尖晶石LiMn2O4及其衍生物的电化学阻抗特性

尖晶石LiMn2O4(以下简称LMO)是锂离子电池正极材料之一，具有价格低廉，资源丰富的特点。锂离子电池的充放电过程实际上是锂离子从正极脱嵌、再嵌入正极的过程。因此Li^ 在正负极材料及电解液中的扩散性能影响着电池的电性能，通过其电化学阻抗谱可得出锂离子的扩散系数及电导率等参数。     

Mg~(2+)掺杂锰酸锂的第一性原理研究

利用基于密度泛函理论的第一性原理平面波超软赝势法对Mg~(2+)掺杂锰酸锂的晶格常数与能带结构、态密度、键布居进行计算和分析,计算结果表明:掺杂Mg~(2+)后将会促使Mn、 O原子的电荷重新分布且其相互作用加强,能带带隙减小,费米能级附近的带数增加,费米能由-1.29 eV增加到-1.02 eV, Mn、 O、 Mg在总态密度中贡献比较大,锂离子贡献比较小且峰型尖锐局域化严重,提高了Li~+的扩散效率, Mn—O键变短,共价性增强,形成的共价键较稳定,其相互作用形成的骨架较稳定不易坍塌.从而提高了材料的循环充放电性能和电池使用寿命.     

Si基AAO模板法制备尖晶石型ZnAl2O4纳米结构

以Si基AAO为模板,以Zn和C粉作蒸发源,通过化学气相沉积法,在不同的温度下反应得到了不同的ZnAl2O4纳米结构.对样品的形貌和成分结构进行了分析.扫描电镜结果显示,在800℃获得的ZnAl2O4样品表面仍保留着AAO模板的孔洞结构.而XRD结果表明,在700,800,900℃下获得的样品都出现了ZnAl2O4衍射...     

Mg2+、Zn2+掺杂CaWO4∶Eu3+荧光粉的发光性质

采用微波加热固相法合成了Mg2+、Zn2+掺杂CaWO4∶Eu3+荧光粉。利用XRD对样品的晶体结构进行表征,通过荧光分光光度仪对样品的激发光谱、发射光谱和能级寿命进行检测和分析。结果表明,Mg2+、Zn2+、Eu3+掺杂CaWO4不影响CaWO4基质的四方晶相。395nm激发下,与CaWO4∶2%Eu3+样品比较,分别掺杂0.5%的Mg2+或Zn2+的样品发光强度提高了1.3倍和2.1倍;与3%Mg2+或3%Zn2+掺杂CaWO4∶2%Eu3粉体发光比较,当Eu3+浓度增加为3%时,粉体的发光强度分别提高了7.3倍和14.8倍;与CaWO4∶3%Eu3+样品比较,3%的Mg2+或Zn2+掺杂后的样品光强分别提高了1.2倍和1.3倍。262nm比395nm激发同一样品的Eu3+的5D0能级寿命有所增加。与单掺2%Eu3+样品比较,随着Mg2+或Zn2+掺杂浓度增加,样品荧光寿命先增加后减小。同样激发波长下,与Mg2+或Zn2+掺杂CaWO4∶2%Eu3+样品荧光寿命相比,Eu3+浓度增加为3%时,样品的荧光寿命明显变短。     

Zn2+掺杂对GdTaO4:Eu3+荧光粉结构和发光性能的影响

采用高温固相反应法制备了掺杂不同浓度Zn2 的GdTaO4:Eu0.1荧光粉,研究了Zn2 掺杂对GdTaO4:Eu3 的结晶性能,晶粒形貌和光致发光特性的影响.以X射线衍射(XRD)、扫描电子显微镜(SEM)、激发-发射谱、衰减时间谱等方法对其性能进行了表征.结果表明,Zn2 掺杂可显著提高GdTaO4:Eu3 的光致发光强度,当掺杂浓度x=0.01时,光强被提高至2.7倍,可归因于的Zn2 进入了GdTaO4:Eu3 基质晶格,产生了一定浓度的氧空位以达到电荷平衡,并导致发光中心Eu3 的晶格场发生畸变;当x=0.13时,光强提高至3.2倍,且其衰减时间被缩短至40%,可归因于Zn2 的助熔剂效果;但当x＞0.13时,ZnO和GdTa7O19杂相的出现将导致发光强度减弱和衰减时间延长.另外,初步探索表明,Li2CO3和.KCl的共掺杂能进一步提高G.dTaO4:Eu0.1,Zn0.13的发光强度.     

SrAl2O4:Eu,Dy发光材料的制备及其特性研究

采用高温固相合成法制得了SrAl2O4:Eu^2 ,Dy^3 发光材料。该磷光体的合成温度在1300－1500℃范围。X－射线衍射分析（XRD）结果表明该磷光体为SrAl2O4晶体结构，属单斜晶系。其晶格常数为：α=8．4424A，b=8.822A,c=5.1607A,β＝93.415。SrAl2O4:Eu^2 ,Dy^3 发光材料的激发光谱和发射光谱均为宽带谱，激发谱峰位在300－450nm范围内，发射波长在520nm附近。这一结果表明该材料的发光是由Eu^2 的5d→4f宽带跃迁产生的。不同的制备条件，如烧成温度、保温时间等对发光材料的显微结构及其发光性能有较大的影响。     

同步辐射XAFS研究高比能LiMn2O4材料的局域结构

用EXAFS和XANES技术研究了高温固相反应法合成尖晶石结构的LiMn2O4中Mn原子的局域结构受到焙烧温度的影响.XANES结果表明,B1峰和B2峰强度分别与Mn3+,Mn4+的含量高低相关,焙烧温度愈高,B1峰的强度愈大.EXAFS给出的结构参数结果进一步表明,LiMn2O4(673K)的Mn-O第一配位和MnMn第二配位的无序度σ1(0.0059nm)和σ2(0.0092nm)分别小于及大于LiMn2O4(973K)的σ1(0.0066nm)和σ2(0.0081nm),LiMn2O4(1073K) 关键词： XAFS 局域结构 尖晶石LiMn2O4     

Cu2+掺杂ZnAl2 O4纳米颗粒的光学性能

采用水热法和热处理技术制备了不同掺杂比例的Zn_(1-x)Cu_xAl_2O_4(x=0,0.05,0.10,0.15,0.20)纳米颗粒,通过X射线衍射(XRD)、场发射透射电子显微镜(FETEM)、傅里叶红外光谱(FT-IR)、X射线光电子能谱(XPS)、光致发光光谱(PL)和紫外可见光谱(UV-Vis)对样品的晶体结构、形貌、元素分布、结合能和光学性能进行表征,并通过第一性原理计算得到了ZnAl_2O_4结构中存在的各种缺陷的能带结构。实验结果表明本方法制备的Zn_(1-x)Cu_xAl_2O_4纳米颗粒为尖晶石结构,XPS能谱说明Zn_(0.9)Cu_(0.10)Al_2O_4样品中Cu~(2+)全部占据了四面体位置,PL光谱显示Cu~(2+)掺杂的样品出现了猝灭现象,紫外光谱表明Cu~(2+)掺杂后样品出现了新的吸收峰。并结合第一性原理计算对样品的光学性质给出了合理解释。     

锂离子电池LiMn1-xFexPO4(0<x<1)正极材料的制备及性能研究

本文采用固相法制备了纯相LiMn_1-xFe_xPO₄/C (x=0.2,0.4,0.6)正极材料,并用X射线衍射(XRD)和扫描电镜(SEM)进行表征,用高精度电池测试系统进行充放电和循环伏安测试.结果表明不同Mn和Fe原子比的电极材料具有很大的性能差异,其中当x=0.4时,材料具有优异的循环稳定性和较高的可逆容量.首次充电容量和放电容量分别达到141.5 mAh/g和125.7 mAh 关键词： 锂离子电池 固相法 1-xFe_xPO₄')" href="#">LiMn_1-xFe_xPO₄ 正极材料     

CeO_2掺杂MgB_2超导材料的特性研究

以Mg粉、B粉、Ce O2粉末为原料,用真空固相反应法制备了系列按1Mg B2+x Ce O2摩尔量比Ce O2掺杂的样品,其中x=0,0.03,0.06,0.09,0.13,0.135,0.14。通过X-射线和扫描电子显微镜,分析了样品的成相和织构。除Mg B2和少量Mg O相外,在Ce O2掺杂的样品中还检测到了Ce B6和少量残留的Ce O2相。XRD的计算表明,随着Ce O2掺杂量的增加,Mg B2的平均晶粒尺寸受到了明显的压制,且Ce B6相含量增加。电阻-温度特性测量表明,掺杂量在x=0.06以内时,Mg B2的超导电输运特性无明显影响,正常态电阻率低,超导转变温度(Tc)超过38K,转变宽度($Tc)小于1K;掺杂量大于0.09以后,观察到正常态电阻率升高,超导电性快速退化;超过0.14后,尽管存在电阻转变,但在测量温度范围内已观测不到零电阻效应。实验除展示Ce O2掺杂抑制Mg B2的成相和晶粒生长外,同时表明晶粒尺度的大小和分布对Mg B2的超导特性影响显著。     

A Facile Method for Synthesis of Porous NiCo2O4 Nanorods as a High‐Performance Anode Material for Li‐Ion Batteries

Porous electrode materials with large specific surface area, relatively short diffusion path, and higher electrical conductivity, which display both better rate capabilities and good cycle lives, have huge benefits for practical applications in lithium‐ion batteries. Here, uniform porous NiCo₂O₄ nanorods (PNNs) with pore‐size distribution in the range of 10–30 nm and lengths of up to several micrometers are synthesized through a convenient oxalate co‐precipitation method followed by a calcining process. The PNN electrode exhibits high reversible capacity and outstanding cycling stability (after 150 cycles still maintain about 650 mA h g^?1 at a current density of 100 mA g^?1), as well as high Coulombic efficiency (>98%). Moreover, the PNNs also exhibit an excellent rate performance, and deliver a stable reversible specific capacity of 450 mA h g^?1 even at 2000 mA g^?1. These results demonstrate that the PNNs are promising anode materials for high‐performance Li‐ion batteries.     

金属氧化物包覆LiMn_2O_4的红外光谱及光电子能谱研究

本文采用溶液化学的方法,在锂离子电池正极材料LiMn2O4上包覆一层金属氢氧化物前驱体,再通过热处理得到稳定的金属氧化物包覆层。傅立叶红外光谱(FIIR)的研究表明,当包覆LiMn2O4中外来金属原子的实际百分比小于1.11%时,不能探测到包覆层红外信号。X射线光电子能谱(XPS)的研究表明,表面包覆层中Al或Mg的存在不仅削弱Mn-O键的作用,而且给体系引入过多的正电荷,导致Mn(2p)结合能的降低。包覆层中的Al2O3和MgO均在加热过程中向LiMn2O4体相中扩散;而包覆层中的SnO2在焙烧后并未进入LiMn2O4晶格内,而是附着于其表面。     

Eu2+掺杂Sr2SiO4长余辉材料的热释光研究

采用高温固相法在弱还原的气氛下合成了Sr2SiO4高亮度的黄色长余辉材料.通过X射线衍射(XRD)分析发现所制得的样品属于α'-Sr2 SiO4斜方品系结构;样品的光致发光特性表明,在320 nm激发光的照射下,出现峰位为490 nm的宽带发射峰.样品余辉特性显示:样品的余辉衰减曲线符合双指数衰减.在温度293～598...     

Carbon‐Coated Supraballs of Randomly Packed LiFePO4 Nanoplates for High Rate and Stable Cycling of Li‐Ion Batteries

One of the key strategies used to obtain high‐rate Li‐ion battery is the reduction of the Li‐ion path length inside the active materials and the enhancement of the ionic diffusion outside the active materials. It is demonstrated that electrochemical performance can be improved significantly at high C‐rates using carbon‐coated spherical aggregates or “supraballs” of randomly packed olivine LiFePO₄ (LFP) nanoplates as cathode active materials. 258 nm LFP nanoplates with 30 nm thickness are synthesized through a high‐temperature solvothermal method, in which short lithium‐ion channels are formed perpendicular to the top or bottom planes. These thin nanoplates are formed into carbon‐coated “supraballs” through a spray‐drying and thermal annealing process, in which nanoplates are not stacked but randomly packed due to relatively fast drying. Internal and external nanoplate ion diffusion is therefore enhanced simultaneously due to the optimal molecular crystalline structure and interparticle pore structures of the nanoplates. Indeed, the initial capacity of the carbon‐coated supraballs is 162 mAh g^?1 (173.34 mAh cm^?3) at 0.1 C and more than 80% is retained (≈130.91 mAh g^?1) at 50 C. Furthermore, they offer durable cycling stability (>500 cycles) at 1 C without compromising their capacity.     

CaAl2O4:Eu2+,Nd3+纳米粉体的合成与发光性质

采用溶胶-凝胶法制备了CaAlO4：Eu^2＋,Nd^3＋纳米粉体发光材料。利用DTA,TG,XRD,SEM,光谱分析等手段对样品进行了结构和性能分析。实验结果表明,800℃烧结的样品形成已CaAl2O4晶相,样品平均晶粒尺寸为20～40nm,与CaAlO4：Eu^2＋,Nd^3＋粗晶材料相比,样品的发光光谱发生了“蓝移”,热释光峰值向高温移动了96℃,且曲线形状变宽,发光衰减是由初始的快衰减和随后的慢衰减构成,发光余辉时间5h。     

Co3O4 Hollow Nanoparticles and Co Organic Complexes Highly Dispersed on N‐Doped Graphene: An Efficient Cathode Catalyst for Li‐O2 Batteries

Rechargeable Li‐O₂ batteries are promising candidates for electric vehicles due to their high energy density. However, the current development of Li‐O₂ batteries demands highly efficient air cathode catalysts for high capacity, good rate capability, and long cycle life. In this work, a hydrothermal‐calcination method is presented to prepare a composite of Co₃O₄ hollow nanoparticles and Co organic complexes highly dispersed on N‐doped graphene (Co–NG), which acts as a bifunctional air cathode catalyst to optimize the electrochemical performances of Li‐O₂ batteries. Co–NG exhibits an outstanding initial discharge capacity up to 19 133 mAh g^?1 at a current density of 200 mA g^?1. In addition, the batteries could sustain 71 cycles at a cutoff capacity of 1000 mAh g^?1 with low overpotentials at the current density of 200 mA g^?1. Co–NG composites are attractive as air cathode catalysts for rechargeable Li‐O₂ batteries.     

A High‐Performance Anode Material for Li‐Ion Batteries Based on a Vertically Aligned CNTs/NiCo2O4 Core/Shell Structure

3D vertically aligned carbon nanotubes (CNTs)/NiCo₂O₄ core/shell structures are successfully synthesized as binder‐free anode materials for Li‐ion batteries (LIBs) via a facile electrochemical deposition method followed by subsequent annealing in air. The vertically aligned CNTs/NiCo₂O₄ core/shell structures are used as binder‐free anode materials for LIBs and exhibit high and stable reversible capacity (1147.6 mAhg^?1 at 100 mAg^?1), excellent rate capability (712.9 mAh g^?1 at 1000 mAg^?1), and good cycle stability (no capacity fading over 200 cycles). The improved performance of these LIBs is attributed to the unique 3D vertically aligned CNTs/NiCo₂O₄ core/shell structures, which support high electron conductivity, fast ion/electron transport in the electrode and at the electrolyte/electrode interface, and accommodate the volume change during cycling. Furthermore, the synthetic strategy presented can be easily extended to fabricate other metal oxides with a controlled core/shell structure, which may be a promising electrode material for high‐performance LIBs.     

Electrochemical activities of yttrium doped spinel LiMn2O4

It was found for the first time that the catalysis of yttrium doping of spinel LiMn₂O₄ can enhance the electrochemical activities of manganese, leading to both improvement of electrochemical capacity and reactivity with the electrolyte of manganese. A proper amount of doping was 0.5%, and such yttrium-doped sample, Li(Y_0.005Mn_0.995)₂O₄, had an initial capacity of 130 mAh g⁻¹ over that of the undoped one with the capacity retention to reach 92.3% exceeding that of the undoped one at 100th cycle.     

水热法制备的Li4-3xEux(MoO4)2微晶及其发光性能

采用水热法制备了Li_4-3xEu_{x(MoO4)2系列红色荧光粉.通过X射线衍射(XRD)、扫描电镜(SEM )和荧光分析(FL)对产物的微结构、形貌和发光性能进行表征分析.XRD分析表明,制备的Li4-3xEux(MoO4)2微晶均为白钨矿四方结构.SEM结果显示:随着x的增大,Li4-3xEux(MoO4)2微晶的晶粒尺寸相应减小,在0.2~0.5 μm之间变化.荧光分析结果表明:源于Eu³⁺的⁵D0→⁷F2和⁵D0→⁷F1电荷转移的592 nm和614 nm的特征发射峰显现明显,后者的发射强度远远大于前者.随着x的增大,样品中Eu³⁺的两个特征发射峰的强度先增大后减小,在x=1.0时达到最大.}