Creation of 3D Textured Graphene/Si Schottky Junction Photocathode for Enhanced Photo‐Electrochemical Efficiency and Stability

This work presents a novel photo‐electrochemical architecture based on the 3D pyramid‐like graphene/p‐Si Schottky junctions. Overcoming the conventional transfer technique by which only planar graphene/Si Schottky junctions are currently available, this work demonstrates the 3D pyramid‐like graphene/p‐Si Schottky junction photocathode, which greatly enhances light harvesting efficiency and exhibits promising photo‐electrochemical performance for hydrogen generation. The formation of 3D pyramid‐like graphene/p‐Si Schottky junctions exhibits enhanced electrochemical activity and promotes charge separation efficiency compared with the bare pyramid Si surface without graphene. The inherent chemical inertness of graphene significantly improves the operational stability of 3D graphene/p‐Si Schottky junction photo‐electrochemical cells. The 3D pyramid‐like graphene/p‐Si Schottky junction photocathode delivers an onset potential of 0.41 V and a saturated photocurrent density of ?32.5 mA cm^?2 at 0 V (vs RHE) with excellent stability comparable to values reported for textured or nanostructured p‐Si photocathodes coated with ultrathin oxide layers by the conventional atomic layer deposition technique. These results suggest that the formation of graphene/Si Schottky junctions with a 3D architecture is a promising approach to improve the performance and durability of Si‐based photo‐electrochemical systems for water splitting or solar‐to‐fuel conversion.     

Boosting the Performance of WO3/n‐Si Heterostructures for Photoelectrochemical Water Splitting: from the Role of Si to Interface Engineering

Metal oxide/Si heterostructures make up an exciting design route to high‐performance electrodes for photoelectrochemical (PEC) water splitting. By monochromatic light sources, contributions of the individual layers in WO₃/n‐Si heterostructures are untangled. It shows that band bending near the WO₃/n‐Si interface is instrumental in charge separation and transport, and in generating a photovoltage that drives the PEC process. A thin metal layer inserted at the WO₃/n‐Si interface helps in establishing the relation among the band bending depth, the photovoltage, and the PEC activity. This discovery breaks with the dominant Z‐scheme design idea, which focuses on increasing the conductivity of an interface layer to facilitate charge transport, but ignores the potential profile around the interface. Based on the analysis, a high‐work‐function metal is predicted to provide the best interface layer in WO₃/n‐Si heterojunctions. Indeed, the fabricated WO₃/Pt/n‐Si photoelectrodes exhibit a 2 times higher photocurrent density at 1.23 V versus reversible hydrogen electrode (RHE) and a 10 times enhancement at 1.6 V versus RHE compared to WO₃/n‐Si. Here, it is essential that the native SiO₂ layer at the interface between Si and the metal is kept in order to prevent Fermi level pinning in the Schottky contact between the Si and the metal.     

Highly Doped 3D Graphene Na‐Ion Battery Anode by Laser Scribing Polyimide Films in Nitrogen Ambient

Conventional graphite anodes can hardly intercalate sodium (Na) ions, which poses a serious challenge for developing Na‐ion batteries. This study details a novel method that involves single‐step laser‐based transformation of urea‐containing polyimide into an expanded 3D graphene anode, with simultaneous doping of high concentrations of nitrogen (≈13 at%). The versatile nature of this laser‐scribing approach enables direct bonding of the 3D graphene anode to the current collectors without the need for binders or conductive additives, which presents a clear advantage over chemical or hydrothermal methods. It is shown that these conductive and expanded 3D graphene structures perform exceptionally well as anodes for Na‐ion batteries. Specifically, an initial coulombic efficiency (CE) up to 74% is achieved, which exceeds that of most reported carbonaceous anodes, such as hard carbon and soft carbon. In addition, Na‐ion capacity up to 425 mAh g^?1 at 0.1 A g^?1 has been achieved with excellent rate capabilities. Further, a capacity of 148 mAh g^?1 at a current density of 10 A g^?1 is obtained with excellent cycling stability, opening a new direction for the fabrication of 3D graphene anodes directly on current collectors for metal ion battery anodes as well as other potential applications.     

A Highly Reversible Nano‐Si Anode Enabled by Mechanical Confinement in an Electrochemically Activated LixTi4Ni4Si7 Matrix

This paper reports a Si‐Ti‐Ni ternary alloy developed for commercial application as an anode material for lithium ion batteries. Our alloy exhibits a stable capacity above 900 mAh g^?1 after 50 cycles and a high coulombic efficiency of up to 99.7% during cycling. To enable a highly reversible nano‐Si anode, melt spinning is employed to embed nano‐Si particles in a Ti₄Ni₄Si₇ matrix. The Ti₄Ni₄Si₇ matrix fulfills two important purposes. First, it reduces the maximum stress evolved in the nano‐Si particles by applying a compressive stress to mechanically confine Si expansion during lithiation. And second, the Ti₄Ni₄Si₇ matrix is a good mixed conductor that isolates nano‐Si from the liquid electrolyte, thus preventing parasitic reactions responsible for the formation of a solid electrolyte interphase. Given that a coulombic efficiency above 99.5% is rarely reported for Si based anode materials, this alloy's performance suggests a promising new approach to engineering Si anode materials.     

Cd2+ affects the growth,hierarchical structure and peptide composition of the biosilica of the freshwater diatom Nitzschia palea (Kützing) W. Smith

Biosilica from diatoms is formed at ambient conditions under the control of biological and physicochemical processes. The changes in growth and biosilica formation through uptake of different concentrations of Cd²⁺ by the diatom Nitzschia palea (Kützing) W. Smith was investigated, correlating Cd²⁺ effects to changes in the biosilica nanostructure and the relative content of the encapsulated biomolecules. Diatom growth rates at different Cd²⁺ concentrations (as 1, 2, 3, 4, and 5 × 10^?1 mg L^?1 CdCl₂) were studied in order to determine the concentrations at which sublethal effects were visible, allowing the harvest of sufficient diatom cells for further experiments. We found a clear correlation between the Cd²⁺ concentrations and both the nanostructure of the biosilica and content of encapsulated peptides. Cd²⁺ induced biosilica deformation was assessed by scanning electron microscopy and attenuated total reflectance‐Fourier Transformed Infrared Spectroscopy (FTIR), revealing that micromorphological changes in frustule features (striae, costae, pores) and nanostructural modifications (structure of the silica and conformation of the encapsulated peptides) occurred at applied Cd²⁺ concentrations of 2 and 3 × 10^?1 mg L^?1. In particular the FTIR contribution of peptides decreased at elevated Cd²⁺ concentrations, whereas shifts in wave number of several relevant organic bonds as C = O stretching (1765 cm^?1) and possibly hydrated sulfate (1160, 1110 and 980 cm^?1) were assigned. Additional analysis of the amide I band showed a relative increase in β‐sheet structure (1680–1620 cm^?1) when Cd²⁺ concentration increased. Cadmium uptake clearly affected the molecular ordering of the biosilica in Nitzschia palea, most probably by interfering in biological or physicochemical processes involved in diatom biosilicification.     

Strategic Pore Architecture for Accommodating Volume Change from High Si Content in Lithium‐Ion Battery Anodes

To be a thinner and more lightweight lithium‐ion battery with high energy density, the next‐generation anode with high gravimetric and volumetric capacity is a prerequisite. In this regard, utilizing high silicon (3579 mAh g^?1) content in the electrode for the anode has been highlighted as a practically relevant approach. However, there still remains a crucial issue related to intrinsic volume expansion (>300%) of silicon upon lithiation, which can directly affect severe electrode swelling as well as accelerate its capacity fading by triggering structural degradation and electrical contact loss between particles. Herein, macropore‐exploited design, which can accommodate the volume change of high silicon content within the extended pore of graphite upon repeated cycling, is introduced. Such unique macropore‐exploited design leads to much less electrode swelling, by preserving its morphological integrity and contact between particles, than that of the comparative group with different sized pore and silicon distribution. As a result, this anode (914 mAh g^?1) demonstrates notable gravimetric (220 Wh kg^?1 at 6000 W kg^?1) and volumetric energy density (623 Wh L^?1 upon full lithiation after 100 cycles), exceeding that of a nano‐silicon blended graphite anode (127 Wh kg^?1 and 229 Wh L^?1) in the full‐cell system.