Li-Mg-N-H体系储氢材料的热力学和动力学调控

Mg（NH₂）₂-2LiH体系储氢材料具有较高的储氢容量和较适宜的热力学性能,并且其吸放氢过程完全可逆,是目前最有望实现大规模应用的固态储氢材料之一。然而,由于该体系在吸放氢过程中具有较高的动力学壁垒,导致其在200℃以上才能实现快速地吸放氢。因此,国际上对该体系储氢材料的研究主要集中在热力学和动力学的调控方面。本文从成分调变、纳米化和掺杂改性等方面,详细综述了Mg（NH₂）₂-2LiH体系储氢材料热力学和动力学调控的研究现状,并提出了其中存在的问题和相应对策,同时指出了将来的研究方向。     

沉积参量及时效时间对 SiO2薄膜残余应力的影响

SiO2 薄膜由电子束蒸发方法沉积而成。用GPI数字波面光学干涉仪测量了不同沉积条件下玻璃基底镀膜前后曲率半径的变化,并确定了 SiO2 薄膜中的残余应力。在其他条件相同的情况下,当沉积温度由 190 ℃升高到350 ℃时,SiO2 薄膜中的压应力由-156 MPa增大为-289 MPa。氧分压由3.0×10-3 Pa升高到13.0×10-3 Pa时,SiO2 薄膜中的应力由-223.5 MPa变为20.4 MPa。通过对薄膜折射率的测量,发现薄膜的堆积密度随沉积条件的改变也发生了规律性的变化。应力的变化主要是由于沉积时蒸发粒子的动能不同,导致薄膜结构不同引起的。同时,在样品的存放过程中,发现随着存放时间的延长,薄膜中的应力表现出了由压应力状态向张应力状态演变的趋势。     

Influences of CO2 laser annealing on mechanical and laser-induced damage properties of ZrO2 thin films

Zirconium dioxide (ZrO₂) thin films were deposited on BK7 glass substrates by the electron beam evaporation method. A continuous wave CO₂ laser was used to anneal the ZrO₂ thin films to investigate whether beneficial changes could be produced. After annealing at different laser scanning speeds by CO₂ laser, weak absorption of the coatings was measured by the surface thermal lensing (STL) technique, and then laser-induced damage threshold (LIDT) was also determined. It was found that the weak absorption decreased first, while the laser scanning speed is below some value, then increased. The LIDT of the ZrO₂ coatings decreased greatly when the laser scanning speeds were below some value. A Nomarski microscope was employed to map the damage morphology, and it was found that the damage behavior was defect-initiated both for annealed and as-deposited samples. The influences of post-deposition CO₂ laser annealing on the structural and mechanical properties of the films have also been investigated by X-ray diffraction and ZYGO interferometer. It was found that the microstructure of the ZrO₂ films did not change. The residual stress in ZrO₂ films showed a tendency from tensile to compressive after CO₂ laser annealing, and the variation quantity of the residual stress increased with decreasing laser scanning speed. The residual stress may be mitigated to some extent at proper treatment parameters.     

Conformational heterogeneity observed in simulations of a pyrene-substituted DNA

NMR studies previously carried out for a DNA system with a pyrene-substituted base did not observe NOEs involving the adenine located 5' to the pyrene, and thus the conformation of the adenine was poorly defined in the resulting family of refined structures. However, chemical shift data suggested that an AT base pair may be present. We have carried out fully unrestrained molecular dynamics simulations starting from several members of the family of structures, and these simulations support the existence of an AT base pair for this region. Simulations in both explicit and implicit solvent were carried out, with each converging to either anti or syn conformation for adenine and base pairing in all cases. During these simulations, large and dramatic conformational changes are observed that suggest pathways for complex conformational changes in the highly packed DNA interior. Our analysis reveals little difference in the energies of these syn and anti conformations, in contrast to control calculations carried out for standard DNA (in the absence of a neighboring pyrene). While no interconversion between the conformations was observed in standard simulations, reversible anti/syn exchange was directly simulated using the locally enhanced sampling approach. No exchange was seen in the non-pyrene control sequence. Together, these results suggest that an increased flexibility is introduced as a consequence of the pyrene substitution, offering an explanation that is consistent with the available experimental data. These results increase our optimism that simulations in atomic detail may provide accurate models for experimental observations in complex systems.     

聚环氧乙烷聚合物电解质基高电压固态锂金属电池的研究进展

采用液态碳酸酯电解质的锂离子电池在遭遇极端工况时, 极易发生泄露、燃烧、甚至爆炸等重大安全事故. 相对比, 聚环氧乙烷(PEO)固态聚合物电解质可以显著提升锂电池的安全性, 并且其优异的可塑性使其可以被制成特定形状进而满足特殊领域的差异化需求; 更为重要的是: PEO固态聚合物电解质与锂金属负极兼容性好. 然而, PEO固态聚合物电解质电化学氧化窗口低, 难以匹配高电压正极材料(≥4 V), 极大限制了其在高电压、高能量密度固态聚合物锂金属电池中的进一步应用. 近期经过国内外科研工作者在PEO固态聚合物电解质结构设计、PEO端羟基改性、含硼锂盐引入、功能型粘结剂设计开发以及正极界面层构筑等方面所做出的不懈努力, PEO固态聚合物电解质基高电压固态锂金属电池取得了系列化重大科研进展. 基于此, 本综述主要从以下八个方面: (1)高电压正极片表面修饰超薄聚合物层、(2)高电压正极颗粒包覆、(3)对碳黑颗粒进行包覆、(4)使用富含羧基的粘结剂、(5)不对称固态聚合物电解质结构设计、(6)正极界面原位形成耐高电压界面层、(7)醚氧官能团(-OCH₃)封端PEO, 提升其本征耐高电压性能、(8)含硼锂盐做添加剂, 详细综述了采用PEO固态聚合物电解质构建的高电压固态锂金属电池所取得的最新研究进展以及相应的高电压固态锂金属电池界面稳定作用机制. 最后还对未来PEO固态聚合物电解质在高电压固态锂金属电池方面所存在的巨大挑战和发展趋势进行了详细展望和总结阐述.     

离子液体-无机颗粒杂化电解质在二次电池中的研究进展

高性能电解质是制备高能量密度、长循环寿命、良好安全性二次电池的关键材料之一.然而,传统的有机以及水系电解质,由于诸多限制（例如,电位窗口窄、离子电导率低、枝晶、"胀气"和腐蚀等）已不能满足安全、高效二次电池的发展需求.近年来,离子液体-纳米颗粒杂化电解质（IL-NPHE）体系由于具有高稳定、不可燃及多种协同特性而备受关注.专注于IL-NPHE研究的最新进展,对此类电解质体系的物化特性及电化学性能进行了归纳.同时,系统总结了离子液体和无机颗粒之间的协同作用机理.基于上述评述,展望了IL-NPHE的未来发展趋势和方向.     

SiO2气凝胶分子动力学模拟研究进展

二氧化硅(SiO2)气凝胶是一种拥有三维骨架网络结构的纳米多孔材料,具有高孔隙率、低密度和低热导率等许多独特的性能.但是由于二氧化硅气凝胶本身的脆性及高温稳定性差等原因,限制了其大规模应用.二氧化硅气凝胶的热力学性能与其内部的三维骨架和孔结构紧密相关,掌握二氧化硅气凝胶内部微结构演化规律与宏观性能的关联,是改善其热力学...     

Rational construction and triethylamine sensing performance of foam shaped α-MoO3@SnS2 nanosheets

Owing to their high surface area, stable structure and easy fabrication, composite nanomaterials with encapsulation structures have attracted considerable research interest as sensing materials to detect volatile organic compounds. Herein, a hydrothermal route is designed to prepare foam shaped α-MoO₃@SnS₂ nanosheets that exhibit excellent sensing performance for triethylamine（TEA）. The developed sensor,based on α-MoO₃@SnS₂ nanosheets, displays a high ...     

Recent progress on electrolyte functional additives for protection of nickel-rich layered oxide cathode materials

In advantages of their high capacity and high operating voltage,the nickel(Ni)-rich layered transition metal oxide cathode materials(LiNi_xCo_yMn_zO₂(NCMxyz,x+y+z=1,x≥0.5)and LiNi_0.8Co_0.15Al_0.05O₂(NCA))have been arousing great interests to improve the energy density of LIBs.However,these Nirich cathodes always suffer from rapid capacity degradation induced by unstable cathode-electrolyte interphase(CEI)layer and destruction of bulk crystal structure.Therefore,varied electrode/electrolyte interface engineering strategies(such as electrolyte formulation,material coating or doping)have been developed for Ni-rich cathodes protection.Among them,developing electrolyte functional additives has been proven to be a simple,effective,and economic method to improve the cycling stability of Nirich cathodes.This is achieved by removing unfavorable species(such as HF,H₂O)or constructing a stable and protective CEI layer against unfavorable reactive species(such as HF,H₂O).Herein,this review mainly introduces the varied classes of electrolyte functional additives and their working mechanism for interfacial engineering of Ni-rich cathodes.Especially,key favorable species for stabilizing CEI layer are summarized.More importantly,we put forward perspectives for screening and customizing ideal functional additives for high performance Ni-rich cathodes based LIBs.