Highly Stable Carbon‐Free Ag/Co3O4‐Cathodes for Lithium‐Air Batteries: Electrochemical and Structural Investigations

Lithium‐air batteries with an aqueous alkaline electrolyte promise a much higher practical energy density and capacity than conventional lithium‐ion batteries. However, high cathode overpotentials are some of the main problems during cycling. In our previous work, a catalyst combination of Ag and Co₃O₄ is found that reduces overpotential significantly, and is highly active and also long‐term stable. In the present investigations, X‐ray diffraction and X‐ray photoelectron spectroscopy are applied to study the structure and composition of the cathode material during oxygen reduction reaction and oxygen evolution reaction. Changes of the oxidation states during cycling are responsible for an enhanced oxygen evolution reaction current density but also for losses due to a lower electronic conductivity of the electrodes. The presence and formation of a mixed oxidation state for silver oxide (Ag^IAg^IIIO₂) at high potentials is identified. In contradiction to literature, time dependent X‐ray diffraction measurements evidence that this phase is not stable under dry conditions and progressively decays to Ag₂O. Electrode mappings show a highly homogeneous oxidation of the electrodes during cycling and quantitative analysis of the observed phases is carried out by Rietveld analysis. Long‐term material behavior completes the investigations.     

Hybrid and Aqueous Lithium‐Air Batteries

Lithium‐air (Li‐air) batteries have become attractive because of their extremely high theoretical energy density. However, conventional Li‐air cells operating with non‐aqueous electrolytes suffer from poor cycle life and low practical energy density due to the clogging of the porous air cathode by insoluble discharge products, contamination of the organic electrolyte and lithium metal anode by moist air, and decomposition of the electrolyte during cycling. These difficulties may be overcome by adopting a cell configuration that consists of a lithium‐metal anode protected from air by a Li⁺‐ion solid electrolyte and an air electrode in an aqueous catholyte. In this type of configuration, a Li⁺‐ion conducting “buffer” layer between the lithium‐metal anode and the solid electrolyte is often necessary due to the instability of many solid electrolytes in contact with lithium metal. Based on the type of buffer layer, two different battery configurations are possible: “hybrid” Li‐air batteries and “aqueous” Li‐air batteries. The hybrid and aqueous Li‐air batteries utilize the same battery chemistry and face similar challenges that limit the cell performance. Here, an overview of recent developments in hybrid and aqueous Li‐air batteries is provided and the factors that influence their performance and impede their practical applications, followed by future directions are discussed.     

Carbonyls: Powerful Organic Materials for Secondary Batteries

The application of organic carbonyl compounds as high performance electrode materials in secondary batteries enables access to metal‐free, low‐cost, environmental friendly, flexible, and functional rechargeable energy storage systems. Organic compounds have so far not received much attention as potential active materials in batteries, mainly because of the success of inorganic materials in both research and commercial applications. However, new requirements in secondary batteries such as flexibility accompanied with low production costs and environmental friendliness, in particular for portable devices, reach the limit of inorganic electrode materials. Organic carbonyl compounds represent the most promising materials to satisfy these needs. Here, recent efforts of the research in the field of organic carbonyl materials for secondary batteries are summarized, and the working principle and the structural design of different groups of carbonyl material is presented. Finally, the influence of conductive additives and binders on the cell performance is closely evaluated for each class of materials.     

Electrochemical Performance Enhancement of 3D Printed Electrodes Tailored for Enhanced Gas Evacuation during Alkaline Water Electrolysis

A zero-gap cell with porous electrodes is a promising configuration for alkaline water electrolysis. However, gas evacuation becomes a challenge in that case, as bubbles can get trapped within the electrode's 3D structure. This work considers a number of 3D printed electrode geometries with so-called triply periodic minimal surfaces (TPMS). The latter is a mathematically defined structure that repeats itself in three dimensions with zero mean curvature, and can therefore be expected to be particularly well-suited to enhance gas evacuation. Another advantage as compared to other state-of-the-art 3D electrodes like foams or felts lies in the fact that their porosity, which determines the available surface area, and their pore size or flow channel dimensions, which determines the degree of bubble entrapment, can be varied independently. By a combined experimental and modeling approach, this work then identifies the structural parameters that direct the performance of such 3D printed TPMS geometries toward enhanced gas evacuation. It is demonstrated that an optimal combination of these parameters allows, under a forced electrolyte flow, for a reduction in cell overpotential of more than 20%. This indicates that efforts in optimizing the electrode's geometry can give a similar electrochemical performance enhancement as optimizing its electro-catalytic composition.     

Fusion of mitochondrial inner membranes by electric fields produces inside-out vesicles: Visualization by freeze-fracture electron microscopy

The fusion of vesicular-shaped mitochondrial inner membranes was observed by a new approach which combines freeze-fracture electron microscopy and electric field-induced fusion. Results show that membrane events caused by the exposure to the electric field can be time-coordinated with sample freezing for subsequent analysis by freeze-fracture electron microscopy.     

Ultrafine Copper Nanopalm Tree‐Like Framework Decorated with Iron Oxide for Li‐Ion Battery Anodes with Exceptional Rate Capability and Cycling Stability

Ultrafine copper nanopalm tree‐like frameworks conformally decorated with iron oxide (Cu NPF@Fe₂O₃) are prepared by a facile electrodeposition method utilizing bromine ions as unique anisotropic growth catalysts. The formation mechanism and control over Cu growth are comprehensively investigated under various conditions to provide a guideline for fabricating a Cu nanoarchitecture via electrochemical methods. The optimized Cu NPFs exhibit ultrathin (<90 nm) and elongated (2–50 µm) branches with well‐interconnected and entangled features, which result in highly desirable attributes such as a large specific surface area (≈6.97 m² g^?1), free transfer pathway for Li⁺, and high electrical conductivity. The structural advantages of Cu NPF@Fe₂O₃ enhance the electrochemical kinetics, providing large reactivity, fast Li⁺/electron transfer, and structural stability during cycling, that lead to superior electrochemical Li storage performance. The resulting Cu NPF@Fe₂O₃ demonstrates a high specific capacity (919.5 mAh g^–1 at 0.1 C), long‐term stability (801.1 mAh g^–1 at 2 C, ≈120% retention after 500 cycles), and outstanding rate capability (630 mAh g^–1 at 10 C).     

Extremely High Yield Conversion from Low‐Cost Sand to High‐Capacity Si Electrodes for Li‐Ion Batteries

Although magnesiothermic reduction has attracted immense attention as a facile route for the fabrication of mass‐scale Si nanostructures for high‐capacity lithium‐ion battery applications, its low conversion yield (<50%) and the discovery of a sustainable and low‐cost precursor remain challenging. Here, an unprecedentedly high final conversion yield (>98%) of magnesiothermic reduction based on control of reaction pressure is reported. The successful use of sand as a nearly infinite and extremely low‐cost source for the high‐yield fabrication of nanostructured Si electrodes for Li‐ion batteries is demonstrated. On the basis of a step‐by‐step analysis of the material's structural, morphological, and compositional changes, a two‐step conversion reaction mechanism is proposed that can clearly explain the phase behavior and the high conversion yield. The excellent charge–discharge performance (specific capacities over 1500 mAh g^‐1 for 100 cycles) of the hierarchical Si nanostructure suggests that this facile, fast, and high‐efficiency synthesis strategy from ultralow‐cost sand particles provides outstanding cost‐effectiveness and possible scalability for the commercialization of Si electrodes for energy‐storage applications.     

Lithium Intercalation Behavior in Multilayer Silicon Electrodes

Next generation lithium battery materials will require a fundamental shift from those based on intercalation to elements or compounds that alloy directly with lithium. Intermetallics, for instance, can electrochemically alloy to Li_4.4M (M = Si, Ge, Sn, etc.), providing order‐of‐magnitude increases in energy density. Unlike the stable crystal structure of intercalation materials, intermetallic‐based electrodes undergo dramatic volume changes that rapidly degrade the performance of the battery. Here, the energy density of silicon is combined with the structural reversibility of an intercalation material using a silicon/metal‐silicide multilayer. In operando X‐ray reflectivity confirms the multilayer's structural reversibility during lithium insertion and extraction, despite an overall 3.3‐fold vertical expansion. The multilayer electrodes also show enhanced long‐term cyclability and rate capabilities relative to a comparable silicon thin film electrode. This intercalation behavior found by dimensionally constraining silicon's lithiation promises applicability to a wide range of conversion reactions.