Lithium-air batteries are considered to be a potential alternative to lithium-ion batteries for transportation applications, owing to their high theoretical specific energy. So far, however, such systems have been largely restricted to pure oxygen environments (lithium-oxygen batteries) and have a limited cycle life owing to side reactions involving the cathode, anode and electrolyte. In the presence of nitrogen, carbon dioxide and water vapour, these side reactions can become even more complex. Moreover, because of the need to store oxygen, the volumetric energy densities of lithium-oxygen systems may be too small for practical applications. Here we report a system comprising a lithium carbonate-based protected anode, a molybdenum disulfide cathode and an ionic liquid/dimethyl sulfoxide electrolyte that operates as a lithium-air battery in a simulated air atmosphere with a long cycle life of up to 700 cycles. We perform computational studies to provide insight into the operation of the system in this environment. This demonstration of a lithium-oxygen battery with a long cycle life in an air-like atmosphere is an important step towards the development of this field beyond lithium-ion technology, with a possibility to obtain much higher specific energy densities than for conventional lithium-ion batteries.
The utility of ferroelectric materials stems from the ability to nucleate and move polarized domains using an electric field. To understand the mechanisms of polarization switching, structural characterization at the nanoscale is required. We used aberration-corrected transmission electron microscopy to follow the kinetics and dynamics of ferroelectric switching at millisecond temporal and subangstrom spatial resolution in an epitaxial bilayer of an antiferromagnetic ferroelectric (BiFeO(3)) on a ferromagnetic electrode (La(0.7)Sr(0.3)MnO(3)). We observed localized nucleation events at the electrode interface, domain wall pinning on point defects, and the formation of ferroelectric domains localized to the ferroelectric and ferromagnetic interface. These results show how defects and interfaces impede full ferroelectric switching of a thin film.
Ferroelectric materials are characterized by a spontaneous polarization, which can be reoriented with an applied electric field. The switching between polarized domains is mediated by nanoscale defects. understanding the role of defects in ferroelectric switching is critical for practical applications such as non-volatile memories. This is especially the case for ferroelectric nanostructures and thin films in which the entire switching volume is proximate to a defective surface. Here we report the nanoscale ferroelectric switching of a tetragonal PbZr 0.2 Ti 0.8 o 3 thin film under an applied electric field using in situ transmission electron microscopy. We found that the intrinsic electric fields formed at ferroelectric/electrode interfaces determine the nucleation sites and growth rates of ferroelectric domains and the orientation and mobility of domain walls, whereas dislocations exert a weak pinning force on domain wall motion.
Polarization switching in ferroelectric thin films occurs via nucleation and growth of 180°d omains through a highly inhomogeneous process in which the kinetics are largely controlled by defects, interfaces and pre-existing domain walls. Here we present the first real-time, atomic-scale observations and phase-field simulations of domain switching dominated by pre-existing, but immobile, ferroelastic domains in Pb(Zr 0.2 Ti 0.8 )O 3 thin films. Our observations reveal a novel hindering effect, which occurs via the formation of a transient layer with a thickness of several unit cells at an otherwise charged interface between a ferroelastic domain and a switched domain. This transient layer possesses a low-magnitude polarization, with a dipole glass structure, resembling the dead layer. The present study provides an atomic level explanation of the hindering of ferroelectric domain motion by ferroelastic domains. Hindering can be overcome either by applying a higher bias or by removing the as-grown ferroelastic domains in fabricated nanostructures.
Lithium-CO 2 batteries are attractive energy storage systems for fulfilling the demand of future large-scale applications such as electric vehicles due to their high specific energy density compared to lithium-ion batteries. However, a major challenge with Li-CO 2 batteries is attaining reversible formation and decomposition of the Li 2 CO 3 and carbon discharge products, along with a lack of mechanistic understanding of the associated charge and discharge reaction mechanisms. In this study, we developed a fully reversible Li-CO 2 battery with overall carbon neutrality using molybdenum disulfide nanoflakes as a cathode catalyst combined with an ionic liquid and dimethyl sulfoxide hybrid electrolyte. This combination of materials produces a multicomponent composite (Li 2 CO 3 /C) product rather than formation of separated carbon and Li 2 CO 3 nanoparticles. The battery shows a superior long cycle life of 500 for a fixed 500 mAh/g capacity per cycle, which is by far the best cycling stability reported in Li-CO 2 batteries, respectively. The long cycle life demonstrates for the first time that covalent CO bond making and breaking chemical transformations can be used in energy storage systems, in addition to the widely studied alkali metal (Li, Na, K)-oxygen ionic-bond making and breaking transformations. Theoretical calculations are used to deduce a mechanism for the reversible discharge/charge processes and explain how the carbon interface with Li 2 CO 3 provides the electronic conduction needed for the oxidation of Li 2 CO 3 , as well as the carbon to generate the CO 2 on charge. The achievement of a reversible, long cycle life Li-CO 2 battery opens the way for use of CO 2 in advanced energy storage systems. Lithium-ion batteries are widely used as electrochemical energy storage systems for consumer electronics [1] ; however, technologies with higher specific energy are needed for electrified transportation applications [2]. Therefore, beyond Li-ion battery chemistries such as rechargeable Li-O 2 batteries have recently garnered much attention This article is protected by copyright. All rights reserved. 3 due to their higher theoretical energy density [3,4]. Li-O 2 batteries generally have limited cyclability, though several studies have reported new concepts that have achieved long cycle life [5,6]. Although far less studied, the Li-CO 2 battery is another beyond Li-ion technology with a theoretical energy density of 1876 Wh/kg [7,8] , far exceeding that of Li-ion batteries (~265 Wh/kg). This type of battery involves CO 2 reduction and evolution reactions during discharge and charge, respectively, on the surface of a porous cathode with an electrolyte based on lithium salts.
In thin film ferroelectric devices, switching of ferroelastic domains can significantly enhance electromechanical response. Previous studies have shown disagreement regarding the mobility or immobility of ferroelastic domain walls, indicating that switching behaviour strongly depends on specific microstructures in ferroelectric systems. Here we study the switching dynamics of individual ferroelastic domains in thin Pb(Zr 0.2 ,Ti 0.8 )O 3 films under electrical and mechanical excitations by using in situ transmission electron microscopy and phase-field modelling. We find that ferroelastic domains can be effectively and permanently stabilized by dislocations at the substrate interface while similar domains at free surfaces without pinning dislocations can be removed by either electric or stress fields. For both electrical and mechanical switching, ferroelastic switching is found to occur most readily at the highly active needle points in ferroelastic domains. Our results provide new insights into the understanding of polarization switching dynamics as well as the engineering of ferroelectric devices.
While α-V2O5 has traditionally been considered as a promising oxide to reversibly intercalate high levels of Mg2+ at high potential, recent reports indicate that previously observed electrochemical activity is dominated by intercalation of H+ rather than Mg2+, even in moderately dry nonaqueous electrolytes. Consequently, the inherent functionality of oxides to intercalate Mg2+ remains in question. By conducting electrochemistry in a chemically and anodically stable ionic liquid electrolyte, we report that, at 110 °C, layered α-V2O5 is indeed capable of reversibly intercalating 1 mol Mg2+ per unit formula, to accumulate capacities above 280 mAh g–1. Multimodal characterization confirmed intercalation of Mg2+ by probing the elemental, redox, and morphological changes undergone by the oxide. After cycling at 110 °C, the electrochemical activity at room temperature was significantly enhanced. The results renew prospects for functional Mg rechargeable batteries surpassing the levels of energy density of current Li-ion batteries.
Controlled switching of resistivity in ferroelectric thin films is demonstrated by writing and erasing stable, nanoscale, strongly charged domain walls using an in situ transmission electron microscopy technique. The resistance can be read nondestructively and presents the largest off/on ratio (≈10(5) ) ever reported in room-temperature ferroelectric devices, opening new avenues for engineering ferroelectric thin-film devices.
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