RESUMEN
The practical application of lithium-oxygen batteries (LOBs) with ultrahigh theoretical energy density faces the problems of poor kinetics and deficient reversibility. The electrolyte is of vital significance to the electrochemical stability and reaction pathway of LOBs due to the formation of soluble products. Here, a 15-crown-5 ether (15C5) is employed to regulate the solvation structure of Li+ and manipulate the reaction mechanism through regulating the binding ability toward Li+. The promoted dissociation of LiNO3 by 15C5 increases the catalytical active anions in the electrolyte and stabilizes the Li-containing reduced oxygen species to promote the solution pathway of discharge product growth. Besides, 15C5 also facilitates the kinetics of the electrochemical decomposition of Li2O2 and prolongs the cycle life to 178 cycles. This work inspires a novel approach to improve the battery performance through electrolyte component design.
RESUMEN
The sluggish ionic transport in thick electrodes and freezing electrolytes has limited electrochemical energy storage devices in lots of harsh environments for practical applications. Here, a 3D-printed proton pseudocapacitor based on high-mass-loading 3D-printed WO3 anodes, Prussian blue analog cathodes, and anti-freezing electrolytes is developed, which can achieve state-of-the-art electrochemical performance at low temperatures. Benefiting from the cross-scale 3D electrode structure using a 3D printing direct ink writing technique, the 3D-printed cathode realizes an ultrahigh areal capacitance of 7.39 F cm-2 at a high areal mass loading of 23.51 mg cm-2 . Moreover, the 3D-printed pseudocapacitor delivers an areal capacitance of 3.44 F cm-2 and excellent areal energy density (1.08 mWh cm-2 ). Owing to the fast ion kinetics in 3D electrodes and the high ionic conductivity of the hybrid electrolyte, the 3D-printed supercapacitor delivers 61.3% of the room-temperature capacitance even at -60 °C. This work provides an effective strategy for the practical applications of energy storage devices with complex physical structure at extreme temperatures.
RESUMEN
Ionic and electronic transport in electrodes is crucial for electrochemical energy storage technology. To optimize the transport pathway of ions and electrons, electrode materials are minimized to nanometer-sized dimensions, leading to problems of volumetric performance, stability, cost, and pollution. Here we find that a bulk hexagonal molybdenum oxide with unconventional ion channels can store large amounts of protons at a high rate even if its particle size is tens of micrometers. The diffusion-free proton transport kinetics based on hydrogen bonding topochemistry is demonstrated in hexagonal molybdenum oxide whose proton conductivity is several orders of magnitude higher than traditional orthorhombic molybdenum oxide. In situ X-ray diffraction and theoretical calculation reveal that the structural self-optimization in the first discharge effectively promotes the reversible intercalation/de-intercalation of subsequent protons. The open crystal structure, suitable proton channels, and negligible volume strain enable rapid and stable proton transport and storage, resulting in extremely high volumetric capacitance (~1750 F cm-3), excellent rate performance, and ultralong cycle life (>10,000 cycles). The discovery of unconventional materials and mechanisms that enable proton storage of micrometer-sized particles in seconds boosts the development of fast-charging energy storage systems and high-power practical applications.