Prussian Blue Analogue (PBA)-Zn aqueous batteries are attractive because of the high potential of PBA against Zn (~1.7 V), relative safety of the system, and high rate capability. But, despite the long cycle life of PBA half-cells, full PBA-Zn battery systems studied thus far have typically reported only up to 100 cycles and suffer significant capacity fade beyond that. In this work we demonstrate that the loss in capacity retention and cycle life is a combined effect of Zn 2+ ion poisoning at the PBA cathode, as well as dendrite formation in the zinc anode. We address both these issues via the use of a dual ion (Na + as the primary charge carrier) electrolyte and hyper-dendritic Zinc (HD Zn) as the anode. The copper hexacyanoferrate (CuHcf) vs. HD Zn system with Na + ion electrolyte demonstrated herein exhibits 90% (83%) capacity retention after 300 (500) cycles at a 5C rate and a 3% reduction in usable capacity from 1C to 5C. Detailed characterization is done using in situ synchrotron energy-dispersive XRD (EDXRD), conventional XRD, XPS, SEM, TEM, and electrochemical techniques.

The low cost, significant reduction potential and relative safety of the zinc electrode is a common hope for a reductant in secondary batteries, but it is limited mainly to primary implementation due to shape change. In this work, we exploit such shape change for the benefit of static electrodes through the electrodeposition of hyper-dendritic nanoporous zinc foam. Electrodeposition of zinc foam resulted in nanoparticles formed on secondary dendrites in a three-dimensional network with a particle size distribution of 54.1-96.0 nm. The nanoporous zinc foam contributed to highly oriented crystals, high surface area and more rapid kinetics in contrast to conventional zinc in alkaline mediums. The anode material presented had a utilization of 88% at full depth-of-discharge (DOD) at various rates indicating a superb rate capability. The rechargeability of Zn 0 /Zn 2+ showed significant capacity retention over 100 cycles at a 40% DOD to ensure that the dendritic core structure was imperforated. The dendritic architecture was densified upon charge-discharge cycling and presented superior performance compared with bulk zinc electrodes.

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The use of liquid cell electron microscopy as a quantitative probe of nanomaterial structures and reactions requires an accurate understanding of how the sample is altered by the imaging electron beam. In particular, changes in the chemical environment due to beam-induced radiolysis can strongly affect processes such as solution-phase nanocrystal synthesis or electrochemical deposition. It is generally assumed that beam effects are uniform throughout the irradiated liquid. Here we show that for a liquid cell filled with water, the inevitable presence of interfaces between water and the surrounding surfaces causes a spatial variation in the energy absorbed by the water near the walls. The mechanism for this effect is that the walls act as a source of secondary and backscattered electrons which diffuse and deposit energy in the water nearby. This increased dose rate then changes the local concentrations of radiolysis species. We quantify and compare the effects for different materials used in practical liquid cells. We show that the dose rate can increase by several times within tens of nanometers of a water/Au interface, locally increasing the concentrations of species such as the hydrated electron. We discuss the implications for materials processes that are typically triggered at the solid-liquid interface.

MnO2-Zn alkaline batteries are one of the most common modern forms of primary battery, due to their relatively high energy density and low cost per kilowatt-hour. Additionally, unlike many other types of primary battery, alkaline cells can theoretically be recharged. Their low cost per kilowatt-hour makes them potentially ideal for applications such as sustainable energy storage or peak demand shaving. However, a phase transformation that occurs in MnO2 after reduction by more than one electron converts it into the electrochemically inactive Mn3O4 phase. This limits the total depth of discharge of the cell significantly. We report the synthesis of a novel electrode material, manganese-doped witherite, for rechargeable alkaline batteries produced by a simple hydrothermal process. The material has been studied via X-ray diffraction and electroanalytical techniques. We show that unaltered witherite has poor electrochemical properties, and that this new material has high capacity and rate capability, even under deep discharge conditions, superior to conventional manganese dioxide.

Multi-photon polymer crosslinking evolves as the core process behind high-resolution additive microfabrication with soft materials for implantable/wearable electronics, tissue engineering, micro-robotics, biosensing, drug delivery, etc. Electrons and soft X-rays, in principle, can offer even higher resolution and printing rates. However, these powerful lithographic tools are difficult to apply to vacuum incompatible liquid precursor solutions used in continuous additive fabrication. In this work, using biocompatible hydrogel as a model soft material, we demonstrate high-resolution in-liquid polymer crosslinking using scanning electron and X-ray microscopes. The approach augments the existing solid state electron/X-rays lithography and beam induced deposition techniques with a wider class of possible chemical reactions, precursors and functionalities. We discuss focused beam crosslinking mechanism, the factors affecting the ultimate feature size and layer-by-layer printing possibilities. The potential of this technology is *

We observe the growth of crystalline SiC nanoparticles on Si(001) at 900 °C using in situ electron microscopy. Following nucleation and growth of the SiC, there is a massive migration of Si, forming a crystalline Si mound underneath each nanoparticle that lifts it 4-5 nm above the initial growth surface. The volume of the Si mounds is roughly five to seven times the volume of the SiC nanoparticles. We propose that relaxation of strain drives the mound formation. This new mechanism for relieving interfacial strain, which involves a dramatic restructuring of the substrate, is in striking contrast to the familiar scenario in which only the deposited material restructures to relieve strain.

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