Rare earth doped CaCu_3Ti_4O_(12) electronic ceramics for high frequency applications

Ca1-xRxCu3Ti4O12(R=La,Y,Gd;x=0,0.1,0.2,0.3) electronic ceramics were fabricated by conventional solid-state reaction method.The microstructure and dielectric properties as well as impedance behavior were carefully investigated.XRD results showed that the secondary phases with the general formula R2Ti2O7 existed at grain boundaries of rare earth doped ceramics,which inhibited abnormal grain growth.The dielectric constant decreased from 4×105 in pure CaCu3Ti4O12(CCTO) ceramics to 2×103 with rare earth doping....

Optics and Spectral Investigation in Dy^(3+)-Doped Borate Glasses

Dy^3＋-doped borate glasses （LBLB） with high effective visible fluorescence emission were synthesized. The absorption spectrum and fluorescence spectrum of this glass were measured and analyzed. By using J-O theory, the oscillator strengths for some absorption transitions were calculated according to the absorption spectra. The intensity parameters Ω1 （t = 2, 4, 6） of Dy^3＋ were determined by using a least-squares fitting approach, and the values are 4.04 × 10^-20, 1.30 × 10^-20 and 1.82 × 10^-20 cm, respectively. The root-mean-square deviation δrma was calculated. Under UV light excitation, Dy^3＋-doped borate glasses （LBLB） emit intense yellowish white lights. The excitation spectrum indicates that argon laser is the effective excitation source in Dy^3＋-doped LBLB glasses

Dy^(3+)/Eu^(3+)双掺杂CaLaGa_(3)O_(7)颜色可调荧光粉的制备与发光性能

本文采用高温固相法成功制备了一系列Eu^(3+)单掺和Dy^(3+)/Eu^(3+)双掺CaLaGa_(3)O_(7)单基质荧光粉。通过X射线衍射和发射光谱对荧光粉的物相及发光性能进行了表征。结果表明,所制备的样品均为四方结构,与基质晶体一致,表明成功合成了Eu^(3+)单掺和Dy^(3+)/Eu^(3+)双掺杂的CaLaGa_(3)O_(7)荧光粉。在波长393 nm近紫外光激发下,Eu^(3+)∶CaLaGa_(3)O_(7)表现出Eu^(3+)的特征红光发射(5 D0→7 F2),并且发光纯度高达100%。共掺Dy^(3+)之后,Dy^(3+)/Eu^(3+)双掺CaLaGa_(3)O_(7)荧光粉不仅可以被波长393 nm的光激发还可以被波长348 nm的光激发。不管是哪个波长的光激发,Dy^(3+)/Eu^(3+)∶CaLaGa_(3)O_(7)发射光谱同时包含了Eu^(3+)的特征红光发射和Dy^(3+)的特征黄光发射(4 F_(9/2)→6 H_(13/2))。通过对发射谱和荧光寿命分析得出,双掺荧光粉中Dy^(3+)和Eu^(3+)之间存在有效的能量传递过程。进一步计算了各个样品对应的色坐标,结果表明当激发波长由348 nm改变为393 nm时,色坐标整体上从黄绿色区域移动到黄橙光区域。因此,Dy^(3+)/Eu^(3+)∶CaLaGa_(3)O_(7)是一种光色可调发光材料,在显示和固态照明方面具有良好的应用前景。

溶胶-凝胶法制备Gd_(4)Ga_(2)O_(9):Dy^(3+)白光发射荧光粉及其性能

通过溶胶-凝胶法制备了具有白光发射的Gd_(4)Ga_(2)O_(9):x%Dy^(3+)荧光粉,利用X射线粉末衍射(XRD)、扫描电子显微镜(SEM)、能谱仪(EDS)、紫外-可见漫反射光谱(UV-Vis DRS)和荧光光谱等对产物的物相结构、形貌、组分和光学性能进行研究,并分析了Dy^(3+)掺杂量对样品的影响。XRD结果表明,所制备的样品为Dy^(3+)掺杂的Gd_(4)Ga_(2)O_(9)单斜晶体和少量Ga_(2)O_(3)杂质相的混合物。紫外-可见漫反射光谱结果表明制备的Dy^(3+)掺杂Gd_(4)Ga_(2)O_(9)晶体是一种光学带隙为5.29 eV的直接带隙半导体。荧光检测结果表明Dy^(3+)掺杂Gd_(4)Ga_(2)O_(9)荧光粉可被属于Gd^(3+)激发带的275 nm紫外光有效激发,并在490 nm和575 nm附近分别发射出属于Dy^(3+)的^(4)F_(9/2)→^(6)H_(15/2)和^(4)F_(9/2)→^(6)H_(13/2)跃迁的蓝色和黄色的强烈光,证实在Gd_(4)Ga_(2)O_(9):Dy^(3+)样品中存在显著的由Gd^(3+)到Dy^(3+)的能量传递发光现象。同时,对其发光机制进行了讨论。样品的发光强度随着Dy^(3+)掺杂量的变化而变化,同时影响着样品的发光颜色,Dy^(3+)掺杂量为1.5%和2%时制备的荧光粉可在紫外光激发下分别发射出CIE色坐标为(0.3362,0.3512)和(0.3381,0.3523)、相关色温为5340 K和5263 K的白色光。研究结果表明Gd_(4)Ga_(2)O_(9):Dy^(3+)是一种潜在的紫外光激发白光发射荧光材料。

Gd_(2)MgTiO_(6):Dy^(3+)荧光粉的制备与发光性能研究

采用高温固相法制备出一系列Dy^(3+)掺杂双钙钛矿Gd_(2)MgTiO_(6)白色荧光粉样品,通过X射线衍射仪和荧光光谱仪对荧光粉样品的晶体结构及荧光性能进行分析和表征。结果表明:在355 nm近紫外光激发下,样品发出极强的蓝光(484 nm)和黄光(575 nm)。通过调节Dy^(3+)的浓度可以使样品发光颜色向白光区移动,因此Gd_(2)MgTiO_(6):Dy^(3+)是一种可调荧光粉。当Dy^(3+)掺杂浓度为3%时可以发出色坐标为(0.3598,0.3946)的白光。Gd_(2)MgTiO_(6)合成方法简便、组份易调控,是一种具有潜在应用价值荧光材料。

Preparation and electrochemical properties of Y-doped Li_3V_2(PO_4)_3 cathode materials for lithium batteries

Y-doped Li3V2（PO4）3 cathode materials were prepared by a carbothermal reduction（CTR） process.The properties of the Y-doped Li3V2（PO4）3 were investigated by X-ray diffraction（XRD） and electrochemical measurements.XRD studies showed that the Y-doped Li3V2（PO4）3 had the same monoclinic structure as the undoped Li3V2（PO4）3.The Y-doped Li3V2（PO4）3 samples were investigated on the Li extraction/insertion performances through charge/discharge, cyclic voltammogram（CV）, and electrochemical impedance spectra（EIS）.The optimal doping content of Y was x=0.03 in Li3V2-xYx（PO4）3 system.The Y-doped Li3V2（PO4）3 samples showed a better cyclic ability.The electrode reaction reversibility was enhanced, and the charge transfer resistance was decreased through the Y-doping.The improved electrochemical perormances of the Y-doped Li3V2（PO4）3 cathode materials were attributed to the addition of Y3＋ ion by stabilizing the monoclinic structure.

Boosting rate and cycling performance of K-doped Na_(3)V_(2)(PO_(4))_(2)F_(3) cathode for high-energy-density sodium-ion batteries

As a promising cathode material,Na_(3)V_(2)(PO_(4))_(2)F_(3)(NVPF)has attracted wide attention for sodium-ion batteries(SIBs)because of its high operating voltage and high structural stability.However,the low intrinsic electronic conductivity and insufficient Na ion mobility of NVPF limit its development.Herein,K-doping NVPF is prepared through a facile ball-milling combined calcination method.The effects of K-doping on the crystal structure,kinetic properties and electrochemical performance are investigated.The results demonstrate that the Na_(2.90)K_(0.10)V_(2)(PO_(4))_(3)F_(3)(K0.10-NVPF)exhibits a high capacity(120.8 mAh g^(-1) at 0.1 C),high rate capability(66 mAh g^(-1) at 30 C)and excellent cycling performance(a capacity retention of 97.5%at 1 C over 500 cycles).Also,the occupation site of K ions in the lattice,electronic band structure and Na-ion transport kinetic property in K-doped NVPF are investigated by density functional theory(DFT)calculations,which reveals that the K-doped NVPF exhibits improved electronic and ionic conductivities,and located K^(+) ions in the lattice to contribute to high reversible capacity,rate capability and cycling stability.Therefore,the K-doped NVPF serves as a promising cathode material for high-energy and high-power SIBs.

Synthesis and Electrochemical Properties of Cr-doped Li_3V_2(PO_4)_3 Cathode Materials for Lithium-ion Batteries

Cr-doped Li3V2（PO4）3 cathode materials Li3V2-xCr（PO4）3 were prepared by a carbothermal reduction（CTR） process. The properties of the Cr-doped Li3V2（PO4）3 were investigated by X-ray diffraction （XRD）, scanning electron microscopic （SEM）, and electrochemical measurements Results show that the Cr-doped Li3V2（PO4）3 has the same monoclinic structure as the undoped Li3V2（PO4）3, and the particle size of Cr-doped Li3V2（PO4）3 is smaller than that of the undoped Li3V2（PO4）3 and the smallest particle size is only about 1 1μm. The Cr-doped Li3V2（PO4）3 samples were investigated on the Li extraction/insertion performances through charge/discharge, cyclic voltammogram （CV）, and electrochemical impedance spectra（EIS）. The optimal doping content of Cr was that x=0.04 in the Li3V2-xCrx（PO4）3 samples to achieve high discharge capacity and good cyclic stability. The electrode reaction reversibility was enhanced, and the charge transfer resistance was decreased through the Cr-doping. The improved electrochemical performances of the Cr-doped Li3V2（PO4）3 cathode materials are attributed to the addition of Cr^3＋ ion by stabilizing the monoclinic structure.

Upconversion luminescence and temperature sensing performance of Er^(3+) ions doped self-activated KYb(MoO_(4))_(2) phosphors

In this work,a series of self-activated KYb(MoO_(4))_(2) phosphors with various x at% Er^(3+) doping concentrations(x=0.5,1,3,5,8,10,15) was synthesized by the solid-state reaction method.The phase structure of the as-prepared samples was analyzed by X-ray diffraction(XRD),XRD Rietveld refinement and Fourier transform infrared(FT-IR) spectroscopy.The as-prepared samples retain the orthorhombic structure with space group of Pbcn even Er^(3+) doping concentration up to 15 at%.High-purity upconversion(UC) green emission with green to red intensity ratio of 55 is observed from the as-prepared samples upon the excitation of 980 nm semiconductor laser and the optimum doping concentration of Er^(3+) ions in the self-activated KYb(MoO_(4))_(2) host is revealed as 3 at%.The strong green UC emission is confirmed as a two-photon process based on the power-dependent UC spectra.In addition,the fluorescence intensity ratios(FIRs) of the two thermally-coupled energy levels,namely ^(2)H_(11/2) and ^(4)S_(3/2).of Er^(3+) ions were investigated in the temperature region 300-570 K to evaluate the optical temperature sensor behavior of the sample.The maximum relative sensitivity(S_(R)) is determined to be 0.0069 K^(-1) at300 K and the absolute sensitivity(S_(A)) is determined to be 0.0126 K^(-1) at 300 K.The S_(A) of self-activated KYb(MoO_(4))2:Er^(3+)is almost twice that of traditional KY(MoO_(4))2:Er^(3+)/Yb^(3+)codoping phosphor.The results demonstrate that Er^(3+) ions doped self-activated KYb(MoO_(4))2 phosphor has promising application in visible display,trademark security and optical temperature sensors.

Dy^(3+)/Tm^(3+)掺杂Na_(2)Gd(PO_(4))(WO_(4))的制备及发光性能研究

采用二次熔融的高温固相法合成了一系列Dy^(3+)/Tm^(3+)共掺钠-钆-磷钨酸盐(NGPW)荧光材料,研究了其光致发光特性和热稳定性,以及CIE与激发波长的映射关系。改变激发波长可以让NGPW∶2%Tm^(3+),xDy^(3+)(x=1%、2%、3%、4%、5%)荧光粉的颜色从蓝色-冷白色-暖白色-黄色连续变化。在356nm和363nm激发下,可实现白光发射。对共掺杂荧光粉的荧光衰减曲线进行表征,验证了该荧光粉中Dy^(3+)和Tm^(3+)之间存在能量转移。详细研究了能量传递效率和能量传递机理。NGPW∶2%Tm^(3+),xDy^(3+)荧光粉有望成为极具潜力的色彩可调的单组分荧光粉。

白光发射新型磷灰石结构荧光粉LiGd(SiO_(4))6O_(2):Bi^(3+),Dy^(3+)的合成及性能研究

采用高温固相法在1350℃下煅烧6 h合成了LGSO:0.04Bi^(3+),xDy^(3+)(x=0.1,0.15,0.2,0.3)荧光粉。荧光粉样品为磷灰石结构,属于六方晶系,具有P63/m空间群结构。LGSO:0.04Bi^(3+),0.15Dy^(3+)具有多个激发带,和两个发射带,峰值分别位于487 nm和576 nm左右,归因于Bi^(3+):^(1)S_(0)→^(3)P_(1)跃迁和Dy^(3+):^(4)F_(9/2)→^(6)H_(13/2)橙黄色发光。CIE坐标在(0.3345,0.3658)达到一个白光区域。综上所述,LGSO:Bi^(3+)与Dy^(3+)荧光粉在紫外激发白光LED中具有潜在的应用价值。

Improving Cyclic Stability and Rate Performance of Lithium Ion Batteries Using La^(3+)Modified LiNi_(0.6)Co_(0.2)Mn_(0.2)O_(2)Cathode Materials

La_(4)NiLiO_(8)-coated NCM622 samples were prepared through a sol-gel method,and the electrochemical performance as cathode materials was investigated.It is revealed that part of the introduced La^(3+)ions produce a coating layer on the surface of NCM622 particles,while the rest occupy the 3b position of the lattice.The optimized sample exhibits a capacity retention of 96.54%after 100 cycles under 1C rate with a discharge specific capacity of 117.54 mAh·g^(-1)under 5C rate,much higher than those of the unmodified sample.The results show that the addition of La^(3+)ion can greatly improve the cyclic stability and the rate performance of NCM622.

高热稳定CaGdAlO_(4)∶Er^(3+)/Yb^(3+)荧光粉的上转换发光及其温度传感性能

获得具有良好热稳定性和发光性能的非接触式光学温度传感材料是目前的研究热点之一,本工作通过高温固相法制备了Er^(3+)/Yb^(3+)共掺CaGdAlO_(4)∶Er_(x),Yb_(0.10)(x=0.006、0.008、0.010、0.012、0.014)荧光粉,尺寸大小分布在0.6~4.2μm。在980 nm激光激发下,该荧光粉在500~700 nm发射谱由两个发射带组成,528和550 nm处两个较强的绿光发射带,归属于Er^(3+)的^(2)H_(11/2)→^(4)I_(15/2)、^(4)S_(3/2)→^(4)I_(15/2)能级跃迁,663 nm处较弱的红光发射带,归属于Er^(3+)的^(4)F_(9/2)→^(4)I_(15/2)能级跃迁。上转换发光强度最大组分为CaGdAlO_(4)∶Er_(0.010),Yb_(0.10)。300~573 K变温发射谱表明,基于荧光强度比FIR_(528/550)参数,温度传感绝对灵敏度S_(A)从44.4×10^(-4) K^(-1)(@300 K)先增大到52.0×10^(-4) K^(-1)(@445 K)随后减小到49.0×10^(-4) K^(-1)(@573 K)。相对灵敏度S_(R)则从0.95×10^(-2) K^(-1)(@300 K)单调减小到0.27×10^(-2) K^(-1)(@573 K)。冷热循环实验表明该材料的热重复性优于98%。结果表明,CaGdAlO_(4)∶Er_(0.010),Yb_(0.10)荧光粉在光学温度传感领域具有潜在的应用前景。

Gd^(3+)掺杂调控BiFeO_(3)-BaTiO_(3)高温无铅压电陶瓷的结构与性能

用于监测航空发动机、重型燃气轮机等重大技术装备高温部件振动状态的压电加速度传感器,需要一种高居里温度压电陶瓷作为敏感元件,而电子元器件的无铅化是环境保护的迫切要求。采用传统的固相反应法制备一种Gd/Mn共掺杂的BF-BT((0.67BiFeO_(3)-0.33Ba_(1-x)Gd_(x)TiO_(3))+0.5%(质量分数)MnO_(2),x=0~0.02)高温无铅压电陶瓷,并研究Gd^(3+)掺杂浓度(x)对BF-BT陶瓷的相组成、微观结构、压电性能、介电弛豫行为及交流阻抗特征的影响。结果表明:所有样品均为单一钙钛矿结构,三方相(R)和四方相(T)共存,且T相含量随x增加而增加;适量的Gd^(3+)(x<0.02)固溶进入钙钛矿点阵之中能够促进BF-BT陶瓷晶粒的生长。掺杂Gd^(3+)的样品表现出增强的弛豫相变行为,相变温度(T_m)随x的增加而减小,而介电弛豫程度(ΔT_(relax))随x的增加而增大。采用R-CPE等效电路模型对BF-BT陶瓷的高温复阻抗谱(Cole-Cole图)进行拟合分析,发现样品在高温下的交流阻抗主要来自晶界的贡献。并且随着Gd^(3+)掺杂浓度的提高,样品的介电弛豫激活能不断增大,证实Gd^(3+)取代Ba^(2+)减少了晶格中氧空位浓度的施主掺杂效应。综合来看,x=0.01的样品具有最优的电学性能:T_(C)=425℃,d_(33)=126 pC/N,k_(p)=25.9%,tanδ=0.059,有望作为一种合适的高温压电材料被应用。

纳米花状MoO_(3−x)负极的制备及电化学性能

三氧化钼(MoO_(3))由于自身理论比容量高、热稳定性好以及二维层状结构,成为目前广受关注的锂离子电池负极材料之一。但是,由于MoO_(3)自身的本征导电率低以及转换反应过程中严重的体积膨胀,限制了MoO_(3)的大规模应用。本文通过质子−电子共掺杂以及高能纳米化方式,在MoO_(3)中引入了氧空位和纳米花结构,制备了纳米花MoO_(3−x)材料,并将其用作锂离子电池负极。通过引入氧空位以及进行纳米化处理,有效改善了材料的导电性能,扩大了范德华间隙,缓冲了材料在长期充放电过程中的体积膨胀。结果表明,所制备的纳米花MoO_(3−x)具有良好的锂离子存储性能,在2 A/g的电流密度下能够循环500圈,比容量能够达到591 mA∙h/g,显著高于以往报道的三氧化钼基负极材料。

钠离子电池正极材料Na_(4)Fe_(3-x)Cr_(x)(PO_(4))_(2)P_(2)O_(7)/C@CNT的制备及电化学性能研究

为改善钠离子电池正极材料Na_(4)Fe_(3)(PO_(4))_(2)P_(2)O_(7)的导电性,提高其充放电性能,采用Cr^(3+)掺杂提高正极材料本征导电性,采用包覆碳和复合碳纳米管(CNT)构筑高效导电网络以加快纳米活性物颗粒间的电子传导,制备并探究了Na_(4)Fe_(3-x)Cr_(x)(PO_(4))_(2)P_(2)O_(7)/C@CNT复合材料的结构与电化学性能。结果表明,当Cr^(3+)掺杂量x为0.075、CNT添加质量分数为3%时,所制备材料表现出较小的电荷传递阻抗和优异的高倍率充放电性能。其0.1 C和20 C倍率下的放电比容量分别达到120.64 mAh/g和87.11 mAh/g,10 C倍率下循环500次后容量保持率高达92.37%。

Dy^(3+)掺杂Y_(2)MgTiO_(6)荧光粉的制备及发光性质研究

通过溶胶-凝胶法制备出一系列Dy^(3+)掺杂的Y_(2)MgTiO_(6)(YMT∶Dy^(3+))荧光粉,并利用X射线衍射仪、扫描电子显微镜、荧光光谱仪对荧光粉的晶体结构、微观形貌及发光性质进行研究和分析。研究结果显示,YMT∶Dy^(3+)荧光粉为双钙钛矿结构,Dy^(3+)掺杂不改变样品的晶体结构。在近紫外光(352 nm)的激发下,样品的发射光谱显示出典型的Dy^(3+)特征发射峰,分别是485 nm处的蓝光、578 nm处的黄光,以及650~700 nm的红光。当Dy^(3+)摩尔浓度x=0.03时,荧光粉出现浓度猝灭效应,其浓度猝灭机制为电偶极子-电偶极子相互作用(d-d)。YMT∶Dy^(3+)荧光粉的CIE色坐标明显受到Dy^(3+)的浓度影响,其中YMT∶0.02Dy^(3+)荧光粉的CIE色坐标为(0.406,0.407),位于暖白光区,可作为一种暖白光荧光粉应用于近紫外激发白光发光二极管(w-LEDs)。

Dy^(3+)/Tb^(3+)单掺硼酸盐玻璃陶瓷的高效可见荧光发射

实验采用高温熔融-退火法分别合成了Tb^(3+)掺杂和Dy^(3+)掺杂的稀土硼酸盐玻璃陶瓷材料。XRD晶相分析表明,所制备的样品为非晶态玻璃陶瓷物质;SEM形貌分析表明,样品表面十分致密,无明显的结晶状物质;光谱特性试验结果表明,在紫外激发下,Tb^(3+)和Dy^(3+)单掺在这种新型硼酸盐玻璃陶瓷中分别发出了强烈的绿色和明亮的黄白光。该类材料在可见显示器件方面具有广阔的应用前景,可用于开发新型彩色光源、荧光显示器件、紫外传感器和可调谐可见光激光器。

Ba_(3-x)B_(6)Si_(2)O_(16)∶xSm^(3+)发光材料的制备及其性能表征

采用高温固相法制备Ba_(3)B_(6)Si_(2)O_(16)∶Sm^(3+)系列发光材料的荧光粉样品,对其进行粉末X射线衍射、荧光光谱、固体紫外-可见漫反射等相关性能的研究与表征,探讨不同的Sm^(3+)离子浓度对Ba_(3-x)B_(6)Si_(2)O_(16)荧光粉发光性能的影响,并对其浓度猝灭机理进行讨论.实验表明,在405 nm近紫外光激发下,Ba_(3-x)B_(6)Si_(2)O_(16)∶xSm^(3+)系列发光材料能够同时发射出571 nm(黄光)和606 nm(橙光)荧光,分别对应于Sm^(3+)离子的4G_(5/2)→6H_(5/2)和4G_(5/2)→6H_(7/2)能级跃迁.当x=0.21时,Ba_(2.79)B_(6)Si_(2)O_(16)∶0.21Sm^(3+)荧光粉发光性能最强;继续增加掺杂Sm^(3+)离子的浓度,则出现浓度猝灭现象.其浓度猝灭机制可以通过相邻Sm^(3+)离子之间的相互作用来解释.所制备的Ba_(3)B_(6)Si_(2)O_(16)∶Sm^(3+)荧光粉可被近紫外光有效激发,在白光LED领域具有潜在的应用前景.

Photocatalytic Activity of Nanosized TiO_2 Enhanced by co-doping with Fe^(3+) and Nd^(3+) Ions

In this study, nanosized TiO2 co-doped with Fe3+ and Nd3+ ions was synthesized via a sol-gel method. The metallic ion doped TiO2 was thoroughly characterized with XRD and UV-vis, and the photocatalytic activity was evaluated by degrading methylene blue (MB) solution. The results indicated that TiO2 crystalline size was reduced and phase transformation of anatase to rutile was suppressed as the content of doped Nd3+ ion increased in the co-doped TiO2. The UV-vis spectra of co-doped TiO2 seemed to simply overlay two spectra of single metal doped TiO2, and had significantly increased absorbance in the ranges of 400～500 nm, 565～600 nm and 730～765 nm as compared to pure TiO2. The photocatalytic activity of co-doped TiO2 was obviously enhanced, and raised about 30% compared to that of pure TiO2 as doped Nd3+ content was 0.15% and Fe3+ content was 0.05%, respectively. The enhanced catalytic activity was attributed to a synergistic effect of two doped ions, where doped Fe3+ ion inhibited the recombination of photogenerated electron and hole, and Nd3+ ion brought more surface carboxyl to promote the degradation reaction.