高压下硝基甲烷分子温度的密度泛函计算

用密度泛函理论在B3LYP/6-311++G(2d,2P)计算水平上对硝基甲烷分子进行了结构优化、频率和热化学分析.发现:在相同温度条件下改变压强,分子熵函数产生了改变,当温度和压强条件相同时,对于不同物质熵函数的改变是相同的.以热力学理论中麦克斯韦关系为基础,通过计算等温过程中分子的熵函数对压强的变化率,用数值拟合方法得到不同压强条件下分子温度的表达式:T=T0+(1-B)[18.3858+0.5392P]V0,式中T0、V0分别表示分子系统初态的温度和体积,T、V分别表示系统在末态的温度和体积,B是体积的压缩比.在选定参数的情况下该表达式可以计算不同压强条件下CHNO含能材料的分子温度.同时,以硝基甲烷为验证,选取基本参数V0和B,计算其在C-J条件对应的爆压14GPa下,分子温度为3461K,对应爱因斯坦温度,相当于3228cm-1的能量,在实验中该能量足以激发硝基甲烷分子内振动能量重新分配过程,有可能激发C-N键的红外振动而引起单分子分解反应的发生.因此,此表达式可用于预测含能材料撞击点火过程单分子分解可能的反应通道.     

The stationary solution of a one-dimensional bipolar quantum hydrodynamic model

In this paper, we consider the existence and uniqueness of stationary solution to the bipolar quantum hydrodynamic model in one dimensional space with general non-constant doping profile. The existence of the stationary solution is proved by Leray-Schauder fixed-point theorem and a crucial truncation technique is used to derive the positive upper and lower bounds of the stationary solution. The uniqueness of the stationary solution is shown by a delicate energy estimate.     

Room-Temperature Salt Template Synthesis of Nitrogen-Doped 3D Porous Carbon for Fast Metal-Ion Storage

The water-soluble salt-template technique holds great promise for fabricating 3D porous materials. However, an equipment-free and pore-size controllable synthetic approach employing salt-template precursors at room temperature has remained unexplored. Herein, we introduce a green room-temperature antisolvent precipitation strategy for creating salt-template self-assembly precursors to universally produce 3D porous materials with controllable pore size. Through a combination of theoretical simulations and advanced characterization techniques, we unveil the antisolvent precipitation mechanism and provide guidelines for selecting raw materials and controlling the size of precipitated salt. Following the calcination and washing steps, we achieve large-scale and universal production of 3D porous materials and the recycling of the salt templates and antisolvents. The optimized nitrogen-doped 3D porous carbon (N-3DPC) materials demonstrate distinctive structural benefits, facilitating a high capacity for potassium-ion storage along with exceptional reversibility. This is further supported by in situ electrochemical impedance spectra, in situ Raman spectroscopy, and theoretical calculations. The anode shows a high rate capacity of 181 mAh g⁻¹ at 4 A g⁻¹ in the full cell. This study addresses the knowledge gap concerning the room-temperature synthesis of salt-template self-assembly precursors for the large-scale production of porous materials, thereby expanding their potential applications for electrochemical energy conversion and storage.     

Recent Progress in High-Performance Lithium Sulfur Batteries: The Emerging Strategies for Advanced Separators/Electrolytes Based on Nanomaterials and Corresponding Interfaces

Lithium-sulfur (Li−S) batteries, possessing excellent theoretical capacities, low cost and nontoxicity, are one of the most promising energy storage battery systems. However, poor conductivity of elemental S and the “shuttle effect” of lithium polysulfides hinder the commercialization of Li−S batteries. These problems are closely related to the interface problems between the cathodes, separators/electrolytes and anodes. The review focuses on interface issues for advanced separators/electrolytes based on nanomaterials in Li−S batteries. In the liquid electrolyte systems, electrolytes/separators and electrodes system can be decorated by nano materials coating for separators and electrospinning nanofiber separators. And, interface of anodes and electrolytes/separators can be modified by nano surface coating, nano composite metal lithium and lithium nano alloy, while the interface between cathodes and electrolytes/separators is designed by nano metal sulfide, nanocarbon-based and other nano materials. In all solid-state electrolyte systems, the focus is to increase the ionic conductivity of the solid electrolytes and reduce the resistance in the cathode/polymer electrolyte and Li/electrolyte interfaces through using nanomaterials. The basic mechanism of these interface problems and the corresponding electrochemical performance are discussed. Based on the most critical factors of the interfaces, we provide some insights on nanomaterials in high-performance liquid or state Li−S batteries in the future.     

Fundamental studies on the intermediate layer of a bipolar membrane: Part III. Effect of starburst dendrimer PAMAM on water dissociation at the interface of a bipolar membrane

Starburst dendrimer polyamidoamine (PAMAM) with ellipsoidal or spheroidal shape is structure-regular and has much more amino groups than conventional polymers. This paper investigates the possibility of these amino groups on water dissociation in a bipolar membrane interface. To do this, a bipolar membrane is prepared by casting the solution of sulfonated poly(phenylene oxide) (SPPO) in dimethyl formamide (DMF) on a commercial anion exchange membrane that is immersed in PAMAM aqueous solution in advance. The existence of PAMAM adsorbed on the membrane is proved by X-ray photoelectron spectroscopy (XPS), and the adsorption amount is evaluated by weighting method. The junction thickness of the prepared bipolar membrane is determined by electrochemical impedance spectroscopy (EIS), and the performance is evaluated by current–voltage curves. The experiments show that both the generation and concentration of PAMAM would strongly affect the characteristics of the bipolar membranes. There exists a transitional concentration for various generations PAMAMs to catalyze effectively the water dissociation, and above or below the transitional concentration the performance of bipolar membranes is decreasing. The higher the generation, the lower the concentration. Moreover, at a fixed solution concentration, there is not the simple relation of monotone decreasing or increasing between the performance of bipolar membranes and the generations of PAMAMs. All these can be explained according to the characteristics of PAMAMs combined with available water dissociation theory.     

High-Entropy Lithium Argyrodite Solid Electrolytes Enabling Stable All-Solid-State Batteries

Superionic solid electrolytes (SEs) are essential for bulk-type solid-state battery (SSB) applications. Multicomponent SEs are recently attracting attention for their favorable charge-transport properties, however a thorough understanding of how configurational entropy (ΔS_conf) affects ionic conductivity is lacking. Here, we successfully synthesized a series of halogen-rich lithium argyrodites with the general formula Li_5.5PS_4.5Cl_xBr_1.5-x (0≤x≤1.5). Using neutron powder diffraction and ³¹P magic-angle spinning nuclear magnetic resonance spectroscopy, the S²⁻/Cl⁻/Br⁻ occupancy on the anion sublattice was quantitatively analyzed. We show that disorder positively affects Li-ion dynamics, leading to a room-temperature ionic conductivity of 22.7 mS cm⁻¹ (9.6 mS cm⁻¹ in cold-pressed state) for Li_5.5PS_4.5Cl_0.8Br_0.7 (ΔS_conf=1.98R). To the best of our knowledge, this is the first experimental evidence that configurational entropy of the anion sublattice correlates with ion mobility. Our results indicate the possibility of improving ionic conductivity in ceramic ion conductors by tailoring the degree of compositional complexity. Moreover, the Li_5.5PS_4.5Cl_0.8Br_0.7 SE allowed for stable cycling of single-crystal LiNi_0.9Co_0.06Mn_0.04O₂ (s-NCM90) composite cathodes in SSB cells, emphasizing that dual-substituted lithium argyrodites hold great promise in enabling high-performance electrochemical energy storage.