Abstract Layered oxide cathode with a Li‐O‐vacancy configuration offers high capacity by leveraging additional oxygen redox reactions. However, it faces severe challenges of sluggish kinetics of oxygen redox reactions and lattice oxygen loss, resulting in slow Li+diffusion and rapid electrochemical degradation. Herein, Ti is introduced as electrochemical inactive element into Li‐O‐vacancy configuration to form Mn/vacancy/Ti arrangement within transition metal layers of layered oxide, achieving a marked increase in average output voltage at high current density compared with Ti‐free counterpart. Not only voltage hysteresis between charge and discharge processes can be significantly reduced, but rate capability can be heightened in Li4/7[□1/7Ti1/7Mn5/7]O2by means of retrained over‐potential and improved Li+diffusivity. Furthermore, theoretical calculations suggest that these improvements stem from Ti substitution, which elongates the Li─O bond and lowers the Li+migration energy barrier. Besides, in situ differential electrochemical mass spectrometry and soft X‐ray absorption spectroscopy reveal the modified Li‐O‐vacancy configuration enables reversible anionic and cationic redox behaviors during cycling. These findings provide a promising strategy for tailoring oxygen redox activity and accelerating Li+diffusion kinetics in layered cathode materials with oxygen redox chemistry.
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3D oxygen vacancy distribution and defect-property relations in an oxide heterostructure
Abstract Oxide heterostructures exhibit a vast variety of unique physical properties. Examples are unconventional superconductivity in layered nickelates and topological polar order in (PbTiO3)n/(SrTiO3)nsuperlattices. Although it is clear that variations in oxygen content are crucial for the electronic correlation phenomena in oxides, it remains a major challenge to quantify their impact. Here, we measure the chemical composition in multiferroic (LuFeO3)9/(LuFe2O4)1superlattices, mapping correlations between the distribution of oxygen vacancies and the electric and magnetic properties. Using atom probe tomography, we observe oxygen vacancies arranging in a layered three-dimensional structure with a local density on the order of 1014 cm−2, congruent with the formula-unit-thick ferrimagnetic LuFe2O4layers. The vacancy order is promoted by the locally reduced formation energy and plays a key role in stabilizing the ferroelectric domains and ferrimagnetism in the LuFeO3and LuFe2O4layers, respectively. The results demonstrate pronounced interactions between oxygen vacancies and the multiferroic order in this system and establish an approach for quantifying the oxygen defects with atomic-scale precision in 3D, giving new opportunities for deterministic defect-enabled property control in oxide heterostructures.
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- Award ID(s):
- 1719875
- PAR ID:
- 10548843
- Publisher / Repository:
- Springer Nature
- Date Published:
- Journal Name:
- Nature Communications
- Volume:
- 15
- Issue:
- 1
- ISSN:
- 2041-1723
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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