This article provides an overview of solution-based methods for the controllable synthesis of metal oxides and their applications for electrochemical energy storage. Typical solution synthesis strategies are summarized and the detailed chemical reactions are elaborated for several common nanostructured transition metal oxides and their composites. The merits and demerits of these synthesis methods and some important considerations are discussed in association with their electrochemical performance. We also propose the basic guideline for designing advanced nanostructure electrode materials, and the future research trend in the development of high power and energy density electrochemical energy storage devices.
Interfaces, WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim. It incorporates referee's comments but changes resulting from the publishing process, such as copyediting,
The combination of oxide and heavier chalcogenide layers
in thin film photovoltaics suffers limitations associated with oxygen
incorporation and sulfur deficiency in the chalcogenide layer or with
a chemical incompatibility which results in dewetting issues and defect
states at the interface. Here, we establish atomic layer deposition
(ALD) as a tool to overcome these limitations. ALD allows one to obtain
highly pure Sb2S3 light absorber layers, and
we exploit this technique to generate an additional interfacial layer
consisting of 1.5 nm ZnS. This ultrathin layer simultaneously resolves
dewetting and passivates defect states at the interface. We demonstrate
via transient absorption spectroscopy that interfacial electron recombination
is one order of magnitude slower at the ZnS-engineered interface than
hole recombination at the Sb2S3/P3HT interface.
The comparison of solar cells with and without oxide incorporation
in Sb2S3, with and without the ultrathin ZnS
interlayer, and with systematically varied Sb2S3 thickness provides a complete picture of the physical processes
at work in the devices.
Cuprous oxide Cu2O is a promising p-type semiconductor for photoelectrochemical (PEC) solar hydrogen generation because it has a suitable bandgap (Eg = 2.0-2.2 eV) and a band alignment adapted to water reduction. In addition, metallic Cu is earth-abundant thus making Cu2O a low-cost material. However, the reduction potential of Cu2O into metallic Cu (0.47 V versus RHE) is lower than that of water which induces a severe instability under irradiation in a PEC cell. Therefore, our recent efforts focused on the growth of a protective overlayer on top of Cu2O in order to stabilize Cu2O when used as a photocathode in an aqueous electrolyte. Among potential protective materials cuprous sulphide Cu2S is another p-type semiconductor with a 1.2 eV bandgap and an appropriate energy level alignment with Cu2O that would allow electrons flowing to the interface. We present here an original and simple method aimed at protecting a compact layer (CL) or nanowires (NWs) of Cu2O with a Cu2S coating. Our method is based on the ions exchange reaction (IER) of O(2-) into S(2-) at the surface of Cu2O itself in a solution-containing Na2S as the sulphur source. The local surface IER implies the formation of a conformal and uniform coating independently on the starting Cu2O morphology, CLs or NWs. As expected, coating Cu2O photocathodes by a conformal Cu2S layer improves their stability and PEC performances.
The synthesis of templates with modulated pore channels by combined mild and hard anodization processes is described. The hard anodization pulses, implemented during anodization, are controlled not only in time length and amplitude, but also in shape: square and exponential signals have been applied. Electrodeposition of Co is subsequently performed to obtain uniform and modulated diameter nanowire arrays. Square and exponential modulated diameter nanowires are imaged by scanning electron microscopy and hcp hexagonal polycrystalline structure is confirmed in all Co nanowires. Magnetic behavior strongly depends on nanowire shape and is interpreted considering the modification of magnetostatic interactions between wires induced by local stray fields from magnetic charges at the ends of the wider segments in modulated wires. As a consequence, magnetization processes under parallel and perpendicular field configurations denote the contribution of both thin and wide segments.
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