The capacity fade of lithium manganate-based cells is associated with the dissolution of Mn from cathode/electrolyte interface due to the disproportionation reaction of Mn(III), and the subsequent deposition of Mn(II) on the anode. Suppressing the dissolution of Mn from the cathode is critical to reducing capacity fade of LiMn 2 O 4 -based cells. Here we report a nanoscale surface-doping approach that minimizes Mn dissolution from lithium manganate. This approach exploits advantages of both bulk doping and surface-coating methods by stabilizing surface crystal structure of lithium manganate through cationic doping while maintaining bulk lithium manganate structure, and protecting bulk lithium manganate from electrolyte corrosion while maintaining ion and charge transport channels on the surface through the electrochemically active doping layer. Consequently, the surface-doped lithium manganate demonstrates enhanced electrochemical performance. This study provides encouraging evidence that surface doping could be a promising alternative to improve the cycling performance of lithium-ion batteries.
Polymer electrolyte fuel cells (PEFCs) are a promising high-efficiency energy conversion technology, but their cost-effective implementation, especially for automotive power, has been hindered by degradation of the electrochemically active surface area (ECA) of the Pt nanoparticle electrocatalysts. While numerous studies using ex situ post-mortem techniques have provided insight into the effect of operating conditions on ECA loss, the governing mechanisms and underlying processes are not fully understood. Toward the goal of elucidating the electrocatalyst degradation mechanisms, we have followed Pt nanoparticle growth during potential cycling of the electrocatalyst in an aqueous acidic environment using in situ anomalous small-angle X-ray scattering (ASAXS). ASAXS patterns were analyzed to obtain particle size distributions (PSDs) of the Pt nanoparticle electrocatalysts at periodic intervals during the potential cycling. Oxide coverages reached under the applied potential cycling protocols were both calculated and determined experimentally. Changes in the PSD, mean diameter, and geometric surface area identify the mechanism behind Pt nanoparticle coarsening in an aqueous environment. Over the first 80 potential cycles, the dominant Pt surface area loss mechanism when cycling to 1.0-1.1 V was found to be preferential dissolution or loss of the smallest particles with varying extents of reprecipitation of the dissolved species onto existing particles, resulting in particle growth, depending on potential profile. Correlation of ASAXS-determined particle growth with both calculated and voltammetrically determined oxide coverages demonstrates that the oxide coverage is playing a key role in the dissolution process and in the corresponding growth of the mean Pt nanoparticle size and loss of ECA. This understanding potentially reduces the complex changes in PSD and ECA resulting from various voltage profiles to a response dependent on oxide coverage.
The evolution of Pt nanoparticle cathode electrocatalyst size distribution in a polymer electrolyte membrane fuel cell (PEMFC) was followed during accelerated stress tests using in-operando anomalous small-angle X-ray scattering (ASAXS). This evolution was compared to that observed in an aqueous electrolyte environment using stagnant electrolyte, flowing electrolyte, and flowing electrolyte at elevated temperature to reveal the different degradation trends in the PEMFC and aqueous environments and to determine the relevance of aqueous measurements to
The mechanism of uranium (U) incorporation into calcite (calcium carbonate) is of fundamental importance to the fate and transport of U at the surface and in the shallow subsurface and has implications for (a) the accuracy of U-Pb and U-series isotope ratio methods used to determine the ages of ancient deposits and (b) potential remediation strategies based on sequestration of U in the subsurface. Extended X-ray absorption fine structure (EXAFS) spectroscopy is uniquely suited to the study of U-calcite systems. The sensitivity of the EXAFS spectrum to the local atomic Ca coordination about U(VI) in the calcite structure results in an increase in the number and amplitude of Ca signals as the U(VI) becomes more ordered within the crystal structure. Our X-ray microprobe (10-microm) measurements of an ancient 298 million-year-old organic-rich calcite (calcrete) clearly revealed three coordination shells of Ca atoms, defining a well-ordered calcite structure about uranyl to a distance of approximately 6.5 angstroms. These results indicate that uranyl is incorporated at the Ca2+ site in calcite and that the uranyl environment may evolve over long time scales, becoming more calcite-like and more stable for long-term sequestration of uranium. These results therefore validate U-related dating methods and show that calcite can be effective at sequestering U in vadose zone sediments.
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