Lithium-rich layered transition metal oxide positive electrodes offer access to anion redox at high potentials, thereby promising high energy densities for lithium-ion batteries. However, anion redox is also associated with several unfavorable electrochemical properties, such as open-circuit voltage hysteresis. Here we reveal that in Li1.17–xNi0.21Co0.08Mn0.54O2, these properties arise from a strong coupling between anion redox and cation migration. We combine various X-ray spectroscopic, microscopic, and structural probes to show that partially reversible transition metal migration decreases the potential of the bulk oxygen redox couple by > 1 V, leading to a reordering in the anionic and cationic redox potentials during cycling. First principles calculations show that this is due to the drastic change in the local oxygen coordination environments associated with the transition metal migration. We propose that this mechanism is involved in stabilizing the oxygen redox couple, which we observe spectroscopically to persist for 500 charge/discharge cycles.
The reaction mechanism of a high capacity lithium-and manganese-rich metal oxide, 0.4Li 2 MnO 3-0.6LiMn 0.5 Ni 0.5 O 2 , has been investigated at the atomic level. High-resolution synchrotron X-ray powder diffraction (HRPD) and X-ray absorption spectroscopy (XAS) were used, respectively, to evaluate the electrochemical charge and discharge reactions in terms of local and bulk structural changes, and variations in the oxidation states of the transition metal ions. Ni Kedge XAS data indicate the participation of nickel in reversible redox reactions, whereas Mn K-edge absorption spectra show that the manganese ions do not participate in the electrochemical reactions. Rietveld refinements of the oxygen occupancy during charge and discharge provide evidence of reversible oxygen release and re-accommodation by the host structure; this unique oxygen participation is likely the main reason for the anomalously high capacity of these electrodes. The HRPD data also show that during the early cycles, characteristic peaks of the Li 2 MnO 3 component disappear when charged to 4.7 V, but reappear on discharge to 2.5 V, consistent with a reversible lithium and oxygen extraction process. The results provide new insights into the charge compensation mechanisms that occur when high capacity, lithium-and manganese-rich electrode materials are electrochemically cycleda topic that is currently being hotly debated in the literature.
The theory of speckle noise in a scanning beam is presented. The general formulas for the calculation of speckle contrast, which apply to any scanning display, are obtained. It is shown that the main requirement for successful speckle suppression in a scanning display is a narrow autocorrelation peak and low sidelobe level in the autocorrelation function of the complex amplitude distribution across a scanning light beam. The simple formulas for speckle contrast for a beam with a narrow autocorrelation function peak were obtained. It was shown that application of a diffractive optical element (DOE) with a Barker code phase shape could use only natural display scanning motion for speckle suppression. DOE with a Barker code phase shape has a small size and may be deposited on the light modulator inside the depth of the focus of the reflected beam area, and therefore, it does not need an additional image plane and complicated relay optics.
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