Sn3InSb4合金嵌Li性能的第一性原理研究

采用第一性原理超软赝势平面波方法计算了Sn₃InSb₄的嵌Li性能,得到各种嵌Li相的嵌Li形成能、理论质量比容量、体积膨胀率、能带结构、态密度和差分电荷密度等.从能量角度分析,Li在嵌入时,优先占据晶胞的四面体间隙位置,然后逐步挤出处于节点位置的Sn原子和In原子.在嵌Li过程中,材料表现出较大的体积膨胀率(11.74%-43.40%),这是导致Sn₃InSb₄作为Li离子电极材料循环性能差的重要原因.态密度计算表明,体系的导电性能首先随嵌Li量的增加而增加,当所有的间隙位置被Li填满,发生Sn的替换反应时,富Li态合金相的导电性反而下降.     

Effects of Single Vacancy on Electronic and Optical Properties for γ-Si3N4

基于密度泛函理论的广义梯度近似方法研究了中性单点缺陷γ-Si₃N₄的能量、电子结构和光学性质. N缺陷的结合能和形成能比Si(8)和Si(4)位的都低,显示γ-Si₃N₄中N缺陷更易形成. 分析了各种缺陷情况下相应的态密度. Si缺陷能形成p型半导体,N缺陷使材料形成间接带隙的n型半导体. Si缺陷情况下,物质有相对大的静态介电常数,在可见光区和红外区,吸收和反射得到显著改善,但是N缺陷却没什么影响.     

钙钛矿晶体的电荷复合动力学研究

本文利用紫外吸收光谱和稳态荧光光谱技术结合理论模型,研究了钙钛矿材料CH₃NH₃PbI₃晶体在光激发过程中的电荷复合动力学行为,进而获得晶体的扩散长度. 电荷载体的扩散长度是判断光电材料的重要参数. 研究通过合成两种不同缺陷态浓度的CH₃NH₃PbI₃晶体,测量这两种晶体在0.019∽4.268 μJ/cm²的激光激发下的时间分辨荧光光谱,利用动力学模型对光谱进行拟合,可以获得每个晶体的掺杂浓度,空穴浓度以及电荷复合参数. 将这些参数结合已有公式,最终可获得每个晶体的电荷载体的扩散长度.     

Mn掺杂LiFePO4的第一性原理研究

采用基于密度泛函理论的第一性原理方法, 计算了不同Mn掺杂浓度LiFe_1-xMn_xPO₄ (x=0,0.25,0.50,0.75) 的电子结构. 同时采用流变相辅助高温固相碳热还原法制备了LiFe_1-xMn_xPO₄ (x= 0,0.25,0.50,0.75) 材料. 理论计算表明: LiFePO₄具有E_g = 0.725 eV的带隙宽度, 为半导体材料. 通过Fe位掺杂25%的Mn离子可最大程度地 减小材料带隙宽度、降低Fe---O键及Li---O键键能, 进而提高材料的电子电导率及锂离子扩散速率. 实验结果亦表明, 当Mn掺杂量x=0.25时, 材料具有最优的电化学性能, 其具有约为158 mAh· g^-1的放电比容量以及551 Wh· kg^-1的能量密度. 理论计算与实验结果非常符合.     

电脉冲对多晶La0.7Ca0.3MnO3比热的影响

对电脉冲诱导的不同电阻态下La_0.7Ca_0.3MnO₃样品的比热进行了研究.实验结果表明,电脉冲导致La_0.7Ca_0.3MnO₃样品比热随电阻状态发生可逆变化.比热随电阻状态的减小而减小.低温比热拟合及不同电阻状态下的比热差与温度关系说明,声子对比热的贡献不随电阻状态变化,磁性和载流子对比热的贡献是导致La_0.7Ca_0.3MnO₃样品比热变化的原因.电脉冲诱导O离子沿一维扩展性缺陷的电化学迁移,导致材料中局部区域的O离子浓度发生变化.O离子浓度的变化导致载流子浓度的变化,同时载流子浓度的变化将使得低温下磁性耦合强度发生变化,从而导致比热发生变化.     

离子注入结合离子交换技术制备KTiOPO4光波导特性研究

用离子注入结合离子交换技术形成了 KTiOPO₄ 平面光波导,研究了离子注入对离子交换波导结构的影响.使用棱镜耦合法测量了波导特性,结果显示形成了表面折射率升高的多模波导,通过背散射技术研究了离子交换后的 Rb 离子分布.实验表明,注入离子导致样品晶格损伤,在 2.8 μm处对离子交换形成了阻挡层,阻止了交换向KTP晶体的更深处进行.     

第一性原理计算研究黑磷嵌锂态的动力学性能

采用基于密度泛函理论的第一性原理方法对锂离子电池负极材料黑磷在嵌锂过程中的产物LiP5,Li3P7以及LiP的晶体结构与电子结构进行了研究与分析．通过计算这几种材料的电子结构,发现黑磷嵌锂后的这几种相均为半导体能带结构,其带隙均比黑磷嵌锂前的带隙大,表明黑磷嵌锂后的电子电导性能降低了．利用弹性能带方法模拟了Li离子在LiP5,Li3P7和LiP材料中的扩散,从理论上得到了Li离子的扩散势垒,并与其他电极材料进行了比较,发现Li离子在各种嵌锂态的材料中都能够比较快速的扩散．计算结果表明,Li在LiP5中的扩散系数大约为10^-4cm2／s,扩散通道是一维的;Li在Li3P7中的扩散系数为10^-7-10^-6cm2／s,扩散通道是三维的;Li在LiP中的扩散系数为10^-8-10^-5cm2／s,扩散通道是三维的．     

低能离子在C60薄膜中引起的辐照效应

用Raman(拉曼)散射技术分析了120keV的H,Ar和Fe离子在C₆₀薄膜中引起的辐照效应,主要指由晶态向非晶态的转变.分析结果表明,在Fe和Ar离子辐照的C₆₀薄膜中,核碰撞主导了由晶态向非晶态的转变过程.而在H离子辐照的情况下,电子能损起主导作用,并发现在H离子辐照过程中,电子能损有明显的退火效应,致使由晶态向非晶态转变的过程中,经历了一个石墨化的中间过程.     

SrMn0.5Fe0.5O3的自旋玻璃态和过渡金属离子价态的研究

采用固相反应法制备了SrMn_0.5Fe_0.5O₃陶瓷样品,并对样品的晶体结构,磁性和离子价态进行了系统的表征与分析. X射线衍射谱的Rietveld拟合表明样品属于理想的立方钙钛矿型结构,Mn离子和Fe离子随机占据B位的O八面体中心. X射线光电子能谱表明Mn离子为+3和+4的混合原子价态,Fe离子为+3价. 样品在大于230K的高温区域呈现Curie顺磁特性,在小于230 K的低温区域样品表现出自旋玻璃态行为,这种特性源于Mn离子和Fe离子之间的交换作用及自身价态和分布的不均匀性. 由于Fe³⁺离子占据O八面体的中心,对顺磁区的Mssbauer谱测量表现为四级分裂.     

内掺过渡金属非典型富勒烯M@C22(M=Sc, Ti, V, Cr, Mn, Fe, Co, Ni) 几何结构、电子结构、稳定性和磁性的密度泛函研究

采用密度泛函理论中广义梯度近似对非典型富勒烯C₂₂和过渡金属内掺衍生物M@C₂₂(M=Sc,Ti,V,Cr,Mn,Fe,Co和Ni)的几何结构和电子结构进行计算研究.发现非典型富勒烯C₂₂的基态结构是含有一个四碳环的单重态笼状结构.过渡金属原子的掺入明显提高了体系的稳定性. C-M键既有一定共价性又有一定离子性.磁性、能级图、轨道分布和态密度图分析表明: M原子的3d轨道和碳笼的C原子的原子轨道之间存在较强的轨道杂化. Ti, Cr, Fe和Ni内掺的结构出现磁性完全猝灭现象. Sc和碳笼间是弱反铁磁作用, V,Mn和Co与碳笼间是弱铁磁作用.     

Antisite defects and Mg doping in LiFePO<Subscript>4</Subscript>: a first-principles investigation

Atomic and electronic structures of LiFePO₄ with the antisite defect and Mg doping at Li and Fe sites have been investigated using first-principles density-functional theory with the on-site Coulomb interaction taken into account. It is demonstrated that the most favorable antisite defect type is the exchange defect, in which Li and Fe ions exchange positions. The resultant longer Fe–O bond and narrower band gap drop a hint that the electronic and ionic transport properties may be improved. For the case of Mg doping, Mg is preferentially doped at the Fe site instead of the Li site to form a new LiFe_1−y Mg _y PO₄ solid solution, leading to a higher ionic conductivity. Moreover, the dependence of the electrochemical properties on the concentration of Mg dopant has also been discussed.     

LiFePO4在不同pH值水溶液中电化学性能表现及其衰减机理

LiFePO₄在含Li⁺水溶液中的电化学性能稳定性与水溶液的pH值密切相关,当溶液的pH值达到11后LiFePO₄在充放电循环过程中的容量衰减十分明显. 通过循环伏安测试、交流阻抗测试、电极充放电性能测试、非原位X射线衍射测试以及化学分析的方式对其容量衰减机理进行了研究. 结果表明LiFePO₄在pH=7的LiNO₃水溶液中具有相对最高的电化学稳定性,但是LiFePO₄材料在水溶液中较之其在有机电解液中依然会有较差的电化学性能表现. 认为LiFePO₄在水介质中的容量衰减现象归因于其在持续充放电过程中的Li、Fe、P溶解,同时电极表面也会附着一层沉淀物. 这些最终导致了材料晶体结构的破坏、电极极化的增大以及电极容量的衰减.     

Effect of C doping on the structural and electronic properties of LiFePO4: A first-principles investigation

Using first-principles calculations within the generalized gradient approximation （GGA） ＋U framework, we inves- tigate the effect of C doping on the structural and electronic properties of LiFePO4. The calculated formation energies indicate that C doped at O sites is energetically favoured, and that C dopants prefer to occupy 03 sites. The band gap of the C doped material is much narrow than that of the undoped one, indicating better electro- conductive properties. To maintain charge balance, the valence of the Fe nearest to C appears as Fe3＋, and it will be helpful to the hopping of electrons.     

Effects of nano-carbon webs on the electrochemical properties in LiFePO4/C composite

LiFePO₄/C composite is one of ways to surmount the lower electrical conductivity of LiFePO₄. In this paper, we suggest a new type of LiFePO₄/C composite in which amorphous nano-carbon webs are wrapping and connecting LiFePO₄ particles. This type of composite was obtained by adapting a new liquid-based powder preparation method, that is, all raw materials (LiFePO₄ and carbon precursor materials) were dissolved in liquid and solidified. This composite was very effective in enhancing the electrochemical properties such as capacity and rate capability. Even as high as at 400 m Ag⁻¹ current density, a capacity of about 105 m Ahg⁻¹ was obtained at 25 °C.     

Electrochemical characterization of ionic liquid based gel polymer electrolyte for lithium battery application

High molecular weight polymer poly(vinylidenefluoride-co-hexafluoropropylene) (PVdF-HFP), ionic liquid 1-ethyl-3-methylimidazolium bis(fluorosulfonyl)imide (EMIMFSI), and salt lithium bis(trifluoromethanesulfonyl)imide (LiTFSI)-based free-standing and conducting ionic liquid-based gel polymer electrolytes (ILGPE) have been prepared by solution cast method. Thermal, electrical, and electrochemical properties of 80 wt% IL containing gel polymer electrolyte (GPE) are investigated by thermogravimetric (TGA), impedance spectroscopy, linear sweep voltammetry (LSV), and cyclic voltammetry (CV). The 80 wt% IL containing GPE shows good thermal stability (~?200 °C), ionic conductivity (6.42?×?10^?4 S cm^?1), lithium ion conductivity (1.40?×?10^?4 S cm^?1 at 30 °C), and wide electrochemical stability window (~?4.10 V versus Li/Li⁺ at 30 °C). Furthermore, the surface of LiFePO₄ cathode material was modified by graphene oxide, with smooth and uniform coating layer, as confirmed by scanning electron microscopy (SEM), and with element content, as confirmed by energy dispersive X-ray (EDX) spectrum. The graphene oxide-coated LiFePO₄ cathode shows improved electrochemical performance with a good charge-discharge capacity and cyclic stability up to 50 cycles at 1C rate, as compared with the without coated LiFePO₄. At 30 °C, the discharge capacity reaches a maximum value of 104.50 and 95.0 mAh g^?1 for graphene oxide-coated LiFePO₄ and without coated LiFePO₄ at 1C rate respectively. These results indicated improved electrochemical performance of pristine LiFePO₄ cathode after coating with graphene oxide.     

Synthesis and electrochemical performance of LiFePO<Subscript>4</Subscript>/C cathode materials from Fe<Subscript>2</Subscript>O<Subscript>3</Subscript> for high-power lithium-ion batteries

Carbon-coated olivine-structured LiFePO₄/C composites are synthesized via an efficient and low-cost carbothermal reduction method using Fe₂O₃ as iron source at a relative low temperature (600 °C). The effects of two kinds of carbon sources, inorganic (acetylene black) and organic (sucrose), on the structures, morphologies, and lithium storage properties of LiFePO₄/C are evaluated in details. The particle size and distribution of the carbon-coated LiFePO₄ from sucrose (LiFePO₄/SUC) are more uniform than that obtained from acetylene black (LiFePO₄/AB). Moreover, the LiFePO₄/SUC nanocomposite shows superior electrochemical properties such as high discharge capacity of 156 mAh g^?1 at 0.1 C, excellent cyclic stability, and rate capability (78 mAh g^?1 at 20 C), as compared to LiFePO₄/AB. Cyclic voltammetric test discloses that the Li-ion diffusion, the reversibility of lithium extraction/insertion, and electrical conductivity are significantly improved in LiFePO₄/SUC composite. It is believed that olivine-structured LiFePO₄ decorated with carbon from organic carbon source (sucrose) using Fe₂O₃ is a promising cathode for high-power lithium-ion batteries.     

Recent developments in the formation and structure of tin-iron oxides by laser pyrolysis

Complex oxides demonstrate specific electric and magnetic properties which make them suitable for a wide variety of applications, including dilute magnetic semiconductors for spin electronics. A tin-iron oxide Sn_1−xFe_xO₂ nanoparticulate material has been successfully synthesized by using the laser pyrolysis of tetramethyl tin-iron pentacarbonyl-air mixtures. Fe doping of SnO₂ nanoparticles has been varied systematically in the 3-10 at% range. As determined by EDAX, the Fe/Sn ratio (in at%) in powders varied between 0.14 and 0.64. XRD studies of Sn_1−xFe_xO₂ nanoscale powders, revealed only structurally modified SnO₂ due to the incorporation of Fe into the lattice mainly by substitutional changes. The substitution of Fe³⁺ in the Sn⁴⁺ positions (Fe³⁺ has smaller ionic radius as compared to the ionic radius of 0.69 Å for Sn⁴⁺) with the formation of a mixed oxide Sn_1−xFe_xO₂ is suggested. A lattice contraction consistent with the determined Fe/Sn atomic ratios was observed. The nanoparticle size decreases with the Fe doping (about 7 nm for the highest Fe content). Temperature dependent ⁵⁷Fe Mössbauer spectroscopy data point to the additional presence of defected Fe³⁺-based oxide nanoclusters with blocking temperatures below 60 K. A new Fe phase presenting magnetic order at substantially higher temperatures was evidenced and assigned to a new type of magnetism relating to the dispersed Fe ions into the SnO₂ matrix.     

Structural and electrochemical properties of Nd-doped LiFePO4/C prepared without using inert gas

To further improve the electrochemical performance of LiFePO₄/C, Nd doping has been adopted for cathode material of the lithium ion batteries. The Nd-doped LiFePO₄/C cathode was synthesized by a novel solid-state reaction method at 750 °C without using inert gas. The Li_0.99Nd_0.01FePO₄/C composite has been systematically characterized by X-ray diffraction, EDS, SEM, TEM, charge/discharge test, electrochemical impedance spectroscopy and cyclic stability. The results indicate that the prepared sample has olivine structure and the Nd³⁺ and carbon modification do not affect the structure of the sample but improve its kinetics in terms of discharge capacity and rate capability. The Li_0.99Nd_0.01FePO₄/C powder exhibited a specific initial discharge capacity of about 161 mAh g^− 1 at 0.1 C rate, as compared to 143 mAh g^− 1 of LiFePO₄/C. At a high rate of 2 C, the discharge capacity of Li_0.99Nd_0.01FePO₄/C still attained to 115 mAh g^− 1 at the end of 20 cycles. EIS results indicate that the charge transfer resistance of LiFePO₄/C decreases greatly after Nd doping.     

Synthesis of spherical LiFePO4/C via Ni doping

Spherical LiFePO₄/C powders were synthesized by the conventional solid-state reaction method via Ni doping. Low-cost asphalt was used as both the reduction agent and the carbon source. An Ni-doped spherical LiFePO₄/C composite exhibited better electrochemical performances compared to an un-doped one. It presented an initial discharge capacity of 161 mAhg⁻¹ at 0.1 C rate (the theoretical capacity of LiFePO₄ with 5 wt% carbon is about 161 mAhg⁻¹). After 50 cycles at 0.5 C rate, its capacity remained 137 mAhg⁻¹ (100% of the initial capacity) compared to 115 mAhg⁻¹ (92% of the initial capacity) for an un-doped one. The electrochemical impedance spectroscopy analysis and cyclic voltammograms results revealed that Ni doping could decrease the resistance of LiFePO₄/C composite electrode drastically and improve its reversibility.