Beth L. Armstrong

Optimization of LiFePO4 nanoparticle suspensions with polyethyleneimine for aqueous processing.

Addition of dispersants to aqueous based lithium-ion battery electrode formulations containing LiFePO(4) is critical to obtaining a stable suspension. The resulting colloidal suspensions enable dramatically improved coating deposition when processing electrodes. This research examines the colloidal chemistry modifications based on polyethyleneimine (PEI) addition and dispersion characterization required to produce high quality electrode formulations and coatings for LiFePO(4) active cathode material. The isoelectric point, a key parameter in characterizing colloidal dispersion stability, of LiFePO(4) and super P C45 were determined to be pH = 4.3 and 3.4, respectively. PEI, a cationic surfactant, was found to be an effective dispersant. It is demonstrated that 1.0 wt % and 0.5 wt % PEI were required to stabilize the LiFePO(4) and super P C45 suspension, respectively. LiFePO(4) cathode suspensions with 1.5 wt % PEI demonstrated the best dispersibility of all components, as evidenced by viscosity and agglomerate size of the suspensions and elemental distribution within dry cathodes. The addition of PEI significantly improved the LiFePO(4) performance.

Optimization of multicomponent aqueous suspensions of lithium iron phosphate (LiFePO4) nanoparticles and carbon black for lithium-ion battery cathodes

Addition of polyethyleneimine (PEI) to aqueous LiFePO4 nanoparticle suspensions improves stability and reduces agglomerate size, which is beneficial to lithium-ion battery cathode manufacturing. This research examines the effect of both PEI concentration and molecular weight (MW) on dispersing LiFePO4 and Super P C45 in multicomponent aqueous suspensions. It is demonstrated that the optimal conditions for obtaining stable suspensions with minimal agglomerate size are 1.5 wt% PEI with MW=2000 g mol(-1) and 5.0 wt% PEI with MW=10,000 g mol(-1) for LiFePO4 and Super P C45, respectively. The mixing sequence also affects rheological properties of these suspensions. It is found that dispersing the LiFePO4 and Super P C45 separately yielded suspensions with superior properties (Newtonian rheological behavior, smaller agglomerate size, improved settling, etc.). In particular, dispersing the LiFePO4 prior to the Super P C45 when making the final multicomponent suspension is found to be beneficial, which was evidenced by higher half-cell discharge capacity.

Scalable production of microbially mediated zinc sulfide nanoparticles and application to functional thin films

A series of semiconducting zinc sulfide (ZnS) nanoparticles were scalably, reproducibly, controllably and economically synthesized with anaerobic metal-reducing Thermoanaerobacter species. These bacteria reduced partially oxidized sulfur sources to sulfides that extracellularly and thermodynamically incorporated with zinc ions to produce sparingly soluble ZnS nanoparticles with ∼5nm crystallites at yields of ∼5gl(-1)month(-1). A predominant sphalerite formation was facilitated by rapid precipitation kinetics, a low cation/anion ratio and a higher zinc concentration compared to background to produce a naturally occurring hexagonal form at the low temperature, and/or water adsorption in aqueous conditions. The sphalerite ZnS nanoparticles exhibited narrow size distribution, high emission intensity and few native defects. Scale-up and emission tunability using copper doping were confirmed spectroscopically. Surface characterization was determined using Fourier transform infrared and X-ray photoelectron spectroscopies, which confirmed amino acid as proteins and bacterial fermentation end products not only maintaining a nano-dimensional average crystallite size, but also increasing aggregation. The application of ZnS nanoparticle ink to a functional thin film was successfully tested for potential future applications.

Investigation of ZnO-Based Polycrystalline Ceramic Scintillators for Use as

ZnO-based scintillators are particularly well suited for use as the associated particle detector in a deuterium-tritium (D-T) neutron generator. Application requirements include the exclusion of organic materials, outstanding timing resolution, and high radiation resistance. ZnO, ZnO:Ga, ZnO:In, ZnO:In,Li, and ZnO:Er,Li have demonstrated fast (sub-nanosecond) decay times with relatively low light yields. ZnO:Ga has been used in a powder form as the associated particle detector for a D-T neutron generator. Unfortunately, detectors using powders are difficult to assemble and the light yield from powders is less than satisfactory. Single-crystal ZnO of sufficient size has only recently become available. New applications for D-T neutron generators require better timing resolution and higher count rates than are currently available with associated particle detectors using YAP:Ce as the scintillator. Recent work suggests that ZnO-based scintillators can provide alpha-particle-excited light yields comparable to YAP:Ce scintillators. ZnO-based polycrystalline ceramic scintillators offer the advantages of high light yield, ease of fabrication, low cost, and robust mechanical properties. Precursor powders used in these studies include ZnO and ZnO:Ga powders synthesized using solution-phase, urea precipitation, and combustion synthesis techniques as well as ZnO powder from a commercial vendor. Precursor powders have been sintered using uniaxial hot pressing and spark plasma sintering techniques. Photoluminescence measurements have confirmed that, for most samples, the emissions from these sintered bodies consist primarily of slow, visible emissions rather than the desired sub-nanosecond near-band-edge emissions. Subsequent hydrogen treatments have shown significant improvements in the luminescence characteristics of some ceramic bodies, while other samples have shown no change in luminescence.

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Metal monochalcogenide quantum dot nanocrystals of ZnS, CdS and SnS were prepared by anaerobic, metal-reducing bacteria using in situ capping by oleic acid or oleylamine. The capping agent preferentially adsorbs on the surface of the nanocrystal, suppressing the growth process in the early stages, thus leading to production of nanocrystals with a diameter of less than 5 nm.

-Particle Detectors

The effects of a cationic polyelectrolyte, polyethylenimine, on the rheological behavior of aqueous mullite and celsian phase, barium strontium aluminosilicate (BSAS) suspensions have been studied to optimize a dip-coating process. The surface of the ceramic particles was characterized in aqueous media using zeta potential measurements. The ionization behavior and hydrodynamic radius of polyethylenimine in aqueous media was characterized by potentiometric titration and dynamic light scattering measurements, respectively. The rheological behavior of concentrated ceramic suspensions containing polyethylenimine was characterized by stress viscometry and elastic modulus measurements. Polyethylenimine imparts repulsive, electrosteric interactions between mullite and BSAS particles in aqueous suspension, resulting in shear thinning flow behavior, linear elastic moduli, and yield stress values that are minimized for suspensions with a critical PEI concentration of 0.2 mg PEI per m 2 of mullite and 0.4 mg PEI per m 2 of BSAS, respectively. The elastic moduli and yield stress of mullite and BSAS suspensions were nearly identical at equivalent fractions of their critical PEI concentration. Uniform coatings were obtained upon dipping SiC, Si3N4, and Si-metal substrates into shear-thinning suspensions containing PEI at 81-88% of the critical concentration. Dense mullite coatings were demonstrated on SiC substrates after sintering at 1400 o C.

In situ capping for size control of monochalcogenide (ZnS, CdS and SnS) nanocrystals produced by anaerobic metal-reducing bacteria

Sequential NanoFermentation (SNF) is a novel process which entails sparging microbially produced gas containing H2S from a primary reactor through a concentrated metal-acetate solution contained in a secondary reactor, thereby precipitating metallic sulfide nanoparticles (e.g., ZnS, CuS, or SnS). SNF holds an advantage over single reactor nanoparticle synthesis strategies, because it avoids exposing the microorganisms to high concentrations of toxic metal and sulfide ions. Also, by segregating the nanoparticle products from biological materials, SNF avoids coating nanoparticles with bioproducts that alter their desired properties. Herein, we report the properties of ZnS nanoparticles formed from SNF as compared with ones produced directly in a primary reactor (i.e., conventional NanoFermentation, or “CNF”), commercially available ZnS, and ZnS chemically synthesized by bubbling H2S gas through a Zn-acetate solution. The ZnS nanoparticles produced by SNF provided improved optical properties due to their smaller crystallite size, smaller overall particle sizes, reduced biotic surface coatings, and reduced structural defects. SNF still maintained the advantages of NanoFermentation technology over chemical synthesis including scalability, reproducibility, and lower hazardous waste burden.

Tailored Rheological Behavior of Mullite and BSAS Suspensions Using a Cationic Polyelectrolyte

We present a method to prepare shear thickening electrolytes consisting of silica nanoparticles in conventional liquid electrolytes with limited flocculation. These electrolytes rapidly and reversibly stiffen to solidlike behaviors in the presence of external shear or high impact, which is promising for improved lithium ion battery safety, especially in electric vehicles. However, in initial chemistries the silica nanoparticles aggregate and/or sediment in solution over time. Here, we demonstrate steric stabilization of silica colloids in conventional liquid electrolyte via surface-tethered PMMA brushes, synthesized via surface-initiated atom transfer radical polymerization. The PMMA increases the magnitude of the shear thickening response, compared to the uncoated particles, from 0.311 to 2.25 Pa s. Ultrasmall-angle neutron scattering revealed a reduction in aggregation of PMMA-coated silica nanoparticles compared to bare silica nanoparticles in solution under shear and at rest, suggesting good stabilization. Conductivity tests of shear thickening electrolytes (30 wt % solids in electrolyte) at rest were performed with interdigitated electrodes positioned near the meniscus of electrolytes over the course of 24 h to track supernatant formation. Conductivity of electrolytes with bare silica increased from 10.1 to 11.6 mS cm-1 over 24 h due to flocculation. In contrast, conductivity of electrolytes with PMMA-coated silica remained stable at 6.1 mS cm-1 over the same time period, suggesting good colloid stability.

Improved ZnS nanoparticle properties through sequential NanoFermentation

The primary goal of the CPAC program at ORNL was to explore the feasibility of introducing various silica-based superhydrophobic (SH) powder additives as a way to improve the corrosion resistance of US Department of Defense (DOD) military-grade chemical agent resistant coating (CARC) systems. ORNL had previously developed and patented several SH technologies of interest to the USMC, and one of the objectives of this program was to identify methods to incorporate these technologies into the USMC’s corrosion-resistance strategy. This report discusses findings of the CPAC and their application.

Shear Thickening Electrolyte Built from Sterically Stabilized Colloidal Particles

The stability of the SiC layer in the presence of free nitrogen will be dependent upon the operating temperatures and resulting nitrogen pressures whether it is at High Temperature Gas-Cooled Reactor (HTGR) temperatures of 1000-1400 C (coolant design dependent) or LWR temperatures that range from 500-700 C. Although nitrogen released in fissioning will form fission product nitrides, there will remain an overpressure of nitrogen of some magnitude. The nitrogen can be speculated to transport through the inner pyrolytic carbon layer and contact the SiC layer. The SiC layer may be envisioned to fail due to resulting nitridation at the elevated temperatures. However, it is believed that these issues are particularly avoided in the LWR application. Lower temperatures will result in significantly lower nitrogen pressures. Lower temperatures will also substantially reduce nitrogen diffusion rates through the layers and nitriding kinetics. Kinetics calculations were performed using an expression for nitriding silicon. In order to further address these concerns, experiments were run with surrogate fuel particles under simulated operating conditions to determine the resulting phase formation at 700 and 1400 C.