碳纳米管与还原氧化石墨烯构建高倍率石墨电极

通过在金属铜箔上均匀排布碳纳米管宏观膜(Carbon nanotubes (CNTs) macrofilm, CMF),制成复合集流体(Cu-CMF),改善活性物质与集流体的结合性,降低电池界面电阻,在活性材料石墨中掺杂还原氧化石墨烯(rGO),增大了活性物质石墨颗粒间的接触位点,最后获得高比容量和化学稳定性的电池。采用扫描电子显微镜和电化学测试等表征技术进行表征,结果表明,基于Cu-CMF复合集流体掺杂rGO的石墨电极,在2 C倍率下发挥102.7 mAh g_^-1的比容量,是未掺杂基于铜箔集流体的石墨电极(27.4 mAh g_^-1)的3.7倍,表现出优异的倍率性能。     

导电Ti3O5包覆纳米铝粉的制备及其作为双离子电池负极材料的电化学性能研究

铝被认为是下一代电池最有前途的负极材料之一, 本文中采用导电的Ti₃O₅作为外壳包覆纳米铝粉来制备Al@Ti₃O₅核壳结构材料, 并将其作为负极材料应用到双离子电池(DIB)中。使用中间相炭微球(MCMB)作为正极材料,Al@Ti₃O₅作为负极材料制作Al@Ti₃O₅-MCMB双离子电池。电池的放电平台可达4.5V, 在电流倍率0.5C下(电流基于正极石墨的理论比容量计算,1C=372mAhg^_-1)放电比容量达到130.6mAhg^_-1,比能量密度为278.8Whkg^_-1。并且在高倍率5C下循环1000次过程中容量基本保持110mAhg^_-1不变,循环后容量保持率达到92.9%。     

298 K下离子液体BMIMPF6 中电沉积制备镧金属薄膜

以无水硝酸镧、1-丁基-3-甲基咪唑六氟磷酸（BMIMPF₆）和助溶剂丙酮为电解液,在室温（298 K）下电沉积制得镧金属薄膜。电解液BMIMPF₆的电化学窗口为-2.5~1.5 V vs. Pt,La³⁺还原为La²⁺发生于-1.7 V vs. Pt,La²⁺还原为La⁰发生于-2.1 V vs. Pt。BMIMPF₆的低吸湿性有利于在空气气氛下电沉积镧。使用扫描电子显微镜和光学显微镜观察到所制备的薄膜织构致密,经能量色散谱和X射线光电子能谱对沉积薄膜进行了表征,确定了薄膜中含有大量镧元素。通过探究电压扫描速率和硝酸镧浓度对La³⁺的电化学行为的影响,证明La³⁺的还原反应是一个受物质扩散控制的不可逆过程,La³⁺在BMIMPF₆中的扩散系数为1.47×10^-9 cm²·s^-1。本研究为获得金属镧薄膜和镧氧化物薄膜提供了一种简便的方法,并且有望用于电沉积制备其它镧系元素薄膜。     

Ti60合金的热变形行为及工艺参数优化

在变形温度600～950℃,应变速率0.001～10s_^-1条件下,采用Thermecmaster-Z型热加工模拟试验机对Ti60合金进行等温恒应变速率压缩实验。通过分析流动应力行为,计算应变速率敏感指数m和应变硬化指数n,并综合考虑加工图和变形微观组织来研究该合金的热变形行为,得到优化的工艺参数范围。研究结果表明,Ti60合金的流动应力-应变曲线在不同热力参数条件下分别呈现流动稳态型和流动软化型。应变速率敏感指数m随着变形温度升高和应变速率降低而增大。应变硬化指数n随着变形温度升高而减小；随着应变速率的增加在低应变速率(0.001～0.1s_^-1)区间增大,在高应变速率(1～10s_^-1)区间减小；随着应变的增加在高温段(800～950℃)的低应变速率(0.001～0.1s_^-1)区间较缓慢地减小,在高温段(800～950℃)的高应变速率(1～10s_^-1)区间以及低温段(600～750℃)的所有应变速率(0.001～10s_^-1)区间较明显地减小。Ti60合金存在两个功率耗散效率峰值区域,其对应的热力参数窗口分别为温度725～875℃,应变速率≤0.003s_^-1和温度875～938℃,应变速率≤0.04s_^-1。从流动应力行为、应变速率敏感指数m、应变硬化指数n以及加工图综合考虑,Ti60合金的最佳热加工工艺参数为：温度800～875℃,应变速率0.001～0.003s_^-1,或温度875～938℃,应变速率0.001～0.04s_^-1。     

熔盐法制备自支撑Ni掺杂Mo2C@CFP复合电极及其电催化析氢性能的研究

Mo₂C具有类似于Pt等贵金属的电子结构和催化特性,有望替代Pt等贵金属成为新型非贵金属析氢催化剂,但是纯Mo₂C导电性差且氢释放动力学慢。为提高Mo₂C的电催化析氢性能,本工作采用低温熔盐法在碳纤维纸(CFP)基底上制备了自支撑Mo₂C电催化剂,研究了Mo和MoO₃钼源、Ni和Ni(NO₃)₂镍源掺杂剂、添加炭黑等因素对合成产物物相、显微形貌和结构、电催化性能的影响。结果表明,炭黑和Ni的引入可以促使Mo₂C晶粒细化以及在表面生成褶皱状结构,能够提供更多活性位点,Ni(NO₃)₂的加入能够使采用MoO₃为钼源合成的Mo₂C的晶粒变成纳米花状结构,大大提高了其比表面积,也促进了反应生成的复合电极Ni(NO₃)₂-Mo₂C_CBO@CFP中的电子转移效率,表现出最佳的HER活性,其η₁₀为117 mV,塔菲尔斜率低至73.8 mV dec^_-1。     

FeTiO3-Fe2O3固溶体合成及其碳热还原研究

为明确Fe₂O₃固溶对FeTiO₃还原过程的影响机理,本文基于粉末煅烧法合成(1-x)FeTiO₃?xFe₂O₃固溶体(0≤x≤1),研究了非等温碳热还原条件下固溶体的还原行为,并采用X射线衍射仪(XRD)和扫描电镜-能谱仪(SEM-EDS)对合成固溶体及还原产物进行表征。结果表明,实验合成固溶体质地均匀,纯度较高,且x越大,FeTiO₃晶格畸变程度越大。固溶体开始还原温度和还原速率(还原度α的增大速率)均随着x值的增加而增加。固溶Fe₂O₃能够促进FeTiO₃还原,且在还原过程中存在过渡相Fe₂TiO₄和Fe₃Ti₃O₁₀。固溶体-石墨交界面首先形成浮士体(FeO)、钛铁尖晶石(Fe₂TiO₄)和TiO₂,进一步还原生成金属Fe和Ti₂O₃。非等温碳热还原过程动力学计算分析,得出表观活化能为295.54 kJ/mol。     

La0.4Sr0.6Co0.7Fe0.2Nb0.1O3- δ -Gd0.2Ce0.8O2- δ 应用于可逆固体氧化物电池对称电极

为制备一种高催化性的对称型固体氧化物电池电极,采用一步法合成了La_0.4Sr_0.6Co_0.7Fe_0.2Nb_0.1O_3-δ-Gd_0.2Ce_0.8O_2-δ（LSCFN-GDC）。以LSCFN-GDC为电池阳极和阴极,La_0.8Sr_0.2Ga_0.83Mg_0.17O_3-δ（LSGM）为电解质,采用流延和丝网印刷工艺制备了结构为LSCFN-GDC||LSGM||LSCFN-GDC的电解质支撑型固体氧化物电池。分别采用固体氧化物燃料电池（SOFC）及固体氧化物电解池（SOEC）2种模式对对称电池性能进行了测试。在850 ℃测试温度下,分别采用湿H₂（3% H₂O）、H₂（0.01% H₂S）、CH₄和C₃H₈为燃料气,电池最大功率密度分别为1.036、0.996、0.479和0.952 W/cm²,电解H₂（50% H₂O）时,1.3 V电解电压下电池电流密度为0.943 A/cm²。LSCFN-GDC具有良好的耐积碳、抗硫和氧化还原稳定性能,能够在湿H₂（0.01% H₂S）、CH₄、H₂（3% H₂O）及H₂（50% H₂O）环境中稳定运行700 h。实验结果表明,一步合成法是一种简便而优化的电极制备方法,LSCFN-GDC||LSGM||LSCFN-GDC固体氧化物电池（SOC）具有广阔的应用前景。     

稀土铈对Ni-GO镀层的组织形貌和性能的影响研究

采用电沉积方法在Q235钢上制备Ni-Go复合镀层,研究添加稀土铈对复合镀层形貌、性能的影响。结果表明,当铈浓度为0.8 g.L_-1^时,得到的复合镀层沉积速率增加到7.142 g.dm_-2^.h_^-1,^,硬度达到608.8 HV,磨损量最小,摩擦系数最低为0.387,自腐蚀电位E_corr(-0.3993 V)更正,同时腐蚀电流I_corr(3.258.10_-6 ^A.cm_-2⁾最小,腐蚀速率最低,复合镀层的耐腐蚀性能最优。研究发现,加入稀土铈后,Ni-1.0GO复合镀层的类似珊瑚状的微大尺寸的凸聚体变成了尺寸较小的珊瑚珠状的小凸聚体,镀层组织得到明显细化。在铈浓度为0.8 g.L_-1^时,Ni-1.0GO-0.8RE复合镀层的组织致密性最好,各种性能达到最佳,主要在于稀土铈提高镀液中微粒的分散能力和阴极极化率的效果,提高氢离子在阴极的析出电位,从而抑制析氢反应的发生,使得复合镀层的性能得到进一步提高。     

铸态粗晶Ti-5553钛合金高温变形行为与机理研究

本文借助Gleeble-3800热模拟试验机系统地研究了铸态粗晶Ti-5553合金在温度700 ℃~1100 ℃、应变速率为0.001 s_^-1~10 s_^-1条件下的高温变形行为。研究结果表明合金的流变应力对变形温度和速率都有强敏感性,流变软化过程也随变形参数的改变呈现出不同的模式。通过经典的动力学模型,建立了合金高温变形的本构关系和激活能分布图,进一步基于动态材料模型构建了合金的热加工图并实现了对不同加工区间变形机制的识别。合金在低温区(700 ℃)和高速率区( 1 s_^-1)均展现出失稳变形的特征,包括外部开裂、绝热剪切带、局部流变等机制,在实际加工中应对这些加工区域进行规避。合金在800 ℃及中低速率( 0.1 s_^-1)变形下的主导机制为α相的动态析出,在中高温(900 ℃-1100 ℃)及中低速率变形下的主导机制为动态回复与动态再结晶的结合。此外,合金在高温较低应变速率(1100 ℃/0.01 s_^-1)条件的变形中表现出大范围动态再结晶的行为特点并伴随稳定的流变软化,因此此条件附近的参数区间被认定为该合金的最优加工窗口,应在实际加工中给予优先考虑。     

NEGATIVE THERMAL EXPANSION PHENOMENA\par OF Mn3(Cu1-xGexN

在氮气保护下于1073 K用固相烧结法制备了Mn₃(Cu_1-xGe_x)N化合物. XRD分析表明, 这类化合物具有Mn₃CuN型反钙钛矿相结构. 采用激光干涉法测量了Mn₃(Cu_1-xGe_x)N化合物的线膨胀系数. 结果表明, 当Ge含量为0.40≦x≦0.60时, Mn₃(Cu_1-xGe_x)N在一定温度范围内出现负热膨胀现象; 随Ge含量的增加, 发生负热膨胀的温度升高且温区变宽, 而负热膨胀性能减弱. 当x=0.60时,发生负热膨胀的温度范围为250-290 K(273 K附近), 线膨胀系数为-65×10^-6 K^-1, 具备应用潜力. 热磁曲线表明, Mn₃(Cu_1-xGe_x)N化合物的负热膨胀现象发生在反铁磁性逐渐向顺磁性转变的过程中,由磁有序逐渐消失、自发磁化强度减小所引起的磁容积效应造成的.     

稀土化合物应用于高能锂硫电池的研究进展

锂硫电池是极具开发潜力和应用前景的新一代高比能金属锂二次电池。拥有独特4f轨道的稀土元素及其化合物具有特殊的光、电、磁与催化等性质,研究发现将稀土化合物引入锂硫电池体系能够有效解决制约锂硫电池发展的穿梭效应和锂枝晶问题并显著提升电池性能。本文全面综述了稀土化合物应用于锂硫电池正极、隔膜和电解质的最新研究进展和动态及其解决锂硫电池关键问题的作用机制,并展望了稀土化合物应用于锂硫电池的未来发展方向。     

Thermal behavior analysis of a pouch type Li[Ni<Subscript>0.7</Subscript>Co<Subscript>0.15</Subscript>Mn<Subscript>0.15</Subscript>]O<Subscript>2</Subscript>-based lithium-ion battery

Since lithium-ion battery with high energy density is the key component for next-generation electrical vehicles,a full understanding of its thermal behaviors at different discharge rates is quite important for the design and thermal management of lithium-ion batteries（LIBs）pack/module.In this work,a 25 Ah pouch type Li[Ni_0.7Co_0.15Mn_0.15]O₂/graphite LIBs with specific energy of200 Wh kg^-1were designed to investigate their thermal behaviors,including temperature distribution,heat generation rate,heat capacity and heat transfer coefficient with environment.Results show that the temperature increment of the charged pouch batteries strongly depends on the discharge rate and depth of discharge.The heat generation rate is mainly influenced by the irreversible heat effect,while the reversible heat is important at all discharge rates and contributes much to the middle evolution of the temperature during discharge,especially at low rate.Subsequently,a prediction model with lumped parameters was used to estimate the temperature evolution at different discharge rates of LIBs.The predicted results match well with the experimental results at all discharge rates.Therefore,the thermal model is suitable to predict the average temperature for the large-scale batteries under normal operating conditions.     

Sodium-beta alumina batteries: Status and challenges

This paper provides a review of materials and designs for sodium-beta alumina battery technology and discusses the challenges ahead for further technology improvement. Sodium-beta alumina batteries have been extensively developed in recent years and encouraging progress in performance and cycle life has been achieved. The battery is composed of an anode, typically molten sodium, and a cathode that can be molten sulfur (Na-S battery) or a transition metal halide incorporated with a liquid phase secondary electrolyte (e.g., ZEBRA battery). In most cases the electrolyte is a dense solid β″-Al₂O₃ sodium ion-conducting membrane. The issues prohibiting widespread commercialization of sodium-beta alumina technology are related to the materials and methods of manufacturing that impact cost, safety, and performance characteristics.     

A Novel cathode material based on polyaniline used for lithium/sulfur secondary battery

Polyaniline polysulfide (SPAn) was prepared for high energy secondary lithium batteries as cathode material. Polyaniline was synthesized via a classical chemical oxidation way, and then HCl was used to substitute the H atoms on the 6 member rings, so that polyaniline chloride (CPAn) was gained. The SPAn was prepared by way of substitute the Cl atoms on the aromatic rings of CPAn by S atoms in assistant of Na₂S and element sulfur. Element analysis tests proved that there are more than 7 S atoms on each aniline structural group. FT-IR, Raman and XPS (X-ray photoelectron spectroscopy) analysis were used to confirm the SPAn's configuration. Button type battery was assembled, and charge–discharge test shows an initial discharge capacity of more than 980 mAh g^?1, which is a grafting value.     

Flexible and Conducting Metal-Fabric Composites Using the Flame Spray Process for the Production of Li-Ion Batteries

The wire flame spray process was used to produce electrically conductive and flexible Al coatings onto diverse textile fabrics. The investigation studied the influence of the spraying parameters and fabric materials on the electrical conductivity of the metal-fabric composites. Furthermore, this study showed that the production of flexible Li-ion batteries having good electrical properties based on the use of such flame-sprayed aluminium cathode current collectors is viable. Results show that a coating quantity threshold of about 20 mg/cm² exists to obtain a sufficient electrical surface conductivity for a commercial use of the produced metal-fabric composites. An excellent electrical surface conductivity of the composites (about 500 S_A) could be achieved through an adequate optimization of the spraying parameters. This conductivity increase enabled a reduction of the coating quantity and thus the flexibility of the fabric materials is better conserved, rendering the use of such composites for flexible batteries even more interesting. This study showed that the production of electrically conductive and flexible metal-fabric composites having sufficient electrical conductivity for the manufacture of flexible Li ions batteries is possible. This new method of producing such batteries represents an alternative to other chemically based processes which are hazardous to the environment because of their chemical nature.     

Ascorbic Acid-Assisted Eco-friendly Synthesis of NiCo<Subscript>2</Subscript>O<Subscript>4</Subscript> Nanoparticles as an Anode Material for High-Performance Lithium-Ion Batteries

We have synthesized NiCo₂O₄ nanoparticles (NCO NPs) using an ascorbic acid-assisted co-precipitation method for the first time. When NCO NPs are used as an anode material for lithium-ion batteries, the cell exhibits superior lithium storage properties, such as high capacity (700 mA h g^?1 after 300 cycles at 200 mA g^?1), excellent rate capabilities (applied current density range 100–1200 mA g^?1), and impressive cycling stability (at 1200 mA g^?1 up to 650 cycles). The enhanced electrochemical properties of NCO NPs are due to the nanometer dimensions which not only offers a smooth charge-transport pathway and short diffusion paths of the lithium ions but also adequate spaces for volume expansion during Li storage. Hence, this eco-friendly synthesis approach will provide a new strategy for the synthesis of various nanostructured metal oxide compounds, for energy conversion and storage systems applications.     

Discharge characteristics of lead dioxide electrode prepared with cementation lead oxide

Lead acid batteries have had restricted applications because of relatively low energy density below 50Wh/kg. Many efforts have achieved lighter battery components such as separators, connections and containers etc. Thus, the most important problem of the lead acid battery is to improve the low capacity of the active material in the positive electrode. The purpose of this study is to improve the utilization of the active material in the lead dioxide electrode for the lead acid battery through the production of lead oxide with better physicochemical characteristics through cementation. A cementation reaction was performed in 1.0wt.%HCl solution using pure magnesium plate as the reductant. We investigated the utilization of the active material and discharge characteristics of the positive electrode with a current density ranging from 3.4 to 108.8mAcm⁻². As a result, the active material utilization was about 72% at 3.48 mAcm⁻² and increased with decreasing current density. The discharge characteristics according to current density are especially very good at high current density     

Synthesis of polyindole and its evaluation for Li-ion battery applications

This study is intended to develop a polyindole-based Li-polymer secondary battery system, which has a high electromotive force together with excellent cycle property and is capable of fast charging and discharging. The batteries include polyindole as the cathode and Li as the anode. LiBF₄ was used as the electrolytic solution with about 3.0 V electromotive force. The battery achieves about 80–70 mAh/g at discharge current densities of 10–10³ A/m². As the theoretical capacity of polyindole is 84 mAh/g, its capacity occurrence rate is 95% at the discharge current density of 10 A/m² with a very high reaction rate. In addition, a discharge capacity at discharge current density of 10³ A/m² maintains 87% of capacity relative to that at 10 A/m². This indicates that this battery is excellent in fast charge and discharge properties. The cyclic life of the battery, which is measured at the current density of 10 A/m² with the discharge depth 60% at 25, is about 30,000 times. This shows the battery system has very excellent cycle property. Summarily, this Li–polyindole battery system would be promising in future applications such as hybrid electric vehicle with the development of the battery system.     

Thermal, micro-structural, and electrical properties of a La1−x Sr x Mn0.85Fe0.05Co0.05Ni0.05O3+δ (x = 0–0.4 mole) cathode system

The oxygen stoichiometry, thermal expansion, morphology, and electrical conductivity of a co-doped perovskitetype cathode system, La_1?x Sr _x Mn_0.85Fe_0.05Co_0.05Ni_0.05O_3+ä (x = 0–0.4 mole), are studied for intermediate-temperature solid oxide fuel cell applications. Sr²⁺-doping led to a decrease in the unit cell volume, oxygen stoichiometry, particle size, and activation energy, and an increase in the coefficient of thermal expansion and electrical conductivity. The sample with x = 0.3 mole exhibited four to five fold weight loss with respect to La_0.75Sr_0.25MnO_3+δ at an intermediate temperature range and suggested the availability of a large number of oxygen vacancies due to a co-doping effect. This sample also showed sufficiently high electrical conductivity (～76 S cm^?1) at 650 °C, a low activation energy (～0.15 eV), and a coefficient of thermal expansion (～12.1 × 10^?6 °C^?1) comparable to those of the adjacent components and submicron sized particles. The experimental results are explained using defect models.