Thermodynamic Modeling of the Au-Ge-X (X = In, Sb, Si, Zn) Ternary Systems.

In this study, the CALPHAD approach was employed to model the thermodynamics of the Au-Ge-X (X = In, Sb, Si, Zn) ternary systems, leveraging experimental phase equilibria data and previous assessments of related binary subsystems. The solution phases were modeled as substitutional solutions, and their excess Gibbs energies were expressed using the Redlich-Kister polynomial. Owing to the unavailability of experimental data, the solubility of the third elements in the Au-In, Au-Sb, and Au-Zn binary intermetallic compounds was excluded from consideration. Additionally, stable ternary intermetallic compounds were not reported in the literature and, thus, were not taken into account in the present thermodynamic calculations. Calculations of liquidus projections, isothermal sections, and vertical sections for these ternary systems have been performed, aligning with existing experimental findings. These thermodynamic parameters form a vital basis for creating a comprehensive thermodynamic database for Au-Ge-based alloys, which is essential for the design and development of new high-temperature Pb-free solders.

Coconstruction of Supramolecular Lithium-Conducting Cross-Linked Networks Based on PVDF and Triblock Polymer Nanomicrosphere Solid-State Polymer Electrolytes for Lithium-Metal Batteries.

Uneven lithium plating and low ionic conductivity currently impede the realization of high-capacity rechargeable lithium metal batteries. And the conventional poly(ethylene oxide) (PEO) solid-state electrolytes are unsuitable for high-energy-density Li anode applications due to their low lithium-ion transference number and high reactivity with Li metal, leading to detrimental dendrite formation and potentially hazardous exothermic reactions with the electrolyte. In this study, we employ a supramolecular approach to develop a novel polymer solid-state electrolyte based on poly(vinylidene fluoride) (PVDF) and a novel triblock polymer nanomicrosphere, (poly(ε-caprolactone)-poly(ethylene glycol)-poly(ε-caprolactone), (PCL-PEG-PCL). The abundance of carbonyl and ether-oxygen functional groups in PCL-PEG-PCL enhances the lithium coordination environment within the polymer solid-state electrolyte. Additionally, the original C-F moieties of PVDF form hydrogen bonds with C-H and terminal hydroxyl groups in PCL-PEG-PCL, collectively creating a multichannel fast Li+-conducting supramolecular cross-linked network. The resulting electrolyte demonstrates a high ionic conductivity of 1.4 × 10-3 S cm-1 and an extended electrochemical window of 5.2 V. Moreover, the electrolyte exhibits a high lithium-ion transference number (tLi+ = 0.63) at room temperature and exhibits excellent interfacial compatibility with the lithium metal anode. For the resulting electrolyte utilized in LiFePO4 batteries, the capacity retention of the cells assembled with this electrolyte exceeds 91.3% after 1000 cycles at 25 °C and 2 C (0.281 mA cm-2).

Strategies for Controlling or Releasing the Influence Due to the Volume Expansion of Silicon inside Si-C Composite Anode for High-Performance Lithium-Ion Batteries.

Currently, silicon is considered among the foremost promising anode materials, due to its high capacity, abundant reserves, environmental friendliness, and low working potential. However, the huge volume changes in silicon anode materials can pulverize the material particles and result in the shedding of active materials and the continual rupturing of the solid electrolyte interface film, leading to a short cycle life and rapid capacity decay. Therefore, the practical application of silicon anode materials is hindered. However, carbon recombination may remedy this defect. In silicon/carbon composite anode materials, silicon provides ultra-high capacity, and carbon is used as a buffer, to relieve the volume expansion of silicon; thus, increasing the use of silicon-based anode materials. To ensure the future utilization of silicon as an anode material in lithium-ion batteries, this review considers the dampening effect on the volume expansion of silicon particles by the formation of carbon layers, cavities, and chemical bonds. Silicon-carbon composites are classified herein as coated core-shell structure, hollow core-shell structure, porous structure, and embedded structure. The above structures can adequately accommodate the Si volume expansion, buffer the mechanical stress, and ameliorate the interface/surface stability, with the potential for performance enhancement. Finally, a perspective on future studies on Si-C anodes is suggested. In the future, the rational design of high-capacity Si-C anodes for better lithium-ion batteries will narrow the gap between theoretical research and practical applications.

ZIF-8@MXene-reinforced flame-retardant and highly conductive polymer composite electrolyte for dendrite-free lithium metal batteries.

Though polymer electrolytes have been regarded as promising separators for solid-state lithium metal batteries, their low ionic conductivity, poor thermostability and inflammability limit their practical applications. Herein, a polymer composite electrolyte consisting of metal-organic frameworks modified Ti3C2-MXene nanosheets (ZIF-8@MXene) and polymer mixture (PE-ZIF-8@MXene) was fabricated. The fabricated nonflammable ZIF-8@MXene nanosheets have abundant functional groups and Lewis acid sites as well as high specific surface area. In the composite electrolyte, ZIF-8@MXene nanosheets increased the dissociation of lithium salts and provided channels for transporting ions, accelerating the Li ion transportation. They also enhanced the tensile strength, thermostability and flame resistance of PE-ZIF-8@MXene. Consequently, the fabricated flame-retardant PE-ZIF-8@MXene presented high ionic conductivity (4.4 mS cm-1), impressive Li+ transference number (0.76) and enhanced tensile strength (3.77 MPa). In addition, the assembled Li|PE-ZIF-8@MXene|Li had a long cycle life of 2000 h, and Li|PE-ZIF-8@MXene|LiFePO4 batteries displayed a capacity retention of 89.6% after 500 cycles.

Highly Conductive and Thermostable Grafted Polyrotaxane/Ceramic Hybrid Polymer Electrolyte for Solid-State Lithium-Metal Batteries.

Although polymer electrolytes have been regarded as potential separator materials for high energy density solid-state lithium-based batteries, their applications were significantly restricted by the low ionic conductivity, poor mechanical strength, and thermostability. Herein, a highly conductive and thermostable hybrid polymer electrolyte was developed by combining poly(vinylidene fluoride-co-hexafluoropropylene)-grafted polyrotaxane and nano-Al2O3 particles. In this unique hybrid, not only the Lewis acid-type Al2O3 and the fluorine groups of polyrotaxane branches exhibited strong integration with ionic species to accelerate the dissociation of lithium salt, improving the Li ionic conductivity, but also the abundant hydroxy functional groups on the surface of Al2O3 hydrogen-bonded with fluorine-containing branches, enhancing the mechanical strength. More importantly, the hybrid electrolyte exhibited superior thermal stability due to the heat resistance of the ceramic filler and the unique bead string structure of polyrotaxane. Consequently, a polymer electrolyte with a comprehensively improved performance was obtained, including high ionic conductivity and Li+ transfer number and superior tensile strength and thermostability. The hybrid electrolyte provided a dendrite-free lithium anode with a long life up to 1800 h and stable solid-state lithium-metal batteries at a high temperature of 80 °C.

Palladium-catalyzed aminations of aryl halides with phosphine-functionalized imidazolium ligands.

A series of 1-(2-diphenylphosphinoferrocenyl)ethyl-3-substituted imidazolium iodides [3-substituent = methyl (1a); isopropyl (1b); tert-butyl (1c); 1-adenosyl (1d); cyclohexyl (1e); 2,6-dimethylphenyl (1f); 2,4,6-trimethylphenyl (1g); 2,6-diisopropylphenyl (1h)] have been prepared and evaluated as ligands in the palladium-catalyzed aminations of aryl halides with various amines. The scope of the coupling process was carried out for various aryl bromides and chlorides with the catalysts generated in situ from a mixture of Pd(OAc)2 and in the presence of a base. NaO t Bu was found the choice of base in combination with dioxane, toluene, or DME as solvent, although NaOH or Cs2CO3 promoted the coupling of 4-bromotoluene with morpholine in moderate conversion. The steric hindrance from the 3-substituent of imidazolium in the hybrid-bidentate chelating system was found to be only beneficial to the substrates without ortho-substituents. The more sterically hindered 1d or 1h promoted the coupling of bromobenzene with morpholine in nearly quantitative conversion with 0.2 mol% of palladium loading in the presence of NaO t Bu at 110 degrees C, and 94% of conversion was afforded with the less sterical demanding 1a for a longer time. However, for the substrates with ortho-substituents, higher conversions were achieved with 1a. The Pd(OAc)2/1d catalytic system was also active for deactivated aryl chloride, and 71% isolated yield for the desired product was realized for coupling of 4-chloroanisole with morpholine at 2 mol% of catalyst loading. The developed catalyst system has been applied successfully to the synthesis of a key building block for a type of functional polymers.