LaF_3表面修饰Li[Li_(0.2)Mn_(0.54)Ni_(0.13)Co_(0.13)]O_2的制备及其电化学性能

分别以Na_2CO_3和NH_3·H_2O为沉淀剂和络合剂,用共沉淀法和950℃高温烧结制备Li[Li_(0.2)Mn_(0.54)Ni_(0.13)Co_(0.13)]O_2,并用湿化学法将LaF_3包覆在Li[Li_(0.2)Mn_(0.54)Ni_(0.13)Co_(0.13)]O_2正极材料表层。用XRD,SEM,TEM等手段表征了LaF_3包覆前后Li[Li_(0.2)Mn_(0.54)Ni_(0.13)Co_(0.13)]O_2颗粒的微观结构和表面形貌,用电化学测试仪检测样品的充放电性能。结果表明,包覆前后材料的结构没有变化,已经成功地将LaF_3包覆在Li[Li_(0.2)Mn_(0.54)Ni_(0.13)Co_(0.13)]O_2表面;LaF_3包覆使Li[Li_(0.2)Mn_(0.54)Ni_(0.13)Co_(0.13)]O_2的电化学综合性能明显提高。在5C高倍率下,LaF_3-Li[Li_(0.2)Mn_(0.54)Ni_(0.13)Co_(0.13)]O_2的放电比容量比原始Li[Li_(0.2)Mn_(0.54)Ni_(0.13)Co_(0.13)]O_2超过了20.3 mAh·g~(-1)。经过100次循环后LaF_3-Li[Li_(0.2)Mn_(0.54)Ni_(0.13)Co_(0.13)]O_2的容量保持率高达94.8%,循环稳定性更佳。这些结果表明,LaF_3包覆改性是提高Li[Li_(0.2)Mn_(0.54)Ni_(0.13)Co_(0.13)]O_2电化学性能切实可行的方法。     

微波烧结LiCo1/3Ni1/3Mn1/3O2电磁场与温度场的仿真模拟

分析了微波烧结的原理和特点,利用COMSOL Multi-physics模拟软件对矩形微波炉进行了仿真模拟,研究了微波烧结正极材料LiCo_(1/3)Ni_(1/3)Mn_(1/3)O_2时电磁场与温度场的分布,测量了粉末样品LiCo_(1/3)Ni_(1/3)Mn_(1/3)O_2的介电常数,并与模拟结果相对照.研究表明:微波在烧结LiCo_(1/3)Ni_(1/3)Mn_(1/3)O_2样品时,炉腔内电磁场的分布受到影响,微波炉内表面的电场强度减弱;材料内部温度场的分布不均匀,材料的下半部分温度较高;同时,在仿真模拟计算过程中,求得LiCo_(1/3)Ni_(1/3)Mn_(1/3)O_2在微波中烧结到不同温度时的能量损耗,根据李赫德涅凯法则计算出其对应的相对介电常数,发现在20~620℃,相对介电常数随温度的上升而变大.根据实验测得的复合介电常数,求出对应温度点LiCo_(1/3)Ni_(1/3)Mn_(1/3)O_2的相对介电常数.利用Origin对仿真模拟计算和实验求得的两组相对介电常数数据进行拟合对比,发现实验求得的LiCo_(1/3)Ni_(1/3)Mn_(1/3)O_2的相对介电常数与仿真模拟计算所得数据趋势吻合.     

Mn_3O_4-石墨烯气凝胶的高效制备及其储锂性能（英文）

以改进的Hummers法制备的Mn~(2+)/氧化石墨烯悬浊液为原料无需添加锰源,采用水热法得到Mn_3O_4含量可调的Mn_3O_4-石墨烯气凝胶(Mn_3O_4-GA)。得益于石墨烯气凝胶相互连通的三维导电网络以及Mn_3O_4纳米粒子和其间的强烈的耦合作用Mn_3O_4-GA表现出了比Mn_3O_4-石墨烯粉末复合物(Mn_3O_4-G)更加优异的储锂性能其中Mn_3O_4-GA-70(Mn_3O_4含量为70%)在100 mA·g~(-1)的电流密度下其可逆比容量达到1073 mA·h·g~(-1),在800 mA·g~(-1)的电流密度下循环200次后其比容量为565 mA·h·g~(-1),保持率为85%。该方法为环境友好制备锰基石墨烯气凝胶提供新思路。     

尿素改性对钠离子电池负极材料NaTi_2(PO_4)_3电化学性能的影响

为提高水溶液钠离子电池负极材料NaTi_2(PO_4)_3(NTP)的导电性和倍率性能,以尿素(CO(NH_2)_2)为碳源采用溶剂热法合成了CO(NH_2)_2/NaTi_2(PO_4)_3(C/NTP)复合负极材料。采用XRD、SEM、TEM、Raman和恒流充放电等手段分析了材料的结构、C/NTP形貌和电化学性能。研究了不同阶段升温速率对C含量、包覆层石墨化程度及对电化学性能的影响。实验结果表明,低于400℃升温速率越小,C/NTP残碳量越高;400~650℃之间升温速率越小,包覆层石墨化程度越高,并提高了其电化学性能;在5C倍率下2℃/min热处理的样品首圈放电比容量为114.9mAh·g~(-1),循环30次后容量保持在91.9mAh·g~(-1);10C下放电比容量为87mAh·g~(-1),20C下放电比容量仍保持在71mAh·g~(-1),展现出高倍率下优异的循环性能。     

氟掺杂改善Li1.2Mn0.56Ni0.16Co0.08O2富锂锰基层状氧化物正极材料的长循环稳定性

针对富锂锰基层状材料xLi_2MnO_3·(1-x)LiMO_2(M为Mn、Co、Ni)存在着充放电循环性能差的缺点,采用溶胶-凝胶法制备氟掺杂Li_(1.2)Mn_(0.56)Ni_(0.16)Co_(0.08)O_(2-x)F_x正极材料,以提高这种材料的长循环充放电性能。研究结果表明,氟掺杂材料的晶体结构与未掺杂材料相似,但氟掺杂明显改善了充放电长循环性能的稳定性。在125 mA/g电流密度下电池循环500次,掺杂5%F的Li_(1.2)Mn_(0.56)Ni_(0.16)Co_(0.08)O_(1.95)F_(0.05)材料比容量保持率为79.2%,并且极大地抑制了放电平台电位的衰减,而未掺杂的Li_(1.2)Mn_(0.56)Ni_(0.16)Co_(0.08)O_2材料的比容量保持率仅为16%,其放电电位平台已经消失。这些结果表明氟掺杂能有效地抑制富锂锰基层状结构正极材料充放电过程中比容量和放电平台的衰减。     

锂离子电池正极材料球形LiNi0.7Co0.15Mn0.15O2的制备和性能

采用化学共沉淀法制备球形前驱体Ni_(0.7)Co_(0.15)Mn_(0.15)(OH)_2,将其与LiOH·H_2O充分混合后高温烧结制备出锂离子电池正极材料球形LiNi_(0.7)Co_(0.15)Mn_(0.15)O_2,用X射线衍射(XRD)、扫描电镜(SEM)、热重-差热分析(TG/DSC)以及恒电流充放电测试对样品进行表征,研究了烧结温度对产物的形貌和电化学性能的影响。结果表明,在750℃合成的LiNi_(0.7)Co_(0.15)Mn_(0.15)O_2物相单一无杂相,具有标准的α-NaFeO_2晶型,为层状嵌锂复合氧化物。SEM测试显示,产物为球形且球形度较好,颗粒粒度均一,分布较窄,平均粒径在10μm左右。在3.0-4.3 V、0.2C充放电条件下,25℃其初始放电容量高达185.2 mA·h/g,30轮循环后容量保持率达到98.32%。可见球形LiNi_(0.7)Co_(0.15)Mn_(0.15)O_2显示了较高的首轮放电容量以及良好的循环性能,表现出较好的电化学性能。     

PVDF-HFP基凝胶电解质用于LiNi0.5Co0.2Mn0.3O2三元正极锂离子电池

以聚偏氟乙烯-六氟丙烯(Poly(vinylidene fluoride-hexafluoropropylene),PVDF-HFP)为聚合物基体,新戊二醇二丙烯酸酯(Neopentyl glycol diacrylate,NPGDA)为交联剂,在引发剂偶氮二异丁腈(2,2′-Azobis(2-methylpropionitrile),AIBN)的作用下通过室温现场聚合法制备凝胶电解质用于锂离子电池。探索不同质量比PVDF-HFP/NPGDA对凝胶电解质性能和LiNi_(0.5)-Co_(0.2)Mn_(0.3)O_2三元正极锂离子电池性能的影响。结果表明,当质量比为1∶1时,凝胶电解质具有较高的离子电导率,为8.45mS·cm~(-1),锂离子迁移数为0.78,电化学窗口为4.5V。在电流密度30mA·g~(-1)恒流充放电,首次放电比容量为143mAh·g~(-1),循环50次后仍高达135.3mAh·g~(-1)。电流密度为300mA·g~(-1)时,放电比容量为100.2mAh·g~(-1)。     

Mn_2O_3/Fe_2O_3/少层石墨烯/硫锂硫电池正极材料的制备及其电化学性能

采用熔盐法、层间催化剥离法、退火工艺及熔化扩散法制备出Mn_2O_3/Fe_2O_3/少层石墨烯/硫复合材料作为锂硫电池正极材料。高导电少层石墨烯构成三维导电网络,为电极反应过程中电子传输提供通道,有利于提升锂硫电池的比容量。金属氧化物颗粒均匀分布在少层石墨烯表面,对多硫化物具有强烈化学吸附作用,能够有效抑制多硫化物的溶解和迁移效应,有利于增强锂硫电池循环稳定性。结果表明,Mn_2O_3/Fe_2O_3/FLG30/S电极显示出高比容量和优异的循环性能。0.1 C倍率下,其初始容量高达886.3 mAh·g~(-1),100圈循环后容量保持率高达88.1%。     

锂离子在正极材料LiNi1/3Co1/3Mn1/3O2中扩散系数的测定

对改进固相反应法合成的锂离子电池层状正极材料LiNi1/3Co1/3Mn1/3O2,利用XRD,SEM对粉体进行了物相结构和形态表征.当电池充放电时,设定电流密度为120mA/g,电压在2.75～4.5V区间,20次循环后放电比容量为164.5mAh/g.在开路电压到4.5V作为材料的锂离子扩散系数测试电压区间进行CITT循环测试,测定了材料在不同电压,不同循环下的扩散系数,测得扩散系数在10-11～10-12 cm2/s范围内;当电压E=4.3V时扩散系数达到最大值2.8×10-11 cm2/s,随着充放电循环的进行,Li+固相扩散系数先增大后减小.     

Na3V2(PO4)3/CN/Rgo复合正极材料的构筑及储钠性能研究

Na3 V2(PO4)3具有理论容量高、钠离子超导体(NASlCON)结构等优势,被认为是一种值得研究和大规模应用的新型钠离子电池正极材料.然而低的电导率导致其电化学性能在大电流充放电条件下不理想.本实验采用固相法制备了一种由氮掺杂碳与还原氧化石墨烯(rGO)共修饰的Na3V2(PO4)3/CN/rGO(NVP/CN/rGO)复合正极材料,并借助材料表征手段、电化学分析技术等对不同含量rGO掺入的NVP/CN/rGO正极材料的微观形貌和电化学性能进行了系统研究.结果显示,NVP/CN/rGO-2复合材料颗粒分布均匀,并表现出较高的可逆容量和优越的循环稳定性.在0.2 C、10 C下可逆容量分别为116.9 mAh·g-1和99.4 mAh·g-1,且在10 C下循环1500次后,容量保持率为97.2％.复合材料表现优异性能的主要原因是:rGO特殊的导电网络结构将孤立的NVP/CN连接起来,提升了颗粒之间的接触电导,使其导电性进一步提高,从而显著提升其电化学性能.     

Influence of Layer-Thickness Ratio on Magnetic Properties in F-La2/3Ca1/3MnO3/AF-La1/3Ca2/3MnO3 Bilayers

Magnetic properties were investigated in ferromagnetic/antiferromagnetic bilayers based on a Ca-doped lanthanum manganite system via hysteretic loops, La_1?x Ca _x MnO₃ grown in?situ on (001) oriented SrTiO₃ crystalline substrates by using a dc sputtering technique at high-pressure (3.5?mbar) pure oxygen as sputter gas and at a substrate temperature of 850?^°C. We grew the antiferromagnetic layer La_1/3Ca_2/3MnO₃ (AF-LCMO) with a given thickness, t _AF, and the ferromagnetic layer La_2/3Ca_1/3MnO₃ (F-LCMO) with a given thickness, t _F. We produced two series of samples: the first one with thickness ratio, t _F/t _AF, of 1/6 and 6/1, maintaining constant the total thickness of the bilayer to 70?nm, and the second one with t _F/t _AF of 3/25, 9/25, 15/25, maintaining constant the antiferromagnetic thickness to 25?nm. Magnetization versus applied field loop was strongly dependent on the t _F/t _AF ratio, which was influenced by both the strains presented in very thin films originated during the growth of the bilayer and the magnetic moment interaction at the ferromagnetic/antiferromagnetic interface due to changes of the electronic structure in this strongly correlated system.     

Structural order in Ba(Zn1/3Ta2/3)O3, Ba(Zn1/3Nb2/3)O3 and Ba(Mg1/3Ta2/3)O3 microwave dielectric ceramics

The process and nature of structural ordering and the factors that influence them have been investigated in the microwave dielectric perovskites, barium zinc tantalate (BZT), barium zinc niobate (BZN), and barium magnesium tantalate (BMT), sintered at various temperatures. The samples were characterized mainly by X-ray powder diffraction and transmission electron microscopy. The results show that short-range 1 : 1 B-site order features strongly in the early stages of ordering in BZT and BZN, but it is extremely rare in BMT, for which most grains commence with 1 : 2 order. As sintering progresses, 1 : 1 order is replaced by 1 : 2 long-range order in BZT and by disorder in BZN. Orientational variants of the ordered domains within grains occur in similar numbers when order is fine-scale, but their distribution is less homogeneous in well-ordered samples. Local inhomogeneities in the degree of order within grains, which will affect dielectric properties, correlate with both residual non-stoichiometry and the presence of dislocations. Incompletely reacted starting materials which may persist to late stages of sintering can also strongly influence order. Anomalously large ordered domains at grain boundaries are attributed to grain-boundary migration accompanied by enhanced diffusion. The results indicate that with starting materials that are well-mixed and homogeneous at the nanoscale, tailoring of physical properties should be possible by controlling the type and degree of order through chemical composition. This revised version was published online in November 2006 with corrections to the Cover Date.     

Creep behaviour of Si3N4/Y2O3/Al2O3/AIN alloys

The compression creep behaviour of pressureless sintered Y₂O₃/Al₂O₃/AIN-doped Si₃N₄ was studied between 1473 and 1673 K, under stresses ranging from 100–300 MPa. Strain rate versus stress and temperature analysis give a stress exponent n1 and an activation energy Q=860 kJ mol^–1. Microstructural change was investigated by transmission electron microscopy. The observed strain whorls, the stress exponent and the activation energy are indicative of a solution-diffusion-precipitation accommodated grain-boundary sliding where the diffusion through the glass is rate controlling.     

双掺杂稀土锰氧化物La2/3(Ca1/3Sr2/3)1/3MnO3薄膜的输运特性

采用射频磁控溅射法制备了Ca、Sr双掺杂La2/3(Ca1/3Sr2/3)1/3MnO3(LCSMO)薄膜。电阻率-温度特性表明,薄膜在387K时发生铁磁金属相-顺磁非导体相相变。同时测试了薄膜在180,230和280K温度下的伏安特性．表明所制备的薄膜具有自阻效应,并分析了产生该现象的原因。     

Dielectric Relaxation and Conductivity of Ba(Mg1/3Ta2/3)O3and Ba(Zn1/3Ta2/3)O3

The frequency dependent dielectric properties of barium magnesium tantalate(BMT),Ba(Mg_(1/3)Ta(2/3))O_3 and barium zinc tantalate(BZT),Ba(Zn_(1/3)Ta_(2/3))O_3 synthesized by solid state reaction technique have been investigated at various temperatures by impedance spectroscopy.BMT and BZT possess cubic structure with lattice parameter a = 0.708 and 0.451 nm,respectively.The resonance peaks due to dielectric relaxation processes are observed in the loss tangent of these oxides.The relaxation in the samples is polydispersive in nature.The temperature dependence of dc conductivity,the most probable relaxation frequency(ω_m) obtained from tanδ vs logw plots and ω_m obtained from imaginary parts of the complex electrical modulus vs logw plots follow the Arrhenius behavior.According to these Arrhenius plots the activation energies of BMT and BZT are about 0.54 and 0.40 eV,respectively.Thus the results indicate that samples are semiconducting in nature.The frequency-dependent electrical data are analyzed in the framework of conductivity and electric modulus formalisms.Both these formalisms show qualitative similarities in relaxation time.Our study points that for complex perovskite oxides with general formula A(B'B")O_3,the dielectric properties significantly depend on the atomic radii of both A and B type cations.BMT and BZT exhibit enhancement in dielectric property compared to their niobate counterparts.They may find several technological applications such as in capacitors,resonators and filters owing to their high dielectric constant and low loss tangent.     

Optical properties of the Al2O3/SiO2 and Al2O3/HfO2/SiO2 antireflective coatings

Investigations of bilayer and trilayer Al₂O₃/SiO₂ and Al₂O₃/HfO₂/SiO₂ antireflective coatings are presented in this paper. The oxide films were deposited on a heated quartz glass by e-gun evaporation in a vacuum of 5 × 10^?3 [Pa] in the presence of oxygen. Depositions were performed at three different temperatures of the substrates: 100 °C, 200 °C and 300 °C. The coatings were deposited onto optical quartz glass (Corning HPFS). The thickness and deposition rate were controlled with Inficon XTC/2 thickness measuring system. Deposition rate was equal to 0.6 nm/s for Al₂O₃, 0.6 nm ? 0.8 nm/s for HfO₂ and 0.6 nm/s for SiO₂. Simulations leading to optimization of the thin film thickness and the experimental results of optical measurements, which were carried out during and after the deposition process, have been presented. The optical thickness values, obtained from the measurements performed during the deposition process were as follows: 78 nm/78 nm for Al₂O₃/SiO₂ and 78 nm/156 nm/78 nm for Al₂O₃/HfO₂/SiO₂. The results were then checked by ellipsometric technique. Reflectance of the films depended on the substrate temperature during the deposition process. Starting from 240 nm to the beginning of visible region, the average reflectance of the trilayer system was below 1 % and for the bilayer, minima of the reflectance were equal to 1.6 %, 1.15 % and 0.8 % for deposition temperatures of 100 °C, 200 °C and 300 °C, respectively.     

Phase developments in the Pb(Zn1/2W1/2)O3-Pb(Zn1/3Ta2/3)O3-Pb(Zn1/3Nb2/3)O3 pseudo-ternary system

The phase stability ranges in the B-site precursor (Zn_1/2W_1/2)O₂-(Zn_1/3Ta_2/3)O₂-(Zn_1/3Nb_2/3)O₂ were determined by X-ray diffraction (XRD), where wolframite, tri-αPbO₂, and columbite phases were identified. Next attempts were carried out (with the addition of PbO) for the system Pb(Zn_1/2W_1/2)O₃-Pb(Zn_1/3Ta_2/3)O₃-Pb(Zn_1/3Nb_2/3)O₃, where the perovskite phase did not develop in the entire compositions investigated. Instead, only the Pb₂WO₅ and pyrochlore phases (along with ZnO) resulted.     

MgO-Al2O3-SiO2-TiO2-Y2O3玻璃的弹性模量

根据硬盘基板用材料的要求，制备了MgO-Al2O3-SiO2-TiO2-Y2O3高弹性模量玻璃（120GPa)，玻璃的弹性模量随组成的变化服从Makishima-Mackenzie理论，MgO,Al2O3,TiO2,Y2O3等具有较高单位体积离解能的氧化物有利于提高玻璃的弹性模量，但玻璃弹性模量的理论计算值低于测试值，这是因为Makishima-Mackenzie理论没有考虑玻璃内阳离子的具体配位，对MgO,Y2O3堆积密度因子的堆导存在误差，因此利用Makishima-Mackenzie理论发展高弹性模量玻璃时应对MgO,Y2O3等氧化物的计算进行修正。     

Dielectric properties of low-fitting Pb(Mg1/3Nb2/3)1−xTixO3-Bi2O3/Li2O ceramics

Dielectric properties of low-firing Pb(Mg_1/3Nb_2/3)_1–x Ti _x O₃-Bi₂O₃/Li₂O ceramics are studied in this work. With the addition of Bi₂O₃/Li₂O eutectic composition, the sintering temperature of PMN_1–x PT _x could be lowered to 900° C. Relaxor behaviour of PMN_1–x PT _x is enhanced by the incorporation of Bi₂O₃/Li₂O due to the substitution of Bi⁺³/Li⁺ into the PMN_1–x PT _x framework. Bi₂O₃/Li₂O eutectic composition is used as a fluxing agent, Curie shifter and depressor. Evaporation of Bi₂O₃/Li₂O and PbO during firing is checked and examined via energy dispersive spectrometry (EDS) and X-ray diffraction (XRD) is used to clarify the Curie shifting and depressing effect of Bi₂O₃/Li₂O.