纳米碳管的电化学贮锂性能

用透射电镜、高分辨透射电镜、X射线衍射和拉曼光谱表征了用催化热解法制备的纳米碳管的结构,研究了纳米碳管的电化学嵌脱锂性能。以纳米级铁粉为催化剂热解乙炔气得到的纳米碳管石墨化程度较低,结构中存在褶皱的石墨层、乱层石墨和微孔等缺陷,具有国交高的贮锂容量,初始容量为640mAh/g,但循环稳定性较差。而以纳米级氧化铁粉为催化剂热解乙烯得到的纳米碳管结构比较规则,循环稳定性较好,但贮锂容量较低,初始容量为282mAh/g。讨论了纳米碳管的结构对其温度特性和不同电流密度下的充放电容易的影响。     

纳米碳管作为氧扩散电极催化层第二相碳载体的电极特性

以纳米碳管和活性碳二元碳材料为催化层碳载体制备了氧扩散电极,采用稳态极化和电化学阻抗技术对其在碱性介质中氧还原反应的电催化活性进行了研究.结果表明,双载体电极比单载体纳米碳管、活性炭电极具有更高的电催化活性,纳米碳管和活性炭质量比为50∶50时双载体电极的催化活性最好;电极动力学参数测试表明,催化层中引入第二相纳米碳管载体提高了电极比表面积、电子导电性和氧还原反应速度;采用浸渍还原法在第二相纳米碳管载体中负载纳米级Pt催化剂,即使在低Pt负载量下(45.7μg/cm2)也明显改善了双载体电极的催化活性.阻抗测试表明,载Pt与未载Pt催化剂的双载体电极均受氧在薄液膜中的扩散控制.     

电化学阴极沉积制备氧化钴/CNTs复合电极的准电容特性

采用电化学阴极沉积还原Co(NO3)2的方法制备了具有准电容特性的氧化钴电极材料,其比容量达到280 F／g,采用CNTs作为电极基体,在其表面均匀的沉积了纳米钴化镍颗粒并由此制备了氧化钴碳纳米管复合电极材料.采用循环伏安,恒流充放电,交流阻抗及扫描电镜等方法考察了复合电极材料的容量特性、阻抗特性、自放电特性以及电极表观特征．实验表明复合电极具有良好的电化学特性,CNTs基体在明显降低氧化镍材料的阻抗的同时还提高了电极材料的电化学容量并拓宽了电极材料的有效工作电位窗,复合电极在1 mol／L KOH电解液中比容量达到322 F／g且表现了良好的电化学可逆性．并分别采用氧化钴／CNTs复合电极作为正极,活性炭纤维作为负极制备了复合型电化学电容器,其工作电压达到1．4 V,电容器质量比容量达到47 F／g．在0．1 A／cm2放电时,复合型电容器的能量密度达到10 Wh／kg,兼具高能量特性和优良的大电流放电特性．     

SrTiO3/α-Fe2O3异质结光阳极光电转换性能

作为一类重要的光电极材料,α-Fe2O3在太阳能转化方面有着潜在的应用前景.但是,光生电子空穴对的再复合导致α-Fe2O3的光电量子产率很低.为了抑制光生电子空穴对的再复合,提高α-Fe2O3的光电量子产率,采用Spin-coating方法在透明导电玻璃FTO(SnO2:F)衬底上制备了SrTiO3/α-Fe2O3异质结薄膜光电极,并对该光电极进行了XRD、SEM、紫外-可见透射光谱的表征.在三电极光电化学测试系统中对薄膜的光电流-电压特性、入射光子电流转化效率(Incident photon to current efficiency,IPCE)对波长的依赖性进行了表征.在相同的Xe灯照射条件下,SrTiO3/α-Fe2O3异质结光电极的光电流及IPCE值大于单一的SrTiO3、α-Fe2O3各自的光电流及IPCE值,这与理论预测的结论一致.     

碳热还原法制备V2O3-C双层包覆磷酸铁锂及其电化学性能

通过V₂O₅的碳热还原反应制备了具有优异倍率性能和循环稳定性的V₂O₃-C双层包覆的磷酸铁锂正极材料. 粉末X射线衍射、元素分析、高分辨投射电镜和拉曼光谱研究表明V2O3相与碳层共包覆于磷酸铁锂颗粒表面. 在V₂O₅的碳热还原反应后,碳含量明显降低,但石墨化程度未发生明显改变. 电化学测试结果表明少量V₂O₃显著改善了磷酸铁锂正极材料的倍率性能和高温循环性能,包含1%氧化钒的复合正极材料在0.2 C放电容量为167 mAh/g,5 C时放电容量为129 mAh/g,并且循环稳定性优异;在55 oC和1 C时放电容量为151 mAh/g,循环100次后无明显容量衰减.     

离子束辅助沉积硅薄膜负极材料的研究

采用离子束辅助沉积法制备了锂离子电池硅薄膜负极材料,研究了硅薄膜的晶体结构、表面形貌和电化学性能.研究结果表明：硅薄膜是非晶态的结构;非晶态硅薄膜发生嵌脱锂反应的电位分别为0.03 V与0.34 V和0.16 V与0.49 V;硅薄膜表现出很高比容量和充放电效率,其可逆比容量和库仑效率分别为3134.4 mAh/g和87.1％;硅薄膜具有优异的循环性能,在0.5C倍率下200次循环后容量保持率为92.2%. 关键词： 硅薄膜 离子束辅助沉积 锂离子电池 负极材料     

表面修饰纳米TiO2的贮氢合金电极的光充电行为

采用水解-沉淀法制备了锐钛矿结构的纳米级TiO2,研究了表面修饰TiO2的贮氢合金电极的光充电、循环伏安及交流阻抗特性.结果表明,表面未修饰TiO2的贮氢合金电极在光照下电极电位基本无变化,而表面修饰TiO2的贮氢合金电极在光照下,电极电位向负方向偏移,可达-0.835V,表明在光照射条件下电极表面有氢原子形成.电化学阻抗谱的结果也表明,表面修饰电极在光照时表面有吸附氢存在,并存在氢原子向贮氢合金内部的扩散过程.扫描电镜观察表明,表面修饰TiO2的贮氢合金电极在光充电后产生的氢原子被贮氢合金吸收引起膨胀,导致表面出现大量微裂纹.     

钠掺杂磷酸铁锂晶格变化和电化学性能

利用固相法合成了钠掺杂的LiFePO₄,结构表征显示钠离子成功地掺入到了晶格中．SEM显示其粒径在1～3 μm．XRD显示钠掺杂样品晶胞变大．电池测试表明样品0.1 C放电150 mAh/g,5和7.5 C下分别放电109和107 mAh/g．1和5 C循环时,与初始放电容量相比,样品容量保持率分别为84%(1000次循环后)和86%(350次循环后),表现了优异的结构稳定性和循环性能．研究表明钠离子掺杂可以有效地提高磷酸铁锂的电化学活性,尤其是循环性能．     

锂离子电池Sn-Al薄膜电极的制备及电化学性能研究

采用磁控溅射沉积技术制备了纳米级Sn-Al合金薄膜电极材料,并用X射线衍射和扫描电子显微镜进行表征,用高精度电池测试系统进行充放电和循环伏安测试.结果表明直流DC与射频RF两种不同的溅射方法制备的Sn-Al薄膜电极具有很大的性能差异,前者DC法制备的材料颗粒细小,表现出稳定的循环性能,其首次放电容量为1060 mAh/g,首次效率为71.7％,电极经过50次循环后比容量保持在700 mAh/g以上.后者RF法制备的材料颗粒较大,放电比容量开始上升,第五次循环后接着逐渐衰减,表现出较差的循环性能. 关键词： 锂离子电池 磁控溅射 Sn-Al合金 电化学性能     

竹节状纳米碳纤维的制备及嵌锂性能研究

以泡沫镍为催化剂 ,在 6 0 0和 70 0℃下 ,以CVD法热解乙炔气体制备大量的纳米碳纤维 .随着制备温度增加 ,纳米碳纤维直径变小 ,竹节状含量减少 ,d0 0 2 值减小 ,微晶片层平面Lc 和La 值增大 ,碳材料的可逆容量则下降 .分别用透射电镜、X射线衍射和拉曼光谱观察和测定了纳米碳纤维的形貌、微结构 ,发现在不同条件下生长的纳米碳纤维有不同的形貌和结构 .对纳米碳纤维的电化学嵌锂性能的研究表明 ,纳米碳纤维的结构对其电化学嵌锂容量和充放电循环寿命起重要影响 ,制备温度越低 ,纳米碳纤维的石墨化程度越差 ,可逆嵌锂容量相应要高一些     

Improvement of lithium battery performance through composite electrode microstructure optimization

The lithium trivanadate Li_1.2V₃O₈ has been investigated during the past decade as a very promising positive electrode material for lithium batteries due to its high theoretical capacity of 360 mAh/g. However, the experimental capacity remains generally much lower than (about half) the theoretical value. To increase electrode cycling performance in batteries, most researchers generally focus their work on the active material optimisation. Here we show that the polymeric binder of the composite electrode may have an important role on the electrode performance. We describe a new tailored polymeric binder combination with controlled polymer-filler (carbon black) interactions that allows the preparation of new and more efficient electrode architecture. Using this polymeric binder, composite electrodes based on Li_1.2V₃O₈ display a room-temperature cycling capacity of 280 mAh/g (C/5 rate, 3.3-2V) instead of 180 mAh/g using a Bellcore-type composite electrode (PLIon^TM technology). We have coupled SEM observations, galvanostatic cycling and electrochemical impedance spectroscopy in order to define and understand the impact of the microstructure of the composite electrode on its electrochemical performance. Derived from these studies, the main key factors that provide efficient charge carrier collection within the composite electrode complex medium will be discussed. Present findings open up new and attractive prospects for electrode performance optimisation. Paper presented at the Patras Conference on Solid State Ionics — Transport Properties, Patras, Greece, Sept. 14–18, 2004.     

Tin based alloys for lithium ion batteries

The electrochemical behaviour of a standard electrodeposited equiatomic nickel-tin alloy has been tested. Such a material can be an interesting candidate to make thin film anodes for lithium ion batteries since it is deposited by a simple electroplating technique. Using standard deposition conditions, 3 μm thick films of NiSn alloy were deposited onto copper current collectors. The électrochemical behavior of the electrodes suggests that the decomposition of the NiSn alloy occurs during the lithium insertion leading to the formation of nickel particles, followed by the formation of Li-Sn alloys. It is believed that the extraction of lithium during the discharge leads to the decomposition of the Li-Sn alloys. However, according to the structural characterizations performed on the samples, there is no clear evidence to support these reactions. Despite an interesting theoretical capacity of 682 mAh/g, the maximum capacity observed in the NiSn thin films was 77 mAh/g. This low value of the capacity is related to a very slow diffusion of lithium throughout the electrode. Paper presented at the 6th Euroconference on Solid State Ionics, Cetraro, Calabria, Italy, Sept. 12–19, 1999.     

Pickering emulsion polymerization of polyaniline/LiCoO2 nanoparticles used as cathode materials for lithium batteries

The oil in water (o/w) emulsions were prepared using aniline dissolved in toluene and LiCoO₂ particles as stabilizers (Pickering emulsions). Pickering emulsions are stabilized by adsorbed solid particles instead of emulsifier molecules. The mean droplet diameter of emulsions was controlled by the mass ratio M (oil)/M (solid particles). The emulsions showed great stability during 3 days. The composite materials containing LiCoO₂ and the conductive polymer polyaniline (PANI) have been prepared by means of polymerization of aniline emulsion stabilized by LiCoO₂ particles. The composite materials were characterized by nanosphere and nanofiber-like structures. The nanofiber-like morphology of the powdered material was distinctly different of the morphologies of the parent materials. The electrochemical reactivity of PANI/LiCoO₂ composites as positive electrode in a lithium battery was examined during lithium ion deinsertion and insertion by galvanostatic charge–discharge testing; PANI/LiCoO₂ (1:4) composite materials exhibited the best electrochemical performance by increasing the reaction reversibility and capacity compared to that of the pristine LiCoO₂ cathode. The first discharge capacity of PANI/LiCoO₂ (1:4) was 167 mAh/g, while that of LiCoO₂ was136 mAh/g.     

Fabrication and lithium electrochemistry of InSe thin film

InSe thin film has been successfully fabricated by pulsed-laser deposition method. Electrochemical behavior of Li/InSe cell has been investigated by Galvanostatic cycling and cyclic voltammetry measurements for the first time. The reversible capacity of InSe electrode of 410 mAh/g with the volumetric capacity of about 3302 mAh/cm³ was achieved at a current density of 0.05 mA/cm². By using XRD and XPS measurements, both alloying/de-alloying processes and selenidation/reduction processes were revealed during the electrochemical cycling of InSe thin film electrode. InSe was found to be a novel candidate of anode materials for rechargeable lithium batteries.     

Synthesis of hierarchical nanospheres Fe<Subscript>2</Subscript>O<Subscript>3</Subscript>/graphene composite and its application in lithium-ion battery as a high-performance anode material

A hierarchically nanospherical α-Fe₂O₃/graphene composite with a homogeneous mono-pore size of 4 nm has been prepared using a hydrothermal method. The composite showed an extremely high rate performance and good cycling stability when applied as an anode material for lithium-ion batteries owing to its unique three dimensional architecture. A specific capacity of 110 mAh/g was obtained at an extremely high current rate of 40 A/g and recover to 830 mAh/g at 0.5 A/g after 60 cycles. After 250 cycles at 2 A/g, the composite electrode exhibited a capacity of 630 mAh/g with a columbic efficiency of 99.5 %.     

DTT-doped MWCNT coating for checking shuttle effect of lithium-sulfur battery

In order to improve the rate and reversible capacity of lithium-sulfur (Li-S) battery, a reagent of dithiothreitol (DTT) was utilized to check the dissolution and shuttle of long-chain lithium polysulfides (LiPSs) by cutting the disulfide bond (–S–S– bonds) in them. The slurry of DTT-doped multi-walled carbon nanotubes (MWCNTs) was coated on the surface of sulfur cathode as a shield to slice the long-chain LiPSs to short-chain ones for checking the dissolution and migration of LiPSs to lithium anode. The morphology and structure of the electrodes were observed by scanning electron microscopy (SEM). The electrochemical performance was tested by galvanostatic charge-discharge, cyclic voltammetry (CV), and electrochemical impedance spectroscopy (EIS). The initial discharge capacity of S-DTT- carbon nanotube paper (CNTP) electrode reached 1670 and 949 mAh/g at 0.05 and 2 C respectively with a coulombic efficiency of over 99%. The electrode maintained a reversible specific capacity of 949 mAh/g after 45 cycles at 2 C. This suggested that the DTT-doped MWCNT coating can restrain shuttle effect and improve the rate and capacity of Li-S battery. The S-DTT-CNTP electrode not only accommodates the volume expansion but also provides stable electronics and ions channels.     

Electrochemical characterization of LiCoO2 as rechargeable electrode in aqueous LiNO3 electrolyte

The development of lithium ion aqueous batteries is getting renewed interest due to their safety and low cost. We have demonstrated that the layer-structure LiCoO₂ phase, the most commonly used electrode material in organic systems, can be successful delithiated and lithiated again in a water-based electrolyte at currents up to 2.70 A/g. The capacity is about 100 mAh/g at 0.135 A/g and can be tuned by cycling the electrode in different potential ranges. In fact, increasing the high cut-off voltage leads to higher specific capacity (up to 135 mAh/g) but the Coulomb efficiency is reduced (from 99.9% to 98.5%). The very good electrode kinetic is probably due to the high conductivity of the electrolyte solution (0.17 Scm^− 1 at 25 °C) but this behavior is affected by the electrode load.     

真空热处理碳纳米管的储氢性能研究

研究了真空热处理对多壁碳纳米管(MWNTs)电化学储氢性能的影响.采用化学气相沉积法(CVD)制备碳纳米管，碳纳米管与LaNi₅储氢合金按质量比1∶10混合，制作成CNTs-LaNi₅电极.电解池采用三电极体系，6mol/L KOH为电解液，Ni(OH)₂为正极，Hg/HgO为参比电极.实验结果表明，在相同的充放电条件下，850℃时CNTs-LaNi₅电极的储氢性能最好，克容量最大为503.6mAh/g，相应的平台电压高达1.18V.从500—850℃随着温度升高，放电量有较大幅度的增加，但到950℃时放电量反而下降.由此可见，碳纳米管的热处理温度对碳纳米管的电化学储氢性能有着较大的影响. 关键词： 碳纳米管(CNTs) 储氢性能 5合金')" href="#">LaNi₅合金 化学气相沉积法(CVD法)     

Phosphazene groups modified sulfur composites as active cathode materials for rechargeable lithium/sulfur batteries

A novel phosphazene groups modified sulfur composites cathode [triphosphazene sulfide composite (PS) or nitroaniline–triphosphazene disulfide composite (NPS)] which can give good affinity with electrolytes was prepared. Their chemical structures were identified by FTIR and XRD analysis. SEM analysis showed PS and NPS had a denser and rougher surface structure than elemental sulfur, with many tiny pores on the surface. Contact angles measurement showed that PS had a hydrophilic surface, which exhibited better affinity of ether solvent. When used as a cathode material in lithium–sulfur batteries, its initial discharge capacity was 1,109 mAh/g for NPS, 784 mAh/g for PS. Discharge capacity of NPS was higher than charge capacity, which implied nitroanilino base on sulfur particles involving in generation of polysulfides.