The structure of sulfur-poly(acrylonitrile)-based Li-sulfur batteries is elucidated and correlated with the electrochemical performance of such devices. Apart from the poly(acrylonitrile)-derived backbone, thioamide as well as poly(sulfide) structures are proposed. Furthermore, the intermediary formation of S8 during cycling and the role of the electrolyte in its reintegration during charging into are addressed. In summary, a comprehensive picture of the chemistry and electrochemistry of Li-sulfur batteries is presented.

Structure-Related Electrochemistry of Sulfur-Poly(acrylonitrile) Composite Cathode Materials for Rechargeable Lithium Batteries

A review on the chemistry, coordination, structure and biological properties of 1-(acyl/aroyl)-3-(substituted) thioureas

Lithium–sulfur (Li/S) technology holds great promise for efficient, safe, and economic next-generation batteries. However, commercialization is limited by some issues, which are related to the fast degradation of Li/S cells and poor rate capability. Existing strategies addressing these issues are often unsuitable for commercialization because of their complexity and lack of scalability. This Letter presents a simple, cheap, and scalable synthesis of a sulfur-based cathode material from commercially available poly(methyl methacrylate)/poly(acrylonitrile) (PMMA/PAN) fibers. Thermal conversion of PMMA/PAN fibers with elemental sulfur yields sulfurized poly(acrylonitrile) (SPAN) with up to 46 wt % covalently bound sulfur. The fibrous morphology with cylindrical macropores helps to form electronic conduction networks in the cathode and provides directed diffusion pathways for ions. Consequently, these Li/SPAN cells show low internal resistances, high initial capacities up to 1672 mAh·g–1sulfur, high rate capab...

Easily Accessible, Textile Fiber-Based Sulfurized Poly(acrylonitrile) as Li/S Cathode Material: Correlating Electrochemical Performance with Morphology and Structure

Liquid–liquid extraction of palladium(II) and gold(III) with N-benzoyl-N′,N′-diethylthiourea and the synthesis of a palladium benzoylthiourea complex

N‐Acyl‐thioharnstoffe – effektive Extraktionsmittel für die Flüssig‐Flüssig‐Extraktion von Metallionen

N-(Thiocarbamoyl)banzamidine 1 und N-(Thiocarbamoyl)-N′-phenyl-benzamidine 2 bilden mit Ni2+-, Pd2+-, Co3+- und Ag+-Ionen in alkoholischer Losung kristalline Innerchelatkomplexe1ah und 2ah mit N/S-Koordination.



Aus ESCA-Spektren wird im Falle der Chelate von 1 als Haftgruppe NH nachgewiesen und ihre hohere Donorfahigkeit im Vergleich mit dem isosterne Sauerstoffhaftatom gegenuber Nickel fest-gestellt. Dies wird durch d-1H-NMR-spektroskopisch bestimmte Werte von ΔGc≠ fur die behinderte Rotation der Et2N-Gruppe an 1 a unterstutzt.



Complex Formation of N-(Thiocarbamoyl) benzamidines



N-(Thiocarbamoyl)benzamidines 1 and N-(Thiocarbamoyl)-N′-phenyl-benzamidines 2 form in alcoholic solutions with Ni2+, Cu2+, Pd2+, Co3+, and Ag+ ions well crystallized chelates 1a h and 2ah, respectively, with N/S coordination.



The X-ray photoelectron spectra evidence the NH group as ligator in the case of chelates of 1 and the increased donor capacity compared with the isosteric oxygen ligator atom bound to nickel. This is confirmed by d-1H-n.m.r. spectroscopy analyzing the value of ΔGc≠ for the rotational barrier for the Et2N group of 1a

Zur Komplexbildung von N-(Thiocarbamoyl)benzamidinen

N-[thio(seleno)carbamoyl] benzimdoylchloride aus N-benzoylthio(seleno)harnstoffen und thiophosgen

Es wurden Innerchelatmetallkomplexe des PdII, NiII, CuII, CoIII und AgI mit α-Cyano-β-amino-dithioacrylsaureestern dargestellt. Die Koordination der Dithiocarbonester-gruppierung und des Aminstickstoffs (S/N-Koordination) wird durch die chemische Verschiebung der S2p- und N1s-Elektronenbindungsenergien in den ESCA-Spektren bewiesen.



Heavy Metal Chelates of α-Cyano-β-amino-dithioacrylates



The inner metal chelates of PdII, NiII, CoIII, and AgI with α-cyano-β-amino-dithioacrylates have been prepared. The coordination of the dithioester group and the amine nitrogen (S/N-coordination) has been proved by the chemical shift of the S2p and N1s electron binding energies in the ESCA spectra.

Schwermetallchelate von α-Cyano-β-amino-dithioacrylsäureestern

Synthesis, Coordination Chemistry and Mass Spectrometric Fragmentation of New N-(Thiocarbamoyl)-benzamidines



Syntheses of N-(thiocarbamoyl)benzamidines from benzimidoylchlorides and aromatic amino acids as starting materials are reported. The prepared compounds were used as ligands for complexing nickel(II) and copper(II)ions. The benzamidines were characterized by mass spectrometric methods. The fragmentation pattern of the benzamidines was derived from the corresponding MIKE-spectra.

Synthese, koordinationschemische und massenspektrometrische Charakterisierung neuartiger carboxylsubstituierter N‐(Thiocarbamoyl)‐benzamidine

Reactions of N-(N′,N′-Dialkyl(aryl)amino-thiocarbonyl)benzimidoylchlorides with Potassium Thiocyanate



The treatment of the title compound N-(amino-thiocarbonyl)-benzimidoylchloride 1 with potassium thiocyanate leads in dependence on the solvents (methanol, acetic acid, acetone) either to the 1,3,5-thiadiazine-2-thione 2a–d or to the ring opened isothiocyanate 4a, b. In the case of methanol the N-(amino-thiocarbonyl)benzimidates were formed as by-products.



The structure of the products is confirmed by analytical data and by chemical transformations. 2a reacts with methyl iodide to form the 2-methylthio-6-morpholino-4-phenyl-1,3,5-thiadiaziniumiodide 3a. From 4a and water the N-(morpholino-thiocarbonyl)benzamide 5a arises. The reaction of morpholine with 4a yields the benzamidine 6a.

G. Weber

Papers

Zur Komplexbildung von N-(Thiocarbamoyl)benzamidinen

N-[thio(seleno)carbamoyl] benzimdoylchloride aus N-benzoylthio(seleno)harnstoffen und thiophosgen

Schwermetallchelate von α-Cyano-β-amino-dithioacrylsäureestern

Synthese, koordinationschemische und massenspektrometrische Charakterisierung neuartiger carboxylsubstituierter N‐(Thiocarbamoyl)‐benzamidine

Zur Reaktion von N‐(N′,N′‐Dialkyl(aryl)amino‐thiocarbonyl)benzimidoylchloriden mit Kaliumthiocyanat