溶胶凝胶法制备锂离子电池正极材料LiNi_(1/3)Mn_(1/3)Co_(1/3)O_2的研究

综述了溶胶凝胶法制备锂离子电池三元正极材料Li Ni1/3Mn1/3Co1/3O2的研究,讨论了三元材料的结构特性,着重从添加有机络合剂、掺杂、包覆改性以及模板辅助等方面探讨对Li Ni1/3Mn1/3Co1/3O2材料电化学性能的影响,并分析三元材料目前存在的问题和未来应用的前景。     

高电压电池储存性能及其容量衰减研究

以Li Ni0.5Mn1.5O4为正极、石墨为负极,制作Li Ni0.5Mn1.5O4/C全电池。并且利用X射线衍射光谱法(XRD)、循环伏安(CV)、能谱仪(EDS)等分析检测手段研究了储存前后的电极活性物质结构和表面状态的变化,测试Li Ni0.5Mn1.5O4电池储存前后电化学性能,并研究了不同荷电态储存后电池容量衰减情况及其相关机理。研究表明,满电态储存后容量衰减最大,达到14.1%,25%荷电态储存后容量衰减最小,为5.9%。X射线衍射光谱法(XRD)结果表明,储存后Li Ni0.5Mn1.5O4尖晶石结构发生一定程度的塌陷;Ni2+和Mn4+发生溶解,并在负极析出;循环伏安测试结果表明,储存后电极极化增大。     

Novel Co‐Mn‐O nanosheet catalyst for CO preferential oxidation toward hydrogen purification

Co‐Mn‐O composite oxide nanosheet catalyst was successfully prepared using a facile urea‐assisted one‐step hydrothermal method in the absence of organic or organic templating reagent. Co‐Mn‐O nanosheet catalyst was optimized by varying hydrothermal process parameters such as molar ratio of Co‐Mn to urea, hydrothermal temperature, and hydrothermal time. Various characterization techniques including scanning electron microscopy, X‐ray diffraction, nitrogen adsorption, X‐ray photoelectron spectroscopy, Raman spectroscopy, and H₂ temperature‐programmed reduction were used to reveal the relationship between catalyst nature and catalytic performance in CO preferential oxidation (CO PROX) in excess H₂. The developed Co‐Mn‐O nanosheet catalyst have demonstrated much superior catalytic performance to Co‐Mn‐O nanoparticle, particularly in the low temperature range, and 100% CO conversion over the developed Co‐Mn‐O nanosheet can be achieved in temperature range of 50 to 150°C at 10,000 mL g^?1 h^?1 of gas hourly space velocity in the standard feed. Furthermore, the almost complete CO removal over Co‐Mn‐O nanosheet at 125°C of low temperature with 94.9% selectivity can be achieved even in the simulated reformed gas. The excellent catalytic performance is ascribed to nanosheet morphology, more surface Co³⁺, smaller average crystallite size, higher reducibility, and strong Co‐Mn interaction. Catalytic stability investigation indicates the developed nanostructured catalyst exhibits high catalytic stability for CO PROX reaction in simulated gas. The developed Co‐Mn‐O nanosheet catalyst can be a potential candidate for catalytic elimination of trace CO from H₂‐rich gas for Proton exchange membrane fuel cell applications. © 2014 American Institute of Chemical Engineers AIChE J, 61: 239–252, 2015     

Mn~(2+)-SCN~--RhB三元缔合体系光度法测定锰的研究

研究了在硫酸介质中,在聚乙烯醇和明胶的协同作用下,锰(II)与硫氰酸根离子形成的络离子能与罗丹明B形成三元缔合物,据此建立了测定锰的新方法。实验最大吸收波长为640 nm,线性回归方程为y=0.1067x,相关系数为0.9997,表观摩尔吸光系数为4.27×105L·mol-1·cm-1,检出限为0.091μg/L,锰浓度在0~1.2μg/10m L范围内与吸光度A有良好的线性关系,用于环境水样中痕量锰的测定,其相对标准偏差为1.1%~2.8%,回收率为96%~104%。     

Effect of enhanced interfacial reaction on the microstructure,phase transformation and mechanical property of Ni–Mn–Ga particles/Mg composites

This study investigated the microstructure, phase transformation and mechanical property of Ni–Mn–Ga particles/Mg composites with a strong interfacial reaction between the particles and the matrix. The strong interfacial reaction was related to the large surface area and energy per unit volume of the flaky shape Ni–Mn–Ga particles that favors the reaction between the particles and matrix. The martensitic transformation behavior was largely weakened due to the interfacial reactions and thus the reduced volume fraction of Ni–Mn–Ga particles. The composites exhibited a much improved compressive strength and ductility in comparison with that of the Ni–Mn–Ga alloy. The compressive plasticity of the composites was decreased when the Ni–Mn–Ga particle content exceeded 40 wt%. In comparison with the Mg-composites with large size Ni–Mn–Ga particles, the composites with small size particles would have a much stronger interfacial reactions, which was detrimental to the phase transformation and mechanical ductility of the composites. The investigation results in this article could provide a reference for the design and preparation of the particles reinforced metal matrix functional composites.     

不同pH的碱性环境中16Mn钢及热影响区应力腐蚀行为

利用电化学技术和U形弯试样浸泡实验研究了16Mn钢及其模拟热影响区(HAZ)在不同pH的碱性硫化物和Cl-介质中的应力腐蚀开裂(SCC)行为与机理.结果表明:16Mn钢原始组织、粗晶组织(空冷组织)和硬化组织(淬火组织)在pH为11.8的碱性硫化物环境中均近似呈钝化状态,维钝电流密度依次降低;随着pH的降低,原始组织和粗晶组织的阳极过程逐渐由钝化态转变为活化态;HAZ中硬化组织、粗晶组织和原始组织在碱性硫化物环境下的SCC敏感性依次降低,其中硬化组织具有明显的SCC特征;随着pH的降低,SCC裂纹有从沿晶裂纹转变为穿晶和沿晶混合裂纹的趋势,并且裂纹的宽度增加.     

16Mn钢长轴裂纹缺陷成因分析

某16Mn钢长轴零件经超声波探伤发现存在缺陷,采用化学成分分析、低倍检验、金相检验、断口分析等方法对缺陷的类型和成因进行了分析。结果表明:该零件原材料中存在的非金属夹杂形成了裂纹源,在加工压力的作用下进一步扩展,最终形成了裂纹缺陷。     

Flow stress and dynamic recrystallization behavior of Al-9Mg-1.1Li-0.5Mn alloy during hot compression process

The flow stress behavior of spray-formed Al-9Mg-1.1Li-0.5Mn alloy was studied using thermal simulation tests on a Gleeble-3500 machine over deformation temperature range of 300-450 °C and strain rate of 0.01-10 s^?1. The microstructural evolution of the alloy during the hot compression process was characterized by transmission electron microscopy (TEM) and electron back scatter diffractometry (EBSD). The results show that the flow stress behavior and microstructural evolution are sensitive to deformation parameters. The peak stress level, steady flow stress, dislocation density and amount of substructures of the alloy increase with decreasing deformation temperature and increasing strain rate. Conversely, the high angle grain boundary area increases, the grain boundary is in serrated shape and the dynamic recrystallization in the alloy occurs. The microstructure of the alloy is fibrous-like and the main softening mechanism is dynamic recovery during steady deformation state. The flow stress behavior can be represented by the Zener-Hollomon parameter Z in the hyperbolic sine equation with the hot deformation activation energy of 184.2538 kJ/mol. The constitutive equation and the hot processing map were established. The hot processing map exhibits that the optimum processing conditions for Al-9Mg-1.1Li-0.5Mn alloy are in deformation temperature range from 380 to 450 °C and strain rate range from 0.01 to 0.1 s^?1.     

高强双相钢表面选择性氧化行为对磷化性能的影响

目的确定高强双相钢表面Si、Mn元素选择性氧化行为对磷化性能的影响,以改善高强双相钢的磷化性能。方法在具备不同表面选择性氧化行为的试样表面制备磷化膜。采用X射线光电子能谱仪(XPS)、辉光光谱仪(GDS)、透射电镜(TEM)等手段,分析高强双相钢表面Si、Mn元素的选择性氧化行为,通过扫描电镜观察磷化膜的结晶状态,并采用电化学技术分析钢板在磷化液中的反应过程。结果当高强钢表面Si含量较少时,表面氧化物主要以弥散分布的小颗粒状Mn Al_2O_4形态存在,能够加快在磷化液中酸蚀反应速度,磷化晶粒均匀、致密,尺寸小于4mm,覆盖率为100%。当高强钢表面Si含量较高时,形成的Mn_2SiO_4容易在晶界聚集,颗粒尺寸较大,减慢了酸蚀反应速度,磷化晶粒尺寸大于8mm,均匀致密性差。而提高材料表面Mn元素的富集程度,可以减轻Mn_2SiO_4聚集的现象,提高酸蚀反应速度,磷化晶粒均匀、致密,尺寸小于4mm,覆盖率100%。结论减轻双相高强钢表面Si元素的富集程度,而提升Mn元素的富集程度,可以加快钢板在磷化液中的酸蚀反应,进而改善磷化性能。     

Crystallization-induced valence state change of Mn2+ → Mn4+ in LiNaGe4O9 glass-ceramics

Tetra-valent manganese (Mn⁴⁺) has been regarded as an efficient non-rare-earth red-light emitting ion, which has stimulated continued search of robust hosts and efficient synthetic methods to stabilize Mn⁴⁺ centers with strong photoluminescence. In this work, we demonstrate a facile synthetic method for Mn⁴⁺ doped glass-ceramic (GC) based on crystallization-induced oxidation state change in an oxide glass. The parent glass with a formula of LiNaGe₄O₉ is fabricated by melt-quenching and crystallization is induced by thermal treatment in air. Oxidation of Mn²⁺ in glass to Mn⁴⁺ in the GC is confirmed by both optical spectroscopy and electron paramagnetic resonance (EPR) measurements. After thermal treatment, the characteristic reddish photoluminescence (PL) of Mn²⁺ in the glass centered at 611 nm disappears and a strong photoluminescence peak at 660 nm attributed to Mn⁴⁺ is observed. The conversion to Mn⁴⁺ after crystallization in the examined system may have strong implications for synthesis of Mn⁴⁺ doped phosphors which always requires rigorous control of the redox equilibrium during synthesis.