis method of flocculation processes considering factors such as surface heterogeneity, showing the possibility of further enhancing the knowledge of cohesive sediment transport.

Impact of Sulfate Adsorption on Particle Morphology during the Precipitation of Ni-Rich Hydroxide Precursors for Li-Ion Battery Cathode Active Materials

Nickel-cobalt-manganese-hydroxides (NixCoyMnz(OH)2, with x+y+z = 1) are utilized as precursor for lithium-ion battery cathode active material (CAM). The physical properties and electrochemical performance of CAM are affected by the morphology, crystallinity and impurity content of the associated NixCoyMnz(OH)2 (with x+y+z = 1) employed for the CAM synthesis. To promote the mechanistic understanding of the NixCoyMnz(OH)2 (with x+y+z = 1) formation, the coprecipitation pH23 °C-value was systematically varied from 8.6–12.7 during the synthesis of Ni0.8Co0.1Mn0.1(OH)2, and the obtained powders were characterized by elemental analysis. A dependency of residual sulfur content and crystallinity of the obtained Ni0.8Co0.1Mn0.1(OH)2 on the pH-value in relation to the point-of-zero-charge (pzc) is revealed. This result is rationalized by a pH-dependent sulfate adsorption equilibrium. Furthermore, a suppression of the growth along the (001) plane of the crystallites due to sulfate adsorption is identified. This in turn governs the vertical primary particle size and thus the porosity of the secondary particles, which was verified by substituting the sulfate ion of the metal feed by nitrate or acetate. Adsorption/desorption experiments demonstrate the possibility to decouple secondary particle morphology and residual impurity content. The demonstrated relationships allow formulating design strategies to tailor the NixCoyMnz(OH)2 (with x+y+z = 1) morphology and its impurity content for CAM synthesis.

Effects of [formula omitted]-pentanol blending on soot formation in swirl-stabilized turbulent spray flames of Jet A-1 in a laboratory gas turbine combustor

Although the influence of alcohol supplement on soot in hydrocarbons fuel combustion in laminar flames and transportation engines is widely investigated, the information from well-controlled spray flames with clean boundary conditions are scarce, especially with kerosene type fuels doped with n-pentanol. Favorable physical properties of n-pentanol makes it an attractive oxygenated fuel extender for transportation fuels. We investigated the effects of adding 10% and 20% n-pentanol, by energy content, to a JetA-1 fuel on sooting characteristics of spray combustion in a swirl-stabilized model combustor. At an identical fuel feed rate, two different air flow rates were considered yielding global equivalence ratios of 0.64 and 0.69. Flow field generated by the combustion of swirling air and the injected fuel was measured using stereoscopic particle image velocimetry, and a diffraction based instrument was utilized to quantify the spray droplet size distribution. Laser-induced incandescence was used to measure the soot concentration distribution within the combustor and to estimate the primary soot particle sizes. Very small but measurable changes were observed in the spray droplet characteristics caused by the addition of n-pentanol to JetA-1. 10% replacement of JetA-1 by n-pentanol reduced the soot volume fractions and the total soot loading in the combustor significantly when the global equivalence ratio was 0.69, whereas with global equivalence ratio of 0.64, soot loading was almost zero. When the n-pentanol replacement increased to 20%, no soot was detected for both air flow rates, probably due to soot volume fractions well below the lower limits of laser-induced incandescence. The primary soot particle diameters covered a range from 25 to 50 nm mostly unaffected by the presence of n-pentanol in JetA-1.

CPFD modeling of hydrodynamics, combustion and NOx emissions in an industrial CFB boiler

The ultra-low NOx emission requirement (50 mg/m3) brings great challenge to CFB boilers in China. To further tap the NOx abatement potential, full understanding the fundamentals behind CFB boilers is needed. To achieve this, a comprehensive CPFD model is established and verified; gas-solid flow, combustion, and NOx emission behavior in an industrial CFB boiler are elaborated; influences of primary air volume and coal particle size on furnace performance are evaluated. Simulation results indicate that there exists a typical core-annular flow structure in the boiler furnace. Furnace temperature is highest in the bottom dense-phase zone (about 950 °C) and decreases gradually along the furnace height. Oxygen-deficient combustion results in high CO concentration and strong reducing atmosphere in the lower furnace. NOx concentration gradually increases in the bottom furnace, reaches maximum at the elevation of secondary air inlet, and then decreases slightly in the upper furnace. Appropriate decreasing the primary air volume and coal particle size would increase the CO concentration and intensify the in-furnace reducing atmosphere, which favors for NOx reduction and low NOx emission from CFB boilers.

Diesel soot combustion in air-NO environment: Evolution of soot physical properties and fragmentation characteristics

Since the oxidation activity of nitrogen oxides on soot is obviously higher than that of O2, it is one of the most effective means to improve soot combustion in diesel particulate filter (DPF) by fully utilizing the oxidation activity of nitrogen oxides in diesel exhaust. This paper investigated the physical properties (i.e. morphology, primary particle diameter, fractal dimension and nanostructure) and oxidation-induced fragmentation characteristics of diesel exhaust soot particles during oxidation degrees (0 %, 20 %, 50 % and 80 %) in different atmospheres (air, air-1000 ppm NO and air-2000 ppm NO). The results showed that during the oxidation process the variation trends of soot morphology in air and air-NO environments were similar, while the number and size of primary particles in an aggregate decreased and the fractal dimension of the aggregate increased with the presence of NO in air atmosphere. With the progress of oxidation, the nanostructure of soot particles became more ordered, while this variation trend was slowed down when NO was added to the air atmosphere. This is because soot particles oxidized in air-NO atmospheres showed less probability of internal oxidation but more external oxidation than those in air atmosphere. Over the oxidation process, the soot aggregate fragmentation rate presented a decreasing variation trend under each oxidizing atmosphere, with a higher aggregate fragmentation rate and more apparent variations in air-NO atmospheres. Moreover, in the air atmosphere, the probability of primary soot particle fragmentation showed a consistent upward trend, while the addition of NO slowed down this trend and showed an upward trend in stages 1(0 % ∼ 20 %) and 2(20 % ∼ 50 %), but a downward trend in stage 3(50 % ∼ 80 %). This suggests that the addition of NO reduces the probability of oxidants (especially O2) entering the particles, which would lead to a decrease in the probability of primary soot fragmentation caused by internal oxidation.

Enhancing fluidization quality of nanoparticle agglomerates by combining vibration, stirring and jet assistances

Gas fluidization is an efficient method to process nanoparticles. In this study, we employ 3D printing to fabricate a hollow stirring structure of blades with jet holes and position it in a vibrating fluidized bed to realize an integration of vibration, stirring and jetting assistance methods, without increasing structural complexity. The fluidization of SiO2, Al2O3 and TiO2 nanoparticle agglomerates with different primary particle sizes and surface properties are investigated. The combination of vibration and stirring improves the bed expansion obviously, while a further addition of the gas jets at a velocity of a few meters per second allows a further small improvement of bed expansion. The jets slightly reduce the agglomerate size in the dense bed, the agglomerate size at the bed outlet, and the elutriation rate. By combining vibration, stirring and jets, the fluidization is enhanced while the elutriation is kept low during fluidization lasting for a few hours.

Synergistic Effect of Strontium and Melt Quenching on the Solidification Microstructure of Hypereutectic Al-Si Alloys.

The synergistic effect between strontium (Sr) and melt quenching on the solidified microstructure of hypereutectic Al-Si alloys was investigated by optical and scanning electron microscopy. The results indicate that melt quenching can suppress the growth of primary Si particles in the solidified structure of the hypereutectic Al-Si alloy, resulting in a significant decrease of in the average size of primary Si particles in Al-(18~22)Si alloys from 30.35~66.31 μm to 15.13~34.63 μm. The synergistic effect between Sr and melt quenching can further inhibit the precipitation of primary Si particles in the Al-18Si alloy. After the addition of Sr to Al-18Si alloy and undergoing melt quenching, the area fraction of primary Si clearly decreases. When the added amount of Sr increases from 0.1 wt.% to 0.5 wt.%, the area fraction of primary Si decreases from 1.13% to 0.16%. With 0.5 wt.% Sr in the tested alloy, the inhibiting effect on primary Si precipitation was significantly improved. Research has shown that the cooling rate has a significant impact on the solidified structure of the melt-quenched Al-18Si-0.5Sr alloy. There exists no primary Si in solidified structures on the area of 1/8R and 1/4R from the surface of the round bar sample, but the area fraction of primary Si increases, respectively, to 1.97% and 12.48% on the area of 1/2R and R from the surface. The higher the cooling rate, the higher the inhibitory effect on the primary Si precipitation in the Al-18Si-0.5Sr alloy.

Translocation of 14C-polystyrene nanoplastics into fish during a very-low concentration dietary exposure

Assessing the dietary accumulation of nanoplastics in animals following very-low exposure concentrations is restricted due to analytical limitations. This study adapted a method for synthesising semi-stable 14C-PS NPs (through styrene polymerisation) in small volumes for deployment in environmental studies. The method was developed with non-labelled material where the final polystyrene product had a primary particle size of 35 ± 8 nm (as measured by transmission electron microscopy). This method was then applied to 14C-labelled styrene to produce radiolabelled polystyrene nanoplastics (14C-PS NPs). The 14C-PS NPs were added (top-dressed) to a commercially available fish feed, with a measured concentration of 27.9 ± 2.1 kBq kg−1 (n = 5), equating to 5.9 μg polystyrene kg−1 feed. Fish (rainbow trout; Oncorhynchus mykiss) were fed this diet at a ration of 2% body weight per day for a period of two weeks. On day 3, 7 and 14, the fish were sampled for the mid intestine, hind intestine, kidney and liver, and measured for tissue radioactivity (determined by liquid scintillation counting). Some background activity was detected in the control samples (e.g., 1–16 and 4–11 Bq g−1 in the hind intestine and liver, respectively) which is due to natural background fluorescence. By the end of the experiment, the hind intestine and liver had significantly elevated radioactivity (25.3 and 15.0 Bq g−1, respectively) compared to the control, indicating the accumulation of nano polystyrene. In the liver, this equated to 1.8 μg polystyrene g−1 dry weight. This study confirms the accumulation of nano particles in vertebrates at low, environmentally relevant concentration, and highlights radiolabelling as a methodological approach suitable for exploring the bioaccumulation of nanoplastics and potential impacts.

Effect of Mo Oxides on the Phase Composition and Characteristics of Mo-10Re Pre-Alloyed Powders Co-Reduced with NH4ReO4.

Mo-Re pre-alloyed powders are crucial raw materials in fabricating Mo-Re alloys, and their properties can significantly impact the properties of the resulting alloys. The powders are usually produced by the co-reduction of a mixture of Mo and Re oxides. However, it remains unclear if the overall characteristics of the produced Mo-Re powders rely on the different combinations of the Mo and Re oxide precursors. Therefore, in this work, a comparative study is conducted on the co-reduction processes of different Mo oxides together with NH4ReO4, along with its influence on the size distribution and phase composition of the resulting Mo-10Re pre-alloyed powders. The results show that MoO3 is more promising than MoO2 as a precursor material. The powders fabricated using MoO3, when compared to MoO2, have a much more uniform size distribution, with a primary particle size ranging from 0.5-4 μm. In addition, it is also beneficial to achieve atomic-scale homogeneous mixing with Mo and Re elements and the formation of a solely Mo(Re) solid solution if MoO3 is used as a precursor oxide. In contrast, such desirable features were not identified when using the MoO2 route. The reason for this discrepancy may relate to whether Mo-O-Re metallurgical bonding has formed during the co-reduction process.

(Invited) Deciphering the Interplay between Thermodynamics and Kinetics during Cathode Calcination

Synthesis of the cathode materials used in lithium ion batteries involve the two steps, coprecipitation and calcination, where in the first step cathode precursors are formed, and later in the second step lithium ions are inserted into these cathode particles through chemical routes. During calcination, the cathode precursors obtained from the coprecipitation is mixed with lithium salt (LiOH or Li2CO3) and heated at high temperatures (~ 650°C – 1000°C) where oxidation and lithiation of the cathode particles take place. Calcination is considered to be of major significance in determining the final state of the cathode particles because it not only determines the extent of oxidation and lithiation experienced by the cathodes, but also substantially influences its morphology (for example, primary particle size, internal porosity, etc.). Significant surface modification of the cathode particles is also possible during calcination, which can impact its charge transfer resistance. Before the oxidation and lithiation of the cathode precursors, removal of water or CO2 is observed. All these chemical changes within the cathode precursors lead to change in its lattice volume, which is reflected as variation in the size of the primary particles. Apart from this, sintering induced change in particle size is also observed during the calcination process. In order to decipher the structural and morphological variations that occur during the calcination of cathode precursors, detailed experimental characterization is conducted in the present context using in situ X-ray diffraction (XRD) and thermogravimetric analysis (TGA) techniques. Atomistic simulations are conducted to decipher the feasibility of different chemical reactions that can possibly occur under elevated temperatures. Impact of reaction rate constant and mass transport in determining the extent of the oxidation and lithiation experienced by the cathode particles is analyzed by using a mesoscale level computational technique. Sintering induced grain growth experienced by the cathode primary particles is also investigated at the mesoscale level, which is demonstrated in Figure 1. Overall, a thorough understanding of the various physicochemical phenomena that occur during the calcination of cathode precursors has been developed using a combination of experimental and computational techniques, which will be discussed in detail. Figure 1

Impact of Morphology of Polycrystalline and Single Crystal Nickel Rich Cathode Particles on Performance

High nickel cathode material (NMC 811) is great candidate for high performance batteries. It has high specific capacity and lower utilization of cobalt. The morphology of the cathode particles is studied in a comprehensive manner, from the impact of synthesis parameters on primary particle size, to experimental characterization and replicating the key morphological features in computational model to elucidate the morphological features critical to the performance. The polycrystalline micron sized secondary particle is comprised of thousands of nanometers sized primary particles. The single crystal is generally 2 to 3 microns in size. The “single crystal” cathode particle may be cluster of few single crystals. The length scales of primary and secondary particles as well as internal porosity of polycrystalline cathode particles changes the characteristic diffusion length as well as surface area available for electrochemical reaction. Similarly, for single crystal, the size and the degree of clustering changes the diffusion characteristics and surface area. These variations are reflected in specific capacities obtained at different C-rates. Gaining an in-depth understanding of correlation of morphological features to performance would be helpful in directing the synthesis process. Figure 1

(Invited) Delineating the Intricacies Involved in the Synthesis of Cobalt-Free High-Nickel Layered Oxide Cathodes for Lithium-Ion Batteries

Improving the energy density and cost of lithium-ion batteries (LIBs) requires a rational compositional design of layered oxide LiNi1-x-yMnxCoyO2 (NMC) cathodes. The prevailing trend is to increase the nickel content in the cathode to maximize energy density, but high-nickel NMC generally suffers from surface and bulk instabilities that shorten battery life. Dopants, such as cobalt, can help mitigate these issues, but its supply shortage issue prohibits its usage especially in the massive electric vehicle market. Our recent finding suggests that a combination of manganese and aluminum in LiNi0.9Mn0.05Al0.05O2 (NMA-90) promotes attractive energy density, cycle life, rate capability and thermal stability, proving that cobalt can be eliminated in high-nickel cathodes. Post-mortem analysis further reveals that the Mn-Al combination provides synergistic improvements in structural and surface stabilities compared to LiNi0.9Mn0.05Co0.05O2 (NMC-90) and LiNi0.9Co0.05Al0.05O2 (NCA-90). A thorough understanding of the relationship between the synthesis condition and optimal materials properties of NMA-90 is necessary to enable its large-scale deployment. We will present findings from the calcination and coprecipitation study of several cobalt-free cathodes to elucidate this relationship. It is revealed that the cycle stability of LiNi0.9Mn0.1O2 (NM-90) is not dependent on Li/Ni mixing or primary particle size, but is dependent on the calcination temperature. Incorporating Al into NM-90 during coprecipitation reactions cause high internal porosity in the hydroxide precursor, which impacts the final morphology of the calcined cathodes and thus their electrochemical stability. The ongoing work in our lab provides insight on the synthesis sensitivity of NMA and strategizes methods to control its electrochemical properties.

Spherical LiMn0.7Fe0.3PO4/C Cathode Materials for Lithium-Ion Batteries

Lithium manganese iron phosphates (LiMnxFe1-xPO4) [1] are attractive as next-generation cathode materials for lithium-ion batteries because they are safer than conventional lithium transition metal oxides (e.g. LiCoO2) [2] and are Co- and Ni-free. However, due to their low electronic conductivity [3], they can deliver much lower electrochemical properties than theoretically expected one. Therefore, many researchers have focused on chemical composition, reducing primary particle size, and carbon coating. On the other hand, granulation of LiMnxFe1-xPO4 primary nanoparticles is effective in improving poor handling of LiMnxFe1-xPO4 primary nanoparticles during cathode slurry preparation. However, electrochemical properties of granulated LiMnxFe1-xPO4 have not been well studied in previous reports. In this study, the electrochemical properties of the spherical LiMn0.7Fe0.3PO4/C composed of primary nanoparticles are reported. Spherical LiMn0.7Fe0.3PO4/C was synthesized by hydrothermal method followed by granulation and carbon coating. The synthesized spherical LiMn0.7Fe0.3PO4/C was characterized using X-ray diffraction (XRD) and scanning electron microscope (SEM). Electrochemical properties of spherical LiMn0.7Fe0.3PO4/C were examined using CR2032 coin-type cells. Fig. 1 (a) shows the SEM images of spherical LiMn0.7Fe0.3PO4/C. As shown in Fig. 1 (a), spherical particle 10 μm in diameter composed of homogeneously sized primary nanoparticles were observed. Fig. 1 (b) shows the galvanostatic charge-discharge curves for spherical LiMn0.7Fe0.3PO4/C at discharge current rates of 0.2, 1, 5, and 10 C in a voltage range of 1.5–4.5 V at 30 °C. Spherical LiMn0.7Fe0.3PO4/C delivered a 0.2 C discharge capacity of 153 mAh g−1. At the 10C rate, spherical LiMn0.7Fe0.3PO4/C also delivered a high discharge capacity of 137 mAh g−1, which was 89 % of the 0.2C discharge capacity. Detailed data of our study including blended cathode of LiNiaMnbCocO2 and spherical LiMn0.7Fe0.3PO4/C will be presented in the meeting.

Preparation and Dispersion Performance of Hydrophobic Fumed Silica Aqueous Dispersion.

Hydrophobic fumed silica (HFS) is a commonly used rheology additive in waterborne coatings. A series of experiments were conducted on the HFS-dispersing technology in this study. The size and structure of HFS primary particles were observed via transmission electron microscopy (TEM). The measurement results of the TEM were D50 = 13.6 nm and D90 = 19.7 nm, respectively. The particle size and dispersion performance of HFS were tested via dynamic light scattering (DLS). Additionally, the HFS aqueous dispersion was prepared and compounded with waterborne polyacrylic latex and polyurethane resin. The elemental distribution of the coatings was characterized using energy dispersive spectroscopy (EDS). The results show that the HFS in a non-ionic polymer dispersant had the best dispersion performance. The particle size of the HFS in the aqueous dispersion is related to the dispersion conditions. Under optimized conditions, the HFS aqueous dispersion can be prepared with a particle size of D50 = 27.2 nm. The HFS aqueous dispersion has stable storage stability. Even after storage for 47 d, the particle size still did not change significantly.