锂离子电池正极材料LiMnyFe1-yPO4的制备及性能研究

采用高速球磨与高温固相反应相结合的方法合成了LiMnyEe1-yPO4（0．1≤y≤1．0）锂离子电池正极材料，并对其晶体结构、表观形貌和电化学性能进行了研究．结果表明，所合成的LiMnyEe1-yPO4为单一橄榄石型结构，粒径分布较均匀．当以小电流密度（0．1C）充放电时，LiMn0．1Fe0．9PO4具有最高的放电比容量，为145mAh／g；LiMn0．6Fe0．4PO4质量比能量最高，达568Wh／kg．LiMnyEe1-yPO4的倍率放电性能随着y的增加而降低，这主要是材料在4．0V平台的容量损失造成的；LiMn0．1Fe0.9PO4具有最佳的倍率性能：以0．5、1．5C倍率进行放电，放电容量分别达到130、109mAh／g．     

掺碳LiFePO4的合成及性能研究

为提高LiFePO4的电化学性能,通过固相合成法制备了掺碳的LiFePO4正极材料,并用XRD、SEM、电化学工作站及充放电测试等对样品的性能进行了研究分析.结果表明,少量的碳掺杂并未改变LiFePO4的晶体结构但显著改善了其电化学性能,LiFePO4/C样品的粒度较小,粒径分布均匀,0.1C首次放电比容量为141.9mAh/g,循环50次后容量下降了11.2mAh/g,以1C倍率首次放电比容量为126.5mAh/g,循环50次后容量保持率为87.2%.     

锂电池正极材料LiNi0.8Co0.1Mn0.1O2的制备与性能

运用"溶胶-喷雾干燥-煅烧"新技术合成了正极材料LiNi0.8Co0.1Mn0.1O2,采用XRD、SEM、电化学阻抗谱(EIS)及充放电测试研究了煅烧温度对所制材料结构和电性能的影响。结果表明,在750~850℃都可制备得到纯相LiNi0.8Co0.1Mn0.1O2。其中,800℃所合成样品具有适宜的晶粒大小、最佳的晶化程度和阳离子有序度,最小的电荷传递阻抗,最大的锂离子扩散系数和最佳的电化学表现。该样品0.2C首次放电容量达到189.1mAh·g-1,以5C循环的放电比容量仍可达到136mAh·g-1,第30周0.2C放电容量达初始容量的97.5%,显示出高容量、良好的倍率与循环性能。     

锂离子电池正极材料Li(MnxFe1-x)PO4的合成及电化学性能的研究

采用高温固相法合成了组成为Li（MnxFe1-x）PO4（x=0、0．2、0．4、0．6、0．8、1．0）的锂离子电池正极材料。通过对合成样品的XRD、SEM及电化学性能（循环性能,大电流放电性能）的研究表明,少量Mn的掺杂未影响到LiFePO4的晶体结构,但显著改善了它的电化学性能。Li（Mn0.2Fe0.8）PO4与LiFePO4材料相比有更好的电化学性能,在低放电倍率（电流密度为20mA／g）时,放电容量为150mAh／g,当放电倍率提高到2C时,放电容量仍可达113mAh／g,且循环性能良好。     

碳源对LiFePO_4/C正极材料性能的影响

以FePO_4·2H_2O、Li_2CO_3和柠檬酸/酒石酸/抗坏血酸为原料,经机械球磨后在惰性气氛中高温煅烧合成LiFePO_4/C正极材料.研究了不同碳源对LiFePO_4结构、形貌及电化学性能的影响.重点考察了碳源为酒石酸时,不同合成温度对材料性能的影响.采用XRD、SEM以及电化学测试等手段对目标产物进行了结构表征和性能测试.结果表明,以酒石酸做碳源时,合成的正极材料物相单一,颗粒细小,粒度均匀,并且具有优良的电化学性能.在室温下以0.1C倍率充放电,首次放电比容量可达155mAh/g,1.0C首次放电比容量为120mAh/g,经过100次循环以后容量仍有109mAh/g.     

LiNi0.9Co0.1O2正极材料的EDTA络合法合成及其性能研究

采用络合法制备了锂离子电池的活性正极材料LiNi0．9Co0．1O2粉体，实验表明合成的LiNi0．9Co0．1O2粉体结晶良好，层状结构发育完善．电池充放电测试结果表明，其容量及循环性能与LiNi0．9Co0．1O2粉体的合成温度有关，其中900℃合成得到的LiNi0．9Co0．1O2材料具有最好的电化学性能，首次放电比容量高达120．5mAh／g，循环30次后可逆放电比容量仍高达118．8mAh／g，容量损失仅为1．4％．文中对容量退化的原因进行了分析．     

用两种碳源制备高性能LiFePO4/C正极材料

为了提高LiFePO4材料的电化学性能,以碳溶胶和葡萄糖两种物质为碳源、采用高温固相法制备了LiFePO4/C复合正极材料.通过XRD、TEM、恒电流充放电等方法研究了材料的结构与电化学性能.XRD结果表明,两种碳源的添加对LiFePO4的晶体结构没有影响.从TEM图上可观测到颗粒外部明显的碳包覆层.电化学性能测试表明,在同样倍率下,以两种碳源制备的LiFePO4/C材料放电比容量高于以单一碳源制备的LiFePO4/C,且表现出优良倍率性能和循环稳定性:在0.1C下的放电比容量达162mAh/g,1C下放电比容量为157mAh/g,循环20次后容量没有任何衰减.     

锂离子电池正极材料LiNi0.5Mn1.5O4的固相法制备及性能研究

以Ni(CH3COO)2·4H2O和Mn(CH3COO)2·4H2O为原料,分别在400、500℃分解3、7h得到镍锰复合氧化物前驱体,再与锂源Li2CO3混匀,在800℃煅烧12h,600℃退火24h得到LiNi0.5Mn1.5O4正极材料。XRD、SEM、EIS和恒流充放电测试结果表明,在400℃、7h制备的前驱体与Li2CO3合成的LiNi0.5Mn1.5O4性能最佳。室温下以0.1C倍率充放电,首次放电比容量达到141.5mAh/g,循环30次后容量保持率为98.55%;以1C倍率充放电,首次放电比容量为120.34mAh/g,循环30次后放电比容量为112.09mAh/g。     

超临界水热制备LiFePO4及煅烧碳包覆改性研究

本文以FeSO_4、H_3PO_4和LiOH为原料,采用超临界水热过程制备了亚微米级LiFePO_4颗粒.在此基础上,为了提升制备的LiFePO_4正极材料的物理和电化学性能,对其进行了后续煅烧碳包覆改性研究.同时,通过XRD、SEM、充放电测试、CV和EIS测试手段,对LiFePO_4正极材料改性前后的结构、形貌和电化学性能进行了表征.结果表明:后续固相煅烧碳包覆改性能够显著改善LiFePO_4的结晶性能,减小颗粒粒径,降低电荷传递阻抗,以及大幅度地提升放电容量和循环性能;以PVP为模板剂、蔗糖为碳源,700℃煅烧1 h得到的LiFePO_4/C颗粒粒径小、分布均一,室温0.2 C倍率的首圈放电比容量为153.1 mAh/g,1 C倍率充放电时,放电比容量可保持在144.2 mAh/g,1 C循环50次,容量保持率达到97.1%.     

无水溶胶-凝胶法制备LiFePO4/C电极材料及其结构和电化学性能

以乙二醇为溶剂，采用溶胶一凝胶法合成了LiFePO4／C．采用X射线衍射、扫描电镜、透射电镜和电化学阻抗谱等分析测试方法，研究了600-750℃范围内合成的LiFePO4／C的微观结构特征、在不同放电倍率下的循环稳定性和放电容量等电化学性能．研究结果表明，合成温度对LiFePO4的结晶状况及LiFePO4／C电极的电化学性能有着显著的影响．700℃烧结的产物结晶完整，颗粒细小（-150nm）均匀，电化学性能有了显著的提高，0．5C的放电容量达到150mAh／g，1C的放电容量仍有141mAh／g，经200个循环，放电容量基本保持不变．     

Structural and optical properties of AlxOy/Pt/AlxOy multilayer absorber

We report on the microstructure and optical properties of Al_xO_y–Pt–Al_xO_y interference-type multilayer films, deposited by electron beam (e-beam) deposition onto corning 1737 glass, silicon (1 1 1) and copper substrates. The structural properties were investigated by Rutherford backscattering spectrometry, X-ray diffraction, scanning electron microscopy, energy dispersive X-ray spectroscopy and atomic force microscopy. The optical properties were extracted from specular reflection/transmission, diffuse reflectance and emissometer measurements. The stratification of the coatings consists of a semi-transparent middle Pt layer sandwiched between two layers of Al_xO_y. The top and bottom Al_xO_y layers were non-stoichiometric with no crystalline phases present. The Pt layer is in the fcc crystalline phase with a broad size distribution and spheroidal shape in and between the rims of Al_xO_y. The surface roughness of the stack was found to be comparable to the inter-particle distance. The optical calculations confirm a high solar absorptance of ∼0.94 and a low thermal emittance of ∼0.06 for the multilayer stack, which is attributed not only to the optimized nature of the multilayer interference stacks, but also to the specific surface morphology and texture of the coatings. These optical characteristics validate the spectral selectivity of the Al_xO_y–Pt–Al_xO_y interference-type multilayer stack for use in high temperature solar-thermal applications.     

Optimization of AlxOy/Pt/AlxOy multilayer spectrally selective coatings for solar-thermal applications

Spectrally selective Al_xO_y/Pt/Al_xO_y multilayer absorber coatings were deposited onto corning 1737 glass, Si (111) and copper substrates using electron beam (e-beam) vacuum evaporator at room temperature. The employment of ellipsometric measurements and optical simulation was proposed as an effective method to optimize and deposit multilayer solar absorber coatings. The optical constants (n and k) measured using spectroscopic ellipsometry, showed that both Al_xO_y layers, which used in the coatings, were dielectric in nature and the Pt layer was semi-transparent. The optimized multilayer coatings exhibited high solar absorptance α ∼ 0.94 ± 0.01 and low thermal emittance ? ∼ 0.06 ± 0.01 at 82 °C. The Rutherford backscattering spectroscopy (RBS) data of Al_xO_y/Pt/Al_xO_y multilayer absorber indicated the Al_xO_y layers present in the coating were nearly stoichiometry. The scanning electron microscope analysis (SEM) result indicated that the average diameter and inter-particles distance of Pt grains were statistically about 146 ± 0.17 nm and 6-10 ± 0.2 nm respectively.     

Interfacial microstructure of NiSix/HfO2/SiOx/Si gate stacks

Integration of NiSi_x based fully silicided metal gates with HfO₂ high-k gate dielectrics offers promise for further scaling of complementary metal-oxide- semiconductor devices. A combination of high resolution transmission electron microscopy and small probe electron energy loss spectroscopy (EELS) and energy dispersive X-ray analysis has been applied to study interfacial reactions in the undoped gate stack. NiSi was found to be polycrystalline with the grain size decreasing from top to bottom of NiSi_x film. Ni content varies near the NiSi/HfO_x interface whereby both Ni-rich and monosilicide phases were observed. Spatially non-uniform distribution of oxygen along NiSi_x/HfO₂ interface was observed by dark field Scanning Transmission Electron Microscopy and EELS. Interfacial roughness of NiSi_x/HfO_x was found higher than that of poly-Si/HfO₂, likely due to compositional non-uniformity of NiSi_x. No intermixing between Hf, Ni and Si beyond interfacial roughness was observed.     

Tc trend in high-Tc superconductors

In our previous works, we have shown that most existing ceramic superconductors can be considered to be built of superconductor-semiconductor composite and we have estimated the change in phonon spectrum of the intrinsic superconductor unit if a semiconductor unit is attached to it. Moreover, the proximity effect under the size quantization condition has been examined in the superconductor-semiconductor composite. Each of the stated effects by itself could causeT _c enhancement in general as more semiconductor blocks are added to the system. We extend our study in this paper to analyze the combined actions of phonon spectral change and proximity effect without size quantization condition onT _c variation in members of the Tl₁ series of high-T _c superconductors. Our results indicate that an optimumT _c is obtained if the stated effects are included in the idealized unit cells of the superconductors made up of a superconductor-semiconductor array.     

Anomalous Hall Effect in Sn1?x?yMnxEuyTe and Sn1?x?yMnxEryTe Mixed Crystals

The Anomalous Hall Effect (AHE) was investigated in IV–VI ferromagnetic semimagnetic semiconductors of Sn_1–x Mn _x Te codoped with either Eu or Er. The analysis of experimental data is as follows. Hall resistivity and magnetization showed that AHE coefficient R _s depends on temperature and its value decreases with thetemperature increase. We observe that above ferromagnet–paramagnet transition temperature R _s changes sign. We discuss the possible physical mechanisms responsible for observed temperature dependence of R _s , particularly change of the sign.     

Synthesis of a new perovskite Pb(Li14Nb34)O3

A high-pressure technique was adopted to obtain perovskite-type $\text{Pb(Li}{}_{\mathrm{<mtext>1</mtext><mtext>4</mtext>}}\text{Nb}{}_{\mathrm{<mtext>3</mtext><mtext>4</mtext>}}\text{)}\text{O}{}_3$. A new perovskite $\text{Pb(Li}{}_{\mathrm{<mtext>1</mtext><mtext>4</mtext>}}\text{Nb}{}_{\mathrm{<mtext>3</mtext><mtext>4</mtext>}}\text{)}\text{O}{}_3$ was characterized to have a cubic symmetry with $\text{a}{}_{\mathrm{<mtext>o</mtext>}}\text{= 4.069}\text{A}\text{?}$; Li and Nb ions in the B-site of perovskite lattice may be in a random arrangement.     

Bulk crystalline BaPb34Bi14O3: A ceramic superconductor

The preparation conditions of the high T_C ceramic superconductor Ba(Pb,Bi)O₃ is correlated with the superconducting transition. Transition onsets of all materials are similar, but transition widths and transition completeness is strongly dependent on firing temperature. Only materials prepared over a narrow temperature range, resulting in a nearly ideal weight loss, have a complete and narrow transition.     

Electrostriction in Pb (Zn13Nb23)O3

The electrostriction in $\text{Pb (Zn}{}_{\mathrm{<mtext>1</mtext><mtext>3</mtext>}}\text{Nb}{}_{\mathrm{<mtext>2</mtext><mtext>3</mtext>}}\text{)}\text{O}{}_3$ crystals has been investigated using a strain gauge method. In the ferroelectric phase below 140 C, the strain vs the electric field shows a hysteresis, which is ascribed to the effect of ferroelectric domains. A quadratic relation holds between the strain x and the electric polarization P as x = QP² above about 170 C in the paraelectric phase. Values of the electrostrictive Q coefficients are determined from the measurements near 190 C, as Q₁₁ = 1.6·10^?2m⁴/C², Q₁₂ = ?0.86·10^?2m⁴/C², and Q₄₄ = 0.85·10^?2m⁴/C².     

Effect of pressure onTc in La2-xBaxCuO4 withx=0.125

The superconducting transition temperature,T _c , of La_2–x Ba _x CuO₄ has been measured under high pressure up to 8 GPa.T _c is found to change drastically at the pressure where the structural phase transition takes place. This finding clearly indicates that there exists an intimate relation between the crystal structure and superconductivity.