In Situ Transmission X-Ray Microscopy of the Lead Sulfate Film Formation on Lead in Sulfuric Acid

Transmission X-ray microscopy is utilized to monitor, in real time, the behavior of the PbSO4 film that is formed on Pb in H2SO4. Images collected from the synchrotron x-rays are coupled with voltammetric data to study the initial formation, the resulting passivation, and the subsequent reduction of the film. It is concluded with support from quartz-crystal-microbalance experiments that the initial formation of PbSO4 crystals occurs as a result of acidic corrosion. In addition, the film is shown to coalesce during the early stages of galvanostatic oxidation and to passivate as a result of morphological changes in the existing film. Finally, it is observed that the passivation process results in the formation of large PbSO4 crystals with low area-to-volume ratios, which are difficult to reduce under both galvanostatic and potentiostatic conditions

Characterization of 3D Interconnected Microstructural Network in Mixed Ionic and Electronic Conducting Ceramic Composites

The microstructure and connectivity of the ionic and electronic conductive phases in composite ceramic membranes are directly related to device performance. Transmission electron microscopy (TEM) including chemical mapping combined with X-ray nanotomography (XNT) have been used to characterize the composition and 3-D microstructure of a MIEC composite model system consisting of a Ce0.8Gd0.2O2 (GDC) oxygen ion conductive phase and a CoFe2O4 (CFO) electronic conductive phase. The microstructural data is discussed, including the composition and distribution of an emergent phase which takes the form of isolated and distinct regions. Performance implications are considered with regards to the design of new material systems which evolve under non-equilibrium operating conditions

Quantified abundance of magnetofossils at the Paleocene–Eocene boundary from synchrotron-based transmission X-ray microscopy

The Paleocene–Eocene boundary (∼55.8 million years ago) is marked by an abrupt negative carbon isotope excursion (CIE) that coincides with an oxygen isotope decrease interpreted as the Paleocene–Eocene thermal maximum. Biogenic magnetite (Fe[subscript 3]O[subscript 4]) in the form of giant (micron-sized) spearhead-like and spindle-like magnetofossils, as well as nano-sized magnetotactic bacteria magnetosome chains, have been reported in clay-rich sediments in the New Jersey Atlantic Coastal Plain and were thought to account for the distinctive single-domain magnetic properties of these sediments. Uncalibrated strong field magnet extraction techniques have been typically used to provide material for scanning and transmission electron microscopic imaging of these magnetic particles, whose concentration in the natural sediment is thus difficult to quantify. In this study, we use a recently developed ultrahigh-resolution, synchrotron-based, full-field transmission X-ray microscope to study the iron-rich minerals within the clay sediment in their bulk state. We are able to estimate the total magnetization concentration of the giant biogenic magnetofossils to be only ∼10% of whole sediment. Along with previous rock magnetic studies on the CIE clay, we suggest that most of the magnetite in the clay occurs as isolated, near-equidimensional nanoparticles, a suggestion that points to a nonbiogenic origin, such as comet impact plume condensates in what may be very rapidly deposited CIE clays.Rutgers University (Board of Governors Professor Research Fund

3D analysis of a LiCoO_2-Li(Ni_(1/3)Mn_(1/3)Co_(1/3))O_2 Li-ion battery positive electrode using x-ray nano-tomography

A full-field high-resolution x-ray nano-tomography technique, transmission x-ray microscopy (TXM), was used to reveal the 3D morphology of the lithium ion battery composite positive electrode: LiCoO_2 (LCO)-Li(Ni_(1/3)Mn_(1/3)Co_(1/3))O_2 (NMC). The TXM method allowed the unambiguous chemical identification of oxide particles by tuning the x-ray energy relative to the transition-metal absorption edges. The NMC particles have a much rougher surface compared to the LCO particles. Cracks due to processing exist in both LCO and NMC particles but the NMC particles exhibit more severe cracking and also tend to have internal pores in addition to radial cracks. Further, the carbon-based phases including the binder and the conductive carbon were identified using Zernike phase contrast imaging

X-ray nanotomography analysis of the microstructural evolution of LiMn_2 O_4 electrodes

One of the greatest challenges for advancing lithium-ion battery (LIB) technology is to minimize cell degradation during operation for long-term stability. To this end, it is important to understand how cell performance during operation relates to complex LIB microstructures. In this report, transmission X-ray microscopy (TXM) nanotomography is used to gain quantitative three-dimensional (3D) microstructure-performance correlations of LIB cathodes during cycling. The 3D microstructures of LiMn_2O_4 (LMO) electrodes, cycled under different conditions, including cycle number, operating voltage, and temperature, are characterized via TXM and statistically analyzed to investigate the impact of cycling conditions on the electrode microstructural evolution and cell performance. It is found that the number of cracks formed within LMO particles correlated with capacity fade. For the cell cycled at elevated temperatures, which exhibits the most severe capacity fade among all cells tested, mechanical cracking observed in TXM is not the only dominant contributor to the observed degradation. Mn^(2+) dissolution, as verified by detection of Mn on the counter electrode by energy dispersive spectrometry, also contributed. The current work demonstrate 3D TXM nanotomography as a powerful tool to help probe in-depth understanding of battery failure mechanisms, which could be applicable to electrode structure optimization for advancing LIB development

X-ray nanotomography analysis of the microstructural evolution of LiMn_2 O_4 electrodes

One of the greatest challenges for advancing lithium-ion battery (LIB) technology is to minimize cell degradation during operation for long-term stability. To this end, it is important to understand how cell performance during operation relates to complex LIB microstructures. In this report, transmission X-ray microscopy (TXM) nanotomography is used to gain quantitative three-dimensional (3D) microstructure-performance correlations of LIB cathodes during cycling. The 3D microstructures of LiMn_2O_4 (LMO) electrodes, cycled under different conditions, including cycle number, operating voltage, and temperature, are characterized via TXM and statistically analyzed to investigate the impact of cycling conditions on the electrode microstructural evolution and cell performance. It is found that the number of cracks formed within LMO particles correlated with capacity fade. For the cell cycled at elevated temperatures, which exhibits the most severe capacity fade among all cells tested, mechanical cracking observed in TXM is not the only dominant contributor to the observed degradation. Mn^(2+) dissolution, as verified by detection of Mn on the counter electrode by energy dispersive spectrometry, also contributed. The current work demonstrate 3D TXM nanotomography as a powerful tool to help probe in-depth understanding of battery failure mechanisms, which could be applicable to electrode structure optimization for advancing LIB development