Visualizing anisotropy in the surface oxidation of germanium by wet etching of patterned nanowedges: proof of concept.

We study the anisotropy in surface oxidation for Ge(100) and (110) in HCl/H2O2 solution complemented by synchrotron X-ray photoemission spectroscopy (SXPS) measurements integrated with an in situ etching chamber. Visual anisotropic demonstration is confirmed by lithographic Ge nanowedges.

Controlled electrochemical etching of nanoporous Si anodes and its discharge behavior in alkaline Si-air batteries.

We report the fabrication of nanoporous silicon (nPSi) electrodes via electrochemical etching to form a porous Si layer with controllable thickness and pore size. Varying the etching time and ethanolic HF concentration results in different surface morphologies, with various degrees of electrolyte access depending on the pore characteristics. Optimizing the etching condition leads to well-developed nPSi electrodes, which have thick porous layers and smaller pore diameter and exhibit improved discharge behavior as anodes in alkaline Si-air cells in contrast to flat Si anode. Although electrochemical etching is effective in improving the interfacial characteristics of Si in terms of high surface area, we observed that mild anodization occurs and produces an oxide overlayer. We then show that this oxide layer in nPSi anodes can be effectively removed to produce an nPSi anode with good discharge behavior in an actual alkaline Si-air cell. In the future, the combination of high surface area nPSi anodes with nonaqueous electrolytes (e.g., room-temperature ionic liquid electrolyte) to minimize the strong passivation behavior and self-discharge in Si could lead to Si-air cells with a stable voltage profile and high anode utilization.

Quasi-perpetual discharge behaviour in p-type Ge-air batteries.

Metal-air batteries continue to become attractive energy storage and conversion systems due to their high energy and power densities, safer chemistries, and economic viability. Semiconductor-air batteries - a term we first define here as metal-air batteries that use semiconductor anodes such as silicon (Si) and germanium (Ge) - have been introduced in recent years as new high-energy battery chemistries. In this paper, we describe the excellent doping-dependent discharge kinetics of p-type Ge anodes in a semiconductor-air cell employing a gelled KOH electrolyte. Owing to its Fermi level, n-type Ge is expected to have lower redox potential and better electronic conductivity, which could potentially lead to a higher operating voltage and better discharge kinetics. Nonetheless, discharge measurements demonstrated that this prediction is only valid at the low current regime and breaks down at the high current density region. The p-type Ge behaves extremely better at elevated currents, evident from the higher voltage, more power available, and larger practical energy density from a very long discharge time, possibly arising from the high overpotential for surface passivation. A primary semiconductor-air battery, powered by a flat p-type Ge as a multi-electron anode, exhibited an unprecedented full discharge capacity of 1302.5 mA h gGe(-1) (88% anode utilization efficiency), the highest among semiconductor-air cells, notably better than new metal-air cells with three-dimensional and nanostructured anodes, and at least two folds higher than commercial Zn-air and Al-air cells. We therefore suggest that this study be extended to doped-Si anodes, in order to pave the way for a deeper understanding on the discharge phenomena in alkaline metal-air conversion cells with semiconductor anodes for specific niche applications in the future.