Oxygen-evolving SnO2-based Ceramic Anodes in Aluminium Electrolysis

This study deals with SnO₂-based ceramic anodes doped with Sb₂O₃ and CuO, aiming at contributing new data regarding their electrochemical behavior in cryolite melts. The performances of the anodes were evaluated by anodic polarization, cyclic voltammetry, and current efficiency and corrosion measurements. The investigation proves that the anodic process of SnO₂-based inert anodes occurs at a low overvoltage and the oxygen discharge takes place in one step with an exchange of two electrons. The current efficiency and corrosion were proved to be dependent on the electrolysis parameters and composition of electrolysis bath. For a long term electrolysis, the dissolution of the anode in the cryolite-alumina melt produced small aluminium contamination(ca. 0.2%, mass fraction).     

Oxygen-evolving SnOz-based Ceramic Anodes in Aluminium Electrolysis

This study deals with SnO2-based ceramic anodes doped with Sb203 and CuO, aiming at contributing new data regarding their electrochemical behavior in cryolite melts. The performances of the anodes were evaluated by anodic polarization, cyclic voltammetry, and current efficiency and corrosion measurements. The investigation proves that the anodic process of SnO2-based inert anodes occurs at a low overvoltage and the oxygen discharge takes place in one step with an exchange of two electrons. The current efficiency and corrosion were proved to be dependent on the electrolysis parameters and composition of electrolysis bath. For a long term electrolysis, the dissolution of the anode in the cryolite-alumina melt produced small aluminium contamination（ca. 0.2%, mass fraction）.     

高铁酸盐在SnO2-Sb2O3/Ti电极上的选择性电化学合成

合成了SnO2-Sb2O3/Ti电极材料.实验结果证实,在14mol/LNaOH水溶液中和完全避免析氧反应的条件下,Fe(Ⅱ)物种在该电极上进行电化学氧化并生成FeO42-.结果表明,Fe(OH)3在浓NaOH溶液中发生酸式电离,形成可溶于水的FeO2-,该离子的浓度随着碱溶液浓度变化而发生明显变化,而且它还是发生化学氧化和电化学氧化的反应物.在SnO2-Sb2O3/Ti电极上,FeO42-的电化学还原起始电位为0.38V(vs.Hg/HgO,14mol/LNaOH),FeO2-电化学氧化起始电位为0.54V.结果还表明,用电化学方法氧化Fe(Ⅱ)物种生成FeO42-是个多步骤过程.     

Ti/SnO2-Sb2O5/PbO2阳极电化学氧化降解咪草烟及其过程监测

电催化高级氧化技术是最近发展起来的新型高级氧化技术之一,具有处理效率高、操作简便、与环境兼容等优点。因此,电化学水处理工艺在无机废水和高浓度、难降解有机废水处理中得到了越来越广泛的应用[1,2]。钛基二氧化铅(Ti/PbO2)是一种新型的不溶性金属氧化物阳极材料,在水溶液     

锂离子电池硅基负极材料的预锂化研究进展

锂离子二次电池已成为日常生活中不可或缺的一部分, 而现有的锂离子电池并不能完全满足电动汽车领域高能量密度的要求, 发展具有高能量密度的电极材料是解决问题的关键. 硅负极因理论比容量高、 脱嵌锂电位低、 来源广泛等优点而备受关注, 但其巨大的体积变化(约300%)以及低的首次库仑效率阻碍了其商业应用. 预锂化技术可以有效提高首次库仑效率、 实现高性能硅基负极, 本文阐述了预锂化的科学必要性, 介绍了各种预锂化的方法以及优缺点, 最后对硅基负极预锂化应用的挑战和前景进行了展望.     

高阳极电势窗口的SnO2-Sb2O3/Ti电极的制备

制备了不同热处理温度和涂层次数的SnO2-Sb2O3/Ti电极,研究了不同电极涂层的氧化物组成,涂层表面形貌和阳极电势窗口及其三者的内在关系,考察了不同制备工艺条件的电极对电催化高铁性能的影响.结果表明430℃是电极最佳的热处理温度,涂层次数增加为30次时,电极具有高的阳极电势窗口,同时能降低高铁氧化还原反应的超电势,更真实的展现高铁电化学生成的热力学原貌.     

阳极电沉积条件对Ti/SnO2-Sb2O5/PbO2+Nano-Co3O4复合电极组成、形貌和结构的影响

本文在涂有中间层SnO2-Sb2O5的Ti基体上,采用阳极复合电沉积法制备了Ti/SnO2-Sb2O5/PbO2+Nano-Co3O4复合电极材料,借助于X射线衍射（XRD）、X射线光电子能谱（XPS）、扫描电镜（SEM）等分析方法研究了制备条件对该复合电极材料的组成、结构和形貌的影响。结果表明,纳米Co3O4的掺杂可提高PbO2电极表面的粗糙度和空隙率;沉积电位、镀液中Co3O4粒子浓度及有机溶剂的添加均对镀层中Co3O4的嵌入量有很大影响。     

Structural Evolution of Pt,Au and Cu Anodes by Electrolysis up to Contact Glow Discharge Electrolysis in Alkaline Electrolytes**

Applying a voltage to metal electrodes in contact with aqueous electrolytes results in the electrolysis of water at voltages above the decomposition voltage and plasma formation in the electrolyte at much higher voltages referred to as contact glow discharge electrolysis (CGDE). While several studies explore parameters that lead to changes in the I–U characteristics in this voltage range, little is known about the evolution of the structural properties of the electrodes. Here we study this aspect on materials essential to electrocatalysis, namely Pt, Au, and Cu. The stationary I–U characteristics are almost identical for all electrodes. Detailed structural characterization by optical microscopy, scanning electron microscopy, and electrochemical approaches reveal that Pt is stable during electrolysis and CGDE, while Au and Cu exhibit a voltage-dependent oxide formation. More importantly, oxides are reduced when the Au and Cu electrodes are kept in the electrolysis solution after electrolysis. We suspect that H₂O₂ (formed during electrolysis) is responsible for the oxide reduction. The reduced oxides (which are also accessible via electrochemical reduction) form a porous film, representing a possible new class of materials in energy storage and conversion studies.     

A ternary phased SnO2-Fe2O3/SWCNTs nanocomposite as a high performance anode material for lithium ion batteries

A new SnO_2-Fe_2O_3/SWCNTs(single-walled carbon nanotubes) ternary nanocomposite was first synthesized by a facile hydrothermal approach.SnO_2 and Fe_2O_3 nanoparticles(NPs) were homogeneously located on the surface of SWCNTs,as confirmed by X-ray diffraction(XRD),transmission electron microscope(TEM) and energy dispersive X-ray spectroscopy(EDX).Due to the synergistic effect of different components,the as synthesized SnO_2-Fe_2O_3/SWCNTs composite as an anode material for lithium-ion batteries exhibited excellent electrochemical performance with a high capacity of 692 mAh·g~(-1) which could be maintained after 50 cycles at 200 mA·g~(-1).Even at a high rate of2000 mA·g~(-1),the capacity was still remained at 656 mAh·g~(-1).     

Ni/Mn3O4/NiMn2O4@RGO空心微球负极的制备及其储钠性能

采用溶剂热法制备前驱体,后经350 °C热处理,首次合成了空心结构的NiMn₂O₄微球以及不同含量氧化石墨烯包覆的Ni/Mn₃O₄/NiMn₂O₄@RGO复合材料. 电化学性能测试表明,复合负极材料中,含25wt%还原氧化石墨烯的材料储钠性能最佳,其在50 mA·g^-1电流密度下,100次循环后放电比容量保持在187.8 mAh·g^-1,且800 mA·g^-1电流密度下的可逆容量高达149.9 mAh·g^-1,明显优于NiMn₂O₄及其他石墨烯基复合材料. 研究指出,复合材料性能的提升得益于空心微球和还原的氧化石墨烯构成的特殊结构,一方面缩短了电子/离子传输距离,缓解了体积效应,另一方面高导电网络有效增强了活性物质利用率.     

Thermal decomposition of Me3SnO2PCl2, Me2Sn(O2PCl2)2 and Ph3SnO2PCl2

TG and DTA studies on Me₃SnO₂PCl₂, Me₂Sn(O₂PCl₂)₂ and Ph₃SnO₂PCl₂ were carried out under dynamic argon atmosphere. The results show that the decomposition proceeds in different stages leading to the formation of Sn₃(PO₄)₂ as a stable product. This compound was characterized by IR spectroscopy. Decomposition schemes involving reductive elimination reactions were proposed.     

水系锌离子电池嵌入负极材料TiX2 (X = S,Se)的储锌机制

水系锌离子电池(ZIBs)以其低成本、高安全性和环境友好的优点受到了研究者的广泛关注,成为大规模电化学储能系统的理想选择之一。然而锌金属负极在应用时面临着锌枝晶生长、腐蚀反应和副反应等难以克服的障碍,严重制约了水系锌离子电池的发展。探索可替代锌金属的储锌负极是应对上述问题的有效策略,因此研究者围绕过渡金属氧化物、硫化物和导电聚合物开展了深入研究。以TiX₂ (X = S, Se)为代表的二维过渡金属硫族化合物(TMDs)具有较大的层间距和快速的离子传输通道,可作为锌离子电池的负极,但其储锌反应机制尚未得到完整的揭示。在本文中,我们使用密度泛函理论(DFT)计算方法系统地研究锌离子在TiX₂中的嵌入反应。首先我们采用群论去描述嵌锌TiX₂的稳定层间构型的特点,定义了一个依赖于超胞并且只涉及平移旋转两种对称操作的群,其子群可以用来描述层间构型的对称性,而且用来描述最稳定构型的子群总是倾向于有最大的阶数。基于该计算得到的一系列对应于不同放电深度的TiX₂的稳定结构,我们发现TiS₂和TiSe₂两种材料在锌嵌入/脱出过程中的开路电压(OCV)均低于0.5 V。态密度(DOS)的计算结果表明TiX₂具有很好的电子导电性,而分波态密度(PDOS)的结果显示随着锌的嵌入闭壳层的Ti⁴⁺还原成开壳层的Ti³⁺,并且伴随着Zn―X键的生成。Bader电荷分析的结果表明随着X的嵌入,X相比Ti得到了更多的负电荷,意味着X也参与了TiX₂的氧化还原过程。爬坡弹性带方法(CINEB)计算的结果证实了Zn²⁺在TiX₂中具有较低的扩散能垒(对于TiS₂是0.333 eV,对于TiSe₂是0.338 eV)。本文的研究结果不仅从本质上证明了TiX₂适合作为锌离子电池的嵌锌负极材料,而且为其他高性能TMDs电池材料的DFT研究提供了新的见解。     

Oxygen ionic transport in Bi2O3-based oxides: II. The Bi2O3–ZrO2–Y2O3 and Bi2O3–Nb2O5–Ho2O3 solid solutions

Electrical conductivity, fluorite-type cubic unit cell volume and thermal expansion of the (Bi_{1− x} Nb _x )_{1− y} Ho _y O_1.5+δ (x=0.05 and 0.08; y=0.10−0.15) and (Bi_{1− x} Zr _x )_{1− y} Y _y O_1.5+δ (x=0.05 and 0.07; y=0.15) solid solutions have been found to decrease regularly with increasing dopant content. Annealing at temperatures below 900 K leads to a phase decomposition and to a sharp decrease in conductivity of the ceramics. Oxygen ion transference numbers have been determined by the e.m.f. method and by Faradaic efficiency measurement to exceed 0.9. A new technique of studying Faradaic efficiency has been proposed and verified using (Bi_0.95Zr_0.05)_0.85Y_0.15O_1.5+δ and Zr_0.90Y_0.10O_1.95 ceramic samples. Received: 31 October 1997 / Accepted: 18 December 1997     

Corrosion behaviour of SiC and Al2O3 reinforced Al 7075 hybrid aluminium matrix composites by weight loss and electrochemical methods

The corrosion study of Al 7075 hybrid metal matrix composites reinforced with equal weight percents (2.5, 5, 7.5, and 10) of silicon carbide and aluminium oxide is investigated in the present work by weight loss and electrochemical methods. In this study, composite specimens prepared by the squeeze casting technique were analyzed at room temperature to estimate the rate of corrosion in a 3.5% NaCl solution for various intervals using the weight loss method. As a consequence, a hybrid Al7075 composite reinforced with 10% SiC and 10% Al₂O₃ had a lower corrosion rate of 0.9997 mmpy than pure Al7075, which had a maximum corrosion rate of 3.4481 mmpy. The corrosion rate of hybrid composites is determined by the tafel polarization method and the electrochemical impedance spectroscopic method. These experiments showed that the corrosion rate of the hybrid metal matrix composite Al7075 + 10% SiC +10% Al₂O₃ was 0.630 mmpy less than that of the monolithic 7075 alloy. The corrosion morphology behaviour of the Al 7075 and their hybrid composite samples is observed by SEM. The SEM micrographs implied that SiC and Al₂O₃ reinforcements with the matrix alloy produced good interfacial and intermetallic bonding and hence decreased the corrosion rate.     

Enhancement of Activity of SnO2-doped In2O3/Al2O3 Catalyst for NO Reduction with Propene in the Presence of H2O and SO2

The selective catalytic reduction of nitrogen oxides by hydrocarbons (HC-SCR) has attracted much attention as an efficient way to remove NO in the presence of excess oxygen1-2. The metal oxides are the most promising catalysts for the SCR of NO because of their high activity and selectivity3-5. In the previous work, the metal oxides such as Ag, Sn, In, Co supported on alumina for NO reduction were investigated6-8, however, the HC-SCR is usually suppressed in the presence of H2O and S…     

Structural and Electrochemical Properties of Li2O-V2O5-B2O3-Bi2O3 Glass and Glass-Ceramic Cathodes for Lithium-Ion Batteries

In this study, 20Li₂O-60V₂O₅-(20 − x)B₂O₃-xBi₂O₃ (x = 5, 7.5, 10 mol%) glass materials have been prepared by the melt-quenching method, and the structure and morphology of the glass materials have been characterized by XRD, FTIR, Raman, and FE-SEM. The results show that the disordered network of the glass is mainly composed of structural motifs, such as VO₄, BO₃, BiO_3, and BiO₆. The electrochemical properties of the glass cathode material have been investigated by the galvanostatic charge-discharge method and cyclic voltammetry, and the results show that with the increases of Bi₂O₃ molar content, the amount of the VO₄ group increases, and the network structure of the glass becomes more stable. To further enhance the electrochemical properties, glass-ceramic materials have been obtained by heat treatment, and the effect of the heat treatment temperature on the structure and electrochemical properties of the glass has been studied. The results show that the initial discharge capacity of the glass-ceramic cathode obtained by heat treatment at 280 °C at a current density of 50 mA·g⁻¹ is 333.4 mAh·g⁻¹. In addition, after several cycles of charging and discharging at a high current density of 1000 mA·g⁻¹ and then 10 cycles at 50 mA·g⁻¹, its discharge capacity remains at approximately 300 mAh·g⁻¹ with a capacity retention rate of approximately 90.0%. The results indicate that a proper heat treatment temperature is crucial to improving the electrochemical properties of glass materials. This study provides an approach for the development of new glass cathode materials for lithium-ion batteries.     

Efficiency of 3D-Ordered Macroporous La0.6Sr0.4Co0.2Fe0.8O3 as an Electrocatalyst for Aprotic Li-O2 Batteries

Li-O₂ batteries (LOBs) with an extremely high theoretical energy density have been reported to be the most promising candidates for future electric storage systems. Porous catalysts can be beneficial for LOBs. Herein, 3D-ordered macroporous La_0.6Sr_0.4Co_0.2Fe_0.8O₃ perovskite oxides (3D-LSCF) are applied as cathode catalysts in LOBs. With a high Brunauer-Emmett-Teller surface area (21.8 m² g⁻¹) and unique honeycomb-like macroporous structure, the 3D-LSCF catalysts possess a much higher efficiency than La_0.6Sr_0.4Co_0.2Fe_0.8O₃ (LSCF) nanoparticles. The unique 3D-ordered macropores play a significant role in the product deposition as well as oxygen and electrolyte transmission, which are crucial for the discharge-charge processes of LOBs.     

High Activity SnO2／Al2O3 Catalyst for NO Reduction in the Presence of Oxygen

The novel sol-gel SnO2/Al2O3 catalysts for selective catalytic reduction NO by propene under lean burn condition were investigated. The results showed thatthe maximum NO conversion was 82% on the SnO2/Al2O3 (5%Sn) catalyst, and the presence of H20 and SO2 improved the catalytic activity at low temperature. The catalytic activity of NO2 reduction by propene is much higher than that of NO at the entire temperature range, and the maximum NO2 conversion reached nearly 100% around the temperature 425℃.