Layer-by-Layer Assembly-Based Electrocatalytic Fibril Electrodes Enabling Extremely Low Overpotentials and Stable Operation at 1 A cm−2 in Water-Splitting Reaction

For the practical use of water electrolyzers using non-noble metal catalysts, it is crucial to minimize the overpotentials for the hydrogen and oxygen evolution reactions. Here, cotton-based, highly porous electrocatalytic electrodes are introduced with extremely low overpotentials and fast reaction kinetics using metal nanoparticle assembly-driven electroplating. Hydrophobic metal nanoparticles are layer-by-layer assembled with small-molecule linkers onto cotton fibrils to form the conductive seeds for effective electroplating of non-noble metal electrocatalysts. This approach converts insulating cottons to highly electrocatalytic textiles while maintaining their intrinsic 3D porous structure with extremely large surface area without metal agglomerations. To prepare hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) electrodes, Ni is first electroplated onto the conductive cotton textile (HER electrode), and NiFe is subsequently electroplated onto the Ni–electroplated textile (OER electrode). The resulting HER and OER electrodes exhibit remarkably low overpotentials of 12 mV at 10 mA cm⁻² and 214 mV at 50 mA cm⁻², respectively. The two-electrode water electrolyzer exhibits a current density of 10 mA cm⁻² at a low cell voltage of 1.39 V. Additionally, the operational stability of the device is well maintained even at an extremely high current density of 1 A cm⁻² for at least 100 h.     

Thermal Shrinkage Engineering Enables Electrocatalysts for Stable Hydrogen Evolution at 2000 mA cm−2

Constructing highly-active and robust electrodes is vital for the industrialized application of water electrolysis to produce green hydrogen. Nevertheless, the strong disturbance of gas bubbles, especially under ampere-level current densities, would bring about the exfoliation of catalytically active materials and performance deterioration. Herein, a Ru-doped Ni(OH)₂ ultrathin nanosheet array vertically grown on nickel foam with a mechanically-robust interface is first constructed by a facile corrosive engineering strategy. Subsequently, thermal shrinkage engineering inspired by heat shrinkable film is applied to avoid the region away from the interface in ultrathin nanosheets from being damaged by the impact of intensive gas evolution. As a result, the final self-supported electrode has plentiful features including robust binding at the electrocatalyst/support interface and amorphous/crystalline heterophase. These features promote the achievement of superior catalytic activity of a small overpotential of 400 mV and activity retention for over 100 h at 2000 mA cm⁻² current density.     

Band offsets at interfaces of (1 0 0)InxGa1−xAs (0 ⩽ x ⩽ 0.53) with Al2O3 and HfO2

The electron energy band alignment at interfaces of In_xGa_1?xAs (0 ? x ? 0.53) with atomic-layer deposited insulators Al₂O₃ and HfO₂ is characterized using combined measurements of internal photoemission of electrons and photoconductivity. The measured energy of the In_xGa_1?xAs valence band top is found to be only marginally influenced by the semiconductor composition. This result suggests that the observed bandgap narrowing from 1.42 to 0.75 eV when the In content increases from 0 to 0.53 occurs mostly through downshift of the semiconductor conduction band bottom. Electron states originating from the interfacial oxidation of In_xGa_1?xAs lead to reduction of the electron barrier at the semiconductor/oxide interface.     

A Durable and Efficient Electrocatalyst for Saline Water Splitting with Current Density Exceeding 2000 mA cm−2

Water electrolysis is promising for industrial hydrogen production to achieve a sustainable and green hydrogen economy, but the high cost of the technology limits its market share. Developing efficient yet economic electrocatalysts is crucial to decrease the cost of electricity and electrolytic cell. Meanwhile, electrolysis in seawater electrolyte can further reduce feedstock cost. Here, a type of electrocatalyst is synthesized, where trace precious metals are strongly anchored on a corrosion-resistive matrix. As an example, the produced Pt/Ni-Mo electrocatalyst only needs an overpotential of 113 mV to reach an ultrahigh current density of 2000 mA cm⁻² in the saline-alkaline electrolyte, demonstrating the best performance reported thus far. It shows high activity and long durability in various electrolytes and under harsh conditions, including strong alkaline and simulated seawater electrolytes, and under elevated temperatures up to 80 ° C. This electrocatalyst is produced on a large scale at a low cost and shows good performance in a commercial membrane electrode assembly stack, demonstrating its feasibility for practical water electrolysis.     

Low temperature,solution-processed ambipolar field-effect transistors based on polymer/self-assembled monolayer modified InOx hybrid structures for balanced hole and electron mobilities exceeding 1 cm2 V−1 s−1

Ambipolar field-effect transistors (FETs) based on solution-processed organic-inorganic bilayer structures were investigated. An amorphous indium oxide (InO_x) film, as the n-type semiconducting layer, was prepared with an environmentally friendly method and annealed at a low temperature; and a low band-gap (LBG) donor–acceptor (D–A) conjugated polymer, FBT-Th₄(1,4), was spin-coated on the InO_x film as the p-type semiconducting layer. To improve the p-type mobility, a self-assembled monolayer (SAM) of octadecyl-phosphonic acid was introduced to modify the surface of InO_x. The ambipolar FETs showed high and well-balanced hole and electron mobilities of 1.1 and 1.5 cm² V⁻¹ s⁻¹, respectively. Furthermore we found that ambipolar FETs could be integrated into functional complementary metal oxide semiconductor (CMOS)-like inverters.     

Antifreezing Zwitterionic Hydrogel Electrolyte with High Conductivity of 12.6 mS cm−1 at −40 °C through Hydrated Lithium Ion Hopping Migration

Hydrogel electrolytes have high room-temperature conductivity and can be widely used in energy storage device. However, hydrogels suffer from the inevitable freezing of water at subzero temperatures, resulting in the diminishment of their conductivity and mechanical properties. How to achieve high conductivity without sacrificing hydrogels’ flexibility at subzero temperature is an important challenge. To address this challenge, a new type of zwitterionic polymer hydrogel (polySH) electrolytes is fabricated. The anionic and cationic counterions on the polymer chains facilitate the dissociation of LiCl. The antifreezing electrolyte can be stretched to a strain of 325% and compressed to 75% at −40 °C and possesses an outstanding conductivity of 12.6 mS cm⁻¹ at −40 °C. A direct hopping migration mechanism of hydrated lithium-ion through the channel of zwitterion groups is proposed. The polySH electrolyte-based-supercapacitor (SC) exhibits a high specific capacitance of 178 mF cm⁻² at 60 °C and 134 mF cm⁻² at −30 °C with a retention of 81% and 71% of the initial capacitance after 10 000 cycles, respectively. The overall merits of the electrolyte will open up a new avenue for advanced ionic conductors and energy storage device in practical applications.     

Metallic Zinc Anode Working at 50 and 50 mAh cm−2 with High Depth of Discharge via Electrical Double Layer Reconstruction

Achieving high-rate and high-areal-capacity Zn anode with high depth of discharge (DOD) offers a bright future for large-scale aqueous batteries. However, Zn deposition suffers from severe dendrite growth and side reactions, which compromises achievable lifetime. Herein, an electrical double layer (EDL) reconstruction strategy is proposed by employing acetone as electrolyte additive to fully address these issues. Experimental and theoretical simulation results reveal that the adsorption priority of acetone to water on Zn creates a water-poor inner Helmholtz layer. Meanwhile, the intense hydrogen bonding effect between acetone and water confines the activity of free water and weakens the Zn²⁺ solvation in the outer Helmholtz layer and diffusion layer. Such ion/molecule rearrangement in EDL suppresses hydrogen evolution, facilitates the desolvation process, and promotes the Zn²⁺ diffusion kinetics, which guides homogeneous Zn nucleation and uniform growth, even in extreme situations. At both ultrahigh current density of 50 mA cm⁻² and areal capacity of 50 mAh cm⁻², the addition of 20 v/v% acetone in 2 m ZnSO₄ extends the lifespan of Zn//Zn symmetric cells from 12 to 800 h, with a high DOD of 73.5%. The effectiveness of this strategy is further demonstrated in the Zn-MnO₂ full batteries at wide temperature range from −30 to 40 °C.     

Paramagnetic Ge dangling bond type defects at (1 0 0)Si1−xGex/SiO2 interfaces (Invited Paper)

The work addresses the occurrence of Ge dangling bond type point defects at Ge_xSi_1?x/insulator interfaces as evidenced by conventional electron spin resonance (ESR) spectroscopy. Using multifrequency ESR, we report on the observation and characterization of a first nontrigonal Ge dangling bond (DB)-type interface defect in SiO₂/(1 0 0)Ge_xSi_1?x/SiO₂/(1 0 0)Si heterostructures (0.27 ? x ? 0.93) manufactured by the condensation technique, a selective oxidation method enabling Ge enrichment of a buried epitaxial Si-rich SiGe layer. The center, exhibiting monoclinic-I (C_2v) symmetry is observed in highest densities of ～7 × 10¹² cm^?2 of Ge_xSi_1?x/SiO₂ interface for x ～ 0.7, to disappear for x outside the ]0.45–0.87[ interval, with remarkably no copresence of Si P_b-type centers. Neither are trigonal Ge DB centers observed, enabling unequivocal spectral analysis. Initial study of the defect passivation under annealing in molecular H₂ has been carried out. On the basis of all data the defect is depicted as a Ge P_b1-type center, i.e., distinct from a trigonal basic Ge P_b(0)-type center (Ge₃Ge). The modalities of the defect’s occurrence as unique interface mismatch healing defect is discussed, which may widen our understanding of interfacial DB centers in general.     

Device characteristics of AlGaN/GaN MIS–HEMTs with high-k HfxZr1−xO2 (x = 0.66, 0.47, 0.15) insulator layer

This study investigates the characteristics of AlGaN/GaN MIS–HEMTs with Hf_xZr_1−xO₂ (x = 0.66, 0.47, and 0.15) high-k films as gate dielectrics. Sputtered Hf_xZr_1−xO₂ with a dielectric constant of 20–30 and a bandgap of 5.2–5.71 eV was produced. By increasing the Zr content of HfZrO₂, the V_TH shifted from −1.8 V to −1.1 V. The highest Hf content at this study reduced the gate leakage by approximately one order of magnitude below that of those Zr-dominated HFETs. The maximum I_DS currents were 474 mA/mm, 542 mA/mm, and 330 mA/mm for Hf content of 66%, 47%, 15% at V_GS = 3 V, respectively.     

Delicately Designed Cyano-Siloxane as Multifunctional Additive Enabling High Voltage LiNi0.9Co0.05Mn0.05O2/Graphite Full Cell with Long Cycle Life at 50 °C

Lithium-ion batteries (LIBs) adopting layered oxide cathodes with high nickel content (Ni ≥ 0.9) always suffer from extremely poor cycle life, especially at elevated temperatures and higher charging cut-off voltages. Adding small amounts of functional additives is considered to be one of the most economic and efficacious strategies to resolve this issue. Herein, cyano-groups are introduced innovatively into a siloxane to delicately synthesize a novel cyano-siloxane additive, namely 2,2,7,7-tetramethyl-3,6-dioxa-2,7-disilaoctane-4,4,5,5-tetracarbonitrile (TDSTCN). Encouragingly, 0.5 wt.% TDSTCN additive enables ultrahigh nickel LiNi_0.9Co_0.05Mn_0.05O₂/graphite (NCM90/Gr) full cells with dramatically increased cycle life, especially at an elevated temperature of 50 °C and a high charging cut-off voltage of 4.5 V. The characterizations reveal that the TDSTCN additive can scavenge HF and promote the formation of robust stable interface layers on NCM90 cathode and Gr anode due to the synergistic effects of cyano-groups and Si−O bonds. These results reveal the great significance of designing one single additive with several functional groups in enhancing the comprehensive electrochemical performances of high Ni LIBs.