Silicon's sensitivity to corrosion has hindered its use in photoanode applications. We found that deposition of a ~2-nanometer nickel film on n-type silicon (n-Si) with its native oxide affords a high-performance metal-insulator-semiconductor photoanode for photoelectrochemical (PEC) water oxidation in both aqueous potassium hydroxide (KOH, pH = 14) and aqueous borate buffer (pH = 9.5) solutions. The Ni film acted as a surface protection layer against corrosion and as a nonprecious metal electrocatalyst for oxygen evolution. In 1 M aqueous KOH, the Ni/n-Si photoanodes exhibited high PEC activity with a low onset potential (~1.07 volts versus reversible hydrogen electrode), high photocurrent density, and durability. The electrode showed no sign of decay after ~80 hours of continuous PEC water oxidation in a mixed lithium borate-potassium borate electrolyte. The high photovoltage was attributed to a high built-in potential in a metal-insulator-semiconductor-like device with an ultrathin, incomplete screening Ni/NiO(x) layer from the electrolyte.

Primary and rechargeable Zn-air batteries could be ideal energy storage devices with high energy and power density, high safety and economic viability. Active and durable electrocatalysts on the cathode side are required to catalyse oxygen reduction reaction during discharge and oxygen evolution reaction during charge for rechargeable batteries. Here we developed advanced primary and rechargeable Zn-air batteries with novel CoO/carbon nanotube hybrid oxygen reduction catalyst and Ni-Fe-layered double hydroxide oxygen evolution catalyst for the cathode. These catalysts exhibited higher catalytic activity and durability in concentrated alkaline electrolytes than precious metal Pt and Ir catalysts. The resulting primary Zn-air battery showed high discharge peak power density B265 mW cm À 2 , current density B200 mA cm À 2 at 1 V and energy density 4700 Wh kg À 1 . Rechargeable Zn-air batteries in a tri-electrode configuration exhibited an unprecedented small charge-discharge voltage polarization of B0.70 V at 20 mA cm À 2 , high reversibility and stability over long charge and discharge cycles.

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Nonaqueous redox fl ow batteries are emerging fl ow-based energy storage technologies that have the potential for higher energy densities than their aqueous counterparts because of their wider voltage windows. However, their performance has lagged far behind their inherent capability due to one major limitation of low solubility of the redox species. Here, a molecular structure engineering strategy towards high performance nonaqueous electrolyte is reported with signifi cantly increased solubility. Its performance outweighs that of the state-of-the-art nonaqueous redox fl ow batteries. In particular, an ionic-derivatized ferrocene compound is designed and synthesized that has more than 20 times increased solubility in the supporting electrolyte. The solvation chemistry of the modifi ed ferrocene compound. Electrochemical cycling testing in a hybrid lithium-organic redox fl ow battery using the assynthesized ionic-derivatized ferrocene as the catholyte active material demonstrates that the incorporation of the ionic-charged pendant signifi cantly improves the system energy density. When coupled with a lithium-graphite hybrid anode, the hybrid fl ow battery exhibits a cell voltage of 3.49 V, energy density about 50 Wh L −1 , and energy effi ciency over 75%. These results reveal a generic design route towards high performance nonaqueous electrolyte by rational functionalization of the organic redox species with selective ligand.

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Fluoroethylene carbonate (FEC) is an effective electrolyte additive that can significantly improve the cycling ability of silicon and other anode materials. However, the fundamental mechanism of this improvement is still not well understood. Based on the results obtained from (6)Li NMR and X-ray photoelectron spectroscopy studies, we propose a molecular-level mechanism for how FEC affects the formation of solid electrolyte interphase (SEI) film: 1) FEC is reduced through the opening of the five-membered ring leading to the formation of lithium poly(vinyl carbonate), LiF, and some dimers; 2) the FEC-derived lithium poly(vinyl carbonate) enhances the stability of the SEI film. The proposed reduction mechanism opens a new path to explore new electrolyte additives that can improve the cycling stability of silicon-based electrodes.

A fundamental understanding of electrochemical reaction pathways is critical to improving the performance of Li-S batteries, but few techniques can be used to directly identify and quantify the reaction species during disharge/charge cycling processes in real time. Here, an in situ (7)Li NMR technique employing a specially designed cylindrical microbattery was used to probe the transient electrochemical and chemical reactions occurring during the cycling of a Li-S system. In situ NMR provides real time, semiquantitative information related to the temporal evolution of lithium polysulfide allotropes during both discharge/charge processes. This technique uniquely reveals that the polysulfide redox reactions involve charged free radicals as intermediate species that are difficult to detect in ex situ NMR studies. Additionally, it also uncovers vital information about the (7)Li chemical environments during the electrochemical and parasitic reactions on the Li metal anode. These new molecular-level insights about transient species and the associated anode failure mechanism are crucial to delineating effective strategies to accelerate the development of Li-S battery technologies.

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