Boosting Pseudocapacitive Behavior of Supercapattery Electrodes by Incorporating a Schottky Junction for Ultrahigh Energy Density.

Pseudo-capacitive negative electrodes remain a major bottleneck in the development of supercapacitor devices with high energy density because the electric double-layer capacitance of the negative electrodes does not match the pseudocapacitance of the corresponding positive electrodes. In the present study, a strategically improved Ni-Co-Mo sulfide is demonstrated to be a promising candidate for high energy density supercapattery devices due to its sustained pseudocapacitive charge storage mechanism. The pseudocapacitive behavior is enhanced when operating under a high current through the addition of a classical Schottky junction next to the electrode-electrolyte interface using atomic layer deposition. The Schottky junction accelerates and decelerates the diffusion of OH‒/K+ ions during the charging and discharging processes, respectively, to improve the pseudocapacitive behavior. The resulting pseudocapacitive negative electrodes exhibits a specific capacity of 2,114 C g-1 at 2 A g-1 matches almost that of the positive electrode's 2,795 C g-1 at 3 A g-1. As a result, with the equivalent contribution from the positive and negative electrodes, an energy density of 236.1 Wh kg-1 is achieved at a power density of 921.9 W kg-1 with a total active mass of 15 mg cm-2. This strategy demonstrates the possibility of producing supercapacitors that adapt well to the supercapattery zone of a Ragone plot and that are equal to batteries in terms of energy density, thus, offering a route for further advances in electrochemical energy storage and conversion processes.

Multilayer Strategy for Photoelectrochemical Hydrogen Generation: New Electrode Architecture that Alleviates Multiple Bottlenecks.

Years of research have demonstrated that the use of multiple components is essential to the development of a commercial photoelectrode to address specific bottlenecks, such as low charge separation and injection efficiency, low carrier diffusion length and lifetime, and poor durability. A facile strategy for the synthesis of multilayered photoanodes from atomic-layer-deposited ultrathin films has enabled a new type of electrode architecture with a total multilayer thickness of 15-17 nm. We illustrate the advantages of this electrode architecture by using nanolayers to address different bottlenecks, thus producing a multilayer photoelectrode with improved interface kinetics and shorter electron transport path, as determined by interface analyses. The photocurrent density was twice that of the bare structure and reached a maximum of 33.3 ± 2.1 mA cm-2 at 1.23 VRHE. An integrated overall water-splitting cell consisting of an electrocatalytic NiS cathode and Bi2S3/NiS/NiFeO/TiO2 photoanode was used for precious-metal-free seawater splitting at a cell voltage of 1.23 V without degradation. The results and root analyses suggest that the distinctive advantages of the electrode architecture, which are superior to those of bulk bottom-up core-shell and hierarchical architectures, originate from the high density of active sites and nanometer-scale layer thickness, which enhance the suitability for interface-oriented energy conversion processes.

Surface Roughening Strategy for Highly Efficient Bifunctional Electrocatalyst: Combination of Atomic Layer Deposition and Anion Exchange Reaction.

Electrocatalytic water splitting, which is an interface-dominated process, can be significantly accelerated by increasing the number of front-line surface active sites (NA ) of the electrocatalyst. In this study, a unique method is used for increasing the NA by converting the smooth ultrathin atomic-layer-deposited nanoshells of the electrocatalysts into nano-roughened active shell layers using a controlled anion-exchange reaction (AER). The coarse thin nanoshells present abundant surface active sites, which are generated owing to the inherent unit-cell volume mismatch induced during the AER. Consequently, the nano-roughened electrodes accelerate the sluggish water reaction kinetics and lower the overpotentials required for the hydrogen and oxygen evolution reactions. In addition, the electronic modulation induced by the nanoshell layer at the core-nanoshell interface amplifies the local electron density, as confirmed using electrochemical analysis data and density functional theory calculations. Because of the integrity of the composite electrodes during water-splitting half-cell reactions, their durability for industrial seawater electrolysis is evaluated. The results indicate that their electrochemical activity does not change significantly after 10 days of continuous overall water splitting.

Three-Dimensional Hierarchical Core/shell Electrodes Using Highly Conformal TiO2 and Co3O4 Thin Films for High-Performance Supercapattery Devices.

The rational design and development of novel electrode materials with promising nanostructures is an effective technique to improve their supercapacitive performance. This work presents high-performance core/shell electrodes based on three-dimensional hierarchical nanostructures coated with conformal thin transition-metal oxide layers using atomic layer deposition (ALD). This effective interface engineering creates disorder in the electronic structure and coordination environment at the interface of the heteronanostructure, which provides many more reaction sites and rapid ion diffusion. At 3 A g-1, the positive CuCo2O4/Ni4Mo/MoO2@ALD-Co3O4 electrode introduced here exhibits a specific capacity of 1029.1 C g-1, and the fabricated negative Fe3O4@ALD-TiO2 electrode significantly outperforms conventional carbon-based electrodes, with a maximum specific capacity of 372.6 C g-1. The supercapattery cell assembled from these two interface- and surface-tailored electrodes exhibits a very high energy density of 110.4 W h kg-1 with exceptional capacity retention over 20,000 cycles, demonstrating the immense potential of ALD for the next generation of supercapacitors.