锂离子电池用纳米Sn/SnSb合金三维复合负极的制备及性能

采用多步电沉积法制备的三维多孔铜箔作为集流体、低温液相化学还原法制备的纳米Sn/SnSb 合金作为负极材料, 制备出一种新型三维多孔结构的纳米Sn/SnSb合金复合负极. 通过与普通负极电化学性能的对比实验发现, 这种新型三维复合负极具有如下优点: 三维多孔网络结构提高了负极活性材料与集流体之间的结合力, 使不含粘结剂电极的制备成为可能; 有效缓解了高容量负极活性材料在充放电过程中的体积膨胀, 提高了负极活性材料的循环性能, 当循环到第30周时, 普通负极剩余容量为初始容量的33%, 而三维复合负极剩余容量为初始容量的41%; 三维铜箔集流体的特殊结构为高容量负极活性材料提供了一个良好的导电环境, 使电极反应进行得更加完全, 从而获得了更高的电极比容量, 普通负极初始容量为480 mAh·g-1, 而三维复合负极达到了800 mAh·g-1. 纳米Sn/SnSb合金三维复合负极良好的电化学性能为锂离子电池负极结构的设计开发提供了新的思路.     

Computer modeling of negative electrode operation in lithium-ion battery: Model of equal-sized grains,galvanostatic discharge mode,calculation of characteristic parameters

A computer simulation of the negative electrode (anode) operation in a lithium-ion battery is performed. A complete research program is carried out in accordance with the recommendations of the theory of porous electrodes: the “model of equal-sized grains of two types” was studied, percolation properties of the anode active layer were researched, values of effective coefficients were calculated for charge transfer and mass transport, a complete system of equations describing operation of the anode is presented. Two specific cases of galvanostatic mode of anode discharge are considered in detail: an “ideal” anode and anode with nanosize particles. Working anode parameters are calculated: optimum bulk concentration of graphite in the active layer, active layer thickness, time of complete anode discharge, its specific electric capacitance and final potential on the active/layer interelectrode space interface. Advisability of working with anodes with nanosize grains and electrolyte with enhanced specific conductivity is shown.     

大电流稀土电解槽阳极结构研究

针对大电流稀土电解槽阳极消耗速率快、阳极消耗变形导致电热场分布不合理的现象,对15 kA大电流稀土电解槽阳极的实际消耗问题进行了分析,并运用COMSOL多物理场耦合软件对阳极消耗过程和不同阳极倾角下的三维电热场进行了耦合模拟分析。结果表明:阳极消耗变形后,电解槽内上部电场分布比下部更加密集,高温区域向液面偏移;随着阳极斜向上倾角的增大,电解槽内电压降低,高温区域向槽底偏移,倾角为4°时电热场分布最为合理。最后结合现场试验,验证了试验结果和模拟结果的一致性。     

锂离子电池纳米负极电极材料

综述了锂离子电池纳米负极材料研究的最新进展,根据材料的化学组成把锂离子电池纳米级负极材料分为金属基纳米负极材料、非金属基纳米负极材料、金属-非金属复合纳米负极材料、纳米氧化物负极材料和其它纳米负极材料。论述了各类材料的优势和存在的问题,探讨了这些材料的主要制备方法与其结构、形貌和电化学性能之间的关系,展望了纳米负极材料用于锂离子电池的前景。     

Study of the Anode Region of a DC Glow Discharge by a Spatially One-Dimensional Hybrid Method

The anode region of a dc glow discharge at low pressure and current is studied by a new self-consistent, spatially one-dimensional hybrid method. The method consists of the coupled solution of the steady-state fluid equations of electrons, ions, and excited atoms and the Poisson equation using the electron transport properties as well as the excitation and ionization frequencies from a strict solution of the non-uniform kinetic equation of the electrons. Results such as the electric potential, the electron velocity distribution function, and the densities of the charge carriers and excited atoms are reported for the anode region of neon glow discharges. Physical properties of the plasma in the anode region known from experiments have been confirmed by the model such as the occurrence of the anode fall, a formation of plateau-like areas of the potential profile in front of the anode, the anode dark space, and the anode glow.     

Computer modeling of positive electrode operation in lithium-ion battery: Model of equal-sized grains,percolation calculations

A computer simulation of the negative electrode (anode) operation in a lithium-ion battery is performed. A complete research program is carried out in accordance with the recommendations of the theory of porous electrodes: the “model of equal-sized grains of two types” was studied, percolation properties of the anode active layer were researched, values of effective coefficients were calculated for charge transfer and mass transport, a complete system of equations describing operation of the anode is presented. Two specific cases of galvanostatic mode of anode discharge are considered in detail: an “ideal” anode and anode with nanosize particles. Working anode parameters are calculated: optimum bulk concentration of graphite in the active layer, active layer thickness, time of complete anode discharge, its specific electric capacitance and final potential on the active/layer interelectrode space interface. Advisability of working with anodes with nanosize grains and electrolyte with enhanced specific conductivity is shown.     

Impact of anode evaporation on the anode region of a high-intensity argon arc

Experimental studies of a free-burning, high-intensity argon arc operated at 800 Torr with a solid, molten, or resolidified copper anode demonstrate that the cathode region is not affected by Cu vapor from the anode. Also Cu vapor concentrations in the arc core (beyond 1 mm from the anode surface) are negligible. In contrast, there is a strong effect of the Cu vapor on the anode region of the arc. The arc fringes become electrically conducting due to the presence of Cu vapor, resulting in a flattening of the current density distribution and a corresponding drop of the temperature in the arc core. At the same time, the overall arc voltage shows a slight drop (<1 V). In the case of the resolidified anode, the overall arc voltage increases, which seems to be associated with the distribution of the stagnation flow in front of the anode due to a dip in the center of the anode.     

Electrochemical study on various types of anode materials in LiCl–KCl eutectic salt used in the electro-winning process

The electrochemical behaviors of the molybdenum, graphite, and glassy carbon anode have been observed during the electrolysis of uranium chloride in an UCl₃–LiCl–KCl molten salt. The cyclic voltammogram data of the molybdenum anode showed that Mo anode could be corroded by the formation of Mo compounds or its dissolution. However, the experimental data of the graphite and the glassy carbon anode showed that the chlorine evolution started from 1.2 V and the anode potential remained stable during uranium electrolysis. Therefore, the graphite and glassy carbon may be used as an inert anode in the electro-winning process of pyroprocessing.     

H型电解池中CO2电化学还原的阳极电解液问题

采用自制的H型电解池开展了KHCO₃溶液中电化学还原CO₂制甲酸的研究. 研究发现,在电解池中长时间电解时阴阳两极间的电压（槽电压）会持续升高,导致电解过程不可持续. 经过恒电位电解、恒电流电解、pH测试以及电解前后阳极室KHCO₃浓度分析等实验研究,作者发现,这是由以下过程引起的：阳极上的析氧反应产生的H⁺与电解液中的HCO₃^-反应生成水和CO₂,导致阳极室的HCO₃^-的消耗,之后阳极室的K⁺被迫扩散进入阴极室而导致阳极室电解质浓度下降. 因此,阳极室电解液导电性下降,进而引起阳极电位的升高. 研究发现,阳极电解液具有碱性时,都可能发生此种现象,因此,为了保证电解过程可持续且保持高的能量转换效率,阳极液的电解质不能是任何具有碱性的物质.     

钕掺杂二氧化铅复合阳极的电化学性能研究

利用电沉积法制备了钕（Nd）掺杂钛（Ti）基二氧化铅（PbO₂）复合阳极,采用扫描电子显微镜（SEM）、X 射线衍射（XRD）、电化学阻抗谱、线性扫描伏安法、循环伏安法等对所制备电极的表面形貌、物相组成及电化学性能进行了分析. 结果表明,Nd 掺杂使得 PbO₂ 阳极表面颗粒变小、结构更加致密,增大了电极比表面积,改善了电极电化学性能. PbO₂ 和 PbO₂-Nd 阳极表层主要为β- PbO₂,Nd 掺杂提高了β- PbO₂ 的结晶纯度,改变了表面相的相对丰度,促进了β(101)晶面形成. PbO₂-Nd 阳极具有更小的电化学反应电阻,更高的析氧电位,更强的电子交换能力和更长的使用寿命. 将所制备电极应用于处理苯酚模拟难降解有机废水,PbO₂-Nd 阳极对苯酚具有更好的电催化氧化效果,降解3 h,苯酚去除率达85.7%,COD 去除率达73.8%. 循环使用6 次,PbO₂-Nd 阳极电催化活性无明显衰减,显示出更好的电催化耐久性.     

Effect of Anode Arc Root Position on the Behavior of the DC Non-transferred Plasma Jet at Field Free Region

A special bi-anode plasma torch that can change the anode arc root position without changing working gas flow rate has been developed to investigate the effect of anode arc root position on the behavior of the plasma jet. It has two nozzle-shaped anodes at different axial distances from the cathode tip. The arc root can be formed at anodes either close to the cathode tip (anode I) or far away from it (anode II) to obtain different attachment positions and arc voltages. The characteristics of pure argon plasma jets operated in different anode modes were measured in the field free region by using an emalpy probe, and the thermal efficiency of the torch was determined by measuring the temperature differences between cooling water flowing in and out of the torch. The results show that compared with the normal arc operated in anode I mode, the elongated arc operated in anode II mode significantly reduced the plasma energy loss inside the torch, resulting in a higher temperature and a higher velocity of the plasma jet in the field free region.     

镧改性镍基阳极固体氧化物燃料电池

研究了镧改性镍基阳极的组成与结构及其电化学性能.XRD结果显示,镧可以与氧化镍反应生成LaNiO3,在复合阳极中可以与氧化锆反应生成La2Zr2O7.SEM结果显示,当镧含量为10%（摩尔比）时,复合阳极的颗粒较小,分布均匀;添加镧可以较好地阻止镍与氧化钇稳定的氧化锆（YSZ）的烧结长大,而且很好地改善镍与YSZ的界面接触;镧改性阳极的微结构得到了明显的改善,大大降低了电池的极化电阻,提高了电池性能,电池在800℃时的最大功率密度由添加前的1.33W/cm2提高到1.61W/cm^2.但当添加过量的镧（20%摩尔比）时,因较多的La2Zr2O7生成,使电池的欧姆和极化电阻明显增加,电池性能降低.     

Nanostructured polyaniline-coated anode for improving microbial fuel cell power output

An approach for improving the power generation of a dual-chamber microbial fuel cell by using a nanostructured polyaniline (PANI)-modified glassy carbon anode was investigated. Modification of the glassy carbon anode was achieved by the electrochemical polymerisation of aniline in 1 M H₂SO₄ solution. The MFC reactor showed power densities of 0.082 mW cm^?2 and 0.031 mW cm^?2 for the nano- and microstructured PANI anode, respectively. The results from electron microscopy scanning confirmed formation of the nanostructured PANI film on the anode surface and the results from electrochemical experiments confirmed that the electrochemical activity of the anode was significantly enhanced after modification by nanostructured PANI. Electrochemical impedance spectroscopic results proved that the charge transfer would be facilitated after anode modification with nanostructured PANI.     

水系锌离子二次电池锌负极的研究进展

锌离子二次电池具有优异的充放电性能、高功率密度和能量密度、低成本、高安全性和环境友好的特点,极具发展前景。金属锌,因优异的导电性、低的平衡电势、高的理论比容量和低成本等因素,是水系二次电池中理想的负极材料,然而也存在着枝晶生长、腐蚀和钝化等问题,限制了锌离子二次电池的可逆容量和循环寿命,通过优化调节锌负极的形貌与表面修饰等方法可以提高电池性能。本文综述了水系锌离子二次电池负极材料的研究进展,涵盖了金属锌负极、复合锌负极和锌合金,且展望了锌负极的发展前景。     

C K‐edge NEXAFS study of fluorocarbon formation on carbon anodes in molten NaF–AlF3–CaF2

Operational instability from processes occurring at the anode during the production of aluminum in the commercial Hall‐Héroult process may lead to an increase in undesirable fluorocarbon emissions, higher energy use, and shorter plant life. One contribution to this instability may be the possible formation of a fluorocarbon film at the electrode interface. Here, the surface composition of graphite anodes after electrolysis in molten NaF–AlF₃–CaF₂ at 990 °C is investigated for evidence of fluorocarbon formation using C K‐edge near edge X‐ray absorption fine structure. Fluorocarbon is identified on an anode surface after prolonged anode effect (very high overpotential with increased cell resistance) and also on an anode surface after normal electrolysis without anode effect. This provides evidence that fluorocarbon formation may occur prior to anode effect lowering the surface tension of the anode and therefore resulting in dewetting to contribute to the onset of the anode effect. Confirmation that such compounds form furthers our understanding of electrochemical reactions of graphite with fluoride and of the fundamental processes that occur in an aluminum smelter cell. Copyright © 2013 John Wiley & Sons, Ltd.     

A novel Mo-based oxide β-SnMoO_4 as anode for lithium ion battery

Recently,the development of new electrode materials for lithium-ion batteries(LIBs)has received intensive attention.As an important family of inorganic materials,mixed Mo-based transition metal oxides system is focused as anode materials.In the present work,a simple route has been adopted for the synthesis of layered-flake-likeβ-SnMo04 Nano-assemblies,which have been explored as potential anode materials for the first time in lithium-ion battery(LIB).Overall,the current reports on metal molybdate as anode materials are still rarely.As the anode material for LIBs,it was observed that the fabricated anode is capable of delivering a steady state capacity of almost 400 mAh/g up to 300 cycles under the influence of200 mA/g current density.Further,the anode material is suitable for use as a rated capacity anode because of its high current density tolerance.The present study can be further extended for the generation of a wide variety of other novel materials for multidisciplinary energy related applications.     

SnNi-deposited carbonaceous mesophase spherule as anode material for lithium ion batteries

Carbonaceous mesophase spherule (CMS) is a commercial anode material for rechargeable lithium batteries. A composite anode material of SnNi deposited carbonaceous mesophase spherule was prepared by co-precipitation method. The structural and electrochemical characterization of the SnNi/CMS composite anode material was studied. According to the measurement of its electrochemical characterization, the prepared SnNi/CMS composite anode material shows much better electrochemical performance than CMS. The first discharge capacity of 360 mA h g⁻¹ was obtained for the SnNi/CMS composite anode material, and its discharge capacity maintained at 320–340 mA h g⁻¹ in the following cycles. It indicates that the modification of CMS with SnNi alloy can further improve the intercalation performance of CMS. SnNi/CMS composite material shows a good candidate anode material for the commercial rechargeable lithium batteries.     

采用简易方法合成直接乙醇固体氧化物燃料电池海胆状Pd催化层

在室温下,通过电位置换反应在固体氧化物燃料电池的Ni-YSZ(钇掺杂氧化锆)阳极表面制备海胆状Pd催化层。该催化层的结构和性能通过SEM、XRD和电化学等表征手段进行表征。结果表明,三维纳米花状Pd催化剂是由在Ni-YSZ阳极表面形成的多条纳米棒有序的组合而成。通过在Ni/YSZ阳极表面引入该催化层,相比与传统Ni-YSZ阳极,燃料电池的最高功率和稳定性都获得了很大的提升。该研究表明,电位置换反应是一种很高效的在传统Ni-YSZ阳极表面制备纳米抗积炭的功能层的方法。     

火试金法测定多金属复杂铜阳极泥中金

铜阳极泥中因含有大量金、银、铂、钯等贵金属而具有较高回收价值,其中金是价值最高的元素,金的精准检测对其综合回收具有重要指导意义。由于生产铜阳极泥的阳极板成分、生产指标控制、设备设施水平等因素的不同,导致其主要成分及含量均有较大差异,实验针对代表性的多金属复杂铜阳极泥,考察了多因素对火试金检测结果的影响。在硅酸度K=1.8、铅扣质量为35 g、氧化铅过量系数为1.8、熔炼温度为1100℃、熔炼升温时间和保温时间均为30 min时,加标回收率在99.4%~101%,RSD为0.15%~0.29%。优化条件下可实现多金属复杂铜阳极泥中金的精准检测。     

Improvement of the charge imbalance caused by the use of a p-type silicon anode in an organic light-emitting diode

An indium-tin oxide anode was replaced with a p-type silicon anode in a bilayer small-molecule organic light-emitting diode. As results, the current increased largely due to the enhanced hole injection and the higher conductivity of the Si anode; the luminous efficiency decreased significantly due to carrier-induced exciton quenching and the worse charge imbalance. Ultra-thin film of SiO₂ grown on the silicon anode improved the luminous efficiency to a certain extent by restraining the hole injection; enhancing electron injection became more desired.