Lithium manganese oxide （LiMn2O4） is a principal cathode material for high power and high energy density electrochemical storage on account of its low cost, non-toxicity, and ease of preparation relative to other ca...Lithium manganese oxide （LiMn2O4） is a principal cathode material for high power and high energy density electrochemical storage on account of its low cost, non-toxicity, and ease of preparation relative to other cathode materials. However, there are well-documented problems with capacity fade of lithium ion batteries containing LiMn2O4. Experimental observations indicate that the manganese content of the electrolyte increases as an electrochemical cell containing LiMn2O4 ages, suggesting that active material loss by dissolution of divalent manganese from the LiMn2O4 surface is the primary reason for reduced cell life in LiMn2O4 batteries. To improve the retention of manganese in the active material, it is key to understand the reactions that occur at the cathode surface. Although a thin layer of electrolyte decomposition products is known to form at the cathode surface, the speciation and reaction mechanisms of Mn^2＋ in this interface layer are not yet well understood. To bridge this knowledge gap, reactive force field （ReaxFF） based molecular dynamics was applied to investigate the reactions occurring at the LiMn2O4 cathode surface and the mechanisms that lead to manganese dissolution. The ReaxFFMD simulations reveal that the cathode-electrolyte interface layer is composed of oxida- tion products of electrolyte solvent molecules including aldehydes, esters, alcohols, polycarbonates, and organic radicals. The oxidation reaction pathways for the electro- lyre solvent molecules involve the formation of surface hydroxyl species that react with exposed manganese atoms on the cathode surface. The presence of hydrogen fluoride （HF） induces formation of inorganic metal fluorides and surface hydroxyl species. Reaction products predicted by ReaxFF-based MD are in agreement with experimentally identified cathode-electrolyte interface compounds. An overall cathode-electrolyte interface reaction scheme is proposed based on the molecular simulation results.展开更多
t In this paper,a facile strategy is proposed to controllably synthesize mesoporous Li_(4)Ti_(5)O_(12)/C nanocomposite embedded in graphene matrix as lithium-ion battery anode via the co-assembly of Li_(4)Ti_(5)O_(12)...t In this paper,a facile strategy is proposed to controllably synthesize mesoporous Li_(4)Ti_(5)O_(12)/C nanocomposite embedded in graphene matrix as lithium-ion battery anode via the co-assembly of Li_(4)Ti_(5)O_(12)(LTO)precursor,GO,and phenolic resin.The obtained composites,which consists of a LTO core,a phenolic-resin-based carbon shell,and a porous frame constructed by rGO,can be denoted as LTO/C/rGO and presents a hierarchical structure.Owing to the advantages of the hierarchical structure,including a high surface area and a high electric conductivity,the mesoporous LTO/C/rGO composite exhibits a greatly improved rate capability as the anode material in contrast to the conventional LTO electrode.展开更多
文摘Lithium manganese oxide （LiMn2O4） is a principal cathode material for high power and high energy density electrochemical storage on account of its low cost, non-toxicity, and ease of preparation relative to other cathode materials. However, there are well-documented problems with capacity fade of lithium ion batteries containing LiMn2O4. Experimental observations indicate that the manganese content of the electrolyte increases as an electrochemical cell containing LiMn2O4 ages, suggesting that active material loss by dissolution of divalent manganese from the LiMn2O4 surface is the primary reason for reduced cell life in LiMn2O4 batteries. To improve the retention of manganese in the active material, it is key to understand the reactions that occur at the cathode surface. Although a thin layer of electrolyte decomposition products is known to form at the cathode surface, the speciation and reaction mechanisms of Mn^2＋ in this interface layer are not yet well understood. To bridge this knowledge gap, reactive force field （ReaxFF） based molecular dynamics was applied to investigate the reactions occurring at the LiMn2O4 cathode surface and the mechanisms that lead to manganese dissolution. The ReaxFFMD simulations reveal that the cathode-electrolyte interface layer is composed of oxida- tion products of electrolyte solvent molecules including aldehydes, esters, alcohols, polycarbonates, and organic radicals. The oxidation reaction pathways for the electro- lyre solvent molecules involve the formation of surface hydroxyl species that react with exposed manganese atoms on the cathode surface. The presence of hydrogen fluoride （HF） induces formation of inorganic metal fluorides and surface hydroxyl species. Reaction products predicted by ReaxFF-based MD are in agreement with experimentally identified cathode-electrolyte interface compounds. An overall cathode-electrolyte interface reaction scheme is proposed based on the molecular simulation results.
基金supported by the National Key Research and Development Program of China(Grant No.2016YFB0101312)the National Natural Science Foundation of China(Grant No.21975157).
文摘t In this paper,a facile strategy is proposed to controllably synthesize mesoporous Li_(4)Ti_(5)O_(12)/C nanocomposite embedded in graphene matrix as lithium-ion battery anode via the co-assembly of Li_(4)Ti_(5)O_(12)(LTO)precursor,GO,and phenolic resin.The obtained composites,which consists of a LTO core,a phenolic-resin-based carbon shell,and a porous frame constructed by rGO,can be denoted as LTO/C/rGO and presents a hierarchical structure.Owing to the advantages of the hierarchical structure,including a high surface area and a high electric conductivity,the mesoporous LTO/C/rGO composite exhibits a greatly improved rate capability as the anode material in contrast to the conventional LTO electrode.
