High-Performance Solid Lithium Metal Batteries Enabled by LiF/LiCl/LiIn Hybrid SEI via InCl3-Driven In Situ Polymerization of 1,3-Dioxolane

The use of poly(1,3-dioxolane) (PDOL) electrolyte for lithium batteries has gained attention due to its high ionic conductivity, low cost, and potential for large-scale applications. However, its compatibility with Li metal needs improvement to build a stable solid electrolyte interface (SEI) toward metallic Li anode for practical lithium batteries. To address this concern, this study utilized a simple InCl₃-driven strategy for polymerizing DOL and building a stable LiF/LiCl/LiIn hybrid SEI, confirmed through X-ray photoelectron spectroscopy (XPS) and cryogenic-transmission electron microscopy (Cryo-TEM). Furthermore, density functional theory (DFT) calculations and finite element simulation (FES) verify that the hybrid SEI exhibits not only excellent electron insulating properties but also fast transport properties of Li⁺. Moreover, the interfacial electric field shows an even potential distribution and larger Li⁺ flux, resulting in uniform dendrite-free Li deposition. The use of the LiF/LiCl/LiIn hybrid SEI in Li/Li symmetric batteries shows steady cycling for 2000 h, without experiencing a short circuit. The hybrid SEI also provided excellent rate performance and outstanding cycling stability in LiFePO₄/Li batteries, with a high specific capacity of 123.5 mAh g⁻¹ at 10 C rate. This study contributes to the design of high-performance solid lithium metal batteries utilizing PDOL electrolytes.     

Mechanism and kinetics investigation of reaction network: 1,3-Dichloro-2-propanol with alkali to prepare epichlorohydrin

Dehydrochlorination of 1,3-dichloropropanol with alkali is a key step to industrially produce epichlorohydrin. But there are many side reactions involved in the synthesis process. In this work, a complete mechanism and kinetics investigation of the related reaction network was constructed. Density functional theory simulation method was first used to simulate the possible reactions so as to confirm the reaction mechanism and simplify the reaction network. Based on the simulation results, the complex reaction network was simplified into a three-step consecutive reaction. The kinetic parameters of the three consecutive steps, including the order of the reaction, the pre-exponential factor, and activation energy, were experimentally determined by conductance and other methods. All the experimental results are basically consistent with the simulation. The obtained kinetics data provide a basis for epichlorohydrin synthesis process optimization.     

Improved Synthesis of Pyrroles and Indoles via Lewis Acid‐Catalyzed Mukaiyama–Michael‐Type Addition/Heterocyclization of Enolsilyl Derivatives on 1,2‐Diaza‐1,3‐Butadienes. Role of the Catalyst in the Reaction Mechanism

The Mukaiyama–Michael‐type addition of various silyl ketene acetals or silyl enol ethers on some 1,2‐diaza‐1,3‐butadienes proceeds at room temperature in the presence of catalytic amounts of Lewis acid affording by heterocyclization 1‐aminopyrrol‐2‐ones and 1‐aminopyrroles, respectively. 1‐Aminoindoles have been also obtained by the same addition of 2‐(trimethylsilyloxy)‐1,3‐cyclohexadiene on some 1,2‐diaza‐1,3‐butadienes and subsequent aromatization. Mechanistic investigations indicate the coordination by Lewis acid of the enolsilyl derivative and its 1,4‐addition on the azo‐ene system of 1,2‐diaza‐1,3‐butadienes. The migration of the silyl group from a hydrazonic to an amidic nitrogen, its acidic cleavage and the final internal heterocyclization give the final products. Based on NMR studies and ab initio calculations, a plausible explanation for the migration of the silyl protecting group is presented.     

A Convenient Procedure for the Synthesis of Acetals from α‐Halo Ketones

A study for determining the scope and limitations of a procedure for synthesising ethylene acetals from haloketones is presented. The method uses 1,2‐bis(trimethylsilyloxy)ethane, BTSE, as reagent and Nafion^®‐TMS as catalyst. Two procedures have been tested: (A) stoichiometric amounts of the haloketone and BTSE and a catalytic amount of Nafion^®‐TMS were heated to reflux in chloroform solution, and (B) stoichiometric amounts of the reactants and a catalytic amount of Nafion^®‐TMS were heated to 90–100 °C in the absence of solvent. The following ketones have been tested: 2‐bromo‐1‐phenyl‐1‐ethanone, 2‐bromo‐cyclopentenone, 3‐bromo‐3‐methyl‐2‐butanone, 3‐chloro‐3‐methyl‐2‐butanone, 1‐bromo‐3,3‐dimethyl‐2‐butanone, 1‐chloro‐3,3‐dimethyl‐2‐butanone, 2‐bromocyclohexanone, 2‐chloro‐1‐cyclohexyl‐1‐ethanone, 1,1‐dibromo‐3,3‐dimethyl‐2‐butanone, 1,3‐dibromo‐3‐methyl‐2‐butanone, 1,3‐dibromo‐2‐butanone, 1,3‐dibromo‐2‐propanone, 2‐chloro‐1‐phenyl‐1‐ethanone, and endo‐2‐bromocamphor. Yields were in the range 57–100% with the exceptions of endo‐2‐bromocamphor which afforded <10% yield and the dibromoketones 1,1‐dibromo‐3,3‐dimethyl‐2‐butanone and 1,3‐dibromo‐3‐methyl‐2‐butanone for which the method failed. Factors determining the scope and limitations are briefly discussed. Full experimental details and spectroscopic data of the acetals are given.