卤化物固态电解质研究进展

全固态电池因其高能量密度和高安全性而成为具有发展前景的下一代储能技术。开发具有高室温离子电导率、优异化学/电化学稳定性、良好正/负极兼容性的固态电解质是实现全固态电池实用化的关键。卤化物固态电解质因其优异的电化学窗口、高正极稳定性、可接受的室温锂离子电导率等优势,受到了广泛的关注。本文通过对近年来卤化物电解质的相关研究进行总结,综述了该类电解质的组成、结构、离子传导路径及制备方法,并分析了金属卤化物电解质的电导率、稳定性特点,归纳了近年来该电解质在全固态电池中具有代表性的应用,并基于以上总结和分析,指出了卤化物固态电解质的研究难点及发展方向。     

Isomeric Oligo(Phenylenevinylene)-Based Covalent Organic Frameworks with Different Orientation of Imine Bonds and Distinct Photocatalytic Activities

Imine-linked covalent organic frameworks (COFs) have been extensively studied in photocatalysis because of their easy synthesis and excellent crystallinity. The effect of imine-bond orientation on the photocatalytic properties of COFs, however, is still rarely studied. Herein, we report two novel COFs with different orientations of imine bonds using oligo(phenylenevinylene) moieties. The COFs showed similar structures but great differences in their photoelectric properties. COF-932 demonstrated a superior hydrogen evolution performance compared to COF-923 when triethanolamine was used as the sacrificial agent. Interestingly, the use of ascorbic acid led to the protonation of the COFs, further altering the direction of electron transfer. The photocatalytic performances were increased to 23.4 and 0.73 mmol g⁻¹ h⁻¹ for protonated COF-923 and COF-932, respectively. This study provides a clear strategy for the design of imine-linked COF-based photocatalysts and advances the development of COFs.     

Reconstruction of Solid Electrolyte Interphase with SrI2 Reactivates Dead Li for Durable Anode-Free Li-Metal Batteries

Without excess Li, anode-free Li-metal batteries (AFLMBs) have been proposed as the most likely solution to realizing highly-safe and cost-effective Li-metal batteries. Nevertheless, short cyclic life puzzles conventional AFLMBs due to anodic dead Li accumulation with a local current concentration induced by irreversible electrolyte depletion, insufficient active Li reservoir and slow Li⁺ transfer at the solid electrolyte interphase (SEI). Herein, SrI₂ is introduced into carbon paper (CP) current collector to effectively suppress dead Li through synergistic mechanisms including reversible I⁻/I₃⁻ redox reaction to reactivate dead Li, dielectric SEI surface with SrF₂ and LiF to prevent electrolyte decomposition and highly ionic conductive (3.488 mS cm⁻¹) inner layer of SEI with abundant LiI to enable efficient Li⁺ transfer inside. With the SrI₂-modified current collector, the NCM532/CP cell delivers unprecedented cyclic performances with a capacity of 129.2 mAh g⁻¹ after 200 cycles.     

Intermediate Formation of Macrocycles for Efficient Crystallization of 2D Covalent Organic Frameworks with Enhanced Photocatalytic Hydrogen Evolution

Covalent organic frameworks (COFs) have gained significant attention as key photocatalysts for efficient solar light conversion into hydrogen production. Unfortunately, the harsh synthetic conditions and intricate growth process required to obtain highly crystalline COFs greatly hinder their practical application. Herein, we report a simple strategy for the efficient crystallization of 2D COFs based on the intermediate formation of hexagonal macrocycles. Mechanistic investigation suggests that the use of 2,4,6-triformyl resorcinol (TFR) as the asymmetrical aldehyde build block allows the equilibration between irreversible enol-to-keto tautomerization and dynamic imine bonds to produce the hexagonal β-ketoenamine-linked macrocycles, the formation of which could provide COFs with high crystallinity in half hour. We show that COF-935 with 3 wt % Pt as cocatalyst exhibit a high hydrogen evolution rate of 67.55 mmol g⁻¹ h⁻¹ for water splitting when exposed to visible light. More importantly, COF-935 exhibits an average hydrogen evolution rate of 19.80 mmol g⁻¹ h⁻¹ even at a low loading of only 0.1 wt % Pt, which is a significant breakthrough in this field. This strategy would provide valuable insights into the design of highly crystalline COFs as efficient organic semiconductor photocatalysts.     

Surface domain potential difference-mediated efficient charge separation on a defective ZnIn2S4 microsphere photocatalyst

Low-efficiency charge separation in metal sulfides is a major obstacle to realizing high photocatalytic performance. Herein, we propose the concept of a similar surface domain potential difference between adjacent microdomains with and without surface S vacancies on ZnIn₂S₄ to mediate charge separation. Defective ZnIn₂S₄ microspheres (DZISNPs) are prepared through a solvothermal method combined with a low-temperature hydrogenation surface engineering strategy. The as-prepared DZISNPs with a narrowed bandgap of 2.38 eV possess a large specific surface area of 178.5 m² g^?1, a pore size of 6.89 nm, and a pore volume of 0.36 cm³ g^?1, which further improves the visible light absorption. The resultant DZISNPs exhibit excellent visible light activity (2.15 mmol h^?1 g^?1), which is ～two-fold higher than that of the original DZISNP. The experimental results and DFT calculations reveal that the enhanced property can be a result of the surface S vacancy-induced surface domain potential difference, promoting the spatial separation of electrons and holes. Furthermore, the long-term stability of the DZISNPs indicates that the formation of surface S vacancies can inhibit the photocorrosion of ZnIn₂S₄. This strategy provides new insights for fabricating highly efficient and stable sulfide photocatalysts.     

Efficient and selective analytical method for the quantification of a β-adrenoceptor agonist,isoproterenol, by LC–MS/MS and its application to pharmacokinetics studies

Isoproterenol (ISO) is a synthetic catecholamine with a powerful cardiac stimulate, bronchial smooth and skeletal muscle relaxation, coronary artery and peripheral vasodilator effects. In this study, a simple, rapid, and selective liquid chromatography–tandem mass spectrometry has been developed for the determination of ISO in rat plasma. Proteins were precipitated in plasma samples with 0.1?g?mL^?1 trichloroacetic acid and the ISO/internal standard (IS) were separated on a C₈ column. The ISO was detected by a triple-quadrupole mass spectrometer with electrospray ionization source. The transitions of m/z 212.1?→?193.9 for ISO and m/z 285.2?→?193.2 for IS were conducted through multiple reaction monitoring mode. This method was linear over the range of 2–500?n?g?mL^?1. The intra- and inter-day assay precision were observed between 3 and 10%. The accuracy was within ±11%. Stability study results demonstrated that ISO was stable in the autosampler at 4°C for 24?hr, and for 8?hr at room temperature. Only one freeze–thaw cycle at ?80°C for 24?hr was found to be stable. The validated method was successfully applied to a pharmacokinetic study of ISO in rats following subcutaneous administration.     

Asymptotic nonlinear stability of a composite wave of two traveling waves to a chemotaxis model

In this paper, we investigate the asymptotic stability of a composite wave consisting of two traveling waves to a Keller–Segel chemotaxis model with logarithmic sensitivity and nonzero chemical diffusion. We show that the composite wave is asymptotically stable under general initial perturbation, which only be needed small in H¹‐norm. This improves previous results. Copyright © 2017 John Wiley & Sons, Ltd.     

超声全矩阵数据联合稀疏重构的多测量向量模型应用

针对单测量向量模型(Single Measurement Vector,SMV)等传统压缩感知方法处理超声全矩阵数据时,存在重构精度低和重构耗时长等问题,本文研究了多测量向量模型(Multiple Measurement Vectors,MMV)应用的可行性。针对铝合金试块中不同深度的φ2 mm横通孔,分别使用MMV模型中的多测量稀疏贝叶斯(Multiple Sparse Bayesian Learning,MSBL)算法和SMV模型中的稀疏贝叶斯(Sparse Bayesian Learning,SBL)算法进行超声全矩阵数据重构,并实施全聚焦成像。随后,引入归一化均方误差和阵列性能因子评价图像和信号的重构效果。实验结果表明,SBL算法在25%采样率时的归一化均方误差为1.9%,而MSBL算法仅需15%采样率即可达到相似效果且耗时更少。     

聚3-己基噻吩：非富勒烯太阳能电池中的量子效率损失和电压损失

聚3-己基噻吩(P3HT)以其合成工艺简单、成本低廉的优势,成为有机光伏领域中最具吸引力的电子给体材料之一。然而,目前P3HT: 非富勒烯太阳能电池的光伏性能仍然较差。在本工作中,我们证明了与P3HT: 富勒烯太阳能电池相比,较快的电荷转移态的非辐射衰减速率(K_nr)是导致P3HT: 非富勒烯太阳能电池中较低的量子效率和较高的电压损失的原因。然后,我们研究了基于非富勒烯受体ZY-4Cl的太阳能电池的工作机理。研究结果表明与P3HT: 非富勒烯体系相比,P3HT: ZY-4Cl中K_nr的降低改善了器件的量子效率,同时降低了电压损失。K_nr降低的原因可以部分归因于电荷转移态能量的增加。此外,给体分子和受体分子之间的距离(DA间距)的增大也是K_nr减少的重要原因。因此,我们得出结论：为了提高P3HT太阳能电池的性能,需进一步降低器件的K_nr,这可通过增加活性层中的DA间距来实现。     

山东龙口北皂煤矿软岩力学特性实验研究

根据室内实验结果, 本文讨论了北皂煤矿的岩石力学性质, 物化特性。泥质岩类的力学性质和水理性质、物化特性有关。泥质岩类具有显著的流动变形和各向异性。