新型Fe基合金电极RE2FeSb2(RE=Y,Dy,Er)放电特性研究

制备了化学计量比为RE2FeSb2(RE=Y,Dy,Er)新型Fe基合金电极.利用恒电流充放电方法测定了RE2FeSb2(RE=Y,Dy,Er)化合物的电化学性能,充放电循环表明RE2FeSb2(RE=Y,Dy,Er)具有2个明显放电平台;分别以3种RE2FeSb2(RE=Y,Dy,Er)合金电极为负极,以Ni(OH)2/NiOOH为正极构成的原电池,首次放电容量分别达到了715.8mAh/g,646.2mAh/g,673.6mAh/g,说明新型Fe基合金电极RE2 FeSb2(RE=Y,Dy,Er)具有很大的放电容量.     

镍电极掺杂[x(Y2O3)+y(Er2O3)]的MH/Ni电池性能研究

研究了在镍电极活性物质中掺杂一定量的[x(Y2O3) +y(Er2O3)](x+y=1,其中x=0,0.5,1.0)对MH/Ni电池的性能影响.利用不同环境温度(25℃～55℃)下恒流充放电、高温(65℃)放电态搁置等方法测试了电池的性能.结果表明,常温下镍电极掺杂[x(Y2O3)+y(Er2O3)]的MH/Ni电池的放电容量和放电平台比未掺杂的电池稍低,但随温度的升高,它的放电容量和高温储存性能等均明显优于未掺杂的电池,镍电极掺杂[x(Y2O3) +y(Er2O3)]提高了MH/Ni电池的高温性能.常温下,电池以1C,100%DOD循环200周后,镍电极掺杂[x(Y2O3) +y(Er2O3)]的MH/Ni电池容量损失较少,利用X射线衍射(XRD)、交流内阻分析结果表明,镍电极活性物质循环后的相结构差别不大,但掺杂的电池循环前后内阻变化较小.综合实验结果,当x=0.5时,电池的性能最佳.     

Raman spectra of RE2O3 （RE=Eu,Gd, Dy,Ho, Er,Tm, Yb,Lu, Sc and Y）：laser-excited luminescence and trace impurity analysis

Raman spectra of a series of cubic rare earth sesquioxides RE2O3 （RE=Eu, Gd, Dy, Ho, Er, Tm, Yb, Lu, Sc and Y） were investigated by Raman spectroscopy with both 532 and 785 nm laser lines. Abundant additional bands due to laser-excited lumines-cence were observed. For Eu2O3, Dy2O3, Ho2O3, Er2O3, Tm2O3 and Yb2O3, the luminescence mainly came from the intrinsic trivalent lanthanide ions, while for Gd2O3, Lu2O3, Sc2O3 and Y2O3, their luminescence were attributed to the trace impurities of other lumines-cent lanthanide ions such as Eu3＋, Nd3＋and Er3＋. This investigation confirmed Raman spectroscopy as a useful tool for detecting trace luminescent lanthanide impurities.     

RE(RE=Nd,Sm,Pr)部分替代La对A_2B_7型合金电化学贮氢性能的影响

La-Mg-Ni系A2B7型合金由于其高的放电容量被认为是最具希望的Ni-MH电池负极材料,然而,低的电化学循环稳定性制约着合金的实际应用。为了改善La-Mg-Ni系A2B7型合金的电化学贮氢性能,用RE(RE=Nd,Sm,Pr)部分替代合金中的La,用感应熔炼及退火工艺制备了La0.8-xRExMg0.2Ni3.35Al0.1Si0.05(RE=Nd,Sm,Pr;x=0,0.2)电极合金。为了抑制Mg在熔炼过程中的挥发,熔炼过程中采用氦气作为保护气氛。用X射线衍射(XRD)和扫描电镜(SEM)分析了铸态及退火态合金的微观结构,并测试了铸态及退火态合金的电化学贮氢性能,比较了不同稀土元素替代La对合金电化学性能的影响。结果表明,铸态及退火态合金包含两个主相,具有Ce2Ni7型结构的(La,Mg)2Ni7相以及Ca Cu5型结构的La Ni5相。RE(RE=Nd,Sm,Pr)部分替代La未影响合金的相组成,但使合金的相含量发生明显改变。此外,元素替代使铸态及退火态合金的组织明显细化。RE(RE=Nd,Sm,Pr)部分替代La显著改善了合金的电化学贮氢性能,包括电化学循环稳定性、放电容量及电化学动力学性能。     

Structure and Magnetocaloric Effect in Tb（ Co1-xSnx）2 Alloys

Recently,researchonmagnetocaloriceffect(MCE)hasattractedagreatdealofinterestinrare earth(RE)basedcompoundsbecauseoftheirenergy efficiencyandenvironmentalsafetyformagneticrefrig eration.Afirst ordermagneticphasetransitionwas foundintheintermetalliccompoundsRECo2(RE=Er,Ho,Dy)withMgCu2typestructure[1,2],leadingtoa largemagneticentropychangeforthesecompounds,whereasasecond ordertransitionwasfoundinTbCo2andGdCo2.IntheintermetalliccompoundsRECo2,theloweringofd electronconcentrationbythesubst…     

H_2A与TBP协同萃取RE(Ⅲ)的性能和机理研究

研究了 1,2 双 (1′ 苯基 3′ 甲基 5′ 氧代吡唑 4′ 基 )乙二酮 [1,2 ](H2 A)与磷酸三丁酯 (TBP)协同萃取RE(Ⅲ ) (RE =La、Pr、Nd、Gd、Dy和Y)的性能。通过考察萃取剂浓度和溶液酸度对RE(Ⅲ )萃取平衡的影响 ,确定了萃取机理和萃合物组成 ,求得了半萃取值pH1/ 2 和萃取反应平衡常数Ks.e .。     

La0.65RE0.10Mg0.25Ni3.5Si0.15(RE=La,Ce,Pr,Nd,Sm)储氢合金的电化学性能及EIS分析

通过感应熔炼制备La0.65RE0.10Mg0.25Ni3.55i0.15(RE =La,Ce,Pr,Nd,Sm)合金.采用X射线衍射方法分析了合金的相结构,研究了其电化学性能,并采用电化学阻抗谱分析了合金电极的放氢动力学特性.研究结果表明,合金是以LaNi5、LaNi3为主相的多相结构,同时合金中少量的Si元素与Mg和Ni元素形成了少量的Mg2 Si相和Ni2Si相.Ce,Pr,Nd,Sm部分替代La以后,合金的放电容量下降,Ce的替代使合金容量大幅度降低.对于本系列合金,La被其他稀土元素部分替代后,合金经过100次循环后的容量保持率略有下降,但除了Pr元素以外,变化值均较小.合金电极的电化学阻抗谱分析表明,中低频区的容抗弧半径依次为Ce ＞La＞ Nd ＞Sm ＞Pr,这表明采用Nd、Sm、Pr替代La后合金电极在碱液中放电过程电荷传递电阻Rct减小,即合金表面活性增加,但Ce替代却导致Ret急剧增大,这可能与Ce在碱液中易形成氧化物降低了合金的表面活性有关.     

电沉积RE-TM(RE=Dy,Nd,Eu;TM=Co)合金膜及其磁性质

在353 K的尿素-乙酰胺-NaBr-KBr熔体中,用恒电位电解法在Cu基片上制备了稀土RE(Dy,Nd,Eu)-铁族TM(Co)合金膜.利用循环伏安法研究了熔体的电化学行为.电化学实验结果表明,在Pt电极上,Co(Ⅱ)+2e→Co(0)是一步完全的不可逆反应,并测得Co(Ⅱ)在Pt电极上的传递系数a以及扩散系数D0.稀土元素(Dy,Nd,Eu)难以被单独沉积,但能被Co(Ⅱ)诱导共沉积.用EDS分析合金膜的成分及含量.用XRD和振动样品磁强计(VSM)分析样品退火前后的晶相和磁性能变化特征.实验结果表明,合金膜的表面形貌和磁性与其成分组成及沉积电位紧密相关,且稀土离子的被诱导能力取决于稀土与铁族原子之间的电负性差值.     

Al88Ni4Y6Er2非晶合金动力学性能

采用单辊旋淬法制备了Al88Ni4Y6Er2非晶合金,用X射线衍射(XRD)、差示扫描量热(DSC)测试手段研究了Al88Ni4Y6Er2非晶合金晶化过程中的动力学性能.发现Al88Ni4Y6Er2非晶合金晶化温度Tx与升温速率φ通过Vogel-Fulcher-Tammnann公式拟合后满足非线性关系.并根据Tx10≈Tk这种近似关系,求得Al88Ni4Y6Er2非晶合金的Kauzmann温度Tk为401 K,由此推断出VFT温度T0不大于401 K.     

元素替代及导电剂对Y_2FeSb_2合金结构和电化学性能的影响

利用电弧熔炼法制备了元素取代前后的Y2FeSb2合金。XRD结果表明,未取代的合金由单一的YSb相组成,La部分取代Y使合金的晶格常数增加,而Ni部分替代Sb的合金由主相YSb相和少量的YNi2、YNi相组成,同时主相的晶格常数也略有增加。电化学测试表明,以Ni粉为导电剂时,La部分取代Y使合金的放电容量有所下降,从34.8 mAh/g下降到了27.3 mAh/g,而Ni替代Sb使合金的放电容量从34.8 mAh/g增加到了51.3 mAh/g,同时使放电电压提高了20 mV,La和Ni同时替代使二者增加的幅度更加明显,特别是放电电压在第50次循环后提高了约300 mV。当Cu粉为导电剂时,Y2FeSb2合金表现出了较大的放电容量(792.6 mAh/g),而La和Ni同时替代后的Y1.5La0.5FeSbNi合金放电容量更是达到了880.8 mAh/g,这主要是由于合金粉和Cu粉在充放电过程中相互作用的缘故。     

Luminescent properties of β-Lu2Si2O7:RE3+(RE=Ce, Tb) nanoparticles by sol-gel method

Nanoscale RE3 (RE=Ce, Tb) doped and codoped lutetium pyrosilicate Lu2Si2O7 (LPS) phosphors were prepared by using the sol-gel method. Heat treatment was performed in the temperature range from 900 to 1100℃. The crystal structure was analyzed by X-ray diffraction (XRD). The results showed that the β-type structure of LPS was obtained at 1100℃. The excitation spectra in the UV and VUV ranges and the emission spectra of the samples were measured at room temperature, and their luminescent properties were studied. The energy transfer from Ce3 to Tb3 in the codoped samples were observed and discussed.     

以氯化稀土为原料制备稀土抛光粉的研究

以氯化稀为原料，研究了焙烧温度，焙烧时间、氟化、合成中间体等条件对制备稀土抛光粉性能的影响，并用粒度仪、ＳＥＭ、ＸＲＤ等分析手段对所得稀土抛光的性能的进行了表征。结果表明，以采用ＮＨ４）２Ｓ沉淀然后ＮａＯＨ转化，经过氟化，所得中间体在９００℃下焙烧３ｈ的制备工艺为宜。     

Photoluminescent properties of Ca2RE8(SiO4)6O2:A (RE=Y, Gd; A=Pb2+, Mn2+) phosphor films prepared by sol-gel process

Ca2RE8(SiO4)6O2:A (RE=Y, Gd; A=Pb2 , Mn2 ) phosphor films were dip-coated on quartz glass substrates through the sol-gel process. X-ray diffraction (XRD), photoluminescence (PL) spectra as well as lifetimes were used to characterize the resulting films. Under short wavelength UV excitation, the film showed a red emission with medium intensity. The decay curve of Mn2 luminescence in Ca2Gd8(SiO4)6O2:Pb Mn film could be fitted into a single exponential function. The lifetime of Mn2 was 10.21 ms in Ca2Gd8(SiO4)6O2.     

Luminescent properties of β-Lu2Si2O7:RE(RE=Ce, Tb) nanoparticles by sol-gel method

Nanoscale RE³⁺ (RE=Ce, Tb) doped and codoped lutetium pyrosilicate Lu₂Si₂O₇ (LPS) phosphors were prepared by using the sol-gel method. Heat treatment was performed in the temperature range from 900 to 1100 °C. The crystal structure was analyzed by X-ray diffraction (XRD). The results showed that the β-type structure of LPS was obtained at 1100 °C. The excitation spectra in the UV and VUV ranges and the emission spectra of the samples were measured at room temperature, and their luminescent properties were studied. The energy transfer from Ce³⁺ to Tb³⁺ in the codoped samples were observed and discussed.     

Research of Three-Dimensional Fluorescence Spectra of RE3+ (RE=Eu, Tb) and Na2WO4 Co-doped Silica Luminescence Materials

In the preparation of this precursor tetraethlortho silicate (TEOS), sodium tungstate, ethyl alcohol, HCl and RECl3 (RE=Eu, Tb) were mixed and then heated at 800℃ for 2h, leading to a luminescent compound. The structure of the materials was characterized by TG-DTA and IR analysis, and the results indicate that the materials were in SiO2 network structure. Three-dimensional fluorescence spectra was used to characterize the luminescent properties of the materials. The luminescence property of doped and un-doped Eu3 or Tb3 and Na2WO4 in silica materials were prepared and measured. The results show that good energy transfer from WO2-4 to Eu3 ion, sensitized the luminescence intensify of Eu3 remarkably. Tb3 ion incorporated silica materials expressed the inverse energy transition from Tb3 to WO2-4, however, we got the materials with homogeneous green blue fluorescent light. Finally, the energy transfer of WO2-4 and Eu3 , WO2-4 and Tb3 were expained by energy levels diagram.     

Preparation and Structure of Mg2-xRExNi （RE = La, Ce, Pr, Nd, Y） Ternary Alloys

A series of Mg2-xNdxNi (x =0.05, 0.1, 0.2, 0.3) alloys and Mg1.95RE0.05Ni (RE= La, Ce, Pr, Nd, Y)ternary alloys were prepared by ball milling of mixted powder of Mg, Ni, RE and sintering under the protection of argon. XRD analysis shows that Mg2-xNdxNi (x = 0.05, 0.1 ) and Mg1.95RE0.05Ni consist of single phase with the same crystal structure as Mg2Ni. While three-phase alloys including Mg2Ni, NdNi and NdMgNi4 were formed in Mg1.8Nd0.2Ni and Mg1.7Nd0.3Ni alloys respectively. The lattice constants of Mg2Ni in those ternary alloys were calculated. The decomposition of Mg2Ni occurs in the milling process of Mg2Ni and Mg1.95RE0.05Ni alloys respectively. For the latter, another earlier reaction occurs in milling process, which means that atoms of RE are separated from crystal structure of Mg2Ni and form relevant oxides by combination with oxygen existed in argon atmosphere.     

用稀土氧化物处理铁水成球墨铸铁的研究

用稀土氧化物渣处理铁水，在１４５０℃下处理２０ｍｉｎ可冶炼出稀土含量０．０１％～０．０４１％，碳当量３．８３％～４．９３％的球墨铸铁。脱Ｓ反应，稀土氧化物还原反应热力学条件具备，搅拌条件良好时，都可获得成功。而铁水Ｐ含量应当降低，以确保铸件力学性能。     

Preparing of Nano-Sized Power RE2O3(RE = La,Y,Gd) by Pyrolying Precursors

The precursors RE (HSal) 3 ( RE = La, Y, Gd; HSal = C6 H4 (OH) COO) were synthesized by the rheological phase reaction method. The mechanism and products of thermal decomposition of precursors was studied by using TG,DTA, gas chromatography-mass spectrometry (GC-MS). Nano-sized RE2O3 ( RE = La, Y and Gd) power were obtained by thermal decomposition of the precursors in air at 800 ℃. TEM measurement indicates that RE2O3 are spherical particles. The middle level diameter ( d50 ) of the particles are 19.3 ( La2O3 ) , 53.8 ( Y2O3 ) and 28.6 nm( Gd2O3 ) respectively by means of laser particles size analyzer.     

Thermochemical Properties of the Complexes RE(HSal)3·2H2O (RE=La, Ce, Pr, Nd, Sm)

Five solid rare earth salicylate complexes were synthesized by low hydrated lathanide chloride and salicylic acid. The complexes in this experiment were identified as the general formula RE(Hsal)3·2H2O(RE=La, Ce, Pr, Nd, Sm) by elemental analysis and EDTA volumetric analysis. IR spectra of the complexes show that carboxyl of salicylic acid coordinates to RE3 ions. Electrochemical behaviors of the complexes on the glass-carbon electrode were researched with cyclic voltammetry (CV). It is indicated that the electrochemical process of the complexes is a one-electron redox process and the electrochemical reversibility of complexes is less than that of the lanthanide chlorides. The constant-volume combustion energies of complexes, ΔcU, were determined with a precise rotating-bomb calorimeter at 298.15 K. Their standard molar enthalpies of combustion, ΔcHθm, and standard molar enthalpies of formation, ΔfHθm, were calculated.