Minsu Gu

Inhibiting the shuttle effect in lithium–sulfur batteries using a layer-by-layer assembled ion-permselective separator

A novel strategy for introducing ion-permselective properties in a conventional polyethylene (PE) separator to inhibit the shuttle effect of polysulfides in high-performance lithium–sulfur batteries is reported. This was accomplished by taking advantage of the pH-responsive multilayers of weak polyelectrolytes such as poly(allylamine hydrochloride) (PAH) and poly(acrylic acid) (PAA) assembled on the PE separator using layer-by-layer (LbL) assembly. It was found that the cationic permselectivity (permeability of cation/anion) of an ultrathin multilayer coated separator is highly tunable with respect to the number of bilayers and external pH, benefiting from fine tuning of the internal charge density of the multilayered films. The movement of polysulfide anions was significantly inhibited by five bilayers of PAH/PAA (ca. 98% with multilayers assembled at pH 3/3), while the movement of Li cations was preserved. As a result, the ion-permselective separator demonstrated a high initial reversible capacity of ca. 1418 mA h g−1 with multilayers assembled at pH 3/3 because of the good permselectivity and the enhanced wetting properties of the LbL treated separator for electrolytes, leading to a significantly improved Coulombic efficiency as compared to a conventional PE separator, i.e., almost 100% over 50 cycles. We anticipate that the permselectivity controllable coating method will be applied for various other membrane technologies.

Functionalized Nanocellulose-Integrated Heterolayered Nanomats toward Smart Battery Separators

Alternative materials obtained from natural resources have recently garnered considerable attention as an innovative solution to bring unprecedented advances in various energy storage systems. Here, we present a new class of heterolayered nanomat-based hierarchical/asymmetric porous membrane with synergistically coupled chemical activity as a nanocellulose-mediated green material strategy to develop smart battery separator membranes far beyond their current state-of-the-art counterparts. This membrane consists of a terpyridine (TPY)-functionalized cellulose nanofibril (CNF) nanoporous thin mat as the top layer and an electrospun polyvinylpyrrolidone (PVP)/polyacrylonitrile (PAN) macroporous thick mat as the support layer. The hierarchical/asymmetric porous structure of the heterolayered nanomat is rationally designed with consideration of the trade-off between leakage current and ion transport rate. The TPY (to chelate Mn(2+) ions) and PVP (to capture hydrofluoric acid)-mediated chemical functionalities bring a synergistic coupling in suppressing Mn(2+)-induced adverse effects, eventually enabling a substantial improvement in the high-temperature cycling performance of cells.

Layer-by-Layer Assembly of Polyoxometalates for Photoelectrochemical (PEC) Water Splitting: Toward Modular PEC Devices

Artificial photosynthesis is considered one of the most promising solutions to modern energy and environmental crises. Considering that it is enabled by multiple components through a series of photoelectrochemical processes, the key to successful development of a photosynthetic device depends not only on the development of novel individual components but also on the rational design of an integrated photosynthetic device assembled from them. However, most studies have been dedicated to the development of individual components due to the lack of a general and simple method for the construction of the integrated device. In the present study, we report a versatile and simple method to prepare an efficient and stable photoelectrochemical device via controlled assembly and integration of functional components on the nanoscale using the layer-by-layer (LbL) assembly technique. As a proof of concept, we could successfully build a photoanode for solar water oxidation by depositing a thin film of diverse cationic polyelectrolytes and anionic polyoxometalate (molecular metal oxide) water oxidation catalysts on the surface of various photoelectrode materials (e.g., Fe2O3, BiVO4, and TiO2). It was found that the performance of photoanodes was significantly improved after the deposition in terms of stability as well as photocatalytic properties, regardless of types of photoelectrodes and polyelectrolytes employed. Considering the simplicity and versatile nature of LbL assembly techniques, our approach can contribute to the realization of artificial photosynthesis by enabling the design of novel photosynthetic devices.

Diffusion controlled multilayer electrocatalysts via graphene oxide nanosheets of varying sizes

Controlling the architecture of hybrid nanomaterial electrodes is critical for understanding their fundamental electrochemical mechanisms and applying these materials in future energy conversion and storage systems. Herein, we report highly tunable electrocatalytic multilayer electrodes, composed of palladium nanoparticles (Pd NPs) supported by graphene sheets of varying lateral sizes, employing a versatile layer-by-layer (LbL) assembly method. We demonstrate that the electrocatalytic activity is highly tunable through the control of the diffusion and electron pathways within the 3-dimensional multilayer electrodes. A larger-sized-graphene-supported electrode exhibited its maximum performance with a thinner film, due to facile charge transfer by the mass transfer limited in the early stage, while a smaller-sized-graphene-supported electrode exhibited its highest current density with higher mass loading in the thicker films by enabling facile mass transfer through increased diffusion pathways. These findings of the tortuous-path effect on the electrocatalytic electrode supported by varying sized graphene provide new insights and a novel design principle into electrode engineering that will be beneficial for the development of effective electrocatalysts.