An efficient isocyanide‐based synthesis of S‐thiocarbamates was discovered and thoroughly investigated. The new reaction protocol is a one‐pot procedure and allows the direct conversion of N‐formamides into thiocarbamates by initial dehydration with p‐toluene sulfonyl chloride to the respective isocyanide and subsequent addition of a sulfoxide component. Contrary to recent literature, which also uses isocyanides as starting material, but with other sulfur reagents than sulfoxides, in this protocol, no isolation and purification of the isocyanide component is necessary, thus significantly decreasing the environmental impact and increasing the efficiency of the synthesis. The new protocol was applied to synthesize a library of sixteen thiocarbamates, applying four N‐formamides and four commercially available sulfoxides. Furthermore, experiments were conducted to investigate the reaction mechanism. Finally, four norbornene‐based thiocarbamate monomers were prepared and applied in controlled ring‐opening metathesis polymerization (ROMP) reactions. The polymers were characterized by size‐exclusion chromatography (SEC) and their properties were investigated utilizing differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA).
The increasing lithium-ion battery production calls for profitable and ecologically benign technologies for their recycling. Unfortunately, all used recycling technologies are always associated with large energy consumption and utilization of corrosive reagents, which creates a risk to the environment. Herein we report a highly efficient mechanochemically induced acid-free process for recycling Li from cathode materials of different chemistries such as LiCoO2, LiMn2O4, Li(CoNiMn)O2, and LiFePO4. The introduced technology uses Al as a reducing agent in the mechanochemical reaction. Two different processes have been developed to regenerate lithium and transform it into pure Li2CO3. The mechanisms of mechanochemical transformation, aqueous leaching, and lithium purification were investigated. The presented technology achieves a recovery rate for Li of up to 70% without applying any corrosive leachates or utilizing high temperatures. The key innovation is that the regeneration of lithium was successfully performed for all relevant cathode chemistries, including their mixture.
The increasing lithium-ion battery production calls for profitable and ecologically benign technologies for recycling and recovering critical components, such as Li. Unfortunately, all currently used industrial ways of recycling are always associated with large energy consumption and utilization of corrosive reagents, which creates a risk to the environment. Herein we report a high efficient mechanochemically induced acid-free process for recycling Li from cathode materials of different and mainly used chemistries such as LiCoO2, LiMn2O4, Li(CoNiMn)O2, and LiFePO4. The introduced technology uses Al as a reducing agent in the mechanochemical reaction. Two different processes have been developed to regenerate lithium from cathode materials and to transform it to the pure Li2CO3. The mechanisms of mechanochemical transformation, aqueous leaching, and the lithium purification process were investigated. The presented technology achieves a recovery rate for Li of up to 70% without applying any corrosive leachates or utilizing high temperatures. The key innovation is that the regeneration of lithium was successfully performed for all relevant cathode chemistries, including their mixture. As a result, the engineered process can be declared universal and therefore be applied for lithium recovery from spent LIBs without the sorting step, thus improving the economic benefit of recycling.
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