Controlling Surface Structure and Primary Particle Size to Enhance Performance and Reduce Gas Evolution in Lithium- and Manganese-Rich Layered Oxide Cathodes.

Practical application of lithium- and manganese-rich layered oxide cathodes has been hindered despite their high performance and low cost owing to high gas evolution accompanying capacity loss even in a conservative voltage window. Here, we control the surface structure and primary particle size of lithium- and manganese-rich layered oxide cathodes not only to enhance the electrochemical performance but also to reduce gas evolution. Sulfur-coated Fm3̅m/R3̅m double reduced surface layers and Mo doping dramatically reduce gas evolution, which entails the improvement of electrochemical performance. With the optimization, we prove that it is competitive enough to conventional high-nickel cathodes in the aspects of gas evolution as well as electrochemical performance in the conservative voltage window of 2.5-4.4 V. Our findings provide invaluable insights on the improvement of electrochemical performance and gas evolution properties in lithium- and manganese-rich layered oxide cathodes.

Fabrication of graphene thin films based on layer-by-layer self-assembly of functionalized graphene nanosheets.

In this study, we present a facile means of fabricating graphene thin films via layer-by-layer (LbL) assembly of charged graphene nanosheets (GS) based on electrostatic interactions. To this end, graphite oxide (GO) obtained from graphite powder using Hummers method is chemically reduced to carboxylic acid-functionalized GS and amine-functionalized GS to perform an alternate LbL deposition between oppositely charged GSs. Specifically, for successful preparation of positively charged GS, GOs are treated with an intermediate acyl-chlorination reaction by thionyl chloride and a subsequent amidation reaction in pyridine, whereby a stable GO dispersibility can be maintained within the polar reaction solvent. As a result, without the aid of additional hybridization with charged nanomaterials or polyelectrolytes, the oppositely charged graphene nanosheets can be electrostatically assembled to form graphene thin films in an aqueous environment, while obtaining controllability over film thickness and transparency. Finally, the electrical property of the assembled graphene thin films can be enhanced through a thermal treatment process. Notably, the introduction of chloride functions during the acyl-chlorination reaction provides the p-doping effect for the assembled graphene thin films, yielding a sheet resistance of 1.4 kΩ/sq with a light transmittance of 80% after thermal treatment. Since the proposed method allows for large-scale production as well as elaborate manipulation of the physical properties of the graphene thin films, it can be potentially utilized in various applications, such as transparent electrodes, flexible displays and highly sensitive biosensors.

Rigiflex lithography-based nanodot arrays for localized surface plasmon resonance biosensors.

We present a facile and robust means of fabricating metallic nanodot arrays for localized surface plasmon resonance (LSPR) biosensors through the strategic coupling of a polymeric template prepared with rigiflex lithography and a subsequent metallization via electrodeposition. Rigiflex lithography provides the capability to realize large-scale nanosized features as well as process flexibility during contact molding. In addition, the electrodeposition process enables wet-based nanoscale metallization with high pattern fidelity and geometric controllability. Generated metallic nanodot arrays can be used as a general platform for LSPR biosensors via the sequential binding of chemicals and biomolecules. Extinction spectra of the corresponding LSPR signal are measured with UV-vis-NIR spectroscopy, from which the pattern size and shape dependence of LSPR are readily confirmed. The feasibility of a very sensitive biosensor is demonstrated by the targeted binding of human immunoglobulin G, yielding subnanomolar detection capability with high selectivity.

Phase controllable transfer printing of patterned polyelectrolyte multilayers.

We introduce a simple and robust method for varying the phase of the patterns in transfer printing of polyelectrolyte multilayers. Simply transferred positive patterns, edge-defined intermediate patterns, and negatively engraved patterns were obtained by manipulating the capillarity of the plasticized polymeric layer from weak to strong. A phase diagram of the pattern transfer was suggested to account for the influences of the temporal and spatial factors in the experiments. In addition, the main role of adhesion at the interfaces in the successful realization of multilayer transfer printing was investigated. It is anticipated that the strategy and ability to control the phase of the patterns transferred may offer a variety of opportunities for functional devices in optics, organic electronics, membranes, and microfluidics.