Designing multifunctional CoOx layers for efficient and stable electrochemical energy conversion

Disordered and porous metal oxides are promising as earth-abundant and cost-effective alternatives to noble-metal electrocatalysts. Herein, we leverage non-saturated oxidation in plasma-enhanced atomic layer deposition to tune structural, mechanical, and optical properties of biphasic CoOx thin films, thereby tailoring their catalytic activities and chemical stabilities. To optimize the resulting film properties, we systematically vary the oxygen plasma power and exposure time in the deposition process. We find that short exposure times and low plasma powers incompletely oxidize the cobaltocene precursor to Co(OH)2 and result in the incorporation of carbon impurities. These Co(OH)2 films are highly porous and catalytically active, but their electrochemical stability is impacted by poor adhesion to the substrate. In contrast, long exposure times and high plasma powers completely oxidize the precursor to form Co3O4, reduce the carbon impurity incorporation, and improve the film crystallinity. While the resulting Co3O4 films are highly stable under electrochemical conditions, they are characterized by low oxygen evolution reaction activities. To overcome these competing properties, we applied the established relation between deposition parameters and functional film properties to design bilayer films exhibiting simultaneously improved electrochemical performance and chemical stability. The resulting biphasic films combine a highly active Co(OH)2 surface with a stable Co3O4 interface layer. In addition, these coatings exhibit minimal light absorption, thus rendering them well suited as protective catalytic layers on semiconductor light absorbers for application in photoelectrochemical devices.

Reduction of Surface Residual Lithium Compounds for Single-Crystal LiNi0.6Mn0.2Co0.2O2 via Al2O3 Atomic Layer Deposition and Post-Annealing

Surface residual lithium compounds of Ni-rich cathodes are tremendous obstacles to electrochemical performance due to blocking ion/electron transfer and arousing surface instability. Herein, ultrathin and uniform Al2O3 coating via atomic layer deposition (ALD) coupled with the post-annealing process is reported to reduce residual lithium compounds on single-crystal LiNi0.6Mn0.2Co0.2O2 (NCM622). Surface composition characterizations indicate that LiOH is obviously reduced after Al2O3 growth on NCM622. Subsequent post-annealing treatment causes the consumption of Li2CO3 along with the diffusion of Al atoms into the surface layer of NCM622. The NCM622 modified by Al2O3 coating and post-annealing exhibits excellent cycling stability, the capacity retention of which reaches 92.2% after 300 cycles at 1 C, much higher than that of pristine NCM622 (34.8%). Reduced residual lithium compounds on NCM622 can greatly decrease the formation of LiF and the degree of Li+/Ni2+ cation mixing after discharge–charge cycling, which is the key to the improvement of cycling stability.

Enhanced thermoelectric performance of defect engineered monolayer graphene

We propose a method of improving the thermoelectric properties of graphene using defect engineering through plasma irradiation and atomic layer deposition (ALD). We intentionally created atomic blemishes in graphene by oxygen plasma treatment and subsequently healed the atomistically defective places using Pt-ALD. After healing, the thermal conductivity of the initially defective graphene increased slightly, while the electrical conductivity and the square of the Seebeck coefficient increased pronouncedly. The thermoelectric figure of merit of the Pt-ALD treated graphene was measured to be over 4.8 times higher than the values reported in the literature. We expect that our study could provide a useful guideline for the development of graphene-based thermoelectric devices.

Enhanced hydrogen generation by reverse spillover effects over bicomponent catalysts

The contribution of the reverse spillover effect to hydrogen generation reactions is still controversial. Herein, the promotion functions for reverse spillover in the ammonia borane hydrolysis reaction are proven by constructing a spatially separated NiO/Al2O3/Pt bicomponent catalyst via atomic layer deposition and performing in situ quick X-ray absorption near-edge structure (XANES) characterization. For the NiO/Al2O3/Pt catalyst, NiO and Pt nanoparticles are attached to the outer and inner surfaces of Al2O3 nanotubes, respectively. In situ XANES results reveal that for ammonia borane hydrolysis, the H species generated at NiO sites spill across the support to the Pt sites reversely. The reverse spillover effects account for enhanced H2 generation rates for NiO/Al2O3/Pt. For the CoOx/Al2O3/Pt and NiO/TiO2/Pt catalysts, reverse spillover effects are also confirmed. We believe that an in-depth understanding of the reverse effects will be helpful to clarify the catalytic mechanisms and provide a guide for designing highly efficient catalysts for hydrogen generation reactions.