矿物锂快离子导体Li1+2xAlxSCyNbyTi2-x-2ySixP3-xO12系统的合成与表征

以LiTi2(PO4)3为母体,天然高岭石为起始原料,经高温固相反应制得了一系列新的锂快离子导体材料Li1+2xA1xScyNbyTi2-x-2ySixP3-xO12(以下简称Sc-Nb-Lisicon).X射线衍射分析表明x=0.1、x=0.2,y≤0.4;x=0.3,y≤0.25的组成范围内能得到类似于Nasicon的三方结构,即空间点群为R3C的合成物.应用交流阻抗技术测试其电导率,结果表明:x=0.1,y=0.3及x=0.2,y=0.15的合成物在室温下有较高的电导率,分别为1.05×10-4S/cm和2.78×10-4S/cm,二者在573K时的电导率可达8.00×10-3S/cm和7.82×10-3S/cm,同时在423～573K具有较低的活化能,分别为31.4kJ/mol和34.8kJ/mol.     

锂快离子导体Li1+2xAlxTiyGe2-x-ySixP3-xO12系统的研究

以高岭石为起始原料,经高温固相反应(～1000℃)合成了Li1+2xAlxTiyGe2-x-ySixP3-xO12(以下简称Ti-Ge-Lisicon)系统的锂快离子导体.应用交流阻抗技术测定的电导率数据结果表明,y=1.5,x=0.2的合成物的电导率最好,400℃时电导率达2.13×10-2S/cm,200～400℃内的电导激活能为30.6kJ/mol.XRD分析结果表明在一定的组成范围内得到空间群为R3c的合成物.     

矿物钠快离子导体Na1+3x+yAlxNdyTi2-x-ySi2xP3-2xO12合成与表征

Na1 3x yAlxNdyTi2-x-ySi2xP3-2xO12钠快离子导体(以下简称Al-Nd-Nasicon)可以用精选的天然叶腊石A12[Si4O10](OH)2为起始原料与其它化合物,经过高温(900～1100℃)固相反应约15h制得.在y=0.3,x≤0.3和y=0.5,x≤0.2的组成范围内可得到具有Nasicon的三方结构空间群属于R3C的固溶体.该相具有较高的电导率,其中起始组成y=0.3,x=0.1的合成物在350℃时电导率为1.80×10-2S/cm.     

Al3+、S6+掺杂的矿物锂快离子导体Li1.2+x-yAl0.1+xTi1.9-xSi0.1SyP2.9-yO12系统的合成与表征

以LiTi2(PO4)3为母体,以天然高岭石为起始原料,经高温固相反应制得了一系列新的锂快离子导体Li1.2 x-yAl0.1 xTi1.9-xSi0.1SyP2.9-yO12(以下简称Al-S-Lisicon).X射线粉末衍射分析结果表明在x≤0.30,y＜0.2 x的组成范围内均能得到类似于Nasicon三方结构的相.应用交流阻抗技术测定电导率的结果表明起始组成为x=0.20,y=0.20的合成物电导率最高,室温下为6.01×10-5S/cm,573K时达1.11×10-2S/cm,其在373～573K间的活化能为28.6kJ/mol,分解电压为3.1V.     

钙钛矿型锂快离子导体Li3xLa0.67-xCryTi1-2yNbyO3系统的研究

以Li3xLn0.67-xTiO3为母体,通过掺杂经高温固相反应制得一系列新的锂快离子导体材料Li3xLa0.67-xCryTi1-2yNbyO3.X射线衍射分析表明x=0.10和y≤0.10的组成范围内能得到钙钛矿型的固溶体.应用交流阻抗技术测试其电导率,结果表明:系统合成物在室温下有较高的体相电导和总电导分别为10-4S/cm和10-5S/cm,其中在x=0.10和y=0.025具有最大值为3.62×10-4S/cm.同时在298～523K具有较低的体相活化能和总活化能,分别约为13～20kJ/mol和35～38kJ/mol.     

锂离子电池正极材料Li2+2xTi1-xCux(NbO4)2的研究

采用高温固相反应合成了Li2+2xTi1-xCux(NbO4)2,XRD分析表明当x≤0.8时均能得到与LiFePO4相同的橄榄石结构.电导率测定结果表明x=0.6的合成物室温电导率最高,为1.26×10-5S/cm,且当x≥0.6时合成物都表现出离子电导的特征.以x=0.6的合成物做成的待测电极与锂片组成电池,在1mol/L的LiPF6/EC+DMC(1∶1)电解液中在0.5～4.6V间以0.10mA/cm2的电流密度进行电池循环测试的结果表明,该电池的首次放电比容量高达805.8mAh/g,放电平台在对Li+/Li电对为2V附近,但其可逆性及循环性均有待改善.     

Zn2+、Ge4+的取代对Li5AlSi2O8的影响

尝试以叶腊石为基体,通过高温固相反应,合成通式为Li5+xAl1-xZnxSi2-2xGe2xO8(x=0.0～1.0)系统锂快离子导体.X射线粉末衍射表明当x≤0.3时体系仍维持原有的Li5AlSi2O8结构(正交晶系);x＞0.5时结构发生明显变化,体系转变成Li6ZnGe2O)8.红外检测显示当x≥0.1红外谱图中出现Li2CO3吸收峰,表明在室温下体系中的Ge4+吸收空气中的CO2而发生分解反应.交流阻抗技术测试交流阻抗表明当温度大于200℃时体系有较高的电导率,最高时为1.11×10-2S/cm(400℃,x=1.0),x≤0.5时离子电导率很低,且不随温度变化.     

Li_(1+x)Ti_(2-x)Cr_xP_3O_(12)系统的相关系与电性

研究了 Li_(1+x)Ti_(2-x)Cr_xP_3O_(12)系统的相组成与电性的关系。结果表明,Cr~(3+)能取代 LiTi_2P_3O_(12)中的Ti~(4+)生成固溶体,直至 x=0.8。在固溶体范围内,电导率随 x 的增加不断升高,至 x=0.8时达到极大。此时在室温和300℃的电导率分别为2.4×10~(-4)和4.8×10~(-2)S/cm,电子迁移数在10~(-4)数量级,分解电压为1.8V。对所得结果从结晶化学角度进行了讨论。     

Na_3Hf_(2-x)TixSi_2PO_(12)系统快离子导体的研究

以 Na_3PO_4、HfO_2、SiO_2为主要原料,铂舟为反应器皿,在900～1200℃的高温下,加热数小时至20h(少数样品达40h),合成了一系列合成物。多数反应在1100～1150℃进行。x=0～0.5的合成物为 NASICON和 HfO_2的二相区。x=0.6～1.0时为 NASICON 单纯相。x>1.0开始出现玻璃态。系统合成物的电导性测定结果发现除母体以外最好的是 x=0.6的合成物。其电导率在400℃时为2.76×10~(-2)(Ω·cm)~(-1)。它的活化能在200～400℃温区里为25.5kJ/mol。     

In3+Nb5+双取代钙钛矿型锂快离子导体Li3xLa0.67-xTiO3的研究

以Li3xLa0.67-xTiO3为母体,通过掺杂经高温固相反应制得了一系列新的锂快离子导体材料Li3xLa0.67-xInyTi1-2yNbyO3.利用X射线衍射分析和交流阻抗技术研究该系统的组成结构和电化学性能.结果表明体系合成温度降低,分解电压提高了;在x=0.10,y＜0.050时,合成物为单一的钙钛矿固溶体,y≥0.050时,则存在In2O3杂相;该体系合成物在室温下有较高的电导率,可达5.81×10-4S/cm,活化能在20～30kJ/mol之间.     

改性沸石对电镀废水中Pb2+、Zn2+、Ni2+的吸附

将天然沸石进行处理制备出多孔质改性沸石颗粒。在静态条件下，研究了改性沸石颗粒对重金属离子Pb^2 ,Zn^2 ,Ni^2 的吸附效果及条件，含Pb^2 ,Zn^2 ,Ni^2 的电镀废水经改性沸石颗粒吸附后，废水中Pb^2 ,Zn^2 ,Ni^2 的含量低于国家排放标准。     

NpO 2 + -UO 2 2+ cation-cation interaction in NaCl-KCl-CsCl and LiCl-KCl-CsCl eutectic melts

Absorption spectra of the NpO ₂ ⁺ ion in UO ₂ ²⁺ -containing NaCl-KCl-CsCl (0.300:0.245:0.455) and LiCl-KCl-CsCl (0.575:0.165:0.260) eutectic melts in the region of the 5f-5f transitions, 700–2000 nm, were studied at 650 and 500°C, respectively. Processing of the spectra allowed the previously discovered phenomenon, cation-cation interaction of actinides in melts, to be interpreted for the first time in terms of the mass action law. It was shown that, at the concentrations of the interacting components studied (C _Np = 0.2 M and C _U = 0.1–2 M), a 1: 1 NpO ₂ ⁺ ·UO ₂ ²⁺ cation-cation complex is formed. Its concentration stability constant was estimated at 0.06(6) and 0.11 1 mol^?1 for the NaCl-KCl-CsCl and LiCl-KCl-CsCl systems, respectively.     

胶团强化超滤中SDS胶团对Cd^2＋，Zn^2＋和Pb^2＋的竞争吸附

胶团强化超滤法是一种将表面活性剂技术和超滤技术结合的新型、高效的重金属废水治理方法.以十二烷基硫酸钠(SDS)为表面活性剂,对含单一镉、锌、铅溶质以及混合溶质体系进行了胶团强化超滤研究,考察了胶团对Cd2 ,Zn2 ,Pb2 的竞争吸附性能.研究发现,当溶液中多种二价重金属离子存在时,各离子之间存在与SDS胶团的竞争吸附,竞争能力为Pb2 ＞Zn2 ＞Cd2 ;Cd-Zn有明显的协同吸附效应,而Cd-Pb,Zn-Pb则表现为拮抗吸附.     

酸改性膨润土吸附去除镍镉离子的研究

在静态条件下,研究了改性膨润土对重金属离子的吸附性能和吸附机理,着重探讨了改性膨润土去除模拟水样中重金属离子Ni2 ,Cd2 的适宜条件及改性膨润土的再生方法.结果表明,改性膨润土对Ni2 ,Cd2 具有较好的吸附性能;pH值是影响改性膨润土对重金属离子吸附的重要因素,不同的金属离子都有其适宜的pH值范围.吸附的最佳条件是pH值5.0～7.0,废水中Ni2 ,Cd2 含量不大于45 mg/L,搅拌时间约60 min.利用改性膨润土吸附处理Ni2 ,Cd2 含量小于45 mg/L的模拟水样,效果很好,Ni2 ,Cd2 的去除率均可分别达到98.5%以上,出水可达到国家排放标准.     

锰矿尾渣对Cu2+和Ni2+的吸附性能研究

研究了锰矿尾渣对重金属离子Cu2 和Ni2 的吸附性能,分析了锰矿尾渣的吸附动力学,就吸附时间、Cu2 和Ni2 浓度及pH值等因素对锰矿尾渣吸附性能的影响作了系统考察,并对锰矿尾渣的吸附机理进行了初步探讨.结果表明,在温度为25°℃、pH值为7.5的条件下,锰矿尾渣对Cu2 和Ni2 的吸附容量可达到1.6 mg/g以上,去除率均可达到97.5%以上,适宜于处理含低浓度Cu2 或Ni2 的废水.锰矿尾渣的吸附机理为离子交换吸附和表面配位吸附.     

On the Eu2+-Mn2+ energy transfer in BaMgF4

Energy transfer from Eu²⁺ to Mn²⁺ ions is shown to occur in BaMgF₄ : Eu, Mn crystals. The efficiency of this transfer is moderate. This is attributed to the fact that Eu²⁺ and Mn²⁺ ions are distributed randomly in the host lattice. Quantitative evaluation leads to the suggestion that the transfer is restricted to only seven neighbors at 4.0 Å and is thus exchange mediated.     

Observable effects of Ca2+ buffers on local Ca2+ signals

Calcium signals participate in a large variety of physiological processes. In many instances, they involve calcium entry through inositol 1,4,5-trisphosphate (IP(3)) receptors (IP(3)Rs), which are usually organized in clusters. Recent high-resolution optical experiments by Smith & Parker have provided new information on Ca(2+) release from clustered IP(3)Rs. In the present paper, we use the model recently introduced by Solovey & Ponce Dawson to determine how the distribution of the number of IP(3)Rs that become open during a localized release event may change by the presence of Ca(2+) buffers, substances that react with Ca(2+), altering its concentration and transport properties. We then discuss how buffer properties could be extracted from the observation of local signals.     

ESR of Cu2+and Tl2+ in thallium borate glasses

The electron spin resonance (ESR) and optical absorption spectra of Cu²⁺ were measured in thallium borate glasses in order to investigate the effects of glass transition temperature,T _g, upon the responses of cupric ion in alkali borate glasses. The ESR of Tl²⁺ induced by-ray irradiation was also obtained. An abrupt increase in the covalency of in-plane Cu²⁺-O-bonding was observed in the Tl₂O system as well as in the Na₂O system in a similar B₂O₃ composition range althoughT _g for the Tl₂O glasses has little dependency on the composition compared with the Na₂O glasses. The trend in the variation of the S-character of the Tl²⁺ unpaired electron with composition agreed with that of the covalency of in-plane Cu²⁺-O-bonding. The structure of the anion group present in Tl₂O glasses was also examined by laser reman spectroscopy.     

Characterization of various Eu2+ sites in Ca2SiO4:Eu2+ and Ba2SiO4:Eu2+ by high-pressure spectroscopy

Photoluminescence of Ba₂SiO₄ and Ca₂SiO₄ activated with Eu²⁺ was investigated at various temperatures (from 10 K to 300 K) and pressures (from ambient to 200 kbar). At ambient pressure and room temperature, under UV excitation both phosphors yielded a green emission band with maxima at 505 nm and 510 nm for Ba₂SiO₄ and Ca₂SiO₄, respectively. The energies of these bands depended on pressure; the pressure shifts were ?12:55 cm^?1/kbar for Ba₂SiO₄:Eu²⁺; and ?5:59 cm^?1/kbar for Ca₂SiO₄:Eu²⁺. In the case of Ca₂SiO₄:Eu²⁺, we observed additional broadband emission at lower energies with a maximum at 610 nm (orange band). The orange and green emission in Ca₂SiO₄:Eu²⁺ had different excitation spectra: the green band could be excited at wavelengths shorter than 470 nm, whereas the orange band — at wavelengths shorter than 520 nm. The pressure caused a red shift of orange emission of 7.83 cm^?1/kbar. The emission peaked at 510 nm was attributed to the 4f⁶5d→4f⁷(⁸S₇₌₂) transition of Eu²⁺ in the β — Ca₂SiO₄:Eu²⁺ phase, whereas the emission peaked at 610 nm — to the γ — Ca₂SiO₄:Eu²⁺ phase. The emission of Ba₂SiO₄:Eu²⁺ peaked at 505 nm was attributed to the 4f⁶5d→ 4f⁷(⁸S_7/2) transition of Eu²⁺ in the β — Ba₂SiO₄ phase.