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 composition of amorphous oxide semiconductors, which are well known for their optical transparency, can be tailored to enhance their absorption and induce photoconductivity for irradiation with green, and shorter wavelength light. In principle, amorphous oxide semiconductor-based thin-film photoconductors could hence be applied as photosensors. However, their photoconductivity persists for hours after illumination has been removed, which severely degrades the response time and the frame rate of oxide-based sensor arrays. We have solved the problem of persistent photoconductivity (PPC) by developing a gated amorphous oxide semiconductor photo thin-film transistor (photo-TFT) that can provide direct control over the position of the Fermi level in the active layer. Applying a short-duration (10 ns) voltage pulse to these devices induces electron accumulation and accelerates their recombination with ionized oxygen vacancy sites, which are thought to cause PPC. We have integrated these photo-TFTs in a transparent active-matrix photosensor array that can be operated at high frame rates and that has potential applications in contact-free interactive displays.
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