To achieve a high reversibility and long cycle life for lithium-oxygen (Li-O) batteries, the irreversible formation of LiO, inevitable side reactions, and poor charge transport at the cathode interfaces should be overcome. Here, we report a rational design of air cathode using a cobalt nitride (CoN) functionalized carbon nanofiber (CNF) membrane as current collector-catalyst integrated air cathode. Brush-like CoN nanorods are uniformly anchored on conductive electrospun CNF papers via hydrothermal growth of Co(OH)F nanorods followed by nitridation step. CoN-decorated CNF (CoN/CNF) cathode exhibited excellent electrochemical performance with outstanding stability for over 177 cycles in Li-O cells. During cycling, metallic CoN nanorods provide sufficient accessible reaction sites as well as facile electron transport pathway throughout the continuously networked CNF. Furthermore, thin oxide layer (<10 nm) formed on the surface of CoN nanorods promote reversible formation/decomposition of film-type LiO, leading to significant reduction in overpotential gap (∼1.23 V at 700 mAh g). Moreover, pouch-type Li-air cells using CoN/CNF cathode stably operated in real air atmosphere even under 180° bending. The results demonstrate that the favorable formation/decomposition of reaction products and mediation of side reactions are hugely governed by the suitable surface chemistry and tailored structure of cathode materials, which are essential for real Li-air battery applications.
Lithium−oxygen (Li−O 2 ) batteries have been intensively investigated in recent decades for their utilization in electric vehicles. The intrinsic challenges arising from O 2 (electro)chemistry have been mitigated by developing various types of catalysts, porous electrode materials, and stable electrolyte solutions. At the next stage, we face the need to reform batteries by substituting pure O 2 gas with air from Earth's atmosphere. Thus, the key emerging challenges of Li−air batteries, which are related to the selective filtration of O 2 gas from air and the suppression of undesired reactions with other constituents in air, such as N 2 , water vapor (H 2 O), and carbon dioxide (CO 2 ), should be properly addressed. In this review, we discuss all key aspects for developing Li−air batteries that are optimized for operating in ambient air and highlight the crucial considerations and perspectives for future air-breathing batteries.
NCL is rationally designed as the stable protective layer on Li metal for dendrite- and oxygen-proof in Li–O2 batteries.
The charge/discharge capacity of current lithium-ion battery cathode materials is limited by the charge compensation of transition-metal redox during the charge/discharge processes. Recently, the use of oxide ion redox for charge compensation has been proposed to realize a higher charge/discharge capacity than that observed for transition-metal redox. Different stabilization mechanisms of the reversible oxide ion redox have been proposed. To clarify the mechanism, analysis of the electronic and local structures around oxygen is required. Because of the high-voltage region in which the oxide ion redox occurs, several reactions such as oxygen gas evolution and/or electrolyte oxidation are often included. Thus, operando measurements are required to directly prove this concept and generalize the understanding of the oxide ion redox. This study employs operando soft/hard X-ray absorption spectroscopy combined with X-ray diffraction spectroscopy for four lithium-excess electrode materials with different chemical bond natures. The experimental data together with online analysis of the generated on-charge gas reveal two extreme cases: significantly enhanced covalent or ionic characters in the metal–oxygen chemical bonds, which are necessary conditions to stabilize the oxidation of the oxide ions. This finding provides new insights with exciting possibilities for designing high energy density cathode materials based on anion redox.
Employing organic redox mediators (ORMs) for lithium−oxygen (Li−O 2 ) batteries has emerged as an important strategy to suppress charging overpotentials. Judicious molecular designs of ORMs can also tailor their redox potential and electrontransfer rate to optimize the catalytic efficiency. However, the stability of ORMs in Li−O 2 cells was scarcely studied. Here, the catalytic efficiency and stability of several important ORMs are assessed through in situ gas analysis and reactivity tests with singlet oxygen. Some well-known ORMs are detrimentally decomposed during the first cycle in Li−O 2 cells, whereas nitroxyl-radical-based ORMs bear the most stable and efficient response. Analogous nitroxyl-radical derivatives further increase round-trip energy efficiency and electron-transfer kinetics. This study underlines chemical stability aspects of ORMs, which are mandatory for the long-term cyclability in Li−O 2 cells. We emphasize that besides the importance of ORMs in these systems and their proper selection, an effective operation of Li−O 2 cells depends also strongly on the stability of the carbonaceous cathodes and the electrolyte solutions. The stability of all the components in these systems is inter-related.
scite is a Brooklyn-based organization that helps researchers better discover and understand research articles through Smart Citations–citations that display the context of the citation and describe whether the article provides supporting or contrasting evidence. scite is used by students and researchers from around the world and is funded in part by the National Science Foundation and the National Institute on Drug Abuse of the National Institutes of Health.
hi@scite.ai
10624 S. Eastern Ave., Ste. A-614
Henderson, NV 89052, USA
Copyright © 2024 scite LLC. All rights reserved.
Made with 💙 for researchers
Part of the Research Solutions Family.