二硼酸锂晶体的压致非晶化研究

二硼酸锂晶体的压致非晶化研究李玉栋，扈士芬，蓝国祥（南开大学物理系天津３０００７１）Ｐｒｅｓｓｕｒｅ－ＩｎｄｕｃｅｄＡｍｏｒｐｈｉｓａｔｉｏｎｏｆＬｉｔｈｉｕｍＤｉｂｏｒｉｔｅ￥ＹｕｄｏｎｇＬｉ；ＳｈｉｆｅｎＨｕａｎｄＧｕｏｘｉａｎｇＬａｎ（Ｄｅｐａ...     

从自旋冰到自旋液态的渡越——结构与磁性质的演化

使用固相反应法得到了Ho_2-xTb_xTi₂O₇（x=0,05,1,15,2）系列多晶样品.X射线衍射（XRD）实验与2K到300K温度区间的直流磁化率测量结果显示,随着Tb即是x的增加,体系由自旋冰Ho₂Ti₂O₇向自旋液Tb₂Ti₂O_{7关键词： 自旋冰 自旋液体 自旋阻挫 晶格结构}     

Contrasting physical properties of the trilayer nickelates Nd_4Ni_3O_(10) and Nd_4Ni_3O_8

We report the crystal structures and physical properties of trilayer nickelates Nd4Ni3O10and Nd4Ni3O8.Measurements of magnetization and electrical resistivity display contrasting behaviors in the two compounds.Nd4Ni3O10shows a paramagnetic metallic behavior with a metal-to-metal phase transition(T^*)at about 162 K,as revealed by both magnetic susceptibility and resistivity.Further magnetoresistance and Hall coefficient results show a negative magnetoresistance at low temperatures and the carrier type of Nd4Ni3O10is dominated by hole-type charge carriers.The significant enhancement of Hall coefficient and resistivity below T*suggests that effective charge carrier density decreases when cooling through the transition temperature.In contrast,Nd4Ni3O8 shows an insulating behavior.In addition,this compound shows a paramagnetic behavior with the similar magnetic moment as that of Nd4Ni3O10derived from the Curie-Weiss fitting.This may suggest that the magnetic moments in both systems are contributed by Nd^3+ ions.By applying pressures up to about 49 GPa,the insulating behavior is still present and becomes even stronger under a high pressure.Our results suggest that the different Ni configurations(Ni^1+/2+ or Ni^2+/3+)and the changes of coordination environment of Ni sites may account for the contrasting behaviors in trilayer nickelates Nd4Ni3O10and Nd4Ni3O8.     

Understanding oxygen reactions in aprotic Li-O_2 batteries

Although significant progress has been made in many aspects of the emerging aprotic Li-O_2 battery system, an indepth understanding of the oxygen reactions is still underway. The oxygen reactions occurring in the positive electrode distinguish Li-O_2 batteries from the conventional Li-ion cells and play a crucial role in the Li-O_2cell's performance(capacity, rate capability, and cycle life). Recent advances in fundamental studies of oxygen reactions in aprotic Li-O_2 batteries are reviewed, including the reaction route, kinetics, morphological evolution of Li_2O_2, and charge transport within Li_2O_2. Prospects are also provided for future fundamental investigations of Li-O_2 chemistry.     

La,V共掺杂的Bi_4Ti_3O_(12)铁电薄膜的溶胶-凝胶法制备及性能测试

采用溶胶-凝胶(sol-gel)工艺在Pt/TiO2/SiO2/p-Si(100)衬底上制备出Bi4Ti3O12(BIT)和Bi3.25La0.75Ti2.97V0.03O12(BLTV)铁电薄膜,研究了La,V共掺杂对BIT薄膜的晶体结构和电学性能的影响.BIT薄膜为c轴择优取向,BLTV薄膜为随机取向,拉曼光谱分析表明V掺杂降低了TiO6(或VO6)八面体的对称性,也增强了Ti—O键(或V—O键)杂化.BLTV薄膜的剩余极化Pr为25.4μC/cm2,远大于BIT薄膜的9.2μC/cm2,表现出良好的铁电性能.疲劳、漏电流测试显示BLTV薄膜具有优良的抗疲劳特性和漏电流特性,表明La,V共掺杂能有效地降低薄膜中的氧空位.     

Lithium/Silver-Doped Cu_2ZnSnS_4 with Tunable Band Gaps and Phase Structures: a First-Principles Study

Doping is an effective approach for improving the photovoltaic performance of Cu_2 ZnSnS_4(CZTS). The doping by substitution of Cu atoms in CZTS with Li and Ag atoms is investigated using density functional theory. The results show that the band gaps of Li_(2 x)Cu_(2(1-x))ZnSnS_4 and Ag_(2 x)Cu_(2(1-x))ZnSnS4 can be tuned in the ranges of 1.30-3.43 and 1.30-1.63 eV, respectively. The calculation also reveals a phase transition from kesterite to wurtzite-kesterite for Li_(2 x)Cu_(2(1-x))ZnSnS_4 as x is larger than 0.9. The tunable band gaps of Li_(2 x)Cu_(2(1-x))ZnSnS_4 and Ag_(2 x)Cu_(2(1-x)) ZnSnS_4 make them beneficial for achieving band-gap-graded solar cells.     

Enhanced ionic conductivity in LAGP/LATP composite electrolyte

Nasicon materials(sodium superionic conductors) such as Li_(1.5)Al_(0.5)Ge_(1.5)(PO_4)_3(LAGP) and Li_(1.4)Al_(0.4)Ti_(1.6)(PO_4)_3(LATP) have been considered as important solid electrolytes due to their high ionic conductivity and chemical stability.Compared to LAGP, LATP has higher bulk conductivity around 10~(-3) S/cm at room temperature; however, the apparent grain boundary conductivity is almost two orders of magnitude lower than the bulk, while LAGP has similar bulk and grain boundary conductivity around the order of 10~(-4) S/cm. To make full use of the advantages of the two electrolytes, pure phase Li_(1.5)Al_(0.5)Ge_(1.5)(PO_4)_3 and Li_(1.4)Al_(0.4)Ti_(1.6)(PO_4)_3 were synthesized through solid state reaction, a series of composite electrolytes consisting of LAGP and LATP with different weight ratios were designed. XRD and variable temperature AC impedance spectra were carried out to clarify the crystal structure and the ion transport properties of the composite electrolytes. The results indicate that the composite electrolyte with the LATP/LAGP weight ratio of 80:20 achieved the highest bulk conductivity which shall be due to the formation of solid solution phase Li1.42 Al0.42 Ge0.3 Ti1.28(PO4)3, while the highest grain boundary conductivity appeared at the LATP/LAGP weight ratio of 20:80 which may be due to the excellent interfacial phase between Li_(1+x)Al_xGe_yTi_(2-x-y)(PO_4)_3/LATP. All the composite electrolytes demonstrated higher total conductivity than the pure LAGP and LATP, which highlights the importance of heterogeneous interface on regulating the ion transport properties.     

Laser scattering,transmittance and low thermal expansion behaviors in Y_(2-x)(ZnLi)_xMo_3O_(12) by forming regular grains

Ceramics usually have irregular grains, cracking, or porosity, which result in their lightproof.Y_2Mo_3O_(12) ceramics have more porosity due to the heavy hygroscopicity.Introducing ZnLi to Y_2Mo_3O_(12) could form regular grains, reduce cracking and porosity.With increasing the content of ZnLi, the grain shapes self-assembly gradually and then the laser scattering and transmittance improve.The laser scattering property and transmittance of diverging rays become the best in ceramics Y_(2-x)(ZnLi)_xMo_3O_(12)(x = 1.0 and 1.2) with regular grains and low thermal expansion.The formation mechanism of regular grains is ascribed to the substitutions of Zn~(2+)and Li+for Y~(3+) in Y_2Mo_3O_(12) resulting in the preferential growth.The investigation in laser scattering, transmittance and low thermal expansion behaviors of Y_(2-x)(ZnLi)_xMo_3O_(12) could pave a way to weaken the strong-laser attack from the high-power laser weapon and the other.     

An Attempt to Prepare Metallic Glasses from Quasicrystals

Icosahedrons in supercooled liquids and glasses are considered to be of significance for the glass formation in alloy systems.Starting from the similarity of the local structure of quasicrystals to the icosahedrons in metallic glasses,a scheme is put forward to prepare metallic glasses based on a well-known quasicrystal Zr_(40)Ti_(40)Ni_(20).A series of(Zr_(40)Ti_(40)Ni_(20))_(100-x)Co_x metallic glasses are fabricated,and the optimized glass forming composition is determined at(Zr_(40)Ti_(40)Ni_(20))_(92)Co_8.The results show that the glass-forming ability of the alloys is closely related to the quasicrystalline phases.The mechanism of the enhanced glass-forming ability is discussed.     

Low thermal expansion and broad band photoluminescence of Zr0.1Al1.9Mo2.9V0.1O12

A new material of Zr0.1Al1.9Mo2.9V0.1O12 is synthesized by the traditional solid state synthesis method.The phase transition,coefficient of thermal expansion,and luminescence properties of Zr0.1Al1.9Mo2.9V0.1O12 are explored with Raman spectrometer,dilatometer,and x-ray diffraction(XRD)diffractometer.The results show that the Zr0.1Al1.9Mo2.9V0.1O12 possesses the strong broad-band luminescence characteristics almost in the whole visible region.The sample is crystallized in a monoclinic structure group of P21/a(No.14)crystallized at room temperature(RT).The crystal is changed from monoclinic to orthorhombic structure when the temperature increases to 463 K.The material has very low thermal expansion performance in a wide temperature range.Its excellent low thermal expansion and strong pale green light properties in a wide temperature range suggest its potential applications in light-emitting diode(LED)and other optoelectronic devices.     

The formation and electrochemical property of lithium-excess cathode material Li<Subscript>1.2</Subscript>Ni<Subscript>0.13</Subscript>Co<Subscript>0.13</Subscript>Mn<Subscript>0.54</Subscript>O<Subscript>2</Subscript> with petal-like nanoplate microstructure

Lithium-excess oxide shows great potential for its high specific capacity of exceeding 280 mAh g^?1. However, the poor rate capability caused by the poor electrochemical kinetics condition as well as the structure instability block the way of its application. Here, we aimed to improve the kinetics circumstance for lithium ion transference through the material bulk by synthesizing lithium-excess oxide with high specific surface area. Petal-like nanoplates and nanoparticles with excellent electrochemical performance were obtained at different sintering temperatures and times by the electrospinning-sintering method, which facilitates the sufficient contact of electrode and electrolyte and helps to reduce the polarization during the electrochemical reaction process. Cyclic voltammetry tests verify that a portion of oxidized oxygen is reduced reversibly at 3.0 V and the reduction of oxygen contributes to the discharge capacity. Electrochemical impedance spectroscopy plots illustrate the ameliorative electrochemical kinetics is conductive to the oxidation of oxygen at 4.5 V.     

Er3+/Yb3+共掺TeO2-Li2O-B2O3-GeO2玻璃系统的光谱性质和热稳定性研究

制备了Er³⁺/Yb³⁺共掺的70TeO₂-5Li₂O-(25-x)B₂O₃-xGeO₂（x=0,5,10,15,20 mol%）系列玻璃, 研究了玻璃的热稳定性能, 测试了玻璃的吸收光谱、荧光光谱以及Er3+离子4I13/2能级荧光寿命, 并根据McCumber理论计算了Er³⁺离子4I13/2→4I15/2跃迁的受激发射截面. 结果表明：随着GeO₂含量的增加, 玻璃的热稳定性逐渐提高, 荧光谱线半高宽（FWHM）保持在70 nm左右, 而荧光强度和Er3+离子4I13/2能级荧光寿命逐渐提高, 研究表明这种玻璃系统是一种具有应用潜能的宽带光纤放大器用的基质材料.     

高压高温下B2O3与Mg和Li3N的反应

 通过B₂O₃与Mg和Li₃N分别在不同温度压力条件下的反应，用X射线方法研究了生成物的物相。当采用Mg与B₂O₃为原料时，其产物是Mg₃B₂O₆；用Li₃N与B₂O₃反应时，产物中除了Li₃BO₃，还有立方氮化硼（cBN）生成。这表明，当原料中含有相同数量B₂O₃时，用Mg和Li₃N分别作触媒合成立方氮化硼，将得到不同的结果。     

Effects of Al particles and thin layer on thermal expansion and conductivity of Al-Y_2Mo_3O_(12) cermets

Low thermal expansion composites are difficult to obtain by using Al with larger positive thermal expansion coefficient(TEC) and the materials with smaller negative TECs. In this investigation, Y_2Mo_3O_(12) with larger negative TEC is used to combine with Al to obtain a low thermal expansion composite with high conductivity. The TEC of Al is reduced by 19%for a ratio Al:Y_2Mo_3O_(12) of 0.3118. When the mass ratio of Al:Y_2Mo_3O_(12) increases to 2.0000, the conductivity of the composite increases so much that a transformation from capacitance to pure resistance appears. The results suggest that Y_2Mo_3O_(12) plays a dominant role in the composite for low content of Al(presenting isolate particles), while the content of Al increases enough to contact each other, the composite presents mainly the property of Al. For the effect of high content Al, it is considered that Al is squeezed out of the cermets during the uniaxial pressure process to form a thin layer on the surface.     

Molten-salt synthesis and composition-dependent luminescent properties of barium tungsto-molybdate-based solid solution phosphors

Pr~(3+)-activated barium tungsto-molybdate solid solution phosphor Ba(Mo_(1-z)W_z)O_4:Pr~(3+)is successfully fabricated via a facile molten-salt approach. The as-synthesized microcrystal is of truncated octahedron and exhibits deep-red-emitting upon blue light excitation. Powder x-ray diffraction and Raman spectroscopy techniques are utilized to investigate the formation of solid solution phosphor. The luminescence behaviors depend on the resulting composition of the microcrystals with fixed Pr~(3+)-doping concentration, while the host lattices remain in a scheelite structure. The forming solid solution via the substitution of [WO_4] for [MoO_4] can significantly enhance its luminescence, which may be due to the fact that Ba(Mo_(1-z)W_z)O_4:Pr~(3+)owns well-defined facets and uniform morphologies. Owing to its properties of high phase purity,well-defined facets, highly uniform morphologies, exceptional chemical and thermal stabilities, and stronger emission intensity, the resulting solid solution phosphor is expected to find potential applications in phosphor-converted white lightemitting diodes(LEDs).     

Tm掺杂的激光晶体生长、结构和光谱性能研究

采用顶部籽晶生长法从K2Mo3O10-B2O3助熔剂中生长出15 mm×15 mm×25 mm优质TmxGd1-x Al3(BO3)4(x=1,0.06)晶体.利用X射线单晶衍射仪测定了TmAl3(BO3)4晶体的结构.对Tm3+GAB晶体进行定向切割,测量得到了σ和π方向的偏振的吸收和发射光谱,并根据Judd-Ofelt理论计算了Tm3+在GdAl3(BO3)4中的J-O参数、各个能级的振子强度、自发辐射几率、荧光分支比等参数.     

Thickness Effect on (La_(0.26)Bi_(0.74))_2Ti_4O_(11) Thin-Film Composition and Electrical Properties

Highly oriented(00l)(La_(0.26)Bi_(0.74))_2Ti_4O_(11 )thin films are deposited on(100) SrTiO_(3 )substrates using the pulsed laser deposition technique.The grains form a texture of bar-like arrays along Sr Ti O_3110directions for the film thickness above 350 nm,in contrast to spherical grains for the reduced film thickness below 220 nm.X-ray diffraction patterns show that the highly ordered bar-like grains are the ensemble of two lattice-matched monoclinic(La,Bi)_4Ti_3O_(12 )and TiO_(2 )components above a critical film thickness.Otherwise,the phase decomposes into the random mixture of Bi_2Ti_2O_(7 )and Bi_4Ti_3O_(4 )spherical grains in thinner films.The critical thickness can increase up to 440 nm as the films are deposited on LaNiO_3-buffered SrTiO_(3 )substrates.The electrical measurements show the dielectric enhancement of the multi-components,and comprehensive charge injection into interfacial traps between(La,Bi)_4Ti_3O_(12 )and TiO_(2 )components occurs under the application of a threshold voltage for the realization of high-charge storage.     

Bi1.8Nd0.2Ti4O11的温致及压致软模相变研究

 采用背用散射的方法，测量了Bi_1.8Nd_0.2Ti₄O₁₁的拉曼光谱。实验结果表明，该掺杂样品发生温致和压致软模相变的温度和压力分别为200 ℃和3.35 GPa。文中讨论了相变点移动的原因及高频声子模随温度和压力的变化。     

Electrical analysis of inter-growth structured Bi_4Ti_3O_(12)-Na_(0.5)Bi_(4.5)Ti_4O_(15) ceramics

Inter-growth bismuth layer-structured ferroelectrics(BLSFs), Bi_4Ti_3O_(12)-Na_(0.5)Bi_(4.5)Ti_4O_(15)(BIT-NBT), were successfully synthesized using the traditional solid-state reaction method. X-ray diffraction(XRD) Rietveld refinements were conducted using GSAS software. Good agreement and low residual are obtained. The XRD diffraction peaks can be well indexed into I2 cm space group. The inter-growth structure was further observed in the high-resolution TEM image. Dielectric and impedance properties were measured and systematically analyzed. At the temperature range 763-923 K(below T_c), doubly ionized oxygen vacancies(OVs) are localized and the short-range hopping leads to the relaxation processes with an activation energy of 0.79-1.01 eV. Above T_c, the doubly charged OVs are delocalized and become free ones, which contribute to the long-range dc conduction. The reduction in relaxation species gives rise to a higher relaxation activation energy ~ 1.6 eV.     

Synergistic effect of magnesium and fluorine doping on the electrochemical performance of lithium-manganese rich (LMR)-based Ni-Mn-Co-oxide (NMC) cathodes for lithium-ion batteries

Mg-doped-LMR-NMC (Li_1.2Ni_0.15-xMg_xMn_0.55Co_0.1 O₂) is synthesized by combustion method followed by fluorine doping by solid-state synthesis. In this approach, we substituted the Ni²⁺ by Mg²⁺ in varying mole percentages (x = 0.02, 0.05, 0.08) and partly oxygen by fluorine (LiF: LMR-NMC = 1:50 wt%). The synergistic effect of both magnesium and fluorine substitution on electrochemical performance of LMR-NMC is studied by electrochemical impedance spectroscopy and galvanostatic-charge-discharge cycling. Mg-F-doped LMR-NMC (Mg 0.02 mol) composite cathodes shows excellent discharge capacity of ~300 mAh g^?1 at C/20 rate whereas pristine LMR-NMC shows the initial capacity around 250 mAh g^?1 in the voltage range between 2.5 and 4.7 V. Mg-F-doped LMR-NMC shows lesser Ohmic and charge transfer resistance, cycles well, and delivers a stable high capacity of ~280 mAh g^?1 at C/10 rate. The voltage decay which is the major issue of LMR-NMC is minimized in Mg-F-doped LMR-NMC compared to pristine LMR-NMC.