Ca掺杂的对LiNi1/3Co1/3Mn1/3O2正极材料及其电化学性能研究

为探讨Ca的掺杂对LiNi_1/3Co_1/3Mn_1/3O₂材料结构和电性能的影响,以草酸为沉淀剂,以不同含量Ca对LiNi_1/3Co_1/3Mn_1/3O₂进行掺杂改性,并通过X射线衍射（XRD）对产品进行表征,探讨了不同Ca含量样品的电化学性能.结果表明：大量Ca掺杂生成明显CaO杂相,而少量Ca掺杂则能顺利进入材料晶格之中.随着Ca掺入,晶体类型不变,但c轴略收缩,形成更紧密的结构. 充放电显示Ca在低倍率(2.5～4.3 V,0.5 C)时,能一定程度提高材料的循环性能;但在高倍率(2.5～4.3 V,5 C)时,能明显提高容量和循环性能.充放电曲线同时显示未掺杂的材料高倍率下极化严重,放电平台严重降低;而Ca掺杂的材料极化状况则不明显,说明Ca掺杂能抑制极化并提高电化学性能.     

Effects of Yb^3＋ codoping on visible and near infrared emissions of Er^3＋-Yb^3＋ codoped Al2O3 powders by the sol-gel method

The 0.1 mol% Er^3＋ and 0-2 mol% Yb^3＋ codoped Al2O3 powders were prepared by the sol-gel method, and the phase structure, including only two crystalline types of doped Al2O3 phase, γ-（Al,Er, Yb）2O3 and θ-（Al,Er, Yb）2O3, was detected at the sintering temperature of 1000℃. The visible and near infrared emissions properties depended strongly on the Yb^3＋ codoping, and the corresponding maximal peak intensities centered at about 523, 545, 660 and 1533 nm were obtained respectively for the 0.1 mol% Er^3＋ and 0.5 mol% Yb^3＋ codoped Al2O3 powders, which were composed of θ-（Al,Er,Yb）2O3 and a small amount of γ-（Al,Er, Yb）2O3 phases. The two-photon absorption process was responsible for the visible up-conversion emissions, and the one-photon absorption process was involved in the near infrared emissions of the Er^3＋-yb^3＋ codoped Al2O3 powders.     

Bi掺杂O3型NaNi0.5Mn0.5O2钠离子电池层状正极材料的制备与储钠性能

O3型NaNi_0.5Mn_0.5O₂拥有高理论比容量且易于制备,是商业钠离子(Na⁺)电池的首选正极材料之一,但其循环稳定性仍面临挑战。利用Bi对NaNi_0.5Mn_0.5O₂进行改性。研究发现,Bi的引入可以在晶粒生长过程中通过调节表面能实现晶粒细化,并且Bi的掺杂增加了层状正极材料的晶胞参数,为Na⁺提供了宽的扩散通道,提高了Na⁺的扩散能力,优化了Na⁺在脱嵌过程中的可逆性。改性后的NaNi_0.495Mn_0.5Bi_0.005O₂实现了在2.0～4.0 V的电势区间内0.2 C倍率下的可逆容量为138.1 mAh/g,在5 C倍率下循环100圈后容量保持率可以达到97%。     

Preparation and luminescence characteristics of Sr3SiO5：Eu^2＋ phosphor for white LED

The Sr3SiO5：Eu^2＋ phosphor was synthesized by high temperature solid-state reaction. The emission spectrum of Sr3SiO5：Eu^2＋ shows two bands centered at 487 and 575 nm, which well agree with the theoretic values of emission spectrum. The excitation spectrum for 575 nm emission center has several excitation bands at 365, 418, 458 and 473 nm. And the results show that the emission spectrum of Sr3SiO5：Eu^2＋ is influenced by the Eu^2＋ concentration. The relative emission spectra of the white-emitting InGaN-based YAG：Ce^3＋ LED and Sr3SiO5：Eu^2＋ LED were investigated. The results show that the color development of InGaN-based Sr3SiO5：Eu^2＋ is better than that of InGaN-based YAG：Ce^3＋, and the CIE chromaticity of InGaN-based Sr3SiO5：Eu^2＋ is （x=0.348, y=0.326）.     

Chemical quenching and inhibition of positronium in Cr<Subscript>2</Subscript>O<Subscript>3</Subscript>/Al<Subscript>2</Subscript>O<Subscript>3</Subscript> catalysts

The pore structure of Cr2O3/Al2O3 catalysts and the surface chemical properties of these pores were characterized by positron lifetime and coincidence Doppler broadening (CDB) measurements. Four lifetime components could be resolved from the positron lifetime spectrum, with two long lifetime components and two short lifetime components. The two long lifetimes τ4 and τ3 are attributed to ortho-positronium (o-Ps) annihilation in large pores and microvoids, respectively. With increasing Cr2O3 content, both τ4 and its intensity I4 show sharp decrease, while τ3 and its intensity I3 keep nearly unchanged. The Doppler broadening S parameters also show sharp decrease with increasing Cr2O3 content. Detailed analysis of the CDB spectrum reveals that the parapositronium (p-Ps) intensity also decreases with increasing Cr2O3 content. This indicates that the change of o-Ps lifetime τ4 is due to the chemical quenching by Cr2O3 but not spin-conversion of positronium. The decrease of o-Ps intensity I4 indicates that Cr2O3 also inhibits positronium formation.     

3,4-dichlorotoluene ammoxidation to 3,4-dichlorobenzonitrile over VPO/SiO<Subscript>2</Subscript> catalyst

Ammoxidation of 3,4-dichlorotoluene (DCT) to prepare 3,4-dichlorobenzonitrile (DCBN) over silica supported vanadium phosphorus oxide catalysts has been studied. On the VPO/SiO₂ catalyst, the influence of the reaction temperature, the molar ratio of air/DCT, the molar ratio of NH₃/DCT in the feed gas and the space velocity (v ₁) on the conversion, yield and selectivity was observed. The most appropriate reaction condition is: reactionT=673 K,n(DCT):n(NH₃):n(air)=1:7:30 andv ₁=250 h⁻¹. At this optimum reaction condition, the conversion of DCT is 97.8%; the molar yield of DCBN is 67.4%. It was found that the addition of element phosphorus can improve the yield of DCBN compared with VO/SiO₂ catalyst. Foundation item: Supported by Youth Chen-Guang Project of the Committee of Science and Technology of Wuhan (20015005042) Biography: Huang Chi(1972-), male, Ph D, Lecture, research direction: ammoxidation.     

Transparent organic light-emitting diodes based on Cs<Subscript>2</Subscript>CO<Subscript>3</Subscript>:Ag/Ag composite cathode

The transparent organic light-emitting diodes (TOLEDs) based on Cs 2 CO 3:Ag/Ag composite cathode are reported in this paper.They show higher efficiency and better stability than the control devices with the Cs 2 CO 3 /Ag cathode.The devices are highly transparent,and show total efficiencies from both sides of the devices comparable with conventional bottom-emitting devices.The electroluminescence (EL) spectrum from the cathode side of the device is closer to the photoluminescence (PL) spectrum of the light...     

Ti掺杂对正极材料LiNi1/3Co1/3Mn1/3O2结构和电化学性能的影响

为研究离子掺杂对锂离子正极材料LiNi1/3Co1/3Mn1/3O2的影响,采用氢氧化物共沉淀法制备了Ti4+掺杂改性的锂离子正极材料LiNi1/3-1/40Co1/3Mn1/3Ti1/40O2、LiNi1/3-Co1/3-1/40Mn1/3Ti1/40O2和LiNi1/3Co1/3Mn1/3-1/40Ti1/40O2,并运用X射线衍射仪和扫描电子显微镜对Ti掺杂改性后正极材料的晶型和微观结构进行表征,通过高精度电池性能检测系统对正极材料的电化学性能进行检测.结果表明:Ti分别取代Ni、Co和Mn对三元复合正极材料进行掺杂改性后,改性材料都保持典型的α-NaFeO2层状结构,且晶型良好;LiNi1/3-Co1/3Mn1/3-1/40Ti1/40O2轮廓最分明,且形貌均一;3种改性材料的电化学性能均有一定程度的提高,其中LiNi1/3Co1/3Mn1/3-1/40Ti1/40O2提高最为明显,在0.1 C、1.0 C和2.0 C倍率下其首次放电比容量分别为145.35、140.79和125.60 mA.h/g,1.0 C倍率下循环30次后的容量保持率为88.06%.     

层状LiNi1/3Mn1/3CO1/3O2正极材料的合成

用碳酸盐同沉淀法合成了LiNi1/3Mn1/3Co1/3O2正极材料,采用XRD(X-RayDiffraction)、SEM(ScanningElectronMicroscope)、差分计时电位法和充放电循环等对材料的物理化学性质及电化学性能进行了测试分析。XRD分析表明在合成温度为800℃或更高时,所合成的产物均为α-NaFeO2型的层状结构,SEM分析表明在合成温度为800或850℃时,产物为微小晶粒团聚成的球形颗粒,合成温度为900℃以上时,产物颗粒发生破碎,形状不规则。950℃合成的LiNi1/3Mn1/3Co1/3O2材料在2·5~4·4V电位区间内,首次放电容量为162mAh·g-1,并具有良好的循环性能。随着充放电电压的升高,首次不可逆放电容量增大,循环稳定性减弱。在低温(800,850℃)下合成的LiNi1/3Mn1/3Co1/3O2材料与高温下(900,950℃)得到的材料性能有很大差别,这是由于在高温和低温下得到材料的结构差别所造成的。     

Synthesis of highly ordered SnO2／Fe2O3 composite nanowire arrays by electrophoretic deposition method

Highly ordered SnO2/Fe2O3 composite nanowire arrays have been synthesized by electrophoretic deposition method. The morphology and chemical composition of SnO2/Fe2O3 composite nanowire arrays are characterized by SEM, TEM, EDX, XPS, and XRD. The results show that the SnO2/Fe2O3 composite nanowires are about 180 nm in width and tens of microns in length, and they are composed of small nanoparticles of tetraganal SnO2 and rhombohedral α-Fe203 with diameters of 10-15nm. The SnO2/Fe2O3 composite nanowires are formed by a series of chemical reactions.     

层状LiNi1/3Mn1/3Co1/3O2正极材料的合成

用碳酸盐同沉淀法合成了LiNi_1/3Mn_1/3Co_1/3O₂正极材料,采用XRD(X7-Ray Diffraction)、SEM (Scanning Electron Microscope)、差分计时电位法和充放电循环等对材料的物理化学性质及电化学性能进行了测试分析。XRD分析表明在合成温度为800℃或更高时,所合成的产物均为α-NaFeO₂型的层状结构,SEM分析表明在合成温 度为800或850℃时,产物为微小晶粒团聚成的球形颗粒,合成温度为900℃以上时,产物颗粒发生破碎,形状不规则。950℃合成的LiNi_1/3Mn_1/3Co_1/3O₂材料在2.5～4.4V电位区间内, 首次放电容量为162 mAh·g^-1, 并具有良好的循环性能。随着充放电电压的升高,首次不可逆放电容量增大, 循环稳定性减弱。在低温(800, 850℃)下合成的LiNi_1/3Mn_1/3Co_1/3O₂材料与高温下(900, 950℃)得到的材料性能有很大差别,这是由于在高温和低温下得到材料的结构差别所造成的。     

Character and fabrication of Al/Al<Subscript>2</Subscript>O<Subscript>3</Subscript>/Al tunnel junctions for qubit application

The superconductive Josephson junction is the key device for superconducting quantum computation. We have fabricated Al/Al2O3/Al tunnel junctions using a double angle evaporation method based on a suspended shadow mask. The Al2O3 junction barrier has been formed by introducing pure oxygen into the chamber during the fabrication process. We have adjusted exposure conditions by changing either the oxygen pressure or the oxidizing time during the formation of tunnel barriers to control the critical current density Jc and the junction specific resistance Rc. Measurements of the leakage in Al/Al2O3/Al tunnel junctions show that the devices are suitable for qubit applications.     

Kinetic studies of the decomposition reaction of adducts of dinuclear Fe(Ⅱ)/O2

Kinetic studies of the decomposition reaction of dinuclear Fe(Ⅱ) adducts [Fe₂(N-Et-HPTB){O₂P(OPh)₂}](Cl- O₄)₂ (1) and [Fe₂(N-Et-HPTB) {O₂P(Ph)₂}] (ClO₄)₂ (2) with O₂ have been carried out at low temperature using UV-vis spectra. The decomposition reaction of Fe(Ⅱ)/O₂ adducts was first-order in the experimental conditions, and the activation parameters were obtained. ?H^¹ = 85.62 kJ·mol^-1, ?S¹ = 19.43 J·mol^-1·K^-1 for compound (1) and ?H^¹ = 97.97 kJ·mol^-1, ?S^¹ = 55.68 J·mol^-1·K^-1 for compound (2). These results are similar to those of dioxygen adducts of other metals complexes and natural enzymes such as methane mono- oxygenase (MMOH).     

Al3+掺杂LiMn2O4的制备及高温循环性能研究

采用沉淀法合成LiMn_2-xAl_xO₄（x=0.01,0.05,0.10,0.20）,pH的范围为10.5～10.6,搅拌速度为350 r/min,水浴温度为55℃,分两次烧结.首次煅烧温度为680℃,保温时间为18 h;第二次煅烧温度为850℃,保温时间为18 h.利用X射线衍射、扫描电子显微镜和电化学方法测试最终产物.测试结果表明：Al³⁺的掺入有效地改善了LiMn₂O₄的高温循环性能,使其高温循环容量衰减得到了有效的抑制,尤其当Al³⁺的掺入量为0.05时,有比其他掺杂量更优的性能.     

锂离子电池LiFePO4/聚并苯复合正极材料的合成与改性研究

通过固相法合成了LiFePO4 /聚并苯(PAS)复合材料.纯的LiFePO4电导率仅为(0.1～1)×10-9 S/cm,合成LiFePO4/PAs复合材料电导率为2.0 S/cm,复合材料的电导率提高了10个数量级.LiFePO4/PAS复合材料具有优异的电化学性能,在室温1C倍率下首次放电容量为140 mA·h/g,经过200次循环后容量仍保持最初容量的97.14%.说明通过包覆PAS材料极大地提高了LiFePO4的大电流充、放电容量和循环性能.     

BiFeO3掺杂Pb（In1/2Nb1/2）O3-Pb（Mg1/3Nb2/3）O3-PbTiO3陶瓷的制备与磁电性能研究

以固相合成法制备了铁酸铋（BiFeO₃,简称BFO）掺杂的铌铟酸铅-铌镁酸铅-钛酸铅（Pb（In_1/2Nb_1/2）O₃-Pb（Mg_1/3Nb_2/3）O₃-PbTiO₃,简称PIN-PMN-PT）多铁性陶瓷材料,X射线衍射（XRD）测试结果表明：样品具有钙钛矿结构,电滞回线显示其铁电性良好,剩余极化值（P_r）可达18 μC·cm^-2.由于BiFeO₃掺杂后,样品电矩减小,氧空位增多,使其铁电畴翻转困难,样品的电性能略有下降,但是其磁性能随BiFeO₃掺入量的增加而逐渐增强,且样品居里温度（T_m）为200℃左右.该材料在电磁学领域有望成为具有应用前景的多铁性材料.     

Synthesis of LiCo<Subscript>0.3</Subscript>Ni<Subscript>0.7</Subscript>O<Subscript>2</Subscript> as cathode materials for lithium ion batteries by citric acid-assisted sol-gel method

The synthesis process of LiCo0.3Ni0.7O2 was investigated by FT-IR, mass spectroscopy, elemental analysis, SEM, BET, TG/DTA and XRD in this paper. The results revealed that lithium and transition metal ions were trapped homogeneously on an atomic scale throughout the precursor. Li2CO3, NiO and CoO are the intermediate products obtained after decomposition of the precursor and Li2CO3 undergoes direct reactions with NiO and CoO to form LiCo0.3Ni0.7O2. Moreover, the kinetics of formation of LiCo0.3Ni0.7O2 by dtrate sol-gel method is faster than the case of the conventional solid-state reaction between lithium carbonate and corresponding reactants. The single phase of LiCo0.3Ni0.7O2 was synthesized at temperature as low as 550℃. The discharge capacity of LiCo0.3Ni0.7O2 increases from 127 to 185 mAh/g as the caldnation temperature increasing from 550 to 750℃. After 100 cycles, the discharge capacity of the sample calcined at 750℃ is 155 mAh/g. The electrochemical study shows that the LiCo0.3Ni0.7O2 has high discharge capacity and good cycling behavior for lithium ion batteries.     

Synthesis and Structure of Polypyrrole Derivatives／V2O5 Nanocomposites

Poly ( N, N, N-trimethyl ( 2-pyrrol-l-yl ) ethyl ammonium iodide )/V2O5 ( PTPAI/V2O5) nanocomposites were synthesized by sol-gel method. This method involved formation of vanadium pentoxide xerogel in the prcscnce of polypyrrole derivatives solution. X-ray diffraction(XRD) indicated that the polypyrrole derivative particles encapsulated in the fibrous V2O5 network and the layered distance significantly increased from 1. 077 39 to 1. 354 56 nm. The interaction between polypyrrole and V2O5 in the ‘nanocomposites‘ was characterized by IR spectroscopy. The Scanning Electron Microscope(SEM) micrographs reveal the structural contrasts between the hybrid materials and the pristine vanadium oxide xerogel.     

共沉淀法合成Ni_(1/3)Co_(1/3)Mn_(1/3)(OH)_2的热力学分析

对Me2+(Me=Ni,Co,Mn)-NH3-OH--H2O共沉淀反应体系进行了热力学分析,采用共沉淀法合成了LiNi1/3Co1/3Mn1/3O2正极材料前驱体Ni1/3Co1/3Mn1/3(OH)2,研究了pH值和氨水浓度[N]对前驱体振实密度的影响.热力学分析表明:以氢氧化钠为沉淀剂、氨水为络合剂,采用共沉淀法合成前驱体的最佳pH值为11,最佳[N]为0.1～0.5mol/L;在此条件下,金属阳离子Ni2+、Co2+和Mn2+的损失最小,分别小于1×10-3、1×10-3和1×10-6mol/L.在pH=11、[N]=0.24mol/L条件下,所合成的前驱体中Ni、Co、Mn的摩尔比为0.324∶0.349∶0.327,与理论设计值1∶1∶1非常接近,其振实密度高达1.32g/cm3.