压水堆核电厂一回路首次钝化工艺研究

压水堆核电厂热态功能试验中的一回路首次钝化对核电厂一回路材料腐蚀控制和减少腐蚀产物等方面具有重要作用。本文结合理论研究与工程实际情况，提出了在热态功能试验过程中钝化膜的生成包含电化学反应和化学反应的观点，阐述了双层膜的生长机理，解释了用电化学测试方法分析钝化工艺过程的合理性，推导出钝化温度与钝化膜反应速率的函数关系式，钝化温度升高，反应速率升高，钝化时间缩短；明确了钝化工艺温度的理论限值应不低于260℃。      

In situ Raman spectroscopic study towards the growth and excellent HER catalysis of Ni/Ni(OH)2 heterostructure

The electrochemical water splitting to produce H₂ in high efficiency with earth-abundant-metal catalysts remains a challenge. Here, we describe a simple “cyclic voltammetry + ageing” protocol at room temperature to activate Ni electrode (AC-Ni/NF) for hydrogen evolution reaction (HER), by which Ni/Ni(OH)₂ heterostructure is formed at the surface. In situ Raman spectroscopy reveals the gradual growth of Ni/Ni(OH)₂ heterostructure during the first 30 min of the aging treatment and combined with polarization measurements, it suggests a positive relation between the Ni/Ni(OH)₂ amount and HER performance of the electrode. The obtained AC-Ni/NF catalyst, with plentiful Ni–Ni(OH)₂ interfaces, exhibits remarkable performance towards HER, with the low overpotential of only 30 mV at a H₂-evolving current density of 10 mA/cm² and 153 mV at 100 mA/cm², as well as a small Tafel slope of 46.8 mV/dec in 1 M KOH electrolyte at ambient temperature. The excellent HER performance of the AC-Ni/NF could be maintained for at least 24 h without obvious decay. Ex situ experiments and in situ electrochemical-Raman spectroscopy along with density functional theory (DFT) calculations reveal that Ni/Ni(OH)₂ heterostructure, although partially reduced, can still persist during HER catalysis and it is the Ni–Ni(OH)₂ interface reducing the energy barrier of H1 adsorption thus promoting the HER performance.     

Advances in multimetallic alloy-based anodes for alkali-ion and alkali-metal batteries

In order to meet the growing demand of portable electronic devices and electric vehicles, enhancements in battery performance metrics are required to provide higher energy/power densities and longer cycle lives, especially for anode materials. Alloying anodes, such as Group IVA elements-based materials, are attracting increasing interest as anodes for next-generation high-performance alkali-metal-ion batteries (AMIBs) owing to their extremely high specific capacities, low working voltages, and natural abundance. Nevertheless, alloying-type anodes usually display unsatisfactory cycle life due to their intrinsic violent volumetric and structural changes during the charge–discharge process, causing mechanical fracture and exacerbating side reactions. In order to overcome these challenges, efforts have been made in recent years to manufacture multimetallic anodes that can accommodate the induced strain, thus showing high Coulomb efficiency and long cycle life. Meanwhile, much work has been conducted to understand the details of structural changes and reaction mechanisms taking place by in-situ characterization methodologies. In this paper, we review the various recent developments in multimetallic anode materials for AMIBs and shed light on optimizing the anode materials. Finally, the perspectives and future challenges in achieving the practical applications of multimetallic alloy anodes in high-energy AMIB systems are proposed.     

Cover Picture: UV‐Light‐Induced Swelling and Visible‐Light‐Induced Shrinking of a TiO2‐Containing Redox Gel (Adv. Mater. 9/2007)

Polyacrylate gels containing Ag⁺ and TiO₂ nanoparticles are shown to swell under UV light and shrink under visible light in water. In work reported by Tetsu Tatsuma and co‐workers on p. 1249, the TiO₂ absorbs UV light and reduces the Ag⁺, whereas the deposited Ag absorbs visible light and dissolves itself. These redox reactions change the interactions between the polymer chains and eventually the volume of the gel, as shown on the cover.     

Electroluminescent zinc sulphide devices produced by sol-gel processing

Zinc sulphide thin film electroluminescent devices doped with Mn or Tb have been produced on p-type Si substrates using a process in which doped zinc oxide films are deposited by a sol-gel drain coating method from a solution of zinc acetate containing a manganese or terbium dopant. The films are then converted to ZnS by heating them in an atmosphere containing hydrogen sulphide which replaces the oxygyn with sulphur. The composition, crystalline structure and optical properties of films have shown that complete conversion from the oxide to the sulphide takes place. The luminescent characteristics of the devices so produced have been measured as a function of the doping concentrations, film thickness, insulator thickness and driving voltage and frequency. It has been found that yellow or green luminescence can be obtained using Mn or Tb doping respectively.     

Electrochemical deposition of MoS2 thin films by reduction of tetrathiomolybdate

Molybdenum sulphide was cathodically electrodeposited from aqueous solutions of sodium tetrathiomolybdate. The as-deposited films were X-ray amorphous with a composition, measured by microprobe analysis, close to MoS₂. Annealing these films in Ar resulted in highly-textured films of MoS₂ with the van der Waals planes parallel to the substrate. A small expansion in the c spacing of the annealed films was explained by the presence of oxygen in the crystals. A direct bandgap of 1.78 eV was found for the annealed films.     

Electrochemical Investigation on the Formation of Dy-Fe Alloy in Molten Chlorides

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Electrochemical determination of estradiol using a poly(l-serine) film-modified electrode

A thin film of poly(l-serine) was prepared via electropolymerization for the determination of trace levels of estradiol. In pH 5.0 phosphate buffer, l-serine was oxidized during the cyclic potential sweeps between −0.60 and 2.0 V, forming a thin film at the electrode surface. The electrochemical behavior of estradiol was investigated. The oxidation peak potential of estradiol shifts negatively at the poly(l-serine) film-coated glassy carbon electrode (GCE) compared with that at the bare GCE. Otherwise, the oxidation peak current greatly increases at the poly(l-serine) film-modified GCE. These phenomena suggest that the poly(l-serine) film exhibits catalytic activity towards the electrochemical oxidation of estradiol. Based on this, a sensitive, rapid and simple electrochemical method was proposed for the determination of estradiol. The limit of detection is evaluated to be 2.0 × 10⁻⁸ mol L⁻¹. Finally, this method was successfully used to determine estradiol in blood serum.     

Electrochemical Study on Formation of Dy-Ni Alloy in Molten Chlorides

ＥｌｅｃｔｒｏｃｈｅｍｉｃａｌＳｔｕｄｙｏｎＦｏｒｍａｔｉｏｎｏｆＤｙ－ＮｉＡｌｌｏｙｉｎＭｏｌｔｅｎＣｈｌｏｒｉｄｅｓＴｏｎｇＹｅｘｉａｎｇ；ＬｉｕＧｕａｎｋｕｎ；ＹａｎｇＱｉｑｉｎ；ＨｏｎｇＨｕｉｃｈａｎ，（童叶翔）（刘冠昆）（杨绮琴）（洪惠婵）...     

The dynamic evolution of aggregated lithium dendrites in lithium metal batteries

Lithium (Li) metal anodes promise an ultrahigh theoretical energy density and low redox potential,thus being the critical energy material for next-generation batteries.Unfortunately,the formation of Li den-drites in Li metal anodes remarkably hinders the practical applications of Li metal anodes.Herein,the dynamic evolution of discrete Li dendrites and aggregated Li dendrites with increasing current densities is visualized by in-situ optical microscopy in conjunction with ex-situ scanning electron microscopy.As revealed by the phase field simulations,the formation of aggregated Li dendrites under high current den-sity is attributed to the locally concentrated electric field rather than the depletion of Li ions.More specif-ically,the locally concentrated electric field stems from the spatial inhomogeneity on the Li metal surface and will be further enhanced with increasing current densities.Adjusting the above two factors with the help of the constructed phase field model is able to regulate the electrodeposited morphology from aggregated Li dendrites to discrete Li dendrites,and ultimately columnar Li morphology.The methodol-ogy and mechanistic understanding established herein give a significant step toward the practical appli-cations of Li metal anodes.