LiFe0.95Ni0.02Mn0.03PO4/C的合成及电化学性能

采用高温固相法合成Ni2+、Mn2+共掺杂的LiFe0.95Ni0.02Mn0.03PO4/C正极材料。通过X射线衍射(XRD)、扫描电镜(SEM)、电化学阻抗谱(EIS)和电化学测试技术等研究材料的结构、形貌和电化学性能。结果表明:Ni2+和Mn2+共掺杂后的LiFe0.95Ni0.02Mn0.03PO4/C材料仍然具有LiFePO4/C橄榄石型晶体结构,且掺杂后材料的放电比容量和循环性能都得到显著改善。在0.1C和1C下放电时,未掺杂LiFePO4/C的首次放电比容量仅分别为153和140 mA.h/g,而Ni2+、Mn2+共掺杂的LiFe0.95Ni0.02Mn0.03PO4/C材料首次放电比容量分别为165和145 mA.h/g,且在1C下循环100次后容量保持率仍然为97.6%。     

锂离子电池富锂材料Li[Li0.2Ni0.2Mn0.6]O2的制备及掺杂改性

以乙酸盐为原料,采用喷雾干燥法制备层状α-NaFeO2结构的富锂正极材料Li[Li0.2Ni0.2Mn0.6]O2及掺杂Cr的Li[Li0.2Ni0.15Cr0.1Mn0.55]O2。采用X射线衍射、扫描电镜、半电池充放电和电化学阻抗谱等方法研究材料的物相、结构、形貌及电化学性能。结果表明:Cr掺杂使材料的颗粒变粗,但不改变材料的结构,而使材料的层状特征更为明显;Cr掺杂后材料的电化学性能得到明显改善,电荷转移阻抗Rct从275.0降低到105.0,循环稳定性和倍率性能均有所改善,Li[Li0.2Ni0.15Cr0.1Mn0.55]O2材料1C倍率下的放电比容量为140.0 mA.h/g,循环50次后放电比容量为133.7 mA.h/g,远高于未掺杂Cr材料的比容量,未掺杂Cr材料在1C倍率下放电比容量为107.1mA.h/g,循环50次后放电比容量为102.1 mA.h/g。     

Ni2+掺杂对Li3V2（PO4）3电化学性能的影响

采用X射线衍射(XRD)、透射电镜(TEM)和电化学方法,研究Ni2+掺杂对正极材料Li3V2(PO4)3的结构、形貌和电化学性能的影响。结果表明:掺杂适量的Ni2+不会改变Li3V2(PO4)3的单斜晶系结构,但可提高材料的电导率,抑制电池在充放电过程的极化。在室温下,Li3(Ni0.05V0.95)2(PO4)3以0.1C倍率放电的初始比容量为115mA.h/g,放电倍率从0.1C增加到0.4C循环60次后,比容量衰减率仅为2.7%,而未掺杂原样Li3V2(PO4)3的初始比容量为129 mA.h/g,60次循环后比容量衰减率约为30.3%;当放电倍率增至1C时,80次循环后,Li3(Ni0.05V0.95)2(PO4)3比容量为99.8 mA.h/g,而原样的比容量为84.1 mA.h/g;当放电倍率增至5C时,循环120次后,Li3(Ni0.05V0.95)2(PO4)3比容量为67.7 mA.h/g,而原样的比容量降为0。循环伏安和交流阻抗测试表明,Li3(Ni0.05V0.95)2(PO4)3的可逆性明显优于Li3V2(PO4)3的可逆性。     

Fe3+掺杂Li4Ti5O12的结构及电化学性能

采用高温固相法合成Li4FexTi5-xO12(x=0.025,0.1,0.2)负极材料。通过X射线衍射、扫描电镜、充放电性能测试等对掺杂Fe3+的Li4Ti5O12材料的组成、结构、形貌进行表征,并对其电化学性能进行研究。结果表明,所合成的材料具有良好的尖晶石结构,无杂相。适当Fe3+掺杂能细化材料,提高材料的电子导电性,使材料的循环性能得到改善。Li4Fe0.025Ti4.975O12的充电容量最佳,0.1C倍率下首次充电比容量达到162.5 mA.h/g,循环性能较好。     

锰掺杂对锂离子电池正极材料Li3V2（PO4）3/C性能的影响（英文）

采用溶胶-凝胶法合成Li3V2-2/3xMnx(PO4)3(0≤x≤0.12)。采用XRD、SEM、XPS、恒流充放电和电化学阻抗谱(EIS)研究Mn掺杂对Li3V2(PO4)3/C结构和电化学性能的影响。XRD研究表明:掺杂少量的Mn2+不会影响材料的结构,所有样品均具有单一相态的单斜结构(P21/n空间群)。XPS分析表明:在Li3V1.94Mn0.09(PO4)3/C中,V和Mn的化合价分别为+3和+2,原料中的柠檬酸在煅烧过程中分解成C而残留在Li3V1.94Mn0.09(PO4)3/C中。电化学测试表明:掺杂Mn改善了电极材料的循环性能和倍率性能,正极材料Li3V1.94Mn0.09(PO4)3/C表现出最好的循环稳定性和倍率性能。在40mA/g的放电电流密度下,循环100次后,Li3V1.94Mn0.09(PO4)3/C的放电容量从158.8mA·h/g衰减到120.5mA·h/g,容量保持率为75.9%,而未掺杂样品的放电容量从164.2mA·h/g衰减到72.6mA·h/g,容量保持率为44.2%。当放电电流密度增加到1C时,Li3V1.94Mn0.09(PO4)3/C的初始放电容量仍能达到146.4mA·h/g,循环100次后,放电容量保持为107.5mA·h/g。EIS测试表明,掺杂适量的Mn2+减小了电荷转移阻抗,这有利于Li+的脱嵌。     

Mg-Co复合掺杂对LiFePO4电化学性能的影响（英文）

通过固相反应制备了Mg2+和Co4+复合掺杂的LiFePO4电极材料。采用X射线衍射、恒电流充放电和循环伏安研究复合掺杂对 LiFePO4结构和电化学性能的影响。结果表明:复合掺杂能够提高 LiFePO4的首次放电比容量,0.1C和1C的放电容量分别达到147.2mA·h/g 和133.3mA·h/g。循环伏安测试结果表明:复合掺杂改善了LiFePO4的导电性能,增强了Li+的脱嵌可逆性。     

复合金属掺杂的LiFePO4/C复合材料的制备与电化学性能研究

以超声波辅助沉淀法合成的纳米级球形FePO4·2H2O为原料,采用碳热还原法制备了复合金属掺杂的LiFePO4/C复合材料。通过X射线衍射(XRD),扫描电镜(SEM),恒电流充放电测试,循环伏安和交流阻抗测试表征了FePO4·2H2O和LiFePO4/C的物相、结构和电化学性能。结果表明,溶液浓度为0.1 mol/L时制备的FePO4·2H2O为分布均匀的纳米级球形颗粒。复合金属掺杂显著提高了LiFePO4的放电比容量,Ni和Nb复合掺杂的LiFePO4/C复合材料表现出了最佳的电化学性能,0.1 C倍率条件下首次放电容量158.8 mAh/g,1 C倍率下首次放电容量150.2 mAh/g,100次循环后容量保持率分别为98.30%和97.8%。Ni和Nb复合掺杂后提高了LiFePO4的锂离子扩散速率和电导率。     

合成温度对正极材料Li3V2（PO4）3/C性能的影响

以V2O5、NH4H2PO4、Li2CO3和C6H8O7·H2O为原料,采用溶胶-凝胶法在600～800℃下合成了锂离子电池正极材料Li3V2(PO4)3/C,利用XRD和蓝电测试系统对材料进行表征,研究了合成温度对材料电化学性能的影响。结果表明:650℃下合成产物中开始出现Li3V2(PO4)3相,700、750和800℃下合成纯相的Li3V2(PO4)3正极材料;750℃合成的样品在放电电流密度为0.1C下首次放电容量为123.5mAh·g-1,并且随电流密度增大到10C时也有较好的循环稳定性。     

Al2O3包覆LiNi0.03Co0.05Mn1.92O4正极材料的制备及其电化学性能

以Al(NO3)3?9H2O为包覆原料，通过燃烧法制备得到LiNi0.03Co0.05Mn1.92O4@Al2O3正极材料。通过X射线衍射(XRD)，场发射扫描电子显微镜(FESEM)和透射电镜(TEM)等表征手段对材料的结构和形貌进行分析，并通过恒电流充放电、循环伏安(CV)、交流阻抗(EIS)等测试分析材料的电化学性能。结果表明，Al2O3包覆没有改变LiNi0.03Co0.05Mn1.92O4的尖晶石型结构，包覆层厚度约10.6nm。LiNi0.03Co0.05Mn1.92O4@Al2O3正极材料电化学性能得到了明显改善，1 C和10 C倍率下初始放电比容量分别为119.9 mAh?g-1和106.3 mAh?g-1，充放电循环500次后容量保持率分别为88.4%和78.2%，而未包覆的LiNi0.03Co0.05Mn1.92O4在1 C和10 C倍率下初始放电比容量分别为121.2 mAh?g-1和104.0 mAh?g-1，500次循环后容量保持率分别为84.1%和67.6%。LiNi0.03Co0.05Mn1.92O4@Al2O3活化能为32.92 kJ?mol-1，而未包覆材料的活化能为36.24 kJ?mol-1，包覆有效降低了材料Li+扩散所需克服的能垒，提高了材料的电化学性能。     

Ti4＋掺杂对Li2FeSiO4／C电化学性能的影响

用溶胶-凝胶法制备Ti4＋掺杂的Li2FeSiO4／C正极材料。用XRD、HRTEM和电化学方法研究了该材料的结构、形貌和电化学性能。结果表明,掺杂适量的Ti4＋不会改变Li2FeSiO4／C的正交晶系结构,可以稳定材料的结构,改善高倍率充放电性能。在室温下,Li2Fe0.97Ti0.03SiO4/C以0．1c倍率放电的首次放电比容量为149．1mA·h／g,20次循环后放电比容量为127．3mA·h／g,且不同倍率下的电化学性能明显优于未掺杂的Li2FeSiO4／C。交流阻抗谱研究表明,适量的Ti4＋掺杂,减小了正极材料在充放电过程中的电荷传递电阻,增加了材料的电子电导率,改善了材料的电化学性能。     

X-ray diffraction study of Ba0.985Na0.015Ti0.985Nb0.015O3, Ba0.6Na0.4Ti0.6Nb0.4O3 and Ba0.3Na0.7Ti0.3Nb0.7O3 compositions

The Ba_0.985Na_0.015Ti_0.985Nb_0.015O₃, Ba_0.6Na_0.4Ti_0.6Nb_0.4O₃ and Ba_0.3Na_0.7Ti_0.3Nb_0.7O₃ compositions of the (1 − x) BaTiO₃–xNaNbO₃ (BTNNx) system have been studied by X-ray diffraction and by measurements of dielectric properties. The specimens with composition BTNN (x = 0.015, 0.40 and 0.70) have been refined by the JANA program from X-ray powder diffraction data. Ceramic samples with composition (1 − x) BaTiO₃ + xNaNbO₃ (where x = 0.015, 0.40 and 0.70) were prepared by calcinations from appropriate mixture of BaCO₃, TiO₂, Na₂CO₃ and Nb₂O₅. The calcined powder was sintered at temperature range 1200–1400 °C. As the composition x increased from 0.015 (and 0.70), the ferroelectric ceramics (x = 0.015, FE) with tetragonal phase changed to the ferroelectric relaxors (RFE, x = 0.40). RFE ceramics showed a peculiar diffuse phase transition and dielectric relaxation at the low temperature (down to 180 K) due to a frustration between RFE and FE state. These ceramics present the classical ferroelectric character when 0 ≤ x < 0.075 and 0.55 < x ≤ 1 and relaxor character when 0.075 ≤ x ≤ 0.55.     

Magnetic, electrical and plastic properties of Fe76Nb2Si13B9, Fe75Ag1Nb2Si13B9 and Fe75Cu1Nb2Si13B9 amorphous alloys

Influence of 1 h annealing in vacuum on magnetic, electrical and plastic properties of Fe₇₆Nb₂Si₁₃B₉, Fe₇₅Ag₁Nb₂Si₁₃B₉ and Fe₇₅Cu₁Nb₂Si₁₃B₉ melt spun ribbons were carefully investigated. It was shown that in all cases soft magnetic properties can be significantly enhanced by applying 1-h annealing at characteristic temperatures T_op. This optimization annealing causes that permeability increases more than 15-times and magnetic losses (tangent of loss angle) achieves a minimum in relation to the as quenched state. Using structural examinations (X-ray and HRTEM) it was shown that for the Fe₇₅Cu₁Nb₂Si₁₃B₉ alloy the optimized microstructure corresponds to a nanocrystalline αFe(Si) phase whereas in other alloys to a relaxed amorphous phase free of iron nanograins. As a consequence of this fact the Fe₇₆Nb₂Si₁₃B₉ and Fe₇₅Ag₁Nb₂Si₁₃B₉ alloys show higher plasticity in comparison to the nanocrystalline Fe₇₅Cu₁Nb₂Si₁₃B₉ alloy. Temperatures of the first stage of crystallization, and related diffusion parameters were determined using measurements of resistivity versus temperature with different heating rates.     

Fe2+-Ni2+-NH3-NH4+-C2O42-H2O体系的沉淀配合平衡热力学

针对草酸盐配位共沉淀热分解还原法制备超细铁镍合金粉过程中Fe2+-Ni2+-NH3-NH4+-C2O42--H2O体系的溶液平衡建立热力学分析模型,并根据模型进行相关计算,揭示反应体系中各物质随pH值、氨及草酸浓度的变化关系。结果表明:溶液中的Fe主要以[Fe(C2O4)n]2 2n络合物形式存在,而铁氨络合物含量很低。当氨含量较低时,溶液中的Ni主要以[Ni(C2O4)n]2 2n存在;氨含量较高时,在酸性条件下,溶液中的Ni主要以[Ni(C2O4)n]2 2n存在,在碱性条件下,则主要以[Ni(NH3)n]2+存在。低pH值下,Ni的沉淀率较Fe的高,而高pH值下,Ni的沉淀率则较Fe的低。     

Thermodynamics and phase diagrams in the binary systems Na2O-SiO2, Na2O-GeO2, Na2O-B2O3, Li2O-B2O3, CaO-B2O3, SrO-B2O3, and BaO-B2O3

We applied our model to the enthalpy of mixing data of the binary systems Na₂O-SiO₂, Na₂O-GeO₂, Na₂O-B₂O₃, Li₂O-B₂O₃, CaO-B₂O₃, SrO-B₂O₃, and BaO-B₂O₃. The most stable composition in the liquid, that is where the enthalpy of mixing is most negative, is with a metal-oxygen ratio of 4 to 3, for monovalent metals (Na and Li) and 3 to 4 for divalent metals (Ba and Ca) in liquid silicates or borates. The same applies to the CaO-SiO₂, CaO-Al₂O₃, PbO-B₂O₃, PbO-SiO₂, ZnO-B₂O₃, and ZnO-SiO₂ systems. The oxygen to metal ratio, its constant value in various types of systems, reflects and describes the structure of the liquid. Using the analyzed enthalpies of mixing data and the available phase diagrams, we calculated the enthalpies of formation of the various binary compounds. The results are in excellent agreement with data in the literature that were obtained from direct solid-solid calorimetry.     

New Zr6CoAs2-type compounds: Y6CoBi2, Ho6CoBi2 and Tm6CoBi2

Results of a powder X-ray diffraction investigation of new ternary compounds are reported. The compounds Y₆CoBi₂ [a=0.8312(1) nm, c=0.4144(1) nm], Ho₆CoBi₂ [a=0.8246(2) nm, c=0.4095(1) nm], and Tm₆CoBi₂ [a=0.8155(2) nm, c=0.4066(1) nm] crystallize in the hexagonal Zr₆CoAs₂-type structure (space group P6b2m No. 189). The Zr₆CoAs₂-type structure is a superstructure of the Fe₂P-type structure.     

Zur Kenntnis von RbBa3Ca4Cu3V7O28

Single crystals of RbBa₃Ca₄Cu₃V₇O₂₈ were prepared above the melting point of the reaction mixture. It crystallizes with hexagonal symmetry, space group C_6V⁴-P6₃mc, a 11.1751, c 12.434 Å, Z = 2. RbBa₃Ca₄Cu₃V₇O₂₈ is the second member of a new structure type of the copper-oxovanadates. Ba²⁺ shows an unusual 12-fold coordination. The two calcium positions are coordinated by trigonal prisms and octahedra respectively. The copper coordination is characterized by a stretched square pyramid. The Cu²⁺ ions are outside the centre nearly in plane of the pyramids.

Zusammenfassung

Einkristalle von RbBa₃Ca₄Cu₃V₇O₂₈ wurden oberhalb des Schmelzpunktes der Reaktionsmischung erhalten. Die Verbindung kristallisiert hexagonal, Raumgruppe C_6V⁴-P6₃mc, a 11.1751, c 12.434 Å, Z = 2. RbBa₃Ca₄Cu₃V₇O₂₈ ist das zweite Beispiel für einen neuen Strukturtyp der Kupfer-Oxovanadate, mit 12-fach koordinierten Ba²⁺ -Ionen. Die zwei Calciumpositionen sind trigonal prismatisch bzw. oktaedrisch koordiniert. Die Koordination der Cu²⁺-Ionen ist durch eine gestreckte Pyramide charakterisiert. Cu²⁺ ist auβerhalb des Polyederzentrums nahezu in der quadratischen Fläche der Pyramide angeordnet.     

Al2O3-Sm2O3-CeO2电解质的性能（英文）

采用溶胶-凝胶法和低温燃烧技术制备Ce1-xSmxO2（x=0,0.1,0.2,0.3）和掺杂Sm和（2%-8%）Al2O3的二氧化铈;研究其合成、结构、致密化、导电性和热膨胀等性能,并利用XRD研究其结构和相组成。结果表明,于1300°C烧结球团,获得致密的陶瓷,于1250°C在Ce0.8Sm0.2O0.2中加入2%和4%的Al2O3以促进烧结。利用扫描电子显微镜观察烧结后球团的表面形貌,使用双探针交流阻抗谱研究总离子电导率。     

Sinterability and dielectric properties of Ba0.55Sr0.4Ca0.05TiO3-CaTiSiO5-Mg2TiO4 composite ceramics

The composite ceramics of Ba_0.55Sr_0.4Ca_0.05TiO₃-CaTiSiO₅-Mg₂TiO₄ (BSCT-CTS-MT) were prepared by the conventional solid-state route. The sintering performance, phase structures, morphologies, and dielectric properties of the composite ceramics were investigated. The BSCT-CTS-MT ceramics were sintered at 1100 °C and possessed dense microstructure. The dielectric constant was tailored from 1196 to 141 as the amount of Mg₂TiO₄ increased from 0 to 50 wt%. The dielectric constant and dielectric loss of 40 wt% Ba_0.55Sr_0.4Ca_0.05TiO₃-10 wt% CaTiSiO₅-50 wt% Mg₂TiO₄ was 141 and 0.0020, respectively, and the tunability was 8.64% under a DC electric field of 8.0 kV/cm. The Curie peaks were broadened and depressed after the addition of CaTiSiO₅. The optimistic dielectric properties made it a promising candidate for the application of tunable capacitors and phase shifters.     

电弧喷涂制备Fe65Cr20Mo7B3.5SiMn1.5W3涂层

在Q235低碳钢板上利用电弧喷涂工艺进行喷涂,以制得Fe65Cr20Mo7B3.5SiMn1.5W3涂层。喷涂材料为自行配制的丝材,按照35%的填充率将配好的粉填充到U型不锈钢外皮中,经过多道拉拔、挤压工艺制成Φ2mm的粉芯丝材。采用X射线衍射仪、扫描电镜、能谱分析仪、透射电镜对涂层的物相和组织形貌及成分进行了表征;采用差示扫描量热仪、显微硬度仪等设备对涂层的热稳定性及显微硬度进行了检测和分析。试验结果表明:涂层组织形貌呈典型的层状组织结构,由变形良好的带状粒子相互搭接堆积而成。涂层含有50.63%的非晶相,同时含有纳米级的晶相。涂层组织均匀、结构致密、孔隙率低,并且涂层硬度高达1040.5HV0.3,属硬质涂层,具有良好的热稳定性。