MS-G技术调控Nd-Fe-B铸态组织研究

采用熔体快淬+晶体生长(MS-G)技术调控Nd-Fe-B铸态组织,研究了铜辊转速及高温热处理对Nd-Fe-B快淬条带组织结构的影响。铜辊转速25 m·s^-1时快淬条带微观晶粒组织均匀,平均晶粒尺寸0.1μm, XRD图谱显示其为Nd₂Fe₁₄B相。Nd-Fe-B快淬条带经880℃热处理2.0 h晶粒均匀长大,平均尺寸0.86μm;冷却到750℃继续热处理2.0 h晶粒进一步均匀长大,平均尺寸达到1.04μm。温度升高会降低Nd₂Fe₁₄B晶粒异常长大临界驱动力Δg_c,缩短异常长大的孕育期,使异常晶粒提早出现,高温+低温两步热处理通过降温处理来延长晶粒异常长大孕育期,从而促进Nd₂Fe₁₄B晶粒在较低温度下继续均匀长大。     

Density Functional Theory Study on the Complete Substitutions of Nd and Fe by Other Rare-earth and Transition-metal Elements in Nd2Fe14B Compound

To search for proper alternatives to improve the magnetic properties of Nd₂Fe₁₄B,using first-principles density functional theory calculations we have systematically studied the R₂M₁₄B(R=lanthanides from La to Lu;M=Mn,Fe,Co,and Ni)compounds with the isomorphic structure of Nd₂Fe₁₄B.The results show that for rare-earth elements,Pr is the most suitable choice for considering as an alternative of Nd.As for the substitution of Fe in Nd₂Fe₁₄ B by other transition-metal elements,Co is much more suitable than Mn and Ni because the latter two result in too significant reduction of the magnetic moment.     

Theoretical Studies on the Electronic Properties of R_2M_(14)B (R = Lanthanides from La to Lu;M = Mn,Fe, Co,and Ni)

To search for an alternative for Nd₂Fe₁₄B,we have studied the electronic structures of R₂M₁₄B compounds,where R stands for rare-earth element and M for Mn,Fe,Co and Ni.By density functional theory(DFT),we discuss the atomic coordination environment and partial density of states(PDOS)in detail,with the emphasis on the interaction between the six kinds of M sites and the R atoms.We systemically calculated the electronic structures of sixty R₂M₁₄B compounds to provide systematic and reliable results for explaining the origination of magnetism,which is important for further development of Nd₂Fe₁₄B based magnet materials.     

质子交换膜燃料电池Pt/C阴极氧还原动力学模拟

质子交换膜燃料电池的商业化应用迫切要求降低其Pt载量. 本文通过Pt/C氧还原电极的动力学模型计算,研究了Pt/C电极中的氧分布、生成电流以及满足实际应用的最小Pt载量. 结果表明：燃料电池Pt/C电极,阴极产生严重浓差极化的催化层厚度为40mm;功率密度达到1.4 W•cm^-2（2.1 A•cm^-2@0.67 V）的电池性能需要3mm左右的Pt/C阴极催化层,阴极Pt载量为0.122 mg•cm^-2,即可使膜电极的阴极铂用量低于0.087 g•kW^-1.     

氢溴储能电池结构的优化和运行条件对电池性能的影响

研究了氢溴电池的电池结构、正极氢溴酸和溴电解质浓度、负极的氢气压力、质子交换膜厚度对氢溴电池的性能和电池效率的影响。对氢溴电池结构进行改进,单电池实现了200 mA·cm^-2电流密度恒流充放电,电池库伦效率100%。溴电极电化学反应受浓差极化控制,提高氢溴酸浓度,电池充电性能提高,同时,溴在氢溴酸的溶解度增大,电池放电性能也提高,氢溴酸浓度由0.5 mol·L^-1提高至1 mol·L^-1,电流密度200 mA·cm^-2,电池的能量效率和电压效率提高27.9%。氢溴电池充电过程,降低电池负极氢出压力,有利于提高充电性能,但膜透酸严重,放电过程中最佳的氢出压力是维持氢在碳纸憎水催化层的单层吸附,充放电过程氢出压力均为40.0 kPa,电池的能量效率80.2%。膜厚度与膜电阻极化和膜透酸密切相关,充电过程,膜由50.0 μm降至15.0 μm,膜透酸严重,负极电化学活性比表面积下降,电池充电性能降低。膜厚度对放电性能的影响还与电流密度有关,电流密度较低时,膜透酸造成负极电化学比表面积下降居主导地位,50.0 μm Nafion膜放电性能更高;电流密度超过200 mA·cm^-2时,膜电阻极化居主导电位,15.0 μm Nafion膜性能更高。采用20.0 μm质子交换膜,在200 mA·cm^-2电流密度循环充放电五次,电池的能量效率和电压效率达到85.3%,库伦效率100%。     

氟掺杂对可逆固体氧化物电池性能的影响及相关动力学研究

可逆固体氧化物电池(RSOC)表现出优异的热力学和动力学性质,被认为是一种很有前途的能量转换装置.制备了两种RSOC电极材料La_0.6Sr_0.4Fe_0.8Co_0.2O₃ (LSFC)和La_0.6Sr_0.4Fe_0.8Co_0.2F_0.1O_2.9 (F_0.1-LSFC),对比了F掺杂对电池放电和电解性能的影响并对电极表面动力学反应进行探究.研究表明F掺杂可降低B位元素价态、提高材料氧空位浓度,进而提高电池性能.700℃,30%H₂O/H₂燃料下,由F_0.1-LSFC组成的RSOC的最大功率密度为234.3 m W·cm^-2,约为LSFC组成的RSOC的1.7倍.并且在1.3 V下,由LSFC和F_0.1-LSFC组成的RSOC...     

CoFeOx/MoO2准平行纳米阵列电极的析氢性能

利用CoFe层状双金属氢氧化物(CoFe LDH)准平行纳米片阵列作为载体前驱体,通过原位负载及煅烧方式,实现了含有氧空位的MoO₂纳米颗粒在纳米片阵列表面的生长。电化学研究结果表明,所得CoFeO_x/MoO₂纳米阵列电极具有高析氢反应(HER)催化活性。该电极在10和1 000 mA·cm^-2时的HER过电位分别为40和217 mV。在50 mA·cm^-2的电流密度下,该电极可以稳定运行125 h。     

HBF4溶液中全铅液流电池

报道了一种HBF₄水溶液中的全铅液流电池,正、负电极电解液均采用Pb（BF₄）₂的HBF₄水溶液.在酸性的四氟硼酸铅电解液中考察了石墨电极和玻碳电极作为工作电极的循环伏安性能,石墨电极较适于用作全铅液流电池的正、负电极.采用石墨电极作为电池的正、负电极并在四氟硼酸铅酸性电解液中进行充放电实验,其中Pb（BF₄）₂浓度分别为0.5、1.0和1.5 mol·L^-1,且保持游离的HBF₄浓度为1.0 mol·L^-1.该电池为单液流电池,不需要隔膜分隔正、负极的电解液,电流密度为10、20和40 mA.cm^-2,当限定充电容量为7.0 mAh.cm^-2,放电电压截止到1.0 V时,平均库仑效率大于87%,平均能量效率大于68%;当电解液采用1.0或1.5 mol·L^-1 Pb（BF₄）₂+1.0 mol·L^-1HBF₄水溶液时,在10及20 mA.cm^-2电流下的能量效率最高可超过74%.     

碳布负载的缺氧型Na2Ti3O7纳米带阵列作为高性能柔性钠离子电池负极材料

作为锂离子电池的理想替代品,钠离子电池因具有能源储备丰富、成本低廉等优点而受到人们的广泛关注。柔性便携式电子产品的发展亟需柔性储能器件的研制。因此,发展一种廉价、高性能的柔性钠离子电池负极材料成了科研工作者的共同目标。在此项工作中,我们通过简单的水热合成和热还原法发展了一种以柔性碳布为基底,与缺氧型的Na₂Ti₃O₇纳米带(NTO)构成三维阵列结构的新型柔性钠离子电池负极材料。复合材料(R-NTO/CC)的导电性和活性位点得到提高,电化学性能也大幅提升,在200 mA·cm^-2的电流密度下,实现100 mAh·cm^-2的面积比容量,且经过200次循环后仍保留最初电容值的80%。此外,这种电极还具有优良的倍率性能,当电流密度提高到400 mA·cm^-2时,仍保持69.7 mAh·cm^-2的面积比容量,是未引入氧空位材料的三倍之多。这种三维缺氧的电极材料可有效提高载流子浓度,缩短离子传输通道,从而大幅提升电极的电化学性能。此工作为设计合成高储钠性能的新型的负极材料提供了一种实用有效的策略。     

氮掺杂碳纳米管高负载金属催化剂在铝空气电池中的应用

在铁基催化剂(Fe-N-C)中引入金属铈,采用高温热解法合成了氮掺杂碳纳米管(NCNTs)高负载金属催化剂(Fe/Ce-NCNTs)。金属铈的引入能更好地促进碳纳米管(CNTs)的生长,锚定更多的铁原子,增加Fe—NX活性位点的数量。Fe/CeNCNTs催化剂在碱性介质中表现出良好的催化活性和稳定性,半波电位为0.86 V(vs RHE)。将Fe/Ce-NCNTs催化剂应用于铝空气电池(AABs),其峰值功率密度可达142 mW·cm^-2,在50 mA·cm^-2电流密度下放电比容量达到865 mAh·g^-1,在高电流密度负载下具有较高的电压。     

NdFeB合金选择氢爆的研究

对NdFeB合金的选择氢爆进行了研究。研究表明，在较低的环境温度和氢气压力下，通过事先对合金中富Nd相的吸氢量进行理论计算并对放人容器内的NdFeB合金量进行定量控制，NdFeB合金在吸氢过程中完全可以实现良好的选择氢爆。SEM观察表明，选择氢爆时其碎裂的方式均为沿晶断裂，爆裂后粉末中的主相晶粒均是单晶粒子，Nd2Fe14B主相晶粒内均无裂纹形成。与完全氢爆相比，选择氢爆后的晶粒较粗大，且较均匀，但细小晶粒较少。     

Preparation, Characterization and Magnetic Properties of PANI/La-substituted LiNi Ferrite Nanocomposites

Magnetic nanocomposites containing polyaniline （PANI）-coated La-substituted LiNi ferrite （LiNi0.5La0.02Fe1.98O4） were synthesized by in situ polymerization in aqueous solution of hydrochloric acid. The nanocomposites exhibited the magnetic hysteresis nature under applied magnetic field. The saturation magnetization （Ms） and coercivity （Hc） varied with the ferrite content. The obtained nanocomposites were characterized by X-ray diffraction （XRD）, transmission electron microscopy （TEM）, scanning electron microscopy （SEM）, Fourier transform infrared spectroscopy （FT-IR）, UV-Visible spectroscopy and vibrating sample magnetometer （VSM）. TEM and SEM studies showed that the nanocomposites present the core-shell structure. The results of XRD patterns, FT-IR and UV-Visible spectra indicated the formation of PANI-LiNi0.5La0.002Fe1.98O4 nanocomposites and showed that the interaction existed between PANI backbone and ferrite particles in the nanocomposites. The bonding mechanism in the nanocomposites has been proposed.     

Synthesis and Crystal Structure of Novel Fe_3 Cluster Compound

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The Electrochemical Properties of Nanocomposite Films Obtained by Chemical In Situ Polymerization of Aniline and Carbon Nanostructures

Interactions between the π bonds in the aromatic rings of polyaniline (PANI) with carbon nanostructures (CNs) facilitate charge transfer between the two components. Different types of phenyleneamine‐terminated CNs, including carbon nano‐onions (CNOs) and single‐walled and multi‐walled carbon nanotubes (SWNTs and MWNTs, respectively), were prepared as templates, and the CN/PANI nanocomposites were easily prepared with uniform core–shell structures. By varying the ratio of the aniline monomers relative to the CNs in the in situ chemical polymerization process, the thickness of the PANI layers was effectively controlled. The morphological and electrical properties of the nanocomposite were determined and compared. The thickness and structure of the PANI films on the CNs were characterized by transmission electron microscopy (TEM), scanning electron microscopy (SEM), and infrared spectroscopy. TEM and SEM revealed that the composite films consisted of nanoporous networks of CNs coated with polymeric aniline. The electrochemical properties of the composites were investigated by cyclic voltammetry and electrochemical impedance spectroscopy. These studies showed that the CN/PANI composite films had lower resistance than pure polymeric films of PANI, and the presence of CNs much improved the mechanical stability. The specific electrochemical capacitance of the CNO/PANI composite films was significantly larger than for pure PANI.     

聚苯胺/H2W2O7层状复合材料的制备研究

以层状钨基氧化物(H2W2O7)为无机主体, 用正庚胺改性后的正庚胺/H2W2O7复合物(HTT)为中间体, 通过离子交换、层间O2引发聚合等步骤成功制备了聚苯胺/H2W2O7层状复合材料(PANI/H2W2O7). X射线衍射、扫描电子显微镜、红外光谱及差热分析结果表明: 聚苯胺分子已成功地嵌入H2W2O7层间, 层状结构没被破坏, 层间距变至1.19 nm; 聚苯胺的嵌入还大大提高了材料的热稳定性. 讨论了无机主体与有机客体之间的相互作用、聚苯胺在层间的排布形式及苯胺和聚苯胺插入层间的反应机理.     

多孔羰基铁/CoFe2O4/聚苯胺复合材料的制备及吸波机理

通过金属点蚀技术制备了表面多孔形貌的羰基铁粉（PCIP）,并采用共沉淀及原位聚合方法,将CoFe₂O₄与聚苯胺（PANI）负载于多孔羰基铁表面,得到具有电磁吸收性能的PCIP/CoFe₂O₄/PANI复合材料.通过扫描电子显微镜（SEM）、X射线衍射仪（XRD）、傅里叶变换红外光谱仪（FTIR）、热重分析仪（TGA）及矢量网络分析仪（VNA）等对复合材料的形貌、成分和吸波性能进行了研究.结果表明,CoFe₂O₄/PANI团聚于PCIP表面,显著提升了复合材料电损耗能力,促进了低频电磁波的1/4波长干涉相消.当苯胺添加量为0.5 mL,复合材料在频率为5.7 GHz时,反射损耗达到-22.9 dB,低频吸波性能得到大幅提升.利用1/4波长干涉相消理论及电磁波界面反射模型对复合材料低频吸波性能提升的内在原因进行了分析.     

Fe_2O_3的制备及其电化学性能研究

分别采用高温热分解法(A)和熔盐法(B)制备了锂离子电池负极材料Fe2O3A和Fe2O3B,其结构与形貌经XRD和SEM表征。分析结果表明,Fe2O3A为三方晶相,呈片状结构团聚而成的类球形颗粒;Fe2O3B随着制备温度的升高,从立方相转变为三方相。充放电测试结果表明,于550℃制备的Fe2O3A和Fe2O3B初始容量分别高达1 312.1 mAh.g-1和1 412.2 mAh.g-1。采用交流阻抗图谱和循环伏安对其充放电过程的界面特性进行分析,发现随着充放电的进行,Fe2O3界面形成SEI膜。     

Preparation of polyaniline grafted multiwalled carbon nanotubes and conductive application in polyetherimide

A methodology for improving antistatic property of polyetherimide (PEI) composite using polyaniline (PANI) grafted multi‐walled carbon nanotubes (MWNTs) as conductive medium was proposed. First, the MWNTs grafted with PANI (PANI‐g‐MWNTs) were prepared by in‐situ polymerization in an emulsion system. Subsequently, PANI‐g‐MWNTs were blended with PEI using N‐methyl‐2‐pyrrolidone as solvent. After removing the solvent, the PEI/PANI‐g‐MWNT composite was prepared. As assisted conductive medium, the grafted PANI molecular chains on MWNT surface were dispersed in the PEI matrix to decrease the percolation value of the antistatic composites. The structure and morphology of PANI‐g‐MWNTs were characterized by Fourier transform infrared spectroscopy, transmission electron microscope, thermogravimetric analysis, and X‐ray powder diffraction, respectively. The dispersion of PANI‐g‐MWNTs in PEI matrix was studied by scanning electron microscope. The electrical performance was characterized by highly resistant meter. The volume resistivity of the conductivity percolation threshold was 1.781 × 10^?8 S/cm when the loading of PANI‐g‐MWNTs was 1.0 wt%. The conductivity of PANI‐g‐MWNTs/PEI composites was found to be higher than that of pristine MWNTs/PEI composite. Copyright © 2012 John Wiley & Sons, Ltd.