Ye Song

Enhanced supercapacitance in anodic TiO2 nanotube films by hydrogen plasma treatment

One-dimensional anodic titanium oxide (ATO) nanotube arrays hold great potential as electrode materials for high-performance electrochemical supercapacitors. However, their poor electronic conductivity limits their practical applications. Here, we develop a hydrogen (H2) plasma treatment method to greatly improve the electrochemical performance of ATO electrodes. Compared with pristine ATO, the nanotubes treated by H2 plasma illumination (ATO-H) present a rough and amorphous layer at the surface of the nanotubes with simultaneously incorporated Ti(3+) and -OH groups. At a current density of 0.05 mA cm(-2) in charge-discharge measurements, the specific capacitance of the ATO-H electrode has substantially increased ~7.4 times, with a value as high as 7.22 mF cm(-2). Moreover, the novel ATO-H electrode has also exhibited excellent rate capability (6.37 mF cm(-2) at a current density of 2 mA cm(-2)) and cycling performance with no degradation after 10,000 cycles.

Facile Method to Enhance the Adhesion of TiO2 Nanotube Arrays to Ti Substrate

The weak adhesion of anodic TiO2 nanotube arrays (TNTAs) to the underlying Ti substrate compromises many promising applications. In this work, a compact oxide layer between TNTAs and Ti substrate is introduced by employing an additional anodization in a fluoride-free electrolyte. The additional anodization results in an about 200 nm thick compact layer near the nanotube bottoms. Scratch test demonstrates that the critical load of TNTAs with the compact oxide layer is a more than threefold increase in comparison with those without the compact layer. Moreover, this facile method can also improve the photoactivity and supercapacitor performances of TNTAs markedly.

Enhanced Photoelectrochemical Water Splitting Performance of Anodic TiO2 Nanotube Arrays by Surface Passivation

One-dimensional anodic titanium oxide nanotube (TONT) arrays provide a direct pathway for charge transport, and thus hold great potential as working electrodes for electrochemical energy conversion and storage devices. However, the prominent surface recombination due to the large amount surface defects hinders the performance improvement. In this work, the surface states of TONTs were passivated by conformal coating of high-quality Al2O3 onto the tubular structures using atomic layer deposition (ALD). The modified TONT films were subsequently employed as anodes for photoelectrochemical (PEC) water splitting. The photocurrent (0.5 V vs Ag/AgCl) recorded under air mass 1.5 global illumination presented 0.8 times enhancement on the electrode with passivation coating. The reduction of surface recombination rate is responsible for the substantially improved performance, which is proposed to have originated from a decreased interface defect density in combination with a field-effect passivation induced by a negative fixed charge in the Al2O3 shells. These results not only provide a physical insight into the passivation effect, but also can be utilized as a guideline to design other energy conversion devices.

Theoretical derivation of anodizing current and comparison between fitted curves and measured curves under different conditions

Anodic TiO2 nanotubes have been studied extensively for many years. However, the growth kinetics still remains unclear. The systematic study of the current transient under constant anodizing voltage has not been mentioned in the original literature. Here, a derivation and its corresponding theoretical formula are proposed to overcome this challenge. In this paper, the theoretical expressions for the time dependent ionic current and electronic current are derived to explore the anodizing process of Ti. The anodizing current-time curves under different anodizing voltages and different temperatures are experimentally investigated in the anodization of Ti. Furthermore, the quantitative relationship between the thickness of the barrier layer and anodizing time, and the relationships between the ionic/electronic current and temperatures are proposed in this paper. All of the current-transient plots can be fitted consistently by the proposed theoretical expressions. Additionally, it is the first time that the coefficient A of the exponential relationship (ionic current j(ion) = A exp(BE)) has been determined under various temperatures and voltages. And the results indicate that as temperature and voltage increase, ionic current and electronic current both increase. The temperature has a larger effect on electronic current than ionic current. These results can promote the research of kinetics from a qualitative to quantitative level.

Morphology Defects Guided Pore Initiation during the Formation of Porous Anodic Alumina

Aluminum (Al) anodization leads to formation of porous structures with a broad spectrum of applications. Naturally or intentionally created defects on Al surfaces can greatly affect pore initiation. However, there is still a lack of systematic understanding on the defect dependent morphology evolution. In this paper, anodization processes on unpolished, polished, and nanoimprinted Al substrates are investigated under high voltages up to 600 V in various acid solutions. A porous structure is obtained on the unpolished and nanoimprinted Al foils with rough surface texture, whereas a compact film can be rationally obtained on the polished Al foil with a highly smooth surface. The observation of surface roughness dependent oxide film morphology evolution could be originated from the high voltages, which increases the threshold requirement of defect size or density for the pore initiation. Electrostatics simulation results indicate that inhomogeneous electric field and its corresponding localized high current induced by the surface roughness facilitate the initiation of nanopores. In addition, the porous films are utilized as templates to produce polydimethylsiloxane nanocone and submicrowire arrays. The nanoarrays with different aspect ratios present tunable wettability with the contact angles ranging from 144.6° to 56.7°, which hold promising potentials in microfluidic devices and self-cleaning coatings.