Mg1.7M0.3(M＝Mg,Ti,Al)Ni贮氢合金结构及性能研究

采用固态烧结法制备了Mg1 7M0 3(M =Mg、Ti、Al)Ni贮氢合金 ,X射线衍射分析结果表明 ,适当提高烧结温度有利于Mg2 Ni相的形成 ;Ti对Mg的取代未引起合金相结构的明显变化 ,而Al取代Mg除有Mg2 Ni相外 ,还有一呈立方晶体结构的新相生成。Ti、Al对Mg的取代 ,不仅提高了Mg2 Ni合金的放电容量 ,同时也提高了合金的循环寿命。     

Mg3MNi2（M=Ti，Al）的晶体结构

Al和Ti对Mg2Ni结构中部分Mg的取代,得到与Mg2Ni晶体结构不同的新型合金．多晶X射线结构分析表明,其化学式为Mg3MNi2(M=Ti,Al),立方晶系,空间群Fd3m,Z=16,48个Mg坐落在48(y),16个M(M=Al,Ti)坐落在16(d)位,32个Ni坐落在32(e)位,Mg3AlNi2的晶胞参数a=1．15474(2)nm,Mg3TiNi2的a=1．16178(2)nm．与Mg2Ni相比,Mg3MNi2合金的晶体密度更大,Mg-Ni键长更长,吸放氢温度降低,循环寿命延长．     

La1＋xMg2-xNi9（x=0，0．5，1．0，1．5）合金的储氢性能及电化学性能研究

利用高频熔炼方法制备了La1＋xMg2-xNi9（x=0，0．5，1．0，1．5）系列合金，并对其进行了XRD分析和储氢容量及电化学性能测定。结果表明：随着La含量增大，合金中LaNi5和（La，Mg）Ni3相转变为LaNi3相，且Mg2Ni相出现，晶胞体积也增大，合金的储氢容量和电化学性能提高；当x=1．5时，Mg2Ni相消失，合金的储氢性能有所下降。当x=1．0时，即La2MgNi9合金具有较好的储氢容量及电化学容量。     

元素Ti对贮氢合金ZrMn0．7V0．2CO0．1Ni1．2相结构和电化学性能的影响

研究了元素Ti对贮氢电极合金ZrMn0.7V0.2Co0.1Ni1.2的相结构、相组成以及电化学性能的影响。结果表明，对于合金Zr1-xTix(Mn0.7V0.2Co0.1Ni1.2)，其母体合金的主相为C15型Laves相，并含有少量的非Laves相Zr7M10；但随着掺Ti量的增加，合金中出现C14型Laves相，而且其含量逐渐增加；在x=0．1～0．2时，合金中还出现少量的TiNi相，而在x=0．4～0．5时，非Laves相Zr7M10和TiNi相全部消失，说明元素Ti大量的掺杂抑制了第二相的产生：而且随着Ti含量的增加，合金中的C15型和C14型Laves相的晶格常数逐渐减小。电化学测试结果发现，当含Ti量x=0．2时，合金有最大放电容量Cmax为354mAh／g，在放电电流为300mAh／g条件下，高倍率放电性能比母体合金提高了15％。     

Al、Ti掺杂对Mg2Ni合金相结构稳定性的影响及其微观机理

采用第一性原理赝势平面波方法,研究元素Al和Ti掺杂对Mg2Ni储氢合金相结构稳定性的影响及其微观机理.结果显示:在掺杂浓度x＝0～0.5范围内,所形成的Mg2Ni型Mg2-xMxNi(M＝Al,Ti)固溶体合金的相结构稳定性随Al掺杂浓度的增大而增强,随Ti掺杂浓度的增大而减弱,且Mg2-xMxNi(M＝Al,Ti)固溶体合金相对于立方结构的Mg3MNi2(M＝Al,Ti)化合物呈现热力学不稳定性,极易分解成由立方结构Mg3MNi2(M＝Al,Ti)和六方结构Mg2Ni组成的复合相,计算结果与实验结果吻合.电子结构分析表明,Al、Ti掺杂Mg2Ni储氢合金的相结构稳定性与体系在低能级区的成键电子数密切相关.     

A2B7型La0.75Mg0.25Ni3．5-xAlx（x=0-0．3）合金相结构及电化学性能

采用感应熔炼方法制备了A2B7型La0.75Mg0.25Ni3．5-xAlx（x=0，0．02，0．06 0.1，0．3）四元贮氢合金，系统研究了Al元素部分替代Ni对A2B7型La0.75Mg0.25Ni3．5合金相结构及电化学性能的影响。X射线衍射（XRD）分析表明：La0.75Mg0.25Ni3．5由单一La2Ni7相组成：Al元素加入后，开始出现CaCu5型LaNi5相，当x=0．3时，LaNis相成为合金的主相。Rietveld分析表明：随着Al含量的增加，LaNi5相逐渐增多，Al的加入利于CaCu5型LaNi5相的形成。电化学测试表明：Al替代Ni对A2B7型合金La0.75Mg0.25Ni3．5电极活化性能影响不大：而最大放电容量随Al在La0.75Mg0.25Ni3．5-xAlx，合金中替代量的增加而减小。当放电电流密度为1600mA／g时，合金的倍率放电性能由68.8％（x=0）增加到81．16％（x=0．1）然后减小到65．67％（x=0.3）。此外，La0.75Mg0.25Ni3．5-xAlx合金电极循环稳定性先增加而后下降。x=0．06时合金电极容量保持率最大（S100=85.21．％）。     

Ni对V55Ti20．5Cr18．1Fe6．4合金吸放氢性能的影响

研究了用Ni元素取代一定量V对V55Ti20．5Cr18．1Fe6．4合金结构与性能的影响。结果表明，随Ni含量的增加，合金有效吸氢量先增大后减小，放氢压力增大，合金吸氢动力学性能也是先有所改善，而后又变差。添加0．1at％Ni有利于改善基体合金V55Ti20．5Cr18．1Fe6．4的吸放氢性能。用Ni元素取代V引起的晶胞体积的变化、放氢平台压力的升高以及杂质相的出现，是影响合金有效吸氢量和吸氢动力学性能的主要因素。     

退火处理对La1．5Mg0．5Ni7．0贮氢合金相结构和电化学性能的影响

研究了退火温度对A287型La1.5Mg0.5Ni7.0合金的相结构和电化学性能的影响。结果表明：铸态合金由LaNi，相、LaMgNi4相、（La，Mg）Ni3相以及Gd2Co7型相组成，退火处理后，合金由Gd2Co7型相、Ce2Ni7型相和PuNi3型（La，Mg）Ni3相组成：随着退火温度升高，PuNi3型相的丰度减小，ce2Ni7型相的丰度增加，（La，Mg）Ni3相的a轴参数、c轴参数和晶胞体积均增大；经1073K保温24h退火后，合金电极具有最高的放电容量（391．2mAh／g），退火温度升高，合金的最大放电容量略有降低：合金电极的循环稳定性随着退火温度的升高不断提高，在1173K时合金电极经150次循环后其电极容量保持率C150／Cmax=82％；合金的高倍率放电性能（HRD）随退火温度升高略有增加，在1173K时，合金电极的HRD最好（HRD900=89．0％）；交换电流密度I0、极限电流密度I1及氢扩散系数D随着退火温度的升高而增大。     

Zr替代Ti对Ti19．5V40Mn16．2Cr9．8Ni14．5合金的影响结构及储氢性能

为改善Ti—V基固溶体型储氢合金的电化学性能，使用少量的Zr部分取代Ti19.5V40Mn16.2Cr9.8Ni14.5合金中的Ti，并采用XRD，SEM以及PCT等测试手段研究替代前后合金微观结构和储氢性能的变化情况。通过XRD和SEM分析表明，（Ti1-xZrx）19.5V40Mn16.2Cr9.8Ni14.5（x=0，0．1，0．15，0．2，0．25，0．3）合金均是由Ti-V基BCC相和C14 Laves相组成。但Zr的部分替代明显增加了C14 Laves相的含量，并使Ti-V基BCC相在减少的同时由树枝状变成了被C14 Laves相包围的岛状。PCT曲线显示：随着Zr替代量的增加。合金的吸放氢平台不断下降，而合金的吸放氢量先有所增加后又逐渐减小。这说明适量提高C14 Laves相的含量对增加Ti—V基固溶体型储氢合金的吸放氢能力有一定的促进作用。     

Zr替代Ti对Ti19．5V40Mn16．2Cr9．8Ni14．5合金的影响Ⅱ：电化学性能

在对合金微观结构和储氢性能研究的基础上，详细考察了少量Zr取代Ti对Ti19．5V40Mn16．2Cr9．8Ni14．5合金电化学性能的影响。通过观察电极的充放电行为，并结合EIS及多种极化曲线的分析结果，发现少量Zr对Ti的取代能够显著提高合金电极的实际电化学容量和循环稳定性，而且还能在一定程度上改善合金的电极动力学性能。对于这些性能的改善，从合金微观结构方面进行了解释。     

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.     

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。     

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.     

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。     

Synthesis and electrochemical properties of LiNi0.4Mn1.5Cr0.1O4 and Li4Ti5O12

Spinel compound LiNi_0.4Mn_1.5Cr_0.1O₄ (LNMCO) and Li₄Ti₅O₁₂ (LTO) were synthesized by the sol-gel method and the solid-state method, respectively. The particle sizes of the products LiNi_0.4Mn_1.5Cr_0.1O₄ and Li₄Ti₅O₁₂ were 0.5 to 2 um and 0.5 to 0.8 um, respectively. All samples exhibited excellent electrochemical properties. A LiNi_0.4Mn_1.5Cr_0.1O₄/Li₄Ti₅O₁₂ (LNMCO/LTO) cell was fabricated and was demonstrated to exhibit good electrochemical properties at the high current rate of 1 C. When the specific capacity was determined based on the mass of the LNMCO cathode, the LNMCO/LTO cell delivered 125 mAh g⁻¹ at 1 C and 77 mAh g⁻¹ at 5 C. The capacity retentions after 30 cycles were 94.4 % and 83.1 %, respectively.